CHE553 Advanced Petroleum Refining Engineering

Prof. Hamid M. Mustafa Department of Chemical Engineering King Saud University, KSA

Office 2B42 Phone: 4676854

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REFERENCES:
1.

2. 3.

4.

5.

Gary, J.H. and Handwerk, G.E Petroleum Refining Technology and Economics, 4th edition, Marcel Dekker Inc., New York, 2001. Nelson, W.L. Petroleum Refinery Engineering, 4th edition, McGraw-Hill, New York, 1980. Mayers, Robert A., editor Handbook of Petroleum Refining Processes,2nd edition, McGraw-Hill, New York, 1997, 3rd edition,2003. Institute of Petroleum (IP), Lucas, Alan G., editor Modern Petroleum Technology, 6th edition, part 2, John Wiley and Sons Ltd, 2000. Institute of Petroleum (IP), Richard A. Dawe (Editor), modern petroleum technology, volume 1, upstream, 6th edition, 6th edition, part 1, John Wiley and Sons Ltd, 2000.

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Introduction Problems facing the refining industry Processing options Refinery configuration Factors affecting configuration Common refinery units , Offsite facilities, Refinery utility systems Crude oil assays Topping unit feed charge systems Blending components Multiple grade products Residual oil upgrading options Future trends influencing refinery configuration

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Thermal cracking Cracking process, cracking catalysts and reaction mechanisms Catalytic cracking Catalytic cracking reactions and reaction mechanisms Catalysts, zeolites Upgrading and treating of FCC feed FCC units , reactor and regenerator models Two stage regenerators Heat balance of FCCU Coke burning Flue gas energy recovery FCCU yield estimation calculations Recent advances in FCC technology Hydrocracking The process, catalysts and reaction mechanisms Recent advances
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Gasoline production Blending streams Production units in a modern refinery Quality, characteristics and specifications Gasoline and driving performance Octane provision and the environment

Additives Oxygenates, TBE, ethanol etc Search for environment friendly additives

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Alkylation Introduction Alkylation chemistry Feed preparation Catalysis Processes and processes configuration Recent developments and future perspectives Solid acid catalysts

Polymerization Introduction Polymerization chemistry, catalysts Comparison to alkylation Refinery scheduling, Product blending to specifications and use of LP.

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Refinery Process Chart

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The primary products of the industry fall into three major categories:
Fuels (motor gasoline, diesel and distillate fuel oil, liquefied petroleum gas, jet fuel, residual fuel oil, kerosene and coke)

Finished nonfuel products (solvents, lubricating oils, greases,

petroleum wax, petroleum jelly, asphalt, and coke)

Chemical industry feed stocks (naphtha, ethane, propane,

butane, ethylene, propylene, butylenes, butadiene, benzene, toluene, and xylene).

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The Refinery

Petroleum refining begins with: crude oil distillation, followed by subsequent processing such as chemical treating, catalytic reforming, hydrotreating, hydrocracking, fluid catalytic cracking and thermal cracking to produce a wide variety of petroleum products. The capacity of the refinery is typically defined by the total capacity of atmospheric distillation units operating in the refinery.

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Common refinery processing units

Crude distillation unit Vacuum distillation unit Catalytic reformer Alkylation unit Hydrocracker Hydrotreater / hydrofiner

fluid catalytic cracker unit

coking unit isomerization unit visbreaker

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The refinery configuration depends on:

1- The 2- The

type of crude most available to the refinery ; and

market requirements for certain products having specifications enforced by the law ; and

3- That

the refinery facility is to work in accordance with environmental and health regulation and bylaws

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No two refineries are identical Once the refinery is constructed switching to another type of crude or change of the product distribution (because of product demand pattern changes or specification changes or environmental and health regulations) will be difficult. Refinery equipment are expensive and long life hence not easy to replace or modify.

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The petroleum refining industry has felt considerable economic pressures arising from a number of factors including:
Oil pricing

Compliance with safety and environmental regulations

Slow rate of increase of demand

Increased costs of labor

The elimination of government subsidies

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Recent and future environmental and safety regulatory changes force the petroleum refining industry to make substantial investments in:
Upgrading certain refinery processes Reducing emissions Alter product compositions

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PROBLEMS FACING REFINERS

Crude oil: availability and quality Oil Price: World oil security, regional groupings, conflicting interests,
OPEC, other suppliers, state-owned oil companies, dominant private companies, regional instability and conflicts

Changing demand and consumption patterns

New automotive engine designs with different fuel requirements

Elimination of leaded gasoline Changing product qualities and specifications Octane race, octane boosting additives, alky lead, oxygenates,
MTBE, ethanol ,etc

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 Ever changing Environmental and health requirements, legislations and

regulations: olefins and aromatics

Altering product formulation, RFG

Emissions regulations and limits:

HCs, CO, NOx, SOx , VOCs, Ozone, PM10, PT

Limited sulfur-content in residual and distillate fuels TRI control, quality monitoring , cost effective means to reduce
emissions

Conservation and Greenhouse effect Alternative Energy Sources New facilities, expansion of existing facilities, additions and modifications
Can you think of more?!!!
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Processing options

Separation based on molecular size and boiling point Changing the molecular size of components Changing the molecular shape of components Removal of contaminants

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Refinery configuration options

Skimming or topping refinery Hydroskimming refinery Conversion refinery

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Factors affecting configuration

Geographical location Products demands Local products specifications and prices Crude available for the refinery

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Multiple grade products

Premium and regular gasolines Kerosene and jet fuel

Diesel and heating oil

Low and high sulfur fuel oils etc.

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Blending Components

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Offcites
Intermediate tankage
Blending Final product tankage Product loading Effluent water Firewater Flare Infrastructure

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Utilities Systems

Steam Electric power Boiler feedwater/ steam condensate Fuel gas Fuel oil Cooling water Nitrogen Plant air Instrument air Raw water Drinking water

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Future Trends influencing refinery configuration

12-

Installation of additional units for production of high quality and fewer contaminants to the environment, particularly for gasoline and diesel. Movement towards economy of scale - large capacity and high conversion refineries Movement towards integration of petrochemical facilities
Power and steam generation becoming high-value products

34-

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The atmospheric distillation unit feed charge systems:

Non-preflash system: crude is sent directly to the atmospheric tower without being processed in any preliminary separation equipment (flash drum or fractionation tower).
Preflash drum system: the desalted crude is heated and preflashed in a flash drum where water and light hydrocarbons are separated and sent directly to the atmospheric tower, the flashed liquid is further heated by heat exchangers and a crude oil furnace and then sent to the flash zone of the atmospheric tower.

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Dual flash system: this is used when it is necessary to process two or more kinds of crude oil having different properties (i.e. sulfur content of residue).
Prefractionator system: a prefractionator is installed to remove gas and a part of the naphtha fraction from the crude oil. This is used for crudes that are rich in gas and naphtha fractions. It is also suitable when the capacity of an existing unit is to be increased.

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The atmospheric distillation unit is one of the largest energy consuming plants in the refinery. It has a complex network of heat exchangers to transfer heat from the hot product streams to the feed. Most refineries import different kinds of crude oils and process them by switching at short intervals. Switching of the crude oil will disturb the steady operation of the atmospheric distillation unit. To overcome this problem advanced control technologies such as Model Predictive Control (MPC) has been successfully applied. With the objectives of: 1- stabilizing product properties 2- improving product yields 3- saving energy 4- automation of crude switch and change in the operation mode.

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Environmental Requirements
The petroleum refining industry is unique, that the environmental requirements aimed at the industry are of two basic types: 1- Requirements mandating specific product qualities for the purpose of reducing the environmental impacts associated with the downstream use of the product. [altering the product formulation with the aim of reducing pollutant releases from use of the finished products (primarily fuels)]. 2- Requirements directed at reducing the environmental impacts of the refineries themselves.

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The slower rate of increase of demand for refined petroleum products is due to
Conservation polices Rising costs of compliance with environmental and safety requirements

The development of substitutes for petroleum

products Increasing prices of petroleum products

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http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html SECTION IV: CHAPTER 2 PETROLEUM REFINING PROCESSES

I. II. III. IV. V. VI.

Introduction Overview of the Petroleum Industry Petroleum Refining Operations Description of Petroleum Refining Processes and Related Health and Safety Considerations Other Refinery Operations Bibliography

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Crude oil Assays

The information provided by a crude oil assay covers
1.

Physical and chemical properties of the crude oil itself. Gravimetric and volumetric breakdown into prescribed fractions.

2.

3.

Some physical and chemical properties of the derived fractions. and

It may also include information on the vacuumflashed yields of atmospheric residue and the associated stream properties.

4.

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The physical and chemical properties of the crude oil provide initial information pertaining to its description and handling requirements:

The density , sulfur and Conradson Carbon Residue values enable preliminary classification of the crude.

The viscosity and pour point determines if any storage and handling conditions are required ,such as heated storage and loading facilities.
The Total Acid Value (TAN) indicates if any special metallurgy needs to be considered in the processing equipment as a result of acid corrosivity of the crude oil.

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A high vapor pressure would indicate increased potential for loss during transport and storage. The metals content of the crude oil, which concentrate in the residue, is a significant impurity if the residue is to be used as feedstock for cracking. Analysis of the of the lighter hydrocarbons present in the crude, enables the refiner to identify any abnormal distribution as well as potential light ends constraints.

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The gravimetric and volumetric breakdown into different fractions is done in laboratories using the TBP equipment. This fractionation gives yield data comparable to that obtained in an industrial distillation unit. The relative yields of distillate fractions and their properties give crude oils their value.

Crude distillation curves pp 30-35 , Gary, J.H. and Handwerk, G.E Petroleum Refining Technology and Economics, 4th edition.

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Crude Quality
Typical Analysis of some crudes
Property
Talih-1 Sudan
43.3 0.01

Arab Extra Light

38.5 1.1

Alameen Egypt
33.4 086

Heglig Sudan
32.3 0.05

Arab Heavy
28.0 2.8

Bakr-9

Egypt
20.9 3.8

Gravity, API
Sulfur content (wt%)

Iron (ppm)
Nickel (ppm)

36 1.6

0.4 0.6

0.0 0.0

60 10

1.0 9.0

108

Vanadium (ppm)
Pour point (F)

1.3

2.2

15

0.9

40

150

60

35

80

-11

55

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Source: Mustafa, H.M., local citation,.2002 and chemistry of petrochemical processes www. gulfpp.com,2001.

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Metal levels of Crudes and residua

Feed
Arabian light Kuwait South belridge (California) Morichal (Venezuela) Arabian Heavy Arabian Heavy AR Beta (Los Angels Beach) Beta AR Beta VR Liaohe (China) Talih (Sudan) Heglig (Sudan)
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Fe (ppm)
35 19 <3 6 60 60 105 78.7 36 60

Ni (ppm)
10 8 60 75 17 28 104 115 296 276.3 1.6 10

V (ppm)
6 30 57 282 55 93 135 220 382 1.3 1.3 <1
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Trace metals in crude

Crude oils contain trace metals V, Ni, Fe in varying quantities The refinability of crudes depends partly on metals content. Metal content in the crude can severely affect the activity of the catalysts and result in lower-value product distribution. The higher ( Ni and V) concentrations imply generally harder processing. Vanadium in fuel oil causes corrosion to turbine blades and refractory of furnace linings and stacks.

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The three factors affecting the technological development of the oil industry.

Economics Safety Environment

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