CN115837278A - Preparation and application of high-defect molybdenum oxysulfide bifunctional catalyst - Google Patents
Preparation and application of high-defect molybdenum oxysulfide bifunctional catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- SHMVRUMGFMGYGG-UHFFFAOYSA-N [Mo].S=O Chemical compound [Mo].S=O SHMVRUMGFMGYGG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 150000002989 phenols Chemical class 0.000 claims abstract description 9
- 229920005610 lignin Polymers 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 5
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000007547 defect Effects 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 16
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000003213 activating effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- CYRPECJLOQEQDX-UHFFFAOYSA-N oxo(sulfanylidene)molybdenum Chemical compound O=[Mo]=S CYRPECJLOQEQDX-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses preparation and application of a high-defect molybdenum oxysulfide bifunctional catalyst, and relates to a constructed molybdenum oxysulfide bifunctional catalyst. Dissolving ammonium molybdate and thiourea in water, performing crystallization treatment in a hydrothermal reaction kettle, and then filtering, washing and drying to obtain molybdenum sulfide nanosheets; roasting the molybdenum sulfide nanosheets in a muffle furnace to obtain a molybdenum oxysulfide composite catalyst; warp H 2 After reduction, the high defect molybdenum oxysulfide bifunctional catalyst is prepared. The catalyst can be used inPreparing aromatic hydrocarbon by atmospheric pressure gas-solid phase hydrodeoxygenation of lignin derived phenolic compounds at the reaction temperature of 300-400 ℃ and H 2 The pressure was 1atm. The catalyst of the invention has low price, shows excellent activity and deoxidation selectivity in the hydrogenation deoxidation reaction of phenols, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to preparation and application of a high-defect molybdenum oxysulfide bifunctional catalyst.
Background
Lignin biomass is the second largest biomass resource in the plant kingdom that reserves are second only to cellulose. The development and utilization of lignin biomass are still in the first stage due to its stable structure. Generally, the utilization of lignin comprises two stages, firstly, the fast pyrolysis is carried out at the temperature of 500-600 ℃ to obtain the biological crude oil, and the main component is phenolic compounds. The biological crude oil has high oxygen content, high viscosity, low heat value and instability, and needs to be further subjected to catalytic hydrodeoxygenation for quality improvement. However, the C-O bond of the phenolic hydroxyl group is extremely strong, and the C-O bond is difficult to break, so that side reactions such as hydrogenation of a benzene ring or severe C-C hydrogenolysis are caused, and the selectivity of target product aromatic hydrocarbon is low, so the key point and difficulty of research are to design an efficient catalyst to ensure that phenols are selectively deoxidized to generate aromatic hydrocarbon. In addition, as the components of the biological crude oil are complex, screening catalysts and exploring a reaction mechanism by adopting model molecules, such as metacresol, anisole, guaiacol and other biological oil components with representative oxygen-containing functional groups are main means of current research, and the method also provides a good theoretical basis for direct hydrodeoxygenation and upgrading of the biological crude oil. In the past research, conventional CoMoS catalysts, noble metal catalysts, oxides, sulfides, and the like have been commonly used as catalysts for phenol hydrodeoxygenation. Among them, the low-priced molybdenum oxide catalyst has been paid attention and searched by many researchers due to its high selective deoxidation performance.
The active center of the molybdenum oxide catalyst is an oxygen vacancy, and phenolic hydroxyl can be effectively activated, so that selective deoxidation is realized. However, the conventional molybdenum oxide has a small content of oxygen vacancies on the surface, and the molybdenum oxide itself has a weak capability of activating hydrogen, so that the activity of the molybdenum oxide catalyst reported in the literature is low. At present, the means of modifying the molybdenum oxide catalyst adopted by researchers is mainly to introduce a noble metal or a transition metal into a molybdenum oxide substrate to improve the capability of activating hydrogen, so that on one hand, the generation of oxygen vacancies on the surface of molybdenum oxide can be promoted, and on the other hand, the deoxidation and the subsequent hydrogenation of phenols can be synergistically catalyzed. However, the benzene ring in phenols tends to react with metals due to the presence of metal components, so that hydrogenation reaction and C — C hydrogenolysis side reaction of the benzene ring easily proceed, thereby decreasing the selectivity of the target deoxygenated product. Therefore, how to fully utilize the characteristic of activating phenolic hydroxyl groups by oxygen vacancies in molybdenum oxide without adding metal and construct an efficient catalyst on the basis of the characteristic is a key problem to be broken through at present.
Disclosure of Invention
Aiming at the defects of few oxygen vacancies and weak hydrogen activation capacity of molybdenum oxide in the prior art, the invention provides a preparation method of a high-defect molybdenum oxysulfide bifunctional catalyst.
The invention also provides application of the high-defect molybdenum oxysulfide bifunctional catalyst prepared by the preparation method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a preparation method of a high-defect molybdenum oxysulfide bifunctional catalyst, which comprises the following steps:
(1) Placing the molybdenum sulfide nanosheets into a muffle furnace for roasting to obtain a molybdenum oxysulfide composite material;
(2) And reducing the molybdenum oxysulfide composite material in a fixed bed to obtain the molybdenum oxysulfide bifunctional catalyst.
Preferably, the molybdenum sulfide nanosheets in step (1) are prepared by:
(1.1) dissolving ammonium molybdate and thiourea in water, and crystallizing in a hydrothermal reaction kettle;
and (1.2) filtering, washing and drying the crystallized product to obtain the molybdenum sulfide nanosheet.
Preferably, the mass ratio of ammonium molybdate to thiourea in step (1.1) is 1.16:1.
preferably, the crystallization temperature in the step (1.1) is 220 ℃, and the crystallization time is 18h.
Preferably, in the step (1), the roasting temperature is 80-550 ℃, the roasting time is 0.5-10h, and the heating rate is 2-10 ℃/min.
Preferably, the reduction temperature in the step (2) is 300-500 ℃, the reduction time is 0.5-4h, and the heating rate is 2-10 ℃/min.
On the other hand, the invention also provides the application of the high-defect molybdenum oxysulfide dual-function catalyst in hydrodeoxygenation of lignin-derived phenolic compounds.
M-cresol was used as the model reactant, with the phenolic hydroxyl group being the primary oxygen-containing functional group of lignin-derived bio-oils. The reaction is carried out in a normal-pressure gas-solid phase reactor, the reaction temperature is 300-400 ℃, the pressure of the reaction hydrogen is 1atm, a quantitative injector is adopted for sample injection, and the reaction product is analyzed and identified by online gas chromatography.
Compared with the prior art, the invention provides the preparation method of the sulfur-molybdenum oxide bifunctional catalyst with rich oxygen vacancies, and the prepared catalyst is applied to the catalytic hydrodeoxygenation of lignin-derived phenolic compounds to prepare aromatic hydrocarbons. The catalyst has the characteristics of activating hydrogen by molybdenum sulfide and efficiently activating oxygen-containing functional groups by oxygen vacancies in molybdenum oxide, and shows excellent catalytic activity and aromatic selectivity in the phenol hydrodeoxygenation reaction.
Drawings
Fig. 1 is an XRD spectrum of the catalysts prepared in example 1 and comparative examples 1-2.
FIG. 2 is NH of catalysts prepared in example 1 and comparative examples 1-2 3 -TPD map.
FIG. 3 is H for the catalysts prepared in example 1 and comparative examples 1-2 2 -D 2 -TPSR spectrum.
FIG. 4 is a graph showing the conversion rate and toluene selectivity of the catalysts prepared in example 1 and comparative examples 1-2 for catalyzing the conversion of m-cresol.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The molybdenum sulfide nanosheet can be a commercially available product or can be self-made in a manner known in the art.
Comparative example 1
Preparation of molybdenum sulfide nanosheet
3.53g of ammonium molybdate tetrahydrate and 3.04g of thiourea were dissolved in 100mL of water, and the solution was placed in a 150mL hydrothermal kettle and placed in an oven for crystallization at 220 ℃ for 18h. And taking out the molybdenum sulfide nanosheet from the oven, cooling to room temperature, filtering, washing and drying to obtain the molybdenum sulfide nanosheet. An XRD spectrogram of the catalyst after being reduced at 400 ℃ is shown in figure 1, and a diffraction peak of the catalyst corresponds to a 2H type molybdenum sulfide nanosheet structure. By NH 3 TPD characterization analyzed the presence of its unsaturated coordination sites, as shown in FIG. 2, for desorbed NH 3 (m/z = 16) quantitative analysis showed that the catalyst had an amount of unsaturated coordination sites of about 32.3. Mu. Mol/g cat .
Comparative example 2
Preparation of molybdenum oxide
And (3) roasting the molybdenum sulfide nanosheet in the comparative example 1 in a muffle furnace at the roasting temperature of 600 ℃ for 3h at the heating rate of 2 ℃/min to obtain the sulfur-free molybdenum oxide catalyst. The XRD spectrogram of the catalyst after being reduced at 400 ℃ is shown in figure 1, and the diffraction peak of the catalyst comprises MoO 3 And MoO 2 The diffraction signal of (1). By NH 3 TPD characterization analyzed the presence of its unsaturated coordination sites, as shown in FIG. 2, for desorbed NH 3 (m/z = 16) quantitative analysis showed that the catalyst had an amount of unsaturated coordination sites of about 33.8. Mu. Mol/g cat It shows that the molybdenum oxide material has very low content of unsaturated coordination sites, which is one of the main reasons of poor activity.
Example 1
Preparation of molybdenum oxysulfide
And (3) roasting the molybdenum sulfide nanosheet in the comparative example 1 in a muffle furnace at the roasting temperature of 300 ℃ for 3h at the heating rate of 2 ℃/min to obtain the molybdenum oxysulfide catalyst. The XRD spectrogram of the catalyst after being reduced at 400 ℃ is shown in figure 1, and the diffraction peak of the catalyst comprises 2H type molybdenum sulfide and MoO 2 The diffraction signal of (1). By NH 3 TPD TableCharacterisation of the unsaturated coordination sites, as shown in FIG. 2, for desorbed NH 3 (m/z = 16) quantitative analysis showed that the catalyst had an amount of unsaturated coordination sites of about 273.4. Mu. Mol/g cat Compared with comparative example 1 and comparative example 2, the method has the advantages of greatly improving the performance of the molybdenum oxysulfide material.
Example 2
Probe reaction of hydrogen activation capability
By means of H 2 -D 2 Temperature-programmed surface reactions were conducted to examine the ability of the three catalysts of comparative example 1, comparative example 2, and example 1 to activate hydrogen, respectively. The probe reaction is carried out in a normal-pressure gas-phase fixed bed reactor, and an online mass spectrum detector is adopted to analyze the product. Firstly, weighing a certain amount of catalyst at 400 ℃ in situ H 2 Reducing for 1h under the atmosphere of (30 mL/min). After the reactor was cooled to room temperature, H was added 2 Switching to 50% of 30mL/min 2 +50％D 2 Gas mixture, at this time H is monitored in real time by a mass spectrometer 2 (m/z＝2)，D 2 (m/z = 4), evolution of the HD (m/z = 3) signal. After the signal stabilized, the reactor was programmed to 400 ℃ at a rate of 5 ℃/min. H of the catalysts obtained in comparative example 1, comparative example 2 and example 1 2 -D 2 The evolution of the temperature-programmed surface reaction as a function of temperature is shown in FIG. 3. The generation of HD means H 2 And D 2 Dissociation activation at the catalyst surface, it is apparent that the initial generation temperature of HD satisfies the following rule: comparative example 1<Example 1<Comparative example 2, which illustrates that comparative example 1 has the strongest H 2 The activation capacity, which is the same as that of example 1, and that of comparative example 2 is the weakest.
Comparative example 3
The catalyst prepared in comparative example 1 catalyzes the hydrodeoxygenation reaction of m-cresol
The m-cresol hydrodeoxygenation reaction is carried out in a normal-pressure gas-solid phase reactor, and the catalyst is H at 400 ℃ and 1atm under the in-situ condition 2 Reducing for 1h in the atmosphere, and adjusting the reaction temperature to 300 ℃. M-cresol was injected into the reaction tube through a quantitative syringe and heated to 220 ℃ at the injection port to vaporize the m-cresol. The flow rate of m-cresol is 0.03mL/h, passing through a catalyst bed layer, and analyzing a product by online gas chromatography. Control of H in the reaction 2 The molar ratio/m-cresol was 90,w/F =3h. The reaction results are shown in fig. 4, and under the current reaction conditions, the conversion of m-cresol was 5% and the selectivity of toluene was 94% over the catalyst of comparative example 1.
Comparative example 4
The catalyst prepared in comparative example 2 catalyzes the hydrodeoxygenation reaction of m-cresol
The reaction evaluation was conducted in the same manner as in comparative example 3. The reaction results are shown in fig. 4, and under the current reaction conditions, the conversion of m-cresol on the catalyst of comparative example 2 was only 3% and the selectivity of toluene was 97%. This indicates that molybdenum oxide alone has poor self-activity and binds to NH 3 TPD (FIG. 2) and H 2 -D 2 The TPSR (figure 3) is characterized easily, the unsaturated coordination sites (oxygen vacancies) on the surface of the catalyst are low in content, and the weak capability of activating hydrogen is the main reason of low activity.
Example 3
The catalyst prepared in example 1 catalyzes the hydrodeoxygenation reaction of m-cresol
The reaction evaluation was conducted in the same manner as in comparative example 3. As shown in FIG. 4, the conversion of m-cresol on the catalyst of example 1 reached 20% and the selectivity of toluene reached 97% under the current reaction conditions. Compared with the activity of example 1, the activity is improved by about 4 times. Bound NH 3 TPD (FIG. 2) and H 2 -D 2 TPSR (FIG. 3) presumably combines MoS with the catalyst 2 The capability of activating hydrogen with high efficiency and rich oxygen vacancy, thereby realizing high-efficiency deoxidation.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a high-defect molybdenum oxysulfide bifunctional catalyst is characterized by comprising the following steps:
(1) Placing the molybdenum sulfide nanosheets into a muffle furnace for roasting to obtain a molybdenum oxysulfide composite material;
(2) And reducing the molybdenum oxysulfide composite material in a fixed bed to obtain the molybdenum oxysulfide bifunctional catalyst.
2. The preparation method of the high-defect molybdenum oxysulfide bifunctional catalyst according to claim 1, characterized in that, in step (1), the molybdenum sulfide nanosheet is prepared by the following steps:
(1.1) dissolving ammonium molybdate and thiourea in water, and crystallizing in a hydrothermal reaction kettle;
and (1.2) filtering, washing and drying the crystallized product to obtain the molybdenum sulfide nanosheet.
3. The method for preparing the high-defect molybdenum oxide bi-functional catalyst according to claim 2, wherein the mass ratio of ammonium molybdate to thiourea in the step (1.1) is 1.16:1.
4. the method for preparing the bifunctional catalyst of molybdenum oxysulfide according to claim 2, characterized in that the crystallization temperature in step (1.1) is 220 ℃ and the crystallization time is 18h.
5. The method for preparing the high-defect molybdenum oxysulfide bifunctional catalyst according to claim 1, characterized in that the calcination temperature in step (1) is 80-550 ℃, the calcination time is 0.5-10h, and the heating rate is 2-10 ℃/min.
6. The method for preparing the high-defect molybdenum oxysulfide bifunctional catalyst according to claim 1, wherein the reduction temperature in the step (2) is 300-500 ℃, the reduction time is 0.5-4h, and the heating rate is 2-10 ℃/min.
7. Use of the high defect molybdenum oxysulfide bifunctional catalyst obtained by the preparation method according to any one of claims 1 to 6, in hydrodeoxygenation of lignin-derived phenolic compounds.
8. The use according to claim 7, wherein the hydrodeoxygenation reaction is carried out in an atmospheric gas-solid phase reactor, the reaction temperature being 300-400 ℃ and the pressure of the reaction hydrogen being 1atm.
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| CN115463662A (en) * | 2022-10-08 | 2022-12-13 | 中国矿业大学 | Preparation of supported intermetallic compound catalyst and application of supported intermetallic compound catalyst in hydrodeoxygenation of lignin-derived phenolic compound |
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