CN106423233A - Transition metal phosphide catalyst, preparing method and application to guaiacol hydrogenolysis reaction - Google Patents
Transition metal phosphide catalyst, preparing method and application to guaiacol hydrogenolysis reaction Download PDFInfo
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- CN106423233A CN106423233A CN201610817491.8A CN201610817491A CN106423233A CN 106423233 A CN106423233 A CN 106423233A CN 201610817491 A CN201610817491 A CN 201610817491A CN 106423233 A CN106423233 A CN 106423233A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
Abstract
The invention discloses a preparing method and application of a transition metal phosphide catalyst to a guaiacol hydrogenolysis reaction. According to the transition metal phosphide catalyst, metal phosphide serves as a main active ingredient, one or more of metal nickel, metal cobalt, metal iron, metal ruthenium, metal rhodium, metal palladium, metal osmium, metal iridium, metal platinum and metal copper are added and serve as second ingredients, and the catalyst can be carried on one or more compound carriers in a carbon material, a molecular sieve and oxide, and is used for the guaiacol catalytic hydrogenolysis reaction. The catalyst can efficiently catalyze guaiacol to be converted into fine chemicals with the high added value under the conditions that the temperature ranges from 150 DEG C to 350 DEG C, and the initial hydrogen pressure is 1 MPa to 6 MPa. The preparing method of the transition metal phosphide catalyst is simple and easy to carry out, both a precursor and the catalyst are stable in air, and the catalyst is the excellent and novel guaiacol hydrogenolysis catalyst with the industrialization potential.
Description
Technical field
The invention belongs to Industrial Catalysis and bioenergy transformation technology field, it is related to a kind of transition metal phosphide catalyst
Preparation method and the application in guaiacol hydrogenolysis.
Background technology
Guaiacol (guaiacol) be a kind of white or slightly yellow crystallization or colourless to pale yellow transparent oily liquids, have
Special aromatic odor, scientific name guaiacol, glycerin ether, guaifenesin, adjacent hydroxyl glycerin ether etc., are a kind of important
Fine-chemical intermediate.Hydroxyl and methoxyl group, the methoxyl group in its molecule functional group is contained in the chemical constitution of guaiacol
Carbon-oxygen bond chemical bond energy the weakest (247 every mole of kilojoule)；The bond energy of the carbon-oxygen bond between aromatic hydrocarbons phenyl ring and phenolic hydroxyl group is
By force (414 every mole of kilojoule).By selecting suitable reaction condition and catalyst, guaiacol is oriented with dissociation, selects
Property the ground part chemical bond therein that ruptures multiple high valuable chemicals can be obtained, such as catechol, phenol, methyl phenyl ethers anisole,
Hexamethylene etc..
Guaiacol can be obtained by the degraded of lignin, and lignin is that a kind of complicated have tridimensional network
Natural high molecular substance, rich in phenyl ring chemical constitution, the content in nature is only second to cellulose, be widely present in timber and
In gramineae plant body.In the monomeric products after its degraded, guaiacol proportion highest.Slurrying and paper industry meeting
The discharge garbage containing lignin in a large number, not only causes the waste of lignin, and environment is caused with huge pollution, will
It carries out waste higher value application, meets national long-range Strategic Demand.
Based on the fundamental realities of the country of China's " oil starvation, few gas ", with the increasingly consumption of petroleum resources, hexamethylene, phenol, benzene first
The traditional preparation methods of the chemicals such as ether will be challenged, and develops new efficient, environmental protection, sustainable development and selectivity height
Syntheti c route extremely urgent.It is rich in phenyl ring chemical constitution, by green sustainable route " lignin-guaiaci lignum in lignin
Phenol-high level chemicals " is come to produce related chemical species be a very promising scheme.
Transition metal phosphide be one similar when there is the compound of metallicity and characteristic of semiconductor, good due to having
Hydrodesulfurization and hydrodenitrogenationactivity activity, become another new the adding with wide application prospect after carbide and nitride
Hydrogen catalyst for refining.It is the triangular prism being formed by metallic atom in the minimum structural unit of transition metal phosphide, radius phase
Larger phosphorus atoms are occupied with the space within triangular prism.Seemingly, but arrangement mode is different for the structure of phosphide and testing sulphide.
Sulfide exposes more two-dimentional basal plane, forms layer structure；Phosphide then has the sphaerocrystal pattern of same sex out-phase, shape
Glomeration structure.Chondritic can make phosphide catalyst surface expose more metallic atoms, provides more coordinations
Unsaturated position, thus improve catalysis activity.
Phosphate reducing process is a kind of method of the prepared phosphide of the propositions such as Oyama and Gopalakrishnan, and it is
Metallic salt is acted on ammonium phosphate salt, generates the presoma of transition metal phosphate, then through temperature-programmed reduction method in H2In
Reduction finally gives transition metal phosphide.Phosphate reducing process prepare initial stage of presoma just by metal with phosphorus in atom
In the range of mutually mix, so being no longer necessary to High Temperature High Pressure phosphorus just can diffuse into phosphide in metal body phase.
Compared with conventional a few class catalyst, phosphide catalyst not only overcomes S in the expensive, sulfide of noble metal
It is easy to run off being difficult, with united catalyst, the shortcoming that uniformly loads, also there is the mating reaction in metal center and acid site, be suitable for urging
Change the hydrogenation deoxidation process of aldehydes matter；Especially Ni-based phosphide catalyst is for the carbon-oxygen bond on removing guaiacol phenyl ring
There is good result, be highly suitable to be applied for the sustainable production line of green of " lignin-guaiacol-high level chemicals ".
Content of the invention
In order to solve problems of the prior art, the present invention provides a kind of transition metal phosphide catalyst and preparation
Method and its application in guaiacol hydrogenolysis.
The technical solution used in the present invention is：Catalyst with metal phosphide as main active component, add metallic nickel,
One of cobalt, ferrum, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper or more than one be the second component, can support in material with carbon element, molecular sieve,
On one of oxide or more than one complex carriers.Catalyst formula Z-AB/C represents, wherein Z is auxiliary agent, and A is transition
One or more of metallic nickel, cobalt, ferrum, copper, platinum, ruthenium, rhodium, palladium, lanthanum, osmium, iridium；B is P elements；C is porous carrier or nothing；
Total loading in catalyst for active component Z-AB is 2-95wt%；Wherein, loading in catalyst for the Z is 0-
30wt%, the A loading in catalyst is 2-95wt%.
Catalyst carrier C is activated carbon (AC), white carbon black (VB), carbon fiber (CF), Graphene (Graphene), CNT
(CT), meso-porous carbon material, gama-alumina (γ-Al2O3), silicon oxide (SiO2), zirconium oxide (ZrO2), titanium oxide (TiO2), sial
One of molecular sieve, phosphate aluminium molecular sieve etc. or more than one complexs.
The preferred loading of active component Z-AB is 5-60wt%, and wherein, the preferred loading of A is 0.1-10wt%, Mo
Preferred loading be 2-30wt%.
A kind of preparation method of transition metal phosphide catalyst, by the soluble-salt of transition metal A and phosphate according to
Selected transition metal mixes generation precipitation with the stoichiometric proportion of P elements in water, and adding nitric acid will be molten for described precipitation
Solution, obtains impregnation liquid；With equi-volume impregnating by impregnation liquid impregnate selected by after carrier, standing, be dried, roasting, obtain catalyst
Presoma；Gained catalyst precursor heats up in hydrogen atmosphere and carries out reduction reaction, is cooled to room temperature after completion of the reaction, obtains
Described transition metal phosphide catalyst.
The precursor of active component A is the nitrate of metal, at least one in halogen, sulfate；
Described phosphate is selected from least one in diammonium phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate；
The soluble-salt of component Z is nitrate, acetate, carbonate or halogenide.
In course of dissolution, temperature is room temperature, and the time is 10-30min；
In standing step, temperature is room temperature, and the time is 5-12h；
In drying steps, temperature is 80-160 DEG C, and the time is 6-18h；
In calcination stepses, temperature is 350-650 DEG C, and the time is 2-8h.
In heating reduction step, heating schedule is warmed up to 350 DEG C for 0.5-2 hour, after with the speed of 0.5-2 DEG C of min-1
Rise to 750 DEG C, and keep 0.5-2 hour, H at this temperature2Air speed is 1000-6000h-1.
In addition, the described transition metal phosphide catalyst that the invention described above provides is urged to guaiacol hydrogenolysis process
The application changed, falls within protection scope of the present invention.
Specifically, guaiacol hydrogenolysis step is as follows：
Described guaiacol hydrogenolysis are placed in intermittent high-pressure reactor and carry out, reaction medium is to be not involved in reacting
Organic solvent, reaction internal standard substance is heat-staple Organic substance, and the concentration of reaction raw materials is 0.01-1mol/L, substrate and catalysis
The mass ratio of agent is 1:1-50:1, the initial pressure filling hydrogen in reactor under room temperature is 1-6MPa, is warming up to reaction temperature
150-350 DEG C, the response time is 1h-6h, and agitation revolution is 100-2000r/min.Reaction finishes and obtains new product, such as：Benzene, first
Benzene, hexamethylene, phenol etc..
Above-mentioned guaiacol molar concentration is 0.1-0.5mol/L.
Above-mentioned organic solvent is hexahydrotoluene, decahydronaphthalenes, oxolane or 1,4- dioxane.
Above-mentioned internal standard substance is dodecane or tridecane.
Reaction temperature is >=250 DEG C, the initial pressure 4-5MPa of hydrogen in reactor under room temperature, and the response time is 3h 4h,
Agitation revolution is 800-1200r/min.
The invention has the beneficial effects as follows：
1. the present invention can be catalyzed guaiacol hydrogenation deoxidation, by the use of soluble metal phosphate as active component A source,
Cheap and easy to get, by infusion process, active component is supported on carrier, is uniformly dispersed, simple to operate；
2. with metal phosphide as main active component, can add a small amount of nickel, cobalt, ferrum, copper, platinum, ruthenium, rhodium, palladium, lanthanum, osmium,
One or more of iridium transition metal is the second component, and catalyst to catalyzing hydrogenating activity is high；
3., with one or more material as carrier, catalyst contact surface can be effectively increased, improve pore structure, improve heat surely
Qualitative, enhancing catalysis activity, saving active component.
4. catalyst hydrogenation activity is high, and benzene selective is high, and catalyst stabilization performance is good, is a kind of excellent to have industry
Change the new guaiacol hydrogenolysis catalyst of potentiality.
Brief description
Fig. 1 is respectively Ni2P/SiO2(20% loading) catalyst, CoP/SiO2(20% loading) catalyst, NiCoP/
SiO2(20% loading) catalyst and carrier active carbon (SiO2) XRD figure.
Specific embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described
Method is conventional method if no special instructions.Described raw material all can be either commercially available from open if no special instructions.
Embodiment 1
Catalyst preparation process：Weigh six water nickel nitrate 1.622g, diammonium phosphate 0.736g respectively, be added to 3.24ml
In deionized water, generate precipitate, be added dropwise over 0.4ml nitric acid in six minutes by resolution of precipitate, obtain impregnation liquid；By gained
Impregnation liquid impregnates isopyknic 2g SiO2On carrier, stand 8h under room temperature, at 110 DEG C, 12h is dried, 500 DEG C of roasting 5h, obtain
Catalyst precursor；Presoma was warmed up to 350 DEG C in hydrogen atmosphere in 1 hour, after risen to the speed of 1 DEG C/min
750 DEG C, and keep 1 hour at this temperature, it is down to room temperature after completion of the reaction, obtain the Ni that loading is 20wt%2P/SiO2Urge
Agent, is labeled as Ni2P/SiO2- 20%.(loading=active component Ni2The quality of P/catalyst gross mass × 100%)
Embodiment 2
Ni2P/SiO2The preparation of catalyst：Similar to embodiment 1, difference is to be changed to loading preparation process
2wt%, obtains the Ni that loading is 2wt%2P/SiO2Catalyst, is labeled as Ni2P/SiO2- 2%.
Embodiment 3
Ni2P/SiO2The preparation of catalyst：Similar to embodiment 1, difference is to be changed to loading preparation process
10wt%, obtains the Ni that loading is 10wt%2P/SiO2Catalyst, is labeled as Ni2P/SiO2- 10%.
Embodiment 4
Ni2P/SiO2The preparation of catalyst：Similar to embodiment 1, difference is to be changed to loading preparation process
30wt%, obtains the Ni that loading is 30wt%2P/SiO2Catalyst, is labeled as Ni2P/SiO2- 30%.
Embodiment 5
Ni2P/SiO2The preparation of catalyst：Similar to embodiment 1, difference is to be changed to loading preparation process
60wt%, obtains the Ni that loading is 60wt%2P/SiO2Catalyst, is labeled as Ni2P/SiO2- 60%.
Embodiment 6
CoP/SiO2The preparation of catalyst：Similar to embodiment 1, difference is for nickel nitrate to be changed to nitre preparation process
Sour cobalt, obtains the Co P/SiO that Co loading is 20wt%2Catalyst, is labeled as CoP/SiO2- 20%.
Embodiment 7
Ni2The preparation of P catalyst：Similar to embodiment 1, difference is not carry out impregnation steps to preparation process, directly
Tap into row standing, drying, roasting etc., obtain Ni2P catalyst, is labeled as Ni2P.
Embodiment 8
The preparation of CoP catalyst：Similar to embodiment 7, difference is that just nickel nitrate is changed to nitric acid to preparation process
Cobalt, obtains CoP catalyst, is labeled as CoP.
Embodiment 9
Fe-Ni2P/SiO2The preparation of catalyst：Similar to embodiment 1, difference is precursor and nitre preparation process
Sour ferrum is dissolved in solution, and incipient impregnation loads on silica, and obtaining Ni loading is 20wt%, and Fe loading is
The Fe-Ni of 1wt%2P/SiO2Catalyst, is labeled as Fe-Ni2P/SiO2- 1%-20%.
Embodiment 10
Pt-Ni2P/SiO2The preparation of catalyst：Similar to embodiment 9, difference is to change ferric nitrate preparation process
For chloroplatinic acid, obtaining Ni loading is 20wt%, and Pt loading is the Pt-Ni of 10wt%2P/SiO2Catalyst, is labeled as Pt-
Ni2P/SiO2- 10%-20%.
Embodiment 11
Pt-CoP/SiO2The preparation of catalyst：Similar to embodiment 10, difference is to change nickel nitrate preparation process
For cobalt nitrate, obtaining Co loading is 20wt%, and Pt loading is the Pt-CoP/SiO of 10wt%2Catalyst, is labeled as Pt-
CoP/SiO2- 10%-20%.
Embodiment 12
Pt-Ni2P/SiO2The preparation of catalyst：Similar to embodiment 9, difference is the load of Fe preparation process
Amount is changed to 30wt%, and the load capacity of Ni is changed to 60wt%, and just obtaining Ni loading is 60wt%, and Pt loading is 30wt%'s
Pt-Ni2P/SiO2Catalyst, is labeled as Pt-Ni2P/SiO2- 30%-60%.
Embodiment 13
NiCoP/SiO2The preparation of catalyst：Similar to embodiment 1, difference is 0.887g six water preparation process
Cobalt nitrate and 0.887 6 water nickel nitrates are together dissolved in deionized water, and incipient impregnation is supported on SiO2On, obtaining loading is
The NiCoP/SiO of 20wt%2Catalyst, is labeled as NiCoP/SiO2- 20%.
Embodiment 14
Ni2P/γ-Al2O3The preparation of catalyst：Similar to embodiment 1, difference is to replace carrier preparation process
For γ-Al2O3, obtain the Ni that loading is 20wt%2P/γ-Al2O3Catalyst, is labeled as Ni2P/γ-Al2O3- 20%.
Embodiment 15
Ni2The preparation of P/AC catalyst：Similar to embodiment 14, difference is to replace with carrier preparation process
AC, obtains the Ni that loading is 20wt%2P/AC catalyst, is labeled as Ni2P/AC-20%.
Embodiment 16
Guaiacol hydrogenation reaction：Will be molten to 0.3104g (2.5mmol) guaiacol and 0.4258g (2.5mmol) dodecane
Solution hexahydrotoluene in volume be 20ml, together with 0.0621g Ni2P/SiO2- 20% catalyst is added between 50ml size
In formula of having a rest reactor, after being passed through five gases of hydrogen exchange, it is flushed with hydrogen gas to 4MPa, is stirred with the speed of 1000r/min, with
When be warming up to 300℃Reaction 4h.After reaction terminates, it is down to room temperature, takes product liquid, with gas chromatograph-mass spectrometer (GC-MS) and gas phase
Chromatograph carries out qualitative and detection by quantitative.Result reaches 96.88% for guaiacol conversion ratio, and primary product is hexamethylene, its product
Rate is 87.28%.
Embodiment 17
Transition metal phosphide catalyst is tested to guaiacol hydrogenation reaction：Experimentation similar to embodiment 16, no
It is to replace with catalyst respectively Co with part2P/SiO2- 20%, NiCoP/SiO2- 20%, the results are shown in Table 1.
Guaiacol hydrogenation reaction Performance comparision (T=300 DEG C, P=4MPa, t=4h) in table 1. different catalysts
As can be seen from the table, the phosphide catalyst that different transition metal component are constituted is anti-to guaiacol hydrogenation deoxidation
The catalytic effect answered is different, wherein with Ni2P/SiO2Catalyst effect is optimum.The product obtaining reaches to the yield of hexamethylene
87.28.%.
Embodiment 18
Ni under different hydrogen initial pressure2P/SiO2To guaiacol hydrogenation reaction：Experimentation similar to embodiment 16,
Difference is that the change of pressure and response time are 2h, the results are shown in Table 2
Ni under table 2. different hydrogen initial pressure2P/SiO2Guaiacol hydrogenation reaction Performance comparision (T=300 on catalyst
DEG C, t=2h)
As can be seen from the table, under certain pressure scope, catalyst shows higher catalysis activity, wherein pressure
During 4Mpa, guaiacol converts substantially, and the selectivity of product hexamethylene reaches highest.
Embodiment 19
Ni under different temperatures2P/SiO2To guaiacol hydrogenation reaction：Experimentation is similar to embodiment 16, difference
It is that the change of temperature and response time are 1h, the results are shown in Table 3
Table 3 differential responses temperature, Ni2P/SiO2Guaiacol hydrogenation reaction Performance comparision (P=4MPa, t=on catalyst
1h)
As can be seen from the table, raise with reaction temperature, the conversion ratio of guaiacol and the yield of hexamethylene are all increasing
Greatly, steeply rise between 200-300 DEG C, the preferably temperature range of this reaction system is >=300 DEG C.
Embodiment 20
Under the differential responses time, transition metal phosphide catalyst is to guaiacol hydrogenation reaction：Experimentation is similar to reality
Apply example 16, difference is the change in response time, the results are shown in Table 4
Under the table 4 differential responses time, guaiacol hydrogenation reaction Performance comparision (T=300 DEG C, P=4MPa) on catalyst
As can be seen from the table, with the increase in response time, the yield of the conversion ratio of guaiacol and hexamethylene rises,
The yield of phenol and methyl phenyl ethers anisole declines.
Claims (10)
1. a kind of transition metal phosphide catalyst it is characterised in that：Described catalyst formula Z-AB/C represents, wherein Z is to help
Agent, A is one or more of transiting metal nickel, cobalt, ferrum, copper, platinum, ruthenium, rhodium, palladium, lanthanum, osmium, iridium；B is P elements；C is many
Hole carrier or nothing；Total loading in catalyst for active component Z-AB is 2-95wt%；Wherein, Z supporting in catalyst
Measure as 0-30wt%, loading in catalyst for the A is 2-95wt%.
2. according to the catalyst described in claim 1 it is characterised in that：Catalyst carrier C is activated carbon, white carbon black, carbon fiber, stone
Black alkene, CNT, meso-porous carbon material, gama-alumina, silicon oxide, zirconium oxide, titanium oxide, Si-Al molecular sieve, phosphate aluminium molecular sieve
One of or more than one complexs.
3. according to the catalyst described in claim 1 it is characterised in that：The loading of active component Z-AB is 5-60wt%, its
In, the loading of Z is 0.1-10wt%, and the loading of A is 2-30wt%.
4. according to a kind of transition metal phosphide catalyst described in claim 1 preparation method it is characterised in that：By activity
The soluble-salt of component A in water in mixes generation according to selected transition metal with the stoichiometric proportion of P elements with phosphate
Precipitation, adds nitric acid by described resolution of precipitate, obtains impregnation liquid；With equi-volume impregnating by impregnation liquid impregnate selected by carrier
Afterwards, stand, be dried, roasting, obtain catalyst precursor；Gained catalyst precursor heats up in hydrogen atmosphere and carries out reduction instead
Should, it is cooled to room temperature after completion of the reaction, obtain described transition metal phosphide catalyst.
5. according to the preparation method described in claim 4 it is characterised in that：The precursor of active component A is the nitrate of metal, halogen
At least one in salt, sulfate；Affiliated phosphate is selected from diammonium phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate at least
A kind of；The soluble-salt of component Z is nitrate, acetate, carbonate or halogenide.
6. according to the preparation method described in claim 4 it is characterised in that：In course of dissolution, temperature is room temperature, and the time is 10-30
Minute；In standing step, temperature is room temperature, and the time is 5-12h；In drying steps, temperature is 80-160 DEG C, and the time is 6-18h；Roasting
Burn temperature in step and be 350-650 DEG C, the time is 2-8h；In heating reduction step, heating schedule is warmed up to for 0.5-2 hour
350 DEG C, after rise to 750 DEG C with the speed of 0.5-2 DEG C of min-1, and at this temperature keep 0.5-2 hour, H2Air speed is
1000-6000h-1.
7. application in guaiacol hydrogenolysis for the transition metal phosphide catalyst described in a kind of claim 1, its feature
It is：Guaiacol hydrogenolysis are carried out in intermittent high-pressure reactor, and reaction medium is the organic solvent being not involved in reacting,
Reaction internal standard substance is heat-staple Organic substance, and the concentration of reaction raw materials is 0.01-1mol/L, and substrate with the mass ratio of catalyst is
1:1-50:1, the initial pressure filling hydrogen in reactor under room temperature is 1-6MPa, is warming up to reaction temperature 150-350 DEG C, instead
It is 1h-6h between seasonable, agitation revolution is 100-2500r/min.
8. according to the application described in claim 7 it is characterised in that：Described organic solvent be hexahydrotoluene, decahydronaphthalenes, four
Hydrogen furan or 1,4- dioxane.
9. according to the application described in claim 7 it is characterised in that：Described internal standard substance is dodecane or tridecane.
10. according to the application described in claim 7 it is characterised in that：Reaction temperature is >=200 DEG C, hydrogen in reactor under room temperature
The initial pressure 3-5MPa of gas, the response time is 1 4h, and agitation revolution is 100-2500r/min.
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| CN110227513A (en) * | 2019-06-26 | 2019-09-13 | 浙江工业大学 | A kind of carbon-based carried metal phosphide catalyst and its preparation method and application |
| CN110694656A (en) * | 2019-09-11 | 2020-01-17 | 天津大学 | Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion |
| CN112657519A (en) * | 2020-12-30 | 2021-04-16 | 华南理工大学 | Nickel phosphide-zirconium phosphate composite catalyst with mesoporous structure and preparation method and application thereof |
| CN112850669A (en) * | 2021-01-29 | 2021-05-28 | 杭州电子科技大学 | Preparation method of palladium-copper phosphide heterodimer material |
| CN113385205A (en) * | 2021-07-16 | 2021-09-14 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
| CN114478198A (en) * | 2022-01-27 | 2022-05-13 | 大连大学 | Method for preparing phenol by catalytic hydrogenation of guaiacol |
| CN115466627A (en) * | 2022-10-12 | 2022-12-13 | 中国石油大学(华东) | Method for carrying out alcoholysis hydrogenation treatment on lignin in papermaking black liquor |
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