catalysts for sorption enhanced dme synthesis …
TRANSCRIPT
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CATALYSTS FOR SORPTION ENHANCEDDME SYNTHESIS (SEDMES)
MADRID-SPAIN
& THE NETHERLANDS
Cristina Peinado; Dalia Liuzzi; Sergio Rojas; Jasper van Kampen; Jurriaan Boon
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Contents
Introduction
Methodology
Results
Conclusions
The SEDMES process. The catalysts
Catalysts preparation. MeS, DDMES and SEDMES catalytic tests
CO and CO2 conversion. Products distribution
Highlights of this study
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Sorbents for in situ water removal
Biomass gasification produces a CO2 rich syngas with highCO2 /CO ratio
Introduction
Catalysts to adjust the CO2/CO ratioSorbents for in situ water removal
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Cu-ZnO-Al2O3 (CZA)
Methanol catalysts
Cu/ZnO/Al2O360/30/10
Zr and Ga doped CZA
• Benchmark catalysts syngas methanol
• syngas with 2-5% CO2
• Higher CO2 content lower methanol productivity
• Higher production of H2O (lower DME productivity)
• Water removal strategies
WGS
Methanol synthesis from
CO2 or CO2-rich syngas
Benchmark catalytsfor low temperatureWGS reaction
Introduction
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Acid solidsγ-Al2O3
HeterpolyacidsSoA catalyst for the
industial process, active above 250 ⁰C
Zeolites
Very active and selectiveat low temperatures
DME catalysts
Very active at hightemperatures
Introduction
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Introduction Methodology
Methanol catalysts
ZnO content
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MeS Methanol Synthesis
Introduction Methodology Results
270 ºC; 25 bar; 7500 h-1;CO2/CO=1.9; CO/CO2/H2: 9/18/73
CZA_comm CZA CZAZ CZAZGa-60
-30
0
30
60
90
CO CO2
CO
X C
onve
rsio
n (%
)
0.0
0.6
1.2
1.8
2.4
3.0
CH3OH/CO
CH
3OH
/CO
XCO2eq.
XCOeq.
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0 20 40 60 80 100 120 140 1600
5
10
15
20
25
30
GC
Sig
nal (
%)
Time (min)
DME CO CO2 CH3OH Ar
DDMESDirect DME Synthesis
Introduction Methodology Results
SEDMESSorption Enhanced DME Synthesis
Pre-breakthroughFresh sorbent 3A
After complete saturation 3A
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CZA_comm CZA CZAZ CZAZGa-60
-30
0
30
60
90
CO CO2
CO
X C
onve
rsio
n (%
)
0.0
0.6
1.2
1.8
2.4
3.0
DME/CO
DM
E/C
O
0%
20%
40%
60%
80%
100%
CZA_comm CZA CZAZ CZAZGa% CO 21.9 23.8 24.7 36.0% CO2 65.7 64.9 64.6 57.6% CH3OH 3.8 4.1 3.8 5.7% DME 8.7 7.2 6.8 0.8
DDMES Direct DME Synthesis
Introduction Methodology Results
1 𝐶𝐶𝐶𝐶 + 2𝐻𝐻2 ↔ 𝑪𝑪𝑪𝑪𝟑𝟑𝑶𝑶𝑪𝑪2 𝐶𝐶𝐶𝐶2 + 3𝐻𝐻2 ↔ 𝑪𝑪𝑪𝑪𝟑𝟑𝑶𝑶𝑪𝑪 + 𝑪𝑪𝟐𝟐𝑶𝑶3 𝐶𝐶𝐶𝐶 + 𝐻𝐻2𝐶𝐶 ↔ 𝐶𝐶𝐶𝐶2 + 𝐻𝐻24 𝟐𝟐𝑪𝑪𝑪𝑪𝟑𝟑𝑶𝑶𝑪𝑪 ↔ 𝑪𝑪𝑪𝑪𝟑𝟑𝑶𝑶𝑪𝑪𝑪𝑪𝟑𝟑 + 𝑪𝑪𝟐𝟐𝑶𝑶
275 ºC; 25 bar; 1080 h-1; CO2/CO=1.9; CO/CO2/H2= 9/18/73 (v/v)
XCO2eq. XCO
eq.
Higher DME production
CH3OH dehydration to DME shift of (eq. 2) equilibrium towards more CH3OH and H2O
High CO production
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SEDMES Sorption Enhanced DME Synthesis
0%
20%
40%
60%
80%
100%
CZA_comm CZA CZAZ CZAZGa% CO 26.8 29.5 44.2 72.4% CO2 2.7 3.6 1.4 1.6% CH3OH 1.0 1.2 0.9 3.3% DME 69.5 65.7 53.5 22.8
XCO2eq. XCO
eq.
CZA_comm CZA CZAZ CZAZGa-60
-40
-20
0
20
40
60
80
100 CO CO2
CO
X C
onve
rsio
n (%
)
0,0
0,4
0,8
1,2
1,6
2,0
2,4
2,8
3,2 DME/CO
DM
E/C
O
Introduction Methodology Results
275 ºC; 25 bar; 1080 h-1; CO2/CO=1.9; CO/CO2/H2= 9/18/73 (v/v)
Very high DME productionLow CO2 in products
Easier separation DME/CO2 downstream
R-wGS
Highest CO productionHighest non converted CH3OH
Lowest DME production
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Introduction Methodology Results Conclusions
• SEDMES approach, based in the in situ removal of H2O during
the direct synthesis of DME from CO2 rich syngas by using a
water sorbent, lead to higher carbon conversions and higher
DME productions
• In situ increasing r-WGS activity by using of promoters increases
CO content (lower CO2/CO ratio) but due to H2O production
affects negatively catalyst performance for methanol production
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Thanks for your attention
Dalia [email protected]
Sergio Rojas [email protected]
Jurriaan Boon [email protected]
Cristina [email protected]
Jasper van [email protected]