Advances in DCC Technology for Light Olefins Production
SINOPEC Research Institute of Petroleum Processing 2010.5
Contents
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 Production
Ethylene: Basically by steam cracking 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 Resources
Propylene resource Steam cracking FCC Others World average 70 28 2 China 61 39 0
Lighter 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 MIO DCC CPP
Feed : VGO VGO+ Resid
Feed : VGO VGO+ Resid
Feed: HVGO VGO+ Resid
Feed : VGO VGO+ Resid
Objective Products : C3,C4 Gasoline
Objective Products: iC4=,iC5= Gasoline
Objective Products : C3=,C4=
Objective Products: C2=,C3=
DCC (Deep Catalytic Cracking)
Maximum production of propylene and butylenes Bridging technology connecting refining & petrochemical
Contents
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 DCCU
DCCDCC-Operating Modes
DCC have two typical operating modes by regulating the operating conditions and catalyst formulations DCC-I: maximum propylene mode DCC-II: maximum propylene plus isoolefins and naphtha mode
FEATURES 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. Special designed zeolite catalysts. maximum propylene production. Flexibility of operating . Hydrocarbon impurity is trace in lighter olefin products.
11
Comparison of DCC and FCC
- Hardware
FCC
Reactor Regenerator
Main fractionator Stabilizer/absorber
DCC
Base Riser and/or fluid bed Base Similar Base Higher vapor/liquid ratio Base Bigger Base Larger capacity
Compressor
Comparison of DCC and FCC
- Operating Conditions
FCC
Reaction Temp. Catalyst/oil Ratio Residence Time Pressure Steam Base Base Base Base Base
DCC
+~50oC 1.5~2 times More Lower More
Comparison of DCC and FCC - Product Yields
FCC
Propylene Isobutylene Naphtha LCO Base Base Base Base
DCC
3~5 times 3 times 50~80% Less
Light olefin Yield of DCC and FCC
25
FCC DCC
Olefin yield, m %
20 15 10 5 0 Ethylene Propylene Butylenes
FEATURES of DCC CATALYST
High olefin selectivity Low hydrogen transfer activity High matrix cracking activity High second cracking activity for gasoline Excellent thermal and hydrothermal stabilities
DCC Commercial Catalysts
Catalyst CHP CHP-2 CRP-S CRP CRP-1 CRP-2 CIP-S CIP-1 CIP-2 CIP CIP-3 CIP-4 CIP-5 MMC-2 MMC MMC-1 DMMC DMMC-1 DCC-, DCC- Shenyang Anqing DCC- DCC- DCC- DCC-, Anqing,TPI Shenyang Jingmen Anqing,TPI, Shenyang ,Jingmen DCC- DCC- DCC- DCC- DCC- DCC- DCC- Jinan Anqing Anqing,TPI Anqing ,TPI Jingmen Jinan Shenyang,Jingmen Brand CHP-1 Process mode DCC- Location Jinan
Contents
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
Application of DCC Technology
Location Jinan, China Jinan, China Anqing, China Daqing, China IPRC, Thailand Jingmen, China Shenyang, China Jinzhou, China Daqing Co./Blue Star Petroleum Co. Aramco, Rabigh Refinery, Saudi Arabia Process mode DCC-I DCC-1&II DCC-I DCC-I DCC-I DCC-II DCC-I&II DCC-I&II DCC-I DCC-I Cap. (Kt/a) 60 150 700 120 1000 800 400 300 500 4500 Start Up Nov. 1990 Jun. 1994 Mar, 1995 May, 1995 May, 1997 Sept. 1998 Oct. 1998 Sept.1999 Oct. 2006 May,2009 Feed Stock VGO+DAO VGO+DAO VGO+CGO VGO+ATB VGO+ATB VGO+VTB VGO+VTB VGO, ATB ATB HVGO
19
Application of refineries expected
NO. 1 2 3 Location Nizhnekamsk, Russia Yanchang, CHINA India Type DCC DCC DCC Capacity, kt/a 1100 1700 2000 Status Under Designing Under Designing Under Designing
20
DCC Light Olefin Yields
Refinery Daqing VGO+ATB Feedstock
3
Anqing VGO Interm. 0.8930 12.0 12.56 550 3.5 18.6 13.8 5.7
TPI VGO+DAO+WAX Naphthenic 0.8686 12.0 13.00 565 5.3 18.5 13.3 5.9
Jinan VGO+DAO Interm. 0.8862 12.2 12.94 564 5.3 19.2 13.2 5.2
paraffinic 0.8621 12.6 13.62 545 3.7 23 17.3 6.9
Density, g/cm UOP
K
o
Hydrogen, wt% Reaction temp., C Ethylene, w% Propylene, wt% Butylenes, wt% Isobutylene, wt%
Integrated DCC plant
Contents
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 Operation
Heavier feedstock should be processed Wild operation condition should be adapted to lower dry gas yield while maintaining same propylene production
R&D on DCC+ Tech.development
Maximizing propylene yield, while ethylene and lighter aromatics are as by-products for petrochemical based refining technology.
Propylene yield of DCC+ is 68 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&D on DCC+ 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 DCC+ Tech.
Technology
Product Yield, wt% Dry gas Ethylene LPG Propylene Gasoline LCO DO Coke Loss 11.90 6.10 42.20 21.00 26.60 6.60 6.10 6.00 0.60 14.13 9.17 42.81 30.26 25.76 8.59 3.58 4.70 0.40
DCC
DCC
Contents
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 catalyst
Innovation in catalyst preparation Innovation in new catalytic components DMMC-1s targets DMMC Higher propene yield Improved distribution of products Better gasoline quality
DMMCDMMC-1
Fresh catalyst AI, % VH2O, mL/g VBET, mL/g After steaming SBET, m2/g SZ, m2/g SM, m2/g Vmicro, mL/g VBET, mL/g
MMC-2 MMCbase base base MMCMMC-2 base base base base base
DMMC-1 DMMCsame level +21% +13% DMMCDMMC-1 +19% +111% same level +100% +13%
DMMCDMMC-1 in Anqing Petrochemical
Product yield, wt% Dry gas LPG Naphtha LCO Slurry Coke propene, wt% Butylene, wt% C2=+C3=+C4= Liquid yields, wt% wt% MMCMMC-2 base base base base base base base base base base DMMC-1 DMMC+ 0.18 + 4.30 - 3.81 + 0.15 - 0.25 - 0.56 + 2.43 + 0.41 + 3.26 + 0.64
DMMCDMMC-1 in Anqing Petrochemical, -comparison of gasoline
Density, g/cm3 HK 50% KK Induction period, min Olefins, v% MON RON MMC-2 base base base base base base base base DMMC-1 same level same level same level same level + 17 - 4.5 same level same level
Contents
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 propylene
Thermal conversion of propylene, wt%
WHSV/hr-1
Reaction temperature/ 550 575 9.72 7.14 5.97 5.64 600 9.62 7.41 5.78 5.23 625 10.94 8.33 7.01 5.67 650 15.14 8.92 7.85 6.01 9.23 7.41 5.91 4.91
0.5 1 2 4
The thermal conversion of propylene is 515 wt%
Catalytic cracking reaction of propylene
The catalytic conversion of propylene,wt%
WHSV/hr-1
550 79.55 76.41 70.42 64.89
575 78.41 73.51 70.00 64.01
600 76.00 69.02 65.46 62.44
625 72.28 71.49 62.43 59.56
650 71.59 70.64 59.08 55.97
2 4 5 8
The catalytic conversion is 5680 wt%
Product slate of propylene catalytic cracking reaction
WHSV /hr-1
Dry gas Propane C4 naphtha diesel coke
Reaction time/s
Conversion. wt
2 4 5 8
9.21 8.34 7.80 6.70
4.94 4.43 3.84 3.51
21.18 35.19 1.54 3.94 3.01 21.14 31.33 1.63 2.15 1.53 20.57 29.25 1.86 2.14 1.30 20.13 27.47 2.41 2.22 0.75
76.00 69.02 65.46 62.44
The PONA of Naphtha
Reaction temperature,600
70 60 50 40 30 20 10 0 2 4
WHSV/hr-1
Content/wt%
P I O N A 5 8
Contents
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
Conclusion Light Olefins DCC Opened up New Routes for Producing
with Heavy Feedstock, Bridging Refining and Petrochemicals . DCC 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
