catalysts for sorption enhanced dme synthesis …
TRANSCRIPT
CATALYSTS FOR SORPTION ENHANCEDDME SYNTHESIS (SEDMES)
MADRID-SPAIN
& THE NETHERLANDS
Cristina Peinado; Dalia Liuzzi; Sergio Rojas; Jasper van Kampen; Jurriaan Boon
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
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
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
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
Introduction Methodology
Methanol catalysts
ZnO content
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.
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
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
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
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
Thanks for your attention
Dalia [email protected]
Sergio Rojas [email protected]
Jurriaan Boon [email protected]
Cristina [email protected]
Jasper van [email protected]