CN105435818A - Surface amphiphilic nano-molybdenum disulfide hydrogenation catalyst and preparation method and application thereof - Google Patents
Surface amphiphilic nano-molybdenum disulfide hydrogenation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN105435818A CN105435818A CN201410499951.8A CN201410499951A CN105435818A CN 105435818 A CN105435818 A CN 105435818A CN 201410499951 A CN201410499951 A CN 201410499951A CN 105435818 A CN105435818 A CN 105435818A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation catalyst
- hydrogenation
- ionic liquid
- accordance
- preferred
- 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-molybdenum disulfide hydrogenation catalyst and a preparation method and an application thereof are provided. The preparation method comprises the steps: preparing an initial reaction mixture from thiomolybdate, a reducing agent, an ionic liquid and deionized water according to a certain sequence and method, then crystallizing in a sealed high pressure reaction kettle and under hydrothermal conditions, and filtering, washing and drying the crystallized product to obtain the surface amphiphilic nano-molybdenum disulfide hydrogenation catalyst. The ionic liquid is used in the synthesis system, and the prepared nano-molybdenum disulfide has good surface amphipathicity and has excellent dispersion and catalytic activity in both polar and non-polar catalytic reaction systems. The nano-molybdenum disulfide provided by the invention shows excellent catalytic activity in suspended bed hydrogenation deasphalting, hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbon hydrogenation and other reactions of coal tar, heavy oil, superheavy oil, residual oil, shale oil and other heavy oils, and has good application prospects in photoelectric conversion, water photocatalysis for hydrogen production and other reactions.
Description
Technical field
The present invention relates to a kind of surperficial amphiphilic nano molybdenum sulfide hydrogenation 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.
Molybdenum bisuphide is a kind of stratified material with class graphene-structured, has showed good application in fields such as catalysis, microelectronics, semiconductors.Loaded molybdenum disulfide catalyst is used as hydrogenation catalyst in PETROLEUM PROCESSING field always, be applied to reaction (ChianelliR., Catal.Today, 2009 such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation dearomatization, hydrogenation deoxidation and HDM, 147,275-286).Non-supported molybdenum bisuphide 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 molybdenum bisuphide 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 molybdenum 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 molybdenum bisuphide dispersiveness wherein of single surperficial sympathy is not very desirable.Therefore gentle solwution method is utilized to have the nano molybdenum disulfide catalyst of surperficial parents to be the keys improving its dispersiveness by chemical synthesis.
CN103086436A discloses a kind of preparation method of nano molybdenum disulfide, it is characterized in that the method adopts two molybdic acid hydrate sodium to be mixed with solution as molybdenum source, using thioacetamide as sulfiding reagent, adds inorganic salts K
2crO
4or H
4o
40SiW
12as additive, stir lower pH value to 13 dripping hydrochloric acid conditioning solution, the precursor solution obtained; Precursor solution is placed in reactor and carries out hydro-thermal reaction, product is cooled to room temperature, suction filtration, washing, under vacuum, drying obtains black solid powder is nano molybdenum disulfide.
CN103585896A discloses a kind of preparation method of stratiform molybdenum sulfide nanometer sheet molecular separation membrane.Utilizing n-BuLi as intercalated molecule, entering in the lattice of molybdenum sulfide by stirring for a long time; Adding water makes n-BuLi decompose, and expands the distance of molybdenum sulfide sheet interlayer, by ultrasonic process, molybdenum sulfide is dispersed into monoatomic layer material.Unnecessary impurity is removed in dialysis, obtains the clean molybdenum sulfide aqueous solution of purifying.The molybdenum sulfide aqueous solution obtained is obtained stratiform molybdenum sulfide nanometer sheet molecular separation membrane by the method for vacuum filtration.The thickness of film passes through the volume-adjustment of the molybdenum sulfide aqueous solution used.The present invention utilizes the method for monoatomic layer material stacks film forming to obtain a kind of molecular selectivity diffusion barrier, and material preparation method is simple, with low cost, and institute obtains film has size selectivity separation performance to different molecular.
CN02117835.6 discloses a kind of new technology of heavy oil floating bed hydrocracking, although this technique catalyst used employs with the composite catalyst of many metals water soluble salts such as iron-nickel-manganese-molybdenum-cobalt, and these water-soluble predecessors not mentioned decompose the sulfide generated is water-soluble or oil-soluble.
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.
CN201310317514.5 discloses a kind of oil-soluble autovulcanization molybdenum catalyst, its preparation method, using method and application.Preparation method comprises: under nitrogen protection, in order molybdenum source, water, vulcanized sodium, solvent, inorganic acid is placed in container, and mixing and stirring also cools at 5-50 DEG C, reaction 10-150min; Add alkylamine and carbon disulfide, stir, be heated to 60-200 DEG C of reaction 3-10h; After reaction terminates, product is fully cooled rear suction filtration, fully wash with methyl alcohol, drying obtains oil-soluble autovulcanization molybdenum catalyst.
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.Although employ ionic liquid in this invention, the process employs the process of excusing from death ripple, and preparation process is physical process, does not belong to chemical synthesis category.
Summary of the invention
The object of the invention is to for the problems referred to above, a kind of surperficial amphiphilic nano molybdenum bisuphide 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 molybdenum bisuphide hydrogenation catalyst prepared by auxiliary agent with ionic liquid, comprise the following steps: (1) adds Thiomolybdate in deionized water, stirs; (2) in said mixture, add reducing agent, stir; (3) in said mixture, add ionic liquid, stir, be configured to initial reaction mixture; (4) initial reaction mixture is transferred in Autoclaves for synthesis, at a certain temperature crystallization certain hour; (5) after crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst after drying.
In above-mentioned method, the Thiomolybdate described in step (1) is one or both in two Thiomolybdates and tetrathiomolybdate, and the cation of Thiomolybdate can be Na
+, K
+, NH
4 +, Li
+, Mg
2+can with thiomolybdate formed the cationic one of soluble-salt or any two more than.
In above-mentioned method, the reducing agent described in step (2) be hydroxylamine hydrochloride, hydrazine hydrate, sodium borohydride, potassium borohydride, the one of polymine or any two more than, the one in preferred sodium borohydride and hydroxylamine hydrochloride or two kinds.
In above-mentioned method, ionic liquid cation described in step (3) 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 above-mentioned method, in step (4) described initial reaction mixture, the concentration of molybdenum is 0.005-2mol/L, preferred 0.008-1.6mol/L.
In above-mentioned method, S:Mo (mol ratio)=2-4:1, preferred 2.2-3.8:1 in step (4) described initial reaction mixture; Reducing agent: Mo (mol ratio)=1-4:1, preferred 1.2-3:1; Ionic liquid: Mo (mol ratio)=0.01-25:1, preferred 0.1-15:1.
In above-mentioned method, the crystallization temperature described in step (4) 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 nano molybdenum disulfide 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 nano molybdenum disulfide 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 fabulous 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 1 prepares molybdenum bisuphide.
Fig. 2 is the TEM photo that embodiment 2 prepares molybdenum bisuphide.
Fig. 3 is the TEM photo that embodiment 3 prepares molybdenum bisuphide.
Fig. 4 is the XRD spectra that embodiment 1 prepares molybdenum bisuphide.
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-ethyl-3-methylimidazole tetrafluoroborate to prepare surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
A certain amount of two thio molybdenum acid sodium [Na are added in 500mL deionized water
2moO
2s
2], make the concentration of molybdenum reach 0.01mol/L, be stirred to evenly; In said mixture, add hydroxylamine hydrochloride, make hydroxylamine hydrochloride: two thio molybdenum acid sodiums (mol ratio) reach 4:1, be stirred to evenly; In said mixture, add ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate, make 1-ethyl-3-methylimidazole tetrafluoroborate: two thio molybdenum acid sodiums (mol ratio) reach 24:1, 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 molybdenum bisuphide hydrogenation catalyst after drying.
Fig. 1 and Fig. 4 sets forth TEM photo and the XRD spectra of molybdenum bisuphide.In Fig. 4, XRD composes peak broadening obviously, shows that sample size is less; The peak of 15.8 ° is attributed to the diffraction maximum of molybdenum bisuphide (002) crystal face, and the peak of 32.7 ° is attributed to the diffraction maximum of molybdenum bisuphide (100) crystal face, and the peak of 55.9 ° is attributed to the diffraction maximum of molybdenum bisuphide (110) crystal face.
Embodiment 2
The present embodiment illustrates the method using 1-butyl-3-methylimidazole hexafluorophosphate to prepare surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
A certain amount of two sulfo-potassium molybdate [K are added in 500mL deionized water
2moO
2s
2], make the concentration of molybdenum reach 0.015mol/L, be stirred to evenly; In said mixture, add potassium borohydride, make potassium borohydride: two sulfo-potassium molybdates (mol ratio) reach 3:1, be stirred to evenly; In said mixture, add ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate, make 1-butyl-3-methylimidazole hexafluorophosphate: two sulfo-potassium molybdates (mol ratio) reach 18:1, 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 10h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst after drying.
Embodiment 3
The present embodiment illustrates the method using 1-propyl group-3-methylimidazole bromine salt to prepare surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
A certain amount of two ammonium thiomolybdate [(NH are added in 500mL deionized water
4)
2moO
2s
2], make the concentration of molybdenum reach 0.5mol/L, be stirred to evenly; In said mixture, add polymine, make polymine: nitric acid molybdenum (mol ratio) reaches 2:1, be stirred to evenly; In said mixture, add ionic liquid 1-propyl group-3-methylimidazole bromine salt, make 1-propyl group-3-methylimidazole bromine salt: two ammonium thiomolybdates (mol ratio) reach 0.01:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 160 DEG C of crystallization 40h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst after drying.
Embodiment 4
The present embodiment illustrates the method using 1-butyl-2,3-methylimidazole tetrafluoroborate to prepare surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
A certain amount of four thio ammonium molybdate [(NH is added in 500mL deionized water
4)
2moS
4], make the concentration of molybdenum reach 0.5mol/L, be stirred to evenly; In said mixture, add sodium borohydride, make sodium borohydride: four thio ammonium molybdate (mol ratio) reaches 3:1, be stirred to evenly; Ionic liquid 1-butyl-2 is added in said mixture, 3-methylimidazole tetrafluoroborate, makes 1-butyl-2,3-methylimidazole tetrafluoroborate: four thio ammonium molybdate (mol ratio) reaches 0.5:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 140 DEG C of crystallization 150h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst after drying.
Embodiment 5
The present embodiment illustrates the method using N-butyl-pyridinium tetrafluoroborate to prepare surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
A certain amount of tetrathiomolybdate sodium (Na is added in 500mL deionized water
2moS
4), make the concentration of molybdenum reach 0.5mol/L, be stirred to evenly; In said mixture, add sodium borohydride, make sodium borohydride: tetrathiomolybdate sodium (mol ratio) reaches 4:1, be stirred to evenly; In said mixture, add ionic liquid N-butyl-pyridinium tetrafluoroborate, make N-butyl-pyridinium tetrafluoroborate: tetrathiomolybdate sodium (mol ratio) reaches 10:1, be stirred to evenly, be configured to initial reaction mixture; Initial reaction mixture is transferred in Autoclaves for synthesis, at 120 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 molybdenum bisuphide hydrogenation catalyst after drying.
Embodiment 6
The present embodiment illustrates the method using TBAB to prepare surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
Tetrathio potassium molybdate (the K of equimolar amounts is added in 500mL deionized water
2moS
4) and two ammonium thiomolybdate [(NH
4)
2moO
2s
2], make the concentration of molybdenum reach 0.5mol/L, be stirred to evenly; In said mixture, add potassium borohydride, make potassium borohydride: tetrathio potassium molybdate (mol ratio) reaches 2.5:1, be stirred to evenly; In said mixture, add ionic liquid TBAB, make TBAB: tetrathio potassium molybdate (mol ratio) reaches 17:1, 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 220h.After crystallization terminates, reactant is cooled to room temperature, filtration, deionized water are washed and are obtained surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst after drying.
Embodiment 7-12
The raw material that following examples use is coalite tar >320 DEG C residue in Shandong, and character is shown in table 1.Embodiment 7-12 adopts high pressure suspending bed reaction technique, and carried out catalytic activity test to the catalyst prepared by embodiment 1-6 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 molybdenum sulfide 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 molybdenum bisuphide)≤300ppm situation, asphaltene removal >98%, 180-360 DEG C of cut yield ≮ 60% in product.
Claims (10)
1. a preparation method for surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst, is characterized in that comprising the following steps:
(1) in deionized water, add Thiomolybdate, reducing agent, ionic liquid, stir, be configured to initial reaction mixture;
(2) initial reaction mixture is transferred in Autoclaves for synthesis, crystallization;
(3) after crystallization terminates, reactant is cooled to room temperature, separating solids product obtains surperficial amphiphilic nano molybdenum bisuphide hydrogenation catalyst.
2. in accordance with the method for claim 1, it is characterized in that: the Thiomolybdate described in step (1) is one or both in two Thiomolybdates and tetrathiomolybdate, 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.
3. in accordance with the method for claim 1, it is characterized in that: the reducing agent described in step (1) be hydroxylamine hydrochloride, hydrazine hydrate, sodium borohydride, potassium borohydride, the one of polymine or any two more than, the one in preferred sodium borohydride and hydroxylamine hydrochloride or two kinds.
4. in accordance with the method for claim 1, it is characterized in that: the ionic liquid cation described in step (1) 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.
5. in accordance with the method for claim 1, it is characterized in that: in step (2) described initial reaction mixture, the concentration of molybdenum is 0.005-2mol/L, preferred 0.008-1.6mol/L.
6. in accordance with the method for claim 1, it is characterized in that: S:Mo (mol ratio)=2-4:1, preferred 2.2-3.8:1 in step (2) described initial reaction mixture;
Reducing agent: Mo (mol ratio)=1-4:1, preferred 1.2-3:1;
Ionic liquid: 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 (2) is 40-200 DEG C, preferred crystallization temperature 60-180 DEG C;
Crystallization time is 1-240h, preferred crystallization time 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 molybdenum bisuphide 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 molybdenum bisuphide 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 |
|---|---|---|---|
| CN201410499951.8A CN105435818B (en) | 2014-09-25 | 2014-09-25 | A kind of surface amphiphilic nano molybdenum disulfide hydrogenation catalyst and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410499951.8A CN105435818B (en) | 2014-09-25 | 2014-09-25 | A kind of surface amphiphilic nano molybdenum disulfide hydrogenation catalyst and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105435818A true CN105435818A (en) | 2016-03-30 |
| CN105435818B CN105435818B (en) | 2018-01-02 |
Family
ID=55546711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410499951.8A Active CN105435818B (en) | 2014-09-25 | 2014-09-25 | A kind of surface amphiphilic nano molybdenum disulfide hydrogenation catalyst and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105435818B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544054A (en) * | 2016-11-25 | 2017-03-29 | 青岛大学 | A kind of Heavy oil hydrogenation method |
| CN106622298A (en) * | 2016-11-15 | 2017-05-10 | 天津大学 | Layered multi-metal molybdenum sulfide catalyst and preparation method |
| CN110170294A (en) * | 2019-05-24 | 2019-08-27 | 广州大学 | A kind of monodisperse class flower ball-shaped MoS2Powder and preparation method thereof |
| CN111057030A (en) * | 2019-12-03 | 2020-04-24 | 天津大学 | Preparation method and application of hydrotalcite-based sulfide catalyst for synthesizing gamma-valerolactone |
| CN111514930A (en) * | 2020-04-30 | 2020-08-11 | 山东理工大学 | Ionic liquid stable single-atom catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559663A (en) * | 2004-02-27 | 2005-01-05 | 中国科学院上海硅酸盐研究所 | Preparation method of microwave auxiliary ion liquid body of nanometer micropowder |
| CN1994895A (en) * | 2006-12-20 | 2007-07-11 | 浙江大学 | Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere |
| US20070158236A1 (en) * | 2006-01-06 | 2007-07-12 | Headwaters Nanokinetix, Inc. | Hydrocarbon-soluble, bimetallic catalyst precursors and methods for making same |
| CN103011292A (en) * | 2012-12-04 | 2013-04-03 | 北京大学 | Nolybdenum disulfide nanometer particle, preparation method and application thereof |
-
2014
- 2014-09-25 CN CN201410499951.8A patent/CN105435818B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559663A (en) * | 2004-02-27 | 2005-01-05 | 中国科学院上海硅酸盐研究所 | Preparation method of microwave auxiliary ion liquid body of nanometer micropowder |
| US20070158236A1 (en) * | 2006-01-06 | 2007-07-12 | Headwaters Nanokinetix, Inc. | Hydrocarbon-soluble, bimetallic catalyst precursors and methods for making same |
| CN1994895A (en) * | 2006-12-20 | 2007-07-11 | 浙江大学 | Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere |
| CN103011292A (en) * | 2012-12-04 | 2013-04-03 | 北京大学 | Nolybdenum disulfide nanometer particle, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| X.-X. ZHAO ET.AL: ""Ionic liquid assisted hydrothermal synthesis of uniform MoS2 microspheres using (NH4)2MoS4 as precursors"", 《MATERIALS RESEARCH INNOVATIONS》 * |
| 赵潇璇等: ""纳米二硫化钼的化学法合成研究进展"", 《材料导报A：综述篇》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622298A (en) * | 2016-11-15 | 2017-05-10 | 天津大学 | Layered multi-metal molybdenum sulfide catalyst and preparation method |
| CN106544054A (en) * | 2016-11-25 | 2017-03-29 | 青岛大学 | A kind of Heavy oil hydrogenation method |
| CN106544054B (en) * | 2016-11-25 | 2018-12-11 | 青岛大学 | A kind of Heavy oil hydrogenation method |
| CN110170294A (en) * | 2019-05-24 | 2019-08-27 | 广州大学 | A kind of monodisperse class flower ball-shaped MoS2Powder and preparation method thereof |
| CN110170294B (en) * | 2019-05-24 | 2021-09-03 | 广州大学 | Monodisperse flower-like spherical MoS2Powder and preparation method thereof |
| CN111057030A (en) * | 2019-12-03 | 2020-04-24 | 天津大学 | Preparation method and application of hydrotalcite-based sulfide catalyst for synthesizing gamma-valerolactone |
| CN111514930A (en) * | 2020-04-30 | 2020-08-11 | 山东理工大学 | Ionic liquid stable single-atom catalyst and preparation method and application thereof |
| CN111514930B (en) * | 2020-04-30 | 2023-07-25 | 山东理工大学 | Ionic liquid stable monoatomic catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105435818B (en) | 2018-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105439203A (en) | Surface amphiphilic nano-molybdenum disulfide hydrogenation catalyst and preparation method and application thereof | |
| CN105435818A (en) | Surface amphiphilic nano-molybdenum disulfide hydrogenation catalyst and preparation method and application thereof | |
| CN106799243B (en) | A kind of surface amphiphilic nano complex sulfide catalyst and the preparation method and application thereof | |
| CN106799241B (en) | A kind of surface amphiphilic nano complex sulfide catalyst and preparation method and application | |
| CN108067257B (en) | Preparation method of high-activity-site-exposed nano molybdenum disulfide hydrogenation catalyst | |
| CA2960807A1 (en) | Methods for synthesis of graphene derivatives and functional materials from asphaltenes, graphene derivatives, 2d materials and applications of use | |
| CA2784140C (en) | Process for producing a copper thiometallate or a selenometallate material | |
| CN105329946A (en) | Molybdenum disulfide nanosheet with rich active sites as well as preparation method and application of molybdenum disulfide nanosheet | |
| US20190135637A1 (en) | High functionalization density graphene | |
| CN111233040A (en) | Method for preparing nano molybdenum disulfide by solvothermal method, catalyst and application | |
| CN106268871A (en) | A kind of load type Co MoS2/LDHS Hydrobon catalyst and application | |
| CN106799240B (en) | A kind of surface amphiphilic nano vulcanization iron catalyst and the preparation method and application thereof | |
| US20080139380A1 (en) | Concentration of active catalyst slurry | |
| CN105498806A (en) | Surface-amphiphilic nano tungsten 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 | |
| CN106799260B (en) | Surface amphiphilic nano composite sulfuration nickel cobalt iron catalyst and the preparation method and application thereof | |
| CN106799242B (en) | A kind of surface amphiphilic nano vulcanization Co catalysts 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 | |
| CN106238074B (en) | A kind of Pt-MoS2The preparation method and application of/LDHS hydrocracking catalyst | |
| CN105498807A (en) | Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof | |
| CN105498803A (en) | Surface-amphiphilic nano tungsten disulfide hydrogenation catalyst, preparation method and application thereof | |
| CN105478144A (en) | Surface amphiphilic nano tungsten disulfide hydrogenation catalyst and preparation method therefor and application thereof | |
| CN106268872A (en) | A kind of support type MoS2/ LDHS Hydrobon catalyst and application | |
| Zhang | Surface Engineering of Colloidal MoS 2 Nanosheets for Tuning Hydrodesulfurization Catalytic Performance |
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 |