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