CN114042456A - Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst - Google Patents
Method for preparing Fe-based catalyst by using biomass as raw material and application of Fe-based catalyst Download PDFInfo
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- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 14
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
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- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 14
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- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
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- 238000005303 weighing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 4
- 238000005406 washing 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
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-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
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229940095098 glycol oleate Drugs 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
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- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 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 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
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- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 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
- 238000007789 sealing Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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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
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- B01J35/615—
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- B01J35/647—
-
- 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
Abstract
The invention discloses a method for preparing a Fe-based catalyst by using 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 a solution A; (b) adding dried tea A into deionized water, stirring, and filtering to obtain tea extractive solution; (c) adding the dried tea B into a potassium hydroxide solution for treatment to obtain an activated biomass material; (d) adding a biomass material into the tea extract to obtain a precursor mixed solution; (e) respectively adding the solution A, a dispersing agent and a nitrogen-containing organic matter into the precursor mixed solution, and performing ultrasonic treatment to obtain an iron-containing suspension; (f) removing the iron-containing suspension solvent, and carrying out high-temperature roasting and passivation treatment to obtain the Fe-based catalyst. The Fe-based catalyst prepared by the invention has low cost and simple and environment-friendly preparation process, and has better catalytic reaction performance in the catalytic hydrogenation reaction of p-chloronitrobenzene.
Description
Technical Field
The invention relates to a method for preparing a Fe-based catalyst by using biomass as a raw material and application of the Fe-based catalyst in catalytic hydrogenation reaction of p-chloronitrobenzene.
Background
Parachloroaniline is an important organic intermediate, and is widely applied to synthesis of dyes, medicines, pesticides and the like. At present, most of parachloroaniline is prepared by using parachloronitrobenzene as a raw material and 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 industrial method commonly used for the production of parachloroaniline. Compared with noble metal catalytic hydrogenation catalysts (such as Pd and Pt-based hydrogenation catalysts), the Fe-based catalyst has the advantages of abundant reserves, low price, easy recovery of magnetism, low Fe element toxicity and the like, and is a metal hydrogenation catalyst which is researched more in recent years. In the preparation of Fe-based catalysts, strong reducing agents such as sodium borohydride are required in order to reduce divalent or trivalent iron ions to species having hydrogenation activity such as zero-valent Fe (Earth and Environmental Science, 675, 2021, 012170), but these reducing agents used and their preparation process 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 draws wide attention of people. However, the Fe-based catalytic material prepared by the method generally has the problems of small specific surface area and unfavorable dispersion of the active center of hydrogenation reaction.
Therefore, the invention mainly relates to a novel preparation method for preparing a Fe-based catalyst by using a biomass extracting solution as a reducing agent and using activated biomass as a carbon source, and application of the Fe-based catalyst in catalytic hydrogenation reaction of p-chloronitrobenzene.
Disclosure of Invention
In order to solve the problems of low specific surface area and the like of catalysts obtained by reduction by using a toxic reduction reagent and a biomass extracting solution in the existing technology for preparing metal catalysts, the invention mainly aims to provide a method for preparing Fe-based catalysts by using the biomass extracting solution as a reducing agent and using activated biomass as a carbon source, so that the specific surface area of the prepared catalysts is improved, and the catalytic hydrogenation reaction performance of the catalysts is improved.
A second object of the present invention is to provide an Fe-based catalyst prepared according to said method.
The third purpose of the invention is to provide the application of the Fe-based catalyst in the catalytic hydrogenation reaction of p-chloronitrobenzene.
The following describes a technical solution adopted to solve the above-described technical 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 a solution A;
(b) adding dried folium Camelliae sinensis A (preferably 40-60 mesh) into deionized water, stirring at 50-90 deg.C (preferably 80 deg.C) for 30-60min (preferably 60min), cooling to room temperature, and filtering to obtain folium Camelliae sinensis extractive solution;
(c) adding dried folium Camelliae sinensis B (preferably 40-60 mesh) into 0.1-2moL/L potassium hydroxide water solution, treating at 60-80 deg.C (preferably 80 deg.C) for 30-60min (preferably 60min), filtering, and washing until the pH of the filtrate is neutral to obtain activated biomass material; the dosage of the potassium hydroxide aqueous solution is preferably that the tea leaves can be completely immersed;
(d) adding the biomass material prepared in the step (c) into a tea extract to obtain a precursor mixed solution;
(e) respectively adding the solution A, a dispersing agent and a nitrogen-containing organic matter into the precursor mixed solution prepared in the step (d), and performing ultrasonic treatment to obtain an iron-containing suspension;
(f) removing the iron-containing suspension solvent, and carrying out high-temperature roasting and passivation treatment to obtain a 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 nitrogen-containing organic matter is 3-5g:3-5g:0.0025-0.01mol:5-9g:2-4g based on the proportion of the tea A, the tea B, the iron-containing inorganic salt, the dispersing agent and the nitrogen-containing organic matter.
The tea leaves A and B in the tea leaves A and B are only used for distinguishing the tea leaves used in different steps, and do not mean that the two tea leaves are necessarily different. The tea leaves A and B are commercially available tea leaves, and can be directly used after being screened.
Further, the iron-containing inorganic salt in the step (a) is an iron nitrate nonahydrate, and the concentration of the solution is preferably 0.05 to 0.3moL/L, more preferably 0.1 moL/L.
Further, in the step (b), the tea leaves A and the deionized water are fed according to the concentration of the tea leaves of 45-60g/L, and more preferably 54.5 g/L.
Further, in the step (b), the concentration of the aqueous solution of potassium hydroxide was 0.5 mol/L.
Further, the nitrogen-containing organic compound in step (e) is one of cyanamide, dicyandiamide, melamine, polypropylene pyrrolidone and urea, and melamine is more preferable.
Further, in the step (e), the dispersant is preferably one of polyethylene glycol-1000, polyethylene glycol-400, polyethylene glycol oleate, tween 60 and sodium lignosulfonate, and more preferably polyethylene glycol-400. Most preferably, the nitrogenous organic compound is melamine, the dispersing agent is polyethylene glycol-400, the feeding ratio of the tea extract, the biomass material, the solution A, the dispersing agent and the nitrogenous organic compound is 3g (calculated by the proportion of the tea A, the tea B, the iron-containing inorganic salt, the dispersing agent and the nitrogenous organic compound): 3 g:0.0025 mol: 5mL of: 2g of the total weight.
Further, the step (e) is specifically carried out 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, then dripping the solution A, and performing ultrasonic treatment to obtain an iron-containing suspension.
Further, the solvent removal in the step (f) mainly adopts a method of evaporating the solvent, and the high-temperature roasting needs to be carried out under the condition of inert atmosphereThe roasting temperature is preferably 600 ℃, and the roasting time is preferably 4 hours. The inert gas is selected from N2Ar or He, preferably high purity N2The purity is more than 99.999 percent.
Further, in the step (f), the passivation gas is preferably 1 v% O2+99v％N2The passivation time is preferably 1 hour.
Further, the ultrasonic treatment comprises the following steps: the ultrasonic power is 100W, and the ultrasonic time is 5-15min, preferably 10 min.
The invention specifically recommends the implementation of the method as follows:
(a) weighing Fe (NO)3)3·9H2Dissolving O in deionized water at 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 tea leaves into deionized water, stirring and heating for 30-60min under the condition of water bath at 50-90 ℃, and then filtering to obtain a tea leaf extracting solution for later use; wherein the tea A and the deionized water are fed according to the concentration of the tea being 45-60 g/L;
(c) preparing a KOH solution with the concentration of 0.5mol/L, adding 40-60-mesh dry tea, stirring and dipping for 30-60min under the condition of a water bath at the temperature of 60-80 ℃, then carrying out suction filtration on a dipping solution, and carrying out washing treatment for multiple times until the pH value of a filtrate is neutral to obtain a biomass material;
(d) adding the biomass material obtained in the step (c) into the tea extract obtained in the step (b) to obtain precursor mixed liquor;
(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, then dripping the solution A, and carrying out 100W ultrasonic treatment for 10min 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 ℃ for 4 hours in a nitrogen atmosphere, cooling to room temperature, and introducing a passivation gas to perform passivation treatment for 1 hour to obtain a Fe-based catalyst; the passivation gas is 1 v% O2+99v％N2；
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 according to the proportion of tea A, tea B, iron-containing inorganic salt, PEG-400 and melamine: 3 g:0.0025 mol: 5mL of: 2g of the total weight.
In a second aspect, the present invention provides an Fe-based catalyst prepared by the method.
The Fe-based catalyst consists of Fe0Iron carbide and 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 catalytic material is not less than 100m2g-1And the pore diameter is not less than 4 nm.
In a third aspect, the invention provides an application of the Fe-based catalyst in a p-chloronitrobenzene catalytic hydrogenation reaction.
Further, the application specifically comprises: adding absolute ethyl alcohol, p-chloronitrobenzene and Fe-based catalyst into a high-pressure reaction kettle; before the reaction, the reactor system is first treated with high-purity H2(purity more than 99.999%) and sealing and cleaning for several times (such as 6 times), then carrying out hydrogenation reaction under the conditions of magnetic stirring (more than 1000rpm), reaction temperature of 120-.
The Fe-based catalyst shows better reaction activity and p-chloroaniline selectivity when p-chloronitrobenzene is subjected to catalytic hydrogenation.
Compared with the prior art, the invention has the following advantages:
(1) the Fe-based catalyst disclosed by the invention takes biomass materials (tea) as raw materials, and is low in cost and simple in preparation process.
(2) The Fe-based catalyst reported by the invention does not use a toxic and high-risk reducing reagent, and the preparation process is green and environment-friendly.
(3) The Fe-based catalyst reported by the invention has better catalytic reaction performance in the catalytic hydrogenation reaction of p-chloronitrobenzene, and shows better reaction activity and product selectivity.
Drawings
Figure 1 is an XRD spectrum of the catalyst prepared in example 1.
Figure 2 is an XRD spectrum of the catalyst prepared in example 2.
Figure 3 is an XRD spectrum of the catalyst prepared in example 3.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited by the following examples.
Example 1
10.10g Fe (NO) are weighed out3)3·9H2O, dissolved in 250mL of deionized water at room temperature to give a 0.1mol/L Fe (III) solution. Weighing 3.00g of dried tea (40-60 meshes), adding into 55mL of deionized water, stirring and heating for 1h under the condition of 80 ℃ water bath, and filtering to obtain 50mL of tea extract for later use. 50ml of KOH solution with the concentration of 0.1mol/L is prepared, 3.00g of dried tea leaves (40-60 meshes) are added, and stirring and dipping treatment are carried out for 1 hour under the condition of 80 ℃ water bath. Then, the impregnation liquid is filtered by suction and washed for a plurality of times until the pH value of the filtrate is approximately equal to 7. Adding the treated folium Camelliae sinensis into the above 50ml folium Camelliae sinensis extractive solution, adding 2.00g melamine, and stirring under heating in 80 deg.C water bath for 15 min. After it was cooled to room temperature, 5ml PEG-400 was added to the solution. Mixing 25mLFe (NO)3)3·9H2O solution (0.1mol/L) was added dropwise to the above solution to form a black suspension. After 100W ultrasonic treatment for 10min, the solvent was evaporated at 98 ℃ to obtain a black precursor sample. The black precursor was calcined in a tube furnace at 600 ℃ for 4h in a high purity nitrogen atmosphere of 99.999%. After the temperature is reduced to room temperature, 1 percent of O is introduced2/N2Passivating 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 indicated the presence of Fe in the catalyst0，Fe3C and graphitic carbon crystal forms. The particle size of the iron-containing particles in the catalyst was estimated to be about 13.3nm by the scherrer equation. N is a radical of2The adsorption characterization test result shows that the specific surface area of the catalyst is 100.3m2 g-1The pore diameter is about 7.2 nm.
Example 2
10.10g Fe (NO) are weighed out3)3·9H2O, dissolved in 250mL of deionized water at room temperature to give a 0.1mol/L Fe (III) solution. Weighing 3.00g of dried tea (40-60 meshes), adding into 55mL of deionized water, stirring and heating for 1h under the condition of 80 ℃ water bath, and filtering 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 stirring and dipping treatment are carried out for 1 hour under the condition of 80 ℃ water bath. Then, the impregnation liquid is filtered by suction and washed for a plurality of times until the pH value of the filtrate is approximately equal to 7. Adding the treated folium Camelliae sinensis into the above 50ml folium Camelliae sinensis extractive solution, adding 2.00g melamine, and stirring under heating in 80 deg.C water bath for 15 min. After it was cooled to room temperature, 5ml PEG-400 was added to the solution. 25mL of Fe (NO)3)3·9H2O solution (0.1mol/L) was added dropwise to the above solution to form a black suspension. After 100W ultrasonic treatment for 10min, the solvent was evaporated at 98 ℃ to obtain a black precursor sample. The black precursor was calcined in a tube furnace at 600 ℃ for 4h in a high purity nitrogen atmosphere of 99.999%. After the temperature is reduced to room temperature, 1 percent of O is introduced2/N2Passivating 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 indicated the presence of Fe in the catalyst0，Fe3C and graphitic carbon crystal forms. The particle size of the iron-containing particles in the catalyst was estimated to be about 14.9nm by the scherrer equation. N is a radical of2The adsorption characterization test result shows that the specific surface area of the catalyst is 191.4m2 g-1The pore diameter is about 6.6 nm.
Example 3
10.10g Fe (NO) are weighed out3)3·9H2O, dissolved in 250mL of deionized water at room temperature to give a 0.1mol/L Fe (III) solution. Weighing 3.00g of dried tea (40-60 meshes), adding into 55mL of deionized water, stirring and heating for 1h under the condition of 80 ℃ water bath, and filtering 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 stirring and dipping treatment are carried out for 1 hour under the condition of 80 ℃ water bath. Then, the impregnation liquid is filtered by suction and washed for a plurality of times until the pH value of the filtrate is approximately equal to 7. Adding the treated tea into the above 50ml tea extractive solutionThen 2.00g of melamine was added and stirred for 15min under heating in a water bath at 80 ℃. After it was cooled to room temperature, 5ml PEG-400 was added to the solution. Mixing 25mLFe (NO)3)3·9H2O solution (0.1mol/L) was added dropwise to the above solution to form a black suspension. After 100W ultrasonic treatment for 10min, the solvent was evaporated at 98 ℃ to obtain a black precursor sample. The black precursor was calcined in a tube furnace at 600 ℃ for 4h in a high purity nitrogen atmosphere of 99.999%. After the temperature is reduced to room temperature, 1 percent of O is introduced2/N2Passivating 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 indicated the presence of Fe in the catalyst0，Fe3C and graphitic carbon crystal forms. The particle size of the iron-containing particles in the catalyst was estimated to be about 13.8nm by the scherrer equation. N is a radical of2The adsorption characterization test result shows that the specific surface area of the catalyst is 207.4m2 g-1The pore diameter is about 4.4 nm.
Example 4
Adopts a stainless steel high-pressure reaction kettle (75 cm)3) The Fe-based catalysts prepared in example 1, example 2 and example 3 were subjected to p-chloronitrobenzene catalytic hydrogenation performance evaluation test experiments.
Firstly, 25ml of absolute ethyl alcohol, 0.3 g of p-chloronitrobenzene and 0.3 g of catalyst are added into a high-pressure reaction kettle. Before the reaction, the reactor system is first treated with high-purity H2(99.999%) was seal-washed 6 times, and then hydrogenation reaction was carried out under magnetic stirring (1000rpm), 423K and 1.1 MPa. The reaction was sampled at intervals and analyzed by gas chromatography equipped with a flame ionization detector (Agilent GC 7890B).
The results of the catalytic hydrogenation performance tests show that under the reaction experimental conditions, the conversion rate of p-chloronitrobenzene can exceed 99 percent after the catalysts of Fe-C-K-0.1, Fe-C-K-0.5 and Fe-C-K-2.0 are subjected to about 10 hours, 5 hours and 7 hours. Meanwhile, when the conversion rate of p-chloronitrobenzene of the Fe-C-K-0.5 catalyst is 100 percent, the selectivity of p-chloroaniline is 100 percent, and the selectivity of the p-chloroaniline of the Fe-C-K-0.1 catalyst and the Fe-C-K-2.0 catalyst is less than 90 percent.
The experimental results show that the Fe-based catalyst prepared by the synthesis method disclosed by the invention has a good p-chloronitrobenzene conversion rate, wherein the selectivity of p-chloroaniline products can reach 100% while the high conversion rate of the Fe-C-K-0.5 catalyst is maintained.
Claims (10)
1. 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 a solution A;
(b) adding dried tea A into deionized water, stirring at 50-90 deg.C for 30-60min, cooling to room temperature, and filtering to obtain tea extractive solution;
(c) adding dried tea B into 0.1-2moL/L potassium hydroxide aqueous solution (preferably 0.5moL/L potassium hydroxide aqueous solution), treating at 60-80 deg.C for 30-60min, filtering, and washing until the pH of the filtrate is neutral to obtain activated biomass material;
(d) adding the biomass material prepared in the step (c) into a tea extract to obtain a precursor mixed solution;
(e) respectively adding the solution A, a dispersing agent and a nitrogen-containing organic matter into the precursor mixed solution prepared in the step (d), and performing ultrasonic treatment to obtain an iron-containing suspension;
(f) removing the iron-containing suspension solvent, and carrying out high-temperature roasting and passivation treatment to obtain a 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 nitrogen-containing organic matter is 3-5g:3-5g:0.0025-0.01mol:5-9g:2-4g based on the proportion of the tea A, the tea B, the iron-containing inorganic salt, the dispersing agent and the nitrogen-containing organic matter.
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 0.05-0.3 mol/L.
3. The method of claim 1, wherein: in the step (b), the tea A and the deionized water are fed according to the concentration of the tea being 45-60 g/L.
4. The method of claim 1, wherein: in the step (e), the nitrogen-containing organic compound is one of cyanamide, dicyandiamide, melamine, polypropylene pyrrolidone and urea; the dispersant is one of polyethylene glycol-1000, polyethylene glycol-400, polyethylene glycol oleate, tween 60 and sodium lignosulfonate.
5. The method of claim 1, wherein: the step (e) is specifically carried out as follows: adding a nitrogenous organic compound into the precursor mixed solution, stirring to dissolve the nitrogenous organic compound, adding a dispersant into the solution at room temperature, then dripping the solution A, and carrying out ultrasonic treatment to obtain the iron-containing suspension.
6. The method of claim 1, wherein: in the step (f), the high-temperature roasting is carried out under the inert atmosphere condition, the roasting temperature is 600 ℃, and the roasting time is 4 hours.
7. The method of claim 1, wherein: in step (f), the passivation gas is 1 v% O2+99v％N2The passivation time is 1 h.
8. The method of claim 1, wherein: the method is implemented as follows:
(a) weighing Fe (NO)3)3·9H2Dissolving O in deionized water at room temperature to obtain 0.05-0.3mol/L solution A containing Fe (III);
(b) weighing 40-60 meshes of dried tea A, adding the dried tea A into deionized water, stirring and heating for 30-60min under the condition of 50-90 ℃ water bath, and then filtering to obtain a tea extract for later use; wherein the tea A and the deionized water are fed according to the concentration of the tea being 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 dipping for 30-60min under the condition of a water bath at the temperature of 60-80 ℃, then carrying out suction filtration on a dipping solution, and carrying out washing treatment for multiple times until the pH value of a filtrate is neutral to obtain a biomass material;
(d) adding the biomass material obtained in the step (c) into the tea extract obtained in the step (b) to obtain precursor mixed liquor;
(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, then dripping the solution A, and carrying out 100W ultrasonic treatment for 10min 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 ℃ for 4 hours in a nitrogen atmosphere, cooling to room temperature, and introducing a passivation gas to perform passivation treatment for 1 hour to obtain a Fe-based catalyst; the passivation gas is 1 v% O2+99v％N2；
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 in terms of the proportion of tea A, tea B, iron-containing inorganic salt, PEG-400 and melamine: 3 g:0.0025 mol: 5mL of: 2g of the total weight.
9. An Fe-based catalyst prepared by the process of claim 1.
10. Use of the Fe-based catalyst according to claim 9 in catalytic hydrogenation of p-chloronitrobenzene.
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