CN101747149B - Method for preparing 1,4-butanediol by two-section hydrogenation of maleic acid dialkyl ester - Google Patents
Method for preparing 1,4-butanediol by two-section hydrogenation of maleic acid dialkyl ester Download PDFInfo
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Abstract
The invention discloses a method for preparing 1,4-butanediol by two-part hydrogenation of maleic acid dialkyl ester, comprising the following steps: (A) connecting a first hydrogenation section and a second hydrogenation section in series; (B) providing raw material containing maleic acid dialkyl ester for the first hydrogenation section; (C) contacting the maleic acid dialkyl ester raw material with hydrogen and catalyst at the first hydrogenation section to produce a product which is mainly 1,4-butanediol and contains at least one of gamma-butyrolactone, tetrahydrofuran and succinic acid dialkyl ester; (D) arranging condensation and recycling separation equipment between two the hydrogenation sections; (E) providing the product of the first hydrogenation section to the second hydrogenation section to serve as raw material by cooling separation; (F) after the unreacted hydrogen of the first hydrogenation section is separated from liquid, putting parts circularly into the first hydrogenation section, and putting parts circularly into the second hydrogenation section; and (G) contacting the product of the first hydrogenation section with the hydrogen and the catalyst at the second hydrogenation section to produce 1,4-butanediol, and a product containing at least one of the gamma-butyrolactone and the tetrahydrofuran.
Description
Technical field
The present invention relates to a kind of two-stage method catalysis alkyl maleate hydrogenation reaction preparation BDO, the optional method for preparing gamma-butyrolactone and/or tetrahydrofuran (THF).In the method, can realize the highly selective of high conversion and the product of raw material by the reaction conditions of controlling two hydrogenation sections.
Background technology
BDO is to develop in recent years important rapidly Organic Chemicals.Because its carbochain is longer than ethylene glycol or propylene glycol, polyester or the urethane synthetic take it as raw material have more balanced physicals.Along with the increase of market to urethane, PBT and full-biodegradable material PBS demand, the demand of BDO also rises greatly.The needs that China all relies on a large amount of imports to produce to satisfy downstream industry every year.Usually the production method of BDO be take with acetylene and formaldehyde as the classical Reppe method of raw material as main, reaction need under high pressure be carried out, required condition is harsh, is difficult for realization.
In recent years, along with the development that butane oxidation prepares the maleic anhydride technology, but adopting, many patents pass through toxilic acid, maleic dialdehyde and the standby BDO of similar hydrogenation compound for catalysis Hydrogenation.US4,609,636 adopt the Pd-Re/C catalyzer, and the toxilic acid aqueous solution is raw material, and at 170～230 ℃, under the 17MPa condition, the selectivity of BDO reaches as high as 79%.CN1129206A adopts the Pd-Ag-Re/C catalyzer, take toxilic acid or maleic anhydride as raw material, at 160 ℃, under the 17MPa condition, moves 109 hours, and the selectivity of BDO is 73.6%.If pressure drops to 8.8MPa, the selectivity of BDO will arrive 50.76% in 46.7 hours in reaction under, will arrive 41.41% in 51 hours under in reaction.US6,008,384 has adopted the two-stage hydrogenation method of using bimetallic catalyst (Ru and the Re) hydrogenation of maleic acid of carbon load, and wherein the effluent of fs is significantly cooled off, and introduces afterwards subordinate phase.US5,196,602 instructions prepare the method for BDO with the two-stage method of sequential operation by maleic dialdehyde and/or hydrogenation of maleic acid, be characterised in that and used different hydrogenation catalysts in each hydrotreating stage.But, under 160～250 ℃, observe toxilic acid and have corrodibility, greatly shortened the expected service life (for example hydrogenator, inside and accessory thereof) of processing unit.
CN1049208C discloses take dialkyl maleate and/or succinic acid dialkyl ester as raw material, prepares the method for BDO in the presence of the Cu-Zn-Cr-Zr non-precious metal catalyst.Be 210～220 ℃ in temperature of reaction, pressure is 7MPa, and the air speed of ester is 0.6h
-1, hydrogen: the ester mol ratio is reaction operation 700 hours under the condition of 224:1, and the selectivity of BDO is more than 70%.US4,584,419 have adopted the method for the standby BDO of dialkyl Hydrogenation.
More than prepare 1 take precious metal as catalyzer in these patents, the method of 4-butyleneglycol exists pressure high, facility investment is significantly increased, the defective that selectivity is low, though and the method take base metal as catalyzer is compared larger improvement with the former, working time is short, and selectivity remains further to be improved, its catalyzer that contains Cr has caused very big harm to producers and environment, and needs to drop into substantial contribution contaminated solution problem.
Summary of the invention
The purpose of this invention is to provide a kind ofly take dialkyl maleate and/or succinic acid dialkyl ester as raw material, use base metal and do not contain chromium component hydrogenation catalyst, by the two-stage hydrogenation method, prepare the method for BDO, gamma-butyrolactone, tetrahydrofuran (THF).
That reaction can be carried out under lower pressure, can carry out in widely used fixed-bed reactor or slurry attitude bed with dibutyl maleinate or other dialkyl as the benefit of raw material.
When raw material was dibutyl maleinate, reaction formula was as follows:
Dibutyl maleinate at first is converted into dibutyl succinate, continues hydrogenation, and primary product comprises BDO, gamma-butyrolactone, tetrahydrofuran (THF) etc.Wherein, 1, can transform mutually by reactions such as addition/cancellation hydrogen and/or water between 4-butyleneglycol, gamma-butyrolactone, several products of tetrahydrofuran (THF), and, by adjusting the operating parameters in two-stage hydrogenation district, can change the ratio of BDO in the product, gamma-butyrolactone, tetrahydrofuran (THF), the preferred BDO of the present invention is reaction product.
Method of the present invention mainly comprises:
(A) be connected in series the first hydrogenation section and the second hydrogenation section;
(B) raw material that contains dialkyl maleate is provided for the first hydrogenation section;
(C) making the dialkyl maleate raw material contact the generation product with hydrogen and catalyzer in the first hydrogenation section is mainly BDO, also contains in gamma-butyrolactone, tetrahydrofuran (THF) and the succinic acid dialkyl ester at least a;
(D) be furnished with condensation and circulation separating device between two hydrogenation sections;
(E) product of the first hydrogenation section offers the second hydrogenation section through refrigerated separation and makes raw material;
(F) after the unreacted hydrogen of the first hydrogenation section and the liquid separation, the part circulation enters the first hydrogenation section, and part enters the second hydrogenation section;
(G) product of the first hydrogenation section contacts with hydrogen and catalyzer in the second hydrogenation section and produces BDO, also contains at least a product of gamma-butyrolactone and tetrahydrofuran (THF);
Employed dialkyl maleate is C
1～C
5Alkyl ester;
Hydrogenation catalyst used therein is comprised of main active ingredient and auxiliary agent, and main active ingredient is cupric oxide, and the first auxiliary agent is zinc oxide, and the second auxiliary agent is aluminum oxide; Cupric oxide accounts for 40～60% in total catalyst weight, and zinc oxide accounts for 20～50%, and aluminum oxide accounts for 10～20%.
The temperature of reaction of two hydrogenation sections is 170～300 ℃, and pressure is 0.1～7MPa, and the air speed of ester is 0.1～10hr
-1, hydrogen/ester mol ratio is 5～250:1.
Technological process of the present invention is: catalyzer is down to temperature of reaction through reducing after processing with temperature of reactor, then passes into dialkyl maleate in the reactor and hydrogen reacts, and can make BDO.Employed dialkyl maleate is C
1～C
5Alkyl ester, n-butyl particularly preferably.
The present invention has special advantage than known technology:
1) two hydrogenation sections among the present invention adopt identical catalyzer.
2) catalyzer of the present invention's employing is non-precious metal catalyst and does not contain the chromium component, and the catalyzer preparation is simple.
3) the present invention mainly can by adjusting the reaction conditions of two-stage hydrogenation, produce BDO and/or gamma-butyrolactone, at least a product in the tetrahydrofuran (THF) flexibly.
4) under lower pressure, has higher BDO selectivity.When pressure is 4～7MPa, the selectivity of BDO is 95.5%.
5) cycle of operation is long, and continuous operation is after 1000 hours, and activity and selectivity and the starting stage of catalyzer are basic identical.
Description of drawings
Fig. 1 is technical process of the present invention and equipment synoptic diagram.
Embodiment
Said hydrogenator can be common fixed-bed reactor among the present invention, also can be that other conventional equipment and technology are for example starched the attitude bed.Said hydrogenator can be the fixed-bed reactor of the series connection of two fixed-bed reactor compositions, also can adopt single fixed-bed reactor to divide two batch reactions.The present invention sees the reaction unit figure among Fig. 1 for details take the tandem reactor that adopts two fixed-bed reactor and form as example.
Implementing when of the present invention, two hydrogenation zone can be combined into single reactor system or each hydrogenation zone can comprise one or more reactor systems.Usually, each hydrogenation zone comprises single fixed-bed reactor.But can adapt to other conventional equipment of temperature, pressure and duration of contact of technique of the present invention and technology for example starches the attitude bed and also can select.Choose wantonly, can use the multistage reactor in each hydrogenation zone.This technique can intermittent type or continuous mode operate, but operation is more economical in a continuous manner.The catalytic amount that needs in each hydrogenation zone and operational condition be modulation separately.
Liquid starting material enters from the top of the first hydrogenation zone.Hydrogen-containing gas is also sent into the first hydrogenation zone continuously.Usually hydrogen and liquid starting material are mixed together rear introducing the first hydrogenation zone.In addition, hydrogen can directly enter the first hydrogenation zone, and after the reaction, through behind the knockout drum, a part passes into the second hydrogenation zone and reacts, and a part enters gas-circulating system with tail gas, and hydrogen also can enter each hydrogenation zone simultaneously.Usually, the stoichiometry of hydrogen will be in excess in other reactant, with the suitable hydrogen partial pressure that guarantees that reaction is effectively carried out, thus the finished product that obtain wishing.
In the first hydrogenation zone, hydrogen and dialkyl maleate raw material one react and make product is BDO and/or gamma-butyrolactone, tetrahydrofuran (THF), and at least a in the corresponding succinic acid dialkyl ester.More particularly, it is 170～250 ℃ that hydrogen and dialkyl maleate are introduced temperature of reaction, and reaction pressure is the first hydrogenation zone of 4～7MPa, then is hydrogenated to 1,4-butyleneglycol and/or gamma-butyrolactone, tetrahydrofuran (THF), and at least a in the corresponding succinic acid dialkyl ester.The reaction conditions of the first hydrogenation zone is like this control, the main task of the first hydrogenation section is that dialkyl maleate is contacted with hydrogen and catalyzer, guarantee that the dialkyl maleate raw material transforms fully, product is 1, at least a in 4-butyleneglycol and/or gamma-butyrolactone, tetrahydrofuran (THF) and the corresponding succinic acid dialkyl ester, guarantee that namely the transformation efficiency of reaction is near 100%.
The effluent of the first hydrogenation zone mainly is 1,4-butyleneglycol and/or gamma-butyrolactone, tetrahydrofuran (THF) and corresponding succinic acid dialkyl ester, and unreacted hydrogen, these effluents are through simple condensation, after the gas-liquid separation, product liquid is sent into the second hydrogenation zone continuously, and gas (hydrogen) part passes into the second hydrogenation zone and reacts, and a part enters gas-circulating system with tail gas.
It is 150～200 ℃ that the reaction product of the first hydrogenation zone offers temperature of reaction, and reaction pressure is the second hydrogenation zone of 4～7MPa.The reaction conditions of the second hydrogenation zone is like this control, regulates the reaction conditions of the second hydrogenation zone, and making the product of the second hydrogenation zone is BDO and/or gamma-butyrolactone, at least a product stream in the tetrahydrofuran (THF), that is, and the selectivity of control reaction.Be the conditioned reaction parameter in the example of the present invention, make the product of the second hydrogenation zone be mainly BDO, and the formation of gamma-butyrolactone and tetrahydrofuran (THF) is minimized.
Unreacted hydrogen is separated and loop back the first hydrogenation zone and contact mixing with the dialkyl maleate raw material.Reclaim and make with extra care BDO by fractionation.The a small amount of byproduct and the unreacted raw material that form, optional hydrotreating stage, preferred the second hydrogenation zone returned.
Method of the present invention is to adopt base metal and do not contain chromium component hydrogenation catalyst, and main active ingredient is cupric oxide, and the first auxiliary agent is zinc oxide, and the second auxiliary agent is aluminum oxide, also can add manganese, alkaline earth metal compound again.This catalyst stability is good, catalyzer continuous operation 1000 hours, and activity has no decline.
The quantity of valuable BDO, gamma-butyrolactone, tetrahydrofuran (THF) product can change in hydrogenation products.It mainly determines by the parameter such as pressure, temperature and the residence time and by the selection of hydrogenation catalyst.
More particularly, implement method of the present invention, adopt the method and apparatus of the dialkyl maleate two-stage method Hydrogenation BDO of the present invention's description, dialkyl maleate can transform simply basically fully, and transformation efficiency is near 100%; The final selectivity of BDO can be up to 93.92%.The more important thing is does not have to form the byproduct that can not utilize.
Below in conjunction with embodiment method of the present invention being described further, is not limitation of the invention.
Embodiment 1
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=200 (mole), LHSV=0.2/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 5MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 2
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), LHSV=0.2/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 6MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 3
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), LHSV=0.2/h, and 180 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 6MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 4
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 180 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), LHSV=0.2/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 6MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 5
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=100 (mole), LHSV=0.2/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 6MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 6
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), LHSV=0.4/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 6MPa, H
2React under the LHSV=0.4/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 7
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 7MPa, H
2/ ester=200 (mole), LHSV=0.2/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 7MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Embodiment 8
With two parts of 4ml (4.5.g) granularity be 20～40 purpose catalyzer to be respectively charged into internal diameter be in the fixed-bed reactor made of two stainless steels of 8mm, then two fixed-bed reactor series connection are packed into the first hydroconversion reaction zone and the second hydroconversion reaction zone.At 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours, then take dibutyl maleinate as raw material, at 210 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), LHSV=0.2/h, and 170 ± 1 ℃ of the second hydroconversion reaction zone temperature of reaction, 6MPa, H
2React under the LHSV=0.2/h/ester=25 (mole), and reaction result sees Table 1.
Table 1: dibutyl maleinate two-stage hydrogenation processing condition and hydrogenation result gather
Claims (8)
1. method for preparing BDO, its key step comprises:
(A) catalyzer is packed in the fixed-bed reactor, then be connected in series the first hydrogenation section and the second hydrogenation section, at 230 ℃, under the condition of normal pressure, pass into hydrogen with the flow velocity of 500ml/min, reduced 12 hours;
(B) raw material that contains dialkyl maleate is provided for the first hydrogenation section;
(C) making the dialkyl maleate raw material contact the generation product with hydrogen and catalyzer in the first hydrogenation section is mainly BDO, also contains in gamma-butyrolactone, tetrahydrofuran (THF) and the succinic acid dialkyl ester at least a;
(D) be furnished with condensation and circulation separating device between two hydrogenation sections;
(E) product of the first hydrogenation section offers the second hydrogenation section through refrigerated separation and makes raw material;
(F) after the unreacted hydrogen of the first hydrogenation section and the liquid separation, the part circulation enters the first hydrogenation section, and part enters the second hydrogenation section;
(G) product of the first hydrogenation section contacts with hydrogen and catalyzer in the second hydrogenation section and produces BDO, also contains at least a product of gamma-butyrolactone and tetrahydrofuran (THF);
The first hydrogenation section and the second hydrogenation section include one or more reactor;
Employed dialkyl maleate is C
1～C
5Alkyl ester;
Hydrogenation catalyst used therein is comprised of main active ingredient and auxiliary agent, and main active ingredient is cupric oxide, and the first auxiliary agent is zinc oxide, and the second auxiliary agent is aluminum oxide; Cupric oxide accounts for 40～60% in total catalyst weight, and zinc oxide accounts for 20～50%, and aluminum oxide accounts for 10～20%;
The temperature of reaction of the first hydrogenation section is 170～250 ℃, and the temperature of reaction of the second hydrogenation section is 150～200 ℃, and the pressure of the first hydrogenation section and the second hydrogenation section is 0.1～7MPa, and the air speed of ester is 0.1～10hr
-1, hydrogen/ester mol ratio is 5～250: 1.
2. in accordance with the method for claim 1, wherein, employed dialkyl maleate is n-butyl.
3. in accordance with the method for claim 1, wherein, the air speed of ester is 0.2～0.5hr
-1The hydrogen of the first hydrogenation section/ester mol ratio is 180～220: 1.
4. in accordance with the method for claim 1, wherein, the hydrogen of the second hydrogenation section/ester mol ratio is 10～30: 1.
5. in accordance with the method for claim 1, wherein, the reaction pressure of the first hydrogenation section is 4～7MPa; The reaction pressure of the second hydrogenation section is 4～7MPa.
6. in accordance with the method for claim 1, wherein, the primary product in the first hydrogenation section is BDO and gamma-butyrolactone, also contains succinic acid dialkyl ester and tetrahydrofuran (THF); The product of the second hydrogenation section mainly is BDO, contains simultaneously a small amount of gamma-butyrolactone and tetrahydrofuran (THF).
7. in accordance with the method for claim 1, wherein, the product liquid of the first hydrogenation section is through the raw material of refrigerated separation processing as the second hydrogenation section.
8. in accordance with the method for claim 1, wherein, the remaining hydrogen of the first hydrogenation section is through separating, and wherein a part passes into the second reactor and reacts, and a part enters gas-circulating system with tail gas.
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| CN101891592B (en) * | 2010-08-12 | 2013-03-13 | 湖南长岭石化科技开发有限公司 | Method for preparing 1,4-butanediol and co-producing tetrahydrofuran and gamma-butyrolactone |
| WO2013076747A1 (en) | 2011-11-25 | 2013-05-30 | Conser Spa | Process for producing 1,4- butanediol by hydrogenating dialkyl maleate in mixed liquid/vapor phase |
| CN107563545A (en) * | 2017-08-17 | 2018-01-09 | 上海大学 | Fine chemistry industry ecological Industrial Area industrial chain construction method using natural gas as raw material |
| JP2024510861A (en) | 2021-03-12 | 2024-03-12 | コンサー エッセ．ピ．ア． | Process for simultaneous production of dialkyl succinate and 1,4-butanediol by hydrogenating dialkyl maleate in two steps |
| CN115894170A (en) * | 2022-11-07 | 2023-04-04 | 中触媒新材料股份有限公司 | Method for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
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