Background technology
1, the 4-butyleneglycol is to develop important rapidly Organic Chemicals in recent years.Because its carbochain is longer than ethylene glycol or propylene glycol, is that raw material synthetic polyester or urethane have more isostatic physicals with it.Along with the increase of market to urethane, PBT and full-biodegradable material PBS demand, 1, the demand of 4-butyleneglycol also rises greatly.China all relies on a large amount of imports to satisfy the needs that downstream industry is produced every year.Common 1, the production method of 4-butyleneglycol is based on acetylene and the formaldehyde classical Reppe method as raw material, and reaction need under high pressure be carried out, and required condition harshness is difficult for realizing.
In recent years, along with the development that butane oxidation prepares the maleic anhydride technology,, many patents pass through toxilic acid, maleic dialdehyde and similar hydrogenation compound for catalysis hydrogenation preparing 1,4-butyleneglycol but adopting.US4,609,636 adopt the Pd-Re/C catalyzer, and the toxilic acid aqueous solution is raw material, at 170~230 ℃, under the 17MPa condition, 1, the selectivity of 4-butyleneglycol reaches as high as 79%.CN1129206A adopts the Pd-Ag-Re/C catalyzer, is raw material with toxilic acid or maleic anhydride, at 160 ℃, under the 17MPa condition, moves 109 hours, and 1, the selectivity of 4-butyleneglycol is 73.6%.If pressure drops to 8.8MPa, 1, the selectivity of 4-butyleneglycol 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 subordinate phase afterwards.US5,196,602 instructions prepare 1 with the two-stage method of sequential operation by maleic dialdehyde and/or hydrogenation of maleic acid, and the method for 4-butyleneglycol is characterised in that and has used different hydrogenation catalysts in each hydrotreating stage.But, under 160~250 ℃, observe toxilic acid and have corrodibility, shortened the expected service life (for example hydrogenator, inside and accessory thereof) of processing unit greatly.
It is raw material that CN1049208C discloses with dialkyl maleate and/or succinic acid dialkyl ester, prepares 1 in the presence of the Cu-Zn-Cr-Zr non-precious metal catalyst, the method for 4-butyleneglycol.In temperature of reaction is 210~220 ℃, and pressure is 7MPa, and the air speed of ester is 0.6h
-1, hydrogen: the ester mol ratio is reaction operation 700 hours under 224: 1 the condition, 1, and the selectivity of 4-butyleneglycol is more than 70%.US4,584,419 have adopted dialkyl hydrogenation preparing 1, the method for 4-butyleneglycol.
More than be Preparation of Catalyst 1 in these patents with the precious metal, there is the pressure height in the method for 4-butyleneglycol, 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, working time is short, selectivity remains further to be improved, its catalyzer that contains Cr has caused very big harm for 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 of is raw material with dialkyl maleate and/or succinic acid dialkyl ester, use base metal and do not contain chromium component hydrogenation catalyst, and by the two-stage hydrogenation method, preparation 1, the method for 4-butyleneglycol, gamma-butyrolactone, tetrahydrofuran (THF).
Is 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 1,4-butyleneglycol, 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 in the product 1, the ratio of 4-butyleneglycol, gamma-butyrolactone, tetrahydrofuran (THF), the present invention is preferred 1, and the 4-butyleneglycol is a reaction product.
Method of the present invention mainly comprises:
(A) the be connected in series first hydrogenation section and the second hydrogenation section;
(B) raw material that contains dialkyl maleate is provided for the first hydrogenation section;
(C) make the dialkyl maleate raw material contact the generation product with hydrogen and catalyzer in the first hydrogenation section and be mainly 1, the 4-butyleneglycol 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 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 1, and the 4-butyleneglycol 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 made up of main active ingredient and auxiliary agent, and main active ingredient is a cupric oxide, and first auxiliary agent is a zinc oxide, and second auxiliary agent is an 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 reduced to temperature of reaction through reducing after handling with temperature of reactor, and feeding dialkyl maleate and hydrogen react in reactor then, can make 1, the 4-butyleneglycol.Employed dialkyl maleate is C
1~C
5Alkyl ester, preferred especially n-butyl.
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 that Preparation of Catalyst is simple.
3) the present invention mainly can produce 1,4-butyleneglycol and/or gamma-butyrolactone, at least a product in the tetrahydrofuran (THF) flexibly by adjusting the reaction conditions of two-stage hydrogenation.
4) under lower pressure, have higher 1,4-butyleneglycol selectivity.When pressure is 4~7MPa, 1, the selectivity of 4-butyleneglycol is 95.5%.
5) cycle of operation is long, and continuous operation is after 1000 hours, and activity of such catalysts and selectivity and starting stage are basic identical.
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 placed in-line fixed-bed reactor that two fixed-bed reactor are formed, and also can adopt one fixed-bed reactor to divide two batch reactions.The present invention is an example with the tandem reactor that adopts two fixed-bed reactor to form, and sees the reaction unit figure among Fig. 1 for details.
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 the conventional equipment of temperature, pressure and duration of contact of technology of the present invention and technology for example starches the attitude bed and also can select for use.Choose wantonly, can use the multistage reactor in each hydrogenation zone.This technology can intermittent type or the successive mode operate, but operation is more economical in a continuous manner.Catalytic amount that needs in each hydrogenation zone and operational condition be modulation separately.
Liquid starting material enters from the top of first hydrogenation zone.Hydrogen-containing gas is also sent into first hydrogenation zone continuously.Usually hydrogen and liquid starting material are mixed together the back and introduce first hydrogenation zone.In addition, hydrogen can directly enter first hydrogenation zone, and after the reaction, through behind the knockout drum, a part feeds 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 first hydrogenation zone, hydrogen and dialkyl maleate raw material one react and make product is 1, at least a in 4-butyleneglycol and/or gamma-butyrolactone, tetrahydrofuran (THF) and the corresponding succinic acid dialkyl ester.More particularly, with hydrogen and dialkyl maleate introducing temperature of reaction is 170~250 ℃, and reaction pressure is first hydrogenation zone of 4~7MPa, is hydrogenated to 1 then, at least a in 4-butyleneglycol and/or gamma-butyrolactone, tetrahydrofuran (THF) and the corresponding succinic acid dialkyl ester.The reaction conditions of first hydrogenation zone is control like this, 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 promptly the transformation efficiency of reaction is near 100%.
The effluent of 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 second hydrogenation zone continuously, and gas (hydrogen) part feeds second hydrogenation zone and reacts, and a part enters gas-circulating system with tail gas.
It is 150~200 ℃ that the reaction product of first hydrogenation zone offers temperature of reaction, and reaction pressure is second hydrogenation zone of 4~7MPa.The reaction conditions of second hydrogenation zone is control like this, regulates the reaction conditions of second hydrogenation zone, and the product that makes second hydrogenation zone is 1,4-butyleneglycol and/or gamma-butyrolactone, and product at least a in the tetrahydrofuran (THF) flows, that is, and the selectivity of control reaction.Be the conditioned reaction parameter in the example of the present invention, make the product of second hydrogenation zone be mainly 1, the 4-butyleneglycol, and the formation of gamma-butyrolactone and tetrahydrofuran (THF) is minimized.
Unreacted hydrogen is separated and loop back first hydrogenation zone and contact mixing with the dialkyl maleate raw material.Reclaim and refining 1 the 4-butyleneglycol by fractionation.The small amounts of by-products and the unreacted raw material that form, optional hydrotreating stage, preferred 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 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 compound again.This catalyst stability is good, catalyzer continuous operation 1000 hours, and activity is not fallen as follows.
Valuable 1 in hydrogenation products, the quantity of 4-butyleneglycol, gamma-butyrolactone, tetrahydrofuran (THF) product can change.It is mainly by parameter such as pressure, temperature and the residence time and by the selection decision of hydrogenation catalyst.
More particularly, implement method of the present invention, the dialkyl maleate two-stage method hydrogenation system 1 that adopts the present invention to describe, the method and apparatus of 4-butyleneglycol, dialkyl maleate can transform simply basically fully, and transformation efficiency is near 100%; 1, the final selectivity of 4-butyleneglycol 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 5MPa, H
2/ ester=200 (mole), 170 ± 1 ℃ of the LHSV=0.2/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), 170 ± 1 ℃ of the LHSV=0.2/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), 180 ± 1 ℃ of the LHSV=0.2/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 180 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), 170 ± 1 ℃ of the LHSV=0.2/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=100 (mole), 170 ± 1 ℃ of the LHSV=0.2/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), 170 ± 1 ℃ of the LHSV=0.4/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 190 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 7MPa, H
2/ ester=200 (mole), 170 ± 1 ℃ of the LHSV=0.2/h and 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 first hydroconversion reaction zone and second hydroconversion reaction zone.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 210 ± 1 ℃ of the first hydroconversion reaction zone temperature of reaction, 6MPa, H
2/ ester=200 (mole), 170 ± 1 ℃ of the LHSV=0.2/h and 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