CN101434550A - Method for preparing 1-naphthylamine from 1-nitronaphthalene - Google Patents
Method for preparing 1-naphthylamine from 1-nitronaphthalene Download PDFInfo
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- CN101434550A CN101434550A CNA2008101745919A CN200810174591A CN101434550A CN 101434550 A CN101434550 A CN 101434550A CN A2008101745919 A CNA2008101745919 A CN A2008101745919A CN 200810174591 A CN200810174591 A CN 200810174591A CN 101434550 A CN101434550 A CN 101434550A
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Abstract
The invention discloses a method for preparing 1-naphthylamine by using 1-nitro-naphthalene. The method is that the 1-nitrobenzene 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 displaced 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 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 1-naphthylamine.
Description
Technical field
The present invention relates to the method that the 1-nitro-naphthalene prepares naphthalidine.
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 realizes having following shortcoming by the conversion of nitro to amino but use Raney's nickel catalyst to carry out shortening by 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 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 alkali; 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 production 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, the 1-nitro-naphthalene with higher-security and higher yields prepares the method for naphthalidine.
Among the present invention, the method that the 1-nitro-naphthalene prepares naphthalidine is: add earlier 1-nitro-naphthalene, ethanol and loaded catalyst in reactor respectively, wherein the amount of alcohol of Jia Ruing is 10～30% of the 1-nitro-naphthalene quality that adds, the nickel catalyst carried amount that adds is 3～6% of the 1-nitro-naphthalene quality that adds, carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, after finishing, reaction carries out solid-liquid separation, 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 1-nitro-naphthalene shortening of the present invention prepares naphthalidine can be to change reaction mass over to the insulation jar to be incubated sedimentation after reaction is finished, and isolates supernatant liquor and carries out the product separation, obtains the 1-nitro-naphthalene; By new 1-nitro-naphthalene and the ethanol of aforementioned quantities adding, will from be incubated jar, fail back reactor continuation use again by isolated bottom solidliquid mixture (catalyzer and a small amount of reaction mixture) simultaneously in the reactor.
The method that 1-nitro-naphthalene shortening of the present invention prepares naphthalidine can also be that the supported catalyst dosage that adds is 4% of 1-nitro-naphthalene 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 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-nitro-naphthalene shortening prepares the method for naphthalidine
In reactor, add 100 gram 1-oil of mirbane earlier, 20% the concentration that adds 1-oil of mirbane quality again is 95% ethanol, 3～6% the loaded catalyst that adds 1-nitro-naphthalene quality again, closed reactor, with the air in the complete replacement reaction kettle of hydrogen, keep being in the still normal pressure (about 0.1MPa) then, and beginning heated and stirred, after reaching 60 ℃, temperature feeds hydrogen 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 95～99%, isolate reaction mixture and catalyzer then, isolated catalyzer returns reactor 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 80 milligrams; To reaction mixture, promptly clear liquid carries out the reaction product separation, obtains naphthalidine 79～82 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, in above-mentioned reaction process, the supported catalyst dosage of adding is 4% of the 1-nitro-naphthalene 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 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-nitro-naphthalene shortening prepares the method for naphthalidine, it is characterized in that in reactor, adding 1-nitro-naphthalene, ethanol and loaded catalyst, wherein the amount of alcohol of Jia Ruing is 10～30% of the 1-nitro-naphthalene quality that adds, the nickel catalyst carried amount that adds is 3～6% of the 1-nitro-naphthalene quality that adds, carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, after finishing, reaction carries out solid-liquid separation, separated liquid supernatant is carried out the product separation, and isolated solid is failed back reaction system again and continued to use.
2,1-nitro-naphthalene shortening according to claim 1 prepares the method for naphthalidine, it is characterized in that changing reaction mass over to the insulation jar after reaction is finished is incubated sedimentation, isolates supernatant liquor and carries out the product separation, obtains naphthalidine; The interior aforementioned quantities of pressing of reactor adds new 1-nitro-naphthalene and ethanol, will fail back reactor continuation use again by isolated bottom solidliquid mixture from the insulation jar simultaneously.
3,1-nitro-naphthalene shortening according to claim 1 and 2 prepares the method for naphthalidine, it is characterized in that the supported catalyst dosage that adds is 4% of 1-nitro-naphthalene 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 |
|---|---|---|---|
| CN2008101745919A CN101434550B (en) | 2008-11-07 | 2008-11-07 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745919A CN101434550B (en) | 2008-11-07 | 2008-11-07 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101434550A true CN101434550A (en) | 2009-05-20 |
| CN101434550B CN101434550B (en) | 2012-11-14 |
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|---|---|---|---|
| CN2008101745919A Expired - Fee Related CN101434550B (en) | 2008-11-07 | 2008-11-07 | Method for preparing 1-naphthylamine from 1-nitronaphthalene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304053A (en) * | 2011-07-22 | 2012-01-04 | 湖南化工研究院 | Preparation method for synthesizing naphthylamine by catalytic hydrogenation |
| CN106946712A (en) * | 2017-03-10 | 2017-07-14 | 江苏华达化工集团有限公司 | The method that fixed bed hydrogenation method produces 1 amino naphthalenes |
| CN107304166A (en) * | 2016-04-25 | 2017-10-31 | 常州市春港化工有限公司 | The industrialized process for preparing of naphthalidine |
| CN107540553A (en) * | 2016-06-23 | 2018-01-05 | 南京大学 | A kind of method that 1 nitronaphthalene catalytic hydrogenation prepares 1 naphthylamines |
-
2008
- 2008-11-07 CN CN2008101745919A patent/CN101434550B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304053A (en) * | 2011-07-22 | 2012-01-04 | 湖南化工研究院 | Preparation method for synthesizing naphthylamine by catalytic hydrogenation |
| CN107304166A (en) * | 2016-04-25 | 2017-10-31 | 常州市春港化工有限公司 | The industrialized process for preparing of naphthalidine |
| CN107304166B (en) * | 2016-04-25 | 2020-05-01 | 九江常宇化工有限公司 | Industrial preparation method of 1-naphthylamine |
| CN107540553A (en) * | 2016-06-23 | 2018-01-05 | 南京大学 | A kind of method that 1 nitronaphthalene catalytic hydrogenation prepares 1 naphthylamines |
| CN107540553B (en) * | 2016-06-23 | 2020-04-24 | 南京大学 | Method for preparing 1-naphthylamine by catalytic hydrogenation of 1-nitronaphthalene |
| CN106946712A (en) * | 2017-03-10 | 2017-07-14 | 江苏华达化工集团有限公司 | The method that fixed bed hydrogenation method produces 1 amino naphthalenes |
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| CN101434550B (en) | 2012-11-14 |
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