CN101434549A - Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene - Google Patents
Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene Download PDFInfo
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- CN101434549A CN101434549A CNA2008101745938A CN200810174593A CN101434549A CN 101434549 A CN101434549 A CN 101434549A CN A2008101745938 A CNA2008101745938 A CN A2008101745938A CN 200810174593 A CN200810174593 A CN 200810174593A CN 101434549 A CN101434549 A CN 101434549A
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- dinitronaphthalene
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- diaminonaphthalene
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Abstract
The invention discloses a method for preparing 1, 4-diaminonaphthalene by using 1, 4-dinitronaphthalene. The method is that the 1,4-dinitronaphthalene, ethanol and a supported catalyst are respectively added into a kettle firstly, wherein, the mass of the ethanol added is 10 percent to 30 percent of that of the 1,4-dinitronaphthalene and the mass of the supported nickel catalyst added is 3 percent to 6 percent of that of the 1, 4-dinitronaphthalene; hydrogenation reaction is carried out at the temperature of 60 DEG C to 90 DEG C for 3 hours to 8 hours and the pressure of the hydrogenation reaction is 1.5 MPa to 3.0 MPa; solid-liquid separation is conducted after the completion of the reaction; product separation is carried out to a supernatant solution separated; and a solid catalyst separated is input into the reaction system for continuous use again.
Description
Technical field
The present invention relates to 1,4-dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene.
Background technology
Nitro-compound is by being reduced to aminocompound, be method preparation the earliest by iron powder and hydrochloric acid, this method is seriously polluted, expressly provide the operational path that to abolish at no distant date for country, most of in recent years this type of produced and all adopted Raney's nickel catalyst, promptly be that catalyzer passes through with the Raney's nickel, shortening and realize by nitro having following shortcoming but use Raney's nickel catalyst to carry out shortening to amino conversion:
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 as commodity with nickel-Al alloy powder form, need before the use aluminium to be dissolved away, under the condition of secluding air, add reaction system behind the wash clean with alkalescence; In addition, the catalytic activity of Raney's nickel often because of treatment condition (as alkali molten with wash conditions) different changing a lot.
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 easy by product (the industrial tar that is referred to as that generates under 100 ℃ of temperature, this makes product yield reduce on the one hand, also may 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 manufacturing cost higher.
4) exist huge potential safety hazard in the production.Because Raney's nickel sees that air easily catches 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 invention provides a kind of prior art deficiency that overcomes, have 1 of higher-security and higher yields, 4-dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene.
Among the present invention, 1,4-dinitronaphthalene preparation 1, the method of 4-diaminonaphthalene is: add 1 respectively earlier in reactor, the 4-dinitronaphthalene, ethanol and loaded catalyst, wherein the amount of alcohol of Jia Ruing is 1 of adding, 10～30% of 4-dinitronaphthalene quality, the nickel catalyst carried amount that adds is 1 of adding, and 3～6% of 4-dinitronaphthalene quality was carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, carry out solid-liquid separation after reaction is finished, separated liquid supernatant is carried out the product separation, and isolated solid is failed back reaction system again and continued to use.
Of the present invention 1,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene can be reaction mass to be changed over to insulation after reaction is finished jar to be incubated sedimentation, isolates supernatant liquor and carries out product and separate, and obtains 1, the 4-dinitronaphthalene; Add in the reactor newly 1 by aforementioned quantities, 4-dinitronaphthalene and ethanol will fail back reactor continuation use again from isolated bottom solidliquid mixture the insulation jar simultaneously.
Of the present invention 1,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene can also be that the supported catalyst dosage that adds is 1,4% of 4-dinitronaphthalene quality, temperature of reaction is 90 ℃, 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 has carried out purification process with the blended inert gas, make its part be in passive state, therefore 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 is less than 100 ℃, therefore can avoid in reactant, generating polymers such as tar fully, 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 chat embodiment as seen, hydrogenation pressure only is 1.5MPa in its optimised process, this pressure obviously will be lower than prior art.In addition, from the present invention as seen, this method can also be simplified whole production technique.
Embodiment
Embodiment: 1,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene
In reactor, add 100 grams 1 earlier, the 4-dinitronaphthalene, add 1 again, 20% concentration of 4-dinitronaphthalene quality is 95% ethanol, add 1 again, 3～6% loaded catalyst of 4-dinitronaphthalene quality, closed reactor, with the air in the complete replacement reaction kettle of hydrogen, keep 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 reactor 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 50 milligrams; To reaction mixture, promptly clear liquid carries out the reaction product separation, obtains 1,4-diaminonaphthalene 69～72 grams.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows that in above-mentioned reaction process, the supported catalyst dosage of adding is 1 of adding, and 4% of 4-dinitronaphthalene quality, the still internal pressure during hydrogenation are 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 following (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 " about loaded catalyst of the present invention) referring to name:
The used supported catalyst preparation method of the present invention following (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 " about loaded catalyst of the present invention) referring to name:
The diatomaceous processing of A
Find according to experiment, very big as the impurity in the diatomite of carrier to the influence of catalyzer, and wherein with the influence of iron for, for effectively removing the iron in the diatomite, generally all adopt acid cleaning process, but find according to relevant test, diatomite is handled and has been adopted following technology that best effect can be arranged, it not only can effectively remove wherein impurity, particularly iron, but also can make catalyst product that best catalytic effect is arranged:
Earlier diatomite is added volume ratio and be its 3 times, concentration is to stir in 3～20% the aqueous hydrochloric acid, continues stirring 1 hour after being warmed up to 90 ℃ again, leach diatomite and wash with water after carry out drying treatment, obtain diatomite as support of the catalyst.
Show after testing, handle resulting diatomite 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 diatomite is handled used best aqueous hydrochloric acid concentration.
The B Preparation of catalysts
Nickel is made nitrate 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, system is heated to 50～80 ℃, 35～55% of adding catalyzer final product quality diatomite 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, carrying out granulating and drying after resulting solid washes with water handles, 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 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 as follows:
(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～
(optimum value is
);
(6) catch fire in the air 170 ℃ of warm spots
(7) reduction ratio (NiO/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 | The Germany Louis product 6504K of that company | The product 0104G of U.S. An Geer company | |
| 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)
1,1,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method of 4-diaminonaphthalene, it is characterized in that in reactor, adding 1, the 4-dinitronaphthalene, ethanol and loaded catalyst, wherein the amount of alcohol of Jia Ruing is 1 of adding, 10～30% of 4-dinitronaphthalene quality, the nickel catalyst carried amount that adds is 1 of adding, and 3～6% of 4-dinitronaphthalene quality was carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, carry out solid-liquid separation after reaction is finished, separated liquid supernatant is carried out the product separation, and isolated solid is failed back reaction system again and continued to use.
2, according to claim 11,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene, it is characterized in that changing reaction mass over to the insulation jar after reaction is finished is incubated sedimentation, isolate supernatant liquor and carry out the product separation, obtain 1, the 4-diaminonaphthalene; Add in the reactor newly 1 by aforementioned quantities, 4-dinitronaphthalene and ethanol will fail back reactor continuation use again from isolated bottom solidliquid mixture the insulation jar simultaneously.
3, according to claim 1 and 21,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene, it is characterized in that the supported catalyst dosage that adds is 1,4% of 4-dinitronaphthalene quality, temperature of reaction is 90 ℃, the still internal pressure during hydrogenation is 1.5MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745938A CN101434549B (en) | 2008-11-07 | 2008-11-07 | Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745938A CN101434549B (en) | 2008-11-07 | 2008-11-07 | Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene |
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| Publication Number | Publication Date |
|---|---|
| CN101434549A true CN101434549A (en) | 2009-05-20 |
| CN101434549B CN101434549B (en) | 2012-05-23 |
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|---|---|---|---|
| CN2008101745938A Expired - Fee Related CN101434549B (en) | 2008-11-07 | 2008-11-07 | Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430416A (en) * | 2010-11-16 | 2012-05-02 | 江苏恒祥化工有限责任公司 | Catalyst for catalytic hydrogenation of 1,8-dinitronaphthalene to prepare 1,8-diaminonaphthalene and preparation method thereof |
| CN106238099A (en) * | 2016-08-22 | 2016-12-21 | 常州大学 | The preparation method and application of 1,5 dinitronaphthalene hydrogenation catalysts |
| CN106467467A (en) * | 2016-08-26 | 2017-03-01 | 南通龙翔化工有限公司 | A kind of method that fixed bed continuous catalytic hydrogenation prepares diaminonaphthalene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60230097D1 (en) * | 2001-05-08 | 2009-01-15 | Mitsui Chemicals Polyurethanes | PROCESS FOR THE PREPARATION OF 1,5-DIAMINONAPHTHALINES |
-
2008
- 2008-11-07 CN CN2008101745938A patent/CN101434549B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430416A (en) * | 2010-11-16 | 2012-05-02 | 江苏恒祥化工有限责任公司 | Catalyst for catalytic hydrogenation of 1,8-dinitronaphthalene to prepare 1,8-diaminonaphthalene and preparation method thereof |
| CN102430416B (en) * | 2010-11-16 | 2013-11-06 | 江苏恒祥化工有限责任公司 | Catalyst for catalytic hydrogenation of 1,8-dinitronaphthalene to prepare 1,8-diaminonaphthalene and preparation method thereof |
| CN106238099A (en) * | 2016-08-22 | 2016-12-21 | 常州大学 | The preparation method and application of 1,5 dinitronaphthalene hydrogenation catalysts |
| CN106238099B (en) * | 2016-08-22 | 2019-07-09 | 常州大学 | The preparation method and application of 1,5- dinitronaphthalene hydrogenation catalyst |
| CN106467467A (en) * | 2016-08-26 | 2017-03-01 | 南通龙翔化工有限公司 | A kind of method that fixed bed continuous catalytic hydrogenation prepares diaminonaphthalene |
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|---|---|
| CN101434549B (en) | 2012-05-23 |
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Granted publication date: 20120523 Termination date: 20181107 |