Methanol synthesis catalyst manufacturing using the green solid-state method

Document Type : Research Paper


1 Chemical Engineering Department,Faculty of Engineering, Arak University, Arak, Iran

2 Chemical Engineering Department, faculty of Engineering, Arak University, Aarak, Iran

3 Chemical Engineering Department, faculty of engineering, Arak University, Arak, Iran

4 Catalyst Research Group Petrochemical Research & Technology Company NPC-RT,Tehran ,iran

5 Chemical Engineering Department, faculty of engineering, Iran University of Science and Technology, Tehran, Iran.


In this research study, methanol synthesis catalysts were manufactured with various mole ratios of metal carbonates (zinc, copper and aluminum carbonate) and ammonium hydrogen carbonate via a green solid-state method that employed a ball mill apparatus. Some parameters for the catalyst preparation, such as Al mole percent, Cu/Zn mole ratio, rotations milling speeds and aging time, were optimized to obtain the maximum catalyst activity. The prepared catalysts were compared with the best quality industrial catalyst under the same temperature and pressure condition in a titanium tabular fixed bed reactor. This novel method has many advantages in comparison to the conventional method. The main advantage of the solid-state method is that the methanol synthesis catalyst can be produced without using solvent. Furthermore, this new method reduces operating costs due to the elimination of the filtration and washing steps. Methanol synthesis catalytic activity was maximized at an optimized mole ratio of Cu/Zn of 1.9234 and an Al mole percent of 8 at the maximum grinding speed (450 rpm) during an aging time of 30 min, which showed higher activity (240 gCH3OH/kg cat.h) in comparison with an industrial catalyst sample (218 gCH3OH/kg cat.h). The production of a green catalyst, which requires less water and results in higher catalyst activity, can be widely used for methanol synthesis catalytic applications.


Main Subjects

[1] Behrens, M., Studt, F., Kasatkin, I., Kühl, S., Hävecker, M., Abild-Pedersen, F., Tovar, M. (2012). The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science, 336, 893-897.
[2] Catino, S. C., Farris, E. (1985). Concise encyclopedia of chemical technology. New York: John Wiley and Sons.
[3] Simpson, A. P., Lutz, A. E. (2007). Exergy analysis of hydrogen production via steam methane reforming. International journal of hydrogen energy, 32(18), 4811-4820.
[4] Koempel, H., Liebner, W. (2007). Lurgi's Methanol To Propylene (MTP®) Report on a successful commercialization. Studies in surface science and catalysis, 167, 261-267.
[5] Huber, F., Venvik, H., Rønning, M., Walmsley, J., Holmen, A. (2008). Preparation and characterization of nanocrystalline, high-surface area Cu Ce Zr mixed oxide catalysts from homogeneous co-precipitation. Chemical engineering journal, 137(3), 686-702.
[6] Lekhal, A., Glasser, B. J., Khinast, J. G. (2001). Impact of drying on the catalyst profile in supported impregnation catalysts. Chemical engineering science, 56(15), 4473-4487.
[7] Bao, J., Liu, Z., Zhang, Y., Tsubaki, N. (2008). Preparation of mesoporous Cu/ZnO catalyst and its application in low-temperature methanol synthesis. Catalysis communications, 9(5), 913-918.
[8] Shi, L., Tan, Y. S., Tsubaki, N. (2012). A solid‐state combustion method towards Metallic Cu–ZnO catalyst without further reduction and its application to low‐temperature Methanol synthesis. ChemCatChem catalysis, 4(6), 863-871.
[9] Casey, T., Chapman, G., 1974. Low temperature methanol synthesis catalyst, US Patent 3 790 505.
[10] Ladebeck, J., Koy, J., Regula, T., 2010. Cu/Zn/Al catalyst for methanol synthesis. US Patent 7 754 651.
[11] Schoenthal, Galeon W., and Lynn H. Slaugh., 1986. Methanol synthesis catalyst, U.S. Patent 4 565 803.
[12] Schneider, M., Kochloefl, K., Ladebeck, J., 1985. Catalyst for methanol synthesis and method of preparing the catalyst, US Patent 4 535 071.
[13] Dienes, E. K., Coleman, R. L., Hausberger, A. L., 1981. Catalyst for the synthesis of methanol, US Patent 4 279 781.
[14] Sun, Y., Sermon, P. A. (1993). Carbon monoxide hydrogenation over ZrO2 and Cu/ZrO2. Journal of the chemical society, chemical communications, (16), 1242-1244.
[15] Nitta, Y., Suwata, O., Ikeda, Y., Okamoto, Y., manaka, T. (1994). Copper-zirconia catalysts for methanol synthesis from carbon dioxide: Effect of ZnO addition to Cu-ZrO2 catalysts. Catalysis letters, 26(3), 345-354.
[16] Mierczynski, P., Kaczorowski, P., Ura, A., Maniukiewicz, W., Zaborowski, M., Ciesielski, R., Maniecki, T. P. (2014). Promoted ternary CuO-ZrO2-Al2O3 catalysts for methanol synthesis. Central european journal of chemistry, 12(2), 206-212.
[17] Lachowska, M., Skrzypek, J. (2004). Methanol synthesis from carbon dioxide and hydrogen over Mn-promoted Copper/Zinc/Zirconia catalysts. Reaction kinetics and catalysis letters, 83(2), 269-273.
[18] Chen, H., Yin, A., Guo, X., Dai, W. L., Fan, K. N. (2009). Sodium hydroxide–Sodium Oxalate-assisted co-precipitation of highly active and stable Cu/ZrO2 catalyst in the partial oxidation of Methanol to Hydrogen. Catalysis letters, 131(3-4), 632-642.
[19] Gao, P., Xie, R., Wang, H., Zhong, L., Xia, L., Zhang, Z., Sun, Y. (2015). Cu/Zn/Al/Zr catalysts via phase-pure hydrotalcite-like compounds for methanol synthesis from carbon dioxide. Journal of CO2 utilization, 11, 41-48.
[20] Zhang, L., Zhang, Y., Chen, S. (2012). Effect of promoter SiO2, TiO2 or SiO2-TiO2 on the performance of CuO-ZnO-Al2O3 catalyst for methanol synthesis from CO2 hydrogenation. Applied catalysis A: General, 415, 118-123.
[21] Tang, X. B., Noritatsu, T., Xie, H. J., Han, Y. Z., Tan, Y. S. (2014). Effect of modifiers on the performance of Cu-ZnO-based catalysts for low-temperature methanol synthesis. Journal of fuel chemistry and technology, 42(6), 704-709.
[22] Słoczyński, J., Grabowski, R., Olszewski, P., Kozłowska, A., Stoch, J., Lachowska, M., Skrzypek, J. (2006). Effect of metal oxide additives on the activity and stability of Cu/ZnO/ZrO2 catalysts in the synthesis of methanol from CO2 and H2. Applied catalysis A: General, 310, 127-137.
[23] Słoczyński, J., Grabowski, R., Kozłowska, A., Olszewski, P., Lachowska, M., Skrzypek, J., Stoch, J. (2003). Effect of Mg and Mn oxide additions on structural and adsorptive properties of Cu/ZnO/ZrO2 catalysts for the methanol synthesis from CO2. Applied catalysis A: General, 249(1), 129-138.
[24] Yang, C., Ma, Z., Zhao, N., Wei, W., Hu, T., Sun, Y. (2006). Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst. Catalysis today, 115(1), 222-227.
[25] Poels, E. K., Brands, D. S. (2000). Modification of Cu/ZnO/SiO2 catalysts by high temperature reduction. Applied catalysis A: General, 191(1), 83-96.
[26] Meshkini, F., Taghizadeh, M., Bahmani, M. (2010). Investigating the effect of metal oxide additives on the properties of Cu/ZnO/Al2O3 catalysts in methanol synthesis from syngas using factorial experimental design. Fuel, 89(1), 170-175.
[27] Park, Colin William, et al., 2015. Methanol synthesis process. US Patent 8 957 117.
[28] Matsumura, Y., & Shen, W. J., 2002. Catalyst for the synthesis of methanol and a method for the synthesis of methanol, US Patent 6 342 538.
[29] Takeuchi, M., Mabuse, H., Watanabe, T., Umeno, M., Matsuda, T., Mori, K., 2000. Copper-based catalyst and method for production thereof, US Patent 6 048 820.
[30] Fukui, H., Kobayashi, M., Yamaguchi, T., Arakawa, H., Okabe, K., Sayama, K., & Kusama, H., 2000. Catalyst for methanol synthesis and reforming, US Patent 6 114 279.
[31] Cameron, C., Chaumette, P., Dang Vu, Q., Bousquet, J., Tournier-Lasserve, J., Desgrandchamps, G., 1996. Process for the production of at least one alkyl tertiobutyl ether from natural gas, US Patent 5 523 493.
[32] Fang, D., Liu, Z., Meng, S., Wang, L., Xu, L., Wang, H. (2005). Influence of aging time on the properties of precursors of CuO/ZnO catalysts for methanol synthesis. Journal of natural gas chemistry, 14(2), 107-114.