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1CEA Valrhô – DTCD/SPDE/LFSM 30/11/2007

Syngas and hydrogen production by thermo-chemical

processes

Supercritical fluids and membraneslaboratory, CEA Rhône Valley center

contact : [email protected]

CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 2

*from P. Lucchese,NTE program director oct 06

CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 4*from P. Lucchese,NTE program director oct 06


The thermo-chemical process of gasification

Pick-up / Transportatio

n

Pre-Treatment50-600°C

Gasification700-1400°CWith partial

pressure air, O2, H2O

Dedusting and Conditionning of

Gas

Fuel SynthesisDiesel Fischer-Tropsch (-CH2-)n

Methanol (CH 3OH)DME (C2H5OH)

BIOMASSE C6H9O4

Cogeneration electricity and

heat

Separation and shift

production of H2

Synthesized gas: CO, H2, CO2, H2O, CH4 + light hydrocarbons, inorganics

H2/CO ~2No CH4Tars < 1 mg/m3Inorganic compounds ~1 à 10 ppb

H2/CO : no criteriaCH4 welcomeTars ~100 mg/m3Inorganic compounds ~1 à 100 ppm

Water electrolysis ~280 kJ/mol

Gasification ~70 kJ/mol

solid or liquid

injection

CEA field of R&D

*from S. Rougé, in charge of the biomass gasification program


C6H9O4 + 2 H2O => 6 CO + 6,5 H2 endothermal

Combustion consumes ~ 2C and 2 H2

4 CO + 4,5 H2

Water gas shift reaction CO + H20 -> H2 + CO2 consumes 1.5 CO (auto) or 2CO (Allo)

Maximal realistic diesel mass yield

~15% ~30% ~50%

6 CO + 6,5 H2

4 CO + 8,5 H24 -CH2-

No shift, external H2

6 CO + 12 H26 -CH2-

Autothermal process Allothermal process (external energy)

Fuel synthesis needs H2/CO ~2

Allothermal process : increase of mass yield

2.5 CO + 6 H22,5 -CH2-

Fuel synthesis is not 100% diesel oriented



H2O

Ar

N2

GasTars

Wood chips (1 mm)

Dry gas : 53 %

Water : 17 %

Char : 15 %

Tars : 14 %

Wood gasification in the Fluidized Bed facility (LFHT)

H2 : 32 %

CO : 33

CH4 : 15

CO2 : 17 %

C2H2 + C2H4 : 3 %

First step : Pyrolysis (Ar) Very fast phenomenon (<1 min)

Pyrolysis+craking of tars under N2+Ar (800°C)

Mass%Mol%

Second step :Steam gasification of the char Much slowlier than pyrolysis (characteristic time = several hours)

T and pH2O higher → faster kinetic

0,0E+00

2,0E-05

4,0E-05

6,0E-05

8,0E-05

1,0E-04

1,2E-04

1,4E-04

800°C,H2O=28vol%

800°C,H2O=56vol%

880°C,H2O=28vol%

App

aren

t kin

etic

con

stan

t (s-

1)H2O

T



Experimental lab scale facility : BioMap

– 2007 progress :• Official Collaboration with EUROPLASMA • Injection of bio-oils in a plasma• Test of fast optic measures in a plasma

– Close future : • Commissioning of BioMap facility• First tests with bio-oils• Tests with a 300kW torch at INERTAM

Fuel +steam

Plasma

BioMapnon transferred torch

20kWelectric arc 20kW1 bar1600°C 1 to 10 kg/h liquid or solid

Objective : analytical study of pyro-gasification in a EFR assisted by a plasma torch, ANR Project Galacsy



Experimental facilities : BANBINO, MATISSE, COLINE

• Calculations at thermodynamic equilibrium : GEMINI, FACTSAGE• Measures under progress :

– µGC, GC-FID, FTIR, catharometers– Tars : tar protocol, SPA, SPME, PID– H2S : colorimeter– Measures off line on gas, solids or materials

using CEA facilities (SEM, XRD, RAMAN…)

COLINE

MATISSE

BANBINO

Objective : behavior of particles and inorganics and hot gas cleaning



INTRODUCTION : SCWO processSupercritical Water Oxidation :a fast and complete oxidation reaction,

destruction efficiency > 99,9%

Low dielectric constantHigh diffusivityLow density

473 673 873 1073(K)

Tc=647 K; Pc= 22,1 MPa)

A rapid and effective mixing between organics and oxygenAn ideal oxidative mediaSalts precipitation

water (300 ml/h) + air (60nL/h)at 250 bar, going through the critical point

A process developed for the destruction of organic wastes, solvents, spent ion exchange resins, since the 80’s from USA to Europe


INTRODUCTION : SCWO process

WaterAirSplitting valve

CO2 + N2

Water+

disso lved salts

Wastes

Heater Cooler

Titanium inner shell

Stirrer

External vessel

BladeHead ofthe stirrer

WaterAirSplitting valve

CO2 + N2

Water+

disso lved salts

Wastes

Heater Cooler

Titanium inner shell

Stirrer

External vessel

BladeHead ofthe stirrer

The double shell reactor concept : flowsheet of the process

Lab-scale experimental set-up for 0,2 Kg/h treatment capacityWorking pressure 30 MPa

Specific developments at CEA (since 90’s) for halogenated solvents, corrosive products and wastes with salts and contaminated solvents


APPLICATION TO BIOMASS GASIFICATION IN H2O-SC

Biomass (sugar, cellulose, lignine, …) H2 + CO + CO2 + CH4 …

Main reaction = hydrolysis


SCWG : typical results (380°C & 230 atm),

SauleSaule Glycerol Glycerol Sorghum (fibre)Sorghum (fibre)HH2 2 %% 5656 3737 4545

CO %CO % 2424 1414 1717

CHCH44 %% 1111 66 1010

COCO22 % % 66 2222 2626

TOC ppmTOC ppm 30003000 14001400 17001700

Gasification % 87Gasification % 87 7272 8181efficiencyefficiency

Mc Gill University


• Strong Influence of the process parameters on the gas composition :• Use of a catalyst like (Ni, Ru, charcoal, NaOH, KHCO3….) or a few oxygen addition allow to :

– Lower the needed temperature– Improve the gasification efficiency– To modify the gas composition, H2, CO and CH4 ratio

OVERVIEW ON BIOMASS GASIFICATION IN H2O-SC

CH4/H2/CO2

H2/CO/CO2

T°C

P (bar)

Tc

Pc

650

400

300 500

liquefa

ction

CH4 major

H2 major (50%)


Energetics

Y. Yoshida et al, Biomass and Bioenergy, 2003.

Higher SCWG energetical efficiency with a biomass with 20-30% humidity


Main studies and pilot installations in the world

Description Localisation

Verena Plant Capacity ~ 100 L.h-1

gasification of residues (wine production, corn scratch,…)

Forschungszentrum Karlsruhe (FzK)

Allemagne

Capacity ~ de 30 L.h-1

tubular reactorProcess Development Unit

(PDU)Enschede/Twente Pays/bas

tubular reactorsmall volume = 20 mL

McGill University

Autoclaves batch reactors for kinetic studies, efficiency determination, parameters studies

Small volumes

Université de HawaiiOsaka Gas

Pacific Northwest National Laboratory

Forschungszentrum KarlsruheUniversité de Hiroshima

Université de TwenteMcGill University

quartz capillary ( bath microreactors) for optical access during heating and reaction

Université de TwenteMcGill University


Supercritical water test bench at LFSM

BatchUnit Reactor 0,6 L, 300 bar, 600 °CBasic studies

POSCEA 2 Pilot double shell flow reactor patentedReactor 0,6 L, 300 bar, 500 °C, 3 L/h

DELIS PilotBased on the double shell flow reactorReactor 3L, 300 bar, 500 °C, 11 L/h


low Temp. (400low Temp. (400°°C); rapid conversion(sec); wet biomassC); rapid conversion(sec); wet biomass

Products: HProducts: H22, CO, CO, CO, CO22, CH, CH44

Zero emission of NOZero emission of NOxx, SO, SOxx,, HAP HAP

Decentralized installations: small conversion installations neaDecentralized installations: small conversion installations near the biomass r the biomass production sites, any preproduction sites, any pre--process for the biomassprocess for the biomass

SCWG Advantages SCWG Advantages vsvs classical Gasificationclassical Gasification

Reactions :Reactions : hydrolysis, oxidation, decompositionhydrolysis, oxidation, decomposition

homogeneous media (water as solvent and reactif)homogeneous media (water as solvent and reactif)

Conversion for all type of biomassConversion for all type of biomassEnergetically favorable for a wet biomass > 30%Energetically favorable for a wet biomass > 30%

Corrosion: materialsCorrosion: materialsPrecipitation of solids (mineral salts,Precipitation of solids (mineral salts,……), plugging), plugging

and Thermodynamical properties estimations for fluids and mixtuand Thermodynamical properties estimations for fluids and mixtures in res in supercritical conditionssupercritical conditions

Expensive Catalysts for some like (Pt, Ni)Expensive Catalysts for some like (Pt, Ni)

Complex chemical kineticsComplex chemical kinetics

Drawbacks, key points


Conclusions : results of our work ?

• Un procédé en développement en Europe et dans le monde

SCWG


• Thank You for your kind attention !!!

[email protected]

IFS : Association Innovation FluidesSupercritiques

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