Wear-resistant copper-containing catalyst for low-temperature synthesis of methanol at low pressure

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at low pressure and provides a wear-resistant catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, and boron and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3 = 1:0.3:(0.15-0.2):(0.1-0.025):(0.25-0.3):(0.08-0.1).

EFFECT: increased mechanical strength and wear resistance of catalyst.

1 tbl

 

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

There are many catalysts day of low-temperature methanol synthesis at low pressure. The most common form of such catalysts is an industrial catalyst SNM-1 (Ed. St-No. 215205, 1969 (USSR)). As analogue accept received GIAP catalyst mole of CuO•0,3 ZnO•(0.15 to 0.2)Cr2O3•(0,05-0,1)MnO•(0,05-0,1)MgO•(0,25-0,3)Al2About3•0,05 HLW labeled DN-8-2 (Patent for invention №2175886. The catalyst for methanol synthesis. Kurylev, A., Cherkasov G.P., A.V. Shchukin, Meshcheryakov, GV Moscow, February 14, 2000 /1/). Analog /1/ is suitable for methanol synthesis at 220-280°and 5 MPa. Its activity exceeds the activity of the catalyst SNM-1, and the selectivity reaches 94-97 wt.%. The closest analogue is the catalyst 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 And 03.02.69). The difference of the catalyst from the catalyst described in the closest analogue, the conclusion is carried out in the method of its production and the ratio of catalyst components.

The proposed catalyst designed to increase the mechanical strength and wear resistance to abrasion of the existing catalysts.

To achieve this goal in the composition of the analogue /1/ injected additive In2About3and examine its influence on the mechanical strength and wear resistance of the obtained catalyst (preparation of all samples of the analog /1/ produced by the method of mixing - deposition and catalyst with the additive - impregnated).

The introduction of boron oxide in the catalyst in an amount up to 25% weight. shows a significant increase in mechanical strength and wear resistance of the obtained catalyst. The marked increase in the pore volume and the operating temperature of the catalyst.

In addition, this goal is achieved by obtaining the catalyst by impregnation wear-resistant base, which includes oxides of boron and aluminium. The introduction of aluminum oxide in the catalyst stabilizes it, increases its strength properties when abrasion and crushing, and provides a high internal surface, moderately good thermal stability of the catalyst.

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=1:0,3:0,21:0,08:0,17:0,3:0,068.

Analysis rezultatov optimization showed the activity and stability of catalyst increases with decreasing content of MnO additives and HLW from the main level.

Whereas studies of catalysts such as NAM to work under pressure of 5 MPa, offer a catalyst of the following chemical composition, mole fraction:

CuO:ZnO:Cr2About3:MgO:Al2About3:In2About3=1:0,3:(0,15-0,2):(0,1-0,025):(0,25-0,3):(0,08-0,1).

An example of the preparation of the catalyst.

Separately receive the solution of the basic aluminum chloride Al2(OH)5Cl. To do this, first of 1500 grams of pure aluminum metal by the electrolytic deposition (I=10-25 A, U=40-80) get the aluminum hydroxide (electrolysis hold up until the weight of the aluminium plate is reduced by 400 g). In the resulting mass is added 220 ml of concentrated hydrochloric acid to pH 3-4. Get 920 ml thixotropic colloidal solution of basic aluminum chloride, which is left to ripen at room temperature. In Mature psevdosily Al2(OH)5Cl impose 128 g of boric acid, H3BO3and mix thoroughly. To obtain spherical granules using the method of hydrocarbon moulding. Spheroidal drops is carried out in a layer of kerosene thickness of 2-3 cm and volume structuring Zola 15% ammonia water.

In the first stage of the pellets is maintained at a temperature of 313 K in 2-3 days is about visually observing the full shrinkage. Then on the second, high temperature, stage of raising temperature at a rate of 10 deg/h up to 423 K and kept at this temperature for 4 hours. Temperature calcination of the pellets in the small regulating heat tracing is as follows:

- temperature rise from 423 K To 473 K - 20 deg/h;

- rise of temperature from 473 K To 773 K - 50 deg/h;

- rise of temperature from 773 K To 1373 K - 100 deg/h;

- excerpt at 1373 K for 4 hours.

Separately receive 60% (based on crystalline) impregnating a solution of a density of 1.56 g/cm3of the salts of copper nitrate [Cu(NO3)2] - 1428 g of zinc nitrate [Zn(NO3)2] - 428 g of magnesium nitrate [Mg(NO3)2] - 88 g of chromium nitrate [Cr(NO3)3] - 243 g with the addition of oxalic acid [H2With2O4•2H2O] - 1100

Impregnation of the granules impregnating solution is carried out at 60-80°within hours. Calcined catalyst for two hours at 500-550°C. the Number of cycles "impregnation-calcination for all samples is equal to three. The result is 950 g of the catalyst composition is shown in table 1.

Table 1
CuOZnOCr2O3MgOAl2O3In2About 3
The molar fraction10,30,170,0620,280,09
The mass fraction47,714,515,41,517,1the 3.8

From the obtained weight of the finished catalyst choose a sample of 100 g, grain size of 0.6-1.5 mm and subjected to the test for abrasion (by the mass loss of granules during tests in a fluidized bed).

Industrial tests of the obtained low-temperature catalyst of low pressure is carried out in the synthesis of methanol, chetyrekhsektornoi installation. For the organization of the fluidized bed without leakage of gas bubbles use a gas grill with holes of 0.5 mm; and the apparatus is placed vertical plane lattice with holes 10 mm

Test conditions: the composition of the synthesis gas (vol.%): CO2- 0,4; - 2,6; N2- 72,8; N2- 24,2; a pressure of 5 MPa; the temperature of 220-260°; space velocity of the synthesis gas 10000 h-1. As pseudoviruses agent use the air. The number of fluidization is equal to 1.5. Time trials - 720 hours.

Abrasion of the catalyst after 240, 480 and 720 hours of testing, respectively equal to 1.5, 2.0 and 2.4 g, which is 1,5; 2,0 and 2.4% wt.

During the test, the catalyst support trail is in store the composition of the source gas, vol.%: hydrogen - 74-77, carbon oxide with 2-4 carbon dioxide - 0,3-0,4, inert impurities 15-20. When 220-260°and 5 MPa carbon monoxide is almost completely converted into methanol.

As shown by industrial tests, this low-temperature catalyst substantially wear-resistant (< 5% wt.), what makes possible its use in industry for carrying out the process in a fluidized bed.

Wear-resistant copper-containing catalyst for low-temperature methanol synthesis at low pressure, obtained by impregnation, comprising the oxides of copper, zinc, chromium, magnesium, aluminum, characterized in that the catalyst additionally contains boron oxide and has the following molar ratio of CuO:ZnO:Cr2O3:MgO:Al2O3:B2O3=1:0,3:(0,15-0,2):(0,1-0,025):(0,25-0,3): (0,08-0,1).



 

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