CN101434548B - Method for preparing diaminobenzene from dinitro benzene - Google Patents
Method for preparing diaminobenzene from dinitro benzene Download PDFInfo
- Publication number
- CN101434548B CN101434548B CN2008101745923A CN200810174592A CN101434548B CN 101434548 B CN101434548 B CN 101434548B CN 2008101745923 A CN2008101745923 A CN 2008101745923A CN 200810174592 A CN200810174592 A CN 200810174592A CN 101434548 B CN101434548 B CN 101434548B
- Authority
- CN
- China
- Prior art keywords
- dinitrobenzene
- reaction
- kettle
- diaminobenzene
- catalyst
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a method for preparing diaminobenzene by using dinitro benzene which refers to paradinitrobenzene or m-dinitrobenzene. The method comprises the steps as follows: the dinitro benzene is added into a kettle firstly and then ethanol and a supported catalyst are added; the kettle is closed and air in the kettle is replaced by using hydrogen; then normal pressure is maintained in the kettle and heating and mixing are carried out; the hydrogen is introduced into the kettle after temperature in the kettle reaches 60 DEG C so as to lead the pressure in the kettle to be maintained at 1.0 MPa to 3.0 MPa and then hydrogenation reaction is started; a conversion ratio can reach 95 percent to more than 99 percent after the hydrogenation for about 3 hours to 8 hours and then a reacted mixture and the catalyst are separated out; the catalyst separated is returned to the kettle for continuous use to supplement the lost catalyst; reaction product separation is carried out to the reacted mixture which is a clear solution so as to obtain the diaminobenzene.
Description
Technical field
The present invention relates to the method for preparing diaminobenzene from dinitro benzene, dinitrobenzene described here is meant paradinitrobenzene, or Meta-dinitrobenzene.
Background technology
Nitro-compound is through being reduced to aminocompound; Be method preparation the earliest through iron powder and hydrochloric acid; This method is seriously polluted, and for country expressly provides the operational path that will abolish at no distant date, most of in recent years this type of produced and all adopted Raney's nickel catalyst; Promptly be that catalyzer passes through shortening and realizes by nitro having following shortcoming to amino conversion but use Raney's nickel catalyst to carry out shortening with the Raney's nickel:
1) uses extremely inconvenience.Because carrying out the Raney's nickel catalyst of shortening, to have active composition be skeleton nickel; But skeleton nickel is very easily caught fire in air; Can't preserve; Can only be with nickel-Al alloy powder form as commodity, need aluminium be dissolved away with alkali before using, under the condition of secluding air, add reaction system behind the wash clean; In addition, the catalytic activity of Raney's nickel is often because of different the changing a lot of treatment condition (dissolving and wash conditions like alkali).
Its byproduct of reaction amount is bigger when 2) using Raney's nickel catalyst, and product yield is low.The Raney's nickel catalyst hydrogenation makes nitro be converted into the amino higher temperature that often needs; General temperature requiredly to be higher than 100 ℃; And the product amino compound that hydrogenation generates is being higher than the easy by product (being referred to as tar in the industry) that generates under 100 ℃ of temperature; This makes product yield reduce on the one hand, also possibly have influence on reaction on the other hand and normally carry out.
3) the catalyst consumption amount is big.Because the raney ni catalysis activity is low, the catalytic amount of required adding is bigger, and is extremely difficult because of catalyst recovery on the other hand, causes the consumption of catalyzer excessive, causes production cost higher.
4) exist huge potential safety hazard in the production.Because Raney's nickel sees that air is prone to catch fire, careless slightly in the operation will presence of fire; There is hydrogen in the hydrogenation workshop simultaneously, very easily blasts.
Summary of the invention
The present invention provides a kind of prior art deficiency that overcomes, and has the method for the preparing diaminobenzene from dinitro benzene of higher-security and higher yields.
Among the present invention; The method of preparing diaminobenzene from dinitro benzene is: in reaction kettle, add earlier dinitrobenzene, ethanol and loaded catalyst respectively; The amount of alcohol that wherein adds is 10～30% of the dinitrobenzene quality that adds, and the nickel catalyst carried amount of adding was carried out hydrogenation reaction 3～8 hours for 3～6% of the dinitrobenzene quality that adds at 60～90 ℃; Hydrogenation reaction pressure is 1.5～3.0MPa; Reaction is carried out solid-liquid separation after accomplishing, and separated liquid supernatant is carried out the product separation, and isolated solid catalyst is failed back reaction system again and continued to use.
The method that dinitrobenzene shortening of the present invention prepares diaminobenzene can be after reaction is accomplished, to change reaction mass over to the insulation jar to be incubated sedimentation, isolates supernatant and carries out the product separation, obtains dinitrobenzene; By new dinitrobenzene and the ethanol of aforementioned quantities adding, will from be incubated jar, fail back reaction kettle continuation use again by isolated bottom solidliquid mixture (catalyzer and a small amount of reaction mixture) simultaneously in the reaction kettle.
The method that dinitrobenzene shortening of the present invention prepares diaminobenzene can also be that the supported catalyst dosage that adds is 4% of dinitrobenzene quality, and temperature of reaction is 90 ℃, and the still internal pressure during hydrogenation is 1.5MPa.
Method of the present invention has adopted the load-type nickel hydrogenation catalyst; The aerial kindling temperature of this catalyzer is greater than 150 ℃; Because catalyzer of the present invention carried out purification process with the blended inert gas, make its part be in passive state, so it can safe storage; The use that in use can directly feed intake need not to carry out activation treatment again.Through actual measurement, its hydrogenation catalyst starting temperature of catalyzer of the present invention is 60 ℃, and the hydrogenation catalyst temperature of reaction is lower than 100 ℃, and can be used for all kinds of nitro-compound hydrogenation catalysts.Because catalyst temperature of reaction of the present invention less than 100 ℃, therefore can avoid in reactant, generating polymers such as tar fully, and reaction is carried out continuously; Test also shows; Catalyzer of the present invention can be reused, and this catalyzer consumption in use is lower than existing all kinds of catalyzer, also is lower than 6504K catalyzer and 0104G catalyzer; And its catalytic effect is higher than existing all kinds of catalyzer, therefore has tangible cost advantage.Pressure during shortening of the present invention is also lower, from after to chat embodiment visible, hydrogenation pressure is merely 1.5MPa in its optimised process, this pressure obviously will be lower than prior art.In addition, visible from the present invention, this method can also be simplified whole production technique.
Embodiment
Embodiment: preparing diaminobenzene from dinitro benzene
The dinitrobenzene that in reaction kettle, adds earlier 100 grams, 20% the concentration that adds the dinitrobenzene quality again is 95% ethanol, adds 3～6% loaded catalyst of dinitrobenzene quality again; Closed reactor with the air in the complete replacement reaction kettle of hydrogen, keeps being in the still normal pressure (being about 0.1MPa) then; And beginning heated and stirred; Feed hydrogen after temperature reaches 60 ℃ in the still, make the still internal pressure remain to 1.0～3.0MPa (test shows that its optimum pressure should be about 1.5MPa), the beginning hydrogenation reaction; Temperature in the kettle remains in 60～90 ℃ of scopes in hydrogenation process; Hydrogenation after about 3 to 8 hours transformation efficiency promptly reach more than 95～99%, isolate reaction mixture and catalyzer then, isolated catalyzer returns reaction kettle and continue to use; The catalyzer of replenish loss amount, test show that the catalytic amount that at every turn only need add is about 30 milligrams; To reaction mixture, promptly clear liquid carries out the reaction product separation, obtains about 61～64 grams of diaminobenzene.In the present invention, the concrete grammar that is adopted is earlier to change reaction system in insulation slurry tank sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding is 4% of the dinitrobenzene quality that adds, and the still internal pressure during hydrogenation is 1.5Mpa, and when temperature of reaction was 90 ℃, transformation efficiency promptly reached more than 99.0% in 4 hours.
The used supported catalyst preparation method of the present invention (also can be called the Chinese invention patent application of " a kind of method for preparing catalyst and catalyzer that is used for catalytic hydrogenation of nitro compound " referring to name) as follows about loaded catalyst of the present invention:
The used supported catalyst preparation method of the present invention (also can be called the Chinese invention patent application of " a kind of method for preparing catalyst and catalyzer that is used for catalytic hydrogenation of nitro compound " referring to name) as follows about loaded catalyst of the present invention:
The diatomaceous processing of A
Find according to experiment, very big as the impurity in the zeyssatite of carrier to the influence of catalyzer, and wherein with the influence of iron for; For effectively removing the iron in the zeyssatite, generally all adopt acid cleaning process, but find according to relevant test; Zeyssatite is handled and has been adopted following technology that best effect can be arranged; It not only can effectively remove impurity wherein, particularly iron, but also can make catalyst product that best catalytic effect is arranged:
Earlier zeyssatite is added volume ratio and be its 3 times, concentration is to stir in 3～20% the aqueous hydrochloric acid, is warmed up to 90 ℃ of continued again and stirs 1 hour, leaches zeyssatite also with the laggard capable drying treatment of water washing, obtains the zeyssatite as support of the catalyst.
Show through detecting, handle resulting zeyssatite in total hole volume 0.15～0.4ml/g scope through the present invention; Its specific surface area is 120～200m
2/ g.Show that according to test it is 10% best that zeyssatite is handled used best aqueous hydrochloric acid concentration.
The B Preparation of catalysts
Nickel is processed nitrate salt earlier, be mixed with the aqueous solution of 1M again, the amount of getting nickel is 45～58% a nickel salt aqueous solution of catalyzer final product quality; Add the silica aqueous solution that contains silicon-dioxide 20% again; The amount of the silica aqueous solution that is added should guarantee to make silica volume wherein to account for 1～4% of catalyzer final product quality, and system is heated to 50～80 ℃, 35～55% of adding catalyzer final product quality zeyssatite under agitation condition; PH value with system transfers to 7.5～8.5 again; Under 50～80 ℃ of conditions, stirred 12～16 hours, carry out solid-liquid separation after the cooling, resulting solid is handled with the laggard capable granulating and drying of water washing; Use hydrogen reduction at 500～700 ℃, under cooling conditions, carry out obtaining the catalyzer finished product after the Passivation Treatment with the Air mixing inert gas that contains volume ratio 5% again.
In the above preparation process, nickel is 55% with catalyzer final product quality ratio in the nitrate salt of used nickel, and system temperature is 60 ℃ in the reaction, and the pH value transfers to 7.8, can obtain the catalyzer of best catalytic effect when the hydrogen reduction temperature is 550 ℃.
The catalyzer actual measurement parameter that obtains through above-mentioned technology is following:
(1) nickel content is 45～58% (the best is 55%);
(2) bulk density is 0.6～0.9g/ml (optimum value is 0.75);
(3) total hole volume 0.15～0.4ml/g (optimum value is 0.35);
(4) specific surface area 120～200m
2(optimum value is 160m to/g
2/ g);
(5) nickel crystal size 40～200
(optimum value be 60
);
(6) catch fire in the air 170 ℃ of warm spots
(7) reduction ratio (Ni0/NiO) 60～80% (optimum value is 70%).
Catalyzer of the present invention and foreign similar catalyst contrast test data see the following form:
| Catalyzer of the present invention | Germany Louis that Company products 6504K | U.S. An Geer Company products 0104G | |
| Nickel content (%) | 55 | 58 | 58 |
| Specific surface area (m 2/g) | 158 | 129 | 109 |
| Total pore volume (ml/g) | 0.36 | 0.36 | 0.35 |
| Bulk density (g/cm 3) | 11.7 | 11.7 | 11.6 |
| Brilliant size (the A of nickel 0) | 55～65 | 55～65 | 55～65 |
| Spontaneous ignition temperature (C 0) | ≥150 | ≥150 | ≥150 |
| The hydrogenation catalyst starting temperature | ≥60 | ≥90 | ≥90 |
Claims (3)
1. the dinitrobenzene shortening prepares the method for diaminobenzene; It is characterized in that in reaction kettle, adding dinitrobenzene, ethanol and loaded catalyst; The amount of alcohol that wherein adds is 10～30% of the dinitrobenzene quality that adds, and the nickel catalyst carried amount of adding was carried out hydrogenation reaction 3～8 hours for 3～6% of the dinitrobenzene quality that adds at 60～90 ℃; Hydrogenation reaction pressure is 1.5～3.0MPa; Reaction is carried out solid-liquid separation after accomplishing, and separated liquid supernatant is carried out the product separation, and isolated solid is failed back reaction system again and continued to use; Described nickel catalyst carried preparation method is: nickel is processed nitrate salt earlier; Be mixed with the aqueous solution of 1M again; The amount of getting nickel is 45～58% a nickel salt aqueous solution of catalyzer final product quality, adds the silica aqueous solution that contains silicon-dioxide 20% again, and the amount of the silica aqueous solution that is added should guarantee to make silica volume wherein to account for 1～4% of catalyzer final product quality; System is heated to 50～80 ℃; Under agitation condition, add the catalyzer final product quality 35～55%, through the zeyssatite that cleanup acid treatment is crossed, the pH value with system transfers to 7.5～8.5 again, under 50～80 ℃ of conditions, stirs 12～16 hours; Carry out solid-liquid separation after the cooling; Resulting solid is handled with the laggard capable granulating and drying of water washing, uses hydrogen reduction at 500～700 ℃, under cooling conditions, carries out obtaining the catalyzer finished product after the Passivation Treatment with the Air mixing inert gas that contains volume ratio 5% again.
2. dinitrobenzene shortening according to claim 1 prepares the method for diaminobenzene, it is characterized in that changing reaction mass over to the insulation jar after reaction is accomplished is incubated sedimentation, isolates supernatant and carries out the product separation, obtains diaminobenzene; The interior aforementioned quantities of pressing of reaction kettle adds new dinitrobenzene and ethanol, will from the insulation jar, fail back reaction kettle continuation use again by isolated bottom solidliquid mixture simultaneously.
3. dinitrobenzene shortening according to claim 1 and 2 prepares the method for diaminobenzene, it is characterized in that the supported catalyst dosage that adds is 4% of dinitrobenzene quality, and temperature of reaction is 90 ℃, and the still internal pressure during hydrogenation is 1.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745923A CN101434548B (en) | 2008-11-07 | 2008-11-07 | Method for preparing diaminobenzene from dinitro benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745923A CN101434548B (en) | 2008-11-07 | 2008-11-07 | Method for preparing diaminobenzene from dinitro benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101434548A CN101434548A (en) | 2009-05-20 |
| CN101434548B true CN101434548B (en) | 2012-03-21 |
Family
ID=40709202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101745923A Expired - Fee Related CN101434548B (en) | 2008-11-07 | 2008-11-07 | Method for preparing diaminobenzene from dinitro benzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101434548B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942485B (en) * | 2012-10-25 | 2014-12-10 | 浙江龙盛化工研究有限公司 | Method for m-dinitrobenzene refinement and effective byproduct utilization |
| CN104592036B (en) * | 2014-12-24 | 2016-10-26 | 上海安赐环保科技股份有限公司 | A kind of Nitrobenzol, dinitro benzene catalyst recovery devices and recovery method thereof |
| CN110467534A (en) * | 2019-09-17 | 2019-11-19 | 四川北方红光特种化工有限公司 | A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141912A (en) * | 1996-05-09 | 1997-02-05 | 河南省科学院化学研究所 | Preparation aromatic amine compound |
| CN1762588A (en) * | 2005-09-26 | 2006-04-26 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
| CN1850329A (en) * | 2006-05-30 | 2006-10-25 | 华东师范大学 | Load-type nickel-metal catalyst and its use |
-
2008
- 2008-11-07 CN CN2008101745923A patent/CN101434548B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141912A (en) * | 1996-05-09 | 1997-02-05 | 河南省科学院化学研究所 | Preparation aromatic amine compound |
| CN1762588A (en) * | 2005-09-26 | 2006-04-26 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
| CN1850329A (en) * | 2006-05-30 | 2006-10-25 | 华东师范大学 | Load-type nickel-metal catalyst and its use |
Non-Patent Citations (3)
| Title |
|---|
| Jose Relvas.Liquid Phase hydrogenation of nitrobenzene over an industrial Ni/SiO2 supported catalyst.《Catalysis Today》.2008,(第133期),全文. * |
| yunfeng Zheng.A Green Reduction of Aromatic Nitro Compounds to Aromatic Amines Over a Novel Ni/SiO2 Catalyst Passivated with a Gas Mixture.《Catal Lett》.2008,(第124期),全文. * |
| 刘迎新.Ni/SiO2催化剂上间二硝基苯液相加氢制间苯二胺.《催化学报》.2003,第24卷(第3期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101434548A (en) | 2009-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| USRE44175E1 (en) | Process for preparing 4-aminodiphenylamines | |
| US8735635B2 (en) | Process for making 1, 2-propane diol from hydrogenation of glycerol | |
| CN101434550B (en) | Method for preparing 1-naphthylamine from 1-nitronaphthalene | |
| CN101434547B (en) | Method for preparing aniline from nitrobenzene | |
| CN101481314B (en) | Method for preparing X substituted aniline from X substituted nitrobenzene | |
| CN101434548B (en) | Method for preparing diaminobenzene from dinitro benzene | |
| CN101475488B (en) | Method for preparing aminotoluene by catalytic hydrogenation of 2,4-dinitrotoluene or/and 2,6-dinitrotoluene | |
| CN101434549B (en) | Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene | |
| CN102952022A (en) | Method for continuously preparing tolylenediamine by utilizing dinitrotoluene, catalyst used in method and preparation method of catalyst | |
| CN100465145C (en) | Process of preparing 1,4-cyclohexane dimethand | |
| CN102050746A (en) | Method for preparing o-chloroaniline | |
| CN101439285B (en) | Method for preparing catalyst for catalytic hydrogenation of nitro compound and catalyst | |
| CN101323579A (en) | Method for preparing m-phenylenediamine | |
| CN101659618A (en) | Preparation method of pentamethyldiethylenetriamine | |
| CN103894188B (en) | A kind of preparation method and applications of palladium-resin C catalyst | |
| CN101514162B (en) | Method for preparing X-substituted diaminobenzene from X-substituted dinitrobenzene | |
| CN100439324C (en) | One-step method for preparing N-alkyl aromatic amine from aromatic nitro substance | |
| CN103992230B (en) | Oil of mirbane mixture containing dinitrobenzene prepares the method for diaminobenzene and aniline | |
| CN110372516A (en) | A method of preparing cyclohexylamine | |
| CN106892829A (en) | The method that p-nitrophenol catalytic hydrogenation prepares para-aminophenol | |
| CN101481315B (en) | Method for preparing X substituted diamino naphthalin from X substituted 1,4-dinitronaphthalene | |
| CN101475489B (en) | Method for preparing X substituted 1-naphthylamine from X substituted 1-nitronaphthalene | |
| CN104193624A (en) | Method of preparing aminotoluene by subjecting 2,4-dinitrotoluene and 2,6-dinitrotoluene to catalytic hydrogenation | |
| CN103804202A (en) | Method for preparing diaminotoluene through catalytic hydrogenation | |
| CN109160871B (en) | Method for preparing n-amyl alcohol by hydrogenation of gamma-valerolactone |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120321 Termination date: 20181107 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |