CN115501886B - Preparation method of catalyst for synthesizing aniline by hydrogenating nitrobenzene at low temperature - Google Patents
Preparation method of catalyst for synthesizing aniline by hydrogenating 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 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 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
- 239000000843 powder Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 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
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 44
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000006227 byproduct 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
- 239000012295 chemical reaction liquid Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000003426 co-catalyst Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 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
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FFEVHTMMGXLTCX-UHFFFAOYSA-N iron nitrobenzene Chemical compound [Fe].[N+](=O)([O-])C1=CC=CC=C1 FFEVHTMMGXLTCX-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000013138 pruning Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000002344 surface layer Substances 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
- B01J23/89—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
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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
- B01J23/8926—Copper and noble metals
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- Y02P20/584—Recycling of catalysts
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Abstract
The application discloses a new method for synthesizing aniline by hydrogenating nitrobenzene at low temperature, which takes nitrobenzene as a raw material, takes hydrogen as a green hydrogen source, and converts nitrobenzene into aniline in the presence of a non-noble metal supported palladium catalyst in a reaction medium at a hydrogen pressure of 1-10bar and a reaction temperature of 0-30 ℃ in a closed container for 0.5-5 h. The application has the advantages of low noble metal loading, mild condition, high efficiency, clean reaction process, no byproducts and waste production, and the like; the nitrobenzene conversion rate and the aniline yield are both greater than 99%; the catalyst can be recycled; the reaction does not need special equipment, is simple and convenient to operate, and is more beneficial to further industrial use.
Description
Technical Field
The application belongs to the technical field of catalytic hydrogenation, and provides a novel preparation method of a non-noble metal supported palladium bimetal synergistic catalyst for nitrobenzene catalytic hydrogenation.
Background
Aniline is one of the most important amine substances, is an important chemical raw material and a fine intermediate, and is also an intermediate for producing spices, plastics, pesticides and the like. The preparation method of aniline mainly comprises two types: firstly, a phenol ammonolysis method and secondly, a nitrobenzene reduction method. The latter can be further subdivided into three types, iron powder reduction, hydrazine hydrate reduction and catalytic hydrogenation respectively [ Industrial organic chemistry,3rd edn,WileyVCH,Weinheim,1997 ]. The reduction method of nitrobenzene iron powder uses complex equipment, causes serious corrosion to the equipment in the production process, needs a large amount of iron powder, and generates serious three-waste pollution. The hydrazine hydrate reduction method cannot meet the requirement of mass production of aniline for enterprises. The nitrobenzene catalytic hydrogenation has the advantages of being capable of being carried out in a gas phase or a liquid phase, good in quality of the prepared product, environment-friendly in production process and simple in operation process, and 85% of the total yield of the aniline in the world is produced by the process nowadays [ applied chemical industry, 2021, 50,1667 ]. Therefore, the development of a mild, high-activity and high-selectivity nitrobenzene hydrogenation catalytic 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 the research on liquid phase hydrogenation catalysts is more. Recently, as the nitrobenzene hydrogenation catalyst, metal catalysts such as Pd, pt, rh, cu, ni have been reported, and SiO has been used in many cases 2 、 TiO 2 、γ-Al 2 O 3 Carbon material, 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; not only does the non-noble metal catalyst not meet the long-term continuous production requirements in the industry, but the reaction conditions are relatively stringent, and generally require higher temperatures and higher pressures. Therefore, it is very important to develop a catalytic system for preparing aniline by hydrogenating nitrobenzene with low price, mild reaction conditions, high activity and high selectivity.
It is well known that heterogeneous catalytic reactions only occur at the surface of 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, the atomic part of the surface layer is replaced by noble metal, so that the loading capacity of the noble metal catalyst is reduced, the utilization rate of the atoms is improved, and synergistic catalysis can be generated between the non-noble metal and the catalyst nano particles, so that the hydrogenation performance of the catalyst is promoted.
Therefore, aiming at the defects of the existing nitrobenzene hydrogenation catalytic system, the method adopts non-noble metal as a carrier, carries noble metal on the surface of the metal carrier, utilizes the synergistic effect between double metals, not only improves the activity of the catalyst, but also reduces the carrying capacity of the noble metal, reduces the production cost, and finally realizes the technical process of preparing aniline by efficiently catalyzing the hydrogenation of nitrobenzene.
Disclosure of Invention
The application aims to solve the technical problems that: aiming at the problems of high cost of a noble metal catalyst, harsh condition of a non-noble metal catalyst and the like in the existing catalyst for synthesizing aniline by hydrogenating nitrobenzene, a non-noble metal supported Pd catalyst is developed, so that the catalyst cost is reduced, and a catalytic system for preparing aniline by hydrogenating nitrobenzene with mild, high activity and high selectivity is realized.
The application solves the technical problems 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 named Pd/M, wherein M is one of Cu, fe, ni or Co, and the load 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 small-particle-size metal M powder, and reducing at a lower hydrogen flow rate, wherein the reduction temperature is 200-400 ℃ and the reduction time is 3-5h;
(2) Adding proper deionized water into the reduced powder in the step (1), and stirring PdCl under magnetic force 2 Slowly dripping the aqueous solution into the solution, and vigorously stirring the solution for 10 to 24 hours;
(3) Filtering and washing the suspension in the step (2) to obtain a precipitate; and drying in vacuum 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 A solution; the concentration of the noble metal ion solution in the step (2) is 56.4mmol/L.
The method for preparing aniline by using the catalyst to catalyze nitrobenzene to carry out selective hydrogenation comprises the following steps: preparing nitrobenzene solution, transferring the nitrobenzene solution to a high-pressure reaction kettle, adding Pd/M catalyst into the high-pressure reaction kettle, introducing hydrogen at a reaction temperature of 0-30 ℃ for 0.5-5h, cooling the reaction kettle to room temperature after the reaction is finished, and separating liquid from the catalyst by a centrifugal method.
Wherein: the mass ratio of Pd/M catalyst to raw material nitrobenzene in the high-pressure reaction kettle is 1:2.5.
The application has the characteristics and beneficial effects that:
1. according to the method, transition metal is used as a carrier to load noble metal, and the synergistic catalysis between bimetallic is utilized, so that the catalytic activity of the catalyst is improved, the consumption of noble metal is reduced, the production cost is reduced, and the process of preparing aniline by catalytic hydrogenation of nitrobenzene with mild, high efficiency and high selectivity is finally realized;
2. the bimetallic catalyst can catalyze nitrobenzene hydrogenation at room temperature with high efficiency and high selectivity, and the catalytic system has mild reaction condition and high reaction efficiency and has important industrial application value.
Drawings
The technical solution of the present application 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 the purpose of illustration only and thus are not limiting the scope of the present application. Moreover, unless specifically indicated otherwise, the drawings are intended to conceptually illustrate the structural construction described herein and are not necessarily drawn to scale.
FIGS. 1-a, b are SEM and EDS diagrams of Pd/Co catalysts provided by the present application;
FIGS. 2-a, b are SEM and EDS diagrams of Pd/Fe catalyst provided by the present application;
FIGS. 3-a, b are SEM and EDS diagrams of Pd/Cu catalyst provided by the present application;
FIGS. 4-a, b are SEM and EDS diagrams of Pd/Ni catalyst provided by the present application;
Detailed Description
First, it should be noted that the specific structure, characteristics, advantages and the like of the present application will be specifically described below by way of examples, however, all descriptions are merely for illustration and should not be construed as limiting the present application in any way. Furthermore, any single feature described or implied in the embodiments mentioned herein may still be continued to be any combination or pruning between such features (or equivalents thereof) to obtain still further embodiments of the application that may not be directly mentioned 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 exemplary 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, unless the context clearly indicates otherwise, and the terms "comprising" and "having" and any variation thereof are intended to cover a non-exclusive inclusion, e.g., a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements explicitly 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, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
The application is described in detail below with reference to fig. 1-a, 1-b.
Example 1
A series of catalysts of Pd/Co, pd/Fe, pd/Cu and Pd/Ni were prepared.
The preparation method of the Pd/Co catalyst comprises the following steps:
the Pd/Co catalyst is prepared through electrochemical displacement process, 2-4g of 500nm diameter cobalt powder is weighed into a reducing pipe and at 215 deg.c with flow rate of 20m 3 Hydrogen gas for reduction/h. 2g of reduced cobalt powder and a 100mL round bottom flask are weighed, a small amount of deionized water is added to moisten the cobalt powder, a magnetic stirrer is started, and a certain amount of H is removed by a pipette 2 PdCl 4 Diluting the solution with 50mL of deionized water, dripping the 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 reacted reaction solution, centrifugally washing 5 times with 50mL of deionized water each time, and drying the precipitate at 40 ℃ under vacuum for 6 hours; finally, the precipitate is ground to prepare the Pd/Co catalyst.
The Pd/Fe catalyst was prepared similarly to Pd/Co, except that: the reduction temperature is 400 ℃ when Pd/Fe is synthesized, and other steps are the same;
the Pd/Cu catalyst was prepared similarly to Pd/Co, except that: the reduction temperature during Pd/Cu synthesis is 200 ℃, and other steps are the same;
the Pd/Ni catalyst was prepared similarly to Pd/Co, except that: the reduction temperature during Pd/Ni synthesis was 360℃and the other steps were the same.
Example 2
An aniline preparation experiment was performed by selectively hydrogenating nitrobenzene 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 a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 100%, the aniline yield is more than 99%, and the reaction result is shown in the 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 a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 79%, the aniline yield is 75%, and the reaction result is 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 a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 1%, the aniline yield is 0, and the reaction result is shown in the 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 2 hours, ethanol is used for washing out a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 32%, the aniline yield is 29%, and the reaction result is shown in the attached table 1.
Simple substance 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 a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 0%, the aniline yield is 0, and the reaction result is shown in the attached table 1.
Simple substance Fe is taken 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 a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 1%, the aniline yield is 0, and the reaction result is shown in the attached table 1.
Simple substance 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 a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 0%, the aniline yield is 0, and the reaction result is shown in the attached table 1.
Simple substance 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 2 hours, ethanol is used for washing out a reaction liquid, centrifugal separation is adopted for the catalyst and the reaction liquid, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 0%, the aniline yield is 0%, and the reaction result is shown in the following table 1.
The simple substance Pd is used as a catalyst, nitrobenzene is 1mmol (123.11 g), toluene is 2mL, the catalyst is 5mg, the hydrogen pressure is 4bar, the reaction temperature is 28 ℃, the reaction is carried out in a high-pressure reaction kettle for 2 hours, the reaction liquid is washed out by ethanol, the catalyst and the reaction liquid are centrifugally separated, the liquid product is analyzed by gas chromatography, the nitrobenzene conversion rate is 30%, the aniline yield is 30%, and the reaction result is shown in the attached table 1.
Evaluation of the Performance of the catalysts in Table 1 for preparing aniline by catalyzing nitrobenzene hydrogenation
Reaction conditions: 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 nitrobenzene hydrogenation to prepare aniline.
Example 3
Stability test of Pd/Co catalyst
The reaction conditions are as follows: nitrobenzene 1mmol, toluene 2mL, the catalyst used was recovered Pd/Co catalyst, wherein the initial reaction conditions of the catalyst were: nitrobenzene 1mmol (123.11 g), toluene 2mL, catalyst 50mg, hydrogen pressure 4bar, reaction temperature 28 ℃, in a high pressure reactor for 2h; and (3) the reaction conditions are the same as the initial conditions when the stability test is carried out, 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 the accompanying table 2.
Table 2 results of Pd/Co catalyst to catalyze Nitrobenzene hydrogenation stability
Reaction conditions 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.
As can be seen from comparing FIGS. 1-2, the Pd/Co catalyst in the Pd/M binary catalyst has the best performance in catalyzing nitrobenzene hydrogenation, which is probably due to the synergistic catalytic effect of the noble metal Pd and the transition metal Co in the Pd/Co catalyst.
Claims (2)
1. The preparation method of the catalyst for synthesizing aniline by nitrobenzene hydrogenation is characterized by comprising the following steps of:
(1) Weighing Co metal powder with the particle size of 10-500 nm, and reducing at the hydrogen flow rate of 10-150 mL/min at the reduction temperature of 200-400 ℃ for 3-5h;
(2) Adding 10-100 mL deionized water into the reduced powder in the step (1), and stirring with magnetic force to obtain H 2 PdCl 4 Or K 2 PdCl 4 Slowly dripping the aqueous solution into the solution, and vigorously stirring the solution for 8 to 24 and h;
(3) Filtering and washing the suspension in the step (2) to obtain a black gray solid, and vacuum drying 4-6h to obtain a Pd/M catalyst;
the Pd/M catalyst takes non-noble metal M as a catalyst carrier and carries noble metal Pd, wherein M is Co, and the Pd loading amount is 0.01-1wt%.
2. An application method of a catalyst for synthesizing aniline by nitrobenzene hydrogenation is characterized in that nitrobenzene is used as a raw material, hydrogen is used as a reducing agent, the hydrogen pressure is 1-10bar, the reaction temperature is 0-30 ℃ and the reaction time is 0.5-5h in the presence of a catalyst Pd/M obtained by the preparation method in claim 1, after the reaction is finished, the reaction kettle is cooled to room temperature, and the liquid is separated from the catalyst by a centrifugal method.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB799871A (en) * | 1955-05-10 | 1958-08-13 | Du Pont | Hydrogenation catalysts and process |
| 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 | Preparation method of supported 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0314873B1 (en) * | 2002-10-18 | 2011-11-29 | process for reforming an alcohol and for producing electric energy from a fuel cell. |
-
2022
- 2022-03-31 CN CN202210345213.2A patent/CN115501886B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB799871A (en) * | 1955-05-10 | 1958-08-13 | Du Pont | Hydrogenation catalysts and process |
| 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 | Preparation method of supported 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 |
|---|
| "Bimetallic PdM (M =Co, Ni) catalyzed hydrogenation of nitrobenzene at the water/oil interface in a Pickering emulsion";Dele Peter Fapojuwo et al.;《Colloids and Surfaces A: Physicochemical and Engineering Aspects》;第1-11页 * |
| "Preparation of cobalt crystals with various morphologies and catalytic performance of platinum-on-cobalt crystal for selective hydrogenation of nitrobenzene";An Pei et al.;《CrystEngComm》;第1-7页 * |
| 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》.2022,第1-7页. * |
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