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PRODUCTION
of
VOLATILE
HYDROCARBONS
HYDROCARBONS PROCESSES
*CRUDE OIL
*NATURAL GAS
ARE KNOWN MAJOR SOURCES
OF
HYDROCARBONS
*CELLULOSIC FIBRE, STARCH,SUGARS, NON-EDIBLE
VEGETABLE OILS
ARE
EMERGING AS RENEWABLE SOURCES OF
HYDROCARBONS
*SHALE GAS COULD BECOME KEY SOURCE IN FUTURE
HYDROCARBONS PROCESSES
CRUDE OIL IS SPLIT INTO
*HYDROGEN
*LIGHTER GASES
*LPG
*LIGHT NAPHTHA
*HEAVY NAPHTHA
*KEROSENE/JET FUEL
*MIDDLE DISTILLATES/DIESEL
*HEAVY GAS OIL
*RESIDUE
USING DISTILLATION PROCESS
HYDROCARBONS PROCESSES
HEAVY MATERIALS
FROM CRUDE DISTILLATION ARE PROCESSED
FURTHER IN
*VACUUM DISTILLATION,
RESIDUES ARE PROCESSED IN
*FLUID CATALYTIC CRACKING
*HYDROCRACKING
*COKER
TO BREAK THEM INTO LIGHTER HYDROCARBONS.
THESE LIGHTER HYDROCARBONS ARE
PROCESSED/USED AS BLENDING COMPONENTS OF
FUELS
COMPONENTS LIKE C4s, C3s, C2s ARE USED TO
RECOVER VALUABLE
ETHYLENE, PROPYLENE, BUTENES
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
NATURAL GAS
FROM WELL HEAD
IS PROCESSED THROUGH
DEHYDRATION, ACID GAS REMOVAL, MERCURY REMOVAL,
AND THEN SPLIT INTO
RESIDUE GAS , NGL,LPG, OR RG, ETHANE, PROPANE,
BUTANES, GASOLINE AS NEEDED
HYDROCARBONS PROCESSES
TYPICAL PROCESSES
FLOW DIAGRAM FOR
WELL HEAD NATURAL GAS
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
VOLATILE SATURATED HYDROCARBONS
METHANE,ETHANE,PROPANE, BUTANES , PENTANES
ARE NATURAL CONSTITUENTS OF
LIGHTER GASES, LPG, LIGHT NAPHTHA OFF CRUDE AND LPG,NGL, GASES
OFF NATURAL GAS.
DIRECT CHEMICAL USES ARE LIMITED FOR THESE
THESE ARE USED MOSTLY TO MAKE
VOLATILE UNSATURATED HYDROCARBONS
ETHYLENE, PROPYLENE, BUTADIENE, BUTYLENES
WHICH ARE BUILDING BLOCKS TO MAKE
POLYMERS
HYDROCARBONS PROCESSES
TYPICAL PETROCHEMICAL
PROCESSES
BLOCK DIAGRAM
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
BOILING POINTS
*METHANE- 111.7 K
*ETHANE- 184.5 K
*PROPANE- 231.1 K
*ISO BUTANE 261.3 K
*N BUTANE 272.7 K
*METHYL BUTANE 301.0 K
*N-PENTANE 309.2 K
* CYCLOPENTANE 322.4 K
BOILING POINT DIFFERENCES ARE GOOD
C4S AND LOWER HYDROCARBONS BOIL AT (OR) BELOW SUB ZERO
DEG C.
CRYOGENIC FRACTIONATION IS NEEDED
HYDROCARBONS PROCESSES
BOILING POINTS
*METHANE- 111.7 K
*ETHYLENE 169.4 K
*ETHANE- 184.5 K
*PROPYLENE 225.4 K
*PROPANE- 231.1 K
*ISO BUTANE 261.3 K
*ISOBUTYLENE
266.3 K
*1-BUTENE 266.9 K
*1,3 BUTADIENE 268.7 K
*N BUTANE 272.7 K
C-2-BUTENE 276.9 K
* T-2-BUTENE 274.9 K
*1,2 BUTADIENE 284.0 K
HYDROCARBONS PROCESSES
BOILING POINTS DIFFERENCE
METHANE C2S ~50 K
C2S- C3S ~ 40 K
C3S- C4S ~ 30 K
C4S- C5S ~ 15 TO 25 K
ETHYLENE- ETHANE ~ 15 K
PROPYLENE- PROPANE ~ 6 K
AMONGST C4S ~ 15 TO 20 K
( C4 SPECIES ARE MANY AND FORM
AZEOTROPES)
HYDROCARBONS PROCESSES
BOILING POINT DIFFERENCES
REASONABLE BETWEEN HYDROCARBONS OF DIFFERENT CARBON
NUMBERS
DISTILLATION CRYOGENIC / NORMAL TEMPERATURE
FIRST CARBON NUMBER WISE FRACTIONS COMPONENTS FRACTIONATION
ETHYLENE- ETHANE, PROPYLENE- PROPANE DONE USING FRACTIONATION
C4S FORM AZEOTROPES- EXTRACTIVE DISTILLATION IS ADOPTED TO
SEPARATE 1,3 BUTADIENE FROM OTHER C4 S
ISOBUTYLENE CAN BE SEPERATED THROUGH CHEMICAL CONVERSION TO
MEK AND CRACKING MEK TO ISOBUTYLENE
HYDROCARBONS PROCESSES
IMPORTANTVOLATILE HYDROCARBONS
ARE THOSE USED FOR MAKING
POLYMERS
*ETHYLENE, *PROPYLENE,
*BUTADIENE, *ISOBUTYLENE ,
*ISOPRENE,
CHEMICAL CONVERSION PROCESSES ARE AVAILABLE
TO PRODUCE THEM EVEN FROM METHANE
HYDROCARBONS PROCESSES
CHEMICAL CONVERSION PROCESSES - OLEFINS
THERMAL CRACKING OF
NAPHTHAS, ETHANE, PROPANE, BUTANES
IS THE MOST POPULAR CHEMICAL CONVERSION PROCESS
FLUID CATALYTIC CRACKING AND COKER
GENERATES
ETHYLENE, PROPYLENE, BUTENES ALONG WITH OTHER
STREAMS USED AS FUEL BLENDING COMPONENTS
FIXED BED CATALYTIC DEHYDROGENATION OF C4 S WAS
POPULAR PROCESS TO MAKE 1,3 BUTADIENE.
HYDROCARBONS PROCESSES
CHEMICAL CONVERSION PROCESSES - OLEFINS
DEHYDROGENATION PROCESSES HAVE CHANGED-CONTINUOUS
REGENERATION OF CATALYST & TARGET OLEFIN
CATALYTIC DEHYDROGENATION WITH CCR
PROPANE TO PROPYLENE AND ISOBUTANE TO ISOBUTYLENE
COMMERCIALLY AVAILABLE
WITH SHALE GAS C4 OLEFINS/ DIOLEFINS PRODUCTION IN THE WORLD
MAY GO DOWN. FIXED BED DEHYDROGENATION MAY GET REVIVED
CATALYTIC PROCESS TO CONVERT METHANOL TO ETHYLENE PROPYLENE
ENABLES USE OF METHANE
METHANE > SYN GAS > METHANOL
HYDROCARBONS PROCESSES
PRODUCTION OF ETHYLENE, PROPYLENE, BUTADIENE
VIA
THERMAL CRACKING ROUTE
HAS
TWO BASIC STEPS
*CONVERSION PROCESS
CONVERT A CANDIDATE MOLECULE / GROUP OF MOLECULES INTO
OLEFINS
*SEPERATION PROCESS
SEPARATE ETHYLENE, PROPYLENE, BUTADIENE FROM MIXTURE OF
CHEMICALS FROM ABOVE CONVERSION PROCESS
PRODUCTION OF ETHANE, PROPANE BUTANES ETC FROM CRUDE /
NATURAL GAS REQUIRES SEPERATION PROCESS ONLY
HYDROCARBONS PROCESSES
THERMAL CRACKING
CONVERSION PROCESS
BASICS/ISSUES
*NUMBER OF MOLECULES INCREASE
*ENDOTHERMIC REACTIONS REQUIRE HEAT TO REACT
*THERMAL CRACKING HIGH TEMPERATURE PROCESS ~ 1000 DEG C
*CATALYTIC DEHYDROGENATION LOWER
* FEED HCs AND PRODUCT (UNSATURATES) IN PARTICULAR TEND TO
POLYMERISE- COKE UP
*METAL CAN ALSO CATALYSE COKE/ POLYMER FORMATION
CONSERVE ENERGY , VALUABLE HYDROCARBONS
*REMAIN ON STREAM 24 X 365
*HSEF
*COSTS OPERATING, CAPITAL
HYDROCARBONS PROCESSES
THERMAL CRACKING-CONVERSION PROCESS
MEASURES
*LOW PRESSURE NEAR ATMOSPHERIC OPERATION
*DILUENT - STEAM IS USED - REDUCES PARTIAL PRESSURE, CARRIES HEAT TO SUPPORT
ENDOTHERMIC REACTIONS , HELPS DEPLETE COKE THROUGH H2O+C REACTION
*NEAR ISOTHERMAL CONDITION-CRACKER FURNACE DESIGN GIVES UNIFORM HEAT ALL
THROUGH THE PATH OF FEED HC
*SHORT RESIDENCE TIME- HIGH SPACE VELOCITIES
*QUENCH TO STOP RXs - TRANSFER LINE EXCHANGERS & OIL QUENCHING
*COKE SUPPRESSORS- SULFUR COMPOUND IN FEED
MULTIPLE HEATERS WITH N+1 CONCEPT & ON LINE DECOKING
*PROCESS /EQUIPMENT DESIGN, CONSTRUCTION, OPERATION ADDRESSING , OVERALL
PROCESS AND PLANT INTEGRITY,OPERABILITY, RELIABILITY, HSEF, AND COSTS.
HYDROCARBONS PROCESSES
THERMAL CRACKING - SEPERATION PROCESS
BASICS/ISSUES
*NEED LOW TEMPERATURE 113 DEG K
*NEED MULTIPLE LEVEL PURIFICATION
* I- CARBON NUMBER WISE
*II- SPECIES IN THE SAME CARBON NUMBER
*III- MEET POLYMERISATION QUALITY
*IV- REMOVE OF NON-TOLERABLES - SULFUR, OXYGENATES, ACETYLENICS, METALS, MOISTURE
etc
*CONSERVE ENERGY, VALUABLE HYDROCARBONS
*ONSTREAM - 365X24
*HSEF
*COSTS OPERATING , CAPITAL
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
MEASURE
PROCESS CONFIGURATION
PROCESS EQUIPMENT DESIGN, CONSTRUCTION,
OPERATION,
ADDRESSING
CONSERVATION OF ENERGY CONSERVATION OF
HYDROCARBONS
PROCESS AND PLANT INTEGRITY
OPERABILITY
RELIABILITY
HSEF
COSTS OPERATING , CAPITAL
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
PROCESS FLOW CONFIGURATION
*PROCESSING OF CRACKER EFFLUENTS IN THREE SECTIONS
HOT, COMPRESSION, AND COLD SECTIONS
THUS USE CRYOGENIC CONDITIONS ONLY FOR LIGHTER MOLECULES
*FURNACE EFFLUENT FIRST COOLED IN TLEs TO GENERATE VERY HIGH
PRESSURE STEAM
*THEN QUENCHED WITH QUENCH OIL IN A SPECIAL PIPE FITTING CALLED
QUENCH FITTING
*THEN QUENCHED IN QUENCH TOWER WITH WATER
* QUENCH TOWER SEPERATES CRACKED PRODUCTS INTO
CRACKED GASES CRACKED LIQUIDS
(1)
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
PROCESS FLOW CONFIGURATION- CRACKED LIQUID
*CRACKED LIQUID IS FIRST STRIPPED OFF LIGHTERS IN A COLUMN.
GASES RECYCLED BACK TO QUENCH TOWER
*THIS LIQUID IS SPLIT IN DEPENTANISER INTO TWO PARTS
C5 FRACTION - C6 PLUS FRACTION
C5s FRACTION IS SPLIT IN DEBUTANISER INTO TWO PARTS
C4s STREAM - C5s STREAM
*C6 PLUS STREAM IS SPLIT IN GASOLINE SPLITTER INTO PYROLYSIS GASOLINE - 210 PLUS
STREAM (PYROLYSIS FUEL OIL)
*THIS HEAVY OIL IS USED FOR QUENCHING OF CRACKER EFFLUENTS
*AFTER STRIPPING OFF LIGHTERS IN A SEPARATE SET OF COLUMNS
PRODUCT OIL IS USED AS CBFS- PYROLYSIS OIL FOR VARIOUS USES
(2)
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
(3)
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
PROCESS FLOW CONFIGURATION-CRACKED GASES
*FRACTANATORS TO MAKE PURE PRODUCTS
*PROPYLENE FRACTIONATORFEED C3s FROM DEPROPANISER ARE PASSED THROUGH
METHYL ACETYLENE+ PROPADIENE CONVERTER.
HYDROGEN IS INJECTED IN REQUIRED QUANTITIES FOR SELECTIVE CONVERSION O TO
PROPYLENE ON A CATALYST BED
UNREACTED HYDROGEN, ASSOCIATED METHANE ARE TAKEN OFF FROM TOP OF CONDENSER
USUALLY A SET OF CONDENSERS ARE USED TO MINIMISE ETHYLENE SLIP ALONG WITH THESE
NON CONDENSABLE GASES
PROPYLENE IS OVERHEAD PRODUCT MAY BE SIDE CUT
LESS PURE PROPYLENE COULD BE SIDE PRODUCT
PROPANE BOTTOM PRODUCT
(7)
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
PROCESS FLOW CONFIGURATION-CRACKED GASES
C4 STREAM -C4 SPECIES ARE MANY- CLOSE BOILING- FORM AZEOTROPES
EXTRACTIVE DISTILLATION IS NEEDED
POLAR SOLVENTS LIKE NMP, DMF, ETC
DISSOLVE 1,3 BUTADIENE AND RENDER ALL OTHER C4 S SEPARATE FROM BUTADIENE
VINYL ACETYLENE, ETHYL ACETYLENE ,PROPADIENE ARE PRESENT IN C4S
SELECTIVE HYDROGENATION UPSTREAM OF ED UNIT IS DONE TO REMOVE THEM
ED UNIT HAS TWO MAIN COLUMNS- EXTRACTIVE DISTILLATION COLUMN AND SOLVENT
STRIPPER.
SOLVENT KEEPS CIRCULATING FROM STRIPPER TO ED TO STRIPPER
TOP OF ED IS RAFFINATE C4S OTHER THAN BD
TOP OF STRIPPER IS EXTRACT BD WITH SOME IMPURITIES
PURE BD IS MADE IN FRACTIONATION COLUMNS FROM EXTRACT
(8)
HYDROCARBONS PROCESSES
THERMAL CRACKING-SEPERATION PROCESS
PROCESS FLOW CONFIGURATION-CRACKED GASES
C5 STREAM - UNSTABLE COMPUNDS- POLYMERISE FORM STICKY GUMS- NO
COMMERCIALLY IMPORTANT CHEMICALS- USED FOR MAKING RESINS OR
HYDROGENATED AND USED FOR GASOLINE BLENDING OR RECYCLE BACK TO
CRACKER
PYROLYSIS GASOLINE STREAM- CONTAINS BENZENE,TOLUENE, C8AS
USUALLY BOTH ARE HYDROGENATED IN TWO STAGES ON FIXED BED CATALYTIC
REACTORS
AFTER FIRST STAGE C5S SEPERATED AND USED FOR GASOLINE BLENDING
COMPLETE HYDROGENATION IS NEEDED FOR EXTRACTING AROMATICS OR
RECYCLING NON AROMATICS FOR CRACKING
SOLVENT EXTRACTION IS ADOPTED TO SEPARATE AROMATICS FROM NONAROMATICS
DUE TO CLOSENESS OF BOILING POINTS
(9)
HYDROCARBONS PROCESSES
TYPICAL
THERMAL CRACKER
FLOW
DIAGRAM
HYDROCARBONS
PROCESSES
HYDROCARBONS PROCESSES
ETHANE , PROPANE THERMAL
CRACKERS ARE SIMILAR TO NAPHTHA
THERMALCRACKER
ETHANE, PROPANE REQUIRE HIGHER
TEMPERATURES THAN NAPHTHA
DEDICATED FURNACES ARE USED
C4 S AND HEAVIES YIELD IS VERY
SMALL FROM ETHANE AND PROPANE
CRACKERS
HYDROCARBONS PROCESSES
PROCESS FOR PRODUCTION OF ETHANE , PROPANE , C4S
FROM NATURAL GAS IS SAME AS THAT IN COLD SECTION OF
THERMAL CRACKER
ETHYLENE, PROPYLENE FRACTIONATORS ARE NOT NEEDED
INSTEAD OF PROPYLENE, ETHYLENE REFRIGERATION, ETHANE
AND PROPANE REFRIGERATION IS USED
HYDROCARBONS PROCESSES
UOP OLEFLEX PROCESS
TARGETS
PROPYLYNE
FROM
PROPANE
ISOBUTENE
FROM
ISOBUTANE
IN A CATALYTIC PROCESS WITH CONTINUOUS
REGENERATION
NEED SPECIFIC FEED
FOR
SPECIFIC OLEFIN
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
UOP/HYDRO
MTO PROCESS
INDICATIVE
DIAGRAM
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
SEPERATION OF OLEFINS IN OLEFLEX AND MTO IS
RELATIVELY SIMPLER AS NUMBER OF SPECIES IS
LESS
OLEFLEX PER PASS CONVERSION IS LOWER
REQUIRING GOOD AMOUNT OF RECYCLE
THUS EQUIPMENT SIZE IN FRACTIONATION IS
RELATIVELY LARGER
MTO PROCESS FRACTIONATION IS LIMITED TO
CHEMICAL GRADES FOR POLYMER GRADES
ADDITIONAL COLUMNS ARE NEEDED
HYDROCARBONS PROCESSES
SUMMING UP THERMAL CRACKING IS THE MAIN STAY FOR
STAND ALONE PETROCHEMICAL COMPLEXES
INTEGRATED REFINERY+PETROCHEMICAL COMPLEXES HAVE
MORE OLEFINS AVAILABLE AT RELATIVELY LOW COST
AFTER SHALE GAS OVERALL BUTADIENE AVAILABILITY MAY
CHANGE HELPING DEHYDROGENATION PROCESS TO COME UP
MTO IS GOOD FOR PLACES WITH VERY CHEAP AND ABUNDANT
AVAILABILITY OF NATURAL GAS
SCOPE FOR DEVELOPMENT IS IN MAKING SEPERATION
PROCESS CHEAPER CAPITAL AND OPERATING
HYDROCARBONS PROCESSES
Convection Section
Hydrocarbon
Feed
120 oC
~
~
Steam Drum
Dilution Steam
380 oC
Cracked Gas to
Separation Section
Desuperheater
BFW
520 C
o
HP Steam
620 oC
1250 oC
Transferline Exchanger
850 oC
Radiant efficiency: 40 42%
Overall efficiency: 92 95 %
Radiant Section
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
HYDROCARBONS PROCESSES
Hydrogen
Utilities
Mixed
Butanes
Gasoline
Material Movements
Acid Gas
Compressor and
Drier Chilling
Steam
Primary
Fractionator
Quench
Feeds
Ethylene
Mixed
Products
Acetylene
Converter
Ethane
Methane
Quench
Fuel Oil
Naphtha
Cracking
Furnaces
NAPD
Converter
Ethane
Propylene
Propane
HYDROCARBONS PROCESSES
Ethane
C3-LPG
C4-LPG
Naphtha
Gasoil
Feed
125
226
300
334
433
Ethylene
100
100
100
100
100
Propylene
35
45
52
60
Butadiene
14
18
Raffinate-1
17
21
Benzene
22
18
Other (fuel)
24
73
141
129
216
HYDROCARBONS PROCESSES
THANKS