CN105688903B - It is a kind of to be used to produce Pt/C catalyst of halogenated aniline and preparation method thereof - Google Patents
It is a kind of to be used to produce Pt/C catalyst of halogenated aniline and preparation method thereof Download PDFInfo
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- CN105688903B CN105688903B CN201610145982.2A CN201610145982A CN105688903B CN 105688903 B CN105688903 B CN 105688903B CN 201610145982 A CN201610145982 A CN 201610145982A CN 105688903 B CN105688903 B CN 105688903B
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- activated carbon
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract 9
- 238000002360 preparation method Methods 0.000 title description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 338
- 239000002243 precursor Substances 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 40
- 229910052788 barium Inorganic materials 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 85
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 36
- 239000008139 complexing agent Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 28
- 150000001553 barium compounds Chemical class 0.000 claims description 27
- 150000003058 platinum compounds Chemical class 0.000 claims description 27
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 230000010355 oscillation Effects 0.000 claims description 14
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 13
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 13
- 239000001509 sodium citrate Substances 0.000 claims description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 13
- 241000370738 Chlorion Species 0.000 claims description 12
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005360 mashing Methods 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 9
- 229910001626 barium chloride Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000006193 liquid solution Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000006298 dechlorination reaction Methods 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 abstract description 3
- 150000001448 anilines Chemical class 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000005181 nitrobenzenes Chemical class 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Chemical group 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of for producing the Pt/C catalyst of halogenated aniline, the catalyst is made of carrier and the active component being carried on the carrier and aided metal component, the carrier is activated carbon, and the active component is Pt, and the aided metal component is La and Ba.The present invention also provides a kind of methods for preparing the catalyst, include the following steps：First, activated carbon is pre-processed；2nd, precursor solution is prepared；3rd, constant temperature in precursor solution is added to after activated carbon is beaten to stir；4th, it restored successively, be filtered, washed processing, obtain Pt/C catalyst.The present invention can solve that platinum dispersion degree in the prior art is low to be difficult to control the technical issues of leading to low catalyst activity, poor selectivity with granule size, platinum is in homogeneously dispersed state in made catalyst, substantially reduce the reaction time, reaction selectivity is high, catalyst activity improves more than 30%, and dechlorination impurity can be controlled in less than 0.1%.
Description
Technical field
The invention belongs to loaded noble metal catalyst preparing technical fields, and in particular to one kind is used to produce halogenated aniline
Pt/C catalyst and preparation method thereof.
Background technology
Halogenated aniline is a kind of important organic intermediate, is had extensively in fields such as medicine, pesticide, dyestuff and daily-use chemical industries
General purposes, market demand are very big.At present, most of chloro aminobenzen is restored by its corresponding nitro compound and is made, industry
It is upper mainly to use iron powder, akali sulphide and catalytic hydrogenating reduction method.Although iron powder reducing method and sodium sulfide reducing method cost are relatively low,
But environmental pollution is serious, eliminates increasingly.Catalytic hydrogenating reduction method is because with Atom economy, environmental-friendly and product and catalysis
The advantages that agent is easily separated and cause concern.Common hydrogenation catalyst mainly has skeleton nickel and carried noble metal.Skeleton nickel exists
There are existing micropores after a large amount of impurity and causticity alkali process in preparation process, and heat resistance is poor, easily forms hot-spot, influence
Hydrogenation conversion and selectivity.The active component of loaded noble metal catalyst is mainly precious metals pt, Pd, Ru, Rh etc..Its
In, Pt is most common, and Ru, Rh etc. are not easily recycled, and are only just used under special circumstances.And Pd is at unvarnished dose
C-X (X=Cl, Br, I) key easily occurs to be broken, except fluoride.In halogenated nitrobenzene selective hydrogenation reduction reaction, commonly use
Carrier have A12O3、TiO2、ZrO2、γ-Fe2O3, AC and CNTs etc., wherein AC is industrial most common.At present, Pt/C
Reaction condition is mild in the reaction because of it for catalyst, and catalytic activity and halogenated aniline selectivity are higher, are widely used in halogenated
Nitrobenzene hydrogenation.However the granular size of Pt/C catalyst that is prepared of conventional method and shape are difficult to control, this makes
The catalyst activity and selectivity that must be prepared is relatively low, and dehalogenation value is high.Therefore, in order to effectively inhibit dehalogenation reaction, how to make
The standby halogenated aniline Pt/C catalyst of production for providing high activity, selectivity and stability already becomes the heat of people's research
Point.
Invention content
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, to provide one kind for producing halogen
For the preparation method of the Pt/C catalyst of aniline.This method can solve that platinum dispersion degree in the prior art is low and granule size is difficult to
Control the technical issues of leading to low catalyst activity, poor selectivity, platinum is greatly shortened in homogeneously dispersed state in made catalyst
In the reaction time, reaction selectivity is high, and catalyst activity improves more than 30%, and dechlorination impurity can be controlled in less than 0.1%.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of Pt/C for being used to produce halogenated aniline
Catalyst, which is characterized in that the catalyst is by carrier and the active component being carried on the carrier and aided metal component
Composition, the carrier are activated carbon, and the active component is Pt, and the aided metal component is La and Ba, Pt in the catalyst
Mass percentage be the mass percentage of 0.5%~5%, La be the mass percentage of 0.005%~0.05%, Ba
It is 0.01%~0.1%.
A kind of above-mentioned Pt/C catalyst for being used to produce halogenated aniline, which is characterized in that the matter of Pt in the catalyst
Amount percentage composition be 0.5%~3%, La mass percentage be 0.005%~0.02%, Ba mass percentage be
0.01%~0.05%.
A kind of above-mentioned Pt/C catalyst for being used to produce halogenated aniline, which is characterized in that the matter of Pt in the catalyst
The mass percentage that the mass percentage that amount percentage composition is 1%, La is 0.01%, Ba is 0.03%.
In addition, the present invention also provides a kind of method for preparing the above-mentioned Pt/C catalyst for being used to produce halogenated aniline,
It is characterized in that, this method includes the following steps：
Step 1: activated carbon is added in hydrogen peroxide solution, filtered out after soaking at room temperature 1h~5h, with pure water into
Property, then the activated carbon after washing is added in ammonia spirit, soaking at room temperature 16h~filter out afterwards for 24 hours, with pure water into
Property, obtain pretreated activated carbon；
Step 2: water-soluble platinum compound, water soluble lanthanum compound, water-soluble barium compound and complexing agent are added in into pure water
Middle stirring is all dissolved to solid matter, is subsequently placed in sonic oscillation 0.5h~2h in ultrasonic oscillator, it is molten to obtain presoma
Liquid；The complexing agent is sodium citrate or disodium ethylene diamine tetraacetate, a concentration of 5g/L of platinum in the precursor solution~
25g/L；
Step 3: before being added to described in step 2 after activated carbon pretreated described in step 1 is beaten with pure water
It drives in liquid solution, 3h~6h is stirred under conditions of being 60 DEG C~80 DEG C in temperature, it then will be added with activated carbon using inorganic lye
The pH value of precursor solution be adjusted to 8~11, continue later be 60 DEG C~80 DEG C in temperature under conditions of stir 0.5h~1h,
Obtain mixed solution；The inorganic lye is sodium hydroxide solution or sodium carbonate liquor；
Step 4: reducing agent is added in mixed solution described in step 3, under conditions of temperature is 70 DEG C~90 DEG C
It stirs 2h~5h and carries out reduction treatment, retained after filtering with pure water to no chlorion, obtain producing halogenated aniline
Pt/C catalyst；The reducing agent is hydrazine hydrate solution or sodium borohydride solution, and the dosage of the reducing agent is 3 times of platinum quality
~10 times.
Above-mentioned method, which is characterized in that the specific surface area of activated carbon described in step 1 is 1000m2/ g~1500m2/
G, the granularity of the activated carbon is 50 μm~74 μm.
Above-mentioned method, which is characterized in that the mass concentration of hydrogen peroxide solution described in step 1 is 5%~15%, institute
The mass concentration for stating ammonia spirit is 1%~10%.
Above-mentioned method, which is characterized in that water-soluble platinum compound described in step 2 be chloroplatinic acid or platinic sodium chloride, institute
Lanthanum compound is stated as lanthanum chloride or lanthanum nitrate, the barium compound is barium chloride or barium nitrate.
Above-mentioned method, which is characterized in that the dosage of complexing agent described in step 2 is 1 times~3 times of platinum quality.
Above-mentioned method, which is characterized in that in step 3 activated carbon mashing solution in activated carbon a concentration of 50g/L~
100g/L。
Above-mentioned method, which is characterized in that the mass concentration of sodium hydroxide solution described in step 3 and sodium carbonate liquor
It is 3%~10%, the mass concentration of hydrazine hydrate solution described in step 4 and sodium borohydride solution is 20%~80%.
Heretofore described room temperature refers to 23 DEG C ± 2 DEG C.
Compared with the prior art, the present invention has the following advantages：
1st, the present invention first carries out soaking at room temperature processing with hydrogen peroxide solution to activated carbon, improves the oxyacid of carrier surface
Property the content of group, the polarity that reduces reproducibility group, enhance surface, so as to improve activated carbon to adsorption of metal ions
Energy is conducive to improve the uniformity of Pt particles；Then by hydrogen peroxide, treated that activated carbon is handled with ammonia spirit, increases
The nitrogen-containing functional group of activated carbon surface, so as to be conducive to improve selectivity of the catalyst in halogenated aniline reaction, certain journey
The poisoning of catalyst organic amine has been resisted on degree.
2nd, successively hydrogen peroxide solution and ammonia spirit carry out soaking at room temperature processing to the present invention to absorbent charcoal carrier, overcome
The shortcomings that a large amount of spent acid and nitrogen dioxide gas being generated during conventionally employed nitric acid high-temperature process activated carbon, while the present invention
Processing is smaller on influences such as the specific surface area of activated carbon and pore structures.
3rd, Pt/C catalyst is modified for aided metal present invention introduces a certain amount of La and Ba, uses it for producing halogenated aniline
Reaction, reaction process do not need to add other auxiliary agents, you can improve reaction selectivity.
4th, the present invention adds in sodium citrate or disodium ethylene diamine tetraacetate in precursor solution, can be with active component platinum
Chela synthetic macromolecule so as to control the distribution of active component on the activated carbon, improves active component and is distributed on the activated carbon
Uniformity, so as to improve the activity of catalyst.
5th, the present invention carries out ultrasonic vibration to precursor solution, and each component substance in solution is enable to be sufficiently mixed
It is even, and active component is enable preferably to be chelated with sodium citrate or disodium ethylene diamine tetraacetate, improve it on the activated carbon
Dispersibility.
6th, the present invention can solve that dispersion degree of the platinum in the prior art on absorbent charcoal carrier surface is low and granularity is big
It is small be difficult to control caused by catalyst activity is low and the technical issues of poor selectivity, in made catalyst, the average grain of platinum particles
Diameter about 10nm, and in homogeneously dispersed state, catalyst activity improves more than 30% than typical catalyst activity, substantially reduces
In the reaction time, reaction selectivity is high, and dechlorination impurity can be controlled in less than 0.1%.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Description of the drawings
Fig. 1 is the TEM photos that the embodiment of the present invention 1 is used to produce the Pt/C catalyst of halogenated aniline.
Specific embodiment
Embodiment 1
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 1%, La in the catalyst is 0.01%, Ba contain
Measure is 0.03%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1200m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 10% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 3h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 5% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 20h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.1g Pt, the water soluble lanthanum compound containing 0.001g La, contain
There are the water-soluble barium compound of 0.003g Ba and 0.2g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 1h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound be chloroplatinic acid, the lanthanum
Conjunction object is lanthanum nitrate, and the barium compound is barium nitrate, and the complexing agent is sodium citrate, and platinum is dense in the precursor solution
It spends for 15g/L；
Step 3: pretreated activated carbon described in step 9.896g step 1 is beaten with pure water, make beating for activated carbon
It in slurry solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, is first 70 DEG C in temperature
Under the conditions of stir 4h, then use mass concentration will be added with the pH of the precursor solution of activated carbon for 7% sodium hydroxide solution
Value is adjusted to 10, continues to obtain mixed solution to stir 1h under conditions of 70 DEG C in temperature later；
Step 4: the sodium borohydride solution that 0.3g mass concentrations are 20% is added in mixed solution described in step 3,
Then stirring 4h carries out reduction treatment under conditions of being 80 DEG C in temperature, filters out solid matter, then with pure water extremely
No chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 2
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 1%, La in the catalyst is 0.05%, Ba contain
Measure is 0.01%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1300m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 8% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 2h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 8% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 18h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.1g Pt, the water soluble lanthanum compound containing 0.005g La, contain
There are the water-soluble barium compound of 0.001g Ba and 0.3g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 1.5h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound be chloroplatinic acid, the lanthanum
Compound is lanthanum nitrate, and the barium compound is barium nitrate, and the complexing agent is sodium citrate, platinum in the precursor solution
A concentration of 20g/L；
Step 3: activated carbon pretreated described in 9.894g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 60g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 65 DEG C
5h is stirred under part, then uses mass concentration will be added with the pH value of the precursor solution of activated carbon for 10% sodium hydroxide solution
10 are adjusted to, continues to obtain mixed solution to stir 1h under conditions of 65 DEG C in temperature later；
Step 4: the hydrazine hydrate solution that 0.5g mass concentrations are 80% is added in mixed solution described in step 3, so
Stirring 3h carries out reduction treatment under conditions of being afterwards 75 DEG C in temperature, solid matter is filtered out, then with pure water to nothing
Chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 3
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 1%, La in the catalyst is 0.02%, Ba contain
Measure is 0.02%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 10% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 2h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 6% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 22h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.1g Pt, the water soluble lanthanum compound containing 0.002g La, contain
There are the water-soluble barium compound of 0.002g Ba and 0.1g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 1h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound be chloroplatinic acid, the lanthanum
Conjunction object is lanthanum nitrate, and the barium compound is barium nitrate, and the complexing agent is sodium citrate, and platinum is dense in the precursor solution
It spends for 15g/L；
Step 3: activated carbon pretreated described in 9.896g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 75g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 75 DEG C
5h is stirred under part, then 10 will be adjusted to added with the pH value of the precursor solution of activated carbon using inorganic base, continues later in temperature
Spend be 75 DEG C under conditions of stir 1h, obtain mixed solution；
Step 4: the hydrazine hydrate solution that 1g mass concentrations are 80% is added in mixed solution described in step 3, then
Stirring 3h carries out reduction treatment under conditions of being 70 DEG C in temperature, solid matter is filtered out, then with pure water to no chlorine
Ion inclusion obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 4
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 1%, La in the catalyst is 0.005%, Ba contain
Measure is 0.025%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1200m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 10% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 4h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 6% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 18h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.1g Pt, the water soluble lanthanum compound containing 0.0005g La,
Water-soluble barium compound containing 0.0025g Ba and 0.1g complexing agents are added in pure water after stirring to solid matter all dissolving,
Sonic oscillation 0.5h in ultrasonic oscillator is placed in, obtains precursor solution；The water-soluble platinum compound is chloroplatinic acid, described
Lanthanum compound is lanthanum nitrate, and the barium compound is barium nitrate, and the complexing agent is sodium citrate, platinum in the precursor solution
A concentration of 15g/L；
Step 3: activated carbon pretreated described in 9.897g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 60 DEG C
3h is stirred under part, then use mass concentration for 5% Na2CO3Solution will be adjusted added with the pH value of the precursor solution of activated carbon
It is 11, continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the sodium borohydride solution that 0.5g mass concentrations are 20% is added in mixed solution described in step 3,
Then stirring 2h carries out reduction treatment under conditions of being 80 DEG C in temperature, filters out solid matter, then with pure water extremely
No chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 5
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 3%, La in the catalyst is 0.015%, Ba contain
Measure is 0.02%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 15% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 5h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 3% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 22h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.3g Pt, the water soluble lanthanum compound containing 0.0015g La,
Water-soluble barium compound containing 0.002g Ba and 0.1g complexing agents are added in pure water after stirring to solid matter all dissolving,
Sonic oscillation 0.5h in ultrasonic oscillator is placed in, obtains precursor solution；The water-soluble platinum compound be platinic sodium chloride, institute
Lanthanum compound is stated as lanthanum chloride, the barium compound is barium chloride, and the complexing agent is disodium ethylene diamine tetraacetate, the forerunner
A concentration of 15g/L of platinum in liquid solution；
Step 3: activated carbon pretreated described in 9.6965g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 60 DEG C
3h is stirred under part, then uses mass concentration that will be adjusted for 10% NaOH solution added with the pH value of the precursor solution of activated carbon
It is 11, continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the sodium borohydride solution that 0.9g mass concentrations are 20% is added in mixed solution described in step 3,
Then stirring 2h carries out reduction treatment under conditions of being 80 DEG C in temperature, filters out solid matter, then with pure water extremely
No chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 6
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, it is the quality percentage of 0.01%, Ba that the mass percentage of Pt, which is the mass percentage of 0.5%, La, in the catalyst
Content is 0.05%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 15% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 5h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 3% to neutrality by the washing active carbon filtered out, in
20h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions and filters out activated carbon, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.05g Pt, the water soluble lanthanum compound containing 0.001g La,
Water-soluble barium compound containing 0.005g Ba and 0.1g complexing agents are added in pure water after stirring to solid matter all dissolving,
Sonic oscillation 0.5h in ultrasonic oscillator is placed in, obtains precursor solution；The water-soluble platinum compound be platinic sodium chloride, institute
Lanthanum compound is stated as lanthanum chloride, the barium compound is barium chloride, and the complexing agent is disodium ethylene diamine tetraacetate, the forerunner
A concentration of 15g/L of platinum in liquid solution；
Step 3: activated carbon pretreated described in 9.944g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 60 DEG C
3h is stirred under part, then use mass concentration for 5% Na2CO3Solution will be adjusted added with the pH value of the precursor solution of activated carbon
It is 11, continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the sodium borohydride solution that 0.5g mass concentrations are 20% is added in mixed solution described in step 3,
Then stirring 2h carries out reduction treatment under conditions of being 80 DEG C in temperature, filters out solid matter, then with pure water extremely
No chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 7
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 1%, La in the catalyst is 0.04%, Ba contain
Measure is 0.05%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 15% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 5h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 3% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 22h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.1g Pt, the water soluble lanthanum compound containing 0.004g La, contain
There are the water-soluble barium compound of 0.005g Ba and 0.1g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 0.5h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound is platinic sodium chloride, described
Lanthanum compound is lanthanum chloride, the barium compound be barium chloride, the complexing agent be disodium ethylene diamine tetraacetate, the presoma
A concentration of 15g/L of platinum in solution；
Step 3: activated carbon pretreated described in 9.891g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 60 DEG C
3h is stirred under part, then use mass concentration for 8% Na2CO3Solution will be adjusted added with the pH value of the precursor solution of activated carbon
It is 11, continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the sodium borohydride solution that 1g mass concentrations are 20% is added in mixed solution described in step 3, so
Stirring 2h carries out reduction treatment under conditions of being afterwards 80 DEG C in temperature, solid matter is filtered out, then with pure water to nothing
Chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 8
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 3%, La in the catalyst is 0.03%, Ba contain
Measure is 0.05%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 12% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 3h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 10% to neutrality by the washing active carbon filtered out,
Filter out activated carbon after impregnating 22h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out extremely
Neutrality obtains pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.3g Pt, the water soluble lanthanum compound containing 0.003g La, contain
There are the water-soluble barium compound of 0.005g Ba and 0.3g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 2h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound be platinic sodium chloride, the lanthanum
Compound is lanthanum chloride, and the barium compound is barium chloride, and the complexing agent is disodium ethylene diamine tetraacetate, and the presoma is molten
A concentration of 25g/L of platinum in liquid；
Step 3: activated carbon pretreated described in 9.692g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 100g/L of activated carbon, is added to described in step 2 in precursor solution, is first 60 DEG C in temperature
Under the conditions of stir 3h, then use mass concentration will be added with the pH value tune of the precursor solution of activated carbon for 10% NaOH solution
It is 10 to save, and continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the sodium borohydride solution that 1.5g mass concentrations are 20% is added in mixed solution described in step 3,
Then stirring 2h carries out reduction treatment under conditions of being 80 DEG C in temperature, filters out solid matter, then with pure water extremely
No chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 9
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 5%, La in the catalyst is 0.03%, Ba contain
Measure is 0.05%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 15% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 5h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 3% to neutrality by the washing active carbon filtered out, in
Impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions and filter out activated carbon afterwards for 24 hours, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.5g Pt, the water soluble lanthanum compound containing 0.003g La, contain
There are the water-soluble barium compound of 0.005g Ba and 0.1g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 0.5h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound is platinic sodium chloride, described
Lanthanum compound is lanthanum chloride, the barium compound be barium chloride, the complexing agent be disodium ethylene diamine tetraacetate, the presoma
A concentration of 15g/L of platinum in solution；
Step 3: activated carbon pretreated described in 9.492g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 60 DEG C
3h is stirred under part, then uses mass concentration that will be adjusted for 5% NaOH solution added with the pH value of the precursor solution of activated carbon
It is 11, continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the hydrazine hydrate solution that 1.5g mass concentrations are 80% is added in mixed solution described in step 3, so
Stirring 2h carries out reduction treatment under conditions of being afterwards 80 DEG C in temperature, solid matter is filtered out, then with pure water to nothing
Chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 10
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 3%, La in the catalyst is 0.05%, Ba contain
Measure is 0.05%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 5% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 1h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 1% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 16h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.3g Pt, the water soluble lanthanum compound containing 0.005g La, contain
There are the water-soluble barium compound of 0.005g Ba and 0.3g complexing agents to add in pure water and stir to solid matter all dissolving, put
The sonic oscillation 0.5h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound is platinic sodium chloride, described
Lanthanum compound is lanthanum chloride, the barium compound be barium chloride, the complexing agent be disodium ethylene diamine tetraacetate, the presoma
A concentration of 5g/L of platinum in solution；
Step 3: activated carbon pretreated described in 9.69g step 1 is beaten with pure water, the mashing for making activated carbon is molten
It in liquid after a concentration of 50g/L of activated carbon, is added to described in step 2 in precursor solution, first in the condition that temperature is 80 DEG C
Then lower stirring 6h uses mass concentration to be adjusted to the pH value of the precursor solution added with activated carbon for 5% NaOH solution
8, continue to obtain mixed solution to stir 1h under conditions of 80 DEG C in temperature later；
Step 4: the hydrazine hydrate solution that 3g mass concentrations are 50% is added in mixed solution described in step 3, then
Stirring 2h carries out reduction treatment under conditions of being 80 DEG C in temperature, solid matter is filtered out, then with pure water to no chlorine
Ion inclusion obtains the Pt/C catalyst for producing halogenated aniline.
Embodiment 11
The present embodiment is used to produce the Pt/C catalyst of halogenated aniline by carrier and the activity being carried on the carrier
Component and aided metal component composition, the carrier are activated carbon, and the active component is Pt, the aided metal component for La and
Ba, the quality percentage that the mass percentage that the mass percentage of Pt is 5%, La in the catalyst is 0.05%, Ba contain
Measure is 0.1%.
The preparation method of Pt/C catalyst that the present embodiment is used to produce halogenated aniline includes the following steps：
Step 1: it is 1500m by specific surface area2/ g, granularity are that 50 μm~74 μm of activated carbon is added to mass concentration and is
In 15% hydrogen peroxide solution, activated carbon is filtered out, then will with pure water after 5h is impregnated under 23 DEG C of ± 2 DEG C of standard atmosphere conditions
Then activated carbon after washing is added in the ammonia spirit that mass concentration is 3% to neutrality by the washing active carbon filtered out, in
Filter out activated carbon after impregnating 22h under 23 DEG C of ± 2 DEG C of standard atmosphere conditions, then with pure water by the washing active carbon filtered out into
Property, obtain pretreated activated carbon；
Step 2: by the water-soluble platinum compound containing 0.5g Pt, the water soluble lanthanum compound containing 0.005g La, contain
There are the water-soluble barium compound of 0.01g Ba and 0.5g complexing agents to add in pure water and stir to solid matter all dissolving, be placed in
Sonic oscillation 0.5h in ultrasonic oscillator, obtains precursor solution；The water-soluble platinum compound be platinic sodium chloride, the lanthanum
Compound is lanthanum chloride, and the barium compound is barium chloride, and the complexing agent is disodium ethylene diamine tetraacetate, and the presoma is molten
A concentration of 15g/L of platinum in liquid；
Step 3: activated carbon pretreated described in 9.485g step 1 is beaten with pure water, make the mashing of activated carbon
It in solution after a concentration of 80g/L of activated carbon, is added to described in step 2 in precursor solution, first in the item that temperature is 60 DEG C
3h is stirred under part, then uses mass concentration that will be adjusted for 3% NaOH solution added with the pH value of the precursor solution of activated carbon
It is 11, continues to obtain mixed solution to stir 0.5h under conditions of 60 DEG C in temperature later；
Step 4: the sodium borohydride solution that 5g mass concentrations are 40% is added in mixed solution described in step 3, so
Stirring 2h carries out reduction treatment under conditions of being afterwards 80 DEG C in temperature, solid matter is filtered out, then with pure water to nothing
Chlorion retains, and obtains the Pt/C catalyst for producing halogenated aniline.
Comparative example 1
This comparative example prepares Pt/C catalyst, the system of this comparative example Pt/C catalyst using method similar to Example 1
Preparation Method the difference is that only with embodiment 1：Hydrogen peroxide and ammonium hydroxide process integration is not used to handle activated carbon, but is used
Traditional nitric acid reflow process pre-processes activated carbon.
Comparative example 2
This comparative example prepares Pt/C catalyst, the system of this comparative example Pt/C catalyst using method similar to Example 1
Preparation Method the difference is that only with embodiment 1：Hydrogen peroxide and ammonium hydroxide process integration is not used to handle activated carbon, but is only adopted
Activated carbon is pre-processed with hydrogen peroxide.
Comparative example 3
This comparative example prepares Pt/C catalyst, the system of this comparative example Pt/C catalyst using method similar to Example 1
Preparation Method the difference is that only with embodiment 1：Hydrogen peroxide and ammonium hydroxide process integration is not used to handle activated carbon, but is only adopted
Activated carbon is pre-processed with ammonium hydroxide.
Comparative example 4
This comparative example prepares Pt/C catalyst, the system of this comparative example Pt/C catalyst using method similar to Example 1
Preparation Method the difference is that only with embodiment 1：Pt metal, La, Ba are contained only in precursor solution, but without complexing agent.
Comparative example 5
This comparative example prepares Pt/C catalyst, the system of this comparative example Pt/C catalyst using method similar to Example 1
Preparation Method the difference is that only with embodiment 1：Pt metal, La and complexing agent are contained only in precursor solution, but without gold
Belong to Ba.
Comparative example 6
This comparative example prepares Pt/C catalyst, the system of this comparative example Pt/C catalyst using method similar to Example 1
Preparation Method the difference is that only with embodiment 1：Pt metal, Ba and complexing agent are contained only in precursor solution, but without gold
Belong to La.
Comparative evaluation is carried out to catalyst performance prepared by 1-11 of the embodiment of the present invention and comparative example 1-6, detailed process is：
By 0.037g 1%Pt/C catalyst (other content Pt/C convert by Pt contents), 30g parachloronitrobenzenes and 60mL methanol
It sequentially adds in reaction kettle, hydrogen is passed through into reactor, carry out catalytic hydrogenation reaction under conditions of pressure is 0.8MPa, instead
It is 80 DEG C to answer temperature, is reacted until Hydrogen Vapor Pressure does not decline, and reaction product is analyzed with gas chromatograph after reaction,
It the results are shown in Table 1.
Table 1 produces the test data of parachloroanilinum using catalyst to catalyzing hydrogenating of the present invention
By table 1, it is apparent that modification Pt/C catalyst prepared by the present invention is prepared in parachloronitrobenzene catalytic hydrogenation
There is higher activity and selectivity in the reaction of parachloroanilinum.Compared with Example 1, comparative example 1 returns activated carbon through nitric acid
Stream process, without using hydrogen peroxide and AMMONIA TREATMENT activated carbon, catalyst reaction activity is not much different, but selectivity and product
Yield is not high, dechlorinated side product>3%；Activated carbon is only used dioxygen water process by comparative example 2, and does not have to AMMONIA TREATMENT, and catalyst is anti-
Should be active constant, but selectivity and product yield be not high, dechlorinated side product>1.5%；Activated carbon is only used ammonium hydroxide by comparative example 3
Processing, and handled without hydrogen peroxide, catalyst choice is higher, but reactivity is lower, and the reaction time increases very much, and product is received
Rate is relatively low；There was only Pt, La, Ba in 4 precursor solution of comparative example, be not added with sodium citrate, catalyst choice is higher, but reacts and live
Property and product yield are lower；There was only Pt, La and sodium citrate in 5 precursor solution of comparative example, do not add in Ba, catalyst choice
It is higher, but reactivity and product yield are lower；There was only Pt, Ba and sodium citrate in 6 precursor solution of comparative example, do not add in
La, catalyst choice is higher, but reactivity and product yield are lower.So it is added when being modified with La, Ba to Pt/C
Sodium citrate or disodium ethylene diamine tetraacetate can improve the activity and selectivity of catalyst；Simultaneously activated carbon by hydrogen peroxide and
After AMMONIA TREATMENT, the performance also very big influence on catalyst.When aided metal, hydrogen peroxide, ammonium hydroxide and several persons of complexing agent are provided simultaneously with,
The activity and selectivity of catalyst is significantly improved simultaneously, and the performance of catalyst reaches best.
Embodiment 1Pt/C catalyst is carried out according to above-mentioned catalytic performance test method to repeat catalytic test, each reaction
Catalyst is washed afterwards, catalytic test result is repeated and is shown in Table 2.
Table 2 repeats catalytic test data
From table 2, it is apparent that the catalyst stability and mithridatism of the present invention are good, catalyst reuse still shows
Go out higher activity and selectivity.
In addition, the TEM photos of 1Pt/C catalyst of the embodiment of the present invention are as shown in Figure 1, as shown in Figure 1, the present invention is made to be urged
The average grain diameter of platinum particles about 10nm in agent, and it is dispersed in absorbent charcoal carrier surface.
It follows that the present invention is modified Pt/C catalyst using aided metal La and Ba, and using hydrogen peroxide and ammonium hydroxide to work
Property charcoal is handled, and is chelated using complexing agent so that and the activity and selectivity of made catalyst is significantly improved simultaneously,
The performance of catalyst reaches best.The present invention can solve dispersion degree of the platinum in the prior art on absorbent charcoal carrier surface
It is low be difficult to control with granule size caused by catalyst activity is low and the technical issues of poor selectivity, in made catalyst, platinum grain
The average grain diameter about 10nm of son, and in homogeneously dispersed state, catalyst activity improves more than 30% than typical catalyst activity,
The reaction time is substantially reduced, reaction selectivity is high, and dechlorination impurity can be controlled in less than 0.1%.
The above is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art substantially makees above example, still fall within technical solution of the present invention
Protection domain in.
Claims (10)
1. a kind of Pt/C catalyst for being used to produce halogenated aniline, which is characterized in that the catalyst is by carrier and is carried on
Active component and aided metal component composition on the carrier, the carrier are activated carbon, and the active component is Pt, described to help
Metal component is La and Ba, and the mass percentage of Pt is that the mass percentage of 0.5%~5%, La is in the catalyst
The mass percentage of 0.005%~0.05%, Ba are 0.01%~0.1%；
The method of Pt/C catalyst for producing halogenated aniline is prepared to include the following steps：
Step 1: activated carbon is added in hydrogen peroxide solution, filtered out after soaking at room temperature 1h~5h, with pure water to neutrality,
Then the activated carbon after washing is added in ammonia spirit, soaking at room temperature 16h~filter out afterwards for 24 hours, with pure water to neutrality,
Obtain pretreated activated carbon；
Step 2: water-soluble platinum compound, water soluble lanthanum compound, water-soluble barium compound and complexing agent are added in pure water and stirred
It mixes to solid matter and all dissolves, be subsequently placed in sonic oscillation 0.5h~2h in ultrasonic oscillator, obtain precursor solution；Institute
Complexing agent is stated as sodium citrate or disodium ethylene diamine tetraacetate, a concentration of 5g/L~25g/L of platinum in the precursor solution；
Step 3: it is added to presoma described in step 2 after activated carbon pretreated described in step 1 is beaten with pure water
It, then will be before added with activated carbon using inorganic lye in temperature to stir 3h~6h under conditions of 60 DEG C~80 DEG C in solution
The pH value for driving liquid solution is adjusted to 8~11, continues to stir 0.5h~1h under conditions of being later 60 DEG C~80 DEG C in temperature, obtain
Mixed solution；The inorganic lye is sodium hydroxide solution or sodium carbonate liquor；
Step 4: reducing agent is added in mixed solution described in step 3, stirred under conditions of being 70 DEG C~90 DEG C in temperature
2h~5h carries out reduction treatment, is retained after filtering with pure water to no chlorion, obtains the Pt/C for producing halogenated aniline
Catalyst；The reducing agent is hydrazine hydrate solution or sodium borohydride solution, and the dosage of the reducing agent is 3 times~the 10 of platinum quality
Times.
A kind of 2. Pt/C catalyst for being used to produce halogenated aniline according to claim 1, which is characterized in that the catalysis
It is the quality hundred of 0.005%~0.02%, Ba that the mass percentage of Pt, which is the mass percentage of 0.5%~3%, La, in agent
It is 0.01%~0.05% to divide content.
A kind of 3. Pt/C catalyst for being used to produce halogenated aniline according to claim 2, which is characterized in that the catalysis
The mass percentage that the mass percentage that the mass percentage of Pt is 1%, La in agent is 0.01%, Ba is 0.03%.
4. a kind of prepare for producing the method for the Pt/C catalyst of halogenated aniline as described in claim 1,2 or 3, feature exists
In this method includes the following steps：
Step 1: activated carbon is added in hydrogen peroxide solution, filtered out after soaking at room temperature 1h~5h, with pure water to neutrality,
Then the activated carbon after washing is added in ammonia spirit, soaking at room temperature 16h~filter out afterwards for 24 hours, with pure water to neutrality,
Obtain pretreated activated carbon；
Step 2: water-soluble platinum compound, water soluble lanthanum compound, water-soluble barium compound and complexing agent are added in pure water and stirred
It mixes to solid matter and all dissolves, be subsequently placed in sonic oscillation 0.5h~2h in ultrasonic oscillator, obtain precursor solution；Institute
Complexing agent is stated as sodium citrate or disodium ethylene diamine tetraacetate, a concentration of 5g/L~25g/L of platinum in the precursor solution；
Step 3: it is added to presoma described in step 2 after activated carbon pretreated described in step 1 is beaten with pure water
It, then will be before added with activated carbon using inorganic lye in temperature to stir 3h~6h under conditions of 60 DEG C~80 DEG C in solution
The pH value for driving liquid solution is adjusted to 8~11, continues to stir 0.5h~1h under conditions of being later 60 DEG C~80 DEG C in temperature, obtain
Mixed solution；The inorganic lye is sodium hydroxide solution or sodium carbonate liquor；
Step 4: reducing agent is added in mixed solution described in step 3, stirred under conditions of being 70 DEG C~90 DEG C in temperature
2h~5h carries out reduction treatment, is retained after filtering with pure water to no chlorion, obtains the Pt/C for producing halogenated aniline
Catalyst；The reducing agent is hydrazine hydrate solution or sodium borohydride solution, and the dosage of the reducing agent is 3 times~the 10 of platinum quality
Times.
5. according to the method described in claim 4, it is characterized in that, the specific surface area of activated carbon described in step 1 is 1000m2/
G~1500m2/ g, the granularity of the activated carbon is 50 μm~74 μm.
6. according to the method described in claim 4, it is characterized in that, the mass concentration of hydrogen peroxide solution described in step 1 is
5%~15%, the mass concentration of the ammonia spirit is 1%~10%.
7. according to the method described in claim 4, it is characterized in that, water-soluble platinum compound described in step 2 for chloroplatinic acid or
Platinic sodium chloride, the lanthanum compound are lanthanum chloride or lanthanum nitrate, and the barium compound is barium chloride or barium nitrate.
8. according to the method described in claim 4, it is characterized in that, the dosage of complexing agent described in step 2 is the 1 of platinum quality
Times~3 times.
9. according to the method described in claim 4, it is characterized in that, in step 3 activated carbon mashing solution in activated carbon it is dense
It spends for 50g/L~100g/L.
10. according to the method described in claim 4, it is characterized in that, sodium hydroxide solution described in step 3 and sodium carbonate are molten
The mass concentration of liquid is 3%~10%, and the mass concentration of hydrazine hydrate solution described in step 4 and sodium borohydride solution is
20%~80%.
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| CN107876016B (en) * | 2017-11-19 | 2020-06-26 | 西安元创化工科技股份有限公司 | Low-temperature liquid-phase dechlorinating agent and preparation method and application thereof |
| CN107970967B (en) * | 2017-11-21 | 2020-07-14 | 江苏扬农化工集团有限公司 | Preparation method of catalyst for preparing chloroarylamine by catalytic hydrogenation |
| CN112174831B (en) * | 2020-11-06 | 2022-08-05 | 西安凯立新材料股份有限公司 | Method for synthesizing o-chloroaniline by using platinum carbon catalyst |
| CN113976114B (en) * | 2021-10-29 | 2024-04-19 | 西安凯立新材料股份有限公司 | Method for catalyzing methyl cyclohexane dehydrogenation by platinum-carbon catalyst |
| CN115178257B (en) * | 2022-06-13 | 2024-06-07 | 浙江工业大学 | Preparation method and application of Pt-Ru-La/C multi-metal catalyst |
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