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 3
*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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 5
*from P. Lucchese,NTE program director oct 06
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 6
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 7
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
*from S. Rougé, in charge of the biomass gasification program
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 8
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
*from S. Rougé, in charge of the biomass gasification program
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 9
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
*from S. Rougé, in charge of the biomass gasification program
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 10
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
*from S. Rougé, in charge of the biomass gasification program
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 11
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 12
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 13
APPLICATION TO BIOMASS GASIFICATION IN H2O-SC
Biomass (sugar, cellulose, lignine, …) H2 + CO + CO2 + CH4 …
Main reaction = hydrolysis
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 14
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 15
• 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%)
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 16
Energetics
Y. Yoshida et al, Biomass and Bioenergy, 2003.
Higher SCWG energetical efficiency with a biomass with 20-30% humidity
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 17
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 18
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 19
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
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 20
Conclusions : results of our work ?
• Un procédé en développement en Europe et dans le monde
SCWG
CEA –Valrhô Supercritical fluids and membranes laboratory-Anne Roubaud 21
• Thank You for your kind attention !!!
IFS : Association Innovation FluidesSupercritiques