CN116037187B - Non-noble metal biomass charcoal composite material and preparation method and application thereof - Google Patents
Non-noble metal biomass charcoal composite material and preparation method and application thereof Download PDFInfo
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- CN116037187B CN116037187B CN202211740687.3A CN202211740687A CN116037187B CN 116037187 B CN116037187 B CN 116037187B CN 202211740687 A CN202211740687 A CN 202211740687A CN 116037187 B CN116037187 B CN 116037187B
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- nitrophenol
- aminophenol
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- biomass charcoal
- charcoal composite
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- 239000002028 Biomass Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000003610 charcoal Substances 0.000 title claims abstract description 37
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 80
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 claims abstract description 12
- 229960001911 glucosamine hydrochloride Drugs 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000008247 solid mixture Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000000197 pyrolysis Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 9
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910015189 FeOx Inorganic materials 0.000 description 7
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910005855 NiOx Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 229910002555 FeNi Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- FFXSKLNKKMNFDZ-UHFFFAOYSA-N iron 4-nitrophenol Chemical compound [Fe].[N+](=O)([O-])C1=CC=C(C=C1)O FFXSKLNKKMNFDZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol, a preparation method thereof and application thereof in catalyzing and hydrogenating the p-nitrophenol into the p-aminophenol. The preparation method comprises the following steps: adding a metal precursor salt solution into a glucosamine hydrochloride solution, fully stirring, adding melamine, and stirring to form a uniformly dispersed suspension; the metal precursor salt is at least one of Fe 3+ salt, co 2+ salt and Ni 2+ salt; and heating the suspension liquid under stirring, evaporating the solvent, and pyrolyzing the obtained solid mixture at 600-900 ℃ in an inert atmosphere to obtain the non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol, and a preparation method and application thereof.
Background
P-aminophenol (p-aminophenol) is an important intermediate for fine chemical industry and is widely used in the fields of medicine, dye, rubber, photography, etc. In the pharmaceutical industry, para-aminophenol is an important raw material for the production of para-acetaminophen (a commonly used antipyretic); in the dye industry, para-aminophenol can be used for synthesizing disperse dyes, acid dyes, direct dyes, sulfur dyes, fur dyes and the like; because of the strong reducibility of the para-aminophenol, the para-phenylenediamine anti-aging agent prepared from the para-aminophenol can be used for producing tire products with excellent performance.
The domestic process route for producing p-aminophenol mainly comprises a reduction method of p-nitrophenol iron powder and a catalytic hydrogenation method of p-nitrophenol. The iron powder reduction method uses iron powder as a reducing agent to reduce the paranitrophenol into the paraaminophenol in a hydrochloric acid medium, has simple process, but high production cost, and simultaneously generates a large amount of waste iron mud to pollute the environment, thereby being a obsolete production process. The method has the advantages of simple process, high product quality and small environmental pollution, and main manufacturers of the p-aminophenol all adopt the p-nitrophenol catalytic hydrogenation route to produce the p-aminophenol.
The key of the catalytic hydrogenation method of p-nitrophenol is the use of a catalyst. The patent specification with publication number CN1237575A discloses a hydrogenation process for preparing p-aminophenol from p-nitrophenol, which takes one or more of Pt/C, pd/C and skeleton Ni as a catalyst; patent specification with publication number CN104356007a discloses a process for producing p-aminophenol using modified raney nickel as catalyst. Considering that noble metal catalysts are expensive, raney nickel or framework nickel is often used as the catalyst in industrial production, but the catalyst has the problems of low catalytic activity, poor selectivity, inconvenient use, difficult recovery and the like. Therefore, the design and preparation of the novel catalyst with low cost, high efficiency and stability is of great significance for preparing the p-aminophenol by hydrogenating the p-nitrophenol. However, most of the currently reported catalysts are suitable for p-nitrophenol reaction in the presence of strong reducing agents such as sodium borohydride, hydrazine hydrate and the like, and the performances of the catalysts are still to be examined when hydrogen is used as the reducing agent. Based on the method, the novel non-noble metal catalyst is designed and prepared, and the high-efficiency and high-selectivity conversion of the p-nitrophenol into the p-aminophenol is realized under the condition of hydrogen reduction.
Disclosure of Invention
The invention provides a preparation method of a non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol, and the prepared non-noble metal biomass charcoal composite material can be applied to the reaction process of preparing the p-aminophenol by catalyzing and reducing the p-nitrophenol with hydrogen.
A preparation method of a non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol comprises the following steps:
1) Adding a metal precursor salt solution into a glucosamine hydrochloride solution, fully stirring, adding melamine, and stirring to form a uniformly dispersed suspension;
The metal precursor salt is at least one of Fe 3+ salt, co 2+ salt and Ni 2+ salt;
2) And heating the suspension to evaporate the solvent under stirring, and pyrolyzing the obtained solid mixture at 600-900 ℃ in inert atmosphere to obtain the non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol.
In order to obtain the catalytic material with high activity and high selectivity, the invention designs and constructs a catalytic system with the following core ideas: the non-noble metal with excellent hydrogenation activity is highly dispersed on the surface of the porous nitrogen-doped carbon carrier to be used as a reactive site. The nitrogen-containing biomass is selected to be pyrolyzed to form a carbon carrier, wherein nitrogen element can interact with metal element to play a role in anchoring metal to inhibit agglomeration of the metal, and the carbon carrier is favorable for forming highly dispersed, uniformly distributed and stably existing active metal species. In order to improve the selectivity of the target product, the nitrogenous biomass (glucosamine hydrochloride) and a specific nitrogenous pore-forming agent (melamine) are combined and pyrolyzed to regulate and control the pore channel structure of the carbon carrier, so that the diffusion, adsorption and desorption of reactants in the catalyst are facilitated, and the occurrence of excessive hydrogenation reaction is inhibited.
Compared with the common noble metal catalyst, the catalyst provided by the invention uses biomass and cheap and easily available non-noble metal as raw materials, so that the preparation cost of the catalyst is reduced, and the operation process is simple and convenient. Compared with Raney nickel and a common carbon carrier supported catalyst, the catalyst provided by the invention has the advantages that a specific nitrogen-containing pore-forming agent melamine is introduced in the preparation process to assist biomass pyrolysis to form the nitrogen-doped carbon carrier with a large specific surface area and rich pore canal structures, wherein nitrogen element can play a role in anchoring and dispersing metal nano particles, and the catalyst is favorable for forming metal species with small particle size and high activity as an active center of a catalytic material. The active metal species of the catalyst can be single metal or double metal alloy, and the excellent metal carrier interaction and alloy effect can ensure that the catalyst can be circularly used for a plurality of times with high activity, does not need additional activation before use, and can efficiently and highly selectively catalyze the hydrogenation of p-nitrophenol to p-aminophenol.
The research of the invention finds that:
1. If other types of biomass such as cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and the like are adopted, the catalytic performance of the obtained material is inferior to that of glucosamine hydrochloride in the application of converting p-nitrophenol into p-aminophenol through hydrogenation.
2. If sodium bicarbonate and the like are adopted as pore formers or other types of nitrogen-containing pore formers such as urea and the like are adopted, the catalytic performance of the obtained material is inferior to that of melamine in the application of converting p-nitrophenol into p-aminophenol through hydrogenation.
In the step (1), the mass ratio of the glucosamine hydrochloride to the melamine can be 1:1-20, preferably 1:2.5-10, more preferably 1:4-6, still more preferably 1:5, and the catalytic performance of the obtained material is better in the application of converting p-nitrophenol into p-aminophenol through hydrogenation under the preferable condition. The reason why too much melamine is added to adversely deteriorate the catalytic performance of the material may be that when the amount of melamine is too large, the decomposition process is too severe to cause collapse of the carbon support.
Preferably, in the step (1), the metal precursor salt is Fe 3+ salt and Co 2+ salt, or Fe 3+ salt and Ni 2+ salt, and the bimetallic alloy has better catalytic effect than single metal as catalytic site.
In the step (1), when the metal precursor salt is Fe 3+ salt and Ni 2+ salt, the molar ratio of Fe 3+ to Ni 2+ is preferably 0.5-3.5:1, more preferably 0.95-1.05:1, and the catalytic performance is better in the application of hydrogenation of p-nitrophenol to p-aminophenol, which is preferably carried out by the obtained material under the condition of Fe 3+、Ni2+ molar ratio.
In the step (1), the mass ratio of the glucosamine hydrochloride to the metal precursor salt may be 1:0.1-1.
In step (1), the metal precursor salt may be at least one of nitrate and chloride, preferably chloride.
In step (1), the metal precursor salt solution may be added to the glucosamine hydrochloride solution for a sufficient period of time, e.g., 2-24 hours, to allow for sufficient interaction.
In the step (1), the stirring time after adding the melamine can be 2-24 hours.
In the step (2), the temperature of the heated and evaporated solvent is 80-120 ℃.
In step (2), the conditions of the pyrolysis may be: the temperature rising rate is 1-10 ℃/min, and the heat preservation time is 1-3 hours at 600-900 ℃.
Preferably, in the step (2), the pyrolysis temperature is 900 ℃, and the catalysis performance of the material obtained at the pyrolysis temperature is better in the application of hydrogenation conversion of p-nitrophenol into p-aminophenol.
In the step (2), the inert atmosphere can be one or more of nitrogen, helium and argon.
In the step (2), the inert atmosphere is preferably introduced in a flowing manner, and the gas flow rate can be 50-500mL/min.
The invention also provides a non-noble metal biomass charcoal composite material which can catalyze and hydrogenate p-nitrophenol into p-aminophenol and is prepared by the preparation method.
The invention also provides application of the non-noble metal biomass charcoal composite material in catalytic hydrogenation of p-nitrophenol into p-aminophenol.
As a general inventive concept, the invention also provides a method for catalyzing and hydrogenating p-nitrophenol into p-aminophenol, which adopts the non-noble metal biomass charcoal composite material to catalyze and hydrogenate the p-nitrophenol into the p-aminophenol.
Preferably, the method for catalytically hydrogenating p-nitrophenol into p-aminophenol adopts hydrogen as a reducing agent, the reaction pressure is 1-5MPa, and the reaction temperature is 80-130 ℃.
For example: adding a certain amount of p-nitrophenol into a high-pressure reaction kettle, dissolving the p-nitrophenol by using solvents such as methanol, ethanol, tetrahydrofuran or water, and adding a certain amount of non-noble metal biomass charcoal composite material serving as a catalyst. After replacing the air in the autoclave with hydrogen for 3-5 times, filling hydrogen into the autoclave again to ensure that the pressure in the autoclave is 1-5MPa, setting the reaction temperature to be 80-130 ℃ and the reaction time to be 1-24h.
Compared with the prior art, the invention has the beneficial effects that:
The non-noble metal biomass charcoal composite material designed and prepared in the invention has the following advantages: on one hand, the use of inexpensive and easily available iron-based non-noble metals (Fe, co and Ni) instead of noble metal Pd can remarkably reduce the cost and has obvious economic benefit; on the other hand, the green renewable biomass is used as a carbon source to form the porous carbon carrier, so that the original value of the porous carbon carrier is greatly improved, and the porous carbon carrier has remarkable social benefit. In addition, the metal precursor and biomass are co-pyrolyzed to form the porous carbon-loaded active metal catalyst structure in one step, so that a series of steps of preparing the carbon carrier firstly and then loading the metal and finally roasting and activating in the traditional method are simplified. Compared with the reported catalyst material, the non-noble metal biomass charcoal composite material prepared by the invention takes hydrogen as a hydrogen source when catalyzing the hydrogenation of the p-nitrophenol, does not need to use strong reducing agents such as sodium borohydride and the like, and is consistent with the catalytic hydrogenation process of the p-nitrophenol in industrial production.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of the Fe-based biomass charcoal composite material FeOx/NC-1 prepared in example 3;
FIG. 2 is a TEM photograph of the Ni-based biomass charcoal composite material NiOx/NC-900 prepared in example 11;
FIG. 3 is a TEM photograph of the Fe-Ni based biomass charcoal composite material FeNi/NC-900 prepared in example 13.
Detailed Description
The invention will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
1G of cellulose was weighed and dispersed in 40mL of deionized water with stirring. 0.81g of ferric nitrate nonahydrate was weighed out and sonicated to dissolve in 10mL of deionized water. The prepared ferric nitrate solution is added into the suspension liquid dispersed with cellulose drop by drop, and the stirring speed is set to be proper and the stirring is continued for 8 hours at room temperature. And transferring the formed uniform suspension into an oil bath at 90 ℃, and maintaining a stirring state until the solvent is evaporated to dryness, so that the obtained solid mixture is the catalyst precursor. And (3) fully grinding the solid mixture, then sending the mixture into a tube furnace for pyrolysis in a nitrogen atmosphere, wherein the nitrogen flow is 200mL/min, the heating rate is 5 ℃/min, the pyrolysis temperature is 700 ℃, and the temperature is kept for 2 hours, so that the Fe-based biomass carbon composite material FeOx/C-1 is finally obtained.
Example 2
1G of cellulose was weighed and dispersed in 40mL of deionized water with stirring. 0.81g of ferric nitrate nonahydrate was weighed out and sonicated to dissolve in 10mL of deionized water. The prepared ferric nitrate solution is added into the suspension liquid dispersed with cellulose drop by drop, and the mixture is stirred for 2 hours at room temperature. Weighing 5g of urea, putting into the suspension, setting a proper stirring speed to form a uniformly dispersed suspension, and continuously stirring at room temperature for 8 hours. And transferring the formed uniform suspension into an oil bath at 90 ℃, and maintaining a stirring state until the solvent is evaporated to dryness, so that the obtained solid mixture is the catalyst precursor. And (3) fully grinding the solid mixture, then sending the mixture into a tube furnace for pyrolysis in a nitrogen atmosphere, wherein the nitrogen flow is 200mL/min, the heating rate is 5 ℃/min, the pyrolysis temperature is 700 ℃, and the temperature is kept for 2 hours, so that the Fe-based biomass carbon composite material FeOx/C-2 is finally obtained.
Example 3
1G of glucosamine hydrochloride was weighed and dissolved in 40mL of deionized water with stirring. 0.54g of ferric chloride hexahydrate was weighed and dissolved in 10mL of deionized water by sonication. The prepared ferric chloride solution is added into the glucosamine hydrochloride solution drop by drop, and stirred for 2 hours at room temperature to form a uniform solution. 5g of melamine is weighed and put into the solution, and a proper stirring speed is set to form a uniformly dispersed suspension, and stirring is continued for 8 hours at room temperature. And (3) transferring the suspension into an oil bath at 90 ℃, and maintaining a uniform stirring state until the solvent is evaporated to dryness, so that the obtained solid mixture is the catalyst precursor. After fully grinding the solid mixture, sending the mixture into a tube furnace for pyrolysis in a nitrogen atmosphere, wherein the nitrogen flow is 200mL/min, the heating rate is 5 ℃/min, the pyrolysis temperature is 700 ℃, and the temperature is kept for 2 hours, so that the Fe-based biomass charcoal composite material FeOx/NC-1 is finally obtained, and the morphology of the Fe-based biomass charcoal composite material FeOx/NC-1 is shown in figure 1.
Example 4
The difference from example 3 was only that the amount of melamine was 2.5g, and the rest was the same, to obtain Fe-based biomass charcoal composite material FeOx/NC-2.
Example 5
The difference from example 3 was only that the amount of melamine was 10g, and the rest was the same, to obtain Fe-based biomass charcoal composite material FeOx/NC-3.
Example 6
The difference from example 3 was only that 0.27g of ferric chloride hexahydrate and 0.24g of nickel chloride hexahydrate were used in place of 0.54g of ferric chloride hexahydrate, and the rest were the same, to obtain Fe-Ni-based biomass charcoal composite material FeNi/NC-700.
Example 7
The difference from example 3 was only that 0.27g of ferric chloride hexahydrate and 0.24g of cobalt chloride hexahydrate were used in place of 0.54g of ferric chloride hexahydrate, and the rest were the same, to obtain Fe-Co-based biomass charcoal composite material FeCo/NC-700.
Example 8
The difference from example 3 was only that 0.48g of nickel chloride hexahydrate was used instead of 0.54g of iron chloride hexahydrate, and the rest was the same, to obtain Ni-based biomass charcoal composite material NiOx/NC-700.
Example 9
The difference from example 8 was only that the pyrolysis temperature was 600℃and the rest were the same, to obtain Ni-based biomass charcoal composite material NiOx/NC-600.
Example 10
The difference from example 8 was only that the pyrolysis temperature was 800℃and the rest was the same, to obtain Ni-based biomass charcoal composite material NiOx/NC-800.
Example 11
The difference from example 8 is that the pyrolysis temperature is 900 ℃ and the rest is the same, so that the Ni-based biomass charcoal composite material NiOx/NC-900 is obtained, and the morphology is shown in figure 2.
Example 12
The difference from example 11 was only that 0.41g of iron chloride hexahydrate and 0.12g of nickel chloride hexahydrate were used in place of 0.48g of nickel chloride hexahydrate, and the remainder were the same, to obtain Fe-Ni-based biomass charcoal composite material Fe 3 Ni/NC-900.
Example 13
The difference from example 12 is that 0.27g of ferric chloride hexahydrate and 0.24g of nickel chloride hexahydrate are used for replacing 0.41g of ferric chloride hexahydrate and 0.12g of nickel chloride hexahydrate, and the rest are the same, so that the Fe-Ni based biomass charcoal composite material FeNi/NC-900 is obtained, and the morphology of the Fe-Ni based biomass charcoal composite material is shown in figure 3.
Example 14
The difference from example 12 was only that 0.14g of ferric chloride hexahydrate and 0.36g of nickel chloride hexahydrate were used in place of 0.41g of ferric chloride hexahydrate and 0.12g of nickel chloride hexahydrate, and the remainder were the same, to obtain Fe-Ni based biomass charcoal composite material FeNi 3/NC-900.
The composites of examples 1-14 were used to catalyze the hydrogenation of p-nitrophenol to p-aminophenol. The catalytic hydrogenation reaction is carried out in a stainless steel high-pressure reaction kettle, and a glass reaction bottle with a vent hole is placed in the reaction kettle, wherein the capacity is 5mL. The experimental procedure was as follows: 28mg of p-nitrophenol, 2mL of ethanol as a solvent, 10mg of the composite material as a catalyst and magneton were charged into a glass reaction flask. The reaction flask was placed in a high-pressure autoclave and sealed, the gas in the autoclave was replaced with H 2 for 3-5 times, and then the reaction pressure was increased. And (3) placing the reaction kettle into a preheated constant-temperature heating jacket, and starting timing after the temperature reaches the reaction temperature. After the reaction is finished, the reaction kettle is placed into cold water for rapid cooling, then the catalyst is separated, and the clear liquid in the reaction bottle is taken for quantitative analysis by a gas chromatography internal standard method.
The reaction conditions and test results are shown in table 1 below.
TABLE 1
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (7)
1. The preparation method of the non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol is characterized by comprising the following steps:
1) Adding a metal precursor salt solution into a glucosamine hydrochloride solution, fully stirring, adding melamine, and stirring to form a uniformly dispersed suspension; the mass ratio of the glucosamine hydrochloride to the melamine is 1:4-6;
The metal precursor salt is Fe 3+ salt and Ni 2+ salt, and the molar ratio of Fe 3+ to Ni 2+ is 0.95-1.05:1;
2) And heating the suspension to evaporate the solvent under stirring, and pyrolyzing the obtained solid mixture at 600-900 ℃ in inert atmosphere to obtain the non-noble metal biomass charcoal composite material capable of catalyzing and hydrogenating p-nitrophenol into p-aminophenol.
2. The method of claim 1, wherein in step (1), the mass ratio of the glucosamine hydrochloride to the metal precursor salt is 1:0.1-1.
3. The method of claim 1, wherein in step (2), the pyrolysis conditions are: the temperature rising rate is 1-10 ℃/min, and the heat preservation time is 1-3 hours at 600-900 ℃.
4. The non-noble metal biomass charcoal composite material which can catalyze and hydrogenate p-nitrophenol into p-aminophenol and is prepared by the preparation method according to any one of claims 1-3.
5. The use of the non-noble metal biomass charcoal composite material according to claim 4 for catalytic hydrogenation of p-nitrophenol to p-aminophenol.
6. A method for catalytically hydrogenating p-nitrophenol to p-aminophenol, which is characterized by catalytically hydrogenating p-nitrophenol to p-aminophenol by using the non-noble metal biomass charcoal composite material of claim 4.
7. The process according to claim 6, wherein hydrogen is used as the reducing agent, the reaction pressure is 1-5MPa, and the reaction temperature is 80-130 ℃.
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| CN104447209A (en) * | 2014-11-19 | 2015-03-25 | 浙江大学 | Method for preparing cyclohexanol by catalyzing by base metal catalyst |
| CN107308937A (en) * | 2017-06-30 | 2017-11-03 | 青岛科技大学 | A kind of hydrothermal preparing process of carbon base catalyst for paranitrophenol catalytic hydrogenation |
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