CN101307042B - Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone - Google Patents
Method for producing 1,4-butanediol and coproducing tetrahydrofuran, and gamma-butyrolactone Download PDFInfo
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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
The present invention relates to a kind of is raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, adopts gas phase hydrogenation to produce 1, the method for 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone.
Background technology
1, the 4-butyleneglycol is a kind of important basic Organic Chemicals, is mainly used in the production tetrahydrofuran (THF), polybutyl terapthalate (PBT), gamma-butyrolactone and urethane (PU).In recent years, because increasing rapidly of thermoplastic elastic fiber and elastomerics demand, in great demand as monomeric PTMEG (polytetramethylene ether diol), PTMG (PTMG), make upstream raw material 1,4-butyleneglycol demand also increases fast, each is big by 1 in the world, and 4-butyleneglycol manufacturer such as BASF, DUPON etc. are numerous and confused to be expanded and can increase production.Tetrahydrofuran (THF) is a kind of excellent solvent and important Organic Chemicals, and its maximum purposes is and 1, and the polycondensation of 4-butyleneglycol generates PTMG, and self polycondensation generates PTMEG.Gamma-butyrolactone is a kind of important Organic Chemicals and fine-chemical intermediate, also be that a kind of functional, solvability is strong, good electrical property, high boiling solvent that stability is high, nontoxic, safe in utilization, have a wide range of applications in fields such as petrochemical complex, medicine, agricultural chemicals, its maximum purposes is to produce methyl-2-pyrrolidone.
In sum, 1,4-butyleneglycol, tetrahydrofuran (THF), gamma-butyrolactone are market in urgent need, the Chemicals that added value is high, therefore, and Development and Production 1, the technology of 4-butanediol and co-producing tetrahydrofuran and gamma-butyrolactone has great importance.
1,4-butyleneglycol production method has Reppe method, Mitsubishi's den process, Kuraray method, butane one cis-butenedioic anhydride method etc.Since wherein butane one cis-butenedioic anhydride method is the eighties, along with C
4The maturation of preparing cis-butenedioic anhydride by oxidation technology grows up, and generally acknowledges that in the world this method is the operational path of Technological Economy optimum.Butane one cis-butenedioic anhydride method mainly comprises following three steps: butane direct oxidation system cis-butenedioic anhydride-cis-butenedioic anhydride esterification system dimethyl maleate-dimethyl maleate hydrogenation system 1,4-butyleneglycol.
1 of Britain DAVY company, 4-butyleneglycol production patented technology (USP4,584,419) has realized industrial application in Korea S, Japan.It adopts the explained hereafter 1 of dimethyl maleate two-stage hydrogenation, 4-butyleneglycol.First section hydrogenation under the condition of 4.5MPa, is converted into gamma-butyrolactone with dimethyl maleate at 200 ℃; Second section is at 180 ℃, 6.0MPa condition under, gamma-butyrolactone partly is converted into 1,4-butyleneglycol and tetrahydrofuran (THF), the main purpose of this technological line is to prevent 1, the double-bond hydrogenation product dimethyl succinate reaction of 4-butyleneglycol and dimethyl maleate forms polymkeric substance, causes the inactivation of catalyzer.This technology more complicated, investment is big.
After this, each company has carried out in the separate unit reactor, is that raw material carries out hydrogenation reaction production 1, the research of 4-butyleneglycol with maleic acid alkyl ester and/or succinic acid dialkyl ester.For example Chinese Fudan University has developed a kind of CuO-ZnO/ carried catalyst (CN200610026696), and the transformation efficiency of dimethyl maleate preferably reaches 100%, and the selectivity of butyleneglycol preferably reaches 75.5%.
1, in the 4-butyleneglycol production technology, be that the catalyzer of main active component is more with CuO, as the disclosed CuO-Cr of EP0143634
2O
3Catalyzer, the disclosed CuO-ZnO catalyzer of WO82/03854, the disclosed CuO-Cr of CN1182732A
2O
3-Al
2O
3Catalyzer, the disclosed CuO-MnO of CN1493569A
2-Al
2O
3Catalyzer, the disclosed CuO-Cr of EP0373947
2O
3-MnO
2Catalyzer etc.This states composition and preparation method that prior art all discloses catalyzer, and the processing condition of using these catalyzer.
At present, the method of carrying out maleic acid alkyl ester and/or succinic acid dialkyl ester hydrogenation reaction in the separate unit reaction all exists the stable bad problem of catalyzer, discover, its major cause is that succinic acid dialkyl ester reacts with the water that reaction produces, generate Succinic Acid, and Succinic Acid is had an effect attached to catalyst surface or with catalyzer consumingly, cause poisoning of catalyst or catalyzer efflorescence, cause feed stock conversion reduction or reactor beds stressor layer to fall increase at last, power consumption increases.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of production 1, the method of 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone, on the basis of simplifying technical process, can effectively solve the poisoning effect of Succinic Acid to catalyzer, catalyst stability is good, and comprehensive catalyzed reaction is effective, and the reactor beds stressor layer falls not have obviously to be increased.
The present invention produces 1, the method of 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone comprises, is raw material with maleic acid alkyl ester and/or succinic acid dialkyl ester, under hydrogen existence and reaction conditions, reaction mass is by first beds of CuO-AO-BO, and wherein AO is Cr
2O
3And/or ZnO, BO is one or more in the element oxides such as Ba, Mg, Ti, Ce, Si, Zr and Mn, and the CuO weight content is 30%～80%, and the AO weight content is 10%～70%, and the BO weight content is 0～40%; Pass through CuO-MO-Al then
2O
3Second beds, wherein MO is one or more in the element oxides such as Mn, Zn, Ba, Mg, Ti, Ce, Si and Zr, the CuO weight content is 30%～80%, the MO weight content is 10%～50%, Al
2O
3Weight content is generally 5%～40%; First beds is 1: 10～10: 1 with the catalyst volume ratio of second beds, and the ratio of optimization is 1: 5～1: 1, and optimized ratio is 1: 4～1: 2.
In the inventive method, the composition of the catalyzer that uses and preparation method all can determine by this area general knowledge in first beds and second beds, during catalyzer is formed, Cu is a main active component, other component is a structural promoter, and catalyzer can adopt conventional coprecipitation method preparation.In the first beds catalyzer, the CuO weight content is preferably 40%～70%, and the AO weight content is preferably 20%～50%, and the BO weight content is preferably 5～30%; In the second beds catalyzer, the CuO weight content is preferably 40%～70%, and the MO weight content is preferably 20%～40%, Al
2O
3Weight content is preferably 10%～30%.Owing to reasons such as preparation process and material purities, must contain a certain amount of other impurity in the catalyzer, as shaping assistant, na oxide, ferriferous oxide etc., content is generally about 2%.Catalyzer is reduced to simple substance Cu with CuO before use, to improve catalyst activity.Also can use dissimilar catalyzer in each beds, catalyzer dissimilar in each bed can use by mixed packing, also can distinguish the layering filling and use.
In the inventive method, described reaction conditions is: 160～240 ℃ of temperature of reaction, the temperature of reaction of optimizing is 180～200 ℃, reaction pressure 4.0～8.0MPa, the reaction pressure of optimizing is 5.0～6.0MPa, hydrogen ester mol ratio 100: 1～400: 1, the hydrogen ester mol ratio of optimization 200: 1～300: 1, volume space velocity 0.1～2.0h during the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
-1, volume space velocity 0.2～0.5h during the liquid of optimization
-1Concrete processing condition can specifically be selected by this area knowledge according to feedstock property and product requirement.
In the inventive method, described maleic acid alkyl ester and/or succinic acid dialkyl ester are generally the dialkyl of C1～C4, as dimethyl maleate and/or dimethyl succinate, diethyl maleate and/or diethyl succinate, dibutyl maleate and/or dibutyl succinate etc.
In the inventive method, reaction process forms the vapourous mixture that is higher than the raw material dew-point temperature for earlier the maleic acid alkyl ester of liquid and/or succinic acid dialkyl ester being vaporized in required ratio in the hot hydrogen logistics, this vapourous mixture is fed be equipped with in the reactor of hydrogenation catalyst then.
In the inventive method, described first beds and second beds can be arranged in the reactor, also can be arranged in placed in-line two reactors, preferably the former can also be provided with the bed of other type catalyst as required to simplify flow process.
The present invention produces 1 by examination maleic acid alkyl ester and/or succinic acid dialkyl ester gas phase hydrogenation, the reaction mechanism of 4-butyleneglycol, tetrahydrofuran (THF), gamma-butyrolactone, poisoning of catalyst and broken major cause are that succinic acid dialkyl ester reacts with the water that reaction produces in the discovery prior art, generate Succinic Acid, and Succinic Acid is had an effect attached to catalyst surface or with catalyzer consumingly, cause poisoning of catalyst or catalyzer efflorescence, cause feed stock conversion reduction or reactor beds stressor layer to fall increase at last, power consumption increases.The inventive method efficiently solves the problems referred to above by optimizing the grating of catalyzer, and simultaneously, the catalyst system of grating has active high, the selection advantages of higher of combined reaction.The inventive method can adopt the separate unit reactor to finish maleic acid alkyl ester and/or the succinic acid dialkyl ester gas phase hydrogenation produces 1, the process of 4-butyleneglycol, tetrahydrofuran (THF), gamma-butyrolactone, solved the poisoning effect of Succinic Acid effectively to catalyzer, catalyst stability is good, the reactor beds stressor layer falls does not see increase, feed stock conversion is greater than 99%, and the product overall selectivity is greater than 99%.
Embodiment
Further specify the inventive method and effect below by embodiment.Wherein catalyzer is formed by weight, forms by ignoring impurity.
Comparative example 1
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is CuO-MnO
2/ Al
2O
3(CuO content is 65%, MnO
2Content is 15%, Al
2O
3Content is 20%), processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 1.Reaction product unit is the quality percentage composition in the table, and transformation efficiency is a molar yield, and the product overall selectivity is the mole selectivity.
Table 1CuO-MnO
2/ Al
2O
3The catalyst stability experimental result
| Time, h | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| Initially | 1.69 | 8.59 | 52.26 | 0.38 | 99.34 | 99.27 |
| 100 | 1.81 | 8.50 | 51.83 | 0.45 | 99.31 | 99.13 |
| 200 | 1.94 | 9.00 | 53.18 | 0.44 | 99.24 | 99.17 |
| 300 | 1.38 | 8.52 | 53.52 | 0.42 | 99.17 | 99.20 |
| 400 | 1.67 | 8.72 | 53.14 | 0.57 | 99.06 | 98.96 |
| 500 | 1.67 | 8.99 | 52.20 | 0.45 | 98.87 | 99.16 |
By example 1 as can be seen, feed stock conversion reduces with prolonging runtime, after estimating end, finds that catalyst strength reduces, and the part catalyzer has powder phenomenon-tion.In operation process, find that increase falls in reactor pressure.
Comparative example 2
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is CuO-Cr
2O
3(CuO content is 57%, Cr
2O
3Content is 43%), processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 2.
Table 2CuO-Cr
2O
3The evaluating catalyst result
| Time, h | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| Initially | 5.61 | 9.12 | 45.35 | 0.40 | 98.52 | 99.20 |
| 100 | 4.44 | 8.63 | 46.73 | 0.45 | 98.60 | 99.12 |
| 200 | 4.15 | 8.90 | 47.21 | 0.40 | 98.61 | 99.22 |
| 300 | 4.09 | 8.63 | 46.38 | 0.39 | 98.59 | 99.22 |
| 400 | 2.91 | 8.33 | 46.87 | 0.41 | 98.62 | 99.16 |
| 500 | 4.18 | 8.43 | 47.82 | 0.40 | 98.65 | 99.21 |
By comparative example 2 as can be seen, it is stable that feed stock conversion keeps in operation process always, but contrast table 1 and table 2 are as can be seen, CuO-Cr
2O
3The relative CuO-MnO of catalyzer initial conversion
2/ Al
2O
3Lower, and 1,4-butyleneglycol content in product liquid is relative also lower.
Embodiment 1
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is the CuO-Cr of different filling ratios
2O
3(with comparative example 2) catalyzer and CuO-MnO
2/ Al
2O
3(with comparative example 1) grading loading, processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 3.
Table 3 catalyzer grading loading test-results
| The filling ratio | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| 1∶4 | 2.29 | 8.96 | 50.58 | 0.49 | 99.29 | 99.12 |
| 1∶3 | 2.46 | 8.78 | 50.19 | 0.47 | 99.26 | 99.18 |
| 1∶2 | 2.85 | 8.29 | 50.11 | 0.46 | 99.11 | 99.19 |
| 1∶1 | 3.03 | 8.59 | 49.81 | 0.46 | 99.03 | 99.18 |
| 2∶1 | 3.19 | 8.43 | 49.48 | 0.44 | 98.75 | 99.22 |
Embodiment 2
With the dimethyl maleate is raw material, carries out gas phase hydrogenation reaction in fixed-bed reactor.Catalyzer is 1: 3 CuO-Cr for the filling ratio
2O
3(with comparative example 2) catalyzer and CuO-MnO
2/ Al
2O
3(with comparative example 1), processing condition are: 190 ℃ of temperature, pressure 6.0MPa, hydrogen ester mol ratio 200: 1, the volume space velocity of dimethyl maleate is 0.25h
-1, reaction result sees Table 4.
Table 4 catalyzer grading loading stability test result
| Time, h | Tetrahydrofuran (THF) | Gamma-butyrolactone | 1, the 4-butyleneglycol | Propyl carbinol | Transformation efficiency, % | Overall selectivity, % |
| Initially | 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 | 99.07 |
| 300 | 2.19 | 9.43 | 49.48 | 0.46 | 99.43 | 99.12 |
| 400 | 2.44 | 8.63 | 48.73 | 0.45 | 99.40 | 99.11 |
| 500 | 2.15 | 8.90 | 49.11 | 0.40 | 99.38 | 99.21 |
By embodiment 2 as can be seen, by the grading loading of catalyzer, catalyst stability is good, and feed stock conversion is greater than 99%, and the product overall selectivity is greater than 99%, and reactor pressure decrease does not increase.
By comparative example 1～2 as can be seen, CuO-Cr
2O
3The good stability of catalyzer, CuO-MnO
2/ Al
2O
3The initial activity of catalyzer is good.By embodiment 1～2 as can be seen, both gratings are used, both can have been brought into play CuO-Cr according to the inventive method
2O
3The advantage of good stability has been brought into play CuO-MnO again
2/ Al
2O
3Catalyzer initial conversion height, 1, the advantage that 4-butyleneglycol output is high improves the whole synthesis reaction effect greatly.
Embodiment 3～6
According to the inventive method, use different catalyzer, cooperate appropriate processing condition, be that raw material carries out hydrogenation reaction with the dimethyl maleate, actual conditions and reaction result see Table 4, table 5 and table 6.If use dissimilar catalyzer in each beds, catalyzer is by the filling of equal volume mixed.Wherein embodiment 6 uses dibutyl maleate and 1: 1 mixture of dibutyl succinate volume ratio to be raw material.
Table 4 embodiment 3～6 catalyzer
Table 5 embodiment 3～6 operational conditions
| Embodiment | Temperature, ℃ | Pressure, MPa | Air speed, 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 |
Table 6 embodiment 3～6 reaction results
Claims (10)
1. produce 1 for one kind, the method of 4-butanediol and co-producing tetrahydrofuran, gamma-butyrolactone, with maleic acid alkyl ester and/or succinic acid dialkyl ester is raw material, it is characterized in that: under hydrogen existence and reaction conditions, reaction mass is by first beds of CuO-AO-BO, and wherein AO is Cr
2O
3And/or ZnO, BO is one or more in Ba, Mg, Ti, Ce, Si, Zr and the Mn element oxide, and the CuO weight content is 30%～80%, and the AO weight content is 10%～70%, and the BO weight content is 0～40%; Pass through CuO-MO-Al then
2O
3Second beds, wherein MO is one or more in Mn, Zn, Ba, Mg, Ti, Ce, Si and the Zr element oxide, the CuO weight content is 30%～80%, the MO weight content is 10%～50%, Al
2O
3Weight content is 5%～40%; First beds is 1: 10～10: 1 with the catalyst volume ratio of second beds.
2. in accordance with the method for claim 1, it is characterized in that the CuO weight content is 40%～70% in the described first beds catalyzer, the AO weight content is 20%～50%, and the BO weight content is 5～30%; In the second beds catalyzer, the CuO weight content is 40%～70%, and the MO weight content is 20%～40%, Al
2O
3Weight content is 10%～30%.
3. according to claim 1 or 2 described methods, it is characterized in that described first beds and the catalyst volume ratio of second beds are 1: 5～1: 1.
4. according to claim 1 or 2 described methods, it is characterized in that described first beds and the catalyst volume ratio of second beds are 1: 4～1: 2.
5. according to claim 1 or 2 described methods, it is characterized in that described reaction conditions is: 160～240 ℃ of temperature of reaction, reaction pressure 4.0～8.0MPa, volume space velocity 0.1～2.0h when hydrogen ester mol ratio 100: 1～400: 1, the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
-1
6. according to claim 1 or 2 described methods, it is characterized in that described reaction conditions is: 180～200 ℃ of temperature of reaction, reaction pressure 5.0～6.0MPa, volume space velocity 0.2～0.5h when hydrogen ester mol ratio 200: 1～300: 1, the liquid of maleic acid alkyl ester and/or succinic acid dialkyl ester
-1
7. according to claim 1 or 2 described methods, it is characterized in that described maleic acid alkyl ester and/or succinic acid dialkyl ester are the dialkyl of C1～C4.
8. according to claim 1 or 2 described methods, it is characterized in that described maleic acid alkyl ester and/or succinic acid dialkyl ester are dimethyl maleate and/or dimethyl succinate, diethyl maleate and/or diethyl succinate or dibutyl maleate and/or dibutyl succinate.
9. according to claim 1 or 2 described methods, it is characterized in that reaction process is the maleic acid alkyl ester of liquid and/or succinic acid dialkyl ester to be vaporized in required ratio to form the vapourous mixture that is higher than the raw material dew-point temperature earlier, feeds this vapourous mixture then and is equipped with in the reactor of hydrogenation catalyst in the hot hydrogen logistics.
10. according to claim 1 or 2 described methods, it is characterized in that described first beds and second beds are arranged in the reactor, or be arranged in placed in-line two reactors.
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Cited By (1)
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| WO2013148923A1 (en) * | 2012-03-30 | 2013-10-03 | Basf Corporation | Catalyst for tetrahydrofuran synthesis |
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| CN105820038B (en) * | 2016-06-07 | 2018-11-13 | 中国石化扬子石油化工有限公司 | Dimethyl succinate Hydrogenation for 1,4- butanediols method |
| CN107778145B (en) * | 2016-08-30 | 2020-11-13 | 中国石油化工股份有限公司 | Method for producing 1, 4-butanediol and/or sec-butanol |
| CN113277996B (en) * | 2021-06-03 | 2023-01-17 | 上海贯新科技有限公司 | Method for flexibly producing tetrahydrofuran and gamma-butyrolactone |
| CN116102425A (en) * | 2023-01-09 | 2023-05-12 | 惠州博科环保新材料有限公司 | Dialkyl succinate hydrogenation method for prolonging service life of hydrogenation catalyst |
| CN116120177A (en) * | 2023-01-09 | 2023-05-16 | 惠州博科环保新材料有限公司 | Method for prolonging service life of catalyst by two-stage hydrogenation of dialkyl maleate |
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