CN115501886A - Preparation method of catalyst for synthesizing aniline by hydrogenation of nitrobenzene at low temperature - Google Patents
Preparation method of catalyst for synthesizing aniline by hydrogenation of nitrobenzene at low temperature Download PDFInfo
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 44
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000012295 chemical reaction liquid Substances 0.000 description 17
- 230000009467 reduction Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000003426 co-catalyst Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 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 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000013112 stability test 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a novel method for synthesizing aniline by hydrogenation of nitrobenzene at low temperature, which takes nitrobenzene as a raw material and hydrogen as a green hydrogen source, and reacts in a closed container for 0.5-5 hours at the hydrogen pressure of 1-10bar and the reaction temperature of 0-30 ℃ in the presence of a non-noble metal supported palladium catalyst in a reaction medium to convert the nitrobenzene into the aniline. The method has the advantages of low precious metal loading capacity, mild conditions, high efficiency, clean reaction process, no byproduct and waste generation and the like; the nitrobenzene conversion rate and the aniline yield are both more than 99 percent; the catalyst can be recycled; no special equipment is needed in the reaction, the operation is simple and convenient, and the method is more favorable for further industrial use.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and provides a preparation method of a novel non-noble metal supported palladium bimetallic synergistic catalyst for catalytic hydrogenation of nitrobenzene.
Background
Aniline is one of the most important amines, is an important chemical raw material and a fine chemical intermediate, and is also an intermediate for producing spices, plastics, pesticides and the like. The preparation method of aniline mainly comprises two types: the phenol ammonolysis method and the nitrobenzene reduction method are adopted. The latter may be further subdivided into three types, iron powder reduction, hydrazine hydrate reduction and catalytic hydrogenation [ Industrial organic chemistry, 3rd edn, wileyVCH, weinheim,1997 ]. The iron powder nitrobenzene reduction method has the disadvantages of complex equipment, severe corrosion to the equipment in the production process, need of using a large amount of iron powder and severe three-waste pollution. The hydrazine hydrate reduction method cannot meet the requirement of enterprises on mass production of aniline. The nitrobenzene catalytic hydrogenation has the advantages of good quality of prepared products, environment-friendly production process and simple operation process, and 85 percent of the total yield of the aniline in the world is produced by the process (applied chemical industry, 2021, 50, 1667). Therefore, the development of a mild, high-activity and high-selectivity nitrobenzene hydrogenation catalyst system has very important economic value and application significance.
The industrial nitrobenzene catalytic hydrogenation method mainly comprises three processes of fixed bed catalytic hydrogenation, fluidized bed catalytic hydrogenation and liquid phase catalytic hydrogenation, wherein liquid phase hydrogenation catalysts are researched more. In recent years, reported nitrobenzene hydrogenation catalysts mainly include metal catalysts such as Pd, pt, rh, cu, ni, etc., and most of them are SiO 2 、 TiO 2 、γ-Al 2 O 3 Carbon materials, etc. as catalyst carriers. In the catalytic systems, the noble metal catalyst has the advantages of high activity, long service life and the like, but the production cost is higher; the non-noble metal catalyst can not meet the requirement of long-time continuous production in the industry, and the reaction conditions are strict and generally need to be carried out at higher temperature and higher pressure. Therefore, it is very important to develop a catalytic system for preparing aniline by nitrobenzene hydrogenation, which is cheap, mild in reaction conditions, high in activity and high in selectivity.
It is well known that heterogeneous catalytic reactions only occur at the surface of the metal nanoparticles, while most of the metal atoms in the core do not exhibit any catalytic activity. Therefore, if non-noble metal is used as a carrier, atoms on the surface layer of the carrier are partially replaced by noble metal, so that the loading capacity of the noble metal catalyst is reduced, the atom utilization rate of the noble metal is improved, and a synergistic catalytic effect is possibly generated between the non-noble metal and catalyst nano particles to promote the hydrogenation performance of the catalyst.
Therefore, aiming at the defects of the prior nitrobenzene hydrogenation catalytic system, the method adopts non-noble metal as a carrier, noble metal is loaded on the surface of the metal carrier, and the synergistic effect of bimetal is utilized, so that not only is the activity of the catalyst improved, but also the loading amount of the noble metal is reduced, the production cost is reduced, and finally, the technical process of efficiently catalyzing nitrobenzene hydrogenation to prepare aniline is realized.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the problems of high cost of noble metal catalysts, harsh conditions of non-noble metal catalysts and the like in the prior catalyst for synthesizing aniline by nitrobenzene hydrogenation, a non-noble metal supported Pd catalyst is developed, so that the cost of the catalyst is reduced, and a mild, high-activity and high-selectivity catalytic system for preparing aniline by nitrobenzene hydrogenation is realized.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a catalyst for synthesizing aniline by hydrogenating nitrobenzene uses non-noble metal as carrier and carries Pd, which is recorded as Pd/M, wherein M is one of Cu, fe, ni or Co, and the carrying amount of Pd is about 0.01-1wt%.
The preparation method of the aniline catalyst by nitrobenzene hydrogenation comprises the following steps:
(1) Weighing a proper amount of metal M powder with small particle size, and reducing at a lower hydrogen flow rate, wherein the reduction temperature is 200-400 ℃ and the reduction time is 3-5h;
(2) Adding a proper amount of deionized water into the reduced powder in the step (1), and stirring the PdCl under magnetic force 2 Slowly dripping the aqueous solution into the solution, and stirring vigorously for 10-24h;
(3) Filtering and washing the suspension in the step (2) to obtain a precipitate; vacuum drying for 4-6h to obtain the Pd/M catalyst.
Wherein: the noble metal ion solution in the step (2) can be H 2 PdCl 4 Or K 2 PdCl 4 Dissolving; the concentration of the noble metal ion solution in the step (2) is 56.4mmol/L.
The method for preparing aniline by catalyzing selective hydrogenation of nitrobenzene by using the catalyst comprises the following steps: preparing a nitrobenzene solution, transferring the nitrobenzene solution to a high-pressure reaction kettle, adding a Pd/M catalyst into the high-pressure reaction kettle, introducing hydrogen gas at 1-10bar, reacting at 0-30 ℃ for 0.5-5h, cooling the reaction kettle to room temperature after the reaction is finished, and separating the liquid from the catalyst by a centrifugal method.
Wherein: the mass ratio of the Pd/M catalyst in the high-pressure reaction kettle to the nitrobenzene serving as the raw material is 1.
The invention has the characteristics and beneficial effects that:
1. according to the method, the transition metal is used as the carrier to load the noble metal, and the synergistic catalytic action among the bimetallic metals is utilized, so that the catalytic activity of the catalyst is improved, the consumption of the noble metal is reduced, the production cost is reduced, and the mild, high-efficiency and high-selectivity technological process for preparing the aniline by catalytic hydrogenation of nitrobenzene is finally realized;
2. the bimetallic catalyst can catalyze nitrobenzene to hydrogenate at room temperature with high efficiency and high selectivity, and the catalytic system has mild reaction conditions and high reaction efficiency and has important industrial application value.
Drawings
The technical solutions of the present invention will be described in further detail below with reference to the accompanying drawings and examples, but it should be understood that these drawings are designed for illustrative purposes only and thus do not limit the scope of the present invention. Furthermore, unless specifically indicated, the drawings are intended to be illustrative of the structural configurations described herein and are not necessarily drawn to scale.
FIGS. 1-a, b are SEM and EDS diagrams of Pd/Co catalyst provided by the present invention;
FIGS. 2-a, b are SEM and EDS diagrams of Pd/Fe catalyst provided by the present invention;
FIGS. 3-a, b are SEM and EDS diagrams of Pd/Cu catalyst provided by the present invention;
FIGS. 4-a, b are SEM and EDS diagrams of Pd/Ni catalyst provided by the present invention;
Detailed Description
First, it should be noted that the specific structures, features, advantages, etc. of the present invention will be described in detail below by way of example, but all the descriptions are only for illustrative purpose and should not be construed as limiting the present invention in any way. Furthermore, any individual technical features described or implicit in the embodiments mentioned herein may continue to be combined or subtracted between any of these technical features (or their equivalents) to obtain still further embodiments of the invention that may not be mentioned directly herein.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and furthermore, the terms "comprises" and "having", and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The present invention will be specifically described with reference to FIGS. 1-a and 1-b.
Example 1
Preparing a series of catalysts of Pd/Co, pd/Fe, pd/Cu and Pd/Ni.
The preparation method of the Pd/Co catalyst comprises the following steps:
the Pd/Co catalyst is prepared by adopting an electrochemical displacement method, weighing 2-4g of cobalt powder with the diameter of 500nm in a reduction tubeAt 215 ℃ using a flow rate of 20m 3 Reduction is carried out with hydrogen per hour. Weighing 2g of reduced cobalt powder and a 100mL round-bottom flask, adding a small amount of deionized water to wet the cobalt powder, starting a magnetic stirrer, and transferring a certain amount of H by using a transfer pipette 2 PdCl 4 Diluting the solution with 50mL of deionized water, and dripping the diluted solution into a round-bottomed flask, wherein the rotating speed of a magnetic stirrer is 500r/min, the stirring temperature is room temperature, and the stirring time is 24 hours; centrifuging the reaction solution after reaction, centrifuging and washing 5 times by 50mL of deionized water each time, and drying the precipitate for 6h at 40 ℃ under vacuum; and finally grinding the precipitate to prepare the Pd/Co catalyst.
The Pd/Fe catalyst was prepared similarly to Pd/Co, except that: the reduction temperature for synthesizing Pd/Fe is 400 ℃, and other steps are the same;
the Pd/Cu catalyst was prepared similarly to Pd/Co, except that: the reduction temperature in the Pd/Cu synthesis is 200 ℃, and other steps are the same;
the Pd/Ni catalyst was prepared similarly to Pd/Co with the following exceptions: the reduction temperature for synthesizing Pd/Ni is 360 ℃, and other steps are the same.
Example 2
An experiment was carried out for the selective hydrogenation of nitrobenzene to aniline using the catalyst of example 1.
Pd/Co is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, the catalyst is 50mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2 hours, ethanol is used for washing out reaction liquid, the catalyst and the reaction liquid are centrifugally separated, the liquid product is analyzed by gas chromatography, the conversion rate of the nitrobenzene is 100 percent, the yield of the aniline is more than 99 percent, and the reaction results are shown in attached table 1.
Pd/Fe is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, the catalyst is 50mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2 hours, ethanol is used for washing out reaction liquid, the catalyst and the reaction liquid are centrifugally separated, the liquid product is analyzed by gas chromatography, the conversion rate of the nitrobenzene is 79 percent, the yield of the aniline is 75 percent, and the reaction results are shown in the attached table 1.
Pd/Cu is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, the catalyst is 50mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2 hours, ethanol is used for washing out reaction liquid, the catalyst and the reaction liquid are centrifugally separated, the liquid product is analyzed by gas chromatography, the conversion rate of the nitrobenzene is 1 percent, the yield of the aniline is 0, and the reaction results are shown in attached table 1.
Pd/Ni is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, the catalyst is 50mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2h, ethanol is used for washing out reaction liquid, the catalyst and the reaction liquid are separated by centrifugation, the liquid product is analyzed by gas chromatography, the conversion rate of the nitrobenzene is 32 percent, the yield of the aniline is 29 percent, and the reaction results are shown in the attached table 1.
The simple substance Co is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, a catalyst is 50mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2h, ethanol is used for washing out reaction liquid, the catalyst and the reaction liquid are separated centrifugally, the liquid product is analyzed by gas chromatography, the conversion rate of the nitrobenzene is 0 percent, the yield of aniline is 0, and the reaction results are shown in attached table 1.
The method comprises the following steps of taking elementary substance Fe as a catalyst, reacting nitrobenzene in an amount of 1mmol (123.11 g), toluene in an amount of 2mL, a catalyst in an amount of 50mg, a hydrogen pressure of 4bar and a reaction temperature of 28 ℃ in a high-pressure reaction kettle for 2 hours, washing out reaction liquid by using ethanol, centrifugally separating the catalyst and the reaction liquid, analyzing a liquid product by using gas chromatography, wherein the conversion rate of the nitrobenzene is 1%, the yield of aniline is 0, and the reaction results are shown in attached table 1.
The method comprises the following steps of taking elementary substance Cu as a catalyst, reacting nitrobenzene in an amount of 1mmol (123.11 g) and toluene in an amount of 2mL in an amount of 50mg in an amount of 1, reacting the mixture in a high-pressure reaction kettle at a reaction temperature of 28 ℃ for 2 hours, washing out reaction liquid by using ethanol, centrifugally separating the catalyst from the reaction liquid, analyzing a liquid product by using gas chromatography, wherein the conversion rate of the nitrobenzene is 0%, the yield of aniline is 0, and reaction results are shown in attached table 1.
The simple substance Ni is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, a catalyst is 50mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2 hours, ethanol is used for washing out reaction liquid, the catalyst and the reaction liquid are centrifugally separated, the liquid product is analyzed by gas chromatography, the conversion rate of the nitrobenzene is 0 percent, the yield of aniline is 0 percent, and the reaction results are shown in attached table 1.
The method comprises the following steps of taking elemental Pd as a catalyst, reacting nitrobenzene in an amount of 1mmol (123.11 g) and toluene in an amount of 2mL, a catalyst in an amount of 5mg, a hydrogen pressure of 4bar, a reaction temperature of 28 ℃ in a high-pressure reaction kettle for 2 hours, washing out a reaction solution with ethanol, centrifugally separating the catalyst from the reaction solution, analyzing a liquid product through gas chromatography, wherein the conversion rate of the nitrobenzene is 30%, the yield of aniline is 30%, and reaction results are shown in attached table 1.
Attached table 1 evaluation of performance of each catalyst in preparation of aniline by hydrogenation of nitrobenzene
Reaction conditions are as follows: nitrobenzene (1 mmol), toluene (2 mL), H 2 Pressure (4 bar), reaction temperature (28 ℃ C.)
As can be seen from Table 1, the Pd/Co catalyst has the best performance in catalyzing the hydrogenation of nitrobenzene to prepare aniline.
Example 3
Stability testing of Pd/Co catalysts
The reaction conditions are as follows: 1mmol of nitrobenzene and 2mL of toluene, wherein the catalyst adopts a recycled Pd/Co catalyst, and the initial reaction conditions of the catalyst are as follows: 1mmol (123.11 g) of nitrobenzene, 2mL of toluene, 50mg of catalyst, 4bar of hydrogen pressure and 28 ℃ of reaction temperature, and reacting in a high-pressure reaction kettle for 2 hours; the reaction conditions during stability test are the same as the initial conditions, after the reaction, the catalyst and the reaction liquid are centrifugally separated, and the liquid product is analyzed by gas chromatography to obtain the conversion rate of nitrobenzene and the yield of aniline. The catalyst was circulated 6 times, and the reaction results are shown in Table 2.
TABLE 2 stability of hydrogenation of nitrobenzene catalyzed by Pd/Co catalyst
Reaction conditions were nitrobenzene (1 mmol), toluene (2 mL), H 2 Pressure (4 bar), reaction temperature (28 ℃ C.)
As can be seen from Table 2, the Pd/Co catalyst has good stability and reusability.
Comparing fig. 1-2, it can be seen that the catalyst Pd/Co in the Pd/M binary catalyst has the best performance for catalyzing nitrobenzene hydrogenation, which may be due to the synergistic catalytic effect between the noble metal Pd and the transition metal Co in the Pd/Co catalyst.
Claims (2)
1. A preparation method of a catalyst for synthesizing aniline by nitrobenzene hydrogenation is characterized by comprising the following steps: nitrobenzene is used as a raw material, hydrogen is used as a reducing agent, the pressure of the hydrogen is 1-10bar, the reaction temperature is 0-30 ℃, the reaction time is 0.5-5h in the presence of a catalyst Pd/M, after the reaction is finished, a reaction kettle is cooled to room temperature, and liquid and the catalyst are separated by a centrifugal method;
the Pd/M catalyst takes non-noble metal M as a catalyst carrier to load noble metal Pd, wherein M is one of Cu, fe, ni and Co, and the load of Pd is 0.01-1wt%.
2. The method for preparing the catalyst for synthesizing the aniline by hydrogenating nitrobenzene according to claim 1, wherein the catalyst comprises the following steps: the preparation method of the Pd/M catalyst comprises the following steps:
(1) Weighing one of Cu, fe, ni and Co metal powder with the grain diameter of 10-500nm, and reducing at the temperature of 200-400 ℃ for 3-5h under the hydrogen flow rate of 10-150 mL/min;
(2) Adding 10-100mL of deionized water into the reduced powder in the step (1), and stirring by magnetic forceLower reaction of H 2 PdCl 4 Or K 2 PdCl 4 Slowly dripping the aqueous solution into the solution, and stirring vigorously for 8-24h;
(3) And (3) filtering and washing the suspension in the step (2) to obtain a dark gray solid, and drying in vacuum for 4-6h to obtain the Pd/M catalyst.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB799871A (en) * | 1955-05-10 | 1958-08-13 | Du Pont | Hydrogenation catalysts and process |
| US20040137288A1 (en) * | 2002-10-18 | 2004-07-15 | Monsanto Technology Llc | Use of metal supported copper catalysts for reforming alcohols |
| CN101157034A (en) * | 2007-11-13 | 2008-04-09 | 上海师范大学 | A non-crystal alloy catalyst as well as its preparing method and purpose |
| CN101670301A (en) * | 2009-09-25 | 2010-03-17 | 南京工业大学 | Method for preparing loaded catalyst for hydrogenation |
| CN104418756A (en) * | 2013-08-28 | 2015-03-18 | 中国科学院烟台海岸带研究所 | Method and catalyst for synthesizing chloroaniline from chloronitrobenzene by virtue of selective catalytic hydrogenation |
| CN109126823A (en) * | 2018-10-23 | 2019-01-04 | 江西理工大学 | Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline |
| CN113145112A (en) * | 2021-04-30 | 2021-07-23 | 福州大学 | Preparation method of Pd-Pt/C catalyst for selective hydrogenation of dinitrotoluene |
-
2022
- 2022-03-31 CN CN202210345213.2A patent/CN115501886B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB799871A (en) * | 1955-05-10 | 1958-08-13 | Du Pont | Hydrogenation catalysts and process |
| US20040137288A1 (en) * | 2002-10-18 | 2004-07-15 | Monsanto Technology Llc | Use of metal supported copper catalysts for reforming alcohols |
| CN101157034A (en) * | 2007-11-13 | 2008-04-09 | 上海师范大学 | A non-crystal alloy catalyst as well as its preparing method and purpose |
| CN101670301A (en) * | 2009-09-25 | 2010-03-17 | 南京工业大学 | Method for preparing loaded catalyst for hydrogenation |
| CN104418756A (en) * | 2013-08-28 | 2015-03-18 | 中国科学院烟台海岸带研究所 | Method and catalyst for synthesizing chloroaniline from chloronitrobenzene by virtue of selective catalytic hydrogenation |
| CN109126823A (en) * | 2018-10-23 | 2019-01-04 | 江西理工大学 | Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline |
| CN113145112A (en) * | 2021-04-30 | 2021-07-23 | 福州大学 | Preparation method of Pd-Pt/C catalyst for selective hydrogenation of dinitrotoluene |
Non-Patent Citations (3)
| Title |
|---|
| AN PEI ET AL.: ""Preparation of cobalt crystals with various morphologies and catalytic performance of platinum-on-cobalt crystal for selective hydrogenation of nitrobenzene"", 《CRYSTENGCOMM》, pages 1 - 7 * |
| DELE PETER FAPOJUWO ET AL.: ""Bimetallic PdM (M =Co, Ni) catalyzed hydrogenation of nitrobenzene at the water/oil interface in a Pickering emulsion"", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》, pages 1 - 11 * |
| JINGWEN LUO ET AL.: "\"Pd/Co Catalyst with High Pd Atom Utilization Efficiency for Nitrobenzene Hydrogenation at Room Temperature: Experimental and DFT Studies\"", 《CHEMISTRY—A EUROPEAN JOURNAL》, pages 1 - 7 * |
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