Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone

A technology of tetrahydrofuran and butanediol, which is applied in the direction of organic chemistry, can solve the problems of increased pressure drop in the reactor bed, poor catalyst stability, and reduced conversion rate of raw materials, etc., and achieves increased bed pressure drop and catalyst stability. Good, optimize the effect of grading

Active Publication Date: 2008-11-19
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] At present, the method of carrying out the hydrogenation reaction of dialkyl maleate and/or dialkyl succinate in a single reaction has the problem of poor stability of the catalyst. Research has found that the main reason is It is the reaction between dialkyl succinate and the water produced by the reaction to

Method used

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  • Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone
  • Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Using dimethyl maleate as raw material, the gas phase hydrogenation reaction is carried out in a fixed bed reactor. The catalyst is CuO-Cr with different loading ratios 2 o 3 (with comparative example 2) catalyst and CuO-MnO 2 / Al 2 o 3 (Same as Comparative Example 1) Graded packing, the process conditions are: temperature 190°C, pressure 6.0MPa, hydrogen ester molar ratio 200:1, volume space velocity of dimethyl maleate is 0.25h -1 , the reaction results are shown in Table 3.

[0030] Table 3 Catalyst graded loading test results

[0031] Filling ratio

Embodiment 2

[0033] Using dimethyl maleate as raw material, the gas phase hydrogenation reaction is carried out in a fixed bed reactor. The catalyst is CuO-Cr with a loading ratio of 1:3 2 o 3 (with comparative example 2) catalyst and CuO-MnO 2 / Al 2 o 3 (with comparative example 1), process condition is: temperature 190 ℃, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h -1 , and the reaction results are shown in Table 4.

[0034] Table 4 Catalyst gradation loading stability test results

[0035]

time, h

THF

murmur

γ-Butine

ester

1,4-butane

diol

Butanol

Conversion rates,

%

total choice

sex,%

initial

2.46

8.96

50.19

0.47

99.26

99.18

100

2.92

8.78

51.19

0.52

99.28

99.05

200

2.13

8.69

49.41

0.51

99.41

99....

Embodiment 3~6

[0039] According to the method of the present invention, different catalysts are used, and suitable process conditions are used, and dimethyl maleate is used as a raw material for hydrogenation reaction. The specific conditions and reaction results are shown in Table 4, Table 5 and Table 6. If different types of catalysts are used in each catalyst bed, the catalysts are mixed and loaded in the same volume ratio. Wherein Example 6 uses a mixture of dibutyl maleate and dibutyl succinate in a volume ratio of 1:1 as a raw material.

[0040] Table 4 Embodiment 3~6 Catalyst

[0041]

[0042] Table 5 Embodiment 3~6 operating conditions

[0043] Example

temperature, ℃

pressure, MPa

Airspeed, h -1

hydrogen / ester ratio

3

190

6.0

0.25

200∶1

4

200

5.0

0.30

300∶1

5

195

6.0

0.40

200∶1

6

190

6.0

0.25

200∶1

[0044] Table 6 ...

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Abstract

The invention relates to a method for producing 1, 4-butanediol and co-producing tetrahydrofuran and gamma-butyrolactone. The method comprises the following steps that: maleic dialkyl ester and/or succinic acid dialkyl ester are/is used as raw material; under hydrogen existence and reaction conditions, reaction material passes through a first catalyst bed layer of CuO-AO-BO, wherein AO is Cr2O3 and/or ZnO, and BO is one or a plurality of Ba, Mg, Ti, Ce, Si, Zr and Mn oxides; then the reaction material passes through a second catalyst bed layer of CuO-MO-Al2O3, wherein MO is one or a plurality of Mn, Zn, Ba, Mg, Ti, Ce, Si and Zr oxides. Compared with the prior art, the method has the advantages that: the raw material conversion rate is more than 99 percent; the total selectivity of 1, 4-butanediol, tetrahydrofuran and gamma-butyrolactone is more than 99 percent; the catalyst stability is good.

Description

technical field [0001] The invention relates to a method of using dialkyl maleate and / or dialkyl succinate as raw materials to produce 1,4-butanediol by gas-phase hydrogenation and co-produce tetrahydrofuran and γ-butyrolactone Methods. Background technique [0002] 1,4-Butanediol is an important basic organic chemical raw material, mainly used in the production of tetrahydrofuran, polybutylene terephthalate (PBT), γ-butyrolactone and polyurethane (PU). In recent years, due to the rapid growth in the demand for thermoplastic elastic fibers and elastomers, the demand for PTMEG (polytetramethylene ether glycol) and PTMG (polytetrahydrofuran ether) as monomers is strong, making the upstream raw material 1,4-butanedi The demand for alcohol is also growing rapidly, and major 1,4-butanediol producers in the world, such as BASF and DUPON, have expanded their production capacity. Tetrahydrofuran is an excellent solvent and an important organic chemical raw material. Its biggest ap...

Claims

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Application Information

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IPC IPC(8): C07D307/08C07D307/33
Inventor 乔凯张宝国张浩袁胜华翟庆铜苏杰
Owner CHINA PETROLEUM & CHEM CORP
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