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Acetic acid hydrogenation catalyst, preparation method and application

A hydrogenation catalyst and catalyst technology, applied in the direction of molecular sieve catalysts, chemical instruments and methods, preparation of hydroxyl compounds, etc., can solve the problems of poor catalyst stability, short service life, catalyst corrosion, etc., achieve high conversion rate, improve catalytic activity, Improve the effect of acid resistance

Pending Publication Date: 2022-05-06
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The above published patents show that the noble metal-supported catalyst is used to hydrogenate acetic acid to produce ethanol, and the reaction selectivity is good, but the conversion rate of acetic acid still has a large room for improvement
In addition, since the acetic acid raw material is acidic, and the hydrogenation reaction system is an exothermic reaction, it will promote the corrosion and damage of the catalyst in the system, resulting in poor catalyst stability and short service life.

Method used

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  • Acetic acid hydrogenation catalyst, preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Add 90.38g of sodium silicate to 500mL deionized water, stir and dissolve at room temperature to obtain solution A; 23.63gCTAB, 14.87g Ni(NO 3 ) 2 ·6H 2 O was added to 500mL deionized water, heated and stirred until dissolved to obtain solution B. After the solution is cooled, add solution A to solution B, and use 1mol / L H 2 SO 4 Adjust the pH to 10 to obtain solution C. After the solution C was continuously stirred for 0.5 h, it was transferred to a stainless steel autoclave for a hydrothermal reaction at 120° C. for 24 h. After the reaction, the hydrothermal reaction solution was lowered to normal temperature, the solid was filtered out, washed with water until neutral, and dried; then the solid was ground into powder (particle size 5-10 μm), and placed in an open muffle furnace at 600°C for 3 hours. The metal Ni-modified MCM-41 molecular sieve (Ni modification amount 3%) was obtained, which was designated as Ni-MCM-1.

[0034] According to the above method and ...

Embodiment 2

[0038] Dissolve 100 mL of polyethylene glycol in 400 mL of distilled water, adjust the pH to 5 with 1 mol / L nitric acid, and then add 0.026 g of EuCl 3 and 0.17g AuCl 3 (molar ratio Au:Eu=5.4:1), 25% ammonia water was added dropwise to adjust the pH value to 10. The supernatant liquid was removed by centrifugation at 10,000 rpm, and the remaining solid was dried overnight at 180°C, and then roasted in a muffle furnace at 600°C for 5h. Finally got Au 2 o 3 -Eu 2 o 3 Composite metal oxides are denoted as AE-1.

[0039] The composite metal oxides AE-2, AE-3, AE-4, and AE-5 were prepared respectively by adjusting the material ratio according to the above method and the amount of raw materials in Table 2.

[0040] Table 2

[0041] EuCl 3 (g)

AuCl 3 (g)

Au:Eu AE-1 0.026 0.17 5.4:1 AE-2 0.026 0.27 8.9:1 AE-3 0.026 0.41 13.5:1 AE-4 0.026 0.52 17.1:1 AE-5 0.026 0.58 19.1:1

[0042] 【Example 1】

[0043] Take 0.5...

Embodiment 3

[0047] According to the method and the amount of raw materials in Example 1, AE-3 and Ni-MCM-2 were mixed to prepare a hydrogenation catalyst, which was designated as NMAE-3.

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Abstract

The invention discloses an acetic acid hydrogenation catalyst as well as a preparation method and application thereof. The structural composition expression of the catalyst is Ni-MCM-AE, wherein AE represents active metal components Au and Eu, and Ni-MCM represents an MCM-41 molecular sieve modified by metal Ni. According to the invention, strong-acid-resistant Au and Eu are used as catalyst active aids, so that the acid resistance and catalytic activity of the catalyst are improved; the active component Ni is distributed in pore channels of the modified molecular sieve through in-situ synthesis, the acid resistance is higher, the active component Ni is not prone to falling off, the active component Ni and Au and Eu components distributed on the surface of the molecular sieve can form a two-stage hydrogenation effect, the catalytic efficiency and the reaction conversion rate are improved, a hydrogenation product is prepared at high conversion rate and high selectivity, and the catalyst is stable in structure and low in cost. And the recycling period is prolonged, and the industrial application cost is saved.

Description

technical field [0001] The invention relates to a hydrogenation catalyst, in particular to an acetic acid hydrogenation catalyst, a preparation method and application, and belongs to the technical field of catalytic hydrogenation. Background technique [0002] In view of the overcapacity of acetic acid and the market situation of oversupply, the hydrogenation of acetic acid to ethanol in the presence of a catalyst has become a new research hotspot. The hydrogenation catalyst used directly affects the operating conditions of the hydrogenation reaction, the conversion rate of acetic acid and the selectivity of ethanol. [0003] US7608744B1 provides a hydrogenation catalyst whose active components are 0.1-20wt% cobalt and other metals (Pt, Pd, Ru, V, Cr, W, Zn, etc.), hydrogenation reaction conditions: 250 ° C, hydrogen space velocity 2500h -1 , pressure 22bar. The selectivity of ethanol exceeds 95%, and the conversion rate of acetic acid is less than 71%. [0004] US7863489...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/03C07C29/149C07C31/08
CPCB01J29/0333C07C29/149B01J2229/183B01J2229/186C07C31/08
Inventor 马德森边新建李俊平黎源张永振袁帅
Owner WANHUA CHEM GRP CO LTD
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