Auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol

A technology of CO2 and catalysts, which is applied in the field of additive modified catalysts, can solve the problems of complex preparation methods, lower methanol selectivity, and low overall yield, and achieve the effects of simple preparation process, high selectivity, and easy industrialization

Inactive Publication Date: 2012-10-10
KUNMING UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Chinese patent CN101327431 relates to a method for preparing a catalyst for synthesizing methanol. This method is to mix and stir the three kinds of precipitates and age them, after washing, drying and roasting, adding graphite and water to the roasted materials, and pressing them into tablets, which are suitable for synthesis Gas composition (v / v): CO13~15%, CO 2 4~6%,H 2 55~65%, the rest is N 2 Methanol catalyst, the catalyst activity and heat resistance are better than the catalyst prepared by the prior art, but the preparation method is more complicated
The catalyst is used for CO 2 Hydrogenation to methanol, the additives added increase the CO 2 conversion rate, but the selectivity of methanol is reduced, and the overall yield is not high

Method used

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  • Auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Example 1: CO and CO 2 The components and the ratio of each component of the co-hydrogenation synthesis methanol catalyst are Cu:Zn:Al molar ratio is 6.0:3.2:0.8, Zr and Mg are not included.

[0018] During preparation, 18.63 grams of Cu (NO 3 ) 2 ·3H 2 O, 12.23 g Zn(NO 3 ) 2 ·6H 2 O and 3.85 g Al(NO 3 ) 3 9H 2 O was dissolved in deionized water and mixed with 1.1mol / L Na 2 CO 3 The solution is co-currently titrated into 100ml of deionized water stirred at a high speed, while keeping the pH of the solution at 7-8, and the reaction temperature at 70°C. Stir the reaction for 1 hour, then leave it to age at room temperature for 2 hours, suction filter, wash, and dry the solid precipitate at 110°C for 12 hours to obtain a catalyst precursor, which is then placed in a muffle furnace and calcined at 500°C for 5 hours. After cooling, grind, tablet, and sieve to obtain a catalyst in the range of 20-40 mesh.

Embodiment 2

[0019] Example 2: CO and CO modified by this additive 2 The components and the ratio of each component of the co-hydrogenation methanol synthesis catalyst are: (CuZnAl): (ZrMg) mass percentage is 99.4%: 0.6%, where Cu: Zn: Al molar ratio is 6.0: 3.2: 0.8, Zr: Mg molar The ratio is 2:1.

[0020] During preparation, 18.52 grams of Cu(NO 3 ) 2 ·3H 2 O, 12.16 g Zn(NO 3 ) 2 ·6H 2 O, 3.82 g Al(NO 3 ) 3 9H 2 O and 0.1420 g Zr(NO 3 ) 4 Dissolve in deionized water, mix it with 1.1mol / L Na 2 CO 3The solution was titrated concurrently into 100ml of deionized water stirred at high speed, while keeping the pH of the solution at 7-8, and the reaction temperature at 70°C. After the nitrate solution was added dropwise, the pH was adjusted to 9, and continued stirring at the reaction temperature React for 1 hour, then stand and age at room temperature for 2 hours, filter with suction, wash the solid precipitate with deionized water, and dry at 110°C for 12 hours to obtain a cataly...

Embodiment 3

[0021] Example 3: CO and CO modified by this additive 2 The components and the ratio of each component of the co-hydrogenation methanol synthesis catalyst are: (CuZnAl): (ZrMg) mass percentage is 98%: 2%, where Cu: Zn: Al molar ratio is 6.0: 3.2: 0.8, Zr: Mg molar The ratio is 2:1.

[0022] During preparation, according to the mass percentage of CuZnAl and ZrMg is 98.0%: 2.0%, weigh 18.25 grams of Cu (NO 3 ) 2 ·3H 2 O, 11.99 g Zn(NO 3 ) 2 ·6H 2 O, 3.77 g Al(NO 3 ) 3 9H 2 O , 0.47 g Zr(NO 3 ) 4 Dissolve in deionized water, mix it with 1.1mol / L Na 2 CO 3 The solution was titrated concurrently into 100ml of deionized water stirred at high speed, while keeping the pH of the solution at 7-8, and the reaction temperature at 70°C. After the nitrate solution was added dropwise, the pH was adjusted to 9 and kept at the reaction temperature to continue Stir the reaction for 1 hour, then leave it to age at room temperature for 2 hours, filter it with suction, wash the solid ...

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Abstract

The invention discloses an auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol. The auxiliary agent-modified catalyst comprises Cu, Zn, Al, Zr and Mg. A mass ratio of (CuZnAl): (ZrMg) is (90.0 to 99.9%): (0.1 to 10%). A mole ratio of Cu: Zn: Al is m: n: l, wherein m is in a range of 5.0 to 6.5; n is in a range of 3.0 to 4.5; and l is equal to 10-m-n. A mole ratio of Zr: Mg is (1.0 to 3.0): (1.0 to 2.0). The auxiliary agent-modified catalyst has a high carbon conversion ratio in CO-CO2 co-hydrogenation synthesis of methanol, and has high selectivity of methanol in products. A preparation method of the auxiliary agent-modified catalyst has simple processes and is prone to industrialization.

Description

Technical field [0001] The present invention relates to a catalyst, in particular to CO and CO 2 The invention discloses an auxiliary modified catalyst for synthesizing methanol by co-hydrogenation, which belongs to the technical field of catalysts. Background technique [0002] Methanol is an extremely important chemical raw material, widely used in organic synthesis, medicine, fuel, dyestuff, its output is second only to synthetic ammonia and ethylene. Methanol is not only C 1 The basic substance of the chemical industry, hundreds of chemical products can be produced from methanol, and it is also an important potential substitute clean fuel. With the change of energy structure, methanol will play a pivotal role in the future society. [0003] From the research situation at home and abroad, the use of CO alone to convert methanol is the main research direction of industrial waste gas recycling. In many cases, however, CO 2 CO and CO coexist in gas sources, such as coa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/80C07C31/04C07C29/154
CPCY02P20/52
Inventor 高文桂刘文艳王华张逢杰
Owner KUNMING UNIV OF SCI & TECH
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