Abstract
The study has focused on the regenerability of the CuO–ZnO–MnO/SAPO-18 (CZMn/S) bifunctional catalyst used in the direct synthesis of dimethyl ether (STD process) from H2 + CO + CO2 feeds. The runs have been conducted in a fixed bed reactor under the following conditions: 250–300 °C; 10–40 bar; 1.25–10.18 gcat h mol −1C ; time on stream, 5–30 h; CO2/CO molar ratio, 0–1; feeding H2 + CO + CO2 with a H2/COx molar ratio of 3. Coke deposition has been determined as the main deactivation cause, and both the measurement of the coke content and the identification of three types of coke have been carried out by means of temperature programmed oxidation analyses. Reaction-regeneration cycle runs have been carried out in a fixed bed isothermal reactor, concluding that it is possible to regenerate the bifunctional catalyst by the combustion of coke with air, at 300 °C (48 h). Under these conditions, the catalyst undergoes a slight Cu sintering in the first reaction-regeneration cycle but recovers completely the remaining activity in the successive cycles.
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Abbreviations
- CC :
-
Coke content (wt%)
- CZMn:
-
CuO–ZnO–MnO metallic function
- CZMn/S:
-
CuO–ZnO–MnO/SAPO-18 bifunctional catalyst
- DME, MeOH:
-
Dimethyl ether and methanol, respectively
- \({\text{F}}_{{{\text{CO}}_{\text{x}} }}^{0} ,\;{\text{F}}_{{{\text{CO}}_{\text{x}} }}\) :
-
Molar flow rate of (CO + CO2) in the reactor inlet and outlet stream, respectively (mol/h) (Eqs. 1 and 2)
- Fi :
-
Molar flow rate of the component i in the reactor outlet stream (mol/h) (Eqs. 1–3)
- ni :
- P:
-
Pressure (bar)
- SBET :
-
BET specific surface area (m2/g)
- SCu, S′Cu :
-
Cu specific surface area (m2/gCu and m2/gcat, respectively)
- T:
-
Temperature (K)
- Vmicropore, Vp :
-
Micropore volume and total pore volume, respectively (cm3/g)
- WGS:
-
Water gas shift reaction
- \({\text{X}}_{{{\text{CO}}_{\text{x}} }}\) :
-
Conversion of CO + CO2, in carbon units (Eq. 1)
- Yi, Si :
-
Yield and selectivity of the lump i, respectively (Eqs. 2 and 3, respectively)
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Acknowledgments
This work was carried out with the financial support of the Ministry of Economy and Competitiveness of the Spanish Government (CTQ2010-19188 and CTQ2013-46173-R), the FEDER funds, the Basque Government (Projects GIC/24-IT-220-07 and IT748-13) and the University of the Basque Country (UFI 11/39). Ainara Ateka is grateful for the Ph.D. grant from the Department of Education, University and Research of the Basque Government (BFI09.69).
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Ateka, A., Pérez-Uriarte, P., Sierra, I. et al. Regenerability of the CuO–ZnO–MnO/SAPO-18 catalyst used in the synthesis of dimethyl ether in a single step. Reac Kinet Mech Cat 119, 655–670 (2016). https://doi.org/10.1007/s11144-016-1057-y
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DOI: https://doi.org/10.1007/s11144-016-1057-y