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