PRODUCTION OF VOLATILE HYDROCARBONS.pptx

HYDROCARBONS PROCESSES

PRODUCTION of

VOLATILE HYDROCARBONS


*CRUDE OIL *NATURAL GAS

ARE KNOWN MAJOR SOURCESOF

HYDROCARBONS

*CELLULOSIC FIBRE, STARCH,SUGARS, NON-EDIBLE VEGETABLE OILS ARE

EMERGING AS RENEWABLE SOURCES OF HYDROCARBONS

*SHALE GAS COULD BECOME KEY SOURCE IN FUTURE


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 FUELSCOMPONENTS LIKE C4s, C3s, C2s ARE USED TO RECOVER

VALUABLE ETHYLENE, PROPYLENE, BUTENES


TYPICAL PETROLEUM REFINERING PROCESSES

FLOW DIAGRAM



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


TYPICAL PROCESSES FLOW DIAGRAM FOR

WELL HEAD NATURAL GAS


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


TYPICAL PETROCHEMICAL PROCESSES

BLOCK DIAGRAM


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

*METHYL BUTANE – 301.0 K*N-PENTANE – 309.2 K* CYCLOPENTANE – 322.4 K


BOILING POINTS DIFFERENCE

METHANE – C2S ~50 KC2S- C3S ~ 40 KC3S- C4S ~ 30 K

C4S- C5S ~ 15 TO 25 KETHYLENE- ETHANE ~ 15 K

PROPYLENE- PROPANE ~ 6 KAMONGST C4S ~ 15 TO 20 K

( C4 SPECIES ARE MANY AND FORM AZEOTROPES)


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


IMPORTANTVOLATILE HYDROCARBONS ARE THOSE USED FOR MAKING

POLYMERS

*ETHYLENE, *PROPYLENE, *BUTADIENE, *ISOBUTYLENE ,

*ISOPRENE,

CHEMICAL CONVERSION PROCESSES ARE AVAILABLE TO PRODUCE THEM EVEN FROM METHANE


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.


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

VIATHERMAL CRACKING ROUTE

HASTWO BASIC STEPS

*CONVERSION PROCESSCONVERT A CANDIDATE MOLECULE / GROUP OF MOLECULES INTO OLEFINS

*SEPERATION PROCESSSEPARATE 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 HYDROCARBONSPROCESS AND PLANT INTEGRITY

OPERABILITYRELIABILITY

HSEF COSTS – OPERATING , CAPITAL


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)


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 PARTSC4s 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)


PROCESS FLOW CONFIGURATION-CRACKED GASES

*CRACKED GASES FROM QUENCH TOWER ARE COMPRESSED IN 4-5 STAGES

*EACH STAGE DISCHARGE IS COOLED AND LIQUID FORMED IS SEPERATED

*THESE LIQUIDS ARE SENT TO TOWERS AT APPROPRIATE LOCATIONS

*AFTER THIRD / FOURTH STAGE GASES ARE GENERALLY FREE FROM C5s

*CAUSTIC WASH IS GIVEN AT THAT STAGE TO REMOVE SULFUR COMPOUNDS

*AFTER FINAL COMPRESSION GASES ARE FED TO ADSORPTION BASED DRYER TO REMOVE MOISTURE

*DRYED GAS IS READY FOR CRYOGENIC PROCESSING (3)



*DRIED GASES ARE PASSED THROUGH A COMPACT PLATE FIN EXCHANGER BLOCK DESIGNED TO EXCHANGE HEAT EFFICIENTLY AMONGST MULTIPLE STREAMS AND COOLED TO ~170 DEG K IN 4 OR 5 STAGES

*CHILLING OCCURS WITH THE HELP OF PROPYLENE , ETHYLENE REFRIGERATIONS + JOULE THOMSON EFFECT +RECOVERY FROM COLD STREAMS

*AFTER EACH STAGE OF CHILLING – GAS AND LIQUID SEPERATED. LIQUID TAKEN OUT AND GAS MOVES FORWARD INTO COLD BOX

*HYDROGEN, OFF GASES, METHANE ARE THE ONLY GASEOUS STREAMS

*ALL OTHER HYDROCARBONS ARE LIQUIFIDE AND TAKEN OUT AS LIQUIDS STREAMS TO COLD FRACTIONATION SECTION

(4)



*CARBON NUMBER WISE SEPERATION IN

TRAIN OF COLUMNS

*DEMETHANISER- OVERHEAD C1S PASSES THROUGH COLD BOX AND LEAVES AS PRODUCT- BOTTOM TO

DEETHANISER

*DEETHANISER- OVERHEAD C2S TO ETHYLENE FRACTIONATOR VIA ACETYLENE CONVERTER-BOTTOM TO

DEPROPANISER

*DEPROPANISER- OVERHEAD C3S TO PROPYLENE FRACTIONATOR VIA MA+PD CONVERTER-BOTTOM C4S TO

DEBUTANISER (5)



*FRACTANATORS TO MAKE PURE PRODUCTS

*ETHYLENE FRACTIONATOR- FEED C2s FROM DEETHANISER ARE PASSED THROUGH ACETYLENE CONVERTER.

HYDROGEN IS INJECTED IN REQUIRED QUANTITIES FOR SELECTIVE CONVERSION OF ACETYLENE TO ETHYLENE 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

ETHYLENE IS OVERHEAD PRODUCT – MAY BE SIDE CUTETHANE BOTTOM PRODUCT

(6)



*FRACTANATORS TO MAKE PURE PRODUCTS

*PROPYLENE FRACTIONATOR- FEED 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 CUTLESS PURE PROPYLENE – COULD BE SIDE PRODUCT

PROPANE BOTTOM PRODUCT (7)



C4 STREAM -C4 SPECIES ARE MANY- CLOSE BOILING- FORM AZEOTROPES

EXTRACTIVE DISTILLATION IS NEEDEDPOLAR 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 C4SSELECTIVE 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 BDTOP OF STRIPPER IS EXTRACT – BD WITH SOME IMPURITIES

PURE BD IS MADE IN FRACTIONATION COLUMNS FROM EXTRACT(8)



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 REACTORSAFTER 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)


TYPICAL THERMAL CRACKER

FLOW DIAGRAM



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

CRACKERETHYLENE, PROPYLENE FRACTIONATORS ARE NOT NEEDED

INSTEAD OF PROPYLENE, ETHYLENE REFRIGERATION, ETHANE AND PROPANE REFRIGERATION IS USED

PROCESS FOR SEPERATION OF OLEFINS LIKE ETHYLENE AND PROPYLENE FROM GASES OF FCC/ COKER IS ALSO SAME AS THAT IN

COLD SECTION OF THERMAL CRACKERSOME OPERATORS DO NOT GO FOR ETHYLENE RECOVERY - PROCESS

CHANGES ACCORDINGLY WITH FOCUS TO RECOVER C3S ONLY

HYDROCARBONS PROCESSES UOP OLEFLEX PROCESS

TARGETS

PROPYLYNEFROM

PROPANE

ISOBUTENEFROM

ISOBUTANE IN A CATALYTIC PROCESS WITH CONTINUOUS REGENERATION

NEED SPECIFIC FEED FOR

SPECIFIC OLEFIN


UOP OLEFLEX PROCESSINDICATIVE DIAGRAM



UOP / HYDRO –MTO PROCESS NEEDS METHANOL AS RAW MATERIAL

CATALYTIC PROCESS WITH CONTINUOUS REGENERATION


UOP/HYDROMTO PROCESS

INDICATIVEDIAGRAM



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


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


Radiant Section

Convection Section

~~

HydrocarbonFeed

Dilution Steam

HP Steam

Desuper-heater

Cracked Gas to

Separation Section

Transferline Exchanger

BFW

Radiant efficiency: 40 – 42%Overall efficiency: 92 – 95 %

850 oC1250 oC

120 oC

620 oC

380 oC

520 oC

Steam Drum




MixedProducts

Quench

Drier

Fuel Oil

Hydrogen

Compressor andChilling

Steam

Quench Methane

AcetyleneConverter

Ethane

Ethylene

PropanePropylene

NAPDConverter

MixedButanes

Gasoline

CrackingFurnaces

Ethane

Naphtha

Acid Gas

PrimaryFractionator

Feeds

Material Movements

Utilities


Ethane C3-LPG C4-LPG Naphtha Gasoil

Feed 125 226 300 334 433

Ethylene 100 100 100 100 100

Propylene 0 35 45 52 60

Butadiene 0 6 1 14 18

Raffinate-1 0 4 4 17 21

Benzene 1 8 9 22 18

Other (fuel) 24 73 141 129 216


THANKS

Documents

PRODUCTION OF VOLATILE HYDROCARBONS.pptx