Coal to ChemicalsCoal to Chemicals

ZhongminZhongmin Liu Liu zml@dicp.ac.cnzml@dicp.ac.cn

Dalian Institute of Chemical Physics, CASDalian Institute of Chemical Physics, CAS2007.05.232007.05.23--24, Beijing24, Beijing

DICPDICP

CheapSynGas

Crude OilCrude OilDevelopedDeveloped

ResourcesResources PetrochemicalProducts

PolyolefinsPE, PP

Acrylates

PolycondensatesPC, PET,

PBT

Solvents

FuelsFuel additives

Coal/BioCoal/Bio--

Natural GasNatural GasDevelopingDeveloping

SynGasSynGas MeOHMeOH

AromaticsAromaticsBenzeneTolueneXylenes

OxygenatesOxygenatesAlcohols, Ethers,

Esters, Acids,Aldehydes

Basic MaterialsBasic Materials

OlefinsOlefinsEthylene

Propylene

Cracking

MDA

C2 Oxy.

MTOMTP

DME

Routes for oil substitution by gas and coal

DME

Formaldahyde

DICPDICP

Roadmap for technology developmentRoadmap for technology development

DemonstrationR&DEthylene glycol

commercial unit in constructionDemonstrationMethanol to poly-formalhyde

Pilot testR&DNeutral gas to ethylene

DemonstrationR&DCoal to acetylene

demonstrationPilot testSyngas to DME

10-50kt/a DemonstrationR&DMethanol to aromatics

commercial unit in constructionProcess developmentSyngas to C2 oxygenates

Large scale commercializationDemonstrationSyngas to fuel and wex

DemonstrationR&DMethanol to diesel

1mt/a commercializationCommercializationMethanol to DME

demonstrationPilot testMethanol to Propylene

commercialization unit in operation

Demonstration test finished

Methanol to Olefin DMTO technology

2010NowProject

DICPDICP

ContentsContents

C2 Oxygenates (ethanol)

Methanol to DME

DMTO technology

DICPDICP

CO + H2C2

Oxygenates

EtOH

AcOOEt

AcOOH

Hydrogenation

Oxidation

Esterification

Catalyst: 1 %Rh/SiO2, 15Kg

Conditions: 310-315oC, 8.2MPa

Yield: 370 g/kg h

30 tons/year

CO Conv. 56.4%

Selec. 73.5 wt%

C2 Oxygenates Synthesis from Syngas (1st Generation)

1 ton of CO yields 0.54 ton C2/oxygenates

DICPDICP

050

100150200250300350400450500

0 200 400 600 800 1000

TOS,h

STY of C2oxy, g/kg-cat.h

01020

3040506070

8090

100

0 200 400 600 800 1000

TOS,h

Selec. of C2oxy, wt%

Long term stability of the catalyst

DICPDICP

Methanol to Methanol to DimethylDimethyl Ether (DME)Ether (DME)Commercialized TechnologyCommercialized Technology

ModifizedModifized ZeoliteZeolite Catalyst, Fixed Bed ReactionCatalyst, Fixed Bed Reaction

100kt/a unit in Hebei

DICPDICP

Methanol to Methanol to DimethylDimethyl Ether (DME)Ether (DME)

Feasibility studyFeasibility study500500Benxi CityBenxi City77Feasibility studyFeasibility study12001200YiliYili Group (Group (NeimengNeimeng))88

Feasibility study Feasibility study completed completed

400400Shanxi Shanxi HuaweiHuawei Engineering Co.Engineering Co.66

Feasibility study Feasibility study completed completed

100100MilkwayMilkway Co (Co (HuaibinHuaibin, Henan), Henan)55DesignDesign2020SanxuSanxu LPG Co. (LPG Co. (ShaowuShaowu, Fujian), Fujian)44

Start operation at Start operation at April of 2007April of 2007

Under Under constructionconstruction

100100HebeiHebei ZhongjieZhongjie Petrochemical Petrochemical GroupGroup

33

Start operation at Start operation at April of 2007April of 2007

Under Under constructionconstruction

100100Ningxia Ningxia BaotaBaota Petrochemical Co.Petrochemical Co.22

Start operation at Start operation at November of 2006November of 2006

Under Under construction construction

5050Shandong Shandong YuhuangYuhuang Chemical Co.Chemical Co.11

StateStateScaleScale((ktkt/a)/a)

CustomerCustomer

Many plant will be constructedMany plant will be constructed

DMTO TechnologyDMTO Technology

DICPDICP

DMTO: R&D Course in DICPDMTO: R&D Course in DICP

Lab testLab testDICPDICPCC22

==+C+C33= = 90%90%

Pilot testPilot testIn Shanghai (In Shanghai (Fluidized BedFluidized Bed))

CC22==+C+C33

==>80%, 1995>80%, 1995

DemoDemoShangxiShangxi, , HuaxianHuaxian

DICPDICPDICPDICPShanxi Shanxi XinxingXinxing CoCoLPECLPEC

2004.082004.08From 1980From 1980 ““7575””,,““8585””, , ““973973””National ProjectNational Project

Pilot testPilot testin DICP (in DICP (Fixed BedFixed Bed))

CC22==+C+C33

==+C+C44==: 85% 1993 : 85% 1993

DICPDICP

DMTO DemonstrationDMTO DemonstrationObjectiveObjective

To develop DMTO technology for the design of large scale To develop DMTO technology for the design of large scale commercial unit commercial unit

PartnerPartnerDalian Institute of Chemical Physics, CASDalian Institute of Chemical Physics, CAS

Providing pilot technology for design and production of the Providing pilot technology for design and production of the catalystcatalyst

Luoyang Petrochemical Engineering Company, SinopecLuoyang Petrochemical Engineering Company, SinopecEngineering designEngineering design

Shanxi Shanxi XinxingXinxing Coal Chemical Technology LtdCoal Chemical Technology LtdInvestment, construction, management, operationInvestment, construction, management, operationjoint venture company: Shanxi Investment Group, joint venture company: Shanxi Investment Group, ZhengdaZhengda Coal Coal Chemical Ltd, Shanxi Coal and Chemical GroupChemical Ltd, Shanxi Coal and Chemical Group

DICPDICP

Design and ConstructionDesign and ConstructionThe corporation started on August The corporation started on August

8 of 20048 of 2004

FFeasibilityeasibility study finished and study finished and

passed on October 11 of 2004passed on October 11 of 2004

Basic design approved on February Basic design approved on February

27 of 200527 of 2005

Construction was finished in Construction was finished in

December of 2005December of 2005

Test was finished in June of 2006Test was finished in June of 2006

DICPDICP

Methanol or Methanol or DimethyletherDimethylether to to Olefin (DMTO) Demonstration Olefin (DMTO) Demonstration Plant Near XiPlant Near Xi’’anan

DICPDICP

FFlow chartlow chart of the of the DMTO demo unitDMTO demo unit

According to the According to the

feasibility study, deep feasibility study, deep

cooling separation cooling separation

would not be tested. would not be tested.

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DMTO catalystDMTO catalyst

Loading catalyst to the Loading catalyst to the DMTO demonstration plantDMTO demonstration plant

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Typical resultsTypical results

30

40

50

60

70

80

90

100

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

Operation time（h）

Con

v.or

sel

ectiv

ity,w

t%

C2=+C3

=

Conv.

C2=+C3

=+C4

C2=

C3=

DICPDICP

Comparison of the product stream Comparison of the product stream comparison: naphtha comparison: naphtha vsvs DMTODMTO

0.0140.014CC44HH66

0.1180.1181.651.6511,,33--CC44HH88

0.00020.00020.460.46CC33HH44

24.8324.839.449.44CC33HH66

38.1038.1031.6931.69CC22HH44

0.670.676.416.41CC22HH66

0.0020.0020.450.45CC22HH22

3.013.0123.6823.68CHCH44

0.030.03HH22SS0.300.300.180.18COCO2.062.0614.1314.13HH22

DMTODMTO（（mol%mol%））Naphtha crackingNaphtha cracking

（（mol%mol%））compositioncomposition

DICPDICP

NOxNOx in flue gasin flue gas

Flue gas from regenerator Flue gas from regenerator CO CO ：：9.62 v%9.62 v%COCO22：： 5.18 v%5.18 v%NOxNOx ：：0.2 0.2 ppmppm

NOxNOx in product gasin product gasppb grade ppb grade

DICPDICP

EconomicsEconomics

85197902742369196342581252424644ROI=12％

83407724725267366159563950694471ROI=10％Price of Olefin mixture (RMB/t)

78067189671859375637512945603961Cost of C2 & C3 olefin mixture (RMB/t)

74506854625856625066447038743278MeOH Cos (RMB/t)

25002300210019001700150013001100Methanol Price (RMB/t)

DMTO

DICPDICP

EconomicsEconomics

1111210736

103609986937587668373785770976456583554184960ROI=12％

1078710411

100359661907284638070755470096395577453574899ROI=10％Price

of Olefin (RMB/t)

9896952091448770818175727179666259035288466742503792Cost of Olefin (RMB/t)

8410804476787314673561415758524644963897329528832431

Naphtha Cost 扣除

副产后石脑油在成本中费用（可变成本）(RMB/t)

6100580055005200480044004000360032002800240021001800Price of Naphtha(RMB/t)

Naphtha Cracking

DICPDICP

Cost: DMTO & Naphtha crackingCost: DMTO & Naphtha cracking

0

2000

4000

6000

8000

10000

12000

0 1000 2000 3000 4000 5000 6000 7000

原料价格（元/吨）

烯烃

成本

（元/吨

）

DMTO烯烃成本

石脑油制烯烃成本Cos

t of O

lefin

Price of feedstock

DMTODMTO Naphtha crackingNaphtha cracking

DICPDICP

Economics: DMTO Economics: DMTO && naphtha crackingnaphtha cracking

Price of Feed

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

Coal to Methanol

Naphtha Cracking

DMTODMTO

DICPDICP

Further development of DMTO Further development of DMTO technologytechnology

The construction of commercially demonstration plant in ChinaThe construction of commercially demonstration plant in ChinaScale: 200kta olefinScale: 200kta olefinWill be approved by NDRCWill be approved by NDRCNew related technology will be appliedNew related technology will be applied

Olefin selectivity ~90%(wt)Olefin selectivity ~90%(wt)

It is expected before the commercial plantIt is expected before the commercial plant

The construction of commercially plant (600kta olefin)The construction of commercially plant (600kta olefin)Scale: 600kta olefinScale: 600kta olefinApproved by NDRC Approved by NDRC

The construction of commercially unit will be licensed outside CThe construction of commercially unit will be licensed outside China hina Many international olefin companies have contact us for the techMany international olefin companies have contact us for the technology nology licensinglicensingPartner is expected for licensing the technology worldwidePartner is expected for licensing the technology worldwide

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