CN115888719A - Magnesium oxide modified aluminum oxide loaded bimetallic nickel-cobalt catalyst and preparation method and application thereof - Google Patents
Magnesium oxide modified aluminum oxide loaded bimetallic nickel-cobalt catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- -1 Magnesium oxide modified aluminum oxide Chemical class 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000012075 bio-oil Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920005610 lignin Polymers 0.000 claims abstract description 27
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 20
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
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- 238000002156 mixing Methods 0.000 claims description 2
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- 230000000694 effects Effects 0.000 abstract description 10
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- 239000002184 metal Substances 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
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- 238000004627 transmission electron microscopy Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of catalyst synthesis, and particularly discloses a magnesium oxide modified aluminum oxide loaded bimetallic nickel-cobalt catalyst, and a preparation method and application thereof. The catalyst is prepared by adopting an impregnation method, and the method is simple and convenient to operate. The surface property of the alumina is changed by a magnesium oxide modification method, the selectivity of cyclohexanol and derivatives thereof in the product is improved, the interaction between active metal and a carrier is enhanced, and the dispersion of nickel and cobalt particles is promoted. In addition, a nickel-cobalt bimetallic is used as an active component of the catalystCompared with single metal nickel, the activity of the catalyst is obviously improved. Meanwhile, the catalyst still keeps high catalytic activity after 5 times of circulation, and has good stability. The catalyst has excellent catalytic effect on the hydrodeoxygenation reaction of lignin bio-oil, and the hydrogen content is 2MPa H at 300 DEG C 2 Under the condition, the yield of cyclohexanol and derivatives thereof in the product can reach 65.6wt%.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a magnesium oxide modified alumina supported bimetallic nickel-cobalt catalyst, and a preparation method and application thereof.
Background
In the current society, excessive exploitation and utilization of fossil energy cause a series of problems such as energy crisis, environmental pollution and greenhouse effect, so that a clean renewable energy capable of replacing fossil energy is urgently needed to be found. Lignin is a natural aromatic polymer with the most abundant reserves in nature, and can be converted into bio-oil with aromatic monomer compounds as main components by depolymerization, and the bio-oil has great potential in the aspect of preparing biofuel and platform compounds. However, the bio-oil obtained by depolymerizing lignin has a series of problems of high oxygen content, high viscosity, low heat value, instability and the like, so that further upgrading modification is needed to obtain high value-added chemicals or fuels. Common upgrading and modification processes are hydrodeoxygenation, catalytic cracking, emulsification, esterification, steam reforming, etc., of which hydrodeoxygenation has been considered one of the most promising bio-oil upgrading processes.
Currently, most research is focused on the hydrodeoxygenation conversion of lignin bio-oils to produce naphthenic fuels. However, cyclohexanol and derivatives thereof can be prepared by selective hydrodeoxygenation of lignin bio-oil by constructing a new catalyst. Cyclohexanol and derivatives thereof are both a typical class of oxygenated fuels and are useful as high value fuel additives; in addition, cyclohexanol can be used as a synthetic raw material for producing a pharmaceutical intermediate and a polymer such as nylon 66. Therefore, the development of a catalyst with high activity, high selectivity and low cost is of great significance for promoting the high-value conversion of the lignin bio-oil.
Commonly used hydrodeoxygenation catalysts mainly include noble metal (Ru, pd, pt, etc.) catalysts and transition metal (Ni, co, fe, cu, etc.) catalysts. Generally speaking, the noble metal catalyst has extremely high activity in the hydrodeoxygenation reaction process, can catalyze the hydrodeoxygenation reaction at relatively low temperature, and avoids carbon deposition and coking on the catalyst and inactivation of the catalyst caused by high temperature. However, noble metal catalysts are expensive and easily poisoned, and therefore, development of transition metal catalysts with high catalytic activity and low cost is a trend of catalysts. Wang et al (Energy environ. Sci.,2012,5, 8244-8260) studied hydrodeoxygenation of pine pyrolysis oil to cyclic alcohol compounds using Raney Ni as a catalyst and isopropanol as a solvent. Although Raney Ni shows high selectivity on cyclic alcohol compounds, methanol generated after hydrodeoxygenation of phenolic compounds in the bio-oil and carboxylic acid substances in the bio-oil can inhibit the catalytic activity of Raney Ni. Galebach et al (Green chem.,2020,22, 8462-8477) dissolve maple in supercritical methanol and convert lignocellulose to C2-C10 alcohols using CuMgAlOx catalyst at 300 deg.C and 20MPa with carbon yields of 70-80%. The average selectivity of C6-C10 cyclic alcohols from maple conversion in a semi-continuous flow reactor in the presence of a CuMgAlOx catalyst was 31%. Although the CuMgAlOx catalyst exhibits better hydrodeoxygenation activity for lignocellulose, the insoluble pyrolysis products produced under severe reaction conditions reduce the selectivity of cyclic alcohols. Song et al (Green chem.,2020,22, 1662-1670) prepared a layered Nb 2 O 5 The Ni-based catalyst loaded by the material shows better hydrodeoxygenation activity to lignin bio-oil in an aqueous phase, and the cyclohexanol and derivatives thereof in the product have higher selectivity. Although the catalyst can keep higher selectivity on cyclohexanol compounds, the dosage of the catalyst is 10 times of that of the lignin bio-oil, and the reaction time is longer and is as long as 10 hours, so that the economic benefit of the reaction is lower, and a further promotion space still exists.
In summary, the prior catalysts for preparing cyclohexanol compounds by hydrodeoxygenation of lignin bio-oil still have the following problems. First, the activity of the catalyst is susceptible to harsh reaction conditions and inhibition by certain components in the bio-oil or hydrodeoxygenation reaction products, resulting in reduced catalytic activity; in addition, the conditions of the catalytic hydrodeoxygenation reaction and the amount of catalyst used are important factors to consider. Although part of the catalysts can keep higher selectivity on the alcohol compounds generated after the biological oil is subjected to hydrodeoxygenation, excessive catalysts are required to be used or the reaction time is longer, the economic benefit of the catalytic hydrodeoxygenation reaction is lower, and the large-scale industrial production and application are not facilitated. Therefore, there is a need to develop a hydrodeoxygenation catalyst that has high activity, high selectivity, low cost, and a simple preparation method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to develop a preparation method of a magnesium oxide modified alumina supported nickel-cobalt bimetallic catalyst.
The invention further aims to provide application of the magnesium oxide modified alumina supported bimetallic nickel-cobalt catalyst in hydrodeoxygenation of lignin bio-oil.
The purpose of the invention is realized by the following scheme:
a preparation method of a magnesium oxide modified alumina supported bimetallic nickel-cobalt catalyst comprises the following steps:
(1) Mixing magnesium salt, aluminum oxide and water, stirring, evaporating to dryness, and calcining in air to obtain white aluminum oxide powder modified by magnesium oxide;
(2) Preparing a mixed solution from soluble nickel salt and cobalt salt, adding the white alumina powder modified by the magnesia obtained in the step (1) into the mixed solution, fully stirring, evaporating to dryness, then calcining in the air, and then calcining in a hydrogen-argon mixed gas to obtain the alumina-supported bimetallic nickel-cobalt catalyst modified by the magnesia.
The magnesium salt in the step (1) is at least one of magnesium chloride, magnesium nitrate and magnesium sulfate, preferably magnesium nitrate hexahydrate; the aluminaIs alpha-Al 2 O 3 、β-Al 2 O 3 And gamma-Al 2 O 3 Preferably gamma-Al 2 O 3 。
The mass ratio of the magnesium salt to the aluminum oxide in the step (1) is (0.10-1.50): (0.20-2.00), preferably, the mass ratio of the magnesium salt to the aluminum oxide is 0.51; the mass volume ratio of the magnesium salt to the water is (0.20-0.70) g:5 to 60ml, preferably (0.30 to 0.60) g:30ml.
The stirring time in the step (1) is 0.5 to 12 hours, preferably 2 hours; the evaporation temperature is 40-150 ℃, and preferably 80 ℃; the calcination in the air is carried out at the temperature of 300-600 ℃ for 1-6 h, preferably at the temperature of 450 ℃ for 4h.
The concentrations of the soluble nickel salt and the soluble cobalt salt in the mixed solution in the step (2) are respectively (0.001-0.350) g/ml and (0.001-0.350) g/ml, and preferably 0.015g/ml and 0.015g/ml; the mass ratio of the magnesia-modified alumina to the soluble nickel salt is (0.10-2.00): (0.10 to 0.60); preferably (0.50 to 1.20): (0.20 to 0.60), more preferably 0.90: (0.30-0.60).
The stirring time in the step (2) is 6-48 h, preferably 24h; the evaporation temperature is 40-150 ℃, and preferably 80 ℃; the calcination temperature in the air is 200-800 ℃ and the calcination time is 1-8 h, preferably, the calcination temperature is 400 ℃ and the calcination time is 4h; the calcination temperature in the hydrogen-argon mixed gas is 300-800 ℃ and the calcination time is 2-8 h, preferably, the calcination temperature in the hydrogen-argon mixed gas is 550 ℃ and the calcination time is 4h. More preferably, the temperature rise procedure of the calcination in the hydrogen-argon mixed gas is that the temperature rise rate is 5 ℃/min and the temperature rise rate is 300-800 ℃.
The flow rate of the hydrogen-argon mixture gas during the calcination in the hydrogen-argon mixture gas in the step (2) is 40-100 mL/min, preferably 80mL/min.
A magnesium oxide modified aluminum oxide loaded bimetallic nickel-cobalt catalyst is prepared by the method.
The magnesium oxide modified aluminum oxide loaded bimetallic nickel-cobalt catalyst is applied to the hydrodeoxygenation reaction of lignin bio-oil.
A method for converting lignin bio-oil into cyclohexanol and derivatives thereof comprises the following steps:
using isopropanol as solvent, using the above-mentioned magnesium oxide modified alumina supported bimetal nickel-cobalt material as catalyst, in the temperature range of 250-350 deg.C, 1-4 MPa H 2 Under the pressure, the lignin bio-oil is converted into cyclohexanol and derivatives thereof through reaction for 2-12 h.
The mass-volume ratio of the isopropanol to the lignin bio-oil to the catalyst is 20mL: (0.05-0.50) g: (0.06-2.50) g; preferably 20mL:0.10g:0.10g.
Preferably, the temperature is 300 ℃ and the reaction time is 5h.
The invention uses transition metal nickel and cobalt as active metal components of the catalyst, which is cheap and easy to obtain, and compared with a single metal nickel-based catalyst, the activity of the catalyst for catalytic hydrodeoxygenation is obviously improved. On the other hand, the surface of the alumina is modified by using the magnesium oxide, so that the crystal structure of the alumina is not damaged, the number of alkaline sites on the surface of the alumina is changed, and the yield of cyclohexanol and derivatives thereof is improved; meanwhile, the addition of the magnesium oxide also enhances the interaction between the active metal particles and the catalyst carrier, promotes the dispersion of the nickel and cobalt particles and improves the catalytic performance of the catalyst.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method of the catalyst has simple process and simple and convenient operation. The wet impregnation method is adopted for the preparation of the catalyst carrier and the catalyst, and the preparation method is very simple.
(2) The catalyst prepared by the invention uses bimetallic nickel-cobalt as the active component of the catalyst, and compared with a single-metal nickel-based catalyst, the catalytic activity and the selectivity of the product are obviously improved.
(3) The catalyst prepared by the invention adopts a strategy of magnesium oxide modification to regulate and control the number of alkaline sites of the catalyst, thereby realizing higher selectivity on cyclohexanol and derivatives thereof. Meanwhile, the addition of the magnesium oxide also increases the interaction between the nickel and cobalt particles and the carrier, promotes the dispersion of the metal nickel and cobalt particles, and improves the catalytic performance and stability of the catalyst.
(4) The catalyst prepared by the invention has excellent catalytic activity on the hydrodeoxygenation reaction of lignin bio-oil, and the activity is 2MPa H at 300 DEG C 2 The yield of the cyclohexanol and the derivatives thereof can reach 65.6wt%. The technology of the invention greatly promotes the hydrodeoxygenation, quality improvement and modification of the lignin bio-oil, thereby promoting the industrial application of the lignin bio-oil.
Drawings
FIG. 1: XRD spectrograms of the catalysts prepared in the embodiment 1, the comparative example 1 and the comparative example 2 of the invention;
FIG. 2: inventive example 1 preparation of catalyst Ni-Co/MgO-Al 2 O 3 Scanning electron microscopy images of (a);
FIG. 3: comparative example 1 of the present invention preparation of Ni/Al catalyst 2 O 3 (A), comparative example 2 preparation of catalyst Ni-Co/Al 2 O 3 Transmission electron micrograph (B) of (A), preparation of catalyst Ni-Co/MgO-Al of example 1 2 O 3 Transmission electron micrograph (C).
FIG. 4: inventive example 1 preparation of catalyst Ni-Co/MgO-Al 2 O 3 EDS-mapping spectrum of (1).
Detailed Description
The present invention will be described in further detail below with reference to examples, comparative examples, and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples and comparative examples were all available on the market in a conventional manner without specific reference.
Example 1
Ni-Co/MgO-Al 2 O 3 Preparation of the catalyst:
(1) Weighing 1.00g of gamma-Al at room temperature 2 O 3 And 0.51g of magnesium nitrate hexahydrate are placed in a beaker filled with 30ml of deionized water, stirred at room temperature for 2 hours, evaporated to dryness in an oil bath kettle at 80 ℃, and then placed in an oven at 50 ℃ for drying for 24 hours.
(2) Will be provided with(1) Grinding the solid obtained after drying to powder, and then placing the powder into a muffle furnace for calcination, wherein the calcination procedure is as follows: heating to 450 deg.C at a rate of 5 deg.C/min, maintaining for 4h, cooling to room temperature after calcination, and taking out the sample to obtain white solid MgO-Al 2 O 3 。
(3) 0.9g of MgO-Al obtained in (2) was weighed 2 O 3 The solid, 0.45g of nickel nitrate hexahydrate and 0.45g of cobalt nitrate hexahydrate are placed in a beaker filled with 30ml of deionized water, fully stirred at room temperature for 24 hours, then dried in an oil bath kettle at 80 ℃ by evaporation, and placed in an oven at 50 ℃ for drying for 24 hours.
(4) Grinding the dried solid in the step (3) into powder, and then placing the powder into a muffle furnace for calcination, wherein the calcination procedure is as follows: raising the temperature to 400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h, naturally cooling to room temperature after calcination, and taking out the sample to obtain a black solid.
(5) Putting the black solid obtained in the step (4) into a quartz tube, taking 8% hydrogen-argon mixed gas as atmosphere, raising the temperature to 550 ℃ at the rate of 5 ℃/min, keeping the temperature for 4h, naturally cooling to room temperature after calcination, taking out a sample to obtain Ni-Co/MgO-Al 2 O 3 A catalyst.
FIG. 2 shows Ni-Co/MgO-Al 2 O 3 Scanning electron microscopy of the catalyst. From the figure, it can be observed that the catalyst surface exhibits a random granular morphology. FIG. 3 (C) shows Ni-Co/MgO-Al 2 O 3 TEM image of the catalyst, the average size of the Ni and Co particles being 17.21nm, compared with Ni-Co/Al, calculated statistically on the particle size distribution 2 O 3 The nickel and cobalt particles (23.93 nm) in the catalyst are reduced in size. The reason is that the addition of magnesium oxide enhances the interaction between the active metal particles and the carrier, facilitating the dispersion of the metal particles. FIG. 4 shows Ni-Co/MgO-Al 2 O 3 EDS-Mapping diagram of catalyst. From the figure, it can be observed that three elements of nickel, cobalt and magnesium are highly dispersed in the catalyst.
Performance testing
0.10g of lignin bio-oil, 0.10g of Ni-Co/MgO-Al 2 O 3 Catalyst, 20ml of isopropanol and 10. Mu.L of n-hexadecaneAdding into a batch stainless steel reaction kettle, sealing, charging hydrogen, discharging, repeating for 3 times to remove air in the kettle, finally charging 2MPa hydrogen into the reaction kettle, and reacting at 300 deg.C for 5h. After the reaction, the reaction solution was rapidly cooled to room temperature by introducing cooling water, and the reaction solution was taken out and filtered through a 0.22 μm organic filter to obtain an organic phase containing the reaction product. And (3) taking 1 mu L of organic phase, carrying out qualitative analysis on the reaction product by adopting gas chromatography-mass spectrometry, and carrying out quantitative calculation on the reaction product by adopting gas chromatography.
Example 2
The reaction procedure and the measurement means were the same as in example 1 except that the reaction temperature was 260 ℃.
Embodiment 3
The reaction procedure and the measurement means were the same as in example 1 except that the reaction temperature was 280 ℃.
Example 4
The reaction procedure and the measurement means were the same as in example 1 except that the reaction temperature was 320 ℃.
Example 5
The reaction procedure and detection means were the same as in example 1 except that the reaction time was 3 hours.
Example 6
The reaction procedure and detection means were the same as in example 1, except that the reaction time was 4 hours.
Example 7
The reaction procedure and detection means were the same as in example 1, except that the reaction time was 6 hours.
Example 8
The reaction procedure and the measurement means were the same as in example 1 except that the amount of the catalyst used was 0.06g.
Example 9
The reaction procedure and the measuring means were the same as in example 1 except that the amount of the catalyst used was 0.08g.
Embodiment 10
The reaction procedure and the measuring means were the same as in example 1 except that the amount of the catalyst used was 0.12g.
Example 11
The reaction procedure and the measurement means were the same as in example 1 except that the amount of the catalyst used was 0.14g.
Comparative example 1
Ni/Al 2 O 3 The preparation of (1):
(1) Weighing 0.90g of gamma-Al at room temperature 2 O 3 0.45g of nickel nitrate hexahydrate is added into a beaker filled with 30ml of deionized water, stirred at room temperature for 24 hours, placed in an oil bath kettle at 80 ℃ to be dried by distillation, and then the obtained solid is placed in an oven at 50 ℃ to be dried for 24 hours.
(2) Grinding the dried solid in the step (1), and then placing the ground solid in a muffle furnace for calcination, wherein the calcination procedure is as follows: heating to 400 ℃ at the heating rate of 5 ℃/min, keeping for 4h, and naturally cooling to room temperature after calcination to obtain a gray solid.
(3) Putting the gray solid obtained in the step (2) into a quartz tube, taking 8% hydrogen-argon mixed gas as atmosphere, raising the temperature to 550 ℃ at the rate of 5 ℃/min, keeping the temperature for 4h, naturally cooling to room temperature after calcination, taking out a sample to obtain Ni/Al 2 O 3 A catalyst.
FIG. 3 (A) shows Ni/Al 2 O 3 Transmission electron microscopy of the catalyst. The average size of the active metallic nickel particles was 17.08nm, calculated statistically on the size of the nickel particles in the catalyst, and the particle size was relatively small.
Performance testing
0.10g of lignin bio-oil and 0.10g of Ni/Al 2 O 3 Adding a catalyst, 20ml of isopropanol and 10 mu L of n-hexadecane into a batch type stainless steel reaction kettle, sealing, filling hydrogen and discharging, repeating for 3 times to achieve the purpose of discharging air in the kettle, finally filling 2MPa of hydrogen into the reaction kettle, and reacting for 5 hours at 300 ℃. After the reaction, the reaction solution was rapidly cooled to room temperature by introducing cooling water, and the reaction solution was taken out and filtered through a 0.22 μm organic filter to obtain an organic phase containing the reaction product. And (3) taking 1 mu L of organic phase, carrying out qualitative analysis on the reaction product by adopting gas chromatography-mass spectrometry, and carrying out quantitative calculation on the reaction product by adopting gas chromatography.
Comparative example 2
Ni-Co/Al 2 O 3 The preparation of (1):
(1) Weighing 0.90g of gamma-Al at room temperature 2 O 3 0.45g of nickel nitrate hexahydrate and 0.45g of cobalt nitrate hexahydrate are added into a beaker filled with 30ml of deionized water, stirred at room temperature for 24 hours, placed in an oil bath kettle at 80 ℃ to be dried by distillation, and then the obtained solid is placed in an oven at 50 ℃ to be dried for 24 hours.
(2) Grinding the dried solid in the step (1), and then placing the ground solid in a muffle furnace for calcination, wherein the calcination procedure is as follows: heating to 400 ℃ at the heating rate of 5 ℃/min, keeping for 4h, and naturally cooling to room temperature after calcination to obtain black solid.
(3) Putting the black solid obtained in the step (2) into a quartz tube, taking 8% hydrogen-argon mixed gas as atmosphere, raising the temperature to 550 ℃ at the rate of 5 ℃/min, keeping the temperature for 4h, naturally cooling to room temperature after calcination, taking out a sample to obtain Ni-Co/Al 2 O 3 A catalyst.
FIG. 3 (B) shows Ni-Co/Al 2 O 3 Transmission electron microscopy of the catalyst. The average particle size of the nickel and cobalt particles in the catalyst is calculated to be 23.93nm compared with Ni/Al 2 O 3 The active metal particle size increases due to: firstly, the total loading of active metal is increased after the cobalt is added, and metal particles are more easily agglomerated; certain interaction exists between the nickel and the cobalt or the addition of the cobalt changes the interaction between the nickel and the cobalt particles and the carrier, thereby causing the change of the particle size.
Performance test
0.10g of lignin bio-oil, 0.10g of Ni-Co/Al 2 O 3 Adding a catalyst, 20ml of isopropanol and 10 mu L of n-hexadecane into a batch type stainless steel reaction kettle, sealing, filling hydrogen and discharging, repeating for 3 times to achieve the purpose of discharging air in the kettle, finally filling 2MPa of hydrogen into the reaction kettle, and reacting for 5 hours at 300 ℃. After the reaction, the reaction solution was rapidly cooled to room temperature by introducing cooling water, and the reaction solution was taken out and filtered through a 0.22 μm organic filter to obtain an organic phase containing the reaction product. Taking 1 mu L of organic phase, and adopting gas chromatography-And carrying out qualitative analysis on the reaction products by mass spectrometry, and carrying out quantitative calculation on the reaction products by adopting gas chromatography.
Description of the embodiments
The detection results of the comparative examples 1-2 and the embodiment examples 1-11 are shown in table one, and it can be seen from the results that the catalyst prepared by the invention has excellent catalytic activity for hydrodeoxygenation reaction of lignin bio-oil, and has the advantages of cheap and easily available preparation raw materials and simple and convenient preparation method operation, the lignin bio-oil is successfully converted into cyclohexanol and derivatives thereof, and the yield of cyclohexanol and derivatives thereof is at a high level. By comparing the yields of cyclohexanol and derivatives thereof, the catalyst is preferably Ni-Co/MgO-Al 2 O 3 The reaction temperature is preferably 300 ℃, the reaction time is preferably 5h, and the amount of the catalyst is preferably 0.10g. Takes lignin bio-oil as a substrate and a catalyst Ni-Co/MgO-Al 2 O 3 The preferred amount is 0.10g, and the yield of cyclohexanol and derivatives thereof reaches 65.6wt% after reaction for 5h at 300 ℃ under the preferred reaction conditions.
TABLE-Hydrodeoxygenation reaction data for Lignin Bio-oil
The prepared catalyst was structurally characterized using X-ray diffraction (XRD), and the results are shown in fig. 1. Comparative Ni-Co/Al 2 O 3 Catalyst and Ni-Co/MgO-Al 2 O 3 The catalyst can find that Al is added after MgO is added 2 O 3 The peak height and the peak width of the diffraction peak of (2) were not changed, indicating that the addition of MgO did not destroy Al 2 O 3 But rather, serves as a modification. Furthermore, ni/Al 2 O 3 And Ni-Co/Al 2 O 3 The medium nickel and the cobalt are both zero-valent, and when magnesium oxide is added, the diffraction of NiO and CoO appearsThe peak, which indicates that the addition of MgO makes it difficult to reduce a portion of the metal oxide particles to the zero valence state, because the addition of MgO enhances the interaction between the metal particles and the support. The morphology of the prepared catalyst was characterized by scanning electron microscopy and the results are shown in fig. 2. As can be seen from the figure, ni-Co/MgO-Al 2 O 3 The surface of the catalyst is in a random granular shape. By Ni/Al 2 O 3 、Ni-Co/Al 2 O 3 、Ni-Co/MgO-Al 2 O 3 The transmission electron microscope images (figure 3) of the three catalysts can be compared to find that the addition of cobalt increases the average size of nickel and cobalt particles, on one hand, the particles are easier to agglomerate due to the increase of the total loading of active metal caused by the addition of cobalt; on the other hand, it may be caused by the fact that some interaction between nickel and cobalt exists or the interaction between the active metal particles and the carrier is changed by the addition of cobalt. After further adding magnesium oxide, the average particle size of the active metal nickel and cobalt is reduced, which shows that the addition of magnesium oxide is favorable for enhancing the interaction between the metal particles and the carrier and promoting the dispersion of the metal particles. Ni-Co/MgO-Al can be observed by EDS-Mapping (FIG. 4) 2 O 3 Mg element, ni element and Co element in the catalyst are highly dispersed.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a magnesium oxide modified alumina supported bimetallic nickel-cobalt catalyst is characterized by comprising the following steps:
a preparation method of a magnesium oxide modified alumina supported bimetallic nickel-cobalt catalyst comprises the following steps:
(1) Mixing magnesium salt, aluminum oxide and water, stirring, evaporating to dryness, and calcining in air to obtain white aluminum oxide powder modified by magnesium oxide;
(2) Preparing a mixed solution from soluble nickel salt and cobalt salt, adding the white alumina powder modified by the magnesia obtained in the step (1) into the mixed solution, fully stirring, evaporating to dryness, then calcining in the air, and then calcining in a hydrogen-argon mixed gas to obtain the alumina-supported bimetallic nickel-cobalt catalyst modified by the magnesia.
2. The method of claim 1, wherein: the soluble magnesium salt in the step (1) is at least one of magnesium chloride, magnesium nitrate and magnesium sulfate; the alumina is alpha-Al 2 O 3 、β-Al 2 O 3 And gamma-Al 2 O 3 At least one of (1).
3. The method of claim 1, wherein: the mass ratio of the magnesium salt to the aluminum oxide in the step (1) is (0.10-1.50): (0.20 to 2.00); the mass volume ratio of the magnesium salt to the water is 0.20-0.70 g:5 to 60ml.
4. The method of claim 1, wherein: the stirring time of the step (1) is 0.5 to 12 hours, and the evaporation temperature is 40 to 150 ℃; the calcining temperature in the air is 300-600 ℃, and the calcining time is 1-6 h.
5. The method of claim 1, wherein: the concentrations of the soluble nickel salt and the soluble cobalt salt in the mixed solution in the step (2) are respectively (0.001-0.350) g/ml and (0.001-0.350) g/ml; the mass ratio of the magnesium oxide modified aluminum oxide to the soluble nickel salt is (0.10-2.00): (0.10-0.60).
6. The method of claim 1, wherein: the stirring time in the step (2) is 6-48 h; the evaporation temperature is 40-150 ℃; the calcination temperature in the air is 200-800 ℃, and the calcination time is 1-8 h; the calcination temperature in the hydrogen-argon mixed gas is 300-800 ℃, and the calcination time is 2-8 h; the temperature rise procedure of the calcination in the hydrogen-argon mixed gas is that the temperature rise rate is 5 ℃/min and the temperature rises to 300-800 ℃.
7. The method of claim 1, wherein: the flow rate of the hydrogen-argon mixed gas in the step (2) during the calcination in the hydrogen-argon mixed gas is 40-100 mL/min.
8. A magnesia-modified alumina-supported bimetallic nickel-cobalt catalyst prepared by the process of any one of claims 1 to 7.
9. Use of the magnesia-modified alumina-supported bimetallic nickel-cobalt catalyst of claim 8 in a lignin bio-oil hydrodeoxygenation reaction.
10. A method for converting lignin bio-oil into cyclohexanol and derivatives thereof is characterized by comprising the following steps:
using isopropanol as solvent, using alumina-supported bimetallic nickel-cobalt modified by magnesium oxide as claimed in claim 8 as catalyst, at 250-350 deg.C, 1-4 MPa H 2 Under the pressure, the lignin bio-oil is converted into cyclohexanol and derivatives thereof through reaction for 2-12 h.
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