PETROCHEMICAL TECHNOLOGY

CHE 464Professor Yahia Abobakr Alhamed

Chairman Chemical and materials Engineering Department

King Abdulaziz UniversityOffice: building 45 _Room 201E-mail: yhamed@kau.edu.sa

Course Outline

TEXT BOOKTEXT BOOK

Sami Matar and Lewis F. Hatch, Chemistry of Petrochemical Chemistry of Petrochemical

Processes, Second Edition, Gulf Processes, Second Edition, Gulf Professional Publishing, 2001Professional Publishing, 2001

Course Outline (Cont)

• Grade Distribution – Major Exam I = 20– Major Exam II = 20 – Term Paper = 20– Final Exam = 40

Course Outline (Cont)

Week

Topics Covered

1 Introduction and overview of petrochemical industries in Saudi Arabia. Major producers of petrochemicals in Saudi Arabia Major petrochemicals produced Economical importance of petrochemical industries in Saudi Arabia Review of chemical engineering processes in petrochemical Industries

2-3 Petrochemicals from methane Synthesis gas

- Chemicals from synthesis gas - ammonia - Urea - Nitric acid - Methanol

Methanol

- Formaldehyde - Acetic acid - Methylamines - Methanol future

Course Outline (Cont)

4-5 Production of olefins Olefins feedstocks

- gas feedstocks - liquid feedstocks - Other processes

Hydropyrolysis Millisecond pyrolysis Coproduct treatment

6-7 Petrochemicals from ethylene Ethylene oxide and ethylene glycol Vinyl chloride Ethylbenzene Ethanol Acetaldehyde Vinyl acetate Acrylic acid (Major exam I)

Course Outline (Cont)

8-9 Petrochemicals from propylene and higher olefins Acrylonitrile Propylene oxide Isopropanol Acrolein Disproportionation reactions Cumene Acetic acid Maleic anhydride MTBE

Course Outline (Cont)

10-11 Petrochemicals from benzene toluene and xylenes Benzene

- Ethylbenzene - Styrene - Cumene - Phenol - Linear alkylbenzene - Maleic anhydride - Cyclohexanol and cyclohexanone - Adipic acid

The methylbenzenes - Toluene - Benzene and xylene production - o-xylene - m-xylene

Course Outline (Cont)

11-12 Thermoplastics, thermosetting and engineering resins polyethylene PVC Poypropylene Polystyrene Thermosets' Engineering resins (Major exam II)

13-14 Term paper presentations Each student is asked to prepare a term paper about a selected petrochemical. Each student should make a 15 minute class presentation followed by 7 minutes question period. The performance of the student is evaluated by the instructor based on the quality of the term paper, presentation and question answering.

Something VERY Important about Term Paper

حتىال العربيه باللغه أكتبهاأيغموض هناك يكون

عقابها العلميه السرقةوسوف المقرر الرسوبفي

أي بدون القول هذا يطبقتساهل

السرقات عن للكشف متوفرهـ برامج هناك كماتعلمون و العلمية

Petroleum and Natural Gas (NG)• Major source of energy

• Source of almost all raw materials used in petrochemical industries.

• Petroleum and Natrural gas respurces are not resources are limited and not renrewable.

• With time it becomes more expensive to produce petroleum and NG.

Petroleum

Petroleum (Cont.)

Petroleum (Cont)

Petroleum (Cont)

COMPOSITION OF CRUDE OILS (Cont.)

The crude oil mixture is composed of the following groups:

• 1. Hydrocarbon compounds (compounds made of carbon and hydrogen).

• 2. Non-hydrocarbon compounds.

• 3. Organometallic compounds and inorganic salts (metallic com- pounds).

COMPOSITION OF CRUDE OILS (Cont.)

Hydrocarbon Compounds (Cont.)– All hydrocarbon classes are present in the crude

mixture, except alkenes and alkynes.

• Alkanes (Paraffins)

• CnH2n+2.

• C1 to C3 alkanes are usually found associated with crude oils in a dissolved state.

• Normal alkanes (n-alkanes, n-paraffins)• Isoparaffins

COMPOSITION OF CRUDE OILS (Cont.)Examples of some Alkanes

COMPOSITION OF CRUDE OILS (Cont.)

Hydrocarbon Compounds (Cont.)

• Cycloparaffins (Naphthenes)• Saturated cyclic hydrocarbons, normally known as

naphthenes

COMPOSITION OF CRUDE OILS (Cont.)Hydrocarbon Compounds (Cont.)

Aromatic Compounds• Lower members of aromatic compounds are

present in small amounts (e.g. Benzene, toluene, and xylenes (BTX) ) in crude oils and light petroleum fractions.

• Binuclear aromatic hydrocarbons are found in fractions heavier than naphtha.

• Trinuclear and polynuclear aromatic hydrocarbons, in com bination with heterocyclic compounds, are major constituents of heavy crudes and crude residues.

COMPOSITION OF CRUDE OILS (Cont.)Examples of Aromatic Compounds

COMPOSITION OF CRUDE OILS (Cont.)

Sulfur Compounds

• H2S is the only important inorganic sulfur compound found in crude oil and it is very corrosive.

• Organosulfur compounds classification:-– Acidic sulfur compounds are the thiols

(mercaptans).– Non-acidic sulfur compounds are thiophene,

sulfides, and disulfides.

COMPOSITION OF CRUDE OILS (Cont.)

• Examples of some sulfur compounds

COMPOSITION OF CRUDE OILS (Cont.)

Nitrogen Compounds• The nitrogen content 0.1 wt% to 0.9 wt%• Nitrogen compounds are concentrated in

heavier petroleum fractions and residues. • Basic nitrogen compounds are mainly those

having apyridine ring. • Non-basic compounds have a pyrrole

structure. • Both pyridine and pyrrole are stable

compounds due to their aromatic nature.

COMPOSITION OF CRUDE OILS (Cont.)

Petroleum Refining products and Processes

Petroleum Refining products and Processes (Cont.)

Vacuum Distillation- Feed is Residue: >C20 -Avoiding high temperatures -Tarry residue results-Vaccum gas oil (Top product)-Fuel oils in power stations and ships, 'base' oil in lubricating oils, bitumen/asphalt

Natural Gas (NG) and Associated Gas (AG)

Natural Gas (NG):

A mixture of C1 to C3 hydrocarbons (mainly CH4) + small amounts of N2, CO2 and H2S . Found in gas reservoirs with no oil present (non-associated gas)

Associated Gas (AG):Present in contact with and/or dissolved in crude oil

and is coproduced with it. • NG and AG are used mainly as an energy source

and basic raw material for petrochemical industry.

Natural Gas (NG) and Associated Gas (AG) (cont.)

Liquefied Petroleum Gas (LPG)

- produced as a by-product of natural gas processing, associated gas or during refining and processing operations of petroleum.

- Mainly contains propane and butane

- Used mainly as domestic fuel and basic raw material for petrochemical industry.

Natural Gas (NG) and Associated Gas (AG) (cont.)

Dry natural Gas:

It is a gas that does not contain an appreciable amount of condensable hydrocarbons.

Wet natural Gas

Contains more than 0.3 gallons of condensable per 1000 cu. ft.

Natural Gas (NG) and Associated Gas (AG) (cont.)

Sour Natural Gas:

- Contains appreciable amounts of hydrogen sulfide and carbon dioxide.

- Needs to remove the acid gases mainly by absorption in amines or caustic solutions

Annual consumption of NG and other oil fractions for different sectors for

Saudi Arabia in 2004 (Source IEA)

0.3

4.4

0.1

1.9

12.0

5.0

1.5

8.5

2.6

21.5

13.5

3.02.2

9.9

6.1

1.2

8.8

0.3

0

5

10

15

20

25

Electricity Plants Energy Sector Industry Transport Petrochemicals

Sector

Ann

ual

Con

sum

ptio

n (m

illi

on t

ones

)

Crude Oil Naphtha LPG

Motor Gasoline Residual Fuel Oil Jet Kerosene

NG Gas/Diesel

More information about Petrochemicals

• http://csis.org/program/energy-and-national-security• http://www.icis.com/v2/chemicals/9076567/vinyl-c

hloride/pricing.html

Types of Chemical Reactors

Ideal Reactor:

- Plug flow Reactor

- Mixed flow reactor

- Batch Reactor

Most Common Units Encountered in

Petrochemical Plants • Reactors of different types• Distillation Columns• Strippers• Absorption and Adsorption Columns • Packed bed • Scuppers• Settlers• Compressors • Gas-solid and liquid – solid separators (e.g. filters,

cyclones … etc.)• Heat exchangers• , and others

Types of Chemical Reactors (Cont.)Batch Reactor

Types of Chemical Reactors (Cont.)Mixed Flow reactor

Types of Chemical Reactors (Cont.)Mixed Flow reactor

Types of Chemical Reactors (Cont.)

Types of Chemical Reactors (Cont.)

Types of Chemical Reactors (Cont.)

Types of Chemical Reactors (Cont.)

Types of Chemical Reactors (Cont.)Fluidized Bed Reactor

Types of Chemical Reactors (Cont.)

Gas-Liquid Contactors Absorption Columns: Used for taking up a soluble gas in a solvent liquid and producing a solution plus a lean exit gas e.g. used in H2S removal from hydrocarbons

Gas-Liquid Contactors (Absorption Columns) Cont.

Gas-Liquid Contactors Stripping: Used fior removing a soluble gas from solution by counter current contact with a inert gas to recover solute gas and regenerate solvent for reuse

Gas-Liquid Contactors (Absorption Columns) Cont.

Liquid-Liquid Contactors (Extraction)

Liquid-Liquid Contactors (Extraction) Cont.

Gas – Solid Separation

Gas – Solid Separation (Cont.)Cyclone Separator: Used to separate solid particles or liquid droplets from gases to permit product recovery or to cut down

product loss and air pollution

Gas – Solid Separation (Cont.)Electrostatic Precipetator: Used to remove fine dusts or mists suspended in gases; features high collection efficiency at

wide variety of operating conditions

Gas – Solid Separation (Cont.)Wet ScrubberEffective means of removing suspended particles from gas stream by contact with liquid shower

Liquid– Solid Separation Spray DryerSuitable for large capacity operation on liquid feed to give powdered, spherical, freeeflowing product; used in production of pigments, detergents, synthetic resins, and

inorganic salts

Liquid– Solid Separation (Cont.) Rotary Drier

Suitable for drying free-flowing granular solids which do not dust or stick; high-temp. versions are

kilns for calcining cement, lime, etc.

Fired HeaterUsed to heat petroleum fractions to distillation or

cracking temperatures in direct-fired tubes

Fired Heater

Continuous fractionator (distillation |Column)Used for high volume continuous separation of complex

mixtures such as petroleum fractions