Methanol and DME Production from Thermal Chemical Conversion of Biomass

China-EU workshop on biofuel, Nov. 4-5, 2004, Beijing

Dr. Dr. JieJie CHANGCHANG

Biomass Synthetic Fuel LaboratoryBiomass Synthetic Fuel LaboratoryGuangzhou Institute of Energy ConversionGuangzhou Institute of Energy ConversionChinese Academy of SciencesChinese Academy of Scienceschangjiechangjie@ms.@ms.giecgiec.ac..ac.cncnhttp://www.http://www.giecgiec.ac..ac.cncn

Outline

1. Introduction2. Usage of Methanol and DME3. Production from Biomass4. Conclusion5. Acknowledgment

Introduction of Biomass Synthetic Fuel Lab

Gasification of BiomassHydrogen Production From BiomassCleaning up and reforming of biomass derived syngasSynthesis of Methanol and DMENovel technologies for liquid fuel production (bio-diesel production via lipase, catalytic cracking of waste tire and plastic under vacuum)

Patents and Publications in BTL

5 patents24 journal papers (include Fuel, Energy & Fuels, Biomass & Bioenergy, Bioresource Technology, etc.)18 conference papers

President of Chinese Academy of Sciences, Dr. Yongxiang Lu Visited our Lab. Oct, 2003

Biomass resources-energy Cycle

Outline

1. Introduction2. Usage of Methanol and DME3. Production from Biomass4. Conclusion5. Acknowledgment

Usage of DME and Metanol

DME (dimethyl ether) CH3OCH3

Substitute of LPG for householdFuel for turbineSubstitute of diesel

Methanol CH3OHSubstitute of gasoline

Properties of DME

Formular CH3OCH3

Explosion limit /%，in air 3.4~17

Molecular Weight 46.07

Ignition Temp./°C 235

Boiling Point /°C -24.9

Vaporization heat /kJ •kg-1

410（-20°C）

Melting Temp. /°C -138.5

Lower heating value / MJ •kg-1 28.4

Vapor pressure /MPa

0.51（20°C） Flash point -41°C

Critical temp. 127 °CLiquid density

/g•cm-30.668

（20°C）

Critical Pressure/ MPa 5.37

DME Diesel Propane Butane Methanol

MW 46.07 190~220 44.11 58.13 32.01Boiling point

/°C-24.9 180~360 -42 -0.5 65

Vapor pressure /kPa

5.1 8.4 2.1 0.32

Liquid density /g•cm-3

0.668 0.84 0.501 0.61 0.79

Liquid viscosity /x104 Pa•s-1

0.15 5.35~6.28 0.10 0.18 0.768

LHV/MJ•kg-1 28.43 42.5 46.36 45.74 19.5Cetane number 55~60 40~55 Octane

number112

Vaporization heat /kJ •kg-1

410 250 370 358 1110

C/% 52.2 86 81.8 82.8 37.5O/% 34.8 0 0 0 50H/% 13 14 18.2 17.2 12.5

D

M

E

Coal

Nature Gas

Biomass

Petroleum Residue/coke

Gasification

Reforming

Steam ReformingPartial Oxidation

Gasification

syngas Civil fuel

Diesel Substitute

Large-scale Fuel gas/steam combined cycles for electricity generation

Small-scale distributed electricity/heat/cold combined supply

Chemical intermediatematerial

syngas

syngas

syngas

Feedstock and Usage of DME

Outline

1. Introduction2. Usage of Methanol and DME3. Production from Biomass4. Conclusion5. Acknowledgment

Liquid Fuel from Biomass

CH1.4O0.6

CH3OH (CH4O)

CH3OCH3 (CH3O 0.5)

CnHm (CH2.x)

A Novel process for methanol and dimethyl ether (DME) production from biomass gasification has been proposed and practiced in GIEC at lab scale.

Co-reforming of biogas and bio-syngas

Energy Crops, Agro-residue, Forest residue

3 billion T

Agro-residue, Organic trash,

manure, sewage

4 billion T

Biomass

Gasification

Anaerobic

Digestion

fertilizer

DME

Methanol

Biomass Gasification for Generation in Sanya

Slurry reactor for DME synthesis

Flow chart of Biomass To Liquid (bench scale)

Liquid Fuel

BiogasCO2+O2+Steam

Biomass

Compressor

High Pressure Vessel

Gasifier

Clean up Reformer

Synthesis reactor

Condenser

5 1 0 5 1 5 5 2 0 5 2 5 5 3 0 5 3 5 5 4 0

0 .2 6

0 .2 8

0 .3 0

0 .3 2

0 .3 4

0 .3 6

0 .3 8

0 .4 0

0 .4 2

0 .4 4

0 .4 6

0 .4 8

0 .5 0ST

Y of

met

hano

(g/g

.cat

.h)

T em p eratu re (K )

C a t1 C a t4C 3 0 6

V(H2)/V(CO)/V(CO2)/V(N2) =47/22/27/4Pressure = 3MPa，SV= 7500h-1

5 0 0 5 0 5 5 1 0 5 1 5 5 2 0 5 2 5 5 3 0 5 3 50 .2 5

0 .3 0

0 .3 5

0 .4 0

0 .4 5

STY

of m

etha

nol (

g/g.

cat.h

)

T e m p e ra tu re ( K )

(1 )

(2 )

(3 )

(4 )

（1）Syngas: V(H2)/V(CO)/V(CO2)/V(N2) =66/27/3/4;（2）Reformed biosyngas: V(H2)/V(CO)/V(CO2)/V(N2)=55/36/5/4;(3) Biosyngas+ H2: V(H2)/V(CO)/V(CO2)/V(N2)=64/14/18/4;（4）Biosyngas: V(H2)/V(CO):V(CO2)/V(N2) =47/22/27/4

1000 1500 2000 2500 3000 3500 4000

20

30

40

50

60

70

80

Con

vers

ion

of C

O (m

ol%

)

GHSV (h-1)

cat25 cat38 cat50

Temperature:553K, P:3MPa

1000 1500 2000 2500 3000 3500 400035

40

45

50

55

60

65

Sel

ectiv

ity o

f CO

to D

ME

(mol

%)

cat25 cat38 cat50

GHSV (h-1)

Temperature:553K,P:3MPa

The effect of Si/Al ratio on the conversion of CO with the GHSV

The effect of Si/Al ratio on the selectivity of DME with the GHSV

480 490 500 510 520 530 540 550 560 570

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

STY

of D

ME

( t-D

ME/

m3 -c

at./h

)

Temperature (K)

16.7% 25% 40% 50% 66.7%

Pressure:3MPaGHSV:3000h-1

10 20 30 40 50 60 70

20

30

40

50

60

70

80

HZSM-5 content (wt%)

Con

vers

ion

of C

O (m

ol%

)

Temperature:543KPressure:3MPaGHSV:3000h-1

20

30

40

50

60

70

80

Selectivity of DM

E (m

ol%)

The effect of contents of HZSM-5 on the space time yield of DME with the temperature

The effect of content of HZSM-5 on the conversion of CO and the selectivity of DME

Outline

1. Introduction2. Usage of Methanol and DME3. Production from Biomass4. Conclusion5. Acknowledgment

Concluding Remarks

Biomass is stainable feed for production of DME and methanolThe Process BTL (biomass gasification, gas cleaning up and reforming, liquid fuel synthesis) is promising in the era of petroleum depleting fastPilot plant should be set up ASAP

Acknowledgment

Financial support from Ministry of Science & Technology, National Science Foundation

Thanks!