dcc(deep catalytic cracking), mip(maximizing iso- · pdf file•who we are?...

COPYRIGHT@SUNJUNNAN

COPYRIGHT@SUNJUNNAN

Oct., 2015

Hongli GUO

SINOPEC Europe Office

DCC(Deep Catalytic Cracking), MIP(Maximizing Iso-

paraffin) and CGP(Clean Gasoline & Propylene)

from SINOPEC

CEE and Turkey Refining and Petrochemicals 13-15th October, 2015|Sofitel Budapest Chain Bridge | Hungary

Outline

1. Brief Introduction to SINOPEC

2. DCC Technology

3. MIP/CGP Technology

4. SINOPEC TECH

•WHO We are?

•中国石化

China Petrochemical Corporation (Sinopec Group) is a super-large petroleum and

petrochemical enterprise group, established in July 1998 on the basis of the former

China Petrochemical Corporation. Sinopec Group is a state-owned company solely

invested by the state, functioning as a state-authorized investment organization in

which the state holds the controlling share. Headquartered in Beijing, Sinopec Group

has a registered capital of RMB 231.6 billion. The board chairman of Sinopec Group is

its legal representative.

中国石油化工集团公司(Sinopec Group)是中国特大型石油石化企业集团，是中国最大的

上、中、下游一体化能源、化工公司之一，是国家独资设立的国有公司、国家授权投资

的机构和国家控股公司，总员工数量92万人，公司注册资本2316亿元，总部设在北京。

July 12th

1983

China Petrochemical

Corporation was founded to

exercise unified leadership,

overall planning and

management of China’s major

refining, petrochemical and

chemical fiber enterprises.

December

1984

Sales arm of China

Petrochemical

Corporation was set up to

unify

the management of the

refined

oil products businesses.

There are a number of significant events in our history we are especially proud of.

July 27th

1998

China Petrochemical

Corporation (Sinopec

Group) was founded.

February 28th

2000

The company independently

launched the China Petroleum

& Chemical Company

(Sinopec Corp.).

March 30th

2000

China National Star

Petroleum

Co., Ltd. was merged into

Sinopec Group, enhancing

the

company’s onshore and

offshore exploration and

production capabilities.

October 18th

2000

Sinopec Corp. was listed in

Hong Kong, New York and

London, thereby becoming

the first Chinese company

listed

on three international markets.

•Our Glorious history

June

2015

SINOPEC is listed No. 2 in

the FORTUNE Global 500.

August 8th

2001

Sinopec Corp. was listed on the

Shanghai Stock Exchange.

January

2008

Mr Min Enze, the founder of

refining catalyst application

science in China and

academician of the Chinese

Academy of Sciences and the

Chinese Academy of

engineering, received the State

Pre-eminent Science and

Technology Award.

August

2009

Sinopec Group acquired Addax

Petroleum, an oil company with

headquarters in Switzerland.

August

2010

The project of transmitting

natural gas from Sichuan

to East China went into

commercial operation..

August

2011

We clearly set our vision to

build

a world-leading energy and

chemical company.

•Business Scope

1.Exploration, Production, storage and transportation, marketing and

comprehensive utilization of oil and natural gas;

2.the production, marketing, storage and transportation of coal;

3.oil refining;

4.the storage, transportation ,wholesale and retail of oil products; the

production, marketing, storage, transportation of petrochemicals, natural gas

chemicals, coal chemicals and other chemical products;

5.the exploration, design, consulting, construction and installation of

petroleum and petrochemical engineering projects;

6.the overhaul and maintenance of petroleum and petrochemical equipments;

7.the research and development, manufacturing and marketing of electrical

and mechanical equipments; the production and marketing of electricity,

steam, water and industrial gas;

8.the research, development, application and consulting services of

technology, e-business, information and alternative energy products……

Upstream Segment Refining & Chemicals Segment Marketing & Service Segment

Oil & Gas Exploration & Production

Refining Chemicals Produciton

Marketing Service

•Core Business

• 409 Organizations in 75 countries and regions;

• 233 overseas organization with permanent delegates in 58 countries and regions;

•Overseas Business

Key Facts

Overseas asset

Accounts for

35.2% Of the total asset in 2011

Overseas sales revenue

Account for

24.5% Of the total sales revenue in 2011

Operations

across

58 Countries and regions in 2014

机构分布 Organizations Distribution

• With total employees of 61860.

•Overseas Business

Key Facts

Overseas asset

Accounts for

35.2% Of the total asset in 2011

Overseas sales revenue

Account for

24.5% Of the total sales revenue in 2011

Operations

across

58 Countries and regions in 2014

人员分布 Employees Distribution

Oil & Gas

Exploration

and Production

1

Oil

Refining 2

Oil Product

Marketing &

Distribution

3

Chemicals 4

International

Operations 5

473 million barrels of

crude oil output

232 Million tons

processing

capacity in 2013

20 million customers

per day served at

our stations

10.04 million tonnes of

ethylene production

1.70 billion barrels of

crude oil traded

•Key Figures

Refining

No. 1

Petrochemical

No. 1

• Core Business

• Ranking in FORTUNE 500

2014年第 3 位

2015年第 2 位

FORTUNE

500

The revenue

in 2014($):

283 bn

Account for：

4.45% Of GDP in

China

SINOPEC R&D Capability

R&D Framework of SINOPEC

SINOPEC

Sci. &Tech. Develop. Dept.

Sci. &Tech. Committee 19 members of CAS &CAE

SR

IPE

PE

PR

IS

SG

RI

RIP

P

FR

IPP

BR

ICI

SR

IPT

QD

SE

I

Sin

op

ecTech

Cata

lyst C

om

pan

y

Su

b R

esearc

h In

st.

5 E

ng

ineerin

g In

c.s


SINOPEC has a complete system for technology research & development, engineering and intellectual property management.

8 Research Institutes 5 Engineering companies (Sinopec Engineering Group)

FRIPP-Fushun Research Institute of Petrochemical Processing

SRIPT-Shanghai Research Institute of Petrochemical Tech

BRICI-Beijing Research Institute of Chemical Industry

QDSEI-Qingdao Safety Engineering Institute

RIPP-Research Institute of

Petroleum Processing

PEPRIS-Exploration & Production Research Institute

SGRI- Geophysical

Research Institute

SRIPE- Research Institute of Petroleum Engineering

637 professionals

764 professionals

719 professionals

1310 professionals

410 professionals 619 professionals

RIPP: R&D of complete set of technology of whole

refinery plant from crude evaluation to oil refining

process, technology and catalyst.

BRICI: Ethylene technology & organic chemical

engineering; polyolefin catalyst & process research;

polymer materials; environmental protection.

SRIPT: R&D of complete set of petrochemical

technology, application of catalysts and processes for

basic organic raw materials, polymer reprocessing and

synthesis.

FRIPP: Development of catalyst and process for

hydrocracking, hydrofining of distillates, wax and special

solvent oil, hydrotreating of residue, semi-generation

reforming.


Outline


2. DCC Technology

3. MIP-CGP Technology

4. SINOPEC TECH

Global Demand for Propylene

From Stm.Crackers

From Refineries

On purposeproduction

Propylene Production by Feedstock

FCC (Fluid Catalytic Cracking)

Reaction temperature ~560oC(DCC-I) and ~530oC(DCC-II)

Residence time longer residence time to enable the cracked

naphtha to proceed secondary reaction for forming light olefins.

Catalyst to oil ratio & catalyst circulation rate Higher catalyst

circulation rate and higher catalyst to oil ratio to provide the heat of

reaction.

Low hydrocarbon partial pressure for higher propylene yields

and less coke formation.

Dilution steam DCC needs more steam than FCC but still much

less than steam cracking.

DCC Operating Conditions

II. SINOPEC DCC Process

Main Characteristics

II. DCC (Deep Catalytic Cracking)

Maximizing productions of

propylene, butylenes & naphtha

with high content of aromatics

and octane number using heavy

oil (VGO, Deasphalted oil, Coker

gas oil, Atmospheric residue,

Vacuum residue, etc.)

Matured Technology for Bridging

Refining & Petrochemical Industry From Sinopec Ripp & SW

Product Yields: DCC vs FCC

FCC DCC

Propylene Base 3~5 times

Isobutylene Base 3 times

Naphtha Base 50~80%

LCO Base Less

Light olefin Yield Comparison between DCC and FCC

0

5

10

15

20

25

Ethylene Propylene Butylenes

Ole

fin

yie

ld,

m%

FCC DCC

II. SINOPEC DCC Process

DCC Light Olefin Yields of Different Feedstock

Refinery Daqing Anqing TPI/IRPC 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 12.2

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

DCC Economic Analysis-provided by S&W

Case

FCC petrochemical

options

DCC petrochemical

options

DCC vs FCC

petrochemical options

(FCC basis)

Products (BPCD)

Propane 6,005 7,334 22.10%

Butane 3,801 3,780 -0.50%

Premium unleaded 2,330 2,225 -4.50%

Regular unleaded 45,014 42,811 -4.90%

Jet fuel 14,710 13,643, -7.30%

Diesel 17,031 12,188 -28.40%

Fuel oil 779 - -

Ethylene(TPA) 61320 66,065 7.70%

Propylene(TPA) 124,100 350,800 182.70%

Benzene(TPA) 63,500 73,300 15.40%

Paraxylene(TPA) 99,300 114,200 15.00%

Butadiene(TPA) 1,825 1,825 -

US$94,129 /day

Jinan Company, SINOPEC

Start up November 1990

First DCC unit in the world

There are 18 DCC units under designing, construction and running in the world

SINOPEC DCC Technology

Jinan

TPI

Petro

Rabigh

Thailand’s TPI

Start up May1997

First DCC unit outside China

Rabigh Refining & Petrochemical Co.

Start up May 2009

The largest capacity 92,000 bbl/d

(4.60 MMT/a)

12 units China

2 units Thailand

1 unit Saudi Arabia

3 units India

DCC Commercial Reference

Outline


2. DCC Technology

3. MIP-CGP Technologies

4. SINOPEC TECH

I.Introduction

• The gasoline specification is increasingly stringent

• About 75% gasoline are come from FCC units

• The feed stock of FCC is deteriorating

• FCC naphtha contributes high percentages of olefins

and sulfur in gasoline pool

Key Issues of Gasoline

I.Introduction

WorkingTargets

MIP Processing:

• Decrease Gasoline olefin and sulfur content

• Improve heavy oil conversion capability

• Improve the product distribution

• Enhance the beneficial returns

M I

P

CGP On the basis of MIP, increase the yield of propylene greatly

28 28

Reaction Principal of MIP Technology

Pre-lifting medium

Regenerated catalyst

Feedstock

Average temp. 490oC

Conventional FCC MIP

Pre-lifting medium


Feedstock

residence time 1.2 seconds residence time

1.2 seconds

residence time 2.3 seconds

residence time 5.0 seconds

530oC

510oC

510oC

Average temp. 520oC

The 1st Reaction Zone •High temperature •Short contact time •High catalyst/oil ratio

The 2nd Reaction Zone • Medium temperature • Long reaction time • Low WHSV

Feedstock


Two Reaction Zone Riser

Quench

Th

e 1

st

rea

cti

on

zo

ne

T

he

2n

d r

ea

cti

on

zo

ne

II. Technical Features

New temperature gradient

large catalyst inventory

Longer residence time

Controlling the first reaction zone and secondary reaction zone separately

Distributor


The 2nd Reaction Zone

The 1st Reaction Zone

Hydrocarbon mixtures

Light hydrocarbons +

Olefins

Cracking

Isomerization

HydrideTransfer

Alkylation

Cracking

Iso-olefins Iso-paraffins

Iso-paraffins and Aromatics

Iso-paraffins or Alkylaromatics

Propylene

HydrideTransfer

Endothermic reactions Carbenium ion formation

Exothermic reaction Carbenium ion transfer


1.reactor-regenerator system

(Riser reactor is different with convention FCC)

2. Fractionation system

(Similar to conventional FCC)

3.Absorption and stabilization system

(Similar to conventional FCC)


Items MIP CGP

Process

Catalyst conventional Special

T in outlet of 1st reactor Low High

T in 2nd reactor Low High

WHSV in 2nd reactor 30-40 -20

Product

Propylene yield Similar to FCC One time higher than FCC

Olefin <35v% <18v%

Octane number Similar to FCC 1-2 unit higher than FCC

1. MIP for maximizing producing clean gasoline

Shanghai MIP: 1.40 Mt/a Production option : Maximizing producing clean gasoline Catalyst : Conventional FCC Catalyst Feedstock: VGO + 40%VR Quenching measures : Spent catalyst

MIP FCC

Density (20oC) , g/cm3 0.8966 0.8967

Residue Carbon, w% 4.68 4.00

H, w% 12.86 12.80

Feedstock Properties

CASE 1

Process MIP FCC

Performance test date 2002-03-28 1999-11-02

Product distribution

Dry gas 2.88 3.79

LPG 14.63 15.44

Gasoline 49.28 44.14

Diesel 21.22 22.57

Slurry Oil 3.04 4.64

Coke 8.64 8.92

Total liquid yield, w% 85.13 82.15

Alkylation gasoline, w% 7.70 6.83

Blended gasoline, w% 56.98 50.97

Olefin in gasoline, w% 34.11 43.10

RON/MON 88.8/80.2 89.4/79.2

CASE 1 Performance Test Result of Shanghai MIP (1.40 Mt/a)


CASE 2 and 3: MIP for maximizing producing clean gasoline

Refineries Gaoqiao Daqing

Processes FCC MIP FCC MIP

Dry gas 3.79 2.92 4.39 2.94

LPG 15.44 13.81 12.47 15.44

LPG/Dry gas 4.07 4.73 2.84 5.25

Propylene 3.43 3.67 4.07 4.88

Gasoline 22.21 26.57 32.67 31.66

Olefin 43.1 34.1 46.50 30.60


2. MIP for maximizing producing liquid yields

Jinxi MIP: 1.80 Mt/a Production option : Maximizing producing liquid yields ( gasoline + diesel ) Catalyst : Conventional FCC Catalyst Feedstock: VGO + 30%VR Quenching measures : Spent catalyst

MIP FCC

Density (20oC) , g/cm3 0.9047 0.8971


H, w% 12.87

Ni, μg/g 3.7 1.4

Ni, μg/g 1.5 1.0


CASE 1

Process MIP FCC


Dry gas 3.00 3.47

LPG 13.39 12.67


Diesel 31.37 32.95


Coke 7.40 7.43





RON/MON 89.4/80.5 89.5/78.8

CASE 1 Performance Test Result of Jinxi MIP

2. MIP for maximizing producing liquid yields

3. MIP-CGP for producing clean gasoline and propylene

CASE 1

Zhenhai CGP: 1.80 Mt/a Production option : Clean gasoline + Propylene Catalyst : Conventional FCC Catalyst Feedstock: VGO + 30%VR Quenching measures : Spent catalyst

MIP FCC

Density (20oC) , g/cm3 0.9084 0.9109


H, w% 12.45 12.28

Ni, μg/g 12.57 18.50

Ni, μg/g 3.15 4.49


Process MIP FCC

Performance test date 12 May 2005 22 Sept 2003


Dry gas 2.65 3.46

LPG 24.45 16.13




Propylene, w% 8.16 5.00




RON/MON 93.6/81.9 92.6/-

CASE 1 Performance Test Result of Zhenhai MIP-CGP


CASE 2 MIP-CGP for producing clean gasoline and propylene

Refineries Zhenhai JiuJiang

Process FCC MIP CGP FCC MIP CGP

Dry gas 3.46 2.51 2.65 3.72 3.16 3.45

LPG 16.13 22.12 24.45 19.11 27.01 27.39

LPG/Dry gas 4.66 8.81 9.23 5.14 8.55 7.98

Propylene 5.00 8.03 8.16 6.29 9.46 8.96

Gasoline 31.00 36.30 33.37 32.91 35.02 32.71

Olefin 39.90 32.80 17.60 41.10 27.70 15.00


Ways to Produce Clean Gasoline

- Integration of MIP-CGP, selective HDS and alkylation techniques

- Integration of FCC, selective HDS and alkylation/etherification techniques

- Integration of MIP-CGP/FCC and S-zorb techniques

4. Commercial reference

R&D Steps

1. Exploratory experiment (1999)

2. Pilot plant test (2000)

3. MIP commercial application (2002)

4. CGP Commercial application (2005)

5. Market promotion (over 30 unit)

Commercial reference (Total process capacity: 40.6Mt/a)

Refineries Location Process Capacity

Mt/a Start-up

Gaoqiao Shanghai 140 04 Feb 2002

Anqing Anqing, Anhui 120 19 Jan 2003

Langxi Heilongjiang 44 13 Sep 2003

Yanchang Group Yanan, Shanxi 140 10 Apr 2004

Zhenhai Ningbo, Zhejiang 180 26 Apr 2004

Xian Xian, Shanxi 60 04 Jul 2004

Cangzhou, Cangzhou, Hebei 120 19 Jun 2004

Jiujiang Jiujiang, Jiangxi 100 23 Jul 2004

Yanshan Beijing 200 16 Apr 2005

Shijiazhuang Shijiazhuang, Hebei 100 25 Jun 2005

Tianjin Tianjin 150 01 Jul 2005

Qingdao Qingdao, Shandong 140 26 Aug 2005


Commercial reference (Total process capacity: 40.6Mt/a)


Mt/a Start-up

Haerbin, CNPC Haerbin, Helongjiang 60 30 Oct 2005

Jinxi, CNPC Jinxi, Liaoning 180 22 Nov 2005

Zhongyuan Henan 50 28 Jun 2006

Hainan Hainan 280 26 Aug 2006

Yanchang Group Xian, Shanxi 200 17 Nov 2006

Jinling Nanjing, Jiangsu 120 27 Nov 2006

Guangzhou, Guangzhou, Guangdong 200 08 Feb 2007

Zhenhai Ningbo, Zhejiang 300 30 Apr 2007

Maoming, Maoming, Guangdong 100 04 Sep 2007

Qianguo, CNPC Daqing, Heilongjiang 100 29 Sep 2007

Qingdao Qingdao, Shandong 290 10 May 2008



Mt/a Start-up

Jinzhou Jinzhou, Liaoning 160

Yanchang Group Yulin, Shanxi 60

Daqing, CNPC Daqing, Heilongjiang 100

Daqing, CNPC Daqing, Heilongjiang 140

Baling Baling, Hunan 105

Huizhou, CNOOC Huizhou, Guangdong 120

MIP or CGP units to be revamped ( 685 Mt/a )


Outline


2. DCC Technology

3. MIP-CGP Technology

4. SINOPEC TECH

Who is SINOPEC TECH

Basic Engineering Design

Detailed Engineering Design

Technical Service

EPC Contractor

Turn-key Project

SINOPEC TECH is a subsidiary company of SINOPEC. It is in charge

of the licensing and transferring of SINOPEC’s Proprietary

technologies and is involved actively in global market.

Process Design Package Note: Providing the PDP is the main business of SinopecTech

47

SINOPEC Technology & Process

Refining Technologies

•SINOPEC can provide multi-technical package solutions targeted for fuel oriented, fuel &

lube oil oriented or petrochemical feedstock oriented refineries with a maximum

processing capacity of 15 MMTA of a single train.

•The specifications of the oil products can meet the requirements of EURO V.

48

Technology & Process of SINOPEC

Refining Technologies

49


What we share -- Technologies and Processes

No. Technology Type Process

1

1. FCC Technologies

FCC Process for Deep Catalytic Cracking (DCC)

2 FCC Process for Maximizing Iso-paraffin（MIP）

3 FCC Process for Producing Clean Gasoline and More Propylene (CGP)

4 Maximizing Iso-olefins Catalytic Cracking Technology (MIO)

5 Maximizing Gas and Diesel FCC Technology (MGD)

6 Catalytic Cracking Technology for Maximum liquefied Gas and High-Octane

Gasoline (MGG ARGG)

7 Feed of Paraffinic Vacuum Residue FCC Technology (VRFCC)

8 Flexible Dual-riser Fluid Catalytic Cracking Process (FDFCC-III)

50




9

2. Hydrocracking

Technologies

Medium Pressure Hydrocracking Technology (RMC)

10 Single-stage Hydrocracking Technology (SHC)

11 Single-stage in Series Hydrocracking Technology (FMD1)

12 Two-stage Hydrocracking Technology for maximum production of middle

distillates (FMD2)

13 Single-Stage, Double-Catalysts Hydrocracking Technology for Producing

More Middle Distillates (FDC)

14 Hydrocracking Technology for Maximum Production of Catalytic

Reforming Feed (FMN)

15 Single-stage in Series and Once-through Hydrocracking Technology for

Producing More Chemical feeds (FMC1)

16 Two-stage Hydrocracking Technology for Producing More Chemical

feeds (FMC2)

17 Hydrocracking Technology for Flexibly Producing Middle-Distillates and

Petrochemical Materials (FHC)

51




18

3. Hydrofining

Technologies

High space velocity reformer feed hydrofining technology

19 Selective Hydrodesulfurization of FCC Gasoline

20 Coker Naphtha Hydrotreating Technology

21 Mercaptans Removal Technology from Jet Fuel in Hydrogen Atmosphere

(RHSS)

22 Ultra Deep Hydrodesulfurization Technology for Diesel (UDS)

23 Technology for Maximally Improving FCC Diesel Cetane Number (LCO)

24 Diesel Hydroupgrading-Isodewaxing Technology (FHI)

25 Medium Pressure Hydroupgrading Technology (MHUG)

26 Full Range Coker Distillate Hydrotreating Technology

27 FCC Feed Pretreating Technology

28 Technology for Fixed-bed Residue Hydortreating (RHT)

29 Technology for Petroleum Wax Hydrofining

52




30

4. Thermal Processing

Technologies

Delayed Coking Technology

31 Visbreaking Technology

32 5. Adsorption Sulfur Removal

Technologies S ZorbTM Sulfur Removal Technology

53


Petrochemical Technologies

54


What we share -- Technologies and Processes of SINOPEC

No. Technology Type Technology Name

1

1.Ethylene/Propylene

Technologies

CBL Cracking Technology

2 Tube with Twisted-tape Technology to Intensify Heat Exchange for Tubular

Cracking Furnace

3 Pyrolysis Gasoline Hydrogenation Technology

4 OCC (Olefin Catalytic Cracking) Technology

55




5

2.Aromatics

Technologies

Ultra Low Pressure Continuous Catalytic Reforming (SLCR)

6 Sulfolane Aromatics Extraction Technology (SAE)

7 Sulfolane Extractive Distillation Technology (SED)

8 S-TDTTM Technology of Toluene Disproportionation and Transalkylation

9 Technology for aromatization of olefins and paraffins to produce aromatics

10 PX Adsorption Separation Process

11 PX Isomerization Process

56

Technology & Process of SINOPEC



12

3.Organic Materials

Production

Technologies

Liquid Phase Alkylation Technology with Circulation for Ethylbenzene

Production (EBLC)

13 S-SMTTM Technology for Production of Styrene by Ethylbenzene

Dehydrogenation

14 MTBE/Butene-1 Process

15 Butadiene Extractive Distillation Technology

16 C5 Distillation Technology

17

4.Rubber Production

Technologies

High Cis-Polybutadiene Rubber Production Technology

18 Technology of Styrene-Butadiene Thermoplastic Elastomer

19 Technology of Solution Polymerized Styrene-Butadiene Rubber (S-SBR)

57




20

5.Others

MTO (Methanol to Olefins) Technology

21 Technology of Absorption Heat Transformer for Recovering Low

Temperature Heat

58

Contact Information

Contact: Hongli Guo Chief Regional Representative, Science, Technology & Licensing SINOPEC Europe Representative Office Tel: +49 69 6690 9450 Fax: +49 69 6690 9422 Mobile: +49 174 8701187 Email: [email protected] Add.: 31st floor, Messe Turm, Friedrich-Erbert-Anlage 49, 60308 Frankfurt am Main, Germany

For more information: http://www.sinopectech.com/english

THANK YOU!

60

dcc(deep catalytic cracking), mip(maximizing iso- · pdf file•who we are?...

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