CN103316676B - Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof - Google Patents
Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof Download PDFInfo
- Publication number
- CN103316676B CN103316676B CN201310187434.2A CN201310187434A CN103316676B CN 103316676 B CN103316676 B CN 103316676B CN 201310187434 A CN201310187434 A CN 201310187434A CN 103316676 B CN103316676 B CN 103316676B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- quality
- active component
- nitrobenzene
- 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.)
- Active
Links
Abstract
The invention discloses a catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and a preparation method thereof. According to the catalyst, a mixture of alpha-Al2O3 and theta-Al2O3 is adopted as a carrier; Pt is adopted as an active component; one of La, Co, Cu, and Cr is adopted as an auxiliary agent; the active component and the auxiliary agent is loaded on the carrier; the mass of Pt is 0.05-0.5% of that of the carrier; the mass of the auxiliary agent is 0-2.5% of that of the carrier; the specific surface area of the carrier is 10-50m<2>*g<-1>; and the shell layer thickness of the catalyst is 0.02-0.10mm. According to the catalyst, with a stepped impregnation method, a soluble salt of platinum and the auxiliary agent are impregnated on the carrier; and through drying, calcining, and reducing, the catalyst with an outer surface area distributed in an egg shell shape is obtained. Compared with existing catalysts, the catalyst provided by the invention has the advantages of high catalytic hydrogenation activity, low cost, long service life, and environment friendliness.
Description
Technical field
The present invention relates to catalyst and preparation field thereof, be specifically related to a kind of for nitrobenzene liquid-phase hydrogenatin synthesis catalyst in aniline and preparation method thereof.
Background technology
Aniline is the intermediate of a kind of important industrial chemicals and fine chemistry industry, is the raw materials for production of dyestuff, spices, rubber chemicals, agricultural chemicals, explosive and diphenyl methane polyurethane (MDI) etc.Kind more than 300 is about had by the fine chemical product of Aniline Production.Especially as the raw materials for production of diphenyl methane polyurethane (MDI), along with the demand of the products such as polyurethane constantly increases, 80% of global aniline output is produced for methyl diphenylene diisocyanate (MDI).In recent years, aniline is one of world's organic intermediate consuming up to a million tons last year, and the production capacity with the continuous growth aniline of the market demand constantly expands, and process units trend maximizes, and has wide market potential.
Industrial production aniline mainly contains three kinds of methods: nitrobenzene iron powder reducing method, and phenol ammoniation process and By Catalytic Hydrogenation of Nitrobenzene method account for 5% of aniline total productive capacity, 10% and 85% respectively.Traditional nitrobenzene iron powder reducing technique, owing to there is the shortcomings such as contaminated environment, energy ezpenditure is large, products of separated is difficult, has been defined as the process route will abolished in the recent period.Although the method that phenol ammoniation process produces aniline is simple, capital expenditure is excessive, and wherein the method is temperature required is 370 DEG C, and energy consumption is high, is unfavorable for suitability for industrialized production.
By Catalytic Hydrogenation of Nitrobenzene method is the main method of current industrial production aniline, has Fixed Bed Gas Phase catalytic hydrogenation method, fluidized bed gas-phase catalytic hydrogenation method and By Liquid-phase Hydrogenation Process three kinds of methods.Fixed bed gas catalysis phase hydrogenation method possesses skills maturation, equipment and simple to operate, the advantages such as small investment, but easily there is hot-spot and cause side reaction and catalyst malfunctioning, need catalyst be regularly replaced.Fluidized bed gas-phase catalytic hydrogenation method, has reaction temperature and is easy to control, the feature of the long service life of catalyst, but there is equipment operating complexity, the shortcomings such as catalyst abrasion is large, and plant investment expense is large, and maintenance expense is high.External liquid-phase hydrogenatin aniline technology successfully solves this series of problem, makes the production technology of aniline more ripe, and in addition, By Liquid-phase Hydrogenation Process also has that side reaction is few, energy consumption is low, plant capacity is large and low cost and other advantages.
What play the role of a nucleus in nitrobenzene liquid-phase hydrogenatin technique is hydrogenation catalyst, and wherein Raney nickel and noble metal catalyst etc. are hydrogenation catalysts conventional in prior art, are also the technological cores of Aniline Production.Catalyst carrier has silica gel, aluminium oxide, diatomite and molecular sieve etc.Nitrobenzene liquid phase hydrogenating catalyst huge number disclosed in domestic and international patent at present, such as: publication number is that the Chinese patent application of CN100441293C discloses a kind of Catalysts and its preparation method for chloronitrobenzene liquid-phase hydrogenatin synthesis chlorobenzene, this catalyst is loading type nickel-based catalyst, but the method exists the shortcomings such as the environmental pollution produced is serious, product purity is low, wayward.Publication number is that the Chinese patent application of CN101333169 discloses a kind of Raney's nickel that adopts the method for o-chloraniline is prepared in o-chloronitrobenzene hydrogenation reduction, and this catalyst has active high, the features such as consumption is few, and reaction temperature is low; But because the activated composition of tool in Raney's nickel catalyst is skeleton nickel, skeleton nickel is not easily preserved in atmosphere, is easy to catch fire, and use this catalyst, byproduct of reaction is many, causes product yield low simultaneously.
In addition, people (the Chem Eng Technol such as Holler Volker, 2000,23 (3): 251-255) glass fiber loaded Pt and Pd catalyst is adopted, under three-phase system, research liquid-phase reduction preparing aniline from nitrobenzene technique, aniline yield rate 100%, the activity of catalyst is 2 times of Traditional liquid phase hydrogenation Pt/C catalyst.Although noble metal carrier catalyst has active high, selective height, the life-span is long, and reclaim and regenerate simple, expensive, cost is high, is unfavorable for suitability for industrialized production.
Summary of the invention
The invention provides a kind of environmental friendliness, the active high catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
For a catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline, be made up of active component, auxiliary agent and carrier: described active component is the quality of Pt, active component Pt is 0.05 ~ 0.5% of carrier quality; Described auxiliary agent is La, Co, Cu, Cr one wherein, and the quality of auxiliary agent is 0.5 ~ 2.5% of carrier quality; Described carrier is Al
2o
3.
Described carrier is α-Al
2o
3with θ-Al
2o
3mixture, wherein α-Al
2o
3quality be 50 ~ 90% of carrier quality.
The specific area of described carrier is 10 ~ 50m
2g
-1, support shapes be spherical, cloverleaf pattern or cylindrical in one.These shapes can make each component disperses on carrier surface, obtain higher specific area, improve the catalytic efficiency of unit mass component.
As preferably, the described catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline, is made up of active component, auxiliary agent and carrier: described active component is the quality of Pt, active component Pt is 0.08 ~ 0.46% of carrier quality; Described auxiliary agent is the one in La, Co, Cu, Cr, and the quality of auxiliary agent is 0.5 ~ 2% of carrier quality; Described carrier is α-Al
2o
3with θ-Al
2o
3mixture, wherein α-Al
2o
3quality be 55 ~ 85% of carrier quality.
The specific area of described carrier is preferably 15 ~ 48m
2g
-1, support shapes preferably spherical, cloverleaf pattern or cylindrical in one.
Described carrier bulk density is preferably 0.3 ~ 0.6g/mL.
The invention provides a kind of preparation method of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline, the product purity that this catalyst reaction performance is good, catalysis is obtained is high, and preparation is simple, it is little to pollute.
The preparation method of the described catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline, comprises the following steps:
(1) aluminium stone powder extrusion is shaped, through super-dry, at 900 ~ 1200 DEG C, calcines 2 ~ 5 hours, obtain carrier;
(2), in solution step (1) gained carrier impregnation formed to soluble salt solutions and water soluble alkali or the acid by active component Pt, after drying, at 250 ~ 600 DEG C, calcine 2 ~ 4 hours, obtain catalyst precarsor A;
(3) step (2) gained catalyst precarsor A is immersed in promoter soluble salt solution, after drying, at 250 ~ 600 DEG C, calcines 2 ~ 4 hours, obtain catalyst precarsor B;
(4) utilize hydrogen to reduce the catalyst precarsor B obtained in step (3), obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
In step (1), described aluminium stone powder is boehmite powder.Boehmite can meet the requirement that reaction mixes dispersion, is first-selected aluminium source.
In step (1), described baking temperature controls at 120 DEG C, and drying time is 2 hours.
In step (2), described active component is eggshell type distribution at carrier surface.Eggshell type distribution can make active component be evenly distributed on carrier, improves the catalytic efficiency of catalyst.
In step (2), as preferably, the soluble-salt of described active component Pt is a kind of in platinum nitrate, sulfurous acid platinum or chloroplatinic acid.When selecting the soluble-salt of above-mentioned platinum salt as active component Pt, the load effect on carrier is relatively good, and obtained catalyst reaction activity is high.
In step (2), as preferably, described water soluble alkali is the one in sodium carbonate, potash or sodium acid carbonate; Described solubility acid is the one in hydrochloric acid, nitric acid, sulfuric acid or citric acid.When selecting solution as water soluble alkali or acid composition of above-mentioned alkalescence or acid solution, can the shell thickness that distributes at carrier surface of regulation activity component.
In step (3), as preferably, described promoter soluble salt is selected in chromic nitrate, cobalt nitrate, copper nitrate or lanthanum nitrate a kind of.When this several soluble-salt is as promoter soluble salt solution, the load effect on carrier is more satisfactory, and adds the catalytic activity of active component in nitrobenzene liquid-phase hydrogenatin synthesis aniline reaction.
In step (4), described hydrogen is the gaseous mixture of nitrogen and hydrogen, and wherein the volume ratio of hydrogen and nitrogen is 1 ~ 4, and described hydrogen reducing temperature is 250 ~ 500 DEG C.
The invention solves in prior art when using iron powder, carried noble metal, Raney's nickel etc. as catalyst reduction preparing aniline from nitrobenzene, the shortcomings such as the environmental pollution produced is serious, product purity is low, wayward, and the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline providing that a kind of preparation technology is simple, catalytic performance is high.This catalyst can show high activity and selectivity under lower reaction temperature and pressure condition, good stability and have the advantages such as method of operating is simple and easy, noble metal utilisation is high, cost is low, environmental pollution is low.The catalyst that the present invention is used for nitrobenzene liquid-phase hydrogenatin synthesis aniline is applicable to being applied in the reaction of nitrobenzene synthesis aniline very much, is easy to industrialization promotion and utilizes, have broad application prospects.
The present invention is used for the preparation method of catalyst of nitrobenzene liquid-phase hydrogenatin synthesis aniline, and preparation technology is simple, controllability good, workable, is easy to suitability for industrialized production, has good economic benefit.
Accompanying drawing explanation
Fig. 1 is the stereoscope cross-sectional view of catalyst prepared by embodiment 1.
Detailed description of the invention
Embodiment 1
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, α-Al
2o
3quality be 55% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.02mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and 900 DEG C of calcinings after 2 hours, obtain Raschig ring type aluminium oxide (bulk density is 0.58g/mL), wherein Raschig ring type alumina support specific area is 50m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 55% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the platinum nitrate solution (platinum content 15%) of 1.16g, be dissolved in water, add 1mL concentrated nitric acid solution again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 400 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.15%.
(3) 4.46g nine water chromic nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with chromic nitrate, the catalyst precarsor A that step (2) obtains is impregnated into prepare in chromium nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 400 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Cr accounts for 0.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:1, reductase 12 hour at 300 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
Obtain catalyst cross-sectional view after the catalyst LEICA M125 stereoscope prepared amplifies 8 times, as shown in Figure 1, visible active component Pt is eggshell type distribution at carrier surface.
Above-mentioned obtained catalyst is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, specific embodiment is as follows:
Be equipped with in the fixed bed reactors of 200mL catalyst, temperature controls at 85 DEG C, Hydrogen Vapor Pressure controls at 6MPa, with the aniline solution that the continuous input weight percentage concentration of measuring pump is the nitrobenzene of 5%, flow is 5L/min, and hydrogen flowing quantity is 0.75L/min, and nitrogen flow is 0.75L/min, make hydrogen and nitrobenzene solution continue through beds and carry out hydrogenation reduction, react sample analysis after 2 hours.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.8%, and the selective of aniline is 99.9%.
Embodiment 2
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 55% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.03mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 900 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/mL) of 3 hours, wherein Raschig ring type alumina support specific area is 50m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 55% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the platinum nitrate solution (platinum content is 15%) of 1.16g, be dissolved in water, add the concentrated hydrochloric acid aqueous solution of 1mL again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 300 DEG C calcine 3 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.15%.
(3) 5.73g cobalt nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with cobalt nitrate, the product that step (2) obtains is impregnated into prepare in cobalt nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 3 hours at the temperature of 300 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Co accounts for 1% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:1, reductase 12 hour at 250 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 2 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, specific embodiment is identical with embodiment 1.
Reacted product gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54) is analyzed, and the conversion ratio of nitrobenzene is 97.6%, and the selective of aniline is 99.2%.
Embodiment 3
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 55% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.06mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 900 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/mL) of 3 hours, wherein Raschig ring type alumina support specific area is 50m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 55% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the solution that 0.15g chloroplatinic acid is prepared, be dissolved in water, add the sodium bicarbonate aqueous solution of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 250 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.05%.
(3) 6.57g copper nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with copper nitrate, the product that step (2) obtains is impregnated into prepare in copper nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 250 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Cu accounts for 1.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:2, reductase 12 hour at 400 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 3 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.5L/min, and nitrogen flow is 1.0L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 97.1%, and the selective of aniline is 99.3%.
Embodiment 4
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 55% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.08mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 900 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/mL) of 2 hours, wherein Raschig ring type alumina support specific area is 50m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 55% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the sulfurous acid platinum solution (platinum content is 15.3%) of 0.38g, be dissolved in water, add the wet chemical of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 600 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.05%.
(3) 9.04g lanthanum nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with lanthanum nitrate, the product that step (2) obtains is impregnated into prepare in lanthanum nitrate hexahydrate, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 600 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent La accounts for 2.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:4, reductase 12 hour at 500 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 4 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.3L/min, and nitrogen flow is 1.2L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 96.8%, and the selective of aniline is 99.9%.
Embodiment 5
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 61% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.03mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 1050 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/ml) of 3 hours, wherein Raschig ring type alumina support specific area is 30m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 61% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the solution that the chloroplatinic acid of 0.46g is prepared, be dissolved in water, add 1mL concentrated hydrochloric acid aqueous solution again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 400 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.15%.
(3) 0.45g nine water chromic nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with chromic nitrate, the product that step (2) obtains is impregnated into prepare in chromium nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 400 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Cr accounts for 0.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:1, reductase 12 hour at 250 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 5 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.75L/min, and nitrogen flow is 0.75L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.4%, and the selective of aniline is 99.9%.
Embodiment 6
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 61% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.07mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 1050 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/ml) of 3 hours, wherein Raschig ring type alumina support specific area is 30m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 61% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the solution that 0.46g chloroplatinic acid configures, be dissolved in water, add the aqueous sodium carbonate of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 300 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.15%.
(3) 8.60g nine water cobalt nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with cobalt nitrate, the product that step (2) obtains is impregnated into prepare in cobalt nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 300 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Co accounts for 1.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:2, reductase 12 hour at 300 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 6 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.5L/min, and nitrogen flow is 1.0L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.9%, and the selective of aniline is 100%.
Embodiment 7
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 61% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.02mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 1050 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/mL) of 3 hours, wherein Raschig ring type alumina support specific area is 30m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 61% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the platinum nitrate solution (platinum content is 15%) of 0.39g, be dissolved in water, add the aqueous sulfuric acid of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 250 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.05%.
(3) 6.57g copper nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with copper nitrate, the product that step (2) obtains is impregnated into prepare in copper nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 300 DEG C, under air atmosphere, obtain catalyst precarsor B.Wherein the quality of auxiliary agent Cu accounts for 1.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:2, reductase 12 hour at 300 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 7 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.5L/min, and nitrogen flow is 1.0L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 97.4%, and the selective of aniline is 98.9%.
Embodiment 8
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline is with Raschig ring type (i.e. single-hole cylindrical shape) aluminium oxide for carrier, wherein α-Al
2o
3quality be 61% of carrier quality, at its area load active component Pt, and active component Pt Raschig ring type alumina surface be eggshell shape distribution, shell thickness is 0.1mm.Below the concrete preparation process of this catalyst:
(1) 116g(200mL is taken) boehmite powder extrusion becomes single-hole cylindrical shape, and at 1050 DEG C of calcinings Raschig ring type aluminium oxide (bulk density is 0.58g/ml) of 3 hours, wherein Raschig ring type alumina support specific area is 30m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 61% of carrier quality.
(2) the Raschig ring type aluminium oxide after step (1) being processed mixes with the sulfurous acid platinum solution (platinum content is 15.3%) of 3.79g, be dissolved in water, add the aqueous sodium carbonate of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 600 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.5%.
(3) 9.04g nine water lanthanum nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with lanthanum nitrate, the product that step (2) obtains is impregnated into prepare in lanthanum nitrate hexahydrate, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 600 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent La accounts for 2.5% of Raschig ring type carrying alumina weight.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:4, reductase 12 hour at 500 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 8 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.3L/min, and nitrogen flow is 1.2L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 94.8%, and the selective of aniline is 98.2%.
Embodiment 9
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline take aluminium oxide as carrier, fashioned into by carrier spherical, wherein α-Al
2o
3quality be 85% of carrier quality, at its area load active component Pt, and active component Pt alumina carrier surface be eggshell shape distribution, shell thickness is 0.09mm.Below the concrete preparation process of this catalyst:
(1) take 116g, about 200mL, 1200 DEG C calcining 5 hours fashion into spherical carrier (bulk density is 0.58g/ml), wherein ball type carrier specific area is 10m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 85% of carrier quality.
(2) spherical alumina support after step (1) being processed mixes with the sulfurous acid platinum solution (platinum content is 15.3%) of 1.14g, be dissolved in water, add the wet chemical of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 400 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.15%.
(3) 4.46g nine water chromic nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with chromic nitrate, the product that step (2) obtains is impregnated into prepare in chromium nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 300 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Cr accounts for 0.5% of carrier quality.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:1, reductase 12 hour at 250 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 9 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.75L/min, and nitrogen flow is 0.75L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.7%, and the selective of aniline is 99.9%.
Embodiment 10
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline take aluminium oxide as carrier, fashioned into by carrier spherical.Wherein α-Al
2o
3quality be 85% of carrier quality, at its area load active component Pt, and active component Pt alumina carrier surface be eggshell shape distribution, shell thickness is 0.03mm.Below the concrete preparation process of this catalyst:
(1) take 116g, about 200mL, 1200 DEG C calcining 5 hours fashion into spherical carrier (bulk density is 0.58g/mL), wherein spherical alumina support specific area is 10m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 85% of carrier quality.
(2) ball type carrier after step (1) being processed mixes with the sulfurous acid platinum solution (content of platinum is 15.3%) of 1.14g, be dissolved in water, add the aqueous sulfuric acid of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 300 DEG C calcine 3 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.15%.
(3) 8.59g nine water cobalt nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with cobalt nitrate, the product that step (2) obtains is impregnated into prepare in cobalt nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 3 hours at the temperature of 300 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Co accounts for 1.5% of carrier quality.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:2, reductase 12 hour at 300 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 10 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.5L/min, and nitrogen flow is 1.0L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.9%, and the selective of aniline is 99.9%.
Embodiment 11
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline take aluminium oxide as carrier, and carrier is fashioned into trifolium-shaped.Aluminium oxide is carrier, wherein α-Al
2o
3quality be 85% of carrier quality, at its area load active component Pt, and active component Pt carrier surface be eggshell shape distribution, shell thickness is 0.05mm.Below the concrete preparation process of this catalyst:
(1) take 116g, about 200ml, at 1200 DEG C of calcinings carrier (bulk density is 0.58g/ml) fashioning into trifolium-shaped of 5 hours, wherein trifolium-shaped alumina support specific area is 10m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 85% of carrier quality.
(2) the trifolium-shaped carrier after step (1) being processed mixes with the solution that the chloroplatinic acid of 0.15g is prepared, be dissolved in water, add the sodium bicarbonate aqueous solution of 1mL1mol/L again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 250 DEG C calcine 2 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.05%.
(3) 6.57g copper nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with copper nitrate, the product that step (2) obtains is impregnated into prepare in copper nitrate solution, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 2 hours at the temperature of 300 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent Cu accounts for 1.5% of carrier quality.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:2, reductase 12 hour at 300 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 11 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.5L/min, and nitrogen flow is 1.0L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.9%, and the selective of aniline is 99.9%.
Embodiment 12
In the present embodiment, a kind of catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline take aluminium oxide as carrier, and carrier is fashioned into trifolium-shaped.Wherein α-Al
2o
3quality be 85% of carrier quality, at its area load active component Pt, and active component Pt carrier surface be eggshell shape distribution, shell thickness is 0.02mm.Below the concrete preparation process of this catalyst:
(1) take 116g, about 200mL, at 1200 DEG C of calcinings carrier (bulk density is 0.58g/ml) fashioning into trifolium-shaped of 5 hours, wherein trifolium-shaped carrier specific area is 10m
2g
-1, obtained by X ray diffracting spectrum Fitting Analysis, α-Al
2o
3quality be 85% of carrier quality.
(2) the trifolium-shaped carrier after step (1) being processed mixes with the platinum nitrate solution (platinum content is 15.%) of 3.87g, be dissolved in water, add the 1ml red fuming nitric acid (RFNA) aqueous solution again, constant temperature impregnation 1 hour at 80 DEG C, then wash with water, dry after at 600 DEG C calcine 4 hours, obtain the catalyst precarsor A that platiniferous mass fraction is 0.5%.
(3) 9.04g lanthanum nitrate is taken, be dissolved in suitable quantity of water the aqueous solution being mixed with lanthanum nitrate, the product that step (2) obtains is impregnated into prepare in lanthanum nitrate hexahydrate, flood 1 hour, drying 4 hours at 120 DEG C of temperature, calcine 4 hours at the temperature of 600 DEG C, under air atmosphere, obtain catalyst precarsor B, wherein the quality of auxiliary agent La accounts for 2.5% of carrier quality.
(4) the catalyst precarsor B obtained in step (3) is joined in fixed bed reactors, pass into hydrogen and nitrogen volume ratio is the gaseous mixture of 1:4, reductase 12 hour at 500 DEG C, obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
The catalyst that embodiment 12 obtains is used for the reaction that aniline is prepared in nitrobenzene liquid-phase hydrogenatin reduction, hydrogen flowing quantity is 0.3L/min, and nitrogen flow is 1.2L/min, and other process conditions are in the same manner as in Example 1.
Reacted product is analyzed with gas-chromatography (chromatogram model: GC2060, chromatographic column: SE-54), and the conversion ratio of nitrobenzene is 99.9%, and the selective of aniline is 99.8%.
Claims (8)
1., for a catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline, be made up of active component, auxiliary agent and carrier, it is characterized in that: described active component is the quality of Pt, active component Pt is 0.05 ~ 0.5% of carrier quality; Described auxiliary agent is the one in La, Co, Cu, Cr, and the quality of auxiliary agent is 0.5 ~ 2.5% of carrier quality; Described carrier is Al
2o
3;
The preparation method of the described catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline, comprises the following steps:
(1) boehmite powder extrusion is shaped, through super-dry, at 900 ~ 1200 DEG C, calcines 2 ~ 5 hours, obtain carrier;
Described carrier is α-Al
2o
3with θ-Al
2o
3mixture, wherein α-Al
2o
3quality be 50 ~ 90% of carrier quality;
(2), in the solution carrier impregnation of step (1) gained formed to soluble salt solutions and water soluble alkali or the acid by active component Pt, after drying, at 250 ~ 600 DEG C, calcine 2 ~ 4 hours, obtain catalyst precarsor A;
(3) step (2) gained catalyst precarsor A is immersed in promoter soluble salt solution, after drying, at 250 ~ 600 DEG C, calcines 2 ~ 4 hours, obtain catalyst precarsor B;
(4) utilize hydrogen to reduce gained catalyst precarsor B in step (3), obtain the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline.
2. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 1, is characterized in that: the specific area of described carrier is 10 ~ 50m
2g
-1; Support shapes be spherical, cloverleaf pattern or cylindrical in one.
3. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 1, is characterized in that: described active component is the quality of Pt, active component Pt is 0.08 ~ 0.46% of carrier quality; Described auxiliary agent is the one in La, Co, Cu, Cr, and the quality of auxiliary agent is 0.5 ~ 2% of carrier quality; Described carrier is α-Al
2o
3with θ-Al
2o
3mixture, wherein α-Al
2o
3quality be 55 ~ 85% of carrier quality.
4. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 2, is characterized in that: the specific area of described carrier is 15 ~ 48m
2g
-1.
5. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 1, is characterized in that: described active component is 0.02 ~ 0.1mm at the thickness that carrier surface distributes.
6. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 1, it is characterized in that, in step (2), the soluble-salt of described active component Pt is the one in platinum nitrate, sulfurous acid platinum or chloroplatinic acid.
7. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 1, it is characterized in that, in step (2), described water soluble alkali is the one in sodium carbonate, potash or sodium acid carbonate, and described solubility acid is the one in hydrochloric acid, nitric acid, sulfuric acid or citric acid.
8. the catalyst for nitrobenzene liquid-phase hydrogenatin synthesis aniline according to claim 1, it is characterized in that, in step (3), described promoter soluble salt is the one in chromic nitrate, cobalt nitrate, copper nitrate or lanthanum nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310187434.2A CN103316676B (en) | 2013-05-17 | 2013-05-17 | Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310187434.2A CN103316676B (en) | 2013-05-17 | 2013-05-17 | Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103316676A CN103316676A (en) | 2013-09-25 |
| CN103316676B true CN103316676B (en) | 2015-04-15 |
Family
ID=49185890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310187434.2A Active CN103316676B (en) | 2013-05-17 | 2013-05-17 | Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103316676B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562032B (en) * | 2016-03-08 | 2018-02-02 | 中国科学院宁波材料技术与工程研究所 | Catalyst, its preparation method and application for the reaction of hydrogenation synthesis parachloroanilinum |
| CN105688903B (en) * | 2016-03-15 | 2018-07-10 | 西安凯立新材料股份有限公司 | It is a kind of to be used to produce Pt/C catalyst of halogenated aniline and preparation method thereof |
| CN111375451B (en) * | 2018-12-29 | 2022-12-13 | 中国石油化工股份有限公司 | Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst |
| CN112108139B (en) * | 2020-09-29 | 2023-05-09 | 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 |
| CN112264038B (en) * | 2020-11-11 | 2023-03-24 | 中国科学院宁波材料技术与工程研究所 | Noble metal loaded eggshell type catalyst and preparation method and application thereof |
| CN115624970B (en) * | 2022-08-18 | 2024-05-07 | 扬州博克莱生物医药科技有限公司 | Catalyst for continuous liquid-phase hydrogenation reduction of nitro compounds in micro-fixed bed, and preparation method and application thereof |
| CN115739080A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院大连化学物理研究所 | Preparation of Pt-based catalyst and application of Pt-based catalyst in preparation of chloroaniline by selective hydrogenation of chloronitrobenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631524A (en) * | 2003-12-25 | 2005-06-29 | 中国科学院大连化学物理研究所 | Catalyst for o-Fluoro nitrobenzene hydrogenation and its preparation and application |
| CN1775351A (en) * | 2005-10-10 | 2006-05-24 | 大连理工大学 | Catalyst for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds and its use method |
| CN102380374A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Preparation method of palladium group hydrogenation catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010159237A (en) * | 2009-01-09 | 2010-07-22 | Nagoya Univ | Method for producing aromatic amine |
-
2013
- 2013-05-17 CN CN201310187434.2A patent/CN103316676B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631524A (en) * | 2003-12-25 | 2005-06-29 | 中国科学院大连化学物理研究所 | Catalyst for o-Fluoro nitrobenzene hydrogenation and its preparation and application |
| CN1775351A (en) * | 2005-10-10 | 2006-05-24 | 大连理工大学 | Catalyst for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds and its use method |
| CN102380374A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Preparation method of palladium group hydrogenation catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 何蓓蓓 等.Pb掺杂改性对Pt/HZSM-5催化剂结构及其催化合成对氨基苯酚反应性能的影响.《石油学报(石油加工)》.2013,第29卷(第1期), * |
| 富氢气氛中CO的选择性氧化-碱金属助剂对Pt/γ-Al2O3 催化剂性能的影响;曹平 等;《工业催化》;20040131;第12卷(第1期);第42页第1.1节 * |
| 负载Pt 催化剂在卤代硝基苯氢化反应中的催化性能研究;韩晓祥 等;《复旦学报( 自然科学版)》;20030630;第42卷(第3期);第428页摘要，第1.1节，1.2节，第429页第2.1节，2.2节，表1，表2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103316676A (en) | 2013-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103316676B (en) | Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof | |
| US8809588B2 (en) | Method for producing aromatic amines | |
| CN103769094B (en) | A kind of egg-shell catalyst for selective hydrogenation, preparation method and application | |
| CN105540588B (en) | The application of α types molybdenum carbide and its metal-modified α types carbide catalyst in hydrogenation of carbon dioxide reaction of carbon monoxide | |
| CN102614870B (en) | Vinylacetylene hydrogenation catalyst and preparation method thereof | |
| JP6877142B2 (en) | Hydrogenation method of aromatic compounds | |
| CN106029638B (en) | The method for hydrogenating 4,4 '-methylene-dianiline (MDA)s | |
| CN102319581B (en) | Efficient oxalic ester hydrogenation catalyst and preparation method thereof | |
| CN1836778A (en) | Metal modified HZSM-5 molecular screen catalyst and its preparation method and uses in preparing methyl formate | |
| CN112898184A (en) | Method for continuously synthesizing alicyclic carbamate | |
| CN103304427B (en) | Method for preparing aniline through low-temperature liquid-phase catalytic hydrogenation | |
| CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
| CN102935365B (en) | Catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate | |
| CN101530805B (en) | Catalyst for preparing tert-olefins by cracking tert-alkyl ethers, preparation method and application thereof | |
| CN106467467A (en) | A kind of method that fixed bed continuous catalytic hydrogenation prepares diaminonaphthalene | |
| CN102698742B (en) | Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same | |
| CN106890670B (en) | A kind of Dimethyl ether carbonylation produces catalyst and its application of methyl acetate | |
| CN102702042B (en) | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process | |
| CN103418414B (en) | Catalyst for 4 nitrodiphenyl amine hydrogenation | |
| CN102350361A (en) | Nickel-based structured catalyst for synthesizing m-phenylenediamine through hydrogenation of m-dinitrobenzene and its preparation method | |
| CN106238099B (en) | The preparation method and application of 1,5- dinitronaphthalene hydrogenation catalyst | |
| CN103288572A (en) | Vinyl acetylene product and preparation method thereof | |
| CN100457710C (en) | Metal salt catalyzed benzene nitrating to prepare nitrobenzene | |
| CN102698743A (en) | Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same | |
| CN103706392B (en) | Double-layer combined catalyst for preparing normal propyl alcohol by glycerine hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |