Production method of petroleum-based thiophane

Abstract

The invention discloses a production method of petroleum-based tetrahydrothiophene, and belongs to the technical field of fine chemicals. Liquid sulfur and hydrogen in the stone chemical engineering process are used as raw materials to synthesize hydrogen sulfide, meanwhile, butane in the stone chemical engineering process is subjected to air oxidation to prepare maleic anhydride, the maleic anhydride is used as a raw material and subjected to a catalytic reaction with hydrogen to synthesize tetrahydrofuran and gamma-butyrolactone, and tetrahydrofuran and hydrogen sulfide are subjected to a catalytic reaction to synthesize tetrahydrothiophene. Compared with a direct catalysis process adopting tetrahydrofuran and hydrogen sulfide, the process has the advantages that the variety of high value-added products is various, the production cost is low, the safety of the production process is high, and the petroleum-based fine chemical industry chain is extended.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fine chemicals, and particularly relates to a production method of petroleum-based tetrahydrothiophene. BACKGROUND

[0002] Tetrahydrothiophene is an important organic chemical intermediate, which is used as a warning agent for gas due to its unique taste. In addition, tetrahydrothiophene has been widely used in the fields of medicine, pesticide, material auxiliary intermediate, etc.

[0003] There are mainly three methods for producing tetrahydrothiophene: (1) Thiophene catalytic hydrogenation method, which uses thiophene as raw material to synthesize tetrahydrothiophene through catalytic hydrogenation reduction reaction. However, this process has problems such as high price of thiophene raw material, high price of catalyst, complex process conditions, high production cost, and no obvious market advantage; (2) 1,4-dibromobutane direct thio method, which uses 1,4-dibromobutane and sodium sulfide containing crystallization water as raw materials, and ethanol as solvent to generate tetrahydrothiophene under the action of iodine catalyst. However, water is generated in this reaction process, which is difficult to separate from the product; (3) Tetrahydrofuran direct thio method, which uses tetrahydrofuran to directly react with hydrogen sulfide to generate tetrahydrothiophene under the action of solid acid catalyst.

[0004] Both tetrahydrofuran and hydrogen sulfide are dangerous chemicals, and there are safety risks in the storage and use of raw materials in the production process. At the same time, there are problems such as high cost of tetrahydrothiophene and low selectivity of tetrahydrothiophene. SUMMARY

[0005] In view of the technical problems existing in the process of directly sulfidizing tetrahydrofuran to prepare tetrahydrothiophene, the present application synthesizes tetrahydrofuran and gamma-butyrolactone from butane in the petroleum refining process by air oxidation to prepare maleic anhydride as raw material and hydrogen through catalytic reaction. Tetrahydrofuran reacts with hydrogen sulfide through catalytic reaction to synthesize tetrahydrothiophene. Butane as raw material is non-toxic, and there is mature storage and transportation technology in industry. The path from butane to tetrahydrothiophene is through step-by-step reaction, which uses low-toxicity raw materials and mature process, and has higher overall safety. At the same time, hydrogen sulfide is derived from sulfur and hydrogen in petroleum chemical industry. The path from butane to tetrahydrothiophene can produce maleic anhydride, tetrahydrofuran and gamma-butyrolactone at the same time, which can realize on-demand production and can alleviate the storage risk of tetrahydrothiophene product and the storage risk of hydrogen sulfide raw material.

[0006] The present application provides the following technical solutions: A production method of petroleum-based tetrahydrothiophene, comprising the following steps: (1) using hydrogen and liquid sulfur as raw materials to synthesize hydrogen sulfide through catalytic reaction; (2) Butane is oxidized by air to produce succinic anhydride as a raw material, and hydrogen gas is used to synthesize tetrahydrofuran and gamma-butyrolactone through catalytic reaction; (3) Tetrahydrofuran is further reacted with hydrogen sulfide to synthesize tetrahydrothiophene through catalytic reaction.

[0007] In some embodiments, in step (1), the hydrogen gas and liquid sulfur are derived from a petrochemical refining process.

[0008] In some embodiments, in step (1), the catalytic reaction uses a carbon-supported catalyst, including one of iron sulfate-copper sulfate, iron nitrate-copper nitrate, iron phosphate-copper phosphate, and iron chloride-copper chloride; preferably, the catalytic reaction temperature is 300-400℃; preferably, the molar ratio of hydrogen gas to liquid sulfur is 1:(1-1.2).

[0009] In some embodiments, in step (1), the carbon-supported catalyst is prepared by impregnating the carbon carrier, active component, and water in equal volumes, drying, and calcining to obtain the carbon-supported catalyst. Preferably, the mass ratio of the active component to the carbon carrier is 1-4:10, and the molar ratio of iron in the iron compound to copper in the copper compound in the active component is 1-4:2; preferably, the drying temperature is 100-120℃, the drying time is 4-24h, the calcination temperature in a nitrogen atmosphere is 450-650℃, and the calcination time is 4-12h.

[0010] In some embodiments, in step (2), the succinic anhydride is synthesized by butane oxidation method, wherein the butane and hydrogen gas are derived from a petroleum refining process.

[0011] In some embodiments, in step (2), the catalytic reaction uses a carbon-supported catalyst, including one of nickel sulfate-copper nitrate, nickel oxalate-zinc sulfate, nickel nitrate-iron chloride, and nickel chloride-cobalt oxalate.

[0012] In some embodiments, in step (2), the carbon-supported catalyst is prepared by impregnating the carbon carrier, active component, and water in equal volumes, drying, and calcining to obtain the carbon-supported catalyst. Preferably, the mass ratio of the active component to the carbon carrier is 1-4:10, and the molar ratio of nickel in the nickel compound to other metals in the other metal compound in the active component is 1-10:1; preferably, the drying temperature is 100-120℃, the drying time is 4-24h, the calcination temperature in a nitrogen atmosphere is 450-650℃, and the calcination time is 4-12h.

[0013] In some embodiments, in step (2), the reaction temperature of the catalytic reaction is 180-300℃, the reaction pressure is 3-10Mpa, the reaction time is 1-20min, and the molar ratio of succinic anhydride to hydrogen gas is 1:(1.1-1.3).

[0014] In some embodiments, in step (3), the catalytic reaction uses a gamma-alumina supported catalyst, including one of iron sulfate-tungstic acid-sodium niobate, iron nitrate-tungstic acid-sodium tantalate, iron chloride-pyrophosphoric acid-ammonium vanadate, cobalt sulfate-tungstic acid-sodium niobate, cobalt nitrate-tungstic acid-sodium tantalate, cobalt chloride-pyrophosphoric acid-ammonium vanadate, copper sulfate-tungstic acid-sodium niobate, copper nitrate-tungstic acid-sodium tantalate, copper phosphate-molybdic acid, zinc nitrate-tungstic acid-sodium tantalate.

[0015] In some embodiments, in step (3), the gamma-alumina supported catalyst is prepared by impregnating the gamma-alumina carrier, active component and water in equal volume, drying and calcining to obtain the gamma-alumina supported catalyst. Preferably, the mass ratio of the active component to the gamma-alumina carrier is 1-4:10, wherein the active component conforms to the type of A-B-C, and the molar ratio of A, B and C is (1-3):1:(1-2), and the drying temperature is preferably 100-120℃, and the drying time is 4-24h.

[0016] In some embodiments, in step (3), the catalytic reaction uses a fixed bed reactor, the reaction temperature is 220-300℃, the reaction time is 1-20min, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:(1.1-1.3).

[0017] In some embodiments, the process flow of the method for producing petroleum-based tetrahydrothiophene according to the present application is as shown in Figure 1 The partial hydrogen and liquid sulfur are integrated into the hydrogen sulfide preparation device (1), the reaction generates hydrogen sulfide, and the hydrogen sulfide buffer tank (2); the maleic anhydride and partial hydrogen are integrated into the reactor (3) for reaction, the crude product stream after reaction is washed in the washing tower (4), wherein the unreacted hydrogen is recycled, the product stream after washing is subjected to rectification in the rectification tower (5) to obtain tetrahydrofuran (product 1) and gamma-butyrolactone (product 2); the tetrahydrofuran and the hydrogen sulfide from the hydrogen sulfide buffer tank (2) are integrated into the premixer (6), mixed and then introduced into the fixed bed reactor (7) to generate tetrahydrothiophene crude product, which is further purified by the crude product tank (8) and the rectification tower (9) to obtain refined tetrahydrothiophene (product 3).

[0018] The present application uses the by-product liquid sulfur, hydrogen and maleic anhydride in petroleum refining engineering as raw materials, uses self-made catalyst, and generates tetrahydrothiophene, tetrahydrofuran and gamma-butyrolactone high-value products through a series of chemical reactions. The production method of the present application overcomes the problems of high production cost, low selectivity of tetrahydrothiophene and low safety of production process.

[0019] The present application has low production cost, mainly adopts butane-tetrahydrothiophene path, wherein, butane raw material is stable and low in cost, three intermediate products can be sold as products, and can also be used as raw materials for series chemical reactions.

[0020] The present application has high selectivity of tetrahydrothiophene, mainly because in the whole catalytic reaction process, the material ratio of tetrahydrofuran to hydrogen sulfide is excess of tetrahydrofuran, and under the catalytic reaction of the series of catalysts, the selectivity of tetrahydrothiophene is higher.

[0021] The present application has high safety in production process, mainly because of butane-tetrahydrothiophene path, wherein, the intermediate production path is mature technology, but after innovative improvement of the catalyst, the reaction temperature and pressure are reduced. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The production process flow chart of coal-based tetrahydrothiophene of the present application is shown.

[0023] In the drawings, 1: hydrogen sulfide preparation integrated equipment; 2: hydrogen sulfide buffer tank; 3: reaction column; 4: washing column; 5: rectifying column a; 6: premixer; 7: fixed bed reactor; 8: crude product tank; 9: rectifying column b. DETAILED DESCRIPTION

[0024] The following detailed description is exemplary in nature and is intended to provide further description of the present application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0025] Example 1 The following process flow is used to prepare tetrahydrothiophene: Figure 1 ):part of hydrogen and liquid sulfur are added into hydrogen sulfide preparation integrated equipment (1) to generate hydrogen sulfide, the hydrogen sulfide buffer tank (2); maleic anhydride and part of hydrogen are added into the reactor (3) to react, the crude product stream after reaction is washed in the washing column (4), wherein, the unreacted hydrogen is recycled, the product stream after washing is distilled in the rectifying column (5) to prepare tetrahydrofuran (product 1) and γ-butyrolactone (product 2); tetrahydrofuran and hydrogen sulfide from the hydrogen sulfide buffer tank (2) are added into the premixer (6), after mixing, they are added into the fixed bed reactor (7) to react to generate tetrahydrothiophene crude product, which is purified through the crude product tank (8) and the rectifying column (9) to obtain refined tetrahydrothiophene (product 3).

[0026] In step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is carbon-supported iron sulfate-copper sulfate catalyst, the catalytic reaction temperature is 300℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1; The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by the equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:10, the molar ratio of iron in the iron sulfate and copper in the copper sulfate is 1:2, the drying temperature is 100°C, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 4h.

[0027] In step (2), maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and γ-butyrolactone under certain conditions. The catalyst is a carbon-supported nickel sulfate-copper nitrate catalyst, and the reactor is used for the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran, wherein the reaction temperature is 180°C, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0028] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by the equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:5, the molar ratio of nickel in the nickel sulfate and copper in the copper nitrate is 1:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0029] In step (3), tetrahydrofuran is further catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is a gamma-alumina-supported iron sulfate-tungstic acid-sodium niobate catalyst, the reaction temperature is 220°C, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0030] The gamma-alumina-supported iron sulfate-tungstic acid-sodium niobate catalyst in step (3) is prepared by the equal-volume impregnation method. The active component and the gamma-alumina are mixed in water at a mass ratio of 3:10, the molar ratio of iron sulfate, tungstic acid, and sodium niobate is 1:1:2, the drying temperature is 110°C, and the drying time is 4h.

[0031] Comparative Example 1 A process similar to that of Example 1 is used to prepare tetrahydrothiophene, wherein in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is a carbon-supported iron sulfate catalyst, the catalytic reaction temperature is 300°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported iron sulfate catalyst in step (1) is prepared by the equal-volume impregnation method. Iron sulfate and carbon carrier are mixed in water at a mass ratio of 1:10, the drying temperature is 100°C, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 4h.

[0032] Step (2), under certain conditions, maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and gamma-butyrolactone. The catalyst is carbon-supported nickel sulfate-copper nitrate catalyst, and the reactor is used for the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran, wherein the reaction temperature is 180℃, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0033] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by an equal volume impregnation method. The active components and the carbon carrier are mixed in water in a mass ratio of 1:5, wherein the molar ratio of nickel in nickel sulfate to copper in copper nitrate is 1:1, the drying temperature is 120℃, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 6h.

[0034] Step (3), tetrahydrofuran is catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is gamma alumina-supported iron sulfate-tungstic acid-sodium niobate catalyst, the reaction temperature is 220℃, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0035] The gamma alumina-supported iron sulfate-tungstic acid-sodium niobate catalyst in step (3) is prepared by an equal volume impregnation method. The active components and the gamma alumina are mixed in water in a mass ratio of 3:10, wherein the molar ratio of iron sulfate, tungstic acid and sodium niobate is 1:1:2, the drying temperature is 110℃, and the drying time is 4h.

[0036] Comparative Example 2 Tetrahydrothiophene is prepared by a similar process flow to Example 1, wherein in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is carbon-supported copper sulfate catalyst, the catalytic reaction temperature is 300℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported copper sulfate catalyst in step (1) is prepared by an equal volume impregnation method. Copper sulfate and a carbon carrier are mixed in water in a mass ratio of 1:10, the drying temperature is 100℃, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 4h.

[0037] Step (2), under certain conditions, maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and gamma-butyrolactone. The catalyst is carbon-supported nickel sulfate-copper nitrate catalyst, and the reactor is used for the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran, wherein the reaction temperature is 180℃, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0038] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by the equal volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:5, the molar ratio of nickel in nickel sulfate to copper in copper nitrate is 1:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0039] In step (3), tetrahydrofuran is synthesized by catalytic reaction of maleic anhydride and hydrogen. The catalyst is a carbon-supported nickel sulfate catalyst. The synthesis of tetrahydrofuran from maleic anhydride and hydrogen is carried out in a reactor, the reaction temperature is 180°C, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0040] The carbon-supported nickel sulfate catalyst in step (2) is prepared by the equal volume impregnation method. Nickel sulfate and the carbon carrier are mixed in water at a mass ratio of 1:5, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0041] Comparative Example 3 Tetrahydrothiophene is prepared by a similar process flow to Example 1. In step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, and the catalyst is a carbon-supported iron sulfate-copper sulfate catalyst. The catalytic reaction temperature is 300°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by the equal volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:10, the molar ratio of iron in iron sulfate to copper in copper sulfate is 1:2, the drying temperature is 100°C, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 4h.

[0042] In step (2), maleic anhydride and hydrogen are catalytically reacted under certain conditions to synthesize tetrahydrofuran and γ-butyrolactone. The catalyst is a carbon-supported nickel sulfate catalyst. The synthesis of tetrahydrofuran from maleic anhydride and hydrogen is carried out in a reactor, the reaction temperature is 180°C, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0043] The carbon-supported nickel sulfate catalyst in step (2) is prepared by the equal volume impregnation method. Nickel sulfate and the carbon carrier are mixed in water at a mass ratio of 1:5, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0044] In step (3), tetrahydrofuran is synthesized by catalytic reaction of maleic anhydride and hydrogen. The catalyst is a carbon-supported nickel sulfate catalyst. The synthesis of tetrahydrofuran from maleic anhydride and hydrogen is carried out in a reactor, the reaction temperature is 180°C, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0045] The gamma-alumina supported iron sulfate-tungstic acid-sodium niobate catalyst in step (3) is prepared by the equal volume impregnation method. The active components and the gamma-alumina are mixed in water at a mass ratio of 3:10, wherein the molar ratio of iron sulfate, tungstic acid and sodium niobate is 1:1:2, the drying temperature is 110°C, and the drying time is 4h.

[0046] Comparative Example 4 The tetrahydrothiophene is prepared by using a similar process flow to that in Example 1, wherein in step (1), hydrogen sulfide is synthesized from hydrogen and liquid sulfur, the catalyst is a carbon supported iron sulfate-copper sulfate catalyst, the catalytic reaction temperature is 300°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon supported iron sulfate-copper sulfate catalyst in step (1) is prepared by the equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 1:10, wherein the molar ratio of iron in iron sulfate to copper in copper sulfate is 1:2, the drying temperature is 100°C, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 4h.

[0047] In step (2), tetrahydrofuran and gamma-butyrolactone are synthesized from maleic anhydride and hydrogen under certain conditions through a catalytic reaction. The catalyst is a carbon supported nickel sulfate catalyst, and the synthesis of tetrahydrofuran from maleic anhydride and hydrogen is carried out in a reactor, wherein the reaction temperature is 180°C, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0048] The carbon supported nickel sulfate catalyst in step (2) is prepared by the equal volume impregnation method. Nickel sulfate and the carbon carrier are mixed in water at a mass ratio of 1:5, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0049] In step (3), tetrahydrothiophene is synthesized from tetrahydrofuran and hydrogen sulfide through a catalytic reaction. The catalyst is a gamma-alumina supported iron sulfate-tungstic acid-sodium niobate catalyst, the reaction temperature is 220°C, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0050] The gamma-alumina supported iron sulfate-tungstic acid-sodium niobate catalyst in step (3) is prepared by the equal volume impregnation method. The active components and the gamma-alumina are mixed in water at a mass ratio of 3:10, wherein the molar ratio of iron sulfate, tungstic acid and sodium niobate is 1:1:2, the drying temperature is 110°C, and the drying time is 4h.

[0051] Comparative Example 5 The similar process flow of Example 1 is used to prepare tetrahydrothiophene, wherein in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is carbon-supported iron sulfate-copper sulfate catalyst, the catalytic reaction temperature is 300℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by an equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 1:10, wherein the molar ratio of iron in iron sulfate to copper in copper sulfate is 1:2, the drying temperature is 100℃, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 4h.

[0052] In step (2), maleic anhydride and hydrogen are catalytically reacted under certain conditions to synthesize tetrahydrofuran and gamma-butyrolactone. The catalyst is a carbon-supported nickel sulfate-copper nitrate catalyst, and the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran uses a reactor, wherein the reaction temperature is 180℃, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0053] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by an equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 1:5, wherein the molar ratio of nickel in nickel sulfate to copper in copper nitrate is 1:1, the drying temperature is 120℃, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 6h.

[0054] In step (3), tetrahydrofuran is further catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is a gamma-alumina supported iron sulfate catalyst, the reaction temperature is 220℃, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0055] The gamma-alumina supported iron sulfate catalyst in step (3) is prepared by an equal volume impregnation method. Iron sulfate and gamma-alumina are mixed in water at a mass ratio of 3:10, and the drying temperature is 110℃ and the drying time is 4h.

[0056] Comparative Example 6 The similar process flow of Example 1 is used to prepare tetrahydrothiophene, wherein in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is carbon-supported iron sulfate-copper sulfate catalyst, the catalytic reaction temperature is 300℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by the equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:10, the molar ratio of iron in the iron sulfate to copper in the copper sulfate is 1:2, the drying temperature is 100°C, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 4h.

[0057] In step (2), maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and γ-butyrolactone under certain conditions. The catalyst is a carbon-supported nickel sulfate-copper nitrate catalyst, and the reactor is used for the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran, wherein the reaction temperature is 180°C, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0058] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by the equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:5, the molar ratio of nickel in the nickel sulfate to copper in the copper nitrate is 1:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0059] In step (3), tetrahydrofuran is further catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is a gamma-alumina supported tungstic acid catalyst, the reaction temperature is 220°C, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0060] The gamma-alumina supported tungstic acid catalyst in step (3) is prepared by the equal-volume impregnation method. Tungstic acid and gamma-alumina are mixed in water at a mass ratio of 3:10, the drying temperature is 110°C, and the drying time is 4h.

[0061] Comparative Example 7 A similar process flow to Example 1 is used to prepare tetrahydrothiophene, wherein in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is a carbon-supported iron sulfate-copper sulfate catalyst, the catalytic reaction temperature is 300°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by the equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:10, the molar ratio of iron in the iron sulfate to copper in the copper sulfate is 1:2, the drying temperature is 100°C, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 4h.

[0062] Step (2), under certain conditions, maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and gamma-butyrolactone. The catalyst is carbon-supported nickel sulfate-copper nitrate catalyst, and the reactor is used for the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran, wherein the reaction temperature is 180℃, the reaction pressure is 3Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0063] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by an equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:5, the molar ratio of nickel in nickel sulfate to copper in copper nitrate is 1:1, the drying temperature is 120℃, the drying time is 6h, and the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 6h.

[0064] Step (3), tetrahydrofuran is catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is gamma alumina supported sodium niobate catalyst, the reaction temperature is 220℃, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0065] The gamma alumina supported sodium niobate catalyst in step (3) is prepared by an equal-volume impregnation method. Sodium niobate and gamma alumina are mixed in water at a mass ratio of 3:10, the drying temperature is 110℃, and the drying time is 4h.

[0066] Example 2 A similar process flow to Example 1 is used to prepare tetrahydrothiophene, wherein step (1) hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide, the catalyst is carbon-supported iron sulfate-copper sulfate catalyst, the catalytic reaction temperature is 350℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.1. The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by an equal-volume impregnation method. The active component and the carbon carrier are mixed in water at a mass ratio of 1:10, the molar ratio of iron in iron sulfate to copper in copper sulfate is 1:2, the drying temperature is 100℃, the drying time is 4h, the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 4h.

[0067] Step (2), under certain conditions, maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and gamma-butyrolactone. The catalyst is carbon-supported nickel sulfate-copper nitrate catalyst, and the reactor is used for the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran, wherein the reaction temperature is 300℃, the reaction pressure is 4Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.1.

[0068] The carbon-supported nickel sulfate-copper nitrate catalyst in step (2) is prepared by the equal-volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 1:5, the molar ratio of nickel in the nickel sulfate and copper in the copper nitrate is 1:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 6h.

[0069] In step (3), tetrahydrofuran is synthesized by catalytic reaction of hydrogen sulfide. The catalyst is a gamma-alumina-supported zinc nitrate-tungstic acid-sodium tantalate catalyst, the reaction temperature is 270°C, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0070] The gamma-alumina-supported zinc nitrate-tungstic acid-sodium tantalate catalyst in step (3) is prepared by the equal-volume impregnation method. The active components and the gamma-alumina are mixed in water at a mass ratio of 3:10, the molar ratio of zinc nitrate, tungstic acid, and sodium tantalate is 1:1:2, the drying temperature is 110°C, and the drying time is 4h.

[0071] Example 3 A similar process flow to Example 1 is used to prepare tetrahydrothiophene, wherein hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide in step (1), the catalyst is a carbon-supported iron nitrate-copper nitrate catalyst, the catalytic reaction temperature is 400°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.2. The carbon-supported iron nitrate-copper nitrate catalyst in step (1) is prepared by the equal-volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 2:5, the molar ratio of iron in the iron nitrate and copper in the copper nitrate is 3:2, the drying temperature is 120°C, the drying time is 12h, the nitrogen atmosphere calcination temperature is 550°C, and the calcination time is 12h.

[0072] In step (2), maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and γ-butyrolactone under certain conditions. The catalyst is a carbon-supported nickel oxalate-zinc sulfate catalyst, the reaction temperature for synthesizing tetrahydrofuran from maleic anhydride and hydrogen is 180°C, the reaction pressure is 6Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.2.

[0073] The carbon-supported nickel oxalate-zinc sulfate catalyst in step (2) is prepared by the equal-volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 2:5, the molar ratio of nickel in the nickel oxalate and zinc in the zinc sulfate is 5:1, the drying temperature is 115°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 600°C, and the calcination time is 8h.

[0074] Step (3) tetrahydrofuran is reacted with hydrogen sulfide to synthesize tetrahydrothiophene through catalysis. The catalyst is a gamma alumina supported iron nitrate-tungstic acid-sodium tantalate catalyst, the reaction temperature is 290°C, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.3.

[0075] The gamma alumina supported iron nitrate-tungstic acid-sodium tantalate catalyst in step (3) is prepared by an equal volume impregnation method. The active components and gamma alumina are mixed in water at a mass ratio of 3:10, wherein the molar ratio of iron nitrate, tungstic acid and sodium tantalate is 2:1:2, the drying temperature is 115°C, and the drying time is 7h.

[0076] Example 4 A similar process flow to Example 1 is used to prepare tetrahydrothiophene, wherein in step (1) hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide under certain conditions, and the catalyst is a carbon supported iron phosphate-copper phosphate catalyst, the catalytic reaction temperature is 400°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.2. The carbon supported iron phosphate-copper phosphate catalyst in step (1) is prepared by an equal volume impregnation method. The active components and carbon support are mixed in water at a mass ratio of 2:5, wherein the molar ratio of iron in iron phosphate to copper in copper phosphate is 1:1, the drying temperature is 120°C, the drying time is 12h, the nitrogen atmosphere calcination temperature is 450°C, and the calcination time is 11h.

[0077] Step (2) under certain conditions, maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and γ-butyrolactone. The catalyst is a carbon supported nickel nitrate-iron chloride catalyst, and the synthesis of tetrahydrofuran from maleic anhydride and hydrogen is carried out in a reactor, wherein the reaction temperature is 250°C, the reaction pressure is 10Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.3.

[0078] The carbon supported nickel nitrate-iron chloride catalyst in step (2) is prepared by an equal volume impregnation method. The active components and carbon support are mixed in water at a mass ratio of 3:10, wherein the molar ratio of nickel in nickel nitrate to iron in iron chloride is 7:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 8h.

[0079] Step (3) tetrahydrofuran is reacted with hydrogen sulfide to synthesize tetrahydrothiophene through catalysis. The catalyst is a gamma alumina supported iron nitrate-tungstic acid-sodium tantalate catalyst, the reaction temperature is 290°C, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.3.

[0080] The gamma-alumina supported ferric chloride-phosphotungstic acid catalyst in step (3) is prepared by the equal volume impregnation method. The active components and the gamma-alumina are mixed in water at a mass ratio of 3:10, wherein the molar ratio of ferric chloride, phosphotungstic acid and ammonium vanadate is 2:1:2, the drying temperature is 115°C, and the drying time is 7h.

[0081] Example 5 The tetrahydrothiophene is prepared by using the similar process flow as in Example 1, wherein in step (1), hydrogen sulfide is synthesized from hydrogen and liquid sulfur under certain conditions, the catalyst is carbon supported iron oxide-copper oxide catalyst, the catalytic reaction temperature is 360°C, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.2. The carbon supported iron oxide-copper oxide catalyst in step (1) is prepared by the equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 2:5, wherein the molar ratio of iron in the iron oxide to copper in the copper oxide is 1:1, the drying temperature is 120°C, the drying time is 12h, the nitrogen atmosphere calcination temperature is 450°C, and the calcination time is 11h.

[0082] In step (2), furan and gamma-butyrolactone are synthesized from maleic anhydride and hydrogen through catalytic reaction under certain conditions. The catalyst is carbon supported nickel nitrate-iron chloride catalyst, the synthesis of furan from maleic anhydride and hydrogen uses a reactor, wherein the reaction temperature is 270°C, the reaction pressure is 8Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.3.

[0083] The carbon supported nickel nitrate-iron chloride catalyst in step (2) is prepared by the equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 3:10, wherein the molar ratio of nickel in the nickel nitrate to iron in the iron chloride is 5:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 8h.

[0084] In step (3), tetrahydrothiophene is synthesized from furan and hydrogen sulfide through catalytic reaction. The catalyst is gamma-alumina supported ferric chloride-phosphotungstic acid catalyst, the reaction temperature is 240°C, and the molar ratio of furan to hydrogen sulfide is 1:1.2.

[0085] The gamma-alumina supported ferric chloride-phosphotungstic acid catalyst in step (3) is prepared by the equal volume impregnation method. The active components and the gamma-alumina are mixed in water at a mass ratio of 3:10, wherein the molar ratio of ferric chloride, phosphotungstic acid and ammonium vanadate is 3:1:2, the drying temperature is 110°C, and the drying time is 7h.

[0086] Example 6 The similar process flow of Example 1 is adopted to prepare tetrahydrothiophene, wherein, in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide under certain conditions, the catalyst is carbon-supported iron phosphate-copper phosphate catalyst, the catalytic reaction temperature is 400℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.2; The carbon-supported iron phosphate-copper phosphate catalyst in step (1) is prepared by an equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 2:5, wherein the molar ratio of iron in iron phosphate to copper in copper phosphate is 1:1, the drying temperature is 120℃, the drying time is 12h, the nitrogen atmosphere calcination temperature is 450℃, and the calcination time is 11h.

[0087] In step (2), maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and gamma-butyrolactone under certain conditions. The catalyst is carbon-supported nickel oxalate-zinc sulfate catalyst, and the reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran uses a reactor, wherein the reaction temperature is 250℃, the reaction pressure is 7.5Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.2.

[0088] The carbon-supported nickel oxalate-zinc sulfate catalyst in step (2) is prepared by an equal volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 3:10, wherein the molar ratio of nickel in nickel oxalate to zinc in zinc sulfate is 3:1, the drying temperature is 120℃, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650℃, and the calcination time is 8h.

[0089] In step (3), tetrahydrofuran is further catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is gamma alumina supported cobalt chloride- pyrophosphoric acid-ammonium vanadate catalyst, the reaction temperature is 270℃, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0090] The gamma alumina supported cobalt chloride-pyrophosphoric acid-ammonium vanadate catalyst in step (3) is prepared by an equal volume impregnation method. The active components and the gamma alumina are mixed in water at a mass ratio of 3:10, wherein the molar ratio of cobalt chloride, pyrophosphoric acid, and ammonium vanadate is 2:1:2, the drying temperature is 110℃, and the drying time is 7h.

[0091] Example 7 The similar process flow of Example 1 is adopted to prepare tetrahydrothiophene, wherein, in step (1), hydrogen and liquid sulfur are used as raw materials to synthesize hydrogen sulfide under certain conditions, the catalyst is carbon-supported iron phosphate-copper phosphate catalyst, the catalytic reaction temperature is 400℃, the catalytic reaction pressure is the production system pressure, and the molar ratio of hydrogen to liquid sulfur is 1:1.2; The carbon-supported iron sulfate-copper sulfate catalyst in step (1) is prepared by the equal-volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 2:5, the molar ratio of iron in the iron sulfate and copper in the copper sulfate is 1:2, the drying temperature is 120°C, the drying time is 12h, the nitrogen atmosphere calcination temperature is 450°C, and the calcination time is 11h.

[0092] In step (2), maleic anhydride and hydrogen are catalytically reacted to synthesize tetrahydrofuran and γ-butyrolactone under certain conditions. The catalyst is a carbon-supported nickel oxalate-zinc sulfate catalyst. The reaction of maleic anhydride and hydrogen to synthesize tetrahydrofuran uses a reactor, the reaction temperature is 300°C, the reaction pressure is 6.5Mpa, and the molar ratio of maleic anhydride to hydrogen is 1:1.2.

[0093] The carbon-supported nickel oxalate-zinc sulfate catalyst in step (2) is prepared by the equal-volume impregnation method. The active components and the carbon carrier are mixed in water at a mass ratio of 3:10, the molar ratio of nickel in the nickel oxalate and zinc in the zinc sulfate is 3:1, the drying temperature is 120°C, the drying time is 6h, the nitrogen atmosphere calcination temperature is 650°C, and the calcination time is 8h.

[0094] In step (3), tetrahydrofuran is catalytically reacted with hydrogen sulfide to synthesize tetrahydrothiophene. The catalyst is a gamma alumina-supported cobalt nitrate-tungstic acid-sodium tantalate catalyst, the reaction temperature is 270, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:1.2.

[0095] The gamma alumina-supported cobalt nitrate-tungstic acid-sodium tantalate catalyst in step (3) is prepared by the equal-volume impregnation method. The active components and the gamma alumina are mixed in water at a mass ratio of 3:10, the molar ratio of cobalt nitrate, tungstic acid, and sodium tantalate is 3:1:2, the drying temperature is 110°C, and the drying time is 7h.

[0096] The liquid sulfur conversion rate, hydrogen sulfide selectivity, maleic anhydride conversion rate, tetrahydrofuran selectivity, γ-butyrolactone selectivity, and tetrahydrothiophene selectivity of Examples 1-7 are shown in Table 1.

[0097] Table 1 Catalyst performance evaluation table The analysis of Example 1, Comparative Example 1, and Comparative Example 2 shows that under the reaction conditions of 300°C, the catalytic performance of the iron-copper double metal salt composite carbon-supported catalyst in the hydrogen sulfide synthesis reaction is better than that of the corresponding single-component carbon-supported catalyst, indicating that the catalytic efficiency of the iron-copper double metal salt composite carbon-supported catalyst is higher than that of the traditional catalyst, and the traditional catalytic reaction temperature is 400-600°C.

[0098] The analysis of Example 1, Comparative Example 3 and Comparative Example 4 shows that, under certain reaction conditions, the nickel-based bimetallic salt composite carbon-supported catalyst has better catalytic performance than the corresponding single-component carbon-supported catalyst in the hydrogen sulfide synthesis reaction, which indicates that the nickel-based bimetallic salt composite carbon-supported catalyst has higher catalytic efficiency than the traditional catalyst, and the sum of the selectivity of tetrahydrofuran and gamma-butyrolactone is 100%.

[0099] The analysis of Example 1, Comparative Example 5, Comparative Example 6 and Comparative Example 7 shows that, under certain conditions, the trimetallic salt composite carbon-supported catalyst has better catalytic performance than the corresponding single-component carbon-supported catalyst in the hydrogen sulfide synthesis reaction, which also indicates that the synthesis cost of the trimetallic salt composite carbon-supported catalyst is much lower than that of the traditional noble metal catalyst.

Claims

1. A method for producing petroleum-based tetrahydrothiophene, comprising the following steps: (1) synthesizing hydrogen sulfide by catalytic reaction using hydrogen and liquid sulfur as raw materials; (2) synthesizing tetrahydrofuran and gamma-butyrolactone by catalytic reaction of butane anhydride as raw material and hydrogen; (3) synthesizing tetrahydrothiophene by catalytic reaction of tetrahydrofuran and hydrogen sulfide.

2. The production method according to claim 1, wherein, In step (1), the catalytic reaction uses a carbon-supported catalyst, including one of iron sulfate-copper sulfate, iron nitrate-copper nitrate, iron oxide-copper oxide, iron chloride-copper chloride.

3. The production method according to claim 1, wherein, In step (1), the catalytic reaction temperature is 300-400℃.

4. The production method according to claim 1, wherein, In step (1), the molar ratio of hydrogen to liquid sulfur is 1:(1-1.2).

5. The production method according to claim 1, wherein, In step (2), the catalytic reaction uses a carbon-supported catalyst, including one of nickel sulfate-copper nitrate, nickel oxalate-zinc sulfate, nickel nitrate-iron chloride, nickel chloride-cobalt oxalate.

6. The production method according to claim 1, wherein, In step (2), the reaction temperature of the catalytic reaction is 180-300℃, the reaction pressure is 3-10 Mpa, and the reaction time is 1-20 min.

7. The production method according to claim 1, wherein, In step (2), the molar ratio of butane anhydride to hydrogen is 1:(1.1-1.3).

8. The production method according to claim 1, wherein, In step (3), the catalytic reaction uses a gamma-alumina-supported catalyst, including one of iron sulfate-tungsten acid-sodium niobate, iron nitrate-tungsten acid-sodium tantalate, iron chloride-pyrophosphoric acid-ammonium vanadate, iron phosphate-molybdate, cobalt sulfate-tungsten acid-sodium niobate, cobalt nitrate-tungsten acid-sodium tantalate, cobalt chloride-pyrophosphoric acid-ammonium vanadate, cobalt phosphate-molybdate, copper sulfate-tungsten acid-sodium niobate, copper nitrate-tungsten acid-sodium tantalate, copper phosphate-molybdate, zinc sulfate-tungsten acid-sodium niobate, zinc nitrate-tungsten acid-sodium tantalate.

9. The production method according to claim 1, wherein, In step (3), the catalytic reaction uses a fixed bed reactor, the reaction temperature is 220-300℃, the reaction time is 1-20 min, and the molar ratio of tetrahydrofuran to hydrogen sulfide is 1:(1.1-1.3).

10. The production method according to claim 1, wherein, The process flow of the production method is as follows: part of hydrogen and liquid sulfur are integrated into hydrogen sulfide preparation equipment 1, and hydrogen sulfide is generated by reaction; butane anhydride and part of hydrogen are introduced into reactor 3 for reaction, the crude product stream after reaction is washed in washing tower 4, wherein the unreacted hydrogen is recycled, the product stream after washing is introduced into rectifying tower 5 for rectification to obtain tetrahydrofuran and gamma-butyrolactone; tetrahydrofuran and hydrogen sulfide from hydrogen sulfide buffer tank 2 are introduced into premixer 6, mixed and then introduced into fixed bed reactor 7 to generate crude tetrahydrothiophene, which is then purified by crude product tank 8 and rectifying tower 9 to obtain refined tetrahydrothiophene.

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