CN1116615A - Method for preparing 1,4-butanediol - Google Patents

Method for preparing 1,4-butanediol Download PDF

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CN1116615A
CN1116615A CN 94108094 CN94108094A CN1116615A CN 1116615 A CN1116615 A CN 1116615A CN 94108094 CN94108094 CN 94108094 CN 94108094 A CN94108094 A CN 94108094A CN 1116615 A CN1116615 A CN 1116615A
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anhydride
acid anhydride
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CN1049207C (en
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童立山
王海京
高国强
张新杰
冯薇荪
李向伟
邓景辉
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

The 1,4-butanediol is prepared by a gas-phase catalytic hydrogenation reaction of maleic anhydride and/or succinic anhydride in the presence of catalyst whose formula is CuaZnCrbMcOx, where a=0.1-1, b=0.1-5, c=0.1-5, X satisfies valence requirements, and M is one element in Group IV B, under conditions: 3-9 MPa, 190-300 deg.C, anhydride volume space velocity of 0.02-0.30/hr and 150-500:1 of mole ratio of H2 to anhydride. It features high space-time yield, selectivity of 1,4-butanediol and stability.

Description

1, the preparation method of 4-butyleneglycol
The present invention relates to 1, the preparation method of 4-butyleneglycol is that raw material carries out gas phase catalytic hydrogenation prepared in reaction 1 with cis-butenedioic anhydride and/or succinyl oxide specifically, the method for 4-butyleneglycol.
1, the 4-butyleneglycol is a kind of important basic Organic Chemicals, is mainly used in production polybutyl terapthalate (PBT), urethane, gamma-butyrolactone, tetrahydrofuran (THF) and softening agent.
Usually, 1, the 4-butyleneglycol is to be raw material with acetylene and formaldehyde, and is under high pressure synthetic, also can be made by gamma-butyrolactone hydrogenation or tetrahydrofuran (THF) hydrolysis.Along with the development that butane oxidation prepares the maleic anhydride technology, since the eighties, adopting the base metal mixed oxide is catalyzer, makes 1, the method for 4-butyleneglycol from the direct vapour phase hydrogenation of cis-butenedioic anhydride.Make great progress, for example, it is catalyzer that the flat 2-25434 of Japanese Patent discloses with the Cu-Zn mixed oxide, by cis-butenedioic anhydride preparation 1, the method of 4-butyleneglycol, cis-butenedioic anhydride transformation efficiency are 100 moles of %, 1, and the selectivity of 4-butyleneglycol reaches 79 moles of %, the deficiency of this method is: cis-butenedioic anhydride liquid volume charging air speed (LHSV) is not high, about 0.03 hour -1, reaction stability is bad, cycle of operation less than 100 hours.It is catalyzer with the Cu-Mn mixed oxide that the flat 2-233632 of Japanese Patent discloses a kind of, by cis-butenedioic anhydride preparation 1, and the method for 4-butyleneglycol, the cis-butenedioic anhydride transformation efficiency is 100 moles of %, 1,4-butyleneglycol selectivity reaches 95 moles of %, but LHSV only had an appointment 0.03 hour -1, when being solvent with the gamma-butyrolactone, LHSV is 0.06 hour -1The time, 1,4-butyleneglycol selectivity only is 67 moles of %, but does not also provide the time of reaction continuous operation.
The purpose of this invention is to provide a kind of is raw material with cis-butenedioic anhydride and/or succinyl oxide, uses non-precious metal catalyst, carries out gas phase catalytic hydrogenation prepared in reaction 1, the method for 4-butyleneglycol under higher LHSV condition, in the long period scope continuously.
The used catalyzer of the present invention is to be that the general formula that 94105927.8 the described method of Chinese patent application makes is Cu according to application number aZnCr bM cO xNon-precious metal catalyst, wherein a=0.1-10, b=0.1-5, c=0.1-5 represent the atomicity of Cu, Cr, M respectively, X is for satisfying the needed oxygen atomicity of other element valence requirement, M is a kind of element that is selected from the IV B family, Zr element preferably, and its preparation process comprises:
(1) Cu, Zn, Zr salt and the chromic trioxide proportion of composing according to this catalyzer is dissolved in the deionized water, make the solution that mixture concentration is 20～50m%, under agitation mix with alkali, co-precipitation takes place, pH value=the 5-7 of control solution filters, washs, in 100-120 ℃ of dry 10-15 hour, at 350-500 ℃ of roasting 20-30 hour, moulding then, make catalyst Precursors;
(2) negate is seated in the fixed-bed reactor in requisition for the catalyst Precursors of amount, in hydrogen or the hydrogen with inert gas dilution, reduces 5-40 hour in 150-300 ℃ under 0.1-2.0MPa pressure.
The method of the invention, its technological process is: catalyzer is reduced to temperature of reaction with temperature of reactor after the reduction pre-treatment, feeds the cis-butenedioic anhydride be dissolved in the solvent and/or succinic anhydride solution and hydrogen then and carry out catalytic hydrogenation in reactor, can make 1, the 4-butyleneglycol.When being reaction raw materials with the cis-butenedioic anhydride, its reaction formula is as follows:
Figure A9410809400051
Its processing condition are: reaction pressure 3-9MPa, 4-7MPa preferably; Temperature of reaction 190-300 ℃, preferably 200-280 ℃; Acid anhydride liquid volume charging air speed 0.02-0.30 hour -1, preferably 0.04-0.30 hour -1H 2/ acid anhydride mol ratio is 150-500: 1,200-500 preferably: 1.
Because cis-butenedioic anhydride is solid-state at normal temperatures, for ease of carrying, usually cis-butenedioic anhydride is dissolved in charging in the solvent, solvent commonly used has C 1-C 4Saturated monohydroxy alcohol, ether, gamma-butyrolactone, diox etc., the common acid anhydride of the consumption of solvent are 0.4-5 times of weight.
The fixed-bed reactor that the present invention mentions can be the tandem reactor groups that, the reactor more than two or two form.The hydrogen of separating from reaction product can recycle.
Finishing reactive mode of the present invention can be intermittently, semi-continuous, but economic way still is the successive reaction mode, i.e. the fixed bed reaction mode.
The method of the invention has space-time yield height (being acid anhydride liquid volume charging air speed height), 1,4 fourth-characteristics such as glycol selectivity height, and method when being solvent with the gamma-butyrolactone, is 0.1 hour at LHSV as described herein -1Condition under, 1, the productive rate of 4-butyleneglycol is very high, reach more than 90 moles, and existing technology is 0.06 hour at LHSV -1Condition under, 1, the selectivity of 4-butyleneglycol has only 67 moles of %, have only as LHSV to drop to 0.03 hour-1 the time, 1, the selectivity of 4-butyleneglycol just can be brought up to 90 moles more than the %.
Another characteristics of the method for the invention are: cycle of operation is long, reaches 1000 hours, this moment 1, and the selectivity of 4-butyleneglycol is still very high, and decaying catalyst can be reused behind the in-situ regeneration in reaction, and regeneration temperature is not more than 300 ℃.
The following examples will the invention will be further described.
Example 1-3
Preparation of catalysts and pre-treatment: be example 1 described method in 94105927.8 the Chinese patent application according to application number, with 261 gram cupric nitrate (chemical pure, the Beijing Chemical Plant), 298 gram zinc nitrate (chemical pure, the Beijing Chemical Plant), 116 gram chromic trioxides (chemical pure, Beijing Chemical Plant), 134 gram zirconium nitrate (chemical pure, the Beijing Chemical Plant) is dissolved in 1000 milliliters of deionized waters, under agitation mixes, control pH=6 ± 1 with ammoniacal liquor, generate precipitation, filter, washing is in 110 ± 10 ℃ of dryings 12 hours, 400 ± 50 ℃ of roastings 24 hours, moulding, making granularity is the catalyst Precursors of 2.5 millimeters * 2 millimeters of φ, its compressive strength be 100 ± 50 newton/centimetre.Getting 62.5 milliliters of these catalyst Precursors internal diameter of packing into is in 23 millimeters of φ, long 1000 millimeters the stainless steel tubular type reactor, use the nitrogen purging reactive system, and with the reactive system pressurising to 1MPa, feed the hydrogen of using nitrogen dilution with 2.5 liters/fractional flow then, density of hydrogen is brought up to 100Vo1% gradually by 2Vo1%, simultaneously, reactor is risen to 295 ± 5 ℃ by room temperature, carry out catalyst reduction, average heating speed is not more than 20 ℃/hour, total about 40 hours of recovery time.
Catalytic hydrogenation reaction: reactor is reduced to temperature of reaction, feed cis-butenedioic anhydride-butanol solution (cis-butenedioic anhydride: technical grade, in the Tianjin and chemical plant to reactor; Propyl carbinol, technical grade, commercially available), react by the listed condition of table 1, reaction product is carried out stratographic analysis, the results are shown in Table 1.
Annotate: compressive strength assay method: RIPP 25-90 (referring to " the petrochemical complex analytical procedure " that people such as Yang Cuiding write, Science Press).
Table 1
Figure A9410809400081
* annotate: LHSV is meant cis-butenedioic anhydride liquid volume charging air speed.
Example 4
Catalyzer, reaction raw materials and reaction unit are with example 1, and the control reaction pressure is that 7MPa, LHSV are 0.1 hour -1, H 2/ acid anhydride mol ratio is 350: 1, and accumulative total turned round more than 1000 hours, and reaction result sees Table 2.
Table 2
Accumulated running time (hour) Temperature of reaction (℃) Transformation efficiency (mole %) Selectivity (mole %)
Tetrahydrofuran (THF) The n-butanols Gamma-butyrolactone 1,4 butyleneglycol
????72 ????219 ????100 ????16 ????0 ????12 ????72
????300 ????220 ????100 ????13 ????4 ????13 ????70
????515 ????220 ????100 ????11 ????3 ????14 ????72
????704 ????219 ????100 ????10 ????3 ????16 ????71
????829 ????220 ????99 ????11 ????1 ????18 ????70
????1003 ????222 ????95 ????14 ????2 ????21 ????63
Example 5
Adopt example 4 described catalyzer, reaction raw materials and reaction unit, still, catalyzer used 1859 hours, and catalyst surface copper crystal grain obviously increases, and causes catalyst activity reduction.Reactor is reduced to room temperature, in the gas volume charging air speed of 1MPa, air is with reactor temperature raising to 295 ± 5 ℃ under 2400 hours-1 conditions, wherein in 150-200 ℃ of scope, 10 ℃/hour of average heating speeds replace air gradually with pure oxygen then, continue oxidation 14 hours, about 54 hours of total oxidization time, press example 1 method then with catalyst reduction, and the charging reaction, reaction result is listed in table 3.
Table 3
Catalyzer Temperature (℃) Pressure (MPa) H 2/ acid anhydride (mole) LHSV (hour -1)?? Transformation efficiency (mole %) Selectivity (mole %)
????THF ????GBL ?1，4-BD
Before the regeneration 236 7 350 0.1 93 ????15 ????33 ?52
After the regeneration 219 7 350 0.1 100 ????9 ????19 ?72
Annotate: (1) LHSV: cis-butenedioic anhydride liquid volume charging air speed;
(2) THF: tetrahydrofuran (THF);
(3) GBL: gamma-butyrolactone;
(4) 1,4-BD:1, the 4-butyleneglycol.
By routine 1-4 as can be seen: the method for the invention has space-time yield height (being cis-butenedioic anhydride liquid volume charging air speed height), 1, characteristics such as 4-butyleneglycol selectivity height.
By example 4,5 as can be seen: the method for the invention is long running period, reaches more than 1000 hours, can reuse behind the reaction in-situ regeneration behind the catalyst deactivation, and regeneration temperature is low, is not more than 300 ℃.
Example 6
Get granularity and be the 26-50 order by 2.7 milliliters of the catalyst Precursors of example 1 method preparation, the internal diameter of packing into is 10 millimeters, length is in 500 millimeters the stainless steel tubular type reactor, use the nitrogen purging reactive system, and pressurising is to 2MPa, feed hydrogen with 30 liters/hour flow to reactor then, be that 50 ℃/hour speed is raised to 280 ℃ with reactor by room temperature simultaneously with average heating speed, and 280 ℃ of maintenances 2 hours, reactor is lowered the temperature, feeding the mixture (mol ratio of cis-butenedioic anhydride and gamma-butyrolactone is 1: 1) of cis-butenedioic anhydride and gamma-butyrolactone in reactor, is 230 ℃ in temperature of reaction, reaction pressure is 6MPa, cis-butenedioic anhydride liquid volume charging air speed is 0.1 hour -1, H 2/ acid anhydride mol ratio is to react under 410: 1 the condition, and stratographic analysis is carried out in sampling, the results are shown in Table 4.
Table 4
Continuous operation time (hour) Transformation efficiency (mole %) Selectivity (mole %)
Tetrahydrofuran (THF) The n-butanols 1,4 butyleneglycol
????69 ????100 ????7 ????2 ????91
????93 ????100 ????7 ????2 ????91
????106 ????100 ????7 ????2 ????91
????115 ????100 ????7 ????2 ????91
????124 ????100 ????7 ????2 ????91
????139 ????100 ????7 ????2 ????91
As can be seen from Table 4, the method for the invention, when being solvent with the gamma-butyrolactone, 1, the productive rate of 4-butyleneglycol is very high, can reach 90 moles more than the %, and existing technology is 0.06 hour at LHSV when being solvent with the gamma-butyrolactone -1Condition under, 1, the selectivity of 4-butyleneglycol has only 67 moles of %.

Claims (10)

1. one kind 1, the preparation method of 4-butyleneglycol is to be raw material with cis-butenedioic anhydride and/or succinyl oxide, carries out gas phase catalytic hydrogenation prepared in reaction 1, the 4-butyleneglycol, and it is characterized in that this method comprises following process: with general formula is Cu aZnCr bM cO xCatalyst loading in fixed-bed reactor, after pre-treatment, reduce to temperature of reaction, feeding is dissolved in cis-butenedioic anhydride and/or the succinic anhydride solution in the solvent, carry out catalytic hydrogenation preparation 1,4 butyleneglycols, its processing condition are: reaction pressure 3-9MPa, temperature of reaction 190-300 ℃, acid anhydride liquid volume charging air speed 0.02-0.30 hour -1, H 2/ acid anhydride mol ratio is 150-500: 1, the consumption of solvent is 0.4～5 times of acid anhydride weight, and the hydrogen of separating from reaction product can recycle.
2. according to the said preparation method of claim 1, it is characterized in that said solvent is C 1-C 4Saturated monohydroxy alcohol, gamma-butyrolactone, diox.
3. according to the said preparation method of claim 1, it is characterized in that at catalyzer general formula Cu aZnCr bM cO xIn, a=0.1-10, b=0.1-5, c=0.1-5 represent that respectively the atomicity of Cu, Cr, M, X are for satisfying the needed oxygen atomicity of other element valence requirement, M is a kind of element that is selected from the IV B family.
4. according to claim 1,3 said preparation methods, it is characterized in that M is the Zr element.
5. according to the said preparation method of claim 1, it is characterized in that the pre-treatment of catalyzer is meant: with general formula Cu aZnCr bM cO xCatalyst Precursors in hydrogen or hydrogen with inert gas dilution, under 0.1-2.0MPa pressure in 150-300 ℃ the reduction 5-40 hour.
6. according to the said preparation method of claim 1, it is characterized in that reaction pressure is 4-7MPa.
7. according to the said preparation method of claim 1, it is characterized in that temperature of reaction is 200-280 ℃.
8. according to the said preparation method of claim 1, it is characterized in that acid anhydride liquid volume charging air speed is 0.04-0.30 hour -1
9. according to the said preparation method of claim 1, it is characterized in that H 2/ acid anhydride mol ratio is 200-500: 1.
10. according to the said preparation method of claim 1, it is characterized in that said fixed-bed reactor can be the tandem reactors groups that, the reactor more than two or two form.
CN94108094A 1994-08-10 1994-08-10 Method for preparing 1,4-butanediol Expired - Fee Related CN1049207C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169958B2 (en) 2002-06-11 2007-01-30 Basf Aktiengesellschaft Method for the production of 1,4- butane-diol by combined gas-phase and liquid-phase hydrogenation
US7271299B2 (en) 2002-06-11 2007-09-18 Basf Aktiengesellschaft Two-stage method for producing butanediol with intermediated separation of succinic anhydride
CN114181038A (en) * 2021-12-24 2022-03-15 常州瑞华化工工程技术股份有限公司 Method for producing 1, 4-butanediol and coproducing succinic anhydride by direct hydrogenation of maleic anhydride

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2772524B2 (en) * 1988-07-15 1998-07-02 東燃株式会社 Method for producing 1,4-butanediol
JP2639462B2 (en) * 1989-03-08 1997-08-13 東燃株式会社 Process for producing 1,4-butanediol and tetrahydrofuran
JP2670698B2 (en) * 1989-03-08 1997-10-29 東燃株式会社 Manufacturing method of 1,4-butanediol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169958B2 (en) 2002-06-11 2007-01-30 Basf Aktiengesellschaft Method for the production of 1,4- butane-diol by combined gas-phase and liquid-phase hydrogenation
US7271299B2 (en) 2002-06-11 2007-09-18 Basf Aktiengesellschaft Two-stage method for producing butanediol with intermediated separation of succinic anhydride
CN114181038A (en) * 2021-12-24 2022-03-15 常州瑞华化工工程技术股份有限公司 Method for producing 1, 4-butanediol and coproducing succinic anhydride by direct hydrogenation of maleic anhydride
CN114181038B (en) * 2021-12-24 2022-10-11 常州瑞华化工工程技术股份有限公司 Method for producing 1,4-butanediol and coproducing succinic anhydride by directly hydrogenating maleic anhydride

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