Wear-resultant copper-containing catalyst for low-temperature methanol synthesis at median-pressure

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to copper-containing catalysts for low-temperature synthesis of methanol in fluidized bed at median pressure and provides catalyst, whose preparation involves impregnation and which contains oxides of copper, zinc, chromium, magnesium, aluminum, boron, and barium and has following molar ratio: CuO:ZnO:Cr2O3, MgO:Al2O3:B2O3:BaO = 1:0.3:(0.014-0.038):(0.047-0.119):(0.05-0.1):(0.007-0.014):(0.0292-0.054).

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 an average pressure.

There are many catalysts for low-temperature methanol synthesis under medium pressure. The most common form of such catalysts is an industrial catalyst SNM-3 (Karavaev M.M., Leonov V.E., Popov I.G., Shepelev ET Technology of synthetic methanol. Under. editor Prof. Karavaeva M.M.-M.: Chemistry, 1984. - 240 C., Il.). As analogue accept received GIAP catalyst mole of CuO•(0,2-0,4)ZnO•(0,2-0,4)Cr2O3•(0.1 to 0.3)MnO•(0,1-0,3)MgO•(0,05-0,1)Al2O3labeled DS-8-1 (Materials of scientific-technical conference of NIRTO. The development marked the methanol synthesis catalyst of high and medium pressure. Kurylev, A., Barkovsky A.I. Novomoskovsk, 9-13 December 1996, Part 1, 49-50. Dept. in VINITI. 5.02.98, No. 331-98 In /1/). Analog /1/ is suitable for methanol synthesis at 220-280°C and 10 MPa. Its activity exceeds the activity of the catalyst SNM-3, and the selectivity reaches 93 to 95 wt.%. The difference of the catalyst from the catalyst described in the closest analogue is the method of its production and the ratio of catalyst components.

The proposed catalyst designed to increase mechanical firmly the tees 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 consists of oxides of boron, aluminum and chromium. 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. The introduction of chromium oxide in the catalyst shows a significant increase in the pore size and improving the durability of the catalyst.

The introduction of additives barium oxide in the catalyst contributes to the increase in its activity and selectivity.

Based on the results of testing the most active samples was selected composition of the catalyst for further optimization, mole D. what if:


Analysis of the results of experiments on the optimization showed that the activity and stability of catalyst increases with decreasing content of additives Cr2About3, MnO and MgO from the main level.

Whereas studies of catalysts of the type DS to work under pressure of 10 MPa, offer a catalyst of the following chemical composition, mole fraction:


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 1000 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 100 g). In the resulting mass is added 70 ml of concentrated hydrochloric acid to pH 3-4. Get 220 ml thixotropic colloidal solution of basic aluminum chloride, which is left to ripen at room temperature.

Separately receive the chromium hydroxide in two ways: heterogeneous (from the dilute salt solution chromium nitrate 33 g with a solution of ammonia water to pH 8, followed by washing the precipitate fine chromium hydroxide is distilled water) and homogeneous (by heating the salt solution chromium nitrate 33 g with the addition of 15 g of urea for 1-1,5 hours to fall a voluminous precipitate followed by washing on the filter).

In Mature psevdosily Al2(OH)5Cl enter svezheosazhdennoi the chromium hydroxide and 14 g of boric acid and mix thoroughly. The resulting suspension is left for 1-2 days to complete peptization the hydroxide precipitate chroma education of the molding material.

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 to visually observe the full shrinkage. Then on the second, high temperature, stage of raising temperature at a rate of 10 deg/hour 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] 1250 g of zinc nitrate [Zn(NO3)2] 375 g of magnesium nitrate [Mg(NO3)2] 104 g of barium nitrate [BA(NO3)2] 53 g and nitrate XP is mA [Cr(NO 3)3] 7 g with the addition of oxalic acid [H2With2O4•2H2About] 964,

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 680 g of the catalyst composition is shown in table 1.

The molar fraction10,30,0260,0830,080,0110,042
The mass fraction64,319,53,22,76,62.41,3

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 medium pressure is carried out in the synthesis of methanol, chetyrekhsektornoi installation. For the organization of the fluidized bed without leakage of gas bubbles and the use of gas distribution grid 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.%): CO20,4; 2,6; N272,8; N224,2; a pressure of 10 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. The test time of 720 hours.

Abrasion of the catalyst after 240, 480 and 720 hours of testing, equal respectively to 1.3; 1.9 and 2.25 g, which is 1.3; 1.9 to 2.25 wt.%.

During the test, the catalyst support the following composition of the source gas, vol.%: hydrogen 74-77, oxide of 2-4 carbon, carbon dioxide of 0.3-0.4, inert impurities 15-20. When 220-260°and 10 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 an average pressure obtained by impregnation, comprising the oxides of copper, zinc, chromium, magnesium, aluminum, characterized in that the catalyst additionally contains oxides of boron and barium, and has the following molar ratio:

CuO:ZnO:Cr 2O3:MgO:Al2O3:B2O3:BaO=1:0,3:(0,014-0,038):(0,047-0,119):(0,05-0,1):(0,007-0,014):(0,0292-0,054).


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