CN109317139B - Preparation of sulfur-doped activated carbon-supported noble metal catalyst and application of sulfur-doped activated carbon-supported noble metal catalyst in hydrogenation reaction of halogenated aromatic nitro compound - Google Patents
Preparation of sulfur-doped activated carbon-supported noble metal catalyst and application of sulfur-doped activated carbon-supported noble metal catalyst in hydrogenation reaction of halogenated aromatic nitro compound Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 halogenated aromatic nitro compound Chemical class 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000000243 solution Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 239000008367 deionised water Substances 0.000 claims abstract description 51
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 20
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000001632 sodium acetate Substances 0.000 claims abstract description 16
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 14
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 239000012065 filter cake Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 3
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 29
- 238000010335 hydrothermal treatment Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- QUIMTLZDMCNYGY-UHFFFAOYSA-N 2,4-dichloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1Cl QUIMTLZDMCNYGY-UHFFFAOYSA-N 0.000 description 6
- 150000001448 anilines Chemical class 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000005181 nitrobenzenes Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/391—
-
- B01J35/393—
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
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- 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
- B01J37/20—Sulfiding
-
- 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
Abstract
The invention discloses a preparation method of a sulfur-doped activated carbon-supported noble metal catalyst and application thereof in hydrogenation reaction of halogenated aromatic nitro compounds, wherein the preparation method comprises the following steps: (1) preparing sulfur-doped activated carbon by a hydrothermal method; (2) adding sulfur-doped activated carbon into deionized water to prepare slurry, dropwise adding a soluble noble metal compound solution while stirring, wherein the noble metal is Pd or Pt, and stirring; adding sodium acetate solution and stirring; dropwise adding an alkaline solution to adjust the pH value to 7-9, and continuously stirring; and then, formaldehyde solution is dripped for reduction to obtain the sulfur-doped active carbon supported noble metal catalyst. The preparation method of the catalyst is simple to operate, low in cost, small in pollution and beneficial to industrial application. The catalyst is applied to the preparation of halogenated aromatic amine by the liquid-phase catalytic hydrogenation of halogenated aromatic nitro compounds, has high conversion rate and selectivity and good stability, and can be recycled for multiple times.
Description
(I) technical field
The invention relates to a preparation method of a sulfur-doped activated carbon supported noble metal catalyst and application thereof in a reaction for preparing halogenated arylamine by selectively hydrogenating a halogenated aromatic nitro compound.
(II) technical background
The heterogeneous catalyst with different types of carriers loaded with noble metals has the advantages of high activity, easy separation and recovery, reusability and the like, and is widely applied to various organic synthesis reactions. The carbon material is unique in pore structure, mechanical property, electrochemical property and the like in a plurality of carrier materials, and the Pd/C catalyst is commercialized and has wide application prospect in various heterogeneous catalytic reactions. However, due to its excessively high activity, when catalyzing selective hydrogenation of a substance having a plurality of reducing functional groups, excessive hydrogenation tends to occur, resulting in low selectivity of the target product. And the Pd nano-particles as the active centers are easy to run off, and are easy to agglomerate or inactivate in the catalytic reaction process due to the higher surface energy of the Pd nano-particles.
The halogenated aniline is an extremely important organic intermediate and is widely applied to synthesis of fine chemicals such as medicines, pesticides and the like. The traditional commercial Pd/C catalyst has the problems of poor selectivity, poor stability and the like in the reaction of preparing the halogenated aromatic amine by selectively hydrogenating the halogenated aromatic nitro compound. Therefore, the method for solving the problems of over-high activity, poor selectivity, easy loss or agglomeration of the Pd/C catalyst has important significance for the industrial production of the halogenated arylamine.
Based on the background, the invention provides a method for doping an activated carbon carrier and then loading noble metal by a hydrothermal method, and the noble metal/doped activated carbon catalyst is prepared. Due to the interaction between the heteroatom and the metal nano-particles, the metal is better dispersed, and the catalyst achieves 100 percent of selectivity in the reaction of preparing the halogenated aromatic amine by selectively hydrogenating the halogenated aromatic nitro compound while keeping the complete conversion of the halogenated aromatic nitro compound.
Disclosure of the invention
The invention aims to provide a preparation method of a sulfur-doped active carbon supported noble metal catalyst, which is simple to operate, low in cost, small in pollution and beneficial to industrial application.
The second purpose of the invention is to provide the application of the sulfur-doped activated carbon supported noble metal catalyst in the preparation of halogenated aromatic amine by liquid-phase catalytic hydrogenation of halogenated aromatic nitro compounds, the catalyst has high conversion rate of the halogenated aromatic nitro compounds and selectivity of the halogenated aromatic amine, and the catalyst has good stability and can be recycled for multiple times.
The technical solution adopted by the present invention to achieve the above object is specifically described below.
On the one hand, the preparation method of the sulfur-doped active carbon supported noble metal catalyst comprises the following steps:
(1) preparing sulfur-doped activated carbon: preparing a sulfur-containing compound into an aqueous solution, preparing activated carbon and the aqueous solution into slurry according to a proportion, placing the slurry into a high-pressure hydrothermal kettle, sealing the high-pressure hydrothermal kettle, carrying out hydrothermal reaction at 180-300 ℃ for 10-50 h, cooling to room temperature, filtering, washing with deionized water until filtrate is neutral, and drying the obtained filter cake in vacuum to obtain sulfur-doped activated carbon; the sulfur-containing compound is Na2S、K2One or a combination of more of S, NaHS and KHS; the mass ratio of the doped sulfur element to the activated carbon is 0.02-0.1: 1, the doping amount of the sulfur element is preferably 4-6 wt%;
(2) preparation of the catalyst: taking sulfur-doped activated carbon, mixing the sulfur-doped activated carbon with a mixture of 1: adding deionized water in a ratio of 3-20 to prepare slurry, heating in a water bath to 30-100 ℃, slowly dropwise adding a soluble precious metal compound solution under magnetic stirring according to a metal loading amount of 1-10 wt%, wherein the precious metal is Pd or Pt, and stirring for 30-300 min; adding a sodium acetate solution, wherein the amount of the sodium acetate is 2-10 wt% of the sulfur-doped activated carbon, and stirring for 30-300 min; dropwise adding an alkaline solution to adjust the pH value to 7-9, and continuously stirring for 30-300 min; then, formaldehyde solution is dripped for reduction, and the reduction is maintained for 30-300 min; and then cooling the temperature to room temperature, filtering, washing a filter cake with deionized water, and then drying in vacuum to obtain the sulfur-doped active carbon supported noble metal catalyst.
Further, the soluble noble metal compound is H2PdCl4Or H2PtCl6。
Further, the alkaline solution is NaOH or KOH solution.
Further, the mass ratio of the formaldehyde to the noble metal is 4-8: 1.
further, the vacuum drying conditions are as follows: drying at 80-120 deg.C for 10-24 hr.
On the other hand, the invention provides the application of the sulfur-doped activated carbon supported noble metal catalyst in the preparation of the halogenated aromatic amine shown in the formula (II) by the liquid-phase catalytic hydrogenation reaction of the halogenated aromatic nitro compound shown in the formula (I),
in formula (I) or formula (II) — R1、-R2、-R3、-R4、-R5Is independently selected from one of the following groups: -F, -Cl, -Br, the remaining other groups each being independently selected from one of the following groups: -H, -CH3、-CH2CH3、-OH、-NH2、-OCH3、-COOCH3、-NHCH2CH3、 N(CH3)2。
Further, in the liquid-phase catalytic hydrogenation reaction, the feeding mass ratio of the halogenated aromatic nitro compound to the sulfur-doped activated carbon-supported noble metal catalyst is 100: 0.1 to 3.0, preferably 100: 0.2 to 1.5.
Further, the liquid-phase catalytic hydrogenation takes methanol and ethanol as solvents, and the addition amount of the reaction solvent is 0.15-2 mL/g based on the mass of the halogenated aromatic nitro compound.
Further, the reaction temperature of the liquid phase catalytic hydrogenation reaction is 60-180 ℃.
Further, in the liquid phase catalytic hydrogenation reaction, the hydrogen pressure is controlled to be 0.5-3.0 MPa.
The liquid phase catalytic hydrogenation reaction of the invention can obtain target products through conventional post-treatment after the reaction is finished, such as: after the reaction is finished, cooling the temperature to room temperature, filtering the reaction mixture, obtaining a filter cake, namely the sulfur-doped active carbon supported noble metal catalyst, and drying and recycling in vacuum for reuse; the target product can be obtained by rectifying or distilling the filtrate.
In the invention, fresh catalyst can be added according to the feeding ratio in the reaction of using the sulfur-doped active carbon-supported noble metal catalyst.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method of the sulfur-doped active carbon supported noble metal catalyst adopts a hydrothermal method to dope sulfur, and is simple, low in cost, small in pollution and beneficial to industrial application; while adding sodium acetate when loading noble metal, the combination of S and Pd can be influenced, so that the S and Pd react completely better and more quickly, and the catalytic activity is influenced;
(2) in the sulfur-doped activated carbon supported noble metal catalyst, the electronic effect between sulfur elements in the carrier and supported noble metal ions can properly reduce the activity of the noble metal catalyst, is beneficial to inhibiting the dechlorination reaction and improving the selectivity of the aromatic nitroaniline; the interaction between the carrier and the loaded metal ions is enhanced by the doping of the sulfur element, so that the metal nano particles are not easy to agglomerate and run off in the catalytic hydrogenation reaction process, and the service life of the catalyst is prolonged;
(3) the selectivity of the halogenated aromatic amine prepared by the catalytic hydrogenation method is more than 99.5 percent and can reach 100 percent at most, and the halogenated aromatic nitro compound can be completely converted;
(4) the catalyst has the advantages of mild use condition, good stability, less catalyst consumption, more application times and long service life.
(IV) detailed description of the preferred embodiments
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
the first embodiment is as follows:
weighing Na2S·9H2O1.4981 g, adding deionized water to prepare 50mL solution, mixing with 10g active carbon, and hydrothermal treating under high pressureCarrying out hydrothermal treatment for 10h at 180 ℃ in a reaction kettle; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 3 and deionized water, slowly adding 0.5mLH dropwise under magnetic stirring in water bath at 30 deg.C2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 30 min; then adding 0.5mL of sodium acetate solution (0.1g/mL), and stirring for 30 min; adjusting the pH value of the solution to 7-9 by using 0.1g/mL NaOH solution, and continuing stirring for 30 min; slowly dripping 0.5mL of formaldehyde solution (37% -40%), and continuously stirring for 30 min; filtering, washing the filter cake with deionized water, and drying the filter cake in vacuum at 110 ℃ for 12h to obtain the sulfur-doped activated carbon-supported Pd catalyst.
Example two:
weighing Na2S·9H2Adding 50mL of deionized water into O3.8216 g to prepare a solution, uniformly mixing with 10g of activated carbon, and performing hydrothermal treatment for 24 hours in a high-pressure hydrothermal reaction kettle at 200 ℃; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 5 and deionized water, slowly adding 1mLH dropwise under magnetic stirring in 80 deg.C water bath2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 100 min; then adding 1.5mL of sodium acetate solution (0.1g/mL), and stirring for 100 min; regulating the pH value of the solution to 7-9 by using 0.1g/mL KOH solution, and continuing stirring for 100 min; slowly dripping 1mL of formaldehyde solution, and continuously stirring for 100 min; filtering, washing the filter cake with deionized water, and drying the filter cake in vacuum at 110 ℃ for 12h to obtain the sulfur-doped activated carbon-supported Pd catalyst.
Example three:
weighing Na2S·9H2Adding 100mL of deionized water into O7.4934 g to prepare a solution, uniformly mixing with 10g of active carbon, and performing hydrothermal treatment for 36h in a high-pressure hydrothermal reaction kettle at the temperature of 250 ℃; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: ratio of 10Preparing slurry with deionized water, slowly adding 2.5mLH dropwise under magnetic stirring in water bath at 100 deg.C2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 60 min; then adding 2.5mL of sodium acetate solution (0.1g/mL), and stirring for 60 min; adjusting the pH value of the solution to 7-9 by using 0.1g/mL NaOH solution, and continuing stirring for 60 min; slowly dripping 0.6mL of formaldehyde solution (37% -40%), and continuously stirring for 60 min; filtering, washing the filter cake with deionized water, and drying the filter cake for 24h at 80 ℃ in vacuum to obtain the sulfur-doped activated carbon-supported Pd catalyst.
Example four:
weighing Na2S·9H2O1.4999 g, adding 50mL of deionized water to prepare a solution, uniformly mixing with 10g of activated carbon, and carrying out hydrothermal treatment for 48h at 240 ℃ in a high-pressure hydrothermal reaction kettle; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 10 and deionized water, slowly adding 1mLH dropwise under magnetic stirring in water bath at 100 deg.C2PtCl6Stirring the solution (the Pt content is 0.05g/mL) for 80 min; then adding 1.5mL of sodium acetate solution (0.1g/mL), and stirring for 80 min; regulating the pH value of the solution to 7-9 by using 0.1g/mL KOH solution, and continuing stirring for 80 min; slowly dripping 1mL of formaldehyde solution (37% -40%), and continuously stirring for 80 min; filtering, washing a filter cake with deionized water, and drying the filter cake for 16h in vacuum at 100 ℃ to obtain the sulfur-doped active carbon-loaded Pt catalyst.
Example five:
weighing K2S1.7568 g, adding 50mL of deionized water to prepare a solution, uniformly mixing with 10g of activated carbon, and performing hydrothermal treatment for 50h in a high-pressure hydrothermal reaction kettle at 300 ℃; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake for 11h at 110 ℃ to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 6 and deionized water, slowly adding 2.5mLH dropwise under magnetic stirring in 80 deg.C water bath2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 100 min; then adding 1.5mL of sodium acetate solution (0.1g/mL), and stirring for 100 min; the solution was adjusted with 0.1g/mL NaOH solutionThe PH value is 8-9, and the stirring is continued for 60 min; slowly dripping 1mL of formaldehyde solution, and continuously stirring for 60 min; filtering, washing the filter cake with deionized water, and drying the filter cake at 120 ℃ for 10h in vacuum to obtain the sulfur-doped activated carbon-supported Pd catalyst.
Example six:
weighing K2S0.7237 g, adding 50mL of deionized water to prepare a solution, uniformly mixing with 10g of activated carbon, and performing hydrothermal treatment for 24h at 260 ℃ in a high-pressure hydrothermal reaction kettle; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 5 and deionized water, slowly adding 1mLH dropwise under magnetic stirring in water bath at 100 deg.C2PtCl6Stirring the solution (the Pt content is 0.05g/mL) for 300 min; then adding 1mL of sodium acetate solution (0.1g/mL), and stirring for 100 min; adjusting the pH value of the solution to 8-9 by using 0.1g/mL NaOH solution, and continuing stirring for 60 min; slowly dripping 0.5mL of formaldehyde solution, and continuously stirring for 100 min; filtering, washing the filter cake with deionized water, and drying the filter cake for 11h in vacuum at 110 ℃ to obtain the sulfur-doped active carbon-loaded Pt catalyst.
Example seven:
weighing 0.8920g of NaHS, adding 60mL of deionized water to prepare a solution, uniformly mixing the solution with 10g of activated carbon, and performing hydrothermal treatment for 24 hours in a high-pressure hydrothermal reaction kettle at 200 ℃; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 10 and deionized water, slowly adding 2.5mLH dropwise under magnetic stirring in water bath at 60 deg.C2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 100 min; then adding 1.25mL of sodium acetate solution (0.1g/mL), and stirring for 100 min; regulating the pH value of the solution to 8-9 by using 0.1g/mL NaOH solution, and continuing stirring for 100 min; slowly dripping formaldehyde solution and continuously stirring for 100 min; filtering, washing the filter cake with deionized water, and drying the filter cake in vacuum at 110 ℃ for 12h to obtain the sulfur-doped activated carbon-supported Pd catalyst.
Example eight:
weighing0.3578g of NaHS, adding 50mL of deionized water to prepare a solution, uniformly mixing the solution with 10g of activated carbon, and performing hydrothermal treatment for 36 hours in a high-pressure hydrothermal reaction kettle at 230 ℃; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 8 and deionized water, slowly adding 1mLH dropwise under magnetic stirring in water bath at 50 deg.C2PtCl6Stirring the solution (the Pt content is 0.05g/mL) for 60 min; then adding 1.5mL of sodium acetate solution (0.1g/mL), and stirring for 60 min; adjusting the pH value of the solution to 7-9 by using 0.1g/mL NaOH solution, and continuing stirring for 60 min; slowly dripping 1mL of formaldehyde solution, and continuously stirring for 30 min; filtering, washing a filter cake with deionized water, and drying the filter cake for 13h in vacuum at 110 ℃ to obtain the sulfur-doped active carbon-loaded Pt catalyst.
Example nine:
weighing 2.2965g of KHS, adding 40mL of deionized water to prepare a solution, uniformly mixing with 10g of activated carbon, and performing hydrothermal treatment for 20h at 250 ℃ in a high-pressure hydrothermal reaction kettle; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake for 11h at 110 ℃ to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 5 and deionized water, slowly adding 1mLH dropwise under magnetic stirring in water bath at 40 deg.C2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 300 min; then adding 2.5mL of sodium acetate solution (0.1g/mL), and stirring for 300 min; adjusting the pH value of the solution to 7-9 by using 0.1g/mL NaOH solution, and continuing stirring for 300 min; slowly dripping 1mL of formaldehyde solution, and stirring for 300 min; filtering, washing the filter cake with deionized water, and drying the filter cake in vacuum at 100 ℃ to obtain the sulfur-doped activated carbon-supported Pd catalyst.
Example ten:
weighing 1.1490g of KHS, adding 70mL of deionized water to prepare a solution, uniformly mixing with 10g of activated carbon, and carrying out hydrothermal treatment for 48h at 300 ℃ in a high-pressure hydrothermal reaction kettle; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. Then 2.5g of the sulfur-doped activated carbon is addedMixing the raw materials in a ratio of 1: 5 and deionized water, slowly adding 2.5mLH dropwise under magnetic stirring in water bath at 100 deg.C2PtCl6Stirring the solution (the Pt content is 0.05g/mL) for 120 min; then adding 1.5mL of sodium acetate solution (0.1g/mL), and stirring for 120 min; adjusting the pH value of the solution to 7-9 by using 0.1g/mL NaOH solution, and continuing stirring for 60 min; slowly dripping a formaldehyde solution, wherein the PH value is neutral; filtering, washing the filter cake with deionized water, and drying the filter cake for 20h at 100 ℃ in vacuum to obtain the sulfur-doped active carbon-loaded Pt catalyst.
Examples eleven to twenty:
examples eleven to twenty examine the performance of the different sulfur-doped, activated carbon-supported noble metal catalysts prepared in examples one to ten in the catalytic hydrogenation to produce halogenated anilines.
Adding 30g of o-chloronitrobenzene, 200mL of ethanol and 0.3g of sulfur-doped carbon material loaded noble metal catalyst into a 500mL stainless steel reaction kettle, closing the reaction kettle, and replacing air in the reaction kettle with hydrogen for three times; heating to 100 ℃ and hydrogen pressure of 1MPa, starting stirring at the stirring speed of 700r/min, and reacting for 6 hours; stopping the reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in table 1.
TABLE 1 catalytic hydrogenation performance of different sulfur-doped activated carbon supported noble metals
| Examples | Catalyst and process for preparing same | Conversion (%) | Selectivity (%) |
| 11 | Example one | 100 | 99.5 |
| 12 | Example two | 100 | 100 |
| 13 | EXAMPLE III | 100 | 100 |
| 14 | Example four | 100 | 99.5 |
| 15 | EXAMPLE five | 100 | 100 |
| 16 | EXAMPLE six | 100 | 99.99 |
| 17 | EXAMPLE seven | 100 | 100 |
| 18 | Example eight | 100 | 100 |
| 19 | Example nine | 100 | 99.8 |
| 20 | Example ten | 100 | 100 |
Examples twenty-one to twenty-eight:
the twenty-first to twenty-eight examples examine the reaction performance of the sulfur-doped carbon material-loaded Pt catalyst on the hydrogenation of different halogenated nitroaromatic compounds to prepare the halogenated aniline. Adding 30g of halogenated nitrobenzene, 100ml of methanol and 0.5g of the sulfur-doped carbon material loaded noble catalyst prepared in the third embodiment into a 500ml stainless steel reaction kettle, closing the reaction kettle, and replacing with hydrogen for three times; heating to 120 ℃ and hydrogen pressure of 1.5MPa, starting stirring at the stirring speed of 900r/min, and reacting for 4 hours; stopping the reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in table 2.
TABLE 2 catalytic hydrogenation performance of sulfur-doped activated carbon-supported noble catalysts on different halogenated nitrobenzenes
Examples twenty-nine to thirty-three:
the twenty-nine to thirty-three examples examine the reaction performance of the sulfur-doped activated carbon-supported Pt catalyst in the preparation of halogenated aniline by catalytic hydrogenation under different hydrogenation reaction conditions. Adding 30g of 2, 4-dichloronitrobenzene, 150ml of ethanol and 1g of the catalyst prepared in the sixth embodiment into a 500ml stainless steel reaction kettle, closing the reaction kettle, and replacing with hydrogen for three times; after the temperature and the hydrogen pressure are increased to the range required by the reaction, stirring is started, the stirring speed is 700r/min, and the reaction is carried out for 3 hours; stopping the reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The results of the experiment are shown in Table 3
TABLE 3 catalytic performance of rhodium catalyst loaded with sulfur-doped carbon material under different hydrogenation reaction conditions
| Examples | Raw materials | Reaction conditions | Conversion (%) | Selectivity (%) |
| 29 | 2, 4-dichloronitrobenzene | 60℃，3MPa | 100 | 99.8 |
| 30 | 2, 4-dichloronitrobenzene | 80℃，2.5MPa | 100 | 99.8 |
| 31 | 2, 4-dichloronitrobenzene | 100℃，2MPa | 100 | 99.9 |
| 32 | 2, 4-dichloronitrobenzene | 140℃，1MPa | 100 | 99.9 |
| 33 | 2, 4-dichloronitrobenzene | 180℃，0.5MPa | 100 | 99.9 |
Example thirty-four:
example thirty-four investigated the application performance of the sulfur-doped activated carbon-supported Pd catalyst prepared in example two in the reaction of preparing o-chloroaniline by selective hydrogenation of p-chloronitrobenzene. Adding 30g of o-chloronitrobenzene, 200mL of absolute ethyl alcohol and 0.3g of sulfur activated carbon loaded Pd metal catalyst into a 500mL stainless steel reaction kettle, closing the reaction kettle, and replacing air in the reaction kettle with hydrogen for three times; raising the temperature and the hydrogen pressure to the range required by the reaction, and starting stirring at the stirring speed of 700 r/min; after reacting for 4h, stopping the reaction, cooling the temperature to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by gas chromatography. The reaction was continued after the catalysis to 0.3g of fresh catalyst of example II, the conditions of the reaction were the same, and the results are shown in Table 4
TABLE 4 application Properties of Pd catalyst supported on sulfur-doped mesoporous carbon
Comparative example
Weighing Na2S·9H2Adding 100mL of deionized water into O7.4934 g to prepare a solution, uniformly mixing with 10g of active carbon, and performing hydrothermal treatment for 36h in a high-pressure hydrothermal reaction kettle at the temperature of 250 ℃; cooling to room temperature, filtering, washing with a large amount of deionized water until the filtrate is neutral, and vacuum drying the obtained filter cake at 110 ℃ for 12h to obtain the sulfur-doped activated carbon. 2.5g of the above sulphur-doped activated carbon was then mixed with 1: 10 and deionized water, slowly adding 2.5mLH dropwise under magnetic stirring in water bath at 100 deg.C2PdCl4Stirring the solution (the Pd content is 0.05g/mL) for 30 min; adjusting the pH value of the solution to 7-9 by using 0.1g/mL NaOH solution, and continuing stirring for 150 min; slowly dripping 0.6mL of formaldehyde solution (37% -40%), and continuously stirring for 150 min; filtering, washing the filter cake with deionized water, and drying the filter cake for 24h at 80 ℃ in vacuum to obtain the sulfur-doped activated carbon-supported Pd catalyst.
The sulfur-doped activated carbon-supported Pd catalyst is used in the reaction for preparing the halogenated aniline through catalytic hydrogenation, the preparation conditions and the reaction time are the same as those in the third embodiment, and the result shows that: the conversion rate of o-chloronitrobenzene is 95 percent, and the selectivity of o-chloroaniline is 99.8 percent.
Claims (10)
1. A preparation method of a sulfur-doped activated carbon supported noble metal catalyst for preparing halogenated aromatic amine shown in a formula (II) by a halogenated aromatic nitro compound shown in a formula (I) through liquid-phase catalytic hydrogenation reaction,
in formula (I) or formula (II) — R1、-R2、-R3、-R4、-R5Is independently selected from one of the following groups: -F, -Cl, -Br, the remaining other groups each being independently selected from one of the following groups: -H, -CH3、-CH2CH3、-OH、-NH2、-OCH3、-COOCH3、-NHCH2CH3、N(CH3)2；
The preparation method comprises the following steps:
(1) preparing sulfur-doped activated carbon: preparing a sulfur-containing compound into an aqueous solution, preparing activated carbon and the aqueous solution into slurry according to a proportion, placing the slurry into a high-pressure hydrothermal kettle, sealing the high-pressure hydrothermal kettle, carrying out hydrothermal reaction at 180-300 ℃ for 10-50 h, cooling to room temperature, filtering, washing with deionized water until filtrate is neutral, and drying the obtained filter cake in vacuum to obtain sulfur-doped activated carbon; the sulfur-containing compound is Na2S、K2One or a combination of more of S, NaHS and KHS; the mass ratio of the doped sulfur element to the activated carbon is 0.02-0.1: 1;
(2) preparation of the catalyst: taking sulfur-doped activated carbon, mixing the sulfur-doped activated carbon with a mixture of 1: adding deionized water in a ratio of 3-20 to prepare slurry, heating in a water bath to 30-100 ℃, slowly dropwise adding a soluble precious metal compound solution under magnetic stirring according to a metal loading amount of 1-10 wt%, wherein the precious metal is Pd or Pt, and stirring for 30-300 min; adding a sodium acetate solution, wherein the amount of the sodium acetate is 2-10 wt% of the sulfur-doped activated carbon, and stirring for 30-300 min; dropwise adding an alkaline solution to adjust the pH to 7-9, wherein the alkaline solution is a NaOH or KOH solution, and continuously stirring for 30-300 min; then, formaldehyde solution is dripped for reduction, and the reduction is maintained for 30-300 min; and then cooling the temperature to room temperature, filtering, washing a filter cake with deionized water, and then drying in vacuum to obtain the sulfur-doped active carbon supported noble metal catalyst.
2. The method of claim 1, wherein: the soluble noble goldThe compound of genus is H2PdCl4Or H2PtCl6。
3. The method of claim 1, wherein: the mass ratio of the formaldehyde to the noble metal is 4-8: 1.
4. the method of claim 1, wherein: the vacuum drying conditions are as follows: drying at 80-120 deg.C for 10-24 hr.
5. The application of the sulfur-doped activated carbon supported noble metal catalyst prepared by the preparation method of claim 1 in the preparation of the halogenated aromatic amine shown in the formula (II) by the liquid-phase catalytic hydrogenation reaction of the halogenated aromatic nitro compound shown in the formula (I),
in formula (I) or formula (II) — R1、-R2、-R3、-R4、-R5Is independently selected from one of the following groups: -F, -Cl, -Br, the remaining other groups each being independently selected from one of the following groups: -H, -CH3、-CH2CH3、-OH、-NH2、-OCH3、-COOCH3、-NHCH2CH3、N(CH3)2。
6. The use of claim 5, wherein: the liquid-phase catalytic hydrogenation takes methanol and ethanol as solvents, and the addition amount of the reaction solvent is 0.15-2 mL/g based on the mass of the halogenated aromatic nitro compound.
7. Use according to claim 5 or 6, characterized in that: in the liquid-phase catalytic hydrogenation reaction, the feeding mass ratio of the halogenated aromatic nitro compound to the sulfur-doped active carbon-supported noble metal catalyst is 100: 0.1 to 3.0.
8. The use of claim 7, wherein: in the liquid-phase catalytic hydrogenation reaction, the feeding mass ratio of the halogenated aromatic nitro compound to the sulfur-doped active carbon-supported noble metal catalyst is 100: 0.2 to 1.5.
9. The use of claim 7, wherein: the reaction temperature of the liquid phase catalytic hydrogenation reaction is 60-180 ℃.
10. The use of claim 9, wherein: in the liquid phase catalytic hydrogenation reaction, the hydrogen pressure is controlled to be 0.5-3.0 MPa.
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