10-Zhongmin Liu - Belfer Center for Science and International Affairs

belfercenter.hks.harvard.edu

10-Zhongmin Liu - Belfer Center for Science and International Affairs

Coal to Chemicals

Zhongmin Liu

zml@dicp.ac.cn

Dalian Institute of Chemical Physics, CAS

2007.05.23-24, 2007.05.23 24, Beijing


Natural Gas

Developing

Coal/Bio- Coal/Bio

DICP DICP

Routes for oil substitution by

Resources Basic Materials

Petrochemical

Crude Oil

Developed

Cracking

MDA

Aromatics

Benzene

Toluene

Xylenes

Products

Polyolefins

PE, PP

Acrylates

Cheap

SynGas

SynGas MeOH

C 2 Oxy.

gas and coal

DME

MTO

MTP

DME

Formaldahyde

Olefins

Ethylene

Propylene

Oxygenates

Alcohols, Ethers,

Esters, Acids,

Aldehydes

Polycondensates

PC, PET,

PBT

Solvents

Fuels

Fuel additives


Roadmap for technology development

Project

Methanol to Olefin DMTO

technology

Methanol to Propylene

Methanol to DME

Methanol to diesel

Syngas to fuel and wex

Syngas to C2 oxygenates

Methanol to aromatics

Syngas to DME

Coal to acetylene

Neutral gas to ethylene

Methanol to poly-formalhyde

DICP DICP

Ethylene glycol

Pilot test

R&D

Demonstration

Process development

R&D

Pilot test

R&D

R&D

Demonstration

R&D

Now

Demonstration test

finished

Commercialization

commercialization unit in

operation

demonstration

1mt/a commercialization

Demonstration

Large scale commercialization

commercial unit in construction

10-50kt/a Demonstration

demonstration

Demonstration

Pilot test

commercial unit in construction

Demonstration

2010


DICP DICP

Contents

C2 Oxygenates (ethanol)

Methanol to DME

DMTO technology


CO + H 2

DICP DICP

C 2 Oxygenates Synthesis from

Syngas (1 st Generation)

Catalyst: 1 %Rh/SiO 2 , 15Kg

Conditions: 310-315 o C, 8.2MPa

Yield: 370 g/kg h

30 tons/year

CO Conv. 56.4%

Selec. 73.5 wt%

Hydrogenation

C 2

Oxygenates

Esterification

EtOH

Oxidation

AcOOEt

1 ton of CO yields 0.54 ton C2 /oxygenates

AcOOH


STY of C2oxy, g/kg-cat.h

Selec. of C2oxy, wt%

DICP DICP

500

450

400

350

300

250

200

150

100

50

0

100

90

80

70

60

50

40

30

20

10

0

0 200 400 600

TOS,h

800 1000

0 200 400 600

TOS,h

800 1000

Long term stability of the catalyst


DICP DICP

Methanol to Dimethyl Ether (DME)

Commercialized Technology

Modifized Zeolite Catalyst, Fixed Bed Reaction

100kt/a unit in

Hebei


1

2

3

4

5

6

7

8

Methanol to Dimethyl Ether (DME)

Ningxia Baota Petrochemical Co.

Hebei Zhongjie Petrochemical

Group

Sanxu LPG Co. (Shaowu ( Shaowu, , Fujian)

Milkway Co (Huaibin ( Huaibin, , Henan)

Shanxi Huawei Engineering Co.

Benxi City

Yili Group (Neimeng ( Neimeng)

DICP DICP

Customer

Shandong Yuhuang Chemical Co.

Many plant will be constructed

Scale

(kt kt/a) /a)

50

100

100

20

100

400

500

1200

State

Under

construction

Under

construction

Under

construction

Design

Feasibility study

completed

Feasibility study

completed

Feasibility study

Feasibility study

Start operation at

November of 2006

Start operation at

April of 2007

Start operation at

April of 2007


DMTO Technology


Lab test

DICP

C =

2 +C3 +C = 90%

From 1980

DICP DICP

DMTO: R&D Course in DICP

DICP

Pilot test

in DICP (Fixed ( Fixed Bed) Bed

C =

2 +C3 = +C +C4 = +C : 85% 1993

Pilot test

In Shanghai (Fluidized ( Fluidized Bed) Bed

C =

2 +C3 = +C >80%, 1995

“75 75”,“85 85”, , “973 973”

National Project

2004.08

Demo

Shangxi, Shangxi,

Huaxian

DICP

Shanxi Xinxing Co

LPEC


Objective

DICP DICP

DMTO Demonstration

To develop DMTO technology for the design of large scale

commercial unit

Partner

Dalian Institute of Chemical Physics, CAS

Providing pilot technology for design and production of the

catalyst

Luoyang Petrochemical Engineering Company, Sinopec

Engineering design

Shanxi Xinxing Coal Chemical Technology Ltd

Investment, construction, management, operation

joint venture company: Shanxi Investment Group, Zhengda Coal

Chemical Ltd, Shanxi Coal and Chemical Group


DICP DICP

Design and Construction

The corporation started on August

8 of 2004

Feasibility easibility study finished and

passed on October 11 of 2004

Basic design approved on February

27 of 2005

Construction was finished in

December of 2005

Test was finished in June of 2006


DICP DICP

Methanol or Dimethylether to

Olefin (DMTO) Demonstration

Plant Near Xi’an Xi an


Flow low chart of the DMTO demo unit

According to the

feasibility study, deep

cooling separation

would not be tested.

DICP DICP


Loading catalyst to the

DMTO demonstration plant

DICP DICP

DMTO catalyst


Conv.or selectivity,wt%

100

90

80

70

60

50

40

30

DICP DICP

Typical results

0 24 48 72 96 120 144 168 192 216 240 264

Operation time(h)

Conv.

C 2 = +C3 = +C4

C 2 =

C 2 = +C3 =

C 3 =


DICP DICP

Comparison of the product stream

comparison: naphtha vs DMTO

composition

H 2

CO

H 2 S

CH 4

C 2 H 2

C 2 H 6

C 2 H 4

C 3 H 6

C 3 H 4

1,3-C 4 H 8

C 4 H 6

Naphtha cracking

(mol% mol%)

14.13

0.18

0.03

23.68

0.45

6.41

31.69

9.44

0.46

1.65

DMTO(mol%

DMTO mol%)

2.06

0.30

3.01

0.002

0.67

38.10

24.83

0.0002

0.118

0.014


DICP DICP

NOx in flue gas

Flue gas from regenerator

CO :9.62 9.62 v%

CO 2 : 5.18 v%

NOx :0.2 0.2 ppm

NOx in product gas

ppb grade


Methanol Price (RMB/t)

MeOH Cos (RMB/t)

Cost of C2 & C3 olefin

mixture (RMB/t)

Price of

Olefin

mixture

(RMB/t)

DICP DICP

ROI=10%

ROI=12%

Economics

1100

3278

3961

4471

4644

DMTO

1300

3874

4560

5069

5242

1500

4470

5129

5639

5812

1700

5066

5637

6159

6342

1900

5662

5937

6736

6919

2100

6258

6718

7252

7423

2300

6854

7189

7724

7902

2500

7450

7806

8340

8519


DICP

DICP

Economics

Economics

11112

1073

6

1036

0

9986

9375

8766

8373

7857

7097

6456

5835

5418

4960

ROI=12%

10787

1041

1

1003

5

9661

9072

8463

8070

7554

7009

6395

5774

5357

4899

ROI=10%

Price

of

Olefin

(RMB/t)

9896

9520

9144

8770

8181

7572

7179

6662

5903

5288

4667

4250

3792

Cost of Olefin

(RMB/t)

8410

8044

7678

7314

6735

6141

5758

5246

4496

3897

3295

2883

2431

Naphtha Cost 扣除

副产后石脑油在成本

中费用(可变成本)

(RMB/t)

6100

5800

5500

5200

4800

4400

4000

3600

3200

2800

2400

2100

1800

Price of Naphtha

(RMB/t)

Naphtha Cracking


烯烃成本(元/吨)

Cost of Olefin

DICP DICP

Cost: DMTO & Naphtha cracking

12000

10000

8000

6000

4000

2000

0

DMTO Naphtha cracking

0 1000 2000 3000 4000 5000 6000 7000

Price of feedstock

原料价格(元/吨)

DMTO烯烃成本

石脑油制烯烃成本


Price of Feed

Economics: DMTO & naphtha cracking

Coal to Methanol

DICP DICP

Methanol Price Price of Poly-olefin (RMB/t)

Naphtha Cracking

DMTO

DMTO


Further development of DMTO

DICP DICP

technology

The construction of commercially demonstration plant in China

Scale: 200kta olefin

Will be approved by NDRC

New related technology will be applied

Olefin selectivity ~90%(wt)

It is expected before the commercial plant

The construction of commercially plant (600kta olefin)

Scale: 600kta olefin

Approved by NDRC

The construction of commercially unit will be licensed outside China China

Many international olefin companies have contact us for the technology

technology

licensing

Partner is expected for licensing the technology worldwide


Thanks!

Thanks