FCC PROCESS FOR DISTILLATES AND OLEFIN GENERATION
ATMOSPHERIC RESID CRACKING
OVERVIEW OF INDIAN FCC UNITS
REFINERY
HPCL HPCL HPCL BPCL BPCL IOCL IOCL IOCL IOCL IOCL IOCL IOCL CPCL CRL RPL ESSAR
LOCATION
MUMBAI VISAKH VISAKH MUMBAI MUMBAI PANIPAT GUJARAT GUJARAT MATHURA HALDIA BARAUNI GUWAHATI CHENNAI KOCHI JAMNAGAR JAMNAGAR
TYPE/DESIG
FCC/EXXON IV FCC/ESSO IV FCC/UOP FCC/UOP FCC/SHELL RFCC/SWEC FCC/UOP RFCC/SWEC FCC/UOP RFCC/SWEC RFCC/SWEC DCC/IOCL FCC/UOP FCC/UOP FCC/UOP FCC/SWEC
CAPACITY
(MMTP/A) 0.4 0.4 0.6 0.6 1.2 0.7 1.0 1.0 1.0 3.0 1.4 0.2 0.6 1.4 7.0 3.0
YEAR OF
COMMISSIONING 1954 1955 1985 1985 1955 1999 1982 1983 2001 2004 1985 1983 1999 2005
SHORT CONTACT TIME RISER FCC COMPLEX
ANALOGIES BETWEEN FLUIDIZATION AND DISTILLATION
FLUIDIZATION REGIMES
AXIAL DENSITY PROFILES IN FLUID BEDS
D) Other Rotary kiln, Spouted Bed, Tray Type, Cyclonic, etc.
REACTOR SYSTEM TEMPERATURE PROFILE
HEAT TRANSFER COEFFICIENT VS. SLIP VELOCITY
VELOCITY PROFILE IN A TRANSFER LINE REACTOR
TYPICAL OP. CONDITIONS OF FCC
FCC FOREIGN FOREIGN CATALYST / OIL WT. RATIO REACTOR REACTOR CONTACT TIME, SEC. FEED END PT. OC REGENERATION TEMP. CARBON ON REGENERATED CATALYST REGENERATOR PRESSURE, Kg/cm2 7 540 1-8 600-621 700-750 0.05-0.10 1.75 UNIT INDIAN 5.5 490 1.5 - 3 540- 560 640-660 0.3-0.6 3.0
TRENDS IN FCC OPERATION IN INDIA
PARAMETERS
FEED DENSITY AT 15oC CCR, WT% BASIC N2 (PPM) FEED 5% POINT, oC FEED METAL CONTENT (Ni + V ) PPM FEED THOUPU M3/Hr COMBINED FEED RATIO (CFR)
REFINERY A
0.886 0.15
NEGLIGIBLE
REFINERY B
0.993 0.12
NEGLIGIBLE
0.90-0.91 0.20-0.30 250-350 370 0.2-0.3 170 1.2 1000 1500
0.89 0.20 150-200 390 0.2-0.3 185 1.23 1100 105
350 LOW 160 1.45
400 LOW 177 1.33 470 445
METAL ON EQ. CATALYST, (PPM Ni 660 V 625
CRACKING
OLEFINS
NAPHTHENES
DEHYDROGENATION
CYCLO OLEFIN AROMATICS
ISOMERIZATION
NAPHTHENES WITH DIFFERENT RINGS
PRINCIPAL REACTIONS IN FLUID CATALYTIC CRACKING
PARAFFINS
CRACKING CRACKING CYCLIZATIONS CYCLIZATIONS BRANCHED PARAFFINS ISOMERIZATION PARAFFINS + OLEFINS LPG OLEFINS
OLEFINS
CYCLIZATIONS CONDENSATION DEHYDROGENATION
BRANCHED
H TRANSFER
PROBLEMS CAUSED BY POLYCYCLIC AROMATICS
THEY ARE HARD TO CRACK THEY MAY DEACTIVATE THE CATALYST THEY MAY BUILD IN RECYCLE STREAMS AND * CAUSE A DECREASE IN LIQUID YIELDS * DEPOSIT IN DOWNSTREAM EQUIPMENT (LOW SOLUBILITY)
TYPICAL UNIT CONSTRAINTS
REGENERATION DESIGN AIR BLOWER GAS COMPRESSOR
FCC PROCESS VARIABLES
HARDWARE CHANGES OPERATING VARIABLES CATALYST FEEDSTOCK
ZEOLITES ARE 10-103 TIMES MORE ACTIVE SiO2-Al2O3 60 140 190 205 ZEOLITE REHX 1000 2370 2420 953
210
513
X ZEOLITE - SiO2/Al2O3 UPTO 2.5 HAS MORE IN NO. BUT WEAKER ACID SITES THIS RATIO IN Y ZEOLITE IS MORE THAN 4 OR ~ 5. IT AHS LESS BUT STRONGER ACID SITES. IT AHS BETTER THERMAL/HYDROTHERMAL STABILITY THAN X-ZEOLITE ZSM-5 HAS XiO2/Al2O3 RATIO > 10 HAS 2 DIMENSIONAL PORE CATALYSTS BASED ON X ZEOLITES HAVE THEREFORE BEEN REPLACED
NO. OF TETRAHERA RING 6 8 10 12 18 MAX FREE DIA Ao 2.8 4.3 6.3 8.0 15.0 EXAMPLE -ERIONITE, A ZSM-5 L,Y,X MOREDENITE FAUJASITE
ZEOLITE MODIFICATIONS
1. (NH4)2SiF6 - ALLOWS ORDERLY REPLACEMENT OF Al WITH Si IN A.Q. MEDIA. PRODUCES HIGH Si/Al ZEOLITE WITH HIGH CRYSTALLINITY AND THERMAL STABILITY SiCl4 - DEALUMINATION RESULTS IN MORE Al ON SURFACE. MeSO OR MACRO PORES NOT FORMED. Si REPLACEMENT ORIGINATE OUTSIDE THE CRYSTAL BUT IN HYDROTHERMAL TREATMENT, Si COMES FROM OTHER PARTS. NaAlCl4 BLOCKS THE PORES FOR SiCl4 ENTRY. EDTA - HAVE LESS Al NEAR SURFACE THAN IN INTERIOR
FCC CATALYST SUITABLE FOR INDIAN UNITS
1. LOW COKE MAKING TENDENCY 2. LOW GAS MAKE 3. HIGHER PRIMARY CRACKING ACTIVITY 4. LOWER SECONDARY CRACKING ACTIVITY 5. CATALYST WITH HIGH LPG ACTIVITY
KEY POINTS OF INCREASING DIESEL
CONVERSION, % = 100 - (SLRRY + HCO+LCO) TO INCREASE LCO YIELD: * DEPRESS CONVERSION (PROCESS) * ENHANCE BOTTOMS CRACKING TO REDUCE SLURRY (CATALYST) * CONVERT HCO TO REDUCE RECYCLE RATIO (CATALYST) * TERMINATE LCO FROM RE-CRACKING (PROCESS) * CUTTING POINT ADJUSTMENT (PROCESS+ADDITIVES)
OPTIMIZATION OF FCC PROCESS FOR THE PRODUCTION OFLIGHT OLEFINS FOR OXYGENATES
1. USY OF USY LOW ACID SITE DENSITY REDUCES H-TRANSFER, INCREASES OLEFINS IN GAS, GASOLINE
2. USY OF ZSM-5 PREFERABLY CRACKS NC7-C12 MOLECULES PRODUCING C3, C4 DUE TO LOW ACID SITE DENSITY 3. NON REGENERATIVE, LOW CONTACT FCC/DCC GIVES HIGHER OLEFIN/PARAFFIN RATIO
NONREG/ DCC GAS, VOL% C3-C4 VOL% C5+NAPH, VOL% C4=/C5 C3=/C3 25-27/45-50 22/43-45 52 0.8 0.86 27
REY
ZSM-5 +REY 27 24
ZSM-5 +REY 27 24 52 0.57 0.75
25
54 0.55 0.72
52 0.57 0.75
MAXIMIZATION OF ISOBUTYLENE AND ISOAMYLENE THROUGH FCC PROCESS
FCC UNITS IN INDIA MAY BE ASKED IN FUTURE TO OPERATE TO MAXIMIZE ISOBUTYLENE/ISOAMYLENE PRODUCTION A STARTING MATERIAL FOR MTBE, TAME ETC. HOWEVER, USY OR USY IN COMBINATION WITH ZSM-5 HAS BEEN ABLE TO INCREASE THE YIELD OF BOTH ISOBUTYLENE /TOTAL C4 OLEFIN RATIO IS FAR FROM THE EQUILIBRIUM VALUES. THUS, THERE IS STILL A BIG SCOPE IN THE DEVELOPMENT OF THE CATALYST FOR THIS PURPOSE SELECTIVITY OF ISOBUTYLENE AND ISOAMYLENE CATALYST iC4= -------------iC5 = -------------Total c5 USY 0.28 0.52 USY/ZSM-5 0.32 0.62 EQUIL 0.45 0.65
NON-REGENERATION CAT. CRACKING
DEVELOPMENTAL STAGE (IN USA AND CHINA)
HIGH SP. VELOCITY LHSV TEMP. CONV. GASOLINE GAS YIELD < 0.01 SEC ~2000 ~620oC COMPARABLE TO FCC 25-50%, RON UPTO 99 ALMOST DOUBLED WITH HIGHER CONC. OF UNSATURATES AT 37 CONV. SMALLER BY FACTOR OF 102 LOW (ONE TON CAT. PROCESSES > 10000 TON FEED)0.3/D FOR 20,000 BPD
REACTOR CAT. MAKE UP RATE
PRODUCT SELECTIVITY SIMILAR TO FCC PROBLEMS: HIGH PRESSURE DROP
TYPICAL YIELD OF LOWER OLEFINS IN DCC AND FCC
PRODUCTS WT% MAXIMUM MAXIMUM PROPYLENE ISO-OLEFIN MODE MODE 6.1 20.5 14.3 5.4 --2.3 14.3 14.6 6.1 9.8 6.5 FCC
ETHYLENE PROPYLENE BUTYLENE IN WITH 1-C4= AMYLENE IN WHICH 1-C5=
0.9 6.8 11.0 3.0 8.5 4.3
CONCLUSION
OPERATING EXPERIENCES IN FCC WITH ZEOLITE CATALYSTS HAVE INDICATED IMPROVEMENTS IN YIELD BUT THERE STILL REMAINS ENORMOUS
SCOPE FOR FURTHER IMPROVEMENTS. THERE ARE SEVERAL AREAS IN WHICH THE REDESIGN OF FCC CATALYSTS AND OPTIMIZATION OF PROCESS
CONDITIONS IS BEING INVESTIGATED IN ORDER TO COMPLY WITH CHANGING DEMANDS
