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Gas-phase hydrocatalyst of dimethyl maleate

A technology of dimethyl maleate and catalyst, applied in the field of catalysts, can solve the problems of reduced selectivity of 1,4-butanediol, increased selectivity of by-product γ-butyrolactone, low selectivity of tetrahydrofuran and the like

Inactive Publication Date: 2005-02-23
NORTH HUAJIN CHEM IND GRP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In a word, the existing dimethyl maleate gas-phase hydrogenation produces 1, and the catalyst of 4-butanediol co-production tetrahydrofuran is all almost 100% under certain raw material space velocity conditions, but the selectivity for tetrahydrofuran is all Low, even if the selectivity of tetrahydrofuran is high, the selectivity of 1,4-butanediol will be greatly reduced, and the selectivity of by-product γ-butyrolactone will be increased

Method used

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Examples

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Comparison scheme
Effect test

example 1

[0019] 156.6 g of Cu(NO 3 ) 2 ·3H 2 O, 54.7 g Al(NO 3 ) 3 9H 2 O, 11.29 g Ni(NO 3 ) 2 ·6H 2 O, 4.21 g Ce(NO 3 ) 3 ·6H 2 O was dissolved in 800ml, 600ml, 300ml, and 300ml of desalted water respectively to make a solution, and then the above four solutions and 185.3 grams of 50% Mn(NO 3 ) 2 The solutions were mixed to prepare a mixed solution, stirred at 40°C, and K 2 CO 3 In the solution, finally adjust the pH value to 6.2±0.2, age at room temperature for 12 hours, then wash, filter, dry at 80°C for 12 hours, and roast at 330°C for 4.5 hours to obtain catalyst A: CuMn 0.8 Al 0.15 Ni 0.06 Ce 0.01 o 2.1 (Oxygen is obtained by calculation, the same below).

example 2

[0021] 96.8 g of Cu(NO 3 ) 2 ·3H 2 O, 30.1 g Al(NO 3 ) 3 9H 2 O, 9.28 g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 400ml, 600ml, and 300ml of desalted water respectively to make a solution, and then the above three solutions were mixed with 21.5 grams of 50% Mn(NO 3 ) 2 The solutions were mixed to prepare a mixed solution, stirred at 40°C, and K 2 CO 3 In the solution, finally adjust the pH value to 7.6±0.1, age at room temperature for 12 hours, then wash, filter, dry at 80°C for 12 hours, and roast at 380°C for 4.5 hours to obtain a compound. The compound contains 15.6 grams of Ce (NO 3 ) 3 ·6H 2 O in acetone solution for 10 hours. After puffing and drying at 80°C, drying for 15 hours, and calcination at 185°C for 24 hours, catalyst B: CuMn was obtained 0.15 Al 0.2 Ni 0.08 Ce 0.06 o 1.62

example 3

[0023] 116.2 g of Cu(NO 3 ) 2 ·3H 2 O, 104.7 g Al(NO 3 ) 3 9H 2 O, 1.7 g dissolved Ni (NO 3 ) 2 ·6H 2 O was made into a solution in 3000ml desalted water, and then mixed with 64.2 grams of 50% Mn(NO 3 ) 2 The solutions were mixed to prepare a mixed solution. A compound was prepared in the manner of Example 2. The compound contains 4.2 grams of Ce(NO 3 ) 3 ·6H 2 Soaked in acetone solution of O for 12 hours, dried at 90°C for 30 hours, and calcined at 140°C for 24 hours to prepare catalyst C: CuMn 0.76 Al 0.58 Ni 0.012 Ce 0.02 o 3.51

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Abstract

A catalyst for gas-phase hydrogenation of dimethyl maleate to produce 1,4-butanediol and co-production of tetrahydrofuran has the following general formula: CuMnaAlbNicMdOx where M is a rare earth element La or Ce, a=0.05-10, b=0.1-30, c=0.01-8, d=0.02-1.5, X is the number of oxygen atoms satisfying the valence state of each metal atom. When the catalyst liquid space velocity of dimethyl maleate reaches 1.3h-1, the conversion rate of dimethyl maleate can reach 100%, the selectivity of 1,4-butanediol can reach 80%, tetrahydrofuran The selectivity can reach 15%.

Description

technical field [0001] The invention relates to a catalyst for producing 1,4-butanediol and tetrahydrofuran through gas-phase hydrogenation of dimethyl maleate. More specifically, the present invention relates to a catalyst for gas-phase hydrogenation of dimethyl maleate containing Cu, Mn, Al, Ni, and M to produce 1,4-butanediol and tetrahydrofuran. The catalyst reaches a liquid space velocity of 1.3h in dimethyl maleate -1 , the conversion rate of dimethyl maleate can reach 100%, the selectivity of 1,4-butanediol can reach 80%, and the selectivity of tetrahydrofuran can reach 15%. technical background [0002] US Patent No. 5,698,749 discloses a Pd-Re catalyst on a non-oxidizing carbon support. At 17.3MPa, temperature 160℃, liquid space velocity 0.38h -1 , under the reaction conditions of hydrogen: dimethyl maleate=65: 1, the conversion rate of dimethyl maleate is 100%, and the selectivity to 1,4-butanediol is 82.3%, and the selectivity to tetrahydrofuran Sex is 6.5%. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/755B01J23/885B01J23/89C07C31/20C07D307/78
Inventor 蓝云飞冷庆海王益波范立成柳彦军秦兵李勇鹏李淑文罗影
Owner NORTH HUAJIN CHEM IND GRP
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