CN1861570A - Tech. of preparing amino benz methyl-phenoxide by nitro methyl-phenoxide mixture catalyzing hydrogenation - Google Patents
Tech. of preparing amino benz methyl-phenoxide by nitro methyl-phenoxide mixture catalyzing hydrogenation Download PDFInfo
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- CN1861570A CN1861570A CN 200610085490 CN200610085490A CN1861570A CN 1861570 A CN1861570 A CN 1861570A CN 200610085490 CN200610085490 CN 200610085490 CN 200610085490 A CN200610085490 A CN 200610085490A CN 1861570 A CN1861570 A CN 1861570A
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Abstract
A process for preparing amino phenylmether from nitro phenylmether mixture by catalytic hydrogenating includes such steps as catalytic hydroreducing reaction between methanol, nitro phenylmether mixture and catalyst, recovering catalyst, decoloring, removing impurities, filtering to obtain liquid phase (the solution of amino phenylmether, methanol and water), separation and refining.
Description
Technical field
The present invention relates to a kind of technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine, belong to the fine chemical technology field.
Background technology
Anisidine (being mainly 2-anisidine and 4-anisidine) is important organic synthesis intermediate.At present, the preparation of 2-anisidine and 4-anisidine is a raw material with 2-Nitroanisole and 4-Nitroanisole respectively usually, make through sodium sulphite reduction or iron powder reducing, this technology exists following shortcoming: consumption is big, cost is high, quality is low, especially waste water, waste sludge discharge amount are big, cause serious environmental to pollute.If the waste water, the waste residue that produce are handled, have so just been increased processing cost, but also existed the hidden danger of secondary pollution.
Summary of the invention
The objective of the invention is shortcoming, provide a kind of production cost low, the technology that good product quality, particularly the production process three wastes are few with Nitroanisole mixture through catalytic hydrogenation preparing anisidine at the prior art existence.
The technical scheme that realizes above-mentioned purpose is: a kind ofly prepare the technology of anisidine with Nitroanisole, described processing step is as follows:
The first step, being solvent with methyl alcohol, is raw material with 2-Nitroanisole and 4-nitrobenzoyl ether mixture, under the catalyzer existence condition, feeds hydrogen, carries out continuously or the reaction of intermittent type catalytic hydrogenating reduction;
Second step, after catalytic hydrogenating reduction reaction finishes, solid-liquid separation is carried out in cooling, pressure release, reaction mass is transported to catalyst recovery devices reclaims catalyzer, the catalyzer of recovery can be recycled, and the material of sloughing catalyzer enters next step;
The 3rd step, in sloughing the material of catalyzer, add the decolouring cleaner, carry out adsorption bleaching and remove miscellaneous operation;
The material that the 4th step, process adsorption bleaching remove miscellaneous operation adopts solid-liquid separating method separation such as filtration, and solid phase is mainly the decolouring cleaner, after regenerating, can be recycled; Liquid phase is mainly the solution of anisidine, first alcohol and water, can prepare corresponding 2-anisidine and 4-aminobenzoic ether product through behind the separation and purification.
Further, described nitrobenzoyl ether mixture can be the mixture of 2-Nitroanisole and 4-Nitroanisole arbitrary proportion, and in the described the first step catalytic hydrogenating reduction reaction, catalyzer is Raney-Ni, also can be Pd-C;
A) further, the reactor of the catalytic hydrogenating reduction reaction in the described the first step is the three-phase fixed-bed catalytic
Reactor also can be the three-phase fluidized bed catalyticreactor, also can be placed in-line stirred-tank reactor, also can be step stirred-tank reactor.
Further, in the described catalytic hydrogenating reduction reaction, granules of catalyst is 0.001mm～10.0mm, and controlled temperature is 60 ℃～160 ℃ during reaction, and working pressure is 1.0MPa～10.0MPa;
Further, the catalyst recovery devices in described second step is the vane type filtration device.
Further, described adsorption bleaching removal of impurities is sorbent materials such as activated carbon, diatomite and molecular sieve, also can be the mixture of two components or three components wherein, and decolouring removal of impurities and filtering temperature are 40-80 ℃.
Chemical equation of the present invention is:
Realize that the main technique equipment that the present invention needs is: catalytic hydrogenating reduction reactor, catalyst recovery devices, solvent recovery unit, Crystallization Separation device etc.
Adopt the benefit of technique scheme to be: (1), utilize Raney-Ni or Pd-C to carry out the catalytic hydrogenating reduction reaction for catalyzer, it is a kind of process for cleanly preparing, little to equipment corrosion, can improve operating environment, reduce advantages such as pollutions, technological process safety, reliable, ten minutes environmental protection; (2, the methyl alcohol of catalytic hydrogenating reduction reaction makees solvent, has the reaction system of reduction viscosity, improves the dispersion state of catalyzer in material and improves heat transfer process, helps improving reaction process, control reaction temperature; (3), adopt three phase fixed bed catalyst chambers, three-phase fluidized bed catalyticreactor, shorten the reaction times, the outer setting interchanger, not only can heat but also can cool off, heat-transfer effect is good, and its stopping property is better than agitator reaction still, can be used for periodical operation, also can be used for operate continuously, improve temperature of reaction and reaction pressure, improve the dispersion state of catalyzer in material, improve reaction process; (4), can realize large-scale industrial production; (5), employed hydrogen can adopt the hydrogen that produced in the methyl alcohol catalyzing manufacturing of hydrogen technology source of supply as hydrogen.(6), per pass conversion can reach more than 85% in the catalytic hydrogenating reduction reaction, owing to adopt filter blade device efficiently, has improved the organic efficiency of catalyzer simultaneously, has reduced the loss of catalyzer, makes the organic efficiency of catalyzer reach 99.5%.In a word, the present invention is a kind of process for cleanly preparing, and preparation technology has cleaning, reliable, and the product yield height, quality is good, purity is high, and production cost is low, advantages such as environmental protection.Have remarkable economic efficiency, environmental benefit and technological competitiveness.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below by embodiment.
Main technique equipment is: catalytic hydrogenating reduction reactor, catalyst recovery devices, solvent recovery unit, Crystallization Separation device etc.Wherein the catalytic hydrogenating reduction reactor can be selected three phase fixed bed catalyst chambers for use, also can select the three-phase fluidized bed catalyticreactor for use, also can select placed in-line stirred-tank reactor for use, also can select step stirred-tank reactor for use, catalyst recovery devices can be selected vane type filtration device and corresponding filtering system for use.
Embodiment one
A kind of 2-Nitroanisole shortening prepares the technology of anisidine, and described processing step is as follows:
1, with methyl alcohol is solvent, it is in three phase fixed bed catalyst chambers of catalyzer that the 2-Nitroanisole is added Raney-Ni, catalyst consumption is 1.0% of a nitro thing, granules of catalyst is 0.9mm, feed the reaction of hydrogen generation catalytic hydrogenating reduction then, hydrogen makes by methyl alcohol catalyzing manufacturing of hydrogen technology, and controlled temperature is 120 ℃ during reaction, and working pressure is 4.0MPa;
2, after the catalytic hydrogenating reduction reaction finishes (is standard no longer to consume hydrogen), carry out solid-liquid separation after cooling, the pressure release, reaction mass is transported to catalyst recovery devices filter blade device and reclaims catalyzer in the filtering system accordingly, the catalyzer that reclaims can be recycled, and the material of sloughing catalyzer enters next step;
3, the material of sloughing catalyzer carries out the separation of liquid liquid, and water carries out rectifying, reclaims methyl alcohol, and oil phase is a 2-anisidine crude product;
4, with methyl alcohol be solvent, 2-anisidine crude product is carried out Crystallization Separation in Crystallization Separation device evaporative crystallization still make with extra care, the amount ratio of 2-anisidine and methyl alcohol is 100g: 250ml, be warmed up to reflux temperature, working pressure is 0.2MPa, under refluxad keep 30min, slowly drop to 0 ℃ then, the crystallization of 2-anisidine is separated out;
5, after solid-liquid separation, isolated mother liquor methyl alcohol are reclaimed by solvent recovery unit, can after filter cake carries out the conventional drying processing, then be the 2-aminobenzoic ether product of preparing directly as the solvent of 2-Nitroanisole catalytic hydrogenation reaction.
Embodiment two
A kind of 4-Nitroanisole shortening prepares the technology of anisidine, and described processing step is as follows:
1, with methyl alcohol is solvent, it is in the three-phase fluidized bed catalyticreactor of catalyzer that the 4-Nitroanisole is added Raney-Ni, catalyst consumption is 4.5% of a nitro thing, granules of catalyst is 1.0mm, feed the reaction of hydrogen generation catalytic hydrogenating reduction then, controlled temperature is 160 ℃ during reaction, and working pressure is 6.0MPa;
2, after the catalytic hydrogenating reduction reaction finishes (is standard no longer to consume hydrogen), carry out solid-liquid separation after cooling, the pressure release, reaction mass is transported to catalyst recovery devices filter blade device and reclaims catalyzer in the filtering system accordingly, the catalyzer that reclaims can be recycled, and the material of sloughing catalyzer enters next step;
3, the material of sloughing catalyzer carries out the separation of liquid liquid, and water carries out rectifying, reclaims methyl alcohol, and oil phase is a 4-anisidine crude product;
4, with methyl alcohol be solvent, 4-anisidine crude product is carried out Crystallization Separation in Crystallization Separation device evaporative crystallization still make with extra care, the amount ratio of 4-anisidine and methyl alcohol is 100g: 250ml, be warmed up to reflux temperature, working pressure is 0.9MPa, under refluxad keep 30min, slowly drop to 30 ℃ then;
5, after solid-liquid separation, isolated mother liquor methyl alcohol are reclaimed by solvent recovery unit, can after filter cake carries out the conventional drying processing, then be the 4-aminobenzoic ether product of preparing directly as the solvent of 4-Nitroanisole catalytic hydrogenation reaction.
Embodiment three
The technology of a kind of 2-Nitroanisole and 4-Nitroanisole mixture through catalytic hydrogenation preparing anisidine, described processing step is as follows:
(1) with methyl alcohol is solvent, with 2-Nitroanisole and 4-Nitroanisole adding Raney-Ni is in three phase fixed bed catalyst chambers of catalyzer, granules of catalyst is 10.0mm, feed the reaction of hydrogen generation catalytic hydrogenating reduction then, controlled temperature is 130 ℃ during reaction, and working pressure is 4.8Mpa;
(2) after the catalytic hydrogenating reduction reaction finishes (is standard no longer to consume hydrogen), carry out solid-liquid separation after cooling, the pressure release, reaction mass is transported to catalyst recovery devices filter blade device and reclaims catalyzer in the filtering system accordingly, the catalyzer that reclaims can be recycled, and the material of sloughing catalyzer enters next step;
(3) material of sloughing catalyzer carries out the separation of liquid liquid, and water carries out rectifying, reclaims methyl alcohol with solvent recovery unit, and oil phase is 2-anisidine and 4-aminobenzoic ether mixture;
(4) 2-anisidine and 4-aminobenzoic ether mixture carry out rising temperature for dissolving in methanol solvate, material is cooled to 10 ℃, the crystallization of 4-anisidine is separated out, is filtered, and filter cake gets 4-aminobenzoic ether product in methanol solvate recrystallizing and refining, vacuum-drying, and purity reaches more than 98%; Previous step has been removed Para-Anisidine liquid material continued to be cooled to 0 ℃, the crystallization of 2-anisidine is separated out, is filtered, and filter cake gets 2-aminobenzoic ether product in methanol solvate recrystallizing and refining, vacuum-drying, and purity reaches more than 98%.
Embodiment four
The technology of a kind of 2-Nitroanisole and 4-Nitroanisole mixture through catalytic hydrogenation preparing anisidine, described processing step is as follows:
(1) with methyl alcohol is solvent, with 2-Nitroanisole and 4-Nitroanisole adding Raney-Ni is that catalyzer is at hydrogenation stirred autoclave (the highest withstand voltage 15MPa), this reactor is equipped with supporting controller, can demonstration or control reaction temperature, pressure and stirring velocity, catalyst consumption is 4.5% of a nitro thing, and granules of catalyst is 1.0mm, feeds the reaction of hydrogen generation catalytic hydrogenating reduction then, controlled temperature is 160 ℃ during reaction, and working pressure is 6.0MPa;
(2) after the catalytic hydrogenating reduction reaction finishes (is standard no longer to consume hydrogen), carry out solid-liquid separation after cooling, the pressure release, reaction mass is transported to catalyst recovery devices filter blade device and reclaims catalyzer in the filtering system accordingly, the catalyzer that reclaims can be recycled, and the material of sloughing catalyzer enters next step;
(3) material of sloughing catalyzer carries out the separation of liquid liquid, and water carries out rectifying, reclaims methyl alcohol with solvent recovery unit, and oil phase is 2-anisidine and 4-aminobenzoic ether mixture;
(4) 2-anisidine and 4-aminobenzoic ether mixture carry out rising temperature for dissolving in methanol solvate, material is cooled to 10 ℃, the crystallization of 4-anisidine is separated out, is filtered, and filter cake gets 4-aminobenzoic ether product in methanol solvate recrystallizing and refining, vacuum-drying, and purity reaches more than 98%; Previous step has been removed Para-Anisidine liquid material continued to be cooled to 0 ℃, the crystallization of 2-anisidine is separated out, is filtered, and filter cake gets 2-aminobenzoic ether product in methanol solvate recrystallizing and refining, vacuum-drying, and purity reaches more than 98%.
Claims (6)
1, a kind of technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine, it is characterized in that: described processing step is as follows:
The first step, being solvent with methyl alcohol, is raw material with 2-Nitroanisole and 4-nitrobenzoyl ether mixture, under the catalyzer existence condition, feeds hydrogen, carries out continuously or the reaction of intermittent type catalytic hydrogenating reduction;
Second step, after catalytic hydrogenating reduction reaction finishes, solid-liquid separation is carried out in cooling, pressure release, reaction mass is transported to catalyst recovery devices reclaims catalyzer, the catalyzer of recovery can be recycled, and the material of sloughing catalyzer enters next step;
The 3rd step, in sloughing the material of catalyzer, add the decolouring cleaner, carry out adsorption bleaching and remove miscellaneous operation;
The material that the 4th step, process adsorption bleaching remove miscellaneous operation adopts solid-liquid separating method separation such as filtration, and solid phase is mainly the decolouring cleaner, after regenerating, can be recycled; Liquid phase is mainly the solution of anisidine, first alcohol and water, can prepare corresponding 2-anisidine and 4-aminobenzoic ether product through behind the separation and purification.
2, the technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine according to claim 1, it is characterized in that: described nitrobenzoyl ether mixture can be the mixture of 2-Nitroanisole and 4-Nitroanisole arbitrary proportion, in the described the first step catalytic hydrogenating reduction reaction, catalyzer is Raney-Ni, also can be Pd-C;
3, the technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine according to claim 1 and 2, it is characterized in that: the reactor of the catalytic hydrogenating reduction reaction in the described the first step is three phase fixed bed catalyst chambers, also the three-phase fluidized bed catalyticreactor can be, also placed in-line stirred-tank reactor can be.
4, the technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine according to claim 1 and 2, it is characterized in that: in the described catalytic hydrogenating reduction reaction, granules of catalyst is 0.001mm～10.0mm, controlled temperature is 60 ℃～160 ℃ during reaction, and working pressure is 1.0MPa～10.0MPa;
5, the technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine according to claim 1 and 2 is characterized in that: the catalyst recovery devices in described second step is the vane type filtration device.
6. the technology of Nitroanisole mixture through catalytic hydrogenation preparing anisidine according to claim 1 and 2, it is characterized in that: the sorbent material that the adsorption bleaching removal of impurities of the 3rd step is adopted is sorbent materials such as activated carbon, diatomite and molecular sieve, it also can be the mixture of two components or three components wherein, decolouring removal of impurities and filtering temperature are 40-80 ℃, and adsorption and decoloration device is a stirring tank.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823972A (en) * | 2010-05-05 | 2010-09-08 | 江苏利田科技有限公司 | Process for cleanly producing o (p) - aminoanisole (phenetidine) by coupling simulated moving bed |
| CN101307003B (en) * | 2008-07-11 | 2011-06-15 | 常州市佳森化工有限公司 | Process for preparing phenetidine and amino phenol by using mixture of nitrophenetol and nitrophenol as raw materials |
| CN102276483A (en) * | 2011-06-30 | 2011-12-14 | 辽宁世星药化有限公司 | Production method of oamino pheylmethyl ether |
| CN101607919B (en) * | 2009-06-22 | 2012-04-25 | 扬州铭睿达化工科技有限公司 | Method for producing aminoanisole by reacting mixed nitrochlorobenzene in aqueous solvent |
| CN105272863A (en) * | 2014-06-11 | 2016-01-27 | 宁夏明盛染化有限公司 | Preparation method for p-anisidine |
| CN106496046A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | The method that solvent-free catalytic hydrogenation produces aminoanisole |
| CN108250085A (en) * | 2014-06-11 | 2018-07-06 | 宁夏明盛染化有限公司 | The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable |
| CN108435208A (en) * | 2018-05-09 | 2018-08-24 | 安庆市鑫富化工有限责任公司 | A kind of regeneration technology of catalyst Raney's nickel and its application |
| CN113024388A (en) * | 2021-03-23 | 2021-06-25 | 宁夏华御化工有限公司 | Preparation method of p-anisidine |
| CN114605274A (en) * | 2022-02-14 | 2022-06-10 | 安徽东至广信农化有限公司 | Production process for synthesizing o-aminoanisole by hydrogenation method |
| CN114773213A (en) * | 2022-03-02 | 2022-07-22 | 安徽东至广信农化有限公司 | Production process of o-aminoanisole |
| CN115591588A (en) * | 2021-07-07 | 2023-01-13 | 中国石油化工股份有限公司（Cn） | Method for recovering liquid phase oxidation catalyst |
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2006
- 2006-06-19 CN CNB2006100854905A patent/CN100475772C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101307003B (en) * | 2008-07-11 | 2011-06-15 | 常州市佳森化工有限公司 | Process for preparing phenetidine and amino phenol by using mixture of nitrophenetol and nitrophenol as raw materials |
| CN101607919B (en) * | 2009-06-22 | 2012-04-25 | 扬州铭睿达化工科技有限公司 | Method for producing aminoanisole by reacting mixed nitrochlorobenzene in aqueous solvent |
| CN101823972A (en) * | 2010-05-05 | 2010-09-08 | 江苏利田科技有限公司 | Process for cleanly producing o (p) - aminoanisole (phenetidine) by coupling simulated moving bed |
| CN101823972B (en) * | 2010-05-05 | 2015-03-25 | 江苏利田科技股份有限公司 | Process for cleanly producing o (p) - aminoanisole (phenetidine) by coupling simulated moving bed |
| CN102276483A (en) * | 2011-06-30 | 2011-12-14 | 辽宁世星药化有限公司 | Production method of oamino pheylmethyl ether |
| CN102276483B (en) * | 2011-06-30 | 2015-04-15 | 辽宁世星药化有限公司 | Production method of oamino pheylmethyl ether |
| CN105272863B (en) * | 2014-06-11 | 2017-12-19 | 宁夏明盛染化有限公司 | The preparation method of paraphenetidine |
| CN105272863A (en) * | 2014-06-11 | 2016-01-27 | 宁夏明盛染化有限公司 | Preparation method for p-anisidine |
| CN108250085A (en) * | 2014-06-11 | 2018-07-06 | 宁夏明盛染化有限公司 | The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable |
| CN106496046A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | The method that solvent-free catalytic hydrogenation produces aminoanisole |
| CN108435208A (en) * | 2018-05-09 | 2018-08-24 | 安庆市鑫富化工有限责任公司 | A kind of regeneration technology of catalyst Raney's nickel and its application |
| CN113024388A (en) * | 2021-03-23 | 2021-06-25 | 宁夏华御化工有限公司 | Preparation method of p-anisidine |
| CN115591588A (en) * | 2021-07-07 | 2023-01-13 | 中国石油化工股份有限公司（Cn） | Method for recovering liquid phase oxidation catalyst |
| CN115591588B (en) * | 2021-07-07 | 2024-03-26 | 中国石油化工股份有限公司 | Method for recovering liquid phase oxidation catalyst |
| CN114605274A (en) * | 2022-02-14 | 2022-06-10 | 安徽东至广信农化有限公司 | Production process for synthesizing o-aminoanisole by hydrogenation method |
| CN114773213A (en) * | 2022-03-02 | 2022-07-22 | 安徽东至广信农化有限公司 | Production process of o-aminoanisole |
| CN114773213B (en) * | 2022-03-02 | 2024-01-02 | 安徽东至广信农化有限公司 | Production process of o-aminoanisole |
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