CN115869942A - Modified palladium-carbon catalyst and preparation method and application thereof - Google Patents
Modified palladium-carbon catalyst and preparation method and application thereof Download PDFInfo
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- CN115869942A CN115869942A CN202211441945.8A CN202211441945A CN115869942A CN 115869942 A CN115869942 A CN 115869942A CN 202211441945 A CN202211441945 A CN 202211441945A CN 115869942 A CN115869942 A CN 115869942A
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- palladium
- carbon
- trichloropyridine
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- carbon catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical class C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 claims abstract description 38
- GPAKJVMKNDXBHH-UHFFFAOYSA-N 2,3,6-trichloropyridine Chemical compound ClC1=CC=C(Cl)C(Cl)=N1 GPAKJVMKNDXBHH-UHFFFAOYSA-N 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005470 impregnation Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 150000001875 compounds Chemical group 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910001422 barium ion Inorganic materials 0.000 claims description 3
- 159000000009 barium salts Chemical class 0.000 claims description 3
- 229910001423 beryllium ion Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- -1 halogen salt Chemical class 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000007529 inorganic bases Chemical group 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910001427 strontium ion Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000001804 chlorine Chemical class 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 18
- 239000007795 chemical reaction product Substances 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000005886 Chlorantraniliprole Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 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 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 239000005889 Cyantraniliprole Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XYBHGJNPHFDGGU-UHFFFAOYSA-L [Na+].[Na+].OC.[O-]C([O-])=O Chemical compound [Na+].[Na+].OC.[O-]C([O-])=O XYBHGJNPHFDGGU-UHFFFAOYSA-L 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- DVBUIBGJRQBEDP-UHFFFAOYSA-N cyantraniliprole Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl DVBUIBGJRQBEDP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000013386 optimize process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005758 Cyprodinil Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HAORKNGNJCEJBX-UHFFFAOYSA-N cyprodinil Chemical compound N=1C(C)=CC(C2CC2)=NC=1NC1=CC=CC=C1 HAORKNGNJCEJBX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VFJRKWVRBRAQIU-UHFFFAOYSA-L disodium;toluene;carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O.CC1=CC=CC=C1 VFJRKWVRBRAQIU-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KNDVJPKNBVIKML-UHFFFAOYSA-N tetraniliprole Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(CN2N=C(N=N2)C(F)(F)F)=NN1C1=NC=CC=C1Cl KNDVJPKNBVIKML-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a modified palladium-carbon catalyst, and a preparation method and application thereof. The preparation method of the palladium-carbon catalyst comprises the following steps: soaking palladium carbon in the soaking solution, adding alcohol after soaking, sealing, heating, cooling, washing and filtering to obtain the palladium-carbon composite material; wherein the impregnation liquid is one or more of barium, magnesium, calcium, strontium and beryllium salt solutions, and the pH value is 1-6. Meanwhile, the palladium-carbon catalyst can be applied to dechlorination and hydrogenation reactions, particularly a reaction for preparing 2,3-dichloropyridine from 2,3, 6-trichloropyridine, the reaction can effectively control over-dechlorination of the 2,3, 6-trichloropyridine, reduce the generation of by-products, enhance the stability of active components, ensure that the conversion rate of the 2,3, 6-trichloropyridine can reach 100 percent, and the selectivity of the 2,3-dichloropyridine can reach more than 97 percent.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a modified palladium-carbon catalyst, and a preparation method and application thereof.
Background
2,3-dichloropyridine is widely applied to pesticides,An important chemical intermediate raw material in the fields of medicine production and the like. 2,3-dichloropyridine is a white to pale yellow solid, slightly soluble in water, and has a molecular formula of C 5 H 3 Cl 2 N, english name: 2, 3-dichlorpyridine, molecular weight 147.99, cas:2402-77-9, melting point 65-69 deg.C, boiling point 242 deg.C (normal pressure). The 2,3-dichloropyridine is mainly used as an intermediate of products such as Chlorantraniliprole (Chlorantraniliprole), cyantraniliprole (Cyantraniliprole), cyprodinil (Cycliciliprole), and tetrazolium amide (Tetraniliprole). In particular, the chlorantraniliprole pesticide has unique action mechanism, broad spectrum, high efficiency, low toxicity, high specificity, environment friendliness and no cross resistance with other pesticides, so that the pesticide has better application and development prospects. Therefore, the method has very important significance for the research of the synthesis process of the 2,3-dichloropyridine which is the main raw material for synthesizing the pesticide.
The method for synthesizing 2,3-dichloropyridine by catalytic reduction of 2,3,6-trichloropyridine is firstly reported in the patent literature, and is the first method for synthesizing 2,3-dichloropyridine, and the reaction route is as follows:
the method takes hydrogen as a reducing agent to reduce 2,3, 6-trichloropyridine into 2,3-dichloropyridine, a catalyst used in the reaction comprises palladium, platinum, ruthenium, nano nickel or nano copper, and an acid-binding agent usually adopts triethylamine or NaOH. The catalyst and the acid-binding agent are expensive, and the reaction product of the acid-binding agent wraps the catalyst, so that the catalyst is easily poisoned and inactivated, and the conversion rate of the 2,3, 6-trichloropyridine and the selectivity of the 2,3-dichloropyridine are low.
CN107721913B discloses a preparation method of 2,3-dichloropyridine, which adopts Pd/C catalyst, methanol as solvent, magnesium hydroxide as acid-binding agent and formic acid as buffering agent. The reaction rate is high in the reaction process, the control is not easy, excessive dechlorination is caused, and the reaction selectivity is still not high.
CN112592313A discloses a preparation method of 2,3-dichloropyridinePreparation method, which adopts Pd/gamma-Al 2 O 3 The catalyst, methanol as solvent and cobalt acetate/manganese as acid-binding agent. Although the method has higher product yield, the post-treatment of the reaction liquid containing the transition metal is very troublesome, the cost is higher, and the noble metal active component after the catalyst is recycled is difficult to recover.
CN109453786B discloses an active carbon supported palladium, iridium, gold and manganese multi-component catalyst for catalyzing the hydrogenation reaction of 2,3, 6-trichloropyridine. Although the catalyst has higher activity, the preparation process of the catalyst is complex, the catalyst contains active components of noble metal and transition metal, the process cost is high, the loss rate of the active components in the reaction process is high, the catalyst is only suitable for fixed bed gas-liquid reaction, and is not suitable for a one-pot method, and the production efficiency is low.
At present, almost all the synthetic methods for preparing 2,3-dichloropyridine from 2,3, 6-trichloropyridine by hydrogenation reduction have the problems of high catalyst preparation cost, low catalyst catalytic performance, low product yield, difficult treatment after reaction, unsuitability for scale-up production and the like. Meanwhile, the selectivity of 2,3, 6-trichloropyridine to prepare 2,3-dichloropyridine is always not ideal, and the maximum selectivity is only 85%. Therefore, the development of a catalyst for efficiently catalyzing the dechlorination and hydrogenation of 2,3, 6-trichloropyridine to prepare 2,3-dichloropyridine is particularly important.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a novel modified palladium-carbon catalyst, a preparation method and application thereof, the catalyst can be used for dechlorination hydrogenation catalytic reaction and further used for preparing 2,3-dichloropyridine, and an optimized process method is provided, the method can effectively control over-dechlorination of the 2,3, 6-trichloropyridine, reduce the generation of byproducts, improve the conversion rate of the 2,3, 6-trichloropyridine and the selectivity of the 2,3-dichloropyridine while reducing the production cost, and the post-reaction treatment is simple and is suitable for industrial amplification production. Specifically, the palladium-carbon catalyst of the invention is used for preparing 2,3-dichloropyridine, which can improve the yield of the 2,3-dichloropyridine to over 90 percent and keep the content of the 2,3-dichloropyridine in the product to over 96 percent.
Means for solving the problems
In order to solve the above problems, the present invention provides a method for preparing a palladium-carbon catalyst, which comprises the following steps:
soaking palladium carbon in the soaking solution, adding alcohol after soaking, heating in a closed state, cooling, washing with water, and filtering to obtain the palladium carbon composite material; wherein the impregnation liquid is one or more of barium, magnesium, calcium, strontium and beryllium salt solutions, and the pH value of the impregnation liquid is 1-6.
Preferably, the molar ratio of the total amount of barium, magnesium, calcium, strontium and beryllium ions in the impregnation liquid to the palladium atoms in the palladium on carbon is from 0.1 to 1, more preferably from 2 to 1, further preferably from 4.
The ratio of the volume of the impregnation liquid to the water absorption volume of the palladium on carbon is from 0.5 to 5, preferably from 0.8 to 2, more preferably 1.
Preferably, the impregnation liquid is a barium salt solution.
Preferably, the impregnation solution has a pH of 2 to 4, more preferably 2.
Further, the impregnation liquid is also a halogen salt solution and/or a nitrate salt solution, preferably a halogen salt solution, more preferably a chloride salt solution.
Preferably, the alcohol is ethanol, methanol, isopropanol or tert-butanol, more preferably ethanol.
Preferably, the time of the impregnation is between 2h and 24h, more preferably 12h.
Further, the temperature of the impregnation is 10-40 ℃.
Preferably, the heating temperature is 120 ℃ to 200 ℃, more preferably 160 ℃ to 200 ℃.
Further, the heating time is 12h-36h, more preferably 24h.
Preferably, the palladium content in the palladium on carbon is 1wt% to 10wt%, more preferably 5wt%.
Preferably, the temperature for reducing the temperature is room temperature.
In another aspect, the present invention provides a palladium on carbon catalyst obtained by the above preparation method.
In another aspect, the invention provides the application of the palladium-carbon catalyst in dechlorination and hydrogenation reactions.
Preferably, the raw material for dechlorination hydrogenation is an aromatic ring or heteroaromatic ring compound substituted by chlorine atoms.
More preferably, the dechlorination hydrogenation reaction is a reaction for preparing 2,3-dichloropyridine from 2,3, 6-trichloropyridine.
In another aspect, the present invention provides a method for preparing 2,3-dichloropyridine, comprising the steps of: 2,3, 6-trichloropyridine, hydrogen and an acid-binding agent are used as raw materials, and the 2,3-dichloropyridine is obtained in an organic solvent under the catalysis of the palladium-carbon catalyst.
Preferably, the organic solvent is a toluene-based solvent, more preferably toluene, xylene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene or 1,3, 5-trimethylbenzene, and further preferably 1,2, 4-trimethylbenzene.
Preferably, the acid scavenger is an inorganic base, more preferably a carbonate or bicarbonate, further preferably sodium carbonate, potassium carbonate or ammonium bicarbonate, most preferably sodium carbonate.
Preferably, the catalyst is charged in an amount of 0.1wt% to 1wt%, more preferably 0.3wt%.
Preferably, the temperature of the reaction is from 20 ℃ to 100 ℃, more preferably 60 ℃.
Preferably, the reaction time is between 6h and 20h, more preferably 14h.
Preferably, the mass ratio of the organic solvent to the 2,3, 6-trichloropyridine is 1.
Preferably, the molar ratio of the acid scavenger to the 2,3, 6-trichloropyridine is 0.2.
Preferably, the hydrogen pressure of the reaction is between 0.1MPa and 2.5MPa, more preferably 2MPa.
ADVANTAGEOUS EFFECTS OF INVENTION
Aiming at the defects and shortcomings of the prior art, the invention provides a palladium-carbon catalyst for efficiently catalyzing 2,3, 6-trichloropyridine to hydrogenate and prepare 2,3-dichloropyridine, and a preparation method and application thereof. The palladium-carbon catalyst has the advantages of simple preparation, convenient recovery, low raw material cost, good catalytic activity and wide application range, and can be used for fixed bed reaction and one-pot intermittent stirring reaction. Meanwhile, when the palladium-carbon catalyst and the optimized process are adopted to prepare the 2,3-dichloropyridine, the excessive dechlorination of the 2,3, 6-trichloropyridine can be effectively controlled, the generation of byproducts is reduced, the conversion rate of the 2,3, 6-trichloropyridine can reach 100 percent, the selectivity of the 2,3-dichloropyridine can reach more than 97 percent, the treatment after the reaction is simple, the stability of active components is strong, the catalyst and other components are easy to recover, and the industrial amplification production is facilitated.
Detailed Description
[ definition of terms ]
In the present invention, the numerical range represented by "numerical value a to numerical value B" means a range including the end points of numerical values a and B.
In the present invention, "room temperature" means 10 ℃ to 40 ℃ and may be 10 ℃ to 30 ℃.
In the present invention, the "toluene-based solvent" means benzene having a methyl substituent, for example, benzene having 1,2,3, 4, 5 or 6 methyl substituents, and the position of the methyl substituent is not limited, for example, benzene having 3 methyl substituents may be 1,2, 4-trimethylbenzene (pseudotrimethylbenzene), 1,2, 3-trimethylbenzene (n-trimethylbenzene) or 1,3, 5-trimethylbenzene (mesitylene).
In the present invention, the "water absorption volume of palladium on carbon" can be measured and calculated by a routine experimental method by those skilled in the art. In the present invention, the "water absorption volume of palladium on carbon" is the product of the water absorption volume of palladium on carbon per unit mass multiplied by the mass of palladium on carbon. The method for measuring the water absorption volume of the palladium-carbon unit mass comprises the following steps: 1g of palladium on carbon was placed in an evaporation dish and water was dropped drop by drop to just reach the volume of water in a fully wetted state.
[ modified Palladium-carbon catalyst and Process for producing the same ]
Firstly, the invention provides a modified palladium-carbon catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: dipping palladium carbon into the dipping solution, adding alcohol after dipping, placing the solution into a sealed container, heating, cooling, washing with water, and filtering to obtain the modified palladium carbon catalyst; wherein the impregnation liquid is one or more of barium, magnesium, calcium, strontium or beryllium salt solutions, and the pH value of the impregnation liquid is 1-6.
In some embodiments, the molar ratio of the total amount of barium, magnesium, calcium, strontium, and beryllium ions in the impregnating solution to palladium atoms in the palladium on carbon is from 0.1 to 1; in some preferred embodiments, the molar ratio is 2; in some more preferred embodiments, the molar ratio is 4; in some further preferred embodiments, the molar ratio is 5.
In some embodiments, the impregnating solution is one or more of a barium, magnesium and calcium salt solution; in some preferred embodiments, the impregnating solution is a barium salt solution.
In some embodiments, the pH of the impregnating solution is 2 to 4, such as 2,3 or 4.
In some embodiments, the impregnating solution is also a halide salt solution and/or a nitrate salt solution; in some preferred embodiments, the impregnating solution is a chloride salt solution.
In some embodiments, the alcohol is ethanol, methanol, isopropanol, or tert-butanol; in some preferred embodiments, the alcohol is ethanol.
In some embodiments, the time for the immersion is 2h to 24h, e.g., 2h, 4h, 8h, 10h, 12h, 14h, or 16h.
In some embodiments, the temperature of the impregnation is room temperature.
In some embodiments, the temperature of the heating is from 120 ℃ to 200 ℃, e.g., 160 ℃, 180 ℃, or 200 ℃.
In some embodiments, the heating is for a time period of 12h to 36h, such as 20h, 24h, or 30h.
In some embodiments, the palladium on carbon is present in an amount of 1wt% to 10wt%, for example 5wt%.
In some embodiments, the reduced temperature is room temperature.
[ use of Palladium-carbon catalyst ]
The invention provides application of the palladium-carbon catalyst in dechlorination and hydrogenation reactions.
In some embodiments, the feed to the dechlorination reaction is an aromatic or heteroaromatic ring compound substituted with a chlorine atom; wherein, the number of the chlorine atoms is not limited, and can be 1 or 2, or more than 2; further, the heteroaromatic ring compound is a heteroaromatic ring compound in which ring-forming atoms contain a N atom.
In some preferred embodiments, the dechlorination hydrogenation reaction is a reaction to produce 2,3-dichloropyridine from 2,3, 6-trichloropyridine.
[ Process for producing 2,3-dichloropyridine ]
The invention provides a preparation method of 2,3-dichloropyridine, which comprises the following steps: 2,3, 6-trichloropyridine, hydrogen and an acid-binding agent are taken as raw materials, and the 2,3-dichloropyridine is obtained in an organic solvent under the catalysis of the palladium-carbon catalyst.
In some embodiments, the organic solvent is a toluene-based solvent; in some preferred embodiments, the organic solvent is toluene, xylene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, or 1,3, 5-trimethylbenzene.
In some embodiments, the acid scavenger is an inorganic base; in some preferred embodiments, the acid scavenger is a carbonate or bicarbonate salt, such as sodium carbonate, potassium carbonate, or ammonium bicarbonate.
In some embodiments, the catalyst charge is 0.1wt% to 1wt%, for example 0.3wt%. In the invention, the feeding amount of the catalyst refers to the mass ratio of the catalyst to the raw material 2,3, 6-trichloropyridine.
In some embodiments, the temperature of the reaction is from 20 ℃ to 100 ℃, e.g., 60 ℃.
In some embodiments, the reaction time is from 6h to 20h, for example 14h.
In some embodiments, the mass ratio of the organic solvent to the 2,3, 6-trichloropyridine is from 1 to 1, e.g., 3.
In some embodiments, the molar ratio of the acid scavenger to the 2,3, 6-trichloropyridine is 0.2.
In some embodiments, the hydrogen pressure of the reaction is from 0.1MPa to 2.5MPa, e.g., 2MPa.
[ examples ]
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The palladium carbon in this example was purchased from Shaanxi Rui New materials, inc.
Wet-based palladium on carbon: water content 70wt%,5wt%, pd. Pd 106.42g/mol.
(1) The maximum water absorption of the palladium-carbon used in the present invention was first determined to be 1mL/g. Taking 5g of palladium carbon (numbered PB/AC-0), mixing 0.88g of anhydrous barium chloride (208.233 g/mol) with 4.8g of hydrochloric acid solution (0.01 mol/L) according to the atomic molar ratio of Ba to Pd being 6;
(2) Mixing the impregnated catalyst with 25mL of ethanol, adding the mixture into a 100mL toughening kettle with a polytetrafluoroethylene lining, sealing the kettle, placing the kettle in a drying oven at the temperature of 180 ℃ for 24 hours, taking out the hydrothermal kettle, placing the hydrothermal kettle, cooling the hydrothermal kettle to room temperature, opening the kettle, washing and filtering the kettle with water, wherein the obtained filter residue is the modified palladium-carbon catalyst with the atomic molar ratio of Ba to Pd being 6, and the number of the obtained filter residue is (PB/AC-6).
Example 2
The atomic molar ratio of Ba to Pd in step (1) of example 1 was changed to 2.
Example 3
The atomic molar ratio of Ba to Pd in step (1) of example 1 was changed to 4.
Example 4
The atomic molar ratio of Ba to Pd in step (1) of example 1 was changed to 5.
Example 5
The atomic molar ratio of Ba to Pd in step (1) of example 1 was changed to 7.
Example 6
The atomic molar ratio of Ba to Pd in step (1) of example 1 was changed to 8.
Example 7
The atomic molar ratio of Ba to Pd in step (1) of example 1 was changed to 10.
Example 8
30g of 2,3, 6-trichloropyridine (182.44 g/mol,1 eq), 90g of mesitylene, 0.42g of the catalyst PB/AC-6 prepared in example 1 (64% water content), 13g of sodium carbonate (105.99 g/mol,0.75 eq) were charged into a 500mL autoclave. Firstly introducing nitrogen to replace air in the kettle, then replacing nitrogen in the kettle with hydrogen, finally keeping the pressure of the hydrogen in the kettle at 2MPa, setting the reaction temperature at 60 ℃, starting heating, finishing the reaction after 14 hours of reaction, cooling to room temperature, decompressing and opening the kettle, washing and leaching reaction liquid, taking filter residues as a catalyst and sodium salt, washing and recycling, taking filtrate as reacted hydrogenated liquid, taking a proper amount of organic phase for gas chromatography analysis, and obtaining a relative result of GC: the conversion of 2,3, 6-trichloropyridine was 100% and the selectivity of 2,3-dichloropyridine was 97.2%.
Examples 9 to 15
The modified catalysts obtained in examples 2,3, 4, 5, 6 and 7 and the unmodified catalyst PB/AC-0 are used in the reaction of hydrogenating 2,3, 6-trichloropyridine to prepare 2,3-dichloropyridine, and the reaction process and the steps are the same as those in example 8. The catalytic effect of the catalyst (conversion of 2,3, 6-trichloropyridine and selectivity of 2, 3-dichloropyridine) is shown in Table 1.
TABLE 1 conversion of 2,3, 6-trichloropyridine and selectivity of 2,3-dichloropyridine over different catalysts
| Examples | Catalyst and process for preparing same | Percent conversion% | Selectivity% |
| Example 8 | PB/AC-6 | 100 | 97.2 |
| Example 9 | PB/AC-2 | 100 | 76.5 |
| Example 10 | PB/AC-4 | 100 | 86.3 |
| Example 11 | PB/AC-5 | 100 | 92.7 |
| Example 12 | PB/AC-7 | 94.4 | 93.3 |
| Example 13 | PB/AC-8 | 86.6 | 87.1 |
| Example 14 | PB/AC-10 | 80.5 | 86.1 |
| Example 15 | PB/AC-0 | 71.6 | 94.7 |
From the above table it can be seen that: the atom mol ratio of Ba to Pd is 4-1; wherein, the modified palladium-carbon catalyst with the molar ratio of 6.
Example 16
The solvent used in example 8 was changed to toluene in the same amount as in example 8, the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 17
The solvent used in example 8 was changed to xylene in the same amount as in example 8, and the other steps were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 18
The solvent used in example 8 was changed to n-trimethylbenzene, the amount used was the same as in example 8, the other operating steps were the same, and the final reaction product was analyzed by gas chromatography.
Example 19
The acid-binding agent used in example 8 was changed to potassium carbonate, the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 20
The acid scavenger used in example 8 was changed to ammonium bicarbonate (1.5 eq), the procedure was otherwise the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 21
The acid-binding agent used in example 8 was changed to magnesium oxide, the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 22
The acid scavenger used in example 8 was changed to sodium hydroxide (1.5 eq), the procedure was otherwise the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 23
The acid-binding agent used in example 8 was changed to triethylamine (1.5 eq), the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 24
The solvent used in example 8 was changed to methanol, the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 25
The solvent used in example 8 was changed to a mixture of methanol and water in a mass ratio of 3; the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 26
The solvent used in example 8 was changed to acetone, the procedure was otherwise the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 27
The solvent used in example 8 was changed to DMF, the other procedures were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
Example 28
The solvent used in example 8 was changed to methanol, the catalyst used was unmodified catalyst PB/AC-0, the amount of acid-binding agent sodium carbonate was 1eq, the other operation steps were the same as in example 8, and the final reaction product was analyzed by gas chromatography.
The results of gas phase analysis of the above reaction products are summarized in Table 2.
TABLE 2 conversion of 2,3, 6-trichloropyridine and selectivity of 2,3-dichloropyridine under different reaction conditions
| Examples | Catalyst and process for producing the same | Solvent(s) | Acid-binding agent | Conversion rate% | Selectivity% |
| Example 8 | PB/AC-6 | Unsym-trimethyl benzene | Sodium carbonate | 100 | 97.2 |
| Example 16 | PB/AC-6 | Toluene | Sodium carbonate | 89.8 | 90.8 |
| Example 17 | PB/AC-6 | Xylene | Sodium carbonate | 95.4 | 91.9 |
| Example 18 | PB/AC-6 | N-trimethylbenzene | Sodium carbonate | 97.8 | 95.0 |
| Example 19 | PB/AC-6 | Unsym-trimethyl benzene | Potassium carbonate | 95.3 | 96.2 |
| Example 20 | PB/AC-6 | Unsym-trimethyl benzene | Ammonium bicarbonate (1.5 eq) | 93.0 | 94.0 |
| Example 21 | PB/AC-6 | Unsym-trimethyl benzene | Magnesium oxide | 100 | 85.9 |
| Example 22 | PB/AC-6 | Unsym-trimethyl benzene | Sodium hydroxide (1.5 eq) | 100 | 13.5 |
| Example 23 | PB/AC-6 | Unsym-trimethyl benzene | Triethylamine (1.5 eq) | 100 | 81.6 |
| Example 24 | PB/AC-6 | Methanol | Sodium carbonate | 99.3 | 68.3 |
| Example 25 | PB/AC-6 | Aqueous methanol solution | Sodium carbonate | 99.4 | 72.1 |
| Example 26 | PB/AC-6 | Acetone (II) | Sodium carbonate | 17.2 | 92.1 |
| Example 27 | PB/AC-6 | DMF | Sodium carbonate | 12.6 | 87.7 |
| Example 28 | PB/AC-0 | Methanol | Sodium carbonate (1 eq) | 99.6 | 36.2 |
As can be seen from table 2: when an alcohol solvent, an aqueous solution of an alcohol solvent, a ketone solvent or an amide solvent is used, the reaction conversion rate or selectivity is not high; when the acid-binding agent is alkaline earth metal oxide, alkali metal hydroxide or organic alkali, the reaction selectivity is poor; when the toluene solvent is used and the acid-binding agent is carbonate or bicarbonate, the reaction conversion rate and the selectivity are both high.
Claims (10)
1. A preparation method of a palladium-carbon catalyst comprises the following steps:
soaking palladium carbon in the soaking solution, adding alcohol after soaking, heating in a closed state, cooling, washing with water, and filtering to obtain the palladium carbon composite material; the impregnation liquid is one or more of barium, magnesium, calcium, strontium and beryllium salt solutions, and the pH value of the impregnation liquid is 1-6.
2. The method according to claim 1,
the molar ratio of the total amount of barium, magnesium, calcium, strontium and beryllium ions in the impregnation liquid to palladium atoms in the palladium carbon is from 0.1 to 10.
3. The method of claim 1 or 2, further comprising at least one of the following conditions:
the ratio of the volume of the impregnation liquid to the water absorption volume of the palladium on carbon is from 0.5 to 5, preferably from 0.8 to 2, more preferably 1;
the impregnation liquid is barium salt solution;
the pH of the impregnation liquid is 2-4, preferably 2;
the impregnation liquid is also a halogen salt and/or nitrate solution, preferably a halogen salt solution, more preferably a chlorine salt solution;
the alcohol is ethanol, methanol, isopropanol or tert-butanol, preferably ethanol.
4. The method of any one of claims 1-3, further comprising at least one of the following conditions:
the dipping time is 2h-24h, and is preferably 12h;
the temperature of the impregnation is 10-40 ℃;
the heating temperature is 120-200 ℃, and preferably 160-200 ℃;
the heating time is 12h-36h, preferably 24h;
the palladium content in the palladium on carbon is 1wt% to 10wt%, preferably 5wt%.
5. A palladium-carbon catalyst obtained by the production method according to any one of claims 1 to 4.
6. Use of a palladium on carbon catalyst obtained by the production process according to any one of claims 1 to 4 or the palladium on carbon catalyst according to claim 5 in a dechlorination hydrogenation reaction; preferably, the raw material of the dechlorination hydrogenation reaction is an aromatic ring or heteroaromatic ring compound substituted by chlorine atoms; more preferably, the dechlorination hydrogenation reaction is a reaction for preparing 2,3-dichloropyridine from 2,3, 6-trichloropyridine.
7. A process for the preparation of 2,3-dichloropyridine comprising the steps of: 2,3, 6-trichloropyridine, hydrogen and an acid binding agent are used as raw materials, and the 2, 3-trichloropyridine is obtained in an organic solvent under the catalysis of the palladium-carbon catalyst obtained by the preparation method according to any one of claims 1 to 4 or the palladium-carbon catalyst according to claim 5.
8. The method of claim 7,
the organic solvent is a toluene solvent, preferably toluene, xylene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene or 1,3, 5-trimethylbenzene, more preferably 1,2, 4-trimethylbenzene.
9. The production method according to claim 7 or 8,
the acid-binding agent is an inorganic base, preferably carbonate or bicarbonate, more preferably sodium carbonate, potassium carbonate or ammonium bicarbonate, and further preferably sodium carbonate.
10. The method of any one of claims 7-9, further comprising at least one of the following conditions:
the feeding amount of the catalyst is 0.1-1 wt%, and 0.3wt% is preferable;
the temperature of the reaction is 20-100 ℃, and preferably 60 ℃;
the reaction time is 6h-20h, preferably 14h;
the mass ratio of the organic solvent to the 2,3, 6-trichloropyridine is 1-5, preferably 3;
the molar ratio of the acid scavenger to the 2,3, 6-trichloropyridine is 0.2;
the hydrogen pressure of the reaction is 0.1MPa to 2.5MPa, preferably 2MPa.
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