The catalyst for methanol synthesis

 

(57) Abstract:

Copper-containing catalyst for low-temperature methanol synthesis at low pressure, obtained by the method of mixing-deposition, comprising the oxides of copper, zinc, chromium, manganese, magnesium, aluminum and barium, wherein the catalyst has the following molar ratio of CuO:ZnO:Cr2O3:MnO:MgO: Al2O3:HLW=1:0,3:(0,15-0,2):(0,05-0,1):(0,05-0,1):(0,25-0,3):0,05. 1 table.

The invention relates to copper-containing catalysts for low-temperature methanol synthesis at low pressure.

There are many catalysts for low-temperature methanol synthesis at low pressure. The most common form of such catalysts is an industrial catalyst SNM - 1 (Ed. St-N 215205, 1969 (USSR)). As analogue accept received GIAP catalyst mole of CuO Is 0.3 ZnO 0.23 Al2O30.1 Cr2O3labeled DN-8-1 (see Development of low-temperature catalyst for methanol synthesis. Tarasov, L. A., Cherkasov, P., Anokhin Century. N. "Mat. nauch.-technology. proc. NF, mhti, Novomoskovsk, 19-23 may 1986 1 o'clock", 1987, pages 196-198/1/). Analog /1/ is intended for the synthesis of methanol at 220 - 280oC and 5 MPa. Its activity is talization for low-temperature methanol synthesis, obtained by the method of mixing - precipitation and containing oxides of copper, zinc or aluminum, manganese, chromium, iron, barium and magnesium. In this catalyst injected copper oxide, chromium oxide, aluminum oxide added in the ratio of 30: 5: 65 to 70:25:5 (SU 218841 A, 03.02.69). The difference of the catalyst from the catalyst described in the closest analogue is the ratio of the catalyst components.

The proposed catalyst designed to increase the activity and selectivity of the existing catalysts.

To achieve this goal in the composition of the analogue /1/ introducing various additives (MnO, MgO, BaO, B2O3, CoO, NiO) and investigate their influence on the activity and selectivity of the resulting catalyst (preparation of all samples of the analog /1/ and catalysts with additives produced by the method of mixing - precipitation).

The introduction of the basic catalyst of Nickel oxide in an amount up to 0.4 wt. % shows a slight decrease in activity. With increasing content of NiO activity of the catalyst decreases sharply at low temperatures. The selectivity of the catalyst with increasing the content of Nickel oxide uniformly decreases due to the formation of water. Impact safety of cobalt oxide in the catalyst at the same rate, that Nickel oxide has on the catalytic properties of a negative impact. When the content of 1 wt.% CoO activity falls almost to zero. Selectivity also decreases sharply when the content of 1 wt.% is only 1.8% compared with 80% for basic catalyst. The introduction of cobalt oxide leads to the formation of organic impurities, but in smaller numbers than their is formed at the industrial catalyst SNM-1.

Not see a significant impact on the activity and selectivity of the catalyst additive oxide of manganese with the content up to 5 wt.% in a sample. Further increase in the amount of MnO leads to a gradual decrease in the selectivity and activity, although the performance on the crude methanol increases slightly. Formed organic impurities, but in quantities smaller than SNM-1 and the analog /1/. The area of optimum temperatures extends to 250 - 290oC. it is Expedient to introduce manganese oxide in an amount up to 5 wt.%, given that it provides additional stabilization of copper as the active component and extends the range of operating pressures synthesis.

Significantly increases the activity of the catalyst analog /1/ when the content of boron oxide in Kolechko pronounced peak of activity as a drain of the crude methanol and plum 100% methanol. The selectivity of the catalyst was slightly reduced only when the content of boron oxide 7 wt.% and more. The formation of organic impurities does not occur if the contents of B2O3does not exceed 1 wt.%.

A peculiar influence on the properties of the catalyst has the introduction of barium oxide. When the content up to 1 wt.% organic impurities are absent. This significantly increases the yield of crude methanol due to the formation of water. The absolute yield of methanol is not changed compared to the base catalyst. With the increasing content of barium oxide to 7 wt.% dramatically increases the yield of crude methanol (from 0.96 to 1.36 ml/cm3h) and the methanol content of from 82 to 90 wt. %, and dimethyl ether. Thus, additives BaO have a positive impact on catalyst properties: allow to increase the activity of the composition in 1.5 times, to improve the selectivity of the process to the level of 91 wt.%.

Based on the results of testing the most active samples was selected composition of the catalyst for further optimization, the molar fraction: CuO:ZnO: Cr2O3:MnO: MgO:Al2O3:BaO:B2O3=1:0.3:0.3: 0.2:0.175:0.225:0.075:0.075.

Analysis of the results of experiments on protected areas is SUB>O3and BaO from the basic level, however, these additives improve or stability of the catalyst during operation, or its selectivity.

Whereas studies of catalysts of type DN and the existing technology of preparation of catalysts to work under pressure of 5 MPa, offer a catalyst of the following chemical composition, mole fraction: CuO:ZnO: Cr2ABOUT3: MnO:MgO: Al2ABOUT3:BaO=1:0.3:(0.15-0.2):(0.05-0.1):(0.05-0.1):(0.25-0.3): 0.05.

An example of the preparation of the catalyst.

Separately receive 58% solution of salts of copper nitrate [Cu(NO3)2] - 1880, zinc nitrate [Zn(NO3)2] - 567 g of manganese nitrate [Mn(NO3)2] - 143 g and a mixture of powders of chromium trioxide [CrO3] - 350 g, carbon primary magnesium [MgCO3Mg(OH)2] - 114 g of aluminum hydroxide [Al(OH)3] - 430 g of barium carbonate [BaCO3] to 100 g of oxalic acid [H2C2O42H2O] - 1450

A mixture of solutions of nitrates and powders thoroughly stirred at 80-90oC for 40 minutes

Get a pasty mass which is dried at 140oC and calcined at 450oC for 6 h, the result of 1770 g of powder catalyst composition shown in the table.

Receive 1947 the finished catalyst, of this mass choose a sample of 100 g, crushed and taken 2 cm3the fraction with a grain size of 2 mm Selected fraction is subjected to the test activity (output methanol) and selectivity (methanol content in raw).

Test conditions: the composition of the synthesis gas (vol.%): CO2- 0.4; - 2.6; H2- 72.8; N2- 24.2; pressure: 5 MPa; the volumetric rate of synthesis gas: 10000 h-1.

Output of crude methanol at 220, 240, 260oC respectively 1.8, 2.2, and 2.0 ml/(cm3h). The methanol content in the raw - 97.4%. The composition of the synthesis gas after the separation of methanol: CO2- 10 ppm; CO - 12 ppm; H2- 75.2% vol.; N2- 24.8% vol.

Industrial tests of low-temperature catalyst DN-8-2 is carried out in the synthesis of methanol. Significant differences in the work column, first working on the catalyst SNM-1, no.

During the test, the catalyst support the following composition of the source gas, vol.%; hydrogen - 74-77, carbon oxide with 2-4 carbon dioxide is 0.3 - 0.4, inert impurities - 15-20. At 220 - 260oC and 5 MPa carbon monoxide is almost completely converted into methanol. For 284 days the catalyst is stable. Analysis of the methanol, pepitone, the catalyst DN-8-2 compared with the copper-containing SNM-1 has the following advantages: the degree of conversion of carbon oxides increases with 25-40% to 90%; consumption norms of raw materials reduced by 5-10%; low CO content can increase the service life of heat exchangers and equipment, reduce the formation of CARBONYLS of iron and eliminate the process of mahanirvana, to reduce the number of stops to eliminate gaps; improving the quality of crude methanol: permanganate number increases from 2 to 40-50 min, the content of organic impurities decreases from 2.5 - 3.5 wt. % to 0.4 wt.%, the water content is reduced to 3 to 5 wt.%, as the methanol content increases to 94 - 97 wt.%, reduces the cost of rectification of the crude methanol; the recovery time of the catalyst decreases from 7 to 3 days.

Copper-containing catalyst for low-temperature methanol synthesis at low pressure, obtained by the method of mixing - deposition, comprising the oxides of copper, zinc, chromium, manganese, magnesium, aluminum and barium, wherein the catalyst has the following molar ratio of CuO : ZnO : CR2O3: MnO : MgO : Al2O3: BaO= 1 : 0,3 : (0,15 - 0,2) : (0,05 - 0,1) : (0,05 - 0,1) : (0,25 - 0,3) : 0,05.

 

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