CN105498806A - Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof - Google Patents

Abstract

A surface amphiphilic nanometer tungsten-molybdenum sulfide hydrogenation catalyst and its preparation method and application. The sulfur-containing tungsten source, sulfur-containing molybdenum source, reducing agent, ionic liquid and deionized water are formulated into an initial reaction mixture according to a certain order and method. Then crystallize under hydrothermal conditions in a sealed high-pressure reactor, and the crystallized product is filtered, washed, and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst. The invention uses ionic liquid in the synthesis system, and the prepared nano-tungsten molybdenum sulfide has good surface amphiphilicity, and has excellent dispersibility and catalytic activity in both polar and non-polar catalytic reaction systems. The nanometer tungsten-molybdenum sulfide catalyst provided by the present invention is used in the suspension bed hydrogenation deasphalting, hydrodesulfurization, hydrodenitrogenation, aromatics hydrogenation and other reactions of heavy oil such as coal tar, heavy oil, super heavy oil, residual oil and shale oil. It shows excellent catalytic activity, and has good application prospects in photoelectric conversion, photocatalytic water hydrogen production and other reactions.

Description

A surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst and its preparation method and application

technical field

The invention relates to a surface amphiphilic nanometer tungsten-molybdenum sulfide catalyst and a preparation method and application thereof, which belong to the field of synthesis and catalytic application of nanomaterials.

Background technique

Suspension bed hydrogenation process is an advanced technology for hydrogenation of heavy unconventional oil (residual oil, heavy oil/ultra heavy oil, shale oil, coal tar heavy component, sandstone oil, oil sand bitumen, etc.) to prepare liquid fuel oil. Suspension-bed hydrogenation process requires catalysts with high activity, high dispersion, high stability, and good economy. It is a challenging task to prepare catalysts suitable for suspension-bed hydrogenation process.

Non-noble metal sulfides are layered materials with a graphene-like structure, which have shown promising applications in the fields of catalysis, microelectronics, and semiconductors. Supported tungsten sulfide and molybdenum sulfide catalysts have been used as hydrogenation catalysts in the field of petroleum processing, and are widely used in reactions such as hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydrodeoxygenation and hydrodemetallization ( Chianelli R., Catal. Today, 2009, 147, 275-286). Unsupported tungsten-molybdenum sulfide is a very promising catalyst suitable for hydrogenation of heavy oil in suspension bed process to prepare clean fuels.

At present, the preparation methods of tungsten sulfide and molybdenum sulfide mainly include high-temperature vulcanization method, precursor decomposition method, solvothermal method, electrochemical deposition method, template method, etc. (Wang S., Materials, 2010, 3, 401-433). However, the sulfide catalysts prepared by these research methods are either water-soluble or oil-soluble. Due to the complex composition of heavy oil, which contains both polar and non-polar substances, the dispersibility of tungsten sulfide with a single surface affinity in it is not ideal. Therefore, the use of mild solution method to chemically synthesize nano-sulfide catalysts with surface amphiphiles is the key to improve their dispersibility.

CN200910226642.2 discloses a method for preparing monodisperse tungsten disulfide nanosheets, using tungsten oxide and sulfur as raw materials, after mixing and activating by ball milling, annealing at 600-700°C for 30-120min at a constant temperature in a protective atmosphere. During the annealing process, a part of the sulfur powder is used as a supplementary sulfur source in advance, and the mass ratio of the supplementary sulfur powder to the reaction mixture is between 0.05-10, and then the single Dispersion of tungsten disulfide nanosheets. The invention prepares a large amount of monodisperse flaky tungsten disulfide nanomaterials through a simple and effective chemical synthesis method, the method is simple and fast, and the production cost is low, and it can be widely used in lubrication and catalysis.

CN201310272706.9 discloses a method of using transition metal tungstate as a catalyst to oxidize and remove sulfide in simulated oil, which can be implemented as follows: (1) Weigh transition metal nitrate, add water to dissolve, add sodium tungstate, Stir at room temperature; collect the product, wash it with water, dry it, and then calcinate the product to obtain the transition metal tungstate; (2) Add the tungstate synthesized in step (1) to the simulated oil, add the oxidant and sixteen Alkyltrimethylammonium bromide, the reaction mixture is cooled to room temperature, and the oil phase is separated; N-N-dimethylformamide is added to continue stirring, the oil phase is separated, the sulfur content is measured and the desulfurization rate is calculated; (3) recovery Tungstate catalyst, drying, washing to remove surface sulfide and reuse after drying.

CN201310317514.5 discloses an oil-soluble self-sulfide molybdenum catalyst, its preparation method, use method and application, wherein the preparation method includes the following steps: (1), under nitrogen protection, molybdenum source, water, sodium sulfide, Put the solvent and inorganic acid in a container, mix and stir evenly, cool at 5-50°C, and react for 10-150min; (2), add alkylamine and carbon disulfide, stir evenly, heat to 60-200°C and react for 3-10h; (3), after the reaction is finished, the product is fully cooled, then suction filtered, fully washed with methanol, and dried to obtain an oil-soluble self-molybdenum sulfide catalyst. The oil-soluble self-sulfided molybdenum catalyst provided by the invention can decompose in situ from the sulfidation to form molybdenum disulfide active components, and is used in the slurry bed hydrocracking process of inferior heavy oil containing high metal, high carbon residue and high sulfur, which can reduce Coke yield, to maintain long-term operation of the device.

CN201210512991.2 discloses a molybdenum disulfide nanoparticle and its preparation method and application. The method comprises the following steps: mixing molybdenite or micron-sized molybdenum disulfide with ionic liquid and/or organic solvent to obtain a mixture, grinding and/or ultrasonicating the mixture, and then separating to obtain the molybdenum disulfide nano particles. The nanometer molybdenum disulfide provided by the invention shows excellent catalytic activity in hydrodesulfurization reaction, hydrogen evolution reaction, methanol oxidation reaction and the like. At the same time, as a semiconductor nanomaterial, it also has application prospects in photoelectric conversion and photocatalytic water splitting. Most importantly, nanomolybdenum disulfide exhibits excellent catalytic performance in the oxygen reduction reaction.

CN201110274120.7 discloses a heavy oil hydrogenation protection catalyst and its preparation and application, using AL ₂ O ₃ or SiO ₂ -containing AL ₂ O ₃ as a carrier, the pore volume of the carrier is 0.98-1.15mL/g, and the specific surface is 340- 380m ² /g, the pore distribution is as follows: the pore volume of the pore diameter <5nm accounts for 10%-15% of the total pore volume, the pore volume of the 5-15nm pore volume accounts for 50%-55% of the total pore volume, and the pore diameter>15nm The pore volume accounts for 25%-40% of the total pore volume; loaded nickel molybdenum sulfur, nickel tungsten sulfur, molybdenum sulfide, tungsten sulfide, cobalt molybdenum sulfur, cobalt tungsten sulfur, nickel cobalt molybdenum sulfur, nickel cobalt tungsten sulfur or cobalt molybdenum nickel A composite catalyst composed of tungsten and Ni ₂ P; the catalyst has suitable pore size, high metal-melting ability, small active component scale, good dispersion and high catalyst activity, and is suitable for heavy oil and heavy oil protection catalysts.

CN200410009977.6 discloses a catalyst preparation method for sulfur-containing transition metal atom clusters. The inventive atomic clusters containing dinuclear, trinuclear and tetranuclear metal molybdenum or tungsten are prepared by metal oxides in acid solution It is prepared through the steps of electrolysis, vulcanization, oxidation, concentration, separation and chemical reaction. This atomic cluster has the following cluster cores: [M ₂ O _n S _2-n ] ^m+ , [M ₃ O _n S _4-n ] ^m+ or [M ₄ O _n S _6-n ] ^m+ , (M= Mo or W, n=0-6, m=0-6). Metals Co, Ni, Cu, Fe, Sn, etc. can form bonds with the cations of this cluster core to form transition metal atom clusters of multi-metal species. The atomic cluster compound of the sulfur-containing transition metal molybdenum or tungsten prepared by the method has a definite atomic or molecular structure and good stability. The supported sulfur-containing aluminum or tungsten atomic clusters have better hydrodesulfurization performance than the catalysts prepared by the traditional impregnation method.

Ionic liquids refer to salts that are in a liquid state at room temperature or near room temperature (below 100°C), and are completely composed of organic cations with relatively large volume and poor symmetry and inorganic anions with small volume. Due to the positive and negative charges The numbers are equal, so they are electrically neutral as a whole. Also commonly referred to as room temperature ionic liquids. Ionic liquids have unique advantages such as adjustable polarity, good solubility, wide liquid range, high thermal stability, and almost negligible vapor pressure. application. (T. Welton, Chem. Rev., 1999, 99, 2071; R. D. Rogers, K. D. Seddon, Nature, 2003, 302, 792.)

CN03115271.6 discloses a preparation method of room temperature ionic liquid. It is characterized in that the target product, room temperature ionic liquid, is used as the reaction medium, and alkylpyridinium ammonium halide or alkylimidazolium ammonium halide and fluorine-containing salt are used as raw materials to prepare the compound composed of alkylpyridinium cation or alkylimidazolium cation and fluorine-containing anion. room temperature ionic liquid. The method has the advantages of simple operation, mild reaction conditions, good product quality and environment-friendly reaction process, and is a preparation method of a green room-temperature ionic liquid.

CN201210512991.2 discloses a molybdenum disulfide nanoparticle and its preparation method and application. The method comprises the following steps: mixing molybdenite or micron-sized molybdenum disulfide with ionic liquid and/or organic solvent to obtain a mixture, grinding and/or ultrasonicating the mixture, and then separating to obtain the molybdenum disulfide nano particles. The nanometer molybdenum disulfide provided by the invention exhibits excellent catalytic activity in hydrodesulfurization reaction, hydrogen evolution reaction, methanol oxidation reaction and the like. At the same time, as a semiconductor nanomaterial, it also has application prospects in photoelectric conversion and photocatalytic water splitting. Most importantly, nanomolybdenum disulfide exhibits excellent catalytic performance in the oxygen reduction reaction.

Contents of the invention

The object of the present invention is to solve the above problems, to provide a surface amphiphilic nanometer tungsten-molybdenum sulfide hydrogenation catalyst and its preparation method and application.

The purpose of the present invention can be achieved in the following ways:

Using solution chemistry method to prepare surface amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst with ionic liquid as auxiliary agent, including the following steps: (1) adding sulfur-containing tungsten source and sulfur-containing molybdenum source to deionized water, stirring evenly to prepare a certain concentration (2) adding a sulfur source to the above mixture, stirring evenly, and reacting at a certain temperature for a certain period of time; (3) adding a reducing agent to the above mixture, stirring uniformly; (4) adding an ionic liquid to the above mixture, Stir evenly, configure the initial reaction mixture; (5) transfer the initial reaction mixture to a high-pressure synthesis kettle, and crystallize at a certain temperature for a certain period of time; (6) after the crystallization is completed, cool the reactant to room temperature, filter, remove The surface amphiphilic nanometer tungsten-molybdenum sulfide hydrogenation catalyst was obtained after washing with ion water and drying.

In the above-mentioned method, the addition method of the sulfur-containing tungsten source and the sulfur-containing molybdenum source described in step (1) can be added at the same time, and can also be sequentially added, that is, add the sulfur-containing tungsten source first and then add the sulfur-containing molybdenum source or first After adding the sulfur-containing molybdenum source, add the sulfur-containing tungsten source.

In the above method, the sulfur-containing tungsten source described in step (1) is one or both of dithiotungstate and tetrathiotungstate, and the cation of thiotungstate can be One or more of cations Na ⁺ , K ⁺ , NH ₄ ⁺ , Li ⁺ , and Mg ²⁺ that form soluble salts by substituting tungstate radicals.

In the above-mentioned method, the sulfur-containing molybdenum source described in step (1) is one or both of dithiomolybdate and tetrathiomolybdate, and the cation of thiomolybdate can be One or more of the cations Na ⁺ , K ⁺ , NH ₄ ⁺ , Li ⁺ , and Mg ²⁺ that form soluble salts with molybdate radicals.

In the above method, the sulfur source in step (2) is one or more of soluble sulfur compounds hydrogen sulfide, ammonium sulfide, sodium sulfide, potassium sulfide, preferably one or two of potassium sulfide and hydrogen sulfide.

In the above method, W:Mo (molar ratio) in step (1)=0.001-1000:1, preferably 0.005-800:1.

In the above method, the reaction temperature in step (2) is 45-98°C, preferably 50-90°C; the reaction time is 0.1-24h, preferably 0.5-20h.

In the above-mentioned method, the reducing agent described in step (3) is one or more of hydroxylamine hydrochloride, hydrazine hydrate, sodium borohydride, potassium borohydride, polyethyleneimine, preferably sodium borohydride and hydroxylamine hydrochloride One or two.

In the above-mentioned method, the ionic liquid cation described in step (4) is alkylimidazole, alkylpyridine, quaternary ammonium ion, quaternary phosphorus ion, guanidine, morpholine, choline, benzimidazole, benzotriazole One or any two or more, and the anion is one or any two or more of halide, tetrafluoroborate, hexafluorophosphate, nitrate, sulfate, carboxylate, phosphate, and carbonate.

In the above method, the concentration of (W+Mo) in the initial reaction mixture in step (4) is 0.001-2 mol/L, preferably 0.005-1.5 mol/L.

In the above method, S in the initial reaction mixture described in step (4): (Mo+W) (molar ratio)=2-6:1, preferably 2.2-5:1;

In the above-mentioned method, reducing agent in the initial reaction mixture described in step (4): (W+Mo) (molar ratio)=1-4:1, preferably 1.2-3:1; Ionic liquid: (W+Mo)( molar ratio)=0.01-25:1, preferably 0.1-15:1.

In the above method, the crystallization temperature in step (5) is 40-200°C, preferably 60-180°C; the crystallization time is 1-240h, preferably 4-180h.

The invention uses ionic liquid in the synthesis system, and the prepared nano-tungsten molybdenum sulfide has good surface amphiphilicity, and has excellent dispersibility and catalytic activity in both polar and non-polar catalytic reaction systems. The nano tungsten molybdenum sulfide catalyst provided by the present invention can be used in one or any two or more suspended bed hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, One or any two or more of the hydrogenation deasphalting reactions have high catalytic activity, and have good application prospects in photoelectric conversion, photocatalytic water hydrogen production and other reactions.

Description of drawings

Fig. 1 is the TEM picture that embodiment 4 prepares tungsten molybdenum sulfide.

Fig. 2 is the XRD spectrogram of the tungsten molybdenum sulfide prepared in Example 4.

detailed description

The following examples further illustrate the present invention, but the present invention is not limited to the following examples. Although the present invention has been described in detail with reference to the following embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the following embodiments, or perform equivalent replacements for some of the features, and these The modification or replacement does not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Example 1

This example illustrates the method of using 1-butyl-3-methylimidazolium tetrafluoroborate to prepare surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Add a certain amount of potassium tetrathiotungstate to 500mL deionized water to make the concentration of tungsten reach 0.02mol/L, and stir until uniform; add a certain amount of sodium dithiomolybdate to make the concentration of molybdenum reach 0.5mol/L Add sodium sulfide aqueous solution to the above mixture to make S:(W+Mo) (molar ratio) reach 2.4:1, stir until uniform, and react at 55°C for 18h; add hydroxylamine hydrochloride to the above mixture to make hydroxylamine hydrochloride: ( W+Mo) (molar ratio) reaches 3.2:1, stir until uniform; add ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate to the above mixture, make 1-butyl-3-methyl Imidazolium tetrafluoroborate: (W+Mo) (molar ratio) reached 20:1, stirred until uniform, and configured as an initial reaction mixture; the initial reaction mixture was transferred to a high-pressure synthesis kettle, and crystallized at 190°C for 6h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Example 2

This example illustrates the method of using 1-propyl-3-methylimidazolium hexafluorophosphate to prepare surface amphiphilic nanometer tungsten-molybdenum sulfide hydrogenation catalyst.

Add a certain amount of potassium dithiotungstate to 500mL deionized water to make the concentration of tungsten reach 0.05mol/L, and stir until uniform; add a certain amount of sodium dithiomolybdate to make the concentration of molybdenum reach 1.5mol/L Stir until uniform, add potassium sulfide aqueous solution to the above mixture, make S:(W+Mo) (molar ratio) reach 4:1, stir until uniform, react at 65°C for 14h; add potassium borohydride to the above mixture to make Potassium borohydride: (W+Mo) (molar ratio) reaches 2.2:1, stir until uniform; add ionic liquid 1-propyl-3-methylimidazolium hexafluorophosphate to the above mixture to make 1-propyl- 3-Methylimidazolium hexafluorophosphate: (W+Mo) (molar ratio) reaches 16:1, stir until uniform, and configure the initial reaction mixture; transfer the initial reaction mixture to a high-pressure synthesis kettle, and crystallize at 190°C 24h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Example 3

This example illustrates the method of using 1-pentyl-3-methylimidazolium bromide to prepare surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Add a certain amount of ammonium dithiotungstate to 500mL deionized water to make the concentration of tungsten reach 0.2mol/L, and stir until uniform; add a certain amount of sodium tetrathiomolybdate to make the concentration of molybdenum reach 1.6mol/L , stir until uniform; add hydrogen sulfide aqueous solution to the above mixture, so that S: (W+Mo) (molar ratio) reaches 4.2:1, stir until uniform, and react at 65°C for 12h; add polyethyleneimine to the above mixture , make polyethyleneimine: (W+Mo) (molar ratio) reach 1.6:1, stir until uniform; add ionic liquid 1-pentyl-3-methylimidazolium bromide to the above mixture, make 1-pentyl -3-Methylimidazolium bromide: (W+Mo) (molar ratio) reaches 0.02:1, stir until uniform, and configure the initial reaction mixture; transfer the initial reaction mixture to a high-pressure synthesis kettle, and crystallize at 165°C for 40h . After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Example 4

This example illustrates the method of using 1-isopropyl-2,3-dimethylimidazolium tetrafluoroborate to prepare surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Add a certain amount of potassium tetrathiotungstate to 500mL deionized water to make the concentration of tungsten reach 1.5mol/L, and stir until uniform; add a certain amount of potassium tetrathiomolybdate to make the concentration of molybdenum reach 0.02mol/L , stir until uniform; add ammonium sulfide aqueous solution to the above mixture, make S:(W+Mo) (molar ratio) reach 5:1, stir until uniform, react at 65°C for 6h; add sodium borohydride to the above mixture, Sodium borohydride: (W+Mo) (molar ratio) reaches 2.6:1, stir until uniform; add ionic liquid 1-isopropyl-2,3-dimethylimidazolium tetrafluoroborate to the above mixture, Make 1-isopropyl-2,3-dimethylimidazolium tetrafluoroborate: (W+Mo) (molar ratio) to 0.6:1, stir until uniform, configure the initial reaction mixture; transfer the initial reaction mixture Put it into a high-pressure synthesis kettle and crystallize at 160°C for 66h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst. Figures 1 and 2 show the TEM photos and XRD spectra of the tungsten and molybdenum sulfide samples prepared in Example 4, respectively. It can be seen that the samples are lamella-stacked nanoparticles of about 50 nm, and the obviously broadened XRD peaks also indicate that the samples have nanoscale dimensions.

Example 5

This example illustrates the method of using N-propylpyridine tetrafluoroborate to prepare surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Add a certain amount of sodium dithiotungstate to 500mL deionized water to make the concentration of tungsten reach 0.25mol/L, and stir until uniform; add a certain amount of ammonium dithiomolybdate to make the concentration of molybdenum reach 1.25mol/L , stir until uniform; add potassium sulfide aqueous solution to the above mixture, make S:(W+Mo) (molar ratio) reach 3.3:1, stir until uniform, react at 80°C for 8h; add sodium borohydride to the above mixture, Sodium borohydride: (W+Mo) (molar ratio) reaches 2.8:1, stir until uniform; add ionic liquid N-propylpyridine tetrafluoroborate to the above mixture, make N-propylpyridine tetrafluoroboron Acid acid: (W+Mo) (molar ratio) reached 18:1, stirred until uniform, and configured as an initial reaction mixture; transferred the initial reaction mixture to a high-pressure synthesis kettle, and crystallized at 90°C for 98h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Example 6

This example illustrates the method of using N-ethylpyridinium bromide salt to prepare surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Add a certain amount of lithium dithiotungstate to 500mL deionized water to make the concentration of tungsten reach 1.15mol/L, and stir until uniform; add a certain amount of potassium dithiomolybdate to make the concentration of molybdenum reach 0.01mol/L , stir until uniform; add potassium sulfide aqueous solution to the above mixture, make S:(W+Mo) (molar ratio) reach 2.6:1, stir until uniform, react at 60°C for 5h; add potassium borohydride to the above mixture, Potassium borohydride: (W+Mo) (molar ratio) reaches 2.5:1, stir until uniform; Add ionic liquid N-ethylpyridinium bromide to the above mixture, make N-ethylpyridinium bromide: (W+ Mo) (molar ratio) reached 18:1, stirred until uniform, and configured as an initial reaction mixture; the initial reaction mixture was transferred to a high-pressure synthesis kettle, and crystallized at 95° C. for 60 h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten sulfide hydrogenation catalyst.

Example 7

This example illustrates the method of using N-propylpyridinium bromide salt to prepare surface amphiphilic nano tungsten sulfide hydrogenation catalyst.

Add a certain amount of ammonium tetrathiotungstate to 500mL deionized water to make the concentration of tungsten reach 0.75mol/L, and stir until uniform; add a certain amount of ammonium dithiomolybdate to make the concentration of molybdenum reach 0.15mol/L , stir until uniform; add sodium sulfide aqueous solution to the above mixture, so that S: (W+Mo) (molar ratio) reaches 4.6:1, stir until uniform, and react at 65 ° C for 6 h; add hydrazine hydrate to the above mixture to make Hydrazine hydrate: (W+Mo) (molar ratio) reaches 2.8:1, stir until uniform; add ionic liquid N-propylpyridinium bromide to the above mixture to make N-propylpyridinium bromide: (W+Mo) (molar ratio) reached 24:1, stirred until uniform, and configured as an initial reaction mixture; the initial reaction mixture was transferred to a high-pressure synthesis kettle, and crystallized at 66° C. for 90 h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Example 8

This example illustrates the method of using tetrabutylammonium bromide to prepare surface amphiphilic nano-tungsten sulfide hydrogenation catalyst.

Add a certain amount of lithium dithiotungstate to 500mL deionized water to make the concentration of tungsten reach 1.2mol/L, and stir until uniform; add a certain amount of potassium tetrathiomolybdate to make the concentration of molybdenum reach 0.02mol/L , stir until uniform; add potassium sulfide aqueous solution to the above mixture, make S:(W+Mo) (molar ratio) reach 2.6:1, stir until uniform, react at 65°C for 6.6h; add hydroxylamine hydrochloride to the above mixture, Make hydroxylamine hydrochloride: (W+Mo) (molar ratio) reach 3.2:1, stir until uniform; Add ionic liquid tetrabutylammonium bromide in the above-mentioned mixture, make tetrabutylammonium bromide: (W+Mo)( Molar ratio) reached 24:1, stirred until uniform, and configured as an initial reaction mixture; the initial reaction mixture was transferred to a high-pressure synthesis kettle, and crystallized at 65°C for 12h. After the crystallization is completed, the reactant is cooled to room temperature with tap water, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Example 9

This example illustrates a method for preparing a surface amphiphilic nano-sized tungsten sulfide hydrogenation catalyst by using a mixed ionic liquid of N-isopropylpyridinium bromide and tetrabutylammonium bromide in an equimolar ratio.

Add the same amount of potassium dithiotungstate and lithium tetrathiotungstate to 500mL deionized water to make the concentration of tungsten reach 0.02mol/L, and stir until uniform; Potassium thiomolybdate and ammonium tetrathiomolybdate, so that the concentration of molybdenum reaches 0.5mol/L, stir until uniform; add hydrogen sulfide aqueous solution to the above mixture, so that S: (W+Mo) (molar ratio) reaches 2.6 : 1, stirred until uniform, reacted at 65°C for 2.8h; added sodium borohydride to the above mixture to make sodium borohydride: (W+Mo) (molar ratio) reach 3.4:1, stirred until uniform; added to the above mixture Add the mixed ionic liquid of N-isopropylpyridinium bromide and tetrabutylammonium bromide in equimolar ratio, so that the ionic liquid: (W+Mo) (molar ratio) reaches 22:1, stir until uniform, and configure the initial Reaction mixture; the initial reaction mixture was transferred to a high-pressure synthesis kettle, and crystallized at 80° C. for 160 h. After the crystallization is completed, the reactant is cooled to room temperature, filtered, washed with deionized water and dried to obtain a surface amphiphilic nano-tungsten-molybdenum sulfide hydrogenation catalyst.

Examples 10-18

The raw material used in the following examples is Shandong medium and low temperature coal tar>320°C residue, and its properties are shown in Table 1. Examples 10-18 used a high-pressure suspended bed reaction process to test the catalytic activity of the catalysts prepared in Examples 1-9, and the results are shown in Table 2.

Table 1 Properties of Karamay super heavy oil atmospheric residue

Table 2 Suspension bed high pressure hydrogenation evaluation results

It can be seen that the surface amphiphilic nano-tungsten molybdenum sulfide provided by the present invention has the advantages of extremely high hydrogenation activity and coking inhibition in the preparation of liquid fuels by hydrogenation conversion of heavy components of coal tar. When the amount of catalyst used (calculated as sulfide) ≤ 300ppm, the removal rate of asphaltenes is > 98%, and the fraction yield at 180-360°C in the product is ≤ 60%.

Claims (10)

1. a preparation method for surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst, is characterized in that comprising the following steps:

(1) in deionized water, add sulfur-bearing tungsten source and sulfur-bearing molybdenum source, sulphur source, heat up and react;

(2) add reducing agent, ionic liquid to said mixture kind, stir and be configured to initial reaction mixture;

(3) initial reaction mixture is transferred to crystallization in Autoclaves for synthesis;

(4) after crystallization terminates, reactant is cooled to room temperature, separating solids product obtains surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.

2. in accordance with the method for claim 1, it is characterized in that: the sulfur-bearing tungsten source described in step (1) is one or both of two thiqtung states and tetrathio tungstates, the cation of thiqtung state is can form the cation Na of soluble-salt with thiotungstate ⁺, K ⁺, NH ₄ ⁺, Li ⁺, Mg ²⁺one or two or more kinds; Sulfur-bearing molybdenum source is one or both of two Thiomolybdates and tetrathiomolybdate, and the cation of Thiomolybdate is can form the cation Na of soluble-salt with thiomolybdate ⁺, K ⁺, NH ₄ ⁺, Li ⁺, Mg ²⁺one or two or more kinds; W:Mo (mol ratio)=0.001-1000:1, preferred 0.005-800:1.Described sulphur source be solubility sulfur-containing compound hydrogen sulfide, ammonium sulfide, vulcanized sodium, potassium sulfide one or two or more kinds, the one of preferred potassium sulfide and hydrogen sulfide or two kinds.

3. in accordance with the method for claim 1, it is characterized in that: the reaction temperature described in step (1) is 45-98 DEG C, preferable reaction temperature 50-90 DEG C; Reaction time is 0.1-24h, preferred reaction time 0.5-20h.

4. in accordance with the method for claim 1, it is characterized in that: the reducing agent described in step (2) be hydroxylamine hydrochloride, hydrazine hydrate, sodium borohydride, potassium borohydride, polymine one or two or more kinds, the one of preferred sodium borohydride and hydroxylamine hydrochloride or two kinds.

5. in accordance with the method for claim 1, it is characterized in that: the ionic liquid cation described in step (2) be alkyl imidazole, alkyl pyridine, quaternary ammonium ion, quaternary phosphonium ion, guanidine, morpholine, choline, benzimidazole, the one of BTA or any two more than, anion is halide ion, tetrafluoroborate, hexafluoro-phosphate radical, nitrate anion, sulfate radical, carboxylate radical, phosphate radical, carbonate.

6. in accordance with the method for claim 1, it is characterized in that: in step (2) described initial reaction mixture, the concentration of (W+Mo) is 0.001-2mol/L, preferred 0.005-1.5mol/L;

S:(Mo+W) (mol ratio)=2-6:1, preferred 2.2-5:1;

Reducing agent: (W+Mo) (mol ratio)=1-4:1, preferred 1.2-3:1; Ionic liquid: (W+Mo) (mol ratio)=0.01-25:1, preferred 0.1-15:1.

7. in accordance with the method for claim 1, it is characterized in that: the crystallization temperature described in step (3) is 40-200 DEG C, preferred crystallization temperature is 60-180 DEG C;

Crystallization time is 1-240h, and preferred crystallization time is 4-180h.

8. in accordance with the method for claim 1, it is characterized in that: the process of separating solids product is filtration, deionized water is washed, drying, obtains product.

9. the surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst prepared of the arbitrary described preparation method of claim 1-8.

10. a kind of in coal tar, heavy oil, extra heavy oil, residual oil, shale oil of a surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst according to claim 9 or the floating bed hydrogenation desulfurization more than any two, hydrodenitrogeneration, hydrogenation aromatics-removing, hydrogenation depitching reaction a kind of or any two is with upper application.