CN109126823A - Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline - Google Patents
Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline Download PDFInfo
- Publication number
- CN109126823A CN109126823A CN201811236209.2A CN201811236209A CN109126823A CN 109126823 A CN109126823 A CN 109126823A CN 201811236209 A CN201811236209 A CN 201811236209A CN 109126823 A CN109126823 A CN 109126823A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- nitrobenzene
- aniline
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/8926—Copper and noble metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the catalyst that nitrobenzene selective hydrogenation prepares aniline, the catalyst is using carbon-based material as catalyst carrier, catalyst is made in load multicomponent metal, it is denoted as: NM-TM/C or NM-TM-TM/C, wherein NM is one of Pt, Ir, Ru, Au, Rh, Pd or Ag, one of TM Ni, Co, Cu or Fe;The catalyst application method: Nitrophenethyl alcohol solution is prepared, and it is transferred into autoclave, NM-TM/C or NM-TM-TM/C catalyst is added into autoclave, and hydrogen is passed through to 1.0-5.0MPa, reaction temperature is 18 DEG C, reaction time 0.5-2.0h, after reaction, reaction kettle is cooled to room temperature, is separated liquid with catalyst using centrifugal method.Rate of catalysis reaction of the present invention is high, aniline selectivity is high, at low cost, energy conservation and environmental protection, nontoxic, reaction temperature is low.
Description
Technical field
The invention belongs to fine chemistry industry and catalysis technical fields more particularly to nitrobenzene selective hydrogenation to prepare urging for aniline
Agent and preparation method, application.
Background technique
Aniline is one of most important amine substance, is a kind of extremely important organic chemical industry's intermediate, is widely used in essence
Thin chemical field.Aniline is mainly used in the synthesis process of dyestuff, drug and resin, also acts as thiofide.Mesh
Before, the industrial method for producing aniline mainly has: (1) nitrobenzene iron powder reducing method;(2) chlorobenzene ammoniation process;(3) nitrobenzene is catalyzed
Hydrogenation method;(4) phenol ammonolysis process.Wherein nitrobenzene iron powder reducing method is the earliest method for preparing aniline, but this method benzene
Amine selectivity and low yield, reaction generate a systems such as amount of heat is difficult to recycle, iron powder dosage is big, pollution environment and equipment corrosion
The shortcomings that column.Major part producer in China's produces aniline using Catalytic Hydrogenation of Nitrobenzene method at present.
It is consulted lot of documents and patent and learns that nitrobenzene liquid phase catalytic hydrogenation catalyst system is according to its different activities position
Type, be broadly divided into Cu base, Ni base (including nickel amorphous alloy catalyst, such as Ni-B or Ni-P catalyst), Pd base, Pt
Base, Au base and multi-element metal (such as PdPt, FeCo) catalyst, in addition, there are also the metallic catalysts such as Co, Ag, Ru, Ir, Rh.With
Upper catalyst has respective advantage and disadvantage, for example, catalytic reaction temperature is excessively high, the low or catalyst of selectivity is at high cost etc..In addition,
Nitrobenzene selective hydrogenation, for evaluating catalyst performance indexes, is carried out relevant rudimentary and is ground frequently as typical model reaction
Study carefully.Therefore, nitrobenzene is efficiently and the research of high-selective and hydrogenating aniline has important application and theoretical value.
In current industrial Catalytic Hydrogenation of Nitrobenzene method mainly include fixed-bed catalytic hydrogenation method, fluidized bed catalytic hydrogenation method and
Liquid-phase Hydrogenation Process etc..Wherein Liquid-phase Hydrogenation Process research is more, such as a kind of patent " technique of synthesizing amino benzene by hydrogenation of nitrobenzene " (application
Number for 201410526666.0), disclose under the catalytic action of Pd, Pt, Rh, Ru or Ni loaded catalyst, reaction temperature
80~200 DEG C;0.1~2.0MPa of Hydrogen Vapor Pressure;3~50h of reaction time.Nano-catalytic plays important angle in heterogeneous catalysis
Color, such as in nitrobenzene hydrogenation, the development of nanocatalyst has become main trend.Such as document Evert Boymans
et.al.Chemoselective hydrogenation of functionalized Nitroarenes using
Supported Mo promoted Pt nanoparticles, ChemCatChem, 2013,5,431-434, synthesis
(0.8%Pt+0.3%Mo)/C catalyst, in the case where reaction pressure is 4bar and reaction temperature is 30 DEG C, manufacturing process of aniline through nitrobenzene hydrogenation
Selectivity up to 99% or more.But most of document all uses monometallic or Catalyzed by Pt/M Bimetallic Nano hydrogenation of chloronitrobenzene, not
See application of the ternary metallic catalyst in nitrobenzene selective hydrogenation aniline.
For some problems existing during current hydrogenation of chloronitrobenzene, this method passes through noble metal-transition metal-transition
Synergistic effect between metal ternary metal not only improves catalyst catalytic performance, selectivity and stability, reduces reaction temperature
Degree can also reduce noble metal dosage, reduce catalyst cost, the final nitrobenzene selective hydrogenation system for realizing energy-saving, environment-friendly and high-efficiency
Aniline process.
Therefore, these problems are based on, provide that a kind of rate of catalysis reaction is high, high, the at low cost, energy-saving ring of aniline selectivity
Guarantor, nontoxic, the lower nitrobenzene selective hydrogenation of reaction temperature prepare the catalyst and catalysis process of aniline, have important
Realistic meaning.
Summary of the invention
High, aniline selectivity that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of rate of catalysis reaction
High, at low cost, energy conservation and environmental protection, nontoxic, the lower nitrobenzene selective hydrogenation of reaction temperature prepare aniline catalyst and
Catalysis process.
The present invention solves its technical problem and adopts the following technical solutions to achieve:
Nitrobenzene selective hydrogenation prepares the catalyst of aniline, and the catalyst is using carbon-based material as catalyst carrier, load
Binary or ternary metal-supported catalyst is made in multicomponent metal, is denoted as: NM-TM/C or NM-TM-TM/C, wherein NM be Pt,
One of Ir, Ru, Au, Rh, Pd or Ag, one of TM Ni, Co, Cu or Fe, wherein NM load capacity is 0.1%-3%,
TM content is 1%-12%.
Nitrobenzene selective hydrogenation prepares the preparation method of catalyst in aniline, includes the following steps:
(1) it takes one or two kinds of transition metal salt solution and ethyl alcohol is added, stir, add alkaline solution, adjust molten
Liquid pH to 10-12;
(2) reducing agent is added in solution obtained in step (1), and is stirred;
(3) it takes catalyst carrier that liquid obtained in step (2) is added, is transferred in the autoclave of the nitrogen containing 1.0MPa,
Mechanical stirring carries out liquid phase chemical reduction reaction 10-20h at 15-35 DEG C;
(4) be filtered, washed and dried transition metal is carried on the sample TM/C or TM-TM/C of carrier;
(5) take TM/C TM-TM/C sample dispersion obtained in step (4) in solution containing precious metal ion, and one
Straight stirring, chemistry displacement 4-12h, is then filtered, washed and is dried and to be obtained catalyst n M-TM/C or NM-TM-TM/ at room temperature
C。
Wherein: the alkaline solution in the step (1) is NaOH solution, Na2CO3Solution or NH3˙H2O;The step (2)
In reducing agent be hydrazine hydrate or ascorbic acid or sodium borohydride;The catalyst carrier is carbon black, active carbon or carbon nanotube.
For further, the preparation method can also include reduction step: by catalyst obtained in step (5)
NM-TM/C or NM-TM-TM/C are in 10%H2+ 90%N2Atmosphere in reductase 12 hour, reduction temperature be 200-600 DEG C, heating
Rate is 2 DEG C/min, NM-TM/C the NM-TM-TM/C catalyst after being restored.
The method for preparing aniline using above-mentioned catalyst nitrobenzene selective hydrogenation: preparing Nitrophenethyl alcohol solution,
And it is transferred into autoclave, NM-TM/C or NM-TM-TM/C catalyst is added into autoclave, and be passed through hydrogen
To 1.0-5.0MPa, reaction temperature is 18 DEG C, and reaction kettle is cooled to room temperature by reaction time 0.5-2.0h after reaction,
Liquid is separated with catalyst using centrifugal method.
Wherein: NM-TM/C or NM-TM-TM/C catalyst quality and raw material Nitrophenethyl alcohol in the autoclave
Nitrobenzene mass ratio is 1:40-100 in solution.
The advantages and positive effects of the present invention are:
1, the present invention passes through noble metal-transition metal binary metal or noble metal-transition metal-transition metal ternary gold
Synergistic effect between category not only improves catalyst catalytic performance, selectivity and stability, reduces reaction temperature, can also reduce
Noble metal dosage reduces catalyst cost, the final nitrobenzene selective hydrogenation aniline process for realizing energy-saving, environment-friendly and high-efficiency;
2, the present invention in ternary metal nanocatalyst can at 18 DEG C of lower temperature efficient highly selective catalysis nitrobenzene
Hydrogen is added to prepare aniline, selective high, the at low cost, energy conservation and environmental protection of catalyst activity height, aniline, nontoxic and reaction are low
Temperature is lower to be carried out, and has important industrial application value.
Detailed description of the invention
Technical solution of the present invention is described in further detail below with reference to drawings and examples, but should
Know, these attached drawings are designed for task of explanation, therefore not as the restriction of the scope of the invention.In addition, except non-specifically
It points out, these attached drawings are meant only to conceptually illustrate structure construction described herein, without to be drawn to scale.
Fig. 1-a is that the STEM of 3%PtNiCo/C catalyst provided in an embodiment of the present invention schemes;
Fig. 1-b is that the Ni member vegetarian noodles in the STEM figure of Fig. 1-a sweeps result figure;
Fig. 1-c is that the Co member vegetarian noodles in the STEM figure of Fig. 1-a sweeps result figure;
Fig. 1-d is that the Pt member vegetarian noodles in the STEM figure of Fig. 1-a sweeps result figure;
Specific embodiment
Firstly, it is necessary to which explanation, illustrates specific structure of the invention, feature and excellent for by way of example below
Point etc., however what all descriptions were intended merely to be illustrated, and should not be construed as to present invention formation any restrictions.This
Outside, any single technical characteristic for being described by or implying in each embodiment mentioned by this paper, still can be in these technologies spy
Continue any combination between sign (or its equivalent) or delete, to obtain this hair that may do not referred to directly herein
Bright more other embodiments.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, in addition, term " includes " and " having " and their any deformation, it is intended that covering is not arranged
His includes, for example, the process, method, system, product or equipment for containing a series of steps or units are not necessarily limited to clearly
Those of list step or unit, but may include be not clearly listed or for these process, methods, product or equipment
Intrinsic other step or units.
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.
The present invention just is illustrated in conjunction with Fig. 1-a, 1-b, 1-c, 1-d below.
Embodiment 1
Prepare a series of catalysis of PtNiCo/C, 3%PtNi/C, 3%PtCo/C, 3%Pt/C, NiCo/C, Ni/C and Co/C
Agent.
The preparation method of 3%Pt/C, Ni/C, Co/C:
Weigh 0.450g-1.350gNiCl2·6H2The mixing of deionized water and ethyl alcohol is added in 250mL conical flask in O
Solvent, magnetic agitation 10min;NaOH solution (Na is added2CO3Solution or ammonium hydroxide) in above-mentioned solution, pH value of solution is adjusted to 10-
12, stir 10min;The sodium borohydride solids of 0.3-1.0g are weighed, is added in said mixture and stirs 10min;It is (living to weigh carbon black
Property charcoal or carbon nanotube) 1.250g in conical flask, continue stir 10min;Substance in conical flask is transferred to autoclave
In, mechanical stirring 18.5h at 18 DEG C, mechanical stirring speed is r=500r/min, is full of 1.0MPa in reaction process mesohigh kettle
Nitrogen;Filtering, respectively for several times with ethyl alcohol and water washing;It is put into 60 DEG C of holding 6h of vacuum oven;It pulverizes, weighs, obtain Ni/C;
The preparation method of Co/C is similar with Ni/C, difference are as follows: the presoma CoCl being added when synthesis Co/C2·6H2O
For 0.450-1.350g, other steps are all the same;
The preparation method of 3%Pt/C uses infusion process, that is, takes a certain amount of H2PtCl6Solution is impregnated in the charcoal of certain mass
Black, active carbon or carbon nanotube are finally 40mLmin in flow-190%N2+ 10%H2It is restored at a temperature of 380 DEG C in atmosphere
3h, heating rate are 2 DEG C of min-1To get catalyst, by adjusting H when preparation2PtCl6The quality of solution and catalyst carrier
So that Pt load quality accounts for the 3% of Pt and total weight of carrier, it is denoted as 3%Pt/C.
The preparation method of 3%PtNi/C, 3%PtCo/C:
The H of certain volume is pipetted with pipette2PtCl6Solution is added in 250mL conical flask;It is dilute that deionized water continuation is added
Release the above-mentioned H pipetted2PtCl6Solution is to 200mL;Take the Ni/C prepared or Co/C that above-mentioned H is added2PtCl6In solution, room temperature
Lower magnetic agitation 12h;Filtration washing is washed for several times with ethyl alcohol and deionized water, obtains black blocks of solid;Above-mentioned solid is put into
Vacuum oven, 60 DEG C of holding 6h, pulverizes, by controlling H2PtCl6The ratio of the quality of solution and Ni/C or Co/C mass to
Being made makes Pt load quality account for the 3% of Pt and total weight of carrier, is denoted as 3%PtNi/C or 3%PtCo/C.
The preparation method of NiCo/C:
The preparation method of NiCo/C is similar with Ni/C, difference are as follows: the presoma that is added is when synthesis NiCo/C
NiCl2·6H2O and CoCl2·6H2Each 0.250-0.675g of O, wherein n (Ni2+):n(Co2+)=1:1, other steps are all the same.
The preparation method of PtNiCo/C:
The preparation of PtNiCo/C is similar to PtNi/C and PtCo/C catalyst, difference are as follows: is added when synthesis NiCo/C
Presoma NiCl2·6H2O and CoCl2·6H2O, wherein n (Ni2+):n(Co2+)=1:1, other steps are all the same.
The preparation of the PtNiCo/C catalyst of different Pt load capacity:
By changing the H being added in PtNiCo/C catalyst preparation process2PtCl6The amount of solution is to obtain with different Pt
3%PtNiCo/C, 1%PtNiCo/C, 0.1%PtNiCo/C catalyst is made in the PtNiCo/C catalyst of load capacity respectively;And
And the STEM figure and member vegetarian noodles of 3%PtNiCo/C catalyst sweep result as shown in attached drawing 1-a, 1-b, 1-c, 1-d, attached drawing 1-a,
1-b, 1-c, 1-d are that the STEM figure for not restoring the catalyst that (roasting) is crossed and first vegetarian noodles are swept as a result, Pt is main as we know from the figure
Be carried in the form of cluster on the nano particle of the element containing Ni and Co, such structure can realize efficient synergistic effect: Pt compared with
It is small, and to H2Absorption and activation capacity it is stronger, Pt is by preferential activation H2Generate activated hydrogen species (H*);Nitrobenzene is adsorbed in
The surface of NiCo relative species, and be activated;Activated hydrogen species (H*) by Hydrogen spillover effect be transferred to the surface NiCo, with activation
Nitrobenzene carry out multistep hydrogenation reaction, ultimately generate aniline, realize efficient catalytic manufacturing process of aniline through nitrobenzene hydrogenation.
The preparation of the 3%PtNiCo/C catalyst synthesized at a temperature of difference thermal reduction:
By the PtNiCo/C catalyst of synthesis respectively in 10%H2+ 90%N2In 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600
DEG C reductase 12 hour, heating rate are 2 DEG C/min, are denoted as 3%PtNiCo/C-X, and wherein X is reduction temperature, respectively 200,
300、400、500、600。
It should be noted that the mass fraction of Pt each means that Pt accounts for the quality of catalyst carrier and Pt mass sum in catalyst
Score, as Pt load quality accounts for the 3% of catalyst carrier and Pt mass sum in 3%PtNiCo/C catalyst.
Embodiment 2
The catalyst prepared in Application Example 1 carries out nitrobenzene selective hydrogenation and prepares aniline experiment.
Ni/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), Ni/C catalyst
0.030g、H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle, catalyst is adopted with reaction liquid
With centrifuge separation, product obtains aniline yield lower than 0.1% through chromatographic quantitative analysis, and reaction result is as shown in appendix 1.
Co/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), Co/C catalyst
0.030g、H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle, catalyst is adopted with reaction liquid
With centrifuge separation, product liquid is analyzed through chromatography and makings, and aniline yield is lower than 0.1%, and reaction result is as shown in appendix 1.
NiCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), NiCo/C is urged
Agent 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h, catalyst and reaction solution in a high pressure reaction kettle
Body is analyzed using centrifuge separation, product liquid through chromatography and makings, and aniline yield is lower than 0.1%, reaction result such as 1 institute of subordinate list
Show.
3%PtNiCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle, catalysis
Agent and reaction liquid are using being centrifugated, and product liquid is analyzed through chromatography and makings, and aniline yield up to 100%, urge by catalyst
Change reaction rate and reaches 2415.0molnitrobenzenemolPt -1h-1, reaction result is as shown in appendix 1.
3%PtNiCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 93.5%, catalyst
Rate of catalysis reaction reaches 3012.5molnitrobenzenemolPt -1h-1, reaction result is as shown in appendix 1.
3%PtNi/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNi/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h, catalyst in a high pressure reaction kettle
With reaction liquid using being centrifugated, product liquid is analyzed through chromatography and makings, and aniline yield is up to 66.3%, the catalysis of catalyst
Reaction rate reaches 1601.5molnitrobenzene molPt -1h-1Reaction result is as shown in appendix 1.
3%PtCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h, catalyst in a high pressure reaction kettle
With reaction liquid using being centrifugated, product liquid is analyzed through chromatography and makings, and aniline yield is up to 81.1%, the catalysis of catalyst
Reaction rate reaches 1960.9molnitrobenzenemolPt -1h-1Reaction result is as shown in appendix 1.
3%Pt/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%Pt/C
Catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle, catalyst with react
Liquid is analyzed using centrifuge separation, product liquid through chromatography and makings, and for aniline yield up to 39.7%, speed is reacted in the catalysis of catalyst
Rate reaches 959.1molnitrobenzene molPt -1h-1Reaction result is as shown in appendix 1.
Each catalyst manufacturing process of aniline through nitrobenzene hydrogenation performance a of subordinate list 1
A reaction condition: Nitrophenethyl alcohol solution (40mL);H2Pressure (1.0MPa);Reaction temperature (18 DEG C)
As can be seen from Table 1,3%PtNiCo/C catalyst manufacturing process of aniline through nitrobenzene hydrogenation performance is best, i.e. ternary gold
The catalytic performance of metal catalyst (3%PtNiCo/C) is urged better than binary metal (3%PtCo/C and 3%PtNi/C) and unit metal
Agent (Ni/C, Co/C and 3%Pt/C).
Embodiment 3
3%PtNiCo/C catalyst stability test.
Reaction condition are as follows: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), catalyst is using recycling
3%PtNiCo/C catalyst, the wherein initial reaction condition of the catalyst are as follows: Nitrophenethyl alcohol solution is that 40mL (wherein contains
Nitrobenzene 11.15mmol), 3%PtNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, in high pressure
0.75h is reacted in reaction kettle;When carrying out stability test, reaction condition are as follows: H2Pressure is 1.0MPa, reaction temperature 18
DEG C, 1h, catalyst and reaction liquid are reacted in a high pressure reaction kettle using being centrifugated, and product liquid is through chromatography and makings point
Analysis, measures the rate of catalysis reaction of aniline yield and catalyst.Catalyst circulation uses 5 times, and reaction result is as shown in subordinate list 2.
2 3%PtNiCo/C catalyst hydrogenation of chloronitrobenzene stability result a of subordinate list
Catalyst (0.03g) | r(molnitrobenzenemolPt -1h-1) | Aniline selectivity | Aniline yield |
PtNiCo/C | 2978.4 | > 99% | 92.4% |
PtNiCo/C | 2939.7 | > 99% | 91.2% |
PtNiCo/C | 3007.4 | > 99% | 93.3% |
PtNiCo/C | 2874.3 | > 99% | 89.2% |
PtNiCo/C | 3009.9 | > 99% | 93.2% |
A reaction condition: Nitrophenethyl alcohol solution (40mL);H2Pressure (1.0MPa);Reaction temperature (18 DEG C);Reaction time
(0.75h)
As can be seen from Table 2,3%PtNiCo/C has good stability.
Embodiment 4
The PtNiCo/C catalyst hydrogenation of chloronitrobenzene of different Pt load capacity prepares aniline performance test.
3%PtNiCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.33h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 30.1%, catalyst
Rate of catalysis reaction reaches 2185.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 3.
1%PtNiCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 1%
PtNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle, catalysis
Agent and reaction liquid are using being centrifugated, and product liquid is analyzed through chromatography and makings, and aniline yield up to 35.8%, urge by catalyst
Change reaction rate and reaches 1733.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 3.
0.1%PtNiCo/C is as catalyst: Nitrophenethyl alcohol solution be 40mL (wherein nitrobenzene-containing 11.15mmol),
0.1%PtNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle,
Using being centrifugated, product liquid is analyzed through chromatography and makings for catalyst and reaction liquid, and aniline yield is up to 33.0%, catalyst
Rate of catalysis reaction reach 4784.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 3.
The PtNiCo/C catalyst hydrogenation of chloronitrobenzene performance a of 3 difference Pt load capacity of subordinate list
A reaction condition: Nitrophenethyl alcohol solution (40mL);H2Pressure (1.0MPa);Reaction temperature (18 DEG C)
As can be seen from Table 3, with the reduction of precious metals pt load capacity, ternary metallic catalyst PtNiCo/C is catalyzed nitro
The performance of prepared from benzene and hydrogen aniline constantly increases.The reason is that dispersion degree improves, Pt atomic surface with the reduction of Pt load capacity
More positive charges will be had, the absorption of nitrobenzene and the desorption of aniline are more advantageous to, to improve Catalytic Hydrogenation of Nitrobenzene
The reaction rate of aniline processed.
Embodiment 5
Influence of the 3%PtNiCo/C catalyst reduction temperature to its catalytic performance.
When reduction temperature is 200 DEG C: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C-200 catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle,
Using being centrifugated, product liquid is analyzed through chromatography and makings for catalyst and reaction liquid, and aniline yield is up to 30.7%, catalyst
Rate of catalysis reaction reach 2227.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 4.
When reduction temperature is 300 DEG C: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C-300 catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle,
Using being centrifugated, product liquid is analyzed through chromatography and makings for catalyst and reaction liquid, and aniline yield is up to 24.2%, catalyst
Rate of catalysis reaction reach 1754.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 4.
When reduction temperature is 400 DEG C: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C-400 catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle,
Using being centrifugated, product liquid is analyzed through chromatography and makings for catalyst and reaction liquid, and aniline yield is up to 21.3%, catalyst
Rate of catalysis reaction reach 1543.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 4.
When reduction temperature is 500 DEG C: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C-500 catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle,
Using being centrifugated, product liquid is analyzed through chromatography and makings for catalyst and reaction liquid, and aniline yield is up to 16.5%, catalyst
Rate of catalysis reaction reach 1733.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 4.
When reduction temperature is 600 DEG C: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtNiCo/C-600 catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 1h in a high pressure reaction kettle,
Using being centrifugated, product liquid is analyzed through chromatography and makings for catalyst and reaction liquid, and aniline yield is up to 8.7%, catalyst
Rate of catalysis reaction reach 628.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 4.
Subordinate list 4 heat-treats temperature to the influence a of 3%PtNiCo/C catalyst hydrogenation of chloronitrobenzene performance
Catalyst (0.03g) | r(molnitrobenzenemolPt -1h-1) | Aniline selectivity | Aniline yield |
3%PtNiCo/C-200 | 2227.0 | > 99% | 30.7% |
3%PtNiCo/C-300 | 1754.0 | > 99% | 24.2% |
3%PtNiCo/C-400 | 1543.0 | > 99% | 21.3% |
3%PtNiCo/C-500 | 1199.0 | > 99% | 16.5% |
3%PtNiCo/C-600 | 628.0 | > 99% | 8.7% |
A reaction condition: Nitrophenethyl alcohol solution (40mL);H2Pressure (1.0MPa);Reaction temperature (18 DEG C);Reaction time
(1h)
As can be known from Table 4, as 3%PtNiCo/C catalyst is in 10%H2+ 90%N2Atmosphere in thermal reduction constantly rise
Height, catalytic activity reduce.The reason is that as reduction temperature increases, Pt nanocluster be carried on the structure on NiCo species surface by
Gradually it is transformed into PtNiCo alloy structure, Pt atom is reduced in the distribution of catalyst surface, to reduce 3%PtNiCo/C catalysis
Agent catalytic performance.
Embodiment 6
The preparation method of 3%PtNiFe/C, 3%PtNiCu/C and 3%RhNiCo/C ternary metal nanocatalyst.
The preparation method of 3%PtNiFe/C catalyst:
Take 0.250-0.675gNiCl2·6H2O and 0.250-0.675gFeCl3·6H2O is put into 250mL conical flask, and
Ethanol water, magnetic agitation 10min is added;NaOH solution (Na is added2CO3Solution or ammonia spirit) in above-mentioned solution, it adjusts
PH value of solution is saved to 10-12, stirs 10min;0.3-1.0g sodium borohydride solids are added in said mixture and stir 10min;Claim
It takes carbon black (active carbon or carbon nanotube) 1.250g in conical flask, continues to stir 10min;Substance transfer in conical flask is supreme
It presses in reaction kettle, mechanical stirring 18.5h at 18 DEG C, mechanical stirring speed is r=500r/min, is filled in reaction process mesohigh kettle
Full 1.0MPa nitrogen;Filtering, respectively for several times with ethyl alcohol and water washing;It is put into 60 DEG C of holding 6h of vacuum oven;It pulverizes, obtains
NiFe/C;Pipette pipettes the H of certain volume2PtCl6Solution (concentration 1gH2PtCl6/ 250mL water), 250mL taper is added
In bottle;Deionized water is added to continue to dilute the above-mentioned H pipetted2PtCl6Solution is to 200mL;0.3gNiFe/C is added above-mentioned
H2PtCl6In solution, magnetic agitation 12h under room temperature;Filtration washing is washed for several times with ethyl alcohol and deionized water, and it is solid to obtain black bulk
Body;Above-mentioned solid is put into vacuum oven, 60 DEG C of holding 6h;It pulverizes, obtains black PtNiFe/C, it should be noted that production
When by adjusting H2PtCl6The quality that the quality of solution and catalyst carrier loads Pt accounts for the score of Pt and carrier gross mass
It is 3%, is denoted as 3%PtNiFe/C.
The preparation of 3%PtNiCu/C catalyst:
By 0.250-0.675g NiCl2·6H2O and 0.250-0.675g CuCl2·2H2O is added to 250mL conical flask
In, and be added in the mixed solution of deionized water and ethyl alcohol, magnetic agitation 10min;NaOH solution (Na is added2CO3Solution or ammonia
Aqueous solution) in above-mentioned solution, pH value of solution is adjusted to 10-12, stirs 10min;0.3-1.0g sodium borohydride solids are added
It states and stirs 10min in mixture;Carbon black (active carbon or carbon nanotube) 1.250g is weighed in conical flask, continues to stir 10min;
Substance in conical flask is transferred in autoclave, mechanical stirring 18.5h at 18 DEG C, mechanical stirring speed is r=500r/
Min is full of 1.0MPa nitrogen in reaction process mesohigh kettle;Filtering, respectively for several times with ethyl alcohol and water washing;It is put into vacuum drying
60 DEG C of holding 6h of case;It pulverizes, obtains NiCu/C;The H of certain volume is pipetted with pipette2PtCl6(concentration is 1g H to solution2PtCl6/
250mL water), it is added in 250mL conical flask;Deionized water is added to continue to dilute the above-mentioned H pipetted2PtCl6Solution is to 200mL;It will
Above-mentioned H is added in the NiCu/C prepared2PtCl6In solution, magnetic agitation 12h under room temperature;Filtration washing, with ethyl alcohol and deionization
Water washing for several times, obtains black blocks of solid;Above-mentioned solid is put into vacuum oven, 60 DEG C of holding 6h;It pulverizes, obtains PtNiCu/
C, it should be noted that by adjusting H when production2PtCl6The quality that the quality of solution and catalyst carrier loads Pt accounts for Pt
And the score of carrier gross mass is 3%, is denoted as 3%PtNiCu/C.
The preparation of 3%RhNiCo/C catalyst:
Take 0.250-0.675gNiCl2·6H2O and 0.250-0.675g CoCl2·6H2O is put into 250mL conical flask,
And the mixed solution of deionized water and ethyl alcohol is added, magnetic agitation 10min;NaOH solution (Na is added2CO3Solution or ammonium hydroxide are molten
Liquid) in above-mentioned solution, pH value of solution is adjusted to 10-12, stirs 10min;The sodium borohydride solids for weighing 0.3-1.0g are added
It states and stirs 10min in mixture;Carbon black (active carbon or carbon nanotube) 1.250g is weighed in conical flask, continues to stir 10min;
Substance in conical flask is transferred in autoclave, mechanical stirring 18.5h at 18 DEG C, mechanical stirring speed is r=500r/
Min is full of 1.0MPa nitrogen in reaction process mesohigh kettle;Filtering, respectively for several times with ethyl alcohol and water washing;It is put into vacuum drying
60 DEG C of holding 6h of case;It pulverizes, obtains NiCo/C;The RhCl of certain volume is pipetted with pipette3(concentration is 1g RhCl to solution3/
250mL water), it is added in 250mL conical flask;Deionized water is added to continue to dilute the above-mentioned RhCl pipetted3Solution is to 200mL;It will
Above-mentioned RhCl is added in the NiCo/C of the 0.3g prepared3In solution, magnetic agitation 12h under room temperature;Filtration washing with ethyl alcohol and is gone
Ion water washing for several times, obtains black blocks of solid;Above-mentioned solid is put into vacuum oven, 60 DEG C of holding 6h;It pulverizes, obtains
RhNiCo/C, it should be noted that by adjusting RhCl when production3The matter that the quality of solution and catalyst carrier loads Rh
It is 3% that amount, which accounts for Rh and the score of carrier gross mass, is denoted as 3%RhNiCo/C.
Embodiment 7
The catalyst prepared in Application Example 6 carries out nitrobenzene selective hydrogenation and prepares aniline experiment.
3%PtNiFe/C is as catalyst:
Nitrophenethyl alcohol solution be 40mL (wherein nitrobenzene-containing 11.15mmol), 3%PtNiFe/C catalyst 0.030g,
H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, catalyst and reaction liquid use from
Heart separation, product liquid are analyzed through chromatography and makings, and up to 89.8%, the rate of catalysis reaction of catalyst reaches aniline yield
2893.3mol nitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
3%PtNiCu/C is as catalyst:
Nitrophenethyl alcohol solution be 40mL (wherein nitrobenzene-containing 11.15mmol), 3%PtNiCu/C catalyst 0.030g,
H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, catalyst and reaction liquid use from
Heart separation, product liquid are analyzed through chromatography and makings, and up to 82.4%, the rate of catalysis reaction of catalyst reaches aniline yield
2654.9molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
3%RhNiCo/C is as catalyst:
Nitrophenethyl alcohol solution be 40mL (wherein nitrobenzene-containing 11.15mmol), 3%RhNiCo/C catalyst 0.030g,
H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, catalyst and reaction liquid use from
Heart separation, product liquid are analyzed through chromatography and makings, and up to 91.8%, the rate of catalysis reaction of catalyst reaches aniline yield
2957.7mol nitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
Embodiment 8
According to the preparation method of catalyst in above embodiments, then be sequentially prepared 3%PtCuFe/C, 3%AuNiCo/C,
3%IrNiCo/C, 3%RuNiCo/C, 3%PdNiCo/C, 3%AgNiCo/C catalyst, and the catalyst of application preparation carries out
Nitrobenzene selective hydrogenation prepares aniline experiment.
When 3%PtCuFe/C is catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PtCuFe/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 74.6%, catalyst
Rate of catalysis reaction reaches 2403.6molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
When 3%AuNiCo/C is catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
AuNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 84.8%, catalyst
Rate of catalysis reaction reaches 2732.2molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
When 3%IrNiCo/C is catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
IrNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 78.5%, catalyst
Rate of catalysis reaction reaches 2529.2molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
3%RuNiCo/C is catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
RuNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 87.9%, catalyst
Rate of catalysis reaction reaches 2832.1molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
3%PdNiCo/C is catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
PdNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 80.2%, catalyst
Rate of catalysis reaction reaches 2584.0molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
3%AgNiCo/C is as catalyst: Nitrophenethyl alcohol solution is 40mL (wherein nitrobenzene-containing 11.15mmol), 3%
AgNiCo/C catalyst 0.030g, H2Pressure is 1.0MPa, reaction temperature is 18 DEG C, reacts 0.75h in a high pressure reaction kettle, urges
Using being centrifugated, product liquid is analyzed through chromatography and makings for agent and reaction liquid, aniline yield up to 65.2%, catalyst
Rate of catalysis reaction reaches 2100.7molnitrobenzene molPt -1h-1, reaction result is as shown in subordinate list 5.
Other ternary metallic catalysts of subordinate list 5 are catalyzed manufacturing process of aniline through nitrobenzene hydrogenation performance a
A reaction condition: Nitrophenethyl alcohol solution (40mL);H2Pressure (1.0MPa);Reaction temperature (18 DEG C)
Subordinate list 1-5 is compared it is found that 3%PtNiCo/C and 3%RhNiCo/C catalyst nitre in ternary metallic catalyst
Base prepared from benzene and hydrogen aniline performance is best, this is because noble metal (Pt or Rh) in 3%PtNiCo/C and 3%RhNiCo/C catalyst
There is more effective synergistic effect or electronic effects with transition metal (NiCo).
It should be noted that Parr4800 autoclave can be used in the autoclave in embodiment.
In conclusion that the present invention can provide a kind of rate of catalysis reaction is high, aniline selectivity is high, at low cost, energy conservation and environmental protection,
Nontoxic, reaction condition low-temp low-pressure nitrobenzene selective hydrogenation prepares the catalyst and catalysis process of aniline.
Above embodiments describe the invention in detail, but content is only the preferred embodiment of the present invention, no
It can be believed to be used to limit the scope of the invention.Any changes and modifications in accordance with the scope of the present application,
It should still fall within the scope of the patent of the present invention.
Claims (8)
1. the catalyst that nitrobenzene selective hydrogenation prepares aniline, it is characterised in that: the catalyst is using carbon-based material as catalyst
Carrier, load multicomponent metal are made binary or ternary metal-supported catalyst, are denoted as: NM-TM/C or NM-TM-TM/C,
Middle NM is one of Pt, Ir, Ru, Au, Rh, Pd or Ag, one of TM Ni, Co, Cu or Fe, and wherein NM load capacity is
0.1%-3%, TM content are 1%-12%.
2. nitrobenzene selective hydrogenation described in a kind of claim 1 prepares the preparation method of catalyst in aniline, feature exists
In: include the following steps:
(1) it takes one or two kinds of transition metal salt solution and ethyl alcohol is added, stir, add alkaline solution, adjust pH value of solution
To 10-12;
(2) reducing agent is added in solution obtained in step (1), and is stirred;
(3) it takes catalyst carrier that liquid obtained in step (2) is added, is transferred in the autoclave of the nitrogen containing 1.0MPa, in 15-
Mechanical stirring carries out liquid phase chemical reduction reaction 10-20h at 35 DEG C;
(4) be filtered, washed and dried transition metal is carried on the sample TM/C or TM-TM/C of carrier;
(5) TM/C TM-TM/C sample dispersion obtained in step (4) is taken to stir in solution containing precious metal ion, and always
It mixes, chemistry displacement 4-12h, is then filtered, washed and is dried and to obtain catalyst n M-TM/C or NM-TM-TM/C at room temperature.
3. the preparation method of nitrobenzene selective hydrogenation preparation catalyst in aniline according to claim 2, it is characterised in that:
Alkaline solution in the step (1) is NaOH solution, Na2CO3Solution or NH3·H2O。
4. the preparation method of nitrobenzene selective hydrogenation preparation catalyst in aniline according to claim 2, it is characterised in that:
Reducing agent in the step (2) is hydrazine hydrate or ascorbic acid or sodium borohydride.
5. the preparation method of nitrobenzene selective hydrogenation preparation catalyst in aniline according to claim 2, it is characterised in that:
The catalyst carrier is carbon black, active carbon or carbon nanotube.
6. according to the preparation method of the described in any item nitrobenzene selective hydrogenation preparation catalyst in aniline of claim 2-5,
Be characterized in that: the preparation method can also include reduction step: by catalyst n M-TM/C or NM- obtained in step (5)
TM-TM/C is in 10%H2+ 90%N2Atmosphere in reductase 12 hour, reduction temperature be 200-600 DEG C, heating rate be 2 DEG C/min,
NM-TM/C NM-TM-TM/C catalyst after being restored.
7. the method that catalyst nitrobenzene selective hydrogenation described in a kind of claim 1 prepares aniline, feature exist
In: Nitrophenethyl alcohol solution is prepared, and is transferred into autoclave, NM-TM/C or NM- is added into autoclave
TM-TM/C catalyst, and hydrogen is passed through to 1.0-5.0MPa, reaction temperature is 18 DEG C, reaction time 0.5-2.0h, reaction knot
Reaction kettle is cooled to room temperature by Shu Hou, is separated liquid with catalyst using centrifugal method.
8. the method that catalyst nitrobenzene selective hydrogenation according to claim 6 prepares aniline, it is characterised in that:
Nitrobenzene matter in NM-TM/C or NM-TM-TM/C catalyst quality and raw material Nitrophenethyl alcohol solution in the autoclave
Amount is than being 1:40-100.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811236209.2A CN109126823B (en) | 2018-10-23 | 2018-10-23 | Method for preparing aniline by selective hydrogenation of nitrobenzene under catalysis of catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811236209.2A CN109126823B (en) | 2018-10-23 | 2018-10-23 | Method for preparing aniline by selective hydrogenation of nitrobenzene under catalysis of catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109126823A true CN109126823A (en) | 2019-01-04 |
CN109126823B CN109126823B (en) | 2021-08-17 |
Family
ID=64809066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811236209.2A Active CN109126823B (en) | 2018-10-23 | 2018-10-23 | Method for preparing aniline by selective hydrogenation of nitrobenzene under catalysis of catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109126823B (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109943862A (en) * | 2019-04-10 | 2019-06-28 | 哈尔滨师范大学 | A kind of method of electrochemical oxidation methanol-fueled CLC dimethoxymethane |
CN110193370A (en) * | 2019-04-23 | 2019-09-03 | 江西理工大学 | The bimetallic catalyst and preparation method, application of furfural selective hydrogenation furfuryl alcohol |
CN110465297A (en) * | 2019-08-27 | 2019-11-19 | 江西理工大学 | A kind of quinoline adds the preparation method of the multi-element metal nanocatalyst of hydrogen |
CN110465308A (en) * | 2019-08-27 | 2019-11-19 | 江西理工大学 | A kind of m-dinitrobenzene adds the bimetallic catalyst of hydrogen meta nitro aniline |
CN110639553A (en) * | 2019-10-21 | 2020-01-03 | 西安凯立新材料股份有限公司 | Iron-cobalt composite carbon-copper catalyst and method for continuously producing 4, 4-diaminodiphenyl ether |
CN110694641A (en) * | 2019-10-10 | 2020-01-17 | 西安凯立新材料股份有限公司 | Method for preparing catalyst for nitro reduction and application |
CN111085241A (en) * | 2019-12-24 | 2020-05-01 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof |
CN111151266A (en) * | 2020-01-10 | 2020-05-15 | 江西理工大学 | Catalyst for electrocatalytic oxidation of formic acid and methanol, preparation method and application |
CN111821999A (en) * | 2019-04-23 | 2020-10-27 | 中南林业科技大学 | Method for treating nitroaromatic substances by using modified carbon black loaded nickel-gold bimetallic nano-catalyst |
CN112108139A (en) * | 2020-09-29 | 2020-12-22 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof |
CN113121359A (en) * | 2021-04-23 | 2021-07-16 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and palladium catalyst with hybrid nano structure |
CN113745544A (en) * | 2021-08-18 | 2021-12-03 | 江西理工大学 | Electrocatalyst, preparation method and application |
CN114188553A (en) * | 2021-12-01 | 2022-03-15 | 武汉理工大学 | Pd/Co-C catalyst, and preparation method and application thereof |
CN114195648A (en) * | 2021-11-22 | 2022-03-18 | 台州学院 | Method for preparing parachloroaniline through selective hydrogenation of parachloronitrobenzene |
CN115501886A (en) * | 2022-03-31 | 2022-12-23 | 西南民族大学 | Preparation method of catalyst for synthesizing aniline by hydrogenation of nitrobenzene at low temperature |
WO2023156832A1 (en) * | 2022-02-16 | 2023-08-24 | Vinati Organics Limited | A process for preparation of highly pure 4-(n-butyl) aniline |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1868580A (en) * | 2006-06-23 | 2006-11-29 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
CN103272601A (en) * | 2013-06-20 | 2013-09-04 | 广西大学 | Preparation method of catalyst for synthesis of aniline through catalytic hydrogenation of nitrobenzene |
CN103480370A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of carbon supported Pd-Pt metallic catalyst for catalytic hydrogenation |
WO2015011716A1 (en) * | 2013-07-23 | 2015-01-29 | Council Of Scientific & Industrial Research | A process for reducing chloronitrobenzene catalyzed by platinum-nanoparticles stabilized on modified montmorillonite clay |
CN106008228A (en) * | 2016-06-14 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Method for synthesizing anilines and catalyst adopted by same |
CN106914255A (en) * | 2017-03-29 | 2017-07-04 | 国家纳米科学中心 | A kind of non-alloyed metal composite and its preparation method and application |
CN107413353A (en) * | 2017-08-18 | 2017-12-01 | 江西理工大学 | The method of decahydronaphthalene, organic solvent are prepared based on tetrahydronaphthalene room temperature catalytic hydrogenation |
CN108290139A (en) * | 2015-10-01 | 2018-07-17 | 孟山都技术公司 | The catalytic hydrogenation of halonitro aromatic compound |
-
2018
- 2018-10-23 CN CN201811236209.2A patent/CN109126823B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1868580A (en) * | 2006-06-23 | 2006-11-29 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
CN103480370A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of carbon supported Pd-Pt metallic catalyst for catalytic hydrogenation |
CN103272601A (en) * | 2013-06-20 | 2013-09-04 | 广西大学 | Preparation method of catalyst for synthesis of aniline through catalytic hydrogenation of nitrobenzene |
WO2015011716A1 (en) * | 2013-07-23 | 2015-01-29 | Council Of Scientific & Industrial Research | A process for reducing chloronitrobenzene catalyzed by platinum-nanoparticles stabilized on modified montmorillonite clay |
CN108290139A (en) * | 2015-10-01 | 2018-07-17 | 孟山都技术公司 | The catalytic hydrogenation of halonitro aromatic compound |
CN106008228A (en) * | 2016-06-14 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Method for synthesizing anilines and catalyst adopted by same |
CN106914255A (en) * | 2017-03-29 | 2017-07-04 | 国家纳米科学中心 | A kind of non-alloyed metal composite and its preparation method and application |
CN107413353A (en) * | 2017-08-18 | 2017-12-01 | 江西理工大学 | The method of decahydronaphthalene, organic solvent are prepared based on tetrahydronaphthalene room temperature catalytic hydrogenation |
Non-Patent Citations (2)
Title |
---|
ZHU LIHUA ET AL: ""RuNiCo-based nanocatalysts with different nanostructures for naphthalene selective hydrogenation"", 《FUEL》 * |
刘君丽等: ""硝基苯液相催化加氢制备苯胺的研究进展"", 《河南化工》 * |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109943862A (en) * | 2019-04-10 | 2019-06-28 | 哈尔滨师范大学 | A kind of method of electrochemical oxidation methanol-fueled CLC dimethoxymethane |
CN111821999A (en) * | 2019-04-23 | 2020-10-27 | 中南林业科技大学 | Method for treating nitroaromatic substances by using modified carbon black loaded nickel-gold bimetallic nano-catalyst |
CN110193370A (en) * | 2019-04-23 | 2019-09-03 | 江西理工大学 | The bimetallic catalyst and preparation method, application of furfural selective hydrogenation furfuryl alcohol |
CN111821999B (en) * | 2019-04-23 | 2023-05-23 | 中南林业科技大学 | Method for treating nitroaromatic hydrocarbon substances by using modified carbon black loaded nickel-gold bimetallic nano catalyst |
CN110465297A (en) * | 2019-08-27 | 2019-11-19 | 江西理工大学 | A kind of quinoline adds the preparation method of the multi-element metal nanocatalyst of hydrogen |
CN110465308A (en) * | 2019-08-27 | 2019-11-19 | 江西理工大学 | A kind of m-dinitrobenzene adds the bimetallic catalyst of hydrogen meta nitro aniline |
CN110694641B (en) * | 2019-10-10 | 2022-08-16 | 西安凯立新材料股份有限公司 | Method for preparing catalyst for nitro reduction and application |
CN110694641A (en) * | 2019-10-10 | 2020-01-17 | 西安凯立新材料股份有限公司 | Method for preparing catalyst for nitro reduction and application |
CN110639553A (en) * | 2019-10-21 | 2020-01-03 | 西安凯立新材料股份有限公司 | Iron-cobalt composite carbon-copper catalyst and method for continuously producing 4, 4-diaminodiphenyl ether |
CN111085241A (en) * | 2019-12-24 | 2020-05-01 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof |
CN111085241B (en) * | 2019-12-24 | 2022-08-12 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof |
CN111151266A (en) * | 2020-01-10 | 2020-05-15 | 江西理工大学 | Catalyst for electrocatalytic oxidation of formic acid and methanol, preparation method and application |
CN112108139A (en) * | 2020-09-29 | 2020-12-22 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof |
CN113121359A (en) * | 2021-04-23 | 2021-07-16 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and palladium catalyst with hybrid nano structure |
CN113745544A (en) * | 2021-08-18 | 2021-12-03 | 江西理工大学 | Electrocatalyst, preparation method and application |
CN114195648A (en) * | 2021-11-22 | 2022-03-18 | 台州学院 | Method for preparing parachloroaniline through selective hydrogenation of parachloronitrobenzene |
CN114188553A (en) * | 2021-12-01 | 2022-03-15 | 武汉理工大学 | Pd/Co-C catalyst, and preparation method and application thereof |
WO2023156832A1 (en) * | 2022-02-16 | 2023-08-24 | Vinati Organics Limited | A process for preparation of highly pure 4-(n-butyl) aniline |
CN115501886A (en) * | 2022-03-31 | 2022-12-23 | 西南民族大学 | Preparation method of catalyst for synthesizing aniline by hydrogenation of nitrobenzene at low temperature |
CN115501886B (en) * | 2022-03-31 | 2023-10-24 | 西南民族大学 | Preparation method of catalyst for synthesizing aniline by hydrogenating nitrobenzene at low temperature |
Also Published As
Publication number | Publication date |
---|---|
CN109126823B (en) | 2021-08-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109126823A (en) | Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline | |
CN107983400B (en) | Reductive amination catalyst and preparation method thereof | |
CN103638937B (en) | For the synthesis of the ethynylation catalyst of Isosorbide-5-Nitrae-butynediols | |
CN110961110B (en) | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination | |
CN105536779B (en) | A kind of preparation method of Pd/TiO2 nano-wire catalyst, catalyst obtained and its application | |
CN108993577A (en) | A kind of catalyst and its preparation method and application of prepared from benzene and hydrogen cyclohexyl benzene | |
CN101157034A (en) | A non-crystal alloy catalyst as well as its preparing method and purpose | |
CN110270375B (en) | Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof | |
CN109225190A (en) | A kind of self-supporting hydrogenation catalyst and its preparation method and application | |
CN110193370A (en) | The bimetallic catalyst and preparation method, application of furfural selective hydrogenation furfuryl alcohol | |
CN109174091A (en) | A kind of Ru-Rh/C bimetallic catalyst and its preparation method and application | |
CN109647394B (en) | Catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof | |
CN101161339B (en) | Application of Chinese lacquer original nickel in the preparation of m-phenylene diamine with m-dinitrobenzene liquid phase hydrogenation | |
CN114054034B (en) | Multi-element copper-based non-noble metal hydrogenation catalyst, and preparation method and application thereof | |
CN100402145C (en) | Catalyst in use for hydrogenation reaction of benzene selection, preparartion method and application | |
CN101711982A (en) | Supported nano Au catalyst for preparing crotyl alcohol and preparation method thereof | |
CN111715264A (en) | Hydrogenation catalyst, preparation method thereof and application of hydrogenation catalyst in catalyzing tetrahydrofurfuryl alcohol hydrogenation to prepare 1, 5-pentanediol | |
CN111196763A (en) | Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof | |
CN113649049B (en) | Maleic anhydride selective hydrogenation catalyst and preparation method and application method thereof | |
CN100357286C (en) | Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol | |
CN102580748A (en) | Amorphous alloy catalyst for hydrogenating dinitrotoluene and application of amorphous alloy catalyst | |
CN105413707A (en) | Bimetallic Pd-Ni/CeO2-TiO2 catalyst for nitrosodimethylamine reduction and preparation method for catalyst | |
CN109107583A (en) | A kind of butynediols half plus hydrogen bimetallic catalyst and the preparation method and application thereof | |
CN101716516A (en) | Attapulgite loaded cobalt-platinum hydrogenation catalyst and preparation method thereof | |
CN103801338B (en) | Catalyst for preparing methyl isobutyl ketone and preparation method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |