CN102000612B - Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst - Google Patents
Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst Download PDFInfo
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- CN102000612B CN102000612B CN 200910034216 CN200910034216A CN102000612B CN 102000612 B CN102000612 B CN 102000612B CN 200910034216 CN200910034216 CN 200910034216 CN 200910034216 A CN200910034216 A CN 200910034216A CN 102000612 B CN102000612 B CN 102000612B
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Abstract
The invention belongs to the technical field of catalyst manufacturing, and provides a carrier of a nitrobenzene hydrogenation catalyst for making aniline for a fluidized bed and a preparation method of acatalyst. The preparation method comprises the following steps: treating crude-pored microspherical silica gel to obtain a silica gel carrier with smaller specific surface and larger bore diameter; dipping solution containing active components onto the carrier by a dipping method; and washing and drying to obtain the finished product of the catalyst. The catalyst has the characteristics of high activity, less possibility of pore path blockage, long service life and the like.
Description
Technical field: the invention belongs to catalyst technical field, be specifically related to the preparation method of a kind of carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and catalyst.
Background technology: the chemical reaction overwhelming majority in the chemical process realizes by catalytic reaction, for the catalytic reaction of strong heat release fluidized-bed reactor commonly used, such as manufacturing process of aniline through nitrobenzene hydrogenation.
As everyone knows, the catalyst system for the nitrobenzene gas phase hydrogenation has copper system, nickel system and noble metal system etc.Catalyst carrier has silica gel, zeolite, activated alumina and diatom scholar etc.Copper catalyst has higher activity and selectivity; Raney nickel is often made the multielement composite catalyst, to keep high selectivity and the activity of reaction, avoids benzene ring hydrogenation.In concrete the production, usually adopt fixed bed or fluidized-bed reactor.
For the used carrier of catalyst, usually use silica to be carrier, mainly be to adopt sodium metasilicate to make by certain technique.
CN 100376480C provides a kind of manufacture method of macro porous silica gel, it is sprayed and polycondensation generation gel particles through gradual reaction and through this prilling granulator by sodium silicate solution and dilute sulfuric acid, this gel particles is warp again: acid bubble, washing, aging, quadratic acid bubble, dry processing obtain the large pore spherical silica gel product.Wherein drying process is that this gel particles that the quadratic acid bubble is processed is pulled out, and drying equipment is at 500～950 ℃ of lower drying and processings.Owing to adopting acid bubble PROCESS FOR TREATMENT, the acid that remains in the silica gel space reduced metal ion and remained in the silica gel hole, had hyperthermia drying to process again, so that can be decomposed volatilization or burning, make noresidue in the macro porous silica gel, improved the catalytic activity as catalyst carrier.It is said that this macro porous silica gel is specially adapted to as catalyst carrier, delustering agent, opening agent, beer filtration medium, paper additive etc.The macro porous silica gel of the method manufacturing not only has following pore structure: average pore size is at 10～45nm, average pore volume 1.00～2.20ml/g, average specific surface area 200～550m
2/ g, and have certain mechanical strength, meet the characteristic that water does not split.
CN 1186254C provides a kind of manufacture method of macro porous silica gel, it is to generate positive silicic acid by sodium silicate solution and dilute sulfuric acid in reactor, by traditional adhesive-preparing technology, solidify through leaving standstill that---------alkali bubble is processed---steam treatment---and soaked salt and process in washing in broken granulation, process through traditional stoving process again, the physical and chemical performance that makes macro porous silica gel is: average pore size is at 10～60nm, average specific surface area 250～350m
2/ g, average pore volume 1.00～2.00ml/g.
For catalyst, normally will contain the method that the salt of active constituent impregnated on the carrier and make.
US5,304,525, US6,818,720 provide respectively a kind of noble metal catalyst for the nitrobenzene gas phase hydrogenation, and active constituent is mainly Pt, Ru etc.
US3,504,035 provide a kind of Cu-Si or Cu-Al catalyst, and Cr, Ba, Zn etc. carry out modification, 200～400 microns of catalyst particle sizes.Adopt fluid bed gas phase hydrogenation method, 250～300 ℃ of reaction temperatures, reaction pressure 0.4～1.0MPa, the mol ratio of nitrobenzene and hydrogen is 1: 3, the initial yield of aniline is greater than 99%.
CN1657162A is by adopting take silica as carrier, take chemical formula as Cu
aCr
bMo
cA
dO
x, wherein A is selected from least a technical scheme among Ni, Zn, Ba, V, Bi, Pb or the Pd, has solved preferably this problem, can be used in the industrial production of manufacturing process of aniline through nitrobenzene hydrogenation.
CN 1301154C provide a kind of reproducible hydrogenation catalyst and preparation method thereof, and it is at SiO
2One or more active components on the carrier among loaded Cu, Fe, CO, Ni, Cr, Mn, the Mo form, catalyst is by any the making in the precipitation method, coprecipitation and the infusion process, catalyst is effective especially to the hydrogenation of aromatic hydrocarbon nitro compound, catalyst life is that existing catalyst is more than one times, catalyst can carry out hydrogenation reaction under normal pressure (or pressurization), method for preparing catalyst is simple.
CN 1251801C provides a kind of preparation method who makes the catalyst of carrier with macro porous silica gel, will usually place alkaline solution by the less particle silica gel in the aperture of sol method production, heating, and the macro porous silica gel carrier is made in drying or roasting; Alkaline solution is one or more mixed solution in carbonate, bicarbonate, formates and the acetate solution of solution, alkali metal and the ammonium of the hydroxide of alkali metal and ammonium.With germanium salt with as the solution impregnation silica-gel carrier of the slaine of co-catalyst, dry, roasting, the germanium that makes macro porous silica gel and be carrier is catalyst based.Germanium salt is the soluble-salt of tri-chlorination germanium or nitric acid germanium.Promoter metal salt is the soluble-salt of transition metal, rare earth metal, alkali metal, alkaline-earth metal.This catalyst has higher activity and selectivity in the reaction of the synthetic c_2-oxygen compound of CO hydrogenation.
Although the carrier that adopts above method to obtain has reached certain effect, but being only suitable for some catalyst uses, and commercially available silica supports often can not reach requirement, and this just need to process before use especially, to be fit to the needs of different catalysts.And with regard to the catalyst of manufacturing process of aniline through nitrobenzene hydrogenation, its used carrier then requires less specific surface, larger aperture, higher mechanical strength.
Its active component of the catalyst of manufacturing process of aniline through nitrobenzene hydrogenation is Cu, and its nitrobenzene conversion ratio just can reach 100% under lower Cu content, and key is how to control reaction speed, prevents the duct obstruction, the extending catalyst life-span.Adopt the catalyst of above method preparation, all reach the purpose of control reaction speed by the modified component of introducing other.
Summary of the invention: the object of the present invention is to provide a kind of suitable the Aniline Production preparation method of catalyst carrier and the preparation method of Fluidized Multicomponent Metallic Oxides Catalysts.
The present invention directly starts with from carrier is processed, and the catalyst that makes has the characteristics such as activity is high, the difficult obstruction in duct, long service life, avoids simultaneously introducing in catalyst multicomponent mixture.
The preparation method of carrier of the present invention processes the gross porosity microsphere silica gel 1～5 hour in the water of 110 ℃～150 ℃ (preferably 130 ℃～150 ℃), then add therein strong acid, regulate the acid concentration mass percent 1%～10% (preferably 2%～6%), 70 ℃～90 ℃ lower immersions 0.5～2.0 hour, through washing, separate, be drying to obtain required carrier.
The physical and chemical performance of silica supports provided by the invention is: the average specific surface is less than 300m
2/ g, average pore size 6～10nm, average pore volume 0.8～1.0ml/g.
General, described strong acid is hydrochloric acid or nitric acid, determines according to the contained anion of the maceration extract that contains active component that the need Kaolinite Preparation of Catalyst is used, contained anion is Cl in the maceration extract
-, then select hydrochloric acid to process; Contained anion is NO in the maceration extract
-, then select nitric acid to process.
Catalyst preparation process of the present invention is: slowly add ammoniacal liquor and be made into the cupric ammine complex solution of clarification as maceration extract in the copper nitrate solution that contains the catalyst activity component, the mol ratio of copper and ammonia is 1: 1～6, then treated carrier is joined in the reactor of cupric ammine complex solution and flood, under 70 ℃～90 ℃ temperature, stirred at leisure 2～5 hours, after dipping is finished solid-liquid is separated, solid particle is through washing, be drying to obtain the catalyst finished product.
General, maceration extract is cupric ammine complex solution; Cupric ammine complex solution is that employing copper nitrate solution and ammoniacal liquor are formulated, and the mol ratio of copper and ammonia is 1: 2～4.
The specific embodiment: carrier of the present invention and catalyst preparation are implemented according to above step, are elaborated below by embodiment.The purpose of enumerating these examples is just in order to explain the present invention, rather than limitation of the present invention.The physical and chemical performance of the used gross porosity microsphere silica gel of the present invention is: specific surface is 363.6m
2/ g, pore volume are 0.8675ml/g, and average pore size is 4.77nm.
Embodiment 1
1000ml water and the commercially available gross porosity microsphere silica gel of 200g are successively added in the autoclave of 2L, being warming up to 95 ℃ after the sealing kept 2 hours, then adding the 70ml red fuming nitric acid (RFNA) kept 2 hours at 70～80 ℃ of g, treating temperature is down to below 50 ℃, material is filtered, washs, until neutral, again the silica gel oven dry is namely got carrier.
Embodiment 2
1000ml water and the commercially available gross porosity microsphere silica gel of 200g are successively added in the autoclave of 2L, being warming up to 120 ℃ after the sealing kept 2 hours, then adding the 70ml red fuming nitric acid (RFNA) kept 2 hours at 70～80 ℃ of g, treating temperature is down to below 50 ℃, material is filtered, washs, until neutral, again the silica gel oven dry is namely got required carrier.
Embodiment 3
1000ml water and the commercially available gross porosity microsphere silica gel of 200g are successively added in the autoclave of 2L, being warming up to 130 ℃ after the sealing kept 2 hours, then adding the 70ml red fuming nitric acid (RFNA) kept 2 hours at 70～80 ℃ of g, treating temperature is down to below 50 ℃, material is filtered, washs, until neutral, again the silica gel oven dry is namely got carrier.
Embodiment 4
1000ml water and the commercially available gross porosity microsphere silica gel of 200g are successively added in the autoclave of 2L, being warming up to 142 ℃ after the sealing kept 2 hours, then adding the 70ml red fuming nitric acid (RFNA) kept 2 hours at 70～80 ℃ of g, treating temperature is down to below 50 ℃, material is filtered, washs, until neutral, again the silica gel oven dry is namely got carrier.
Embodiment 5
1000ml water and the commercially available gross porosity microsphere silica gel of 200g are successively added in the autoclave of 2L, being warming up to 150 ℃ after the sealing kept 2 hours, then adding the 70ml red fuming nitric acid (RFNA) kept 2 hours at 70～80 ℃ of g, treating temperature is down to below 50 ℃, material is filtered, washs, until neutral, again the silica gel oven dry is namely got carrier.
Comparative example 1
Carry out the physical and chemical performance analysis with commercially available silica gel and above-described embodiment 1～embodiment 5 are silica obtained, the results are shown in Table 1.
The physical and chemical performance of the silica gel of table 1 treatment of different temperature
| Sequence number | Specific surface m 2/g | Pore volume ml/g | Average pore size nm |
| Commercially available silica gel | 363.6 | 0.8675 | 4.77 |
| Embodiment 1 | 346.9 | 0.8727 | 5.03 |
| Embodiment 2 | 320.4 | 0.8961 | 5.59 |
| Embodiment 3 | 282.9 | 0.8731 | 6.17 |
| Embodiment 4 | 221.6 | 0.8716 | 7.87 |
| Embodiment 5 | 210.3 | 0.8702 | 8.08 |
Embodiment 6
Be that 180～220 microns commercially available gross porosity microsphere silica gel successively adds in the autoclave of 2L with 1000ml water and 200g particle diameter, being warming up to 150 ℃ after the sealing kept 2 hours, then adding the 100ml concentrated hydrochloric acid kept 2 hours at 70～80 ℃ of g, treating temperature is down to below 50 ℃, material is filtered, washs, until neutral, again the silica gel oven dry is namely got carrier.
Comparative example 2
Being that 180～220 microns commercially available gross porosity microsphere silica gel and above-described embodiment 6 are silica obtained with particle diameter carries out the physical and chemical performance analysis, and the results are shown in Table 2.
Physical and chemical performance before and after 180～220 microns silica gel reamings of table 2
| Sequence number | Specific surface m 2/g | Pore volume ml/g | Average pore size nm |
| 180～220 microns silica gel | 368.7 | 0.9174 | 4.976 |
| Embodiment 6 | 239.6 | 0.8563 | 7.147 |
The preparation of embodiment 7 catalyst
The catalyst preparation is to carry out in closed reactor, implements by following several steps.1. prepare cuprammonia: the ammoniacal liquor of getting 100ml10M joins in the copper nitrate solution of 500ml 0.5M, is mixed with the cupric ammine complex solution of clarification.2. dipping: get 200g in the silica gel that reaming is processed joins 1. cupric ammine complex solution, kept 4 hours under stirring, dipping is finished.3. separate, washing, drying: will flood material and carry out Separation of Solid and Liquid, solid material to neutral, carries out drying through washing again, gets the catalyst finished product.This catalyst copper content is 17.5%, specific surface 432.5m
2/ g, pore volume 0.72ml/g, average pore size 3.5nm.
The preparation of embodiment 8 catalyst
The catalyst preparation is to carry out in closed reactor, implements by following several steps.1. prepare cuprammonia: the ammoniacal liquor of getting 200ml10M joins in the copper nitrate solution of 500ml0.5M, is mixed with the cupric ammine complex solution of clarification.2. dipping: get silica gel that 200g processes without reaming and join in 1. the cupric ammine complex solution, kept 5 hours 90 ℃ of lower stirrings, dipping is finished.3. separate, washing, drying: will flood material and carry out Separation of Solid and Liquid, solid material to neutral, carries out drying through washing again, gets the catalyst finished product.This catalyst copper content is 16.5%, specific surface 456.7m
2/ g, pore volume 0.66ml/g, average pore size 2.8nm.
The preparation of embodiment 9 catalyst
The catalyst preparation is to carry out in closed reactor, implements by following several steps.1. prepare cuprammonia: the ammoniacal liquor of getting 100ml10M joins in the copper nitrate solution of 500ml 0.5M, is mixed with the cupric ammine complex solution of clarification.2. dipping: get silica gel that 200g processes without reaming and join in 1. the cupric ammine complex solution, kept 4 hours under stirring, dipping is finished.3. separate, washing, drying: will flood material and carry out Separation of Solid and Liquid, solid material to neutral, carries out drying through washing again, gets the catalyst finished product.This catalyst copper content is 19.6%, specific surface 469.5m
2/ g, pore volume 0.64ml/g, average pore size 2.8nm.
Claims (6)
1. the preparation method of a carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed, it is characterized by: it is that 110 ℃～150 ℃ water was processed 1～5 hour in temperature that the gross porosity microsphere silica gel is placed the enclosed high pressure reactor, then add therein strong acid, regulate the acid concentration mass percent 1%～10%, 70 ℃～90 ℃ lower immersions 0.5～2.0 hour, through washing, separate, be drying to obtain required carrier; The physical and chemical performance of carrier is: the average specific surface is less than 300m
2/ g, average pore volume 0.8～1.0ml/g, average pore size 6～10nm.
2. the preparation method of carrier as claimed in claim 1, the treatment temperature that it is characterized in that the gross porosity microsphere silica gel is 130 ℃～150 ℃.
3. the preparation method of carrier as claimed in claim 1 is characterized in that strong acid is hydrochloric acid or nitric acid, determines according to the contained anion of the maceration extract that contains active component that the need Kaolinite Preparation of Catalyst is used, and contained anion is Cl in the maceration extract
-, then select hydrochloric acid to process; Contained anion is NO in the maceration extract
-, then select nitric acid to process.
4. the preparation method of carrier as claimed in claim 1, the mass percent that it is characterized in that used acid is 2%～6%.
5. a fluid bed is with the preparation method of manufacturing process of aniline through nitrobenzene hydrogenation catalyst, it is characterized by: in the copper nitrate solution that contains the catalyst activity component, slowly add ammoniacal liquor and be made into the cupric ammine complex solution of clarification as maceration extract, the mol ratio of copper and ammonia is 1: 1～6, then the carrier of the described method of claim 1 preparation is joined in the reactor of cupric ammine complex solution and flood, under 70 ℃～90 ℃ temperature, stirred at leisure 2～5 hours, after dipping is finished solid-liquid is separated, solid particle is through washing, be drying to obtain the catalyst finished product.
6. the preparation method of catalyst as claimed in claim 5, the mol ratio that it is characterized in that cupric ammine complex solution copper and ammonia is 1: 2～4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910034216 CN102000612B (en) | 2009-09-02 | 2009-09-02 | Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst |
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|---|---|---|---|
| CN 200910034216 CN102000612B (en) | 2009-09-02 | 2009-09-02 | Carrier of nitrobenzene hydrogenation catalyst for making aniline for fluidized bed and preparation method of catalyst |
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| CN102000612B true CN102000612B (en) | 2013-03-06 |
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| CN102744066A (en) * | 2012-05-08 | 2012-10-24 | 中国石油化工股份有限公司 | Nitrobenzene hydrogenation aniline preparation catalyst for fluidized bed |
| CN106914255B (en) * | 2017-03-29 | 2020-03-03 | 国家纳米科学中心 | Non-alloy metal compound and preparation method and application thereof |
| CN107746380B (en) * | 2017-11-06 | 2020-04-07 | 宁夏中盛新科技有限公司 | Industrial production method of 2-amino-4-acetamino anisole |
| CN111135822B (en) * | 2018-11-06 | 2021-11-09 | 中国科学院大连化学物理研究所 | Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound |
| CN112536033B (en) * | 2019-09-20 | 2023-05-26 | 中国石油化工股份有限公司 | Catalyst for preparing o-toluidine by hydrogenation of o-nitrotoluene and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010056035A1 (en) * | 1996-07-23 | 2001-12-27 | Emmanuel Auer | Multimetallic catalyst and process for preparing substituted aromatic amines |
| CN1768941A (en) * | 2004-11-05 | 2006-05-10 | 中国石油化工股份有限公司 | Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene |
| CN1861254A (en) * | 2006-06-13 | 2006-11-15 | 吉化集团公司 | Catalyst for fluidized bed gaseous hydrogenation of nitrobenzene to produce aniline, and process therefor |
| CN1896000A (en) * | 2003-02-21 | 2007-01-17 | 青岛海洋化工有限公司 | Production of macroporous silica gel |
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- 2009-09-02 CN CN 200910034216 patent/CN102000612B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010056035A1 (en) * | 1996-07-23 | 2001-12-27 | Emmanuel Auer | Multimetallic catalyst and process for preparing substituted aromatic amines |
| CN1896000A (en) * | 2003-02-21 | 2007-01-17 | 青岛海洋化工有限公司 | Production of macroporous silica gel |
| CN1768941A (en) * | 2004-11-05 | 2006-05-10 | 中国石油化工股份有限公司 | Preparation method of fluidized bed catalyst for aniline production by gas phase hydrogenation of nitrobenzene |
| CN1861254A (en) * | 2006-06-13 | 2006-11-15 | 吉化集团公司 | Catalyst for fluidized bed gaseous hydrogenation of nitrobenzene to produce aniline, and process therefor |
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