Professor Ayman M. Atta

Petrochemicals from raw materials to end product

Presentation Outlines

Downstream petrochemicals

Reforming of petroleum products

Surfactants industry

Introduction of Petrochemicals

Solvents Diesel fuel Motor Oil Bearing Grease Ink Floor Wax Ballpoint Pens Football Cleats

Upholstery Sweaters Boats Insecticides Bicycle Tires Sports Car Bodies Nail Polish Fishing lures

Dresses Tires Golf Bags Perfumes Cassettes Dishwasher parts Tool Boxes Shoe Polish

Motorcycle Helmet Caulking Petroleum Jelly Transparent Tape CD Player Faucet Washers Antiseptics Clothesline Curtains Food Preservatives Basketballs Soap

Vitamin Capsules Antihistamines Purses Shoes Dashboards Cortisone Deodorant Footballs

Putty Dyes Panty Hose Refrigerant Percolators Life Jackets Rubbing Alcohol Linings

Skis TV Cabinets Shag Rugs Electrician's Tape Tool Racks Car Battery Cases Epoxy Paint

Mops Slacks Insect Repellent Oil Filters Umbrellas Yarn Fertilizers Hair Coloring

Roofing Toilet Seats Fishing Rods Lipstick Denture Adhesive Linoleum Ice Cube Trays Synthetic Rubber

Speakers Plastic Wood Electric Blankets Glycerin Tennis Rackets Rubber Cement Fishing Boots Dice

Nylon Rope Candles Trash Bags House Paint Water Pipes Hand Lotion Roller Skates Surf Boards

Shampoo Wheels Paint Rollers Shower Curtains Guitar Strings Luggage Aspirin Safety Glasses

Antifreeze Football Helmets Awnings Eyeglasses Clothes Toothbrushes Ice Chests Footballs Combs CD's & DVD's Paint Brushes Detergents

Vaporizers Balloons Sun Glasses Tents Heart Valves Crayons Parachutes Telephones

Enamel Pillows Dishes Cameras Anesthetics Artificial Turf Artificial limbs Bandages

Dentures Model Cars Folding Doors Hair Curlers Cold cream Movie film Soft Contact lenses Drinking Cups

Fan Belts Car Enamel Shaving Cream Ammonia Refrigerators Golf Balls Toothpaste Gasoline

Classification according density API

Light crude (API above 25) brown contains large amount of distillates.

Heavy crude (API<20), brownish black.

Gases (LPG) Liquid (Paraffin and

NAPHTHENES) Solid (resins and

asphaltenes)

Hydrocarbon 1. Alkanes

2. Cycloalkanes(naphthens)

3. Arenes (aromatic)

4. Alkenes and alkynes

5. Naphthenoaromatic

Non-hydrocarbons 1. Sulphur compound

2. Oxygen and nitrogen compounds

3. Metallic compounds

LPG (C1-C4) BP 25 oC.

Naphthas (C5-C9) BP 60-110 oC.

Motor spirit, petrol-gasoline (C5-C10) BP 30-65 oC.

Kerosene (C10-C16) BP 65-170 oC.

Aviation turbine fuel (jet) (C10-C14) BP 65-170 oC.

Diesel fuel (gas fuel (C14-C20) BP 175-270 oC.

Fuel oil (C16-C20) BP 275-370 oC.

Petroleum hydrocarbon solvent

Lubricating oil (C20-C50)

Petroleum waxes

Bitumens

Petroleum cocke

Petrochemicals industry

upstream intermediate downstream

THE PETROCHEMICAL INDUSTRY CHEMICALS DERIVED FROM PETROLEUM

PRODUCTS

FEEDSTOCKS

PRIMARY

PETROCHEMCALS

(BUILDING BLOCKS)

SECONDARY

PETROCHEMICALS

END PETROCHEMICAL

PRODUCTS

PROFILE

methane

methanol

HCHO

CH3COOH

ethane

ethylene

EO

VC

St

C2H5OH

PE

propane

ethylene propylene

butane naphtha Crude oil

naphtha

ETHYLENE

PROPYLENE

BUTYLENE

BUTADIENE

RUBBER

BENZENE

ethylene propylene

PP

PO

ISOPROP

CUMENE

FEED STOCK

Petroleum refining

Separation process

Conversion

(reforming)

Treating process (removal of impurities)

Petroleum refining methods Separation process (distillation, absorption and solvent extraction

Conversion process (reforming)

1. Thermal cracking

2. Catalytic cracking

3. Coking

4. Pyrolysis

Finishing process (removal of impurities).

Refining and reforming

Separation process

distillation

Atmospheric distillation

LPG

Light naphtha

Heavy naphtha

Kerosene and gas oil

Vacuum distillation

Lube oil

bitumen

absorption Solvent

extraction

Petroleum refining principles

Petroleum reforming Conversion process

Thermal cracking

Catalytic cracking

Pyrolysis (production of ethylene and propylene from naphtha and petroleum residue).

Coking (conversion of residue to 15-38 %coke, 49-77 %liquid product, 7-17 %gasoline).

Thermal conversion Temperature 470-580 oC

Pressure 5 atm.

Conversion of hydrocarbons to low molecular weight

Conversion of heavy naphtha to gasoline

Mechanism completed by radical reaction.

The gasoline contains olefin.

Reactions:

Olefin smaller olefin and diolefin

Naphthenes shorter side chain

Aromatics asphaltenes

Thermal cracking

Cracking of hydrocarbons n-paraffin > isoparaffin > cycloparaffin >aromatic>aromatic

naphthenes >polynuclear

Mechanism dodecane hexane +hexene

C12H26 425 oC C6H4 + C6H12

Cn H2n+2 C2H5

. + C n-2H. 2n-3

C2H5. + Cn H2n+2 C2H6 + Cn H.

2n+1

-CH3. -H.

Cn-1H2n-2 CnH2n

PETROCHEMICAL PROCESSES

Basic Processes: (1)Steam Cracking:

(2)Reforming:

Other Processes:

GAS(TO FUEL)

ETHANE

ETHYLENE

PROPANE

PROPYLENE

BUTANE 900

C

BUTADIENE

NAPHTHA (AND CO-PRODUCTS)

GASOLINE

GAS OIL

LIQUID

(TO FUEL)

STEAM

THE STEAM CRACKER

ETHYLENE 30%

PROPYLENE 15%

BUTADIENE 10%

GASOLINE 25%

OTHER

PRODUCTS

OTHER

PRODUCTS 20% 20%

ETHYLENE 80%

ETHANE

FEEDSTOCK

NAPHTHA

FEEDSTOCK

PRODUCTS FROM STEAM CRACKING

Comparison Thermal cracking Catalytic cracking

Heavy oil converted to olifine + isoparaffine + coke

Heavy oil converted to gasoline having aromatic and isoparaffin

Reaction completed at high temperature

Reaction at low temperature and catalyst

It is done in liquid and vapour by radical mechanism

It is done in liquid phase by carbonium ion mechanism

It is applied in small scale

It is applied in large scale

Catalytic reforming It is used to improve octane number of gasoline after thermal

cracking.

Reaction conditions:

1. Reaction completed in presence of hydrogen gas. It required shorter time than thermal.

2. Reforming catalyst

a- metal such as Pt, Pa, Ni (used for hydrogenation and dehydrogenation)

b- supported on acidic oxide (alumina or silica-Al). It provides the acid necessary to catalyze carbonium ion involved in isomerization or hydrocracking

3. Concentration of catalyst varies between 0.3-0.6 %.

4. It is completed in a media of hydrogen containing gases (80 % hydrogen gas).

Catalytic reforming yields gases usable in the synthesis of ammonia, methanol and other compounds.

Chemistry of catalytic reforming Platforming

It is based on using of Pt applied on the surface of alumina.

Temperature between 480-510 oC.

Pressure at 15-30 atmosphere

Yield BTX mixture.

Pressure at 50 atm yields high octane number gasoline (98 octane).

Alkylation conditions H2SO4 or HCl or AlCl3 used as catalysts.

High temperature and pressure are required.

Olifine/isoparaffin is ¼

Reaction completed by carbonium ion mechanism followed by isomerization

1- DEHYDROGENATION ( production of aromatic)

+ H2 3

C H 3 C H

3

+ 3 H

2

2- HYDROCRACKING ( high molecular weight n-paraffin --> low molecular weight)

C 9 H

2 0 + H2 C

4 H

1 0 + C 5 H

1 2

3- DEHYDROCYCLIZATION (n-paraffin to aromatic )

C H 3 ( C H

2 )

5 C H

3

C H 3

+ 4 H

2

4- ISOMERIZATION (n-hydrocarbon to branched)

C H 3

+ 3 H2

C H 3

C H 3

C H 3

C H 3

+ 4 H

2

Catalytic Reforming reactions

alkylation is used to convert isobutylene and isobutane to gasoline

conversion of gases to gasoline

conditions:

a- H 2 S O

4 or HCl or A l C l

3 are used as catalyst in commercial process.

b- high temperature and pressure are required

c- ratio between isoprapane ; olifine (4 : 1).

mechanism

C = C H 2

C H 3

C H 3

+ H +

C +

C H 3

C H 3

C H 3

C = C H 2

C H 3

C H 3

C - C H 2 - C +

C H 3

C H 3

C H 3

C H 3

C H 3

C H - C H 3

C H 3

C H 3

- H +

C - C H 2 - C H

C H 3

C H 3

C H 3

C H 3

C H 3

C H 3

+ C +

C H 3

C H 3

C H 3

- H + C = C H

2

C H 3

C H 3

polymerization Conversion of butylene to polymeric gasoline

Reaction is completed in H2SO4 or H3PO4

Isobutylene is converted to diisobutylene in presence of 60 % H2SO4 and diisobutylene converted to isooctane in presence of H2 (Ni) at 50 oC.

Mechanism completed by carbonium ion mechanism.

polymerization is used to convert unsaturated hydrocarbon to gasoline

butylene polymeric gasoline

reaction completed in the presence of H 2 S O

4

or H 3 P O

4

C = C H 2

+

C H 3

C H 3

C H 3

C H 3

C = C H 2

H2SO4

70 oC

C - C H = C

C H 3

C H 3

C H 3

C H 3

C H 3

+ C - C H 2 - C = C H

2

C H 3

C H 3

C H 3

C H 3

2-2-4trimethylpentene

1-pentene

mechanism

C = C H 2

C H 3

C H 3

+ H +

C +

C H 3

C H 3

C H 3

C = C H 2

C H 3

C H 3

C - C H 2 - C +

C H 3

C H 3

C H 3

C H 3

C H 3

- H +

- H +

C - C H = C

C H 3

C H 3

C H 3

C H 3

C H 3

+

C - C H 2 - C = C H

2

C H 3

C H 3

C H 3

C H 3

H2

N i a t 5 0

o C

C - C H 2 - C H

C H 3

C H 3

C H 3

C H 3

C H 3 ISO-OCTANE

Catalytic cracking It used to produce gasoline with superior quality.

Catalyst used to increase the rate of cracking.

Increase production of more useful gas.

Types of catalyst

1. Natural clays

2. Synthetic material (zeolites based on silica 12.5 % and alumina 87.5 %).

Lose of activity by coke deposition

Catalyst poisonous can be deleted by catalytic regenaration at heating of catalyst at 600 oC.

Reactions Dehydrogenation.

Hydrocracking

Dehydrocyclization

isomerization

Reaction of catalytic cracking

n-paraffin aromatic + H2 (dehydrocyclization)

Naphthenes olefin + paraffin

Aromatics are cracked slowly to coke

PhCH2CH3 CH2=CH2 + Benzene

Disadvantages of catalytic cracking

1. Lose activity of catalyst (coke deposition on catalyst surface).

2. Catalyst poisonous (ctatalytic regeneration at 600 OC).

Catalytic cracking Conversion of heavy oil to gasoline

It is used to produce gasoline having superior quality (antiknock values).

Catalyst used to increase rate of cracking and improve product quality and suppresses the formation of unstable hydrocarbons.

Light gases were not formed and increased formation of more useful gases.

Types of catalysts

1. Natural clay

2. Synthetic materials (zeolite based on silica and alumina) crystalline alumino silicates. (12.5 wt% alumina + 87.5 wt % silica).

Catalysts used as fine powder or pellets.

mechanisms HA H+ + A- init

H+ + RCH=CH2 RCH+CH3 propg

RCH+CH3 + A- RCH=CH2 + HA

REACTION USED TO INCREASE STABILITY of Carbonium ion

1. isomerized to stable

1ry 2ry 3ry carbonium ion

RCH+CH2CH3 RCH (CH3)CH2+ RC+(CH3)2

2. Formation of stable product

RCH+CH3 + C4H10 C4H9+ + RCH2CH3

RCH+CH3 + C4H8 C4H9+ + RCH=CH2

3. CONVERSION OF CARBONIUM ION TO OLIFINE AND SMALLER CARBONIUM ION

CH3CH+CH2R R+ + CH3CH=CH2

Ethylene –The Source of Chemicals

Steam

Cracking

Process

At 900 oC

Rate=12-24 Kg/m3

Ethylene

Propylene

Cyclopentadiene

Aromatics

Benzene

Isoprene

Pentadiene

Butadiene

Drive Cracking Slate

Critical to Adhesive

Polymers

Byproducts of

Ethylene Production

Gas

Feed

Liquid

Feed

~3% of the 7% left

for Chemicals

ETHYLENE + OXYGEN ETHYLENE OXIDE

+ WATER ETHANOL

+ CHLORINE VINYL CHLORIDE

+ BENZENE STYRENE

+ ETHYLENE POLYETHYLENE

THE MAJOR PETROCHEMICALS

From the six building blocks plus

four other simple materials , notably

oxygen, water, chlorine and

ammonia almost all the major

petrochemicals are made.

PROPYLENE + OXYGEN PROPYLENE OXIDE

+ WATER ISOPROPANOL

+ AMMONIA ACRYLONITRIEL

+ BENZENE PHENOL

+ PROPYLENE POLYPROPYLENE

THE MAJOR PETROCHEMICALS

Production of olefin

Crude

distillation

stabilizer

Steam

cracker

Hydrocracker

crude

370-510 oC

150-230 oC

C3/C4

gas

naphtha

gas

Fuel oil

olefin

gas

naphtha

Fuel oil

Production of aromatic by reforming and hydrocracking

Crude oil

distillation

stabilizer

hydrocracker crude

reformer

Cocking unit

Thermal naphtha

coke

Aromatic

extraction

aromatic

naphtha

510 oC

SECONDARY PETROCHEMICALS

(The Major petrochemicals)

ETHYLENE OXIDE PHENOL

ETHYLENE GLYCOL FORMALDEHYDE

VINYL CHLORIDE PHETHALIC UNHYDRIDE

STYRENE UREA

CAPROLACTAM MELAMINE

ACRYLONITRILE ALCOHOLES

TERPHETHALIC ACID ADIPIC ACID

DIMETHYL TERPHETHALATE ETHYL BENZENE

DODECYL BENZENE ETHYLENE DICHLORIDE

CYCLOHEXANE CUMENE