CN101747189B - Method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation - Google Patents
Method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation Download PDFInfo
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- CN101747189B CN101747189B CN2008102388834A CN200810238883A CN101747189B CN 101747189 B CN101747189 B CN 101747189B CN 2008102388834 A CN2008102388834 A CN 2008102388834A CN 200810238883 A CN200810238883 A CN 200810238883A CN 101747189 B CN101747189 B CN 101747189B
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Abstract
The invention discloses a method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation, comprising: A) supplying raw material containing maleic acid dialkyl ester for a reactor; B) causing the maleic acid dialkyl ester raw material, hydrogen and catalyst to contact to obtain a liquid product in the hydrogenation reaction zone of the reactor; and C) carrying out cooling separation treatment to the liquid product to obtain a target product. The reaction condition of the hydrogenation reaction zone is as follows: the reaction temperature is 80-280 DEG C, the pressure is 0.1-7 MPa, the airspeed of the maleic acid dialkyl ester is 0.1-10hr-1, the molar ratio of the hydrogen to ester is 5-250:1; the catalyst consists of a main active component and auxiliary agents, wherein the main active component is copper oxide, and the auxiliary agents are alumina and zinc oxide; and the copper oxide accounts for 40-60% of the total weight of the catalyst, the zinc oxide accounts for 20-50%, the alumina accounts for 10-20 %, the conversion rate of the maleic acid dialkyl ester is 100%, and the selectivity of the succinic acid dialkyl ester approaches to 100%.
Description
Technical field
The present invention relates to a kind of method of catalysis alkyl maleate hydrogenation prepared in reaction succinic acid dialkyl ester.
Background technology
Succinic acid dialkyl ester is the important source material of red high performance pigments DPP (pyrrolopyrrole diketone); Be CIBA house journal product, this type of pigment has degree of staining height, lovely luster, weather resistance advantages of higher, and production process is not almost polluted; Still be all to be the kind that has very much development prospect on the performance economically; Brought rich profit since listing, for CIBA company, but because Intellectual Property Rights, other companies can't produce.Wherein main diisopropyl ester amber acid is to be obtained through esterification by Succinic Acid and Virahol, and this reaction seems fairly simple, but the not strong catalyzer of imitating, and reaction yield is lower.
Tabutrex is a kind of colourless transparent liquid, is used for resin, and the manufacturing of plastics and auxiliary agent and gc stationary liquid also are important Organic Chemicals.Conventional compound method is to adopt sulfuric acid to make catalyzer to be got by Succinic Acid and propyl carbinol esterification in the industry.Vitriolic strongly-acid, severe corrosive, be prone to cause that side reaction (like charing, oxidation, polymerization etc.) and environmental pollution are the problems that current chemical industry is needed solution badly, this method product yield is low, of poor quality, and equipment corrosion is serious, and " three wastes " quantity discharged is big.The focus of people's research in recent years concentrates on solid acid and replaces sulfuric acid catalysis synthesizing ester product.
Disclose in CN 200610117295.6, CN 1049208C, CN 99113206.8 and US 4584419 these patents with dialkyl maleate and/or succinic acid dialkyl ester raw material gas phase hydrogenation preparation 1, the method for 4-butyleneglycol.All relate to the reaction that dibutyl maleinate is converted into Tabutrex in the reaction mechanism of these methods, the further hydrogenation of Tabutrex just generates and comprises 1 then, the product of 4-butyleneglycol, gamma-butyrolactone, THF etc.The method that in these patents with the precious metal is Preparation of Catalyst exists pressure high; Facility investment is significantly increased, the defective that selectivity is low, though and be that the method for catalyzer is compared bigger improvement with the former with the base metal; But working time is short; Selectivity remains further to be improved, and contains poisonous composition Cr in the catalyzer, has caused environmental pollution.
Summary of the invention
The object of the present invention is to provide a kind of method of alkyl maleate hydrogenation produce succinic acid dialkyl.
For realizing above-mentioned purpose, the present invention passes through the add-on of control hydrogen with the high conversion of realization raw material and the highly selective of product.Method continuous operation of the present invention is after 1000 hours, and activity of such catalysts and selectivity and starting stage are basic identical.
Specifically, key step of the present invention comprises:
A) to reactor drum the raw material that contains dialkyl maleate is provided;
B) hydroconversion reaction zone at reactor drum makes dialkyl maleate raw material, hydrogen and catalyzer contact, obtains containing the product liquid of succinic acid dialkyl ester;
C) product liquid is handled through refrigerated separation and is promptly obtained title product, and the remaining hydrogen of hydroconversion reaction zone gets into gas-circulating system through separating the back with tail gas;
The reaction conditions of hydroconversion reaction zone: temperature of reaction is 80～280 ℃, and pressure is that (preferred 4～7MPa), the air speed of dialkyl maleate is 0.1～10hr to 0.1～7MPa
-1(preferred 0.2～0.5hr
-1), hydrogen: the ester mol ratio is 5～250:1 (preferred 80～150:1);
Catalyzer is made up of main active ingredient and auxiliary agent, and main active ingredient is a cupric oxide, and auxiliary agent is aluminum oxide and zinc oxide, and 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 dialkyl maleate that the present invention adopts is C
1～C
5Alkyl ester, preferentially recommend n-butyl.
The reactor drum that the present invention adopts is fixed-bed reactor or slurry attitude bed, and its reaction can be a successive reaction, also can be rhythmic reaction.
The present invention prepares succinic acid dialkyl ester through the method for control hydrogenation, makes hydrogenation reaction stop at this step of succinic acid dialkyl ester, thereby makes succinic acid dialkyl ester.Is that reaction can carried out under lower pressure and the temperature, can in widely used fixed-bed reactor or slurry attitude bed, carry out with dibutyl maleinate as the benefit of raw material.
Description of drawings
Fig. 1 is a reaction unit synoptic diagram of the present invention.
Embodiment
When raw material was dibutyl maleinate, reaction formula was as follows:
Dibutyl maleinate at first is converted into Tabutrex, and Tabutrex can continue hydrogenation under certain conditions, and product comprises 1,4-butyleneglycol, gamma-butyrolactone, THF etc.Wherein, 1, can transform mutually through reactions such as addition/cancellation hydrogen and/or water between 4-butyleneglycol, gamma-butyrolactone, several kinds of products of THF, the preferred Tabutrex of the present invention is a reaction product.
Its technological process of the present invention is: catalyzer is reduced to temperature of reaction with temperature of reactor after the reduction pre-treatment, feeding dialkyl maleate and hydrogen react in reactor drum then, can make succinic acid dialkyl ester.Employed dialkyl maleate is C
1～C
5Alkyl ester, preferred especially n-butyl.
Reactor drum among the present invention can be known fixed-bed reactor, also can be that other conventional equipment and technology are for example starched the attitude bed.Present embodiment is the example (see figure 1) with known fixed-bed reactor.
When embodiment of the present invention, reactor drum can or comprise one or more reactor drums for single reactor drum.Usually, reactor drum comprises single reactor drum.But other conventional equipment and the technology that can adapt to temperature, pressure and the duration of contact of technology of the present invention are for example starched the attitude bed and also can be selected for use.Choose wantonly, reactor drum can use the multistage reactor drum.This technology can intermittent type or the successive mode operate, but more economical with the continuous mode operation.
Liquid starting material gets into through the top of pump 1 from reactor drum 2.Hydrogen-containing gas is also sent into reactor drum continuously through purification pot 3,4 and mass flowmeter 5.Usually hydrogen and liquid starting material are mixed together the back and introduce bed bioreactor.In addition, hydrogen can directly get into reactor drum, after the reaction, through behind the knockout drum 6, gets into gas-circulating system with tail gas.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 hoping.
In fixed-bed reactor, hydrogen and dialkyl maleate raw material one react and make product and be mainly succinic acid dialkyl ester, contain sometimes a spot of 1,4-butyleneglycol and/or gamma-butyrolactone.More particularly; It is 80～280 ℃ that hydrogen and dialkyl maleate are introduced temperature of reaction, and reaction pressure is that (preferred pressure is in 4～7MPa) the reactor drum, to be hydrogenated to succinic acid dialkyl ester then to 0.1～7MPa; Sometimes contain a spot of 1,4-butyleneglycol and/or gamma-butyrolactone.The reaction conditions of fixed-bed reactor is control like this; Dialkyl maleate is contacted with hydrogen and catalyzer; Guarantee that the dialkyl maleate raw material transforms fully, product is mainly succinic acid dialkyl ester, but will control reaction conditions; Avoid the further hydrogenation of succinic acid dialkyl ester to generate 1,4-butyleneglycol and/or gamma-butyrolactone, THF.
Therefore, the reaction conditions of control in the fixed-bed reactor make dialkyl maleate the selectivity of transformation efficiency and succinic acid dialkyl ester all near 100%.The elute of reactor drum mainly is succinic acid dialkyl ester and unreacted hydrogen, and these elutes are through simple condensation, and after the gas-liquid separation, product liquid is sent into the product stock jar continuously, and gas (hydrogen) gets into gas-circulating system with tail gas to be continued to use.Reclaim and make with extra care succinic acid dialkyl ester through fractionation.The small amounts of by-products and the unreacted raw material that form, optional is to return in the fixed-bed reactor.
The present invention adopts base metal and does not contain chromium component hydrogenation catalyst, and main active ingredient is a cupric oxide, and first auxiliary agent is a zinc oxide, and second auxiliary agent is an aluminum oxide, also can add manganese, alkaline earth metal cpds again.Cupric oxide accounts for 40～60% in total catalyst weight, and zinc oxide accounts for 20～50%, and aluminum oxide accounts for 10～20%.This catalyst stability is good, catalyzer continuous operation 1000 hours, and activity is not fallen as follows.
More particularly, the method for the hydrogenation produce succinic acid dialkyl of efficient, the stably catalyzed dialkyl maleate that adopts that the present invention describes, dialkyl maleate can transform simply basically fully, and transformation efficiency is near 100%; The selectivity of succinic acid dialkyl ester is also near 100%.The more important thing is does not have to form sub product not capable of using.
Below in conjunction with embodiment method of the present invention being further specified, is not to qualification of the present invention.
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 100 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 110 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 150 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=128 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 120 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=128 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 120 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=33 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 110 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=14 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
Embodiment 7
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 110 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
Embodiment 8
With 4ml (4.8.g) granularity is that 20～40 purpose catalyzer internal diameter of packing into is in the fixed-bed reactor processed of the stainless steel of 8mm.At 230 ℃, under the condition of normal pressure, the flow velocity feeding hydrogen with 500ml/min reduced 12 hours, was raw material then with the dibutyl maleinate, at 100 ± 1 ℃ of hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=100 (mole), LHSV=0.2/h reacts, and reaction result is seen table 1.
Claims (8)
1. the method for an alkyl maleate hydrogenation produce succinic acid dialkyl, its key step comprises:
A) catalyzer is packed in the fixed-bed reactor,, under the condition of normal pressure, feed hydrogen, reduced 12 hours, to fixed-bed reactor the raw material that contains dialkyl maleate is provided then with the flow velocity of 500ml/min at 230 ℃;
B) hydroconversion reaction zone at fixed-bed reactor makes dialkyl maleate raw material, hydrogen and catalyzer contact, obtains containing the product liquid of succinic acid dialkyl ester;
C) product liquid is handled through refrigerated separation and is promptly obtained title product;
The reaction conditions of hydroconversion reaction zone: temperature of reaction is 80～120 ℃, and pressure is 0.1～7MPa, and the air speed of dialkyl maleate is 0.1～10hr
-1, hydrogen: the ester mol ratio is 5～250: 1;
Catalyzer is made up of main active ingredient and auxiliary agent, and main active ingredient is a cupric oxide, and auxiliary agent is aluminum oxide and zinc oxide, and cupric oxide accounts for 40～60% in total catalyst weight, and zinc oxide accounts for 20～50%, and aluminum oxide accounts for 10～20%.
2. according to the described method of claim 1, wherein, dialkyl maleate is C
1～C
5Alkyl ester.
3. according to claim 1 or 2 described methods, wherein, dialkyl maleate is a n-butyl.
4. according to the described method of claim 1, wherein, the air speed of dialkyl maleate is 0.2～0.5hr
-1
5. according to the described method of claim 1, wherein, hydrogen: the ester mol ratio is 80～150: 1.
6. according to the described method of claim 1, wherein, the reaction pressure of hydroconversion reaction zone is 4～7MPa.
7. according to the described method of claim 1, wherein, the remaining hydrogen of hydroconversion reaction zone gets into gas-circulating system through separating the back with tail gas.
8. according to the described method of claim 1, wherein, reaction is successive reaction or rhythmic reaction.
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|---|---|---|---|
| CN2008102388834A CN101747189B (en) | 2008-12-03 | 2008-12-03 | Method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation |
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| CN2008102388834A CN101747189B (en) | 2008-12-03 | 2008-12-03 | Method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation |
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| CN101747189B true CN101747189B (en) | 2012-07-11 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008235A (en) * | 1989-12-21 | 1991-04-16 | Union Carbide Chemicals And Plastics Technology Corporation | Catalysts of Cu-Al-third metal for hydrogenation |
| US5606099A (en) * | 1995-02-22 | 1997-02-25 | Bayer Aktiengesellschaft | Process for the preparation of succinic acid dialkyl esters |
| CN1565728A (en) * | 2003-06-18 | 2005-01-19 | 中国石油天然气股份有限公司 | Catalyst and method for preparing 1,5 pentanediol by hydrogenation of 1,5 dimethyl glutarate |
-
2008
- 2008-12-03 CN CN2008102388834A patent/CN101747189B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008235A (en) * | 1989-12-21 | 1991-04-16 | Union Carbide Chemicals And Plastics Technology Corporation | Catalysts of Cu-Al-third metal for hydrogenation |
| US5606099A (en) * | 1995-02-22 | 1997-02-25 | Bayer Aktiengesellschaft | Process for the preparation of succinic acid dialkyl esters |
| CN1565728A (en) * | 2003-06-18 | 2005-01-19 | 中国石油天然气股份有限公司 | Catalyst and method for preparing 1,5 pentanediol by hydrogenation of 1,5 dimethyl glutarate |
Non-Patent Citations (2)
| Title |
|---|
| 张跃 等."丁二酸二乙酯加氢制备1，4-丁二醇的工艺研究".《精细石油化工》.2008,第25卷(第1期),第21-24页. |
| 张跃 等."丁二酸二乙酯加氢制备1,4-丁二醇的工艺研究".《精细石油化工》.2008,第25卷(第1期),第21-24页. * |
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