CN115445607A - Preparation method of palladium-carbon catalyst for disproportionated rosin - Google Patents
Preparation method of palladium-carbon catalyst for disproportionated rosin Download PDFInfo
- Publication number
- CN115445607A CN115445607A CN202110645633.8A CN202110645633A CN115445607A CN 115445607 A CN115445607 A CN 115445607A CN 202110645633 A CN202110645633 A CN 202110645633A CN 115445607 A CN115445607 A CN 115445607A
- Authority
- CN
- China
- Prior art keywords
- palladium
- acid
- chelating agent
- activated carbon
- aqueous 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 21
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 130
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 66
- 239000002738 chelating agent Substances 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000002978 peroxides Chemical class 0.000 claims abstract description 9
- 239000013081 microcrystal Substances 0.000 claims abstract description 7
- -1 halogen ions Chemical class 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- 235000019254 sodium formate Nutrition 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims 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 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BDUIBJCGBNINBM-UHFFFAOYSA-N acetic acid N'-ethylethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CCNCCN BDUIBJCGBNINBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000004820 halides Chemical class 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 150000002940 palladium Chemical class 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 210000003278 egg shell Anatomy 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution 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
- 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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a palladium-carbon catalyst for disproportionating rosin, which introduces a chelating agent in the preparation process, wherein the chelating agent can generate stronger interaction with palladium to generate a complex, and simultaneously, the introduction of the chelating agent can also play a role in stabilizing the pH value of an aqueous solution containing a palladium compound and the chelating agent, so that the oxidation-reduction potential of palladium can be reduced. The method further introduces peroxide in the preparation process, which can effectively eliminate strong reduction centers on the surface of the activated carbon, and the prepared palladium-carbon catalyst has high content of metal palladium microcrystals, good dispersibility, high thermal stability, namely sintering resistance and high activity.
Description
Technical Field
The invention relates to preparation of a palladium-carbon catalyst, in particular to a preparation method of a high-activity palladium-carbon catalyst for disproportionated rosin.
Background
Disproportionated rosin has wide application in industry. Disproportionated rosin potassium soap is an important auxiliary raw material in the production of synthetic rubber, and is used as an emulsifier for emulsion polymerization in the production of synthetic rubbers such as butylbenzene, chloroprene, butyronitrile, acrylonitrile, butadiene and styrene (ABS) copolymer and the like.
The main component of rosin is represented by the molecular formula C 20 H 30 O 2 The resin acids of (1) have a conjugated double bond in a tricyclic mother skeleton and are chemically active, and thus, it is usually necessary to perform a hydrogenation, a disproportionation reaction or the like to produce a stabilized rosin.
Disproportionation refers to a process of hydrogen transfer between molecules of a compound in which some molecules are dehydrogenated and others are hydrogenated. The disproportionating of rosin is that under the action of catalyst, partial hydrogen atoms in polar acid type resin acid are eliminated to rearrange double bonds and form stable benzene ring structure in the carbon ring of the three-ring mother nucleus, i.e. dehydrogenating polar acid, and the eliminated hydrogen atoms are accepted by the other part of resin acid, such as pimaric acid, to produce dihydropolar acid.
The catalyst for preparing disproportionated rosin is mainly a palladium-carbon catalyst, and some reports have been made abroad about the preparation method of the palladium-carbon catalyst, and the method mainly comprises the following points:
(1) Direct impregnation adsorption. For example, the palladium salt is treated with a water-soluble metal hydroxide or basic carbonate and then reduced to metallic palladium by a reducing agent. Or the sodium tetrachloropalladate or palladium chloride is dripped on the carbon carrier, most of palladium is immediately deposited into a glossy metal palladium film, and the catalyst prepared by the method has lower activity. Theoretically, this is due to the fact that palladium salts are directly reduced to metallic palladium by functional groups present on the surface of activated carbon, such as aldehyde groups or free electrons, thereby causing metal migration and grain growth, so that the catalysts prepared in this way are relatively poor in activity and unstable.
(2) The manner of adding the solvent. If a high molecular surfactant is added in the preparation process of the catalyst, palladium is prevented from entering pores of the carrier, so that the catalyst with high activity is obtained. For example, palladium salt is dissolved in an organic solvent, activated carbon is immersed in an organic solvent containing palladium salt, palladium is adsorbed on the activated carbon, and then palladium is deposited on a carbon support, but the catalyst thus prepared is difficult to adsorb, and mainly a uniform distribution type catalyst of palladium makes it difficult to obtain an eggshell distribution type catalyst of palladium.
Disclosure of Invention
In order to overcome the defects that in the prior art, palladium ions are directly reduced by functional groups such as aldehyde groups or free electrons on the surface of active carbon to cause aggregation and cannot form an eggshell type uniformly-distributed structure, the invention provides a preparation method of a high-activity palladium-carbon catalyst for disproportionating rosin. The invention improves the type of functional groups on the surface of the active carbon, establishes an anchor point structure and a complex, well improves the external electronic environment of palladium salt, stabilizes an active center and provides a preparation method of a high-activity palladium-carbon catalyst for disproportionated rosin.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a palladium-carbon catalyst for disproportionating rosin comprises the following steps:
the palladium-carbon catalyst is prepared by pickling activated carbon, impregnating the activated carbon into an aqueous solution containing a palladium compound and a chelating agent, and carrying out aging treatment and reduction treatment.
According to the invention, the method comprises the following steps:
1) Acid washing, water washing and drying are carried out on the active carbon;
2) Soaking the activated carbon obtained in the step 1) into an aqueous solution containing halogen ions, filtering and drying;
3) Soaking the activated carbon obtained in the step 2) into an aqueous solution containing a palladium compound and a chelating agent;
4) Carrying out aging treatment and reduction treatment on the activated carbon obtained in the step 3) to prepare the palladium-carbon catalyst.
According to the invention, in step 1), the activated carbon is coconut shell carbon, for example, granular or shaped coconut shell carbon of 5 to 50 mesh. The specific surface area of the active carbon is 800-1500 m 2 /g。
According to the invention, in step 1), the activated carbon is washed with a mineral acid, for example, 0.01 to 5mol/l of the mineral acid is used for 0.5 to 8 hours. The inorganic acid is at least one selected from hydrochloric acid, nitric acid or phosphoric acid.
According to the invention, in step 1), the washing is performed by washing the activated carbon with deionized water, for example, to neutrality.
According to the invention, in step 1), the drying is carried out, for example, at 80 to 150 ℃ for 0.5 to 10 hours.
According to the invention, in step 2), the halide ion is, for example, br or I. The halogen ion is derived from potassium halide, hydrogen halide, sodium halide, such as potassium bromide, hydrogen bromide, sodium bromide, potassium iodide, hydrogen iodide, sodium iodide.
According to the present invention, in the step 2), the concentration of the halogen ion in the aqueous solution containing the halogen ion is 0.01 to 0.5 mol/liter, for example, 0.01 mol/liter, 0.02 mol/liter, 0.03 mol/liter, 0.05 mol/liter, 0.08 mol/liter, 0.1 mol/liter, 0.2 mol/liter, 0.3 mol/liter, 0.4 mol/liter, 0.5 mol/liter.
According to the invention, in step 2), the soaking time is 2 to 10 hours, for example 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours. One of the key points of the invention is that the acid-washed activated carbon is soaked by aqueous solution containing halogen ions, and the halogen ions are adsorbed on the surface of the activated carbon in the soaking process. Because the halogen ions can be very uniformly distributed on the surface of the activated carbon and have better affinity acting force with the palladium and the surface of the activated carbon, the anchoring effect of the surface of the activated carbon on the palladium is increased, so that the migration activity of the palladium can be reduced, the grain growth of eel metal palladium is prevented or prolonged, and the catalytic activity of the palladium-carbon catalyst is increased.
According to the invention, in step 2), the drying is carried out, for example, at 80 to 150 ℃ for 0.5 to 5 hours.
According to the present invention, in step 2), the amount of the halogen ion in the aqueous solution containing the halogen ion is 0.1 to 3.0 times, for example, 0.5 to 2 times, for example, 0.1 times, 0.2 times, 0.3 times, 0.4 times, 0.5 times, 0.6 times, 0.7 times, 1 times, 1.2 times, 1.5 times, 1.8 times, 2 times, 2.5 times, and 3 times the saturated adsorption amount of the halogen ion by the activated carbon.
According to the present invention, in step 3), the molar ratio of the chelating agent to the palladium in the palladium-containing compound in the aqueous solution of the palladium-containing compound and the chelating agent is 0.01 to 2, for example, 0.01.
According to the invention, in step 3), the aqueous solution containing the palladium compound and the chelating agent further contains peroxide; the molar ratio of the peroxide to palladium in the palladium-containing compound is 0.08 to 16, and is, for example, 0.08.
According to the invention, in step 3), the pH value of the aqueous solution containing the palladium compound and the chelating agent is 1-9, for example 5-6.5, so that the oxidation-reduction potential of palladium can be reduced, palladium ions can not be reduced by surface groups of the activated carbon when palladium is loaded on the activated carbon, and thus the palladium ions can be very uniformly distributed on the surface of the activated carbon, thereby greatly improving the content and the dispersion performance of metal palladium microcrystals.
According to the invention, in step 3), the aqueous solution containing the palladium compound and the chelating agent contains 0.01 to 5wt% of palladium, such as 0.2 to 3.6wt%, for example, 0.01wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.5wt%, 3wt%, 3.6wt%, 3.8wt%, 4wt%, 4.2wt%, 4.5wt%, 5wt%.
According to the invention, in step 3), the palladium-containing compound is selected from at least one of a palladium halide, an acetate of palladium (such as palladium acetate), a nitrate of palladium, chloropalladic acid, a basic salt of chloropalladic acid or a palladium-ammonia complex.
According to the invention, in step 3), the chelating agent is selected from at least one of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, and ethyl ethylenediaminetriacetic acid.
According to the invention, in step 3), the peroxide is selected from at least one of hydrogen peroxide or sodium hypochlorite.
According to the invention, in the step 3), the introduction of the chelating agent can generate stronger interaction with palladium to generate a complex, and meanwhile, the introduction of the chelating agent can also play a role in stabilizing the pH value of an aqueous solution containing a palladium compound and the chelating agent, so that the redox potential of palladium can be reduced, when palladium is loaded on activated carbon, palladium ions cannot be reduced by surface groups of the activated carbon, and thus the palladium ions can be very uniformly distributed on the surface of the activated carbon, and the content and the dispersion performance of metal palladium microcrystals are greatly improved.
The invention also introduces peroxide to carry out oxidation treatment on the activated carbon, so that oxygen-containing genes on the surface of the activated carbon are increased, the strong reduction center on the surface of the activated carbon is effectively eliminated, the electronic environment around the active metal palladium is changed, the solution containing palladium compounds cannot be directly reduced when being adsorbed on the active surface, and the catalyst has higher hydrogenation performance.
According to the invention, in step 4), the aging treatment is carried out for 1 to 50 hours, preferably 1 to 24 hours, and the temperature of the aging treatment is room temperature.
According to the present invention, in step 4), the reduction treatment is preferably performed using a reducing agent, and it is also preferable to perform the reduction treatment by immersing the aged activated carbon in an aqueous solution of a reducing agent. Wherein the reducing agent is at least one selected from formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or hydrogen.
According to the present invention, in the step 4), the mass ratio of the activated carbon and the reducing agent in the step 3) is not particularly limited, and the activated carbon in the step 3) may be reduced.
According to the invention, in step 4), the temperature of the reduction treatment is 0 to 200 ℃, preferably 50 to 120 ℃, and the time of the reduction treatment is 0.5 to 24 hours, preferably 1 to 10 hours.
According to the invention, in step 4), the palladium-carbon catalyst is obtained by reduction treatment, preferably washing to neutrality.
The invention also provides the palladium-carbon catalyst prepared by the method, wherein the weight percentage of metal Pd in the palladium-carbon catalyst is 0.05-5 wt%, preferably 0.2-5 wt%.
According to the invention, the palladium-carbon catalyst has an eggshell type structure, and the metal palladium is uniformly distributed on the surface of the activated carbon.
According to the invention, the metal palladium microcrystal with the grain diameter less than 3nm in the palladium-carbon catalyst accounts for more than 90% of the total number of palladium crystal grains.
The invention has the beneficial effects that:
the invention provides a preparation method of a high-activity palladium-carbon catalyst for disproportionated rosin, which introduces a chelating agent in the preparation process, wherein the chelating agent can generate stronger interaction with palladium to generate a complex, and simultaneously, the introduction of the chelating agent can also play a role in stabilizing the pH value of an aqueous solution containing a palladium compound and the chelating agent, so that the oxidation-reduction potential of palladium can be reduced, when palladium is loaded on active carbon, palladium ions cannot be reduced by surface groups of the active carbon, and thus the palladium ions can be very uniformly distributed on the surface of the active carbon, and the content and the dispersion performance of metal palladium microcrystals are greatly improved. The method further introduces peroxide in the preparation process, which can effectively eliminate strong reduction centers on the surface of the activated carbon, and the prepared palladium-carbon catalyst has high content of metal palladium microcrystals, good dispersibility, high thermal stability, namely sintering resistance and high activity. The preparation method of the palladium-carbon catalyst is simple, and the adopted method does not produce any negative effect on the catalyst, and is suitable for industrial production.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
100 g of 5-8 meshes of coconut shell activated carbon with the specific surface area of 1050m 2 And g, removing dust adsorbed on the surface of the activated carbon and loose parts on the surface, washing by using 0.4mol/L nitric acid at the washing temperature of 80 ℃, then washing to be neutral by using deionized water, and drying for 8 hours at the temperature of 120 ℃. Preparing a soaking solution with Br ion concentration of 0.01mol/L by using potassium bromide and water, soaking the activated carbon for 10 hours in equal volume, and drying for 8 hours at 120 ℃ for later use.
Then 40 ml of aqueous solution of chloropalladic acid with 0.5wt% of palladium content is prepared, 1.0 ml of ethylenediamine tetraacetic acid with 2wt% is added, then the pH value is adjusted to 4-6 by alkali to form palladium glue solution, and after the palladium glue solution is stabilized for 200 minutes, the palladium glue solution is sprayed on the treated active carbon to obtain the catalyst precursor.
The catalyst precursor is placed at room temperature for aging treatment, after aging for 12 hours, 20 g of 5wt% sodium formate and 200 g of pure water are used for preparing a reducing solution, the catalyst precursor is soaked in the reducing solution for 4 hours, and then the reducing solution is washed to be neutral by pure water, so that the catalyst is obtained.
Example 2
All conditions were as in example 1 except that 1.0 ml of 2wt% ethyl ethylenediamine triacetic acid and 0.5 ml of 30% hydrogen peroxide were added.
Example 3
All conditions were as in example 1 except that 1.0 ml of 2wt% disodium ethylenediaminetetraacetate, 0.5 ml of 30% hydrogen peroxide and 0.5 ml of sodium hypochlorite were added.
Comparative example 1
50 g of 5-8 mesh coconut shell activated carbon is weighed, and the specific surface area is 1050m 2 And/g, removing dust adsorbed on the surface of the activated carbon and loose parts on the surface, washing by using 0.5mol/L nitric acid, then washing to be neutral by using deionized water, and drying for 5 hours at 120 ℃ for later use.
Activated carbon was pre-impregnated with a citric acid solution having a concentration of 0.1mol/L at room temperature for 15 minutes, then filtered, and dried at 120 ℃ for 2 hours. 1.25 g of an aqueous solution of chloropalladic acid containing 20wt% of palladium was weighed, then surfactants of potassium dodecyl polyoxyethylene ether phosphate and sodium carbonate were added thereto, the pH of the solution was adjusted to 5.5, and then deionized water was added until the amount of the solution just submerged in the activated carbon support. And (3) impregnating the active component solution of the catalyst into the carrier, ageing for 24 hours, reducing by using a sodium formate solution, washing by using pure water to be neutral, and drying to obtain the palladium-carbon catalyst.
Evaluation of test
300 g of rosin and 0.06 g of palladium-on-carbon catalyst (prepared in examples 1 to 3 and comparative example 1) having a palladium content of 5wt% were weighed into a three-necked flask, evacuated to remove air, charged with nitrogen gas and pressurized while maintaining a small flow rate, and heated by microwave radiation to melt the rosin, and the reaction conditions were set as follows: the temperature is 270 ℃, the time is 2 hours, the microwave radiation power is 800W, and the stirring speed is 300 r/min. After the reaction was complete, the product was cooled to 200 ℃ and then transferred to a filter to filter out the catalyst. The evaluation results of rosin disproportionation are summarized in Table 1.
TABLE 1 evaluation results of rosin disproportionation
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a palladium-carbon catalyst for disproportionating rosin comprises the following steps:
and (2) pickling activated carbon, soaking and drying the activated carbon by halogen, soaking the activated carbon into an aqueous solution containing a palladium compound and a chelating agent, and performing aging treatment and reduction treatment to prepare the palladium-carbon catalyst.
2. The method of manufacturing of claim 1, wherein the method comprises the steps of:
1) Acid washing, water washing and drying are carried out on the active carbon;
2) Soaking the activated carbon obtained in the step 1) into an aqueous solution containing halogen ions, filtering and drying;
3) Infiltrating the activated carbon of the step 2) into an aqueous solution containing a palladium compound and a chelating agent;
4) Carrying out aging treatment and reduction treatment on the activated carbon obtained in the step 3) to prepare the palladium-carbon catalyst.
3. The preparation method according to claim 2, wherein in the step 1), the acid washing is performed by washing the activated carbon with 0.01 to 5mol/l of inorganic acid for 0.5 to 8 hours; the inorganic acid is at least one selected from hydrochloric acid, nitric acid or phosphoric acid.
4. The production method according to claim 2 or 3, wherein, in step 2), the halogen ion is Br or I; the halogen ions are derived from potassium bromide, hydrogen bromide, sodium bromide, potassium iodide, hydrogen iodide and sodium iodide; the concentration of the halogen ions in the aqueous solution containing the halogen ions is 0.01-0.5 mol/L; the soaking time is 2 to 10 hours; the drying is carried out for 0.5 to 5 hours at the temperature of between 80 and 150 ℃.
5. The production method according to any one of claims 2 to 4, wherein in step 3), the molar ratio of the chelating agent to palladium in the palladium-containing compound in the aqueous solution of the palladium-containing compound and the chelating agent is from 0.01 to 2.
6. The production method according to any one of claims 2 to 5, wherein in step 3), the aqueous solution containing the palladium compound and the chelating agent further contains a peroxide; the molar ratio of the peroxide to the palladium in the palladium-containing compound is 0.08-16, and the peroxide is selected from at least one of hydrogen peroxide and sodium hypochlorite.
7. The production method according to any one of claims 2 to 6, wherein, in step 3), the pH of the aqueous solution containing the palladium compound and the chelating agent is 1 to 9.
Preferably, in the step 3), the mass percentage of palladium in the aqueous solution containing the palladium compound and the chelating agent is 0.01-5 wt%.
8. The production method according to any one of claims 2 to 7, wherein, in step 3), the palladium-containing compound is selected from at least one of a halide of palladium, an acetate of palladium (such as palladium acetate), a nitrate of palladium, chloropalladic acid, a basic salt of chloropalladic acid, or a complex of palladium ammonia;
in the step 3), the chelating agent is at least one selected from ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid and ethyl ethylenediamine triacetic acid.
9. The production method according to any one of claims 2 to 8, wherein, in the step 4), the time of the aging treatment is 1 to 50 hours, and the temperature of the aging treatment is room temperature.
Preferably, in the step 4), the aged activated carbon is immersed in an aqueous solution of a reducing agent for reduction treatment; wherein the reducing agent is selected from at least one of formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or hydrogen.
Preferably, in the step 4), the temperature of the reduction treatment is 0-200 ℃, and the time of the reduction treatment is 0.5-24 hours.
10. The palladium-carbon catalyst prepared by the method of any one of claims 1 to 9, wherein the weight percentage of the metal Pd in the palladium-carbon catalyst is 0.05 to 5wt%.
Preferably, the metal palladium microcrystals with the particle size of less than 3nm in the palladium-carbon catalyst account for more than 90% of the total number of palladium crystal grains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110645633.8A CN115445607A (en) | 2021-06-09 | 2021-06-09 | Preparation method of palladium-carbon catalyst for disproportionated rosin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110645633.8A CN115445607A (en) | 2021-06-09 | 2021-06-09 | Preparation method of palladium-carbon catalyst for disproportionated rosin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115445607A true CN115445607A (en) | 2022-12-09 |
Family
ID=84294690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110645633.8A Pending CN115445607A (en) | 2021-06-09 | 2021-06-09 | Preparation method of palladium-carbon catalyst for disproportionated rosin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115445607A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2056939C1 (en) * | 1992-12-11 | 1996-03-27 | Институт катализа СО РАН | Catalyst for disproportioning colophony |
| CN1436595A (en) * | 2002-12-11 | 2003-08-20 | 南化集团研究院 | Prepn process of Pd/C loaded noble metal catalyst |
| CN1672787A (en) * | 2005-01-07 | 2005-09-28 | 贵研铂业股份有限公司 | Rosin-disproportionating high activity Pd/C catalyst preparing process |
| CN1709571A (en) * | 2004-06-18 | 2005-12-21 | 中国石油化工股份有限公司 | Method for preparing load type palladium/carbon catalyst |
| CN101152634A (en) * | 2006-09-29 | 2008-04-02 | 大连科诺催化有限公司 | Process for preparation of palladium/carbon catalysts |
| CN103394347A (en) * | 2013-07-23 | 2013-11-20 | 河海大学 | Preparation method of high-activity palladium-carbon catalyst |
-
2021
- 2021-06-09 CN CN202110645633.8A patent/CN115445607A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2056939C1 (en) * | 1992-12-11 | 1996-03-27 | Институт катализа СО РАН | Catalyst for disproportioning colophony |
| CN1436595A (en) * | 2002-12-11 | 2003-08-20 | 南化集团研究院 | Prepn process of Pd/C loaded noble metal catalyst |
| CN1709571A (en) * | 2004-06-18 | 2005-12-21 | 中国石油化工股份有限公司 | Method for preparing load type palladium/carbon catalyst |
| CN1672787A (en) * | 2005-01-07 | 2005-09-28 | 贵研铂业股份有限公司 | Rosin-disproportionating high activity Pd/C catalyst preparing process |
| CN101152634A (en) * | 2006-09-29 | 2008-04-02 | 大连科诺催化有限公司 | Process for preparation of palladium/carbon catalysts |
| CN103394347A (en) * | 2013-07-23 | 2013-11-20 | 河海大学 | Preparation method of high-activity palladium-carbon catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101424042B1 (en) | Supported pd/c catalyst and the preparation method thereof | |
| CN102350348B (en) | Copper-based catalyst used in preparation of glycol by catalytic hydrogenation of oxalate ester and preparation method thereof | |
| CN109622000B (en) | Non-noble metal acetylene selective hydrogenation catalyst and preparation method and application thereof | |
| CN111013603B (en) | Supported PdCu bimetallic catalyst for acetylene selective hydrogenation reaction and preparation method thereof | |
| CN111715268A (en) | Catalyst with nitrogen-doped carbon material as carrier and preparation method thereof | |
| CN106881097B (en) | It is used to prepare the bismuth catalyst of copper containing carrier and preparation method thereof of 1,4- butynediols | |
| CN108889303B (en) | Supported high-dispersion copper-based catalyst for preparing methanol from carbon dioxide, preparation method and application thereof | |
| CN113731460A (en) | N-P modified acetylene hydrochlorination non-noble metal catalyst and preparation method and application thereof | |
| CN107008223B (en) | The adsorbent and preparation method thereof of low-load amount high dispersive type benzene refining desulfurization | |
| CN117380183B (en) | Preparation method and application of supported palladium nanoparticle catalyst | |
| CN114618551A (en) | Supported nano alloy catalyst and universal preparation method | |
| CN104959136B (en) | A kind of preparation method for adding hydrogen into resin egg-shell catalyst | |
| CN1329117C (en) | Method for preparing hydrogenising selectively palladium/carbon catalyzer | |
| CN115445607A (en) | Preparation method of palladium-carbon catalyst for disproportionated rosin | |
| CN1698952A (en) | Method for preparing supported palladium/carbon catalyst | |
| CN108187670B (en) | Palladium catalyst loaded with hydroxyl activated carbon and preparation method thereof | |
| CN106964385B (en) | It is used to prepare the carrier-free copper bismuth catalyst and preparation method thereof of 1,4- butynediols | |
| CN115555014A (en) | High-activity palladium-carbon catalyst and preparation method and application thereof | |
| CN102672196A (en) | Method for preparing metal colloid at normal temperature | |
| CN103877974B (en) | A kind of preparation method of low carrying capacity super-small selective hydrogenation palladium/carbon catalyst | |
| CN107684930B (en) | Preparation method of catalyst for preparing cyclohexanone by phenol hydrogenation | |
| CN114931946A (en) | Pt/C composite catalyst and preparation method and application thereof | |
| CN109433194B (en) | Nano palladium catalyst and preparation method and application thereof | |
| CN108069830B (en) | Method for synthesizing 1, 4-butynediol and coproducing propiolic alcohol by formaldehyde ethynylation | |
| CN100402144C (en) | Method for preparing catalyst for refining of crude terephthalic acid |
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 |