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Method for one-step production of 1, 4-butanediol through dimethyl maleate liquid phase hydrogenation

A technology of dimethyl maleate liquid and dimethyl maleate, which is applied in the field of one-step production of 1,4-butanediol by liquid-phase hydrogenation of dimethyl maleate, which can solve complex product composition and multi-equipment Investment, high separation costs and other issues, to achieve the effect of saving equipment investment costs and saving heat energy

Active Publication Date: 2022-07-01
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the gas-phase hydrogenation of dimethyl maleate has received extensive research attention, its hydrogenation in the liquid phase has been seldom studied. Compared with gas-phase hydrogenation, liquid-phase hydrogenation can save the consumption of raw material vaporization process. On the other hand, it can also reduce the amount of hydrogen required for high hydrogen-ester ratio, which is very in line with the current double-carbon policy advocated by the country
Currently only CN103946201A announces the preparation of butanediol by liquid-phase hydrogenation of dimethyl maleate, but this method needs two-step hydrogenation, that is, earlier dimethyl maleate is converted into dimethyl succinate on a precious metal catalyst , and then convert dimethyl succinate to butanediol on a copper-based catalyst, which requires more equipment investment and noble metal catalyst cost than one-step hydrogenation, and the obtained target product BDO is obtained within 0.2h -1 The lower yield is only 84.0%, the product composition is complex, and the separation cost is high

Method used

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  • Method for one-step production of 1, 4-butanediol through dimethyl maleate liquid phase hydrogenation
  • Method for one-step production of 1, 4-butanediol through dimethyl maleate liquid phase hydrogenation
  • Method for one-step production of 1, 4-butanediol through dimethyl maleate liquid phase hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Dissolve 13.686 g (ie, 0.0567 mol) of copper nitrate trihydrate in 26 mL of deionized water, referred to as solution A. Dissolve 29.1274 g (ie 0.140 mol) of ethyl orthosilicate in 31 mL of ethanol, and mix to form solution B. After mixing A and B solution and stirring for about 45min to make it evenly mixed, solution C is formed. A four-necked flask was placed on the water bath, and 0.25 mol / L of ammonium carbonate solution and C solution were added dropwise at a constant speed with a constant pressure dropping funnel at 80°C, and the drop of ammonium carbonate solution or solution C was adjusted according to the detection result of pH test paper. Accelerate, keep the pH of the liquid in the flask at 7 ± 0.5, and add dropwise time for 120 minutes. After the liquid was added dropwise, it was aged at 80°C for 18h.

[0045] After the aging, it was washed with suction filtration with 400 mL of deionized water until there was no obvious moisture, and then it was dried in a...

Embodiment 2

[0048] Take 1 g of the calcined catalyst in Example 1 and put it into a 500 mL flask, dissolve 0.05 g of 3-aminopropyltrimethoxysilane in 80 g of methanol, and mix it with the catalyst evenly. Then the flask was placed in a water bath at 45° C. under stirring for 3 h. The obtained blue suspension was washed by centrifugation, the washing solvent was methanol, and then dried at 80° C. for 12 hours, and the obtained catalyst was designated as catalyst B.

[0049] See Example 1 for the catalyst evaluation process of this example. The obtained results are: dimethyl maleate conversion 100%, DMS selectivity 11.72%, BDO selectivity 79.47%, r-butyrolactone selectivity 7.35%, tetrahydrofuran selectivity 1.46%, see Table 1 and appendix for details. figure 1 . It can be seen from the reaction results that after the catalyst of Example 1 is modified with 3-aminopropyltrimethoxysilane, the hydrogenation ability of dimethyl succinate DMS is improved. However, this example is not doped wi...

Embodiment 3

[0051] Dissolve 12.639 g (ie 0.0523 mol) copper nitrate trihydrate and 1.647 g (ie 0.00554 mol) zinc nitrate hexahydrate in 26 mL of deionized water, denoted as solvent A. Dissolve 29.1274 g (ie 0.14 mol) of ethyl orthosilicate in 31 mL of ethanol, and form solution B after mixing. After A and B liquids are mixed and stirred uniformly, solution C is formed. Put a four-necked flask on a water bath, and at 80°C, add 0.25 mol / L ammonium carbonate solution and C solution dropwise at a constant speed with a constant pressure dropping funnel, and adjust the dropping rate of ammonium carbonate solution or solution C according to the detection result of pH test paper. , keep the pH of the liquid in the flask at 7±0.5, and the dripping time is 120 minutes. After the liquid was added dropwise, it was aged at 80°C for 18h.

[0052] After the aging, it was washed with 400 mL of deionized water by suction filtration until there was no obvious moisture, and then it was dried in a blast dr...

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Abstract

The invention relates to a method for one-step production of 1, 4-butanediol through liquid phase hydrogenation of dimethyl maleate. The method comprises the following steps: adding dimethyl maleate, a catalyst and a solvent dioxane into a high-pressure reaction kettle, sealing, introducing hydrogen until the pressure is 5-7MPa, and reacting for 7-12 hours at 140-220 DEG C while stirring to obtain 1, 4-butanediol, the catalyst is a copper-zinc-magnesium catalyst or a silylation reagent modified copper-zinc-silicon catalyst; according to the invention, 1, 4-butanediol with the yield of 97.8% can be obtained under the temperature and pressure condition equivalent to or milder than that of gas phase hydrogenation, which is higher than that of most hydrogenation in the prior art, and heat and hydrogen consumption required by raw material gasification are saved.

Description

technical field [0001] The invention provides a method for preparing 1,4-butanediol by one-step liquid-phase hydrogenation of dimethyl maleate, and a copper-based catalyst suitable for the method. Background technique [0002] 1,4-Butanediol (BDO) is an important organic and fine chemical raw material, which is widely used in the pharmaceutical, textile, automotive and daily chemical industries, especially in the production of thermoplastic polyester PBAT, degradable plastic PBS The field has broad prospects. Affected by the national degradable plastics and dual-carbon policy, the planned production capacity of degradable plastics PBAT / PBS in recent years has exceeded 15 million tons, and the demand for 1,4-butanediol has increased significantly. As of December 2021, the price of BDO has been More than 30,000 yuan / ton, so how to increase the output of BDO green and efficient is very important. At present, 80% of the domestic BDO production capacity adopts the Reppe metho...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/17B01J23/72B01J23/80B01J31/02C07C31/20
CPCC07C29/177B01J23/72B01J23/002B01J31/0274B01J31/0275B01J23/80B01J2523/00C07C31/207B01J2523/17B01J2523/27B01J2523/41B01J2523/22
Inventor 赵玉军刘伟黄汇江徐艳
Owner TIANJIN UNIV
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