CN101168536A - Method for producing tetrahydrofuran - Google Patents

Method for producing tetrahydrofuran Download PDF

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Publication number
CN101168536A
CN101168536A CNA2007101906507A CN200710190650A CN101168536A CN 101168536 A CN101168536 A CN 101168536A CN A2007101906507 A CNA2007101906507 A CN A2007101906507A CN 200710190650 A CN200710190650 A CN 200710190650A CN 101168536 A CN101168536 A CN 101168536A
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reaction
tetrahydrofuran
catalyzer
tungsten
thf
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殷恒波
李海霞
卢燕
姜廷顺
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Jiangsu University
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Jiangsu University
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Abstract

The invention relates to a method for preparing tetrahydrofuran, namely, the reaction alcoholization technology is adopted, molybdophosphoric heteropoly acid is taken as catalyst to catalyse 1,4-butanediol to prepare the tetrahydrofuran through cyclodehydration, fistly, the classic ether process is adopted to prepare the molybdophosphoric heteropoly acid which is taken as the catalyst, the eaction alcoholization technology is adopted to catalyse 1,4-butanediol to prepare the tetrahydrofuran through the cyclodehydration. The reaction conditions are as follows: calculated according to the mass ratio, the proportion of 1,4-butanediol : catalyst is equal to 1 : 10<-4>-1 : 10<-3>, the reaction temperature is 190-230 DEG C, and the reaction time is 15-90 minutes. The tetrahydrofuran prepared by the invention has the advantages that the selectivity is high, the production rate is high, the purity is high, the pollution is little, the reaction conditions are easy to be controlled, and the production process is simple.

Description

A kind of method for preparing tetrahydrofuran (THF)
Technical field
The present invention relates to a kind of method for preparing tetrahydrofuran (THF), refer in particular to and mix tungsten phosphato-molybdic heteropolyacid H 3PMo 12-nW nO 40XH 2O (n=1～11) is a catalyzer, adopts reaction rectification technique catalysis 1, and the cyclodehydration of 4-butyleneglycol prepares the method for tetrahydrofuran (THF).
Background technology
Tetrahydrofuran (THF) (THF) is a kind of high polarity, the low poison solvent of lower boiling, excellent property, be widely used as the solvent of topcoating, protective system and film coating, its topmost purposes is to produce polytetramethylene ether diol (PTMEG), polyurethane elastomer and polyurethane artificial leather etc.Also be used as the solvent in esterification and the polyreaction, do the raw material of more synthetic hormone drugs in the medicine.But the throughput of China's tetrahydrofuran (THF) is not high.Along with domestic to polyurethane elastomeric fiber and elastomerics, the growth of the focus consumption of spandex etc., the demand of tetrahydrofuran (THF) also will increase sharply.
China mainly adopts the furfural method to produce tetrahydrofuran (THF), and this method raw material consumption is many, complex process, and unit scale is little, and output is few, and environmental pollution is serious.With traditional strong protonic acids such as phosphoric acid, sulfuric acid, nitric acid is catalyzer, 1,4-butyleneglycol (BDO) is simple for the cyclodehydration of raw material liquid phase prepares tetrahydrofuran (THF) technology, the catalyst activity height, but they are serious to equipment corrosion, and liquid acid catalyst and product separation difficulty pollute environment.Heteropolyacid catalyst is just becoming the research focus of present environmental friendliness chemistry as the chief component of green catalysis.
Li Haixia, Yin Hengbo, Hu Tongjie etc. have delivered the article that is entitled as " load type silicotungstic acid catalysis 1; cyclodehydration of 4-butyleneglycol prepares tetrahydrofuran (THF) " 2005 the 2nd phases, factors such as the strength of acid of having studied interaction between bearer type, carrier and the heteropolyacid of carried heteropoly acid catalyst, catalyzer and acid amount are to catalysis 1, the influence that 4 butyleneglycol cyclodehydrations prepare THF, with this patent adopt reaction rectification technique with mix the tungsten phospho-molybdic acid be catalyzer to 1, it is different that the cyclodehydration of 4-butyleneglycol prepares tetrahydrofuran (THF).
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing tetrahydrofuran (THF), promptly adopt reaction rectification technique with mix the tungsten phospho-molybdic acid be catalyzer to 1, the cyclodehydration of 4-butyleneglycol prepares tetrahydrofuran (THF).
Be specially:
The Preparation of catalysts method adopts classical extracted with diethyl ether method, and the tungsten phosphato-molybdic heteropolyacid of preparing of mixing proves that through characterization methods such as ICP, IR, TG-DSC, XRD the heteropolyacid of preparing belongs to the heteropolyacid of A type Keggin structure, and its expression formula is respectively: H 3PMo 10.6W 1.1O 4022H 2O, H 3PMo 8.7W 3O 4019H 2O, H 3PMo 6.5W 4.8O 4012H 2O, H 3PMo 4.8W 6.8O 4015H 2O, H 3PMo 3.3W 8.5O 4011H 2O, H 3PMo 1.2W 10.6O 4012H 2O.
With the heteropoly phosphorus molybdenum tungstic acid of preparing is catalyzer, adopts reaction rectification technique catalysis 1, and the cyclodehydration of 4-butyleneglycol prepares tetrahydrofuran (THF).Reaction conditions is as follows, and press mass ratio and calculate, 1, the 4-butyleneglycol: the ratio of catalyzer is=1: 10 -4-1: 10 -3, temperature of reaction: 190-230 ℃, the reaction times: 15-90min.
The present invention adopts reaction rectification technique, has good catalytic activity than pure heteropolyacid catalyst equally with carried heteropoly acid catalyst after heteropolyacid mixes.
Description of drawings
Fig. 1: catalyzer H 3PMo 10.6W 1.1O 4022H 2O catalysis 1, the 4-butyleneglycol prepares the active testing of tetrahydrofuran (THF).
Fig. 2: catalyzer H 3PMo 4.8W 6.8O 4015H 2O catalysis 1, the 4-butyleneglycol prepares the active testing of tetrahydrofuran (THF).
Fig. 3: catalyzer H 3PMo 1.2W 10.6O 4012H 2O catalysis 1, the 4-butyleneglycol prepares the active testing of tetrahydrofuran (THF).
Fig. 4: with H 3PMo 4.8W 6.8O 4015H 2O is the TG-DSC spectrogram of example.
Wherein the mole number of each catalyzer of Fig. 1 is 0.075mmol, and the mole number of each catalyzer of Fig. 2 is 0.227mmol, and the mole number of each catalyzer of Fig. 3 is 0.378mmol.The catalyzer of each icon correspondence is respectively among each figure:
■ represents H 3PMo 12O 4011H 2O, ▲ expression H 3PMo 10.6W 1.1O 4022H 2O, ● expression H 3PMo 8.7W 3O 4019H 2O, represent H 3PMo 6.5W 4.8O 4012H 2O, △ represent H 3PMo 4.8W 6.8O 4015H 2O, zero expression H 3PMo 3.3W 8.5O 4011H 2O, ◇ represent H 3PMo 1.2W 10.6O 4012H 2O
Embodiment
The present invention will be further described below in conjunction with specific embodiment:
Embodiment 1
H 3PMo 10.6W 1.1O 4022H 2O Preparation of catalysts and catalytic activity test:
Take by weighing the Na of 8.95g earlier 2HPO 412H 2The Na of O and 66.54g 2MoO 42H 2O is dissolved in 25ml and 80m1 water respectively, after temperature of reaction is 90 ℃ of following stirring reaction 30min, adds the Na of 8.25g 2WO 42H 2The aqueous solution 100ml of O, 90 ℃ are continued stirring reaction 30min down, behind the cool to room temperature, drip dense H while stirring 2SO 4(98%) pH value to 1.5～2 are regulated in acidifying, and the about 15ml of the vitriol oil (98%) consumption adds in the sulfuric acid process temperature of reaction and keeps below 50 ℃, add sulfuric acid after, be to continue stirring reaction 8h under 90 ℃ again in temperature of reaction, be cooled to room temperature, placement is spent the night.Reaction finishes the afterreaction thing and goes to separating funnel, adds the 100ml ether and fully vibrates, and gradation adds 1: 1 H again 2SO 420ml, vibrate, leave standstill, isolate lower floor's yellow oily material, utilize the ether in the isolated yellow oily material of flowing air stream blowing, with remaining solids water-soluble (the about 30ml of water), in vacuum drier, use vitriol oil condensing crystal, obtain bright orange green crystal after the filtration, wash with water, dry, promptly get H 3PMo 10.6W 1.1O 4022H 2O stores in the moisture eliminator standby.
The catalyst activity testing method: get 1 of 100ml, the 4-butyleneglycol adds the H of 0.378mmol (57mg) when being heated to 230 ℃ of boilings 3PMo 10.6W 1.1O 4022H 2O is that catalyzer is made rectification process, and adopts gas chromatography analysis method to analyze 1 in smart distilled product and the reactor, and the concentration of 4-butyleneglycol and tetrahydrofuran (THF) is calculated transformation efficiency.The transformation efficiency of catalyzer just reached more than 90% when as shown in Figure 1, the reaction times was 18 minutes.
Embodiment 2
H 3PMo 4.8W 6.8O 4015H 2O Preparation of catalysts and catalytic activity test:
Take by weighing the Na of 8.95g earlier 2HPO 412H 2The Na of O and 30.24g 2MoO 42H 2O is dissolved in 25ml and 80ml water respectively, after temperature of reaction is 90 ℃ of following stirring reaction 30min, adds the Na of 57.72g 2WO 42H 2The aqueous solution 100ml of O, 90 ℃ are continued stirring reaction 30min down, behind the cool to room temperature, drip dense H while stirring 2SO 4(98%) pH value to 1.5～2 are regulated in acidifying, and the about 15ml of the vitriol oil (98%) consumption adds in the sulfuric acid process temperature of reaction and keeps below 50 ℃, add sulfuric acid after, be to continue stirring reaction 8h under 90 ℃ again in temperature of reaction, be cooled to room temperature, placement is spent the night.Reaction finishes the afterreaction thing and goes to separating funnel, adds the 100ml ether and fully vibrates, and gradation adds 1: 1 H again 2SO 4Each 20ml, vibrate, leave standstill, isolate lower floor's yellow oily material, utilize the ether in the isolated yellow oily material of flowing air stream blowing, with remaining solids water-soluble (the about 30ml of water), in vacuum drier, use vitriol oil condensing crystal, obtain bright orange green crystal after the filtration, wash with water, dry, promptly get H 3PMo 4.8W 6.8O 4015H 2O stores in the moisture eliminator standby.
The catalyst activity testing method: get 100 milliliters 1, the 4-butyleneglycol is heated to 230 ℃ of whens boiling and adds the H of 0.227mmol (40.2mg) 3PMo 4.8W 6.8O 4015H 2O is that catalyzer is made rectification process, and adopts gas chromatography analysis method to analyze 1 in smart distilled product and the reactor, and the concentration of 4-butyleneglycol and tetrahydrofuran (THF) is calculated transformation efficiency.As shown in Figure 2, the H of 0.227mmol 3PMo 4.8W 6.8O 4015H 2When O made catalyzer, the reaction times was that the transformation efficiency of 19 minutes catalyzer can reach 94%.
As shown in Figure 4, with H 3PMo 4.8W 6.8O 4015H 2O is an example, H 3PMo 4.8W 6.8O 4015H 2What the O heteropolyacid the first step lost is crystal water, weightless 7.58%, and corresponding has located an endotherm(ic)peak for 88.8 ℃ at the DSC curve, this peak correspondence be losing of physical adsorption (zeolite) moisture.What second step lost is combination water, weightless 3.54%, the water molecule number that its quality that loses loses corresponding to each Keggin structural unit, these water moleculess link to each other with acid proton by hydrogen bond in heteropolyacid, in the heteropolyacid crystal with protonated oxonium ion (H 5O 2 +OrH 3O +) state exist, corresponding locates also to have an endotherm(ic)peak for 158 ℃ at the DSC curve.The 3rd step, what lose was water of constitution, weightless 1.15%, corresponding in the DSC curve 496 ℃ located an exothermic peak.The losing of this part water shows that mixing the thermolysis that the tungsten phosphato-molybdic heteropolyacid loses all acid protons and Keggin structure begins, and the Keggin structure of heteropolyacid has been decomposed to form mixed oxide fully.As shown in table 1 in addition, the data results that characterizes in conjunction with TG-DSC shows that each catalyzer exothermic peak temperature raises along with the increase of mixing the tungsten amount, shows along with the increase of mixing the tungsten amount, and the thermostability of catalyzer increases.
Table 1: the TG-DSC analytical results of each catalyzer:
HPAs Endothermic 1 Endothermic 2 Exothermic
T(℃) -H 2O T(℃) -H 2O T(℃) -H 2O
H 3PMo 12O 40·12H 2O 74.9 7.17 116.7 4.85 416.0 1.54
H 3PMo 10.6W 1.1O 40·22H 2O 98.2 13.36 117.0 8.64 435.0 1.53
H 3PMo 8.7W 3O 40·19H 2O 91.9 10.94 121.8 8.06 457.0 1.48
H 3PMo 6.5W 4.8O 40·12H 2O 85.1 6.22 127.1 6.10 469.0 1.51
H 3PMo 4.8W 6.8O 40·15H 2O 88.8 10.22 158.0 4.78 496.0 1.52
H 3PMo 3.3W 8.5O 40·11H 2O 72.0 6.90 161.8 4.1 518.9 1.52
H 3PMo 1.2W 10.6O 40·12H 2O 68.1 7.18 169.1 4.82 561.1 1.54
Embodiment 3
H 3PMo 1.2W 10.6O 4012H 2O Preparation of catalysts and catalytic activity test:
Take by weighing the Na of 8.95g earlier 2HPO 412H 2The Na of O and 6.05g 2MoO 52H 2O is dissolved in 25ml and 80ml water respectively, after temperature of reaction is 90 ℃ of following stirring reaction 30min, adds the Na of 90.71g 2WO 42H 2The aqueous solution 100ml of O, 90 ℃ are continued stirring reaction 30min down, behind the cool to room temperature, drip dense H while stirring 2SO 4(98%) pH value to 1.5～2 are regulated in acidifying, and the about 15ml of the vitriol oil (98%) consumption adds in the sulfuric acid process temperature of reaction and keeps below 50 ℃, add sulfuric acid after, be to continue stirring reaction 8h under 90 ℃ again in temperature of reaction, be cooled to room temperature, placement is spent the night.Reaction finishes the afterreaction thing and goes to separating funnel, adds the 100ml ether and fully vibrates, and gradation adds 1: 1 H again 2SO 430ml, vibrate, leave standstill, isolate lower floor's yellow oily material, utilize the ether in the isolated yellow oily material of flowing air stream blowing, with remaining solids water-soluble (the about 30ml of water), in vacuum drier, use vitriol oil condensing crystal, obtain bright orange green crystal after the filtration, wash with water, dry, promptly get H 3PMo 1.2W 10.6O 4012H 2O.Store in the moisture eliminator standby.
The catalyst activity testing method: get 100 milliliters 1, the 4-butyleneglycol is heated to 230 ℃ of whens boiling and adds the H of 0.075mmol (15mg) 3PMo 1.2W 10.6O 4012H 2O is that catalyzer is made rectification process, and adopts gas chromatography analysis method to analyze 1 in smart distilled product and the reactor, and the concentration of 4-butyleneglycol and tetrahydrofuran (THF) is calculated transformation efficiency, as shown in Figure 3, and the H of 0.075mmol 3PMo 1.2W 10.6O 4012H 2When O made catalyzer, the reaction times was that 20 minutes conversion of raw material reach more than 96%.
Therefore by a series of tungsten phosphato-molybdic heteropolyacid (H that mix 3PMo 12-nW nO 40N=1～11) active testing result has etc. at catalyzer under the situation of mole number as can be seen, and along with catalyzer is mixed the increase of tungsten amount, activity of such catalysts and speed of reaction all improve thereupon.This is the result of regulating catalyst physico-chemical property.W 6+Replace Mo 6+Significantly improved catalyzer to 1, the catalytic activity of 4-butyleneglycol cyclodehydration reaction, and also the employing reaction rectification technique can better separated product tetrahydrofuran (THF) and water.

Claims (3)

1. mix the tungsten phosphato-molybdic heteropolyacid as the application of catalyzer at the preparation tetrahydrofuran (THF), promptly at first adopt phosphato-molybdic heteropolyacid is mixed the tungsten modification, prepare difference and mix the heteropoly phosphorus molybdenum tungstic acid of tungsten amount, adopt reaction rectification technique separated product tetrahydrofuran (THF) and water again, with the heteropoly phosphorus molybdenum tungstic acid is catalyzer, catalysis 1, the cyclodehydration of 4-butyleneglycol prepares tetrahydrofuran (THF).
2. the described tungsten phosphato-molybdic heteropolyacid of mixing of claim 1 is as the application of catalyzer at the preparation tetrahydrofuran (THF), be specially: at first adopt classical extracted with diethyl ether legal system to be equipped with the different tungstenic phosphato-molybdic heteropolyacids of tungsten amount of mixing, be catalyzer with the heteropoly phosphorus molybdenum tungstic acid of preparing again, adopt reaction rectification technique catalysis 1, the cyclodehydration of 4-butyleneglycol prepares tetrahydrofuran (THF); Reaction conditions is as follows: presses mass ratio and calculates, and 1, the 4-butyleneglycol: the ratio of catalyzer is=1: 10 -4-1: 10 -3, temperature of reaction: 190-230 ℃, the reaction times: 15-90min.
3. the described tungsten phosphato-molybdic heteropolyacid of mixing of claim 2 is as the application of catalyzer at the preparation tetrahydrofuran (THF), and it is characterized in that: classical extracted with diethyl ether method is specially: the mol ratio that adds tungsten and phosphorus according to molybdenum is 12: 1 a ratio, takes by weighing Na earlier 2HPO 412H 2O and Na 2MoO 42H 2O, soluble in water respectively, at 90 ℃ of following stirring reaction 30min, add the Na of stoichiometric ratio 2WO 42H 2The aqueous solution of O, 90 ℃ are continued stirring reaction 30min down, behind the cool to room temperature, drip dense H while stirring 2SO 4PH value to 1.5～2 are regulated in acidifying, add in the sulfuric acid process temperature of reaction and keep below 50 ℃, add sulfuric acid after, be to continue stirring reaction 6-10h under 90 ℃ again in temperature of reaction, be cooled to room temperature, placement is spent the night; Reaction finishes the back and mixes the tungsten phosphato-molybdic heteropolyacid with extracted with diethyl ether, utilize flowing air stream to blow down ether in the isolated yellow oily material then, remaining solids is water-soluble, condensing crystal, filtration, wash, dry, must mix the tungsten phosphato-molybdic heteropolyacid, store in the moisture eliminator standby.
CNA2007101906507A 2007-11-27 2007-11-27 Method for producing tetrahydrofuran Pending CN101168536A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103936697A (en) * 2014-04-17 2014-07-23 河北师范大学 Method for catalytically synthesizing tetrahydrofuran
CN106795533A (en) * 2013-03-20 2017-05-31 Cj第制糖株式会社 Prepared by the O acylhomoserines from microorganism and be derived from biological homoserine lactone hydrochloride and the method from biological organic acid
CN109894152A (en) * 2019-03-20 2019-06-18 曲阜师范大学 It is a kind of for the method for preparing catalyst and its gained catalyst of synthesizing tetrahydrofuran and application
CN110698438A (en) * 2019-10-16 2020-01-17 中国石化长城能源化工（宁夏）有限公司 Method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under catalysis of solid catalyst
CN113135890A (en) * 2020-01-17 2021-07-20 北京化工大学 Method for preparing tetrahydrothiophene by adopting double-component catalyst
CN114425447A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Heteropolyacid modified catalyst, preparation method and application thereof, and butylene oxidative dehydrogenation method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106795533A (en) * 2013-03-20 2017-05-31 Cj第制糖株式会社 Prepared by the O acylhomoserines from microorganism and be derived from biological homoserine lactone hydrochloride and the method from biological organic acid
CN103936697A (en) * 2014-04-17 2014-07-23 河北师范大学 Method for catalytically synthesizing tetrahydrofuran
CN103936697B (en) * 2014-04-17 2016-04-13 河北师范大学 A kind of method catalyzing and synthesizing tetrahydrofuran (THF)
CN109894152A (en) * 2019-03-20 2019-06-18 曲阜师范大学 It is a kind of for the method for preparing catalyst and its gained catalyst of synthesizing tetrahydrofuran and application
CN109894152B (en) * 2019-03-20 2021-11-05 曲阜师范大学 Preparation method of catalyst for synthesizing tetrahydrofuran, catalyst obtained by preparation method and application of catalyst
CN110698438A (en) * 2019-10-16 2020-01-17 中国石化长城能源化工（宁夏）有限公司 Method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under catalysis of solid catalyst
CN113135890A (en) * 2020-01-17 2021-07-20 北京化工大学 Method for preparing tetrahydrothiophene by adopting double-component catalyst
CN113135890B (en) * 2020-01-17 2022-08-26 北京化工大学 Method for preparing tetrahydrothiophene by adopting double-component catalyst
CN114425447A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Heteropolyacid modified catalyst, preparation method and application thereof, and butylene oxidative dehydrogenation method
CN114425447B (en) * 2020-10-15 2024-01-30 中国石油化工股份有限公司 Heteropoly acid modified catalyst, preparation method and application thereof and butene oxidative dehydrogenation method

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