CN110813296B - Preparation method of nano-porous Ni-Fe alloy catalyst - Google Patents

Preparation method of nano-porous Ni-Fe alloy catalyst Download PDF

Info

Publication number
CN110813296B
CN110813296B CN201910948877.6A CN201910948877A CN110813296B CN 110813296 B CN110813296 B CN 110813296B CN 201910948877 A CN201910948877 A CN 201910948877A CN 110813296 B CN110813296 B CN 110813296B
Authority
CN
China
Prior art keywords
alloy catalyst
preparing
catalyst according
temperature
nanoporous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910948877.6A
Other languages
Chinese (zh)
Other versions
CN110813296A (en
Inventor
胡勋
亓敬波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN201910948877.6A priority Critical patent/CN110813296B/en
Publication of CN110813296A publication Critical patent/CN110813296A/en
Application granted granted Critical
Publication of CN110813296B publication Critical patent/CN110813296B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a preparation method of a nano-porous Ni-Fe alloy catalyst, which deoxidizes a zinc oxide template through high-temperature hydrogen reduction. Firstly, preparing a composite metal oxide precursor containing Zn, Ni and Fe elements by a hydrothermal synthesis method, then filtering, washing and drying the obtained precursor, and finally, reducing the obtained composite metal oxide by hydrogen at a high temperature to remove zinc oxide and obtain the nano porous metal catalyst. The nano-porous Ni-Fe alloy catalyst prepared by the method has the beneficial effects of rich pores, large specific surface area and good catalytic activity, has the advantages of mild reaction conditions, high raw material conversion rate and high benzene selectivity in the product when being used for the hydrodeoxygenation reaction of lignin-based phenols, does not need to use strong acid or strong base to remove a template, and is environment-friendly in preparation process.

Description

Preparation method of nano-porous Ni-Fe alloy catalyst
Technical Field
The invention relates to the technical field of preparation of nano catalysts, and mainly relates to a preparation method of a nano porous Ni-Fe alloy catalyst.
Background
Lignin has gained increasing attention as a cheap and abundant biomass resource for its development and utilization. The utilization of lignin as a raw material for the production of liquid fuels or chemicals is an effective way for the high-value utilization thereof. Catalytic hydrodeoxygenation of lignin-based bio-oils to varying degrees can yield various chemicals or fully hydrodeoxygenated hydrocarbon fuels. Because the lignin structure is rich in benzene rings, the benzene ring structure is remained in the hydrodeoxygenation process to obtain the benzene platform compound, and the benzene platform compound has higher economic benefit.
The key to the preparation of benzene chemicals from lignin-based phenolic compounds is the study of suitable catalysts. The metal Ni is a high-efficiency phenol hydrodeoxygenation catalyst and is widely applied, but the Ni catalyst is high in activity and easy to perform saturated hydrogenation on benzene rings. The metal Fe catalyst can realize high selectivity of benzene compounds, but the catalytic activity of the metal Fe catalyst is low. The prepared Ni-Fe bimetallic alloy catalyst can make up the defects of the Ni-Fe bimetallic alloy catalyst and the Fe bimetallic alloy catalyst, and realizes the quantitative and efficient conversion of lignin-based phenols to benzene compounds through the synergistic effect. The Ni-Fe bimetallic catalyst for hydrodeoxygenation of lignin-based phenols researched at present is mostly a supported catalyst, and the upper limit of the activity of the supported catalyst is limited by the supported amount. Almost no report is made on the synthesis method of the bulk Ni-Fe alloy catalyst, particularly the bulk Ni-Fe alloy with a nano-porous structure.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of a nano porous Ni-Fe alloy catalyst, the method has the advantages of simple and environment-friendly process, low cost, uniform size distribution of the obtained catalyst, large specific surface area and high activity, and the catalyst is used for hydrogenation and deoxidation of lignin-based phenols.
In order to achieve the above object, the present invention is realized by:
the method comprises the following steps:
(1) sequentially adding a precursor of metal zinc, a precursor of metal nickel, a precursor of metal iron and alkali into deionized water to prepare a solution with a certain concentration, and magnetically stirring until the solution is fully dissolved;
(2) transferring the solution obtained in the step (1) into a hydrothermal kettle for hydrothermal reaction, and filtering, washing and drying the product after the reaction is finished;
(3) and (3) placing the dried sample in the step (2) into a tubular furnace, and introducing hydrogen to reduce at high temperature.
As a preferred embodiment, in the step (1), the precursor of the metallic zinc is one of zinc nitrate hexahydrate, zinc acetate dihydrate, zinc sulfate heptahydrate and anhydrous zinc chloride.
As a preferred embodiment, in the step (1), the precursor of the metallic nickel is one of nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel sulfate hexahydrate and nickel dichloride hexahydrate.
In a preferred embodiment, in the step (1), the precursor of metallic iron is one of ferric nitrate nonahydrate, ferric sulfate hydrate and ferric trichloride hexahydrate.
As a preferred embodiment, the step (A), (B), (C) and C)1) Zn in the obtained solution2+The concentration of (A) is 0.1-0.5 mol/L, preferably 0.2; ni2+The concentration of (A) is 0.1-0.5 mol/L, preferably 0.2; the concentration of the alkali is 0.1-1 mol/L, preferably 0.8; ni2+With Fe3+The molar ratio of (0.5-10): 1, preferably 5: 1.
as a preferred embodiment, in the step (1), the base is one of urea, ammonia water, sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.
As a preferred embodiment, in the step (2), the hydrothermal reaction conditions are: the temperature is 100-180 ℃, preferably 120 ℃; the time is 2-24 h, preferably 18 h.
As a preferred embodiment, in step (3), the reduction conditions are: the temperature is 400-800 ℃, preferably 700 ℃; the time is 1-6 h, preferably 2 h.
As a preferred embodiment, the catalyst is used for hydrodeoxygenation of lignin-based phenols.
In a preferred embodiment, the lignin is dissolved in 40mL of dodecane to prepare a reaction solution, and the reaction solution is prepared by: weighing the catalyst according to the mass ratio of the catalyst being 5:1, putting the reaction solution and the catalyst into a reaction kettle, sealing, introducing hydrogen for replacement for 5 times, then introducing 2MPa hydrogen at room temperature, stirring at the speed of 700r/min, heating while stirring to the reaction temperature of 220 ℃, and reacting for 2 hours.
The invention also discloses application of the catalyst in catalytic hydrogenation and deoxidation reaction of guaiacol, which is characterized in that guaiacol is dissolved in 40mL of dodecane to prepare reaction liquid, and reactants in mass ratio: weighing the catalyst in a ratio of 5: 1; putting the reaction solution and a catalyst into a reaction kettle, sealing, introducing hydrogen for replacing for 5 times, then introducing 2MPa hydrogen at room temperature, stirring at the speed of 700r/min, heating while stirring to the reaction temperature of 220 ℃, and reacting for 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph.
The invention has the beneficial effects that:
(1) the method has the advantages of simple process, cheap and easily-obtained raw materials, low cost, short production period, high yield and repeatability, and is suitable for large-scale industrial production.
(2) Compared with the prior art, the method can realize the complete removal of the template and avoid the corrosion and pollution of strong alkali.
(3) The obtained nano porous bimetallic catalyst has the advantages of uniform size, large specific surface area, high activity for the hydrodeoxygenation reaction of lignin-based phenols and high selectivity of the benzene in the product.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
A preparation method of a nano-porous Ni-Fe alloy catalyst comprises the following steps:
(1) adding 10mmol of Zn (NO)3)2·6H2O、10mmol Ni(NO3)2·6H2O、2mmol Fe(NO3)3·9H2O and 40mmol CO (NH)2)2Sequentially adding into a beaker filled with 50mL of deionized water, and magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.2mol/L, Ni2+Has a concentration of 0.2mol/L, urea, i.e., an alkali, of 0.8mol/L, Ni2+With Fe3+In a molar ratio of 5: 1.
(2) transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 120 ℃, keeping the temperature for 18 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying the sample in the constant-temperature drying oven at 80 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing hydrogen with the flow rate of 100mL/min, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, cooling, collecting the sample, and sealing and storing.
Example 2
A preparation method of a nano-porous Ni-Fe alloy catalyst comprises the following steps:
(1) 15mmol of Zn (CH)3COO)2·2H2O、5mmol NiSO4·6H2O、5mmol FeCl3·6H2O and 5mmol NH3·H2Sequentially adding O into a beaker filled with 50mL of deionized water, and magnetically stirring for 30min to fully dissolve O to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.3mol/L, Ni2+Has a concentration of 0.1mol/L, an alkali, i.e., aqueous ammonia concentration of 0.1mol/L, Ni2+With Fe3+Is 1: 1.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 100 ℃, keeping the temperature for 24 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying the sample in the constant-temperature drying oven at 80 ℃.
(3) Putting the dried sample in a tubular furnace, introducing hydrogen with the flow rate of 100mL/min, and raising the temperature to 400 ℃ at the speed of 5 ℃/min; and preserving the temperature for 6h, and collecting and sealing and storing the sample after cooling.
Example 3
A preparation method of a nano-porous Ni-Fe alloy catalyst comprises the following steps:
(1) adding 5mmol of ZnSO4·7H2O、25mmol Ni(CH3COO)2·4H2O、25mmol H2O·Fe2(SO4)3And 50mmol Na2CO3Sequentially adding into a beaker filled with 50mL of deionized water, and magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.1mol/L, Ni2+Has a concentration of 0.5mol/L, a concentration of 1mol/L of alkali, i.e. sodium carbonate, Ni2+With Fe3+Is 0.5: 1.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 180 ℃ and keeping for 2 hours, then naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in the constant-temperature drying oven at 80 ℃.
(3) Putting the dried sample in a tubular furnace, introducing hydrogen with the flow rate of 100mL/min, and raising the temperature to 800 ℃ at the speed of 5 ℃/min; and preserving the temperature for 1h, and collecting and sealing and storing the sample after cooling.
Example 4
A preparation method of a nano-porous Ni-Fe alloy catalyst comprises the following steps:
(1) 25mmol of ZnCl2、15mmol NiCl2·6H2O、1.5mmol Fe(NO3)3·9H2O and 10mmol K2CO3Sequentially adding into a beaker filled with 50mL of deionized water, and magnetically stirring for 30min to fully dissolve the deionized water to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.5mol/L, Ni2+Has a concentration of 0.3mol/L, a concentration of a base, i.e., potassium carbonate, of 0.5mol/L, Ni2+With Fe3+Is 10: 1.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 150 ℃, keeping for 10 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in a constant-temperature drying oven at 80 ℃.
(3) Putting the dried sample in a tubular furnace, introducing hydrogen with the flow rate of 100mL/min, and raising the temperature to 500 ℃ at the speed of 5 ℃/min; and preserving the temperature for 4h, and collecting and sealing and storing the sample after cooling.
Example 5
A preparation method of a nano-porous Ni-Fe alloy catalyst comprises the following steps:
(1) 20mmol of Zn (NO)3)2·6H2O、20mmol NiSO4·6H2O、5mmol Fe(NO3)3·9H2Sequentially adding O and 10mmol NaOH into a beaker filled with 50mL of deionized water, and magnetically stirring for 30min to fully dissolve the O and the 10mmol NaOH to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.4mol/L, Ni2+Has a concentration of 0.4mol/L, a concentration of 0.2mol/L of an alkali, i.e., sodium hydroxide, Ni2+With Fe3+Is 4: 1.
(2) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 160 ℃ and keeping for 8 hours, then naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in a constant-temperature drying oven at 80 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing hydrogen with the flow rate of 100mL/min, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 3h, cooling, collecting the sample, and sealing and storing.
Example 6
A preparation method of a nano-porous Ni-Fe alloy catalyst comprises the following steps:
(4) adding 5mmol of Zn (CH)3COO)2·2H2O、20mmol Ni(NO3)2·6H2O、2.5mmol FeCl3·6H2Sequentially adding O and 10mmol KOH into a beaker filled with 50mL deionized water, and magnetically stirring for 30min to fully dissolve the O and the 10mmol KOH to obtain a clear solution, wherein Zn is contained in the clear solution2+Has a concentration of 0.1mol/L, Ni2+Has a concentration of 0.4mol/L, a concentration of 0.3mol/L of an alkali, i.e., potassium hydroxide, Ni2+With Fe3+Is 8: 1.
(5) Transferring the solution to a hydrothermal reaction kettle with the capacity of 100mL, putting the reaction kettle into a constant-temperature drying oven, heating to 110 ℃, keeping for 20 hours, naturally cooling to room temperature, carrying out vacuum filtration on a sample, repeatedly washing the sample with deionized water to be neutral, and finally drying in a constant-temperature drying oven at 80 ℃.
(6) And (3) placing the dried sample in a tubular furnace, introducing hydrogen with the flow rate of 100mL/min, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 1h, cooling, collecting the sample, and sealing and storing.
The sample is observed by using SEM and the particle size is counted, the specific surface area and the pore size distribution of the sample are measured by using a BET specific surface area analyzer, and the average particle size, the total pore volume, the specific surface area and the average pore size of the nano-porous nickel-iron bimetal prepared in each example are shown in Table 1.
TABLE 1 average particle diameter, total pore volume, specific surface area and average pore diameter of the samples of the examples of the present invention
Figure BDA0002224894570000061
Application example 1
0.12g of the catalyst synthesized in example 1, 0.6g of guaiacol and 40mL of n-dodecane are put into a reaction kettle, hydrogen is introduced for 5 times after the reaction kettle is closed, then 2MPa of hydrogen is introduced at room temperature, the stirring rate is 700r/min, the reaction kettle is heated to the reaction temperature of 220 ℃ while stirring, and the reaction time is 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph. The conversion of guaiacol and the selectivity to the desired benzene are shown in Table 2.
Application example 2
0.12g of the catalyst synthesized in example 2, 0.6g of guaiacol and 40mL of n-dodecane are put into a reaction kettle, hydrogen is introduced for 5 times after the reaction kettle is closed, then 2MPa of hydrogen is introduced at room temperature, the stirring rate is 700r/min, the reaction kettle is heated to the reaction temperature of 220 ℃ while stirring, and the reaction time is 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph. The conversion of guaiacol and the selectivity to the desired benzene are shown in Table 2.
Application example 3
0.12g of the catalyst synthesized in example 3, 0.6g of guaiacol and 40mL of n-dodecane are put into a reaction kettle, hydrogen is introduced for 5 times after the reaction kettle is closed, then 2MPa of hydrogen is introduced at room temperature, the stirring rate is 700r/min, the reaction kettle is heated to the reaction temperature of 220 ℃ while stirring, and the reaction time is 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph. The conversion of guaiacol and the selectivity to the desired benzene are shown in Table 2.
Application example 4
0.12g of the catalyst synthesized in example 4, 0.6g of guaiacol and 40mL of n-dodecane were put into a reaction kettle, and after closing, hydrogen was introduced for 5 times, and then 2MPa of hydrogen was introduced at room temperature with a stirring rate of 700r/min, and while stirring, the temperature was raised to 220 ℃ and the reaction time was 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph. The conversion of guaiacol and the selectivity to the desired benzene are shown in Table 2.
Application example 5
0.12g of the catalyst synthesized in example 5, 0.6g of guaiacol and 40mL of n-dodecane are put into a reaction kettle, hydrogen is introduced for 5 times after the reaction kettle is closed, then 2MPa of hydrogen is introduced at room temperature, the stirring rate is 700r/min, the reaction kettle is heated to the reaction temperature of 220 ℃ while stirring, and the reaction time is 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph. The conversion of guaiacol and the selectivity to the desired benzene are shown in Table 2.
Application example 6
0.12g of the catalyst synthesized in example 6, 0.6g of guaiacol and 40mL of n-dodecane were put into a reaction kettle, and after closing, hydrogen was introduced for 5 times, and then 2MPa of hydrogen was introduced at room temperature with a stirring rate of 700r/min, and while stirring, the temperature was raised to 220 ℃ and the reaction time was 2 hours. The product is qualitatively and quantitatively analyzed by gas chromatograph-mass spectrometer and gas chromatograph. The conversion of guaiacol and the selectivity to the desired benzene are shown in Table 2.
TABLE 2 results of the catalytic hydrodeoxygenation reaction of guaiacol in application examples 1-6
Application example Percent conversion of guaiacol Benzene selectivity/%
1 95 73
2 57 53
3 65 37
4 36 48
5 61 42
6 81 55
As can be seen from table 2, when the products obtained in examples 1 to 6 of the present invention are applied to the hydrodeoxygenation reaction of guaiacol, the conversion rate of guaiacol can reach 95%, and the conversion rate of the product obtained in example 1 is the highest.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (13)

1. A preparation method of a nano-porous Ni-Fe alloy catalyst is characterized by comprising the following steps:
(1) sequentially adding a precursor of metal zinc, a precursor of metal nickel, a precursor of metal iron and alkali into deionized water to prepare a solution with a certain concentration, and magnetically stirring until the solution is fully dissolved;
(2) transferring the solution obtained in the step (1) into a hydrothermal kettle for hydrothermal reaction, and filtering, washing and drying the product after the reaction is finished;
(3) and (3) placing the dried sample in the step (2) into a tubular furnace, and introducing hydrogen to reduce at high temperature.
2. The method for preparing a nanoporous Ni-Fe alloy catalyst according to claim 1, wherein in step (1), the precursor of metallic zinc is one of zinc nitrate hexahydrate, zinc acetate dihydrate, zinc sulfate heptahydrate, and anhydrous zinc chloride.
3. The method for preparing a nanoporous Ni-Fe alloy catalyst according to claim 1, wherein in step (1), the precursor of metallic nickel is one of nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel sulfate hexahydrate, and nickel dichloride hexahydrate.
4. The preparation method of the nanoporous Ni-Fe alloy catalyst according to claim 1, wherein in the step (1), the precursor of metallic iron is one of ferric nitrate nonahydrate, ferric sulfate hydrate and ferric trichloride hexahydrate.
5. The method for preparing a nanoporous Ni-Fe alloy catalyst according to claim 1, wherein the Zn in the solution obtained in step (1)2+The concentration of (A) is 0.1-0.5 mol/L; ni2+The concentration of (A) is 0.1-0.5 mol/L; ni2+With Fe3+The molar ratio of (0.5-10): 1.
6. the method for preparing a nanoporous Ni-Fe alloy catalyst according to claim 1, wherein the Zn in the solution obtained in step (1)2+The concentration of (b) is 0.2 mol/L; ni2+The concentration of (b) is 0.2 mol/L; ni2+With Fe3+In a molar ratio of 5: 1.
7. the method for preparing a nanoporous Ni-Fe alloy catalyst according to any one of claims 2-5, wherein in step (1), the base is one of urea, ammonia, sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide.
8. The method for preparing a nano-porous Ni-Fe alloy catalyst according to claim 7, wherein in the step (2), the hydrothermal reaction conditions are as follows: the temperature is 100-180 ℃; the time is 2-24 h.
9. The method for preparing a nano-porous Ni-Fe alloy catalyst according to claim 7, wherein in the step (2), the hydrothermal reaction conditions are as follows: the temperature is 120 ℃; the time is 18 h.
10. The method for preparing a nanoporous Ni-Fe alloy catalyst according to claim 8, wherein in step (3), the reduction conditions are: the temperature is 400-800 ℃; the time is 1-6 h.
11. The method for preparing a nanoporous Ni-Fe alloy catalyst according to claim 8, wherein in step (3), the reduction conditions are: the temperature is 700 ℃; the time is 2 h.
12. The method of claim 1, wherein the catalyst is used for hydrodeoxygenation of lignin-based phenols.
13. The method for preparing the nanoporous Ni-Fe alloy catalyst according to claim 12, wherein the lignin is dissolved in 40mL of dodecane to prepare the reaction solution, and the reaction solution is prepared by: weighing the catalyst according to the mass ratio of the catalyst being 5:1, putting the reaction solution and the catalyst into a reaction kettle, sealing, introducing hydrogen for replacement for 5 times, then introducing 2MPa hydrogen at room temperature, stirring at the speed of 700r/min, heating while stirring to the reaction temperature of 220 ℃, and reacting for 2 hours.
CN201910948877.6A 2019-10-08 2019-10-08 Preparation method of nano-porous Ni-Fe alloy catalyst Active CN110813296B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910948877.6A CN110813296B (en) 2019-10-08 2019-10-08 Preparation method of nano-porous Ni-Fe alloy catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910948877.6A CN110813296B (en) 2019-10-08 2019-10-08 Preparation method of nano-porous Ni-Fe alloy catalyst

Publications (2)

Publication Number Publication Date
CN110813296A CN110813296A (en) 2020-02-21
CN110813296B true CN110813296B (en) 2021-10-08

Family

ID=69548688

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910948877.6A Active CN110813296B (en) 2019-10-08 2019-10-08 Preparation method of nano-porous Ni-Fe alloy catalyst

Country Status (1)

Country Link
CN (1) CN110813296B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111420658B (en) * 2020-04-22 2023-07-04 上海大学 Ir/Ru alloy oxygen precipitation catalyst and preparation method and application thereof
CN112371129B (en) * 2020-12-01 2022-09-13 宁夏大学 Preparation method of spherical MOFs-derived carbon-coated nickel catalyst for catalytic conversion of guaiacol
CN113247900A (en) * 2021-05-20 2021-08-13 济南大学 Method for preparing NiFe-P-C material
CN115709088A (en) * 2022-06-21 2023-02-24 南京红太阳生物化学有限责任公司 Preparation method of piperidine deoxidation catalyst
CN115106088B (en) * 2022-07-18 2023-10-20 广东工业大学 Preparation method and application of NiFe magnetic nano catalyst material
CN117123281B (en) * 2023-08-03 2024-03-26 宁夏大学 Long-acting catalyst of carbon-coated Fe-Ni alloy, and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0820831A (en) * 1994-07-07 1996-01-23 Sumitomo Electric Ind Ltd Production of metallic porous body
CN101891182B (en) * 2010-07-07 2012-01-11 天津大学 Method for preparing carbon nano-onions with core-shell structure by using gamma-Fe-Ni alloy as catalyst
CN104368345A (en) * 2014-11-20 2015-02-25 北京化工大学 Preparation method and catalytic application of supported type high-dispersion nickel-based alloy catalyst
CN110052270A (en) * 2019-04-30 2019-07-26 天津大学 A kind of mesoporous carbon spheres nickel-loaded iron alloy nanoparticles catalyst and the preparation method and application thereof

Also Published As

Publication number Publication date
CN110813296A (en) 2020-02-21

Similar Documents

Publication Publication Date Title
CN110813296B (en) Preparation method of nano-porous Ni-Fe alloy catalyst
WO2019109831A1 (en) Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen
WO2019109830A1 (en) Method of preparing molybdate complex hollow microspheres and application thereof
CN110773218A (en) Nitrogen-doped biochar-loaded metal nickel catalyst and application thereof
CN102275962B (en) Preparation method and application of nano-alumina
CN112827495B (en) Preparation method of heat storage/catalysis integrated material
CN110743555B (en) Preparation method of nano porous metal nickel catalyst
CN110534755A (en) A kind of preparation method and application of zinc-base metal-organic framework material and its nitrogen co-doped carbon-based oxygen reduction electro-catalyst of iron
CN107233890A (en) A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application
CN104209514A (en) Method for preparing Ni@C or Co@C core-shell nanoparticles
CN109921040A (en) The carbon-based elctro-catalyst of a kind of Ni, Fe doping and its preparation and application
CN110586117A (en) Co3O4/CuMoO4Composite and preparation method and application thereof
CN105728018A (en) ZSM-5 zeolite catalyst for alkylating benzene and methanol, preparation method and application thereof
CN111250092B (en) Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst
CN113816432B (en) Nanosheet self-assembled spherical ferrous molybdate material and preparation method and application thereof
CN111137927A (en) Preparation method of nickel copper cobaltate nanoparticles and application of nickel copper cobaltate nanoparticles in catalyzing ammonia borane hydrolysis to produce hydrogen
CN105385965B (en) Method for preparing CoB amorphous alloy based on ZIF-67 framework material
CN102744085A (en) Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation
CN101612596B (en) Method for deoxidizing solid catalyst precursor
CN110180543A (en) A kind of solid-carrying type Cu2The preparation method and applications of O/Cu@ACSs photochemical catalyst
CN103846108A (en) Preparation method of catalyst carrier for preparing substitute natural gas from coal-based syngas
CN102500386A (en) Preparation method for cerium nickel composite oxide catalytic material
CN105056953A (en) Preparation method of magnetic spinel supported NiB catalyst
CN103055882A (en) Preparation method for multi-metal monolithic tar cracking catalyst
CN105498780A (en) Cu/ZnO catalyst, preparation method thereof and application thereof to CO2 chemical conversion

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant