CN115845919A - Nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst - Google Patents
Nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 82
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 82
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000919 ceramic Substances 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 16
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 12
- 238000007664 blowing Methods 0.000 claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 19
- 150000002815 nickel Chemical class 0.000 claims description 17
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- 229940078494 nickel acetate Drugs 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010000 carbonizing Methods 0.000 claims description 12
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical group [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- BGKIECJVXXHLDP-UHFFFAOYSA-N 1,2,3-trichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1Cl BGKIECJVXXHLDP-UHFFFAOYSA-N 0.000 claims description 3
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 claims description 3
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 238000006298 dechlorination reaction Methods 0.000 abstract description 12
- 239000003112 inhibitor Substances 0.000 abstract description 11
- 238000003763 carbonization Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 238000004817 gas chromatography Methods 0.000 description 11
- -1 chloronitrobenzene-n-butanol Chemical compound 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nitrogen-doped phenolic resin nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst, which is prepared by immersing cordierite honeycomb ceramic in nitrogen-doped liquid phenolic resin containing metallic nickel salt, taking out the cordierite honeycomb ceramic, blowing off redundant resin, heating for curing, and then heating in argon atmosphere for carbonization. The invention realizes high integration of active metal nickel and dechlorination inhibitor, and the dechlorination inhibitor is not required to be added repeatedly as a consumable product for each reaction.
Description
1. Field of the invention
The invention relates to a method for preparing a nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst and application of the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst in a reaction for synthesizing chloroaniline by catalytic hydrogenation of chloronitrobenzene.
2. Background of the invention
Chloroaniline is an important fine chemical product and organic intermediate, and is widely applied to synthesis of fine chemical products such as medicines, dyes, pesticides and the like. At present, chloronitrobenzene is mainly used as a raw material in industry, and the chloroaniline is synthesized by several methods such as iron powder reduction, alkali sulfide or hydrazine hydrate reduction, sulfonation ammonolysis, catalytic hydrogenation reduction and the like. Compared with other methods, the catalytic hydrogenation reduction method has the characteristics of less three-waste emission, high product yield and good product quality, and is the most advanced and environment-friendly production technology at present.
Common hydrogenation catalysts for the catalytic hydrogenation reaction of chloronitrobenzene comprise Raney Ni catalysts and supported noble metal catalysts such as Pd and Pt, and the supported noble metal catalysts have higher use cost, but the catalytic activity and the reaction selectivity are obviously superior to those of the Raney Ni catalysts. This is because the catalytic hydrogenation of chloronitrobenzene is often accompanied by hydrogenolysis dechlorination side reactions, and when Raney Ni catalyst is used, additional dechlorination inhibitor is required to improve the product selectivity. Dechlorination inhibitors are typically bases or other electron donating compounds that alter certain electrical properties of the catalyst through metal particle interactions, thereby increasing the selectivity of the reaction. To date, a variety of dechlorination inhibitors have been discovered, e.g., morpholine, pK b <3 organic amine or triphenyl phosphate, triphenyl phosphite, alkaline additive, formamidine salt, thiazole, etc. But the additional addition of the dechlorination inhibitor increases the production cost on one hand, and on the other hand, the dechlorination inhibitor is difficult to separate from the product, thereby reducing the product quality.
The metal-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst can fully exert the advantages of good mass transfer performance, large geometric surface area, pressure reduction, high mechanical strength, good wear resistance and good thermal stability of the monolithic catalyst, has the characteristics of large specific surface area, rich surface groups and high chemical stability of a porous carbon material, and is very suitable for the requirement of catalytic hydrogenation reaction of a continuous fixed bed. However, although the integral catalyst with inlaid nickel porous carbon coated honeycomb ceramics obtained in the patent ZL201910587980.2 (the integral catalyst with inlaid metal porous carbon coated honeycomb ceramics, and the preparation method and application thereof) has high catalytic activity, the reaction selectivity is obviously different from that of the integral catalyst with inlaid precious metals such as palladium and platinum prepared by the same method, and the selectivity of the catalytic hydrogenation reaction of chloronitrobenzene needs to be further improved.
Phenolic resins are generally obtained by polymerizing phenol or its homologues (such as cresol, xylenol) and formaldehyde, and depending on the type of raw material used, the ratio of phenol to aldehyde, and the type of catalyst, two different types of resins can be obtained, thermoplastic and thermosetting. The thermoplastic phenolic resin is polymerized under the condition that the using amount (mol) of the phenol exceeds the using amount (mol) of the aldehyde and the existence of the acid catalyst, and the thermosetting phenolic resin is polymerized under the condition that the using amount (mol) of the aldehyde exceeds the using amount (mol) of the phenol and the existence of the alkaline catalyst. Since the organic amine is generally alkaline, it can be used as a polymerization catalyst to promote the polymerization of phenol or its homologues (such as cresol and xylenol) with formaldehyde to form phenolic resin, and can also be used as a dechlorination inhibitor in the catalytic hydrogenation reaction of chloronitrobenzene due to the electron-donating property of nitrogen element. The nitrogen-doped inlaid nickel porous carbon-coated honeycomb ceramic monolithic catalyst has unique effect and effect on improving the selectivity of the catalytic hydrogenation reaction of chloronitrobenzene. Based on the background, the invention provides a method for coating a honeycomb ceramic monolithic catalyst with nitrogen-doped phenolic resin matrix inlaid with nickel porous carbon and application thereof.
3. Summary of the invention
The invention provides a nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst and application thereof.
A nitrogen-doped phenolic resin-based inlaid nickel porous carbon-coated honeycomb ceramic monolithic catalyst and application of the catalyst in the reaction of synthesizing chloroaniline by catalytic hydrogenation of chloronitrobenzene. The catalyst is prepared by the following method: cordierite honeycomb ceramic (cylindrical, 45.8mm in diameter, 80mm in height, square in shape, and 54cell/cm in pore density, manufactured by Yixing non-metallic chemical mechanical works, ltd. Of Jiangsu province) 2 Wall thickness 0.22 mm) is immersed in a bath containing metalTaking out nickel salt and nitrogen-doped liquid phenolic resin, blowing off redundant resin, heating for curing, and then heating in an argon atmosphere for carbonization to prepare the nitrogen-doped phenolic resin based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst, which is prepared by the following method: mixing phenol and formaldehyde, adding organic amine and nickel salt, and polymerizing for 1-5 h (preferably 2-4 h, most preferably 3 h) at 30-90 ℃ (preferably 40-80 ℃, most preferably 70 ℃) to obtain liquid phenolic resin; immersing cordierite honeycomb ceramic into the liquid phenolic resin, immersing for 3-5 h at 50-70 ℃ (preferably immersing for 4h at 60 ℃), taking out, blowing off redundant resin in a pore channel, completely curing at 100 ℃ in an air atmosphere (in the embodiment of the invention, the complete curing can be ensured after 8 h), carbonizing for 2-8 h at 200-800 ℃ in an argon atmosphere (preferably carbonizing for 3-7 h at 300-700 ℃, and most preferably carbonizing for 5h at 500 ℃), and obtaining the nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst;
the volume of the formaldehyde is 1-1.5mL/g (preferably 1.1-1.4mL/g, most preferably 1.3 mL/g) based on the mass of the phenol; the organic amine is one or a mixture of more than two of triethylamine, ethylenediamine, urea and melamine (preferably one or a mixture of two of urea and triethylamine, and most preferably triethylamine); the mass ratio of the phenol to the organic amine to the nickel salt is 40:0.2 to 1.0:5 to 20 (preferably 40.
In one embodiment of the invention the flow rate of argon through the ceramic structure is 100mL/min.
Preferably, the nickel salt is one or a mixture of two or more of nickel nitrate, nickel carbonate, nickel acetate and nickel oxalate, more preferably one or a mixture of two of nickel acetate and nickel oxalate, and most preferably nickel acetate.
The impregnation treatment is to attach liquid phenolic resin containing organic amine and nickel salt to the surface of the honeycomb ceramic and evaporate water as much as possible, the curing treatment is to completely cure the liquid phenolic resin containing organic amine and nickel salt on the surface of the honeycomb ceramic, the carbonization treatment is to decompose and change the organic amine, nickel salt and phenolic resin on the surface of the honeycomb ceramic, the organic amine is decomposed to form doped nitrogen, the nickel salt is decomposed and reduced to form metallic nickel particles, the phenolic resin is decomposed and carbonized to form a porous carbon structure, and finally the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon coated honeycomb ceramic monolithic catalyst is prepared.
In a second aspect, the invention provides an application of the nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst in a reaction for synthesizing chloroaniline by catalytic hydrogenation of chloronitrobenzene.
Further, the chloronitrobenzene is p-chloronitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, 3, 4-dichloronitrobenzene or 2,3, 4-trichloronitrobenzene.
Specifically, the application is as follows: and (2) loading the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a hydrogen-nitrogen mixed gas serving as a reaction gas and a chloronitrobenzene normal butanol solution serving as a raw material into the fixed bed reactor, reacting at 50-100 ℃ under normal pressure, and condensing and collecting the obtained reaction liquid.
In one embodiment of the invention, chloroaniline may be isolated by gas chromatography. The product collected by condensation of the invention has high selectivity and purity, and can be directly used as a crude product in industrial application.
Further, the method for synthesizing chloroaniline by catalytic hydrogenation of chloronitrobenzene is preferably as follows: loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the fixed bed reactor at the flow rate of 1ml/min, and introducing hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) into a fixed bed reactor at a flow rate of 80ml/min under normal pressure conditionsReacting at 70 ℃, condensing and collecting the product, and analyzing the conversion rate of chloronitrobenzene and the selectivity of chloroaniline by gas chromatography. Namely, it is preferable that the concentration of chloronitrobenzene in the n-butanol solution of chloronitrobenzene is 0.05g/ml and the flow rate of the n-butanol solution of chloronitrobenzene is 1ml/min; the volume ratio of hydrogen to nitrogen in the hydrogen-nitrogen mixed gas is 3:1, the flow rate of the hydrogen-nitrogen mixed gas is 80ml/min.
Compared with the prior art, the invention has the beneficial effects that: the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst realizes high integration of active metal nickel and a dechlorination inhibitor, and the dechlorination inhibitor is not required to be added repeatedly as a consumable product for each reaction. Compared with a Raney Ni catalyst, a supported noble metal catalyst and a conventional honeycomb ceramic monolithic catalyst coated with inlaid nickel porous carbon, the catalyst has unique advantages in the reaction of synthesizing chloroaniline by catalytic hydrogenation of chloronitrobenzene: 1) Compared with Raney Ni catalyst, the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst does not need to be additionally added with a dechlorination inhibitor in the catalytic hydrogenation reaction of chloronitrobenzene, so that the comprehensive leading of catalytic performance (activity, selectivity and stability) and use cost is realized; 2) Compared with a supported noble metal catalyst, the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst has comparable catalytic activity and selectivity in the catalytic hydrogenation reaction of chloronitrobenzene, but has obvious advantages in the aspects of reaction stability and use cost; 3) Compared with the conventional nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst, the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst shows higher selectivity advantage in the catalytic hydrogenation reaction of chloronitrobenzene.
4. Detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
The cordierite honeycomb ceramics used in the following examples were purchased from limited chemical and mechanical factories of Yixing non-metal in Jiangsu provinceCompany, cylindrical, 45.8mm in diameter, 80mm in height, square in hole shape, 54 cells/cm in hole density 2 And the wall thickness is 0.22mm.
Examples 1 to 4
The examples compare the effect of phenol and formaldehyde ratios on the preparation of nitrogen doped phenolic resin based nickel damascene porous carbon coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: phenol and formaldehyde were each mixed as 1 (g) according to table 1: 1.1 (ml) to 1 (g): 1.4 (ml) were mixed, and then 0.5g of triethylamine and 15g of nickel acetate were added, respectively, and polymerization was carried out at 70 ℃ for 3 hours. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4h, taking out, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the mixture for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a p-chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing a hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) is introduced into a reactor at the flow rate of 80ml/min, the reaction is carried out at 70 ℃ under the normal pressure condition, the product is collected by condensation, and the conversion rate of p-chloronitrobenzene and the selectivity of p-chloroaniline are obtained by gas chromatography analysis. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 1
| Examples | Phenol (g) | Formaldehyde (ml) | Selectivity (%) | Conversion (%) |
| 1 | 40 | 44 | 95 | 91 |
| 2 | 40 | 48 | 96 | 96 |
| 3 | 40 | 52 | 96 | 97 |
| 4 | 40 | 56 | 96 | 94 |
Examples 5 to 8
The examples compare the effect of organic amine species on nitrogen doped phenolic resin based inlaid nickel porous carbon coated honeycomb ceramic monolithic catalysts and are compared with inorganic base sodium hydroxide. The preparation method of the catalyst comprises the following steps: 40g of phenol was mixed with 52ml of formaldehyde, and then 0.5g of organic amine (or sodium hydroxide) and 15g of nickel acetate were added, respectively, and polymerized at 70 ℃ for 3 hours. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4h, taking out, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the catalyst for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a p-chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing a hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) introducing the mixture into a reactor at the flow rate of 80ml/min, reacting at 70 ℃ under the condition of normal pressure, collecting products through condensation, and analyzing the conversion rate of p-chloronitrobenzene and the selectivity of p-chloroaniline by gas chromatography. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 2
Examples 9 to 11
The examples compare the effect of nickel salt species on nitrogen doped phenolic resin based inlaid nickel porous carbon coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: 40g of phenol were mixed with 52ml of formaldehyde, and then 0.5g of triethylamine and 15g of nickel salt were added, respectively, and polymerized at 70 ℃ for 3 hours. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4 hours, taking out the cordierite honeycomb ceramic, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the catalyst for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, and adding the catalyst with the concentration of 0.05g/mlThe chloronitrobenzene-n-butanol solution was passed into the reactor at a flow rate of 1ml/min while a hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) is introduced into a reactor at the flow rate of 80ml/min, the reaction is carried out at 70 ℃ under the normal pressure condition, the product is collected by condensation, and the conversion rate of p-chloronitrobenzene and the selectivity of p-chloroaniline are obtained by gas chromatography analysis. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 3
| Examples | Nickel salt | Selectivity (%) | Conversion (%) |
| 9 | Nickel nitrate | 95 | 79 |
| 10 | Nickel carbonate | 95 | 87 |
| 11 | Nickel oxalate | 94 | 90 |
Examples 12 to 17
The example compares the effect of triethylamine dosage on nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: 40g of phenol and 52ml of formaldehyde are mixed, and then triethylamine and 15g of nickel acetate are added respectively according to certain mass, and polymerization is carried out for 3h at 70 ℃. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4h, taking out, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the catalyst for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a p-chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing a hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) introducing the mixture into a reactor at the flow rate of 80ml/min, reacting at 70 ℃ under the condition of normal pressure, collecting products through condensation, and analyzing the conversion rate of p-chloronitrobenzene and the selectivity of p-chloroaniline by gas chromatography. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 4
| Examples | Triethylamine (g) | Selectivity (%) | Conversion (%) |
| 12 | 0.3 | 65 | 90 |
| 13 | 0.4 | 89 | 95 |
| 14 | 0.6 | 97 | 98 |
| 15 | 0.7 | 99 | 99 |
| 16 | 0.8 | 99 | 98 |
| 17 | 0.9 | 99 | 96 |
Examples 18 to 23
The examples compare the effect of nickel acetate dosage on nitrogen doped phenolic resin based inlaid nickel porous carbon coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: 40g of phenol were mixed with 52ml of formaldehyde, and then 0.5g of triethylamine and a certain amount of nickel acetate were added, respectively, and polymerized at 70 ℃ for 3 hours. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4h, taking out, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the catalyst for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing parachloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) is introduced into a reactor at the flow rate of 80ml/min, the reaction is carried out at 70 ℃ under the normal pressure condition, the product is collected by condensation, and the conversion rate of p-chloronitrobenzene and the selectivity of p-chloroaniline are obtained by gas chromatography analysis. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 5
| Examples | Nickel acetate (g) | Selectivity (%) | Conversion (%) |
| 18 | 8 | 99 | 22 |
| 19 | 10 | 99 | 39 |
| 20 | 12 | 98 | 53 |
| 21 | 14 | 96 | 96 |
| 22 | 16 | 96 | 98 |
| 23 | 18 | 95 | 99 |
Examples 24 to 28
The examples compare the effect of polymerization conditions on nitrogen doped phenolic resin based inlaid nickel porous carbon coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: 40g of phenol is mixed with 52ml of formaldehyde, then 0.5g of triethylamine and 15g of nickel acetate are respectively added, and polymerization is carried out for 2-4 h at the temperature of 40-80 ℃. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4h, taking out, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the catalyst for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a p-chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing a hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) introducing the mixture into a reactor at the flow rate of 80ml/min, reacting at 70 ℃ under the normal pressure condition, collecting products through condensation, and obtaining the p-chloronitrobenzene conversion rate and the p-chlorobenzeneAmine selectivity was obtained by gas chromatography analysis. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 6
Examples 29 to 36
The examples compare the effect of carbonization conditions on nitrogen doped phenolic resin based nickel damascene porous carbon coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: 40g of phenol were mixed with 52ml of formaldehyde, and then 0.5g of triethylamine and 15g of nickel acetate were added, respectively, and polymerized at 70 ℃ for 3 hours. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4h, taking out, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the mixture for 3 to 7 hours at 300 to 700 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a p-chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing a hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) is introduced into a reactor at the flow rate of 80ml/min, the reaction is carried out at 70 ℃ under the normal pressure condition, the product is collected by condensation, and the conversion rate of p-chloronitrobenzene and the selectivity of p-chloroaniline are obtained by gas chromatography analysis. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 7
Examples 37 to 40
The examples compare the catalytic hydrogenation reaction performance of chloronitrobenzene of nitrogen-doped phenolic resin-based inlaid nickel porous carbon coated honeycomb ceramic monolithic catalysts. The preparation method of the catalyst comprises the following steps: 40g of phenol were mixed with 52ml of formaldehyde, and then 0.7g of triethylamine and 15g of nickel acetate were added, respectively, and polymerized at 70 ℃ for 3 hours. And then, soaking the cordierite honeycomb ceramic into the liquid phenolic resin at 60 ℃ for 4 hours, taking out the cordierite honeycomb ceramic, and blowing off the redundant resin in the pore channel. Then curing the liquid phenolic resin for 8 hours at 100 ℃ in an air atmosphere. And finally carbonizing the catalyst for 5 hours at 500 ℃ in an argon atmosphere of 100ml/min to prepare the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst.
Loading the 1 nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml into the reactor at the flow rate of 1ml/min, and simultaneously introducing hydrogen-nitrogen mixed gas (V) H2 :V N2 = 3) introducing the mixture into a reactor at the flow rate of 80ml/min, reacting at 70 ℃ under the condition of normal pressure, collecting products through condensation, and analyzing the conversion rate of chloronitrobenzene and the selectivity of chloroaniline by gas chromatography. A sample taken at 8h of reaction time was analyzed as shown in the following table.
TABLE 8
| Examples | Chloronitrobenzene | Selectivity (%) | Conversion (%) |
| 37 | O-chloronitrobenzene | 99 | 99 |
| 38 | M-chloronitrobenzene | 98 | 99 |
| 39 | 3, 4-dichloronitrobenzene | 99 | 99 |
| 40 | 2,3, 4-trichloronitrobenzene | 99 | 99 |
Examples 41 to 43
The examples compare the catalytic hydrogenation performance of Raney Ni, pd/C (3%) and Pt/C (3%) for p-chloronitrobenzene. The catalysts are all commercial varieties. 200ml of p-chloronitrobenzene-n-butanol solution with the concentration of 0.05g/ml is added into the autoclave reactor, and then a certain amount of hydrogenation catalyst is added. After gas replacement, the reaction is carried out under the conditions that the hydrogen pressure is 1MPa, the reaction temperature is 80 ℃ and the stirring speed is 1000 r/min until the hydrogen is not consumed any more. After the reaction is finished, cooling to room temperature, filtering the catalyst to obtain a product, and analyzing the p-chloronitrobenzene conversion rate and the p-chloroaniline selectivity by gas chromatography. The analytical results are shown in the following table.
TABLE 9
| Examples | Hydrogenation catalyst | Mass of catalyst (g) | Selectivity (%) | Conversion (%) |
| 41 | Raney Ni | 2 | 89 | 99 |
| 42 | Pd/C(3％) | 1 | 97 | 99 |
| 43 | Pt/C(3％) | 1 | 98 | 99 |
Claims (10)
1. The nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst is characterized by being prepared by the following method: mixing phenol and formaldehyde, adding organic amine and nickel salt, and polymerizing for 1-5 h at 30-90 ℃ to obtain liquid phenolic resin; immersing cordierite honeycomb ceramic into the liquid phenolic resin, immersing for 3-5 h at 50-70 ℃, taking out, blowing off redundant resin in a pore channel, completely curing at 100 ℃ in an air atmosphere, and carbonizing for 2-8 h at 200-800 ℃ in an argon atmosphere to obtain the nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst;
the volume of the formaldehyde is 1-1.5mL/g based on the mass of the phenol; the organic amine is one or a mixture of more than two of triethylamine, ethylenediamine, urea and melamine; the mass ratio of the phenol to the organic amine to the nickel salt is 40:0.2 to 1.0:5 to 20.
2. The nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst of claim 1, wherein: the nickel salt is one or a mixture of more than two of nickel nitrate, nickel carbonate, nickel acetate and nickel oxalate.
3. The nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst of claim 2, wherein: the nickel salt is one or a mixture of nickel acetate and nickel oxalate.
4. The nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst of claim 3, wherein: the nickel salt is nickel acetate.
5. The nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst of claim 1, wherein: the organic amine is one or a mixture of urea and triethylamine.
6. The nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst of claim 1, wherein: the mass ratio of the phenol to the organic amine to the nickel salt is 40:0.3 to 0.9:8 to 18.
7. The use of the nitrogen-doped phenolic resin inlaid nickel porous carbon coated honeycomb ceramic monolithic catalyst as claimed in claim 1 in the reaction of synthesizing chloroaniline by catalytic hydrogenation of chloronitrobenzene.
8. The use of claim 7, wherein: the chloronitrobenzene is p-chloronitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, 3, 4-dichloronitrobenzene or 2,3, 4-trichloronitrobenzene.
9. The use according to claim 7, characterized in that the use is: and (2) loading the nitrogen-doped phenolic resin-based nickel-inlaid porous carbon-coated honeycomb ceramic monolithic catalyst into a fixed bed reactor, introducing a hydrogen-nitrogen mixed gas serving as a reaction gas and a chloronitrobenzene normal butanol solution serving as a raw material into the fixed bed reactor, reacting at 50-100 ℃ under normal pressure, and condensing and collecting the obtained reaction liquid.
10. The use of claim 9, wherein: the concentration of chloronitrobenzene in the n-butyl alcohol solution of chloronitrobenzene is 0.05g/ml, and the flow rate of the n-butyl alcohol solution of chloronitrobenzene is 1ml/min; the volume ratio of hydrogen to nitrogen in the hydrogen-nitrogen mixed gas is 3:1, the flow rate of the hydrogen-nitrogen mixed gas is 80ml/min.
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