CN109569661A

CN109569661A - The preparation method of tetrathio tungstate solution and its preparation method and application and sulfurized hydrogenation catalyst

Info

Publication number: CN109569661A
Application number: CN201710910894.1A
Authority: CN
Inventors: 韩伟; 高杨; 龙湘云; 李明丰; 杨清河; 聂红; 邓中活
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-09-29
Filing date: 2017-09-29
Publication date: 2019-04-05

Abstract

The present invention relates to hydrogenation catalyst preparation fields, disclose the preparation method of a kind of tetrathio tungstate solution and its preparation method and application and sulfurized hydrogenation catalyst, the preparation method of tetrathio tungstate solution includes: that (1) mixes Tungstenic compound, organic sulphur source and water, obtains mixture；(2) mixture is reacted under the conditions of being 4-11 for 20-100 DEG C and/or pH；Wherein, organic sulphur source is the sulphur-containing substance that can be hydrolyzed under the conditions of step (1) and/or step (2).Preparation method provided by the invention is and easy to operate without using irritation and the hydrogen sulfide that is more toxic, and tetrathio tungstate solution obtained can prepare sulfurized hydrogenation catalyst directly as maceration extract without crystallization and purification.

Description

Tetrathio tungstate solution and its preparation method and application and sulfurized hydrogenation catalysis The preparation method of agent

Technical field

The present invention relates to hydrogenation catalyst preparation fields, and in particular to tetrathio tungstate solution and preparation method thereof and sulphur The preparation method of change type hydrogenation catalyst.

Background technique

Hydrogen addition technology is the production most important means of clear gusoline, and wherein efficient hydrogenation catalyst is then the core of hydrogen addition technology Heart technology.It is to help active constituent with group VIII metal Ni or Co, with γ-A1 with group vib metal W or Mo for main active component₂O₃ Or modified γ-A1₂O₃Loaded catalyst for carrier is current industrial widely used hydrogenation catalyst.Tradition preparation Technology mainly uses dipping means that the oxidized form presoma of active component is introduced to carrier duct, by aging, drying, roasting Obtain hydrogenation catalyst.Wherein, Co, Ni, Mo and W active component exist in the form of an oxide.But in actual use plus hydrogen is urged The existence form of agent active component is the oxide morphology of Co, Ni, Mo and W, and therefore, hydrogenation catalyst must pass through before Vulcanization activation, referred to as presulfurization.

Although conventional fabrication techniques obtain large-scale industrial application due to the advantages that easy to operate, at low cost, still deposit In a series of problems.On the one hand, when using oxidized form active component as presoma, no matter in dipping ageing process or in drying Roasting process, with Al₂O₃Surface often has strong interaction, is not only easy to cause active component in carrier surface point It dissipates unevenly, also results in the generation of excessive Al-O-Mo chemical bond, then cause active component to be difficult to complete cure, while easily Excessive low activity I class activity phase is formed, active metal utilization rate is low (referring to CN 103143365A).In addition, with Mo base catalyst For preparation, the presoma ion Mo that generallys use₇O₂₄ ^6-Often induce Al₂O₃Surface dissociation generates Al³⁺, then anti-therewith Anderson type heteropolyanion Al (OH) should be formed₆Mo₆O₁₈ ^3-, it is fired generation and is difficult to by the big crystal grain MoO of full cure₃ And Al₂(MoO₄)₃Species improve to be unfavorable for catalytic activity (referring to J.A.Bergwerff et al., Journal of the American Chemical Society 2004,126:14548；J.A.Bergwerff et al.,Catalysis Today 2008,130:117.), therefore, hydrogenation catalyst is difficult to realize using traditional dipping technique and has both high active component Dispersion degree and high sulphidity, cause catalytic activity ideal not to the utmost.On the other hand, pre-vulcanization process uses in conventional fabrication techniques Be " in device " sulfurization technology, i.e., first oxidized catalyst is packed into hydrogenator, then during continuous heating It is passed through hydrogen into reactor and vulcanizing agent is vulcanized, although this technology is still the technology being most widely used at present, it Still remain a series of problems: 1) vulcanization time is too long, and delay goes into operation；2) sulfidation easily causes corrosion of equipment, aging；3) Vulcanizing agent is inflammable, toxic, easily pollutes the environment；4) higher cost etc.." in device " sulfurization technology there are aiming at the problem that, CN1861258A、CN1861260A、CN101088619A、CN101088620A、CN1994567A、CN101279296A、 CN101491725A, US6365542 develop a series of " outside device " sulfurization technologies, and such technology mainly includes two lines: the A kind of technology path is first by vulcanizing agent (elementary sulfur, vegetable oil, organic sulfur compound, organic polysulfide, sulfone and sulfoxide etc.) It is introduced into using the method for distillation, melting or dipping in the gap of the hydrogenation catalyst of oxidation state, is then existed in inert gas Under thermally treated make catalyst vulcanization；Second of technology path be in special prevulcanisation-devices, in hydrogen and hydrogen sulfide or The presulfurization of oxidized catalyst is completed in the presence of labile organic sulfurizing agent.However, no matter being vulcanized using " in device ", also Be " outside device " vulcanization, be required to catalyst and first pass through oxidation state presulfurization again, cause catalyst preparation process complicated, economy compared with Difference.

To realize that Hydrobon catalyst has greater activity component dispersion degree, and guarantee active component full cure, together When avoid the problem that sulfidation exists " in device ", simplify " outside device " vulcanize route, sulfurized hydrogenation catalyst was straight in recent years It connects preparation route and has obtained more and more concerns and exploration.

The prior art mostly uses the active component predecessor of sulphided state during preparing sulfurized hydrogenation catalyst.Mesh The predecessor for being suitable as sulphided state active component of preceding report has tetrathiomolybdate, alkyl tetrathiomolybdate, tetrathio Tungstates, molybdenum trisulfide and tungsten trisulfide etc..But these compounds often exist synthesis process it is complicated, it is expensive, preparation A series of problems, such as process waste discharge is more, water-soluble effect is poor seriously limit the application of sulfide type catalyst.

US4604278 is disclosed using ammonium paramolybdate [(NH₄)₆Mo₇O₂₄·4H₂O] ammonia spirit it is anti-with hydrogen sulfide gas The method that four thio ammonium molybdate should be prepared, reaction temperature are room temperature, and the reaction time is 3 hours, to promote hydrogen sulfide gas It absorbs, improves the utilization rate of hydrogen sulfide, set sealing, band press operation (reaction pressure 1-1.5MPa) for reaction process, But its disclosed method still fails to get rid of needs and handles severe toxicity, the hydrogen sulfide gas of stench this problem.

CN105585048A reports a kind of compound using molybdenum and solid sulfurizing agent according to certain Mo/S molar ratio The method for mixing and reacting synthesis ammonium thiomolybdate in the solution, the advantages of this method are not to be related to irritation ammonium hydroxide and play The use of toxicity hydrogen sulfide gas, crystallized product high income, but to promote reaction balance mobile to ammonium thiomolybdate direction, it needs Take the mode for vacuumizing or blasting inert gas that the ammonia of generation is discharged from reaction solution during the preparation process, this is undoubtedly So that preparation process is cumbersome, energy consumption is higher, and preparation process has ammonia generation, and environment is unfriendly, in addition, the molybdenum of its report The reaction time of compound and solid sulfurizing agent is short, fails to efficiently use solid sulfurizing agent, causes wastage of material.

CN1557696A discloses a kind of tetrathio ammonium tungstate (NH₄)₂WS₄Preparation method, this method is using tungstates With ammonium sulfide (NH₄)₂S solution reaction method is prepared, it is characterised in that tungstates is using ammonium metatungstate (NH₄)₆W₇O₂₄· 4H₂O, when reaction ammonium metatungstate (NH used₄)₆W₇O₂₄·4H₂O must be through ammonia solvent, the amount of concentrated ammonia liquor used are as follows: and concentrated ammonia liquor/ Ammonium metatungstate=1-2/1 (mL/g), then again with ammonium sulfide (NH₄)₂S solution reaction, the molar ratio of both are as follows: S/W=4-6/ 1, reaction temperature are as follows: -90 DEG C of room temperature, the reaction time are as follows: 0.5-3 hours, the quiescent crystallization time are as follows: 8-24 hours；It finally will knot Crystalline substance is washed through filtering, washing and dehydrated alcohol, and purpose product tetrathio ammonium tungstate (NH can be obtained in drying at room temperature₄)₂WS₄.The party Method reaction condition mitigates, and the reaction time is short, and without handling the hydrogen sulfide gas of severe toxicity, stench, but this method is needed using thorn Swash the ammonium hydroxide and ammonium sulfide solution of property tanginess, and the yield of the tetrathio ammonium tungstate of the preparation method is up for further It improves.

CN105800691A reports a kind of preparation method of tetrathio ammonium tungstate, which is characterized in that the preparation method includes: by one Quantitative ammonium sulfide solution is added in the compound of tungsten, controls W/S molar ratio=1/4-8, and reaction temperature is -100 DEG C of room temperature, Reaction time is -5 hours 0.5 hour, and the mode for vacuumizing during the reaction or blasting inert gas into reaction solution will be anti- The ammonia that should be generated in the process is discharged from reaction solution, and appropriate ammonium salt is added into reaction solution, is cooled to room temperature, and stand knot 0.5-24 hours brilliant, high-purity tetrathio ammonium tungstate is made through drying at room temperature again after being washed with solvent in finally filtering；It is wherein described The compound of tungsten is tungstates or tungstic acid；The ammonium sulfide is vulcanization ammonium product or directly prepares according to ammonium sulfide preparation method Ammonium sulfide is for reacting out；The molar ratio of the compound of the tungsten and the ammonium salt being added after reaction are as follows: W/NH₄=1/ 0.5-10.The advantages of this method is the hydrogen sulfide gas without using irritating ammonium hydroxide and severe toxicity, stench, but to promote reaction It balances and needs to take the mode for vacuumizing or blasting inert gas that will produce during the preparation process to the movement of ammonium thiomolybdate direction Raw ammonia is discharged from reaction solution, this undoubtedly makes preparation process cumbersome, and energy consumption is higher, and preparation process has ammonia production Raw, environment is unfriendly, in addition, ammonium sulfide decomposition rate is fast, fails to efficiently use S atom, causes wastage of material.

To sum up, there is preparation process complexity in the method for preparing tetrathio tungstates at present, use irritation and toxicity mostly Biggish hydrogen sulfide, preparation process has the problems such as ammonia generation, not only causes damages to operator, but also causes dirt to environment Dye prepares that tetrathio tungstates method energy consumption is higher and operation difficulty is larger in addition, existing, therefore, limits to a certain extent The industrial applications of these methods.

Summary of the invention

For the complexity of preparation process existing for prior art tetrathio tungstates, preparation process has an ammonia generation, energy consumption compared with The high and biggish defect of operation difficulty, the present invention provide the preparation method of the new tetrathio tungstate solution of one kind and by this method The application in sulfurized hydrogenation catalyst of tetrathio tungstate solution obtained and above-mentioned tetrathio tungstate solution and The preparation method of sulfurized hydrogenation catalyst.Preparation method provided by the invention is without using irritation and the vulcanization being more toxic Hydrogen, and it is easy to operate, tetrathio tungstate solution obtained can prepare vulcanization type directly as maceration extract without crystallization and purification Hydrogenation catalyst.

The present invention provides a kind of preparation method of tetrathio tungstate solution, the preparation method the following steps are included:

(1) Tungstenic compound, organic sulphur source and water are mixed, obtains mixture；

(2) mixture is reacted under the conditions of being 4-11 for 20-100 DEG C and/or pH；

Wherein, organic sulphur source is the sulphur-containing substance that can be hydrolyzed under the conditions of step (1) and/or step (2).

The present invention provides the tetrathio tungstate solutions as made from above-mentioned preparation method.

The present invention provides above-mentioned tetrathio tungstate solutions to prepare the application in sulfurized hydrogenation catalyst.

The present invention also provides a kind of preparation method of sulfurized hydrogenation catalyst, the preparation method the following steps are included: Carrier is impregnated using tetrathio tungstate solution, is then roasted under inert atmosphere or reducing atmosphere, wherein described four The preparation method that thiqtung state solution provides through the invention is made.

The present inventor passes through the study found that during preparing tetrathio tungstate solution, by Tungstenic compound, After organic sulphur source and water mixing, reaction, which can be prepared, under the conditions of being 4-11 for 20-100 DEG C and/or pH is highly suitable for sulphur The tetrathio tungstate solution of change type hydrogenation catalyst, and without using irritation and the vulcanization being more toxic in reaction process Hydrogen is not needed using ammonium hydroxide hydrotropy yet, and without ammonia emission in preparation process, energy consumption is lower and easy to operate.It traces it to its cause possibility It is due to first, the reaction condition and sulphur source of present invention mixture as obtained by strict control step (1), can effectively control The O-S exchange reaction being formed in the hydrolysis of machine sulphur source and the release of sulfidion and organic sulphur source and Tungstenic compound, Under conditions of organic solvent-free or ammonium hydroxide hydrotropy, it is ensured that the generation of tetrathio tungstates, second, the present invention can effectively control O- The speed of S exchange, and the release of hydrogen sulfide and ammonia is avoided, the utilization rate of sulphur source is improved, wastage of material is avoided.This hair The tetrathio tungstate solution of bright offer is used for the preparation of sulfurized hydrogenation catalyst, is conducive to the promotion of catalyst performance, and And sulfurized hydrogenation catalyst directly can be prepared using tetrathio tungstate solution as maceration extract, and without purifying crystallization, the present invention Only containing a small amount of volatile foreign ion, such as CH in the tetrathio tungstate solution of offer₃COO^-、NH₄ ⁺, in subsequent catalyst In agent preparation process, in heat treatment or drying process, it can remove naturally.

Compared with prior art, the preparation method of tetrathio tungstate solution provided by the invention has the advantages that

(1) it is not needed without using irritation and the hydrogen sulfide being more toxic using ammonium hydroxide hydrotropy in reaction process yet；

(2) without ammonia emission in preparation process, energy consumption is lower and easy to operate；

(3) rate of release that can control S is more advantageous to the progress of O-S exchange, has both been avoided that hydrogen sulfide discharged, and energy It is enough more efficiently to utilize organic sulphur source, avoid wastage of material；

(4) only containing a small amount of volatile foreign ion in tetrathio tungstate solution provided by the invention, such as CH₃COO^-、NH₄ ⁺, in subsequent catalyst preparation process, in heat treatment or drying process, can remove naturally, eliminate tradition In hydrogenation catalyst preparation process, need that tetrathio tungstate solution purifying crystal is first obtained tetrathio tungstates, then by its The tedious steps of dissolution；

(5) it in tetrathio tungstate solution preparation process provided by the invention, does not need to take pumping true during the preparation process The ammonia of generation is discharged mode that is empty or blasting inert gas from reaction solution, and the prior art in order to reaction it is smooth into Row, when using ammonium sulfide (inorganic sulphur source) as vulcanizing agent, it is necessary to take the mode for vacuumizing or blasting inert gas will production Raw ammonia discharge, the operation is not only cumbersome, and while ammonia is discharged, inevitably excludes hydrogen sulfide together, make The utilization rate for obtaining sulphur source is smaller, and the sulphidity of W is lower.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Specific embodiment

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

The present invention is fully hydrolyzed organic sulphur source by the condition of rate-determining steps (2) reaction, can control organic The hydrolysis rate of sulphur source, and make O-S exchange more abundant, sulphur source is efficiently used, avoids the waste of raw material, and operated Journey is simple.

A preferred embodiment of the invention, step (2) reaction carry out in confined conditions.This kind preferably Embodiment, avoids the spilling of hydrogen sulfide, not only avoids environmental pollution and is effectively utilized sulphur source.

And the prior art mostly uses hydrogen sulfide as sulphur source during preparing tetrathio tungstate solution, in order to enable Tungsten source is substantially soluble in water, adds into cosolvent, such as ammonium hydroxide, so that needing during entire tetrathio tungstate solution using tool The ammonium hydroxide of irritant smell, and can not overcome the problems, such as the hydrogen sulfide gas for needing to handle severe toxicity, stench；And use ammonium sulfide When as vulcanizing agent, it is necessary to take the mode for vacuumizing or blasting inert gas that the ammonia of generation is discharged, the operation is not only It is cumbersome, and while ammonia is discharged, inevitably hydrogen sulfide is excluded together, so that the utilization rate of sulphur source is smaller, the sulphur of W Change degree is lower.

There is no particular limitation for concentration of the present invention to Tungstenic compound in the mixture, in the preferably described mixture, With WO₃Meter, the concentration of Tungstenic compound are 100-1000g/L, further preferably 200-700g/L, still more preferably for 300-400g/L。

In the present invention, under preferable case, the Tungstenic compound is inorganic Tungstenic compound；It is further preferred that described Tungstenic compound is selected from one of ammonium metatungstate, ammonium phosphotungstate, ammonium tungstate and sodium tungstate or a variety of.

In the present invention, in order to obtain more preferably water-soluble effect, cosolvent can be properly added.One kind according to the present invention is excellent Embodiment is selected, this method further includes that cosolvent is introduced into the mixture, and the cosolvent is selected from ammonium hydroxide, phosphoric acid and oxalic acid At least one of.There is no particular limitation for additional amount of the present invention to the cosolvent, as long as can obtain more preferably water-soluble Effect.

The present invention is wider to the range of choice of the dosage of organic sulphur source and Tungstenic compound, as long as making in terms of element sulphur Organic sulphur source is not less than 4, preferably 4-6:1 with the molar ratio of the Tungstenic compound of elemental metal, further preferably For 4.5-5.5:1.The reaction requirement of the two can either be met using this kind of preferred embodiment, and raw material can be efficiently used, It does not result in waste of resources.

Mixture of the present invention reacts under the conditions of being 4-11 for 20-100 DEG C and/or pH can both make O-S exchange fill Divide and carry out, and sulphur source is avoided to lose, in order to enable O-S exchange is more abundant, in preferred steps (2), the time of the reaction is 0.5-100h, further preferably 10-100h, it is further preferred that in step (2), the mixture at 30-95 DEG C and/ Or pH be 4-11 under the conditions of react 10-80h.

A preferred embodiment of the invention, in step (2), the mixture is 4-5.5 in pH or pH is 9.5-11, temperature react 24-80h under the conditions of being 30-60 DEG C.

According to another preferred method of implementation of the present invention, in step (2), the mixture is 5.5-9.5, temperature in pH 10-80h is reacted under the conditions of being 30-95 DEG C.

Organic sulfide can be realized by modulation acidity and/or temperature using the preferred embodiment of above-mentioned steps (2) Object occurs hydrolysis with more appropriate speed and releases H₂S or S^2-, then H₂S or S^2-In the meeting constantly tungsten salt of " attack " oxidation state O^2-O-S exchange reaction occurs for lattice position, generates thiqtung state.This kind of preferred embodiment, sulphur source utilization rate is higher, and sulphur It is more preferable to change effect.

The present invention is wider to the range of choice for the time reacted in step (2), and those skilled in the art can be according to reality PH value and reaction temperature suitably selected.

, according to the invention it is preferred to adjust pH by the way that acid and/or alkali are added into the mixture in step (2).The acid It can be organic acid, be also possible to inorganic acid, there is no particular limitation to this by the present invention.

In accordance with the present invention it is preferred that the acid is in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid and citric acid At least one, further preferably hydrochloric acid.Using preferred embodiment provided by the invention, the impurity element of introducing is in vulcanization type Hydrogenation catalyst prepares late stage and can remove naturally, will not influence the performance of tetrathio tungstate solution.

In accordance with the present invention it is preferred that the alkali is selected from least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide, into one Step is preferably sodium hydroxide and/or ammonium hydroxide.

A preferred embodiment of the invention, the preparation method the following steps are included:

Organic sulphur source be selected from list monothioester shown in L- cysteine, thioamides, formula (2) shown in formula (1) with At least one of dithioesters shown in formula (3),

In formula (1), R¹For H, NH₂-、CH₃-、CH₃CH₂-、CH₃NH- or (CH₃)₂N-, R²And R³Be each independently H or C1-C4 alkyl；In formula (2), R⁴For H or C1-C4 alkyl, R⁵For C1-C4 alkyl；In formula (3), R⁶For H or C1-C4 alkyl, R⁷For C1-C4 alkyl, the C1-C4 alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group or tert-butyl.R² And R³It can be identical or different.

According to the present invention, organic sulphur source can hydrolyze to be various under the conditions of step (1) and/or step (2) Sulphur-containing substance.It is preferred that organic sulphur source is selected from thioamides shown in L- cysteine, formula (1), list sulphur shown in formula (2) For at least one of dithioesters shown in ester and formula (3),

In formula (1), R¹For H, NH₂-、CH₃-、CH₃CH₂-、CH₃NH- or (CH₃)₂N-, R²And R³Be each independently H or C1-C4 alkyl；In formula (2), R⁴For H or C1-C4 alkyl, R⁵For C1-C4 alkyl；In formula (3), R⁶For H or C1-C4 alkyl, R⁷For C1-C4 alkyl, the C1-C4 alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group or tert-butyl.R² And R³It can be identical or different.Further preferred organic sulphur source is thioamides, still more preferably institute shown in formula (1) Stating organic sulphur source is at least one of thioformamide, thioacetamide and thiopropionamide, most preferably thioacetamide.

According to the present invention, wider to the range of choice of the concentration of the tetrathio tungstate solution, those skilled in the art It can be selected according to the actual situation.For example, if tetrathio tungstate solution to be used for the system of sulfurized hydrogenation catalyst Standby process can calculate required tetrathio tungstate solution to load the tungsten of specific quantity by the water absorption rate of carrier Concentration.The concentration of tetrathio tungstate solution appropriate in order to obtain, can be as being diluted mixture obtained by step (2) Or concentration, it is therefore preferable that this method further includes that mixture obtained by step (2) is diluted or is concentrated.

A preferred embodiment of the invention, every 1L tetrathio tungstate solution, contains 150-1350g's WS₄ ^2-, the further preferably WS of 300-1000g₄ ^2-, the further preferably WS of 400-500g₄ ^2-。

Only containing a small amount of volatile foreign ion in above-mentioned tetrathio tungstate solution provided by the invention, such as CH₃COO^-、NH₄ ⁺, in subsequent sulfurized hydrogenation catalyst preparation process, it can remove naturally, it therefore, can be by above-mentioned acquisition Tetrathio tungstate solution does not need crystallization and purification and obtains tetrathio tungstates to be dissolved again as leaching directly as maceration extract Stain liquid, simplifies operating procedure.

In addition, directly preparing sulfurized hydrogenation catalyst using tetrathio tungstate solution, active gold can be efficiently used Belong to component W, the waste of active metal W is avoided, while W itself is existed in the form of sulphided state, it is possible to prevente effectively from metal and load A series of problems brought by strong interaction between body can successfully avoid auxiliary agent Co (Ni) from vulcanizing before it, improve and live Property metal utilization, obtains II class Co (Ni)-W-S activity phase of high activity.

The present invention provides a kind of preparation method of sulfurized hydrogenation catalyst, the preparation method the following steps are included: using Tetrathio tungstate solution impregnates carrier, then roasts under inert atmosphere or reducing atmosphere, wherein the tetrathio The preparation method that tungstate solution provides through the invention is made.

A preferred embodiment of the invention, this method further include that group VIII metal member is introduced into catalyst The step of element.

There is no particular limitation for the method for introducing group VIII metallic element in opposite direction catalyst of the invention, such as can adopt Use infusion process.Group VIII metallic element and wolfram element can with co-impregnation on carrier, can also with step impregnation in carrier it On.Specifically, group VIII metal salt can be added in the tetrathio tungstates, carrier is impregnated, then in institute It states and is roasted under inert atmosphere or reducing atmosphere；It can also be and carrier is impregnated using tetrathio tungstate solution, then exist It is roasted under inert atmosphere or reducing atmosphere, obtains solid material, then using the solution containing group VIII metal salt to described Solid material is impregnated, and is then roasted.

There is no particular limitation for additional amount of the present invention to the group VIII metallic element, vulcanizes in order to which a more step improves The dosage of the Hydrogenation of type hydrogenation catalyst, the preferably described tetrathio tungstates, group VIII metal and carrier makes, system In the catalyst obtained, the molar ratio of group VIII metallic element and W element is 0.3-0.7:1, on the basis of the total amount of catalyst, In terms of oxide, W content is 5-45 weight %, further preferably 10-35 weight %.

When using step impregnation, the concentration of the solution of the group VIII metal salt is not particularly limited in the present invention, Preferably, the concentration of the solution of the group VIII metal salt is 0.1-1mol/L, further preferably 0.3-1mol/L.

In the present invention, under preferable case, the group VIII metal salt is selected from nitrate, carbonate, the chlorine of cobalt and/or nickel One of salt dissolving, sulfate and acetate are a variety of.

There is no particular limitation to the dipping by the present invention, can be various dipping methods commonly used in the art, example Such as incipient impregnation, details are not described herein.

According to the present invention, the inert atmosphere can by one of nitrogen, argon gas and helium or a variety of offers, preferably by Nitrogen provides.

According to the present invention, the reducing atmosphere can be by hydrogen and/or hydrogen sulfide and optionally inert gas offer.

Inert gas can be contained in the reducing atmosphere, when in the reducing atmosphere contain inert gas when, hydrogen and/ Or the volume content of hydrogen sulfide is not less than 5%.

In the present invention, it is preferred to which the product obtained after dipping is dried before the roasting, the roasting is then carried out It burns.There is no particular limitation for condition of the present invention to the drying, such as temperature can be 50-100 DEG C, and time 2-10h is Prevent sulphur source from losing, the preferably described drying carries out under an inert atmosphere.

There is no particular limitation for condition of the present invention to the roasting, it is preferable that the condition of the roasting includes: in 300- It roasts 1-6 hours at 750 DEG C, is roasted 2-4 hours further preferably at 350-550 DEG C.

Catalyst made from preparation method using sulfurized hydrogenation catalyst provided by the invention, before use, being not required to Presulfurization is carried out, and II class Co (Ni)-W-S activity phase with greater catalytic performance can be obtained.

The preparation method of thiqtung state solution provided by the invention can be construed to, by modulation aqueous solution it is acid or/ With the temperature for improving aqueous solution, so that it may which realization, which allows, is dissolved in organic sulfur compound therein with certain speed generation hydrolysis release H out₂S or S^2-(by taking thioacetamide as an example, as shown in formula (4)), then H₂S or S²In the meeting constantly tungsten salt of " attack " oxidation state O^2-Oxygen-sulphur exchange reaction occurs for lattice position, thiqtung state is generated, as shown in formula (5)~formula (8).Using prepared Thiqtung state solution be maceration extract prepare supported sulfided tungsten catalyst process can by formula (9) describe (carrier is with γ- Al₂O₃For): thiqtung state is impregnated first to γ-Al₂O₃Channel surfaces formed composite material WS₄ ^2-/γ-Al₂O₃, this is multiple Condensation material is fired under the protection of inert gas or reducibility gas, by intermediate product MoS₃/γ-Al₂O₃It is further Pyrolysis, finally obtains supported sulfided tungsten hydrogenation catalyst WS₂/γ-Al₂O₃。

3CH₃CSNH₂+6H₂O→3CH₃COONH₄+3H₂S↑ (4)

H₂S/S^2-+WO₄ ^2-→WSO₃ ^2- (5)

H₂S/S^2-+WSO₃ ^2-→WS₂O₂ ^2- (6)

H₂S/S^2-+WS₂O₂ ^2-→WS₃O^2- (7)

H₂S/S^2-+WS₃O^2-→WS₄ ^2- (8)

WS₄ ^2-+γ-Al₂O₃→WS₄ ^2-/γ-Al₂O₃→WS₃/γ-Al₂O₃→WS₂/γ-Al₂O₃ (9)

In fact, judging the salting liquid that preparation method of the present invention obtains for thiqtung state solution and determining thiqtung state The effective ways of concentration are to carry out X-ray photoelectron respectively to the sulfurized hydrogenation catalyst for using it to prepare as maceration extract Energy spectrum analysis (XPS) measurement and the measurement of X-ray fluorescence spectra (XRF) method, the former can be used to analyze tungsten adds in vulcanization type Sulphidity in hydrogen catalyst, and then speculate whether the precursor salt of tungsten component is thiqtung state, and the latter can then measure catalysis The content of tungsten component in agent, and then speculate thiqtung state synthesized by the present invention (with WS₄ ^2-Meter) in the solution dense Degree.Wherein, X-ray fluorescence spectra (XRF) method uses ZSX-100e type Xray fluorescence spectrometer, using Rh target, in electric current It is measured under conditions of 50mA, voltage 50kV.X-ray photoelectron spectroscopy analyzes (XPS) in ESCALab 250 model x-ray photoelectron It is carried out on energy disperse spectroscopy (Britain's VG Products), uses radiation source for AlK α, resolution ratio 0.5eV is inside designated as the C1s of pollution carbon Combination can (Eb=285.0eV) condition obtain.Wherein, sulphidity is by obtaining XPS data processing, specific processing method It can be found in document Han etal., Journal of Materials Chemistry 2012,22:25340.

Embodiment 1

(1) preparation of tetrathio tungstate solution

Ammonium metatungstate of the 100mL containing 35.0g is prepared (with WO₃Meter), the solution of the thioacetamide of 55.0g, drip thereto Adding 2.4mol/L salt acid for adjusting pH value is 6.0, under confined conditions, through aging 24 hours at 60 DEG C, carries out UV, visible light to product Absorption spectrum (UV-Vis) analytical proof, obtains thiqtung state solution S -1；

(2) preparation of sulfurized hydrogenation catalyst

Thiqtung state solution S -1 is concentrated into 48.0mL, to 60.0g diameter 1-5mm γ-Al₂O₃Particle (imbibition Rate 0.8mL/g) saturation dipping 2 hours, dipping finishes drying 4 hours at 30 DEG C, then in H₂Under atmosphere protection, at 360 DEG C Lower roasting 3 hours, obtains monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S-1.Metal contains in catalyst Cat-S-1 The results are shown in Table 1 for amount and sulphidity analysis.

Embodiment 2

(1) preparation of tetrathio tungstate solution

Sodium tungstate of the 100mL containing 35.0g is prepared (with WO₃Meter), the solution of the thioacetamide of 60.0g, be added dropwise thereto 2.4mol/L salt acid for adjusting pH value is 7.0, under confined conditions, then through aging 48 hours at 30 DEG C, carries out UV, visible light to product Absorption spectrum (UV-Vis) analytical proof, obtains thiqtung state solution S -2；

(2) preparation of sulfurized hydrogenation catalyst

Thiqtung state solution S -2 is concentrated into 48.0mL, to 60.0g diameter 1-5mm γ-Al₂O₃Particle (imbibition Rate 0.8mL/g) saturation dipping 2 hours, dipping finishes drying 4 hours at 50 DEG C, then in H₂Under atmosphere protection, at 500 DEG C Lower roasting 2 hours, obtains monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S-2.Metal contains in catalyst Cat-S-2 The results are shown in Table 1 for amount and sulphidity analysis.

Embodiment 3

(1) preparation of tetrathio tungstate solution

Ammonium tungstate of the 100mL containing 35.0g is prepared (with WO₃Meter), 5.0g oxalic acid, 45.0g thioacetamide solution (pH About 5), under confined conditions, through aging 10 hours at 50 DEG C, ultraviolet-visible absorption spectroscopy (UV-Vis) analysis card is carried out to product It is bright, obtain thiqtung state solution S -3；

(2) preparation of sulfurized hydrogenation catalyst

Thiqtung state solution S -3 is concentrated into 48.0mL, to 60.0g diameter 1-5mm γ-Al₂O₃Particle (imbibition Rate 0.8mL/g) saturation dipping 1 hour, dipping finishes drying 4 hours at 30 DEG C, then in N₂Under atmosphere protection, at 400 DEG C Lower roasting 3 hours, obtains monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S-3.Metal contains in catalyst Cat-S-3 The results are shown in Table 1 for amount and sulphidity analysis.

Embodiment 4

(1) preparation of tetrathio tungstate solution

Ammonium phosphotungstate of the 100mL containing 35.0g is prepared (with WO₃Meter), the solution of the thioacetamide of 55.0g, wherein being added dropwise 2.4mol/L sulphur acid for adjusting pH value is 4.0, under confined conditions, then through aging 36 hours at 40 DEG C, carries out UV, visible light to product Absorption spectrum (UV-Vis) analytical proof, obtains thiqtung state solution S -4；

(2) preparation of sulfurized hydrogenation catalyst

Thiqtung state solution S -4 is concentrated into 48.0mL, to 60.0g diameter 1-5mm γ-Al₂O₃Particle (imbibition Rate 0.8mL/g) dipping 0.5 hour, dipping finishes drying 3 hours at 50 DEG C, then in H₂S/H₂(H₂The volumetric concentration of S is 10%) it under atmosphere protection, is roasted 6 hours at 460 DEG C, obtains monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S- 4.The results are shown in Table 1 for tenor and sulphidity analysis in catalyst Cat-S-4.

Embodiment 5

(1) preparation of tetrathio tungstate solution

Ammonium phosphotungstate of the 100mL containing 35.0g is prepared (with WO₃Meter), 5.0g ammonium hydroxide, 60.0g thioacetamide solution (pH is about 9) carries out ultraviolet-visible absorption spectroscopy (UV-Vis) to product under confined conditions, then through aging 72 hours at 95 DEG C Analytical proof obtains thiqtung state solution S -5；

(2) preparation of sulfurized hydrogenation catalyst

Thiqtung state solution S -5 is concentrated into 48.0mL, to 60.0g diameter 1-5mm γ-Al₂O₃Particle (imbibition Rate 0.8mL/g) dipping 1h, it is 2 hours dry at 80 DEG C in a nitrogen atmosphere, then in H₂Under atmosphere protection, roasted at 360 DEG C 3 hours, obtain monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S-5.Tenor and sulphur in catalyst Cat-S-5 The results are shown in Table 1 for the analysis of change degree.

Comparative example 1

Supported sulfided tungsten hydrogenation catalyst is prepared using oxidation state tungsten salt solution.Specifically: weigh ammonium metatungstate 12.5g is made into maceration extract about 80mL, γ-Al of the dipping 100g diameter in 1-5mm₂O₃Carrier (imbibition rate 0.8mL/g) 2h, then It places and is then vulcanized in baking oven in 120 DEG C of dry 10h, 500 DEG C of roasting 4h.Conditions of vulcanization are as follows: in H₂S/H₂(H₂The body of S Product concentration is 10%) in atmosphere, in 4.0MPa, 360 DEG C of vulcanizations 4h, H₂S/H₂The air speed of gaseous mixture is 1.5h^-1.Obtain monometallic Sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-D-1.Tenor and sulphidity analysis result are listed in catalyst Cat-D-1 In table 1.

Embodiment 6

(1) preparation of tetrathio tungstate solution

Ammonium metatungstate of the 100mL containing 35g is prepared (with WO₃Meter), the solution of the thioacetamide of 60.0g；2.4mol/ is added dropwise L salt acid for adjusting pH value is 6.0, under confined conditions, then through aging 24 hours at 60 DEG C, carries out ultraviolet-visible absorption spectroscopy to product (UV-Vis) analytical proof obtains thiqtung state solution S -6；

(2) preparation of sulfurized hydrogenation catalyst

16.1g nickel acetate is added into solution S -6, adds water constant volume (or heating concentration) to 48mL, then to 60.0g diameter In the γ-Al of 1-5mm₂O₃Particle (imbibition rate 0.8mL/g) saturation dipping 2 hours, dipping finished drying 4 hours at 30 DEG C, so Afterwards in H₂It under atmosphere protection, is roasted 3 hours at 360 DEG C, obtains bimetallic sulfide type catalyst NiW/ γ-Al₂O₃, it is denoted as Cat-S-6.The results are shown in Table 1 for tenor and sulphidity analysis in catalyst Cat-S-6.

Comparative example 2

Supported sulfided tungsten hydrogenation catalyst is prepared using oxidation state tungsten salt solution.Specifically: weigh ammonium metatungstate 12.5g, nickel nitrate 16.0g are made into maceration extract about 80mL, γ-Al of the dipping 100g diameter in 1-5mm₂O₃Carrier (imbibition rate 2h in 0.8mL/g) is then placed and is then vulcanized in baking oven in 120 DEG C of dry 10h, 500 DEG C of roasting 4h.Conditions of vulcanization is same Comparative example 1 obtains bimetallic sulfide type catalyst NiW/ γ-Al₂O₃, it is denoted as Cat-D-2.Tenor in catalyst Cat-D-2 The results are shown in Table 1 with sulphidity analysis.

Embodiment 7

(1) preparation of tetrathio tungstate solution

Ammonium metatungstate of the 100mL containing 35g is prepared (with WO₃Meter), the solution of the thioacetamide of 60.0g；2.4mol/ is added dropwise L salt acid for adjusting pH value is 6.0, under confined conditions, then through aging 24 hours at 60 DEG C, carries out ultraviolet-visible absorption spectroscopy to product (UV-Vis) analytical proof obtains thiqtung state solution S -7；

(2) preparation of sulfurized hydrogenation catalyst

16.1g cobalt acetate is added into solution S -7, adds water constant volume (or heating concentration) to 48mL, then to 60.0g diameter In the γ-Al of 1-5mm₂O₃Particle (imbibition rate 0.8mL/g) saturation dipping 2 hours, dipping finished drying 4 hours at 30 DEG C, so Afterwards in H₂It under atmosphere protection, is roasted 3 hours at 360 DEG C, obtains bimetallic sulfide type catalyst CoW/ γ-Al₂O₃, it is denoted as Cat-S-7.The results are shown in Table 1 for tenor and sulphidity analysis in catalyst Cat-S-7.

Comparative example 3

Supported sulfided tungsten hydrogenation catalyst is prepared using oxidation state tungsten salt solution.Specifically: weigh ammonium metatungstate 12.5g, cobalt nitrate 16.0g are made into maceration extract about 80mL, γ-Al of the dipping 100g diameter in 1-5mm₂O₃Carrier (imbibition rate 2h in 0.8mL/g) is then placed and is then vulcanized in baking oven in 120 DEG C of dry 10h, 500 DEG C of roasting 4h.Conditions of vulcanization is same Comparative example 1 obtains bimetallic sulfide type catalyst CoW/ γ-Al₂O₃, it is denoted as Cat-D-3.Tenor in catalyst Cat-D-3 The results are shown in Table 1 with sulphidity analysis.

Embodiment 8

(1) preparation of tetrathio tungstate solution

Ammonium metatungstate of the 100mL containing 35.0g is prepared (with WO₃Meter), the solution of the thioacetamide of 60.0g, wherein being added dropwise 2.4mol/L salt acid for adjusting pH value is 6.0, under confined conditions, then through aging 24 hours at 60 DEG C, carries out UV, visible light to product Absorption spectrum (UV-Vis) analytical proof, obtains thiqtung state solution S -8；

(2) preparation of sulfurized hydrogenation catalyst

Thiqtung state solution S -8 is concentrated into 48.0mL, to 60.0g diameter 1-5mm γ-Al₂O₃Particle (imbibition Rate 0.8mL/g) saturation dipping 2 hours, dipping finishes drying 4 hours at 30 DEG C, then in H₂Under atmosphere protection, at 360 DEG C Lower roasting 3 hours, obtains monometallic cure type catalyst W/ γ-Al₂O₃, the solution of 42ml nickel acetate containing 6.8g is then prepared, Dipping dry 4 hours, H at 2 hours, 30 DEG C₂Roasting (temperature is 360 DEG C, and the time is 3 hours) obtains bimetallic vulcanization under atmosphere Type catalyst n iW/ γ-Al₂O₃, it is denoted as Cat-S-8.Tenor and sulphidity analysis result are listed in table in catalyst Cat-S-8 In 1.

Embodiment 9

According to the method for embodiment 1, unlike, in step (1), aging described in the preparation of tetrathio tungstate solution Process carries out in open environment, obtains monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S-9.Catalyst Cat-S- The results are shown in Table 1 for tenor and sulphidity analysis in 9.

Embodiment 10

According to the method for embodiment 4, the difference is that, in step (1), in the preparation of tetrathio tungstate solution, wherein dripping Adding 2.4mol/L sulphur acid for adjusting pH value is 4.0, then through aging 36 hours at 80 DEG C, obtains monometallic sulfide type catalyst W/ γ- Al₂O₃, it is denoted as Cat-S-10.The results are shown in Table 1 for tenor and sulphidity analysis in catalyst Cat-S-10.

Embodiment 11

According to the method for embodiment 5, the difference is that, increase the amount of ammonium hydroxide, so that pH value of solution is 10, obtains monometallic vulcanization Type catalyst W/ γ-Al₂O₃, it is denoted as Cat-S-11.Tenor and sulphidity analysis result are listed in table in catalyst Cat-S-11 In 1.

Comparative example 4

According to the method for embodiment 1, thio using the ammonium sulfide replacement of identical molal quantity in terms of element sulphur unlike Acetamide obtains monometallic sulfide type catalyst W/ γ-Al₂O₃, it is denoted as Cat-D-4.In catalyst Cat-D-4 tenor and The results are shown in Table 1 for sulphidity analysis.

In following table table 1, WS₄ ^2-Content refers to 1L tetrathio tungstate solution, WS₄ ^2-Mass content, which can lead to It crosses and is calculated, in system provided by the invention, only WS₄ ^2-Thermal decomposition could generate WS₂, therefore, WS₄ ^2-Content specifically calculates Method is as follows:

Pass through WO in 1L tetrathio tungstate solution₃Content conversion 1L tetrathio tungstate solution in WS₄ ^2-Content, so Afterwards with WS in 1L tetrathio tungstate solution₄ ^2-Content multiplied by the W of obtained catalyst prod sulphidity.By taking embodiment 1 as an example, WO in 1L tetrathio tungstate solution₃Content be 350g, be scaled WS₄ ^2-It is multiplied by sulphidity (0.978) for 471g, 471g 460.6g contains 460.6g WS that is, in 1L tetrathio tungstate solution₄ ^2-。

Tenor and sulphidity analyze result in 1 catalyst of table

Test example

In this test example, to the de- of the hydrogenation catalyst provided using hydrogenation catalyst provided by the present invention and comparative example Sulphur and denitrification activity are evaluated in accordance with the following methods, and list result.

Hydrodesulfurization: being original with the cyclohexane solution of 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) mass content 1% Material evaluates the desulphurizing activated of catalyst on the continuous high pressure reaction assembly of WFSP3050 of Tianjin Xian Quan instrument company production. It is not required to before the reaction to presulfiding of catalyst processing.Reaction condition are as follows: 4.0MPa, 340 DEG C, hydrogen to oil volume ratio 300, oil inlet flow For 8mL/h.After stable reaction 3h, reaction 4h sampling, sample is surveyed sulphur nitrogen instrument with HS-500 type high frequency-infrared and is analyzed, and activity is used 4,6-DMDBT desulfurization degree (average value of 10 samples) indicates, the results are shown in Table 2.

Hydrodenitrogeneration: using the n-heptane solution of quinoline (Q) mass content 1% as raw material, in Tianjin Xian Quan instrument company The denitrification activity of catalyst is evaluated on the continuous high pressure reaction assembly of the WFSP3050 of production.It is not required to before the reaction to the pre- sulphur of catalyst Change processing.Reaction condition are as follows: 4.0MPa, 340 DEG C, hydrogen to oil volume ratio 400, oil inlet flow is 8mL/h.After stable reaction 3h, instead 4h is answered to sample, sample is surveyed sulphur nitrogen instrument with HS-500 type high frequency-infrared and analyzed, and (10 samples are averaged activity with the denitrification percent of Q Value) it indicates, it the results are shown in Table 2.

Reaction desulfuration (nitrogen) rate X is calculated as follows:

The hydrodesulfurization of 2 catalyst of table, denitrification activity evaluation result

Using the thio type of support type of thiqtung state solution provided by the invention preparation it can be seen from the result of table 1 W sulphidity in hydrogenation catalyst is close to 100%, while according to the content of W it can be deduced that the synthesis material of thiqtung state In W component substantially all be loaded to carrier surface, solution preparation process of the further indirect proof in thiqtung state, oxygen Very adequately exchange has been carried out between sulphur.

Compared with the hydrogenation catalyst of conventional method preparation it can be seen from the result of Tables 1 and 2, with provided by the invention The sulfurized hydrogenation catalyst of thiqtung state solution preparation, either monometallic sulfide type catalyst or more metal vulcanization types Catalyst, tungsten active component substantially completely vulcanize, and much higher than the state of cure (vulcanization) of active metal on conventional catalyst, substantially increase The utilization rate of active metal, it is even more important that compared with the vulcanization type catalyst with same metal load capacity, this hair The catalyst of bright offer has considerably better hydrodesulfurization, denitrification activity.The above results sufficiently show provided by the present invention adopt The route of hydrogenation catalyst is prepared with thiqtung state solution, the superiority for having conventional preparation route incomparable.

The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims

1. a kind of preparation method of tetrathio tungstate solution, which is characterized in that the preparation method the following steps are included:

2. preparation method according to claim 1, wherein in the mixture, with WO₃Meter, the concentration of Tungstenic compound are 100-1000g/L, preferably 200-700g/L.

3. preparation method according to claim 1 or 2, wherein organic sulphur source in terms of element sulphur with elemental metal Tungstenic compound molar ratio be 4-6:1.

4. preparation method described in any one of -3 according to claim 1, wherein in step (2), the time of the reaction is 0.5-100h, it is preferable that the mixture reacts 10-80h under the conditions of being 4-11 for 30-95 DEG C and/or pH；

Preferably, the mixture is 4-5.5 in pH or pH is 9.5-11, and temperature reacts 24-80h under the conditions of being 30-60 DEG C；

Preferably, the mixture is 5.5-9.5 in pH, and temperature reacts 10-80h under the conditions of being 30-95 DEG C.

5. preparation method described in any one of -4 according to claim 1, wherein by the mixture in step (2) Middle addition acid and/or alkali adjust pH；Preferably, the acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid and citric acid At least one of, preferably hydrochloric acid；The alkali is selected from least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide, preferably Sodium hydroxide and/or ammonium hydroxide.

6. preparation method described in any one of -5 according to claim 1, wherein this method further includes into the mixture Cosolvent is introduced, the cosolvent is selected from least one of ammonium hydroxide, phosphoric acid and oxalic acid.

7. preparation method described in any one of -6 according to claim 1, wherein

The Tungstenic compound is inorganic Tungstenic compound；

Preferably, the Tungstenic compound is selected from one of ammonium metatungstate, ammonium phosphotungstate, ammonium tungstate and sodium tungstate or a variety of.

8. preparation method according to any one of claims 1-7, wherein organic sulphur source is selected from L- semi-gloss ammonia At least one of thioamides shown in acid, formula (1), dithioesters shown in list monothioester and formula (3) shown in formula (2),

In formula (1), R¹For H, NH₂-、CH₃-、CH₃CH₂-、CH₃NH- or (CH₃)₂N-, R²And R³It is each independently H or C1-C4 alkane Base；

In formula (2), R⁴For H or C1-C4 alkyl, R⁵For C1-C4 alkyl；

In formula (3), R⁶For H or C1-C4 alkyl, R⁷For C1-C4 alkyl；

Preferably, organic sulphur source is thioamides, further preferably thioformamide, thioacetyl shown in formula (1) At least one of amine and thiopropionamide, most preferably thioacetamide.

9. preparation method described in any one of -8 according to claim 1, wherein step (2) reaction is in confined condition Lower progress.

10. tetrathio tungstate solution made from the preparation method as described in any one of claim 1-9.

11. tetrathio tungstate solution according to claim 10, wherein every 1L tetrathio tungstate solution contains The WS of 150-1350g₄ ^2-, preferably comprise the WS of 300-1000g₄ ^2-。

12. tetrathio tungstate solution described in claim 10 or 11 is preparing the application in sulfurized hydrogenation catalyst.

13. a kind of preparation method of sulfurized hydrogenation catalyst, the preparation method the following steps are included:

Carrier is impregnated using tetrathio tungstate solution, is then roasted under inert atmosphere or reducing atmosphere, wherein institute Tetrathio tungstate solution is stated to be made by preparation method described in any one of claim 1-9.

14. preparation method according to claim 13, wherein this method further includes introducing group VIII gold into catalyst The step of belonging to element；

Preferably, the dosage of tetrathio tungstates, group VIII metal and carrier makes, in catalyst obtained, Section VIII The molar ratio of race's metallic element and W element is 0.3-0.7:1, and on the basis of the total amount of catalyst, in terms of oxide, W content is 5-45 weight %.