CN113135890B - Method for preparing tetrahydrothiophene by adopting double-component catalyst - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a method for preparing tetrahydrothiophene by adopting a two-component catalyst, relating to the technical field of synthetic chemical engineering and comprising the following steps: 1, 4-butanediol is dehydrated and cyclized in a catalytic molecule of heteropoly acid 1 under the heating condition to generate tetrahydrofuran, and then the tetrahydrofuran reacts with hydrogen sulfide under the catalysis of heteropoly acid 2 under the same condition to produce target product tetrahydrothiophene. The invention has the beneficial effects that: compared with the prior art, the preparation method has the advantages of higher reaction speed, less catalyst consumption, higher selectivity, lower reaction temperature, simple post-treatment and only water as a byproduct, and completely realizes green production.
Description
Technical Field
The invention relates to the technical field of synthetic chemical engineering, in particular to a method for preparing tetrahydrothiophene by adopting a two-component catalyst.
Background
Tetrahydrothiophene has the advantages of stable property, difficult oxidation, convenient storage, difficult odor disappearance, no habitual passivation to human smell, complete combustion, small required addition amount, difficult equipment corrosion and the like, and is widely used as a fuel gas warning agent. By 2020, the annual natural gas consumption in China is expected to reach 3600 billion cubic meters, the consumption of the tetrahydrothiophene is 30mg/mL according to the national standard which is slightly lower than the international standard, at this time, the annual demand of the natural gas for the tetrahydrothiophene exceeds one million tons, the annual domestic yield is less than three thousand tons, and the tetrahydrothiophene faces a huge market gap.
The traditional production process of tetrahydrothiophene adopts molybdenum disulfide or palladium supported on activated carbon as a catalyst, and hydrogen is used for reducing thiophene to produce tetrahydrothiophene. CN1485322A discloses a method for preparing tetrahydrofuran, which comprises: contacting a hydrogenatable precursor selected from maleic acid, succinic acid and gamma-butyrolactone or a mixture of more than one of the hydrogenatable precursors with hydrogen under liquid phase conditions in the presence of a hydrogenation catalyst, separating and collecting tetrahydrofuran, wherein the hydrogenation catalyst is composed of one noble metal selected from palladium, platinum, ruthenium and rhenium and one or more than one non-noble metal selected from copper, zinc, manganese, aluminum, iron and nickel which are loaded on an activated carbon carrier. However, thiophene as a raw material is extremely expensive, and the production method has extremely high cost and is not suitable for the market.
CN105949171A discloses a method for producing tetrahydrothiophene by using single-component heteropolyacid loaded on active alumina as a catalyst and using 1, 4-butanediol and refined hydrogen sulfide as raw materials. The heteropoly acid is used as a green catalyst, but the reaction involves two steps, the mechanism of the two steps is different, a single catalyst component is difficult to meet the requirement, and the disadvantages of high reaction temperature, poor catalyst selectivity, low product purity and the like exist. More cost-effective and efficient production processes have become a research hotspot in this field.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing tetrahydrothiophene by adopting a two-component catalyst.
The invention solves the technical problems through the following technical means:
a method for preparing tetrahydrothiophene by adopting a two-component catalyst comprises the following steps: 1, 4-butanediol is dehydrated and cyclized in a catalytic molecule of heteropoly acid 1 under the heating condition to generate tetrahydrofuran, and then the tetrahydrofuran reacts with hydrogen sulfide under the same condition under the catalytic action of heteropoly acid 2 to generate target product tetrahydrothiophene.
Has the advantages that: the reaction mechanisms of the two steps are different, and a single catalyst is difficult to meet the requirements.
When only heteropoly acid 1 is added, the reaction speed of the reaction in the first stage is higher, but the reaction basically only stays in the first stage, the yield of the target product generated in the second stage is extremely low, the product mainly comprises tetrahydrofuran, and the purity of tetrahydrothiophene is less than 5 percent.
When only the heteropoly acid 2 is added, the reaction speed of the reaction in the first stage is greatly reduced, so that the overall reaction speed is reduced, and the reaction speed is about 50 percent slower than that of the double-component heteropoly acid under the same condition.
Compared with the prior art, the preparation method has the advantages of higher reaction speed, less catalyst consumption, higher selectivity, lower reaction temperature, simple post-treatment and only water as a byproduct, and completely realizes green production.
Preferably, the method for preparing tetrahydrothiophene by using the two-component catalyst comprises the following steps:
(1) weighing heteropoly acid 1 and heteropoly acid 2, mixing, placing in a muffle furnace for calcining and activating for 4-5h, and then cooling under the condition of nitrogen to prepare a bi-component catalyst;
(2) adding 1, 4-butanediol into a reactor, adding the double-component catalyst prepared in the step (1), heating to a reaction temperature, stirring, introducing hydrogen sulfide gas continuously in the reaction process, stopping introducing the hydrogen sulfide gas in a molar ratio of the total amount of the introduced hydrogen sulfide gas to the 1, 4-butanediol of not less than 5:1, reacting for 0.5-2h, stopping introducing the gas, stirring and heating, cooling, standing, and taking an upper layer solution which is tetrahydrothiophene after the solution is layered.
Has the advantages that: experimental data indicate that with only any one or more of heteropolyacids 1 undergoing catalytic reaction, the reaction will stay in the first stage, with the main product being tetrahydrofuran rather than tetrahydrothiophene. The conversion of tetrahydrofuran to tetrahydrothiophene can be accomplished by adding heteropolyacid 2.
If the molar ratio of the total amount of hydrogen sulfide gas to the 1, 4-butanediol is less than 5:1, the purity of the product tetrahydrothiophene will decrease.
Preferably, the heteropoly acid 1 is one of phosphotungstic acid, phosphotungstomolybdic acid, phosphomolybdovanadic acid, germanium tungstic acid and germanium vanadic acid.
Preferably, the heteropoly acid 1 is phosphotungstic acid.
Preferably, the heteropoly acid 2 is one of silicotungstic acid, silicotungstic vanadic acid, silicomolybdic vanadate and phosphomolybdic acid.
Preferably, the heteropoly acid 2 is silicotungstic acid.
Preferably, the molar ratio of the heteropoly acid 1 to the heteropoly acid 2 is 1: 9-7: 3.
Has the advantages that: if the molar ratio of the heteropoly acid 1 to the heteropoly acid 2 is not in the range, the reaction stays in the first stage, the main product is tetrahydrofuran, or the reaction in the first stage is incomplete, and the conversion rate of the raw materials is low.
Preferably, the calcination activation temperature in the step (1) is 150-600 ℃.
Preferably, the mass ratio of the 1, 4-butanediol to the two-component catalyst in the step (2) is 50: 1-500: 1.
Has the advantages that: when the mass ratio of the 1, 4-butanediol to the two-component catalyst is 50: 1-500: 1, the highest reaction speed can be kept, the reaction speed can be reduced below the range, the reaction cost can be increased above the range, and the difficulty in subsequent catalyst recovery is increased.
Preferably, the reaction temperature in the step (2) is 160-260 ℃.
Has the advantages that: the lowest reaction temperature of the present application is 160 ℃, and the reaction temperature can be reduced.
Preferably, the lower layer solution in the step (2) is dried and then calcined to obtain the mixed heteropoly acid catalyst.
Has the advantages that: the bi-component heteropoly acid catalyst can be recycled after being dried and calcined.
Preferably, the drying temperature is 80 ℃, the calcining temperature is 200-300 ℃, and the calcining time is 4-5 h.
The invention has the advantages that:
(1) compared with the prior art, the preparation method has the advantages that the reaction speed is higher, the same reaction is completed under the same condition, and the time required by the reaction is only 30% of the time required by the prior art;
(2) the preparation method of the invention has the advantages of small catalyst usage amount and higher selectivity, and the reaction selectivity can reach 100 percent and is higher than the highest 99 percent of the prior art; the reaction temperature is lower, the lowest reaction temperature only needs 160 ℃, and is far lower than 300 ℃ in the prior art; the post-treatment is simple, and the byproduct is only water, so that the green production is completely realized;
(3) the mixed catalyst can be recycled by simple evaporation and calcination.
Drawings
FIG. 1 is a graph showing the concentration of each component in a solution in example 1 of the present invention as a function of time.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
The reaction formula for preparing tetrahydrofuran is as follows:
(1)
(2)
wherein cat represents a catalyst;
the preparation process of the invention relates to two steps, the two steps have different reaction mechanisms, almost no by-product is generated, but the catalysts acting on the two steps are different, and the catalytic synthesis efficiency can be improved.
The total reaction formula for preparing tetrahydrofuran is as follows:
example 1
Method for preparing tetrahydrothiophene by adopting double-component catalyst
(1) Weighing 0.22g of phosphotungstic acid and 0.32g of silicotungstic acid, mixing, calcining and activating in a muffle furnace at 300 ℃ for 4h, and then cooling in a nitrogen atmosphere;
(2) weighing 100.0g of 1, 4-butanediol, pouring into a reactor, adding the mixed acid catalyst activated in the step (1), starting stirring and heating, heating to 200 ℃, continuously introducing hydrogen sulfide gas, wherein the molar ratio of the total amount of the introduced hydrogen sulfide gas to the 1, 4-butanediol is 6:1, reacting for 0.5h, stopping stirring and heating, and stopping introducing gas. And naturally cooling and layering, taking the upper layer solution which is a pure tetrahydrothiophene product, drying the lower layer solution at the temperature of 80 ℃ to obtain a mixed acid crystal, and calcining the mixed acid crystal in a muffle furnace at the temperature of 300 ℃ for 4 hours for recycling.
FIG. 1 is a graph showing the change of the concentration of each component in the solution of example 1 with time, which is obtained by taking a small amount of sample solution at each time point, diluting the sample solution by 50 times with ethanol, measuring the content by gas chromatography, and fitting a curve, and it can be seen that the raw materials and the intermediate products in the solution have reacted completely at 30min, and only water and the target product tetrahydrothiophene have remained.
The determination shows that the conversion rate of the raw material 1, 4-butanediol reaches 100%, the purity of the product tetrahydrothiophene reaches 99.7%, and the reaction selectivity reaches 100%.
Example 2
Method for preparing tetrahydrothiophene by adopting double-component catalyst
(1) Weighing 0.29g of phosphomolybdic vanadate and 0.21g of silicotungstic vanadate, mixing, calcining and activating in a muffle furnace at 200 ℃ for 5 hours, and then cooling in a nitrogen atmosphere;
(2) weighing 100.0g of 1, 4-butanediol, pouring into a reactor, adding the mixed acid catalyst activated in the step (1), starting stirring and heating, heating to 200 ℃, continuously introducing hydrogen sulfide gas, wherein the molar ratio of the total amount of the introduced hydrogen sulfide gas to the 1, 4-butanediol is 6:1, reacting for 1 hour, stopping stirring and heating, and stopping introducing gas. And naturally cooling and layering, taking the upper layer solution which is a pure tetrahydrothiophene product, drying the lower layer solution at the temperature of 80 ℃ to obtain a mixed acid crystal, and calcining the mixed acid crystal in a muffle furnace at the temperature of 200 ℃ for 5 hours for recycling.
The determination shows that the conversion rate of the raw material 1, 4-butanediol reaches 98.7%, the purity of the product tetrahydrothiophene reaches 99.6%, and the reaction selectivity reaches 96.7%.
Example 3
Method for preparing tetrahydrothiophene by adopting double-component catalyst
(1) Weighing 0.51g of germanium tungstic acid and 0.27g of silicon molybdenum vanadate (the molar ratio is 1: 1), mixing, calcining and activating in a muffle furnace at 300 ℃ for 4h, and then cooling in a nitrogen atmosphere;
(2) weighing 100.0g of 1, 4-butanediol, pouring into a reactor, adding the mixed acid catalyst activated in the step (1), starting stirring and heating, heating to 180 ℃, continuously introducing hydrogen sulfide gas, wherein the molar ratio of the total amount of the introduced hydrogen sulfide gas to the 1, 4-butanediol is 5.5:1, reacting for 2 hours, stopping stirring and heating, and stopping introducing gas. And naturally cooling and layering, taking the upper layer solution which is a pure tetrahydrothiophene product, drying the lower layer solution at 80 ℃ to obtain a mixed acid crystal, and calcining the mixed acid crystal in a muffle furnace at 300 ℃ for 4 hours to recycle.
The determination shows that the conversion rate of the raw material 1, 4-butanediol reaches 97.5%, the purity of the product tetrahydrothiophene reaches 99.3%, and the reaction selectivity reaches 96.3%.
Comparative example 1
This comparative example differs from example 1 in that: addition of only Heteropoly acid 1
(1) Weighing 0.54g of phosphotungstic acid, mixing, calcining and activating in a muffle furnace at 300 ℃ for 4h, and then cooling in a nitrogen atmosphere;
(2) weighing 100.0g of 1, 4-butanediol, pouring into a reactor, adding activated mixed acid catalyst, starting stirring, heating, raising the temperature to 200 ℃, continuously introducing hydrogen sulfide gas, reacting for 0.5h, stopping stirring and heating, and stopping introducing gas. And naturally cooling and layering, and taking the upper layer solution to obtain the tetrahydrothiophene.
In the comparative example, only heteropoly acid 1 is added, the reaction speed of the reaction is high in the first stage, but the reaction basically stays in the first stage, the yield of the target product generated in the second stage is extremely low, the product mainly comprises tetrahydrofuran, and the purity of tetrahydrothiophene in the product is less than 5%.
Comparative example 2
The comparative example differs from example 1 in that: addition of only heteropolyacid 2
(1) Weighing 0.54g of silicotungstic acid, mixing, calcining and activating in a muffle furnace at 300 ℃ for 4h, and then cooling in a nitrogen atmosphere;
(2) weighing 100.0g of 1, 4-butanediol, pouring into a reactor, adding activated mixed acid catalyst, starting stirring, heating, raising the temperature to 200 ℃, continuously introducing hydrogen sulfide gas, reacting for 0.5h, stopping stirring and heating, and stopping introducing gas. And naturally cooling and layering, and taking the upper layer solution to obtain the tetrahydrothiophene.
In the comparative example, only heteropoly acid 2 is added, the reaction speed of the reaction in the first stage is greatly reduced, so that the overall reaction speed is reduced, the conversion rate of 1, 4-butanediol is 70 percent, and the used time is about 4 times of the used time of the double-component heteropoly acid under the same conditions
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing tetrahydrothiophene by adopting a two-component catalyst is characterized by comprising the following steps: the method comprises the following steps: weighing heteropoly acid 1 and heteropoly acid 2, mixing, calcining and activating to prepare a two-component catalyst; 1, 4-butanediol is dehydrated and cyclized in a catalytic molecule of the two-component catalyst under the heating condition to generate tetrahydrofuran, and then the tetrahydrofuran reacts with hydrogen sulfide under the catalytic action of the two-component catalyst under the same condition to generate a target product, namely tetrahydrothiophene; wherein the heteropoly acid 1 is one of phosphotungstic acid, phosphotungstomolybdic acid, phosphomolybdic acid, germanium tungstic acid and germanium vanadic acid; the heteropoly acid 2 is one of silicotungstic acid, silicotungstovanadic acid, silicomolybdic vanadate and phosphomolybdic acid.
2. The method for preparing tetrahydrothiophene according to claim 1, wherein said method comprises the steps of: the method for preparing tetrahydrothiophene by adopting the two-component catalyst comprises the following steps:
(1) weighing heteropoly acid 1 and heteropoly acid 2, mixing, placing in a muffle furnace for calcining and activating for 4-5h, and then cooling under the condition of nitrogen to prepare a bi-component catalyst;
(2) adding 1, 4-butanediol into a reactor, adding the double-component catalyst prepared in the step (1), heating to a reaction temperature, stirring, introducing hydrogen sulfide gas, wherein the molar ratio of the total amount of the introduced hydrogen sulfide gas to the 1, 4-butanediol is not less than 5:1, stopping introducing gas, stirring and heating after reacting for 0.5-2h, cooling, standing, and taking an upper layer solution which is tetrahydrothiophene after the solution is layered.
3. The method for preparing tetrahydrothiophene according to claim 1, wherein said method comprises the steps of: the heteropoly acid 1 is phosphotungstic acid.
4. The method for preparing tetrahydrothiophene according to claim 2, wherein said method comprises the steps of: the molar ratio of the heteropoly acid 1 to the heteropoly acid 2 is 1: 9-7: 3.
5. The method for preparing tetrahydrothiophene according to claim 2, wherein said method comprises the steps of: the calcination activation temperature in the step (1) is 150-600 ℃.
6. The method for preparing tetrahydrothiophene according to claim 2, wherein said method comprises the steps of: the mass ratio of the 1, 4-butanediol to the two-component catalyst in the step (2) is 50: 1-500: 1.
7. The method for preparing tetrahydrothiophene according to claim 2, wherein said method comprises the steps of: the reaction temperature in the step (2) is 160-260 ℃.
8. The method for preparing tetrahydrothiophene according to claim 2, wherein said method comprises the steps of: and (3) drying and calcining the lower layer solution in the step (2) to obtain the mixed heteropoly acid catalyst.
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2020
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