MANUFACTURE OF ETHYL ACRYLATE FROM GLYCEROL

A Plant Design Presented to The Faculty of the Chemical Engineering

In Partial Fulfilment of the Requirements for the Degree of Bachelor of Science in Chemical Engineering

Prepared by: Ada, Mark Neil C. Banta, Mhadel A. Fonte, Ver Jeneth F. Judilla, Agnes Dorothy D. Pagasartonga, Mon Eric P.

October 2012

APPROVAL SHEET

In partial fulfillment of the requirement for the Degree of Bachelor of Science in Chemical Engineering, this thesis entitled, Manufacture of Ethyl Acrylate from Glycerol proposed and submitted by Mark Neil C. Ada, Mhadel A. Banta, Ver Jeneth F. Fonte, Agnes Dorothy D. Judilla and Mon Eric P. Pagasartonga is hereby recommended for approval by

Engr. Jerry G. Olay Panelist

Engr. Merlinda A. Palencia, Ph.D. Panelist

Engr. Renato C. Ong Adviser Chemical Engineering Department Adamson University Accepted and approved as partial compliance of the requirement for the Degree of Bachelor of Science in Chemical Engineering.

Engr. Jerry G. Olay Chairperson Chemical Engineering Department Adamson University

Letter of Transmittal

September 24, 2012

Engr. Renato C. Ong Ch. E. Department

Sir: In compliance to the requirements leading to the Degree of Bachelor of Science in Chemical Engineering, the endorsement hereby take the pleasure in transmitting this plant design entitled Manufacture of Ethyl Acrylate from Glycerol.

Respectfully yours,

Mark Neil C. Ada

Mhadel A. Banta

Ver Jeneth F. Fonte

Agnes Dorothy D. Judilla

Mon Eric P. Pagasartonga

ACKNOWLEDGMENT This Plant Design is a combined effort of the group and several others who, in one way or another, contributed to the completion of this requirement. Therefore, it is only fitting that we acknowledge some of these people. Firstly, this Plant Design could not have been accomplished without the supervision of Engr. Renato Ong. He consistently encouraged and challenged us to work with our best endeavors throughout the academic program. For all your effort and patience, we thank you. We would also like to give our deepest gratitude to all the authors mentioned in the bibliography section. The collected knowledge from these references made this Plant Design possible. To Engr. Jerry Olay, the chairperson of the Chemical Engineering Department; and to all the faculty members, including Dr. Merlinda Palencia, Dr. Erickson Roque, Engr. Sherrie Mae Medez, and Engr. Albert Evangelista, we send our sincerest appreciation to each of you for all the guidance. Furthermore, to Engr. Mike Lester Raypan, our personal friend, we deeply appreciate every advice and all the help we received throughout the research and design process. We are, of course, forever grateful for the unending love and support of our families and personal friends. Regardless of how long and tedious the entire process took, these people were behind us all the way. The grace and heart

everyone has shown us especially through the down times served as our inspiration to keep pushing forward. Also, we extend our gratitude to our ChE friends: Engr. Raymond Kenneth Dionisio, Engr. Kim Marie Barias, Engr. Leanna Mamorno, Khenbert Tecon, and Edrian Bautista, for their earlier work, and the support they have given since. Moreover, to our colleagues: Pinky Atregenio, Chessyrr Baylon, Camille Candelaria, Shienah Ricarte, Rose Ann Suapero, and John Christopher Emalada; for always being with us in the countless hours of waiting, for all the shared laughter that kept our sanity, and simply for the company in the past few years, and hopefully for many more years in the future, from the bottom of our hearts, thank you. Lastly, and most important of all, to God, who never failed to pull us when everyone else cannot push anymore, we thank You with our entirety.

TABLE OF CONTENTS

CHAPTER 1 I. II. III.

Product Description Introduction Product Profile Raw Materials Profile 2 6 10

CHAPTER 2 I. II. III.

Review of Related Literature Introduction Lists of Related Literatures Summary of Related Literature A. Process Description B. Product Literature C. Raw Material Literature D. Design and Equipment Literature 49 72 77 97 35 40

CHAPTER 3 I. II. III.

Process Description Introduction Process Flow Diagram Detailed Process Description 130 136 137

CHAPTER 4 I. II. III. IV.

Plant Capacity Determination Introduction Supply and Demand Analysis Raw Material Availability Conclusion 160 164 169 170

CHAPTER 5 I. II. III. IV. V.

Mass and Energy Balance Introduction Overall Mass & Energy Balance Diagram Summary of Basis, Assumptions and Equations Mass Balance per Equipment Energy Balance per Equipment 174 176 177 188 216

CHAPTER 6 I. II. III.

Equipment Design Introduction Summary of Assumptions and Design Equations Equipment Design 1. Dehydration Reactor 2. Shell and Tube Heat Exchanger 3. Absorption Column 279 292 309 244 246

4. Esterification Reactor 5. Pervaporator

338 354

CHAPTER 7 I. II. III.

Cost Estimation Introduction Estimation of Capital Investment Estimation of Product Cost 375 380 381

CHAPTER 8 I. II.

Economic Evaluation Introduction Analysis and Interpretation A. Rate of Return on Investment B. Net Present Worth C. Break-even Point Analysis III. IV. Conclusion Detailed Computations 437 438 439 440 441 436

APPENDICES Appendix A: References for Product and Raw Material Description Appendix B: References for Review of Related Literature Appendix C: References for Process Description Appendix D: References for Plant Capacity Determination Appendix E: References for Mass and Energy Balance Appendix F: References for Equipment Design Appendix G: References for Cost Estimation Appendix H: References for Economic Evaluation

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CHAPTER I

PRODUCT DESCRIPTION

CHAPTER I PRODUCT DESCRIPTION I. INTRODUCTION Acrylic esters make the main product derived from acrylic acid and traditionally produced by using propylene as raw material. They account for 55% of global demand. About half of the crude acrylic acid is processed to purified (glacial) acrylic acid, which is further processed both on-site (captive use) and by external downstream users. The other half of crude acrylic acid is transformed into various acrylate esters at the production sites. Identical to glacial acrylic acid, these acrylic esters serve as commercial products, which are further processed both on-site and by external downstream users. Currently, the trend of using sustainable materials for production is increasing in popularity due to the changes in global climate and as fossil sources for hydrocarbons run short. For this reason, the production of fuel from renewable sources such as biodiesel production is developing fast. In the biodiesel industry, the biodiesel is produced through the transesterification of natural oils where one mole of such oil yields three moles of hydrocarbon chains and one mole of glycerol. The hydrocarbon chains are used as biodiesel fuels and the by-product is glycerol. Due to the increasing awareness of climate change, these industries are projected to increase, thus increasing in the glycerol production. However, the

demand for glycerol is not increasing with the same tendency. This causes the price for glycerol to decrease, making it an interesting carbon source for intermediates. It is known that crude oil price is increasing. In connection to that, the propylene price increases as well, since it is mainly crude oil based. This can lead to increasing prices for acrylic acid production. On the other hand, glycerol prices are decreasing. The reason: Glycerol is not an important intermediate. It is mostly used in small amounts for cosmetics and for the food industry. Global glycerol demand is not increasing so fast as the bio-diesel production. The use of glycerol produced during the bio-diesel process has potential to be an environmentally carbon source for the production of acrylic acid. Moreover, the economical valorisation of glycerol makes the bio-diesel production more attractive. Replacing propylene by glycerol would be an indirect step for improving the sustainability in environmental care. The manufacturing process of acrylic acid from glycerol involves first the dehydration of glycerol to acrolein in phase gas, in the presence of solid catalysts such as sulfated zirconia has been developed. These catalysts deactivate slowly so as to permit long reaction cycles and low reactor volumes. The dehydration of glycerol to acrolein takes place in the gas phase and can be expressed as:

That means, for each mole of glycerol, one mol of acrolein and two moles of water (steam) are formed. In the case of the dehydration of glycerol, the reaction is carried out in the presence of a solvent. The reaction takes place in a catalyst fix bed, heated up by an oven with a heat homogenization system to assure the heat homogenization. The gaseous products coming out from the reactor are condensed in a glass reflux heat exchanger. The liquid is collected in a continuously glass cooled double-coated flask. A sample can be taken for the analysis, or the condensate can be transferred to the product flask. The next process is the oxidation of acrolein which produces the product, acrylic acid. This takes place in another catalyst fixed bed. The catalyst used is vanadium-molybdenum oxide.

Technical Grade Acrylic Acid which usually has a purity of about 95%. Technical acrylic acid is suitable for the production of commodity acrylate esters. Acrylic Acid and its esters (which include methyl, ethyl, n-butyl, and 2-ethylhexyl acrylate) are among the most versatile monomers for providing performance properties to a wide variety of polymers. Major markets for the commodity esters include surface coating, adhesive and sealants, textiles, plastic additives, and paper treatment.

Acrylic esters may also be used in solutions and emulsions; the ethyl ester is used in water-based paints and binders in non-woven fabrics; methyl ester as the copolymer component of acrylic fibres; the butyl ester in the water-based paints and adhesives; and the 2-ethylhexyl ester, used like the butyl ester as well as for stick-on labels and sealants. Co-polymers and blends of methyl methacrylate, butyl acrylate and ethyl hexyl acrylate are used in acrylic gloss paints where the acrylates typically represent between 20 and 30 percent (dry basis) of the formulation.

II. PRODUCT PROFILE Acrylic acid and its esters have served, for more than 30 years, as an essential building block in the production of some of our most commonly used industrial and consumer products. One of its esters, ethyl acrylate, is used in the production of polymers including resins, plastics, rubber, and denture material. It is a clear liquid with an acrid penetrating odor. The human nose is capable of detecting this odor at a thousand times lower concentration than is considered harmful if continuously exposed for some period of time. Acrylic acid and its esters readily combine with themselves or other monomers which are used in the manufacture of various plastics, coatings, adhesives, elastomers, as well as floor polishes, and paints. A. PRODUCT IDENTIFICATION Product Name IUPAC Molecular Formula Molecular Weight Specific gravity Melting point Ethyl Acrylate Ethyl propenoate C 5 H 8O 2 100.12 g/mole 0.922 (20C) -72C

Boiling point Viscosity Surface tension Vapor pressure Vapor density Solubility in water

99.5 C 0.55 Pas (25 C) 25.2 mN/m (20C) 29.3 mmHg (20C) 3.45 1.5 g/100g (25 C)

B. PRODUCT COMPOSITION SUBSTANCE Ethyl acrylate Acrylic acid Ethanol CONCENTRATION BY WEIGHT 98% 1% 1%

C. HAZARD IDENTIFICATION Physical State and Appearance Color Liquid Colorless to Light Yellow

Odor

Penetrating Lachrymator (Strong) Product may react violently with water to

Incompatibility with various substances

emit toxic gases or it may become selfreactive under conditions of shock or increase in temperature or pressure.

Corrosivity Stability

Non-corrosive in presence of glass. Stable

D. PRODUCT TRANSPORT, HANDLING AND STORAGE Keep locked up Keep container dry. Keep away from heat. Keep away from sources of ignition. Keep away from direct sunlight or strong incandescent light. Ground all Handling equipment containing material. Do not ingest. Do not breathe

gas/fumes/vapour/spray. Never add water to this product Avoid shock and friction. In case of insufficient ventilation, wear

suitable respiratory equipment. If ingested,

seek medical advice immediately and show the container or the label. Avoid contact with skin and eyes. Flammable materials should be stored in a separate safety storage cabinet or room. Keep away from heat. Keep away from sources of ignition. Keep container tightly Storage closed. Keep in a cool, well-ventilated place. Ground all equipment containing material. A refrigerated room would be preferable for materials with a flash point lower than 37.8C (100F).

E. PRODUCT SAFETY (Refer to Appendix, Material Safety and Data Sheet)

F. APPLICATION Use as main raw material in production of acrylic latex paint.

III. RAW MATERIALS PROFILE GLYCEROL Glycerol is the common name of propane-triol. It is a sweet tasting, highly viscous colorless and odorless liquid with no known toxic properties. Glycerol has many direct utilization fields, such as cosmetics, lubricants or explosives, and other applications. Glycerol is a side-product of bio-diesel production. Natural oils are triglycerides. The transesterification of one mole of such an oil yields three moles of hydrocarbon chains and one mole of glycerol. The hydrocarbon chains are used as bio-diesel fuels. Due to the developments in the bio-diesel industry, the glycerol production is also increasing. Since the demand for glycerol is not increasing with the same tendency, the glycerol price is decreasing, which makes it an interesting carbon source for intermediates. A. RAW MATERIAL IDENTIFICATION Raw Material Name Glycerol 1, 2, 3-propanetriol Synonyms Glycerine Glycol alcohol Chemical Family Alcohol

10

Molecular Formula

C 3 H 5(OH) 3

Structural Formula

Molecular Weight Density Specific gravity Melting point Boiling point Solubility Appearance Color Odor Surface tension

92.10 g/mol 1.261 g/cm 1.261 17.8 C (64.2F) 290 C (554F) Partially soluble in water Clear oily liquid colorless odorless 64.00 mN/m at 20 C

11

B. RAW MATERIAL COMPOSITION SUBSTANCE Glycerol Water CONCENTRATION BY WEIGHT <60% >40%

C. HAZARD IDENTIFICATION Physical State Stability Flammability Incompatibility Liquid (viscous) stable Slight Reactive with oxidizing agents

D. STABILITY AND REACTIVITY Stable under ordinary conditions of use and Stability storage. Hazardous Decomposition Products Toxic gases and vapor may be released if involved in a fire. Glycerin decomposes upon heating above 290C, forming

12

corrosive gas (acrolein). Hazardous Polymerization Will not occur. Strong oxidizers. Can react violently with acetic anhydride, calcium oxychloride, Incompatibilities chromium hydrides. Heat, Conditions to Avoid incompatibles. flames, ignition sources and oxides and alkali metal

E. HANDLING AND STORAGE Crude Handling glycerol is shipped to

refiner/manufacturing plants in standard tank cars or tank wagons. Glycerol solidifies at lower temperatures, and should be kept warm during

Storage

transportation and storing. Large storage tanks should contain a heated loop from a boiler or other heat source. Also, the boiler room should be heated to prevent the

13

glycerol from gelling in the fuel lines, fuel filters, and the boiler itself.

F. RAW MATERIAL SAFETY (Refer to Appendix, Material Safety and Data Sheet) G. APPLICATION Glycerol is used as the major raw material for the manufacture of acrylic acid and thus converting the acrylic acid to ethyl acrylate.

14

 AIR Air is mainly composed of nitrogen, oxygen, and argon, which together constitute the major gases of the atmosphere. The remaining gases are often referred to as trace gases. Dry air contains roughly (by volume) 78.09% nitrogen, 20.95% oxygen, 0.93% argon, 0.039% carbon dioxide, and small amounts of other gases. Air also contains a variable amount of water vapor, on average around 1%. While air content and atmospheric pressure varies at different layers, air suitable for the survival of terrestrial plants and terrestrial animals is currently only known to be found in Earth's troposphere and artificial atmospheres. A. RAW MATERIAL IDENTIFICATION Raw Material Name Appearance and Odor Vapor Density @ 70F Specific Gravity Molecular Weight Solubility in Water (v/v) Vapor Pressure Air Colorless and odorless gas 1.2 kg/m3 (0.0749 lb/ft3) Not applicable 28.97 0.0292 Gas, ambient

15

Freezing Point Boiling Point (1 atm) Specific Volume (ft3/lb):

-216.2C (-357.2F) -194.3C (-317.8F) 13.8 (for Nitrogen)

B. RAW MATERIAL COMPOSITION COMPONENT Nitrogen Oxygen COMPOSITION BY MOLE 79% 21%

C. STABILITY AND REACTIVITY Normally stable in gaseous state. Air which contains excess oxygen may present the Stability same hazards as liquid oxygen and could react violently with organic materials such as oil and grease. Materials with which Substance is Incompatible Hazardous Polymerization Fuels may form explosive mixtures with air. Will not occur

16

Contact Conditions to Avoid

with

incompatible

materials.

Avoid exposing cylinders to extremely high temperatures, which could cause the cylinders to rupture.

D. HANDLING AND STORAGE Protect cylinders against physical damage. Store in cool, dry, well-ventilated, fireproof area, away from flammable or combustible Handling materials and corrosive atmospheres. Store away from heat and ignition sources and out of direct sunlight. Do not allow area where cylinders are stored to exceed 52C. Use only DOT or ASME code containers. Store containers away from heavily

trafficked areas and emergency exits. Cylinders should be stored in dry, wellStorage ventilated areas away from sources of heat. Cylinders should be stored upright and be firmly secured to prevent falling or being knocked over. 17

E. RAW MATERIAL SAFETY (Refer to Appendix, Material Safety and Data Sheet)

F. APPLICATION Air serves as a reactant in the process of converting acrolein to acrylic acid (oxidation process).

18

 ETHYL ALCOHOL Ethyl alcohol is classified as a primary alcohol, meaning that the carbon its hydroxyl group attaches to has at least two hydrogen atoms attached to it as well. Many ethanol reactions occur at its hydroxyl group. Ethanol is often abbreviated as EtOH, using the common organic chemistry notation of representing the ethyl group (C 2 H 5 ) with OH. Ethanol has widespread use as a solvent of substances intended for human contact or consumption, including scents, flavorings, colorings, and medicines. In chemistry, it is both an essential solvent and a feedstock for the synthesis of other products.

A. RAW MATERIAL IDENTIFICATION Raw Material Name Appearance Odor Specific Gravity Molecular Formula Molecular Weight Solubility Ethanol Colorless clear liquid Mild, pleasant 0.790 C 2 H 5OH 46.0414 Miscible

19

Vapor Pressure Vapor Density Melting Point Boiling Point

59.3 mmHg @ 20C 1.59 -114.1C 78C

B. RAW MATERIAL COMPOSITION

COMPONENT Ethanol

CONCENTRATION BY WEIGHT 100%

C. STABILITY AND REACTIVITY

Stability

Stable Excess heat, incompatible materials,

Conditions of Instability

water/moisture Strong oxidizing agents, acids, alkali Materials with which Substance is Incompatible metals, ammonia, hydrazine, peroxides, acid anhydrides, silver oxide, acid

chlorides.

20

Hazardous Decomposition Products Polymerization

Carbon

monoxide,

carbon

dioxide,

irritating and toxic fumes and gases. Will not occur

D. HANDLING AND STORAGE

Wash thoroughly after handling. Use only in a well-ventilated area. Ground and bond containers when transferring material. Use spark-proof tools and explosion proof equipment. Avoid contact with eyes, skin Handling and clothing. Keep container tightly closed. Avoid contact with heat, sparks and flame. Avoid ingestion and inhalation. Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames. Keep away from heat, sparks and flame. Keep away from the source of ignition. Storage Store in a tightly closed container. Keep from oxidizing materials. Store in a cool,

21

well-ventilated

area

away

from

incompatible substances.

E. RAW MATERIAL SAFETY (Refer to Appendix, Material Safety and Data Sheet)

F. APPLICATION Ethanol is used as a reactant in the esterification process of acrylic acid yielding to ethyl acrylate and water.

22

 TUNGSTATED ZIRCONIA Tungstated Zirconia is a heterogeneous catalyst which is composed of Zirconium Oxide (Zirconia) and Tungsten Oxide. Zirconia serves as the carrier of the Tungsten Oxide which is the more active component in the system. This catalyst will be used in the dehydration process of glycerol. A. RAW MATERIAL IDENTIFICATION Zirconium Oxide Raw Material Name Appearance Odor Color Taste Molecular Weight Specific Gravity Zirconium Oxide Powdered solid Odorless White Tasteless 123.22 5.85 Insoluble in cold water, hot water. Slightly Solubility soluble in Hydrochloric acid, Nitric Acid. Slowly soluble in HF.

23

Melting Point Boiling Point

2680C 4300C

Tungsten Oxide Raw Material Name Appearance Odor Color Molecular Weight Specific Gravity Solubility Melting Point Boiling Point Tungsten Oxide Powdered solid Odorless yellow to yellow-green 231.85 7.16 Insoluble in cold water 1473C 4300C

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B. RAW MATERIAL COMPOSITION COMPONENT Zirconium Oxide 90% (CAS 1314-23-4) Tungsten Oxide 10% (CAS 1314-35-8) CONCENTRATION BY WEIGHT

C. HANDLING AND STORAGE Raw Material Name Handling Zirconium Oxide Do not breathe dust. Keep away from incompatibles such as oxidizing agents. Keep container tightly Storage closed. Keep container in a cool, wellventilated area.

Raw Material Name Handling

Tungsten Oxide

Keep away from heat. Keep away from

25

sources of ignition. Empty containers; evaporate the residue under a fume hood. Do not ingest. Do not breathe dust. Avoid contact with eyes. Wear suitable protective clothing. In case of insufficient ventilation, wear suitable respiratory equipment. If ingested, seek medical advice immediately. Keep container dry. Keep in a cool place. Ground all equipment containing material. Storage Keep container tightly closed. Keep in a cool, well-ventilated place.

D. RAW MATERIAL SAFETY (Refer to Appendix, Material Safety and Data Sheet) E. APPLICATION Tungstated Zirconia serves as a catalyst in the process of dehydration of glycerol to acrolein.

26

 VANADIUM-MOLYBDENUM OXIDE Vanadium-Molybdenum Oxide Catalyst is a type of heterogeneous catalyst which is composed of Vanadium (IV) Oxide and Molybdenum Trioxide. This catalyst will be used for the oxidation process of acrylic acid. A. RAW MATERIAL IDENTIFICATION Vanadium (IV) Oxide Raw Material Name Vanadium (IV) Oxide

Appearance Odor Color Molecular Weight Specific Gravity Solubility Melting Point

crystalline powder odorless blue 82.94 4.339 Insoluble in water 1967 oC

27

Molybdenum Trioxide Raw Material Name Molybdenum Trioxide

Appearance Odor Molecular Weight Specific Gravity Solubility in water Melting Point Boiling Point

yellow solid odorless 143.94 4.69 2.055 g/100 mL (70 C) 795 C 1155 C

B. RAW MATERIAL COMPOSITION COMPONENT Vanadium(IV) Oxide (CAS 12036-21-4) Molybdenum Trioxide (CAS 1313-27-5) 84% CONCENTRATION BY WEIGHT 16%

28

C. HANDLING AND STORAGE

Raw Material Name

Vanadium(IV) Oxide Open and handle container with care. Wash thoroughly after use. Store away

Handling

from halogens. Do not get in eyes, on skin or clothing. Do not breathe dust, vapor, mist, gas. Keep container tightly closed. Store in a

Storage cool, dry, well-ventilated area.

Raw Material Name

Molybdenum Trioxide Protect from physical damage. Containers of this material may be hazardous when

Handling

empty since they retain product residues (dust, solids); observe all warnings and precautions listed for the product. Keep in a tightly closed container.

Storage Store in a cool, dry, ventilated area away

29

from sources of heat, incompatibilities.

moisture and

D. RAW MATERIAL SAFETY (Refer to Appendix, Material Safety and Data Sheet)

E. APPLICATION Vanadium-Molybdenum Oxide Catalyst serves as a catalyst in the process of oxidation of acrolein to acrylic acid.

30

 SULFURIC ACID Sulfuric acid is a highly corrosive strong mineral acid. It is a very important commodity chemical. The historical name for this acid is oil of vitriol. It is a viscous liquid and is soluble in water at all concentrations. The corrosiveness of it is mainly due to its strong acidic nature, strong dehydrating property and if concentrated strong oxidizing property. Principal uses include lead-acid batteries for cars and other vehicles, mineral processing, fertilizer manufacturing, oil refining, wastewater processing and chemical synthesis. A. RAW MATERIAL IDENTIFICATION Raw Material Name Appearance Odor Specific Gravity Molecular Formula Molecular Weight Solubility Viscosity Sulfuric acid Colorless to slightly yellow liquid with pungent odor 1.834 (20 C) H 2 SO 4 98.08 Miscible in water 26.7 cP (20C)

31

Melting Point Boiling Point

10.31C 337C

B. RAW MATERIAL COMPOSITION COMPONENT Sulfuric acid CONCENTRATION 18 M (98 %wt)

C. STABILITY AND REACTIVITY Stability Stable Oxidizers, Acids, Metals, Bases, Alkalis, Reducing agents, Water, Organics, Metal carbides. Product is water reactive. Hazardous Decomposition Products Polymerization SOx, Hydrogen Gas

Materials with which Substance is Incompatible

Will not occur

32

D. HANDLING AND STORAGE Keep container tightly closed in a cool, Handling well-ventilated place. Store in a secure area suitable for toxic material. Storage Keep locked up and out of the reach of children. Never add water to this product.

E. RAW MATERIAL SAFETY (Refer to Appendix, Material Safety and Data Sheet)

F. APPLICATION Sulphuric acid is used as a catalyst in the process of esterification of acrylic acid to the product ethyl acrylate.

33

CHAPTER II

REVIEW OF RELATED LITERATURE

34

CHAPTER II REVIEW OF RELATED LITERATURE I. INTRODUCTION Biodiesel is made through a catalyzed chemical reaction

(transesterification) between oils or fats and an alcohol (usually methanol). It has showed its importance as renewable and clean source of fuel for diesel engines. Common feedstocks are pure vegetable oil (e.g., soybean, canola, sunflower), rendered animal fats, or waste vegetable oils. Strong bases such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) are commonly used as catalysts. As the biodiesel industry is rapidly expanding, a glut of crude glycerol is being created. Crude glycerol is the major by-product of the biodiesel industry. In general, for every 100 pounds of biodiesel produced, approximately 10 pounds of crude glycerol are created. Because this glycerol is expensive to purify for use in food, pharmaceutical, or cosmetics industries, biodiesel producers must seek alternative methods for its disposal. Glycerol itself can not be burnt as a fuel, because at high temperatures it polymerizes and partially oxidizes to toxic acrolein. Besides it is also very difficult to use the glycerol coming from biodiesel production for its traditional uses in pharmacy and cosmetic since it does not have the required purity. 35

As a growing concern in the abundance of waste glycerol and the lack of areas to dispose this large waste stream, combustion of glycerol may be one of the simplest solutions. Clean combustion of glycerol is not possible because of its properties. In particular, burning of it will produce acrolein which is the thermal decomposition product of glycerol and is toxic at very low concentrations. With the increasing expansion of biomass as raw material in general, and biodiesel production in particular, glycerol is expected to become a major chemical platform for future biorefineries since it has emerged as an important organic building block. However, developing selective glycerol based catalytic processes is a major challenge. Thus, a high number of patents and research papers are being published nowadays. The dehydration of glycerol into acrolein has been known since the nineteenth century. Acrolein or acrylic aldehyde is used as intermediate for the production of many useful compounds as acrylic acid, acrylic acid esters, super absorber polymers and detergents. A sustainable and cost efficient dehydration of glycerol to acrolein could offer an alternative for the current commercial catalytic petrochemical process based on the reaction of propylene over a Bi/Mo-mixed oxide catalyst. In addition, direct synthesis of acrylonitrile and acrylic acid from glycerol is an attractive approach since both compounds are useful chemicals as raw materials for various synthetic resins, paints, fibbers etc.

36

Gas-phase catalytic oxidation of acrolein to acrylic acid has been given attention since late 1960s being concerned with the development of the two-step process fro production of acrylic acid from propene via acrolein as an intermediate. Acrylic acid is a versatile chemical that can be esterified, aminated or otherwise modified and polymerised to complex molecular arrangements to suit requirements. This characteristic enables a broad range of reactions for providing performance characteristics to a range of polymers. A high purity form (often referred to as glacial acrylic acid) is produced by a second distillation or crystallisation that reduces aldehyde impurities (especially furfural) which inhibit polymerisation. Different grades of glacial acrylic acid are available with flocculants requiring higher purity levels than dispersants and some other applications while a technical grade of acrylic acid may be produced by a simple distillation to produce a grade of acid suitable for the manufacture of acrylic esters, but unsuitable for polymerisation. The esters are produced by reacting acrylic acid with alcohols especially ethanol, methanol and butanol that may be saponified, converted to other esters or amides by aminolysis. Acrylates are derivatives of acrylic acid (such as methyl and ethyl acrylate) whose properties have been sufficiently modified to enable of acrylic acid to be used in different media as emulsion and solution polymers. As emulsions, these products may be used as coatings, finishes and binders leading to applications in paints, adhesives, and polishes with solutions used for industrial

37

coatings. Two-third of the world's production of acrylic acid is used to produce acrylic esters (acrylates) primarily for use in emulsions and solution polymers for latex-based paints, coatings, adhesives and textiles. Ethyl and methyl acrylates are manufactured on a continuous basis by passing acrylic acid and a small excess of the alcohol in a reactor bed at elevated temperature extracted at a yield of about 90 to 95 percent. Acrylic esters may be polymerised, catalysed by heat and oxidising agents in solution or emulsion methods to form long-chain thermoplastic resins. Broadly, acrylic ester polymers are colourless, insoluble in aliphatic hydrocarbons and resistant to alkali, mineral oils and water so that with good resistance to degradation, adhesion and electrical properties, they are widely used. Researches show varieties of glycerol transformations and processing that include the manufacture of ethyl acrylate. There are three major processes involve in this conversion, the dehydration of glycerol into acrolein, oxidation to form acrylic acid and esterification to produce ethyl acrylate. Synthesis of acrylic acid from glycerol represents an economic advantage since the latter does not contribute to global warming. Acrylates are used in a broad range of applications directly as a resin, or as solution or emulsion. The following provides an indication of typical applications with the market share expressed as a percentage of all acrylic acid applications as acrylic acid. Surface coatings, such as paints, represent the largest application for 38

acrylic esters at about 19 per cent of the market. Demand, that was motivated by the convenience of water-based paints especially the superior acrylic-based emulsions, is now being driven by regulations and interests to reduce atmospheric release of volatile organic compounds (VOCs) used as solvents in traditional (alkyd-based) surface coatings. This sector is growing at 3 to 5 per cent per year with faster growth for newer more sophisticated applications. Extensive research is applied to acrylic chemistry and with a very broad range of alternative processes, this activity has become specialised with patents and proprietary knowledge. There are now more manufacturers of specialty acrylic esters (that do not themselves manufacture acrylic acid) than there are manufacturers of the acid. The esters are generally produced near major traditional markets and suppliers of acrylic acid.

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II. LISTS OF RELATED LITERATURES BOOKS Gavin T. et al. (2008). Chemical Engineering Design Principles, Practice and Economics of Plant and Process Design. 2nd Ed. U.S.: Elsevier, Inc. Geankoplis, Christie J. (1993). Transport Processes and Unit Operations. 3rd Ed. Prentice-Hall International, Inc. McCabe. W. et al. (2001). Unit Operations of Chemical Engineering. 6th Ed. New York: McGraw-Hill Octave L. et al. (1999). Chemical Reaction Engineering. 3rd Ed. John Wiley & Son, Inc. Perry, R. and Green, D. (2008). Perrys Chemical Engineers Handbook. 8th Ed. New York: McGraw-Hill Shah, R. et al. (2003). Fundamentals of Heat Exchanger Design. John Wiley & Sons. Treybal, Robert E. (1981). Mass-Transfer Operations. 3rd Ed. New York: McGraw-Hill Ullmans (2004). Processes and Process Engineering. Wiley-VCH, Vol. 3. ENCYCLOPEDIA Kirk-Othmer (1999). Concise Encylopedia of Chemical Technology. 4th Ed. New York: John Wiley & Sons, Inc. 40

INTERNET Acrylic Acid. Retrieved from www.chemsystems.com Acrylic Acid manufacture in Western Australia Retrieved from http://www.chemlink.com.au/acryful.htm Acrylic Acid Production: Separation and Purification. Lin, Stephany et al. http://www.owlnet.rice.edu/~ceng403/gr2499/aagrp4.html Acrylic Acid Production via the Catalytic Partial Oxidation of Propylene: Separation Design http://www.owlnet.rice.edu/~ceng403/gr21099/acrylicacid2.htm Compilation of Henrys Law Constant for Inorganic and Organic Species of Potential Importance in Environmental Chemistry http://www.mpch-mainz.mpg.de/~sander/res/henry.html Ethanol http://www.chemeurope.com/en/encyclopedia/Ethanol.html Gases of the Air Retrieved from http://scifun.chem.wisc.edu/chemweek/pdf/airgas.pdf Method for Production of Acrylic Acid http://www.patentstorm.us/patents/7332624/fulltext.html Pervaporation An Overview http://www.cheresources.com/content/articles/separationtechnology/pervaporation-an-overiew 41

 Production of Acrylic Acid http://sbioinformatics.com/design_thesis/Acrylic_Acid/Acrylic-2520Acid.htm Sulfuric Acid http://www.chemeurope.com/en/encyclopedia/Sulfuric_acid.html The Mechanism for the Esterification Reactor http://www.chemguide.co.uk/physical/catalysis/esterify.html Turbine & High Efficiency Axial Flow Agitators http://www.feldmeier.com/cutsheets/turbine_agitator.pdf JOURNALS Alvarez, M et al. (2007). Evaluation of Liquid-Liquid Extraction Process for Separating Acrylic Acid Produced from Renewable Sugars. Chai, Song-Hai et al. (2007). Sustainable Production of Acrolein: Gas-phase Dehydration of Glycerol over Nb 2 O 5 Catalyst. Journal of Catalysis 250: 342349. Chengwang, Z. Acrylic Acid: Raw material cost pushed prices of acrylic acid and esters. Cortes-Jacome, M.A. et al. (2006). Generation of WO 3 -ZrO 2 Catalysts from Solid Solutions of Tungsten in Zirconia. Journal of Solid State Chemistry 179: 2663-2673.

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 Deleplanque, J. et al. (2010). Production of Acrolein and Acrylic Acid through Dehydration and Oxydehydration of Glycerol with Mixed Oxide Catalysts. Catalysis Today 157: 351-358. El-Zanati, E. et al. (2006). Modeling and Simulation of Butanol Separation from Aqueous Solutions Using Pervaporation. Journal of Membrane Science 280 (2006) 278283. Fan, X. et al. (2010). Glycerol (Byproduct of Biodiesel Production) as a Source for Fuels and Chemicals - Mini Review. The Open Fuels & Energy Science Journal, Vol. 3, 17-22. Guerrero-Perez, M.O. et al. (2009). Recent Inventions in Glycerol Transformations and Processing. Recent Patents on Chemical Engineering, Vol. 2, No. 1. Kaszonyi, A. et al. (2009). Bioglycerol: A New Platform Chemical. 44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009. Kim, Y.T. et al. (2010). Gas-phase Dehydration of Glycerol over ZSM-5 Catalysts. Microporous and Mesoporous Materials 131: 28-36. Kraai, G. et al. (2008). Kinetic Studies on the Rhizomucor miehei lipase catalyzed Esterification Reaction of Oleic acid with 1-butanol in a Biphasic System. Biochemical Engineering Journal 41 (2008) 8794.

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 Kujawski, W. (2000). Application of Pervaporation and Vapor Permeation in Environmental Protection. Polish Journal of Environmental Studies Vol. 9, No. 1 (2000), 13-26 Lipnizki, F. et al (1999). Simulation and Process Design of Pervaporation Plate-and-Frame Modules to Recover Organic Compounds from Waste Water. Institution of Chemical Engineers Trans IChemE, Vol 77, Part A, May 1999. Tao, L.Z. et al. (2010). Sustainable Production of Acrolein: Acidic Binary Metal Oxide Catalysts for Gas-phase Dehydration of Glycerol. Catalysis Today 158: 310-316. Tichy, Josef (1997). Oxidation of Acrolein to Acrylic Acid over VanadiumMolybdenum Oxide Catalysts. Applied Catalysts A: General 157: 363-385. Ulgen, A. and Hoelderich, W. (2009). Conversion of Glycerol to Acrolein in the Presence of WO 3 /ZrO 2 Catalysts. CatalLett 131:122-128 Wang, F. et al. (2009). Catalytic Dehydration of Glycerol over Vanadium Phosphate Oxides in the Presence of Molecular Oxygen. Journal of Catalysis 268, 260-267. PATENTS AlArifi, S. et al. (2011). Synthesis of Acrylic or Methacrylic Acid/Acrylate or Methacrylate Ester Polymers Using Pervaporation. European Patent Number 2325214 United States Patent Number 2011/0124829 44

 Bunning, D. et al. (1991). Process for Producing Acrylic Ester. United States Patent Number 4999452 Diefenbacher, A. et al. (2009). Process for Preparing Acrylic Acid. United States Patent Number 7566804 Dubois, Jean-Luc (2010). Method for Preparing Acrylic Acid from Glycerol. United States Patent Number 2010/0168471 Dubois, Jean-Luc (2010). Process for Manufacturing Acrolein from Glycerol. United States Patent Number 2010/0204502 Dubois, J.L. et al. (2008). Method for Producing Acrylic Acid from Glycerol. United States Patent Number 2008/0183013 Dubois, J.L. et al. (2008). Process for Dehydrating Glycerol to Acrolein. United States Patent Number 2008/0146852 United States Patent Number 2008/0214880 United States Patent Number 7396962 Elder, J. et al. (2003). Process for Preparing and Purifying Acrylic Acid From Propelyne Having Improved Capacity. US Patent Number 6639106 Figueras, F. et al. (2006). Tungsten Catalysts. United States Patent Number 2006 /0091045 Hammon, U. et al. (1993). Catalytic Gas-phase Oxidation of Acrolein to Acrylic Acid.

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United States Patent Number 5264625 Hecquet, G. et al. (2000). Process for the Manufacture of Acrylic Acid from Acrolein by a Redox Reaction and Use of a Solid Mixed Oxide Composition as Redox System in the said reaction. United States Patent Number 6025523 Hego, M. et al. (1998). Process and Apparatus for Purification of a Gas Stream Containing Acrolein. United States Patent Number 5770021 Hershberger, B.L., et al. (2005). Method of Producing Ethyl Acrylate. United States Patent Number 2005/0107629 Ishidoya, M. et al. (1992). Resin Composition for Use as Paint. United States Patent Number 5091492 Ishii, Y. et al. (2006). Method for Purification of Acrylic Acid. Unites States Patent Number 7048834 Jones, L. et al. (1994). Process for the Production of Plasticizers and Polyolesters. United States Patent Number 5324853 Kang, S. et al. (2009). Method for Producing (Meth) Acrylic Acid. United States Patent Number 7632968 Kang, S. et al. (2008). Method for Producing (Meth) Acrylic Acid. United States Patent Number 7319169

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 Krabetz, R. et al. (1986). Production of Acrylic Acid by Oxidation of Acrolein. United States Patent Number 4620035 Kautter, C.T. et al. (1969). Esterification of Acrylic Acid. United States Patent Number 3458561 Neher, A. et al. (1995). Process for the Production of Acrolein. United States Patent Number 005387720 Rezkallah, Areski (2008). Method for Purification of Glycerol. United States Patent Number 2008/0249338 Ruppel, W. et al. (1998). Catalytic Gas-Phase Oxidation of Acrolein to Acrylic Acid. United States Patent Number 5739391 Sato, T. et al. (1982). Process for Preparing and Recovering Acrylic Acid. United States Patent Number 4317926 Shidhar, Srinivasan (1995). Process for the Removal of Water from Acrylic Acid. United States Patent Number 5463121 Soohoo, T. et al. (2007). Membrane-assisted Fluid Separation Apparatus and Method. United States Patent Number 7758754 Tanimoto, M. et al. (2011). Process for Producing Acrolein and/or Acrylic Acid.

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United States Patent Number 2011/0015432 Tanimoto, M. et al. (2010). Process for Producing Acrolein and Acrylic Acid. United States Patent Number 2010/0249455 Yukawa, Yoshiyuki (2009). Water-Based Paint Compositions. United States Patent Number 2009/0099298 OTHER REFERENCES Alzate, Javier Fontalvo (2006). Design and Performance of Two-Phase Flow Pervaporation and Hybrid Distillation Processes. Arda, Ulgen (2009). Conversion of Glycerol to the Valuable Intermediates of Acrolein and Allyl Alcohol in the Presence of Heterogeneous Catalysts. Gott, Paige (2009). Variation in the Chemical Composition of Crude Glycerin. Prieto, Sergio Sabater (2007). Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant. Pyle, Denver J. (2008). Use of Biodiesel-Derived Crude Glycerol for the Production of Omega-3 Polyunsaturated Fatty Acids by the Microalga Schizochytriumlimacinum. US outlook for Acrylic Acid & Derivatives with forecast to 2006-2011 (THE FREEDONIA GROUP, INC.) Xu, Weihua (2001). Design and Development of a Pervaporation Membrane Separation Module.

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III. SUMMARY OF RELATED LITERATURE A. PROCESS DESCRIPTION Dehydration of Glycerol to Acrolein Conversion of glycerol to acrolein has been known since the nineteenth century and there are several recent patents describing this process, but the majority of them describe as the dehydration of glycerol to form acrolein. Acrolein is a highly toxic material with extreme lachrymatory properties. At room temperature acrolein is liquid with volatility and flammability somewhat similar to acetone. It is usually synthesized on the site of production to minimize the storage and transportation because of the flammability, reactivity and toxicity of acrolein. According to Guerrero-Perez et al. in Recent Inventions in Glycerol Transformations and Processing from Recent Patents on Chemical Engineering, 2009, Vol. 2, No.1, dehydration of glycerol to acrolein is normally performed over acid catalysts. Glycerol can be supplied to the reactor in liquid or in gas phase but it was found that acrolein yields were lower in liquid phase than in gas phase. As by Y.T. Kim et al. in their work entitled Gas-phase dehydration of glycerol over ZSM-5 catalysts from Microporous and Mesoporous Materials 131(2010), they include to the study the information that high glycerol conversion and selectivity for acrolein can be modulated in the gas-phase reaction. In the invention of Dubois of US Patent 2010/0168471 with title Method for Preparing Acrylic Acid from Glycerol, he stated that the use of an aqueous solution of glycerol has a 49

drawback of producing a stream containing not only the acrolein produced and the by-products, but also a large quantity of water, originating partly from the glycerol solution, and partly from the water produced by the dehydration reactor. There are different types of catalysts that can be incorporated in the dehydration process. The best catalysts that would yield acrolein over 70%, discussed by A. Kaszonyi et al. in the Bioglycerol: A new Platform Chemical from the paper released by the 44th International Petroleum Conference (Slovak Republic, September 21-22, 2009), are the most acidic catalysts with Hammett acidity constants H 0 between -10 and -16. The catalysts at lower acidity will relatively easily deactivate and acrolein yield will be below 60%. Supported by Dubios et al. from US Patent 2008/0214880 with invention title Process for Dehydrating Glycerol to Acrolein, they claimed that the process is accompanied by a strongly acidic solid catalyst with Hammett acidity H 0 of between -9 and 18 and preferably between -10 and -16. A. Ulgen and W. Hoelderich describe the Conversion of Glycerol to Acrolein in the Presence of WO 3 /ZrO 2 Catalysts (CatalLett, 2009, 131:122-128). They reported that with their collaboration with Arkema, they found out that WO 3 /ZrO 2 catalysts yields 73-80% of acrolein. Among the various solid-acid catalysts studied by S. Prieto in his dissertation entitled Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant, such as 50

HZSM5, H Beta Zeolite, Phosphated zirconia and WO 3 /ZrO 2 . He found out that experiments carried out with the WO 3 /ZrO 2 catalyst are the most promising. The data on his experiments is as follows.

Tungsten zirconia catalysts based from US Patent 2006/0091045 (Figueras et al.) provide an alternative to reactions which are catalyzed by means of acid sites and they are deactivated to a lesser extent. With high melting point at 3003 K, low thermal conductivity and high resistance to corrosion, Zirconium oxides or zirconia (ZrO 2 ) is widely used as catalyst. M.A. Cortes-Jacome et al. on Journal of Solid State Chemistry 179 (2006) discussed on their study with title Generation of WO 3 -ZrO 2 catalysts from solid solutions of tungsten in zirconia that zirconia modified with sulphate, phosphate, heteropolyacids HPA, tungsten and molybdenum has emerged as an alternative catalysts to substitute chlorinated alumina and liquid acid catalysts because zirconia based catalysts can be regenerated easily. Among those different modifications, tungsten oxide dispersed on zirconia seems to be the most stable. Prieto reported that tungsten zirconia 51

catalysts offer inherent advantages from the standpoint of industrial application, such as higher stability under high-temperature treatments, lower deactivation rates during catalysis, and easier regeneration. Reaction of the dehydration of glycerol to acrolein is given in this mechanism.

Summary of the above mechanism is given below

Aqueous glycerol which is the major by-product during the biodiesel production is supplied to the reactor. US Patent 2010/0168471 discussed that dehydration reaction is carried at a temperature of between 150 C and 500 C, preferably between 250 C and 350 C, and at a pressure between 1 and 5 bar, preferably between 1 and 3 bar. Ulgen et al. stated that at temperatures higher than 240 C, glycerol is extensively converted. The acrolein selectivity, however, 52

shows a maximum at 280 C. At lower temperatures the intermolecular dehydration, yielding oligomers of glycerol, is thermodynamically favoured over the desired intramolecular dehydration forming acrolein. At temperatures higher than 280 C, the formation of CO and CO 2 is possible. These two reasons are responsible for the selectivity decrease of acrolein. That is also supported by the fact that the untrapped product mass increased with rising temperatures, from 0.1 wt% at 240 C to 2.0 wt% at 320 C. In the mini review Glycerol as a Source for Fuels and Chemicals conducted by X. Fan et al., they reported that a study has been conducted showing lower pressures are effective for rapid removing the more volatile products from the catalyst sites thus achieving a long catalysts service life. Prieto included in his study that when the glycerol solution reaches 200 C, the mixture is completely evaporated. Between 104 and 200 C, the system is a mixture of liquid and vapor. The molar composition of the vapour fraction, y1, can be obtained by reading on the condensation curve, and the molar composition of the liquid fraction, x1, by reading on the vaporization curve. The dehydration of glycerol leads to acrolein as a main product. He concluded that the glycerol conversion has the following findings: Increases with the temperature because the dehydration of glycerol to acrolein is endothermic. However, the kinetic can limit the process. Decreases when concentrated glycerol solutions are used.

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 Decreases when high glycerol solution feed flows are used. That is expected because faster feed flows achieve lower residence times. While the selectivity of acrolein have these Increases with the temperature until approximately 280 - 285 C, and then decreases a little. Decreases with the glycerol concentration. Increases with the glycerol solution feed flow. An approach for finding an optimum working point can be determined. To get a complete glycerol conversion it is better to work at high temperatures. Around 280 C the acrolein production is the highest. However, at higher temperatures, close to 300 C, the formation of acrolein decreases a little, and the formation of by-products increases with the temperature. Therefore, a temperature, around 285 C will be appropriate to produce the highest amount of acrolein at a complete glycerol conversion and to minimize the formation of byproducts. The glycerol concentration should be not too high because at high glycerol concentrations, the glycerol conversion and acrolein selectivity decreases. According to the US Patent 5387720, gas phase reaction is preferable since it enables a degree of conversion of the glycerol of close to 100% to be obtained. A proportion of about 10% of the glycerol is converted into acetol, which is present as the major by-product in the acrolein solution. 54

Prieto also reported that An appropriate feed flow could be the minimal flow, which produces complete conversion or close to 100 % and high acrolein selectivity, but not too high to avoid the formation of acetol. In the previous analysis, it was predicted that a temperature near 280 C achieves the highest acrolein selectivity at complete glycerol conversion. Now, the optimization results can be examined with temperatures between 274 and 290 C. However, the solutions, which achieve the highest selectivity for acrolein, show that the optimal temperature is around 275 - 280 C. Keeping in mind the kinetic effect over the reaction, high temperatures will favor the reaction. However, over 290 C neither complete glycerol conversion nor high acrolein selectivity is reached. The explanation to this effect could be due to the boiling point of pure glycerol. Over 290 C pure glycerol burns, which leaves less glycerol to be converted into acrolein and, of course, less acrolein to be produced. This effect can explain why at high temperatures the reaction works not so well, even being an endothermic reaction. The effect of the glycerol burning has to be also taken in account.

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 Removal of Water-Rich Stream by Absorption Absorption is further utilized to achieve high purity of acrolein coming from the stream produced in the dehydration reactor. According from the work of Jean-Luc Dubois entitled Method for Preparing Acrylic Acid from Glycerol (US Patent No. 2010/0168471), The invention relates to a method for preparing acrylic acid from an aqueous glycerol solution, comprising a first step of dehydration of the glycerol to acrolein, in which an intermediate step is implemented, consisting in at least partly condensing the water and heavy by-product present in the stream issuing from the first dehydration step. The solution provided by the invention constitutes an optimization between the quantity of water fed to the first stage dehydration reactor and the quantity of water introduced into the second stage oxidation reactor. The solution consists in at least partly condensing the water present in the stream issuing from the dehydration reaction of the aqueous glycerol solution, to prevent the second stage catalyst from being deactivated too rapidly, on the other hand, and to prevent the acrylic acid solution produced from being too dilute, on the other. In the method according to the invention, the expression at least partly condensing means that 20% to 95%, preferably 40% to 90%, of the water present

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in the stream issuing from the first step is removed in the intermediate step before being sent to the second stage reactor. The partial condensation unit may be an absorption column optionally coupled to an evaporator, a heat exchanger, a condenser, a dephlegmator, and any apparatus well known to a person skilled in the art, serving to carry out a partial condensation of an aqueous stream. The acrolein-rich stream, stripped of the heavy by-products and most of the water, is sent to the oxidation reactor where the acrolein can then be oxidized to acrylic acid with a controlled and higher partial pressure. The productivity of the reactor is thereby improved. The method according to the invention, even though it requires an additional unit associated with the intermediate step, has the advantage of using an economical raw material and of being able to optimize the two reaction stages separately. This increase the acrylic acid productivity and selectivity. The method remains demonstrably economical. Purification of acrolein is described in the US Patent No. 5770021 entitled Process and Apparatus for Purification of a Gas Stream Containing Acrolein, This process includes cooling the reaction mixture in a cooling tower, where it is brought into contact with condensing liquid, an effluent gas containing

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predominantly non-condensable and acrolein being recovered at the top of the tower. Accordingly, the present invention provides a process for the purification of acrolein present in a feed gas stream including acrolein, water, by-products and inert gases, originating particularly from the first reactor, which process comprises, in a first stage, fractionating the feed gas stream into a gaseous effluent and a liquid stream in a cooling column operating such that the temperature of the liquid stream at the bottom of the column is lower than or equal to the condensation temperature of the feed gas stream, the difference in the temperature not exceeding 20C, preferably not exceeding 10C; and then, in a second stage, condensing the gaseous effluent at a temperature that is lower the 20C to give a liquid fraction and a purified gaseous fraction. As used herein, the term inert gases is intended to mean all of the gaseous compounds that remain in the gaseous phase from the beginning to the end of the production process of the invention and that are found in the purified gaseous fraction after condensation stage. In this respect, the inert gases in the mixture to be purified may, in what follows, be occasionally called noncondensable since they are not condensed under the temperature and pressure conditions used in the process of invention. The inert gases generally include nitrogen, oxygen, and other gases from air.

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The circulation of the gaseous stream in the column counter-currentwise to a cold liquid result in condensation of the water and other condensable components that may be present. The condensed liquid flows back down under gravity to the bottom of the column. The gases at the top of the column are depleted in impurities and include acrolein and non-condensable gases. The temperature of the gases at the top of the column preferably ranges from 30 to 60C, and still more preferably from 50 to 60C. The temperature of the liquid stream at the bottom of the column is preferably less that 20C, and more preferably less than 10C, lower than the condensation temperature of the feed gas stream. Preferably, the temperature of the liquid stream at the bottom of the column is substantially equal to the condensation temperature of the gaseous mixture introduced into the column to reduce to a minimum condensation of acrolein and degradation; in most cases it is lower than 100C. The condensation temperature of the gaseous mixture originating from the catalytic dehydration of glycerol preferably ranges from 70 to 90C, at a pressure of approximately 1.2x105 Pa. The cooling column preferably operates at a pressure ranging from 105 to 3x105 Pa. The recycled stream generally contains organic acids and preferably less than 2%, more preferably less than 1.5%, by weight of acrolein and at least 90% by weight of water.

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 Oxidation of Acrolein to Acrylic Acid Acrylic acid is used as a precursor for a wide variety of chemicals in the polymers and textile industries. Direct synthesis of acrylic acid from glycerol is an attractive approach since it is useful as raw material for various synthetic resins, paints, fiber etc. The process involves two steps, a dehydration of glycerol to acrolein which was mentioned earlier followed by gas-phase catalytic oxidation carried out with an oxide catalyst. Oxidation of acrolein to acrylic acid has been known since late 1960s attached with the manufacture of acrylic acid from propylene but Prieto reported that crude oil is still the main propylene source and we cannot afford to utilize more crude oil due to its scarcity. Using raw material like glycerol will be an alternative also it has the advantage of being renewable meeting the criteria connected to the concept of green chemistry. According to J. Tichy in his work refer to Oxidation of acrolein to acrylic acid over vanadium-molybdenum oxide catalysts, he reported that oxidation of acrolein proceeds favourably with a stoichiometric excess of oxygen, and the reaction temperature should not exceed 573 K or else it will yield an undesirable radical reaction. He also believed that among the recommended catalysts, the most efficient system for the conversion of acrolein to acrylic acid involve oxide systems based on Mo-V, Mo-Co, V-Sb and heteropolyacids. US Patent 20100168471 also suggested the catalysts made of formulations containing Mo

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and/or V and/or W and/or Cu and/or Sb and/or Fe should be used in the catalytic reaction. The present invention (US 5264625) based on the patent made by Hammon, et. Al, Catalytic Gas-phase Oxidation of Acrolein to Acrylic Acid, aims to provide a process for the catalytic gas-phase oxidation of acrolein to acrylic acid in an fixed bed reactor having contacting tubes, at elevated temperature on catalytically active oxides with a conversion of acrolein for a single pass of 95%. We have found that this object is highly achieved wherein the reaction temperature in the flow direction along the contacting tubes (along the reaction axis) in a first reaction zone before the starting reaction gases containing the reactants enter the contacting tubes is from 260 to 300C until a methacrolein conversion of a 95% has been reached, with the proviso that the reaction temperature in this secondary reaction zone is not lower than 240C. Conversion of crude glycerol to acrylic acid via acrolein as its intermediate step is shown in this stoichiometric reactions.

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Oxidation reaction from acrolein to acrylic acid.

Based on the US Patent 20100168471, oxidation reaction takes place at temperature of between 200 C and 350 C, preferably from 250 C to 320 C and under the pressure of between 1 and 5 bar. The reaction is carried out in the presence of molecular oxygen which may be in the form of air having a content of between 3 to 20% by volume, with regard to the incoming stream and optionally in the presence of inert gases such as N 2 . The inert gases necessary for the method may be optionally consist in full or in part of gases obtained at the top of the absorption column. US Patent 5264625 described the oxidation process is highly exothermic. It is therefore required to control the reaction temperature in order to obtain a highly selective conversion of acrolein to acrylic acid. Industrial production of acrylic acid is at present carried out by vapour phase catalytic oxidation of acrolein. A tandem reaction of dehydration and oxidation process of converting glycerol to acrylic acid was made by Prieto. He said that the experiment ran successfully and acrolein was completely converted to acrylic acid.

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In the Figure 4.23, the experiment ran successfully. No acrolein was found anymore. That means a complete oxidation to acrylic acid took place. Other by-products, like acetic acid and propionic acid were also observed. Due to the oxidation, acetaldehyde and propanal were oxidized to their correspondent acids. It is important to mention that mass loss was observed during the reaction. In the Figure 4.23, after the first hour of the reaction no products were found. Almost a mass loss of 100 % in carbon mass was observed. This can be explained due to the amount of oxygen used in the reaction (see section 4.4.3.2 and Figure 4. 24). The percentage of mass loss decreases with the reaction time, as long as acrylic acid and other by-products such acetic and propionic acid, were formed. At the stationary-state around 25 % of mass loss was found. Around 40 % of acrylic

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acid, 10 % of acetic acid and 3 % of propionic acid were found. The 25 % of mass loss should be due to the burning of compounds on the catalytic particles. For the oxidation reaction, the reaction temperature in the oxidation catalyst increases gradually during 140 minutes, and after that, it remains constant at 310 C. This means that the oxidation reaction is taking place. The higher the reaction temperature in the oxidation catalytic bed, the higher is the formation of acrylic acid. Once the temperature is stabilized at 310 C, the formation of acrylic acid remains also constant at around 40 %. After 300 minutes, when the oxygen flow was switched off, the temperature of the oxidation catalytic bed dropped to 286 C. That means, that no exothermic reaction was taking place and in consequence no acrylic acid was formed.

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 Esterification of Acrylic Acid to form Ethyl Acrylate Various acrylic esters are useful chemicals. Esterification of acrylic acid with alcohol has commercially been performed by using liquid catalysts such as sulfuric acid, hydrofluoric acid, and para-toluenesulfonic acid; however these are toxic, corrosive and often hard to remove from the solution.

From US Patent 20050107629 Method for Producing Ethyl Acrylate by Rohm and Haas Company: The present invention is directed to a continuous process for producing ethyl acrylate and for recovering acrylic acid, ethyl acrylate, ethanol and water from an esterification reactor mixture containing acrylic acid, ethyl acrylate, ethanol, water and acid catalyst.

This invention relates to a method for combining acrylic acid and ethanol, and processing the reaction products to produce ethyl acrylate in improved yield. Fresh crude acrylic acid, ethanol, and esterification catalyst are fed to the esterification reactor. Typical components of the bottoms stream comprise acrylic acid, at 60 to 90% and acrylic acid dimer (AOPA), at 10 to 40%. The acrylic acid from the bottoms stream comprises from 5% to 15% of the total acrylic acid fed to the esterification reactor. The molar ratio of acrylic acid to ethanol is from 1 to 65

1.1 to 1 to 1.5, preferably from 1 to 1.1 to 1 to 1.2. The esterification reactor temperature is maintained at from 85 C. to 105 C., at reactor pressures from 220-320 mm Hg. At least one heat exchanger may be used to control the temperature of esterification reactor.

According to US Patent 3458561 (Esterification of Acrylic Acid), the minimum temperature at which the esterification is achieved depends upon the boiling point of the formed acrylic acid ester, of the azeotrope formed from the acrylic acid ester and water, respectively, as well as whether one uses subatmospheric pressure, atmospheric pressure, or super-atmospheric pressure. In general, temperature between 70 to180 C is employed. This invention relates to a novel process for esterifying acrylic acid, more specifically this method pertains to a novel combination of variables which results in the obtention of acrylic acid esters in high yields by a simplified and more economical esterification which combination also includes the ester product recovery. A number of processes are known which are directed to the conversion of acrylic acid and an alcohol to the corresponding acrylic ester in the presence of an esterification catalyst. However, the following problems exist: (a) ethyl acrylate, ethanol and water form an azeotrope boiling at 77.1 C, at a pressure of 760 mm. Of mercury, which azeotope at a rather great expense can be processed further to recover the ester product; (b) the polymerization tendency of acrylic 66

acid and its ester reduces to a considerable degree the alternatives which may be taken when carrying out the esterification reaction. Esterification of acrylic acid is possible in a liquid as well as in a gas phase. Of primary importance as an esterification catalyst is sulfuric acid and/ or a sulfonic acid. In respect to the amounts at which these catalysts have been utilized, the catalyst should be used in amounts such as about 0.01% sulphuric acid per mole of acrylic acid. In order to achieve the desired reaction, the reduction of the formation of a ternary azeotrope of the ester, alcohol and water and obtaining only the ester-water mixture, contrary to the heretofore recognized methods, exceptionally large amounts of acid are necessary such as from 5 to 50% by weight of sulfuric acid or 10 to 80% by weight of the above describe sulfonic acid. Preferably an amount of the acid is chosen, which comprises 7 to 35% by weight of the sulfuric acid or 20 to 70% by weight of the sulfonic acid on the basis of the reboiler contents. Considering the esterification speed and conversion and avoiding at the same time the formation of undesirable side reactants, the best results are obtained when using in the reboiler from 10 to 25% by weight of sulfuric acid or 30 to 50% by weight one of the aforementioned sulfonic acid with a residence time of 3 hours. The reaction of acrylic acid and alcohol is as follows:

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From US Patent No. 20050107629, Reacting the acrylic acid and ethanol to yield ethyl acrylate in a conversion of at least 90% on acrylic acid, and yielding the esterification reaction mixture comprising ethyl acrylate, acrylic acid, ethanol and water. From Biochemical Engineering Journal 41 (2008) 8794 by G.N. Kraai et al., In esterification reactions, a batch reactor equipped with four baffles and a six-bladed turbine impeller is used. From Turbine & High Efficiency Axial Flow Agitators,

http://www.feldmeier.com/cutsheets/turbine_agitator.pdf, The speed range for commercially available turbine agitator is 63 to 73 rpm.

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 Purification of Ethyl Acrylate by Pervaporation Among the different membrane separation technologies, pervaporation is presently considered as a process unit with high potential to recover organic compounds from aqueous organic mixtures using hydrophobic membranes. This application is of particular interest to the chemical industry since integration of pervaporation into waste water treatment includes the opportunity to recover organic compounds to a standard that both water and organic compounds could be reused without additional processing. Hence this approach might offer both environmental and economical benefits to industry. Pervaporation is characterized by the evaporation of water from permeate side. In vacuum pervaporation, the heat required for evaporation is supplied from the feed side. Consequently, there will be a temperature gradient in direction of the feed. A major problem in the esterification of polyacrylic or methacrylic acid is removing water from the reaction mixture during its production due to the presence of an azeotropic water-alcohol mixture. Sometimes the boiling points of alcohol and water are very close and sometimes some crosslinking reaction occurs at high temperature. The extraction of water from the reaction mixture using a traditional technique such as distillation is a non-economical method. Pervaporation is an energy efficient and high selective extraction process for the extraction of volatile products and for the dehydration of organic chemicals. The productivity and conversion rate can be significantly increased. 69

From EP 2325214A1, the present invention relates to the synthesis of ethyl acrylate by esterification of acrylic acid with alcohol assisted by the pervaporation technique for extracting water.

A major problem in the esterification of polyacrylic or methacrylic acid is removing water from the reaction mixture during its production due to the presence of an azeotropic water-alcohol mixture. Sometimes the boiling points of alcohol and water are very close and sometimes some crosslinking reaction occurs at high temperature. The extraction of water from the reaction mixture using a traditional technique such as distillation is a non-economical method. The object of the present inventions is further solved by a use of a membrane in the production of acrylate ester, for extracting water produced during esterification of acrylic acid with alcohol in the presence of an acid as catalyst. In one embodiment of the use, the membrane comprises or is made of polyvinylalcohol modified and crosslinked with a crosslinking agent at 2-6 weight%, preferably at 2-5 weight-%, using different technique. In one embodiment of the use, the membrane has a thickness of about 5-200m, preferably of about 2255 m, most preferably of about 25 m. The method according to the invention allows for the production of copolymers and terpolymers at controlled composition (0-99 %mole). The pervaporation apparatus employed in this invention is similar to that used by different authors, such as Bing Cao et al. 70

Pervaporation is an energy efficient and highly selective extraction process for the extraction of volatile products and for the dehydration of organic chemicals. The productivity and conversion rate can be significantly increased when the reaction is coupled with pervaporation, i. e., a pervaporation reactor. Techno-economic studies revealed that pervaporation reactors have good market potential in process industries. The combination of an esterification reaction of polyacrylic or polymethacrylic acid with a pervaporation process increases the conversion of reversible reactions, such as esterification, by removing selectively the water formed from the reacting mixture. Thus, the yield of the conversion is greatly enhanced. An esterification reaction between an alcanol and a carboxylic acid in the presence of a catalyst is a reversible reaction, and a high industrial conversion can be achieved by adding a large excess of acid. A water selective pervaporation membrane can be used in the esterification reactor. This can shift the equilibrium to the right, thus reducing excess reactants.

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B. PRODUCT LITERATURE Ethyl acrylate is an organic compound primarily used in the preparation of various polymers. Ethyl acrylate can be prepared by several industrial methods. Acrylonitrile can be reacted with ethanol using sulfuric acid as a catalyst to produce ethyl acrylate. It may also be prepared from acetylene, carbon monoxide and ethanol. Ethyl acrylate is used to form paint coatings that is resistant to water, sunshine, and weather. These coatings retain flexibility even at low temperatures. EA is also used in industrial finishes and coatings for cans and coils. Fabrics gain texture and durability when ethyl acrylate is added during their manufacture. Ethyl acrylate also imparts dirt resistance, improves abrasion, and binds pigments to fabric. Paper is coated with ethyl acrylate to make it water-resistant. Magazines, books, business paper, frozen food packaging, and folding boxboards have such coatings, making them resistant to water, grease, and oil. Ethyl acrylate is also used in adhesives for envelopes, labels, and decals. Caulk, glazing, and various sealants also contain Ethyl acrylate. Leather products, such as automotive upholstery, furniture, clothing, and shoes contain EA so that top coatings do not migrate. Ethyl acrylate is also used as a fragrance additive in various soaps, detergents, creams, lotions, perfumes, and as a synthetic fruit essence. Ethyl acrylate is also found in such household items as nail mending kits and in medical items that assist with the binding of tissues, sealing wounds, etc.

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Acrylic esters make the main product derived from acrylic acid. They account for 55% of global demand. About half of the crude acrylic acid is processed to purified (glacial) acrylic acid, which is further processed both on-site (captive use) and by external downstream users. The other half of crude acrylic acid is transformed into various acrylate esters at the production sites. Identical to glacial acrylic acid, these acrylic esters serve as commercial products, which are further processed both on-site and by external downstream users. Glacial acrylic acid is used in the manufacture of super absorbing polymers (SAP), which account for 32% of the global demand for acrylic acid. Acrylic acid and basic alkyl esters (methyl, ethyl, butyl and 2-ethylhexyl esters) are used for the manufacture of polymer dispersions, adhesives, super absorbent polymers, flocculants, detergents, varnishes, fibres and plastics as well as chemical intermediates. Greater attention is now paid to environmental protection and energy saving. Research organizations and production enterprises are developing and disseminating various environmental protection and energy saving technologies. The radiation curing technology takes special acrylic esters as major raw materials and UV rays or electron beams as initiators to polymerize acrylic esters into polymer films. Compared with conventional polymerization methods, this technology does not use chemical initiators, polymerization takes place at normal temperature and no heat is used. Initiators are saved and energy consumption is reduced.

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Acrylic esters and derivatives represent about 65 per cent of the market for acrylic acid in the USA, slightly higher than in Australia.

Acrylates are used in a broad range of applications directly as a resin, or as solution or emulsion. The following provides an indication of typical applications with the market share expressed as a percentage of all acrylic acid applications as acrylic acid (ie. including the previously described polyacrylic acids).

Surface coatings, such as paints, represent the largest application for acrylic esters at about 19 per cent of the market. Demand, that was motivated by the convenience of water-based paints especially the superior acrylic-based emulsions, is now being driven by regulations and interests to reduce atmospheric release of volatile organic compounds (VOCs) used as solvents in traditional (alkyd-based) surface coatings. This sector is growing at 3 to 5 per cent per year with faster growth for newer more sophisticated applications (such as UV radiation-curable polymers).

The Australian surface coating industry is dominated by ICI Australia, Wattyl and Taubmans using emulsions made by companies such as Rohm and Haas and BASF from imported ethyl and other acrylic esters. The paint industry in Australia, like in other developed countries, is growing at about 2 per cent per year.

74

Adhesives and sealants are the second largest application for a broad range of esters that represents about 15 per cent of acrylic acid applications. Though this sector is closely related to the variable and slower growing construction sector, like the surface coating sector it has been stimulated by concerns about VOCs. This sector has been growing at 4 to 6 per cent per year in most markets and faster in Asian textile-producing regions with growing construction sectors. Textiles represent about 11 per cent of the market for acrylic esters in the USA of which about 90 per cent is used as emulsions for use in non-woven fabrics and textile treatment, and only 10 per cent for textile fibres. Growth in the USA has been about 2 per cent but substantially faster in some Asian countries. A range of acrylic esters are used to produce plastic forms and sheets representing about 8 per cent of the market that is growing at about 3 per cent.

Demand has increased for acrylic acid derivatives, specifically ethyl acrylates used in the production of surface coatings. Still, the growth is being limited by the current global inventory of crude acrylic acid. Due to growing demand for acrylic acid derivatives led by SAPs, many of the major producers have responded by expanding plants and building new production facilities at key sites throughout the world.

75

Table 2.1. Countries that Produce Ethyl Acrylate (kg)

YEAR COUNTRIES China,

2005

2006

2007

2008

12,630 People's Republic

3,004

204,234

49,296

Indonesia 566,880 (Includes West Irian) 248,345 417,487 643,563

Japan 143,065 (Excludes Okinawa) 106,540 738,500 235,582

Korea, 1,547,700 Rep. of (South) 1,631,096 1,400,716 1,026,230

Malaysia 1,572,684
(Federation of Malaya)

1,913,767

7,425,932

6,851,514

Singapore

1,373,245

1,674,298

1,457,535

4,571,053

South Africa, 326,445 Rep. of 650,925 23,550 -

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C. RAW MATERIAL LITERATURE Glycerol Glycerol, propane-1, 2, 3-triol, glycerin, a trihyhdric alcohol, is a clear, water-white, viscous, sweet-tasting hygroscopic liquid at ordinary room temperatures above its melting point. Glycerol occurs naturally in combined form as glycerides in all animal and vegetable fats and oils, and is recovered as a byproduct when these oils are saponified in the process of manufacturing soap, when the fats are split in the production of fatty acids, or when fats are esterified with methanol in the production of methyl esters. The uses of glycerol number in thousands, with large amounts going into the manufacture of drugs, cosmetics, toothpaste, methane foam, synthetic resins and ester gums. Tobacco processing and foods also consume large amounts either as glycerol or glycerides. Glycerol was introduced by Sergio Sabater Prieto to his work Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant. Glycerol is the common name of propane-triol. It is a sweet tasting, highly viscous colorless and odorless liquid with no known toxic properties. Glycerol has many direct utilization fields, such as cosmetics, lubricants or explosives, and other 1300 applications, but not enough market possibilities to take all the glycerol from diesel production. 77

Glycerol is a side-product of bio-diesel production. Natural oils are triglycerides. The transesterification of one mole of such an oil yields three moles of hydrocarbon chains and one mole of glycerol. The hydrocarbon chains are used as bio-diesel fuels. Due to the developments in the bio-diesel industry, the glycerol production is also increasing. Since the demand for glycerol is not increasing with the same tendency, the glycerol price is decreasing, which makes it an interesting carbon source for intermediates. The dehydration of glycerol to acrolein is an adequate reaction with interesting economic and environmental aspects. Bio-diesel is produced from agricultural products and not from crude oil. Glycerol is formed as a by-product during the transesterification process, which is the key step for the production of bio-diesel. The use of glycerol produced during the bio-diesel process has potential to be an environmentally carbon source for the production of acrylic acid. Moreover, the economical valorisation of glycerol makes the bio-diesel production more attractive. Replacing propylene by glycerol would be an indirect step for improving the sustainability in environmental care. It is known that crude oil price is increasing. In connection to that, the propylene price increases as well, since it is mainly crude oil based. On the other hand, glycerol prices are decreasing. The reason: Glycerol is not an important

78

intermediate. It is mostly used in small amounts for cosmetics and for the food industry. Global glycerol demand is not increasing so fast as the bio-diesel production. The following diagram compares the price evolution of propylene and different qualities of glycerol. In the thesis made by Denver J. Pyle with title Use of Biodiesel-Derived Crude Glycerol for the Production of Omega-3 Polyunsaturated Fatty Acids by the Microalga Schizochytriumlimacinum, the crude glycerol produced during the biodiesel production process is impure and of little economic value. The impurities include methanol and soaps. Biodiesel producers use excess methanol to drive the chemical transesterification and do not recover the entire methanol. Therefore, it is present in the glycerol layer. Also, free fatty acids present in the initial feedstock can react with the base to form soaps that are soluble in the glycerol layer. In addition to methanol and soaps, crude glycerol also contains a variety of elements such as calcium, magnesium, phosphorous, or sulfur. It has been reported that glycerol makes up anywhere from 65% to 85% (w/w) of the crude glycerol streams (Gonzalez-Pajuelo et al., 2005; Mu et al., 2006). The remaining weight in the crude glycerol streams is mainly methanol and soaps. The wide range of the purity values can be attributed to different glycerol purification methods used by the biodiesel producers and the different feedstocks used in biodiesel production. For example, Thompson and He (2006) have 79

characterized the glycerol produced from various biodiesel feedstocks. It was found that the crude glycerol from any feedstock is generally between 60 and 70 % (wt) glycerol. Mustard seed feedstocks had a lower level (62%) of glycerol, while soy oil feedstock had 67.8 % glycerol and waste vegetable had the highest level (76.6 %) of glycerol. According to US Patent 2008/0249338 (Method for Purification of Glycerol), aside from glycerol, crude glycerol from biodiesel production typically contains methanol, water, inorganic salts and salts of fatty acids. Levels of inorganic salts typically are from 5% to 50%. Levels of inorganic salts are from 1% to 5%. These levels typically are expressed together in terms of total cation concentration, which usually is from 0.2% to 5%. Crude glycerol contains water, and may also be diluted further with water to reduced load on the column and aid in the separation, so that typical water levels can be from 5% to 40%. In some embodiments of the invention, glycerol concentration in the crude glycerol introduced into the resin bed is at least 20%, alternatively at least 30%, alternatively at least 40%, alternatively at least 50%, alternatively at least 60%, alternatively at least 70%, alternatively at least 75%.

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 Air The air around us is a mixture of gases, mainly nitrogen and oxygen, but containing much smaller amounts of water vapor, argon, and carbon dioxide, and very small amounts of other gases. Air also contains suspended dust, spores, and bacteria. Because of the action of wind, the percent composition of air varies only slightly with altitude and location. Air retrieved from http://scifun.chem.wisc.edu/chemweek/pdf/airgas.pdf The amount of water in the air varies tremendously with location, temperature, and time. In deserts and at low temperatures, the content of water vapor can be less than 0.1% by volume. In warm, humid zones, the air may contain over 6% water vapor. Air is the commercial source for many of the gases it contains. It is separated into its components by fractional distillation of liquefied air. Before air is liquefied, water vapor and carbon dioxide are removed, because these substances solidify when cooled and would clog the pipes of the air liquefaction plant. The dry, CO2-free air is compressed to about 200 atmospheres. This compression causes the air to become warm, and the heat is removed by passing the compressed air through radiators. The cooled, compressed air is then allowed to expand rapidly. The rapid expansion causes the air to become cold, so cold that

81

some of it condenses. By the alternate compressing and expanding of air, most of it can be liquefied. Nearly all commercial oxygen (over 95%) is produced by fractional distillation of liquid air. It boils at -183EC. Oxygen is the third highest-volume chemical produced in the U.S., and most of this product is more than 99.5% pure. Oxygen is paramagnetic, that is, it is attracted to a magnet. Liquid oxygen is pale blue. The major commercial uses of oxygen are in metal manufacturing (30%), metal fabricating (33%), and in health services (13%). In the steel industry, oxygen is passed through impure molten iron in a blast furnace to oxidize and remove impurities such as carbon, sulfur, phosphorus, and silicon. Oxygen is also used as the oxidant in torch cutting of steel. In this process, the steel is heated by an oxygen-acetylene flame, and a stream of hot oxygen is directed at the hot steel. The hot steel is oxidized by the hot oxygen and erodes away, severing the steel. Oxygen is also used extensively in the chemical industry, such as in the production of nitric acid, HNO3, from ammonia, NH3.
Oxygen occurs mainly as an element in the atmosphere. It makes up 20.948 percent of the atmosphere. It also occurs in oceans, lakes, rivers, and ice caps in the form of water. Nearly 89 percent of the weight of water is oxygen. Oxygen is also the most abundant element in the Earth's crust. Its abundance is estimated at about 45 percent in the earth.

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Oxygen also reacts with many compounds. Combustion is one of the examples, that is, it helps other compounds to burn. Another is oxidation. From the term itself, it is the addition of oxygen to a compound yielding another kind of compound. The process of oxidation of acrolein to form acrylic acid was done with the aid of a catalyst. The best suited catalyst used is a multi-metal oxide which in the case of this process is the vanadium-molybdenum oxide catalyst.

Oxygen occurs in all kinds of minerals. Some common examples include the oxides, carbonates, nitrates, sulfates, and phosphates. Oxides are chemical compounds that contain oxygen and one other element. Calcium oxide, or lime or quicklime (CaO), is an example. Carbonates are compounds that contain oxygen, carbon, and at least one other element. Sodium carbonate, or soda, soda ash, or sal soda (Na 2 CO 3 ), is an example. It is often found in detergents and cleaning products.

Nitrates, sulfates, and phosphates also contain oxygen and other elements. The other elements in these compounds are nitrogen, sulfur, or phosphorus plus one other element. Examples of these compounds are potassium nitrate, or saltpeter (KNO 3 ); magnesium sulfate, or Epsom salts (MgSO 4 ); and calcium phosphate (Ca 3 (PO 4 )2 ).

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 Tungstated Zirconia Catalyst Prieto discussed the effect of tungsten zirconia in his dissertation entitled Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant. Tungsten zirconia materials are very attractive, environmentally friendly solid acids. Although less active than their sulfate-promoted counterparts, tungston zirconia catalysts offer inherent advantages over the former from the standpoint of industrial application, such as higher stability under hightemperature treatments, lower deactivation rates during catalysis, and easier regeneration7. A minimum level of WOx is required to stabilize the tetragonal phase of the zirconia support on annealing in air at high temperatures (typically 973 1173 K) needed to produce catalytically active materials. Iglesia and coworkers reported that the acid activity of WOx-ZrO2 materials is a unique function of the tungsten surface density rather than the W loading or calcinations temperature independently. When this parameter is considered, a maximum in the catalyst activity is found at intermediate values of the tungsten density. It has been proposed that strong Brnsted acid sites responsible for the high catalytic activity of WOx-ZrO2 develop on reduction of W+6 species in the presence of H2 or other reductants, such alkanes or alcohols, to compensate the excess of negative charge in the polyoxotungstated domains. These types of acid sites are termed temporary acid sites, in opposition to the permanent acidity present in calcined WOx-ZrO2 84

samples. By themselves, the latter acid sites cannot account for the observed catalytic activity. At tungsten coverages well below the monolayer, isolated monotungstate species predominate on the zirconia surface. These species are difficult to reduce and thus do not allow the formation of catalytically active Brnsted acid sites. In contrast, highly reducible three-dimensional WO3 crystallites coexist with the two-dimensional amorphous polytungstates at coverages exceeding the monolayer, resulting a decreasing accessibility to the active WOx species. Thus, the occurrence of a maximum in the catalytic activity at intermediate WOx surface densities represents a compromise between the accessibility to the surface WOx species and their reducibility. Ulgen et al. Conversion of Glycerol to Acrolein in the Presence of WO 3 /ZrO 2 Catalysts discussed that ZrO 2 powder and WO 3 /ZrO 2 pellets with 19 wt% WO 3 were kindly provided by St. GobainNorpro, Ohio, USA. WO 3 /ZrO 2 powders with five different WO 3 contents (between 2.11 and 15.43 wt% WO 3 ) were obtained from Daiichi KKK, Japan, via Arkema CRRA, France. In these cases there is nothing disclosed about the method of preparation. These Daichii KKK catalysts were used without prior modification. Several homemade catalysts have been prepared according to the following impregnation method recipe, which was conducted under ambient atmosphere. A certain amount of ammonium (para) tungstate (Sigma Aldrich, Germany) and 200 mL of water were heated to 80C and stirred 2 h, yielding a 85

clear solution. Into this solution, ZrO2 (Provided by St. Gobain/Norpro, Ohio, USA) was added and stirred for another 4 h. After evaporation of the water, the remaining slurry was placed in a ceramic bowl and dried 6 h at 110C followed by calcination at 600C for 6 h. Both drying and calcination steps were conducted in a box shaped programmable oven (Nabertherm N 7 with a Logotherm S 19 Program Controller, T max = 1,000C) under ambient pressure and atmosphere without addition of any gases. The obtained powder was formed to pellets under 10 tons for 20 min, which was then crushed and sieved. A fraction of 0.51.0 mm particle size was used for the characterisation and screening experiments. Figueras, F. et al. Tungsten Catalyst with US Patent No. 2006/0091045 stated that Zirconia oxide or zirconia (ZrO 2 ) is a solid which used in catalysis. Amongst the physical properties which make it suitable for this application is its high melting point (3003 K), low thermal conductivity and high resistance to corrosion by acids. With regard to the chemical properties, zirconia is an amphoteric support, as in alumina, that can be used in oxidation and reduction reactions. Crystallization and sintering of the crystallites by means of calcination are not desirable for use as a support.

86

Zirconia can be synthesized by various means, such as precipitation in an aqueous solution of zirconium salts, such as ZrOCl 3 8H2O,

ZrO(NO 3 )2H2O,ZrCl 4 , or the sol-gel method. Tungsten/Zirconia (W-ZrO2) catalysts have been known for some time and provide an alternative to reactions which are catalyzed by means of acid sites. The advantage which these solids have compared with sulphates is that they are deactivated to a lesser extent. They have been describes by Hino and Arata as strong acid catalysts. The definition as a superacid which was initially adopted has been downgraded and it is now commonly accepted that they are strong acids which are capable of isomerising linear paraffins into isoparaffins at approximately 523 K. Since the acid sites have not been able to be identified, these solids are characterized by a chemical composition and a method of preparation.

87

 Vanadium-Molybdenum Oxide Catalyst Josef Tichy in his work entitled, Oxidation of Acrolein to Acrylic acid over Vanadium-Molybdenum Oxide Catalysts accounted that, The first reports published in scientific literature which claim the advantages of vanadium-molybdenum oxide catalysts in the oxidation of acrolein to acrylic acid are due to Kitahara et al. [1,2]. The authors undertook extensive research into the catalyst pre-treatment, the weight ratio of constituents, type of support, magnitude of particles, amount of the active components coated, and the way of preparation. On the basis of the results obtained they chose as the most favorable catalyst one containing the components MoO 3 , V 2 0 5 , and Al 2 0 3 in the molar ratio of 8:1:0.4 coated on spongy aluminum with a 17.8 wt% content of the active constituents. With the acrolein concentration of 3.4 vol%, molar ratio of oxygen to acrolein equal to 1.65, that of water to acrolein equal to 16.5, the time factor of 1.64 s, and the temperature of 573 K it was possible to achieve the acrolein conversion degree of 97.3% and the yield of acrylic acid equal to 85.7% with the catalyst mentioned. According to the authors experience, the optimum oxidation degree of the catalytically effective components was attained when the catalyst was preliminarily exposed to action of air at temperature of 573 K and finally stabilized in reduction atmosphere by action of the starting reaction mixture at 673 K.

88

With the aim of improving the properties of vanadium-molybdenum oxide catalyst and shortening the lengthy process necessary for establishing the stationary state, the paper [3] suggests the use of ethylenediamine as the reducing agent directly in its preparation, using SiO 2 in the form of aerosil for the support. The preparation started from two solutions, namely

hexaammoniumheptamolybdate solution and ammonium vanadate solution with three fold molar amount of ethylenediamine with respect to vanadium. The solutions were mixed and aerosol was added thereto. The suspension thus obtained was concentrated at 353 K to give a paste. For perfect homogeneity it is recommended to use a spray drier. Calcination at 453 K and annealing in air at 573 K gave the optimum catalyst with the molar ratio of Mo:V = 5:1 and with the content of active constituent on support equal to 30 wt.%. With the catalyst thus prepared it was possible to obtain 100% conversion of acrolein and 96% yield of acrylic acid from a gaseous mixture of the following composition (vol%): acrolein 4, oxygen 6.6, steam 25, and nitrogen 64.4. Oxides of carbon and CH 3 COOH being determined as the reaction side products. The catalyst specific surface determined by the BET method from nitrogen adsorption was 57 m2g-1. The catalyst is blue in color, and amorphous according to the X-ray diffraction. The crystallization takes place at temperatures above 600 K, but it is accompanied by a color change to yellow and a substantial loss of activity due to the oxidation of V4+ to V5+.

89

 Ethyl Alcohol Ethanol is miscible (mixable) in all proportions with water and with most organic solvents. It is useful as a solvent for many substances and in making perfumes, paints, lacquer, and explosives. Alcoholic solutions of non-volatile substances are called tinctures; if the solute is volatile, the solution is called a spirit. Commercial Alcohols have grown to be the largest manufacturer and supplier of industrial grade alcohol (ethyl alcohol or ethanol). The uses of the product include industrial applications (such as solvents, detergents, paints, printing inks, photo-chemical applications, latex processing, dyes, etc.), the beverage market, medicinal, pharmaceutical and food products. Because of ethanol's ease of production and because exposure to low amounts does negligible harm, it has widespread use as a solvent for substances intended for human contact or consumption, including scents, flavorings, colorings, and medicines. In chemistry it is both an essential solvent and a feedstock for the synthesis of other products. Because it burns cleanly, ethanol has a long history as a fuel, including as a fuel for internal combustion engines.

Under acid-catalyzed conditions, ethanol reacts with carboxylic acids to produce ethyl esters and water: RCOOH + HOCH 2 CH 3 RCOOCH 2 CH 3 + H 2 O 90

For this reaction to produce useful yields it is necessary to remove water from the reaction mixture as it is formed.

Ethanol can also form esters with inorganic acids. Diethyl sulfate and triethyl phosphate, prepared by reacting ethanol with sulfuric and phosphoric acid respectively, are both useful ethylating agents in organic synthesis. Ethyl nitrite, prepared from the reaction of ethanol with sodium nitrite and sulfuric acid, was formerly a widely-used diuretic.

(http://www.chemeurope.com/en/encyclopedia/Ethanol.html)

As a reactive chemical, ethanol in common with all alcohols reacts with acids to produce esters. Examples include ethyl acrylate, which is used as a reactive diluent in specialised coatings, and ethyl acetate, which is a widely used solvent in paint and coating formulations. Ethanol is used in the production of ethylamines, which in turn are reactive industrial chemicals used in downstream speciality applications including agrochemicals and pharmaceuticals. It can also be used to make ethoxypropanol, an increasingly used glycol ether solvent in coating formulations (CEFIC, 2003). The relationship of the introduced amounts of acrylic acid and alcohol in reference to the reboiler content, depends, in general, upon the available equipment, the amount of the sulfuric acid in the reboiler, and the esterification temperature.

91

Esterification of acrylic acid with the necessary amount of ethanol can, for example, be conducted by adding from one half to twice the amount of acrylic acid, based on the weight of the reboiler content, when employing about 20% by weight of p-toluene sulfonic acid in the reboiler, which is at a temperature of 140 and at a pressure of 760 mmHg. (US Patent No.3458561)

According

the

the

Method

of

Producing

Ethyl

Acrylate

(US2005/0107629), the invention relates to a method for combining acrylic acid (AA) and ethanol, and processing the reaction products to produce ethyl acrylate (EA). Feeding to the esterification reactor acrylic acid and ethanol, in a molar ratio of from 1 to 1.1 to 1.5, and the acid catalyst; wherein at least a portion of the acrylic acid is derived from a bottoms stream from a crude acrylic acid distillation column, said bottoms stream comprising from 60 to 90% acrylic acid.

92

 Sulfuric Acid Sulfuric acid, H 2 SO 4 , is a strong mineral acid. It is soluble in water at all concentrations. It was once known as oil of vitriol. Sulfuric acid has many applications, and is one of the top products of the chemical industry. Principal uses include ore processing, fertilizer manufacturing, oil refining, wastewater

processing, and chemical synthesis.

Sulfuric acid is a very important commodity chemical, and indeed, a nation's sulfuric acid production is a good indicator of its industrial strength. The major use (60% of total production worldwide) for sulfuric acid is in the "wet method" for the production of phosphoric acid, used for manufacture of phosphate fertilizers as well as trisodium phosphate for detergents.

Sulfuric acid is used for a variety of other purposes in the chemical industry. For example, it is the usual acid catalyst for the conversion of cyclohexanoneoxime to caprolactam, used for making nylon. It is used for making hydrochloric acid from salt via the Mannheim process.

(http://www.chemeurope.com/en/encyclopedia/Sulfuric_acid.html)

Conversion of carboxylic acid and an alcohol to form its corresponding ester is done with the presence of an acidic catalyst. Usually, sulfuric acid is used as a catalyst in the esterification process.

93

Esterification of acrylic acid is possible in a liquid as well as in a gas phase. Of primary importance as an esterification catalyst is sulfuric acid and/or a sulfonic acid, e.g., p-toluene sulfonic acid. In respect to the amount at which these catalysts have been utilized, German Patent No. 1,006,843 and published German Patent application No. 1,161,259 teach, for example, that the catalyst should be used in amounts such as about 0.01% sulfuric acid per mole acrylic acid. (US Patent No.3458561)

The sulfuric acid is employed in an amount sufficient to both catalyze the reaction and to serve as a dehydrating agent or desiccant for the by-product water. Accordingly, the sulfuric acid should be employed in an amount greater than about 0.05 moles per mole of carboxylic acid to be esterified and preferably above 0.1 moles and of sulfuric acid per mole of carboxylic acid, which is sufficient to both catalyze the dehydrate the water. Most desirably, from about 0.1 to about 0.5 moles of sulfuric acid and most preferably about 0.2 moles will be employed per mol of carboxylic acid. The reaction is carried out at elevated temperatures, conveniently reflux conditions. With methanol as the alcohol and a carboxylic acid having from about 6 to about 22 carbon atoms a temperature will be on the order of about 70 to about 100 C. However, temperatures on the order at about 40 to about 120 C. and more preferably 60 to about 80 C. will be employed. The specific temperature employed will be determined however by the specific alcohol employed and specific carboxylic acid to be esterified. In the laboratory reflux

94

periods of about 1 to 2 hours were sufficient to provide yields of methyl isooctanoate in the methanol esterification of isooctanoic acid employing about 1.5 to about 2 moles of methanol per mole of isooctanoic acid which provided the ester of greater than 99% purity. In contrast, in reactions not using an excess of sulfuric acid (only a catalytic amount) time periods of reflux of about 10 hours or more were required to provide about an 80% yield of ester of lower purity even with a seven molar excess of methanol. Again, the reaction period will depend on the specific alcohol employed and specific acid to be esterified. Generally reaction periods will not need to exceed about 4 hours and the reaction will be complete (about 90% yield) usually within 1 to about 3 hours employing the preferred levels of carboxylic acid, alcohol and sulfuric acid. After completion of

the esterification the sulfuric acid layer is removed and any unesterified acid is removed as the sodium salt by an alkaline aqueous wash. The ester may be dried by azeotropic distillation with an aliphatic hydrocarbon solvent such as heptane. The unreacted carboxylic acid in the aqueous alkaline wash can be recovered by acidification with an acid, preferably spent sulfuric acid, from

the esterification step. It has now been discovered that the use of a significant excess of sulfuric acid in the reaction provides unexpectedly high yields of the desired ester and the ester is of high purity. The sulfuric acid not only acts as a catalyst for the reaction but the excess acid further unites with, dessicates, removes or

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immobilizes the water of reaction by forming a second phase, resulting in an increased yield of the ester, in excess of 90% of the acid being converted to the ester. The ester further is of high purity of about 99%. While the present invention is applicable to any esterification of a carboxylic acid with an alcohol, it is of particular interest to the esterification of longer chain carboxylic acids such as the branched acids having about 6 to about 22 carbon atoms with lower alkyl alcohols containing from 1 to about 4 carbon atoms, which esters may be subsequently converted to diketones which are useful as metal extractants.

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D. DESIGN AND EQUIPMENT LITERATURE Fixed-Bed Catalytic Reactor Synthesis of glycerol to acrolein may take place in a fixed bed reactor, fluidized bed or moving fluidized bed reactor, or in a modular configuration. Among the following reactors, fixed-bed or packed-bed reactor is the most appropriate to use. A fixed-bed reactor typically is a cylindrical vessel that is uniformly packed with catalyst pellets. Non-uniform packing of catalyst may cause channeling that could lead to poor heat transfer, poor conversion, and catalyst deactivation due to hot spots. The bed is loaded by pouring and manually packing the catalyst or by sock loading. As discussed earlier, catalysts may be regular or shaped porous supports, uniformly impregnated with the catalytic ingredient or containing a thin external shell of catalyst. Catalyst pellet sizes usually are in the range of 0.1 to 1.0 cm (0.039 to 0.39 in). (Perrys Chemical Engineers Handbook 8th Edition) Packed-bed reactors are easy to design and operate. The reactor typically contains a manhole for vessel entry and openings at the top and bottom for loading and unloading catalyst, respectively. A metal support grid is placed near the bottom, and screens are placed over the grid to support the catalyst and prevent the particles from passing through. In some cases, inert ceramic balls are 97

placed above and below the catalyst bed to distribute the feed uniformly and to prevent the catalyst from passing through, respectively. One has to guard the bed from sudden pressure surges as they can disturb the packing and cause maldistribution and bypassing of feed. (Perrys Chemical Engineers Handbook 8th Edition) There are two basic types of fixed-bed reactors: those in which the solid is a reactant and those in which the solid is a catalyst. Many examples of the first type can be found in the extractive metallurgical industries. In the chemical process industries, the designer will normally be concerned with the second type: catalytic reactors. Industrial fixed-bed catalytic reactors range in size from small tubes, a few centimeters diameter, to large-diameter packed beds. Fixed-bed reactors are used for gas and gas-liquid reactions. Heat transfer rates in large-diameter packed beds are poor, and where high heat transfer rates are required, fluidized beds should be considered. Fixed-bed reactors for industrial syntheses are generally operated in a stationary mode over prolonged production runs, and design therefore concentrates on achieving an optimum stationary operation. According to several experiments that had been conducted (Deleplanque, J. et al. and US Patent 5264625), most of them uses vertical fixed-bed reactor.

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Ullman reported that the Stability, dynamics, and control of fixed-bed reactors with strongly exothermic reactions has been studied in great detail since the early 1970s. The numerous publications could give the impression that this is a particular critical reactor type with a large potential risk. In fact, the opposite is true. Compared to a liquid-phase reactor of the same size, a fixed-bed reactor with a gas-phase reaction contains a mass of reactants several orders of magnitude smaller. There is therefore no danger of runaway exothermic reaction due to reactants accumulating in the reactor, especially as the heat capacity of the catalyst mass additionally damps the uncontrolled temperature rise. Nevertheless, instabilities can arise in fixed-bed reactors, particularly with strong exothermic reactions, and can lead to excess temperature that can damage the catalyst and the reactor construction materials. Fixed-bed reactors for industrial syntheses are generally operated over a long production period with almost constant operating parameters. The task of process control engineering is simply to keep these parameters optimal. In contrast, for supply or disposal plants that have several users or suppliers in the production network, there are frequent changes of feed material and throughput which require fast, automatic reaction control. Examples are fixed-bed reactors for synthesis gas production or off-gas treatment. US Patent 2010/0204502 A1 The process according to the invention may be carried out in the gas phase or in the liquid phase, preferably in the gas phase. 99

When the dehydration reaction is carried out in the gas phase, various process technologies may be used, namely fixed-bed process, fluidized-bed process or circulating fluidized-bed process. The dehydration of glycerol may also be carried out in the liquid phase in a conventional reactor for a liquid phase reaction, but also in a catalytic distillation type reactor. The contact time is the ratio of the volume of the catalyst bed to the volume of gaseous reactants conveyed per second. The average temperature and pressure conditions in a bed may vary depending on the nature of the catalyst, the nature of the catalyst bed and the size of the catalyst. It is possible to use, as the support, any material such as silica, alumina, titanium oxide, silicon carbide, silica/alumina mixture, silicates, borates or carbonates on condition that these products are stable under the reaction condition to which the catalyst will be subjected. Sabater Prieto Sergio reported that the The design of the reactor consists in the determination of the appropriate dimensions to carry out the dehydration of glycerol in a large scale. In practice, it is necessary to carry out the determination of the catalytic volume, which will be placed in the reactor. Therefore, it is necessary to know the dimensions of the catalytic fix-bed for the pilot scale apparatus before the determination of the reactor dimensions. It is necessary to know the behaviour of the reaction in the lab scale apparatus. In this way, the glycerol conversion is the main factor, as well as, the glycerol solution flow. 100

By plotting the glycerol conversion versus the ratio, volume of catalyst / pure glycerol flow, a curve was obtained. At high conversion increases, until it reaches a 100% conversion.

The objective of this curve is to determine the break point, when the glycerol conversion reaches 100%. At this point of conversion, there is a ratio, volume of catalyst/glycerol flow (V cat /Fglycerol ). By choosing a certain scale up factor for the production, which means, a scale factor, for pumped glycerol, the catalytic volume for the scale up can be calculated. It can be observed that the break point for the glycerol conversion is found approximately at a V cat /Fglycerol = 0.5 0.6. This is the smallest ratio, or in other words, the highest feed flow for a constant catalytic bed, which can be used to obtain a 100% glycerol conversion.

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 Multitubular Fixed-Bed Catalytic Reactor Catalytic fixed-bed reactors are the most important type of reactor for the synthesis of large scale basis chemicals. In these reactors, the reaction take place in the form of a heterogeneous catalyzed gas reaction on the surface of catalysts that are arranged as so-called fixed bed in the reactor. Oxidation process can be operated using a multitubular fixed-bed catalytic reactor. Advantages of using multitubular fixed-bed are that it is easy scalability and preferably employed for large-scale industrial implementations. According to Perrys Chemical Engineers Handbook (R. Perry and D. Green), multitubular reactor are designed for highly endothermic reactors because it allows uniform distribution of heat. As discussed earlier, heat management is an important issue in the design of fixed-bed reactors. A series of adiabatic fixed beds with interbed cooling (heating) may be used. For very highly exothermic (endothermic) reactions, a multitubular reactor with catalyst packed inside the tubes and cooling (heating) fluids on the shell side may be used. The tube diameter is typically greater than 8 times the diameter of the pellets (to minimize flow channeling), and the length is limited by allowable pressure drop. The heat transfer required per volume of catalyst may impose an upper limit on diameter as well. Multitubular reactors require special procedures for catalyst loading that charge the same amount of catalyst to each tube at a definite rate to ensure uniform loading, which in turn 102

ensures uniform flow distribution from the common header. After filling, each tube is checked for pressure drop. In addition to the high surface area for heat transfer/volume, the advantage of a multitubular fixed-bed reactor is its easy scalability. A bench-scale unit can be a full-size single tube, a pilot plant can be several dozen tubes, and a large-scale commercial reactor can have thousands of tubes. Disadvantages include high cost and a limit on maximum size (tube length and diameter, and number of tubes). According to Ullmans Processes and Process Engineering, the features of this kind of reactor include temperature control with liquid or gaseous fluid n the shell side space to improve heat transfer. Also this kind of reactor is practical in the production of acrylic acid from acrolein. Reactions that are extremely

temperature-sensitive are carried out in reactors in which indirect heat exchange occurs via a circulating heat transfer medium integrated in the fixed bed. The most common arrangement is the multitubular fixed-bed reactor, in which the catalyst is arranged in the tubes and the heat carrier circulates externally around the tubes. The development of reactors in which the heat exchange surfaces are integrated in the fixed bed to supply or remove the heat of reaction as close as possible to the reaction site occurred in parallel with the development of multistage adiabatic reactors with intermediate heating or cooling. Ullman reported that the multitubular fixed-bed reactor constitutes the oldest and still predominant representative of the class of fixed-bed reactors. Here 103

the catalyst packing is located in the individual tubes of the tube bundle. The heat transfer medium is circulated around the tube bundle and through an external heat exchanger, in which the heat of reaction is supplied or removed. Whereas with endothermic reactions, circulating gas can be used as heat transfer medium, for strongly exothermic reactions exclusively liquid or boiling heat transfer medium are used. Only in this way can the catalyst temperature be held in the narrow temperature range necessary for selective reaction control. Initially, the integration of heat exchange in the fixed bed was utilized to ensure as isothermal a reaction control as possible, which is why the reactors of this type are commonly termed isothermal reactors. They are characterized by reaction tubes of 20-80 mm internal diameter and a carefully designed flow control of the liquid heat transfer medium, with largely constant heat transfer conditions throughout the tube bundle and maximum temperature changes of the heat transfer medium in the tube bundle of a few degrees. Because of the small mass storage capacity compared to liquid-phase reactors, the danger of sudden reaction of accumulated reactants in gas-phase multitube fixed-bed reactors is low. Leaving out the peculiarities of individual cases, the following safety risk can be assumed for fixed-bed reactors: 1. Leaks which result in the release of large amounts of gas or vapour and the formation of explosive clouds.

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2. Leaks resulting in release of large amounts of liquid heat transfer media (oils, salt melts). 3. Occurrence of ignitable or decomposable gas mixtures in the reactor. 4. Melting of the reactor due to a runaway reaction. According to US Patent No. 5264625, the process for the catalytic gasphase oxidation of acrolein to acrylic acid is suited using a multitubular fixed-bed catalytic reactor. It is an object of the present invention to provide a process for the catalytic gas-phase oxidation of acrolein to acrylic acid in a fixed-bed reactor having contacting tubes, at elevated temperature on catalytically active oxides with a conversion of acrolein for a single pass of 95%, which has a reaction temperature program which is improved with respect to increased selectivity of formation of acrylic acid We have found that this object is achieved by a process for the catalytic gas-phase oxidation of acrolein to acrylic acid in a fixed-bed reactor with contacting tubes, at elevated temperature on catalytically active oxides with a conversion of acrolein for a single pass of 95%, wherein the reaction temperature in the flow direction along the contacting tubes (along the reaction axis) in a first reaction zone before the starting reaction gases containing the reactants enter the contacting tubes is from 260 to 300C until an acrolein

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conversion of from 20 to 40% is reached, and the reaction temperature is subsequently reduced by a total of from 5 to 40C, abruptly or successively in steps or continuously along the contacting tubes until an acrolein conversion of a

95% has been reached, with the proviso that the reaction temperature in this
second reaction zone is not lower than 240C. The use of multitubular fixed-bed reactor was also recommended in the invention entitled Catalytic Gas-Phase Oxidation of Acrolein to Acrylic Acid (US Patent No. 5739391). As stated in their invention, We have found theta this object is achieved by a process for the catalytic gas-phase oxidation of acrolein to acrylic acid in a multiple contact tube fixed-bed reactor through whose space surrounding the contact tubes only one heatexchange medium circuit is passed, at elevated temperature on catalytically active multi-metal oxides with an acrolein conversion for a single pass of 95 mole% and an acrylic formation selectivity of 90 mol%, which comprises firstly passing the heat-exchange medium through the multiple contact tube fixed-bed reactor

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Batch Stirred Tank Reactor The batch reactor has the advantage of small instrumentation cost and

flexibility of operation (may be shut down easily and quickly). It has the disadvantage of high labor and handling cost, often considerable shutdown time to empty, clean out, and refill, and poorer quality control of the product. Hence we may generalize to state that the batch reactor is well suited to produce small amounts of material and to produce many different products from one piece of equipment. On the other hand, for the chemical treatment of materials in large amounts the continuous process is nearly always found to be more economical. In the batch reactor, the reactants are initially charged into a container, are well mixed, and are left to react for a certain period. The resultant mixture is then discharged. This is an unsteady-state operation where composition changes with time; however, at any instant the composition throughout the reactor is uniform. Stirred tanks are common gas-liquid reactors. Reaction requirements dictate whether the gas and liquid are in a batch or continuous mode. For a liquid-phase reaction with a long time constant, a batch mode may be used. The reactor is filled with liquid, and gas is continuously fed into the reactor to maintain pressure. If by-product gases form, these gases may need to be purged continuously. If gas solubility is limiting, a higher-purity gas may be continuously fed (and, if required, recycled). As the liquid residence time decreases, product

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may be continuously removed as well. (Perrys Chemical Engineers Handbook 8th Edition) A basic stirred tank design is shown in Fig. 19-30. Height/diameter ratio is H/D = 1 to 3. Heat transfer may be provided through a jacket or internal coils. Baffles prevent movement of the mass as a whole. A draft tube can enhance vertical circulation. The vapor space is about 20 percent of the total volume. A hollow shaft and impeller increase gas circulation by entraining the gas from the vapor space into the liquid. A splasher can be attached to the shaft at the liquid surface to improve entrainment of gas. A variety of impellers is in use. The pitched propeller moves the liquid axially, the flat blade moves it radially, and inclined blades move it both axially and radially. (Perrys Chemical Engineers Handbook 8th Edition) Gases may be dispersed in liquids by spargers or nozzles. However, more intensive dispersion and redispersion are obtained by mechanical agitation. The gas is typically injected at the point of greatest turbulence near the injector tip. Agitation also provides the heat transfer and, if needed, keeps catalyst particles (in a three-phase or slurry reactor) in suspension. Power inputs of 0.6 to 2.0 kW/m3 (3.05 to 10.15 hp/1000 gal) are suitable. Bubble sizes depend on agitation as well as on the physical properties of the liquid. They tend to be greater than a minimum size regardless of power input due to coalescence. (Perrys Chemical Engineers Handbook 8th Edition) 108

The reactor may be modeled as two ideal reactors, one for each phase, with mass transfer between the phases. For example, if the gas has limited solubility and is sparged through a liquid, the gas may be modeled as a PFR and the liquid as a CSTR. Mass-transfer coefficients vary, e.g., as the 0.7 exponent on the power input per unit volume (with the dimensions of the vessel and impeller and the superficial gas velocity as additional factors). (Perrys Chemical Engineers Handbook 8th Edition) In esterification reactions, a batch reactor equipped with four baffles and a six-bladed turbine impeller is used according to the Biochemical Engineering Journal 41 (2008) 8794 by G.N. Kraai et al. Batch reactors are used widely in industry at all scales. Batch reactors are tanks, commonly provided with agitation and a method of heat transfer (usually by coils or external jacket). This type of reactor is primarily employed for relatively slow reactions of several hours duration, since the downtime for filling and emptying large equipment can be significant. Agitation is used to maintain homogeneity and to improve heat transfer. Since residence time is uniform, a batch reactor is preferred for better yields and to obtain a higher selectivity. A batch of reactants is introduced into the reactor operated at the desired conditions until the target conversion is reached. Batch reactors are typically tanks in which stirring of the reactants is achieved using internal impellers, gas bubbles, or a pump around loop where a fraction of the reactants is removed and externally 109

recirculated back to the reactor. Temperature is regulated via internal cooling surfaces (such as coils or tubes), jackets, reflux condensers, or pump-around loop that passes through an exchanger. Batch processes are suited to small production rates, to long reaction times, to achieve desired selectivity, and for flexibility in campaigning different products. Stirred tank (agitated) reactors consist of a tank fitted with a mechanical agitator and a cooling jacket or coils. They are operated as batch reactors or continuously. Several reactors may be used in series. The stirred tank reactor can be considered the basic chemical reactor, modelling on a large scale the conventional laboratory flask. Tank sizes range from a few liters to several thousand liters. They are used for homogeneous and heterogeneous liquid-liquid and liquid-gas reactions, and for reactions that involve finely suspended solids, which are held in suspension by the agitation. As the degree of agitation is under the designers control, stirred tank reactors are particularly suitable for reactions where good mass transfer or heat transfer is required. When operated as a continuous process, the composition in the reactor is constant and the same as the product stream, and, except for very rapid reactions, this will limit the conversion that can be obtained in one stage. The power requirements for agitation will depend on the degree of agitation required and will range from about 0.2 kW/m3 for moderate mixing to 2 kW/m3 for intense mixing. 110

According to US Patent 20050107629 and US5324853 Method for producing Ethyl Acrylate: In producing ethyl acrylate and for recovering acrylic acid, ethyl acrylate, ethanol and water from an esterification reactor mixture containing acrylic acid, ethyl acrylate, ethanol, water, heavy ends, and acid catalyst; the reaction vessel includes a mixing means which is capable of internally recirculating at least 2.5 volumes of reactor liquid per minute. The said mixing means comprising a reactor impeller and at least one baffle disposed about the side wall of the reaction vessel. The mixing means further comprises a draft tube disposed about the impeller. This draft tube is formed from either a flat sheet or heat coils. The reactor impeller is capable of minimizing the internal recirculation of said reaction mixture such that said reaction mixture from said lower region of said reaction vessel is recirculated to said upper region before it returns to said reactor impeller. The reaction vessel has a height to diameter ratio of less than 1.4. The reactor impeller is either a pitched blade turbine or a hydrofoil type turbine. Each baffle has a width greater than 1/12th of the diameter of reaction vessel; whereby each baffle aids in minimizing surface turbulence and vortexing.

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 Shell and Tube Heat Exchanger

If larger flows are involved, a shell and tube exchanger is used, which is the most important type of exchanger in use in the process industries. In these exchangers the flow is continuous. Many tubes in parallel are used where one fluid flows inside these tubes. The tubes, are arranged in a bundle, are enclosed in a single shell and the other fluid flows outside the tubes in the shell side. The simplest shell and tube exchanger is a 1 shell pass and 1 tube pass, or a 1-1 counterflow exchanger. The cold fluid enters and flows inside through all the tubes in parallel in one pass. The hot fluid enters at the other end and flows counterflow across the outside of the tubes. Cross baffles are used so that the fluid is forced to flow perpendicular across the tube bank rather than parallel with it. This added turbulence generated by this cross flow increases the shell-side heattransfer coefficient. (Transport Processes and Unit Operations by C. Geankoplis, 3rd edition)

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Shown above is a bundle of small-diameter tubes which are arranged parallel to each other and reside inside a much larger-diameter tube called the shell. The tubes are all manifold together at other end so that the tube fluid enters the left side and is distributed equally among the tubes. At the right side, the fluid exits from each tube, is mixed together in a second manifold, and then leaves as a single stream. The second fluid, called the shell fluid flows in the space in between the outside of tube. Baffle plates inside the shell force the shell fluid to flow across the tubes repeatedly as the fluid moves along the length of the shell. The shell and tube exchanger is by far the most common type of heat transfer equipment used in the chemical and allied industries. The advantages of this type are as follows: 1. The configuration gives a large surface area in a small volume; 2. Good mechanical layout: a good shape for pressure operation; 3. Uses well-established fabrication techniques; 4. Can be constructed from a wide range of materials; 5. Easily cleaned; 6. Well-established design procedures. Essentially, a shell and tube exchanger consists of a bundle of tubes enclosed in a cylindrical shell. The ends of the tubes are fitted into tube sheets, which separate the shell-side and tube-side fluids. Baffles are provided in the shell to direct the fluid flow and support the tubes. 113

The bundle of tubes in a shell and tube heat exchanger can be stacked in one of the two different ways

The use of triangular pitch allows the tubes to be more tightly packed more tubes and therefore more area per unit volume of shell. This makes the shell cheaper. On the other hand, the square pitch has the advantage that it is easier to clean. As described in the chapter 15: Heat-Exchange Equipment of Unit Operations of Chemical Engineering, 6th ed. by McCabe W. et al. In an exchanger, the shell-side and tube-side heat transfer coefficients are of comparable importance, and both must be large if a satisfactory overall coefficient is to be attained. The velocity and turbulence of the shell-side liquid are as important as those of the tube-side fluid. To promote crossflow and raise the average velocity of the shell-side fluid, baffles are installed in the shell. In construction, common practice is to cut away a segment having a height equal to one-fourth the inside diameter of the shell. Such baffles are called 25 percent baffles. The baffles are perforated to receive the tubes. To minimize leakage, the clearances between baffles and shell and tubes should be small. The baffles are

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supported by one or more guide rods, which are fastened between the tube sheets by setscrews. To fix the baffles in place, short sections of tube are slipped over the rod between the baffles. In assembling such an exchanger, it is necessary to do the tube sheets, support rods, spacers, and baffles first and then to install the tubes. The stuffing box provides for an expansion. This construction is practicable only for small shells. Shell diameters are standardized. For shells up to and including 23 in. the diameters are fixed in accordance with the American Society for Testing and Materials (ASTM) pipe standards. These shells are constructed of rolled plate. The distance between the baffles (center to center) is the baffle pitch, or baffle spacing. It should not be less than one-fifth the diameter of the shell or more than the inside diameter of the shell. Tubes are usually attached to the tube sheets by grooving the holes circumferentially and rolling the tube ends into holes by means of a rotating tapered mandrel, which stresses the metal of the tube beyond the elastic limit, so the metal flows into the grooves. In high-pressure exchangers, the tubes are welded or brazed to the tube sheet after rolling.

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 Tray Tower Absorption Column

Absorption is a process that refers to the transfer of a gaseous pollutant from a gas phase to a liquid phase. The absorption process can be categorized as physical or chemical. Physical absorption occurs when the absorbed compound dissolves in the liquid; chemical absorption occurs when the absorbed compound and the liquid react. Liquids commonly used as solvents include water, mineral oils, non-volatile hydrocarbon oils, and aqueous solutions. Gas absorbers are most often used to remove soluble inorganic contaminants from an air stream. The design of an absorber used to reduce 116

gaseous pollutants from process exhaust streams involves many factors including the pollutant collection efficiency, pollutant solubility in the absorbing liquid, liquid-to-gas ratio, exhaust flow rate, pressure drop, and many construction details of the absorbers such as packing, plates, liquid distributors, entrainment separators, and corrosion-resistant materials. In absorption, mass transfer of the gaseous pollutant into the liquid occurs as a result of a concentration difference between the liquid and gas phase. Absorption continues as long as a concentration difference exists where the gaseous pollutant and liquid are not in equilibrium with each other. The concentration difference depends on the solubility of the gaseous pollutant in the liquid. Absorbers remove gaseous pollutants by dissolving them into a liquid called the absorbent. In designing absorbers, optimum absorption efficiency can be achieved by doing the following: Providing a large interfacial contact area Providing for good mixing between the gas and liquid phases Allowing sufficient residence, or contact, time between the phases Choosing a liquid in which the gaseous pollutant is very soluble Solubility is a very important factor affecting the amount of a pollutant, or solute that can be absorbed. Solubility is a function of both the temperature and, to a lesser extent, the pressure of the system. As temperature increases, the amount of

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gas that can be absorbed by a liquid decreases. From the ideal gas law: as temperature increases, the volume of a gas also increases; therefore, at the higher temperatures, less gas is absorbed due its larger volume. Pressure affects the solubility of a gas in the opposite manner. By increasing the pressure of a system, the amount of gas absorbed generally increases. Solubility data are obtained at equilibrium conditions. This involves putting measured amounts of a gas and a liquid into a closed vessel and allowing it to sit for a period of time. Eventually, the amount of gas absorbed into the liquid will equal the amount coming out of the solution. At this point, there is no net transfer of mass to either phase, and the concentration of the gas in both the gaseous and liquid phases remains constant. The gas-liquid system is at equilibrium. Equilibrium conditions are important in operating an absorption tower. If equilibrium were to be reached in the actual operation of an absorption tower, the collection efficiency would fall to zero at that point since no net mass transfer could occur. The equilibrium concentration, therefore, limits the amount of solute that can be removed by absorption. The most common method of analyzing solubility data is to use an equilibrium diagram. An equilibrium diagram is a plot of the mole fraction of solute in the liquid phase, denoted as x, versus the mole fraction of solute in the gas phase, denoted as y.

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Under certain conditions, Henrys law may also be used to express equilibrium solubility of gas-liquid systems. Henrys law is expressed as: p = Hx where: p = partial pressure of solute at equilibrium, Pa x = mole fraction of solute in the liquid H = Henrys law constant, Pa/mole fraction Henrys law can be written in a more useful form bt dividing both equation by the total pressure, P T , of the system. The left side of the equation becomes the partial pressure divided the total pressure, which equals the mole fraction in the gas phase, y. The equation will now become: y = Hx where: y = mole fraction of gas in equilibrium with liquid H = Henrys law constant, mole fraction in vapour per mole fraction in liquid x = mole fraction of the solute in equilibrium The most widely used model for describing the absorption process is the two-film, or double-resistance, theory, which was first proposed by Whitman in 1923. The model starts with the three-step mechanism of absorption. From this mechanism, the rate of mass transfer was shown to depend on the rate of migration

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of a molecule in either the gas or liquid phase. The two-film model starts by assuming that the gas and liquid phases are in turbulent contact with each other, separated by an interface area where they meet. This assumption may be correct, but no mathematical expressions adequately describe the transport of a molecule through both phases in turbulent motion. Two-Film Theory

Therefore, the model proposes that a mass-transfer zone exists to include a small portion (film) of the gas and liquid phases on either side of the interface. The mass-transfer zone is comprised of two films, a gas film and a liquid film on their respective sides of the interface. These films are assumed to flow in a laminar, or

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streamline, motion. In laminar flow, molecular motion occurs by diffusion, and can be categorized by mathematical expressions. For gas absorption, the two devices most often used are the packed tower and the plate tower. Both of these devices, if designed and operated properly, can achieve high collection efficiencies for a wide variety of gases. Other scrubbing systems can be used for absorption, but are limited to cases where the gases are highly soluble. For example, spray towers, venturis, and cyclonic scrubbers are designed assuming the performance is equivalent to one single equilibrium stage (i.e., NOG = 1) (Perry 1973). Tray towers and similar devices bring about stepwise contact of the liquid and the gas and are therefore countercurrent multistage cascades. On each tray of a sieve-tray tower, for example, the gas and liquid are brought into intimate contact and separated and the tray thus constitutes a stage. It is convenient to use the parallel flow as an arbitrary standard for design and for measurement of performance of actual trays regardless of their method of operation. For this purpose a theoretical, or ideal, tray is defined as one where the average composition of all the gases leaving the tray is in equilibrium with the average composition of all the liquid leaving the tray.

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 Pervaporator Pervaporation, in its simplest form, is an energy efficient combination of membrane permeation and evaporation. It's considered an attractive alternative to other separation methods for a variety of processes. For example, with the low temperatures and pressures involved in pervaporation, it often has cost and performance advantages for the separation of constant-boiling azeotropes. Pervaporation is also used for the dehydration of organic solvents and the removal of organics from aqueous streams. In pervaporation, a multi-component liquid stream is passed across a membrane that preferentially permeates one or more of the components. As the feed liquid flows across the membrane surface, the preferentially permeated components pass through the membrane and are removed as a permeate vapor. Characteristics of the pervaporation process

The separation is carried out by running a feed stream of the liquid mixture across a separation membrane under pervaporator conditions. By pervaporator conditions, we mean that the vapor pressure of the component that it is desired to 122

separate into the permeate stream is maintained at a lower level on the permeate side than on the feed side, and the pressure on the permeate side is such that the permeate is in the gas phase as it emerges from the membrane. The process results, therefore, in a permeate vapor stream enriched in the desired component and a residue liquid stream depleted in that component.

In a first aspect, the process is carried out using multiple membrane modules or elements arranged in series within a single tube, so that the residue stream exiting the first module in the series forms the feed to the second module, and so on, until the final or product residue stream is withdrawn from the last module in the series.

To maintain adequate transmembrane flux, the feed solution under treatment is heated within the tube as it passes from one module to the next. This interstage heating or reheating is achieved by blocking the straight flow path from the residue end of one module to the feed end of the next, and by heating the outside surface of the tube. Instead of passing directly to the inlet of the next module, the feed is directed in a flow path in the annular space between the inside wall or surface of the tube and the outer casing or surface of the membrane module that it has just exited. By forcing the stream to flow at least partially back along the outside of the module, it is brought into heat exchanging contact with the inside surface of the tube.

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Simplified Pervaporation Process

The process divides the feed stream into a treated residue stream and a permeate stream, either or both of which may be desired products of the process. For example, if the feed solution is a dilute solution of ethanol in water, the process of the invention may be used to form a more concentrated ethanol product as the permeate stream. Likewise, if the feed solution is ethanol containing just a few percent of water, the process of the invention may be used to dehydrate the ethanol, forming a purified ethanol product as the residue stream.

The membrane modules or elements are housed in a tube. The tube serves to house and support the membrane elements and provide a directed fluid flow. In addition, the tube conducts heat to warm the feed solution as it passes along the train of modules, and may provide a pressure-withstanding function if the pressure 124

conditions under which the separation process is carried out are substantially different from the pressure outside the tube.

The outside of the tube may be heated in any appropriate manner. Preferably, low grade steam is used if available.

The membrane used to perform the separation may be any type of membrane capable of performing an appropriate separation under

pervaporation conditions. Suitable membranes include polymeric membranes, inorganic membranes, such as ceramic membranes, and membranes containing inorganic particles embedded in a polymeric matrix. For example, if the feed solution is to be dehydrated, a hydrophilic membrane, such as a polyvinyl alcohol membrane, may be used. If the feed solution is a mixture of olefins and paraffins, a hydrophobic membrane, such as a fluorinated polyimide membrane, may be used.

The membranes and modules may take any convenient cylindrical form, such as flat sheets wound into spiral-wound modules, potted hollow fibers or tubular membranes that will fit into the tube so as to leave an annular space between the outer longitudinal surface of a membrane module and the inside surface of the tube. The configuration of the process and apparatus of the invention is not suitable for plate-and-frame modules, as these are usually assembled in stacks, not housed in tubes or cylindrical pressure vessels.

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The series includes at least two modules, and will typically include three, four, five or six modules mounted end to end in the tube. The modules are connected as described above such that a feed stream under treatment may enter the feed end of the first module, flow through the modules in turn and exit as a final residue stream from the residue end of the last module. The modules are also connected by a permeate pipe or pipes, through which the collected permeate stream from the series can flow.

The driving force for transmembrane permeation is the difference between the vapor pressure of the feed liquid and the vapor pressure on the permeate side. This pressure difference is generated at least in part by operating with the feed liquid at above ambient temperature, usually above 30 C., and typically in the range 30-120 C. Optionally, the permeate side may also be maintained under vacuum to increase the driving force.

To heat the feed solution as it passes along the chain of modules, the feed solution is prevented from flowing in a straight line immediately from the residue end of one module to the feed of the next. Instead, the feed solution exiting the residue end of a module is directed at least partially back along the outside of the module it has just exited, into a reheating space or zone between the outer longitudinal surface of that module and the inside surface of the tube. The reheated residue solution is then directed out of the reheating space to the feed inlet end of the next module. 126

Any solution that may be treated by pervaporation may be treated by the process of the invention. Most commonly, the liquid to be treated will be a solution of one or more organic components in water, or of water in an organic solvent or solvent mixture, but solutions containing only organic or only inorganic components may also be treated. Separation of aromatics from paraffins in an oil refinery, removal of organic sulfur compounds from hydrocarbon mixtures, dehydration of bioethanol, recovery of ethanol from fermentation broth, and removal of volatile organic compounds (VOCs) from wastewater are typical representative examples of separations in which the process of the invention can be used to advantage.

The separation is carried out by running a feed stream of the liquid mixture across a separation membrane under pervaporation conditions.

By pervaporation conditions, we mean that the vapor pressure of the component that it is desired to separate into the permeate stream is maintained at a lower level on the permeate side than on the feed side, and the pressure on the permeate side is such that permeate is in the gas phase as it emerges from the membrane. The process results, therefore, in a permeate vapor stream enriched in the desired component or components and a residue liquid stream depleted in that component or components.

Alternatively, the design can be simplified by permanently welding end 203 to the body of the vessel or manufacturing as a unitary part of the body of 127

the vessel. The modules must then be loaded or unloaded from one end only, but the manufacturing cost of the vessel may be reduced.

The tube or housing may be made of any convenient material. Housings are usually made of metal, conforming to appropriate codes for the operating conditions to which they are to be exposed. Pervaporation processes are not usually operated at feed pressures substantially different from atmospheric, although they may be operated at high temperatures, above 100 C. In the case that the feed is introduced at ambient pressure, and 40 C., for example, a housing made from a plastic may suffice, so long as the material has adequate thermal conductivity. In the case that the feed is under high hydraulic pressure, or very hot, a stainless or carbon steel housing, for example, may be needed. In general, we prefer to use metal housings.

A feed port, 217, and a residue port, 218, are positioned near the ends of the housing. One or both of the end plates or heads is fitted with, or adapted to accept, permeate collection pipe,209, through which treated permeate is removed from the processing train. Alternatively, a flanged permeate port to which the permeate pipes are connected could be provided.

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CHAPTER III

PROCESS DESCRIPTION

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CHAPTER III PROCESS DESCRIPTION I. INTRODUCTION Conversion of glycerol into valuable-added chemicals are appearing in recent years as a result of glycerol availability since it is the main by-product in the biodiesel production and in other processes concerning biomass as raw material. A higher number of applications focus in transforming crude glycerol into more valuable chemicals since it is a molecule rich in functionalities, with three -OH groups. Thus, several factors, its low price, availability and its functionalities, make glycerol very attractive as starting material for many industrial processes. P. Sabatier 1918 has described the catalytic conversion of glycerol to acrolein. In 1948, H.E. Hoyt et al. have patented a heterogeneous catalyzed continuous process for the production of acrolein from glycerol. In that patent the consistence of the catalyst material has been reported as diatomaceous earth supported ortho-phosphoric acid, which has been mixed with a petroleum oil fraction with a boiling point of about 300- 400 C. The acrolein yield is claimed to be 72.3 %. A manufacturing process of acrolein by dehydration of glycerol in phase gas, in the presence of solid catalysts having an acidity of Hammett H0 between -9 130

and -18 such as sulfated zirconia has been developed. These catalysts deactivate slowly so as to permit long reaction cycles and low reactor volumes. (Sergio Sabater Prieto) Acrolein also can be prepared from glycerol using subcritical and supercritical water as the reaction media. This method has shown a certain potential for the dehydration of glycerol, although the conversion and acrolein selectivity achieved are not significant enough for industrial application. The addition of a mineral acid to the water is necessary to obtain high acrolein yields, although the presence of an acid intensifies the corrosive effect. Thus, for an attractive commercial process for the acrolein synthesis from glycerol in the near future, low corrosive anions stable under this reaction conditions are needed. Dehydration of glycerol has been performed in liquid phase with zeolites; it was found that acrolein yields were lower in liquid phase than in gas phase. In this sense, a recent patent claims that glycerol in water can be converted into acrolein, olefins, and acetaldehyde catalyzed by zeolites in a continuous fluidizedbed reactor. This reaction system allows better heat and mass transfer than fixedbed reactors, along with the possibility of performing continuous regeneration if needed. The highest yield to acrolein was obtained at 350C with a ZSM5 zeolitebased catalyst. (Guerrero-Perez et al.)

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Acrylic acid is manufactured from glycerol in two steps via acrolein in a gas phase using special catalysts.

The first stage is the dehydration of glycerol to acrolein using a tungsten zirconia catalyst is an endothermic reaction (at about 280C). In the second stage, oxidation of acrolein to acrylic acid, the acrolein gas is passed over a molybdenum vanadium oxide catalyst is a strongly exothermic reaction (at about 300C). The crude acrolein coming from the first reactor is cooled to about 100C. Acrolein containing impurities will be absorbed in water in a purifying process before continuing to the second reactor. In the oxidation process, the acrolein is passed through multi-metal oxides in a multitube fixed-bed reactor at temperature of about 300C. From the published US Patent by Jean-Luc Dubois entitled Method for Preparing Acrylic Acid from Glycerol, Patent No.: US 2010/0168471 A1: Glycerol is produced by the methanolysis of vegetable oils at the same time as the methyl esters which are employed in particular as motor fuels or fuels in diesel and home-heating oil. It is a natural product, available in large quantities, and can be stored and transported without difficulty. It has the 132

advantage of being a renewable raw material meeting the criteria associated with the new concept of green chemistry. The development of glycerol has attracted considerable research, and the preparation of acrylic acid is one of the alternatives considered. The invention related to a method of preparing acrylic acid from an aqueous glycerol solution, comprising a first step of dehydration of the glycerol to acrolein, carried out in the gas phase in the presence of a catalyst and under a pressure of between 1 and 5 bar, and a second step of oxidation to acrylic acid. Acrylic acid is a corrosive chemical that is miscible in water, alcohol, and esters and polymerizes readily in the presence of oxygen forming acrylic resins. For this reason, the product is usually stabilized with polymerization inhibitors such as methyl ethyl hydroquinone (MEHQ). There are two grades of acrylic acid commercially available: Technical Grade Acrylic Acid which usually has about 94 percent acrylic acid content. Technical (also referred to as crude) acrylic acid is suited for the production of commonly acrylate esters. Major markets for the commodity esters include surface coatings, adhesives and sealants, textiles, plastic additives, and paper treatment. Glacial Grade Acrylic Acid is generally used to designate grades of the acid with acrylic acid content between 98 to 99.7 percent; although in the literature of 133

many companies selling the product, glacial grade is typically listed as having 99.5 to 99.7 percent acrylic acid content. Glacial acrylic acid is suited for the production of super absorbent polymers (fro disposable diapers), detergents, water treatment and dispersants. For esters, whose manufacture is normally integrated with an acrylic acid plant, the purification step is undertaken after the esterification process. The technical grade of the acid is therefore not traded. Acrylates are derivatives of acrylic acid (such as methyl and ethyl acrylate) whose properties have been sufficiently modified to enable of acrylic acid to be used in different media as emulsion and solution polymers. As emulsions, these products may be used as coatings, finishes and binders leading to applications in paints, adhesives, and polishes with solutions used for industrial coatings. Two-third of the world's production of acrylic acid is used to produce acrylic esters (acrylates) primarily for use in emulsions and solution polymers for latex-based paints, coatings, adhesives and textiles. According to the Esterification of Acrylic Acid from US Patent No. 3458561, The invention related to a novel process for esterifying acrylic acid. A number of processes are known which are directed to the corresponding acylic acid and an alcohol to the corresponding acrylic ester in the presence of an esterification catalyst. Esterification of acrylic acid is possible in a liquid as well

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as in gas phase. Of primary importance as an esterification catalyst is sulphuric acid.

Acrylic esters may be polymerised, catalysed by heat and oxidising agents in solution or emulsion methods to form long-chain thermoplastic resins. Broadly, acrylic ester polymers are colourless, insoluble in aliphatic hydrocarbons and resistant to alkali, mineral oils and water so that with good resistance to degradation, adhesion and electrical properties, they are widely used. Surface coatings, such as paints, represent the largest application for acrylic esters at about 19 per cent of the market. Demand, that was motivated by the convenience of water-based paints especially the superior acrylic-based emulsions, is now being driven by regulations and interests to reduce atmospheric release of volatile organic compounds (VOCs) used as solvents in traditional (alkyd-based) surface coatings. This sector is growing at 3 to 5 per cent per year with faster growth for newer more sophisticated applications (such as UV radiation-curable polymers).

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III. DETAILED PROCESS DESCRIPTION EQUIPMENT NAME: Preheater EQUIPMENT CODE: B-1

Crude Glycerol Glycerol <60% Water >40%

Preheated Crude Glycerol T = 180-350C Glycerol <60% Water >40% T = 180-350C P = 1-2 bar

Preheater is a general term to describe any device designed to heat fluid before another process with the primary objective of increasing the thermal efficiency of the process. Also, the unit serves to impart latent heat to a fluid. Glycerol conversion can be modulated in the gas-phase reaction and it was found that acrolein yields were higher. The heated crude glycerol will be sent to dehydration reactor. Heating is conducted to introduce the crude glycerol stream already in the gaseous phase.

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Prieto included in his study that when the glycerol solution reaches 200 C, the mixture is completely evaporated. Between 104 and 200 C, the system is a mixture of liquid and vapor (Prieto, Sergio Sabater. Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant).Crude glycerol solution is first sent to a preheater before sending to the dehydration reactor. The charge sent into the reactor may be preheated to a preheating temperature of the order of around 180C to 350C. (From US 2010/0204502)

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EQUIPMENT NAME: Dehydration Reactor EQUIPMENT CODE: R-1 Crude Glycerol (from B-1) T = 180-350C Glycerol <60% Water >40%

T = 250-280C P = 1-3 bar

Crude Acrolein T = 250-280C Acrolein (30-40%) Acetol<5% Water <60% Inert gases (H2, O2)

Preheated crude glycerol is sent to a fixed bed reactor containing tungstated zirconia, a dehydration catalyst, with temperature ranging from 250-280C and pressure of 1-3 bar. The glycerol undergoes dehydration reaction to produce the acrolein and acetol, which is the major by-product of the reaction. Reaction of the dehydration of glycerol to acrolein is given below.

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At temperatures higher than 240 C, glycerol is extensively converted. The acrolein selectivity shows a maximum at 280 C. At lower temperatures the intermolecular dehydration, yielding oligomers of glycerol, is thermodynamically favoured over the desired intramolecular dehydration forming acrolein. At temperatures higher than 280 C, the formation of CO and CO 2 is possible. These two reasons are responsible for the selectivity decrease of acrolein. (From Ulgen et al. Conversion of Glycerol to Acrolein in the Presence of WO 3 /ZrO 2 Catalysts) By S. Prieto in his dissertation entitled Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant, he reported that tungsten zirconia catalysts are the most promising because it offer inherent advantages from the standpoint of industrial application, such as higher stability under hightemperature treatments, lower deactivation rates during catalysis, and easier regeneration. An approach for finding an optimum working point can be determined. To get a complete glycerol conversion it is better to work at high temperatures. Around 280 C the acrolein production is the highest. However, at higher temperatures, close to 300 C, the formation of acrolein decreases a little, and the formation of by-products increases with the temperature. Therefore, a 140

temperature, around 285 C will be appropriate to produce the highest amount of acrolein at a complete glycerol conversion and to minimize the formation of byproducts. The glycerol concentration should be not too high because at high glycerol concentrations, the glycerol conversion and acrolein selectivity decreases. Formation of acetol with acetone as an intermediate step is also considered in the dehydration of glycerol to acrolein.

According to the US Patent 5387720, gas phase reaction is preferable since it enables a degree of conversion of the glycerol of close to 100% to be obtained. A proportion of about 10% of the glycerol is converted into acetol, which is present as the major by-product in the acrolein solution.

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EQUIPMENT NAME: Heat Exchanger EQUIPMENT CODE: H-1

Crude Acrolein (from R-1) T = 250-280C Acrolein (30-40%) Acetol<5% Water <60% Inert gases (H2, O2) T = 100-150C P = 1-2 bar

Cooled Crude Acrolein T = 250-280C Acrolein (30-40%) Acetol<5% Water <60% Inert gases (H2, O2)

The gas stream from the dehydration reactor is sent to a heat exchanger where it is cooled to a temperature of 100-150C from a temperature of 250-280 C before sending the said stream to a condensation unit where water-rich stream with heavy by-product is removed from the crude acrolein stream. Based from the invention made by Dubois (US 2010/0168471), The gas stream leaving the first reactor is cooled to 151C in a heat exchanger. According to the invention based from the US Patent 5770021, Process and Apparatus for Purification of a Gas Stream containing Acrolein, In the first stage of the process of the invention, the feed gas stream that typically originates from 142

the gas-phase oxidation of glycerol is preferably cooled from its production temperature to a temperature ranging from 100 to 200C and is introduced into the bottom part of the cooling column.

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EQUIPMENT NAME: Absorption Column EQUIPMENT CODE: A-1 Top Stream T = 50-60C Acrolein (90-95%) Inert gases (H2, O2) Water

Absorbing Solvent Water (100%)

T = 50-60C P = 1-2 bar Cooled Crude Acrolein (from H-1) T = 250-280C Acrolein (30-40%) Acetol<5% Water <60% Inert gases (H2, O2)

Bottom Stream Water >90% Acetol<10% Acrolein <1.5%

In the first stage of the purification process, the feed gas stream that typically originates from the gas-phase dehydration of glycerol to acrolein is preferably cooled from its production temperature to a temperature ranging from 100 to 150C and is introduced into the bottom part of the cooling column.

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Accordingly, the gaseous effluent may be subjected to an absorption operation and be carried out in an absorption column. The water circulates countercurrentwise to the effluent with a mass flow rate preferably ranges from 0.005 to 0.05. (US Patent No. 5770021) The invention relates to a method for preparing acrylic acid from an aqueous glycerol solution, comprising a first step of dehydration of the glycerol to acrolein, in which an intermediate step is implemented, consisting in at least partly condensing the water and heavy by-product present in the stream issuing from the first dehydration step. The method according to the invention, even though it requires an additional unit associated with the intermediate step, has the advantage of using an economical raw material and of being able to optimize the two reaction stages separately. The method remains demonstrably economical. (US Patent No. 2010/0168471) Purification of acrolein is described in the US Patent No. 5770021 entitled Process and Apparatus for Purification of a Gas Stream Containing Acrolein. The circulation of the gaseous stream in the column countercurrentwise to a cold liquid results in condensation of the water and other condensable components that may be present. The condensed liquid which includes acetol, water and some part of acrolein flows back down under gravity to the bottom of the column. The gases at the top of the column composed of acrolein, water and

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non-condensable gases. The temperature of the gases at the top of the column preferably ranges from 30 to 60C, and still more preferably from 50 to 60C. The cooling column preferably operates at a pressure ranging from 105 to 3x105 Pa. The bottom stream generally contains organic acids and preferably less than 2%, more preferably less than 1.5%, by weight of acrolein and at least 90% by weight of water.

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EQUIPMENT NAME: Preheater EQUIPMENT CODE: B-2

Acrolein Stream (from A-1) T = 50-60C Acrolein (90-95%) Inert gases (H2, O2) Water T = 180-250C P = 1-2 bar

Preheated Acrolein T = 180-250C Acrolein (90-95%) Inert gases (H2, O2) Water

Stream that exits at the top of the absorption column is sent to a preheater. This equipment operates at temperature of 180C to 250C. Acrolein from the absorption column is first sent to a preheater before sending to the oxidation reactor. The charge sent into the reactor may be preheated to a preheating temperature of the order of around 180C to 350C. (From US 2010/0204502) The acrolein from the absorption column will pass first to a preheater before entering the oxidation reactor in order to reach the desired temperature attainable in the reactor. Steam will serve as the heating medium.

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EQUIPMENT NAME: Oxidation Reactor EQUIPMENT CODE: R-2

Preheated Acrolein (from B-2) T = 180-250C Acrolein (90-95%) Inert gases (H2, O2) Water

Air

T = 250-300C P = 1-5 bar

Crude Acrylic Acid T = 250-300C Acrylic Acid (50-55%) Acrolein <0.10% Inert gases (N2, H2, O2) Water <0.80%

The heated stream mixture from the heat exchanger is then sent to a reactor for the oxidation process. The oxidation reactor comprises of an oxidation catalyst, vanadium-molybdenum oxide, at T = 250-300C and P = 1-5 bar. The acroleinrich stream, stripped of the heavy by-products and most of the water, is sent to the oxidation reactor where acrolein can then be oxidized to acrylic acid.

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According to J. Tichy in his work refer to Oxidation of acrolein to acrylic acid over vanadium-molybdenum oxide catalysts, he reported that oxidation of acrolein proceeds favourably with a stoichiometric excess of oxygen, and the reaction temperature should not exceed 573 K or else it will yield an undesirable radical reaction. He also believed that among the recommended catalysts, the most efficient system for the conversion of acrolein to acrylic acid involve oxide systems based on Mo-V, Mo-Co, V-Sb and heteropolyacids. US Patent 20100168471 also suggested the catalysts made of formulations containing Mo and/or V and/or W and/or Cu and/or Sb and/or Fe should be used in the catalytic reaction. Conversion of crude glycerol to acrylic acid via acrolein as its intermediate step is shown in this stoichiometric reactions.

Oxidation reaction from acrolein to acrylic acid.

According from the two inventions (US Patent 5264525 and US Patent 5739391), A process for the catalytic gas-phase oxidation of acrolein to acrylic

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acid in a fixed-bed with contacting tubes, at elevated temperature on catalytically active oxides with a conversion of acrolein for a single pass of 95%. We have found that this object is highly achieved wherein the reaction temperature in the flow direction along the contacting tubes (along the reaction axis) in a first reaction zone before the starting reaction gases containing the reactants enter the contacting tubes is from 260 to 300C until a acrolein conversion of a 95% has been reached, with the provision that the reaction temperature in this secondary reaction zone is not lower than 240C. Based on the US Patent 20100168471, Oxidation reaction takes place at temperature of between 200 C and 350 C, preferably from 250 C to 320 C and under the pressure of between 1 and 5 bar. The reaction is carried out in the presence of molecular oxygen which may be in the form of air having a content of between 3 to 20% by volume, with regard to the incoming stream and optionally in the presence of inert gases such as N 2 . The inert gases necessary for the method may be optionally consist in full or in part of gases obtained at the top of the absorption column. US Patent 5264625 entitled Catalytic Gas-phase Oxidation of Acrolein to Acrylic Acid described the oxidation process is highly exothermic. It is therefore required to control the reaction temperature in order to obtain a highly selective conversion of acrolein to acrylic acid.

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EQUIPMENT NAME: Dehumidifying Condenser EQUIPMENT CODE: C-1

Uncondensed and inert gases Acrolein <3% Inert gases (N2, H2, O2)

Crude Acrylic Acid (from R-2) T = 250-300C Acrylic Acid (50-55%) Acrolein <0.10% Inert gases (N2, H2, O2) Water <0.80%

Condensate T = 100-150C Acrylic Acid (80-85%) Water (15-20%) T = 90-100C P = 1-2 bar

The gas effluent from the oxidation reactor is first sent to a condenser where it is cooled to a temperature of 60-100C from a temperature of 250-300C. The crude acrylic acid from the second reactor will pass through a dehumidifying condenser where acrolein and other inert gases will separate from the acrylic acid-water mixture. The acrylic acid and water will be condensed and be sent to the esterification reactor.

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Based from the invention made by Sridhar (US 005463121A), The gas stream leaving the reactor is cooled to 60-100C in a heat exchanger before undergo the pervaporation process.

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EQUIPMENT NAME: Esterification Reactor EQUIPMENT CODE: R-3

Condensate (from C-1) T = 90-100C Acrylic Acid (80-85%) Water (15-20%)

Ethanol

Sulfuric Acid Solution (Catalyst)

T = 70-180 C P = 0.3-0.6 bar

Crude Ethyl Acrylate T = 70-180C Ethyl Acrylate (70-80%) Water (20-25%) Acrylic Acid <1.0% Ethanol <0.50%

Acrylic acid free of inert gases from the condenser and ethanol are fed to the esterification reactor. The minimum temperature at which the esterification is achieved depends upon the boiling point of the formed acrylic acid ester and water. In general, a reboiler temperature between 70 to 180C with pressure of 760 mm of mercury, is employed. The novel esterification can be carried out by

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continuously introducing about equimolar amount of acrylic acid and alcohol in the reboiler zone or sump of a reactor.(US Patent No. 3458561) The recommended catalyst in the reaction is Sulfuric Acid. A number of processes are known which are directed to the conversion of acrylic acid and an alcohol to the corresponding acrylic ester in the presence of an esterification catalyst. Considering the esterification speed and conversion and avoiding at the same time the formation of undesirable side reactants, the best results are obtained when using in the reboiler, from 10 to 25% by weight of sulfuric acid.(US Patent No. 3458561) The reaction of acrylic acid and alcohol is as follows:

Reacting the acrylic acid and ethanol to yield ethyl acrylate in a conversion of at least 90% on acrylic acid, and yielding the esterification reaction mixture comprising ethyl acrylate, acrylic acid, ethanol and water.(US Patent No. 20050107629)

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EQUIPMENT NAME: Heat Exchanger EQUIPMENT CODE: H-2 T = 80-100C P = 1-2 bar

Crude Ethyl Acrylate (from R-3) T = 70-180C Ethyl Acrylate (70-80%) Water (20-25%) Acrylic Acid <1.0% Ethanol <0.50%

Cooled Crude Ethyl Acrylate T = 80-100C Ethyl Acrylate (70-80%) Water (20-25%) Acrylic Acid <1.00% Ethanol <0.50%

The gas effluent from the esterification reactor is first sent to a heat exchanger where it is cooled to a temperature of 80-100C from a temperature of 70-180C. The mixture of ethyl acrylate, water, acrylic acid and ethanol from the third reactor reactor will pass counter-currently to the heat exchanger before entering the ethyl acrylate purification process. Water will serve as the cooling medium. Based from the invention made byAbdullah (EP 2 325 214 A1), The step of pervaporation is carried out at a temperature in the range of about 30C to about 100C.

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EQUIPMENT NAME: Pervaporator EQUIPMENT CODE: PV-1

Permeate Water T = 60-100C P = 1-2 bar

Cooled Crude Ethyl Acrylate (from H-2) T = 80-100C Ethyl Acrylate (70-80%) Water (20-25%) Acrylic Acid <1.0% Ethanol <0.50%

Retained Material Stream T = 60-100C Ethyl Acrylate (90-99%) Acrylic Acid <1.0% Ethanol <0.50%

This unit will separate water from the crude ethyl acrylate. The water will pass through the membrane inside the unit and be separated leaving the ethyl acrylate, ethanol and acrylic acid in the retained material stream. Pervaporation of water will operate at 60-100 C and atmospheric pressure.

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Solvent dehydration is the most common application of pervaporation. Transport rates of components through the membrane mixtures of components with close boiling point and azeotropic mixture can be effectively separated. (W. Kujawski, Polish Journal of Environmental Studies Vol.9, No.1 (2000)). The product from the third heat exchanger is sent to a pervaporator. Water scrubbed, ethyl acrylate, acrylic acid, and ethanol goes to the bottom of the column. Based from Polish Journal of Environmental Studies Vol.9, No.1 of W. Kujawski, Water is continuously extracted in a side pervaporation from the mixture containing ester, acid and alcohol. According to the patent invented by Abdullah (EP 2 325 214 A1), The purification process allows for the production of ethyl acrylate at controlled composition (0-99 mol-%)

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EQUIPMENT NAME: Condenser EQUIPMENT CODE: C-2 T = 10-15C P = 1-2 bar

Retained Material Stream (from PV-1) T = 60-100C Ethyl Acrylate (90-99%) Acrylic Acid <1.0% Ethanol <0.50%

Ethyl Acrylate (Product) T = 10-15C Ethyl Acrylate (90-99%) Acrylic Acid <1.0% Ethanol <0.50%

The product from the pervaporator is sent to a condenser where it is cooled to a temperature of 10-15C from a temperature of 60-100C until it reaches its liquid state. The final product composes of ethyl acrylate with 90-99% purity. Impurities present in the product are acrylic acid and ethanol. Component Ethyl Acrylate Acrylic Acid Ethanol Mole % 98% 1% 1% Mass % 99% 0.60% 0.40%

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CHAPTER IV

PLANT CAPACITY DETERMINATION

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CHAPTER IV PLANT CAPACITY DETERMINATION I. INTRODUCTION Acrylic acid has served, for more than 30 years, as an essential building block in the production of some of our most commonly used industrial and consumer products. Approximately two-thirds of the acrylic acid manufactured is used to produce acrylic esters - methyl acrylates, butyl acrylates, ethyl acrylates, and 2-ethylhexyl acrylates - which, when polymerized are ingredients in paints, coatings, textiles, adhesives, plastics, and many other applications. The remaining one-third of the acrylic acid is used to produce polyacrylic acid, or crosslinked polyacrylic acid compounds, which have been successfully, used in the manufacture of hygienic products, detergents, and wastewater treatment chemicals. The largest application for acrylates esters is the production of surface coatings (48%), followed by adhesives and sealants (21%), plastic additives and comonomers (12%), paper coatings, and textiles and surface coatings account for 55% of acrylates ester consumption. Acrylic acid and esters are perhaps the most versatile series of monomers for providing performance characteristics to thousands of polymer formulations.

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Incorporation of varying percentages of acrylates monomers permits the production of thousands of formulations for latex and solution copolymers, copolymer plastics and cross-linkable polymer systems. Their performance characteristicswhich impart varying degrees of tackiness, durability, hardness and glass transition temperaturespromote consumption in many end-use applications.

The world acrylic acid business is characterized by the involvement of a relatively few major players who have both globalized and set up a range of strategic alliances, joint ventures and new integrated companies. According to the leading suppliers of acrylic acid, the annual demand growth will stay at the level of 5% in the coming years. Glacial acrylic acid is used in the manufacture of super absorbing polymers (SAP), which account for 32% of the global demand for acrylic acid. They predict

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the following demand growth figures for various segments of acrylic acid consumption: 3.6% per year for acrylates and 5% per year for super absorbent. The global market is set to continue to grow in excess of 3%/year, pulled by Asia, China, and India in particular. Exports of acrylic monomers from the US will slow, as foreign additions to capacity come online, particularly in the Asia/Pacific region. In spite of the recent economic woes of that region (which have caused the delay or cancellation of some projects), capacity is expected to increase significantly, eroding export markets for US producers. The largest volume application for acrylics will continue to be in the manufacture of paints and coatings. Acrylic monomers (both acrylate and methacrylate types) are widely used as the base resin in coatings due to their compatibility in reformulated products. The bulk of demand is concentrated in architectural coatings, where product reformulation has nearly reached saturation levels. Growth will therefore be greater in industrial and specialty coatings, an area in which reformulation has lagged due to higher performance requirements. Ethyl acrylate is used to form paint coatings that are resistant to water, sunshine, and weather. These coatings retain flexibility even at low temperatures. EA is also used in industrial finishes and coatings for cans and coils. Fabrics gain texture and durability when ethyl acrylate is added during their manufacture. Ethyl acrylate also imparts dirt resistance, improves abrasion, and binds pigments to fabric. Paper is coated with ethyl acrylate to make it water-resistant. Magazines, 162

books, business paper, frozen food packaging, and folding boxboards have such coatings, making them resistant to water, grease, and oil. Ethyl acrylate is also used in adhesives for envelopes, labels, and decals. Caulk, glazing, and various sealants also contain Ethyl acrylate. Ethyl acrylate is also used as a fragrance additive in various soaps, detergents, creams, lotions, perfumes, and as a synthetic fruit essence. Ethyl acrylate is also found in such household items as nail mending kits and in medical items that assist with the binding of tissues, sealing wounds, and ileostomy appliances.

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II. SUPPLY AND DEMAND ANALYSIS A. INTRODUCTION Demand has increased for acrylic acid derivatives, specifically ethyl acrylates used in the production of surface coatings. Still, the growth is being limited by the current global inventory of crude acrylic acid. Due to growing demand for acrylic acid derivatives led by SAPs, many of the major producers have responded by expanding plants and building new production facilities at key sites throughout the world. The table below shows the percentage use of Ethyl Acrylate in surface coatings, adhesives and sealants, plastic additives, paper coatings, and textiles. Table 4.1. Percent Consumption of Ethyl Acrylate Application Surface coatings Adhesives and sealants Plastic additives Paper coatings, and textiles Total % Consumption 48 21 12 19 100

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B. DEMAND ANALYSIS In the Philippines, large percentage of ethyl acrylate is use in paint industry particularly in the manufacture of water-based latex paints. Acrylic acid and esters are perhaps the most versatile series of monomers for providing performance characteristics to thousands of polymer formulations. Incorporation of varying percentages of acrylates monomers permits the production of thousands of formulations for latex and solution copolymers, copolymer plastics and cross-linkable polymer systems. The tables below show the plant capacity of some paint industries that uses ethyl acrylate and the percent composition of paint.

Table 4.2. Plant Capacity of Some Paint industries in the Philippines that uses Ethyl Acrylate Company Nippon Paint Philippines, Inc. (Cabuyao, Laguna) Boysen Paint (Trece Martires, Cavite) Total Annual capacity, tons/yr 30,000

818,776 848,776

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Paints are used to protect metals, timber, or plastered surfaces from the corrosive effects of weather, heat, moisture or gases etc and to improve their appearance. The binder, or resin, is the actual film forming component of paint. It imparts adhesion, binds the pigments together, and strongly influences such properties as gloss potential, exterior durability, flexibility, and toughness. Binders include synthetic or natural resins such as acrylics, polyurethanes, polyesters, melamine resins, epoxy, or oils. Table 4.3. Percent Composition of Paint Components Binder (Ethyl acrylate) Pigment (coloring) Extender (Calcium carbonate) Dispersant Rheology Modifier Thickener Auxiliary binder Water Total Percent by weight 21 5 13 2 1 3 3 52 100

166

C. SUPPLY ANALYSIS There is no industry that produces Ethyl Acrylate in the Philippines. The succeeding data is the importation of Ethyl Acrylate in the Philippines from year 2004 to 2008 acquired from the National Statistics Office of the Philippines.

Table 4.4. Importation Data Ethyl Acrylate (in kilograms)

YEAR COUNTRIES China, People's Rep. Of Indonesia (Includes West Irian) Japan (Excludes Okinawa) Korea, Rep. of (South) Malaysia (Federation of Malaya) Singapore

2005

2006

2007

2008

12,630

3,004

204,234

49,296

566,880

248,345

417,487

643,563

143,065

106,540

738,500

235,582

1,547,700

1,631,096

1,400,716

1,026,230

1,572,684

1,913,767

7,425,932

6,851,514

1,373,245

1,674,298

1,457,535

4,571,053

167

South Africa, Rep. of United States of America TOTAL

326,445

650,925

23,550

3,763,022

1,799,191

220

369,128

9,307,671

8,027,166

11,668,174

13,746,366

The table shows the top five countries that export Ethyl Acrylate in the Philippines; United States of America, Singapore, Korea, Indonesia and Malaysia. The average annual importation of Ethyl Acrylate amounts to 10,687,344 kg or about 10,687.344 MT. The average annual percentage increase in importation between 2005 and 2008 is 16.14%.

168

III. MAJOR RAW MATERIAL AVAILABILITY The raw material to be used for the production of Ethyl Acrylate is crude glycerol. Glycerol is known to be one of the by-products in the production of Biodiesel. Every 1000 kg of biodiesel about 100 kg of raw glycerol are obtained. The table below shows the annual production of Biodiesel based on the top three Biodiesel-producing plants in the country.

Table 4.5. Total Annual Coco-Biodiesel Production of the Biggest Biodiesel Plant in the Philippines Annual Capacity, Biodiesel Producers L/yr Chemrez Technology Inc. Senbel Fine Chemicals Inc. Romtron Philippines Mt. Holy Coco TOTAL
*density of biodiesel ~ 0.88 kg/L

Glycerol Production, MT/yr (By-product) 5,280 3,168 26.4 352 8,826.40

60,000,000 36,000,000 300,000 4,000,000 100,300,000

The total annual production of biodiesel is about 100,300,000 litres. Thus, the annual crude glycerol production, based on the biodiesel production in the country, is about 8,826.4 MT.

169

IV. CONCLUSION To estimate the amount of Ethyl Acrylate produced using glycerol as the major raw material, the equation below is used. Molar mass of glycerol = 92.08 kg/kmol Molar mass of ethyl acrylate = 100.08 kg/kmol From Chapter 3: Conversion of glycerol to acrolein = 90% Conversion of acrolein to acrylic acid = 98% Conversion of acrylic acid to ethyl acrylate = 99%

170

From Table 4.2: Annual Capacity of Nippon Paint Phil. Inc. = 30,000 tons/yr From Table 4.3: Percent Composition of Ethyl Acrylate in Paint = 21% Annual Demand of Ethyl Acrylate

Calculation of Glycerol needed based on the Ethyl Acrylate (EA) Demand:

The basis in determining the plant capacity of the proposed plant is based on the annual Ethyl Acrylate demand of Nippon Plant Philippines, Inc. The availability of the major raw material, glycerol is based on the annual production of biodiesel in the Philippines. The annual demand of Ethyl Acrylate of Nippon Paint amounts to about 6,300 tons. Based from the calculated amount of glycerol above, we have concluded to source out from the two of the largest biodiesel producers namely Chemrez Technology Inc. and Senbel Fine Chemicals Inc., with an amount of 5,280 MT and 3,168 MT, respectively.

171

Since the availability of the major raw material from the two biodiesel companies (8,448 MT glycerol) exceeds the amount needed (6,100 MT glycerol), we aim to manufacture 5,700 MT annually of ethyl acrylate to supply the demand of the local paint industry. The plant will operate at 24 hours daily in 300 days per year.

172

CHAPTER V

MASS AND ENERGY BALANCE

173

CHAPTER V MASS AND ENERGY BALANCE I. INTRODUCTION In the successful operation of a manufacturing plant, the amount of product to be produced in a certain amount of raw materials is needed in the study to determine the feasibility of the project. Thus the material balance established together with amount of energy consumption per amount of product or raw materials will determine the cost of product. All material balances are based upon the law of conservation of mass. By this law, every unit of mass entering a system or process must subsequently leave as mass. However, chemical and/or physical changes may have occurred in the system so that the form of feed and products may be expected to change. The law of entering equal to leaving generally applies on the material as well as the energy balance. The amount of raw material supply to the reactor will be equal to the product produce in each reactor, thus the balance between the products and raw material is established through its chemical reaction. In every balance, the second law of thermodynamics is applied which states that the energy cannot be destroyed but can be exchanged, stored and transformed into its different forms but the total amount do not change. The amount of heat

174

needed, water to be fed in each reactor was determined through energy balance established by the chemical reaction in each reactor.

175

176

III.

SUMMARY OF BASIS, ASSUMPTIONS AND EQUATIONS A. MASS BALANCE Glycerol Preheater (B 1) Crude glycerol will be completely evaporated at 280C.

(Ref:Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant, Sergio SabaterPrieto) Dehydration Reactor (R 1) 100% glycerol conversion

(Ref: Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant by Sergio SabaterPrieto Process for Dehydrating Glycerol to Acrolein. United States Patent Number 2008/0214880 by Dubois J.L. et.al.) 90% of glycerol will be dehydrated producing acrolein, the rest is converted to acetone. All acetone formed will react with water producing acetol. (Ref: Process for Dehydrating Glycerol to Acrolein. United States Patent Number 2008/0214880 by Duboi, J.L. et.al.)

177

 Heat Exchanger (H 1) The gaseous products from R-1 are cooled to 150C.

(Ref: Process for Dehydrating Glycerol to Acrolein. United States Patent Number 2008/0214880 by Dubois, J.L. et.al.) Absorption Column (A 1) All inert gases go to the top portion of the column. 90% of the entering water vapor is condensed. Bottom products consist of 1.5% acrolein.

(Ref: Process and Apparatus for Purification of a Gas Stream Containing Acrolein. United States Patent Number 5770021 by Hegoet.al.) Acrolein Preheater (B 2) Preheater operates at temperature of 180C to 250C.

(Ref:Process for manufacturing Acrolein from Glycerol US Patent 2010/0204502 by Dubois et..al.) Oxidation Reactor (R - 2) 98% of acrolein fed is converted to acrylic acid. All O 2 from air will be consumed.

178

Oxygen from feed will serve as the excess O 2 . Mass ratio of catalyst to acrolein is about 1:50.

(Ref: Catalytic Gas-phase Oxidation of Acrolein to Acrylic Acid. United States Patent Number 5264625 by Hammon, U. et. al.) Dehumidifying Condenser (C 1) The gaseous products from R-2 are cooled to 90C. All acrylic acid and water are condensed. Esterification Reactor (R 3) 99% of acrylic acid fed is converted to ethyl acrylate.

(Ref: Method for Producing Ethyl Acrylate Patent No. 20050107629A1 by Hershberger et. al.) Equimolar amounts of acrylic acid and alcohol is fed in the reactor. 36 N H 2 SO 4 is added to make a concentration of 18% H 2 SO 4 in the reactor feed. (Ref: Esterification of Acrylic Acid Patent No. 3458561 by Kautteret.al.)

179

 Heat Exchanger (H 2) The crude ethyl acrylate from R-3 is cooled to 100C.

(Ref: Esterification of Acrylic Acid Patent No. 3458561 by Kautteret.al. Synthesis of acrylic or methacrylic acid/acrylate or methacrylate ester polymers using pervaporation, Patent No. 2 325 214 A1 by SaadAIArifi, Abdullah) Pervaporator (PV 1) Ethyl acrylate content in the retentate is >98 mol%.

(Ref: Synthesis of acrylic or methacrylic acid/acrylate or methacrylate ester polymers using pervaporation, Patent No. 2 325 214 A1 by SaadAIArifi, Abdullah) Water is continuously extracted from the mixture containing ester, acid and alcohol. (Ref: Polish Journal of Environmental Studies Vol.9, No.1 by W. Kujawski)

180

 Condenser (C 2) The retentate from PV-1 is cooled to 15C. Ethyl acrylate is in liquid phase at 15C and 1 atm. (Ref: Ethyl acrylate MSDS, www.cameochemicals.com)

181

B. ENERGY BALANCE Constants Used In Energy Balance Code Equipment Constants From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

B1

Glycerol Preheater

From Standard Thermodynamic Properties of Chemical Substances (2000):

From Steam Table: From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

From Acrolein MSDS (Cameo Chemicals): H1 Heat Exchanger From (http://www.chemeo.com/cid/34-484-7):

From Unit Operations in Chemical Engineering, 7th Edition, Warren McCabe et al. (2004):

182

From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

From Acrolein MSDS (Cameo Chemicals): B-2 Acrolein Preheater

From Unit Operations in Chemical Engineering, 7th Edition, Warren McCabe et al. (2004):

From Steam Table: From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

From Acrolein MSDS (Cameo Chemicals):

From Acrylic Acid MSDS (Cameo Chemicals): R-2 Oxidation Reactor

From Unit Operations in Chemical Engineering, 7th Edition, Warren McCabe et al. (2004):

From (http://www.chemeo.com/cid/45-811-1):

183

From Optimization of the Dehydration of Glycerol to Acrolein by SabaterPrieto (2007): From Acrolein MSDS (Cameo Chemicals):

From Unit Operations in Chemical Engineering, 7th Edition, Warren McCabe et al. (2004):

From Acrylic Acid MSDS (Cameo Chemicals):

C1

Dehumidifying Condenser From ChE Handbook, 8th Edition:

From (http://www.sbioinformatics.com/design_thesis/Acrylic_Ac id/Acrylic-2520acid_-2520Properties&uses.pdf):

From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004): From Ethyl Acrylate MSDS (Cameo Chemicals):

R-3

Esterification Reactor

From Acrylic Acid MSDS (Cameo Chemicals):

184

From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

From Thermodynamic Properties of the Aqueous Sulfuric Acid System to 350 K, Frank Zeiknik:

From (http://www.chemeo.com/cid/45-811-1):

From (http://www.sbioinformatics.com/design_thesis/Acrylic_Ac id/Acrylic-2520acid_-2520Properties&uses.pdf):

From Steam Table: From Ethyl Acrylate MSDS (Cameo Chemicals):

From Acrylic Acid MSDS (Cameo Chemicals): H -2 Heat Exchanger From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

185

From Ethyl Acrylate MSDS (Cameo Chemicals):

From Acrylic Acid MSDS (Cameo Chemicals): C-2 Condenser From General Chemistry, 7th Edition, Kenneth Whitten et al. (2004):

186

Basis for Calculation: Plant Capacity: 5,700 MT/yr Production Rate: 19,000 kg/day Working days: 300 days/yr Conversion: Dehydration Reactor: 90% conversion of glycerol to acrolein Oxidation Reactor: 98% conversion of acrolein to acrylic acid Esterification Reactor: 99% conversion of acrylic acid to ethyl acrylate Assumptions for losses: Absorption Column: 1.5% acrolein is found at the bottom stream of the unit Glycerol Requirement

Feed Requirement (60% Crude Glycerol)

187

IV. MASS BALANCE PER EQUIPMENT

GLYCEROL PREHEATER

Crude Glycerol T = 25C

T = 280 C

Vaporized Crude Glycerol T = 280 C

B-1
Glycerol Water Total

Glycerol Water Total

20,400.00 kg 13,600.00 kg --------------------34,000.00 kg

20,400.00 kg 13,600.00 kg --------------------34,000.00 kg

Assumption: Complete evaporation at 250 C (Prieto, Sergio Sabater,2007) page 81

Input: Crude Glycerol (Liquid Phase) = 34,000.00 kg

Output: Crude Glycerol (Gas Phase) = 34,000.00 kg

188

DEHYDRATION REACTOR
Tungstated Zirconia (Catalyst) Zirconium Oxide 8,044.70 kg Tungsten Oxide 824.87 kg ---------------8,869.57 kg

Vaporized Crude Glycerol T = 280 C

T = 280 C P=1-3 bar

Crude Acrolein T = 280 C Acrolein Water H2 O2 Acetol 11,173.92 kg 20,386.88 kg 89.48 kg 708.95 kg 1,640.77 kg --------------------34,000.00 kg

R-1

Glycerol Water Total

20,400.00 kg 13,600.00 kg --------------------34,000.00 kg

Tungstated Zirconia

8,869.57 kg

Input: Vaporized Crude Glycerol Tungstated Zirconia = = 34,000.00 8,869.57 kg kg

----------------------------Total Input = 42,869.57 kg

Output: Crude Acrolein Tungstated Zirconia = = 34,000.00 8,869.57 kg kg

----------------------------Total Output = 42,869.57 189 kg

Assumptions: 100% glycerol conversion. Ratio of mass of feed to mass of catalyst is 3.83. (Sergio SabaterPrieto (2007). Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant) (Dubois, J.L. et al. (2008). Process for Dehydrating Glycerol to Acrolein. United States Patent Number 2008/0214880) 90% of glycerol is converted into acrolein, the rest to acetone. All acetone produced will then be converted to acetol. (Dubois, J.L. et al. (2008). Process for Dehydrating Glycerol to Acrolein. United States Patent Number 2008/0214880)

Data: Component Glycerol Acetol Acrolein Water H2 O2 Molecular Weight 92.08 74.06 56.04 18.02 2.02 32.00

Computations: Feed: Crude Glycerol Glycerol Water 20,400.00 13,600.00 kg kg

--------------------34,000.00 kg 190

Reactions involved:

Acrolein Production: Glycerol Acrolein

Acetone Production: Glycerol Acetone

191

Acetol Production: Acetone Acetol

Water Balance:

192

Amount of Catalyst:

Components:

Product: Crude Acrolein Acrolein Water H2 O2 Acetol kg kg kg kg kg --------------------34,000.00 kg

193

HEAT EXCHANGER

Crude Acrolein T = 280 C Acrolein Water H2 O2 Acetol 11,173.92 kg 20,386.88 kg 89.48 kg 708.95 kg 1,640.77 kg --------------------34,000.00 kg

T = 150 C

Cooled Crude Acrolein T = 150 C Acrolein Water H2 O2 Acetol 11,173.92 kg 20,386.88 kg 89.48 kg 708.95 kg 1,640.77 kg --------------------34,000.00 kg

H-1

Input: Crude Acrolein = 34,000.00 kg

Output: Cooled Crude Acrolein = 34,000.00 kg

194

ABSORPTION COLUMN Acrolein Top Stream Water H2 O2 10,905.28 kg 2,038.68 kg 89.48 kg 708.95 kg --------------------13,742.39 kg

T = 60 C

Absorbing Solvent T = 30C

Cooled Crude Acrolein T = 150 C Acrolein Water H2 O2 Acetol 11,173.92 kg 20,386.88 kg 89.48 kg 708.95 kg 1,640.77 kg --------------------34,000.00 kg

A-1

Water

16,000.00 kg

Bottom Stream Acetol 1,640.77 kg Water 34,348.20 kg Acrolein 268.64 kg --------------------36,257.61 kg 34,000.00 16,000.00 kg kg

Input: Cooled Crude Acrolein Water = =

--------------------Total Input = 50,000.00 kg

Output: Top Stream Bottom Stream = = 13,742.39 36,257.61 kg kg

-----------------Total Output = 50,000.00 195 kg

Assumptions: All inert gases go to the top portion of the column. 90% of the entering water vapor is condensed. Bottom products consist of 1.5% acrolein. (Hugo et al. (1998) Process and Apparatus for Purification of a Gas Stream Containing Acrolein)

Data: Components Acetol Acrolein Water Molecular Weight 74.06 56.04 18.02 Boiling Point (C) 145 53 100

Computations: Feed: Crude Acrolein Acrolein Water H2 O2 Acetol 11,173.92 20,386.88 89.48 708.95 1,640.77 kg kg kg kg kg

--------------------34,000.00 kg

196

Absorbing Solvent: Henrys constant for acetol in water is 0.43 atm/mole fraction.

Minimum liquid-to-gas ratio:

Converting to mass units:

197

Bottom Stream:

Solving equations 1 and 2,

Note:*condensed water vapour from the gaseous feed not included

Top Stream:

Acrolein Balance:

198

Top Product: Acrolein Water H2 O2 kg kg kg kg --------------------kg

199

ACROLEIN PREHEATER

Acrolein Stream T = 60 C Acrolein Water H2 O2 10,905.28 kg 2,038.68 kg 89.48 kg 708.95 kg --------------------13,742.39 kg

T = 200 C

Heated Acrolein Stream T = 200 C Acrolein Water H2 O2 10,905.28 kg 2,038.68 kg 89.48 kg 708.95 kg --------------------13,742.39 kg

B-2

Input: Acrolein Stream = 13,742.39 kg

Output: Heated Acrolein Stream = 13,742.39 kg

200

OXIDATION REACTOR
Vanadium-Molybdenum Oxide (Catalyst) Vanadium (IV) Oxide 34.90 kg Molybdenum Trioxide 183.21 kg ------------218.11 kg

Air Stream N2 T=30 C O2

10,044.71 kg 3,051.52 kg -------------------13,096.23 kg Crude Acrylic Acid T = 300 C

Heated Acrolein Stream T = 200 C Acrolein Water H2 O2 10,905.28 kg 2,038.68 kg 89.48 kg 708.95 kg --------------------13,742.39 kg

T = 300 C P =1-5 bar

R-2

Acrylic Acid Acrolein Water N2 O2 H2

13,738.70 kg 218.10kg 2,038.68 kg 10,044.71 kg 708.95 kg 89.48 kg -------------------26,838.62 kg

Vanadium-Molybdenum Oxide

218.11 kg

Input: Heated Acrolein Stream Air Stream Vanadium-Molybdenum Oxide = = = 13,742.39 13,096.23 218.11 kg kg kg

--------------------Total Input = 27,056.73 kg

Output: Crude Acrylic Acid Vanadium-Molybdenum Oxide = = 26,838.62 218.11 kg kg

--------------------Total Output = 27,056.73 201 kg

Assumptions: 98% of acrolein is converted to acrylic acid. Mass ratio of catalyst to acrolein is 1:50. (Hammon, U. et al. Catalytic Gas-phase Oxidation of Acrolein to Acrylic Acid. United States Patent Number 5264625)

Data: Component Acrylic Acid Acrolein Water Air N2 O2 Molecular Weight 72.04 56.04 18.02 28.84 28.00 32.00

Computations: Feed: Acrolein Stream Acrolein Water H2 O2 10,905.28 2,038.68 89.48 708.95 kg kg kg kg

--------------------13,742.39 kg

202

Reaction Involved: Acrylic Acid Production: Acrolein Acrylic Acid

Amount of Catalyst:

Components:

203

Product: Crude Acrylic Acid Acrylic Acid Acrolein Water N2 O2 H2 708.95 89.48 2,038.68 kg kg kg kg kg kg

-------------------26,838.62 kg

204

DEHUMIDIFYING CONDENSER

Uncondensed Vapor and Inert Gases Acrolein N2 O2 H2 218.10 kg 10,044.71 kg 708.95 kg 89.48 kg ------------------11,061.24 kg

Crude Acrylic Acid T = 300 C

T = 90C

Condensed Crude Acrylic Acid T = 90C

C-1
13,738.70 kg 218.10 kg 2,038.68 kg 10,044.71 kg 708.95 kg 89.48 kg -------------------26,838.62 kg Acrylic Acid Water

Acrylic Acid Acrolein Water N2 O2 H2

13,738.70 kg 2,038.68 kg --------------------15,777.38 kg

Input: Crude Acrylic Acid = 26,838.62 kg

Output: Uncondensed Vapor and Inert Gases Condensed Crude Acrylic Acid = = 11,061.24 15,777.38 kg kg

-------------------Total Output = 205 26,838.62 kg

ESTERIFICATION REACTOR
Sulfuric Acid Solution (Catalyst) Sulfuric Acid 4,966.28 kg Water 101.35 kg -----------------------5,067.63 kg

Ethanol Stream T = 25 C Ethanol 8,784.10 kg

T = 140 C P = 0.3-0.6 bar

Crude Ethyl Acrylate T = 140 C

Condensed Crude Acrylic Acid T = 90C Acrylic Acid Water 13,738.70 kg 2,038.68 kg --------------------15,777.38 kg

R-3
Ethyl Acrylate Acrylic Acid Water Ethanol

18,895.35 kg 137.38 kg 5,440.91 kg 87.84 kg --------------------24,561.48 kg

Input: Acrylic Acid Ethanol Stream Water Sulfuric Acid Solution

Sulfuric Acid Solution 5,067.63 kg

= = = =

13,738.70 8,784.10 2,038.68 5,067.63

kg kg kg kg

--------------------Total Input = 29,629.11 kg

Output: Crude Ethyl Acrylate Sulfuric Acid Solution = = 24,561.48 5,067.63 kg kg

--------------------Total Output = 29,629.11 206 kg

Assumptions: 99% of acrylic acid fed is converted to ethyl acrylate. (Hershberger et al., Method for Producing Ethyl Acrylate Patent No. 20050107629A1) Equimolar amounts of acrylic acid and alcohol is fed in the reactor. (Kautter et al., Esterification of Acrylic Acid Patent No. 3458561) 36 N H 2 SO 4 is added to make a concentration of 18% H 2 SO 4 in the reactor feed.

Data: Component Acrylic Acid Ethanol Ethyl Acrylate Water Molecular Weight 72.04 46.06 100.08 18.02

Computations: Feed:

207

Reaction involved: Ethyl Acrylate Production:

Ethanol

Acrylic Acid

Ethyl Acrylate

Ethanol (EtOH) Balance:

208

Water (H 2 O) Balance:

Amount of Catalyst Added:

Basis: 1 Liter of Solution

209

Solving equations 1, 2 and 3,

Product: Crude Ethyl Acrylate Ethyl Acrylate Acrylic Acid Water Ethanol 18,895.35 137.38 5,440.91 87.84 kg kg kg kg

--------------------24,561.48 kg

210

HEAT EXCHANGER

Crude Ethyl Acrylate T = 140 C

T =100 C

Cooled Crude Ethyl Acrylate T = 100 C

H-2

Ethyl Acrylate Acrylic Acid Water Ethanol

18,895.35 kg 137.38 kg 5,440.91 kg 87.84 kg --------------------24,561.48 kg

Ethyl Acrylate Acrylic Acid Water Ethanol

18,895.35 kg 137.38 kg 5,440.91 kg 87.84 kg --------------------24,561.48 kg

Input: Total Input = 24,561.48 kg

Output: Total Output = 24,561.48 kg

211

PERVAPORATOR Permeate T = 100 C Water Cooled Crude Ethyl Acrylate T = 100 C

T = 100 C

5,440.91 kg

PV-1
Retentate T = 100 C Ethyl Acrylate Acrylic Acid Ethanol 18,895.35 kg 137.38 kg 87.84 kg --------------------19,120.57 kg

Ethyl Acrylate Acrylic Acid Water Ethanol

18,895.35 kg 137.38 kg 5,440.91 kg 87.84 kg --------------------24,561.48 kg

Input: Cooled Crude Ethyl Acrylate = 24,561.48 kg

Output: Permeate Retentate = = 5,440.91 19,120.57 kg kg

-----------------------------Total Output = 24,561.48 212 kg

Assumptions: Ethyl acrylate content in the retained material stream is<99% by moles. (SaadAIArifi, Abdullah, Synthesis of acrylic or methacrylic acid/acrylate or methacrylate ester polymers using pervaporation, Patent No. 2 325 214 A1) Water is continuously extracted from the mixture containing ester, acid and alcohol (W. Kujawski, Polish Journal of Environmental Studies Vol.9, No.1)

Data: Component Ethyl Acrylate Acrylic Acid Ethanol Molecular Weight 100.08 72.04 46.06

Computations: Feed: Ethyl Acrylate (EA) = 18,895.35 kg Acrylic Acid (AA) = 137.38 kg Water = 5,440.91 kg Ethanol (EtOH) = 87.84 kg

213

Top Stream: Water (H 2 O) Balance:

Retentate:

Component Ethyl Acrylate Acrylic Acid Ethanol

Mole % 98 1 1

Mass % 99 0.60 0.40

214

CONDENSER

Retentate T = 100 C

T =15 C

Ethyl Acrylate (Product) T = 15 C

C-2
18,895.35 kg 137.38 kg 87.84 kg --------------------19,120.57 kg Ethyl Acrylate Acrylic Acid Ethanol

Ethyl Acrylate Acrylic Acid Ethanol

18,895.35 kg 137.38 kg 87.84 kg --------------------19,120.57 kg

Input: Total Input = 19,120.57 kg

Output: Total Output = 19,120.57 kg

215

V.

ENERGY BALANCE PER EQUIPMENT

GLYCEROL PREHEATER

Crude Glycerol
(60% Glycerol Solution)

B-1

Vaporized Crude Glycerol

T = 280 C

T = 25C

Steam T = 300C

Glycerol:

216

Water:

217

Steam at 300oC = 1404.60 kJ/kg

Steam Requirement:

218

DEHYDRATION REACTOR

Vaporized Crude Glycerol T = 280 C

T = 280 C P=1-3 bar

Crude Acrolein T = 280 C

R-1

Reactants:

Vaporized Crude Glycerol

COMPONENT Glycerol Water

MASS (kg) 20,400.00 13,600.00

Cp (kJ/kg K) 0.92 1.88 mCp=

mCp (kJ/K) 18,768.00 25,568.00 44,336.00

219

Reaction:

Acrolein Production: Glycerol

COMPONENT MASS (kg) MW n(kmol) H f (kJ/kmol) Acrolein Water Glycerol 11,173.92 56.04 7,186.08 18.02 18,360.00 92.08 199.39 398.78 199.39 -87,800.00 -241,800.00 -597,000.00 -17,506,602.95 -96,425,890.53 -119,036,924.41

Acrolein
nH f (kJ)

Acetone Production: Glycerol

COMPONENT MASS (kg) MW n(kmol)

Acetone
H f (kJ/kmol) -216,690.00 -597,000.00 nH f (kJ) -4,800,690.70 -13,226,324.93

Acetone Glycerol

1,286.74 58.08 2,040.00 92.08

22.15 22.15

220

Acetol Production: Acetone

COMPONENT MASS (kg) MW

Acetol
n(kmol) H f (kJ/kmol) -422,650.00 -216,690.00 -241,800.00 nH f (kJ) -9,363,662.03 -4,800,690.70 -5,356,993.92

Acetol Acetone Water

1,640.77 1,286.74 399.23

74.06 58.08 18.02

22.15 22.15 22.15

Product: COMPONENT Acrolein Acetol Water H2 O2 MASS (kg) 11,173.92 1,640.77 20,386.85 89.48 708.95 Cp (kJ/kg K) 1.27 1.39 1.88 14.36 0.92 mCp= mCp (kJ/K) 14,190.88 2,280.67 38,327.29 1,284.93 652.23 56,736.01

221

222

HEAT EXCHANGER

Crude Acrolein
T = 280 C

T = 150 C

Cooled Crude Acrolein

T = 150 C

H-1

T = 90 C

Cooling Water T = 28C

COMPONENT Acrolein Acetol Water H2 O2

MASS (kg) 11,173.92 1,640.77 20,386.85 89.48 708.95

Cp (kJ/kg K) 1.27 1.39 1.88 14.36 0.92 mCp=

mCp (kJ/K) 14,190.88 2,280.67 38,327.29 1,284.93 652.23 56,736.01

223

Mass of Cooling Water:

224

ACROLEIN PREHEATER

Acrolein Stream
T = 60C

T = 200 C

Heated Acrolein Stream

T = 200C

B-2

Steam T = 300C

COMPONENT Acrolein Water H2 O2

MASS (kg) 10,905.28 2,038.69 89.48 708.95

Cp (kJ/kg K) 1.27 1.88 14.36 0.92 mCp=

mCp (kJ/K) 13,849.70 3,832.73 1,284.93 652.23 19,619.60

Steam at 300oC = 1,404.60 kJ/kg

225

Steam Requirement:

226

OXIDATION REACTOR

Air Stream
T = 30C

Heated Acrolein Stream

T = 200C
T = 280 C P=1-5 bar

Crude Acrylic Acid

T = 300C

R-2

T = 90C

Cooling Water T = 28C

Reactants: Heated Acrolein COMPONENT Acrolein Water H2 O2 MASS (kg) 10,905.28 2,038.69 89.48 708.95 Cp (kJ/kg K) 1.27 1.88 14.36 0.92 mCp= mCp (kJ/K) 13,849.70 3,832.73 1,284.93 652.23 19,619.60

227

Air

Reaction:

Acrylic Acid Production: Acrolein COMPONENT MASS (kg) MW n(kmol) H f (kJ/kmol) Acrylic Acid Acrolein 13,738.70 72.04 10,687.17 56.04 190.71 190.71 -372,200.00 -70,982,011.94 -87,800.00 -16,743,998.29 Acrylic Acid nH f(kJ)

228

Product: COMPONENT Acrylic Acid Acrolein Water N2 O2 H2 MASS (kg) 13,738.70 218.10 2,038.68 10,044.71 708.95 89.48 Cp (kJ/kg K) 1.36 1.27 1.88 1.07 0.92 14.36 mCp= mCp (kJ/K) 18,684.63 276.99 3,832.72 10,747.84 652.23 1,284.93 35,479.34

Mass of Cooling Water:

229

DEHUMIDIFYING CONDENSER
Uncondensed Vapor and Inert Gases
T = 90C

Crude Acrylic Acid

T = 300C

T = 90 C

C-1
T = 90C

Condensed Crude Acrylic Acid

Acrylic Acid Water
T = 90 C

Cooling Water T = 28C

Uncondensed Vapor and Inert Gases (non-condensables): COMPONENT Acrolein N2 O2 H2 MASS (kg) 218.10 10,044.71 708.95 89.48 Cp (kJ/kg K) 1.27 1.07 0.92 14.36 mCp= mCp (kJ/K) 276.99 10,747.84 652.23 1,284.93 12,961.99

230

Crude Acrylic Acid (condensables):

Acrylic Acid:

231

Water:

232

Mass of Cooling Water:

233

ESTERIFICATION REACTOR

Ethanol Stream
T = 25C

Sulfuric Acid Solution (Catalyst) T=25C

T = 140 C P=0.3-0.6 bar

Crude Ethyl Acrylate

Condensed Crude Acrylic Acid T = 90C

Sulfuric Acid

R-3

Ethyl Acrylate Acrylic Acid Water Ethanol

T = 140 C

Steam at 200C

Reactant:

Condensed Crude Acrylic Acid COMPONENT Acrylic Acid Water MASS (kg) 13,738.70 2,038.68 Cp (kJ/kg K) 2.01 4.18 mCp= mCp (kJ/K) 27,614.79 8,521.68 36,136.47

234

Reaction:

Ethyl Acrylate Formation:

Ethanol

Acrylic Acid

Ethyl Acrylate H f (kJ/kmol) -370,600.00 -241,800.00 -372,200.00 -235,100.00

COMPONENT Ethyl Acrylate Water Acrylic Acid Ethanol

MASS (kg) 18,895.33 3,402.22 13,601.31 8,696.26

MW 100.08 18.02 72.04 46.06

n(kmoles) 188.80 188.80 188.80 188.80

nH f(kJ) -69,970,108.24 -45,652,380.39 -70,272,191.82 -44,387,553.76

Product: COMPONENT Ethyl Acrylate Water Acrylic Acid Ethanol Sulfuric Acid MASS (kg) 18,895.35 5,440.90 137.38 87.84 4,967.64 Cp (kJ/kg K) 1.45 1.88 1.36 0.95 1.42 mCp= mCp (kJ/K) 27,398.26 10,228.88 186.84 83.80 7,029.21 44,926.99

235

COMPONENT Ethanol Acrylic Acid

MASS (kg) 87.84 137.38

H vap (kJ/kg) 855.00 628.82 mHvap=

mH vap (kJ) 75,103.20 86,387.29 161,490.49

Steam at 200oC = 1,938.6 kJ/kg

Steam Requirement:

236

HEAT EXCHANGER

Crude Ethyl Acrylate Ethyl Acrylate Acrylic Acid Water Ethanol

T = 140 C

T = 100 C

Cooled Crude Ethyl Acrylate

T = 100 C

H-2

T =75 C

Cooling Water T = 28C

COMPONENT Ethyl Acrylate Acrylic Acid Water Ethanol

MASS(kg) 18,895.33 137.38 5,440.90 87.84

Cp(kJ/kg.K) 1.45 1.36 1.88 0.95 mCp=

mCp(kJ/K) 27,398.23 186.84 10,431.17 83.80 37,897.75

237

Mass of Cooling Water:

238

CONDENSER

Ethyl Acrylate Stream Ethyl Acrylate Acrylic Acid Ethanol

T = 100 C
T =80 C

T = 25 C

Cooled Ethyl Acrylate (Final Product)

T = 15 C

C-2
Cooling Water T = 28C

Acrylic Acid:

239

Ethyl Acrylate:

240

Ethanol:

241

Mass of Cooling Water:

242

CHAPTER VI

EQUIPMENT DESIGN

243

CHAPTER VI EQUIPMENT DESIGN I. INTRODUCTION

appropriate design considerations. In the design of the equipment, there are several factors to be considered: the dimensional analysis, the choice of materials, and the energy requirement. The dimensional analysis will determine the capacity necessary to handle the required volume of the

In a manufacturing process, the equipment to be used must have

materials involved. The choice of materials is an important consideration in reactions, strength to loads, and stresses. The energy requirement will then determine the power consumption of the equipment in specified operating conditions.

order to account for significant parameters like resistance to chemical

such as temperature and pressure in order to attain equilibrium as well as to get the desired outcome or product. For these reasons, the equipment in energy and proper design. which certain processes take place has to be supplied with the necessary provide the proper environment, space, time, temperature and pressure. The 244 In case of chemical reactions, it is necessary that the equipment

For each unit operation, standard operating conditions need to be set

mechanism whereby energy maybe supplied or removed as required in the chemicals involved must have significant strength at the extremes of maintaining equilibrium must also be provided. To establish limits of space for a reaction, the material used to confine

pressure and temperature that may be encountered. A temperature limitation

would be dictated by the highest temperature used in the equipment and heat flow.

could be either the maximum temperature of the reaction or the temperature For every equipment of a certain type, there applies a certain design

required to produce the necessary temperature gradient to ensure adequate equation. There is a limitation to every type of equipment and certain equations may not be applicable at all times. Therefore, thorough materials to be handled is necessary. understanding of the type and nature of the equipment as well as the For this chapter, the equipments chosen to be designed are the

Dehydration Reactor, Absorption Column, Shell and Tube Heat Exchanger, Pervaporator, and Esterification Reactor.

245

II.

SUMMARY OF ASSUMPTIONS AND DESIGN EQUATIONS

1. DEHYDRATION REACTOR A. Assumptions A. Vessel Design:

(Ref: Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant by Prieto, Sergio Sabater)

From Material and Energy Balance:

Ratio:

(Ref: Chemical Engineering Design Principles, Practice and Economics of Plant and Process Design by GavinTowler, 2nd edition,)

246

B. Catalytic Fixed Bed From Material and Energy Balance:

C. For Height of Ceramic Balls Support (CBS) Mass of Ceramic Balls Support is 5% of the total weight of the catalyst (Ref: Process for Manufacturing Acrolein from Glycerol by Dubois)

D. Shell Thickness E j = Efficiency of Longitudinal Joints expressed as a function = 0.8; Double V or U butt joint for ts=1/8 to 1/4 in c = Allowance for Corrosion (in) = (Ref: Process Equipment Design by Hesse and Rushton)

S u = 655 MPa for S31000; Ultimate Stress of Material (Ref: ChE Handbook, 8th Edition; Table 25-11)

247

Fm = 1.0; material factor or grade of steel Fr = 1.06; stress relieving factor Fa = 1.12; radiographing factor Fs = 0.2; type of steel factor (Ref: Process Equipment Design by Hesse and Rushton)

E. Insulation Design: For Fire Clay:

(Ref: Perrys Chemical Engineers Handbook, 8th Ed, p 2-459) F. Pump Design: The mechanical, kinetic, and potential energies do not change appreciably, and the velocity and static-head terms can be dropped.

(Ref: page 208 of Unit Operations of Chemical Engineering 5th Ed. by

McCabe and Smith)

248

(Ref: B-1 preheater)

B. Design Equations Volume of Reactor:

(Ref: Chemical Reaction Engineering, Octave Levenspiel, 3rd Edition) For Height of Ceramic Balls Support:

For Maximum Internal Pressure (P) P = gH + 14.7

249

 Shell Thickness (t s ) Using API-ASME design equation for Cylindrical Shells

(Ref: Process Equipment Design by Hesse and Rushton, Equation 4-3) Head Thickness ( t h ) Using API-ASME design equation for Ellipsoidal Head

(Ref: Process Equipment Design by Hesse and Rushton, Equation 4-5) Bottom Thickness; t b For vessel with agitator, tb = th Maximum Stress (S)

(Ref: Process Equipment Design by Hesse and Rushton, Equation 4-1)

250

G. Pump Design: Bernoulli Equation:

(Ref: Unit Operations of Chemical Engineering 5th Ed. by McCabe and Smith, Equation 4.32, p. 78)

Equation for Blowers and Compressors:

(Ref: Unit Operations of Chemical Engineering 5th Ed. by McCabe and Smith, Equation 8.23)

251

2. SHELL AND TUBE HEAT EXCHANGER A. Assumptions 1. 1 batch per day will be used. 2. BASCO TYPE 500 Model 08072 Heat Exchanger with tube diameter of 5/8 will be used. 3. 1 tube pass will be used with a Rotated Square Pitch arrangement. 4. Using 70% pump efficiency for the tube side fluid.

B. Design Equations Heat Exchanger Design: Heat Transfer Equation

252

Tube Side: Using BASCO TYPE 500 Heat Exchanger Model 08072 with tube Diameter of 5/8 Number of Tubes = 76 Shell Diameter = 8-5/8 Surface Area of 74.5ft2 Length of Tube

Rotated Square Pitch

Clearance

No. of tubes in center row

253

Shell Side: Shell Diameter

Baffle Diameter

(Ref: Chemical Engineering Volume 6, 4th Edition by Coulson and Richardson, Table 12-5 p. 651) Baffle Spacing

(Ref: of Chemical Engineering by Coulson and Richardson, Table 12.5 p. 595) Pump Design:

(Ref: Perrys Chemical Engineering Handbook 8th Ed. By Perry et.al, p.1027) 254

3. ABSORPTION COLUMN A. Assumptions The plate structure must be designed to support the hydraulic loads on the plate during operation, and the loads imposed during construction and maintenance. Typical design values used for these loads are: Hydraulic load: 600 N/m2 live load on the plate, plus 3000 N/m2 over the downcomer seal area. Erection and maintenance: 1500 N concentrated load on any structural member.

Tray spacing must be specified to compute column diameter. As spacing is increased, column height is increased but the column diameter is reduced. A spacing of 24 in., which provides ease of maintenance, is optimal for wide range of conditions; however, a smaller spacing may be desirable for smalldiameter columns with large number of stages; and larger spacing is frequently used for large-diameter columns with a small number of stages. Foaming factor is 0.85. Fraction of flooding is taken as 0.80.

255

B. Design Equations Entrainment flooding capacity in tray tower (Figure 6.24. Separation Process Principles by Henley and Seader 2nd ed.) Correcting for C F for surface tension, foaming tendency, and the ratio of vapor hole area Ah to tray active area A according to the empirical relationship: (Equation 6-42. Separation Process Principles by Henley and Seader 2nd ed.)

Flooding velocity (Equation 6-40. Separation Process Principles by Henley and Seader 2 nd ed.)

256

 Column diameter (Equation 6-44. Separation Process Principles by Henley and Seader 2 nd ed.)

Number of theoretical plates (Equation 14-33. Perrys Chemical Engineers Handbook 8th ed.)

Overall tray efficiency (Using Figure 14-9. Perrys Chemical Engineers Handbook 8th ed.) Number of actual plates (Equation 14-44. Perrys Chemical Engineers Handbook 8th ed.)

Relationship between angle subtended by chord, chord height and chord length (Using Figure 11.34. Chemical Engineeering Design by R. Sinnott and G. Towler)

257

 Relation between hole area and pitch (Using Figure 11 .35. Chemical Engineeering Design by R. Sinnott and G. Towler) Vessel design equation: API-ASME Code for shell thickness

Internal pressure

for flanged and dished head e = 1.0 Head thickness (for head with pressure on the concave side):

Bottom thickness (for head with pressure on the convex side)

258

4. ESTERIFICATION REACTOR A. Assumptions For Vessel Volume (V) Vapor Space = 20%

Residence time = 3 hours (Ref: Kautter et al., Esterification of Acrylic Acid Patent No. 3458561) For vessel diameter and height: In esterification reactions, a batch reactor equipped with four baffles and a six-bladed turbine impeller is used. (Ref: G.N. Kraai et al. / Biochemical Engineering Journal 41 (2008) 8794) For V= 4 to 200 m3 H/D = 0.75-1.5; with turbine mixer and 4 baffles where: H = 1.5D

(Ref: Ch.E. HB, p.18-13)

259

 Shell Thickness: Material for Construction: S31600 For Stainless 316 or S31600, the recommended stress at 140C (284F) is 15,776.71 psi (Ref: Plant Design and Economics for Chemical Engineers by Peters and Timmerhaus, 5th Edition, Table 12-10 p.555) Corrosion Factor (C) = 1/16 in e = 0.70; for Double-Welded Butt Joint if not radiographed n = rotational speed =63 rpm (Ref: Turbine & High Efficiency Axial Flow Agitators, http://www.feldmeier.com/cutsheets/turbine_agitator.pdf) KT for disk turbine with six blades: KT = 5.75 (Ref: Unit Operations in Chemical Engineering, McCabe & Smith, Table 9.2, p. 262) Motor Efficiency = 80%

260

 For Heating System: F = Safety factor = 1.5

(Ref: Engineering Page: Typical Overall Heat Transfer Coefficients retrieved from: http://www.engineeringpage.com/technology/ thermal/transfer.html)

Tube Type: 1 BWG

Inside Diameter of the Tube = Distance of coil from the tank wall (d c ) = 6in = 0.5 ft = 0.15 m (Ref: ChE Handbook pg. 11-21)

For Insulation Design: Insulating Material: Calcium Silicate Thermal Conductivity, (Ref: Thermal Insulation Handbook, p. 8, Table 3.3.1)

261

B. Design Equations For Vessel Volume (V) Using 20% allowance for vapor space:

For Vessel Diameter and Height (From Ch.E. HB, p.18-13)

H = 1.5D For Maximum Internal Pressure (P) P = gH + 14.7 Shell Thickness (t s ) Using ASME-UPV Code, design equation for cylindrical shells (from Peters & Timmerhaus 5th Edition, Table 12-10 p. 544):

262

 Head Thickness ( t h ) Using ASME-UPV Code, design equation for ellipsoidal head (from Peters & Timmerhaus 5th Edition, Table 12-10 p. 544):

Bottom Thickness; t b For vessel with agitator, tb = th Impeller Diameter; Da (p. 241, Unit Operations of Chemical Engg by Mc Cabe and Smith 6th edition)
Da 1 = D 3

Impeller width; W (p. 241, Unit Operations of Chemical Engg by Mc Cabe and Smith 6th edition)

W 1 = Da 5

263

 Impeller Length; L (p. 241, Unit Operations of Chemical Engg by Mc Cabe and Smith 6th edition)

L 1 = Da 4
Distance from the vessel floor; E (p. 241, Unit Operations of Chemical Engg by Mc Cabe and Smith 6th edition)

E 1 E 1 3D Da 1 = ; = ; E = a = Da = ; Dt = 3 D a Dt 3 3Dat 3 3 Dt 3
Baffle Width, J; (p. 241, Unit Operations of Chemical Engg by Mc Cabe and Smith 6th edition)

1 J 1 3D J = ; = ;J = a 12 Dt 12 3Da 12
Depth of Liquid in Vessel, h:

264

 Power Consumption of impeller (P)

P = k T n 3 Da5
Heating System Heating transfer area: From ChE Handbook p. 11-20, eq. 11-39 ;

F = Safety factor = 1.5

From ChE Handbook 7th Ed pg. 11-21

Distance of coil from the tank wall (d c ) = 6 in = 0.1524 m

265

266

5. PERVAPORATOR A. Assumptions Operating Pressure = 10 bar (from Berghof Filtration and Plant Engineering) P feed side = P retentate side = 1 atm P permeate side = 0.1332 atm (European Patent No. EP 2 325 214 A1, Synthesis of Acrylic or Methacrylic acid/Acrylate or Methacrylate Ester Polymers Using Pervaporation) Membrane: Material: Polyvinyl Alcohol (PVA) Membrane Thickness = 25 m Nominal Pore Size = non-porous (European Patent No. EP 2 325 214 A1, Synthesis of Acrylic or Methacrylic acid/Acrylate or Methacrylate Ester Polymers Using Pervaporation)

267

Modules: Type of Module: Tubular (Page 16, Membrane Filtration Handbook) Module Type = MO 63G_I10HD V Berghof HyperFlux Tubular Module Material of Construction = Fiber Reinforced Plastic (FRP), Resin Membrane Area/module = 12.2 m2 Module Length = Tube Length = 3 m Outer Diameter of Module = 156.4 mm Internal Diameter of Tube = 10.3 mm No. of Tubes/module = 72 Tube Arrangement = Triangular Pitch

Module Connection = Parallel Feed-Permeate Differential Pressure = -0.20...+10 bar DUMMY: Diameter = 156.4 mm Length = 3 m

268

BEND (VICTAULIC CONNECTION NO. 3006305) Diameter = 168.3 mm Thickness = 3 mm Center Distance = 458 mm Length = 363 mm Material = Stainless Steel 1.4571

PERMEATE CONNECTION (VICTAULIC-CLAMP WITH FLASH GAP SEALING) Diameter = 60.3 mm Socket = 50 mm Length 1 = 58 mm Length 2 = 57 mm Material = Polyvinyl Chloride-Unplasticised (PVC-U)

269

INLET-OUTLET CONNECTION (VICTAULIC-CLAMP WITH FLASH GAP SEALING) Diameter = 168.3 mm Thickness = 3 mm Length = 200 mm Material = Stainless Steel 1.4571

STRAP Clear Height = 230 mm Inner Width = 163 mm Thread Length = 80 mm Thread = M8 Material = Stainless Steel 1.4301

SADDLE Broadth = 20 mm Bore = 10 mm 270

Height = 20 mm Module Center Height = 90 mm Length = 200 mm Distance = 170 mm Material = Polypropylene (PP) (Ref: Berghof Filtration and Plant Engineering, HyperFlux Tubular Module, retrieved from http://www.lindenfiltration.com /uploads/2/8/7/6/2876985/tub_mod.pdf)

Viscosity of the Feed = 0.6406 cP (Ref: Perrys Chemical Engineering Handbook, Table 2-412, 8th Edition.) Velocity is assumed to be 5 m/s to give a turbulent flow and a good mass transfer based on page 1036 of Unit Operations of Chemical Engineering, 5th Ed.

Operating time: 110 min (Time-Dependence of Pervaporation Performance for the Separation of Ethanol/Water Mixtures through Polyvinyl Alcohol Membrane, by Gewei Li, Wei Zhang, Juping Yang, Xinping Wang) 271

Type of Pump = centrifugal pump (Membrane Filtration Handbook, p. 38) Material of Construction = stainless steel (Perrys Chemical Engineering Handbook 7th Edition, page 10-24)

B. Design Equations 1. Unit Operations of ChE, McCabe and Smith, Equation 29.48, p. 1040, 7th Edition

Where: J = permeate flux = mass transfer coefficient C 1 = concentration of AA at retentate C s = concentration of AA at feed

272

2. Unit Operation of ChE, McCabe and Smith, Equation 30.55, p. 1041, 7th Ed.

Where: Dv = diffusivity T = temperature (K) ro = radius of particles (cm) = viscosity (cP)

3. Unit Operations of ChE, McCabe and Smith, Equation 3.8, p. 59, 5th Ed.

Where: Nre = Reynolds Number D = Diameter of Vessel v = Velocity of fluid = viscosity

273

4. Unit Operation of ChE, McCabe and Smith, Equation 3.10, p. 53, 7th Edition

Where: NSc = Schmidt Number = viscosity = density Dv = diffusivity

5. Unit Operations of ChE, McCabe and Smith, Equation 17.71, p. 545, 7th Edition

Where: NSh = Sherwood Number Re = Reynolds Number Sc = Schmidt Number

274

6. Unit Operations of ChE, McCabe and Smith, Equation 17.71, p. 545, 7th Edition

Where: = mass transfer coefficient N Sh = Sherwood Number D = diameter of tube D v = diffusivity

7. Unit Operations of Chemical Engineering, McCabe and Smith, Equation 30.49, p. 1037, 5th Edition:

Where: u = permeate flux Q m = membrane permeability P = transmembrane pressure

275

8. Transmembrane Pressure (P):

Where: = partial vapor pressure of more volatile component on feed side = partial vapor pressure of more volatile component on permeate side

9. ChE Handbook 7th Edition, p. 10-23 Equation 10-50:

Where: H = total dynamic head (Pa) Q = capacity (m3/hr)

10. From Berghof Module Data Sheet:

276

11. From Berghof Module Data Sheet:

Where: Pressure Drop along Module = (kPa) v =Cross Flow Velocity (m/s) L = Module Length (m)

277

III. EQUIPMENT DESIGN

278

SPECIFICATION SHEET Date : IDENTIFICATION Name Dehydration Reactor Code R-1 Unit/s required 1 To convert Glycerol to Acrolein FUNCTION Continuous OPERATION Fixed Bed Reactor TYPE 1.24 m3/hr VOLUMETRIC FLOWRATE Glycerol, Water, Tungstated Zirconia MATERIAL HANDLED (catalyst) DESIGN DATA Pressure (P) 183.2 kPa Density () 1,141.7 kg/m3 Temperature 280oC Specifications Material of Construction S31600 Diameter 1.1 m Height (H) 4.3 m Head thickness (t h ) 3 mm Shell thickness (t s ) 3 mm Bottom thickness (t b ) 3 mm Type of Joint Double V/U butt joint Joint Efficiency 80 % Catalyst Bed Height 2m Diameter 1.1 m Catalyst Bed Support Material Alumina ceramic ball Diameter 1.1 m Height (above the catalyst) 0.12 m Height (bottom of the catalyst) 0.23 m Insulation Design Outside Diameter 1.18 m Thickness 40 mm Insulating Material Fire Clay Thermal Conductivity 1.02 Compressor Design Compressor Type Power Requirement Centrifugal Compressor 1.5 HP 279

Inlet

th= 3 mm

ts= 3 mm

Hbed support= 0.12 m H = 4.3 m Hbed= 2 m

Hbed support= 0.23 m th= 3 mm Catalyst Dump Flange

Outlet

D = 1.1 m

Fixed Bed Reactor 280

Design Calculation

From Material & Energy Balance: Feed: Component Glycerol Water Density (kg/m3) 1,261.00 1,000.00 TOTAL kg 20,400.00 13,600.00 34,000.00 kgmol 221.55 755.56 977.10

Reaction Involved: For acrolein:

90% Conversion glycerol acrolein (1)

10% Convesion (2) glycerol acetone

acetone

acetol

281

For continuous process: Calculation for space time From Chemical Reaction Engineering, Octave Levenspiel, 3rd Edition Derivation: For reactor containing catalyst particle:

Elementary slice of solid catalyzed reactor At steady state a material balance for reactant A gives

In symbols

In differential form

Thus

282

Where:

(Ref: Optimization of the Dehydration of Glycerol to Acrolein and a Scale up in a Pilot Plant by Prieto, Sergio Sabater)

Based from the graph, to obtain a 100% conversion of glycerol to 0.6

should be equal

(Ref: Chemical Reaction Engineering, Octave Levenspiel, 3rd Edition)

283

For reaction (1) From Material and Energy Balance:

For reaction (2) From Material and Energy Balance:

284

With a safety factor of 20%:

For volume of catalyst: From Material and Energy Balance:

For volume of Ceramic Balls Support (CBS): (Ref: Process for Manufacturing Acrolein from Glycerol by Dubois)

(Ref:Chemical Engineering Design Principles, Practice and Economics of Plant and Process Design by GavinTowler, 2nd edition)

285

Ratio:

For Catalytic Fixed Bed Height and Diameter:

For Height of Ceramic Balls Support (CBS): (Ref: Process for Manufacturing Acrolein from Glycerol by Dubois)

From Albrights Chemical Engineering Handbook by Lyle F. Albright

286

Shell Thickness: From Process Equipment Design by Hesse and Ruston, Equation 4-3 Using API-ASME design equation for Cylindrical Shells

Where: ts P = Shell Thickness (in) = Maximum Allowable Working Pressure (psi)

D = Inside Diameter of the Shell before Corrosion Allowance is added (in) S = Maximum Allowable Working Stress (psi) using S31000

E j = Efficiency of Longitudinal Joints expressed as a fraction = 0.8; Double V or U butt joint for ts=1/8 to 1/4 in (Process Equipment Design by Hesse and Ruston) c = Allowance for Corrosion (in) =

Maximum Stress (S) From Process Equipment Design by Hesse and Ruston, Equation 4-1

Where: S u = 655 MPa for S31000; Ultimate Stress of Material (ChE Handbook, 8th Edition; Table 25-11) Fm = 1.0; material factor or grade of steel Fr = 1.06; stress relieving factor Fa = 1.12; radiographing factor Fs = 0.2; type of steel factor

287

For Maximum Internal Pressure:

288

Head and Bottom Thickness: From Process Equipment Design by Hesse and Ruston, Equation 4-5 Using API-ASME design equation for Ellipsoidal Head

Insulation Design: From Material & Energy Balance:

Di Do

From ChE Handbook, 7th Ed, p 2-335 For a reactor with temperature of 280C, the recommended insulation material is Fire Clay with a thermal conductivity of

289

Compressor Design: Bernoulli Equation:

For blowers and compressors: (From page 208 of Unit Operations of Chemical Engineering 5th Ed. by McCabe and Smith) In blowers and compressors the mechanical, kinetic, and potential energies do not change appreciably, and the velocity and static-head terms can be dropped. Also, on the assumption that the compressor is frictionless, and with this simplifications the equation becomes

290

Power requirement:

291

SPECIFICATION SHEET Date IDENTIFICATION Name Heat Exchanger Code H-1 Units required 1 To cool the Crude Acrolein FUNCTION Continuous OPERATION Shell and Tube Heat Exchanger TYPE 7,500,000 kJ/day DUTY Acrolein, Acetol, Water, Hydrogen, MATERIAL HANDLED Oxygen DESIGN DATA Shell Side Design Tube Side Design Fluid Handled Crude Acrolein Fluid Handled Water Mass Flow rate 9.44 kg/s Mass Flow rate 7.90 kg/s Volumetric Flow rate 0.0094 m3/s Velocity 0.2106 m/s Velocity 0.5935 m/s Temperature 280C 150C Temperature 28C 90C Outer Diameter 16 mm Bundle Diameter 204 mm Inside Diameter 14 mm Shell Diameter 219 mm Length of tubes 2m Wall Thickness 3 mm Tube surface area 4.70 m2 Baffle Spacing 43.8 mm Number of tubes 76 Baffle Diameter 214 mm Tube Pitch 19.85 mm Double-Welded Type of Joint Pressure Drop 21.9 kPa Butt Joint Joint Efficiency 80 % Clearance 3.97 mm Shell Material G10200 Tube Material S50200 Pump Design Pump Type Centrifugal Power Requirement 4 HP

292

2m

Shell and Tube Heat Exchanger

293

Tube Arrangement

Outside Diameter = 5/8 in = 15.88 mm Using Rotated Square Pitch (From Plant Design and Economics by Peter and Timmerhaus)

Tube Pitch, p t = 1.25 D o = 1.25 (15.88 mm) = 19.85 mm Clearance = 0.25 D o = 0.25 (15.88 mm) = 3.97 mm

3.97 mm

19.85 mm

294

Design Calculations for Heat Exchanger From Material & Energy Balance: Amount of Heat, Q = 7,375,680.66 kJ/day

Cooling Water Mass Flow = 28,432.74 kg/day Design Operation: Operation: 1 Batch per Day Operating Time: 1 hour

Heat Transfer Equation: Logarithmic Mean Temperature Difference Crude Acrolein Temperature in (oC) Temperature out (oC) 280 150 Cooling Water 28 90

295

Overall Heat Transfer Coefficient Overall Heat transfer coefficient of shell and tube heat exchanger

(Ref: Chemical Engineering Vol. 6, 4th Edition by Coulson and Richardson, Table 12.1 p. 637) Heat Transfer Area

296

Tube Side Design Fluid Handled Mass Flow Rate Mass Flow Rate : : Crude Acrolein 34,000 kg/day

Volumetric Flow Rate (GPM)

For a Surface Area of = 4.7012 m2 50.60 ft2 (Ref: Basco Type 500 Heat Exchangers Model 08072 Standard Straight Tube Type) Surface Area = 62.1 ft2 Number of tubes = 76 Tube Outside Diameter (D o ) = 5/8 15.88 mm

297

Shell Diameter = 8 5/8 0.2191 m Maximum Flow Rate (GPM) = 461 GPM Using 5/8 in OD BWG 20, Outside Diameter (Do) = 15.88 mm Inside Diameter (Di) = 14.097 mm Length of Tubing Required

Tube Side Velocity From BASCO TYPE 500 HEAT EXCHANGERS Velocity factor = 1.47 (for 5/8 tubing)

298

Pitch Type: Rotated Square Pitch Tube Pitch, p t = 1.25 D o = 1.25 (15.88 mm) = 19.85 mm Clearance = 0.25 D o = 0.25 (15.88 mm) = 3.97 mm Pressure Drop

(Ref: Equation 12.18 p.666 Chemical Engineering Vol. 6, 4th Edition by Coulson and Richardson) Evaluating for J f , Viscosity of solution mostly Acrolein= 0.05632 Pa-s (Ref: www.epa.gov/hpv/pubs/summaries/acriolein/c13462rs.pdf)

From Fig. 12.24 p. 668 of Chemical Engineering Vol. 6 4th Ed. By Coulson and Richardson 0 299

Therefore:

300

Pump Design

Pressure Head (Ref: p. 10-27 Perrys Chemical Engineering Handbook 8th Ed. By Perry et.al)

301

Shell Side Design Fluid Handled Mass Flow Rate Mass Flow Rate : : Water 28,432.74 kg/day

Bundle Diameter

Shell Diameter From BASCO TYPE 500 HEAT EXCHANGERS

Baffle Diameter and Spacing (Ref: Chemical Engineering Volume 6, 4th Edition by Coulson and Richardson, Table 12-5 p. 651)

302

Number of tubes in center row

Pressure Drop (Ref: Chemical Engineering Vol. 6, 4th Edition by Coulson and Richardson)

Velocity, us From BASCO TYPE 500 HEAT EXCHANGERS Velocity factor of shell = 10

303

Evaluating diameter, d e , from Eq. 12.22 p. 672 of Chemical Engineering Vol. 6 4th Ed. By Coulson and Richardson

Evaluating for J f , Viscosity of water at average temperature of 37.5oC= 0.704 mPa-s (Ref: Perrys ChE Handbook 8th Edition, T 2-313 p. 2-432)

From Fig. 12-30 p. 674 of Chemical Engineering Vol. 6 4th Ed. By Coulson and Richardson

304

Therefore:

Using 5/8 in OD BWG 20, Outside Diameter (Do) = 15.88 mm Inside Diameter (Di) = 14.097 mm

V tubes = N T x S x L T

D = 2.8905 m (superficial diameter for the flow of cooling water) 305

Shell Thickness Material of Construction Joint Efficiency Corrosion Allowance : : : G10200 Double Welded V-butt 0.80 : 1/16 in

From Process Equipment Design by Hesse and Rushton, Equation 4-3 Using API-ASME design equation for Cylindrical Shells

Where: ts P = Shell Thickness (in) = Maximum Allowable Working Pressure (psi)

D = Inside Diameter of the Shell before Corrosion Allowance is added (in) S e = Maximum Allowable Working Stress (psi) using G10200 = Efficiency of Longitudinal Joints expressed as a fraction

306

= 0.8; Double V or U butt joint for ts=1/8 to 1/4 in (Process Equipment Design by Hesse and Rushton) c = Allowance for Corrosion (in) = Working Pressure = gh; h= superficial diameter Pressure Head = Atmospheric Pressure + Working Pressure = 101 325 Pa + 1000 kg/m3 (9.8 m/s2) (2.8905 m) = 129 651.90 Pa = 18.8045 psi From table 4-1 of Process Equipment Design by Hesse and Rushton, Fs = 25% for temperatures up to 650 F S =Su x Fm x Fa x Fr x Fs Su = 65000 psi Fm = 1.0 Fr = stress relieving factor = 1.0 Fa = radiographing factor = 1.0 Fs = 0.25 (Eq. 4-1 p.84 of PED by Hesse and Ruston) (G10200; ChE Handbook 8th ed p 25-32 table 25-8)

307

Assuming stress relieving and radiographing factors are not employed: S = 65,000 psi x 1.0 x 1.0 x 1.0 x 0.25 S = 16,250 psi From Process Equipment Design by Hesse and Rushton, Equation 4-3 Using API-ASME design equation for Cylindrical Shells

308

SPECIFICATION SHEET Absorption Column Item: 1 Number required: A-1 Code: To purify acrolein from the dehydration reactor Function: Continuous Operation: Tray column Type: Cross flow INTERNAL CONDITIONS Top Bottom Crude acrolein Vapor to tray 3 Rate 3.9 m /s 6.9 m3/s Density 1.2 kg/m3 0.68 kg/m3 Pressure 100 kPa 100 kPa Temperature 55C to 60C 140C to 150C Water Liquid from tray Rate 2.22 L/s 5.1 L/s 3 Density 1000 kg/m 1000 kg/m3 Temperature 25C to 30C 55C to 60C Viscosity 0.85 cP 0.50 cP OPERATING DATA Column diameter 1.5 m Tray space 600 mm Total trays in section 5 trays Column height 3.5 m Number of passes Single pass Downcomer type Segmental Weir height 100 mm Clearance height 90 mm Hole size 13 mm Hole pitch 35 mm TECHNICAL/MECHANICAL DATA Tray type Sieve tray Tray material Stainless steel Tray thickness 6 mm Downcomer material Stainless steel Downcomer bar thickness 6 mm Support ring material Stainless steel Support ring thickness 6 mm Support ring width 50 mm 309

CONSTRUCTION AND MATERIALS Material of Construction: Stainless steel UNS S31600 Shell thickness: 4 mm Weld profile: Single U butt joint Welding efficiency: 70% Head type: Flanged and dished head Head thickness: 4 mm Bottom thickness: 7 mm PUMP DESIGN Pump type: Centrifugal Power requirement: 1.5 HP

310

1.5 m

Gas Out Liquid

Sieve tray

600 mm

3.5 m
6 mm

4 mm

Gas In

Liquid

Absorption Column

311

PLATE AREA

p = 35 mm

d = 13 mm

TOP VIEW OF ARRANGEMENT ON A TRAY

312

TYPICAL CROSS-FLOW PLATE (SIEVE)

313

MATERIALS HANDLED Basis: 2 hours operation Feed: 34,000 kg

Liquid properties (water) Density, x Viscosity, x @30C Surface tension

314

Properties of Gas (acrolein stream)

315

TRAY-TOWER DESIGN

Diameter The overall height of the column will depend on the plate spacing. Plate spacing from 0.15 m (6 in.) to 1 m (36 in.) are normally used. The spacing chosen will depend on the column diameter and operating conditions. Close spacing is used with small-diameter columns, and where head room is restricted; as it will be when a column is installed in a building. For columns above 1 m diameter, plate spacing of 0.3 to 0.6 m will normally be used, and 0.5 m (18 in.) can be taken as an initial estimate. This would be revised, as necessary, when the detailed plate design is made. (Chemical Engineeering Design by R. Sinnott and G. Towler)

316

estimate: for tray spacing = 24 in., from Fig. 6.24, C F = 0.39 ft/s Fig.6.24 (Separation Process Principles by Henley and Seader 2nd ed.)

317

Correcting for C F for surface tension, foaming tendency, and the ratio of vapor hole area Ah to tray active area A according to the empirical relationship: (Equation 6-42. Separation Process Principles by Henley and Seader 2 nd ed.)

Solving for flooding velocity (Equation 6-40. Separation Process Principles by Henley and Seader 2 nd ed.)

318

Column diameter (Equation 6-44. Separation Process Principles by Henley and Seader 2 nd ed.)

Typically, the fraction of flooding, f, is taken as 0.80.

Tray spacing must be specified to compute column diameter. As spacing is increased, column height is increased but the column diameter is reduced. A spacing of 24 in., which provides ease of maintenance, is optimal for wide range of conditions; however, a smaller spacing may be desirable for small-diameter columns with large number of stages; and larger spacing is frequently used for large-diameter columns with a small number of stages.

319

Tray spacing with their corresponding column diameter: Tray Spacing 36 in. 24 in. 18 in. 12 in. 9 in. 6 in. Computed diameter 1.3 m 1.5 m 1.8 m 2.0 m 2.3 m 2.5 m

Column diameter = 1.5 m Tray spacing = 24 in. (600 mm) Number of Theoretical Plates (Equation 14-33. Perrys Chemical Engineers Handbook 8th ed.)

320

Henrys law constant for acetol is 0.43 atm/mole fraction:

321

Tray Efficiency The OConnell parameter for gas absorbers is L /KM L , where L is the liquid density, lb/ft3; L is the liquid viscosity, cP; M is the molecular weight of the liquid; and K = y/x. . (Perrys Chemical Engineers Handbook 8th ed., p. 14-15)

According to the OConnell graph for absorbers (Using Fig. 14-9. Perrys Chemical Engineers Handbook 8th ed.) the overall tray efficiency is estimated to be 60 percent.

322

Number of Actual Plates (Equation 14-44. Perrys Chemical Engineers Handbook 8th ed.)

The required number of actual trays is 3/0.60 = 5 trays

Height of the Column The required height of a gas absorption tower for physical solvents depends on (1) the phase equilibria involved; (2) the specified degree of removal 323

of the solute from the gas; and (3) the mass-transfer efficiency of the device. These three considerations apply to both tray and packed towers. Items 1 and 2 dictate the required number of theoretical stages (tray tower). Item 3 is derived from the tray efficiency and spacing (tray tower). For tray towers, the approximate design methods described below may be used in estimating the number of theoretical stages, and the tray efficiencies and spacings for the tower. (Perrys Chemical Engineers Handbook 8th ed., p. 14-9)

actual plates = 5 plates tray spacing = 600 mm tray thickness = 6 mm height of the column = (5 x 600 mm) + (5 x 6 mm) = 3030 mm Vapor space = 20% height of the column = 3030 mm x 1.2 = 3600 mm height of column = 3.5 m

324

PRIMARY TRAY CONSIDERATIONS Number of Passes Trays smaller than 1.5-m (5-ft) diameter seldom use more than a single pass; those with 1.5- to 3-m (5- to 10-ft) diameters seldom use more than two passes. Four-pass trays are common in high liquid services with towers larger than 5-m (16-ft) diameter. (Perrys Chemical Engineers Handbook 8th ed., p. 1429)

Number of passes: Single Pass

Tray Spacing Taller spacing between successive trays raises capacity, leading to a smaller tower diameter, but also raises tower height. There is an economic tradeoff between tower height and diameter. As long as the tradeoff exists, tray spacing has little effect on tower economies and is set to provide adequate access. 325

In towers with larger than 1.5-m (5-ft) diameter, tray spacing is typically 600 mm (24 in), large enough to permit a worker to crawl between trays. In very large towers (>6-m or 20-ft diameter), tray spacings of 750 mm (30 in) are often used. In chemical towers (as distinct from petrochemical, refinery, and gas plants), 450 mm (18 in) has been a popular tray spacing. With towers smaller than 1.5 m (5 ft), tower walls are reachable from the manways, there is no need to crawl, and it becomes difficult to support thin and tall columns, so smaller tray spacing (typically 380 to 450 mm or 15 to 18 in) is favored. Towers taller than 50 m (160 ft) also favour smaller tray spacings (400 to 450 mm or 16 to 18 in). (Perrys Chemical Engineers Handbook 8th ed., p. 14-29) Tray spacing: Using 1.5 meter diameter, the tray spacing is 24 in. (600 mm)

Outlet Weir The outlet weir should maintain a liquid level on the tray high enough to provide sufficient gas-liquid contact without causing excessive pressure drop, downcomer backup, or a capacity limitation. Weir heights are usually set at 40 to 80 mm (1.5 to 3 in). In this range, weir heights have little effect on distillation efficiency [Van Winkle, Distillation, McGraw-Hill, New York, 1967; Kreis and Raab, IChemE Symp. Ser. 56, p. 3.2/63 (1979)]. In operations where long residence times are necessary (e.g., chemical reaction, absorption, stripping)

326

taller weirs do improve efficiency, and weirs 80 to 100 mm (3 to 4 in) are more common (Lockett, Distillation Tray Fundamentals, Cambridge University Press, Cambridge, England, 1986). (Perrys Chemical Engineers Handbook 8th ed., p. 14-29)

Weir height: 4 in. (100 mm)

Downcomers A downcomer is the drainpipe of the tray. It conducts liquid from one tray to the tray below. Due to the density difference, most of this gas disengages in the downcomer and vents back to the tray from the downcomer entrance. Some gas bubbles usually remain in the liquid even at the bottom of the downcomer, ending on the tray below [Lockett and Gharani, IChemE Symp. Ser. 56, p. 2.3/43 (1979)]. The straight, segmental vertical downcomer (Fig. 14-23a) is the most common downcomer geometry. It is simple and inexpensive and gives good utilization of

327

tower area for downflow. (Perrys Chemical Engineers Handbook 8th ed., p. 1431)

Figure 11.34. Relationship between angle subtended by chord, chord height and chord length (Ref: Chemical Engineeering Design by R. Sinnott and G. Towler)

328

Clearance under the Downcomer Restricting the downcomer bottom opening prevents gas from the tray from rising up the downcomer and interfering with its liquid descent (downcomer unsealing). A common design practice makes the downcomer clearance 13 mm (0.5 in) lower than the outlet weir height (Fig. 14-25) to ensure submergence at all times [Davies and Gordon, Petro/Chem Eng., p. 250 (November 1961)]. This practice is sound in the froth and emulsion regimes, where tray dispersions are liquid-continuous, but is ineffective in the spray regime where tray dispersions are gas-continuous and there is no submergence. Also, this practice can be unnecessarily restrictive at high liquid loads where high crests over the weirs sufficiently protect the downcomers from gas rise. (Perrys Chemical Engineers Handbook 8th ed., p. 14-31)

Clearance height: 3.5 in. (90 mm) 329

Hole Sizes Small holes slightly enhance tray capacity when limited by entrainment flood. Reducing sieve hole diameters from 13 to 5 mm ( to 3/ 16 in) at a fixed hole area typically enhances capacity by 3 to 8 percent, more at low liquid loads. Small holes are effective for reducing entrainment and enhancing capacity in the spray regime (Q L < 20 m3/hm of weir). Hole diameter has only a small effect on pressure drop, tray efficiency, and turndown. On the debit side, the plugging tendency increases exponentially as hole diameters diminish. Smaller holes are also more prone to corrosion. While 5-mm (3/ 16 -in) holes easily plug even by scale and rust, 13-mm ( in) holes are quite robust and are therefore very common. The small holes are only used in clean, noncorrosive services. Holes smaller than 5 mm are usually avoided because they require drilling (larger holes are punched), which is much more expensive. For highly fouling services, 19- to 25-mm ( to 1in) holes are preferred. (Perrys Chemical Engineers Handbook 8th ed., p. 1431) Hole size: 0.5 in. (13 mm)

330

Provisional Plate Design

Perforated Area

331

Figure 11 .35. Relation between hole area and pitch (Ref: Chemical Engineeering Design by R. Sinnott and G. Towler) From figure above, lp /d h = 2.7 (satisfactory, within 2.5 to 4.0), lp = 35 mm

332

Number of Holes

MATERIAL OF CONSTRUCTION Using API-ASME Code For Shell Thickness, t S

For stainless 316 or S31600:

333

The plate structure must be designed to support the hydraulic loads on the plate during operation, and the loads imposed during construction and maintenance. Typical design values used for these loads are: Hydraulic load: 600 N/m2 live load on the plate, plus 3000 N/m2 over the downcomer seal area. Erection and maintenance: 1500 N concentrated load on any structural member.

334

Verify if Fa and Fr are mandatory

Radiographing and relieving may not be employed since 0.14 in. < 0.91 in.

335

For Flanged and Dished Head Thickness Head thickness (for head with pressure on the concave side)

Bottom thickness (for head with pressure on the convex side)

336

Pump Design: Power output (theoretical) (Equation 10-51. Perrys Chemical Engineers Handbook 8th ed.)

Power Requirement: For a basis of 70% efficiency of the motor: Power actual (Equation 10-55. Perrys Chemical Engineers Handbook 8th ed.)

337

SPECIFICATION SHEET Date : IDENTIFICATION Name Esterification Reactor Code R-3 Unit/s required 1 To convert Acrylic Acid to Ethyl Acrylate FUNCTION Batch OPERATION Stirred Tank TYPE 35 m3 CAPACITY MATERIAL HANDLED Acrylic Acid, Ethanol, Water, Sulfuric Acid DESIGN DATA Pressure (P) 147.8 kPa Density () 1,020.20 kg/m3 Temperature 140C SPECIFICATIONS Material of Construction S31600 Diameter 3.1 m Height (H) 4.7 m Head thickness (t h ) 5 mm Shell thickness (t s ) 5 mm Bottom thickness (t b ) 5 mm Type of Joint Double-Welded Butt Joint Joint Efficiency 70 % IMPELLER DESIGN Impeller Type Turbine Impeller Diameter 1m (D a ) No. of Blades 6 Impeller Length (L) 0.3 m No. of Baffles 4 Impeller Width (W) 0.2 m Impeller Power 13 HP Impeller Height 1m Requirement from Bottom (E) Rotational Speed 63 rpm Width of Baffles (J) 0.3 m HEATING COIL DESIGN Heat Transfer 4.6 m2 Number of Turns 8 Area Temperature 200C Diameter of the Coil 2.3 m Diameter of the 1 in Distance between 0.4 m Tube Coils Length of the Coil 58.2 m Height of Coils 3.5 m

338

INSULATION DESIGN Outside Diameter 3.11 m Thickness 2 mm

Insulating Material Thermal Conductivity

Calcium Silicate 0.05728 W/(mK)

339

Esterification Reactor

340

Batch reactor equipped with four baffles using a 6-blade turbine impeller Top view

Blade

Baffle

Side View

341

Design Calculations For Reactor Volume:

(Ref: Kautter et al., Esterification of Acrylic Acid Patent No. 3458561) From Material & Energy Balance: Feed: Component Acrylic acid Ethanol Water Sulfuric Acid Density (kg/m3) 1,050 790 1,000 1,840 TOTAL kg 13,738.70 8,784.10 2,146.28 4,967.64 29,636.72

342

With a vapor space of 20%:

For vessel diameter and height: In esterification reactions, a batch reactor equipped with four baffles and a sixbladed turbine impeller is used. (Ref: G.N. Kraai et al. / Biochemical Engineering Journal 41 (2008) 8794) (Ref: Ch.E. HB, p.18-13) For V= 4 to 200 m3 H/D = 0.75-1.5; Basis: H = 1.5D Using cylindrical vessel, with turbine mixer and 4 baffles

343

For Maximum Internal Pressure:

Shell Thickness: From Plant Design and Economics for Chemical Engineers by Peters and Timmerhaus, 5th Edition, Table 12-10 p.555: For Stainless 316 or S31600, the recommended stress at 140C (284F) is:

344

Using ASME-UPV Code, design equation for cylindrical shells (from Peters and Timmerhaus 5th Edition, Table 12-10 p. 554):

Where: t S = shell thickness (in) P = maximum allowable working pressure (psi) r = inside radius of the shell before corrosion allowance is added (in) S = maximum allowable working stress (psi) using S31600 e = efficiency of joints expressed as a fraction = 0.70; for Double-Welded Butt Joint if not radiographed (From Plant Design and Economics for Chemical Engineers by Peters and Timmerhaus 5th Edition, Table 12-10 p. 555) c = allowance for corrosion (in) = 1/16 in

345

Head and Bottom Thickness: Using ASME-UPV Code, design equation for ellipsoidal head (from Peters and Timmerhaus 5th Edition, Table 12-10 p.554):

Impeller Design: (Ref: Unit Operations by McCabe &Smith 6th Edition p.241) Impeller Diameter; Da

Impeller width; W

346

Impeller Length; L

Distance vessel floor; E

Baffle Width, J;

Depth of Liquid in Vessel, h;

Volume of Impeller:

347

Power Consumption of Impeller: From Turbine & High Efficiency Axial Flow Agitators, http://www.feldmeier.com/cutsheets/turbine_agitator.pdf: Speed range for commercially available turbine agitator is 63 to 73 rpm. To compute for Reynolds Number: n = rotational speed = 63 rpm = 1.05 rev/s Da = impeller diameter = 1.03 m

N Re = 438,782.51 Since Re>104

flow

is turbulent

KT for disk turbine with six blades (table 9.2, McCabe & Smith p. 262) K T = 5.75 348

For a motor efficiency of 80%,

Heating Coil Design: (From ChE Handbook p. 11-20, eq. 11-39) QF = UATLM ; F = Safety factor = 1.5

From Material and Energy Balance:

Temperature of Feed:

349

C Steam T1 T2 Liquid t1 t2 200 200 83 140

(Ref: Engineering Page: Typical Overall Heat Transfer Coefficients retrieved from: http://www.engineeringpage.com/technology/thermal/transfer.html)

350

From ChE Handbook 7th Ed pg. 11-21 Economical Diameter of the Tube for shop fabrication = 25.4 mm = 1 in BWG

Diameter of the Tube = Length of coil:

From ChE Handbook pg. 11-21 Distance of coil from the tank wall (d c ) = 6in = 0.5 ft = 0.15 m

351

Total Volume of Tank, V T:

352

Insulation Design: ri
ro

From ChE Handbook, 8th Ed, p 2-459 For Calcium Silicate:

353

SPECIFICATION SHEET IDENTIFICATION Name of Equipment Equipment Code Number of Unit/s Required Function Operation Type Materials Handled DESIGN DATA Capacity Operating Pressure Transmembrane Pressure Power Requirement MEMBRANE DESIGN Membrane Material Thickness Nominal Pore Size Total Membrane Area MODULE DESIGN Module Type Material of Construction Membrane Area/module Length Outer Diameter of Module Internal Diameter of Tube No. of Tubes/module Tube Arrangement Total Number of Modules Required Module Connection Module Arrangement Feed-Permeate Differential Pressure Pressure Drop along Module MO 63G_I10HD V Berghof HyperFlux Tubular Module Fiber Reinforced Plastic (FRP), Resin 12.2 m2 3m 156.4 mm 10.3 mm 72 Triangular Pitch 32 Parallel 32 rows -0.20...+10 bar 3.48 bar Polyvinyl Alcohol (PVA) 25 m Non-Porous 381.3 m2 14.39 m3/hr 10 bar 0.25 bar 7 HP Pervaporator PV 1 1 To remove water from the Ethyl Acrylate product stream Continuous Tubular Ethyl Acrylate, Acrylic Acid, Ethanol, Water

354

MODULE CONNECTIONS DESIGN DUMMY Diameter 156.4 mm Length 3m No. of Dummy Required 32 BEND VICTAULIC CONNECTION NO. 3006305 Diameter 168.3 mm Thickness 3 mm Center Distance 458 mm Length 363 mm Material Stainless Steel 1.4571 No. of Bends Required 32 PERMEATE CONNECTION VICTAULIC-CLAMP WITH FLASH GAP SEALING Diameter 60.3 mm Socket 50 mm Length 1 58 mm Length 2 57 mm Polyvinyl Chloride-Unplasticised Material (PVC-U) No. of Permeate Connections Required 64 INLET-OUTLET CONNECTION VICTAULIC-CLAMP WITH FLASH GAP SEALING Diameter 168.3 mm Thickness 3 mm Length 200 mm Material Stainless Steel 1.4571 No. of Inlet-Outlet Connection 128 Required MODULE FIXING PARTS DESIGN STRAP Clear Height Inner Width Thread Length Thread Material No. of Strap Required SADDLE Broadth 230 mm 163 mm 80 mm M8 Stainless Steel 1.4301 192 20 mm 355

Bore Height Module Center Height Length Distance Material No. of Saddles Required

10 mm 20 mm 90 mm 200 mm 170 mm Polypropylene (PP) 192

356

Cutaway of the MO 63G_I10HD V Berghof HyperFlux Tubular Module

One Unit Module Assembly Overview 357

358

Module Design: Using commercially available MO 63G_I10HD V Berghof HyperFlux Tubular Module from Berghof Filtration and Plant Engineering Data Sheets:

Dummy Design:

359

Inlet-/Outlet Connection Design:

Permeate Connection Design:

360

Bend Design:

Module Fixing Parts Design: Strap:

361

Saddle:

362

Detailed Computations: Materials Handled: Quantity (kg) Ethyl Acrylate Acrylic Acid Water Ethanol Total Feed 18895.35 137.38 5548.51 87.84 24669.08 Permeate 0 0 5548.51 0 5548.51 Retentate 18895.35 137.38 0 87.84 19120.57

Temperature (C) Pressure (atm)

100 1

100 0.1332

100 1

Feed: Substance Size (nm) Molecular Density Volume Mass (kg) Mass Weight (kg/m3) (m3) Fraction (kg/kgmol) (X i ) 45 100.08 920 20.54 18895.35 0.7660 35 0.275 0.44 72.04 18.02 46.06 1050 1000 790 936.96 0.1308 5.549 0.1112 26.33 137.38 0.0056

Ethyl Acrylate Acrylic Acid Water Ethanol TOTAL

5548.51 0.2249 87.84 0.003561 24669.08 1

363

Permeate: Substance Size (nm) Molecular Density Volume Mass (kg) Mass 3 3 Weight (kg/m ) (m ) Fraction (kg/kgmol) (X i ) 0.275 18.02 1000 5.549 5548.51 1

Water

Retentate: Substance Size (nm) Molecular Density Volume Mass (kg) Mass Weight (kg/m3) (m3) Fraction (kg/kgmol) (X i ) 45 100.08 920 20.54 18895.35 0.9882 35 0.44 72.04 46.06 1050 790 920.12 0.1308 0.1112 20.78 137.38 0.007185 87.84 0.004594 19120.57 1

Ethyl Acrylate Acrylic Acid Ethanol TOTAL

To solve for Diffusivity: Unit Operation of ChE, McCabe and Smith, Equation 30.55, p. 1041, 7th Edition

Where:

Dv = diffusivity T = temperature (K) = radius of particles (cm) = 45 nm 4.5x10-6 cm = viscosity (cP) = 0.6406 cP

364

To solve for Reynolds Number: Unit Operations of ChE, McCabe and Smith, Equation 3.8, p. 59, 5th Ed.

To solve for Schmidt Number: Unit Operation of ChE, McCabe and Smith, Equation 3.10, p. 53, 7th Edition

7216.23

365

To solve for Sherwood Number (for high Schmidt Number) Unit Operations of ChE, McCabe and Smith, Equation 17.71, p. 545, 7th Edition

48,157.45 To solve for Mass Transfer Coefficient (K c ): Unit Operations of ChE, McCabe and Smith, Equation 17.71, p. 545, 7th Edition

Where: N Sh = Sherwood Number D = diameter of tube D v = diffusivity

366

To solve for permeate flux (u): Unit Operations of ChE, McCabe and Smith, Equation 29.48, p. 1040, 7th Edition

Where: J = permeate flux = mass transfer coefficient C 1 = concentration of EA at retentate C s = concentration of EA at feed For Cs (from material balance):

For C 1 :

367

Table: Conversion factors for Permeate flux m/s 2.78 x 10-7 4.72 x 10-7 m/h 10-3 1.698 x 10-3 L/m2-h 1 1.698 Gal/ft2-day 0.589 1

368

To solve for Permeability (Q m): Unit Operations of Chemical Engineering, McCabe and Smith, Equation 30.49, p. 1037, 5th Edition:

Where: J = permeate flux Q m = membrane permeability P = transmembrane pressure

Transmembrane Pressure (P): Using Raoults Law: At feed: At permeate:

369

Permeability (Q m): Unit Operations of Chemical Engineering, McCabe and Smith, Equation 30.49, p. 1037, 5th Edition:

To solve for Area of the Membrane: Operating time: 110 min 1.83 h ; (from Time-Dependence of Pervaporation

Performance for the Separation of Ethanol/Water Mixtures through Polyvinyl Alcohol Membrane, by Gewei Li, Wei Zhang, Juping Yang, Xinping Wang)

370

Module Design: Using commercially available MO 63G_I10HD V Berghof HyperFlux Tubular Module from Berghof Filtration and Plant Engineering: ID = 0.0103 m L=3m l=

A module = 12.2 m2 To Solve for Number of Modules:

To solve for Pressure Drop along Module:

371

From Berghof HyperFlux Tubular Module Data Sheet:

where: Pressure Drop along Module = [kPa] v =Cross Flow Velocity [m/s] L = Module Length [m]

372

TYPE OF PUMP: Based on Membrane Filtration Handbook, the recommended pump for operating pressures up to 15 bar is a centrifugal pump made of stainless steel. It is also compatible with a wide range of capacities including To solve for Power Requirement: From ChE Handbook 7th Edition, p. 10-23 Equation 10-50: .

Where: H =

Q=

For a pump efficiency of 70%, the actual power is:

373

CHAPTER VII

COST ESTIMATION

374

CHAPTER VII COST ESTIMATION I. INTRODUCTION A project to be feasible must present a process that yields a profit. The different types of cost involved in manufacturing processes should be studied well so that the proposal will be acceptable. It is very important to estimate the total expenses and the total revenue for a project that has a small amount of investment but has a large amount of profit thereafter. The main goal is to maximize the profit but not at the expense of the quality. Large amount of capital is required to purchase the necessary equipments, land and service facilities, as well as piping and process controllers, for a plant to operate. Herewith, the cost estimation presents the detailed estimation in establishing a feasible Ethyl Acrylate Manufacturing Plant which uses glycerol as major raw material. Detailed computations of investment cost and operational cost were shown here.

A. Total Capital Investment For a plant capacity of 5,700 MT/year, operating at 24 hours a day and 300 days a year, Total Capital Investment amounts to about PhP 331.43 M. The Fixed Capital Investment is determined from the Direct Capital Investment which includes 15.95% (PhP 52.87 M) purchased equipment delivered, 7.50% (PhP

375

24.85 M) installation, 5.74% (PhP 19.03 M) instrumentation and control, 10.85% (PhP 35.95 M) piping system, 2.87% (PhP 9.52 M) building, 1.75% (PhP 5.82 M) electrical system, 1.60% (PhP 5.29 M) yard improvement and 11.17% (PhP 37.01 M) service facilities. The Fixed Capital Investment (FCI) which represents the amount necessary for the complete cost and installation of the process equipment is computed based on the five major equipments being designed in the previous chapter, namely: dehydration reactor, heat exchanger, absorption column, esterification reactor and pervaporator. It is assumed that the cost of these five equipments represent 45.45 percent of the total equipment cost of the entire plant. Also, the working capital that is necessary to finance the plant operations is computed and added to the fixed capital investment to get the Total Capital Investment. Thus, in this design:

Fixed Capital Investment Working Capital Total Capital Investment

= = =

PhP 266,474,677.25 PhP 64,952,672.24 PhP 331,427,349.49

376

B. Total Production Cost It is then necessary to determine the total production cost per kilogram of the product to see if the given design will yield a considerable amount of profit. The total production cost is determined from the manufacturing cost which includes the variable production cost, fixed charges, and plant overhead cost, and the general expenses.

Manufacturing Cost General Expenses Total Production Cost

= = =

PhP 45.73/kg EA PhP 9.48/kg EA PhP 55.21/kg EA

377

Equations: Fixed Capital Investment (FCI) = Direct Production Cost + Indirect Production Cost (Plant Design and Economics for Chemical Engineers, Peters et. al., 5 th ed., p.233) Total Capital Investment = Fixed Capital Investment + Working Capital (Plant Design and Economics for Chemical Engineers, Peters et. al., 5 th ed., p.232) A. Manufacturing Cost = Direct Production Cost + Fixed Charges + Plant Overhead Cost (Plant Design and Economics for Chemical Engineers, Peters et. al., 5 th ed., p.262) B. Total Production Cost = Manufacturing Cost + General Expenses (Plant Design and Economics for Chemical Engineers, Peters et. al., 5 th ed., p.259) C. Marshall and Swift Equipment Cost Index From Chemical Engineering Journal, April 2012 issue MSI for Process Equipment (4th Quarter 2011) = 1,597.70 378

MSI for Process Equipment (2002) = 1,104.20 From Plant Design and Economics for Chemical Engineers by Peters and Timmerhaus, 5th Edition, Table 6-2, page 238 MSI for Process Equipment (2000) = 1,089.00 D. From Manila Bulletin, August 15, 2012 1 US$ = PhP 41.94 PhP 42.00

379

II. ESTIMATION OF CAPITAL INVESTMENT Plant Capacity Plant Operation Dollar Exchange : : : 5,700 MT /yr 24 hrs /day US$ 1.00 PhP 42.00
% A. Direct Costs Purchased Equipment Delivered Installation Instrumentation and Control Piping System Building Electrical System Yard Improvement Service Facilities TOTAL DIRECT COSTS B. Indirect Costs Engineering and Supervision Construction Expenses Legal Expenses Constructors Fee Contingency TOTAL INDIRECT COSTS FIXED CAPITAL INVESTMENT WORKING CAPITAL TOTAL CAPITAL INVESTMENT 5.26 6.54 0.64 3.51 7.02 22.97 80.40 19.60 100.00 17,447,746.73 21,677,503.51 2,114,878.39 11,631,831.15 23,263,662.30 76,135,622.07 266,474,677.25 64,952,672.24 331,427,349.49 N I J K L M 15.95 7.50 5.74 10.85 2.87 1.75 1.60 11.17 57.43 52,871,959.77 24,849,821.09 19,033,905.52 35,952,932.65 9,516,952.76 5,815,915.58 5,287,195.98 37,010,371.84 190,339,055.18 A B C D E F G H COST (PhP) EXHIBIT

380

III. ESTIMATION OF PRODUCT COST Plant Capacity Plant Operation Dollar Exchange : : : 5,700 MT /yr 24 hrs /day US$ 1.00 PhP 42.00

COST PRODUCTION (PhP/kg EA)

EXHIBIT

I. MANUFACTURING COST A. Direct Production Cost Raw Material Operating Labor Direct Supervisory and Clerical Labor Utilities Maintenance and Repair Operating Supplies Laboratory Charges TOTAL DIRECT PRODUCTION COST B. Fixed Charges Depreciation Local Taxes Insurance TOTAL FIXED CHARGES C. Plant Overhead Cost MANUFACTURING COST II. GENERAL EXPENSES Administrative Cost Distribution and Marketing Research and Development GENERAL EXPENSES TOTAL PRODUCTION COST 1.17 11.00 5.00 17.17 100.00 0.65 6.07 2.76 9.48 55.21 1.77 2.12 0.59 4.48 3.51 82.83 0.9764 1.17 0.33 2.47 1.94 45.73 DD CC BB 59.05 0.66 0.10 9.09 5.08 0.76 0.10 74.85 32.60 0.37 0.06 5.02 2.80 0.42 0.06 41.32 AA

381

EXHIBIT A

TOTAL COST OF PURCHASED EQUIPMENT

Schedule Dehydration Reactor Heat Exchanger Absorption Column Esterification Reactor Pervaporator Total PhP PhP PhP PhP PhP PhP 10,838,176.18 32,474.30 2,931,380.70 2,370,071.18 3,052,142.21 19,224,244.57 A-1 A-2 A-3 A-4 A-5

Assuming that the cost of five equipment is 45.45% of the Total equipment cost,

(Basis of Assumption: We designed 5 (1 unit of R-1, 1 unit of H-1, 1 unit of A-1, 1 unit of R-3 and 1 unit of PV-1) out of 11 or about 45.45 % of the total equipment but most of them are the expensive ones)

Total Cost of Purchased Equipment (Delivered) Using 25% delivery cost

382

SCHEDULE A-1

Equipment Equipment Code Type Material of Construction

: DEHYDRATION REACTOR : R-1 : Fixed Bed Reactor : S31600

From Equipment Design Design Capacity Diameter = 1.1 m Height = 4.30 m Mass of Catalyst Bed = 8,869.57 kg Composition: 9.3 wt% WO 3 ; 90.7 wt% ZrO 2 Present cost Cost of Vessel (Packed): For Stainless Steel: For Diameter = 1.1 m

(PD & E Peters & Timmerhaus 5th Ed.; Figure 15-16; p. 796)

383

For Diameter= 1.1 m; Height = 4.30 m

Cost of Catalyst Bed: For WO 3 : For ZrO 2 : (ProChem, Inc., Retrieved from http://www.prochemonline.com/)

Present FOB Cost of R-1 in Philippine Currency:

= PhP 10,838,176.18

384

SCHEDULE A-2

Equipment Equipment Code Type Material of Construction Shell Tube

: HEAT EXCHANGER : H-1 : Shell and Tube Heat Exchanger

: G10200 : S50200

From Equipment Design Tube Diameter = 0.016 m Heating Surface = 4.70 m2 Present cost For Tube Diameter = 0.016 m

(PD & E Peters & Timmerhaus 5th Ed.; Figure 14-21; p. 683) For Carbon Steel Shell & Stainless Steel Tube: Material Adjustment Factor = 1.70 (PD & E Peters & Timmerhaus 5th Ed.; Figure 14-19; p. 682)

385

For Heating Surface = 4.70 m2

Present FOB Cost of H-1 in Philippine Currency:

= PhP 32,474.30

386

SCHEDULE A-3

Equipment Equipment Code Type Material of Construction Tray Column

: ABSORPTION COLUMN : A-1 : Tray Column

: S31600 : S31600

From Equipment Design Diameter = 1.5 m Height = 3.5 m No. of Trays = 5

Present cost Cost of Column: For Height = 3.5 m Diameter = 1 m

387

For 316 Stainless Steel: Material Adjustment Factor = 3.0 (PD & E Peters & Timmerhaus 5th Ed.; Figure 15-11; p. 793)

Cost of Trays: For Sieve Tray (Stainless Steel): Diameter = 1.5 m

For 5 trays: Quantity Factor = 2.30 (PD & E Peters & Timmerhaus 5th Ed.; Figure 15-11; p. 793)

388

Present FOB Cost of A-1 in Philippine Currency:

= PhP 2,931,380.70

389

SCHEDULE A-4

Equipment Equipment Code Type Material of Construction

: ESTERIFICATION REACTOR : R-3 : Stirred Reactor : S31600

From Equipment Design Power Consumption = 13 HP Present cost For Double-arm sigma mixers: Power Consumption = 13 HP

(PD & E Peters &Timmerhaus 5th Ed.; Figure 13-14; p. 627)

Present FOB Cost of R-3 in Philippine Currency:

= PhP 2,370,071.18 390

SCHEDULE A-5

Equipment Equipment Code Type Material of Construction Membrane Material Module

: PERVAPORATOR : PV-1 : Tubular

: Polyvinyl Alcohol : Fiber Reinforced Plastic (FRP), Resin

From Equipment Design Total Membrane Area = 381.30 m2

Present cost For Membrane Area =1 m2

Typical investment in a complete system, including pumps, tubes, membranes and controls (Membrane Filtration Handbook; Table 37; p. 117)

391

Present FOB Cost of PV-1 in Philippine Currency:

=PhP 3,052,142.21

392

EXHIBIT B

Installation Cost

Installation of process equipment includes the cost of labor. The foundations support platforms, constructions related expenses and other factors related to the erection of the purchase equipment are part of the estimation of the installation cost.

47% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Installation Cost

= 0.47 (PhP 52,871,959.77) = PhP 24,849,821.09

393

EXHIBIT C

Instrumentation and Control Cost

Instrumentation and control involves the installation labor cost and purchase of auxiliary machines used for the control of equipment. Auxiliary equipment involves the pressure and temperature and flow controller of the plant.

36% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Instrumentation and Control Cost = 0.36 (PhP 52,871,959.77) = PhP 19,033,905.52

394

EXHIBIT D

Piping (Installed)

The piping cost covers the cost of labor in its installation, cost of pipes, valves, fittings and all other piping related requirement for the piping erection of the facility.

68% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Piping, Installed

= 0.68 (PhP 52,871,959.77) = PhP 35,952,932.65

395

EXHIBIT E

Buildings (Including Services)

Cost of buildings includes the cost of installation for the erection of administrative offices the cost of plumbing, heating, lighting ventilation and other similar services.

18% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Buildings (Including Services) = 0.18 (PhP 52,871,959.77) = PhP 9,516,952.76

396

EXHIBIT F

Electrical Systems (Installed)

The electrical system consists of four major components namely, power wiring, lighting, transformation and service and instrument and control wiring.

11% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Electrical Systems (Installed) = 0.11 (PhP 52,871,959.77) = PhP 5,815,915.58

397

EXHIBIT G

Yard Improvement

Yard improvements includes the fencing, grading, roads, sidewalks, railroad sidings, landscaping and any other similar items related to yard improvements.

10% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Yard Improvement

= 0.10 (PhP 52,871,959.77) = PhP 5,287,195.98

398

EXHIBIT H

Service Facilities

This includes the utilities for supplying steam, water, power, and fuel for the chemical processes and operations. Waste disposal, fire protection and miscellaneous service items such as shops, clinics or first aid quarters and cafeterias require capital investment that are included under general heading of service facilities.

70% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Service Facilities = 0.70 (PhP 52,871,959.77) = PhP 37,010,371.84

399

EXHIBIT I

Engineering and Supervision

The cost for construction design and engineering, including internal or licensed software, computer-aided drafts, purchasing, accounting, travel, and the plant supervisory services must be part of the capital investment.

33% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Engineering and Supervision = 0.33 (PhP 52,871,959.77) = PhP 17,447,746.73

400

EXHIBIT J

Construction Expenses

This includes construction labor and other construction related expenses, construction tools and rentals, construction payroll, construction tariffs, insurance and permits, miscellaneous equipment installation and other fees related to construction process.

41% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Construction Expenses

= 0.41 (PhP 52,871,959.77) = PhP 21,677,503.51

401

EXHIBIT K

Legal Expenses

Legal costs refer mostly to the processing of land purchase, equipment purchase and construction contracts. Understanding and proving compliance with the government, environmental and safety requirements constitute major sources of legal cost.

4% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Legal Expenses

= 0.04 (PhP 52,871,959.77) = PhP 2,114,878.39

402

EXHIBIT L

Contractors Fee

The contractors fee is the payment involve for the construction contract and other related charges.

22% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Contractors Fee

= 0.22 (PhP 52,871,959.77) = PhP 11,631,831.15

403

EXHIBIT M

Contingency

A contingency amount is included in the estimation of the project cost in recognition of the fact of the occurrence in the unexpected events and charges that inevitable increase the cost of the project. Events such as storms, flood, transportation accidents, strikes, price changes, errors of the estimation and unforeseen expenses may occur as such, it should have its own appropriation.

44% (Purchased Equipment Delivered) from P&T, Table 6-9, Fluid Processing Plant, p. 251

Contingency

= 0.44 (PhP 52,871,959.77) = PhP 23,263,662.30

404

EXHIBIT N

WORKING CAPITAL

The Working Capital for an Industrial plant consist of the total amount of money invested in (1) Raw Materials (2) Finished Products (3) Cash on Hand for Operating Expenses (4) Accounts Receivable (5) Accounts and Taxes Payable.

Working Capital = RAW MATERIALS + LABOR COST + UTILITIES

Schedule Raw Material Labor Utilities A. Water B. Steam C. Electricity Total PhP PhP PhP PhP 655,365.47 6,886,730.34 1,038,932.79 64,952,672.24 N-3 N-4 N-5 PhP PhP 55,744,433.64 627,210.00 N-1 N-2

TOTAL WORKING CAPITAL = PhP 64,952,672.24

405

SCHEDULE N-1

RAW MATERIAL

Raw material that is used in the process is one of the major costs in a production operation. Raw materials refer in general to those materials that are directly consumed in making the final product; this includes chemical reactants, and constituents and additives included in the product. Crude Glycerol Price: PhP 9.03/kg glycerol (PHP 12.90/kg for Refined Glycerol, assume price of raw glycerol is 30% lower.) Supplier: ChemSynergy Asia, Inc. (Manufacturer) Philippines Cost of Glycerol:

= PhP 27,631,800.00 Ethanol (99.9 wt %) Price: PhP 35.56/kg ethanol (Reference: Platts Energy News, Prices & Data; Lower domestic output from Philippines pushes Asian ethanol prices higher, Retrieved from http://www. platts.com/RSSFeedDetailedNews/RSSFeed/Petrochemicals/7948330) Cost of Ethanol:

= PhP 28,112,633.64

Total Raw Materials Cost = PhP 55,744,433.64 406

SCHEDULE N-2

Operating Labor Estimating labor requirements as a function of plant capacity is based on adding the various principal processing steps on the flow sheet. In this method, a process step is defined as any unit operation or unit process, unit process, or combination thereof that takes place in one or more units of grinding, extracting, fermenting, filtering, distilling etc. Plant Capacity per day = 19,000 kg Ethyl Acrylate Using Fig. 6 9 Peters & Timmerhaus, 5th ed. (Line C: Large Equipment, highly automated or fluid processing only):

Number of Process steps = 6

(Reference: http://www.nwpc.dole.gov.ph/pages/ncr/cmwr_table.html)

Operating Labor = PhP 627,210.00

407

SCHEDULE N-3

UTILITIES

The cost for utilities, such as steam, electricity and cooling water varies widely depending on the amount needed plant location and source.

Water Cost: PhP 20.16/m3 H 2 O (Reference: http://122.54.214.222/waterrates/RatesTable.asp) From Material Balance and Energy Balance: Equipment Heat Exchanger (H-1) Absorption Column (A-1) Oxidation Reactor (R-2) Condenser (C-1) Heat Exchanger (H-2) Condenser (C-2) Total Water Required/day 28,432.74 kg 16,000.00 kg 184,972.63 kg 81,722.91 kg 7,708.75 kg 42,365.28 kg 361,202.31 kg

408

SCHEDULE N-4 UTILITIES

Steam From Material and Energy Balance: Equipment Glycerol Preheater (B-1) Acrolein Preheater (B-2) Esterification Reactor (R-3) Total Steam Required/day 49,776.18 kg 1,955.53 kg 1,040.17 kg 52,771.88 kg

Depreciable Boiler Cost For Steam capacity of 1 kg/s and pressure of 1,825 kPa:

(PD & E Peters & Timmerhaus 5th Ed.; Figure B-3; p. 892) For Industrial Steam Generation,

(PD & E Peters & Timmerhaus 5th Ed.; Table 7-8; p. 310) 409

Power Generation Cost For Capacity = 1 kg/s (Efficiency = 60%) (Reference: Hurst Boiler and Welding Company, Inc.) Meralco Rate: PhP 10.8578/kw-hr (Industrial consumer) (Reference: http://meralco.com.ph/pdf/newsandupdates/2012 /NW00112.pdf)

Fuel Cost For Bunker C Fuel Oil:

(Reference: http://www.engineeringtoolbox.com/fuel-oil-combustionvalues-d_509.html) 410

(Reference: Pilipinas Shell Petroleum Corporation) From Material and Energy Balance:

Then,

411

SCHEDULE N-5

Electricity Meralco Rate: PhP 10.8578/kw-hr (Industrial consumer) (Reference: http://meralco.com.ph/pdf/newsandupdates/2012 /NW00112.pdf) 1. Dehydration Reactor: P = 1.5 HP 1.1185 kW Operating Time = 24 hrs/day

= PhP 26,232.01 2. Heat Exchanger: P = 4 HP 2.9828 kW Operating Time = 24 hrs/day

= PhP 69,955.16 3. Absorption Column: P = 1.5 HP 1.1185 kW Operating Time = 24 hrs/ day

= PhP 26,232.01

412

4. Esterification Reactor: P = 13 HP 9.6941 kW Operating Time = 24 hrs/day

= PhP 227,354.25 5. Pervaporator: P = 7 HP 5.2199 kW Operating Time = 24 hrs/day

= PhP 122,421.52

Assuming that the Electricity Cost of five equipments is 45.45% of the Total Electricity Cost,

413

EXHIBIT AA

DIRECT PRODUCTION COST

Cost (PhP) / kg EA Raw Material Operating Labor Direct Supervisory and Clerical Labor Utilities Maintenance and Repair Operating Supplies Laboratory Charges Total PhP PhP PhP PhP PhP 5.02 2.80 0.42 0.06 41.32 PhP PhP PhP 32.60 0.37 0.06

Schedule AA-1 AA-2 AA-3

AA-4 AA-5 AA-6 AA-7

TOTAL DIRECT PRODUCTION COST = PhP 41.32/kg EA

414

SCHEDULE AA-1

Raw Material Crude Glycerol Price: PhP 9.03/kg glycerol (PhP 12.90/kg for Refined Glycerol, assume price of raw glycerol is 30% lower.) Supplier: ChemSynergy Asia, Inc. (Manufacturer) Philippines Cost of Glycerol:

= PhP 16.16/ kg EA Ethanol (99.9 wt %) Price: PhP 35.56/kg ethanol (Reference: Platts Energy News, Prices & Data; Lower domestic output from Philippines pushes Asian ethanol prices higher, Retrieved from http://www.platts.com/RSSFeedDetailedNews/RSSFeed/Petrochemicals/794 8330) Cost of Ethanol:

= PhP 16.44/ kg EA Total Raw Materials Cost = PhP 32.60/ kg EA

415

SCHEDULE AA-2

Operating Labor

Plant Capacity per day = 19,000kg Ethyl Acrylate Using Fig. 6 9 Peters & Timmerhaus, 5th ed. (Line C: Large Equipment, highly automated or fluid processing only)

Number of Process steps = 6

(http://blog.pinoydeal.ph/pinoydeal/2011-minimum-wage-rates)

Operating Labor = PHP 0.37/kg EA

416

SCHEDULE AA-3

Direct Supervisory and Clerical Labor

In a manufacturing operation, a certain amount of direct supervisory and clerical assistance is always required. The necessary amount of this type of labor is closely related to the total amount of operating labor, complexity of the operation, and product quality standards. The cost for direct supervisory and clerical labor averages about 15 percent of the cost for operating labor.

15% (Operating Labor) from Peter and Timmerhaus, 5th Ed.

417

SCHEDULE AA-4

Utilities

A. Total Water Cost B. Total Steam Cost C. Total Electricity Cost Total Utilities Cost

PhP PhP PhP PhP

0.38/kg EA 4.03/kg EA 0.6076/kg EA 5.02/kg EA

A. Total Water Cost Cost: PhP 20.16/m3 H 2 O (Reference: http://122.54.214.222/waterrates/RatesTable.asp)

From Material and Energy Balance Equipment Heat Exchanger (H-1) Absorption Column (A-1) Oxidation Reactor (R-2) Condenser (C-1) Heat Exchanger (H-2) Condenser (C-2) Total Water Required/day 28,432.74 kg 16,000.00 kg 184,972.63 kg 81,722.91 kg 7,708.75 kg 42,365.28 kg 361,202.31 kg

418

419

B. Total Steam Cost Cost: PhP 1.45/kg steam (Steam Cost Computation, refer to page 298) From Energy Balance: Equipment Glycerol Preheater (B-1) Acrolein Preheater (B-2) Esterification Reactor (R-3) Total Steam Required/day 49,776.18 kg 1,955.53 kg 1,040.17 kg 52,771.88 kg

420

C. Total Electricity Cost Meralco Rate: PhP 10.8578/kw-hr (Industrial consumer) (Reference: http://meralco.com.ph/pdf/newsandupdates/2012/ NW00112.pdf)

1. Dehydration Reactor: P = 1.5 HP 1.1185 kW Operating Time = 24 hrs/day

= PhP 0.0153/kg EA 2. Heat Exchanger: P = 4 HP 2.9828 kW Operating Time = 24 hrs/day

= PhP 0.0409/kg EA 3. Absorption Column: P = 1.5 HP 1.1185 kW Operating Time = 24 hrs/ day

= PhP 0.0153/kg EA

421

4. Esterification Reactor: P = 13 HP 9.6941 kW Operating Time = 24 hrs/day

= PhP 0.1330/kg EA 5. Pervaporator: P = 7 HP 5.2199 kW Operating Time = 24 hrs/day

= PhP 0.0716/kg EA

Assuming that the Electricity Cost of three equipments is 45.45% of the Total Electricity cost,

422

SCHEDULE AA-5

MAINTENANCE AND REPAIR

Annual cost for equipment maintenance and repairs may range from 2% 20% of the equipment cost. Charges for plant buildings average 3% - 4% of the building cost. The total plant cost per year for maintenance and repairs ranges from 2% to 10% of the fixed capital investment.

6% (Fixed Capital Investment) from Peter and Timmerhaus, 5th Ed.

423

SCHEDULE AA-6

Operating Supplies

In any manufacturing operation, many miscellaneous suppliers are needed to keep the process functioning efficiently. These are not considered raw materials or maintenance and repair material but as operating supplies. Some of these items include charts, lubricants, test chemicals and custodial supplies. The annual cost for these types is about 15% of the total cost of maintenance and repair.

15% (Maintenance and Repair) from Peter and Timmerhaus, 5th Ed.

424

SCHEDULE AA-7

Laboratory Charges

These include the costs of laboratory tests for control of operations and for product quality control. This cost may be taken as 15% of the operating labor.

15% (Operating Labor) from Peter and Timmerhaus, 5th Ed.

425

EXHIBIT BB

FIXED CHARGES

Cost (PhP) / kg EA Depreciation Local Taxes Insurance Total PhP PhP PhP PhP 0.98 1.17 0.33 2.47

Schedule BB-1 BB-2 BB-3

TOTAL FIXED CHARGES = PhP 2.47/kg EA

426

SCHEDULE BB-1

Depreciation

The equipment, buildings and other material objects comprising a manufacturing plant require an initial investment that must be paid back and this is done by charging depreciation as a manufacturing expense. Depreciation rates are very important in determining the amount of income tax. Using Straight-Line Method:

Where: V = the original investment in the property at the start of the recovery period = the total purchase equipment cost delivered = PhP 52,871,959.77 n = length of the straight-line recovery period = 9.5 years, Manufacture of chemicals and allied products (Table 7-8 of Peters and Timmerhaus 5th ed., p. 310)

427

SCHEDULE BB-2

Local Taxes

The magnitude of local property taxes depends on the particular locality of the plant and the regional laws. Annual property taxes for plants in highly populated areas are ordinarily in the range of 2% - 4% of the fixed capital investment.

2.5% (Fixed Capital Investment) from Peter and Timmerhaus, 5th Ed.

428

SCHEDULE BB-3

Insurance

Insurance rate depends on the type of process being carried out in the manufacturing operation and on the extent of available protection facilities. These rates amount to about 0.7% of the fixed capital investment per year.

0.7% (Fixed Capital Investment) from Peter and Timmerhaus, 5th Ed.

429

EXHIBIT CC

PLANT OVERHEAD COST

In plant overhead costs, the expenditure required for routine plant services. Non manufacturing machinery, equipment, and buildings are necessary for many of the general plant services, and the fixed charges and direct cost for these items are part of the plant overhead cost.

60% (O.L. + Supervisory + M and R) from Peter and Timmerhaus, 5th Ed.

430

EXHIBIT DD

GENERAL EXPENSES

General expenses constitutes mainly of indirect cost on production.

It

includes Administrative Costs, Product distribution and as well as expenses for Research and development. From Plant Design and Economics by Peters and Timmerhaus, General expenses comprise for the 15-25% of the total product cost.

Cost (PhP) / kg EA Administrative Cost Distribution and Marketing Research and Development Total PhP PhP PhP PhP 0.65 6.07 2.76 9.48

Schedule DD-1 DD-2 DD-3

TOTAL GENERAL EXPENSES = PhP 9.48/kg EA

431

SCHEDULE DD-1

Administrative Cost

Salaries and wages for administrator, secretaries, accountants, computer support staff, engineering and legal personnel are part of the administrative expenses, along with cost for office supplies and equipment, outside communications, administrative buildings and other overhead items related to administrative activities.

20% (O.L. + Supervisory + M and R) from Peter and Timmerhaus, 5th Ed.

432

SCHEDULE DD-2

Distribution and Marketing Cost

Salaries, wages, supplies and other expenses for sales offices, commissions and travelling expenses for sales representatives, shipping expenses, cost of containers advertising expenses and technical sales services are included in this category.

11% (Total Product Cost) from Peter and Timmerhaus, 5th Ed.

TPC = Manufacturing Cost + Administrative Cost + Distribution and Marketing + Research and Development

433

SCHEDULE DD-3

Research and Development

Research and development costs include salaries and wages for all personnel directly connected with this type of work, fixed and operating expenses for all machinery and equipment involved, cost for materials and supplies and consultants fee.

5% (Total Product Cost) from Peter and Timmerhaus, 5th Ed.

434

CHAPTER VIII

ECONOMIC EVALUATION

435

CHAPTER VIII ECONOMIC EVALUATION

I.

INTRODUCTION Whenever a new project is to be considered, it requires a commitment of

capital funds also known as investment. Whenever investment is to be made to a certain project, it is important to evaluate the profitability of the project since the main purpose of the investments is to generate income. Total profit alone cannot be used as basis whether the project is profitable or not. If the goal of an investment is to merely earn a profit, any investment that gives profit would be acceptable regardless of how much and how long the return of the investment would be. The objective of the profitability analysis is to give a measure of the attractiveness or possibility of the project for possible course of action. It is therefore important to consider the profitability analysis method to be used in order to give a reliable measure of the economic feasibility of the project. There are various methods that can be used in determining the profitability. These methods are divided into those that consider the time value of money and those that are not. Methods that do not consider the time value of money includes: a) Rate of Return on Investment (ROI), b) Payback Period, c) Net Return. The methods that consider the time value of money are a) Discounted Cash Flow Rate of Return, and b) Net Present Worth. In this study, the methods used in

436

profitability analysis are the Rate of Return on Investment and Net Present Worth. Break Even analysis is also presented on the latter part of this chapter. II. Analysis and Interpretation At present time, there is no existing plant of Ethyl Acrylate in the country. For the purpose of economic evaluation of the project, the international market price is considered. The international market price of ethyl acrylate (Reference: ICIS Pricing) is US$ 1,810 per ton or nearly PhP 83.81 per kilogram. The Total Production Cost (TPC) for the proposed Ethyl Acrylate plant is found to be PhP 55.21 per kilogram. Since the Total Production Cost is lower than the selling price of the competitor, it is safe to say that the proposed plant will be profitable. Also, because the product is imported, 10-15% additional cost will be added to the price. A selling price of PhP 75.00 per kilogram of Ethyl Acrylate is therefore proposed. It is 10.50% lower than the international market price. A. Rate of Return on Investment Using the Rate of Return on Investment as the first method of analysis, we can be able to determine how fast the return on investment would be. Higher ROI value is advantageous for the project. Also, the higher the value of ROI, the better is the project because the faster will be the return on investment of the project. For a capital investment of PhP 331.43 M and a selling price of PhP 75.00 per kilogram of Ethyl Acrylate, the expected net annual profit amounts to PhP 437

112.82 M. Current loan rate is 18.05% (Reference: Bangko Sentral ng Pilipinas). In this case, the rate of return on investment is 34.04%, which means that the project is still profitable but the investment cannot be recovered immediately in one year of operation of the project. B. Net Present Worth In the second method of analysis which is the Net Present Worth method, the profitability of the project can be evaluated by comparing the net present cash inflows to the net present outflows. If the net present cash inflows or the net present worth equivalent of annual profit is higher than the net present worth of cash outflows or investments, then the net present worth of the project would be higher than zero indicating that the project is economically profitable. The higher the value of net present worth the better and more profitable the project is. For this project, the estimated net annual profit is equal to PhP 112.82 M. Using 20 years of operation of the plant and a minimum attractive rate of return (MARR) of 12.50% (Reference: Bangko Sentral ng Pilipinas), the calculated net present worth of the project is PhP 485.55 M. This is a positive value indicating that the project is profitable because the net present worth equivalent of the annual profit is significantly higher than the present worth of investment.

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C. Break-even Point Analysis To determine the rate of production of the plant capacity necessary in order to have a profit, the break-even point analysis must be considered. The production rate that would give a gross sales equivalent to total production cost is known as the break-even point because the net profit zero. The break-even point can be computed by dividing the total fixed cost by the difference of selling price and total variable cost. From the previous chapter, the fixed cost and variable cost (Total Direct Production Cost) amounts to PhP 13.89/kg EA and PhP 41.32/kg EA, respectively. Fixed cost comprises of Fixed Charges, Plant Overhead Cost and General Expenses. In this case, the calculated percent break-even point is about 41.23%. This means that the plant should always operate at a production rate higher than 41.23% of the actual plant capacity (5,700 MT EA/yr), corresponding to 2,350 MT EA/yr, in order to have a net profit. If the plant operated at a rate lower than 2,350 MT EA/yr, the plant will not be profitable on each operation.

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III.

Conclusion The main objective of this work is to demonstrate the economic advantage

of using glycerol as a major raw material in producing ethyl acrylate. Based on the analysis, the project would be profitable. This is evident since the attained net present worth equivalent of the annual profit is a positive value. Also, the project would yield a high rate of return on investment (34.04%) which implies that the project is worth investing for. In conclusion, this plant design would absolutely be economically feasible.

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IV.

Detailed Computations

A. Rate of Return on Investment

Profit Estimation (Z) Using the equation presented by Peters & Timmerhaus in Plant Design and Economics for Chemical Engineers:

Where:

n Z TCI

= Plant Capacity, kg/yr = Net annual profit, PhP/yr = Total capital investment

The proposed market price of Ethyl Acrylate is PhP 75.00/kg EA Plant Capacity is 5,700,000 kg/yr
TPC =PhP 55.21/kg TCI = PhP 331,427,349.49

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B.

Net Present Worth Calculation

From Bangko Sentral ng Pilipinas, the loan interest for long term period (more than 5 years) is 12.50%. From Plant Design and Economics for ChE by Peters & Timmerhaus

Where:

PW A i n

= present worth equivalent of net annual profit = net annual profit = annual interest rate = period of operation = 20 years

Estimated net annual net profit is PhP 112,821,716.88 Initial investment is PhP 331,427,349.49

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C. Break-even Point (BEP)

At break-even point, net annual profit (Z) = 0

Where:

= Fixed Cost, PhP/ yr = Fixed Charges + Plant Overhead Cost + General Expenses

S V

= Selling Price, PhP/ kg = PhP 75.00/kg EA = Variable cost, PhP/kg

From Cost Estimation: Fixed Charges = PhP 2.47/kg EA Plant Overhead Cost = PhP 1.94/kg EA General Expenses = PhP 9.48/kg EA Variable Cost (Total Direct Cost) = PhP 41.32/kg EA

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