CN101481315B - Method for preparing X substituted diamino naphthalin from X substituted 1,4-dinitronaphthalene - Google Patents
Method for preparing X substituted diamino naphthalin from X substituted 1,4-dinitronaphthalene Download PDFInfo
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- CN101481315B CN101481315B CN2008101742060A CN200810174206A CN101481315B CN 101481315 B CN101481315 B CN 101481315B CN 2008101742060 A CN2008101742060 A CN 2008101742060A CN 200810174206 A CN200810174206 A CN 200810174206A CN 101481315 B CN101481315 B CN 101481315B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing X substituted 1, 4-diaminonaphthalene by X substituted 1, 4-dinitronaphthalene; wherein the X can be any one of -F, -Cl, -Br, -OCH3, -OH or-R, R is saturated hydrocarbyl with one or more carbons, the position of X in 1, 4-dinitronaphthalene is the sixth or ninth position. The method comprises the following steps: X substituted 1, 4-dinitronaphthalene, ethanol and a supported catalyst are added into a reaction kettle; wherein the mass of the added ethanol is 10-30% of the mass of the added 1, 4-dinitronaphthalene and the mass of the added supported nickel catalyst is 3-6% of the mass of the added 1, 4-dinitronaphthalene; hydrogenation reaction is carried out for 3-8 hours at the temperature between 60 and 90 DEG C under the pressure of 1.5-3.0MPa; solid-liquid separation is carried out after the reaction is finished; products are separated from the separated supernatant fluid and the separated solid catalyst is transferred back to a reaction system for recycling.
Description
Technical field
It is substituted 1 to the present invention relates to X, and it is substituted 1 that the 4-schneiderite prepares X, the method for 4-diaminonaphthalene, wherein X can be-F ,-Cl ,-Br ,-OCH
3,-OH, perhaps-among the R any, R is the saturated hydrocarbyl of 1 carbon or 1 above carbon, X is 1, the position in the 4-schneiderite is 6 or 9.
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 the shortening realization by the conversion of nitro to amino, have following shortcoming 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 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 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 it is substituted 1 to have an X of higher-security and higher yields, and it is substituted 1 that the 4-schneiderite prepares X, the method for 4-diaminonaphthalene.
Among the present invention, X is substituted 1, and the 4-schneiderite prepares X substituted 1; The method of 4-diaminonaphthalene is: it is substituted 1 in reaction kettle, to add earlier X respectively, 4-schneiderite, ethanol and loaded catalyst, the X substituted 1 of the amount of alcohol that wherein adds for adding; 10～30% of 4-schneiderite quality, the nickel catalyst carried amount of adding is substituted 1 for the X that adds, 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 catalyst is failed back reaction system again and continued to use.
X of the present invention substituted 1; It is substituted 1 that the 4-catalytic hydrogenation of dinitronaphthalene prepares X, and 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 carry out product and separate; It is substituted 1 to obtain X, the 4-schneiderite; It is substituted 1 to add new X by aforementioned quantities in the reaction kettle, and 4-schneiderite and ethanol will fail back reaction kettle continuation use from isolated bottom solidliquid mixture (catalyzer and a small amount of reaction back mixture) the insulation jar simultaneously again.
X of the present invention substituted 1; It is substituted 1 that the 4-catalytic hydrogenation of dinitronaphthalene prepares X, and the method for 4-diaminonaphthalene can also be that the supported catalyst dosage that adds is that X is substituted 1,4% of 4-schneiderite quality; 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 1:-F is substituted 1, and 4-catalytic hydrogenation of dinitronaphthalene preparation-F is substituted 1, the 4-diaminonaphthalene, wherein-and F is 1, and the position in the 4-schneiderite is 6.
It is substituted 1 in reaction kettle, to add earlier the F of 100 grams, the 4-schneiderite, and adding-F substituted 1 again; 20% concentration of 4-schneiderite quality is 95% ethanol, and adding-F is substituted 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 99.0%; 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 90 milligrams; To reaction mixture, promptly clear liquid carries out reaction product and separates, obtain-F is substituted 1,4-diaminonaphthalene 73 grams～76 grams.In the present invention, the concrete grammar that is adopted is to change in the insulation slurry tank reaction system over to sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-F is substituted 1,4% of 4-schneiderite quality, the still internal pressure during hydrogenation are 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency promptly reached more than 99.0% in 4 hours.
Embodiment 2:-Cl is substituted 1, and 4-catalytic hydrogenation of dinitronaphthalene preparation-Cl is substituted 1, the 4-diaminonaphthalene, and wherein F is 1, and the position in the 4-schneiderite is 9.
In reaction kettle, add earlier 100 grams-Cl is substituted 1, the 4-schneiderite, adding-Cl substituted 1 again; 20% concentration of 4-schneiderite quality is 95% ethanol, and adding-Cl is substituted 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 90 milligrams; To reaction mixture, promptly clear liquid carries out reaction product and separates, obtain-Cl is substituted 1,4-diaminonaphthalene 72 grams～75 grams.In the present invention, the concrete grammar that is adopted is to change in the insulation slurry tank reaction system over to sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-Cl substituted 1; 4% of 4-schneiderite quality; 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.
Embodiment 3:-Br is substituted 1, and 4-catalytic hydrogenation of dinitronaphthalene preparation-Br is substituted 1, the 4-diaminonaphthalene, wherein-and Br is 1, and the position in the 4-schneiderite is 9.
In reaction kettle, add earlier 100 grams-Br is substituted 1, the 4-schneiderite adds Br substituted 1 again; 20% concentration of 4-schneiderite quality is 95% ethanol, and it is substituted 1 to add Br 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 90 milligrams; To reaction mixture, promptly clear liquid carries out reaction product and separates, obtain-Br is substituted 1,4-diaminonaphthalene 76 grams～79 grams.In the present invention, the concrete grammar that is adopted is to change in the insulation slurry tank reaction system over to sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-Br substituted 1; 4% of 4-schneiderite quality; 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.
Embodiment 4:-OCH
3Substituted 1,4-catalytic hydrogenation of dinitronaphthalene preparation-OCH
3Substituted 1, the 4-diaminonaphthalene, wherein-OCH
31, the position in the 4-schneiderite is 9.
Adding 100 restrains in reaction kettle earlier-OCH
3Substituted 1,4-schneiderite, adding-OCH again
3Substituted 1,20% concentration of 4-schneiderite quality is 95% ethanol, adding-OCH again
3Substituted 1,3～6% loaded catalyst of 4-schneiderite quality, closed reactor; With the air in the complete replacement reaction kettle of hydrogen, keep then being normal pressure (being about 0.1MPa) in the still, and the 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 90 milligrams; To reaction mixture, promptly clear liquid carries out the reaction product separation, obtains-OCH
3Substituted 1,4-diaminonaphthalene 72 grams～75 grams.In the present invention, the concrete grammar that is adopted is to change in the insulation slurry tank reaction system over to sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-OCH
3Substituted 1,4% of 4-schneiderite quality, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency promptly reached more than 99.0% in 4 hours.
Embodiment 5:-OH is substituted 1, and 4-catalytic hydrogenation of dinitronaphthalene preparation-OH is substituted 1, the 4-diaminonaphthalene, wherein-and OH is 1, and the position in the 4-schneiderite is 9.
In reaction kettle, add earlier 100 grams-OH is substituted 1, the 4-schneiderite, adding-OH substituted 1 again; 20% concentration of 4-schneiderite quality is 95% ethanol, and adding-OH is substituted 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 90 milligrams; To reaction mixture, promptly clear liquid carries out reaction product and separates, obtain-OH is substituted 1,4-diaminonaphthalene 74 grams～77 grams.In the present invention, the concrete grammar that is adopted is to change in the insulation slurry tank reaction system over to sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-OH substituted 1; 4% of 4-schneiderite quality; 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.
Embodiment 6:-C
2H
5Substituted 1,4-catalytic hydrogenation of dinitronaphthalene preparation-C
2H
5Substituted 1, the 4-diaminonaphthalene, wherein-C
2H
51, the position in the 4-schneiderite is 9.
Adding 100 restrains in reaction kettle earlier-C
2H
5Substituted 1,4-schneiderite, adding-C again
2H
5Substituted 1,20% concentration of 4-schneiderite quality is 95% ethanol, adding-C again
2H
5Substituted 1,3～6% loaded catalyst of 4-schneiderite quality, closed reactor; With the air in the complete replacement reaction kettle of hydrogen, keep then being normal pressure (being about 0.1MPa) in the still, and the 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 90 milligrams; To reaction mixture, promptly clear liquid carries out the reaction product separation, obtains-C
2H
5Substituted 1,4-diaminonaphthalene 71 grams～74 grams.In the present invention, the concrete grammar that is adopted is to change in the insulation slurry tank reaction system over to sedimentation to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-C
2H
5Substituted 1,4% of 4-schneiderite quality, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency promptly reached more than 99.0% in 4 hours.
Relevant experiment also shows, adopts method of the present invention to be used for 1 carbon or to substituted 1 more than the stable hydrocarbon of 1 carbon, the 4-schneiderite carries out shortening all has the result similar with aforementioned result.
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
; (optimum value is
);
(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.X substituted 1, it is substituted 1 that the 4-catalytic hydrogenation of dinitronaphthalene prepares X, the method for 4-diaminonaphthalene, and X is-F ,-Cl ,-Br ,-OCH
3,-OH, perhaps-among the R any, R is the saturated hydrocarbyl of 2 above carbon, X is 1; Position in the 4-schneiderite is 6, and it is substituted 1 to it is characterized in that in reaction kettle adding X, 4-schneiderite, ethanol and nickel catalyst carried; The amount of alcohol that wherein adds is substituted 1 for the X that adds, 10～30% of 4-schneiderite quality, the X substituted 1 of the nickel catalyst carried amount of adding for 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; 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 ℃; 35～55% of adding catalyzer final product quality the zeyssatite after acid cleaning process is handled under agitation condition, 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. X substituted 1 according to claim 1; The 4-catalytic hydrogenation of dinitronaphthalene prepares X substituted 1; The method of 4-diaminonaphthalene 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; It is substituted 1 to obtain X, the 4-diaminonaphthalene; It is substituted 1 to add new X by aforementioned quantities in the reaction kettle, and 4-schneiderite and ethanol will fail back reaction kettle continuation use from isolated bottom solidliquid mixture the insulation jar simultaneously again.
3. X substituted 1 according to claim 1 and 2; The 4-catalytic hydrogenation of dinitronaphthalene prepares X substituted 1; The method of 4-diaminonaphthalene is characterized in that the supported catalyst dosage that adds is that X is substituted 1,4% of 4-schneiderite quality; Temperature of reaction is 90 ℃, and the still internal pressure during hydrogenation is 1.5MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101742060A CN101481315B (en) | 2008-11-07 | 2008-11-07 | Method for preparing X substituted diamino naphthalin from X substituted 1,4-dinitronaphthalene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101742060A CN101481315B (en) | 2008-11-07 | 2008-11-07 | Method for preparing X substituted diamino naphthalin from X substituted 1,4-dinitronaphthalene |
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| CN101481315B true CN101481315B (en) | 2012-05-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112792A (en) * | 1989-05-16 | 1992-05-12 | Lok Cornelis M | Nickel/silica catalyst and the preparation and use thereof |
| CN1100403A (en) * | 1994-05-07 | 1995-03-22 | 营口市江汇化工厂 | Iron powder-adding preparation process of 1.5,1.8-diamido naphthalene mixture |
| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| 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 |
-
2008
- 2008-11-07 CN CN2008101742060A patent/CN101481315B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112792A (en) * | 1989-05-16 | 1992-05-12 | Lok Cornelis M | Nickel/silica catalyst and the preparation and use thereof |
| CN1100403A (en) * | 1994-05-07 | 1995-03-22 | 营口市江汇化工厂 | Iron powder-adding preparation process of 1.5,1.8-diamido naphthalene mixture |
| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Yunfeng Zheng et al..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),268-276. * |
| 胡涛等.不同载体上的镍催化剂的氢化性能研究.《食品与机械》.2005,第21卷(第3期),21-23. * |
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