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Preparation method for anhydrous formaldehyde

An anhydrous formaldehyde and methanol technology, applied in the preparation of organic compounds, the preparation of carbon-based compounds, chemical instruments and methods, etc., can solve the problems of low catalyst activity and stability, poor reaction selectivity, and high reaction temperature, and achieve selective High, mild reaction conditions, simple preparation effect

Inactive Publication Date: 2015-03-25
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] The main problems of the above routes are: low catalyst activity and stability, high reaction temperature (generally higher than 600°C), poor reaction selectivity, etc.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Weigh 100 g of ZSM-5 molecular sieve, the molecular sieve has a silicon-aluminum ratio of 25, perform proton exchange three times in 0.5 M ammonium nitrate, and roast at 600° C. for 4 hours. Immerse it in a mixed solution of palladium chloride and zinc chloride, dry it, roast it at 350°C for 1 hour, and reduce it under a hydrogen atmosphere at 400°C for 3 hours to obtain the main active metal (Pd:molecular sieve:promoter (Zn)=20:100: 5 (mass ratio) supported molecular sieve catalyst, filled into a reaction tube after molding, and filled with a 5mm bed layer. Under normal pressure, nitrogen gas is used as a carrier gas, methanol is injected by a micropump, reacted at 250 ° C, and the feed The space velocity was 35ml / (g·s), the conversion rate of methanol was 80% and the yield of formaldehyde was 50% as detected by gas chromatography on-line.

Embodiment 2

[0019] Weigh 100g Y molecular sieve, the molecular sieve has a silicon-aluminum ratio of 2.7, perform proton exchange in 1.0M ammonium nitrate for 3 times, and calcinate at 500°C for 4h. Immerse it in a mixed solution of chloroauric acid and ferric chloride, dry it, roast it at 450°C for 3 hours, and reduce it under a hydrogen atmosphere at 450°C for 2 hours to obtain the main active metal (Au):molecular sieve:promoter (Fe)=15:100 : 15 (mass ratio) supported molecular sieve catalyst, filled into a reaction tube after molding, filled with a 5mm bed, under normal pressure, argon gas as a carrier gas, injected by a micropump, reacted at 450 ° C, and injected The material space velocity was 35ml / (g·s), the conversion rate of methanol was 75% and the yield of formaldehyde was 70% as detected by gas chromatography on-line.

Embodiment 3

[0021] Weigh 100g Y molecular sieve, the molecular sieve has a silicon-aluminum ratio of 5.6, perform proton exchange in 1.0M ammonium nitrate for 3 times, and calcinate at 500°C for 4h. Immerse it in a mixed solution of chloroauric acid and ferric chloride, dry it, roast it at 450°C for 3 hours, and reduce it under a hydrogen atmosphere at 450°C for 2 hours to obtain the main active metal (Au):molecular sieve:promoter (Fe)=15:100 : 15 (mass ratio) supported molecular sieve catalyst, filled into a reaction tube after molding, and filled with a 5mm bed layer, under normal pressure, argon gas as a carrier gas, methanol was injected by a micropump, and reacted at 450 ° C. The feed space velocity was 35ml / (g·s), the conversion rate of methanol was 55% and the yield of formaldehyde was 45% as detected by gas chromatography on-line.

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Abstract

The invention relates to a preparation method for anhydrous formaldehyde. The method adopts a metal loaded acidic molecular sieve catalyst, which is composed of a main active metal, a molecular sieve carrier and a cocatalyst. The specific process includes: using a fixed bed and fluidized bed reactor, charging methanol with a micro-sample injection pump at a charging space velocity of 10-60ml / (g.s), and carrying out reaction at 200-900DEG C, with the methanol conversion rate being 60%-90% and the formaldehyde yield being 45%-85%. According to the preparation method for anhydrous formaldehyde involved in the invention, the catalyst is easy to prepare and has high stability, the reaction conditions are relatively mild, the reaction does not need to be carried out at high temperature, and the conversion rate of methanol and the formaldehyde yield are both high.

Description

technical field [0001] The invention relates to a preparation method of anhydrous formaldehyde, in particular to the preparation of anhydrous formaldehyde by anaerobic dehydrogenation of methanol. Background technique [0002] Formaldehyde is an important organic chemical raw material. It is mainly used to produce phenolic resin, melamine resin and other materials. It can also be used to produce chemical products such as urotropine and 1,4-butanediol. Important raw materials for specialty chemicals, etc. [0003] Industrial production of formaldehyde mostly uses methanol oxidation. According to theoretical calculations, its product is a mixture of formaldehyde and water (molar ratio 1:1). Since the vapor pressure of formaldehyde aqueous solution is low and formaldehyde and water form an azeotrope, the energy consumption of separation and purification to prepare anhydrous formaldehyde is high. However, the production processes such as synthetic resin and preparation of uro...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C47/04C07C45/00B01J29/44B01J29/14B01J29/74B01J29/26
CPCC07C45/512B01J29/126B01J29/26B01J29/44B01J29/7415C07C47/04
Inventor 王峰王业红徐杰张超锋张晓辰
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI