Dcc Conference

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Advances in DCC Technology for Light Olefins Production SINOPEC Research Institute of Petroleum Processing SINOPEC Research Institute of Petroleum Processing 2010.5 2010.5

Transcript of Dcc Conference

Page 1: Dcc Conference

Advances in DCC Technology for

Light Olefins Production

SINOPEC Research Institute of Petroleum ProcessingSINOPEC Research Institute of Petroleum Processing

2010.52010.5

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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

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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

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Propylene ResourcesPropylene Resources

Propylene resource World

average

China

Steam cracking 70% 61%Steam cracking 70% 61%

FCC 28% 39%

Others 2% 0

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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

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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

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DCCDCC ((DDeep eep CCatalytic atalytic CCracking)racking)

• Maximum production of propylene and

butylenes

77

• Bridging technology connecting refining &

petrochemical

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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

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Schematic Diagram of DCCUSchematic Diagram of DCCU

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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

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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.

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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

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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

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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

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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%

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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

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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

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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

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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

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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

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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

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Integrated Integrated DCC plantDCC plant

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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

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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

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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.

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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.

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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

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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

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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

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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%

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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

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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

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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

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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

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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

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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

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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

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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

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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.

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