CN103920506A - Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof - Google Patents
Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof Download PDFInfo
- Publication number
- CN103920506A CN103920506A CN201410191266.9A CN201410191266A CN103920506A CN 103920506 A CN103920506 A CN 103920506A CN 201410191266 A CN201410191266 A CN 201410191266A CN 103920506 A CN103920506 A CN 103920506A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- hydrogenation deoxidation
- sulfide catalyst
- high hydrogenation
- 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.)
- Pending
Links
Abstract
The invention relates to a preparation method for a double-metal-sulfide catalyst. Soluble molybdate and nickel salt or cobalt salt serves as a raw material, thiourea or thioacetamide serves as a sulfur source, and a Ni(Co)-S/MoS2 catalyst is prepared through a two-step hydrothermal method. The method particularly comprises the following steps: MoS2 is prepared in a high pressure reactor through the hydrothermal method first, then the nickel salt or cobalt salt and the sulfur source are added into the reactor of the obtained MoS2 to be evenly mixed, the reactor is sealed and heated, a reaction is conducted for a certain period of time, and Ni-S or Co-S is deposited on the MoS2, so that the Ni(Co)-S/MoS2 catalyst is prepared. The preparation method is characterized in that the specific area of the Ni(Co)-S/MoS2 catalyst prepared through the two-step hydrothermal method is large, high temperature vulcanization is not required in the preparation process, the preparation condition is mild, the catalyst is used for hydrodeoxygenation, a target product has high yield and good repeatability, and hydrodeoxygenation activity of the catalyst is high.
Description
Technical field
The present invention relates to bimetallic sulfide catalyst of a kind of high hydrogenation deoxidation activity and preparation method thereof, can be used for, in the catalytic hydrodeoxygenation reaction of oxygenatedchemicals in bio oil and true bio oil, belonging to biomass energy catalytic refining technical field.
Background technology
Along with the continuous exhaustion of the non-renewable fossil energy such as coal, oil and natural gas and the severe environmental problem of utilizing process to produce thereof, develop and prepare renewable clean substitute energy source for petroleum being subject to global extensive concern.Bio oil, a kind of liquid fuel that biomass high-temperature thermal cracking is obtained, is disposed to the carbon dioxide amount of having a net increase of, the pernicious gas (SO in environment due to it while having burning
x, NO
x) and content of beary metal almost nil, therefore be acknowledged as the most potential and optimal renewable nonpetroleum alternative energy source in the world, its exploitation can significantly reduce the dependency degree of the mankind to fossil energy, and existing many countries have carried out the research work that biomass pyrolysis for liquid production is prepared bio oil in the world.The maximum deficiency of bio oil is that its oxygen content is much higher than conventional crude, the deficiency such as cause that oil product fuel value is low, corrosivity strengthens, oil product is perishable and intersolubility is poor.Therefore, develop bio oil as renewable nonpetroleum alternative energy source, must carry out to it upgrading, modification of catalytic hydrodeoxygenation, effectively to reduce oxygen content in bio oil, obtain efficient, high-quality alternative energy source truly.
At present, have multiple as the catalyst of bio oil hydrogenation deoxidation.As CN10301355A discloses a kind of method for preparing catalyst of preparing liquid alkane fuel containing the deoxidation of oxygen aromatic hydrogenation, this method is carried out stable metal nano particle taking the water-soluble high-molecular substance with acid site as carrier, thereby prepares acid-metal dual-functional hydrogenation dehydrogenation catalyst; CN102698788A discloses a kind of by the synthetic method of complexing agent employing original position, Pt metal is loaded on the ordered mesoporous molecular sieve Al-SBA-15 of Al modification, thereby prepare the high dispersive bifunctional catalyst for phenol hydrogenation deoxidation; CN102728393A discloses a kind of method that adopts mechanical ball milling calcine technology to prepare non-loading type nanometer Ni-Mo-W-S ternary hydrogenation deoxidation catalyst; CN103086436A discloses a kind of employing hydro-thermal method and has prepared flower-shaped and rod-like nano MoS
2method.But there is the deficiencies such as the little or deoxy activity of higher, the easy inactivation of production cost, specific area is not good enough in these catalyst, has seriously hindered its commercial Application.
The preparation of industrial used Ni (Co)-Mo-S catalyst mainly adopts reduction-sulfurization method, and this method needs higher preparation temperature, and needs to adopt hydrogen reducing, and prepared catalyst activity is lower.B. [Chem. Eng. Sci. 79 (2012) 1-7 such as Yoosuk, Fuel 91 (2012) 246-252] report that employing one step hydro thermal method prepares the method for Ni (Co)-Mo-S catalyst, this catalyst shows good catalytic activity in the hydrogenation deoxidation reaction of phenol.Prepared its specific surface of bimetallic sulfide catalyst of this method is less, and reduces with the increase of additive dosage.According to the concerted catalysis mode inference of bimetallic sulfide catalyst, adopt the prepared catalyst of one step hydro thermal method, most of Ni-wherein or Co-sulfide will be wrapped in catalyst the inside, and bimetallic synergy cannot obtain the performance of maximum efficiency.
For the problems referred to above, the present invention adopts two one-step hydrothermals to prepare Ni (Co)-S/MoS
2catalyst, this method has not only improved the specific area of catalyst, has also improved bimetallic concerted catalysis effect in catalyst.This preparation process technique is simple, and mild condition does not need pyrolytic or hydrogen reducing, and prepared catalyst has good hydrogenation deoxidation catalytic activity.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides bimetallic sulfide catalyst of the simple high hydrogenation deoxidation activity of a kind of technique and preparation method thereof.
Technical scheme of the present invention is:
A bimetallic sulfide catalyst for high hydrogenation deoxidation activity, this catalyst is Ni (Co)-S/MoS
2, by Ni (Co)-S and MoS
2composition.
The preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, comprises the steps:
1. prepare MoS
2: molybdate is dissolved in deionized water, adds sulphur source to be stirred to and dissolve completely, then pour in autoclave, airtight kettle cover, is uniformly mixed, and reacts at a certain temperature decrease temperature and pressure after certain hour, opens reaction kettle cover;
2. prepare Ni (Co)-S/MoS
2catalyst: nickel salt or cobalt salt are dissolved in deionized water, add sulphur source after stirring and dissolving, this solution to be poured in the reactor of 1. opening before under ultrasonic wave, airtight kettle cover, be uniformly mixed, react at a certain temperature after certain hour, by catalyst separation, washing, alcohol wash, dry.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, described soluble molybdenum hydrochlorate is one or both in ammonium molybdate or sodium molybdate.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, described sulphur source is one or both in thiocarbamide or thioacetamide.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, the sulphur of described step in 1. and the mol ratio of molybdenum are 2.0～10.0.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, the reaction temperature of described step in is 1. 150～350 DEG C; Reaction time is 12～48 hours.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, the nickel salt of described step in is 2. one or more in nickelous sulfate, nickel nitrate, nickel chloride or nickel acetate; The cobalt salt of described step in is 2. one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride or cobalt acetate.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, the Ni (Co) of described step in is 2. 0.01～2.0 with Mo mol ratio.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, S and Ni (Co) mol ratio of described step in is 2. 1.0～5.0.
Further, the preparation method of the bimetallic sulfide catalyst of above-mentioned high hydrogenation deoxidation activity, the reaction temperature of described step in is 2. 150～350 DEG C; Reaction time is 12～48 hours.
Beneficial effect of the present invention is:
(1) Ni (Co)-S/MoS that prepared by the present invention
2specific surface area of catalyst is large, has good catalytic activity, can be applied in the catalytic hydrodeoxygenation reaction of oxygenatedchemicals in bio oil or true bio oil, and the high and favorable reproducibility of the target product productive rate of gained, the hydrogenation deoxidation activity of catalyst is high.
(2) the present invention adopts two one-step hydrothermals to prepare Ni (Co)-S/MoS
2catalyst, this method has not only improved the specific area of catalyst, has also improved bimetallic concerted catalysis effect in catalyst, and its catalytic activity is obviously better than the similar catalyst that conventional method and one step hydro thermal method make.
(3) preparation technology of the present invention is simple, mild condition, and preparation process, without high temperature vulcanized, does not need pyrolytic or hydrogen reducing, prepared Ni (Co)-S/MoS
2environmentally friendly.
Brief description of the drawings
Ni-S/MoS prepared by Fig. 1 embodiment of the present invention 2
2the Co-S/MoS preparing with embodiment 3
2the X-ray powder diffraction figure of catalyst.
Ni-S/MoS prepared by Fig. 2 embodiment of the present invention 2
2the Co-S/MoS preparing with embodiment 3
2the transmission electron microscope picture of catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details, but the present invention is not limited to this.
Illustrate: it is pure that the reagent adopting in following examples is analysis, and water is ultra-pure water.
Ni (Co)-S/MoS that the present invention is prepared
2catalyst characterizes by following means: adopt Rigaku D/max2550 18 KW to turn the amorphous structure of target X-ray diffractometer mensuration catalyst; Utilize the pattern of the JSM – 6360LV scanning electronic microscope observation catalyst of company of NEC.
Embodiment 1
1.39g ammonium molybdate is dissolved in 150ml deionized water, adds 1.81g thiocarbamide stirring and dissolving, then pour in 300ml reactor, airtight kettle cover, is uniformly mixed, and reacts after 12 hours at 200 DEG C and is cooled to 40 DEG C, opens reaction kettle cover.0.17g nickel nitrate is dissolved in 30ml deionized water, after adding 0.08g thiocarbamide to dissolve, in the reactor of uncapping before this solution is added, airtight kettle cover, under 300r/min, be uniformly mixed, react 12 hours at 200 DEG C, after reaction finishes, obtain black precipitate, through washing, after alcohol wash, be placed at 40 DEG C of vacuum drying chambers dry 5 hours.
In autoclave, add the catalyst of 86.5 g n-dodecanes, 13.5 g p-methyl phenols and the above-mentioned preparation of 0.60 g, install autoclave reaction unit, get rid of air in still, then rise to 300 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900r/min, and Hydrogen Vapor Pressure is 4.0MPa, sustained response 6h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of p-methyl phenol reaches 97.9%, and deoxidation rate reaches 97.6%.
Embodiment 2
1.39g ammonium molybdate is dissolved in 150ml deionized water, adds 1.81g thiocarbamide stirring and dissolving, then pour in 300ml reactor, airtight kettle cover, is uniformly mixed, and reacts after 12 hours at 200 DEG C and is cooled to 50 DEG C, opens reaction kettle cover.0.50g nickel nitrate is dissolved in 30ml deionized water, after adding 0.23g thiocarbamide to dissolve, in the reactor of uncapping before this solution is added, airtight kettle cover, under 300r/min, be uniformly mixed, react 12 hours at 200 DEG C, after reaction finishes, obtain black precipitate, through washing, after alcohol wash, be placed at 40 DEG C of vacuum drying chambers dry 5 hours.
In autoclave, add the catalyst of 86.5 g n-dodecanes, 13.5 g p-methyl phenols and the above-mentioned preparation of 0.60 g, install autoclave reaction unit, get rid of air in still, then rise to 300 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900r/min, and Hydrogen Vapor Pressure is 3.0MPa, sustained response 6h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of p-methyl phenol reaches 100%, and deoxidation rate reaches 100%.
Embodiment 3
1.39g ammonium molybdate is dissolved in 150ml deionized water, adds 1.81g thiocarbamide stirring and dissolving, then pour in 300ml reactor, airtight kettle cover, is uniformly mixed, and reacts after 12 hours at 200 DEG C and is cooled to 50 DEG C, and opening reactor should.0.50g cobalt nitrate is dissolved in 30ml deionized water, after adding 0.23g thiocarbamide to dissolve, in the reactor of uncapping before this solution is added, airtight kettle cover, under 300r/min, be uniformly mixed, react 12 hours at 200 DEG C, after reaction finishes, obtain black precipitate, through washing, after alcohol wash, be placed at 40 DEG C of vacuum drying chambers dry 5 hours.
In autoclave, add the catalyst of 86.5 g n-dodecanes, 13.5 g p-methyl phenols and the above-mentioned preparation of 0.10 g, install high pressure reaction assembly, get rid of air in still, then rise to 250 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900r/min, and Hydrogen Vapor Pressure is 4.0MPa, sustained response 6h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of p-methyl phenol reaches 100%, and deoxidation rate reaches 100%.
Fig. 1 is Ni-S/MoS prepared by embodiment 2
2the Co-S/MoS preparing with embodiment 3
2x-ray powder diffraction figure.Result shows, Ni-S/MoS
2in contain Ni-S and MoS
2thing phase, Co-S/MoS
2in contain Co-S and MoS
2thing phase.
Ni-S/MoS prepared by Fig. 2 embodiment 2
2the Co-S/MoS preparing with embodiment 3
2transmission electron microscope picture.Result demonstration, Ni-S covers MoS
2upper, Co-S covers MoS
2on.
Embodiment 4
1.39g ammonium molybdate is dissolved in 150ml deionized water, adds 1.81g thiocarbamide stirring and dissolving, then pour in 300ml reactor, airtight kettle cover, is uniformly mixed, and reacts after 12 hours at 200 DEG C and is cooled to 50 DEG C, opens reactor.0.84g cobalt nitrate is dissolved in 30ml deionized water, after adding 0.28g thiocarbamide to dissolve, in the reactor of uncapping before this solution is added, airtight kettle cover, under 300r/min, be uniformly mixed, react 12 hours at 200 DEG C, after reaction finishes, obtain black precipitate, after washing, alcohol wash, be placed in 40 DEG C of vacuum drying chambers and be dried 5 hours.
In autoclave, add the catalyst of 86.5 g n-dodecanes, 13.5 g p-methyl phenols and the above-mentioned preparation of 0.10 g, install high pressure reaction assembly, get rid of air in still, then rise to 250 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900r/min, and Hydrogen Vapor Pressure is 4.0MPa, sustained response 3h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of p-methyl phenol reaches 100%, and deoxidation rate reaches 100%.
Embodiment 5
The catalyst that adds 86.75 g n-dodecanes, 13.25 g benzaldehydes and 0.60 g embodiment 2 to prepare in autoclave, install high pressure reaction assembly, get rid of air in still, then rise to 275 DEG C with the speed of 10 DEG C/min from room temperature, adjusting rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 5 h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of benzaldehyde reaches 100 %, and deoxidation rate reaches 100%.
Embodiment 6
The catalyst that adds 85 g n-dodecanes, 15 g acetophenones and 0.60 g embodiment 2 to prepare in autoclave, install high pressure reaction assembly, get rid of air in still, then rise to 225 DEG C with the speed of 10 DEG C/min from room temperature, adjusting rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 5 h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of acetophenone reaches 100 %, and deoxidation rate reaches 100%.
Embodiment 7
The catalyst that adds 84.49 g n-dodecanes, 15.51 g p methoxy phenols and 0.10 g embodiment 4 to prepare in autoclave, install high pressure reaction assembly, get rid of air in still, then rise to 275 DEG C with the speed of 10 DEG C/min from room temperature, adjusting rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 5h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of p methoxy phenol reaches 100%, and deoxidation rate reaches 100%.
Embodiment 8
The catalyst that adds 86.34 g n-dodecanes, 13.76 g hydroquinones and 0.20 g embodiment 4 to prepare in autoclave, install high pressure reaction assembly, get rid of air in still, then rise to 275 DEG C with the speed of 10 DEG C/min from room temperature, adjusting rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 4 h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of hydroquinones reaches 100%, and deoxidation rate reaches 100%.
Embodiment 9
The catalyst that adds 87.49 g n-dodecanes, 12.51 g cyclohexanol and 0.10 g embodiment 4 to prepare in autoclave, install high pressure reaction assembly, get rid of air in still, then rise to 250 DEG C with the speed of 10 DEG C/min from room temperature, adjusting rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 3 h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of cyclohexanol reaches 100%, and deoxidation rate reaches 100%.
Claims (10)
1. a bimetallic sulfide catalyst for high hydrogenation deoxidation activity, is characterized in that: this catalyst is Ni (Co)-S/MoS
2, by Ni (Co)-S and MoS
2composition.
2. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity claimed in claim 1, is characterized in that comprising the following steps:
1. prepare MoS
2: molybdate is dissolved in deionized water, adds thiocarbamide to be stirred to and dissolve completely, then pour in autoclave, airtight kettle cover, is uniformly mixed, and reacts at a certain temperature after certain hour, and decrease temperature and pressure, opens reaction kettle cover;
2. prepare Ni (Co)-S/MoS
2catalyst: nickel salt or cobalt salt are dissolved in deionized water, add sulphur source after stirring and dissolving, this solution to be poured in the reactor of 1. uncapping before under ultrasonic wave, airtight kettle cover, be uniformly mixed, under uniform temperature, react after certain hour, by catalyst separation, washing, alcohol wash, dry.
3. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: described molybdate is one or both in ammonium molybdate or sodium molybdate.
4. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: described sulphur source is one or both in thiocarbamide or thioacetamide.
5. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: described nickel salt is one or more in nickelous sulfate, nickel nitrate, nickel chloride or nickel acetate.
6. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: described cobalt salt is one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride or cobalt acetate.
7. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: the sulphur of described step in 1. and the mol ratio of molybdenum are 2.0～10.0.
8. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: the reaction temperature of described step in is 1. 150～350 DEG C; Reaction time is 12～48 hours.
9. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: the Ni (Co) of described step in is 2. 0.01～2.0 with Mo mol ratio; S and Ni (Co) mol ratio of described step in is 2. 1.0～5.0.
10. the preparation method of the bimetallic sulfide catalyst of high hydrogenation deoxidation activity according to claim 2, is characterized in that: the reaction temperature of described step in is 2. 150～350 DEG C; Reaction time is 12～48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410191266.9A CN103920506A (en) | 2014-05-08 | 2014-05-08 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410191266.9A CN103920506A (en) | 2014-05-08 | 2014-05-08 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103920506A true CN103920506A (en) | 2014-07-16 |
Family
ID=51139039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410191266.9A Pending CN103920506A (en) | 2014-05-08 | 2014-05-08 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103920506A (en) |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104998605A (en) * | 2015-07-07 | 2015-10-28 | 三峡大学 | Decoloring agent and synthesis method therefor |
| CN105463566A (en) * | 2015-11-25 | 2016-04-06 | 中国科学技术大学 | Liquid phase method for epitaxial growth of MoSe2-XnSem heterogeneous nano structures |
| CN105669337A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for converting lignin and model compound thereof |
| CN105688942A (en) * | 2016-03-14 | 2016-06-22 | 西安建筑科技大学 | Preparation method of layered MoS2-Ni nano-composite |
| CN105753070A (en) * | 2016-02-25 | 2016-07-13 | 华侨大学 | Controllable preparation method of Co-Mo-S (cobalt-molybdenum-sulfur) ternary metal sulfide |
| CN106319558A (en) * | 2016-08-31 | 2017-01-11 | 天津市大陆制氢设备有限公司 | Efficient and porous MoS2-Zn hydrogen evolution electrode and preparation method thereof |
| CN106479560A (en) * | 2015-08-27 | 2017-03-08 | 中国科学院青岛生物能源与过程研究所 | A kind of bi-component transient metal sulfide nanotube and its preparation method and application |
| CN106964373A (en) * | 2017-04-28 | 2017-07-21 | 湘潭大学 | A kind of hydrophobic oleophilic oil type hydrogenation deoxidation catalyst and its preparation method and application |
| CN107159270A (en) * | 2017-05-27 | 2017-09-15 | 湘潭大学 | A kind of magnetic hydrogenation deoxidation catalyst and its preparation method and application |
| CN108855145A (en) * | 2018-06-21 | 2018-11-23 | 青岛大学 | A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application |
| CN109003824A (en) * | 2018-06-29 | 2018-12-14 | 安阳师范学院 | Ternary cobalt nickel selenides nano-chip arrays electrode material and preparation method thereof |
| CN109235024A (en) * | 2018-09-04 | 2019-01-18 | 北京邮电大学 | A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load |
| CN109364952A (en) * | 2018-09-30 | 2019-02-22 | 中国科学院山西煤炭化学研究所 | By catalyst and preparation method and the application of aromatic nitro compound and benzaldehyde or furfural and its derivative synthesizing imine |
| CN109675589A (en) * | 2019-02-26 | 2019-04-26 | 湘潭大学 | A kind of composite catalyst and preparation method thereof for hydrogenation deoxidation reaction |
| CN109759093A (en) * | 2019-03-07 | 2019-05-17 | 陕西理工大学 | A kind of molybdenum disulfide load monatomic catalyst of Ir and the preparation method and application thereof |
| CN109972160A (en) * | 2019-04-23 | 2019-07-05 | 重庆文理学院 | A kind of preparation method of novel double-function catalyzing electrolysis water electrode |
| CN110070993A (en) * | 2018-01-24 | 2019-07-30 | 南京大学 | The preparation method of carbon nano-tube film high load Mn-Co sulfide flexible electrode material |
| CN110270353A (en) * | 2019-04-16 | 2019-09-24 | 青岛科技大学 | The preparation and application of load transitions bimetallic chalcogen compound nano material in situ |
| CN110479314A (en) * | 2019-08-27 | 2019-11-22 | 天津大学 | A kind of molybdenum base sulfide bimetallic catalyst and preparation method |
| CN110586133A (en) * | 2019-09-11 | 2019-12-20 | 天津大学 | Niobium acid-based sulfide composite material and preparation method thereof |
| CN112694126A (en) * | 2019-10-22 | 2021-04-23 | 中国科学院大连化学物理研究所 | Preparation method of high-dispersion nickel modified molybdenum disulfide |
| CN112713012A (en) * | 2021-01-26 | 2021-04-27 | 重庆茨文科技有限公司 | Zn-doped Co9S8Loaded MoS2Method for producing composite material and use thereof |
| CN113120970A (en) * | 2021-03-26 | 2021-07-16 | 东南大学 | Method for preparing compound containing crystal water cobalt sulfate and redox graphene |
| CN113351230A (en) * | 2021-06-21 | 2021-09-07 | 华侨大学 | Isolated cobalt atom doped single-layer or few-layer MoS2Process for preparing catalyst |
| CN113663696A (en) * | 2021-08-31 | 2021-11-19 | 湘潭大学 | Preparation method and application of Co-Mo-S catalyst |
| CN114345375A (en) * | 2022-01-11 | 2022-04-15 | 南昌航空大学 | Bimetallic sulfide nanoflower catalyst for degrading organic pollutants in water and preparation method thereof |
| CN114950493A (en) * | 2022-06-15 | 2022-08-30 | 湘潭大学 | Molybdenum-based sulfide supported catalyst and in-situ preparation method and application thereof |
| CN115159452A (en) * | 2022-08-19 | 2022-10-11 | 上海大学 | Bimetal sulfide composite magnesium-based hydrogen storage material and preparation method thereof |
| CN115382559A (en) * | 2022-08-30 | 2022-11-25 | 湘潭大学 | Bifunctional catalyst for hydrodeoxygenation reaction and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831315A (en) * | 2009-03-10 | 2010-09-15 | Ifp公司 | Use will come from the method for the raw material hydrogenation deoxidation of renewable source with limited decarboxylation conversion based on the catalyzer of nickel and molybdenum |
| CN102728393A (en) * | 2012-07-10 | 2012-10-17 | 中南大学 | Non-loaded type nano hydrogenation deoxidation catalyst and preparation method thereof |
| CN103285886A (en) * | 2013-03-07 | 2013-09-11 | 中国石油大学(华东) | Catalyst for synthesis of decalin by one-step hydrogenation of naphthalene and method thereof |
-
2014
- 2014-05-08 CN CN201410191266.9A patent/CN103920506A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831315A (en) * | 2009-03-10 | 2010-09-15 | Ifp公司 | Use will come from the method for the raw material hydrogenation deoxidation of renewable source with limited decarboxylation conversion based on the catalyzer of nickel and molybdenum |
| CN102728393A (en) * | 2012-07-10 | 2012-10-17 | 中南大学 | Non-loaded type nano hydrogenation deoxidation catalyst and preparation method thereof |
| CN103285886A (en) * | 2013-03-07 | 2013-09-11 | 中国石油大学(华东) | Catalyst for synthesis of decalin by one-step hydrogenation of naphthalene and method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 彭会左: "水热法制备钼基硫化催化剂及其加氢脱氧性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 3, 15 March 2014 (2014-03-15) * |
| 钦柏豪: "水热法合成钼基硫化态加氢脱硫催化剂及其性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 1, 15 January 2014 (2014-01-15) * |
Cited By (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669337A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for converting lignin and model compound thereof |
| CN104998605A (en) * | 2015-07-07 | 2015-10-28 | 三峡大学 | Decoloring agent and synthesis method therefor |
| CN106479560B (en) * | 2015-08-27 | 2018-11-27 | 中国科学院青岛生物能源与过程研究所 | A kind of bi-component transient metal sulfide nanotube and its preparation method and application |
| CN106479560A (en) * | 2015-08-27 | 2017-03-08 | 中国科学院青岛生物能源与过程研究所 | A kind of bi-component transient metal sulfide nanotube and its preparation method and application |
| CN105463566A (en) * | 2015-11-25 | 2016-04-06 | 中国科学技术大学 | Liquid phase method for epitaxial growth of MoSe2-XnSem heterogeneous nano structures |
| CN105463566B (en) * | 2015-11-25 | 2018-04-10 | 中国科学技术大学 | A kind of epitaxial growth MoSe2‑XnSemThe liquid phase process of hetero nano structure |
| CN105753070B (en) * | 2016-02-25 | 2017-07-21 | 华侨大学 | A kind of controllable method for preparing of Co Mo S ternary metal sulfide |
| CN105753070A (en) * | 2016-02-25 | 2016-07-13 | 华侨大学 | Controllable preparation method of Co-Mo-S (cobalt-molybdenum-sulfur) ternary metal sulfide |
| CN105688942A (en) * | 2016-03-14 | 2016-06-22 | 西安建筑科技大学 | Preparation method of layered MoS2-Ni nano-composite |
| CN106319558B (en) * | 2016-08-31 | 2018-05-08 | 天津市大陆制氢设备有限公司 | A kind of MoS of high-efficiency multiple2- Zn hydrogen-precipitating electrodes and preparation method thereof |
| CN106319558A (en) * | 2016-08-31 | 2017-01-11 | 天津市大陆制氢设备有限公司 | Efficient and porous MoS2-Zn hydrogen evolution electrode and preparation method thereof |
| CN106964373B (en) * | 2017-04-28 | 2019-07-26 | 湘潭大学 | A kind of hydrophobic oleophilic oil type hydrogenation deoxidation catalyst and its preparation method and application |
| CN106964373A (en) * | 2017-04-28 | 2017-07-21 | 湘潭大学 | A kind of hydrophobic oleophilic oil type hydrogenation deoxidation catalyst and its preparation method and application |
| CN107159270B (en) * | 2017-05-27 | 2019-07-16 | 湘潭大学 | A kind of magnetism hydrogenation deoxidation catalyst and its preparation method and application |
| CN107159270A (en) * | 2017-05-27 | 2017-09-15 | 湘潭大学 | A kind of magnetic hydrogenation deoxidation catalyst and its preparation method and application |
| CN110070993B (en) * | 2018-01-24 | 2021-06-22 | 南京大学 | Preparation method of carbon nanotube film high-load Mn-Co sulfide flexible electrode material |
| CN110070993A (en) * | 2018-01-24 | 2019-07-30 | 南京大学 | The preparation method of carbon nano-tube film high load Mn-Co sulfide flexible electrode material |
| CN108855145B (en) * | 2018-06-21 | 2020-10-02 | 青岛大学 | Two-step method for preparing cobalt sulfide/molybdenum sulfide composite material and application of cobalt sulfide/molybdenum sulfide composite material in hydrogen evolution reaction |
| CN108855145A (en) * | 2018-06-21 | 2018-11-23 | 青岛大学 | A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application |
| CN109003824A (en) * | 2018-06-29 | 2018-12-14 | 安阳师范学院 | Ternary cobalt nickel selenides nano-chip arrays electrode material and preparation method thereof |
| CN109235024A (en) * | 2018-09-04 | 2019-01-18 | 北京邮电大学 | A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load |
| CN109364952A (en) * | 2018-09-30 | 2019-02-22 | 中国科学院山西煤炭化学研究所 | By catalyst and preparation method and the application of aromatic nitro compound and benzaldehyde or furfural and its derivative synthesizing imine |
| CN109364952B (en) * | 2018-09-30 | 2021-06-18 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing imine from aromatic nitro compound and benzaldehyde or furfural and derivatives thereof, preparation method and application |
| CN109675589A (en) * | 2019-02-26 | 2019-04-26 | 湘潭大学 | A kind of composite catalyst and preparation method thereof for hydrogenation deoxidation reaction |
| CN109675589B (en) * | 2019-02-26 | 2021-10-29 | 湘潭大学 | Composite catalyst for hydrodeoxygenation reaction and preparation method thereof |
| CN109759093B (en) * | 2019-03-07 | 2022-02-22 | 陕西理工大学 | Molybdenum disulfide supported Ir monatomic catalyst and preparation method and application thereof |
| CN109759093A (en) * | 2019-03-07 | 2019-05-17 | 陕西理工大学 | A kind of molybdenum disulfide load monatomic catalyst of Ir and the preparation method and application thereof |
| CN110270353A (en) * | 2019-04-16 | 2019-09-24 | 青岛科技大学 | The preparation and application of load transitions bimetallic chalcogen compound nano material in situ |
| CN109972160A (en) * | 2019-04-23 | 2019-07-05 | 重庆文理学院 | A kind of preparation method of novel double-function catalyzing electrolysis water electrode |
| CN110479314A (en) * | 2019-08-27 | 2019-11-22 | 天津大学 | A kind of molybdenum base sulfide bimetallic catalyst and preparation method |
| CN110479314B (en) * | 2019-08-27 | 2021-12-31 | 天津大学 | Molybdenum-based sulfide bimetallic catalyst and preparation method thereof |
| CN110586133A (en) * | 2019-09-11 | 2019-12-20 | 天津大学 | Niobium acid-based sulfide composite material and preparation method thereof |
| CN112694126A (en) * | 2019-10-22 | 2021-04-23 | 中国科学院大连化学物理研究所 | Preparation method of high-dispersion nickel modified molybdenum disulfide |
| CN112694126B (en) * | 2019-10-22 | 2021-09-14 | 中国科学院大连化学物理研究所 | Preparation method of high-dispersion nickel modified molybdenum disulfide |
| CN112713012A (en) * | 2021-01-26 | 2021-04-27 | 重庆茨文科技有限公司 | Zn-doped Co9S8Loaded MoS2Method for producing composite material and use thereof |
| CN113120970A (en) * | 2021-03-26 | 2021-07-16 | 东南大学 | Method for preparing compound containing crystal water cobalt sulfate and redox graphene |
| CN113351230A (en) * | 2021-06-21 | 2021-09-07 | 华侨大学 | Isolated cobalt atom doped single-layer or few-layer MoS2Process for preparing catalyst |
| CN113663696A (en) * | 2021-08-31 | 2021-11-19 | 湘潭大学 | Preparation method and application of Co-Mo-S catalyst |
| CN114345375A (en) * | 2022-01-11 | 2022-04-15 | 南昌航空大学 | Bimetallic sulfide nanoflower catalyst for degrading organic pollutants in water and preparation method thereof |
| CN114950493A (en) * | 2022-06-15 | 2022-08-30 | 湘潭大学 | Molybdenum-based sulfide supported catalyst and in-situ preparation method and application thereof |
| CN115159452A (en) * | 2022-08-19 | 2022-10-11 | 上海大学 | Bimetal sulfide composite magnesium-based hydrogen storage material and preparation method thereof |
| CN115382559A (en) * | 2022-08-30 | 2022-11-25 | 湘潭大学 | Bifunctional catalyst for hydrodeoxygenation reaction and preparation method and application thereof |
| CN115382559B (en) * | 2022-08-30 | 2023-09-22 | 湘潭大学 | Double-function catalyst for hydrodeoxygenation reaction and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103920506A (en) | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof | |
| Buller et al. | Nanostructure in energy conversion | |
| Liu et al. | Preparation of SnO2–Co3O4/C biochar catalyst as a Lewis acid for corncob hydrolysis into furfural in water medium | |
| Zhai et al. | Bimetal Co8Ni2 catalyst supported on chitin-derived N-containing carbon for upgrade of biofuels | |
| Tavasoli et al. | Influence of the blend nickel/porous hydrothermal carbon and cattle manure hydrochar catalyst on the hydrothermal gasification of cattle manure for H2 production | |
| CN110841661A (en) | Preparation method and application of 1T-2H molybdenum disulfide @ cadmium sulfide composite nanomaterial | |
| CN110961123B (en) | All-solid-state direct Z-type ZnIn prepared by hydrothermal method2S4-MoSe2High-efficiency photocatalyst | |
| LU500927B1 (en) | MoSe2/DEFECT-RICH ZnIn2S4/CdSe DUAL Z-SCHEME PHOTOCATALYST FOR PHOTOCATALYTIC WATER SPLITTING TO HYDROGEN | |
| CN108218673B (en) | Method for catalyzing selective depolymerization of lignin by non-noble metal | |
| Deng et al. | Catalytic pyrolysis of pine needle biomass over Fe–Co–K catalyst for H2-rich syngas production: Influence of catalyst preparation | |
| CN109482212B (en) | Preparation of low-temperature self-assembled molybdenum carbide nanowire catalyst and application of catalyst in biomass hydrodeoxygenation | |
| CN109647459A (en) | A kind of preparation method for the Ni-based phosphide that composition is controllable | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN103638938B (en) | A kind of preparation method of the catalyst for biological oil hydrodeoxygenation | |
| Li et al. | Transforming biomass tar into a highly active Ni-based carbon-supported catalyst for selective hydrogenation-transalkylation of guaiacol | |
| Zhang et al. | On-demand, highly tunable, and selective 5-hydroxymethylfurfural hydrogenation to furan diols enabled by Ni and Ni3Ga alloy catalysts | |
| CN107138169B (en) | Two-dimensional sulfide nano-junction hydrogen production photocatalyst, and preparation method and application thereof | |
| Guo et al. | Selective hydrodeoxygenation of guaiacol to cyclohexanol over NixCoyAlz catalysts under mild conditions | |
| Wang et al. | Bimetallic ordered mesoporous carbon from lignin for catalytic selective hydrogenation of levulinic acid to γ-valerolactone | |
| Shao et al. | Selective conversion of levulinic acid to gamma-valerolactone over Ni-based catalysts: Impacts of catalyst formulation on sintering of nickel | |
| CN104326875B (en) | A kind of xylogen hydrogenation degraded preparation bio oil method | |
| CN107185556B (en) | Preparation method of high-efficiency photocatalyst based on non-noble metal transition element sulfide | |
| Wang et al. | Anchoring Co on CeO2 nanoflower as an efficient catalyst for hydrogenolysis of 5-hydroxymethylfurfural | |
| Lin et al. | NiCo/SiO2 nanospheres for efficient synergetic decarboxylation of fatty acids and upgrading of municipal sludge HTL bio-crude to biofuels | |
| Zhao et al. | Effective synthesis of ethyl levulinate via alcoholysis of furfuryl alcohol over simple nickel-titanium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140716 |
|
| WD01 | Invention patent application deemed withdrawn after publication |