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Transcript of Dcc Conference
Advances in DCC Technology for
Light Olefins Production
SINOPEC Research Institute of Petroleum ProcessingSINOPEC Research Institute of Petroleum Processing
2010.52010.5
ContentsContents• 1.Introduction
• 2. DCC Technology and Characteristics
• 3. Commercial Performance of DCC
Technology
• 4. Development in DCC+ Technology
• 5. Next Generation DMMC-1 Type Catalyst
• 6. Propylene Transformation during DCC
• 7. Summary
Light Olefin ProductionLight Olefin Production
• Ethylene:
Basically by steam cracking
• Propylene: (worldwide average)• Propylene: (worldwide average)
Around 70% is produced by steam cracking
Around 28% is from FCC
A small amount is through C3 dehydrogenation
and other processes
Propylene ResourcesPropylene Resources
Propylene resource World
average
China
Steam cracking 70% 61%Steam cracking 70% 61%
FCC 28% 39%
Others 2% 0
Lighter olefin Resource in ChinaLighter olefin Resource in China
Lighter olefin is mainly produced by FCC
in China :
1. FCC capacity in China ranks the 2nd in
the world
2.RIPP developed FCC family technologies
Ways to Light Olefins
MGG
Feed :
VGO
MIO
Feed :
VGO
DCC
Feed:HVGO
CPP
Feed :
VGOVGO
VGO+
Resid
Objective
Products :
C3,C4
Gasoline
VGO
VGO+
Resid
Objective
Products:
iC4=,iC5=
Gasoline
HVGO
Objective
Products :
C3=,C4=
VGO
VGO+
Resid
Objective
Products:
C2=,C3=
VGO+
Resid
DCCDCC ((DDeep eep CCatalytic atalytic CCracking)racking)
• Maximum production of propylene and
butylenes
77
• Bridging technology connecting refining &
petrochemical
ContentsContents• 1.Introduction
• 2. DCC Technology and Characteristics
• 3. Commercial Performance of DCC
Technology
• 4. Development in DCC+ Technology
• 5. Next Generation DMMC-1 Type Catalyst
• 6. Propylene Transformation during DCC
• 7. Summary
Schematic Diagram of DCCUSchematic Diagram of DCCU
DCCDCC--Operating ModesOperating Modes
DCC have two typical operating modes by
regulating the operating conditions and
catalyst formulationscatalyst formulations
• DCC-I: maximum propylene mode
• DCC-II: maximum propylene plus iso-
olefins and naphtha mode
FEATURES of DCC PROCESSFEATURES of DCC PROCESS
• Processing heavy feeds (VGO, Deasphalted oil, Coker gas oil,
Atmospheric residue, Vacuum residue, Others)
• Riser reactor plus fluid bed reactor with continuous reaction/
regeneration circulation operation.
• Reaction temperature is much lower than that of steam cracking.
1111
• Special designed zeolite catalysts.
• maximum propylene production.
• Flexibility of operating .
• Hydrocarbon impurity is trace in lighter olefin products.
Comparison of DCC and FCCComparison of DCC and FCC
-- HardwareHardware
FCC DCC
Reactor Base Riser and/or fluid bed
Regenerator Base Similar
Main fractionator Base Higher vapor/liquid ratio
Stabilizer/absorber Base Bigger
Compressor Base Larger capacity
Comparison of DCC and FCCComparison of DCC and FCC
-- Operating ConditionsOperating Conditions
FCC DCC
Reaction Temp. Base +~50oC
Catalyst/oil Ratio Base 1.5~2 times Catalyst/oil Ratio Base 1.5~2 times
Residence Time Base More
Pressure Base Lower
Steam Base More
Comparison of DCC and FCCComparison of DCC and FCC
-- Product YieldsProduct Yields
FCC DCC
Propylene Base 3~5 times
Isobutylene Base 3 times
Naphtha Base 50~80%
LCO Base Less
Light olefin Yield of DCC and FCCLight olefin Yield of DCC and FCC
15
20
25Olefin yield, m%
FCC DCC
0
5
10
Ethylene Propylene Butylenes
Olefin yield, m%
FEATURES of DCC CATALYSTFEATURES of DCC CATALYST
• High olefin selectivity
• Low hydrogen transfer activity
• High matrix cracking activity• High matrix cracking activity
• High second cracking activity for gasoline
• Excellent thermal and hydrothermal
stabilities
DCC Commercial CatalystsDCC Commercial Catalysts
Catalyst Brand Process mode Location
CHPCHP-1 DCC-Ⅰ Jinan
CHP-2 DCC-Ⅰ Jinan
CRP
CRP-S DCC-Ⅰ Anqing
CRP-1 DCC-Ⅰ Anqing,TPI
CRP-2 DCC-Ⅰ Anqing ,TPI
CIP-S DCC-Ⅱ Jingmen
CIP
CIP-1 DCC-Ⅱ Jinan
CIP-2 DCC-Ⅱ Shenyang,Jingmen
CIP-3 DCC-Ⅰ Anqing,TPI
CIP-4 DCC-Ⅱ Shenyang
CIP-5 DCC-Ⅱ Jingmen
MMCMMC-2 DCC-Ⅰ,Ⅱ Anqing,TPI, Shenyang ,Jingmen
MMC-1 DCC-Ⅰ,Ⅱ Shenyang
DMMC DMMC-1 DCC-Ⅰ Anqing
ContentsContents1.Introduction
2. DCC Technology and Characteristics
3. Commercial Performance of DCC Technology
4. Development in DCC+ Technology4. Development in DCC Technology
5. Next Generation DMMC-1 Type Catalyst
6. Propylene Transformation during DCC
7. Summary
Application of DCC Technology
Location Process mode Cap. (Kt/a) Start Up Feed Stock
Jinan, China DCC-I 60 Nov. 1990 VGO+DAO
Jinan, China DCC-1&II 150 Jun. 1994 VGO+DAO
Anqing, China DCC-I 700 Mar, 1995 VGO+CGO
Daqing, China DCC-I 120 May, 1995 VGO+ATB
1919
IPRC, Thailand DCC-I 1000 May, 1997 VGO+ATB
Jingmen, China DCC-II 800 Sept. 1998 VGO+VTB
Shenyang, China DCC-I&II 400 Oct. 1998 VGO+VTB
Jinzhou, China DCC-I&II 300 Sept.1999 VGO, ATB
Daqing Co./Blue Star Petroleum Co. DCC-I 500 Oct. 2006 ATB
Aramco, Rabigh Refinery, Saudi Arabia DCC-I 4500 May,2009 HVGO
Application of refineries expected
NO. Location Type Capacity, kt/a Status
1 Nizhnekamsk, Russia DCC 1100 Under Designing
2 Yanchang, CHINA DCC 1700 Under Designing
2020
3 India DCC 2000 Under Designing
DCC Light Olefin YieldsDCC Light Olefin Yields
Refinery Daqing Anqing TPI Jinan
Feedstock
VGO+ATB VGO VGO+DAO+WAX VGO+DAO
paraffinic Interm. Naphthenic Interm.
Density, g/cm3
0.8621 0.8930 0.8686 0.8862
UOP K 12.6 12.0 12.0 12.2UOP K 12.6 12.0 12.0 12.2
Hydrogen, wt% 13.62 12.56 13.00 12.94
Reaction temp.,oC 545 550 565 564
Ethylene, w% 3.7 3.5 5.3 5.3
Propylene, wt% 23 18.6 18.5 19.2
Butylenes, wt% 17.3 13.8 13.3 13.2
Isobutylene, wt% 6.9 5.7 5.9 5.2
Integrated Integrated DCC plantDCC plant
ContentsContents• 1.Introduction
• 2. DCC Technology and Characteristics
• 3. Commercial Performance of DCC
Technology
• 4. Development in DCC+ Technology
• 5. Next Generation DMMC-1 Type Catalyst
• 6. Propylene Transformation during DCC
• 7. Summary
DCCU OperationDCCU Operation
• Heavier feedstock should be processed
• Wild operation condition should be adapted to • Wild operation condition should be adapted to
lower dry gas yield while maintaining same
propylene production
R&DR&D on DCCon DCC++ Tech.developmentTech.development
� Maximizing propylene yield, while ethylene and lighter
aromatics are as by-products for petrochemical based
refining technology.
� Propylene yield of DCC+ is 6~8 times that of conventional
FCC. The total yield of propylene plus ethylene is equal to
that of steam cracking. New type of reactor and catalysts
will be designed.
R&DR&D on DCCon DCC++ Tech.Tech.
�Lower value stream, such as C4 fraction, lighter
gasoline, even LCO will be recycled to produce
more propylene, while ethylene is as by-product.
�Heavy gasoline fraction was used as a feedstock
for aromatic extraction to obtain blending
aromatics rich in BTX.
Pilot Plant Results of DCCPilot Plant Results of DCC+ Tech.
Technology DCC DCC+
Product Yield, wt%
Dry gas 11.90 14.13
Ethylene 6.10 9.17
LPG 42.20 42.81 LPG 42.20 42.81
Propylene 21.00 30.26
Gasoline 26.60 25.76
LCO 6.60 8.59
DO 6.10 3.58
Coke 6.00 4.70
Loss 0.60 0.40
ContentsContents• 1.Introduction
• 2. DCC Technology and Characteristics
• 3. Commercial Performance of DCC
Technology
• 4. Development in DCC+ Technology
• 5. Next Generation DMMC-1 Type Catalyst
• 6. Propylene Transformation during DCC
• 7. Summary
Innovations in DMMC catalystInnovations in DMMC catalyst
DMMCDMMC--11
•• Innovation in catalyst Innovation in catalyst preparationpreparation
•• Innovation in new Innovation in new catalytic componentscatalytic componentscatalytic componentscatalytic components
•• DMMCDMMC--1’s targets1’s targets
–– Higher propene yieldHigher propene yield
–– Improved distribution of productsImproved distribution of products
–– Better gasoline qualityBetter gasoline quality
Fresh catalystFresh catalyst MMCMMC--22 DMMCDMMC--11
AI, %AI, % basebase same levelsame level
VVH2OH2O, mL/g, mL/g basebase +21%+21%
VVBETBET, mL/g, mL/g basebase +13%+13%
After steamingAfter steaming MMCMMC--22 DMMCDMMC--11After steamingAfter steaming MMCMMC--22 DMMCDMMC--11
SSBETBET, m, m22/g/g basebase +19%+19%
SSZZ, m, m22/g/g basebase +111%+111%
SSMM, m, m22/g/g basebase same levelsame level
VVmicromicro, mL/g, mL/g basebase +100%+100%
VVBETBET, mL/g, mL/g basebase +13%+13%
DMMCDMMC--1 in Anqing Petrochemical1 in Anqing Petrochemical
Product yield, wt%Product yield, wt% MMCMMC--22 DMMCDMMC--11
Dry gasDry gas base base + 0.18+ 0.18
LPGLPG basebase + 4.30+ 4.30
NaphthaNaphtha base base -- 3.813.81
LCOLCO basebase + 0.15+ 0.15LCOLCO basebase + 0.15+ 0.15
SlurrySlurry base base -- 0.250.25
CokeCoke basebase -- 0.560.56
propene, wt%propene, wt% base base + 2.43+ 2.43
Butylene, wt%Butylene, wt% basebase ++ 0.410.41
CC22==+C+C33
==+C+C44== base base + 3.26+ 3.26
LiquidLiquid yields,yields, wtwt%% basebase + 0.64+ 0.64
DMMCDMMC--1 in Anqing Petrochemical, 1 in Anqing Petrochemical,
--comparison of gasolinecomparison of gasoline
MMC-2 DMMC-1
Density, g/cm3 base same level
HK,℃ base same levelsame level
50%,℃ base same levelsame level50%,℃ base same levelsame level
KK,℃ base same levelsame level
Induction period, min base + 17
Olefins, v% base - 4.5
MON base same level
RON base same level
ContentsContents• 1.Introduction
• 2. DCC Technology Description and
Characteristics
• 3. Commercial Performance of DCC
Technology
• 4. Development in DCC+ Technology
• 5. Next Generation DMMC-1 Type Catalyst
• 6. Propylene Transformation during DCC
• 7. Summary
Thermal reaction of propyleneThermal reaction of propylene
WHSV/hr-1Reaction temperature/℃
550 575 600 625 650
0.5 9.23 9.72 9.62 10.94 15.14
• Thermal conversion of propylene, wt%
• The thermal conversion of propylene is 5~15 wt%
0.5 9.23 9.72 9.62 10.94 15.14
1 7.41 7.14 7.41 8.33 8.92
2 5.91 5.97 5.78 7.01 7.85
4 4.91 5.64 5.23 5.67 6.01
Catalytic cracking reaction of propyleneCatalytic cracking reaction of propylene
WHSV/hr-1
550 ℃ 575 ℃ 600 ℃ 625 ℃ 650 ℃
2 79.55 78.41 76.00 72.28 71.59
• The catalytic conversion of propylene,wt%
• The catalytic conversion is 56~80 wt%
2 79.55 78.41 76.00 72.28 71.59
4 76.41 73.51 69.02 71.49 70.64
5 70.42 70.00 65.46 62.43 59.08
8 64.89 64.01 62.44 59.56 55.97
Product slate of propylene catalytic cracking reactionProduct slate of propylene catalytic cracking reaction
WHSV
/hr-1Reaction
time/s
Conversion.
wt%
Dry gas Propane C4 naphtha diesel coke
2 9.21 4.94 21.18 35.19 1.54 3.94 3.01 76.00
4 8.34 4.43 21.14 31.33 1.63 2.15 1.53 69.02
5 7.80 3.84 20.57 29.25 1.86 2.14 1.30 65.46
8 6.70 3.51 20.13 27.47 2.41 2.22 0.75 62.44
The PONA of NaphthaThe PONA of Naphtha
Reaction temperature,600 ℃
50
60
70
Content/wt%
P
I
0
10
20
30
40
50
2 4 5 8WHSV/hr-1
Content/wt%
I
O
N
A
ContentsContents• 1.Introduction
• 2. DCC Technology Description and
Characteristics
• 3. DCC Technology Commercial Performances
• 4. Future Focus on DCC Technology
• 5. Next Generation DMMC-1 Type Catalyst for
Deep Catalytic Cracking
• 6. Propylene Transformation during DCC
• 7. Summary
ConclusionConclusionDCC Opened up New Routes for Producing Light Olefins
with Heavy Feedstock, Bridging Refining and
Petrochemicals .
DCC is a perfect technology with 15 years experience inDCC is a perfect technology with 15 years experience in
catalyst, design and commercial operation.
R&D and innovations in DCC technology will keep it in
the leading position on lighter olefin production from heavy
oil feed.
Thanks!Thanks!