CN107159270A - A kind of magnetic hydrogenation deoxidation catalyst and its preparation method and application - Google Patents
A kind of magnetic hydrogenation deoxidation catalyst and its preparation method and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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Abstract
The present invention discloses a kind of magnetic hydrogenation deoxidation catalyst and its preparation method and application.The catalyst is by Co and MoS2Composition, wherein Co/Mo mol ratios are 0.05 ~ 1, and preparation method is as follows：First by MoS2It is dispersed in alcoholic solution, Co is then prepared using solvent-thermal method3O4And deposition is covered in MoS2Surface, the black particle that separating, washing, drying is obtained 120 ~ 350 DEG C of reduction treatments in the hydrogen gas atmosphere, obtains Co MoS2Catalyst, preparation method of the invention is simple, environmental protection, and prepared catalyst has magnetic, and has excellent hydrogenation deoxidation catalytic activity to phenolic compound, can separate and recover catalyst using magnet in liquid phase reactor, the rate of recovery reaches more than 99%.
Description
Technical field
The invention belongs to catalyst preparation field, and in particular to a kind of magnetic hydrogenation deoxidation catalyst and preparation method thereof and
Using specifically in the catalytic hydrodeoxygenation reaction of phenols oxygenatedchemicals.
Background technology
The problems such as due to the increasingly depleted of fossil energy and its using the environmental pollution brought, bio-oil, one kind source
In the fluid oil of biomass through pyrolysis, it is considered to be a kind of green, environmental protection and most potential substitute energy source for petroleum, it is developed
Enjoy international extensive concern.However, containing the oxygenatedchemicals such as a large amount of phenols in lignin oil, cause combustion heat value it is low,
The deficiency such as intersolubility is poor, viscosity is big, be corrosive.By catalytic hydrodeoxygenation, refine, alternative goes deoxygenation to improve oil product
Quality.Because the oxygen in phenolic compound is joined directly together with phenyl ring, the activation energy required for carbon-oxygen bond in fracture phenolic hydroxyl group is very
Height, causes the reaction temperature of the direct deoxidation of phenols high, but can improve the selectivity of aromatic hydrocarbons in product, reduces hydrogen gas consumption.If
Want to reduce the reaction temperature, key is to prepare high-activity hydrogenation dehydrogenation catalyst.
Sulfide catalyst is a kind of low effective catalyst of active good, cost, is widely used in catalysis biological oil
The hydrogenation deoxidation reaction of oxygenatedchemicals, but the catalytic activity of catalyst that different preparation method is obtained differs greatly.Document 1
[Chem. Eng. Sci. 2012, 79:1] method that Co-Mo-S catalyst is prepared using one step hydro thermal method, institute are reported in
Obtaining catalyst has preferable hydrogenation deoxidation activity, and arenes selectivity is higher in product；Patent CN103920506A is disclosed
One kind prepares Co-S/MoS using two one-step hydrothermals2Method, what its hydrogenation deoxidation catalytic activity was prepared apparently higher than one-step method
Catalyst, and with excellent direct deoxy activity.If but these catalyst are used in liquid-phase hydrogenatin deoxygenation, exist
The problem of separation is difficult,, will using magnetic field after catalytic reaction terminates if the magnetic hydrogenation deoxidation catalyst of tool can be prepared
Catalyst therein is can be easily separated, is conducive to the recycling of catalyst.
Most of documents, which are mainly used, prepares the magnetic catalyst of tool, such as [J. of document 2 by core of ferroso-ferric oxide
Catal., 2011, 282:155] a kind of Fe is reported3O4@MoS2The preparation method of magnetic catalyst.According to patent
CN103920506A method, needs strong acidic environment because prepared by the hydro-thermal of cobalt sulfide, cobalt is added using one step hydro thermal method
It is difficult to when sulfide or two one-step hydrothermals covering cobalt sulfide.Therefore, the present invention is with MoS2For substrate, using solvent heat
Method is by Co3O4Dispersed deposition is in MoS2Surface, then obtain through hydrogen-liquid-phase reduction having magnetic Co-MoS2, it is phenols chemical combination
The catalytic hydrodeoxygenation of thing is refined to provide a kind of efficient, environment-friendly catalyst and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of preparation method and applications of magnetic hydrogenation deoxidation catalyst, the catalyst
There is simple preparation method, the active height of hydrogenation deoxidation, magnetic, easily separated from liquid phase.
The technical scheme is that：
A kind of magnetic hydrogenation deoxidation catalyst, by Co and MoS2Composition, wherein Co/Mo mol ratios are 0.05 ~ 1, and catalyst
Magnetic, which is conducive to reclaiming in liquid phase reactor, to be reused.
The preparation method of above-mentioned magnetic hydrogenation deoxidation catalyst, comprises the following steps：
1. first by MoS2It is scattered in alcoholic solution, is 0.05 ~ 1 addition cobalt saline solution, ultrasonic vibration point by Co/Mo mol ratios
After dissipating, confined reaction in hydrothermal reaction kettle is moved to, black powder is obtained through centrifugation, washing, vacuum drying；
2. above-mentioned black powder and solvent are added in autoclave, after reduction treatment under hydrogen environment, that is, obtains magnetic
Hydrogenation deoxidation catalyst.
Further, step 1. described in alcohol to be more than one or both of methanol, ethanol, propyl alcohol, butanol, preferably
Ethanol.
Further, step 1. described in cobalt salt be cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate in one kind or two
More than kind, preferred cobalt acetate.
Further, step 1. described in confined reaction temperature be 120 ~ 250 DEG C, the reaction time be 1 ~ 10 hour.
Further, step 2. described in solvent to be more than one or both of alcohol, ether, ketone, alkane, aromatic hydrocarbons.
Further, step 2. described in hydrogen environment for hydrogen and inert nitrogen gas or argon gas one or two
Composition.
Further, step 2. middle reduction treatment temperature be 120 ~ 350 DEG C, processing time be 0.1 ~ 10 hour.
Above-mentioned magnetic hydrogenation deoxidation catalyst is applied in the reaction of the hydrogenation deoxidation of phenolic compound.
The beneficial effects of the present invention are：
Preparation method of the present invention is very simple, and mild condition is controllable, selected low in raw material price, and preparation cost is low, gained magnetic
Co-MoS2Catalyst, in the catalytic hydrodeoxygenation of phenols, very efficiently, the conversion ratio and DNA vaccine of phenols to be all up to
100%, and product aromatics selectivity also close to 100%.Products obtained therefrom of the present invention has magnetic, in liquid-phase hydrogenatin deoxidation process
In, the rate of recovery of catalyst is very high, is conveniently recycled for multiple times.Gained catalyst of the invention has excellent direct deoxidation selection
Property, its catalytic activity is substantially better than common similar catalyst, and catalyst is substantially easily recycled, in removal process
Loss late is very low（The rate of recovery reaches more than 99%）, and stability is good, is recycled for multiple times, activity is held essentially constant.
Brief description of the drawings
Fig. 1 is that magnet collects magnetic Co-MoS in liquid phase2The state diagram of catalyst.
Fig. 2 is Co-MoS2The XRD spectrum of catalyst.
Embodiment
The present invention is described in further detail by following examples.
Reagent used is that analysis is pure in embodiment, and water is ultra-pure water.
Co-MoS prepared by the present invention2The magnetic of catalyst is collected black powder analysis in liquid phase using magnet and judged.
Embodiment 1
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained
The aqueous solution of 0.0311g cobalt acetates, ultrasonic vibration was transferred in reactor and reacted at 150 DEG C after 3h after 30 minutes, will be black
After the washing of color precipitation, alcohol are washed, be dried in vacuo, pour into reactor, add 30 mL n-dodecanes, with hydrogen exclusion kettle
Air, then handles after 1 h at 200 DEG C, black powder is separated, and washs and is dried in vacuo, obtains Co-MoS2Catalyst.
12.5 g n-dodecanes, 4.8 g p-methyl phenols and 0.03 g embodiments 1 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 225 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 1 h after, the conversion ratio of p-methyl phenol up to 100%,
Methylbenzene selective is 99.7%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 2
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained
The aqueous solution of 0.0156g cobalt acetates, ultrasonic vibration was transferred in reactor and reacted at 150 DEG C after 3h after 30 minutes, will be black
After the washing of color precipitation, alcohol are washed, be dried in vacuo, pour into reactor, add 30 mL ethanol, with the air in hydrogen exclusion kettle,
Then handled at 200 DEG C after 1 h, black powder is separated, washed and be dried in vacuo, obtain Co-MoS2Catalyst.
12.5 g n-dodecanes, 4.8 g p-methyl phenols and 0.03 g embodiments 2 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 250 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 3 h after, the conversion ratio of p-methyl phenol up to 99.6%,
Methylbenzene selective is 99.8%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 3
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained 0.311g
The aqueous solution of cobalt acetate, ultrasonic vibration was transferred in reactor and reacted at 150 DEG C after 3h, by black precipitate water after 30 minutes
Wash, alcohol is washed, be dried in vacuo after, pour into reactor, add 30 mL n-dodecanes, with hydrogen exclude kettle in air, then
Handled at 200 DEG C after 1 h, black powder is separated, washed and be dried in vacuo, obtain Co-MoS2Catalyst.
12.5 g n-dodecanes, 4.8 g p-methyl phenols and 0.03 g embodiments 3 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 250 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 2 h after, the conversion ratio of p-methyl phenol up to 99.7%,
Methylbenzene selective is 99.6%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 4
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained 0.118
The aqueous solution of g cobalt chlorides, ultrasonic vibration was transferred in reactor and reacted at 120 DEG C after 10 h, black is sunk after 30 minutes
Form sediment after washing, alcohol washes, be dried in vacuo, pour into reactor, add 30 mL normal octanes, with the air in hydrogen exclusion kettle, so
Handled afterwards at 200 DEG C after 1 h, black powder is separated, washed and be dried in vacuo, obtain Co-MoS2Catalyst.
12.5 g n-dodecanes, 4.8 g p-methyl phenols and 0.03 g embodiments 4 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 225 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 1 h after, the conversion ratio of p-methyl phenol up to 100%,
Methylbenzene selective is 99.8%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 5
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained
The aqueous solution of 0.0311g cobalt acetates, ultrasonic vibration was transferred in reactor and reacted at 250 DEG C after 1 h after 30 minutes, will be black
After the washing of color precipitation, alcohol are washed, be dried in vacuo, pour into reactor, add 30 mL acetophenones, with the sky in nitrogen exclusion kettle
Gas, is re-filled with hydrogen, is then handled at 200 DEG C after 1 h, black powder is separated, and washs and is dried in vacuo, obtains Co-
MoS2Catalyst.
12.5 g n-dodecanes, 5.4 g paraethyl phenols and 0.03 g embodiments 5 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 225 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 1 h after, the conversion ratio of paraethyl phenol up to 100%,
Ethylbenzene selectivity is 99.6%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 6
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained
The aqueous solution of 0.0311g cobalt acetates, ultrasonic vibration was transferred in reactor and reacted at 250 DEG C after 1 h after 30 minutes, will be black
After the washing of color precipitation, alcohol are washed, be dried in vacuo, pour into reactor, add 30 mL it is decahydronaphthalene how, with hydrogen exclusion kettle
Air, then handles after 1 h at 200 DEG C, black powder is separated, and washs and is dried in vacuo, obtains Co-MoS2Catalyst.
12.5 g n-dodecanes, 4.8 g p-methyl phenols and 0.03 g embodiments 6 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 225 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 1 h after, the conversion ratio of p-methyl phenol up to 99.8%,
Methylbenzene selective is 99.7%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 7
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained
The aqueous solution of 0.0311g cobalt acetates, ultrasonic vibration was transferred in reactor and reacted at 250 DEG C after 1 h after 30 minutes, will be black
After the washing of color precipitation, alcohol are washed, be dried in vacuo, pour into reactor, add 30 mL methyl phenyl ethers anisoles, with the sky in argon gas exclusion kettle
Gas, is re-filled with hydrogen, is then handled at 350 DEG C after 0.1 h, black powder is separated, and washs and is dried in vacuo, obtains Co-
MoS2Catalyst.
12.5 g n-dodecanes, 2.76 g o-methoxyphenols and 0.03 g embodiments 7 is added in autoclave to make
Standby catalyst, installs device, excludes air in kettle using displacement method, then rises to 250 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, is reacted after 4 h, the conversion ratio of o-methoxyphenol reaches
99.8%, benzene selective is 98.9%, after reaction, separation and recovery of catalyst can be used further into lower secondary response using magnet, circulation
After reaction 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches 99%
More than.
Embodiment 8
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained
The aqueous solution of 0.0933g cobalt acetates, ultrasonic vibration was transferred in reactor and reacted at 200 DEG C after 3 h after 30 minutes, will be black
After the washing of color precipitation, alcohol are washed, be dried in vacuo, pour into reactor, add 30 mL n-dodecanes, with hydrogen exclusion kettle
Air, then reacts after 1 h at 250 DEG C, black powder is separated, and washs and is dried in vacuo, obtains Co-MoS2Catalyst.
Add prepared by 12.5 g n-dodecanes, 2.44 g hydroquinones and 0.03 g embodiments 8 in autoclave
Catalyst, installs device, excludes air in kettle using displacement method, then rises to 250 DEG C from room temperature with 10 DEG C/min speed,
Adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, is reacted after 3 h, and the conversion ratio of hydroquinones is up to 99.7%, and benzene is selected
Selecting property is 99.0%, after reaction, separation and recovery of catalyst can be used further into lower secondary response using magnet, after circular response 3 times,
The hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 9
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained 0.11 g
The aqueous solution of cobalt nitrate, ultrasonic vibration was transferred in reactor and reacted at 200 DEG C after 3 h after 30 minutes, by black precipitate water
Wash, alcohol is washed, be dried in vacuo after, pour into reactor, add 30 mL hexadecanes, with hydrogen exclude kettle in air, then
Handled at 220 DEG C after 1 h, black powder is separated, washed and be dried in vacuo, obtain Co-MoS2Catalyst.
12.5 g n-dodecanes, 5.4 g paraethyl phenols and 0.03 g embodiments 9 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 225 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 2 h after, the conversion ratio of paraethyl phenol up to 100%,
Ethylbenzene selectivity is 99.0%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Embodiment 10
0.2 g MoS prepared by hydro-thermal method2Powder is scattered in 72 mL absolute ethyl alcohols, is then added 8 mL and is contained 0.14 g
The aqueous solution of cobaltous sulfate, ultrasonic vibration was transferred in reactor and reacted at 250 DEG C after 2 h after 30 minutes, by black precipitate water
Wash, alcohol is washed, be dried in vacuo after, pour into reactor, add 30 mL hexadecanes, with hydrogen exclude kettle in air, then
Handled at 200 DEG C after 2 h, black powder is separated, washed and be dried in vacuo, obtain Co-MoS2Catalyst.
12.5 g n-dodecanes, 4.8 g p-methyl phenols and 0.03 g embodiments 10 is added in autoclave to prepare
Catalyst, install device, using displacement method exclude kettle in air, then rise to 225 from room temperature with 10 DEG C/min speed
DEG C, adjustment rotating speed be 900 r/min, Hydrogen Vapor Pressure be 4.0 MPa, reaction 2 h after, the conversion ratio of p-methyl phenol up to 100%,
Methylbenzene selective is 99.0%, after reaction, separation and recovery of catalyst can be used further into lower secondary response, circular response using magnet
After 3 times, the hydrogenation deoxidation activity of catalyst is held essentially constant, and the rate of recovery of each post catalyst reaction all reaches more than 99%.
Claims (9)
1. a kind of magnetic hydrogenation deoxidation catalyst, it is characterised in that by Co and MoS2Composition, with magnetic, wherein Co/Mo moles
Than for 0.05 ~ 1.
2. the preparation method of the magnetic hydrogenation deoxidation catalyst described in claim 1, it is characterised in that comprise the following steps：
1. first by MoS2It is scattered in alcoholic solution, is 0.05 ~ 1 addition cobalt saline solution by Co/Mo mol ratios, ultrasonic vibration disperses
Afterwards, confined reaction in reactor is moved to, black powder is obtained through centrifugation, washing, vacuum drying；
2. above-mentioned black powder and solvent are added in autoclave, after reduction treatment under hydrogen environment, that is, obtains magnetic
Hydrogenation deoxidation catalyst.
3. the preparation method of magnetic hydrogenation deoxidation catalyst according to claim 2, it is characterised in that step 1. described in
Alcohol to be more than one or both of methanol, ethanol, propyl alcohol, butanol.
4. the preparation method of magnetic hydrogenation deoxidation catalyst according to claim 2, it is characterised in that step 1. described in
Cobalt salt to be more than one or both of cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate.
5. the preparation method of magnetic hydrogenation deoxidation catalyst according to claim 2, it is characterised in that step 1. described in
Confined reaction temperature be 120 ~ 250 DEG C, the reaction time be 1 ~ 10 hour.
6. the preparation method of magnetic hydrogenation deoxidation catalyst according to claim 2, it is characterised in that step 2. described in
Solvent be one or more kinds of in alcohol, ether, ketone, alkane, aromatic hydrocarbons.
7. the preparation method of magnetic hydrogenation deoxidation catalyst according to claim 2, it is characterised in that step 2. described in
Hydrogen environment be hydrogen and inert nitrogen gas or one or two kinds of compositions of argon gas.
8. the preparation method of magnetic hydrogenation deoxidation catalyst according to claim 2, it is characterised in that step 2. middle reduction
The temperature of processing is 120 ~ 350 DEG C, and processing time is 0.1 ~ 10 hour.
9. application of the magnetic hydrogenation deoxidation catalyst in the hydrogenation deoxidation reaction of phenolic compound described in claim 1.
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| CN109046409A (en) * | 2018-09-11 | 2018-12-21 | 浙江理工大学 | A kind of preparation method of phosphatization cobalt-molybdenum disulfide nano sheet@carbon nanotube |
| 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 |
| CN110227479A (en) * | 2019-06-12 | 2019-09-13 | 中国科学院过程工程研究所 | It is a kind of magnetism catalyst with base of molybdenum p-nitrophenol catalysis in application method |
| 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 |
| KR20210127527A (en) | 2020-04-14 | 2021-10-22 | 고려대학교 세종산학협력단 | Molybdenum sulfide nanosheets with transition metal and preparation method thereof |
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| CN108786856A (en) * | 2018-05-29 | 2018-11-13 | 江苏大学 | A kind of MoS2/Co3O4The preparation method and applications of heterojunction photocatalyst |
| CN109046409A (en) * | 2018-09-11 | 2018-12-21 | 浙江理工大学 | A kind of preparation method of phosphatization cobalt-molybdenum disulfide nano sheet@carbon nanotube |
| 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 |
| CN110227479A (en) * | 2019-06-12 | 2019-09-13 | 中国科学院过程工程研究所 | It is a kind of magnetism catalyst with base of molybdenum p-nitrophenol catalysis in application method |
| CN110227479B (en) * | 2019-06-12 | 2021-04-06 | 中国科学院过程工程研究所 | Application method of magnetic molybdenum-based catalyst in p-nitrophenol catalysis |
| KR20210127527A (en) | 2020-04-14 | 2021-10-22 | 고려대학교 세종산학협력단 | Molybdenum sulfide nanosheets with transition metal and preparation method thereof |
| 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 |
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