SU858917A1 - Method of regeneration of copper-zinc-chromium catalyst for hydrogenating carbonyl compounds - Google Patents

Description

This goal is achieved by reducing the reduction of the methane-zinc-chromium catalyst to hydrogenate carbonyl compounds by treating the catalyst with a reducing agent, which uses hydrogen, under a pressure of 50-300 atm with a stepwise increase in temperature at a rate of l-lOC / h to 260 ° C with a shutter speed of 6-10 hours in the range from 95 to 26 ° C. Distinctive features of the method are the use of hydrogen as a hydrogen generator and the performance of hydrogen testing at a pressure of 50300 atm with a stepwise increase in temperature. urs at speeds up delayed for 6-10 hours in the range of from 95 to 260 G, the reduction proposed method has the following advantages. The service life of the catalyst obtained in this way is not less than 6 months, i.e. increases compared with the service life of the catalyst, restored by a known method, not less than 6 times. P, p and me R 1 (comparative). Honey-zinc-chromium catalyst composition, wt.%: Oxides oxides - 13.3, chromium oxides 24, 7, zinc oxides - 54.2, aluminum oxides - 4.4, magnesium oxides - 1.7 and previously calcined 350 ° C, heated into the reactor and heated to 12 ° C at a rate of 10 ° C / h in a stream of nitrogen after temperature equalization throughout the catalyst bed, the temperature is increased at a rate of 2 ° C / h to 15 ° C, then gradually the nitrogen is replaced with gas of composition Еес,%: С0285 СО1-2 MI2-3 and the temperature is raised to 200 ° C, then it is aged to a constant concentration of CO + CO or H at the inlet and outlet of the reactor. This completes the reduction process, replacing the gas with hydrogen to carry out the hydrogenation process. The hydrogenation process was carried out at a pressure of 250 atm, a rate under the circulating hydrogen 2 of the feed, a temperature of 220–230 ° C, and a flow rate of the feed of the feed of 2 v / v of the catalyst per hour. The raw material is a dehydrated hydroformylation product, which is sawn through, which is associated with oil aldehydes. The composition of the feedstock and the hydrogenate is included in the table. 1. The conversion of oil alcegia gradually decreases and the black & 30 grams of work is 82.5%. Example 2. A copper-zinc-chromium catalyst composition, as indicated in example 1, is loaded into the reactor, hydrogen is passed through the catalyst to a residual oxygen content of not more than 0.5% by volume, and the hydrogen pressure is gradually generated at 60 ° C atm. ZOOO hydrogen on / about catalyst per hour produces a stepped temperature rise: up to C - 10 ° C per hour; from 6O to 85 - per hour; from 85 to 95 - 2-3 per hour; from 95 to 1-2С per hour; from 10О to 2-3С. per hour; from 150 to 220 - for 1-2 hours; from 220 to 260 ° - 5 ° C per hour; when the temperature reaches 95, 100, 120, 150, 210, 260 ° C, the catalyst is aged for 6 hours and at a temperature of 195 ° C for 1 hour. Then the temperature is lowered to the working temperature and the process of hydrogenation of propylene hydroformylation products is carried out conditions of example 1. At the same time, the degree of aldehyde conversion is practically not at all and after 6 months is 98%. The results are presented in Table. I. PRI me R 3 (comparative). Copper-zinc-chromium catalyst containing, wt.%: Copper oxide - 54.5, zinc oxide - 12.0, chromium oxide - 14, magnesium oxide - O, 2, manganese oxide - 0.2, aluminum oxide - 19 , 1, pre-calcined at 350 ° C, is loaded into the reactor and reconditioned under conditions analogous to example 1.. After replacing the reducing gas with hydrogen, hydrogenation of the dimeric fraction of the condensation product of n-butyric aldehyde containing aldehydes Cg under a pressure of 28 O atm, at a temperature of 240-250 C, feed rate of the feed of 1 v / v of catalyst per hour and feed rate of circulating hydrogen is carried out 2.5 nm / kg of raw material. The composition of the raw material and hydrogenate are given in table. 2. The degree of aldehyde conversion of Cg decreased after 20 days of operation from 99 to 88.2%. Example 4. A copper-zinc-chromium catalyst composition, as in Example 3, is loaded into the reactor and the catalyst is reduced to Lod with a hydrogen pressure of 15 O atm, as in Example 2, after which the product is hydrogenated

58SS9176.

the composition according to example 3 and under the conditions of the hydri-as in example 1, the analorans similar to example 3 are restored, similarly to example 1. After the reduction and

Hydrogenate is given in Table. 2. replacement gas for hydrogen

The degree of aldehyde conversion through the hydrogenation of the product is carried out, containing 60 days was 94.8%, and then npiaK-5 and its methyl esters of acids P

Tically not changed, prodopzhatelnx: pressure 300 atm, temperature,

test 125 days. raw materials feed speed 0.3 v / v katali Example 5 (comparative). Honey congestion per hour, the flow rate of the circulating

but- "inc-chromium catalyst containing 3000 hydrogen feedstock. Commoner; wt.%: copper oxides - 35.5, oxides of the raw material and hydrogenate are given in

zinc - 29.0, chromium oxide - 20.3, oxide. four.

aluminum - 12.0, manganese oxide - 1.7, Conversion rate of methyl ethers of magnesium oxide - 1.5, previously pro-acids decreased from 9O to 74% hardened at 5050s, loaded into the reaction after 2O days of the catalyst, torus and the reduction is carried out by the method 15. Example 8. Me, the bottom is zinc-chromium analogous to example 1. After replacing the catalyst composition, as in example 1, the reducing gas for hydrogen is restored-analogously to example 2, hydrogenation of the hydroformed product is followed carry out the hydrogenation of the proliferation of olefins containing the product, with holding metipovye esters kisaldegidy CL-Cfl, at a pressure of 300 atm Olot composition as in Example 7, at a temperature of 26O ° C x podachiuslovi speed similar to the Example 7 ,. The composition of the raw material is 0.8 v / v of catalyst per hour, raw material and hydrogenation are given in table. 4. the rate of circulation of circulating hydrogen The degree of conversion of methyl esters 3 raw materials. The composition of the feedstock and hydro-acids was after 4O days of nizat are given in table. 3. 595% and then up to 6O days of work, the aldehyde conversion rate decreased almost continuously, from 98 to 80% after 2O days. Worker. Example 9. Me bottom zinc-chromium catalyst catalyst. as in the example

Example 6. Copper-zinc-chromo-3, restore nitric bromine catalyst composition, as in example 30SI under a pressure of 150 ATM, containing

5, is loaded into the reactor and restored-in vol /%: hydrogen - 47, nitrogen - 52, swept under hydrogen pressure 50 atm of an analogue - 1, when the circulating pump is supplied to example -2. Hydrogenation of the product of the city ZOOO v / v catalyst per hour and

the hydroformylation of Cg-Cg olefins with a stepwise increase in temperature and a ratio similar to that of example 5, which is carried out in accordance with the exposure of the catalyst, is reduced under conditions analogous to those of example 2.

5. The composition of the feedstock and the hydrogenate is given. After the end of the process, the following are restored to table. 3.and the nitric mixture is replaced by

The degree of conversion of aldehydes through hydrogen and the process of hydrogenation of the product

40 days was 94% and then practically condensation of n-butyric aldehyde osusically remained unchanged until 6O days. Under the conditions of example 3. Composition

work catalyst and hydrogenated hydrogenated are given in table.2.

Example 7 (comparative). Aldehyde Cg Honey Conversion at ZO day is an early zinc-chromium catalyst composition, the bots decreased from 99 to 9O%.

0)

0

I p

yu a

H

m

but

0)

s

sh

0)

oh ct

but

L,

S

and and

g n

and

cv

a s × 0

g H

II

858917

The composition of the raw materials and girogene in examples 5-. and 6

Toluene (dissolving the composition of raw materials and hydrogenates as examples 7 and 8 11.0 Meganop Methyl esters 89.3 9.0 acids C-C 69.1 Alcohols C-C 10.7 10.9 High-boiling

Ether conversions,

90 wt.%

Table 3

 Table 4

95

94

96

74 10.09D11.811.711.6 17.923.32.74.65.3 62.457, O73.773.072.5 9.710.611.89.710.6

86891714

Claims (2)

Claims. stepwise increase in temperature (with The method of restoring copper coating of chromium for 6–10 h in the range from 95 m catalyst to the hydrogenation of carcass to 260 C. bpn compounds by treatment with ka s ta / gizatora restorer under pressure-Sources of information, and at elevated temperatures, from whatever they are taken into account during the examination characterized by the fact that, with the goal1. USSR author's certificate obtaining a catalyst with stable ak-Ni 218834, cl. In ch101 3 37/18, 1967., as a reducing agent, 2. Author's certificate of the USSR use hydrogen and hydrogen treatment No. 356872, -l. At 01 J 37/18, 1970 lead h under pressure., 50-300 atm at (prototype). speed 1-10 °) C / h to with hold