CN103894209A - Catalyst applicable to dechlorination and hydrogenation of chlorination aromatic hydrocarbon, preparation method and application method of catalyst - Google Patents
Catalyst applicable to dechlorination and hydrogenation of chlorination aromatic hydrocarbon, preparation method and application method of catalyst Download PDFInfo
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- CN103894209A CN103894209A CN201410100754.4A CN201410100754A CN103894209A CN 103894209 A CN103894209 A CN 103894209A CN 201410100754 A CN201410100754 A CN 201410100754A CN 103894209 A CN103894209 A CN 103894209A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 27
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 39
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 14
- 229910052759 nickel Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000010903 husk Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 34
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000003610 charcoal Substances 0.000 claims description 24
- 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 17
- 235000019253 formic acid Nutrition 0.000 claims description 17
- 238000002803 maceration Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 13
- 238000006396 nitration reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 16
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- -1 chloro phenol compound Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
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- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- FRCCEHPWNOQAEU-LDSHLKOWSA-N cis-heptachlordane Chemical compound ClC1=C(Cl)[C@@]2(Cl)[C@H]3C=C[C@H](Cl)[C@H]3[C@]1(Cl)C2(Cl)Cl FRCCEHPWNOQAEU-LDSHLKOWSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DFBKLUNHFCTMDC-PICURKEMSA-N dieldrin Chemical compound C([C@H]1[C@H]2[C@@]3(Cl)C(Cl)=C([C@]([C@H]22)(Cl)C3(Cl)Cl)Cl)[C@H]2[C@@H]2[C@H]1O2 DFBKLUNHFCTMDC-PICURKEMSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003993 organochlorine pesticide Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a catalyst applicable to dechlorination and hydrogenation of chlorination aromatic hydrocarbon. The catalyst takes coconut shell carbon as a carrier; the preparation method comprises the following steps: dipping soluble salts of palladium and nickel by adopting a dipping method under the condition of negative pressure, and then loading the soluble salts of palladium and nickel on the coconut shell carbon which is pretreated by mixed acid containing nitric acid and hydrochloric acid to obtain a catalyst precursor; drying the catalyst precursor to obtain a catalyst product. The catalyst prepared by the method is excellent in catalytic performance on chlorination aromatic hydrocarbon, high in selectivity and long in service life; meanwhile, non-noble metals are introduced into active components of the catalyst, so that the usage amounts of the non-noble metals are greatly reduced, and the performance of the catalyst is better than that of the palladium catalyst.
Description
Technical field
The present invention relates to load type bimetal catalyst, be specifically related to a kind of hydrogenation catalyst for chlorination aromatic hydrocarbon dechlorination and preparation and application.
Background technology
Chloro organic cpd is important industrial chemicals, organic synthesis intermediate and organic solvent, is widely used in the industries such as chemical industry, medicine, agricultural chemicals, dyestuff, electronics.But, when chlorinatedorganic extensive use also to human health and the day by day serious threat of environment structure.For example, a lot of organo-chlorine pesticides (lindane, drinox and dieldrite etc.) and chlorobenzene class, chloro phenol compound have toxicity and " three cause effect " (carcinogenic, teratogenesis, mutagenesis); Extensive use, existence and the enrichment in food chain of Polychlorinated biphenyls are even more serious to the harm of human body; In municipal waste burning and chloro organic cpd production process, discharge bioxin (PCDD/Fs) and classified as one-level carcinogen by the World Health Organization.12 kinds of controlled chemistry materials of 3 class of first announcement of UNEP's " about Convention of Stockholm of persistence organic pollutant (POPs) " are chloro organic cpd.Therefore, how effectively to eliminate the pollution of the harm of chloro debirs to human health and environment extremely urgent.
At present, the method that chloro organic cpd pollutant is eliminated mainly comprises biodegradation, photocatalytic degradation, burning, wet method catalytic oxidation, catalysis dechlorination hydrogenation etc.In high concentration cl organic degradation process of generation, light degradation and biodegradation efficiency are lower, degrade thorough not; High temperature incineration and wet method catalyzing oxidizing degrading condition are comparatively harsh, and the incomplete burning of chloro organic cpd easily generates the higher bioxin of toxicity, also can discharge NO simultaneously
xand greenhouse gases CO
2thereby, cause the secondary pollution to environment.Catalysis dechlorination hydrogenation process reaction condition is relatively gentle, and the chlorine atom in reactant has generated the organic compound that can recycle when being eliminated, and without CO
2discharge.Therefore, catalysis dechlorination hydrogenation has the feature of low waste discharge, is the green catalysis process that Atom economy is high, the treatment technology that is considered to eliminate a kind of simple, effective of chlorinatedorganic environmental pollution and has prospect.
At present, the dechlorination hydrogenation process of bibliographical information mainly adopts the catalyst that contains nickel or noble metal, wherein noble metal catalyst dechlorination hydrogenation activity is better than nickel-base catalyst, but these catalyst all exist because HCl is poisoning, carbon distribution or sintering etc. are former thereby cause the problem of inactivation, and especially in gas phase dechlorination hydrogenation process, deactivation phenomenom is more remarkable.Design and the low cost dechlorination hydrogenation catalyst of preparing high activity and stability are one of important topics urgently to be resolved hurrily.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of catalytic activity high, long service life, the Catalysts and its preparation method for chlorination aromatic hydrocarbon dechlorination hydrogenation that cost is low.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation, take coconut husk charcoal as carrier, take Metal Palladium, nickel as active component, described Nickel Content In Catalyst is 5～25% of vehicle weight, and palladium content is vehicle weight 0.1～5%.
The preparation method of the described catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation, comprises the following steps:
(a) in the nitration mixture that carrier coconut husk charcoal to be added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid be 1: 1 according to volume ratio, the mass volume ratio of described carrier coconut husk charcoal and nitration mixture is 1:2g/ml, boil 4～10 hours, then filter, wash to the pH value of filtrate be 5～7, the coconut husk charcoal of gained is dried to 5～10 hours at 120 ℃, obtain the coconut husk charcoal of acid treatment, for subsequent use;
(b is dissolved in the water palladium soluble salt and nickel soluble salt, obtains maceration extract, and in described maceration extract, the concentration of palladium is 0.005～0.3mol/L, and the concentration of nickel is 0.6～2.2mol/L;
(c) maceration extract that adds step (b) to obtain in the coconut husk charcoal obtaining to step (a) floods, and the mass volume ratio of described coconut husk charcoal and maceration extract is 1:2g/ml, 60～90 ℃ of dipping temperatures, and dip time is 3～7 hours, obtains catalyst precursor;
(d) catalyst precursor step (c) being obtained, under nitrogen protection, is dried 10～16 hours at 160～200 ℃, obtains the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation.
The described palladium soluble salt of step (b) is preferably the one in palladium bichloride, six ammonium chloropalladates, palladium nitrate.
The described nickel soluble salt of step (b) is preferably the one in nickel chloride, nickel acetate, six water nickel nitrates.
The using method of the described catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation, carry out according to the following steps before use reduction activation:
(1) after the activated solution that is 5～10% by the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation with mass percent concentration mixes, react 2 hours at 70～75 ℃, described is 0.9～1.1:1g/ml for the catalyst of chlorination aromatic hydrocarbon dechlorination hydrogenation and the mass volume ratio of activated solution;
(2), with the heating rate temperature reaction of 8～10 ℃/h 3 hours, between temperature raising period, added 3～7.5ml mass percent concentration every 1 hour and be 99% activated solution;
(3) after activated solution has been added, be warming up to 110～120 ℃ and continue reaction 6～8h, finish reaction, under nitrogen protection, at 180～220 ℃, dry 10～15h, obtains the catalyst after reduction activation.
The described activated solution of step (1) is preferably the one in aqueous formic acid, aqueous sodium formate solution, the potassium formate aqueous solution.
Preparation method for chlorination aromatic hydrocarbon dechlorination hydrogenation catalyst of the present invention, take coconut husk charcoal as carrier, under condition of negative pressure, employing infusion process on the pretreated coconut husk charcoal of the nitration mixture through nitric acid and hydrochloric acid composition, obtains catalyst precarsor by the soluble-salt dip loading of palladium, nickel; Catalyst precarsor drying is obtained to catalyst prod.Catalyst prepared by the present invention has good catalytic performance to chlorination aromatic hydrocarbon, selective high, long service life; In catalyst activity component, introduce base metal, reduce widely the consumption of precious metal palladium, and performance is better than palladium catalyst simultaneously.
Compared with prior art, tool has the following advantages catalyst prepared by the present invention:
1, catalyst activity is high, selectively high, and long service life is used it for the catalytic reaction of chlorobenzene dechlorination hydrogenation, and chlorobenzene conversion ratio, more than 99.2%, moves 1000 hours continuously, its conversion ratio and selectively still more than 98%;
2, cost is low, in catalyst activity component, introduces base metal, has reduced widely the consumption of precious metal palladium, has significantly reduced catalyst cost;
3, method for preparing catalyst of the present invention is simple, is easy to industrialization.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
(a) 200 grams of carrier coconut husk charcoals being added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid is in the 400ml nitration mixture being mixed to get at 1: 1 according to volume ratio, boil 4 hours, filter, wash to the pH value of filtrate be 5, the coconut husk charcoal of gained is dried 5 hours at 120 ℃, obtain the pretreated coconut husk charcoal of nitration mixture, for subsequent use;
(b) 0.34 gram of palladium bichloride and 110 grams of nickel chlorides are dissolved in the water, are mixed with 400ml maceration extract;
(c) 200 grams of coconut husk charcoals by the described method processing of step (a) are put into rotary evaporator, step (b) is prepared to the maceration extract obtaining, be expelled to the coconut husk carbon surface of rotation with nitrogen, then control dipping temperature 80 ℃ of reactions 5 hours, obtain catalyst precursor;
(d) catalyst precursor step (c) being obtained is at N
2under protection at 190 ℃ dry 14 hours, obtain for 310 grams of the catalyst of chlorination aromatic hydrocarbon dechlorination hydrogenation.
By formic acid reduction activation catalyst:
300 grams of catalyst that obtain are as mentioned above put into rotary evaporator, and adding 319ml mass percent concentration is 8% formic acid solution.Mixing after 2 hours, dispersion becomes evenly, is white in color; Use oil bath that reactant is heated to 75 ℃ of reactions 2 hours; Then in three hours, the heating rate with 8 ℃/h is warming up to 99 ℃ from 75 ℃; During this period, added the formic acid solution of 3ml mass percent concentration 99% every 1 hour.After formic acid solution is added, oil bath is warmed up to 115 ℃, and reduction reaction 7h finishes reaction.Under nitrogen protection, by the catalyst obtaining dry 15h at 180 ℃, obtain 300 grams of catalyst after reduction activation.Sample number into spectrum JS-01.
Embodiment 2
(a) 200 grams of carrier coconut husk charcoals being added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid is in the 400ml nitration mixture being mixed to get at 1: 1 according to volume ratio, boil 6 hours, filter, wash to the pH value of filtrate be 6, the coconut husk charcoal of gained is dried 6 hours at 120 ℃, obtain the pretreated coconut husk charcoal of nitration mixture, for subsequent use;
(b) 22 grams of palladium nitrates and 50 gram of six water nickel nitrate are dissolved in the water, are mixed with 400ml maceration extract;
(c) 200 grams of coconut husk charcoals by the described method processing of step (a) are put into rotary evaporator, step (b) is prepared to the maceration extract obtaining, be expelled to the coconut husk carbon surface of rotation with nitrogen, then control dipping temperature 60 ℃ of reactions 7 hours, obtain catalyst precursor;
(d) catalyst precursor step (c) being obtained is at N
2under protection at 200 ℃ dry 10 hours, obtain for 270 grams of the catalyst of chlorination aromatic hydrocarbon dechlorination hydrogenation.
By formic acid reduction activation catalyst:
270 grams of catalyst that obtain are as mentioned above put into rotary evaporator, and adding 271ml mass percent concentration is 6% formic acid solution.Mixing after 2 hours, dispersion becomes evenly, is white in color; Use oil bath that reactant is heated to 70 ℃ of reactions 2 hours; Heating rate with 10 ℃/h in three hours is warming up to 100 ℃ from 70 ℃; During this period, adding 7ml mass percent concentration every 1 hour is 99% formic acid solution.After formic acid solution is added, oil bath is warmed up to 110 ℃, and reduction reaction 8h finishes reaction.Under nitrogen protection, by the catalyst obtaining dry 13h at 190 ℃, obtain 270 grams of catalyst after reduction activation.Sample number into spectrum JS-02.
Embodiment 3
(a) 200 grams of carrier coconut husk charcoals being added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid is in the 400ml nitration mixture being mixed to get at 1: 1 according to volume ratio, boil 8 hours, filter, wash to the pH value of filtrate be 6, the coconut husk charcoal of gained is dried 8 hours at 120 ℃, obtain the pretreated coconut husk charcoal of nitration mixture, for subsequent use;
(b) 3.3 gram of six ammonium chloropalladate and 120 grams of nickel acetates are dissolved in the water, are mixed with 400ml maceration extract;
(c) 200 grams of coconut husk charcoals by the described method processing of step (a) are put into rotary evaporator, step (b) is prepared to the maceration extract obtaining, be expelled to the coconut husk carbon surface of rotation with nitrogen, then control dipping temperature 70 ℃ of reactions 6 hours, obtain catalyst precursor;
(d) catalyst precursor step (c) being obtained is at N
2under protection at 160 ℃ dry 16 hours, obtain for 321 grams of the catalyst of chlorination aromatic hydrocarbon dechlorination hydrogenation.
By sodium formate reduction activation catalyst
300 grams of catalyst that obtain are as mentioned above put into rotary evaporator, and adding 308.5ml mass percent concentration is 7% formic acid solution.Mixing after 2 hours, dispersion becomes evenly, is white in color; Use oil bath that reactant is heated to 75 ℃ of reactions 2 hours; Heating rate with 8 ℃/h in three hours is warming up to 99 ℃ from 75 ℃; During this period, added successively the formic acid solution that 7.5ml, 5ml and 5ml mass percent concentration are 99% every 1 hour.After formic acid solution is added, oil bath is warmed up to 110 ℃, and reduction reaction 6h finishes reaction.Under nitrogen protection, by the catalyst obtaining dry 12h at 200 ℃, obtain approximately 300 grams of catalyst after reduction activation.Sample number into spectrum JS-03.
Embodiment 4
(a) 200 grams of carrier coconut husk charcoals being added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid is in the 400ml nitration mixture being mixed to get at 1: 1 according to volume ratio, boil 10 hours, filter, wash to the pH value of filtrate be 7, the coconut husk charcoal of gained is dried 10 hours at 120 ℃, obtain the pretreated coconut husk charcoal of nitration mixture, for subsequent use;
(b) 3.4 grams of palladium bichlorides and 53 grams of nickel chlorides are dissolved in the water, are mixed with 400ml maceration extract;
(c) 200 grams of coconut husk charcoals by the described method processing of step (a) are put into rotary evaporator, step (b) is prepared to the maceration extract obtaining, be expelled to the coconut husk carbon surface of rotation with nitrogen, then control dipping temperature 90 ℃ of reactions 3 hours, obtain catalyst precursor;
(d) catalyst precursor step (c) being obtained is at N
2under protection at 170 ℃ dry 15 hours, obtain for approximately 255 grams of the catalyst of chlorination aromatic hydrocarbon dechlorination hydrogenation.
By formic acid reduction activation catalyst
225 grams of catalyst that obtain are as mentioned above put into rotary evaporator, and adding 234ml mass percent concentration is 9% formic acid solution.Mixing after 2 hours, dispersion becomes evenly, is white in color; Use oil bath that reactant is heated to 72 ℃ of reactions 2 hours; Heating rate with 9 ℃/h in three hours is warming up to 99 ℃ from 70 ℃; During this period, adding 3.5ml mass percent concentration every 1 hour is 99% formic acid solution.After formic acid solution is added, oil bath is warmed up to 120 ℃, and reduction reaction 6h finishes reaction.Under nitrogen protection, by the catalyst obtaining dry 10h at 220 ℃, obtain 225 grams of catalyst after reduction activation.Sample number into spectrum JS-04.
Comparative example 1
This comparative example is derived from bibliographical information (Highly stable Pd/CeO
2catalyst for hydrodechlorination of chlorobenzene.Applied Catalysis B:Environmental, 2003,46:587-594).To adding in cerous nitrate solution ammoniacal liquor hydrolysis to obtain gel, this gel at 120 ℃ after dry 12h again in 500 ℃ of roasting 6h, obtain ceria supports.Adopt the method for deposition-precipitation to prepare palladium supported on ceria catalyst, process is as follows: with PdCl
2for presoma, use 1M Na
2cO
3for precipitating reagent, be about at pH under 10.5 condition and precipitate 1 hour, by sediment filter, after washing several times, dry 3h, 500 ℃ of roasting 5h Kaolinite Preparation of Catalysts at 120 ℃.Sample number into spectrum JS-05.
0.8 gram of catalyst preparing is as stated above placed in to quartz tube reactor, uses 30mL/min H
2after 300 ℃ of reduction 4h, reaction temperature is down to 140 ℃, pass into chlorobenzene with the speed of 4mL/h, the mol ratio of hydrogen and chlorobenzene is 3, and while reacting 1 hour, chlorobenzene conversion ratio approaches 100%, and when reaction 5h, chlorobenzene conversion ratio is reduced to 75.6% left and right.As can be seen here, although Pd catalyst serviceability temperature is lower, stability is relatively poor.
Comparative example 2
This comparative example is derived from a kind of patent of invention---" method of preparing novel hydrogenation and dechlorination catalyst " of Zhang Minghui of Nankai University etc., Chinese invention patent publication number CN101007280A.The NiB amorphous alloy (10～250nm) of non-loading type and nano nickel powder (5～100nm) are joined to PdCl
2in solution (Pd accounts for catalyst weight 0.01%～5%), stir until Pd ion by simple substance Ni displacement completely, product through deionized water washing to neutral, dry after at 200 ℃ crystallization 2.0h; Loaded catalyst is at PdCl
2in solution, add NiB amorphous alloy or nano-nickel powder last, add immediately carrier, stir until Pd ion by simple substance Ni displacement completely, product through deionized water washing to neutral, dry after at 200 ℃ crystallization 2.0h.Sample number into spectrum JS-06.
The catalyst preparing is as stated above added in 100ml compressive reaction still to 70 ℃ of reaction temperatures, pressure 1.0MPa, catalyst amount 6%(weight ratio), the ethanolic solution of 60ml chlorobenzene (4.2g), 1.2g NaOH, chlorobenzene conversion ratio 85.3% after reaction 5h.As can be seen here, although this catalyst reaction temperature is low, catalyst can not recycle, and cost of material is high.
The catalyst performance evaluation that embodiment 1～4 prepares:
After being mixed with 100 grams of coconut husk charcoals, 100 grams of catalyst after embodiment 1～4 reduction activation fill in fixed bed reactors temperature programming with air speed 20h
-1pass into hydrogen to 290 ℃ of left and right of reaction temperature, then reduce hydrogen gas space velocity to 18h
-1, by after chlorobenzene heating vaporization take air speed as 0.9h
-1speed pass into fixed bed reactors reactions, after product water absorbs, adopt gas-chromatography to carry out analytical gas product content (for consistent with comparative example, being the data of testing after reaction 5h), result is as following table:
| Embodiment | Catalyst numbering | Chlorobenzene conversion ratio/% |
| 1 | JS-01 | 99.3 |
| 2 | JS-02 | 99.2 |
| 3 | JS-03 | 99.4 |
| 4 | JS-04 | 99.5 |
| 5 | JS-05 | 75.6 |
| 6 | JS-06 | 85.3 |
Claims (6)
1. for a catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation, take coconut husk charcoal as carrier, take Metal Palladium, nickel as active component, it is characterized in that described Nickel Content In Catalyst is 5～25% of vehicle weight, palladium content is vehicle weight 0.1～5%.
2. the preparation method of the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation according to claim 1, is characterized in that comprising the following steps:
(a) carrier coconut husk charcoal being added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acid is in the nitration mixture forming at 1: 1 according to volume ratio, the mass volume ratio of described carrier coconut husk charcoal and nitration mixture is 1:2g/ml, boil 4～10 hours, then filter, wash to the pH value of filtrate be 5～7, the coconut husk charcoal of gained is dried to 5～10 hours at 120 ℃, obtain the coconut husk charcoal of acid treatment, for subsequent use;
(b is dissolved in the water palladium soluble salt and nickel soluble salt, obtains maceration extract, and in described maceration extract, the concentration of palladium is 0.005～0.3mol/L, and the concentration of nickel is 0.6～2.2mol/L;
(c) maceration extract that adds step (b) to obtain in the coconut husk charcoal obtaining to step (a) floods, and the mass volume ratio of described coconut husk charcoal and maceration extract is 1:2g/ml, 60～90 ℃ of dipping temperatures, and dip time is 3～7 hours, obtains catalyst precursor;
(d) catalyst precursor step (c) being obtained, under nitrogen protection, is dried 10～16 hours at 160～200 ℃, obtains the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation.
3. the preparation method of the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation according to claim 2, is characterized in that the described palladium soluble salt of step (b) is the one in palladium bichloride, six ammonium chloropalladates, palladium nitrate.
4. the preparation method of the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation according to claim 2, is characterized in that the described nickel soluble salt of step (b) is the one in nickel chloride, nickel acetate, six water nickel nitrates.
5. the using method of the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation claimed in claim 1, is characterized in that carrying out according to the following steps before use reduction activation:
(1) after the activated solution that is 5～10% by the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation with mass percent concentration mixes, react 2 hours at 70～75 ℃, described is 0.9～1.1:1g/ml for the catalyst of chlorination aromatic hydrocarbon dechlorination hydrogenation and the mass volume ratio of activated solution;
(2), with the heating rate temperature reaction of 8～10 ℃/h 3 hours, between temperature raising period, added 3～7.5ml mass percent concentration every 1 hour and be 99% activated solution;
(3) after activated solution has been added, be warming up to 110～120 ℃ and continue reaction 6～8h, finish reaction, then under nitrogen protection, dry 10～15h, obtains the catalyst after reduction activation at 180～220 ℃.
6. the using method of the catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation according to claim 5, is characterized in that the described activated solution of step (1) is the one in aqueous formic acid, aqueous sodium formate solution, the potassium formate aqueous solution.
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| CN110975881A (en) * | 2019-11-20 | 2020-04-10 | 扬州联博药业有限公司 | Dechlorination catalyst for synthesizing metacycline hydrochloride and preparation method and application thereof |
| CN110975881B (en) * | 2019-11-20 | 2023-03-10 | 扬州联博药业有限公司 | Dechlorination catalyst for synthesizing metacycline hydrochloride and preparation method and application thereof |
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