petrochemicals from raw materials to end product
TRANSCRIPT
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
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 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
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.
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