CN101434549B - 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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- CN101434549B CN101434549B CN2008101745938A CN200810174593A CN101434549B CN 101434549 B CN101434549 B CN 101434549B CN 2008101745938 A CN2008101745938 A CN 2008101745938A CN 200810174593 A CN200810174593 A CN 200810174593A CN 101434549 B CN101434549 B CN 101434549B
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- schneiderite
- nickel
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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-schneiderite preparation 1, the method for 4-diaminonaphthalene.
Background technology
Nitro-compound is through being reduced to aminocompound; Be the method preparation through iron powder and hydrochloric acid the earliest, this method is seriously polluted, expressly provides the operational path that will 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 with nickel-Al alloy powder form as commodity, need aluminium be dissolved away with alkalescence 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 prone to generate by product and (is referred to as tar in the industry being higher than 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 manufacturing 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 1 of higher-security and higher yields, 4-schneiderite preparation 1, the method for 4-diaminonaphthalene.
Among the present invention, 1,4-schneiderite preparation 1; The method of 4-diaminonaphthalene is: in reaction kettle, add 1 respectively earlier, and 4-schneiderite, ethanol and loaded catalyst, the amount of alcohol that wherein adds is 1 of adding; 10～30% of 4-schneiderite quality, the nickel catalyst carried amount of adding is 1 of adding, 3～6% of 4-schneiderite quality; Carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, and reaction is carried out solid-liquid separation after accomplishing; 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 after reaction is accomplished, to change reaction mass over to insulation jar to be incubated sedimentation, isolates supernatant and carries out product and separate, and obtains 1, the 4-schneiderite; Add in the reaction kettle newly 1 by aforementioned quantities, 4-schneiderite and ethanol will fail back reaction kettle continuation use from isolated bottom solidliquid mixture the insulation jar simultaneously again.
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-schneiderite 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 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: 1,4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene
In reaction kettle, add 100 grams 1 earlier, the 4-schneiderite adds 1 again; 20% concentration of 4-schneiderite quality is 95% ethanol, adds 1 again, 3～6% loaded catalyst of 4-schneiderite quality; 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 the beginning heated and stirred, after reaching 60 ℃, temperature feeds hydrogen in the still, and 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 to be continued to use, the catalyzer of replenish loss amount, and test shows 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-schneiderite 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 (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)
1.4-catalytic hydrogenation of dinitronaphthalene preparation 1, the method for 4-diaminonaphthalene is characterized in that in reaction kettle, adding 1; 4-schneiderite, ethanol and nickel catalyst carried, the amount of alcohol that wherein adds is 1 of adding, 10～30% of 4-schneiderite quality; The nickel catalyst carried amount that adds is 1 of adding, and 3～6% of 4-schneiderite quality was carried out hydrogenation reaction 3～8 hours 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 35～55% the zeyssatite of handling through acid cleaning process of catalyzer final product quality, 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. 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 accomplished is incubated sedimentation; Isolate supernatant and carry out the product separation, obtain 1, the 4-diaminonaphthalene; Add in the reaction kettle newly 1 by aforementioned quantities, 4-schneiderite and ethanol will fail back reaction kettle continuation use from isolated bottom solidliquid mixture the insulation jar simultaneously again.
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-schneiderite quality, temperature of reaction is 90 ℃, the still internal pressure during hydrogenation is 1.5MPa.
Priority Applications (1)
| 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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| CN101434549B true CN101434549B (en) | 2012-05-23 |
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| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464874A (en) * | 2001-05-08 | 2003-12-31 | 三井化学株式会社 | Process for preparation of 1,5-diaminonaphthalenes |
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| CN1464874A (en) * | 2001-05-08 | 2003-12-31 | 三井化学株式会社 | Process for preparation of 1,5-diaminonaphthalenes |
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