CN103819346A - Production equipment and production technology of precursor of 4-aminodiphenylamine - Google Patents
Production equipment and production technology of precursor of 4-aminodiphenylamine Download PDFInfo
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- CN103819346A CN103819346A CN201410098622.2A CN201410098622A CN103819346A CN 103819346 A CN103819346 A CN 103819346A CN 201410098622 A CN201410098622 A CN 201410098622A CN 103819346 A CN103819346 A CN 103819346A
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- mirbane
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Abstract
The invention relates to a production technology of a precursor of 4-aminodiphenylamine. The technology comprises the following steps: respectively processing and degassing nitrobenzene and phenylamine through an alkali metal oxide or a hydroxide; continuously feeding the processed phenylamine and concentrated quaternary ammonium alkali catalyst to a tubular condensation reactor by flow measurement according to a certain ratio after concentrating the quaternary ammonium alkali catalyst in vacuum; firstly, reacting the phenylamine to form aniline anions; continuously adding the processed nitrobenzene at different positions of the tubular condensation reactor from a plurality of points and controlling the water yield, so that the anions generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine condensed liquid by replacing hydrogen reaction on nitrobenzene by nucleophilic addition. The technology disclosed by the invention is reasonable in steps and composition and advanced in equipment, and is used raw material enters a continuous production device of a high-efficiency reactor pipeline after being pretreated under a totally-enclosed condition, so as to produce the 4-nitrosodiphenylamine and the 4-nitrodiphenylamine.
Description
Technical field
The present invention relates to a kind of precursor of 4-ADPA, be specially by aniline and directly react synthetic with oil of mirbane, reaction is caused by alkali, it forms aniline negatively charged ion by reaction, and negatively charged ion is prepared production technique and the equipment of 4-nitrosodiphenylamine and 4 nitrodiphenyl amine by the hydrogen on nucleophilic addition substituted-nitrobenzene subsequently.
Background technology
4-nitrosodiphenylamine and 4-nitrodiphenylamine are a kind of precursors of producing the 4-ADPA with antiozonidate, oxidation inhibitor and stablizer that is widely used in.
In prior art, preparation of industrialization 4-nitrosodiphenylamine and 4-nitrodiphenylamine majority are directly to be reacted with oil of mirbane by aniline using quaternary ammonium hydroxide as alkali.Patent CN1193010A disclose a kind of alkali containing oxyhydroxide and/or oxide groups and heterogeneous catalyst exist under and under inertia aprotonic solvent exists, the method for use hydrogen hydrogenation oil of mirbane under the pressure of 0～200 ℃ and 0.1～150 bar.Although existing method has realized highly selective and high yield, exist due to resolution problem under quaternary ammonium hydroxide poor heat stability high temperature; In prior art, also useful compound alkali as a catalyst is realized industrialization, but while existing reaction to finish, there is solid matter to separate out to cause the obstruction of pipeline and pump, and reclaim and have certain difficulty while separating at compound alkaline catalysts, because having mineral alkali and salt will guarantee finite concentration, catalyzer be difficult for thoroughly separated cause consume high, want fully to reclaim and must water consumption strengthen, catalyst concn will too lowly cause when concentrated energy consumption very large, comparatively difficulty of the analysis of each component content when catalyst recirculation after recovery is used, the accuracy of proportioning is poor.
Summary of the invention
The present invention directly with oil of mirbane reacts preparation 4-nitrosodiphenylamine using quaternary ammonium hydroxide as alkali by aniline for solution is existing and 4-nitrodiphenylamine catalyzer easily decomposes and reclaims difficult, further reduce the problem of energy consumption and raw material consumption, provide a kind of and utilized known advantage and eliminated their shortcoming, processing step composition rationally, under the advanced fully-closed state of equipment by raw materials used carrying out entered to high efficiency reactor pipeline continuous production device manufacture 4-nitrosodiphenylamine and 4-nitrodiphenylamine technique after pre-treatment.
The present invention is achieved through the following technical solutions:
The present invention is respectively by alkalimetal oxide or hydroxide treatment and degassed by oil of mirbane, aniline; Quaternary Ammonium Alkali Catalyst is after concentrated under vacuum, aniline after treatment with concentrated after Quaternary Ammonium Alkali Catalyst enter continuously tubular type condensation reactor by flow metering according to a certain ratio, first make aniline reaction form aniline negatively charged ion, the complex compound that adds continuously oil of mirbane after treatment to make negatively charged ion generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine and Quaternary Ammonium Alkali Catalyst formation by the H-H reaction on nucleophilic addition substituted-nitrobenzene at tubular type condensation reactor different positions multiple spot is subsequently condensated liquid (for the preparation of the precursor of 4-ADPA).
Season, ammonia alkali catalyzer was quaternary ammonium hydroxide Tetramethylammonium hydroxide.
Enter oil of mirbane before condensation reaction, aniline respectively by alkalimetal oxide or hydroxide treatment and degassed, object is removed and in raw material, is dissolved and acidic substance and the part of absorption are unfavorable for that oil of mirbane, aniline condensation reaction generate the gas of object product.
Through alkalimetal oxide or hydroxide treatment and degassed after aniline enter continuously by a certain percentage after vacuum state concentrating unit by controlling flow with Quaternary Ammonium Alkali Catalyst by a certain percentage by controlling flow, converge and enter continuously static mixer and fully mix and finally enter tubular type condensation reactor (inner with heat transfer tube) and form aniline negatively charged ion through row dehydration and reaction, oil of mirbane adds at tubular type condensation reactor different positions multiple spot, along with three kinds of raw materials enter the mixture of reactor continuously through the increase of tubular type condensation reactor distance, water content can reduce gradually, condensation reaction meeting is progressively accelerated.
For effectively controlling the amount of side reactions such as generating nitrogen benzide, azophenlyene, by control dehydrating amount to the last generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine and the complex compound mixture of quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer formation be in condensated liquid remaining nitrobenzene 1-2%, the amount that this mode has not only been controlled side reaction has also effectively suppressed the decomposition of quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer, and remaining oil of mirbane and on a small quantity nitrogen benzide can all generate aniline by follow-up shortening and recycle after separating.
The tubular type condensation reactor that the present invention adopts, Lower Half composes in parallel by organizing heat-exchanging tube bundle more, ensure enough heat interchanging areas water in vaporization reaction system at a lower temperature, top multiple spot is provided with Despumation device, the aniline that reactor is distilled out--water azeotrope shifts out reaction system in time in steam state mode, ensures that reaction is to expecting that object product direction moves.
In condensation reaction, have two-step reaction, the first step is caused by quaternary ammonium hydroxide Tetramethylammonium hydroxide, first makes aniline reaction form aniline negatively charged ion; Second step oil of mirbane makes negatively charged ion generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine by the H-H reaction on nucleophilic addition substituted-nitrobenzene, because having water, second step reaction generates, and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer is to enter reaction system with aqueous solution state, want to make second step reaction smooth, must guarantee that oil of mirbane adds a water-content to be less than certain value, take to add mode at tubular type condensation reactor different positions multiple spot, control nitro by difference heat-exchanging tube bundle
Benzene adds water-content a little, makes oil of mirbane enter reaction system and is fully reacted with shortest time highly selective.
The processing parameter of condensation reaction control is: quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer vacuum state thickening temperature is: 72-78(℃), pressure (vacuum tightness)-0.085～-0.095(Mpa), concentrated rear content 35%-36%(weight); The proportioning of oil of mirbane, quaternary ammonium hydroxide Tetramethylammonium hydroxide and aniline is 1:1-10:20-100(mole), optimum ratio is 1:1-4:20-60(mole), this proportioning is a dynamic proportioning at tubular type condensation reactor different positions take oil of mirbane as benchmark; Oil of mirbane drips water yield control in some reaction system: oil of mirbane is 1:4-6(mole with water ratio), water herein refers to water of hydration (being crystal water) water in addition; Reaction pressure (vacuum tightness)-0.096--0.1(Mpa); Temperature of reaction is 40-85(℃), the best is 60-78(℃); In tubular type condensation reactor, residence time of material is 1-3(hour); Oil of mirbane residual volume 1-2%(quality in condensated liquid).
The present invention carries out pre-treatment and removes and in raw material, dissolve and acidic substance and the part of absorption are unfavorable for oil of mirbane take oil of mirbane and aniline as raw material, the gas of aniline condensation reaction, multipoint mode adds oil of mirbane, and control oil of mirbane residual volume when oil of mirbane drips some reaction system water-content and condensation reaction termination, effectively suppress the yield that improved of side reaction, reduce going bad and consuming of expensive season ammonia alkali Tetramethylammonium hydroxide catalyzer, remaining oil of mirbane can all generate aniline by follow-up shortening with a small amount of nitrogen benzide and recycle after separating, reaction preference is greater than 99%, under fully-closed state, move, continuity is strong, level of automation is high, labour intensity is low, environmental pollution is little, equipment corrosion is little, energy consumption is low is to be conducive to ecological and economical better technical scale technique and device.
A production unit for the precursor of 4-ADPA, comprises vacuum outgas washing tank device, vacuum concentrating apparatus, flow rate control device, static mixer, pressure control device, tubular type condensation reactor;
Wherein, vacuum outgas washing tank device comprises aniline vacuum outgas washing tank, oil of mirbane vacuum outgas washing tank; Quaternary Ammonium Alkali Catalyst enters vacuum concentrating apparatus through flow rate control device, and aniline enters aniline vacuum outgas washing tank through flow rate control device; Quaternary Ammonium Alkali Catalyst after vacuum concentration, aniline after the degassed pre-treatment of vacuum outgas washing tank, after pipeline converges, connect static mixer, static mixer is through connecting pipe of pipeline formula condensation reactor;
Oil of mirbane enters oil of mirbane vacuum outgas washing tank through flow rate control device, and oil of mirbane vacuum outgas washing tank is through connecting pipe of pipeline formula reactor; Pressure control device one end connects tubular type condensation reactor, and the other end connects aniline---water storage tank;
Tubular type condensation reactor, Lower Half composes in parallel by organizing heat-exchanging tube bundle more, and top multiple spot is provided with Despumation device; On tubular type condensation reactor, be provided with condensated liquid discharge port.
Accompanying drawing explanation
Accompanying drawing is the process flow sheet of the production technology and equipments of a kind of 4-nitrosodiphenylamine and 4-nitrodiphenylamine;
Wherein: 1, vacuum concentrating apparatus, 2, aniline vacuum outgas washing tank, 3 oil of mirbane vacuum outgas washing tanks, 4, static mixer, 5 heat transfer tubes, 6 tubular type condensation reactors, 7 Despumation devices, 8, pressure control device, 9, aniline---water storage tank, 10, condensated liquid discharge port.
Embodiment
Embodiment (industrialized unit embodiment)
First open oil of mirbane, aniline, quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyst transport pump is 13.2 cubic meters/hour by Flow-rate adjustment control aniline flow, oil of mirbane flow is 2 cubic meters/hour, respectively continuously by the vacuum outgas washing tank processing of alkali metal hydroxide (30%NaOH) is housed, object is to remove in raw material to dissolve and acidic substance and the part of absorption are unfavorable for oil of mirbane, the gas of aniline condensation reaction, through alkali metal hydroxide process and degassed after oil of mirbane (adding 4 of tubular type condensation reactor different positionss) respectively be 0.6 cubic meter/hour from starting point, 0.6 cubic meter/hour, 0.5 cubic meter/hour, 0.3 cubic meter/hour, through alkali metal hydroxide process and degassed after aniline and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer enter continuously after vacuum state concentrating unit and enter through static mixer and arrive tubular type condensation reactor (inside is with heat transfer tube) by controlling 6 cubic meters/hour of flows, control reaction pressure (vacuum tightness)-0.096(Mpa), temperature of reaction is 76(℃), material is 3(hour through the tubular type condensation reactor time), along with oil of mirbane can reduce through the increase water content of tubular type condensation reactor distance gradually in adding with streams of tubular type condensation reactor difference, condensation reaction meeting is progressively accelerated, by control deviate from the water yield until in condensated liquid the remaining mass content of oil of mirbane be 1-2%, now by-product nitrogen benzide, azophenlyene equivalent are minimum, and finally generating the complex compound mixture that 4-nitrosodiphenylamine and 4-nitrodiphenylamine and quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer form is condensated liquid.Be 99.06% with respect to transform portion oil of mirbane selectivity.
The processing parameter of condensation reaction control is: quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer vacuum state thickening temperature is: 72-78(℃), pressure (vacuum tightness)-0.085～-0.095(Mpa), concentrated rear content 35%-36%(weight); The proportioning of oil of mirbane, quaternary ammonium hydroxide Tetramethylammonium hydroxide and aniline is 1:1-10:20-100(mole), optimum ratio is 1:1-4:20-60(mole), this proportioning is a dynamic proportioning at tubular type condensation reactor different positions take oil of mirbane as benchmark; Oil of mirbane drips water yield control in some reaction system: oil of mirbane and water of hydration (being crystal water) water is in addition than being 1:4-6(mole); Reaction pressure (vacuum tightness)-0.096--0.1(Mpa); Temperature of reaction is 40-85(℃), the best is 60-78(℃); In tubular type condensation reactor, residence time of material is 1-3(hour); Oil of mirbane residual volume 1-2%(quality in condensated liquid).
Claims (7)
1. a production technique for the precursor of 4-ADPA, is characterized in that: oil of mirbane, aniline are passed through respectively to alkalimetal oxide or hydroxide treatment and degassed; Quaternary Ammonium Alkali Catalyst is after concentrated under vacuum, aniline after treatment with concentrated after Quaternary Ammonium Alkali Catalyst enter continuously tubular type condensation reactor by flow metering according to a certain ratio, first make aniline reaction form aniline negatively charged ion, add continuously the nitro benzo control water yield after treatment at tubular type condensation reactor different positions multiple spot subsequently, make negatively charged ion generate 4-nitrosodiphenylamine and 4-nitrodiphenylamine condensated liquid by the H-H reaction on nucleophilic addition substituted-nitrobenzene.
2. production technique according to claim 1, is characterized in that: oil of mirbane, season ammonia alkali catalyzer and mole proportioning of aniline be 1:1-10:20-100, preferred mole of proportioning is 1:1-4:20-60.
3. production technique according to claim 1, is characterized in that: in oil of mirbane dropping point reaction system, water yield control oil of mirbane and water mol ratio are 1:4-6.
4. production technique according to claim 1, is characterized in that: reaction pressure is-0.096～-0.1Mpa; Temperature of reaction is 40～85 ℃, and the best is 60～78 ℃; In tubular type condensation reactor, residence time of material is 1-3 hours.
5. production technique according to claim 1, is characterized in that: the remaining mass content 1-2% of oil of mirbane in condensated liquid.
6. production technique according to claim 1, is characterized in that: quaternary ammonium hydroxide Tetramethylammonium hydroxide catalyzer vacuum state thickening temperature is: 72～78 ℃, pressure is-0.085～-0.095Mpa, concentrated rear weight content 35%～36%.
7. a production unit for the precursor of 4-ADPA, is characterized in that: comprise vacuum outgas washing tank device, vacuum concentrating apparatus, flow rate control device, static mixer, pressure control device, tubular type condensation reactor;
Wherein, vacuum outgas washing tank device comprises aniline vacuum outgas washing tank, oil of mirbane vacuum outgas washing tank; Quaternary Ammonium Alkali Catalyst enters vacuum concentrating apparatus through flow rate control device, and aniline enters aniline vacuum outgas washing tank through flow rate control device; Quaternary Ammonium Alkali Catalyst after vacuum concentration, aniline after the degassed pre-treatment of vacuum outgas washing tank, after pipeline converges, connect static mixer, static mixer is through connecting pipe of pipeline formula condensation reactor;
Oil of mirbane enters oil of mirbane vacuum outgas washing tank through flow rate control device, and oil of mirbane vacuum outgas washing tank is through connecting pipe of pipeline formula reactor; Pressure control device one end connects tubular type condensation reactor, and the other end connects aniline---water storage tank;
Tubular type condensation reactor, Lower Half composes in parallel by organizing heat-exchanging tube bundle more, and top multiple spot is provided with Despumation device; On tubular type condensation reactor, be provided with condensated liquid discharge port.
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Cited By (4)
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| CN107686449A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | Reducing tubular type reactor assembly and the method with its 4 nitrodiphenylamine of preparation and 4 nitrosodiphenylamines |
| CN109232275A (en) * | 2018-10-26 | 2019-01-18 | 科迈化工股份有限公司 | A kind of preparation method of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine |
| CN114478202A (en) * | 2022-02-16 | 2022-05-13 | 江苏飞宇医药科技股份有限公司 | Method for continuously preparing 2- (2,2, 2-trifluoroethoxy) phenol |
| CN116554038A (en) * | 2022-11-10 | 2023-08-08 | 圣奥化学科技有限公司 | Polyalkyl p-phenylenediamine anti-aging agent, intermediate thereof and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686449A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | Reducing tubular type reactor assembly and the method with its 4 nitrodiphenylamine of preparation and 4 nitrosodiphenylamines |
| CN109232275A (en) * | 2018-10-26 | 2019-01-18 | 科迈化工股份有限公司 | A kind of preparation method of 4 nitrodiphenyl amine and 4- nitrosodiphenylamine |
| CN109232275B (en) * | 2018-10-26 | 2021-06-11 | 科迈化工股份有限公司 | Preparation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine |
| CN114478202A (en) * | 2022-02-16 | 2022-05-13 | 江苏飞宇医药科技股份有限公司 | Method for continuously preparing 2- (2,2, 2-trifluoroethoxy) phenol |
| CN116554038A (en) * | 2022-11-10 | 2023-08-08 | 圣奥化学科技有限公司 | Polyalkyl p-phenylenediamine anti-aging agent, intermediate thereof and preparation method thereof |
| CN116554038B (en) * | 2022-11-10 | 2024-04-12 | 圣奥化学科技有限公司 | Polyalkyl p-phenylenediamine anti-aging agent, intermediate thereof and preparation method thereof |
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