CN114042456B - Method for preparing Fe-based catalyst by taking biomass as raw material and application of Fe-based catalyst - Google Patents
Method for preparing Fe-based catalyst by taking biomass as raw material and application of Fe-based catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 title abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 106
- 241001122767 Theaceae Species 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002161 passivation Methods 0.000 claims description 13
- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 11
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910001567 cementite Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 2
- 229940095098 glycol oleate Drugs 0.000 claims 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 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006185 dispersion 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940092665 tea leaf extract Drugs 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing an Fe-based catalyst by taking biomass as a raw material and application of the Fe-based catalyst. The method comprises the following steps: (a) Dissolving iron-containing inorganic salt in deionized water to obtain solution A; (b) Adding the dried tea A into deionized water, stirring, and filtering to obtain tea extractive solution; (c) Adding the dried tea B into potassium hydroxide solution to obtain activated biomass material; (d) Adding biomass materials into the tea leaf extracting solution to obtain a precursor mixed solution; (e) Respectively adding the solution A, the dispersing agent and the nitrogenous organic matters into the precursor mixed solution, and carrying out ultrasonic treatment to obtain an iron-containing suspension; (f) And removing the iron-containing suspension solvent, and roasting at high temperature and passivating to obtain the Fe-based catalyst. The Fe-based catalyst prepared by the method has the advantages of low cost, simple and environment-friendly preparation process, and better catalytic reaction performance in the catalytic hydrogenation reaction of the p-chloronitrobenzene.
Description
Technical Field
The invention relates to a method for preparing an Fe-based catalyst by taking biomass as a raw material and application of the Fe-based catalyst in catalytic hydrogenation of p-chloronitrobenzene.
Background
Para-chloroaniline is an important organic intermediate and is widely used in the synthesis of dyes, medicines, pesticides and the like. At present, most of p-chloroaniline is prepared from p-chloronitrobenzene serving as a raw material by adopting a metal reduction method, an electrochemical reduction method, a catalytic hydrogenation reduction method and other reduction methods. The catalytic hydrogenation reduction method has the advantages of advanced process, high yield, environmental protection and the like, and is an industrialized method commonly used for p-chloroaniline production. Compared with noble metal catalytic hydrogenation catalysts (such as Pd and Pt-based hydrogenation catalysts), the Fe-based catalyst has the advantages of rich reserve, low price, easy recovery of magnetism, low toxicity of Fe element and the like, and is a metal hydrogenation catalyst which has been studied more in recent years. In the preparation of Fe-based catalysts, strong reducing agents such as sodium borohydride are required to reduce divalent or trivalent iron ions to zero-valent Fe-like hydrogenation-reactive species (Earth and Environmental Science,675, 2021, 012310), but these reducing agents used and the preparation thereof cause environmental pollution. Compared with the inorganic reducing agent, the preparation of the metal catalyst by using the biomass extracting solution rich in tea polyphenol as the reducing agent has the characteristics of green, environmental protection and the like, and is widely paid attention to people. However, the Fe-based catalytic material prepared by the method generally has the problems of smaller specific surface area and adverse dispersion of hydrogenation reaction active centers.
Therefore, the invention mainly relates to a novel preparation method for preparing an Fe-based catalyst by taking biomass extract as a reducing agent and activated biomass as a carbon source, and application of the Fe-based catalyst in catalytic hydrogenation of p-chloronitrobenzene.
Disclosure of Invention
In order to solve the problems of low specific surface area and the like of the catalyst obtained by reduction by using a toxic reducing agent and a biomass extracting solution in the existing metal catalyst preparation technology, the primary purpose of the invention is to provide a method for preparing an Fe-based catalyst by taking the biomass extracting solution as a reducing agent and activated biomass as a carbon source, so that the specific surface area of the prepared catalyst is improved, and the catalytic hydrogenation reaction performance of the catalyst is improved.
A second object of the present invention is to provide an Fe-based catalyst prepared according to the method.
The third object of the invention is to provide the application of the Fe-based catalyst in the catalytic hydrogenation reaction of p-chloronitrobenzene.
The following describes the technical means adopted to solve the above-mentioned problems.
In a first aspect, the present invention provides a method for preparing an Fe-based catalyst from biomass, the method comprising the steps of:
(a) Dissolving iron-containing inorganic salt in deionized water to obtain solution A;
(b) Adding dried tea A (preferably 40-60 mesh) into deionized water, stirring at 50-90deg.C (preferably 80deg.C) for 30-60min (preferably 60 min), cooling to room temperature, and filtering to obtain tea extractive solution;
(c) Adding dried tea B (preferably 40-60 mesh) into 0.1-2moL/L potassium hydroxide water solution, treating at 60-80deg.C (preferably 80deg.C) for 30-60min (preferably 60 min), filtering, and washing until pH of filtrate is neutral to obtain activated biomass material; the potassium hydroxide aqueous solution is preferably used in an amount to completely submerge the tea leaves;
(d) Adding the biomass material prepared in the step (c) into a tea leaf extracting solution to obtain a precursor mixed solution;
(e) Respectively adding the solution A, the dispersing agent and the nitrogenous organic matters into the precursor mixed solution prepared in the step (d), and carrying out ultrasonic treatment to obtain an iron-containing suspension;
(f) Removing the iron-containing suspension solvent, and roasting at high temperature and passivating to obtain an Fe-based catalyst;
in the steps (d) and (e), the feeding ratio of the tea extract, the biomass material, the solution A, the dispersing agent and the nitrogenous organic matters is 3-5g, 0.0025-0.01mol, 5-9g and 2-4g based on the proportion of the tea A, the tea B, the iron-containing inorganic salt, the dispersing agent and the nitrogenous organic matters.
The tea A and the tea B are only used for distinguishing the tea used in different steps, and do not represent that the two kinds of tea are necessarily different. The tea A and the tea B are commercial tea, and can be directly used after being screened.
Further, the iron-containing inorganic salt in the step (a) is ferric nitrate nonahydrate, and the concentration of the solution is preferably 0.05 to 0.3moL/L, more preferably 0.1moL/L.
Further, in step (b), tea A and deionized water are fed at a tea concentration of 45-60g/L, more preferably 54.5g/L.
Further, in the step (b), the concentration of the aqueous potassium hydroxide solution was 0.5mol/L.
Further, the nitrogen-containing organic compound in step (e) is one of dicyandiamide, melamine, polypropylene pyrrolidone, urea, more preferably melamine.
Further, the dispersing agent in the step (e) is preferably one of polyethylene glycol-1000, polyethylene glycol-400, polyethylene glycol oleate, tween 60 and sodium lignin sulfonate, more preferably polyethylene glycol-400. Most preferably, the nitrogen-containing organic compound is melamine, the dispersing agent is polyethylene glycol-400, and the feeding ratio of the tea extract, the biomass material, the solution A, the dispersing agent and the nitrogen-containing organic matters is 3g:3g:0.0025mol:5mL:2g.
Further, step (e) is specifically performed as follows: adding a nitrogen-containing organic compound into the precursor mixed solution, stirring (heating if necessary) to dissolve the nitrogen-containing organic compound, adding a dispersing agent into the solution at room temperature, dripping the solution A, and performing ultrasonic treatment to obtain the iron-containing suspension.
Further, the solvent removal in the step (f) mainly adopts a solvent evaporation method, the high-temperature roasting is required to be performed under the inert atmosphere condition, the roasting temperature is preferably 600 ℃, and the roasting time is preferably 4 hours. The inert gas is selected from N 2 Ar or He, preferably high purity N 2 The purity is above 99.999%.
Further, in step (f), the passivation gas is preferably 1v% O 2 +99v％N 2 The passivation time is preferably 1h.
Further, the ultrasonic treatment is as follows: the ultrasonic power is 100W, and the ultrasonic time is 5-15min, preferably 10min.
The invention specifically recommends that the method is implemented as follows:
(a) Weighing Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water under the condition of room temperature to obtain 0.05-0.3mol/L solution A containing Fe (III) ions;
(b) Weighing 40-60 mesh dry tea leaves, adding the dry tea leaves into deionized water, stirring and heating the tea leaves for 30-60min under the water bath condition of 50-90 ℃, and then filtering to obtain tea leaf extract for later use; wherein tea A and deionized water are fed according to the tea concentration of 45-60 g/L;
(c) Preparing KOH solution with the concentration of 0.5mol/L, adding 40-60 mesh dry tea, stirring and soaking for 30-60min under the water bath condition of 60-80 ℃, carrying out suction filtration on the soaking solution, and carrying out washing treatment for multiple times until the pH value of the filtrate is neutral to obtain a biomass material;
(d) Adding the biomass material obtained in the step (c) into the tea leaf extracting solution obtained in the step (b) to obtain a precursor mixed solution;
(e) Adding melamine into the precursor mixed solution, stirring under the water bath heating condition of 60-90 ℃ to dissolve the melamine, cooling to room temperature, adding PEG-400 into the solution, dripping the solution A, and performing ultrasonic treatment for 10min at 100W to obtain an iron-containing suspension;
(f) Heating the iron-containing suspension to evaporate the solvent to obtain a black precursor, roasting the black precursor in a tube furnace for 4 hours in a nitrogen atmosphere at 600 ℃, cooling to room temperature, and then introducing passivation gas to perform passivation treatment for 1 hour to obtain the Fe-based catalyst; the passivation gas is 1v% O 2 +99v％N 2 ；
In the steps (d) and (e), the feeding ratio of the tea extract, the biomass material, the solution A, PEG-400 and the melamine is 3g based on the proportion of tea A, tea B, iron-containing inorganic salt, PEG-400 and melamine: 3g:0.0025mol:5mL:2g.
In a second aspect, the present invention provides an Fe-based catalyst prepared by the method.
The Fe-based catalyst is composed of Fe 0 The Fe-based catalyst material comprises iron carbide and a carbon carrier, wherein the particle size of the iron-containing nano particles is 10-30 nanometers, the carbon carrier mainly contains graphite carbon species, and the specific surface area of the Fe-based catalyst material is not less than 100m 2 g -1 The pore diameter is not less than 4nm.
In a third aspect, the invention provides an application of the Fe-based catalyst in catalytic hydrogenation of p-chloronitrobenzene.
Further, the application is specifically: absolute ethanol and p-ethyl alcoholAdding chloronitrobenzene and an Fe-based catalyst into a high-pressure reaction kettle; the reactor system is first treated with high purity H prior to reaction 2 (purity of 99.999% or more) is sealed and washed for a plurality of times (for example, 6 times), and then hydrogenation reaction is carried out under the conditions of magnetic stirring (1000 rpm or more), reaction temperature of 120-160 ℃ (preferably 150 ℃), and hydrogen pressure of 1-1.3MPa (preferably 1.1 MPa) to generate the parachloroaniline.
The Fe-based catalyst shows good reaction activity and product p-chloroaniline selectivity in the catalytic hydrogenation reaction of p-chloronitrobenzene.
Compared with the prior art, the invention has the following advantages:
(1) The Fe-based catalyst disclosed by the invention takes biomass materials (tea leaves) as raw materials, and has the advantages of low cost and simple preparation process.
(2) The Fe-based catalyst reported by the invention does not use a toxic and dangerous reducing reagent, and the preparation process is environment-friendly.
(3) The Fe-based catalyst reported by the invention has better catalytic reaction performance in the catalytic hydrogenation reaction of the p-chloronitrobenzene, and shows better reaction activity and product selectivity.
Drawings
Fig. 1 is an XRD spectrum of the catalyst prepared in example 1.
Fig. 2 is an XRD spectrum of the catalyst prepared in example 2.
Fig. 3 is an XRD spectrum of the catalyst prepared in example 3.
Detailed Description
The technical scheme of the present invention is further described by the following specific examples, but the scope of the present invention is not limited by the following examples.
Example 1
10.10g of Fe (NO) was weighed out 3 ) 3 ·9H 2 O was dissolved in 250mL of deionized water at room temperature to give a 0.1mol/L Fe (III) solution. 3.00g of dry tea (40-60 meshes) is weighed and added into 55mL of deionized water, and the mixture is stirred and heated for 1h under the water bath condition of 80 ℃ and then filtered to obtain 50mL of tea extract for later use. 50ml of KOH solution having a concentration of 0.1mol/L was prepared, and 3.00g of dried tea leaves (40 to the upper60 mesh), and stirring and soaking for 1h under the water bath condition of 80 ℃. And then carrying out suction filtration on the impregnating solution, and carrying out washing treatment for a plurality of times until the pH value of the filtrate is approximately equal to 7. The treated tea leaves were added to the 50ml tea extract, then 2.00g melamine was added, and stirred for 15min under water bath heating at 80 ℃. After it had cooled to room temperature, 5ml of EG-400 was added to the solution. 25mLFe (NO) 3 ) 3 ·9H 2 O solution (0.1 mol/L) was added dropwise to the above solution to form a black suspension. After 10min of ultrasonic treatment at 100W, the solvent was evaporated at 98℃to obtain a black precursor sample. The black precursor was baked in a tube furnace for 4 hours at 600 ℃ under a high purity nitrogen atmosphere of 99.999%. After cooling to room temperature, 1%O is introduced 2 /N 2 And (3) carrying out passivation treatment on the gas for 1h to obtain the Fe-C-K-0.1 catalyst. The XRD spectrum of the catalyst is shown in figure 1. XRD characterization indicates the presence of Fe in the catalyst 0 ，Fe 3 C and graphitic carbon crystalline forms. The particle size of the iron-containing particles in the catalyst was estimated to be about 13.3nm by the schehler equation. N (N) 2 The adsorption characterization test result shows that the specific surface area of the catalyst is 100.3m 2 g -1 The pore size was about 7.2nm.
Example 2
10.10g of Fe (NO) was weighed out 3 ) 3 ·9H 2 O was dissolved in 250mL of deionized water at room temperature to give a 0.1mol/L Fe (III) solution. 3.00g of dry tea (40-60 meshes) is weighed and added into 55mL of deionized water, and the mixture is stirred and heated for 1h under the water bath condition of 80 ℃ and then filtered to obtain 50mL of tea extract for later use. 50ml of KOH solution with the concentration of 0.5mol/L is prepared, 3.00g of dried tea leaves (40-60 meshes) are added, and the mixture is stirred and immersed for 1 hour under the water bath condition of 80 ℃. And then carrying out suction filtration on the impregnating solution, and carrying out washing treatment for a plurality of times until the pH value of the filtrate is approximately equal to 7. The treated tea leaves were added to the 50ml tea extract, then 2.00g melamine was added, and stirred for 15min under water bath heating at 80 ℃. After it had cooled to room temperature, 5ml of EG-400 was added to the solution. 25mL of Fe (NO) 3 ) 3 ·9H 2 O solution (0.1 mol/L) was added dropwise to the above solution to form a black suspension. After 10min of ultrasonic treatment at 100W, the solvent is evaporated at 98 ℃,a black precursor sample was obtained. The black precursor was baked in a tube furnace for 4 hours at 600 ℃ under a high purity nitrogen atmosphere of 99.999%. After cooling to room temperature, 1%O is introduced 2 /N 2 And (3) carrying out passivation treatment on the gas for 1h to obtain the Fe-C-K-0.5 catalyst. The XRD spectrum of the catalyst is shown in figure 2. XRD characterization indicates the presence of Fe in the catalyst 0 ，Fe 3 C and graphitic carbon crystalline forms. The particle size of the iron-containing particles in the catalyst was estimated to be about 14.9nm by the schehler equation. N (N) 2 The adsorption characterization test result shows that the specific surface area of the catalyst is 191.4m 2 g -1 The pore size was about 6.6nm.
Example 3
10.10g of Fe (NO) was weighed out 3 ) 3 ·9H 2 O was dissolved in 250mL of deionized water at room temperature to give a 0.1mol/L Fe (III) solution. 3.00g of dry tea (40-60 meshes) is weighed and added into 55mL of deionized water, and the mixture is stirred and heated for 1h under the water bath condition of 80 ℃ and then filtered to obtain 50mL of tea extract for later use. 50ml of KOH solution with the concentration of 2mol/L is prepared, 3.00g of dried tea leaves (40-60 meshes) are added, and the mixture is stirred and immersed for 1 hour under the water bath condition of 80 ℃. And then carrying out suction filtration on the impregnating solution, and carrying out washing treatment for a plurality of times until the pH value of the filtrate is approximately equal to 7. The treated tea leaves were added to the 50ml tea extract, then 2.00g melamine was added, and stirred for 15min under water bath heating at 80 ℃. After it had cooled to room temperature, 5ml of EG-400 was added to the solution. 25mLFe (NO) 3 ) 3 ·9H 2 O solution (0.1 mol/L) was added dropwise to the above solution to form a black suspension. After 10min of ultrasonic treatment at 100W, the solvent was evaporated at 98℃to obtain a black precursor sample. The black precursor was baked in a tube furnace for 4 hours at 600 ℃ under a high purity nitrogen atmosphere of 99.999%. After cooling to room temperature, 1%O is introduced 2 /N 2 And (3) carrying out passivation treatment on the gas for 1h to obtain the Fe-C-K-2.0 catalyst. The XRD spectrum of the catalyst is shown in figure 3. XRD characterization indicates the presence of Fe in the catalyst 0 ，Fe 3 C and graphitic carbon crystalline forms. The particle size of the iron-containing particles in the catalyst was estimated to be about 13.8nm by the schehler equation. N (N) 2 The adsorption characterization test result shows that the specific surface area of the catalyst is 207.4m 2 g -1 The pore size was about 4.4nm.
Example 4
Stainless steel autoclave (75 cm) 3 ) The Fe-based catalysts prepared in example 1, example 2 and example 3 were subjected to a test experiment for evaluating the catalytic hydrogenation reaction performance of p-chloronitrobenzene.
First, 25ml of absolute ethanol, 0.3 g of p-chloronitrobenzene and 0.3 g of a catalyst were charged into a high-pressure reactor. The reactor system is first treated with high purity H prior to reaction 2 (99.999%) was sealed and washed 6 times, and then hydrogenation was carried out under magnetic stirring (1000 rpm), 423K and 1.1 MPa. The reaction was sampled at intervals and analyzed using a gas chromatograph equipped with a flame ionization detector (Agilent GC 7890B).
The test results of the catalytic hydrogenation reaction performance show that under the reaction experimental conditions, the conversion rate of the p-chloronitrobenzene can be over 99% after about 10 hours, 5 hours and 7 hours of the Fe-C-K-0.1, fe-C-K-0.5 and Fe-C-K-2.0 catalysts. Meanwhile, when the p-chloronitrobenzene conversion rate of the Fe-C-K-0.5 catalyst is 100%, the p-chloroaniline selectivity is 100%, and the p-chloroaniline selectivity of the Fe-C-K-0.1 and the Fe-C-K-2.0 catalysts are less than 90%.
The experimental result shows that the Fe-based catalyst prepared by the synthetic method disclosed by the invention has a good p-chloronitrobenzene conversion rate, wherein the selectivity of the Fe-C-K-0.5 catalyst to the chloroaniline product can reach 100% while the high conversion rate is maintained.
Claims (10)
1. A method for preparing an Fe-based catalyst for catalytic hydrogenation reactions from biomass, the method comprising the steps of:
(a) Dissolving iron-containing inorganic salt in deionized water to obtain solution A;
(b) Adding the dried tea A into deionized water, stirring at 50-90deg.C for 30-60min, cooling to room temperature, and filtering to obtain tea extractive solution;
(c) Adding the dried tea B into 0.1-2moL/L potassium hydroxide aqueous solution, treating at 60-80deg.C for 30-60min, filtering, and washing until pH of filtrate is neutral to obtain activated biomass material;
(d) Adding the biomass material prepared in the step (c) into a tea leaf extracting solution to obtain a precursor mixed solution;
(e) Respectively adding the solution A, the dispersing agent and the nitrogenous organic matters into the precursor mixed solution prepared in the step (d), and carrying out ultrasonic treatment to obtain an iron-containing suspension;
(f) Removing the iron-containing suspension solvent, roasting at 600 ℃ and passivating to obtain the Fe-based catalyst, wherein the Fe-based catalyst is prepared from Fe 0 The Fe-based catalyst comprises iron carbide and a carbon carrier, wherein the particle size of the iron-containing nano particles is 10-30 nanometers, and the specific surface area of the Fe-based catalyst is not less than 100m 2 g -1 The aperture is not smaller than 4 nm;
in the steps (d) and (e), the feeding ratio of the tea extract, the biomass material, the solution A, the dispersing agent and the nitrogenous organic matters is 3-5g, 0.0025-0.01mol, 5-9g and 2-4g based on the proportion of the tea A, the tea B, the iron-containing inorganic salt, the dispersing agent and the nitrogenous organic matters.
2. The method of claim 1, wherein: the iron-containing inorganic salt in the step (a) is ferric nitrate nonahydrate, and the concentration of the solution is 0.05-0.3mol/L.
3. The method of claim 1, wherein: in the step (b), the tea A and deionized water are fed according to the tea concentration of 45-60 g/L.
4. The method of claim 1, wherein: in the step (c), the concentration of the aqueous potassium hydroxide solution is 0.5mol/L.
5. The method of claim 1, wherein: in the step (e), the nitrogen-containing organic compound is one of cyanamide, dicyandiamide, melamine and urea; the dispersing agent is one of polyethylene glycol-1000, polyethylene glycol-400, polyethylene glycol oleate, tween 60 and sodium lignin sulfonate.
6. The method of claim 1, wherein: step (e) is specifically performed as follows: adding a nitrogen-containing organic compound into the precursor mixed solution, stirring to dissolve the nitrogen-containing organic compound, adding a dispersing agent into the solution at room temperature, then dripping the solution A, and performing ultrasonic treatment to obtain the iron-containing suspension.
7. The method of claim 1, wherein: in the step (f), the high-temperature roasting is performed under the inert atmosphere condition, the roasting temperature is 600 ℃, and the roasting time is 4h.
8. The method of claim 1, wherein: in step (f), the passivation gas is 1v% O 2 + 99 v% N 2 The passivation time was 1h.
9. The method of claim 1, wherein: the method is implemented as follows:
(a) Weighing Fe (NO) 3 ) 3 ·9H 2 O is dissolved in deionized water under the condition of room temperature to obtain 0.05-0.3mol/L of solution A containing Fe (III);
(b) Weighing 40-60 mesh dry tea A, adding into deionized water, stirring and heating at 50-90 ℃ for 30-60min, and filtering to obtain tea extract for later use; wherein tea A and deionized water are fed according to the tea concentration of 45-60 g/L;
(c) Preparing a KOH solution with the concentration of 0.5mol/L, adding 40-60 mesh dry tea B, stirring and soaking for 30-60min under the water bath condition of 60-80 ℃, carrying out suction filtration on the soaking solution, and carrying out washing treatment for multiple times until the pH value of the filtrate is neutral to obtain a biomass material;
(d) Adding the biomass material obtained in the step (c) into the tea leaf extracting solution obtained in the step (b) to obtain a precursor mixed solution;
(e) Adding melamine into the precursor mixed solution, stirring under the water bath heating condition of 60-90 ℃ to dissolve the melamine, cooling to room temperature, adding PEG-400 into the solution, dripping the solution A, and performing ultrasonic treatment for 10min at 100W to obtain an iron-containing suspension;
(f) Heating the iron-containing suspension to evaporate the solvent to obtain a black precursor, roasting the black precursor in a tube furnace at 600 ℃ under nitrogen atmosphere for 4h, cooling to room temperature, and then introducing passivation gas for passivation treatment for 1h to obtain the Fe-based catalyst; the passivation gas is 1v% O 2 + 99 v% N 2 ；
In the steps (d) and (e), the feeding ratio of the tea extracting solution, the biomass material, the solution A, PEG-400 and the melamine is 3g based on the proportion of tea A, tea B, iron-containing inorganic salt, PEG-400 and melamine: 3g:0.0025mol:5mL:2g.
10. The use of the Fe-based catalyst prepared by the preparation method according to claim 1 in the catalytic hydrogenation of p-chloronitrobenzene.
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