CN105498807A - Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof - Google Patents
Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN105498807A CN105498807A CN201410495418.4A CN201410495418A CN105498807A CN 105498807 A CN105498807 A CN 105498807A CN 201410495418 A CN201410495418 A CN 201410495418A CN 105498807 A CN105498807 A CN 105498807A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- preferred
- hydrogenation
- add
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, a preparation method and an application thereof. The preparation method includes the following steps: preparing an initial reaction mixture from a tungsten source, a molybdenum source containing sulfur, a sulfur source, a reduction agent, an ionic liquid and deionized water according to certain sequences and methods; performing crystallization in a sealed high-pressure reaction kettle under a hydrothermal condition; and filtering, washing and drying a crystallized product to prepare the surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst. In the synthetic system, the ionic liquid is employed so that the nano tungsten molybdenum sulfide has excellent surface amphipathy and has great dispersibility and catalytic activity in both polar and non-polar catalytic reaction systems. The nano tungsten molybdenum sulfide catalyst has great catalytic activity in hydrogenation deasphaltizing, hydrogenation desulfurization, hydrogenation denitrification, aromatic hydrocarbon hydrogenation of heavy oil, such as coal tar, heavy oil, ultra-heavy oil, residual oil, shale oil and the like, with a suspended bed. The nano tungsten molybdenum sulfide has great application prospect in the reactions of photovoltaic conversion, photo-catalytic water producing reaction and the like.
Description
Technical field
The present invention relates to a kind of surperficial amphiphilic nano tungsten sulfide molybdenum catalyst and preparation method thereof and application, belong to synthesis and the catalytic applications of nano material.
Background technology
Suspension bed hydrogenation process is the advanced technology of the unconventional oil of heavy (residual oil, heavy oil/extra heavy oil, shale oil, coal tar heavy duty component, sandstone oil, oil sands bitumen etc.) Hydrogenation for liquid-fuel oil.Suspension bed hydrogenation process requires that catalyst has high activity, polymolecularity, high stability, good economy, and the catalyst that preparation is applicable to suspension bed hydrogenation process is a challenging problem.
Non-noble metal sulfided thing is a kind of stratified material with class graphene-structured, has showed good application in fields such as catalysis, microelectronics, semiconductors.Loaded tungsten sulfide, molybdenum sulfide catalyst are used as hydrogenation catalyst in PETROLEUM PROCESSING field always, be widely used in the reaction (ChianelliR. such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation dearomatization, hydrogenation deoxidation and HDM, Catal.Today, 2009,147,275-286).Non-supported sulfuration tungsten is that a kind of being expected to very much is applicable to the catalyst of suspension bed process heavy oil Hydrogenation for clean fuel.
The preparation method of current tungsten sulfide, molybdenum sulfide mainly contains (WangS., Materials, 2010,3,401-433) such as high temperature vulcanized method, presoma decomposition method, solvent-thermal method, electrochemical deposition method, template.But the sulfide catalyst prepared of these research methods at present, or be water miscible, or be oil-soluble.Because mink cell focus composition is very complicated, simultaneously containing polarity and apolar substance, the tungsten sulfide dispersiveness wherein of single surperficial sympathy is not very desirable.Therefore gentle solwution method is utilized to have the nanometer sulfide catalyst of surperficial parents to be the keys improving its dispersiveness by chemical synthesis.
CN200910226642.2 discloses a kind of preparation method of single dispersing tungsten disulfide nano slices; with tungsten oxide and sulphur for raw material; after ball milling admixture activation; in protective atmosphere at 600-700 DEG C cycle annealing 30-120min; in cycle annealing process, preamble part sulphur powder sulphur source as a supplement in advance, supplements the mass ratio of sulphur powder and reactant mixture between 0.05-10; then cool to the furnace in protective atmosphere after below 250 DEG C, single dispersing tungsten disulfide nano slices can be obtained.The present invention has prepared a large amount of single dispersing sheet Wolfram disulfide nano materials by simple and effective chemical synthesis process, method simple and fast, and production cost is low, and it can extensive use in lubrication and catalysis.
It is the method that catalyst oxidation removes simulated oil medium sulphide content that CN201310272706.9 discloses a kind of transition metal tungstates that adopts, can implement as follows: (1) takes transition metal nitrate, be dissolved in water, add sodium tungstate, at room temperature stir; After collecting product washing, dry, then product is calcined, obtain transition metal tungstates; (2) tungstates that step (1) is synthesized is joined in simulated oil, add oxidant and softex kw, reactant mixture is cooled to room temperature, separate oil phase; Continue and add N-N-dimethyl formamide continuation stirring, separate oil phase, measure sulfur content and also calculate desulfurization degree; (3) reclaim tungstate catalysts, oven dry, washing are reused after removing the drying of surface sulfide thing.
CN201310317514.5 discloses a kind of oil-soluble autovulcanization molybdenum catalyst, its preparation method, using method and application, wherein preparation method comprises the following steps: (1), under nitrogen protection, in order molybdenum source, water, vulcanized sodium, solvent, inorganic acid are placed in container, mixing and stirring also cools at 5-50 DEG C, reaction 10-150min; (2), add alkylamine and carbon disulfide, stir, be heated to 60-200 DEG C of reaction 3-10h; (3), reaction terminate after product is fully cooled rear suction filtration, fully wash with methyl alcohol, drying obtains oil-soluble autovulcanization molybdenum catalyst.Oil-soluble autovulcanization molybdenum catalyst provided by the invention autovulcanization decomposition in situ can form molybdenum bisuphide active component, for in the inferior heavy oil slurry bed system hydrocracking process containing high metal, high carbon residue, high-sulfur, coke yield can be reduced, holdout device long-term operation.
CN201210512991.2 discloses a kind of nanometer MOS 2 particle and preparation method thereof and application.The method comprises the steps: molybdenite or micron order molybdenum bisuphide and ionic liquid and/or organic solvent to carry out being mixed to get mixture, is carried out by this mixture grinding and/or ultrasonic, then namely obtains described nanometer MOS 2 particle through being separated.The nano molybdenum disulfide that this invention provides shows fabulous catalytic activity in the oxidation reaction etc. of hydrodesulfurization reaction, Hydrogen evolving reaction, methyl alcohol.Meanwhile, as a kind of semiconductor nano material, it has application prospect equally in opto-electronic conversion and photocatalysis water-splitting etc.Most importantly, nano molybdenum disulfide shows very excellent catalytic performance in oxygen reduction reaction.
CN201110274120.7 discloses a kind of heavy-oil hydrogenation guard catalyst and Synthesis and applications thereof, with AL
2o
3or containing SiO
2aL
2o
3for carrier, carrier pore volume is 0.98-1.15mL/g, specific surface 340-380m
2/ g, pore size distribution is as follows: the pore volume of bore dia < 5nm accounts for the 10%-15% of total pore volume, and the pore volume of bore dia 5-15nm accounts for the 50%-55% of total pore volume, and the pore volume of bore dia > 15nm accounts for the 25%-40% of total pore volume; Nickel-loaded molybdenum sulphur, nickel tungsten sulphur, molybdenum sulfide, tungsten sulfide, cobalt molybdenum sulphur, cobalt tungsten sulphur, nickel cobalt molybdenum sulphur, nickel cobalt tungsten sulphur or the same Ni of cobalt molybdenum nickel tungsten
2p carries out the composite catalyst combined; This catalyst has aperture and is suitable for, melts that metal ability is high, active component yardstick is little, good dispersion degree, catalyst activity are high, is applicable to being applied to heavy oil and heavy oil guard catalyst.
CN200410009977.6 discloses a kind of method for preparing catalyst of sulfur-bearing Transition Metal Cluster Compounds compound, the clusters containing two cores, three cores and four-core metal molybdenum or tungsten of this invention be by metal oxide electrolysis in acid solution, sulfuration, oxidation, concentrated, to be separated and the step such as chemical reaction prepares.This kind of clusters has following bunch of core: [M
2o
ns
2-n]
m+, [M
3o
ns
4-n]
m+or [M
4o
ns
6-n]
m+, (M=Mo or W, n=0-6, m=0-6).Metal Co, Ni, Cu, Fe, Sn etc. can the cation Cheng Jian of bunch core therewith, form the Transition Metal Cluster Compounds compound of many metals species.The clusters of the sulfur-bearing transition metal molybdenum that this kind of method prepares or tungsten has clear and definite atom or molecular structure and good stability.Loaded sulfur-bearing aluminium or the clusters of tungsten have better hydrodesulfurization performance than catalyst prepared by traditional dipping method.
Ionic liquid refers to the salt combined at the inorganic anion of complete relatively large by volume, organic cation that symmetry is poor in liquid condition of room temperature or near room temperature (lower than 100 DEG C) and small volume, because positive and negative charge number is equal, thus show electroneutral on the whole.Usually also referred to as ionic liquid at room temperature.The advantage that ionic liquid has that polarity is adjustable, solubility property is good, liquid journey wide ranges, heat endurance are high and almost negligible vapour pressure etc. is unique, the field such as to prepare in extraction, catalysis, organic synthesis and inorganic material and achieves and apply widely.(T.Welton，Chem.Rev.，1999，99，2071；R.D.Rogers，K.D.Seddon，Nature，2003，302，792.)
CN03115271.6 discloses a kind of preparation method of ionic liquid at room temperature.It is characterized in that adopting target product and ionic liquid at room temperature to be reaction medium, with alkyl pyridine ammonium halide or alkyl imidazole ammonium halide and containing villiaumite for raw material, prepare the ionic liquid at room temperature be made up of alkylpyridiniium cation or alkylimidazolium cation and fluo anion.The method is easy and simple to handle, and reaction condition is gentle, and good product quality, and course of reaction environmental friendliness are a kind of preparation methods of green ionic liquid at room temperature.
CN201210512991.2 discloses a kind of nanometer MOS 2 particle and preparation method thereof and application.The method comprises the steps: molybdenite or micron order molybdenum bisuphide and ionic liquid and/or organic solvent to carry out being mixed to get mixture, is carried out by this mixture grinding and/or ultrasonic, then namely obtains described nanometer MOS 2 particle through being separated.This nano molybdenum disulfide provided by the invention shows fabulous catalytic activity in the oxidation reaction etc. of hydrodesulfurization reaction, Hydrogen evolving reaction, methyl alcohol.Meanwhile, as a kind of semiconductor nano material, it has application prospect equally in opto-electronic conversion and photocatalysis water-splitting etc.Most importantly, nano molybdenum disulfide shows very excellent catalytic performance in oxygen reduction reaction.
Summary of the invention
The object of the invention is to for the problems referred to above, a kind of surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst and preparation method thereof and application are provided.
Object of the present invention can realize in the following manner:
Adopt solution chemical method, be that surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst prepared by auxiliary agent with ionic liquid, comprise the following steps: (1) adds tungsten source and sulfur-bearing molybdenum source in deionized water, stirs and is configured to certain density solution; (2) in said mixture, add sulphur source, stir, react certain hour at a certain temperature; (3) in said mixture, add reducing agent, stir; (4) in said mixture, add ionic liquid, stir, be configured to initial reaction mixture; (5) initial reaction mixture is transferred in Autoclaves for synthesis, at a certain temperature crystallization certain hour; (6) after crystallization terminates, reactant is cooled to room temperature, uses conventional solid-liquid separation means, as filtration, deionized water washing also drying, obtain surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In the methods described above, the feed postition in the tungsten source described in step (1) and sulfur-bearing molybdenum source can be add simultaneously, also can be that order adds, add sulfur-bearing molybdenum source or first add Hou Jiawu source, sulfur-bearing molybdenum source after namely first adding tungsten source.
In the methods described above, tungsten source described in step (1) is one or two or more kinds of the solubility Tungstenic compounds such as wolframic acid, sodium tungstate, potassium tungstate, ammonium tungstate, tungstate lithium, tungsten chloride, nitric acid tungsten, acetic acid tungsten, the one in preferred wolframic acid, potassium tungstate and tungsten chloride or any two or three kinds.
In the methods described above, the sulfur-bearing molybdenum source described in step (1) is one or both of two Thiomolybdates or tetrathiomolybdate, and the cation of Thiomolybdate can for forming the cation Na of soluble-salt with thiomolybdate
+, K
+, NH
4 +, Li
+, Mg
2+one or two or more kinds.
In the methods described above, W:Mo (the mol ratio)=0.001-1000:1 described in step (1), preferred 0.005-800:1.
In the methods described above, the sulphur source described in step (2) is one or two or more kinds of the solubility sulfur-containing compounds such as hydrogen sulfide, ammonium sulfide, vulcanized sodium, potassium sulfide, the one of preferred potassium sulfide and hydrogen sulfide or two kinds.
In the methods described above, the reaction temperature described in step (2) is 45-98 DEG C, and preferable reaction temperature is 50-90 DEG C; Reaction time is 0.1-24h, and the preferred reaction time is 0.5-20h.
In the methods described above, the reducing agent described in step (3) 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.
In the methods described above, ionic liquid cation described in step (4) be one in alkyl imidazole, alkyl pyridine, quaternary ammonium ion, quaternary phosphonium ion, guanidine, morpholine, choline, benzimidazole, BTA or any two more than, anion be one in halide ion, tetrafluoroborate, hexafluoro-phosphate radical, nitrate anion, sulfate radical, carboxylate radical, phosphate radical, carbonate or any two more than.
In the methods described above, in step (4) described initial reaction mixture, the concentration of (W+Mo) is 0.001-2mol/L, preferred 0.005-1.5mol/L.
In the methods described above, S:(Mo+W in step (4) described initial reaction mixture) (mol ratio)=1.2-6:1, preferred 1.5-5:1; 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.
In the methods described above, the crystallization temperature described in step (5) is 40-200 DEG C, and preferred crystallization temperature is 60-180 DEG C; Crystallization time is 1-240h, and preferred crystallization time is 4-180h.
The present invention employs ionic liquid in synthetic system, and it is amphiphilic that prepared nanometer sulfuration tungsten has well surface, in polarity, nonpolar catalystic converter system, all have fabulous dispersiveness and catalytic activity.A kind of in coal tar, heavy oil, extra heavy oil, residual oil, shale oil of nanometer sulfuration tungsten catalyst provided by the invention or the floating bed hydrogenation desulfurization more than any two, hydrodenitrogeneration, hydrogenation aromatics-removing, hydrogenation depitching reaction a kind of or any two showed very high catalytic activity with upper, have a good application prospect in the reaction such as opto-electronic conversion, the hydrogen manufacturing of photocatalysis water.
Accompanying drawing explanation
Fig. 1 is the TEM photo that embodiment 2 prepares sulfuration tungsten.
Fig. 2 is the XRD spectra that embodiment 2 prepares sulfuration tungsten.
Detailed description of the invention
The present invention is described further for following embodiment, but the present invention is not limited to following embodiment.Although with reference to once embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, it still can be modified to the technical scheme that following each embodiment is stated, or equivalent replacement is carried out to wherein Partial Feature, and these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Embodiment 1
The present embodiment illustrates the method using 1-butyl-3-methyl imidazolium tetrafluoroborate to prepare surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In 500mL deionized water, add a certain amount of sodium tungstate, make the concentration of tungsten reach 0.01mol/L, be stirred to evenly; Add a certain amount of two thio molybdenum acid sodiums, make the concentration of molybdenum reach 0.1mol/L and add sodium sulfide solution in said mixture, make Na
2s:(W+Mo) (mol ratio) reaches 2.6:1, is stirred to evenly, at 65 DEG C of reaction 16h; In said mixture, add hydroxylamine hydrochloride, make hydroxylamine hydrochloride: (W+Mo) (mol ratio) reaches 3.5:1, be stirred to evenly; In said mixture, add ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, make 1-butyl-3-methyl imidazolium tetrafluoroborate: (W+Mo) (mol ratio) reaches 22:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 200 DEG C of crystallization 4h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 2
The present embodiment illustrates the method using 1-propyl group-3-methylimidazole hexafluorophosphate to prepare surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In 500mL deionized water, add a certain amount of potassium tungstate, make the concentration of tungsten reach 0.015mol/L, be stirred to evenly; Add a certain amount of two sulfo-potassium molybdates, make the concentration of molybdenum reach 0.001mol/L; Be stirred to and evenly in said mixture, add potassium sulfide aqueous solution, make K
2s:(W+Mo) (mol ratio) reaches 5:1, is stirred to evenly, at 55 DEG C of reaction 16h; In said mixture, add potassium borohydride, make potassium borohydride: (W+Mo) (mol ratio) reaches 2.4:1, be stirred to evenly; In said mixture, add ionic liquid 1-propyl group-3-methylimidazole hexafluorophosphate, make 1-propyl group-3-methylimidazole hexafluorophosphate: (W+Mo) (mol ratio) reaches 15:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 180 DEG C of crystallization 22h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.Fig. 1 and Fig. 2 sets forth TEM photo and the XRD spectra of sulfuration tungsten sample prepared by embodiment 2, and can see that sample is the lamella accumulation nano particle of about 50nm, the XRD of obvious broadening composes peak and also shows that sample has nano level size.
Embodiment 3
The present embodiment illustrates the method using 1-amyl group-3-methylimidazole bromine salt to prepare surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In 500mL deionized water, add a certain amount of nitric acid tungsten, make the concentration of tungsten reach 0.5mol/L, be stirred to evenly; Add a certain amount of tetrathiomolybdate sodium, make the concentration of molybdenum reach 1.5mol/L, be stirred to evenly; In said mixture, add hydrogen sulfide solution, make hydrogen sulfide: (W+Mo) (mol ratio) reaches 2.1:1, be stirred to evenly, at 56 DEG C of reaction 16h; In said mixture, add polymine, make polymine: (W+Mo) (mol ratio) reaches 1.8:1, be stirred to evenly; In said mixture, add ionic liquid 1-amyl group-3-methylimidazole bromine salt, make 1-amyl group-3-methylimidazole bromine salt: (W+Mo) (mol ratio) reaches 0.05:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 155 DEG C of crystallization 45h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 4
The present embodiment illustrates the method using 1-isopropyl-2,3-methylimidazole tetrafluoroborate to prepare surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In 500mL deionized water, add a certain amount of acetic acid tungsten, make the concentration of tungsten reach 0.5mol/L, be stirred to evenly; Add a certain amount of tetrathio potassium molybdate, make the concentration of molybdenum reach 0.05mol/L, be stirred to evenly; In said mixture, add ammonium sulfide solution, make ammonium sulfide: (W+Mo) (mol ratio) reaches 2.2:1, be stirred to evenly, at 62 DEG C of reaction 5h; In said mixture, add sodium borohydride, make sodium borohydride: (W+Mo) (mol ratio) reaches 2.7:1, be stirred to evenly; Ionic liquid 1-isopropyl-2 is added in said mixture, 3-methylimidazole tetrafluoroborate, makes 1-isopropyl-2,3-methylimidazole tetrafluoroborate: (W+Mo) (mol ratio) reaches 0.2:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 130 DEG C of crystallization 75h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 5
The present embodiment illustrates the method using N-propyIpyridine tetrafluoroborate to prepare surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In 500mL deionized water, add a certain amount of tungsten chloride, make the concentration of tungsten reach 0.05mol/L, be stirred to evenly; Add a certain amount of two ammonium thiomolybdates, make the concentration of molybdenum reach 1.25mol/L, be stirred to evenly; In said mixture, add potassium sulfide aqueous solution, make potassium sulfide: (W+Mo) (mol ratio) reaches 3.2:1, be stirred to evenly, at 86 DEG C of reaction 3h; In said mixture, add sodium borohydride, make sodium borohydride: (W+Mo) (mol ratio) reaches 3.2:1, be stirred to evenly; In said mixture, add ionic liquid N-propyIpyridine tetrafluoroborate, make N-propyIpyridine tetrafluoroborate: (W+Mo) (mol ratio) reaches 12:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 100 DEG C of crystallization 96h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 6
The present embodiment illustrates the method using N-ethylpyridine bromine salt to prepare surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst.
In 500mL deionized water, add a certain amount of wolframic acid, make the concentration of tungsten reach 0.15mol/L, be stirred to evenly; Add a certain amount of two sulfo-potassium molybdates, make the concentration of molybdenum reach 0.1mol/L, be stirred to evenly; In said mixture, add potassium sulfide aqueous solution, make potassium sulfide: (W+Mo) (mol ratio) reaches 2.8:1, be stirred to evenly, at 60 DEG C of reaction 4h; In said mixture, add potassium borohydride, make potassium borohydride: (W+Mo) (mol ratio) reaches 2.4:1, be stirred to evenly; In said mixture, add ionic liquid N-ethylpyridine bromine salt, make N-ethylpyridine bromine salt: (W+Mo) (mol ratio) reaches 12:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 95 DEG C of crystallization 160h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano tungsten sulfide hydrogenation catalyst after drying.
Embodiment 7
The present embodiment illustrates the method using N-propyIpyridine bromine salt to prepare surperficial amphiphilic nano tungsten sulfide hydrogenation catalyst.
In 500mL deionized water, add a certain amount of ammonium tungstate, make the concentration of tungsten reach 0.05mol/L, be stirred to evenly; Add a certain amount of two ammonium thiomolybdates, make the concentration of molybdenum reach 0.15mol/L, be stirred to evenly; In said mixture, add sodium sulfide solution, make vulcanized sodium: (W+Mo) (mol ratio) reaches 2.2:1, be stirred to evenly, at 65 DEG C of reaction 4h; In said mixture, add hydrazine hydrate, make hydrazine hydrate: (W+Mo) (mol ratio) reaches 2.9:1, be stirred to evenly; In said mixture, add ionic liquid N-propyIpyridine bromine salt, make N-propyIpyridine bromine salt: (W+Mo) (mol ratio) reaches 22:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 68 DEG C of crystallization 160h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 8
The present embodiment illustrates the method using TBAB to prepare surperficial amphiphilic nano tungsten sulfide hydrogenation catalyst.
In 500mL deionized water, add a certain amount of tungstate lithium, make the concentration of tungsten reach 1.5mol/L, be stirred to evenly; Add a certain amount of tetrathio potassium molybdate, make the concentration of molybdenum reach 0.01mol/L, be stirred to evenly; In said mixture, add potassium sulfide aqueous solution, make potassium sulfide: (W+Mo) (mol ratio) reaches 2.3:1, be stirred to evenly, at 65 DEG C of reaction 6.8h; In said mixture, add hydroxylamine hydrochloride, make hydroxylamine hydrochloride: (W+Mo) (mol ratio) reaches 3.3:1, be stirred to evenly; In said mixture, add ionic liquid TBAB, make TBAB: (W+Mo) (mol ratio) reaches 18:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 60 DEG C of crystallization 12h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 9
The N-isopropyl pyridine bromine salt of the present embodiment explanation equimolar ratio mixing and TBAB mixed ionic liquid prepare the method for surperficial amphiphilic nano tungsten sulfide hydrogenation catalyst.
In 500mL deionized water, wolframic acid and the tungsten chloride of amount of substance such as to add, make the concentration of tungsten reach 0.02mol/L, be stirred to evenly; Add amount of substance than two sulfo-potassium molybdate and the four thio ammonium molybdates for 3:7, make the concentration of molybdenum reach 0.4mol/L, be stirred to evenly; In said mixture, add hydrogen sulfide solution, make hydrogen sulfide: (W+Mo) (mol ratio) reaches 2.8:1, be stirred to evenly, at 75 DEG C of reaction 2.2h; In said mixture, add sodium borohydride, make sodium borohydride: (W+Mo) (mol ratio) reaches 3.2:1, be stirred to evenly; In said mixture, add mixed ionic liquid, make ionic liquid: (W+Mo) (mol ratio) reaches 24:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 80 DEG C of crystallization 180h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst after drying.
Embodiment 10-18
The raw material that following examples use is coalite tar >320 DEG C residue in Shandong, and character is shown in table 1.Embodiment 10-18 adopts high pressure suspending bed reaction technique, and carried out catalytic activity test to the catalyst prepared by embodiment 1-9 respectively, result illustrates in table 2.
Table 1 Kelamayi super-viscous oil reduced crude character
Table 2 suspension bed high-pressure hydrogenation evaluation result
Can see, the nanometer sulfuration tungsten of surperficial parents provided by the invention prepares in liquid fuel the advantage having high hydrogenation activity and suppress coking at coal tar heavy duty component hydro-conversion.In catalyst use amount (in sulfide)≤300ppm situation, asphaltene removal >98%, 180-360 DEG C of cut yield >60% in product.
Claims (10)
1. surperficial amphiphilic nano sulfuration tungsten hydrogenation catalyst and preparation method thereof and an application, is characterized in that comprising the following steps:
(1) in deionized water, add tungsten source, sulfur-bearing molybdenum source, sulphur source, heat up and react;
(2) in said mixture, add reducing agent, ionic liquid, 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, the tungsten source that it is characterized in that described in step (1) be solubility Tungstenic compound wolframic acid, sodium tungstate, potassium tungstate, ammonium tungstate, tungstate lithium, tungsten chloride, nitric acid tungsten, acetic acid tungsten one or two or more kinds, the one in preferred wolframic acid, potassium tungstate and tungsten chloride or any two or three kinds; Described sulfur-bearing molybdenum source is one or both of two Thiomolybdates or 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; 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 W:Mo (the mol ratio)=0.001-1000:1 described in step (1), preferred 0.005-800:1.
4. 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, preferred 50-90 DEG C; Reaction time is 0.1-24h, preferred 0.5-20h.
5. in accordance with the method for claim 1, the reducing agent that it is characterized in that 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; Described ionic liquid cation 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 be halide ion, tetrafluoroborate, hexafluoro-phosphate radical, nitrate anion, sulfate radical, carboxylate radical, phosphate radical, the one of carbonate or any two more than.
6. in accordance with the method for claim 1, it is characterized in that the concentration of (W+Mo) in step (2) described initial reaction mixture is 0.001-2mol/L, preferred 0.005-1.5mol/L; S:(Mo+W in initial reaction mixture) (mol ratio)=1.2-6:1, preferred 1.5-5:1; 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 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410495418.4A CN105498807B (en) | 2014-09-25 | 2014-09-25 | A kind of surface amphiphilic nano vulcanization tungsten hydrogenation catalyst and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410495418.4A CN105498807B (en) | 2014-09-25 | 2014-09-25 | A kind of surface amphiphilic nano vulcanization tungsten hydrogenation catalyst and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105498807A true CN105498807A (en) | 2016-04-20 |
| CN105498807B CN105498807B (en) | 2018-03-20 |
Family
ID=55707341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410495418.4A Active CN105498807B (en) | 2014-09-25 | 2014-09-25 | A kind of surface amphiphilic nano vulcanization tungsten hydrogenation catalyst and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105498807B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840617A (en) * | 2005-03-29 | 2006-10-04 | 中国科学院大连化学物理研究所 | Sulfide catalyst for hydrogenation desulfurization and denitrogenation and its preparation process and use |
| CN101658792A (en) * | 2009-09-17 | 2010-03-03 | 大连理工大学 | Preparation method of transition metal sulfide catalytic material and catalytic application thereof |
| US20140066293A1 (en) * | 2012-09-05 | 2014-03-06 | Chevron U.S.A. Inc. | Hydroconversion Multi-Metallic Catalyst and Method For Making Thereof |
-
2014
- 2014-09-25 CN CN201410495418.4A patent/CN105498807B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840617A (en) * | 2005-03-29 | 2006-10-04 | 中国科学院大连化学物理研究所 | Sulfide catalyst for hydrogenation desulfurization and denitrogenation and its preparation process and use |
| CN101658792A (en) * | 2009-09-17 | 2010-03-03 | 大连理工大学 | Preparation method of transition metal sulfide catalytic material and catalytic application thereof |
| US20140066293A1 (en) * | 2012-09-05 | 2014-03-06 | Chevron U.S.A. Inc. | Hydroconversion Multi-Metallic Catalyst and Method For Making Thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIN MA ET AL.: "Synthesis and characterization of MoS2 nanostructures with different morphologies via an ionic liquid-assisted hydrothermal route", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105498807B (en) | 2018-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106799241B (en) | A kind of surface amphiphilic nano complex sulfide catalyst and preparation method and application | |
| CN105439203B (en) | A kind of surface amphiphilic nano molybdenum disulfide hydrogenation catalyst and preparation method and application | |
| CN106799243B (en) | A kind of surface amphiphilic nano complex sulfide catalyst and the preparation method and application thereof | |
| CN101658792A (en) | Preparation method of transition metal sulfide catalytic material and catalytic application thereof | |
| EP2526062B1 (en) | Process for producing a copper thiometallate or a selenometallate material | |
| CN105435818B (en) | A kind of surface amphiphilic nano molybdenum disulfide hydrogenation catalyst and preparation method and application | |
| WO2011091221A2 (en) | Manganese tetrathiotungstate material | |
| CA2784208A1 (en) | Nano-tetrathiometallate or nano-tetraselenometallate material | |
| CN105498806A (en) | Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof | |
| CN106799240B (en) | A kind of surface amphiphilic nano vulcanization iron catalyst and the preparation method and application thereof | |
| CN105498805A (en) | Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof | |
| CN105498804A (en) | Surface amphiphilic nano-tungsten sulfide molybdenum sulfide hydrogenation catalyst, preparation method and application thereof | |
| CN106799239B (en) | A kind of surface amphiphilic nano vulcanization Raney nickel and the preparation method and application thereof | |
| CN105498807A (en) | Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof | |
| CN106799260B (en) | Surface amphiphilic nano composite sulfuration nickel cobalt iron catalyst and the preparation method and application thereof | |
| EP2526061B1 (en) | Process for producing a thiometallate or a selenometallate material | |
| EP2526060B1 (en) | Process for producing a thiometallate or a selenometallate material | |
| CN106238074B (en) | A kind of Pt-MoS2The preparation method and application of/LDHS hydrocracking catalyst | |
| CN106799242B (en) | A kind of surface amphiphilic nano vulcanization Co catalysts and the preparation method and application thereof | |
| CN107601492A (en) | A kind of preparation method of two-dimentional graphite-like structure material | |
| CN105478144A (en) | Surface amphiphilic nano tungsten disulfide hydrogenation catalyst and preparation method therefor and application thereof | |
| CN107841336B (en) | A kind of heavy oil floating bed hydrocracking method | |
| CN105498803A (en) | Surface-amphiphilic nano tungsten disulfide hydrogenation catalyst, preparation method and application thereof | |
| CN103240096B (en) | Method for preparing mixed metal catalyst | |
| RU2612222C2 (en) | Method for producing catalyst of oil fractions hydrotreatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |