Methanol synthesis from CO2 hydrogenation over CuAl2O3 catalysts modified by

ZnO ZrO2 MgO.pdf

Catalyst: CZZMA (Cu/𝛾-Al2O3 catalysts modified by ZnO, ZrO2 and MgO)

Preparation: 𝛾-Al2O3 particles are impregnated with Cu2+, Zn2+, Zr4+ and Mg2+ ions with a molar ratio
of 2:1:0.9:0.1. The used amount of metal Cu was 10 wt% relative to the weight of support Al2O3.

Comparison catalysts: four catalysts such as CZZA (ions solution contained 2Cu:1Zn:1Zr), CZrA
(2Cu:1Zr), CZnA (2Cu:1Zn) and CA (only containing Cu)

Advantages of CZZMA:

- It is deduced that improvement on catalytic performance of Cu/Al2O3 is due to increase on

the Cu dispersion.
- Introduction of CZZMA gives the highest dispersion of Cu2+ and the metallic surface area of
Cu2+ particles on the catalyst surface

Factors:

MgO Content: CO2 conversion, selectivity, space-time yield first increase with MgO and then
decrease. Co Selectivity exhibits a reverse trend.

GHSV: CO2 conversion and MeOH selectivity on CZZMA catalyst slightly decrease with the increasing
GHSV, however CO selectivity exhibits a reverse trend. High GHSV will give a short contact time of
reactant gas with catalytic active sites.
Catalyst Activation temperature: both selectivity and STY toward MeOH increase with the
increasing activation temperature, and however CO selectivity exhibits a reverse trend at <250 ‘C.
Optimal temp: 250’C

(Reason for high Co selectivity** : High T  aggregation of Cu particle  large Cu results in low
activity of absorbing and activating H2, disadv for MeOH synthesis  but it is easy for RWGS rxn on
larger Cu)

Hydrogenation Temp: increase CO2 conversion with the increasing hydrogenation temperature is
rapid in the low-temperature region (<270 ‘C) and becomes slow in the high-temperature one (>270
‘C). Recommended temp: 270’C

Hydrogenation Pressure: selectivity of MeOH increase rapidly with the increasing reaction pressure.
It is because that a high pressure promotes the formation of formates intermediates on the alkali
sites of catalysts surface. A high pressure also inhibits RWGS rxn. Optmal pressure: 28atm.
Kinetic model: the mechanism of supported Cu–ZnO catalysts retains the characteristics of the
competitive Langmuir–Hinshelwood microkinetic model developed for bare Cu. Appendix
(Alex) Ag addition to CuO-ZrO2 catalysts promotes methanol synthesis via
CO2 hydrogenation.pdf
Catalyst: Adding Ag to CuO-ZrO2 catalyst (Ag/CuO-ZrO2)

Preparation /conditions:
CO2/H2/N2 = 1/3/1, catalyst loading = 500 mg, W/Ftotal = 1000 mgCat s mL-1, reaction temperature =
230 ‘C, pressure = 10 bar.

Determine the optimal benchmark catalyst: CuO-ZrO2 (CuZr-1) at pH 8. At the pH, the catalyst
exhibits a mesoporous form.

Addition of Ag to benchmark catalyst:

- 4 types of catalyst tested. (CuZr-1, 5 wt%Ag/CuZr-1, 10 wt%Ag/CuZr-1, 10 wt%Ag/ZrO2)

- Methanol production rate for Ag(5)/CuZr-1 and Ag(10)/CuZr-1 were nearly the same.

Advantages:
- Ag/CuO-ZrO catalyst contains special active sites which improves the methanol synthesis.
- H2 can adsorb dissociatively on completely reduced CuO-ZrO2 (metallic Cu) and Ag/ZrO2
(metallic Ag), while H2 can adsorb non-dissociatively on completely reduced Ag/CuO-ZrO2.

Thermodynamic model: Dissociative Langmuir isotherm