CN117463312B - Hydrotalcite-like structured nickel-based catalyst and preparation method and application thereof - Google Patents
Hydrotalcite-like structured nickel-based catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN117463312B CN117463312B CN202311833682.XA CN202311833682A CN117463312B CN 117463312 B CN117463312 B CN 117463312B CN 202311833682 A CN202311833682 A CN 202311833682A CN 117463312 B CN117463312 B CN 117463312B
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- water
- hydrotalcite
- based catalyst
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000019253 formic acid Nutrition 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- -1 nickel magnesium aluminum Chemical compound 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000011777 magnesium Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 24
- 229910017107 AlOx Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 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 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 4
- 229960001545 hydrotalcite Drugs 0.000 abstract description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000002638 heterogeneous catalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910003281 Ni-Mg-Al Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- B01J23/007—Mixed salts
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a hydrotalcite-like structured nickel-based catalyst, a preparation method and application thereof, and relates to the technical field of catalytic materials. The catalyst is prepared by using nickel magnesium aluminum ternary hydrotalcite as a precursor, wherein the molar ratio of nickel magnesium aluminum is (0.05-3): (0.1 to 5): the catalyst is prepared by using a reverse precipitation method, and has the advantages of simple process and low cost. The catalyst has uniformly dispersed active sites and abundant alkaline sites on the surface of the catalyst. The catalyst disclosed by the invention is used for the reaction of preparing formic acid by CO 2 hydrogenation, can effectively improve the yield of formic acid under a relatively mild condition, and keeps excellent stability.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a hydrotalcite-like structured nickel-based catalyst, and a preparation method and application thereof.
Background
The main products of the recycling of CO 2 are hydrocarbon products (C xHy) and hydrocarbon-oxygen products (C xHyOz), and generally, the energy utilization rate of the hydrocarbon-oxygen products is higher, wherein the reaction of preparing formic acid by hydrogenating CO 2 is widely focused as the reaction with 100% of the atomic economic utilization rate.
At present, a catalytic system for preparing formic acid by CO 2 hydrogenation, a low-activity non-noble metal catalyst and an environment-friendly homogeneous catalyst are difficult to realize industrial application. For example, in the case of homogeneous synergistic catalytic systems of ionic liquid 1, 2-dimethyl-3-butylimidazole acetate (BMMI.oac) and precursor [ Ru 3(CO)12 ] reported in literature (ACS CATALYSIS,2018,8 (3): 1628-1634), even though there is very high reactivity (TON=17000, TOF=102.4 h -1), there is a problem that the ionic liquid is difficult to separate from the product; the reaction rate of the prepared foam-like Ni@Ni (OH) 2 heterogeneous catalyst reported in literature (Nanoscale, 2021,13 (19): 8931-8939) is only 6 mmol.g -1·h-1. In addition, the stability of heterogeneous catalysts is also very problematic, as reported in literature (APPLIED CATALYSIS B: environmental,2023,335,122873), and most data Ru-based catalysts, after 5 cycles, exhibit a 50% decrease in the reaction performance. The Cu-based catalyst reported in the literature (Journal of CO 2. U. Tisation, 2020,41,101267) also showed a decrease in activity of at least 30% after 5 cycles. Therefore, the development of a non-noble metal heterogeneous catalyst with high activity and high stability is important for the hydrogenation reaction of CO 2 to prepare formic acid.
Disclosure of Invention
The invention aims to provide a hydrotalcite-like structured nickel-based catalyst, a preparation method and application thereof, and solves the problems of low formate yield, slow reaction rate and poor catalyst stability existing in the process of preparing formic acid by CO 2 hydrogenation by using a non-noble metal heterogeneous catalyst.
In order to achieve the above purpose, the present invention provides a method for preparing a hydrotalcite-like structured nickel-based catalyst, which specifically comprises the following steps:
S1, dissolving a certain amount of water-soluble nickel salt, water-soluble magnesium salt and water-soluble aluminum salt in water to obtain a metal salt solution;
s2, dissolving a certain amount of sodium carbonate and sodium hydroxide in water, stirring, and then heating in an oil bath to obtain a precipitant;
S3, taking two parts of precipitants, firstly placing one part of precipitant into a reaction container, then dropwise adding a metal salt solution, dropwise adding the other part of precipitant into the mixed solution in the dropwise adding process to maintain the pH at 7-11, and aging for 6-12 hours at 60-80 ℃ after metal ions in the metal salt solution are completely precipitated to obtain turbid liquid;
s4, filtering and washing the turbid liquid to obtain a filter cake;
S5, drying the filter cake at the temperature of 100-150 ℃ for 8-12 hours to obtain a catalyst precursor;
S6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 3-8 hours at 400-600 ℃ to obtain nickel-magnesium-aluminum metal oxide;
and S7, placing the nickel-magnesium-aluminum metal oxide into a tube furnace, heating to 500-800 ℃, and roasting for 3-8 hours under the mixed atmosphere of H 2 and Ar to obtain the supported Ni/Mg aAlOx catalyst.
Preferably, in the step S1, the water-soluble nickel salt is one of nickel nitrate, nickel chloride or nickel acetylacetonate; the water-soluble magnesium salt is one of magnesium nitrate or magnesium chloride; the water-soluble aluminum salt is one of aluminum nitrate or aluminum chloride.
Preferably, in the step S1, the molar ratio of the water-soluble nickel salt, the water-soluble magnesium salt and the water-soluble aluminum salt is (0.05-3): (0.1-5): 1, a step of; the concentration of the obtained metal salt solution is 0.5mol/L-4mol/L.
Preferably, in the step S2, the molar ratio of sodium carbonate to sodium hydroxide is (0.2-0.7): 1, a step of; the concentration of the prepared precipitant is 1.5mol/L-4mol/L.
Preferably, in the step S3, the dropping speed of the metal salt solution is 40-120mL/min.
Preferably, in the step S7, the molar ratio of H 2 to Ar is 1:9.
The invention also provides a hydrotalcite-like structured nickel-based catalyst prepared by the preparation method, wherein the chemical formula of the nickel-based catalyst is Ni/Mg aAlOx, a represents the molar ratio of Mg/Al, the range is 0-5, and x is 1.5-6.5.
The invention also provides application of the nickel-based catalyst in the reaction of preparing formic acid by CO 2 hydrogenation.
Preferably, the nickel-based catalyst is applied to the reaction of preparing formic acid by CO 2 hydrogenation, and the specific application steps are that the catalyst is placed in a high-pressure slurry-bed batch reactor, naHCO 3 is added, then hydrogen is introduced, and the reaction is carried out for 6h-24h under the conditions that the reaction temperature is 25-150 ℃ and the reaction pressure is 3-5 MPa.
Preferably, the catalyst is used in an amount of 0.1g to 0.5g, naHCO 3 is used in an amount of 1g to 2g, the volume of water in the slurry bed is 10mL to 30mL, and the rotating speed is 800rpm to 1200rpm.
Therefore, the invention provides a hydrotalcite-like structured nickel-based catalyst, and a preparation method and application thereof, and compared with the prior art, the nickel-based catalyst has the following specific beneficial effects:
(1) The invention takes Ni-Mg-Al hydrotalcite as a precursor to prepare the supported Ni/Mg aAlOx catalyst with hydrotalcite-like structure, the catalyst has the memory effect of the hydrotalcite-like structure, and after the catalyst is subjected to liquid phase reaction, the original layered structure can be restored, and the loss and migration of active centers are inhibited to a certain extent, so that the stability of the catalyst is improved, and the catalyst provided by the invention still keeps higher activity after 40 hours of operation and is far higher than other non-noble metal heterogeneous catalysts;
(2) The catalyst prepared by the invention is applied to the reaction of preparing formic acid by CO 2 hydrogenation, the catalyst can accurately regulate and control the alkaline site property of the catalyst surface so as to achieve the aim of regulating and controlling the adsorption mode of CO 2, and compared with other non-noble metal heterogeneous catalysts, the catalyst has more weak alkaline sites and medium alkaline sites, and can better promote the generation and desorption of formate, the catalyst provided by the invention can catalyze CO 2 hydrogenation, the selectivity of formate can reach 100%, the yield can reach more than 30%, and the reaction rate can also reach more than 500 mg.g cat -1·h-1;
(3) The catalyst provided by the invention has mild application conditions, the reaction temperature of the catalyst for preparing formic acid by CO 2 hydrogenation is below 100 ℃, the pressure is below 5MPa, the reaction conditions are far lower than those of other catalytic systems, and the catalyst provided by the invention does not need the addition of organic alkali liquor when being used for preparing formic acid by CO 2 hydrogenation, has simple product separation, is environment-friendly, has relatively lower process requirements, low investment cost and small potential safety hazard.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is an XRD contrast pattern of Ni/Mg aAlOx catalysts prepared in example 1, example 2, comparative example 3 according to the present invention;
FIG. 2 is a TEM image of the Ni/Mg 0.2AlOx catalyst prepared in example 2 of the present invention;
FIG. 3 is a TEM image of the Ni/Mg 0.2AlOx catalyst prepared in example 2 of the present invention after five cycles;
FIG. 4 is a schematic diagram of the apparatus of a slurry bed gap reactor used in the present invention;
Reference numerals
1-H 2 steel cylinders; 2-a one-way stop valve; 3-stainless steel micro high-pressure reaction kettle; 4-a standard pressure gauge; 5-controller.
Detailed Description
The invention provides a preparation method of a hydrotalcite-like structured nickel-based catalyst, which specifically comprises the following steps:
S1, dissolving a certain amount of water-soluble nickel salt, water-soluble magnesium salt and water-soluble aluminum salt in water to obtain a metal salt solution;
s2, dissolving a certain amount of sodium carbonate and sodium hydroxide in water, stirring, and then heating in an oil bath to obtain a precipitant;
S3, taking two parts of precipitants, firstly placing one part of precipitant into a reaction container, then dropwise adding a metal salt solution, dropwise adding the other part of precipitant into the mixed solution in the dropwise adding process to maintain the pH at 7-11, and aging for 6-12 hours at 60-80 ℃ after metal ions in the metal salt solution are completely precipitated to obtain turbid liquid;
s4, filtering and washing the turbid liquid to obtain a filter cake;
S5, drying the filter cake at the temperature of 100-150 ℃ for 8-12 hours to obtain a catalyst precursor;
S6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 3-8 hours at 400-600 ℃ to obtain nickel-magnesium-aluminum metal oxide;
and S7, placing the nickel-magnesium-aluminum metal oxide into a tube furnace, heating to 500-800 ℃, and roasting for 3-8 hours under the mixed atmosphere of H 2 and Ar to obtain the supported Ni/Mg aAlOx catalyst.
In the invention, the water-soluble nickel salt in the step S1 is one of nickel nitrate, nickel chloride or nickel acetylacetonate; the water-soluble magnesium salt is one of magnesium nitrate or magnesium chloride; the water-soluble aluminum salt is one of aluminum nitrate or aluminum chloride. The mole ratio of the water-soluble nickel salt, the water-soluble magnesium salt and the water-soluble aluminum salt is (0.05-3): (0.1-5): 1, preferably 2:0.2:1, a step of; the concentration of the obtained metal salt solution is 0.5mol/L-4mol/L.
In the present invention, the molar ratio of sodium carbonate to sodium hydroxide in step S2 is (0.2 to 0.7): 1, a step of; the concentration of the prepared precipitant is 1.5mol/L-4mol/L.
In the invention, the dropping speed of the metal salt solution in the step S3 is 40-120mL/min.
In the present invention, the molar ratio of H 2 to Ar in step S7 is 1:9.
The invention also provides the hydrotalcite-like structured nickel-based catalyst prepared by the preparation method, and the chemical formula of the catalyst is Ni/Mg aAlOx, wherein a represents the molar ratio of Mg/Al, the range is 0-5, preferably 0.2, and x is 1.5-6.5.
The invention also provides application of the catalyst in the reaction of preparing formic acid by CO 2 hydrogenation, the catalyst is placed in a high-pressure slurry bed batch reactor, naHCO 3 is added, naHCO 3 and H 2 are used as raw materials, the reaction is carried out for 6H-24H under the conditions that the reaction temperature is 25-150 ℃ and the reaction pressure is 3-5 MPa, and the purpose of using NaHCO 3 as the raw materials is to simulate the state of CO 2 dissolved in NaOH alkali liquor. The dosage of the catalyst is 0.1g-0.5g, the dosage of NaHCO 3 is 1g-2g, the volume of water in the slurry bed is 10mL-30mL, and the rotating speed is 800rpm-1200rpm.
As shown in fig. 4, the high-pressure slurry-bed intermittent reactor comprises a stainless steel micro high-pressure reaction kettle, one end of the stainless steel micro high-pressure reaction kettle is connected with an H 2 steel cylinder through a conduit, a one-way stop valve is arranged on the conduit, and the stainless steel micro high-pressure reaction kettle is also connected with a controller and a standard pressure gauge. And (3) placing the prepared sodium bicarbonate solution into a reaction kettle, packaging the reaction kettle, introducing hydrogen with the pressure of 0.5MPa into the reaction kettle to replace air in the kettle, and circulating for three times. Then the reaction pressure is raised, and all valves are closed. Setting the reaction temperature and the rotating speed, and starting the reaction. After the reaction is finished, the reaction kettle is opened, kettle liquid is collected, and the supernatant is taken after centrifugation.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the hydrotalcite-like structured nickel-based catalyst comprises the following specific preparation steps:
S1, 4.36gNi (NO 3)3·6H2O,14.07gAl(NO3)3·9H2 O and 1.92g Mg (NO 3)2·6H2 O are dissolved in 100mL deionized water to obtain a metal salt solution;
S2, dissolving 3.71g of anhydrous Na 2CO3 and 3.20g of NaOH in 60mL of deionized water, stirring at room temperature until the solution is clear and transparent, and heating the solution to 65 ℃ in an oil bath to obtain a precipitant;
S3, taking two precipitants, dripping a metal salt solution into the first precipitant at the speed of 60mL/h, slowly dripping the second precipitant during the dripping, maintaining the pH value to be 8, and aging for 12 hours at the temperature of 65 ℃ after the dripping is completed to obtain turbid liquid;
s4, filtering the turbid liquid, and washing with water to obtain a filter cake;
s5, drying the filter cake at 110 ℃ for 12 hours to obtain a catalyst precursor;
s6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain nickel-magnesium-aluminum metal oxide;
S7, placing nickel magnesium aluminum metal oxide into a tube furnace, and reducing for 6 hours under the condition of a mixed atmosphere of H 2 and Ar and 650 ℃ to obtain a catalyst Ni/Mg 0.2AlOx;
The XRD pattern of the catalyst prepared in this example is shown in FIG. 1.
The catalyst prepared in the embodiment is used in the reaction of preparing formic acid by CO 2 hydrogenation, and the performance of the catalyst is tested and evaluated. 0.1g of catalyst Ni/Mg 0.2AlOx is selected and put into a high-pressure slurry bed batch reactor, then NaHCO 3 1.26.26 g is added, H 2 is introduced, naHCO 3 and H 2 are used as raw materials, the reaction time is 8 hours under the condition that the reaction temperature is 100 ℃ and the reaction pressure is 4MPa, the volume of water in the slurry bed is 15mL, and the rotating speed is 900rpm. The results of the performance test of the catalyst are shown in table 1.
Example 2
The preparation method of the hydrotalcite-like structured nickel-based catalyst comprises the following specific preparation steps:
S1, 4.36gNi (NO 3)3·6H2O,14.07gAl(NO3)3·9H2 O and 3.85g Mg (NO 3)2·6H2 O are dissolved in 100mL deionized water to obtain a metal salt solution;
S2, dissolving 3.71g of anhydrous Na 2CO3 and 3.20g of NaOH in 60mL of deionized water, stirring at room temperature until the solution is clear and transparent, and heating the solution to 65 ℃ in an oil bath to obtain a precipitant;
S3, taking two precipitants, dripping a metal salt solution into the first precipitant at the speed of 60mL/h, slowly dripping the second precipitant during the dripping, maintaining the pH value to be 8, and aging for 12 hours at the temperature of 65 ℃ after the dripping is completed to obtain turbid liquid;
s4, filtering the turbid liquid, and washing with water to obtain a filter cake;
s5, drying the filter cake at 110 ℃ for 12 hours to obtain a catalyst precursor;
s6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain nickel-magnesium-aluminum metal oxide;
S7, placing nickel magnesium aluminum metal oxide into a tube furnace, and reducing for 6 hours under the condition of a mixed atmosphere of H 2 and Ar and 650 ℃ to obtain a catalyst Ni/Mg 0.5AlOx;
The XRD pattern of the catalyst prepared in this example is shown in FIG. 1.
The catalyst prepared in the embodiment is used in the reaction of preparing formic acid by CO 2 hydrogenation, and the performance of the catalyst is tested and evaluated. 0.1g of catalyst Ni/Mg 0.5AlOx is selected and put into a high-pressure slurry bed batch reactor, then NaHCO 3 1.26.26 g is added, H 2 is introduced, naHCO 3 and H 2 are used as raw materials, the reaction time is 8 hours under the condition that the reaction temperature is 100 ℃ and the reaction pressure is 4MPa, the volume of water in the slurry bed is 15mL, and the rotating speed is 900rpm. The results of the performance test of the catalyst are shown in table 1.
Example 3
This example differs from example 1 in that the reaction time was changed to 24 hours during performance testing and evaluation of the catalyst, which was designated as Ni/Mg 0.2AlOx -24 hours. The rest is the same as in example 1, and no further description is given here. The results of the performance test of the catalyst are shown in table 1.
Example 4
This example differs from example 1 in that the catalyst used in this example was the catalyst of example 1 after five cycles, and was designated as Ni/Mg 0.2AlOx -particle. The rest is the same as in example 1, and no further description is given here. The results of the performance test of the catalyst are shown in table 1.
Comparative example 1
The catalyst used in this comparative example was a common commercial nickel powder, and the remainder was the same as in example 1, and no further description is given here. The results of the performance test of the catalyst are shown in table 1.
Comparative example 2
The comparative example adopts an impregnation method to prepare a nickel-based catalyst, and the specific preparation steps comprise:
S1, 18.75g of Al (NO 3)3·9H2 O and 2.56g of Mg (NO 3)2·6H2 O are dissolved in 100ml of deionized water to obtain a metal salt solution;
S2, dissolving 3.71g of anhydrous Na 2CO3 and 3.20g of NaOH in 60mL of deionized water, stirring at room temperature until the solution is clear and transparent, and heating the solution to 65 ℃ in an oil bath to obtain a precipitant;
S3, taking two precipitants, dripping a metal salt solution into the first precipitant at the speed of 60mL/h, slowly dripping the second precipitant during the dripping, maintaining the pH value to be 8, and aging for 12 hours at the temperature of 65 ℃ after the dripping is completed to obtain turbid liquid;
s4, filtering the turbid liquid, and washing with water to obtain a filter cake;
s5, drying the filter cake at 110 ℃ for 12 hours to obtain a catalyst precursor;
s6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain magnesium aluminum metal oxide;
S7, 1.35gNi (NO 3)3·6H2 O is dissolved in 15mL of deionized water, 1g of magnesium aluminum metal oxide is poured into a salt solution, and then the mixed solution is subjected to rotary evaporation at 35 ℃ and 100 rpm;
And S8, placing the mixture obtained after rotary steaming into a muffle furnace for calcination at 550 ℃ for 4 hours, and then reducing for 6 hours under the condition of 650 ℃ in a mixed atmosphere of H 2 and Ar in a tubular furnace to finally obtain the catalyst Ni/Mg 0.2AlOx -I.
The XRD pattern of the catalyst prepared in this comparative example is shown in FIG. 1.
The catalyst prepared in the comparative example is used in the reaction of preparing formic acid by hydrogenating CO 2, and the performance of the catalyst is tested and evaluated. 0.1g of catalyst Ni/Mg 0.2AlOx -I is selected to be put into a high-pressure slurry bed batch reactor, 1.26g of NaHCO 3 is added, H 2 is introduced, naHCO 3 and H 2 are used as raw materials, the reaction time is 8 hours under the condition that the reaction temperature is 100 ℃ and the reaction pressure is 4MPa, the volume of water in the slurry bed is 15mL, and the rotating speed is 900rpm. The results of the performance test of the catalyst are shown in table 1.
Comparative example 3
The catalyst is prepared by adopting a physical grinding method in the comparative example, and the specific preparation steps comprise:
S1, 18.76g Al (NO 3)3·9H2 O and 2.56g Mg (NO 3)2·6H2 O are dissolved in 100ml deionized water to obtain a metal salt solution;
S2, dissolving 3.71g of anhydrous Na 2CO3 and 3.20g of NaOH in 60mL of deionized water, stirring at room temperature until the solution is clear and transparent, and heating the solution to 65 ℃ in an oil bath to obtain a precipitant;
S3, taking two precipitants, dripping a metal salt solution into the first precipitant at the speed of 60mL/h, slowly dripping the second precipitant during the dripping, maintaining the pH value to be 8, and aging for 12 hours at the temperature of 65 ℃ after the dripping is completed to obtain turbid liquid;
s4, filtering the turbid liquid, and washing with water to obtain a filter cake;
s5, drying the filter cake at 110 ℃ for 12 hours to obtain a catalyst precursor;
s6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain magnesium aluminum metal oxide;
s7, grinding 1G of magnesium aluminum metal oxide and 0.35G of NiO together until the mixture is uniformly mixed and dispersed, reducing the mixture in a tube furnace for 6 hours under the condition of a mixed atmosphere of H 2 and Ar in the tube furnace and 650 ℃, and finally obtaining the catalyst Ni/Mg 0.2AlOx -G.
The XRD pattern of the catalyst prepared in this comparative example is shown in FIG. 1.
The catalyst prepared in the comparative example is used in the reaction of preparing formic acid by hydrogenating CO 2, and the performance of the catalyst is tested and evaluated. 0.1G of catalyst Ni/Mg 0.2AlOx -G is selected to be put into a high-pressure slurry bed batch reactor, 1.26G of NaHCO 3 is added, H 2 is introduced, naHCO 3 and H 2 are used as raw materials, the reaction time is 8 hours under the condition that the reaction temperature is 100 ℃ and the reaction pressure is 4MPa, the volume of water in the slurry bed is 15mL, and the rotating speed is 900rpm. The results of the performance test of the catalyst are shown in table 1.
TABLE 1
；
As shown in the data in Table 1, when the reaction time is 8 hours, the yield of the formic acid prepared by catalyzing CO 2 hydrogenation with the Ni/Mg aAlOx catalyst taking Ni-Mg-Al hydrotalcite as a precursor is basically more than 30%, and the formate generation rate can also exceed 400 mg.g cat -1·h-1. In addition, when the reaction time reaches 24 hours, the yield is kept stable, which means that the decomposition of formate or further hydrogenation does not occur, and the stability of the catalyst is ensured to a certain extent.
As can be seen from fig. 1, the main valence of the active centers of examples 1 and 2 and comparative examples 2 and 3 is Ni 0 (2θ=44.51°), while the half-width of the diffraction peak of example 1 and example 2 is larger, which indicates that the hydrotalcite-like structure of the catalyst is smaller in particle size and more uniform in dispersion.
As can be seen from fig. 2 and 3, after the reaction, the catalyst is changed from uniformly distributed particles to regular columns due to the hydrotalcite-like structure of the catalyst. This structural transformation is beneficial to inhibiting the loss and oxidation of the active site and plays a vital role in preventing the deactivation of the catalyst.
Compared with the common pure nickel powder (comparative example 1) and the nickel-based catalysts prepared by the impregnation method and the physical grinding method (comparative example 2 and comparative example 3), the hydrotalcite-like structured nickel-based catalyst metal carrier provided by the invention, which takes Ni-Mg-Al hydrotalcite as a precursor, has stronger interaction force, so that the catalyst has stronger catalytic activity.
The adsorption performance of CO 2 was verified using the catalysts prepared in example 2, comparative example 2 and comparative example 3, the adsorption temperature was 50 ℃, the adsorption time was 1h, and the adsorption performance results are shown in table 2.
TABLE 2
；
From the data in table 2, it can be seen that the hydrotalcite-like nickel-based catalyst prepared by the reverse precipitation method has more weak alkaline sites and medium alkaline sites, which promotes the nickel-based catalyst provided by the invention to have stronger activation capability of CO 2, so that the catalyst can exhibit stronger catalytic activity.
Therefore, the invention provides a hydrotalcite-like structured nickel-based catalyst, a preparation method and application thereof, and the invention prepares the hydrotalcite-like structured supported Ni/Mg aAlOx catalyst by using a reverse precipitation method, and the catalyst has high catalytic activity and strong stability, is used in a CO 2 hydrogenation formic acid preparation reaction, can realize the conversion of CO 2 into formic acid under relatively mild reaction conditions, and keeps good structural stability.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (8)
1. The application of the hydrotalcite-like structured nickel-based catalyst in the reaction of preparing formic acid by CO 2 hydrogenation is characterized in that the preparation method of the hydrotalcite-like structured nickel-based catalyst specifically comprises the following steps:
S1, dissolving a certain amount of water-soluble nickel salt, water-soluble magnesium salt and water-soluble aluminum salt in water to obtain a metal salt solution;
s2, dissolving a certain amount of sodium carbonate and sodium hydroxide in water, stirring, and then heating in an oil bath to obtain a precipitant;
S3, taking two parts of precipitants, firstly placing one part of precipitant into a reaction container, then dropwise adding a metal salt solution, dropwise adding the other part of precipitant into the mixed solution in the dropwise adding process to maintain the pH at 7-11, and aging for 6-12 hours at 60-80 ℃ after metal ions in the metal salt solution are completely precipitated to obtain turbid liquid;
s4, filtering and washing the turbid liquid to obtain a filter cake;
S5, drying the filter cake at the temperature of 100-150 ℃ for 8-12 hours to obtain a catalyst precursor;
S6, grinding the catalyst precursor into powder, then placing the powder into a muffle furnace, and roasting for 3-8 hours at 400-600 ℃ to obtain nickel-magnesium-aluminum metal oxide;
S7, placing nickel magnesium aluminum metal oxide into a tube furnace, heating to 500-800 ℃, and roasting for 3-8 hours under the mixed atmosphere of H 2 and Ar to obtain a supported Ni/Mg aAlOx catalyst;
The chemical formula of the nickel-based catalyst prepared by the preparation method is Ni/Mg aAlOx, wherein a represents the molar ratio of Mg/Al, the range is 0-5, and x is 1.5-6.5.
2. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 1 in the hydrogenation of CO 2 to formic acid, wherein: in the step S1, the water-soluble nickel salt is one of nickel nitrate, nickel chloride or nickel acetylacetonate; the water-soluble magnesium salt is one of magnesium nitrate or magnesium chloride; the water-soluble aluminum salt is one of aluminum nitrate or aluminum chloride.
3. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 1 in the hydrogenation of CO 2 to formic acid, wherein: in the step S1, the molar ratio of the water-soluble nickel salt, the water-soluble magnesium salt and the water-soluble aluminum salt is (0.05-3): (0.1-5): 1, a step of; the concentration of the obtained metal salt solution is 0.5mol/L-4mol/L.
4. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 1 in the hydrogenation of CO 2 to formic acid, wherein: in the step S2, the molar ratio of sodium carbonate to sodium hydroxide is (0.2-0.7): 1, a step of; the concentration of the prepared precipitant is 1.5mol/L-4mol/L.
5. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 1 in the hydrogenation of CO 2 to formic acid, wherein: in the step S3, the dropping speed of the metal salt solution is 40-120mL/min.
6. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 1 in the hydrogenation of CO 2 to formic acid, wherein: in the step S7, the molar ratio of H 2 to Ar is 1:9.
7. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 1 in the hydrogenation of CO 2 to formic acid, wherein: the application of the nickel-based catalyst in the reaction of preparing formic acid by CO 2 hydrogenation comprises the steps of placing the catalyst in a high-pressure slurry bed batch reactor, adding NaHCO 3, then introducing hydrogen, and reacting for 6-24 hours under the conditions that the reaction temperature is 25-150 ℃ and the reaction pressure is 3-5 MPa.
8. The use of a hydrotalcite-like structured nickel-based catalyst according to claim 7 in the hydrogenation of CO 2 to formic acid, wherein: the dosage of the catalyst is 0.1g-0.5g, the dosage of NaHCO 3 is 1g-2g, the volume of water in the slurry bed is 10mL-30mL, and the rotating speed is 800rpm-1200rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311833682.XA CN117463312B (en) | 2023-12-28 | 2023-12-28 | Hydrotalcite-like structured nickel-based catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311833682.XA CN117463312B (en) | 2023-12-28 | 2023-12-28 | Hydrotalcite-like structured nickel-based catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117463312A CN117463312A (en) | 2024-01-30 |
| CN117463312B true CN117463312B (en) | 2024-08-16 |
Family
ID=89640167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311833682.XA Active CN117463312B (en) | 2023-12-28 | 2023-12-28 | Hydrotalcite-like structured nickel-based catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117463312B (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8424672D0 (en) * | 1984-09-29 | 1984-11-07 | Bp Chem Int Ltd | Production of formic acid |
| CN101811052A (en) * | 2010-04-16 | 2010-08-25 | 济南大学 | Diesel vehicle soot combustion catalyst prepared by taking hydrotalcite-like compound as precursor and preparation method thereof |
| CN105289619B (en) * | 2015-11-19 | 2018-06-29 | 中科合成油技术有限公司 | Nickel-base catalyst and preparation method thereof with add hydrogen in 5 hydroxymethyl furfural in application |
| CN105879876B (en) * | 2016-05-09 | 2019-03-05 | 太原理工大学 | The preparation method of nickel-base catalyst for methane and carbon dioxide preparing synthetic gas by reforming |
| WO2019096190A1 (en) * | 2017-11-15 | 2019-05-23 | Solvay Sa | Process for producing formic acid |
| CN108889303B (en) * | 2018-07-20 | 2021-02-12 | 太原理工大学 | Supported high-dispersion copper-based catalyst for preparing methanol from carbon dioxide, preparation method and application thereof |
| CN111072487B (en) * | 2019-12-16 | 2021-03-26 | 中国科学院大连化学物理研究所 | Method for preparing hexamethylene diamine based on cyclohexene |
| CN113292411B (en) * | 2021-06-16 | 2022-06-21 | 厦门大学 | Application of perovskite catalyst in preparation of formic acid by catalyzing carbon dioxide hydrogenation and preparation method |
| KR102689182B1 (en) * | 2021-12-16 | 2024-07-29 | 한국화학연구원 | Method for formic acid from carbon dioxide using dualcatalyst |
| CN116408089A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN115350706B (en) * | 2022-08-29 | 2023-07-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of hydrogenation thermocatalytic ternary metal MOF derivative catalyst |
| CN115779907A (en) * | 2023-02-03 | 2023-03-14 | 潍坊三力本诺化学工业有限公司 | Catalyst for preparing low-carbon hydrocarbons by carbon dioxide hydrogenation and preparation method and application thereof |
-
2023
- 2023-12-28 CN CN202311833682.XA patent/CN117463312B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Highly selective hydrogenation of CO2 into formic acid on a nano-Ni catalyst at ambient temperature: Process, mechanisms and catalyst stability;Chuan-Shu He et al.;《Journal of CO2 Utilization》;20170402;第19卷;摘要、第2.3节 * |
| hydrogenation and condensation of acetone over Ni/MgO-Al2O3 Prepared hydrotalcite Precursors;Yanming Shen et al.;《Journal of Chemical of Japan》;20160720;第49卷(第7期);第1.1节、第1.3节 * |
| Yanming Shen et al..hydrogenation and condensation of acetone over Ni/MgO-Al2O3 Prepared hydrotalcite Precursors.《Journal of Chemical of Japan》.2016,第49卷(第7期),第1.1节、第1.3节. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117463312A (en) | 2024-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Progress in adsorption-enhanced hydrogenation of CO2 on layered double hydroxide (LDH) derived catalysts | |
| CN101455964B (en) | Preparation method of nickel based metal load type catalyst | |
| CN114829004B (en) | Method for preparing Ni-X-based oxide catalyst and application of Ni-X-based oxide catalyst in transfer hydrogenation | |
| CN110102313B (en) | Preparation of ruthenium-nickel core-shell bimetallic nano-catalyst with limited domain structure and application of ruthenium-nickel core-shell bimetallic nano-catalyst in catalyzing selective hydrogenation of dimethyl terephthalate | |
| CN110327933A (en) | Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application | |
| CN110743544A (en) | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| CN112547067A (en) | Preparation method of catalyst for slurry bed methane synthesis reaction | |
| CN113694929B (en) | Supported single-atom copper-based metal oxide catalyst, and preparation method and application thereof | |
| CN117463312B (en) | Hydrotalcite-like structured nickel-based catalyst and preparation method and application thereof | |
| CN104028267B (en) | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst | |
| CN115155602B (en) | Metal oxide-copper composite catalyst and preparation method and application thereof | |
| CN111686740B (en) | Preparation method of methanol synthesis catalyst | |
| CN110935478B (en) | Preparation method of methanol synthesis catalyst | |
| CN115487814B (en) | Dual-function catalyst, preparation method and application thereof, and method for preparing glycol from carbohydrate raw material | |
| CN107537495A (en) | A kind of preparation method and application of synthesis gas ethanol Cu Co catalyst | |
| CN113070069A (en) | Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and preparation method and application thereof | |
| CN105861024A (en) | Application method of cobalt-based Fischer-Tropsch synthesis catalyst | |
| CN112023933A (en) | Preparation method of catalyst for preparing methanol from synthesis gas | |
| CN110665499A (en) | Low-content supported ruthenium metal catalyst and preparation method thereof | |
| CN104525193A (en) | Method for preparing loaded catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene | |
| CN113332998B (en) | High-dispersion ruthenium nanoparticle catalyst loaded on brucite and application of catalyst in preparing acetic acid by catalyzing ethanol liquid phase oxidation | |
| CN115212885B (en) | Cobalt silicate derived cobalt-based catalyst for directly preparing low-carbon alcohol from synthesis gas, preparation method and pretreatment method | |
| CN111849581B (en) | Preparation method of low-temperature FCC gasoline dearsenicating agent | |
| CN107486210A (en) | A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof |
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 |