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Preparation method of 1,3-propylene glycol

A technology of propylene glycol and low-carbon alcohol, applied in 1 field, can solve the problems of high price, flammable acrolein, high toxicity, etc., and achieve the effects of reducing the cost of product concentration and increasing the use efficiency

Inactive Publication Date: 2003-03-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, acrolein is flammable, highly toxic, highly irritating, and expensive, making it difficult to realize industrial production

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] In a 250ml round-bottom flask with stirring, add 10mmol carbonyl cobalt catalyst, 2.7mmol dibenzo30-crown-10, 167mmol sodium carbonate, 100ml ethanol, 32ml ethyl chloroacetate, at 49±1℃, P CO Under the condition of =0.1MPa, carbon monoxide was introduced at a flow rate of 40ml / min. After 5 hours of reaction, the solid matter was filtered out, and diethyl malonate was obtained by distillation under reduced pressure.

[0020] Take the particles as the 26-40 mesh hydrogenation catalyst CuMn 0.2 Al 0.4 O 1.9 3.2 grams were put into a stainless steel tubular reactor with an inner diameter of 8mm and a length of 400mm. Hydrogen was introduced for reduction at 200°C and 2MPa at a flow rate of 200ml / min for 10 hours. Then, diethyl malonate was used as the raw material. At reaction temperature 185±1℃, pressure 6.7±0.2MPa, liquid hourly space velocity 0.24 hours -1 Under the condition of hydrogen / ester=400:1 mol / mol, the product obtained was tested by FID with a gas chromatograph pac...

Embodiment 2

[0022] In a 150ml conical flask with stirring, add 10mmol carbonyl cobalt catalyst, 16.7mmol potassium carbonate, 39ml ethanol, 21ml ethyl chloroacetate, at 70±1℃, P CO Under the condition of =0.1MPa, pass carbon monoxide and react for 3 hours to obtain diethyl malonate.

[0023] The catalyst in the hydrogenation reaction is CuMn 0.5 Al 0.7 O 2.8 The reaction temperature was 191±2°C, hydrogen / ester=600:1 mol / mol, pressure 6.0±0.2 MPa, and other conditions were the same as in Example 1. The product was chromatographed, and the yield of 1,3-propanediol was 60 mol%.

Embodiment 3

[0025] In a 250ml round-bottom flask with stirring, add 10mmol carbonyl cobalt catalyst, 16.7mmol tetramethylammonium bromide, 71.4mmol sodium carbonate, 100ml ethanol, 11ml ethyl chloroacetate, at 60±1℃, P CO Under the condition of =0.1MPa, pass carbon monoxide and react for 3 hours to obtain diethyl malonate.

[0026] The catalyst in the hydrogenation reaction is CuAlO 2.5 , Reaction temperature is 188±2℃, hydrogen / ester=300:1mol / mol, pressure is 6.7±0.2MPa, liquid hourly space velocity is 0.18 hours -1 The other conditions were the same as in Example 1. The product was analyzed by chromatography, and the yield of 1,3-propanediol was 66 mol%.

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PUM

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Abstract

The preparation method of 1,3-propanediol includes the following steps: 1). in the presence of cobalt carbonyl catalyst, cocatalyst and low-carbon alcohol solvent, under the condition of the pressureis 0.1-0.4 MPa and temp. is 30-90 deg.C making C1-C4 alkyl chldoroacetate and CO produce carbonylation reaction and cottecting dialkyl malonate; and 2). making dialkyl malonate contact with hydrogenation catalyst, and under the condition of the pressure is 3.l0-10 MPa, temp. is 150-250 deg.C, ratio of hydrogen gas and ester is 100-800:1(mol) and liquid hourly space velocity is 0.1-0.5 hr(-1) making hydrogenation reaction. The general formula of the described catalyst is CuMnaAlbOx, in which a=0-1, b is 0.01-1.2 and x is oxygen atomicity for meeting valency requirements of other elements. Its reaction condition is moderate, and its product yield is high.

Description

Technical field [0001] The invention relates to a method for preparing 1,3-propanediol. Background technique [0002] 1,3-Propanediol is an important organic chemical raw material, mainly used to produce polymers, such as thermoplastic polyurethane, poly 1,3-propylene terephthalate (PTT), copolyester ether, etc. It can also be used as a solvent, Freezing agent and protective agent. Among them, the performance of PTT prepared by using it instead of 1,4-butanediol and ethylene glycol is better than PBT (polyethylene terephthalate) and PET (polyethylene terephthalate) ). [0003] The preparation method of 1,3-propanediol in the prior art mainly has the following two routes: [0004] (1) 1,3-propanediol is prepared by hydroformylation and hydrogenation using ethylene oxide as a raw material. For example, US 5689016 uses cobalt carbonyl promoted by rhodium carbonyl as the hydroformylation catalyst, and Ni, Co, Ru, Pt, and Pd are the hydrogenation catalysts. The concentration of 3-hydr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/149C07C31/20
Inventor 王海京段启伟张建国高国强蒋大智
Owner CHINA PETROLEUM & CHEM CORP