CN114192140A - Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof - Google Patents
Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof Download PDFInfo
- Publication number
- CN114192140A CN114192140A CN202111669247.9A CN202111669247A CN114192140A CN 114192140 A CN114192140 A CN 114192140A CN 202111669247 A CN202111669247 A CN 202111669247A CN 114192140 A CN114192140 A CN 114192140A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- activated carbon
- palladium
- solution
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 159
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 claims abstract description 96
- 239000002184 metal Substances 0.000 claims abstract description 96
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims description 62
- 238000002791 soaking Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000012696 Pd precursors Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical group CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- GPAKJVMKNDXBHH-UHFFFAOYSA-N 2,3,6-trichloropyridine Chemical compound ClC1=CC=C(Cl)C(Cl)=N1 GPAKJVMKNDXBHH-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- -1 salt nickel nitrate hexahydrate Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005886 Chlorantraniliprole Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/8906—Iron 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- 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
- B01J23/8926—Copper 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
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing 2, 3-dichloropyridine, which comprises a sheet-shaped activated carbon carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary metal, the mass percent of the palladium in the catalyst is 0.01-0.2%, and the mass percent of the auxiliary metal is 0.005-0.05%. The metal content in the catalyst is greatly reduced, the cost of the catalyst is greatly reduced, the catalyst is used for synthesizing 2, 3-dichloropyridine, the catalytic efficiency is high, the content of noble metal palladium is low, the performance is stable, the catalyst can be stably used for more than 90 days, the product conversion rate is 100%, and the selectivity is more than 95%.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for synthesizing 2, 3-dichloropyridine and a preparation method thereof.
Background
2, 3-dichloropyridine is a key intermediate of a novel insecticide chlorantraniliprole, and the market demand is increased year by year.
Chinese patent CN 112142652A discloses a method and a device for producing 2, 3-dichloropyridine, which comprises the steps of firstly activating a catalyst in a tubular reaction tube at 500 ℃ under nitrogen, then cooling to the reaction temperature (70-100 ℃), adding 2,3, 6-trichloropyridine and an acid-binding agent, and reacting under hydrogen. The service life of the catalyst is more than 60h, the product selectivity is more than 98 percent, and the conversion rate is 100 percent. The patent adopts M-N/APO-5 as a catalyst, wherein M represents Pt/Pd/Zn/Ni; n represents Co, Mg and Ca, the content of M is 0.5-10%, the content of N is 0.5-10%, and a specific catalyst preparation method is not given. The catalyst in the patent has high metal content, high price and short service life of more than 60 hours.
Chinese patent CN 112194617A discloses a method and a device for synthesizing 2, 3-dichloropyridine, which comprises the steps of firstly activating a catalyst in a tubular reaction tube at 400 ℃ under nitrogen, then cooling to the reaction temperature (100-250 ℃), adding an organic solvent solution of 2,3, 6-trichloropyridine, and reacting under hydrogen, wherein the service life of the catalyst is over 60 hours, the product selectivity is over 98 percent, and the conversion rate is 100 percent. The patent adopts an M/MCM-41 molecular sieve as a catalyst, M represents Pt/Pd/Zn/Ni, the content of M is 0.5-10%, and a specific catalyst preparation method is not given. The same catalyst in the patent has high metal content, higher catalyst price and shorter service life which is only more than 60 hours.
Chinese patent CN201910665611.0 discloses a catalyst for synthesizing 2, 3-dichloropyridine, which takes powdery gamma-alumina loaded with Pd and Pt as a catalyst to catalyze 2,3, 6-trichloropyridine to synthesize 2, 3-dichloropyridine, wherein the conversion rate of raw materials is 100%, and the selectivity is about 95%. The catalyst adopts palladium-platinum bimetal, the mass percentage of Pd is 2.5-4.5%, and the mass percentage of Pt is 0.5-2.5%. The catalyst has more noble metals, higher price, and complex preparation process because palladium and platinum need to be reduced respectively. The method is required to be a batch reaction, the reaction efficiency is low, and meanwhile, the reaction needs high pressure and has high requirements on equipment, so that the method is not beneficial to industrial production.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for 2, 3-dichloropyridine synthesis and a preparation method thereof, aiming at the defects in the prior art. The catalyst is used for synthesizing 2, 3-dichloropyridine by fixed bed reaction, can be stably used for more than 90 days, has the product conversion rate of 100 percent and the selectivity of more than 95 percent, and has the advantages of high catalytic efficiency, low content of noble metal, stable performance and the like.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for synthesizing 2, 3-dichloropyridine is characterized by comprising a sheet-shaped activated carbon carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary metal, the mass percentage content of the palladium in the catalyst is 0.01-0.2%, the mass percentage content of the auxiliary metal is 0.005-0.05%, and the auxiliary metal is one or more of iron, nickel, zinc and copper.
The catalyst for synthesizing 2, 3-dichloropyridine is characterized in that the specific surface area of the flake activated carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The catalyst for synthesizing 2, 3-dichloropyridine is characterized in that the mass percent of palladium in the catalyst is 0.05-0.2%, and the mass percent of the auxiliary metal is 0.01-0.05%.
The catalyst for synthesizing 2, 3-dichloropyridine is characterized in that the mass percent of palladium in the catalyst is 0.1%, and the mass percent of the auxiliary metal is 0.02%.
In addition, the invention also provides a method for preparing the catalyst, which is characterized by comprising the following steps:
adding activated carbon into a tubular furnace, treating for 3-6 h at 500-1000 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight to obtain a pretreated activated carbon carrier;
step two, uniformly mixing the dispersant A and an aqueous solution of soluble salt of the assistant metal to obtain an assistant metal solution;
step three, adding the pretreated activated carbon carrier in the step one into the auxiliary agent metal solution in the step two, soaking for 4-10 h, adjusting the pH value of a soaking system to 8-10 by using a sodium hydroxide solution, continuously soaking for 2h, filtering, and drying to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
regulating the pH value of the palladium dichlorotetrammine solution to 8.5 by using ammonia water, adding a dispersing agent B into the palladium dichlorotetrammine solution with the pH value regulated, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying to constant weight;
and step six, reducing the product dried in the step five for 2 to 4 hours at the temperature of between 150 and 250 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
The method is characterized in that in the second step, the dispersing agent A is polyethylene glycol-400, polyvinylpyrrolidone or sodium polyacrylate, and the mass of the dispersing agent A is 1-5 times of that of the metal of the auxiliary agent.
The method is characterized in that the soluble salt of the auxiliary metal in the second step is nitrate.
The method is characterized in that the dispersant B in the fourth step is hexamethylphosphoric triamide or 1-hydroxyethylidene-1, 1-diphosphonic acid, and the molar weight of the dispersant B is 0.5-4 times of that of palladium.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the pretreatment of the activated carbon is carried out by adopting ammonia gas high-temperature treatment, the activated carbon is washed to ensure that the pH value of the activated carbon is 7-8, and the activated carbon is dried in an oven at 120 ℃ to constant weight to obtain the pretreated activated carbon. Can realize the uniform nitrogen doping of the active carbon, and the subsequent washing process can remove the redundant ammonia gas absorbed by the active carbon.
2. The mass percentage of palladium in the catalyst is 0.01-0.2%, and the mass percentage of the promoter metal is 0.005-0.05%. The metal content is greatly reduced, and the cost of the catalyst is greatly reduced.
3. According to the invention, the auxiliary metal and the noble metal palladium are respectively adsorbed, and the matched dispersing agent is added in the two adsorption processes, so that the metal is uniformly dispersed, and the metal utilization rate is high.
4. The catalyst of the invention has simple preparation method and good repeatability, and the prepared metal particles are small and can be highly dispersed on the carrier, thereby greatly prolonging the service life of the catalyst.
5. The catalyst is used for synthesizing 2, 3-dichloropyridine by a fixed bed reaction, can be stably used for more than 90 days, has the product conversion rate of 100 percent and the selectivity of more than 95 percent, and has the advantages of high catalytic efficiency, low content of noble metal, stable performance and the like.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
Example 1
The catalyst comprises a sheet-shaped activated carbon carrier and a metal component loaded on the carrier, wherein the metal component comprises palladium and an auxiliary metal, the mass percentage of the palladium in the catalyst is 0.2%, the mass percentage of the auxiliary metal is 0.05%, and the auxiliary metal is iron. The specific surface area of the sheet-shaped active carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
adding 80g of activated carbon into a tubular furnace, treating for 5 hours at 500 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, taking 0.1809g Fe (NO)3)3·9H2Dissolving O in 80mL of deionized water, then adding 0.05g of polyethylene glycol-400, and uniformly mixing to obtain an auxiliary agent metal solution;
step three, adding 50g of the activated carbon carrier pretreated in the step one into the auxiliary agent metal solution in the step two, soaking for 5 hours, adjusting the pH value of a soaking system to 8 by using 2% sodium hydroxide solution, continuing soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
dissolving 0.2306g of palladium dichlorotetramine in 80mL of deionized water, adjusting the pH value of the palladium dichlorotetramine solution to 8.5 by using ammonia water, adding 0.0842g of hexamethylphosphoric triamide into the palladium dichlorotetramine solution with the pH value adjusted, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
and step six, reducing the product dried in the step five for 4 hours at 150 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 1
This comparative example differs from example 1 in that: and (3) directly washing the activated carbon by deionized water to ensure that the pH value is 7-8 without the process of pretreating the carrier by ammonia in the step one, and drying the activated carbon in an oven at 120 ℃ to constant weight to obtain the pretreated activated carbon.
Example 2
The catalyst comprises a sheet-shaped activated carbon carrier and a metal component loaded on the carrier, wherein the metal component comprises palladium and an auxiliary metal, and the mass percentage of the palladium in the catalyst is 0.05%The mass percentage content of the auxiliary metal is 0.01 percent, and the auxiliary metal is nickel. The specific surface area of the sheet-shaped active carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
adding 80g of activated carbon into a tubular furnace, treating for 3 hours at 800 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, taking 0.0248g Ni (NO)3)2·6H2Dissolving O in 80mL of deionized water, adding 0.02g of polyvinylpyrrolidone, and uniformly mixing to obtain an assistant metal solution;
step three, adding 50g of the activated carbon carrier pretreated in the step one into the auxiliary agent metal solution in the step two, soaking for 5 hours, adjusting the pH value of a soaking system to 10 by using 2% sodium hydroxide solution, continuing soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
dissolving 0.0577g of palladium tetrammine dichloride in 80mL of deionized water, adjusting the pH value of the palladium tetrammine dichloride solution to 8.5 by using ammonia water, adding 0.0536g of 1-hydroxyethylidene-1, 1-diphosphonic acid into the pH value-adjusted palladium tetrammine dichloride solution, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
and step six, reducing the product dried in the step five for 2 hours at 250 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 2
This comparative example differs from example 2 in that: and step two is omitted, and the auxiliary agent metal salt nickel nitrate hexahydrate and the dispersant polyvinylpyrrolidone are not added.
Example 3
The catalyst of this example comprises a sheetThe catalyst comprises a activated carbon carrier and a metal component loaded on the carrier, wherein the metal component comprises palladium and an auxiliary metal, the mass percentage content of the palladium in the catalyst is 0.175%, the mass percentage content of the auxiliary metal is 0.04%, and the auxiliary metal is zinc. The specific surface area of the sheet-shaped active carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
adding 80g of activated carbon into a tubular furnace, treating for 4.5 hours at 600 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, taking 0.0909Zn (NO)3)2·6H2Dissolving O in 80mL of deionized water, then adding 0.05g of sodium polyacrylate, and uniformly mixing to obtain an auxiliary agent metal solution;
step three, adding 50g of the activated carbon carrier pretreated in the step one into the auxiliary agent metal solution in the step two, soaking for 5 hours, adjusting the pH value of a soaking system to 9 by using 2% sodium hydroxide solution, continuing soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
dissolving 0.1845g of palladium dichlorotetrammine in 80mL of deionized water, adjusting the pH value of the palladium dichlorotetrammine solution to 8.5 by using ammonia water, adding 0.1347g of hexamethylphosphoric triamide into the palladium dichlorotetrammine solution with the pH value adjusted, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
and step six, reducing the product dried in the step five for 3 hours at 200 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 3
The comparative example differs from example 3 in that: in step four 0.1845g of tetraamminepalladium dichloride were changed to 0.1458g of palladium chloride and no ammonia was used to adjust the pH to 8.5.
Example 4
The catalyst comprises a sheet-shaped activated carbon carrier and a metal component loaded on the carrier, wherein the metal component comprises palladium and an auxiliary metal, the mass percentage content of the palladium in the catalyst is 0.1%, the mass percentage content of the auxiliary metal is 0.02%, and the auxiliary metal is copper. The specific surface area of the sheet-shaped active carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
adding 80g of activated carbon into a tubular furnace, treating for 4 hours at 700 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, taking 0.038g of Cu (NO)3)2·9H2Dissolving O in 80mL of deionized water, adding 0.03g of polyvinylpyrrolidone, and uniformly mixing to obtain an assistant metal solution;
step three, adding 50g of the activated carbon carrier pretreated in the step one into the auxiliary agent metal solution in the step two, soaking for 5 hours, adjusting the pH value of a soaking system to 8.5 by using 2% sodium hydroxide solution, continuing soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
dissolving 0.1153g of palladium tetrammine dichloride in 80mL of deionized water, adjusting the pH value of the palladium tetrammine dichloride solution to 8.5 by using ammonia water, adding 0.0857g of 1-hydroxyethylidene-1, 1-diphosphonic acid into the pH value-adjusted palladium tetrammine dichloride solution, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
and step six, reducing the product dried in the step five for 2.5 hours at 220 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Comparative example 4
This comparative example differs from example 4 in that: in the fourth step, 1-hydroxyethylidene-1, 1-diphosphonic acid is not added.
Example 5
The catalyst of the embodiment comprises a sheet-shaped activated carbon carrier and metal components loaded on the carrier, wherein the metal components comprise palladium, promoter metals such as iron and nickel, the mass percentage of the palladium in the catalyst is 0.01%, and the mass percentage of the promoter metals is 0.005% (iron is 0.002%, nickel is 0.003%). The specific surface area of the sheet-shaped active carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
adding 80g of activated carbon into a tubular furnace, treating for 3 hours at 1000 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, 0.0073g of Fe (NO) is taken3)3·9H2O and 0.0068g Ni (NO)3)2·6H2Dissolving O in 80mL of deionized water, adding 0.0125g of polyvinylpyrrolidone, and uniformly mixing to obtain an assistant metal solution;
step three, adding 50g of the activated carbon carrier pretreated in the step one into the auxiliary agent metal solution in the step two, soaking for 10 hours, adjusting the pH value of a soaking system to 8.5 by using 2% sodium hydroxide solution, continuously soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
step four, dissolving 0.0115g of palladium tetraammine dichloride in 80mL of deionized water, adjusting the pH value of the palladium tetraammine dichloride solution to 8.5 by ammonia water, adding 0.0337g of hexamethyl phosphoric triamide into the palladium tetraammine dichloride solution with the pH value adjusted, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
and step six, reducing the product dried in the step five for 2.5 hours at 220 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Example 6
The catalyst of the embodiment comprises a sheet-shaped active carbon carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and auxiliary metal iron, nickel, zinc and copper, the mass percentage content of the palladium in the catalyst is 0.1%, the mass percentage content of the auxiliary metal is 0.02% (iron 0.005%, nickel 0.005%, zinc 0.005% and copper 0.005%), and the specific surface area of the sheet-shaped active carbon carrier is 900m2/g～1500m2The particle size is 20-30 meshes.
The preparation method of the catalyst of the embodiment comprises the following steps:
adding 80g of activated carbon into a tubular furnace, treating for 6 hours at 500 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight at 120 ℃ to obtain a pretreated activated carbon carrier;
step two, 0.0181g of Fe (NO) is taken3)3·9H2O，0.0124g Ni(NO3)2·6H2O，0.0114Zn(NO3)2·6H2O，0.0095g Cu(NO3)2·9H2Dissolving O in 80mL of deionized water, then adding 0.01g of sodium polyacrylate, and uniformly mixing to obtain an auxiliary agent metal solution;
step three, adding 50g of the activated carbon carrier pretreated in the step one into the auxiliary agent metal solution in the step two, soaking for 4 hours, adjusting the pH value of a soaking system to 8.5 by using 2% sodium hydroxide solution, continuing soaking for 2 hours, filtering, and drying in an oven at 120 ℃ to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
dissolving 0.1153g of palladium tetrammine dichloride in 80mL of deionized water, adjusting the pH value of the palladium tetrammine dichloride solution to 8.5 by using ammonia water, adding 0.1944g of 1-hydroxyethylidene-1, 1-diphosphonic acid into the pH value-adjusted palladium tetrammine dichloride solution, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying in an oven at 120 ℃ to constant weight;
and step six, reducing the product dried in the step five for 2.5 hours at 220 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
Example 7
The method for synthesizing 2, 3-dichloropyridine by catalyzing 2.3.6-trichloropyridine through hydrogenation by using the catalyst comprises the following steps: weighing 10g of catalyst sample, filling the catalyst sample on normal-pressure fixed bed catalyst performance evaluation equipment, introducing nitrogen to replace air in a reactor, changing the nitrogen into hydrogen, and keeping the introduction of the hydrogen, wherein the gas flow is 100 ml/min. The temperature of the reaction tube was raised to 200 ℃ at a rate of 2 ℃/min for 30min and then lowered to the reaction temperature. 2.3.6-trichloropyridine is dissolved in methanol solution to prepare 2.3.6-trichloropyridine solution, 2,3, 6-trichloropyridine solution is conveyed to a fixed bed reactor through a metering pump and is contacted with hydrogen to generate dechlorination reaction on a catalyst, the reacted materials flow out from the bottom of a reaction tube, and are condensed and separated from gas and liquid, redundant hydrogen is discharged out of the reactor, liquid phase products are collected, and the samples are taken for gas chromatography analysis. 2.3.6-trichloropyridine has a mass space velocity of 0.2h-1。
Results and discussion
The 2,3, 6-trichloropyridine is hydrogenated to 2, 3-dichloropyridine by the method of example 6 and by the catalysts of examples 1, 2,3, 4 and 5 and comparative examples 1, 2,3 and 4 respectively, and the reaction results are shown in the following table.
TABLE 1 catalytic effect of the catalyst in the hydrogenation of 2,3, 6-trichloropyridine to 2, 3-dichloropyridine
As can be seen from Table 1, the catalyst prepared by the method is suitable for catalyzing 2.3.6-trichloropyridine hydrogenation to synthesize 2.3-dichloropyridine, and due to the doping modification of activated carbon, the addition of an auxiliary metal and a dispersing agent matched with the auxiliary metal, the use of palladium tetrammine dichloride and the use of the dispersing agent matched with the active metal palladium, the conversion rate and the selectivity of the catalyst are greatly improved, the conversion rate of a product is 100%, the selectivity is over 95%, and the catalytic efficiency is high.
Using the catalyst prepared in example 1 as an example, the reaction was carried out under the reaction conditions of example 7, and the results of the 90-day reaction are shown in the following Table.
TABLE 2 catalytic Effect of the catalyst of example 1 in catalyzing the hydrogenation of 2,3, 6-trichloropyridine to 2, 3-dichloropyridine for 90 days
As can be seen from Table 2, the catalyst of the present invention can be stably used for more than 90 days, the product conversion rate is 100%, the selectivity is maintained at more than 95%, and the catalyst has the advantages of high catalytic efficiency, low noble metal content, stable performance, etc.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. The catalyst for synthesizing 2, 3-dichloropyridine is characterized by comprising a sheet-shaped activated carbon carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary metal, the mass percentage content of the palladium in the catalyst is 0.01-0.2%, the mass percentage content of the auxiliary metal is 0.005-0.05%, and the auxiliary metal is one or more of iron, nickel, zinc and copper.
2. The catalyst for 2, 3-dichloropyridine synthesis according to claim 1, wherein the sheet-like activated carbon carrier has a specific surface area of 900m2/g～1500m2The particle size is 20-30 meshes.
3. The catalyst for synthesizing 2, 3-dichloropyridine according to claim 1, wherein the mass percent of palladium in the catalyst is 0.05-0.2%, and the mass percent of the promoter metal is 0.01-0.05%.
4. The catalyst for 2, 3-dichloropyridine synthesis according to claim 3, wherein the mass percent of palladium in the catalyst is 0.1%, and the mass percent of the promoter metal is 0.02%.
5. A process for preparing a catalyst according to any one of claims 1 to 4, comprising the steps of:
adding activated carbon into a tubular furnace, treating for 3-6 h at 500-1000 ℃ in an ammonia atmosphere, then washing until the pH value of the activated carbon is 7-8, and drying the washed activated carbon to constant weight to obtain a pretreated activated carbon carrier;
step two, uniformly mixing the dispersant A and an aqueous solution of soluble salt of the assistant metal to obtain an assistant metal solution;
step three, adding the pretreated activated carbon carrier in the step one into the auxiliary agent metal solution in the step two, soaking for 4-10 h, adjusting the pH value of a soaking system to 8-10 by using a sodium hydroxide solution, continuously soaking for 2h, filtering, and drying to constant weight to obtain the auxiliary agent metal-loaded activated carbon;
regulating the pH value of the palladium dichlorotetrammine solution to 8.5 by using ammonia water, adding a dispersing agent B into the palladium dichlorotetrammine solution with the pH value regulated, and uniformly stirring to obtain a palladium precursor solution;
step five, adding the activated carbon loaded with the auxiliary metal in the step three into the palladium precursor solution in the step four, uniformly stirring, soaking for 24 hours, filtering, and drying to constant weight;
and step six, reducing the product dried in the step five for 2 to 4 hours at the temperature of between 150 and 250 ℃ in a hydrogen atmosphere to obtain the catalyst for synthesizing the 2, 3-dichloropyridine.
6. The method according to claim 5, wherein the dispersant A in the second step is polyethylene glycol-400, polyvinylpyrrolidone or sodium polyacrylate, and the mass of the dispersant A is 1-5 times of that of the metal of the auxiliary agent.
7. The method of claim 5, wherein the soluble salt of the promoter metal in step two is a nitrate.
8. The method according to claim 5, wherein the dispersant B in step IV is hexamethylphosphoric triamide or 1-hydroxyethylidene-1, 1-diphosphonic acid, and the molar amount of the dispersant B is 0.5-4 times that of the palladium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111669247.9A CN114192140B (en) | 2021-12-30 | 2021-12-30 | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111669247.9A CN114192140B (en) | 2021-12-30 | 2021-12-30 | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114192140A true CN114192140A (en) | 2022-03-18 |
| CN114192140B CN114192140B (en) | 2024-06-25 |
Family
ID=80657723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111669247.9A Active CN114192140B (en) | 2021-12-30 | 2021-12-30 | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114192140B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400750A (en) * | 2022-09-29 | 2022-11-29 | 西安凯立新材料股份有限公司 | Catalyst for preparing saturated ketone by hydrogenation of multi-double-bond unsaturated ketone and preparation method and application thereof |
| CN116059998A (en) * | 2023-01-19 | 2023-05-05 | 利尔化学股份有限公司 | Bimetallic catalyst and preparation method and application thereof |
| CN116351412A (en) * | 2023-01-17 | 2023-06-30 | 西安凯立新材料股份有限公司 | Supported bimetallic catalyst for antioxidant 44PD synthesis and catalytic method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01193246A (en) * | 1988-01-27 | 1989-08-03 | Daicel Chem Ind Ltd | Production of 2,3-dichloropyridine |
| WO2012122746A1 (en) * | 2011-03-13 | 2012-09-20 | 联化科技股份有限公司 | Method for preparing 2,3-dichloropyridine |
| CN109453786A (en) * | 2018-12-03 | 2019-03-12 | 西安凯立新材料股份有限公司 | A kind of catalyst and its preparation method and application being used to prepare 2,3- dichloropyridine |
| CN109535173A (en) * | 2018-12-10 | 2019-03-29 | 西安凯立新材料股份有限公司 | A kind of high method applied active palladium carbon catalyst and catalyze and synthesize biotin |
| CN110280239A (en) * | 2019-07-23 | 2019-09-27 | 西安凯立新材料股份有限公司 | A kind of synthesis 2,3- dichloropyridine catalyst and its preparation method and application |
| CN110961110A (en) * | 2019-12-23 | 2020-04-07 | 上海华谊（集团）公司 | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine |
-
2021
- 2021-12-30 CN CN202111669247.9A patent/CN114192140B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01193246A (en) * | 1988-01-27 | 1989-08-03 | Daicel Chem Ind Ltd | Production of 2,3-dichloropyridine |
| WO2012122746A1 (en) * | 2011-03-13 | 2012-09-20 | 联化科技股份有限公司 | Method for preparing 2,3-dichloropyridine |
| CN109453786A (en) * | 2018-12-03 | 2019-03-12 | 西安凯立新材料股份有限公司 | A kind of catalyst and its preparation method and application being used to prepare 2,3- dichloropyridine |
| CN109535173A (en) * | 2018-12-10 | 2019-03-29 | 西安凯立新材料股份有限公司 | A kind of high method applied active palladium carbon catalyst and catalyze and synthesize biotin |
| CN110280239A (en) * | 2019-07-23 | 2019-09-27 | 西安凯立新材料股份有限公司 | A kind of synthesis 2,3- dichloropyridine catalyst and its preparation method and application |
| CN110961110A (en) * | 2019-12-23 | 2020-04-07 | 上海华谊（集团）公司 | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400750A (en) * | 2022-09-29 | 2022-11-29 | 西安凯立新材料股份有限公司 | Catalyst for preparing saturated ketone by hydrogenation of multi-double-bond unsaturated ketone and preparation method and application thereof |
| CN115400750B (en) * | 2022-09-29 | 2024-06-07 | 西安凯立新材料股份有限公司 | Catalyst for preparing saturated ketone by hydrogenating multi-double bond unsaturated ketone, and preparation method and application thereof |
| CN116351412A (en) * | 2023-01-17 | 2023-06-30 | 西安凯立新材料股份有限公司 | Supported bimetallic catalyst for antioxidant 44PD synthesis and catalytic method thereof |
| CN116351412B (en) * | 2023-01-17 | 2024-05-28 | 西安凯立新材料股份有限公司 | Supported bimetallic catalyst for antioxidant 44PD synthesis and catalytic method thereof |
| CN116059998A (en) * | 2023-01-19 | 2023-05-05 | 利尔化学股份有限公司 | Bimetallic catalyst and preparation method and application thereof |
| CN116059998B (en) * | 2023-01-19 | 2024-08-16 | 利尔化学股份有限公司 | Bimetallic catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114192140B (en) | 2024-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114192140B (en) | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method thereof | |
| CN107497488B (en) | Preparation method and application of Au-Pd monatomic alloy catalyst with high hydrogenation selectivity | |
| CN101502802B (en) | Preparation method of catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride | |
| CN111135840B (en) | Preparation method of supported monatomic dispersed noble metal catalyst | |
| CN111185237B (en) | Selective hydrogenation catalyst, preparation method and application thereof | |
| CN110280239B (en) | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method and application thereof | |
| CN106748813B (en) | A kind of synthesis N, the method for N '-dibenzyl-ethylenediamin | |
| CN112371173B (en) | Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof | |
| CN108380208B (en) | Pd-Mg/C catalyst for preparing 2, 3-dichloropyridine by catalytic hydrogenation of 2,3, 6-trichloropyridine and preparation method thereof | |
| CN110270375B (en) | Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof | |
| CN113713841B (en) | Acetylene copper chloride-based catalyst and preparation method and application thereof | |
| CN113731465A (en) | Pd/N-CNTs catalyst, and preparation method and application thereof | |
| CN114160145A (en) | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof | |
| CN113262820B (en) | M is provided with 1 Catalyst with@MOFs structure, preparation method and application | |
| CN110841635A (en) | High-dispersion Pd-Ag supported acetylene hydrogenation catalyst and preparation method thereof | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN113600181A (en) | Preparation method of nano palladium supported catalyst | |
| CN113209992A (en) | Sulfur-containing Ni-based atom cluster compound catalyst for carbon-carbon triple bond selective hydrogenation and preparation method thereof | |
| CN113304760A (en) | High-dispersion platinum-based catalyst and preparation method and application thereof | |
| CN114436208B (en) | Catalytic hydrogen supply system based on organic liquid and hydrogen supply method thereof | |
| CN114849753B (en) | Preparation method and application of palladium metal cluster catalyst | |
| CN114522714B (en) | Platinum-series catalyst with hydroxylated boron nitride as carrier and preparation method thereof | |
| CN115138359B (en) | Supported single-atom synergistic nanoparticle bimetallic catalyst and preparation and application thereof | |
| CN115624970A (en) | Catalyst for reducing nitro compound by continuous liquid phase hydrogenation of micro-fixed bed, and preparation method and application thereof | |
| CN114345336A (en) | Transition metal molybdenum modified palladium silver-alumina catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |