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Preparation method of 1,3-propylene glycol

A technology of propylene glycol and malonic acid, applied in 1 field, can solve the problems of high price, flammability and high toxicity of acrolein, and achieve the effect of reducing the cost of product concentration and increasing the use efficiency

Inactive Publication Date: 2004-07-07
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 stirred round bottom flask, add 10mmol carbonyl cobalt catalyst, 2.7mmol dibenzo-30-crown-10, 167mmol sodium carbonate, 100ml ethanol, 32ml ethyl chloroacetate, at 49±1℃, P CO =0.1MPa condition, pass into carbon monoxide with the flow rate of 40ml / min, after reacting for 5 hours, filter off solid matter, diethyl malonate is obtained by distillation under reduced pressure.

[0020] Take the particles as 26-40 mesh hydrogenation catalyst CuMn 0.2 Al 0.4 o 1.9 3.2 grams of packing inner diameter is 8mm, and length is in the stainless steel tubular reactor of 400mm, at 200 ℃, under 2MPa, pass into hydrogen reduction 10 hours with the flow velocity of 200ml / min, then, take diethyl malonate as raw material, At a reaction temperature of 185±1°C, a pressure of 6.7±0.2MPa, and a liquid hourly space velocity of 0.24 hours -1 , under the condition of hydrogen / ester=400:1mol / mol, the obtained product was detected by FID with a gas chromatograph with PEG 20000 packed ...

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°C, P CO =0.1MPa, feed 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 is 191±2°C, hydrogen / ester=600:1 mol / mol, pressure 6.0±0.2MPa, all the other conditions are the same as in Example 1, the product is analyzed by chromatography, and the yield of 1,3-propanediol is 60mol%.

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 =0.1MPa, feed carbon monoxide and react for 3 hours to obtain diethyl malonate.

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

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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 pressure is 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 present invention relates to a preparation method of 1,3-propanediol. Background technique [0002] 1,3-propanediol is an important organic chemical raw material, mainly used in the production of polymers, such as thermoplastic polyurethane, polytrimethylene terephthalate (PTT), copolyester ether, etc. Coolants and protectants. Among them, the performance of PTT prepared by using it instead of 1,4-butanediol and ethylene glycol is better than that of PBT (1,4-butylene terephthalate) and PET (polyethylene terephthalate). ). [0003] In the prior art, the preparation method of 1,3-propanediol mainly contains the following two routes: [0004] (1) Using ethylene oxide as raw material, prepare 1,3-propanediol through hydroformylation and hydrogenation. For example, US 5689016 uses cobalt carbonyl promoted by rhodium carbonyl as hydroformylation catalyst, and Ni, Co, Ru, Pt, Pd are hydrogenation catalysts, and the concentration of 3-hydroxypropional...

Claims

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Application Information

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Patent Type & Authority Patents(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