CN111644177A - Iron-nickel bimetallic catalyst, preparation method and application - Google Patents
Iron-nickel bimetallic catalyst, preparation method and application Download PDFInfo
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- CN111644177A CN111644177A CN202010437185.8A CN202010437185A CN111644177A CN 111644177 A CN111644177 A CN 111644177A CN 202010437185 A CN202010437185 A CN 202010437185A CN 111644177 A CN111644177 A CN 111644177A
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- iron
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- bimetallic catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 33
- 229910052786 argon Inorganic materials 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 16
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 239000012692 Fe precursor Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 9
- 229940117916 cinnamic aldehyde Drugs 0.000 description 9
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an iron-nickel bimetallic catalyst, a preparation method and application, wherein single-substance iron is subjected to acid treatment to remove surface oxides and pollutants, and then the cleaned single-substance iron precursor is added into an aqueous solution of nickel salt for ion exchange; and cleaning and drying the iron-nickel sample subjected to ion exchange, putting the iron-nickel sample into a tubular furnace, carrying out heat treatment after the temperature is raised to a certain temperature through a program in a hydrogen-argon atmosphere, and naturally cooling to room temperature to obtain the iron-nickel bimetallic catalyst. Compared with the prior art, the preparation method is simple and efficient, the reaction conditions are mild, the preparation method is easy to implement, the requirements on instruments and equipment are not strict, the cost of raw materials and equipment is low, and the large scale is easy to realize. The obtained iron-nickel bimetallic catalyst shows excellent catalytic activity and higher selectivity in catalyzing the selective reduction of unsaturated aldehyde.
Description
Technical Field
The invention belongs to the technical field of preparation of transition metal catalysts and selective catalytic hydrogenation thereof, and particularly relates to an iron-nickel bimetallic catalyst, a preparation method and application thereof.
Background
The conversion of some low value-added compounds into high value-added compounds by selective catalytic hydrogenation has become an important approach in the modern chemical industry. However, there still exist some problems in the selective catalytic hydrogenation process, such as complex catalyst preparation process, poor application stability, easy loss and agglomeration of active components, and harsh conditions. Catalytic activity is more difficult to control, particularly for non-noble metal catalysts, however non-noble metals make them attractive as catalysts due to their economy, ready availability and abundance. Many non-noble metals have been utilized as hydrogenation catalysts for organic materials. The composition, structure and performance of a single metal catalyst are difficult to regulate and control.
Compared with a single metal structure, the bimetal structure has a special electronic structure and surface properties; the method not only keeps the physicochemical properties of the original single metal component, but also can regulate and control the characteristics of light, electricity, magnetism, catalysis and the like, and has high value for the expansion of the application field.
Because the iron-nickel bimetallic catalyst has a special electronic structure and unique surface properties, the iron-nickel bimetallic catalyst shows good application prospect in the field of catalysis, and common iron-nickel bimetallic catalysts have the following characteristics: nickel-iron alloy catalysts, nickel-iron oxide catalysts, nickel-iron hydroxide catalysts, and the like.
The synthesis method of the iron-nickel bimetallic catalyst mainly comprises a solid phase method, a gas phase method and a liquid phase method. Wherein the melting method, the mechanical alloying method and the thermal decomposition method all belong to solid phase methods; the method has the characteristics of high yield, easy realization of industrialization and the like, but needs long-time high-temperature heating or annealing and is difficult to control the surface structure. The vapor phase method mainly includes a thermal evaporation method, a sputtering method, a chemical vapor deposition method, a microwave plasma method and the like; the gas phase method generally has higher requirements on instruments and equipment, the process technology is more complex, the yield is very low, and the large-scale industrial production is difficult to realize. The liquid phase synthesis method mainly comprises the following steps: liquid phase reduction, precipitation, hydrothermal, sol-gel, ion exchange, and the like; the liquid phase method has the advantages of convenient operation, simple synthesis process, low cost, uniform particle size and controllable strength, and relatively more extensive application; however, the liquid phase synthesis method has the problems of uneven composition, easy agglomeration of particles and the like.
Disclosure of Invention
The invention aims to provide an iron-nickel bimetallic catalyst and a preparation method thereof. The preparation method is simple, green and efficient, and can be used for quickly preparing a large amount of high-activity iron-nickel bimetallic catalysts.
The invention also provides an application of the iron-nickel bimetallic catalyst for unsaturated aldehyde hydrogenation reaction, and the selective catalytic addition reduction of unsaturated aldehyde is realized under relatively mild reaction conditions.
The specific technical scheme of the invention is as follows:
a preparation method of an iron-nickel bimetallic catalyst comprises the following steps:
A. adding simple substance iron into a nickel salt solution, stirring for reaction, then separating, washing and drying the obtained solid by deionized water to obtain an iron-nickel composite material after ion exchange;
B. calcining the obtained iron-nickel composite material subjected to ion exchange in a hydrogen-argon atmosphere, and naturally cooling to room temperature to obtain the iron-nickel bimetallic catalyst.
In the step A, the elementary substance iron is selected from foamed iron or iron powder, wherein the particle size of the iron powder is 50-2000 meshes.
In the step A, stirring and reacting for 6-16 h.
Step A, the nickel salt solution is the solution with oxygen removed.
The whole process of the step A is carried out under the protection of argon;
further, before the elemental iron is used, the elemental iron is cleaned, and the specific cleaning method comprises the following steps: adding the elementary iron into a dilute acid solution, cleaning the elementary iron precursor under the condition of ultrasonic or stirring, then washing for 2-3 times by using a mixed solution of ethanol and water with a volume ratio of 1:1, wherein oxygen in the solution is removed, and drying in a vacuum drying oven at 60 ℃. The whole cleaning process is carried out under the protection of argon. Wherein the dilute acid solution is one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid, and the concentration of the dilute acid solution is 0.001-0.5 mol/L. The diluted acid solution is used for removing oxygen dissolved in the liquid by using an argon blowing deoxidation mode before use. And (4) removing surface oxides and pollutants by using dilute acid washing.
In the step A, argon is introduced for 30min before the nickel salt solution is used, and oxygen in the solution is removed. The nickel salt is selected from one of nickel nitrate, nickel sulfate, nickel chloride, nickel fluoride, nickel acetate or nickel acetylacetonate; the concentration of the nickel salt solution is 0.001mol/L-2 mol/L.
Further, the mass ratio of the elementary substance iron to the nickel salt in the step A is 20:1-5: 2.
The separation in the step A specifically comprises: and a magnet is adopted to attract solid materials to realize solid-liquid separation.
The drying in the step A is vacuum drying.
In the step B, the calcination temperature is 300-500 ℃. Specifically, the method comprises the following steps: the temperature is raised from the room temperature to 300-500 ℃ at 4-5 ℃/min, and the temperature is maintained for calcination at the temperature, preferably for 1h, during which the temperature is maintained in a hydrogen-95% argon mixed atmosphere with 5% hydrogen by volume.
Further, all liquid reagents in the preparation method of the iron-nickel bimetallic catalyst, including water or ethanol mixed solution, are used for removing dissolved oxygen in liquid in an argon blowing deoxidation mode before use.
All the steps in the preparation method of the iron-nickel bimetallic catalyst are carried out under the protection of argon.
Further, the prepared iron-nickel bimetallic catalyst is stored under the protection of argon.
The iron-nickel bimetallic catalyst provided by the invention is prepared by the method. The product is an iron-nickel bimetallic catalyst formed on the basis of foamed iron, and has an open and irregular three-dimensional porous structure in the overall appearance, and the diameters of pore channels are mainly distributed between 200 and 500 mu m.
The invention provides an application of an iron-nickel bimetallic catalyst, in particular to an application in selective hydrogenation reaction of unsaturated aldehyde.
The specific application method comprises the following steps:
adding a nickel-iron bimetallic catalyst, isopropanol and unsaturated aldehyde into a high-pressure reaction kettle, replacing air in the reaction kettle with high-purity hydrogen, keeping the hydrogen pressure of 1-8MPa in the reaction kettle, heating to 80-220 ℃ under the stirring condition for reaction for 2h, and evaluating the reaction result by gas chromatography-mass spectrometry;
or, in a tubular high-pressure reactor, adding an iron-nickel bimetallic catalyst into the tubular reactor, heating the tubular reactor to 80-220 ℃, simultaneously enabling the mixed solution of isopropanol and cinnamaldehyde to pass through the tubular reactor under the pressure of 2-8MPa, and evaluating the reaction result by gas chromatography-mass spectrometry after reacting for 2 h.
The invention discloses a preparation method of an iron-nickel bimetallic catalyst, which takes simple substance iron as a main body and prepares the iron-nickel bimetallic catalyst by ion exchange and heat treatment in hydrogen atmosphere; the specific method comprises the following steps: removing surface oxides and pollutants from the elementary iron in an acid treatment mode, and then adding the cleaned elementary iron precursor into an aqueous solution of nickel salt for ion exchange; and cleaning and drying the iron-nickel sample subjected to ion exchange, putting the iron-nickel sample into a tubular furnace, carrying out heat treatment after the temperature is raised to a certain temperature through a program in a hydrogen-argon atmosphere, and naturally cooling to room temperature to obtain the iron-nickel bimetallic catalyst. The catalyst shows better catalytic activity and selectivity in the selective hydrogenation reaction of catalyzing unsaturated aldehyde.
Compared with the prior art, the preparation method is simple and efficient, the reaction conditions are mild, the preparation method is easy to implement, the requirements on instruments and equipment are not strict, the equipment cost of raw materials is low, and the large scale is easy to realize. The obtained iron-nickel bimetallic catalyst shows excellent catalytic activity and higher selectivity in catalyzing the selective reduction of unsaturated aldehyde.
Drawings
FIG. 1 shows the morphology of the Fe-Ni bimetallic catalyst prepared in example 3 before and after catalytic hydrogenation reaction; in the figure, a is the form before catalytic hydrogenation reaction, and b is the form after catalytic reaction;
FIG. 2 is a STEM photograph and elemental distribution of the iron-nickel bimetallic catalyst prepared in example 3; in the figure, a is a STEM photo of an iron-nickel bimetallic catalyst, b is distribution of iron elements, and c is distribution of nickel elements;
FIG. 3 is an X-ray photoelectron spectrum of the bimetallic iron-nickel catalyst; in the figure, a is a total spectrogram, b is a nickel element high-resolution spectrogram, and c is an iron element high-resolution spectrogram.
Detailed Description
All solutions, acid solutions, water or ethanol mixed solutions (all liquid reagents of the invention) are used for removing dissolved oxygen in the liquid by using an argon blowing deoxidation mode before use. The equipment, container, etc. need to be filled with argon first.
All the steps in the preparation method of the iron-nickel bimetallic catalyst are carried out under the protection of argon.
Example 1
A preparation method of an iron-nickel bimetallic catalyst comprises the following steps:
A. adding 20g of 300-mesh iron powder into 200mL of 0.001mol/L diluted hydrochloric acid, cleaning for 30min under an ultrasonic condition, attracting the iron powder by using a magnet and pouring out a cleaning solution, then adding a mixed solution of ethanol and water in a volume ratio of 1:1 to wash the cleaned iron powder for 2 times, drying in a vacuum drying oven at 60 ℃ to obtain an iron powder precursor, and carrying out the whole cleaning process under the protection of argon.
B. And meanwhile, introducing argon into 200mL of 0.5mol/L nickel nitrate solution for 30min to remove oxygen in the solution, adding the washed and dried iron powder precursor into the nickel nitrate solution, mechanically stirring for 6h in an argon protective atmosphere, separating in a separation mode of magnet attraction, cleaning the iron-nickel composite material subjected to ion exchange, and then drying in vacuum.
C. And (2) putting the iron-nickel composite material subjected to ion exchange after vacuum drying into a tubular furnace, introducing a hydrogen-argon mixed gas of argon with the volume fraction of 5% and 95% of the argon for 20min, starting to raise the temperature of the tubular furnace to 400 ℃ at the heating rate of 4 ℃/min, carrying out heat preservation and calcination for 1h, naturally cooling to room temperature to obtain an iron-nickel bimetallic catalyst, and storing the catalyst under the protection of argon.
An application of an iron-nickel bimetallic catalyst, which comprises the following specific application methods:
taking 1g of the prepared iron-nickel bimetallic catalyst, putting the iron-nickel bimetallic catalyst into a high-pressure reaction kettle, and adding 10mL of isopropanol solvent and 0.2mL of cinnamaldehyde. After the air in the system is replaced by high-purity hydrogen, the pressure of the hydrogen in the reaction kettle is kept at 2 MPa. Then, the temperature of the reaction system is increased to 100 ℃ at the heating rate of 2 ℃/min, after the reaction is carried out for 2 hours, the determination of the product type and the content is determined by gas chromatography-mass spectrometry, the conversion rate of the cinnamaldehyde is 71.3 percent, and the selectivity of the main product phenylpropyl aldehyde is 90.2 percent.
Example 2
A preparation method of an iron-nickel bimetallic catalyst comprises the following steps:
A. adding 5g of 100-mesh iron powder into 100mL of 0.001mol/L dilute sulfuric acid, cleaning for 30min under ultrasonic conditions, attracting the iron powder by a magnet, pouring out the cleaning solution, and adding a mixed solution of ethanol and water to wash for 3 times.
B. And introducing argon into 50mL of 0.1mol/L nickel acetate solution for 30min to remove oxygen in the solution, then adding the washed iron powder precursor into the nickel acetate solution, mechanically stirring for 10h in an argon protective atmosphere, separating and washing the iron-nickel composite material subjected to ion exchange in a magnet attraction separation mode, and performing vacuum drying.
C. And (2) putting the iron-nickel composite material subjected to ion exchange after vacuum drying into a tubular furnace, introducing hydrogen-argon mixed gas with the volume fraction of hydrogen accounting for 5% into the tubular furnace for 20min, starting to raise the temperature in the tubular furnace to 400 ℃ at the temperature rise speed of 4 ℃/min, keeping the temperature for 1h, naturally cooling to room temperature to obtain an iron-nickel bimetallic catalyst, and storing the catalyst under the protection of argon.
An application of an iron-nickel bimetallic catalyst, which comprises the following specific application methods:
and (3) putting 1g of the prepared iron-nickel bimetallic catalyst into a high-pressure reaction kettle, and adding 10mL of isopropanol solvent and 0.2mL of cinnamaldehyde. After the air in the system is replaced by high-purity hydrogen, the hydrogen pressure in the reaction kettle is kept at 3 MPa. And the temperature of the reaction system was raised to 150 ℃ at a temperature rise rate of 2 ℃/min. After the catalytic reaction is carried out for 2 hours, the types and the contents of the products are determined by gas chromatography-mass spectrometry, the conversion rate of the cinnamaldehyde is 77.9 percent, and the selectivity of the main product phenylpropyl aldehyde is 85.2 percent.
Example 3
A preparation method of an iron-nickel bimetallic catalyst comprises the following steps:
A. the bulk density is 0.09g/cm3Adding 10g of the foamed iron into 50mL of 0.01mol/L diluted acid, cleaning for 30min under the ultrasonic condition, attracting the foamed iron by a magnet, pouring out the cleaning solution, and adding a mixed solution of ethanol and water for cleaning for 2 times.
B. And introducing argon into 100mL of 0.5mol/L nickel chloride solution for 30min to remove oxygen in the solution, adding the cleaned foam iron precursor into the nickel chloride solution, mechanically stirring for 10h in an argon protective atmosphere, separating and cleaning the iron-nickel composite material subjected to ion exchange in a magnet attraction separation mode, and drying in vacuum.
C. And (2) putting the iron-nickel composite material subjected to ion exchange after vacuum drying into a tubular furnace, introducing hydrogen-argon mixed gas with the volume fraction of 5% by adopting hydrogen into the tubular furnace for 20min, starting to raise the temperature to 450 ℃ at the temperature rise speed of 4 ℃/min, keeping the temperature for 1h, naturally cooling to room temperature to obtain the iron-nickel bimetallic catalyst, and storing the catalyst under the protection of argon.
An application of an iron-nickel bimetallic catalyst, which comprises the following specific application methods:
5g of the prepared iron-nickel bimetallic catalyst is put into a tubular reactor with the inner diameter of 6mm, and 50mL of isopropanol solvent and 1mL of cinnamaldehyde are added into the system. After the air in the system is replaced by high-purity hydrogen, the pressure of the hydrogen in the reaction kettle is kept at 4 MPa. And the temperature of the reaction system was raised to 100 ℃ at a temperature rise rate of 2 ℃/min. After the catalytic reaction is carried out for 4 hours, the types and the contents of the products are determined by gas chromatography-mass spectrometry, the conversion rate of the cinnamaldehyde is 82.3 percent, and the selectivity of the main product phenylpropyl aldehyde is 95.4 percent.
The prepared catalyst is characterized (based on the catalyst in example 3), and as can be seen from the scanning electron microscope picture of the iron-nickel bimetallic catalyst based on the foamed iron in fig. 1, the iron-nickel bimetallic catalyst formed based on the foamed iron shows an open and irregular three-dimensional porous structure in the overall morphology, and the diameters of the pore channels are mainly distributed between 200 and 500 μm, which is not only beneficial to the mass transfer of reactants in the pore channels, but also beneficial to the catalytic reaction, and can also ensure the structural stability of the catalyst. The electron energy spectrum surface scanning analysis is carried out on the iron-nickel bimetallic catalyst before the reaction to determine the distribution of the reaction nickel on the surface of the foamed iron, and the result is shown in figure 2. It can be clearly found that the nickel element is uniformly dispersed on the surface of the foam iron (a-c in figure 2). In addition, as can be seen from the X-ray photoelectron spectroscopy (XPS) of the iron-nickel bimetallic catalyst (a in fig. 3), the prepared catalyst mainly contains two metal elements of iron and nickel, which indicates that the catalyst formed by the foamed iron and the metal nickel salt is an iron-nickel bimetallic catalyst, while as can be seen from the XPS high resolution spectroscopy (b-c in fig. 3) of the Fe and the Ni elements, Fe appears on the surface of the catalyst0Ni represents Ni0State.
Example 4
A preparation method of an iron-nickel bimetallic catalyst comprises the following steps:
A. the bulk density is 0.09g/cm310g of the foamed iron (B) was added to 50mL of 0.005mol/L sulfuric acid, washed under ultrasonic conditions for 30min, attracted with a magnet and poured out the washing solution, and washed 2 times with a mixed solution of ethanol and water.
B. And introducing argon into 100mL of 0.1mol/L nickel sulfate solution for 30min to remove oxygen in the solution, adding the cleaned foam iron precursor into the nickel sulfate solution, mechanically stirring for 16h in an argon protective atmosphere, separating and cleaning the iron-nickel composite size subjected to ion exchange in a magnet attraction separation mode, and performing vacuum drying.
C. Putting the iron-nickel composite size subjected to ion exchange after vacuum drying into a tubular furnace, introducing hydrogen-argon mixed gas with the hydrogen extraction integral fraction of 5% into the tubular furnace for 20min, starting to raise the temperature to 450 ℃ at the temperature rise speed of 4 ℃/min, keeping the temperature for 1h, naturally cooling to room temperature to obtain the iron-nickel bimetallic catalyst, and storing the catalyst under the protection of argon.
An application of an iron-nickel bimetallic catalyst, which comprises the following specific application methods:
5g of the prepared iron-nickel bimetallic catalyst is put into a tubular reactor with the inner diameter of 6mm, and 50mL of isopropanol solvent and 1mL of cinnamaldehyde are added into the system. After the air in the system is replaced by high-purity hydrogen, the hydrogen pressure in the reaction kettle is kept at 3 MPa. And the temperature of the reaction system was raised to 120 ℃ at a temperature rise rate of 2 ℃/min. After the catalytic reaction is carried out for 4 hours, the types and the contents of the products are determined by gas chromatography-mass spectrometry, the conversion rate of the cinnamaldehyde is 64.2 percent, and the selectivity of the main product phenylpropyl aldehyde is 92.5 percent.
The above detailed description of the preparation and use of the bimetallic iron-nickel catalyst with reference to the embodiments is illustrative and not restrictive, and several embodiments may be cited within the limits of the present invention, and it is therefore intended that changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the iron-nickel bimetallic catalyst is characterized by comprising the following steps of:
A. adding simple substance iron into a nickel salt solution, stirring for reaction, then separating, washing and drying the obtained solid by deionized water to obtain an iron-nickel composite material after ion exchange;
B. calcining the obtained iron-nickel composite material subjected to ion exchange in a hydrogen-argon atmosphere, and naturally cooling to room temperature to obtain the iron-nickel bimetallic catalyst.
2. The method according to claim 1, wherein in step A, the elemental iron is selected from the group consisting of foamed iron and iron powder.
3. The method according to claim 1, wherein in the step A, the reaction is carried out for 6 to 16 hours with stirring.
4. The method according to claim 1, wherein in step a, the nickel salt is selected from one of nickel nitrate, nickel sulfate, nickel chloride, nickel fluoride, nickel acetate, and nickel acetylacetonate.
5. The method according to claim 1 or 4, wherein the ratio of the amounts of the elemental iron and nickel salt in step A is 20:1 to 5: 2.
6. The method according to claim 1 or 4, wherein in step B, the calcination temperature is 300-500 ℃.
7. The method of claim 1 or 4, wherein the calcination is carried out for a period of 1 hour.
8. The preparation method of any one of claims 1 to 4, wherein all liquid reagents in the preparation method of the iron-nickel bimetallic catalyst are used for removing dissolved oxygen in liquid by means of argon blowing deoxidation before use; all steps were performed under argon protection.
9. An iron-nickel bimetallic catalyst prepared by the preparation method of any one of claims 1 to 8.
10. Use of the iron-nickel bimetallic catalyst prepared by the preparation method of any one of claims 1 to 8 in selective hydrogenation of unsaturated aldehydes.
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