CN107442134B - Rhodium/nickel alloy nano catalyst and preparation method and application thereof - Google Patents
Rhodium/nickel alloy nano catalyst and preparation method and application thereof Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 99
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 71
- 229910000629 Rh alloy Inorganic materials 0.000 title claims abstract description 69
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 20
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims abstract description 8
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003607 modifier Substances 0.000 claims description 13
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- PWDGLIWNOMOQHM-UHFFFAOYSA-N ethanol;hydrazine;hydrate Chemical compound O.NN.CCO PWDGLIWNOMOQHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 12
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 20
- 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 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000007405 data analysis Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- DAQWSROBHHTPDO-UHFFFAOYSA-N [Ni].[Rh] Chemical compound [Ni].[Rh] DAQWSROBHHTPDO-UHFFFAOYSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 238000005275 alloying Methods 0.000 description 1
- -1 aminopropyl Chemical group 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a rhodium/nickel alloy nano catalyst and a preparation method and application thereof, belonging to the field of nano catalyst research; the catalyst is spherical and polyhedral rhodium/nickel alloy nano particles, the size distribution of the prepared rhodium/nickel alloy nano catalyst particles is 12-58nm, and the molar ratio of rhodium to nickel in the catalyst is 0.01-0.05: 1; the method takes nickel acetate and rhodium trichloride as raw materials to prepare rhodium/nickel nano alloy catalysts with different particle sizes and microstructures, then takes 1-nitroanthraquinone and hydrogen as raw materials, adopts the catalysts to carry out reaction, raises the reaction temperature to 100-160 ℃, and carries out heat preservation reaction for 2-8h to obtain high-purity 1-aminoanthraquinone; the catalyst prepared by the invention has the advantages of low consumption, high catalytic activity and high stability; the method for preparing the 1-aminoanthraquinone by adopting the catalyst has simple process requirements, is green and environment-friendly, and is suitable for industrial requirements.
Description
Technical Field
The invention relates to a rhodium/nickel alloy nano catalyst and a preparation method and application thereof, belonging to the field of nano catalyst research.
Technical Field
The 1-aminoanthraquinone is one of important intermediate of anthraquinone dye, and has wide use range and great use amount. With the development of dye industry, the demand of 1-aminoanthraquinone is very large at home and abroad. In China, 1-nitroanthraquinone is usually used as a raw material in the industrial production technology of 1-aminoanthraquinone, and the 1-nitroanthraquinone is prepared by reduction of sodium hydrosulfite, sodium sulfide and the like and reoxidation. The products produced by the processes have stable quality, low production cost, simple operation and low technical difficulty, but can generate a large amount of environmental pollutants, and the treatment pressure of the three wastes is very high; the same problem exists with the sulphonation ammoniation process. The ammonolysis method generates less environmental pollutants, but needs to carry out the reaction under higher pressure, the ammonium nitrite generated in the reaction can be rapidly decomposed in water, and the heating at high temperature has explosion danger, thereby having the problem of production safety. In order to solve the problems, a new process which is clean, efficient, simple in process, low in cost and high in product purity needs to be developed on the basis of the existing production method.
The catalytic hydrogenation reduction method is a green process at present, and compared with an alkali sulfide method, the catalytic hydrogenation reduction method does not generate a large amount of sulfur-containing waste liquid which is difficult to treat, and the product yield is high. In addition, some green processes, such as hydrazine hydrate method, electrochemical method and the like, are available, but the process still stays in the laboratory research stage due to higher cost, and the industrial value is not reflected. Therefore, the research on the synthesis of the 1-aminoanthraquinone through the selective hydrogenation of the 1-nitroanthraquinone under the catalysis of the rhodium/nickel alloy nano catalyst has important research significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a rhodium/nickel alloy nano catalyst which is used for catalytically synthesizing 1-aminoanthraquinone. The preparation method of the catalyst is simple, does not generate three wastes, and is green and environment-friendly; meanwhile, the catalyst is less in dosage, high in catalytic activity, high in selectivity and stable in performance when the 1-aminoanthraquinone is catalytically synthesized.
The technical scheme of the invention is as follows:
the invention firstly provides a rhodium/nickel alloy nano catalyst which is spherical and polyhedral rhodium/nickel alloy nano particles, and the size distribution of the prepared rhodium/nickel alloy nano catalyst particles is 12-58 nm.
A preparation method of a rhodium/nickel alloy nano catalyst is characterized in that rhodium trichloride and nickel acetate are used as raw materials, hydrazine hydrate or sodium borohydride is used as a reducing agent, and the rhodium/nickel alloy nano catalyst is prepared in the presence of an organic modifier.
The preparation method comprises the following specific steps:
according to different proportions of metal rhodium and metal nickel in a rhodium/nickel alloy nano catalyst, accurately weighing a certain amount of metal precursors of rhodium trichloride and nickel acetate of Rh and Ni, respectively dissolving the metal precursors of rhodium trichloride and nickel acetate in 40mL of absolute ethanol solution, stirring and mixing, adding 20mL of ethanol solution of an organic modifier, mixing and stirring at 30-60 ℃ for 20min, adjusting the pH value of a reaction solution by using NaOH ethanol solution with a certain concentration, then after the temperature is raised to 70 ℃, dropwise adding 100mL of hydrazine hydrate ethanol solution or sodium borohydride ethanol solution with a certain concentration into the reaction solution, reacting for 4-8h, washing with absolute ethanol for multiple times, and drying in vacuum to obtain the required catalyst.
In the above preparation method, the ethanol solution of the organic modifier, the ethanol solution of NaOH, the ethanol solution of hydrazine hydrate or the ethanol solution of sodium borohydride is a solution obtained by dissolving the organic modifier in absolute ethanol, and the concentrations of the organic modifier and the hydrazine hydrate are the concentrations of the substances in absolute ethanol.
Wherein the organic modifier is 3- (aminopropyl) triethoxysilane (APTS), and the mass of the organic modifier is 10 wt% of the total mass of Rh and Ni precursors.
The molar ratio of rhodium to nickel in the alloy nano catalyst prepared by the method is 0.01-0.05: 1.
Wherein, the pH value of the reaction solution is adjusted to 10-14 by adopting 0.5-1.5mol/L ethanol solution of NaOH.
Wherein the concentration of the ethanol solution of hydrazine hydrate or the ethanol solution of sodium borohydride is 0.5-0.9 mol/L.
The rhodium/nickel alloy nano metal catalyst prepared by the preparation method is applied to catalytic synthesis of 1-aminoanthraquinone, and the synthesis steps are as follows:
(1) putting 1-nitroanthraquinone and N, N-Dimethylformamide (DMF) into a reaction kettle, and adding a rhodium/nickel alloy nano catalyst, wherein the proportion of the 1-nitroanthraquinone to the DMF to the rhodium/nickel alloy nano catalyst is as follows: 3g, 150mL, 0.03g to 0.3 g;
(2) installing a reaction device, introducing nitrogen to purge for about 5 minutes, removing air in the reaction kettle, introducing high-purity hydrogen, increasing the pressure to 0.5-1.0MPa, slowly heating to 160 ℃ and keeping the temperature for reaction for 2-8 hours, wherein the stirring speed is 600 r/min;
(3) after the reaction was complete, the reaction mass was cooled to room temperature. The samples were analyzed by liquid chromatography.
The invention has the advantages that:
the rhodium/nickel alloy nano catalyst is prepared in the presence of an organic modifier, namely silane coupling agent APTS, and the steric hindrance effect and the electrostatic effect of the silane coupling agent APTS and functional groups such as aminopropyl, ethoxy and the like of the silane coupling agent APTS. The influence of the modifier on the size, the morphology and the microstructure of the rhodium/nickel alloy nano particles is not reported so far. Under the experimental condition, the silane coupling agent APTS induces and generates spherical and polyhedral rhodium/nickel alloy nano particles, the size distribution of the prepared rhodium/nickel alloy nano catalyst particles is 12-58nm, and the rhodium/nickel alloy nano catalyst particles have good dispersibility and better catalytic activity and stability in the catalytic reaction process.
The method for preparing 1-aminoanthraquinone by anthraquinone sulfonation and ammonolysis, nitration-substitution, anthraquinone nitration and reduction and the like has a great deal of pollution, and the 1-nitroanthraquinone catalytic hydrogenation method is distinguished by the advantages of environmental protection. The unitary nano Pd, Ni and other catalysts commonly used for the reaction of selectively hydrogenating 1-nitroanthraquinone to generate 1-aminoanthraquinone have the defects of easy agglomeration, easy deactivation, poor stability and the like, and the binary alloy nano metal catalyst becomes a new research hotspot due to better stability and higher catalytic performance. In the invention, the rhodium/nickel alloy nano catalyst is firstly adopted to be applied to the reaction of preparing 1-aminoanthraquinone by hydrogenating 1-nitroanthraquinone. Alloying of metal in the rhodium/nickel alloy nano catalyst prepared under the experimental condition not only improves the sintering resistance of particles, but also changes the electronic performance and the geometric structure of active components of the catalyst, and shows more excellent catalytic activity and selectivity in the selective hydrogenation reaction of catalytic nitroarene. The catalytic activity of the rhodium/nickel alloy nano catalyst is not only influenced by the size and the shape of the rhodium/nickel alloy nano catalyst, but also the proportion of rhodium and nickel in the catalyst is an important factor influencing the activity of the catalyst. Experiments show that when the ratio of rhodium to nickel is 0.04:1, under the experimental conditions, the conversion rate of raw materials and the selectivity of products in the reaction of preparing 1-aminoanthraquinone by hydrogenating 1-nitroanthraquinone are both 100%. The catalyst has high activity, good stability and mild reaction conditions, avoids high-temperature and high-pressure reaction, thereby avoiding the generation of a large amount of byproducts, improving the selectivity of the catalyst, ensuring high product purity and being beneficial to the further development of downstream products.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1:
(1) preparation of the catalyst:
rhodium trichloride and nickel acetate are used as raw materials, hydrazine hydrate is used as a reducing agent, and the rhodium/nickel alloy nano catalyst is prepared in the presence of an organic modifier.
When the molar ratio of rhodium to nickel is 0.04:1, the rhodium/nickel alloy catalyst (Rh/Ni alloy)0.04Ni) preparation: 0.2106g of RhCl were weighed out separately3·3H2O, 4.9768g of C4H6NiO4.4H2O and 0.5187g of 3- (aminopropyl) triethoxysilane (APTS) were dissolved in 50mL, 90mL and 20mL of absolute ethanol by ultradispersion to give RhCl3·3H2O and C4H6NiO4.4H2Mixing the ethanol solution of O with ethanol solution of 3- (aminopropyl) triethoxysilane (APTS) at 50 deg.C under stirring for 20 min. Adjusting pH to 13 with 0.8mol/L ethanol solution of NaOH, dropwise adding 100mL of 0.75mol/L anhydrous ethanol solution of hydrazine hydrate into the reaction solution, reacting at 70 deg.C for 6h, washing the product with ethanol for several times, and vacuum drying to obtain Rh0.04Ni alloy nano catalyst.
(2) 1-nitroanthraquinone selective catalytic hydrogenation is carried out to prepare 1-aminoanthraquinone:
3g of 1-nitroanthraquinone and 0.24g of Rh were accurately weighed0.04Weighing 150mL of DMF (dimethyl formamide) of a Ni alloy nano catalyst, and placing the obtained product in a high-pressure reaction kettle; introducing high-purity nitrogen to replace air for 5min, introducing hydrogen to the pressure of 0.8MPa, sealing the reaction kettle, stirring at the speed of 600rpm, and reacting at the temperature of 130 ℃ for 6 h. After the reaction is finished, the product is subjected to sample composition analysis by using a high performance liquid chromatography by adopting an external standard method. The product selectivity and feedstock conversion are shown in table 1.
Example 2:
as in example 1, only the catalyst amounts were changed: 0.03g, 0.09g, 0.15g, 0.24g, 0.3g, 1-nitroanthraquinone selective hydrogenation reaction was carried out. The product selectivity and feedstock conversion are shown in table 1.
Table 1 shows the values at 0.8MPa H2Under the pressure, the reaction temperature is 130 ℃, the reaction is carried out for 6 hours under the condition of heat preservation, and when the dosage of the catalyst is different, the rhodium/nickel alloy nano catalyst selectively catalyzes the selectivity of 1-aminoanthraquinone which is a hydrogenation reaction product of 1-nitroanthraquinone and the conversion rate of the raw materials; according to the data analysis in table 1, the dosage of the rhodium/nickel alloy nano catalyst has an important influence on the catalytic activity of the catalyst in the reaction of selectively catalyzing 1-nitroanthraquinone to prepare 1-aminoanthraquinone through hydrogenation. When the dosage of the rhodium/nickel alloy nano catalyst is 0.24g, under the experimental condition, the conversion rate of the 1-nitroanthraquinone and the selectivity of the 1-aminoanthraquinone are both 100 percent.
TABLE 1 influence of different catalyst dosages on the selectivity and raw material conversion rate of catalytically synthesized 1-nitroanthraquinone
Example 3:
as in example 1, only the temperature of the autoclave was changed to: the selective hydrogenation reaction of 1-nitroanthraquinone is carried out at 100 ℃, 110 ℃, 130 ℃, 150 ℃ and 160 ℃. The product selectivity and feedstock conversion are shown in table 2.
Table 2 shows the values of H at 0.8MPa2Reacting for 6 hours under the conditions of pressure and catalyst dosage of 0.24g and different reaction temperatures under heat preservation, wherein the rhodium/nickel alloy nano catalyst selectively catalyzes the selectivity of 1-aminoanthraquinone, a 1-nitroanthraquinone hydrogenation reaction product, and the conversion rate of raw materials; according to the data analysis in table 2, under the experimental conditions, the reaction temperature has an important influence on the catalytic activity of the rhodium/nickel alloy nano catalyst in the reaction of selectively catalyzing 1-nitroanthraquinone to prepare 1-aminoanthraquinone. When the reaction temperature is 130 ℃, the conversion rate of the 1-nitroanthraquinone and the selectivity of the 1-aminoanthraquinone are both 100 percent. When the reaction temperature is lower, the conversion rate of the 1-nitroanthraquinone is lower; when the reaction temperature is higher, a large amount of byproducts are generated, and the selectivity of the target product 1-aminoanthraquinone is reduced.
TABLE 2 influence of different translation temperatures on the selectivity and conversion of starting materials for the catalytic synthesis of 1-nitroanthraquinone
Example 4:
as in example 1, only the reaction times were changed to: and carrying out selective hydrogenation reaction on the 1-nitroanthraquinone for 2h, 4h, 6h and 8 h. The product selectivity and feedstock conversion are shown in table 3.
Table 3 shows the measured values at 0.8MPa H2Under the pressure and the catalyst dosage of 0.24g, the reaction temperature is 130 ℃, and under different reaction times, the rhodium/nickel alloy nano catalyst selectively catalyzes the selectivity of 1-aminoanthraquinone which is a 1-nitroanthraquinone hydrogenation reaction product and the conversion of raw materialsThe conversion rate; according to the data analysis in table 3, under the experimental conditions, the reaction time has an important influence on the catalytic activity of the rhodium/nickel alloy nano catalyst in the reaction of selectively catalyzing 1-nitroanthraquinone to prepare 1-aminoanthraquinone. When the reaction time is 6 hours, the conversion rate of the 1-nitroanthraquinone and the selectivity of the 1-aminoanthraquinone are both 100 percent. When the reaction time is short, the reaction is insufficient, and the conversion rate of the 1-nitroanthraquinone is low; when the reaction time is longer, a small amount of by-products are generated, and the selectivity of the target product 1-aminoanthraquinone is reduced.
TABLE 3 influence of different reaction times on the selectivity and conversion of the starting materials for the catalytic synthesis of 1-nitroanthraquinone
Example 5:
in the same way as example 1, only the ratio of rhodium to nickel in step 1 is changed as follows: 0:1, 0.01:1, 0.04:1, 0.05:1, 1:0, mixing RhCl3·3H2The quality of O is changed as follows: 0g, 0.0527g, 0.1053g, 0.1580g, 0.2106g, 0.2633g and 0.2633g, respectively to prepare Ni and Rh0.01Ni、Rh0.02Ni、Rh0.03Ni、Rh0.04Ni、Rh0.05Ni and Rh nano alloy catalyst is subjected to 1-nitroanthraquinone selective hydrogenation reaction. In order to compare with the catalytic performance of the rhodium/nickel nano alloy catalyst, the rhodium-nickel composite catalyst (Rh) is prepared by the molar ratio of rhodium to nickel being 0.04:10.04@ Ni) to carry out 1-nitroanthraquinone selective hydrogenation reaction. The product selectivity and feedstock conversion are shown in table 4.
Table 4 shows the values at 0.8MPa H2Under the pressure, when the dosage of the catalyst is 0.24g, the reaction temperature is 130 ℃, the reaction is carried out for 6 hours under the condition of heat preservation, and the rhodium/nickel alloy nano catalyst with different rhodium-nickel molar ratios selectively catalyzes the selectivity of the 1-aminoanthraquinone hydrogenation reaction product and the conversion rate of the raw materials.
According to the data analysis in table 4, under the experimental conditions, the composition of the catalyst has an important influence on the catalytic activity of the rhodium/nickel alloy nano catalyst in the reaction of selectively catalyzing 1-nitroanthraquinone to prepare 1-aminoanthraquinone. When the molar ratio of rhodium to nickel in the catalyst isAt 0.04:1, the conversion of 1-nitroanthraquinone and the selectivity of 1-aminoanthraquinone were both 100%. The conversion rate of the 1-nitroanthraquinone is improved along with the increase of the molar ratio of the rhodium to the nickel, but when the molar ratio of the rhodium to the nickel is higher than 0.04, byproducts are generated, and the selectivity of the target product 1-aminoanthraquinone is reduced. And comparing Rh with a core-shell structure0.04The Rh/Ni alloy nanoparticles prepared by the experiment show more excellent catalytic activity, and show that the morphology and the microstructure have important influence on the catalytic activity of the binary alloy nano metal catalyst.
TABLE 4 influence of rhodium/nickel alloy nanocatalysts of different rhodium-to-nickel molar ratios on the selectivity and raw material conversion rate of catalytic synthesis of 1-nitroanthraquinone
Example 6:
in the same manner as in example 1, only the pH of the reaction solution during the catalyst preparation was changed to: 10. 11, 12, 13 and 14, and carrying out selective hydrogenation reaction on the 1-nitroanthraquinone. The product selectivity and feedstock conversion are shown in table 5.
Table 5 shows the measured values at 0.8MPa H2Under the pressure, when the dosage of the catalyst is 0.24g, the reaction temperature is 130 ℃, the reaction is carried out for 6 hours under the condition of heat preservation, and the selectivity of the 1-aminoanthraquinone hydrogenation reaction product 1-aminoanthraquinone and the conversion rate of the raw materials are selectively catalyzed by the rhodium/nickel alloy nano catalyst prepared in the reaction liquid with different pH values.
According to the data analysis in table 5, in the process of preparing the rhodium/nickel alloy nano catalyst under the experimental conditions, the pH value has important influence on the size, the morphology and the crystal structure of the prepared rhodium/nickel alloy nano particles, and influences the catalytic activity of the rhodium/nickel alloy nano particles in catalyzing the hydrogenation of 1-nitroanthraquinone to prepare 1-aminoanthraquinone. When the pH value is 13, the average particle size of the prepared rhodium/nickel alloy nano particles is 21nm, the particles have a spherical polycrystalline structure, and the surfaces of the particles have point defects. When the alloy nano-particles are used as a catalyst, the conversion rate of the 1-nitroanthraquinone and the selectivity of the 1-aminoanthraquinone are both 100 percent. With the increase of the pH value, the particle size of the particles is gradually reduced, and the microstructure of the particles is changed. When the pH value is 13, the average particle size of the rhodium/nickel alloy nanoparticles is 12nm, but no point defects exist on the surface, the conversion rate of the 1-nitroanthraquinone is 97.6 percent, and the selectivity of the 1-aminoanthraquinone is 96.7 percent.
TABLE 5 influence of rhodium/nickel alloy nanocatalysts prepared under different pH values on the selectivity and raw material conversion rate of catalytic synthesis of 1-nitroanthraquinone
Example 7:
as in example 1, the concentration of the hydrazine hydrate ethanol solution during the catalyst preparation was changed only as follows: 0.5mol/L, 0.65mol/L, 0.75mol/L and 0.9mol/L, and carrying out 1-nitroanthraquinone selective hydrogenation reaction. The product selectivity and feedstock conversion are shown in Table 6.
TABLE 6 at 0.8MPa H2Under the pressure, when the dosage of the catalyst is 0.24g, the reaction temperature is 130 ℃, the reaction is carried out for 6 hours under the condition of heat preservation, and the selectivity of the 1-aminoanthraquinone hydrogenation reaction product 1-aminoanthraquinone and the conversion rate of the raw materials are selectively catalyzed by the rhodium/nickel alloy nano catalyst prepared under different hydrazine hydrate concentrations.
According to data analysis in table 6, in the process of preparing the rhodium/nickel alloy nano catalyst under the experimental conditions, the concentration of the reducing agent hydrazine hydrate has important influence on the size, the morphology and the crystal structure of the prepared rhodium/nickel alloy nano particles, and influences the catalytic activity of the rhodium/nickel alloy nano particles in catalyzing the hydrogenation of 1-nitroanthraquinone to prepare 1-aminoanthraquinone. When the concentration of hydrazine hydrate is 0.75mol/L, the average particle size of the prepared rhodium/nickel alloy nano particles is 21nm, the particles have a spherical polycrystalline structure, and the surfaces of the particles have point defects. When the alloy nano-particles are used as a catalyst, the conversion rate of the 1-nitroanthraquinone and the selectivity of the 1-aminoanthraquinone are both 100 percent. With the hydrazine hydrate concentration of 0.9mol/L, the average particle size of the prepared spherical rhodium/nickel alloy nano particles is 19nm, and the agglomeration phenomenon occurs.
TABLE 6 influence of catalysts prepared from ethanol solutions of hydrazine hydrate of different concentrations on the selectivity and conversion of starting materials for the catalytic synthesis of 1-nitroanthraquinone
Example 8:
as in example 1, the concentration of the NaOH in ethanol solution during the catalyst preparation was changed only to: 0.5mol/L, 0.8mol/L, 1.0mol/L and 1.5mol/L, and carrying out 1-nitroanthraquinone selective hydrogenation reaction. The product selectivities and feedstock conversions are shown in Table 7.
Table 7 shows the measured values at 0.8MPa H2Under the pressure, when the catalyst dosage is 0.24g, the reaction temperature is 130 ℃, and the rhodium/nickel alloy nano catalyst prepared under different NaOH concentrations is reacted for 6 hours under the heat preservation condition to selectively catalyze the selectivity of the 1-aminoanthraquinone hydrogenation reaction product 1-nitroanthraquinone and the conversion rate of the raw materials.
According to data analysis in table 7, in the process of preparing the rhodium/nickel alloy nano catalyst under the experimental conditions, the concentration of the NaOH ethanol solution has an important influence on the dispersibility and size of the prepared rhodium/nickel alloy nano particles, and influences the catalytic activity of the prepared rhodium/nickel alloy nano particles in catalyzing hydrogenation of 1-nitroanthraquinone to prepare 1-aminoanthraquinone. When the concentration of the NaOH ethanol solution is 0.8mol/L, the average particle size of the prepared rhodium/nickel alloy nano particles is 21nm, the particles have a spherical polycrystalline structure, and the surfaces of the particles have point defects. When the alloy nano-particles are used as a catalyst, the conversion rate of the 1-nitroanthraquinone and the selectivity of the 1-aminoanthraquinone are both 100 percent. Along with the increase of the concentration of the NaOH ethanol solution, the particle size agglomeration phenomenon is obvious, and the catalytic activity of the catalyst is reduced. When rhodium/nickel alloy nanoparticles prepared under the condition that the concentration of NaOH ethanol solution is 1.5mol/L are selected as the catalyst, the conversion rate of 1-nitroanthraquinone is 65.2 percent, and the selectivity of 1-aminoanthraquinone is 68.1 percent.
TABLE 7 influence of catalysts prepared from NaOH ethanol solutions of different concentrations on the selectivity and feedstock conversion for the catalytic synthesis of 1-nitroanthraquinone
Example 9:
in the same way as in example 1, in the catalyst preparation process, 0.5mol/L ethanol solution of sodium borohydride is used as a reducing agent, 1.5mol/L ethanol solution of NaOH is used to adjust the pH value of the solution, and the particle size of the prepared rhodium/nickel alloy nanoparticles is 48 nm. The catalyst is used for carrying out 1-nitroanthraquinone selective hydrogenation reaction. At 0.8MPa H2Under the pressure, when the dosage of the catalyst is 0.24g, the reaction temperature is 130 ℃, the reaction is carried out for 6 hours under the condition of heat preservation, the selectivity of the prepared rhodium/nickel alloy nano catalyst for selectively catalyzing 1-nitroanthraquinone hydrogenation reaction product 1-aminoanthraquinone is 63.9 percent, and the conversion rate of the raw material is 57.6 percent. Comparative example 1 rhodium/nickel catalysts were prepared with different particle sizes under different reducing agent conditions. At the same time, it has further been demonstrated that particle size has a significant influence on its catalytic activity.
Claims (6)
1. A preparation method of a rhodium/nickel alloy nano catalyst is characterized by comprising the following specific preparation steps:
accurately weighing a certain amount of metal precursors of Rh and Ni, namely rhodium trichloride and nickel acetate, respectively dissolving the metal precursors of Rh and Ni in an absolute ethanol solution, stirring and mixing, adding an ethanol solution of an organic modifier, mixing and stirring at 30-60 ℃, adjusting the pH value of a reaction solution to 10-14 by using a NaOH ethanol solution with a certain concentration, dropwise adding a hydrazine hydrate ethanol solution or a sodium borohydride ethanol solution with a concentration of 0.5-0.9mol/L into the reaction solution after the temperature is raised to 70 ℃, reacting for 4-8h, washing the reaction solution for multiple times by using absolute ethanol, and drying in vacuum to obtain the required catalyst; the organic modifier is 3- (aminopropyl) triethoxysilane (APTS), and the mass of the organic modifier is 10 wt% of the total mass of Rh and Ni precursors;
the molar ratio of rhodium to nickel in the catalyst is 0.01-0.05:1, the catalyst is spherical or polyhedral rhodium/nickel alloy nano particles, and the size distribution of the rhodium/nickel alloy nano catalyst particles is 12-58 nm.
2. The method according to claim 1, wherein the pH of the reaction solution is adjusted by using 0.5 to 1.5mol/L NaOH in ethanol.
3. A method for catalytically synthesizing 1-aminoanthraquinone by using a catalyst, which is characterized in that the catalyst is a rhodium/nickel alloy nano catalyst, and the catalyst is the rhodium/nickel alloy nano catalyst prepared by the method of claim 1.
4. The method for catalytic synthesis of 1-aminoanthraquinone according to claim 3, characterized in that the specific synthesis steps are as follows:
(1) putting 1-nitroanthraquinone and N, N-Dimethylformamide (DMF) into a reaction kettle, and adding a rhodium/nickel alloy nano catalyst, wherein the proportion of the 1-nitroanthraquinone to the DMF to the rhodium/nickel alloy nano catalyst is as follows: 3g, 150mL, 0.03g to 0.3 g;
(2) installing a reaction device, introducing nitrogen for purging, removing air in the reaction kettle, introducing high-purity hydrogen, increasing the pressure to 0.5-1.0MPa, slowly heating to 100-;
(3) after the reaction is finished, cooling the reaction material to room temperature; the samples were analyzed by liquid chromatography.
5. The method for catalytic synthesis of 1-aminoanthraquinone according to claim 4, characterized in that the ratio of 1-nitroanthraquinone, DMF, rhodium/nickel alloy nano-catalyst in step (1) is as follows: 3g, 150mL, 0.24 g-0.3 g.
6. The method for catalytic synthesis of 1-aminoanthraquinone according to claim 4, characterized in that in step (2), the pressure is 0.8MPa, the temperature is slowly raised to 130 ℃, and the reaction is carried out for 6h under the condition of heat preservation.
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