Contents

1. 1.0 Introduction ......................................................................................................................... 1 2. 2.0 Butenediol Production Process ............................................................................................ 1 3. 3.0 Comparisons of the Key Process .......................................................................................... 2 4. 4.0 Process Description .............................................................................................................. 6 5. 5.0 Design Synthesis Approach .................................................................................................. 6 6. 6.0 Process Synthesis Approach ................................................................................................ 7 7. 7.0 Distillation Sequencing......................................................................................................... 7 8. 8.0 Reference ............................................................................................................................. 9

1.0 Introduction
This report addresses the process design and synthesis of a butenediol production plant of an annual production rate of 1600Mt/year at operational hours of 10 hours per day. Three alternative methods of manufacturing of butenediol have been identified, studied and compared in terms of economic potential, safety and environmental impact to ensure a profitable, safe and sustainable design is synthesised. Butenediol is an odourless and almost colourless or pale yellow liquid that is miscible with almost all organic solvents and water. It has a boiling and melting point of 235C and 10C respectively with a specific gravity of 1.067 and vapour density of 3.0. In terms of safety, it is harmful if swallowed and if in contact it can cause irritation to the skin, respiratory system and eyes. In general, butenediol has a large number of applications and it is widely used in pharmaceuticals, textile, and agriculture and polymer industries, in resin manufacturing and also in synthesising of chemical intermediates. Furthermore having 2 replaceable hydroxyl groups and one double bond a large number of chemicals and intermediates are possible from its downstream processing.

Used as a starting material for the production of endosulfan, a commonly used insectide by Diels-Alder reaction of butenediol with hexachlorocyclopentadiene. Hydroformylation of butenediol in the production of Vitamin A. Used for the production of pyridoxine (Vitamin B6) and as bactericide. Used as an additive in paper industry and as a stabilizer in resin manufacture. Lubricant for bearing system and in the synthesis of allyl phosphates Used in the synthesis of diarylate monomer. Used in the preparation of biologically active haloacetate.

2.0 Butenediol Production Process

The three alternative processes practised industrially in producing butenediol are: I. Ethynylation reaction in which formaldehyde and acetylene are reacted in the presence complex cuprous acetylide catalyst to generate butynediol which then further undergo partial catalytic hydrogenation to produce the desired product butenediol. Vapour phase chlorination of butadiene to obtained a mixture of 3, 4-dichlorobutene and 1, 4-dichlorobutene which then undergo hydrolysis process in an aqueous alkaline solution to produce the desired product. Process for the preparation of 2-butene-1, 4-diol comprising contacting a mixture of water and 1, 2-epoxy-3-butene with a catalyst comprising a metal halide, zeolite and a non-protic solvent.

II.

III.

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3.0 Comparisons of the Key Process

Process Ethynylation of formaldehyde to 1,4butynediol, followed by hydrogenation of 1,4-butynediol to 2-butene-1,4-diol Step 1: CH2O + 2C2H2 HOCH2CC CH2OH + CHCCH2OH Step 2: HOCH2CC CH2OH + 3H2 HOCH2CH=CHCH2OH + HOCH2CH2CH2CH2OH Step 1: Temperature: 90C Pressure: 400kPa Catalyst: Cuprous Acetylide Step 2: Temperature :60C Pressure: 550kPa Catalyst: Pd/ Activated Carbon Fibre Chlorination of 1,3-butadiene to dichlorobutenes, which then undergoes chlorination to 2-butene-1,4-diol Step 1: CH2=CHCH=CH2 + Cl2 ClCH2CH=CHCH2Cl Step 2: ClCH2CH=CHCH2Cl + 2HCOONa + 2H2O HOCH2CH=CHCH2OH + 2HCOOH + 2NaCl Step 1: Temperature: 70-175C Pressure: 1atm Step 2: Temperature: 70-150C Pressure: 1atm Catalyst: Copper Selective hydrolysis of 1,2-epoxy-3-butene directly to 2-butene-1 ,4-diol Step 1 CH2=CH-CH=CH2 +O2 CH2=CHCHOCH2 Step 2 CH2=CHCHOCH2+ H2O HOH2CCH=CHCH2OH For step 1 Temperature: 120-350 C Pressure: 1-3bar Catalyst: Silver For step 2 Temperature: 75C Pressure: 3bar Catalyst: Potassium Iodide, Zeolite, non protic solvent Step 1 Butadiene is contacted with an oxygencontaining gas in the presence of certain silver catalysts. Obtaining a high yield of epoxybutene also requires the presence of an inert gas diluent in the gas feed to the epoxidation zone. Step 2 2|Page

Reaction

Operating Conditions

Reactants

Step 1: Mixing acetylene and formaldehyde before feeding to the reactor containing copper acetylide catalyst in the absence of gas phase to produce the intermediate product 1,4-butynediol. Step 2: Reacting 1,4-butynediol with hydrogen as a

Step 1: Involves the use of substantially plug flow technique of reacting chlorine vapour and butadiene vapour resulting in high yield of dichlorobutenes. Step 2: Hydrolysing dichlorobutenes in the presence of water by using aqueous solution of

limiting reactant by using activated carbon fibres with impregnated Palladium (PD/ACF) as catalyst to yield 2-butene-1,4-diol. Economic Potential The by-product butanediol is used crosslinking agent for thermoplastic urethanes, polyester plasticizers, paints and coatings, copolyester hot melt and solvent-borne adhesives whereas butanol primarily used as a solvent, as an intermediate in chemical synthesis, and as a fuel. By mixing the gaseous acetylene and aqueous formaldehyde outside the reaction vessel, capital cost on designing the reaction chamber to withstand about ten to twelve times the operating pressure can be compromised. Catalyst can be used for a much longer on stream periods because the pressure losses are much less with a single phase feed passed through a fixed bed reactor. Lower mechanical stresses occur. Using platinum based catalyst hydrogenation reaction eliminates formation of side products butraldehyde, crotyl alcohols,butanol acetals thus increasing selectivity of desired product. for the like and the

sodium formate and copper as a catalyst contribute to high yield and selectivity of 2butene-1,4-diol. The by-product formic acid is used in finishing textiles and paper and in the manufacture of insecticides and fumigants. Sodium chloride is heavily used in various industrial uses.

The epoxybutene is reacted with water to produce butenediol.

To recover the epoxybutene in the first step directly from the epoxidation effluent a series of compressors are required to compress the gaseous effluents to pressure sufficiently high to liquefy the epoxybutene. This would drastically increase the capital Formic acid is corrosive at high cost. concentration may corrode the pipelines in long term, thus corrosion resistant pipelines Plus series of heat exchangers are also should be acquired which add ups the needed to remove the heat of compression capital cost. and maintain the epoxybutene at a temperature which would minimise the byBy adding of hydroxide/ product formation. carbonate/bicarbonate salt after the reaction, formate can be reused repeatedly. By just adding water at 100-400C to the gaseous feed the deactivated catalyst can be reactivate to its original activity.

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Downside

Nil

Reactor wall temperature if not maintained near the vapour phase mixture cause the accumulation of liquid products on the walls of the reactor. Higher temperature causes build-up of coke like material on the reactor wall. If the temperature of the reactants or the wall is so low as to allow condensation or if the temperature exceeds 230C, the undesired products increased.

If the recovery of the epoxybutene from the epoxidation effluents is not done under mild condition, it will favour yield of undesired products.

Environmental Acetylene: This gas will be dissipated rapidly in well-ventilated areas. Due to its low solubility it would be rare for water to become critically polluted from accidental releases. Not expected to be harmful to aquatic life. Biodegraded through various plant and bacterial systems by inactivating atmospheric acetylene through their nitrogen- fixing mechanisms. Its a simple asphyxiant gas. Formaldehyde: It biodegrades readily in air, water and soil under both aerobic and anaerobic conditions. Butenediol, Butanediol Readily biodegradable Stable in water, no hydrolysis reaction. Butanol

Butadiene butadiene evaporates to the air, even from water and soil; and butadiene breaks down quickly in sunlight and degrades in the air with a half-life of less than two hours. Chlorine Causes environmental harm at low levels. Harmful to organisms living in water and soil. It reacts with other chemicals in water and air to form chlorinated chemicals. Because of its reactivity, chlorine is not likely to move through the ground and enter groundwater Sodium Formate Readily biodegradable not harmful to aquatic organisms Formic Acid Readily biodegradable

3,4-epoxy-1-butene Readily biodegradable 1,3-butadiene Slightly toxic to aquatic

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Safety

Contribute to the formation of Harmful to aquatic organism ; alter pH photochemical smog when it reacts with other volatile organic carbon substances in air. Because 1-butanol is readily soluble in water, the chemical is expected to be fairly mobile in the soil and may leach into groundwater. Absence of coherent gaseous acetylene The material of construction of the entire phases eliminates the chances of explosion. system should be one which does not interfere with the chlorination reaction or To ensure reaction chamber is completely promote retention of condensate filled with liquid, a liquid withdrawal means are provided at the uppermost point of the Chlorine gas is very poisonous and forms chamber so that formation of cavities in hydrochloric acid when react with the which gases could collect can be avoided. moisture in air causing excessive corrosion. Dilution of acetylene with inert nitrogen gas and stainless steel walled reactor is used to work safely with acetylene at pressure up to 200atm Acetylene cylinders are isolated from oxygen and other oxidisers because it is an extremely flammable and unstable gas. At certain condition it decomposed explosively to its constituent elements. Formaldehyde is a highly toxic regardless of the method of inhalation. Hydrogen gas poses an immediate fire and explosive hazard when concentrations exceed 4%. Formic acid concentration. is corrosive at

Reactor is design in shell and tube design so that it allows removal of the heat of reaction in order to prevent an exothermic temperature excursion from occurring. Oxygen concentration varies for the type of inert diluent used its strictly kept below the explosive limit.

high By adding inert to the reactor containing hydrocarbon and oxygen, prevent the mixt ure from igniting causing explosion.

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4.0 Process Description

Acetaldehyde and a mixture of formaldehyde, water and methanol are fed into a packed bed reactor, PBR-01 operating at 90C and 4.5 bar. The main reaction is the formation of 1,4-butynediol and the side reaction is the formation of propagyl-ol. All of the products formed, the side products and the unreacted raw materials are discharged from the liquid outlet. The mixtures are separated through distillation in DC-01 and high purity methanol is formed in the vapour outlet. The liquid outlet is fed into DC-02 to separate out 1,4-butynediol from other components, which mainly consists of water vapour. Water and some impurities in overhead stream are condensed before sent for wastewater treatment. 1,4-Butynediol and hydrogen gas is fed separately into a continuously stirred reactor at a temperature and pressure of 60 C and 6 bar. The main reaction is the hydrogenation of 1,4-butynediol to 2-butene-1,4-diol while side reactions are the further hydrogenation of 2-butene-1,4-diol to 1,4-butanediol and the hydrogenation to butanol with the removal of water. The liquid outlet from the reactor is then passed to DC3 where the desired product 2-butene-1,4-diol is separated from the reaction mixture. The top distillate from DC3 are produced in trace amounts, therefore they are stored and subsequently flared. The bottom distillate is further purified with DC4 to separate 2-butene-1,4-diol from 1,4-butynediol and traces of other elements. This gives a final product with a high purity of 97% while 1,4-butynediol is recycled back into the reactor.

5.0 Design Synthesis Approach

Fluid Package Selection NRTL is used for the ethynalation of formaldehyde to solve the vapourliquid equilibrium and liquid-liquid equilibrium while for hydrogenation of butynediol, PSRV is used as non-ideal chemicals such as alcohol is present in the system. For the hydrogenation process, hydrogen gas is set as the limiting reactant to lessen the continuous hydrogenation of butynediol to butanediol. For ethynalation of formaldeyde to butynediol, formaldehyde is the limiting reactant to maintain reaction selectivity at high value The annual production of butynediol in 2008 was 5000 tonnes/year. Taking a 5% increase in demand every year, the plant is built with a capacity of 1600t/year to meet the demand. Before recycling the liquid stream of DC2 to the reactor, one tenth of the flow is purged to prevent accumulation in the system. 1) Gaseous waste from the hydrogenation reactor and the distillation columns can be flared. Hydrogen gas exiting the hydrogenation reactor can be used as a part of the fuel element, in addition to fresh fuel sources. 2) Liquid waste consisting of water with traces of impurities is to be sent for wastewater treatment.

Limiting Reactants

Basis of Production

Purge Stream Waste Management

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Reactor Selection

A packed bed reactor with immobilised catalyst is chosen to be used for ethynylation of formaldehyde to prevent catalyst leaching. For hydrogenation of butynediol, a stirred tank is chosen to increase mass and heat transfer. No Vapour Flowrate in R1 There is no vapour flowrate in R1 because formaldehyde gas is fully used up (set as the limiting reactant) while methanol, reaction product butynediol and side product propagyl-ol are liquid at reactor conditions, therefore exit through the liquid outlet Throttling Valve Butynediol recycle stream is cooled to a lower temperature before a throttling valve is used to reduce the pressure. This is to prevent any possible damage due to excessive heat.

6.0 Process Synthesis Approach

The heuristics applied for the process synthesis are as follows: 1) Butynediol is used in excess as it is not toxic or flammable at the operating temperature and hydrogen is used as the limiting reactant to reduce of the risk of explosion, should any leakages occur. 2) The liquid stream of DC2 is purged at a rate of one tenth of its flow to prevent accumulation in the system. The reason for purging is due to difficulty of separation of butynediol from the other components in the stream. 3) The pressure of acetylene is first raised using a compressor before the temperature is adjusted to reactors requirement using a heater. This is to ensure the temperature matches exactly the required value. 4) The reaction conditions and catalyst used are set to obtain the highest yield and minimise the by-products formation; this is done with referring to patents and journals. 5) The compression ratio of acetylene gas is using a one-stage compressor is set <4, at 3.2

7.0 Distillation Sequencing

The first need to determine distillation sequencing came into the picture when methanol , water and 1,4-Butynediol ( Boiling point of 64oC, 100oC and 238OC respectively ) needed to be separated. Since there are 3 products here, the number of possible distillation sequences are: Ns =
( ( ) )

, P = Number of products = 3.

Solving the equation will result in a total of 2 possible

sequences being applicable here. The sequence chosen was to separate methanol from the mixture first, then followed by the separation of water and 1,4-Butynediol . This sequence, based on heuristics, was chosen because:

1)

Methanol is thermally unstable and will fully vaporise at relatively lower temperatures than water and 1,4-Butynediol.

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2) This sequence is better in the sense of pure final products one by one are removed as distillates and 1,4-Butynediol , which is the raw product to the 2nd reactor, is separated with 99% purity. 3) Separation points are sequenced in order of decreasing relative volatility so the more difficult (1,4-Butynediol -water) separation is made in the absence of methanol. Also, to prove that this sequence is the more cost effective approach, Marginal Vapour Flow (MVF) calculation was performed. The vapour flow plays a role in the required column diameter and trays, and also reflects the utility costs. The results are displayed in the table below: Distillation Sequence A/ BC , B / C AB / C , A/B Marginal Vapour Flow 0.0014 14.85 A = Methanol, B = Water, C = Butynediol

Table 7.1 : Comparison between distillation sequence and marginal vapour flow. The sequence with a lower MVF is favoured, hence proving that the sequence chosen for our design is the best possible sequence. Similarly, using the same techniques, the distillation sequencing to separate butanol, 2-Butene-1,4diol and 1,4-Butynediol is determined. However, some contradictions with the heuristics on sequences selection may occur as they do not apply for all cases and need to be treated with logical thinking. Components with the greatest molar percentage in the feed, which is 2-Butene-1,4-diol could not be separated first. This is because the separation of butanol, which has a greater relative volatility compared to 2-Butene-1,4-diol, can be done easier. Besides, as 2-Butene-1,4-diol is the desired product, separating it from a mixture of impurities still in the system will affect its final purity.

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8.0 Reference
United States Patent. 1996. Process the Preparation of 1,4 Butenediol. [ONLINE] Available at: https://docs.google.com/viewer?url=patentimages.storage.googleapis.com/pdfs/US5530167.pdf. [Accessed 21/10/2013]. United States Patent. 1999. Process for the preparation of 1,4 butenediol from epoxybutene. [ONLINE] Available at: https://docs.google.com/viewer?url=patentimages.storage.googleapis.com/pdfs/US5959163.pdf. [Accessed 21 October 13]. United States Patent. 1997. preparation of 3,4 epoxy,1-butene. [ONLINE] Available at: http://www.google.com/patents/US5618954. [Accessed 21 October 13]. United States Patent. 1998. recovery of 3,4 epoxy 1 butene from 1,3 butadiene oxidation effluents. [ONLINE] Available at: http://www.google.com/patents/US5756779. [Accessed 21 October 13]. Journal of Japan Petroluem Institute. 2008. catalytic hydrogenation of 2 butyne 1,4 diol activity, selectivity, and kinetic studies. [ONLINE] Available at: http://scitation.aip.org/content/aip/journal/jcp/70/5/10.1063/1.437772. [Accessed 21 October 13]. European Patent Specification. 1980. A process for the preparation of 1,4 butynediol and related catalyst. [ONLINE] Available at: https://data.epo.org/publication-server/rest/v1.0/publicationdates/20130814/patents/EP2420051NWB1/document.pdf. [Accessed 21 October 13]. United States Patent. 1977. Chlorination of Butadiene. [ONLINE] Available at: https://docs.google.com/viewer?url=patentimages.storage.googleapis.com/pdfs/US4049729.pdf. [Accessed 21 October 13]. United States Patent. 1975. process for preparing 2 butene 1,4 diol from dichlorobutenes. [ONLINE] Available at: https://docs.google.com/viewer?url=patentimages.storage.googleapis.com/pdfs/US3911032.pdf. [Accessed 21 October 13]. United States Patent. 1984. process for the catalytic hydrogenation of 1,4 butynediol to 1,4 butanediol. [ONLINE] Available at: https://docs.google.com/viewer?url=patentimages.storage.googleapis.com/pdfs/US2953605.pdf. [Accessed 21 October 13].

United States Patent. 1976. process for the manufacture of butynediol. [ONLINE] Available at: https://docs.google.com/viewer?url=patentimages.storage.googleapis.com/pdfs/US3957888.p df. [Accessed 21 October 13].

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