CN114308062A - Preparation method and application of bimetallic supported catalyst - Google Patents
Preparation method and application of bimetallic supported catalyst Download PDFInfo
- Publication number
- CN114308062A CN114308062A CN202111506935.3A CN202111506935A CN114308062A CN 114308062 A CN114308062 A CN 114308062A CN 202111506935 A CN202111506935 A CN 202111506935A CN 114308062 A CN114308062 A CN 114308062A
- Authority
- CN
- China
- Prior art keywords
- supported catalyst
- calcining
- catalyst
- preparing
- palladium
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 150000005181 nitrobenzenes Chemical class 0.000 claims abstract description 8
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 43
- 238000001354 calcination Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 27
- 239000012298 atmosphere Substances 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 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 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 150000002940 palladium Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 150000003303 ruthenium Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride 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
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 33
- 238000011068 loading method Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000011148 porous material Substances 0.000 description 18
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 17
- 239000000758 substrate Substances 0.000 description 12
- 239000002274 desiccant Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 9
- 239000012716 precipitator Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000002336 sorption--desorption measurement Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 150000001448 anilines Chemical class 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 4
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- -1 aromatic amino compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of metal supported catalysts, and discloses a preparation method and application of a bimetallic supported catalyst. The method comprises the steps of preparing an active carrier through synthesis and oxidation, uniformly mixing a loaded metal salt aqueous solution with the active carrier, and synthesizing the double-metal loaded catalyst under the irradiation of ultraviolet light. When the catalyst is applied to the reaction of generating the halogenated aniline by the catalytic hydrogenation of the halogenated nitrobenzene, the catalyst has good activity and selectivity, when the molar ratio of the halogenated nitrobenzene to the catalyst-loaded metal is up to 8000:1, the conversion rate can reach 100%, the selectivity can reach 99%, and the product yield can reach 98.1%. The bimetal supported catalyst of the invention has simple preparation process and can reduce production cost and environmental pollution.
Description
Technical Field
The invention belongs to the technical field of metal supported catalysts, and particularly relates to a preparation method and application of a bimetallic supported catalyst.
Background
The aromatic amino compound is an important organic intermediate and is widely used for synthesizing dyes, medicines, pesticides and the like. With the development of the dye, rubber, medicine and pesticide industries, the demand of halogenated aniline is rising year by year, and downstream products produced by using the halogenated aniline as a raw material and markets are good. With the development of the dye, material, medicine and pesticide industries in China, the demand of aniline and halogenated aniline is increasing year by year. O-chloroaniline is obtained by reducing o-chloronitrobenzene, and at present, several methods such as iron powder reduction, alkali sulfide or hydrazine hydrate reduction, sulfonation ammonolysis, liquid phase catalytic hydrogenation and the like are mainly adopted in industry to synthesize chloroaniline from nitrochlorobenzene. Wherein, in the iron powder reduction method, iron powder is easy to agglomerate, a large amount of iron mud is generated, slag is difficult to remove, and the environment is seriously polluted; the sodium sulfide reduction method has the defects of complex reduction route, low product yield, large waste liquid amount and the like; the adoption of the sulfonation and ammonolysis method needs to add a mercury salt positioning agent, and is easy to cause environmental pollution. The backward industrialized halogenated arylamine production technology can not meet the domestic market demand, and has the defects of high production cost, serious environmental pollution, low yield and the like, so that the development of a clean and environment-friendly production process is urgently needed.
In contrast, catalytic hydrogenation reduction is carried out under the condition of air isolation, products are not easy to oxidize, used organic solvents can be recovered, catalysts can be regenerated and recycled, production capacity is high, environmental pollution is low, and the method is especially important at present with continuously improved environmental protection requirements. However, the catalytic hydrogenation reduction process of the halogenated nitrobenzene faces the problem that the halogen atoms are easily removed to produce aniline as a byproduct.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a preparation method and application of a bimetallic catalyst. Compared with the traditional impregnation loading method, the preparation method provided by the invention has the advantages that the catalytic performance is improved, and the stability of the catalyst structure is kept.
In order to achieve the above object, the first technical solution adopted by the present invention is:
a preparation method and application of a bimetal supported catalyst comprise the following steps:
at room temperature, simultaneously dropwise adding the nickel salt solution and the ammonia water solution, mixing and stirring for reaction, and continuously stirring for reaction for 0.5-3 h after the dropwise adding of the nickel salt solution is finished;
heating and boiling the mixed solution after the stirring reaction to remove ammonia gas, cooling to room temperature, standing for 1-3h, and performing first centrifugal washing, vacuum drying and calcining to obtain an active carrier; and
preparing aqueous solution of palladium salt and ruthenium salt, adding the active carrier, fully stirring and uniformly mixing, irradiating by ultraviolet light, and carrying out secondary centrifugal washing, vacuum drying and calcining to obtain the bimetallic supported catalyst.
Further, the nickel salt is selected from any one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate, and Ni in the nickel salt solution2+The concentration of (A) is 0.05-0.6 mol/L.
Further, the mass percent concentration of the ammonia water solution is 1-20 wt%, preferably 5-10 wt%.
Further, the solvents washed in the first centrifugal washing, vacuum drying and calcining treatment are deionized water and ethanol, the vacuum drying temperature is 60-90 ℃, the calcining atmosphere is air, the calcining temperature is 500-800 ℃, and the calcining time is 3-6 h;
the solvents in the second centrifugal washing, vacuum drying and calcining treatment are deionized water and ethanol, and the vacuum drying temperature is 60-90 ℃; the calcining atmosphere is air, the calcining temperature is 100-300 ℃, and the calcining time is 1-3 h.
Further, the palladium salt is selected from any one or more of palladium nitrate, palladium sulfate, palladium chloride and palladium acetate;
the ruthenium salt is selected from one or more of ruthenium nitrate, ruthenium sulfate, ruthenium chloride and ammonium chlororuthenate.
Further, the mass ratio of the total mass of the palladium salt and the ruthenium salt to the active carrier is 1: 40-600.
Further, the total loading amount of palladium and ruthenium in the bimetallic supported catalyst is 0.1-0.6 wt%, preferably 0.1-0.3 wt%.
Further, the ultraviolet light irradiation time is 8-72 h, preferably 24-32 h.
The second technical scheme adopted by the invention is as follows: the bimetallic supported catalyst prepared by the preparation method of the first technical scheme is adopted.
The third technical scheme adopted by the invention is as follows:
the application of the bimetallic supported catalyst in the second technical scheme in the reaction of generating the halogenated aniline by catalytic hydrogenation of the halogenated nitrobenzene is that the mass ratio of the halogenated nitrobenzene to the metal supported by the catalyst is (7000-8500): 1, the conversion rate of the halogenated nitrobenzene reaches 100%, the selectivity of the halogenated aniline reaches more than 99%, and the product yield reaches more than 98%.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the metal supported catalyst synthesized by the prior art, the bimetallic supported catalyst prepared by the invention is used for hydrogenation reaction of halogenated nitrobenzene, and has very high activity and selectivity. Because the bimetallic supported catalyst prepared by the invention has high activity, the catalytic hydrogenation reaction temperature is 60-80 ℃, so that the energy consumption and the production safety risk can be reduced. When the molar ratio of the reaction substrate to the loaded metal reaches 8000:1, the conversion rate is up to 100%, the selectivity is up to 99%, the product yield is up to 98.1%, the high selectivity can reduce the production cost of product separation and purification, and can reduce environmental pollution at the same time.
2. Compared with the traditional method for preparing the metal-loaded catalyst by the impregnation loading method, the catalyst prepared by ultraviolet irradiation in the invention improves the catalytic performance and keeps the stability of the catalyst structure.
Drawings
FIG. 1 is an XRD spectrum of each of the catalysts synthesized in example 1 of the present invention and comparative examples 1, 2 and 3;
FIG. 2 is a graph showing the conversion rate of each catalyst synthesized in example 1 and comparative examples 1, 2 and 3, respectively, in catalytic hydrogenation of o-chloronitrobenzene according to the present invention, as a function of the molar ratio of the reaction substrate to the supported metal;
FIG. 3 is a graph showing the change of the conversion rate of each catalyst synthesized in example 1 of the present invention and comparative examples 1, 2 and 3 in the catalytic hydrogenation of o-chloronitrobenzene with the reaction temperature;
FIG. 4 is a graph showing the variation of the selectivity of each catalyst synthesized in example 1 and comparative examples 1, 2 and 3 to o-chloronitrobenzene in the catalytic hydrogenation reaction with the conversion rate;
FIG. 5 is a graph showing the yield of the o-chloronitrobenzene in the catalytic hydrogenation reaction of the catalysts of example 1 and comparative examples 1, 2 and 3 according to the present invention as a function of the conversion rate.
Detailed Description
Example 1
150g of nickel nitrate hexahydrate is weighed, deionized water is used for preparing 0.5mol/L solution, 10 mass percent of ammonia water solution is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 5h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.055 g of PdCl containing 59.5% by weight of palladium2Drying agent and 0.03 g RuCl containing 37 wt% of ruthenium3·3H2Preparing an aqueous solution from an O dry agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 32 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.15 wt% and the loading of metallic ruthenium to be 0.05 wt%; using an automatic adsorption apparatus (B)ET) test, the low-temperature nitrogen physical adsorption-desorption is carried out, and the specific surface area of the catalyst is 25.28m2(ii)/g, pore volume 0.1746cc/g, pore diameter 27.64 nm.
Example 2
150g of nickel sulfate hexahydrate is weighed, deionized water is used for preparing 0.3mol/L solution, 10 mass percent of ammonia water solution is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel sulfate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 6h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.055 g of PdCl containing 59.5% by weight of palladium2Drying agent and 0.03 g RuCl containing 37 wt% of ruthenium3·3H2Preparing an aqueous solution from an O dry agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 8 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.15 wt% and the loading of metallic ruthenium to be 0.05 wt%; the low-temperature nitrogen physical adsorption-desorption is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 25.29m2(ii)/g, pore volume 0.1747cc/g, pore diameter 27.66 nm.
Example 3
75g of nickel sulfate hexahydrate and 75g of nickel chloride hexahydrate are weighed, deionized water is used for preparing 0.5mol/L solution, 1% ammonia water solution in mass fraction is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 3h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.021 g of palladium-containing solutionPdCl in an amount of 59.5 wt%2Drying agent and 0.024 g RuCl containing 37 wt% of ruthenium3·3H2Preparing an aqueous solution from an O dry agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 32 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.06 wt% and the loading of metallic ruthenium to be 0.04 wt%; the physical adsorption-desorption of the nitrogen at low temperature is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 25.24m2(ii)/g, pore volume 0.1768cc/g, pore diameter 27.86 nm.
Example 4
50g of nickel nitrate hexahydrate, 50g of nickel sulfate hexahydrate and 50g of nickel chloride hexahydrate are weighed, deionized water is used for preparing 0.05mol/L solution, 10% ammonia water solution in mass fraction is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining at 800 ℃ for 5h in air atmosphere to obtain the active NiO carrier.
0.16 g of Pd (NO) containing 41 wt% of palladium3)2Drying agent and 0.06 g RuCl containing 37 wt% ruthenium3·3H2Preparing an aqueous solution from an O dry agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 32 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.3 wt% and the loading of metallic ruthenium to be 0.1 wt%; the low-temperature nitrogen physical adsorption-desorption is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 25.30m2(ii)/g, pore volume 0.1728cc/g, pore diameter 27.50 nm.
Example 5
Weighing 150g of nickel chloride hexahydrate, preparing 0.6mol/L solution by using deionized water, using 10% ammonia water solution as a precipitator, simultaneously dropwise adding the two solutions into a reactor filled with 100 mL of deionized water, and stirring and reacting at normal temperature. And after the dropwise addition of the nickel chloride aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 4 h at 500 ℃ in air atmosphere to obtain the active NiO carrier.
0.18 g of Pd (NO) containing 41 wt% of palladium3)2Drying agent and 0.09 g of RuCl containing 37 wt% of ruthenium3·3H2Preparing an aqueous solution from an O dry agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 72 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.35wt% and the loading of metallic ruthenium to be 0.15 wt%; the low-temperature nitrogen physical adsorption-desorption is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 25.32m2(ii)/g, pore volume 0.1695cc/g, pore diameter 27.45 nm.
Example 6
100g of nickel sulfate hexahydrate and 50g of nickel acetate tetrahydrate are weighed, deionized water is used for preparing 0.5mol/L solution, ammonia water solution with the mass fraction of 20% is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 5h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.21g of Pd (NO) containing 41 wt% of palladium3)2A dry agent and 0.15 g of (NH) containing 31 wt% of ruthenium4)2RuCl6Drying agent and 100g of deionized waterPreparing the sub-water into an aqueous solution, adding 20g of active NiO carrier, fully stirring and uniformly mixing, irradiating for 32h by using ultraviolet light while fully stirring, centrifugally washing, drying at 80 ℃ in vacuum, and calcining for 2h at 200 ℃ in air atmosphere to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.4 wt% and the loading of metallic ruthenium to be 0.2 wt%; the physical adsorption-desorption of the nitrogen at low temperature is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 25.46m2(ii)/g, pore volume 0.1661cc/g, pore diameter 27.32 nm.
Comparative example 1
150g of nickel nitrate hexahydrate is weighed, deionized water is used for preparing 0.5mol/L solution, 10 mass percent of ammonia water solution is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 5h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.055 g of PdCl containing 59.5% by weight of palladium2Drying agent and 0.03 g RuCl containing 37 wt% of ruthenium3·3H2Preparing an aqueous solution from an O dry agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring for 32h, centrifugally washing, drying at 80 ℃ in vacuum, and calcining at 200 ℃ in an air atmosphere for 2h to obtain the bimetallic supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.15 wt% and the loading of metallic ruthenium to be 0.05 wt%; the physical adsorption-desorption of the nitrogen at low temperature is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 48.39m2(ii)/g, pore volume 0.1495cc/g, pore diameter 8.45 nm.
Comparative example 2
150g of nickel nitrate hexahydrate is weighed, deionized water is used for preparing 0.5mol/L solution, 10 mass percent of ammonia water solution is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 5h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.07 g of PdCl with a palladium content of 59.5 wt%2Preparing an aqueous solution by using a drying agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 32 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the single-metal supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of metallic palladium to be 0.2 wt%; the low-temperature nitrogen physical adsorption-desorption is tested by adopting an automatic adsorption instrument (BET), and the specific surface area of the catalyst is 24.81m2(ii)/g, pore volume 0.1678cc/g, pore diameter 26.42 nm.
Comparative example 3
150g of nickel nitrate hexahydrate is weighed, deionized water is used for preparing 0.5mol/L solution, 10 mass percent of ammonia water solution is used as a precipitator, the two solutions are simultaneously dripped into a reactor filled with 100 mL of deionized water, and stirring reaction is carried out at normal temperature. And after the dropwise addition of the nickel nitrate aqueous solution is finished, continuously stirring for 1 h, then heating and boiling for 0.5h to remove ammonia gas in the solution, cooling, standing at room temperature for 2h, and then centrifugally washing until the filtrate is neutral. Vacuum drying at 80 ℃, and calcining for 5h at 600 ℃ in air atmosphere to obtain the active NiO carrier.
0.11 g of RuCl containing 37 wt% of ruthenium3·3H2Preparing an aqueous solution from an O drying agent and 100g of deionized water, adding 20g of an active NiO carrier, fully stirring and uniformly mixing, irradiating for 32 hours by using ultraviolet light while fully stirring, centrifugally washing, drying in vacuum at the temperature of 80 ℃, and calcining for 2 hours at the temperature of 200 ℃ in an air atmosphere to obtain the single-metal supported catalyst. The sample prepared above was tested by plasma emission spectroscopy (ICP) to determine the loading of ruthenium metal to be 0.2 wt%; the catalyst ratio of the low-temperature nitrogen physical adsorption-desorption is tested by adopting an automatic adsorption instrument (BET)Surface area 23.69m2(ii)/g, pore volume 0.1681cc/g, pore diameter 25.37 nm.
Referring to fig. 1, there is shown an XRD spectrum of each of the catalysts synthesized in example 1 and comparative examples 1, 2 and 3. As can be seen from fig. 1, the catalyst prepared in example 1 of the present invention exhibits a better crystal phase, and the supported metallic palladium and ruthenium are highly dispersed and uniform on the active carrier, compared to the respective catalysts synthesized in comparative examples 1, 2 and 3, and also the structural stability of the catalyst is well maintained.
Experimental example 1
The catalyst samples prepared in example 1 and comparative examples 1, 2 and 3 were subjected to o-chloronitrobenzene hydrogenation. The reaction conditions are as follows: PH value2=0.5 MPa, T =60 ℃, T =1 h, at the ratio n of the amounts of o-chloronitrobenzene and of the substance of the catalyst supporting metalSubstrate:nSupported metalIn the range of =4000-10000, the hydrogenation activity, the product yield and the product selectivity of the catalyst were evaluated. The results are shown in FIGS. 2 and 4 to 5.
Referring to FIG. 2, the curves of the conversion rate of each catalyst synthesized in example 1 and comparative examples 1, 2 and 3 according to the invention in catalytic hydrogenation reaction of o-chloronitrobenzene with the molar ratio of the reaction substrate to the supported metal are shown. The experimental results show that example 1> comparative example 2> comparative example 3> comparative example 1. For example 1, the conversion still reached 100% when the molar ratio of reaction substrate to supported metal was up to 8000:1, whereas comparative example 1 had only 50% conversion at a molar ratio of reaction substrate to supported metal of 8000:1, comparative example 2 had 86% conversion and comparative example 3 had 75% conversion. Therefore, the activity of the bimetallic supported catalyst prepared by ultraviolet irradiation is higher than that of a single-metal supported catalyst, and is obviously higher than that of a bimetallic catalyst prepared without ultraviolet irradiation.
Referring to FIGS. 4 and 5, the selectivity and yield of the o-chloronitrobenzene catalytic hydrogenation reaction according to the present invention are shown in example 1 and comparative examples 1, 2 and 3. The experimental results show that example 1 is selective > comparative example 1> comparative example 3> comparative example 2, and example 1 is yield > comparative example 3> comparative example 2> comparative example 1. For the catalyst of example 1, when the maximum yield of the product is 98.1%, the molar ratio of the reaction substrate to the supported metal is 8000:1, the conversion rate of the reactant is 100%, and the selectivity is 99%; for the catalyst of comparative example 1, when the maximum yield of the product is 56.9%, the molar ratio of the reaction substrate to the supported metal is 4000:1, the conversion rate of the reactant is 68%, and the selectivity is 84%; for the catalyst of comparative example 2, when the maximum yield of the product is 74.8%, the molar ratio of the reaction substrate to the supported metal is 6000:1, the conversion rate of the reactant is 100%, and the selectivity is 75%; for the catalyst of comparative example 3, when the maximum yield of the product was 80.8%, the molar ratio of the reaction substrate to the supported metal was 6000:1, the conversion of the reactant was 92%, and the selectivity was 88%. Therefore, the bimetallic supported catalyst prepared by the method shows the best catalytic performance for the catalytic hydrogenation reaction of o-chloronitrobenzene, and the product yield and selectivity are obviously higher than those of the catalyst prepared by the traditional impregnation method and a single metal catalyst, so that the production cost and the environmental pollution are more favorably reduced.
Experimental example 2
The catalyst samples prepared in example 1 and comparative examples 1, 2 and 3 were subjected to o-chloronitrobenzene hydrogenation. The reaction conditions are as follows: PH value2=0.5 MPa, the ratio n of the amounts of o-chloronitrobenzene and the metal-carrying substance of the catalystSubstrate:nSupported metal=9000, t =1 h, and the hydrogenation activity, product yield, and product selectivity of the catalyst were evaluated in the range of 40-160 ℃. The results are shown in FIG. 3.
Referring to FIG. 3, the curves of the conversion rate of each catalyst synthesized in example 1 and comparative examples 1, 2 and 3 according to the present invention in catalytic hydrogenation of o-chloronitrobenzene with reaction temperature are shown. The experimental results show that example 1> comparative example 2> comparative example 3> comparative example 1. Therefore, the activity of the bimetallic supported catalyst prepared by ultraviolet irradiation is higher than that of a single-metal supported catalyst, and is obviously higher than that of a bimetallic catalyst prepared without ultraviolet irradiation.
Experimental examples 1 and 2 show that the bimetallic catalyst prepared in example 1 is applied to the catalytic hydrogenation reaction of o-chloronitrobenzene, and the amount ratio of the o-chloronitrobenzene to the metal-loaded substance of the bimetallic supported catalyst is (7000-8500): 1, the conversion rate of o-chloronitrobenzene reaches 100%, the selectivity of o-chloroaniline reaches more than 99%, and the product yield reaches more than 98%. Compared with the catalyst prepared by the traditional impregnation method, the catalyst prepared by the method disclosed by the embodiment of the invention has better catalytic performance, and meanwhile, the stability of the catalyst structure is kept, so that the production cost and the environmental pollution can be reduced.
Experimental example 3
The catalyst samples prepared in examples 1, 2, 3 and 4 were subjected to o-bromonitrobenzene hydrogenation. The reaction conditions are as follows: PH value2=0.5 MPa, the ratio n of the amounts of o-bromonitrobenzene and the metal-carrying substance of the catalystSubstrate:nSupported metal= 7000-8500: 1, t =1 h, in the range of 60-80 ℃, the hydrogenation activity, product yield and product selectivity of the catalyst were evaluated.
Experimental example 3 is carried out on the basis of the preferable reaction conditions of the experimental examples 1 and 2, and the experimental results show that the bimetallic catalysts prepared in the examples 1, 2, 3 and 4 are applied to the o-bromonitrobenzene catalytic hydrogenation reaction, the o-bromonitrobenzene and the bimetallic supported catalyst are supported at the temperature of 60-80 ℃, and the ratio of the amounts of the substances of the o-bromonitrobenzene and the bimetallic supported catalyst is (7000-) -8500): 1, the conversion rate of o-bromonitrobenzene reaches 100%, the selectivity of o-bromoaniline reaches more than 99%, and the product yield reaches more than 98%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a bimetal supported catalyst is characterized by comprising the following steps:
at room temperature, simultaneously dropwise adding the nickel salt solution and the ammonia water solution, mixing and stirring for reaction, and continuously stirring for reaction for 0.5-3 h after the dropwise adding of the nickel salt solution is finished;
heating and boiling the mixed solution after the stirring reaction to remove ammonia gas, cooling to room temperature, standing for 1-3h, and performing first centrifugal washing, vacuum drying and calcining to obtain an active carrier; and
preparing aqueous solution of palladium salt and ruthenium salt, adding the active carrier, fully stirring and uniformly mixing, irradiating by ultraviolet light, and carrying out secondary centrifugal washing, vacuum drying and calcining to obtain the bimetallic supported catalyst.
2. The method for preparing a bimetallic supported catalyst as in claim 1, wherein the nickel salt is selected from any one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate, and Ni is contained in the nickel salt solution2+The concentration of (A) is 0.05-0.6 mol/L.
3. The method for preparing a bimetallic supported catalyst as in claim 1, wherein the concentration of the aqueous ammonia solution is 1-20 wt%, preferably 5-10 wt%.
4. The method for preparing the bimetallic supported catalyst as in claim 1, wherein the solvents for washing in the first centrifugal washing, vacuum drying and calcining treatment are deionized water and ethanol, the vacuum drying temperature is 60-90 ℃, the calcining atmosphere is air, the calcining temperature is 500-800 ℃, and the calcining time is 3-6 h;
the solvents in the second centrifugal washing, vacuum drying and calcining treatment are deionized water and ethanol, and the vacuum drying temperature is 60-90 ℃; the calcining atmosphere is air, the calcining temperature is 100-300 ℃, and the calcining time is 1-3 h.
5. The process for preparing a bimetallic supported catalyst as in claim 1, wherein the palladium salt is selected from any one or more of palladium nitrate, palladium sulfate, palladium chloride and palladium acetate;
the ruthenium salt is selected from one or more of ruthenium nitrate, ruthenium sulfate, ruthenium chloride and ammonium chlororuthenate.
6. The method for preparing a bimetallic supported catalyst as in claim 1 or 5, wherein the mass ratio of the total mass of the palladium salt and the ruthenium salt to the active carrier is 1: 40-600.
7. The process for preparing a bimetallic supported catalyst as in claim 1, wherein the total amount of the palladium and ruthenium is 0.1-0.6 wt%, preferably 0.1-0.3 wt%.
8. The method for preparing a bimetallic supported catalyst as in claim 1, wherein the UV irradiation time is 8-72 h, preferably 24-32 h.
9. A bimetallic supported catalyst obtainable by the process according to any one of claims 1 to 8.
10. Use of the bimetallic supported catalyst of claim 9 in the catalytic hydrogenation of nitrohalogenated benzenes to haloanilines, characterized in that the ratio of the amounts of nitrohalogenated benzene and metal-supported catalyst material is (7000-8500): 1, the conversion rate of the halogenated nitrobenzene reaches 100%, the selectivity of the halogenated aniline reaches more than 99%, and the product yield reaches more than 98%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111506935.3A CN114308062A (en) | 2021-12-10 | 2021-12-10 | Preparation method and application of bimetallic supported catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111506935.3A CN114308062A (en) | 2021-12-10 | 2021-12-10 | Preparation method and application of bimetallic supported catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114308062A true CN114308062A (en) | 2022-04-12 |
Family
ID=81051526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111506935.3A Pending CN114308062A (en) | 2021-12-10 | 2021-12-10 | Preparation method and application of bimetallic supported catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114308062A (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4361500A (en) * | 1979-05-22 | 1982-11-30 | Magyar Tudomanyos Akademia Kosponti Hivatala | Process for the preparation of supported metal catalysts |
KR20020040011A (en) * | 2000-11-23 | 2002-05-30 | 김상남 | Catalyst manufacturing method for Brown gas |
JP2008104906A (en) * | 2006-10-23 | 2008-05-08 | Catalysts & Chem Ind Co Ltd | Method for manufacturing catalyst for removing carbon monoxide |
CN101658788A (en) * | 2009-09-24 | 2010-03-03 | 西华师范大学 | Catalyst for greenly synthesizing halogenated arylamine by means of high-efficiency catalytic hydrogenation of halogenated aromatic nitro compound and preparation method thereof |
CN106732568A (en) * | 2016-12-07 | 2017-05-31 | 南京大学 | A kind of preparation method and application of parachloronitrobenzene selective hydrogenation parachloroanilinum catalyst |
CN109569686A (en) * | 2018-11-28 | 2019-04-05 | 浙江工业大学 | The preparation and the application in halonitro benzene hydrogenation that nitrogen modifies charcoal supported noble metal hydrogenation catalyst |
CN113398924A (en) * | 2021-05-28 | 2021-09-17 | 烟台大学 | Metal catalyst and preparation and application thereof |
CN113578316A (en) * | 2021-08-27 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene |
-
2021
- 2021-12-10 CN CN202111506935.3A patent/CN114308062A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4361500A (en) * | 1979-05-22 | 1982-11-30 | Magyar Tudomanyos Akademia Kosponti Hivatala | Process for the preparation of supported metal catalysts |
KR20020040011A (en) * | 2000-11-23 | 2002-05-30 | 김상남 | Catalyst manufacturing method for Brown gas |
JP2008104906A (en) * | 2006-10-23 | 2008-05-08 | Catalysts & Chem Ind Co Ltd | Method for manufacturing catalyst for removing carbon monoxide |
CN101658788A (en) * | 2009-09-24 | 2010-03-03 | 西华师范大学 | Catalyst for greenly synthesizing halogenated arylamine by means of high-efficiency catalytic hydrogenation of halogenated aromatic nitro compound and preparation method thereof |
CN106732568A (en) * | 2016-12-07 | 2017-05-31 | 南京大学 | A kind of preparation method and application of parachloronitrobenzene selective hydrogenation parachloroanilinum catalyst |
CN109569686A (en) * | 2018-11-28 | 2019-04-05 | 浙江工业大学 | The preparation and the application in halonitro benzene hydrogenation that nitrogen modifies charcoal supported noble metal hydrogenation catalyst |
CN113398924A (en) * | 2021-05-28 | 2021-09-17 | 烟台大学 | Metal catalyst and preparation and application thereof |
CN113578316A (en) * | 2021-08-27 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene |
Non-Patent Citations (2)
Title |
---|
倪永红: "辐射技术与材料合成", 31 July 2011, 安徽师范大学出版社, pages: 95 - 97 * |
施嘉杰;谢旅维;林诚宇;林棋;: "对氯硝基苯加氢反应的高效催化剂研究", 闽江学院学报, no. 02, pages 1 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110270348B (en) | Noble metal monatomic catalyst and preparation and application thereof | |
CN113019414B (en) | Hydrogenation catalyst, preparation method and application thereof | |
CN109569686B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of halogenated nitrobenzene | |
CN109317139B (en) | Preparation of sulfur-doped activated carbon-supported noble metal catalyst and application of sulfur-doped activated carbon-supported noble metal catalyst in hydrogenation reaction of halogenated aromatic nitro compound | |
CN105833864B (en) | A kind of support type nano spherical particle palladium catalyst and its preparation method and application | |
CN105195140B (en) | A kind of palladium/alkali metal compound loaded catalyst and its preparation method and application | |
CN106540698A (en) | A kind of preparation method of the loading type nickel-based catalyst of chloronitrobenzene selective hydrogenation synthesis chloro aminobenzen | |
CN114849694B (en) | Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof | |
CN109453779A (en) | A kind of TiO2The preparation method and application of the sepiolite supported type nickel-base catalyst of modification | |
Zhang et al. | Nickel-decorated gC 3 N 4 hollow spheres as an efficient photocatalyst for hydrogen evolution and oxidation of amines to imines | |
CN105797719B (en) | Load type double-metal/multimetal reforming catalyst and preparation method and application for m-nitrobenzene sulfonic acid hydrogenation synthesis metanilic acid | |
CN110813356A (en) | CdIn2S4-C3N4Composite photocatalyst and preparation method and application thereof | |
Ma et al. | The preparation and photocatalytic activity of Ag-Pd/g-C3N4 for the coupling reaction between benzyl alcohol and aniline | |
CN107970967B (en) | Preparation method of catalyst for preparing chloroarylamine by catalytic hydrogenation | |
CN102553583B (en) | Mesoporous carbon-loaded gold nano catalyst and application thereof | |
CN109759109B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of nitrobenzene compounds | |
CN111185214A (en) | Alumina biomass charcoal composite material, preparation method and application thereof | |
CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
CN113976131A (en) | Heterogeneous catalyst and method for preparing 2, 5-furandimethylamine from 5-hydroxymethylfurfural | |
CN102909034A (en) | Preparation of supported gold-nickel alloy nanocatalyst | |
CN111408398B (en) | Nitrogen-doped mesoporous carbon supported metal catalyst and preparation method and application thereof | |
CN114308062A (en) | Preparation method and application of bimetallic supported catalyst | |
CN111389398A (en) | Preparation method of hierarchical hollow silica confinement cuprous oxide visible-light-driven photocatalyst | |
CN115301277A (en) | Bimetallic nitrogen heterocyclic carbon catalyst and preparation method and application thereof | |
CN110116018B (en) | Noble metal-coated silicon molecular sieve catalytic material 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 |