CN100494159C - Process of producing nitrobenzether aminobenzether amidobenzether from chlorobenzene - Google Patents
Process of producing nitrobenzether aminobenzether amidobenzether from chlorobenzene Download PDFInfo
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Abstract
A process for preparing nitrophenylether, aminophenylether and amidophenylether between chlorobenzene and acid mixture removing water, liquid-liquid separation to obtain organic phase consisting of o-, p- and meta-nitro chlorobenzene compounds, etherifying said mixture, recovering etherifying agent, vacuum distilling, separating and refining meta-nitro chlorobenzene, removing chloride salt generated in etherification, crystallizing separation, recrystallizing p- and o-nitro phenylether compounds, catalytic hydrogenating reaction, nitrifying reaction to obtain 2,4-drinitro phenylether, catalytic hydroreducing reaction to obtain 2,4-diamino phenylether, and aceylating reaction to obtain 2-amino-4-acetylamino phenylether.
Description
Technical field
The present invention relates to a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate, belong to the fine chemical technology field with chlorobenzene.
Background technology
Nitro phenylate, amino phenylate and amido phenylate are the important intermediate of industry such as dyestuff, medicine, spices.
The nitro phenylate; amino phenylate and amido phenylate (mainly are o-Nitrophenyl methyl ethers; p-Nitromethoxybenzene; Ortho Anisidine; Para-Anisidine; 2; 4-dinitrobenzene methyl ether; 2; the 4-diamino anisole; 2-amino-4-acetyl-anisidine etc.) conventional production methods mainly is raw material with the chlorobenzene; the nitro-chlorobenzene mixture is produced in reaction through mixed acid nitrification; the nitro-chlorobenzene mixture gets o-Nitrochlorobenzene respectively through rectifying-Crystallization Separation; m-nitrochlorobenzene and p-Nitrophenyl chloride finished product; p-Nitrophenyl chloride and o-Nitrochlorobenzene carry out the corresponding ortho-nitrophenyl ether of etherification reaction production respectively; the p-nitrophenyl ether product; with p-nitrophenyl ether and ortho-nitrophenyl ether is that raw material adopts methods such as Sodium Sulphide or iron powder reducing; produce adjacent amino phenylate; the p-aminophenyl ether product is that raw material is through acidylate to the amino phenylate of neighbour; two is nitrated; reduction waits reaction to produce products such as amido phenylate.
The committed step of traditional with the chlorobenzene is raw material production nitro phenylate, amino phenylate and amido phenylate is that the nitro-chlorobenzene mixture is produced in reaction through mixed acid nitrification, the nitro-chlorobenzene mixture gets o-Nitrochlorobenzene, m-nitrochlorobenzene and p-Nitrophenyl chloride finished product respectively through rectifying-Crystallization Separation, and o-Nitrochlorobenzene, m-nitrochlorobenzene and p-Nitrophenyl chloride finished product are as the corresponding deep processed product of reaction raw materials production.Though the nitrated production mixing of chlorobenzene nitro-chlorobenzene has sophisticated technology and disposal of three wastes method, but the nitro-chlorobenzene mixture is produced in the sepn process of o-Nitrochlorobenzene, m-nitrochlorobenzene and p-Nitrophenyl chloride through rectifying-Crystallization Separation, the rectifying tower investment is big, the rectifying energy consumption is big, the cost height, make holding at high price of o-Nitrochlorobenzene and p-Nitrophenyl chloride, technical process is long, operational condition is harsh, the operational safety performance is poor, the rectifying tower investment is big, energy consumption is big, and mixes nitro-chlorobenzene through rectifying-more unmanageable waste residue of Crystallization Separation operation generation; Adopt quantity of three wastes such as Sodium Sulphide or iron powder reducing big simultaneously, product quality is poor; For example; if 2-amino-4-acetyl-anisidine is done initial raw material from Para-Anisidine; through intermittently nitrated, sodium sulfide reducing, acidylate three-step reaction total recovery are about 76%; large amount of organic enters the three wastes; the production of Para-Anisidine also produces a large amount of three wastes in addition; so the production of 2-amino-4-acetyl-anisidine is comparatively insoluble problem in dyestuff circle, the cost height, environmental pollution is serious.Main three wastes problem is: nitration waste water, wash water, reduced iron mud, phenolic wastewater in sodium sulfide reducing waste water and the etherificate in wash water and the Para-Anisidine.Therefore nitro phenylate, amino phenylate and amido phenylate production cost height, technical process is long, operational condition is harsh, the operational safety performance is poor, investment and energy consumption are big.
Summary of the invention
The objective of the invention is investment height at present production technique existence, the separation costs height, big and the situation that is difficult to administer of quantity of three wastes, provide a kind of technical process short, speed of response is fast, the selectivity height, sepn process is simple, production cost is low, and security is reliable, and production process does not have the technology with chlorobenzene production nitro phenylate, amino phenylate and amido phenylate of the three wastes.
The technical scheme that realizes above-mentioned purpose is: present production process is recombinated; use continuous thermal insulating nitration rapidly and efficiently; etherificate and catalytic hydrogenation reaction device; by reacting and separating coupling; the accretion gender gap; utilize Crystallization Separation purified technology and adopt the Crystallization Separation purification techniques of etherifying agent for solvent; with the chlorobenzene is raw material cleaner production nitro phenylate; amino phenylate and amido phenylate technology; this technology is mainly by nitrated; etherificate; the reduction of etherificate product shortening; etherificate product two is nitrated; two nitrated product shortening reduction; reaction such as two nitrated reduzate selectively acylatings and corresponding separation and purification unit process are formed; with the chlorobenzene is raw material; produce o-Nitrophenyl methyl ether; p-Nitromethoxybenzene; Ortho Anisidine; Para-Anisidine; 2; 4-dinitrobenzene methyl ether; 2; 4-diamino anisole and 2-amino-4-acetyl-anisidine process is an example, and main chemical reactions and technology are:
(1) be that raw material obtains mixing nitro-chlorobenzene through mixed acid nitrification with the chlorobenzene:
(2) with methyl alcohol be solvent and raw material of etherification, directly mix and carry out etherification reaction and obtain mixing neighbour, p-Nitromethoxybenzene with nitro-chlorobenzene:
(3) be that solvent crystallization separates adjacent, p-Nitromethoxybenzene with methyl alcohol, then, respectively isolating Nitroanisole hydrogenating reduction got Ortho Anisidine and Para-Anisidine:
(4) carry out two nitrated reactions with nitration mixture and adjacent this methyl ether of nitro and p-Nitromethoxybenzene mixture, mainly obtain 2,4-dinitrobenzene methyl ether also has the 2 of minute quantity:
(5) 2,4-dinitrobenzene methyl ether hydrogenating reductions obtain 2, the 4-diamino anisole:
(6) 2,4-diamino anisoles and acetic anhydride acylation reaction generate 2-amino-4-acetyl-anisidine:
The technical scheme that realizes above-mentioned purpose is: a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate with chlorobenzene, and described processing step is as follows:
(1). nitration reaction is raw material and nitration mixture generation nitration reaction with the chlorobenzene, and the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water;
(2). evaporation concentration steams water and remaining a small amount of nitric acid under the material decompression of nitration reaction;
(3). liquid liquid separates, and the material of evaporation concentration carries out liquid liquid to be separated, and water is mainly waste acid liquor, separates through removal of impurities, for recycling; Organic phase is mainly o-Nitrochlorobenzene, p-Nitrophenyl chloride, m-nitrochlorobenzene and small amount of impurities;
(4). etherification reaction, under the acid binding agent existence condition, etherification reaction takes place and generates ortho-nitrophenyl ether and p-nitrophenyl ether in o-Nitrochlorobenzene in the nitro-chlorobenzene mixture and p-Nitrophenyl chloride in etherifying agent;
(5). distillation, after the recovery etherifying agent, separate through removal of impurities, etherifying agent is for recycling;
(6). vacuum distilling, obtain the m-nitrochlorobenzene crude product, the m-nitrochlorobenzene crude product obtains the m-nitrochlorobenzene product through adopt the crystallization method separation and purification in etherifying agent;
(7). solid-liquid separation, remove the salt that generates in the etherification reaction process, chlorate can be produced the chlorate product after separating, liquid phase is mainly p-nitrophenyl ether and ortho-nitrophenyl ether, it has two technologies, and the one, carry out Crystallization Separation, the 2nd, directly enter (13) step and carry out two nitrated reactions;
(8). Crystallization Separation, with p-nitrophenyl ether and the cooling of ortho-nitrophenyl ether mixture material, the p-Nitromethoxybenzene crystallization is separated out, and filters, and filter cake enters p-nitrophenyl ether crystallizer, and filtrate enters ortho-nitrophenyl ether recrystallizer;
(9). p-nitrophenyl ether is refining, in p-nitrophenyl ether crystallizer, adopts organic solvent to carry out the recrystallization separation and purification, filters, and filter cake is the p-nitrophenyl ether product;
(10). p-nitrophenyl ether catalytic hydrogenation reaction, p-Nitromethoxybenzene carries out the p-aminophenyl ether that the catalytic hydrogenating reduction reaction makes in organic solvent, after the catalytic hydrogenating reduction reaction finishes, reclaim catalyzer through solid-liquid separation, adsorption bleaching obtains the p-aminophenyl ether product;
(11). ortho-nitrophenyl ether is refining, in ortho-nitrophenyl ether crystallizer, filtrate is continued cooling, and the crystallization of ortho-nitrophenyl ether is separated out, filtered, and filter cake carries out the recrystallization separation and purification, obtains the ortho-nitrophenyl ether product;
(12). ortho-nitrophenyl ether catalytic hydrogenation reaction, o-Nitrophenyl methyl ether carries out the adjacent amino phenylate that the catalytic hydrogenating reduction reaction makes in organic solvent, after the catalytic hydrogenating reduction reaction finishes, reclaim catalyzer through solid-liquid separation, adsorption bleaching obtains adjacent amino-benzene ether product;
(13). two nitrated reactions, solid-liquid separation in the 7th step is got ortho-nitrophenyl ether and the p-nitrophenyl ether mixture is raw material and nitration mixture generation nitration reaction, the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water;
(14). evaporation concentration, with the material reduction vaporization that previous step produces, the water that the nitration reaction process produces is removed, concentrate nitration mixture;
(15). liquid liquid separates, and after evaporation concentration finishes, carries out liquid liquid and separates, and water is mainly waste acid liquor, can recycle, oil phase is mainly 2, the 4-dinitrodiphenyl ether, can enter next step and carry out catalytic hydrogenation reaction, also can get 2 by separation and purification, 4-dinitrobenzene ether product;
(16). catalytic hydrogenating reduction is a solvent with the etherifying agent, in the presence of catalyzer, 2,4-dinitrodiphenyl ether and hydrogen generation catalytic hydrogenating reduction prepared in reaction 2,4-diamino phenylate;
(17). after catalytic hydrogenating reduction reaction finished, solid-liquid separation was carried out in cooling, pressure release, reaction mass is transported to catalyst recovery devices reclaims catalyzer, and the catalyzer of recovery can be recycled, and the material of sloughing catalyzer enters next step;
(18). at previous step catalytic hydrogenating reduction material 2; in the reactor of 4-diamino anisole solution; the acid binding agent that adds acylation reaction; add solution of acetic anhydride, carry out acylation reaction, after the acylation reaction; crystallisation by cooling, filtration; filter cake is 2-amino-4-acetyl-anisidine crude product, and the filter cake 2-amino-4-kharophen phenylate crude product of previous step is carried out separation and purification, prepares 2-amino-4-acetyl amino phenyl ether product.
Further, described nitro phenylate is o-Nitrophenyl methyl ether or p-Nitromethoxybenzene or 2,4-dinitrobenzene methyl ether, or o-Nitrophenetole, p-Nitrophenetole, the ortho-nitrophenyl propyl ether, the p-nitrophenyl propyl ether, 2,4-dinitrobenzene ether and 2, a kind of in the 4-dinitrobenzene propyl ether, described amino phenylate is an Ortho Anisidine, Para-Anisidine, 2, a kind of in the 4-diamino anisole, or o-phenetidine, p-phenetidine, adjacent amino-benzene propyl ether, the p-aminophenyl propyl ether, 2,4-diaminophenetole and 2, a kind of in the 4-diaminobenzene propyl ether, described amido phenylate is 2-amino-4-acetyl-anisidine or 2-amino-4-acetphenetidide or 2-amino-4-kharophen propyl phenyl ether.
Further, described etherifying agent is methyl alcohol or ethanol or propyl alcohol, and described organic solvent is identical reagent with etherifying agent.
Further, acid binding agent is a sodium hydroxide in described the 4th step, or a kind of in the yellow soda ash, magnesiumcarbonate, volatile salt, lime carbonate, bicarbonate of ammonia, sodium bicarbonate, magnesium oxide, calcium oxide, acid binding agent is a volatile salt in the 18 step, or a kind of in the yellow soda ash, magnesiumcarbonate, lime carbonate, bicarbonate of ammonia, sodium bicarbonate, magnesium oxide, calcium oxide.
Further, chlorobenzene and nitration mixture carry out the continuous thermal insulating nitration reaction in liquid liquid Fast Mixing Equipment.
Further, the nitro-chlorobenzene and the mixed acid liquid mixture that obtain after chlorobenzene and the nitration mixture generation nitration reaction, this mixture through evaporation dewater, liquid liquid separates, water is for reclaiming refuse acid, through returning adiabatic nitration nitration mixture system after the removal of impurities processing, oil phase be mainly the nitro-chlorobenzene mixture as in the etherification reaction process, o-Nitrochlorobenzene and p-Nitrophenyl chloride generate ortho-nitrophenyl ether and p-nitrophenyl ether respectively, m-nitrochlorobenzene does not participate in reaction.
Further, behind the etherification reaction, an operational path wherein is that oil of mirbane ether mixture employing etherifying agent is that solvent adopts the Crystallization Separation method to produce ortho-nitrophenyl ether and p-nitrophenyl ether product, and ortho-nitrophenyl ether and p-nitrophenyl ether product are proceeded catalytic hydrogenating reduction and produced adjacent amino phenylate and p-aminophenyl ether product; Wherein another operational path is that the etherificate mixture is directly proceeded the continuous thermal insulating nitration reaction.
Further, after two nitrated reactions finish, after the evaporation concentration end, liquid liquid separates, and water is mainly waste acid liquor, oil phase is mainly 2, the 4-dinitrodiphenyl ether obtains 2,4-dinitrobenzene ether product through separation and purification, oil phase generates 2,4-diamino phenylate by directly carrying out the catalytic hydrogenating reduction reaction.
Further, with 2, the 4-dinitrodiphenyl ether is a raw material, under the catalyzer existence condition, feeds hydrogen, carries out continuously or the reaction of intermittent type catalytic hydrogenating reduction.
Further, after the catalytic hydrogenating reduction reaction finishes, carry out solid-liquid separation after cooling, the pressure release, reaction mass is transported to catalyst recovery devices reclaims catalyzer, and the material of sloughing catalyzer enters next step carry out acylation reaction in the acetylization reaction device, at previous step catalytic hydrogenating reduction material 2, in the reactor of 4-diaminobenzene ethereal solution, the acid binding agent that adds acylation reaction adds solution of acetic anhydride, carries out acylation reaction; After the acylation reaction, separation and purification is prepared 2-amino-4-acetyl amino phenyl ether product, and perhaps directly adopting etherifying agent is solvent, produces 2,4-diaminobenzene ether product by adopting the Crystallization Separation method.
After adopting technique scheme; the present invention only need use nitrator; methyltertiarvbutyl ether reactor; the catalytic hydrogenation reaction device; the acylation reaction device; crystallizer; equipment such as filtration unit; and need not to use rectifying tower; overcome existing nitro phenylate production process and mainly carried out the corresponding ortho-nitrophenyl ether of etherification reaction production respectively with o-Nitrochlorobenzene and the p-Nitrophenyl chloride finished product that obtains by separation; the shortcoming of p-nitrophenyl ether has particularly been avoided nitro-chlorobenzene process rectifying-Crystallization Separation process complex operations condition harshness in the production process; drawbacks such as facility investment and process cost are big.Production technique of the present invention and method are process for cleanly preparing, have that production cost is low, production stability and an advantage safe, that process does not have the three wastes, can directly carry out large-scale industrial production.
Description of drawings
Accompanying drawing is the schema of the technology of raw material cleaner production nitro phenylate, amino phenylate and amido phenylate with the chlorobenzene for the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
As shown in the figure; a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate with chlorobenzene; raw material is a chlorobenzene, and the equipment that the present invention will use is nitrator, methyltertiarvbutyl ether reactor, catalytic hydrogenation reaction device, acylation reaction device, crystallizer, filtration unit etc.
Embodiment one
A kind of is raw material cleaner production o-Nitrophenyl methyl ether, p-Nitromethoxybenzene, Ortho Anisidine, Para-Anisidine, 2 with the chlorobenzene, 4-dinitrobenzene methyl ether, 2, the technology of 4-diamino anisole and 2-amino-4-acetyl-anisidine, described processing step is as follows:
(1). nitration reaction, with the chlorobenzene is raw material, chlorobenzene carries out adiabatic nitration through the nitration mixture of being made up of nitric acid and sulfuric acid and obtains the nitro-chlorobenzene mixture in the static mixing nitrator, the dehydration value that adopts nitration mixture is between 2.0-3.2, chlorobenzene is 1:1.05 with the ratio of nitric acid, the continuous thermal insulating nitration reaction takes place in continuous static mixing tank thermal insulation nitration device, and service temperature is between 65～140 ℃, and the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water;
(2). evaporation concentration, the material that reacts through continuous thermal insulating nitration is decompressed to 98.0kPa, steams water and residue nitric acid, and liquid liquid separates then;
(3). liquid liquid separates, and the material of evaporation concentration carries out liquid liquid to be separated, and water is mainly waste acid liquor, separates through removal of impurities, for recycling; Organic phase is mainly o-Nitrochlorobenzene, p-Nitrophenyl chloride, m-nitrochlorobenzene and small amount of impurities, carries out the raw material of etherification reaction as next step;
(4). etherification reaction, under etherifying agent methyl alcohol and acid binding agent sodium hydroxide existence condition, etherification reaction takes place in the complex etherified device of continuous static, methyl alcohol and sodium hydroxide ratio are for about 100m1:16.0g, total mole of o-Nitrochlorobenzene and p-Nitrophenyl chloride is about 1.0:1.10 with the sodium hydroxide mol ratio, and continuous etherification reaction takes place about 140 ℃;
(5). distillation, at 60 ℃ of left and right sides evaporative distillations, behind the recovery etherifying agent methyl alcohol, separate through removal of impurities, methyl alcohol is for recycling;
(6). vacuum distilling, after Methanol Recovery, continue to obtain the mixture of m-nitrochlorobenzene and water in vacuum distilling, the m-nitrochlorobenzene crude product obtains m-nitrochlorobenzene product P 1 through adopt the crystallization method separation and purification in methyl alcohol;
(7). solid-liquid separation, remove the salt that generates in the etherification reaction process, sodium-chlor can be produced the sodium-chlor product after separating, liquid phase is mainly p-Nitromethoxybenzene and o-Nitrophenyl methyl ether, it has two technologies, and the one, carry out Crystallization Separation, the 2nd, directly enter (13) step and carry out two nitrated reactions;
(8). Crystallization Separation, material is cooled to 13 ℃, the p-Nitromethoxybenzene crystallization is separated out, is filtered, and filtrate enters in the ortho-nitrophenyl ether crystallizer, and filter cake enters the p-Nitromethoxybenzene recrystallizer;
(9). p-Nitromethoxybenzene is refining, in the p-Nitromethoxybenzene crystallizer, the ratio that adds p-Nitromethoxybenzene and methyl alcohol is: 300g:500ml, under agitation condition, be warming up to the methanol eddy temperature, make material dissolution, be cooled to 13 ℃ of crystallizations, filtration then, filter cake gets p-Nitromethoxybenzene product P 3 through vacuum-drying, and purity reaches more than 99%;
(10). the p-Nitromethoxybenzene catalytic hydrogenation reaction, at the hydrogenation stirred autoclave, catalyzer is self-control Raney-Ni catalyzer, under the processing condition of 120 ℃ of temperature of reaction, reaction pressure 1.6MPa, after reaction process is complete, under agitation condition, mass transport to leaf filtration unit and corresponding filtering system, is reclaimed catalyzer in order to applying mechanically, through adsorption bleaching, obtain Para-Anisidine product P 5, purity reaches more than 96%;
(11). o-Nitrophenyl methyl ether is refining, in the o-Nitrophenyl methyl ether crystallizer, filtrate continuation is cooled to 0-9 ℃, and the o-Nitrophenyl methyl ether crystallization is separated out, is filtered, the filter cake recrystallization, the ratio that adds o-Nitrophenyl methyl ether and methyl alcohol is: 200g:500ml, under agitation condition, make material dissolution, be cooled to 2 ℃ of crystallizations, filtration then, filter cake gets o-Nitrophenyl methyl ether product P 2 through vacuum-drying, and purity reaches more than 98%.
(12). the o-Nitrophenyl methyl ether catalytic hydrogenation reaction, at hydrogenation stirred autoclave (the highest withstand voltage 15MPa), catalyzer is the Raney-Ni catalyzer, stirring velocity is not less than 400r/min, under the processing condition of 120 ℃ of temperature of reaction, reaction pressure 1.6MPa, reaction times is about 9h, and the transformation efficiency of o-Nitrophenyl methyl ether is more than 98.0%.After reaction process was complete, under agitation condition, to leaf filtration unit and corresponding filtering system, the recovery catalyzer was prepared against and is applied mechanically, and through adsorption bleaching, obtains Ortho Anisidine product P 4 with mass transport, and purity reaches more than 96%;
(13). two nitrated reactions, solid-liquid separation in the 7th step is got o-Nitrophenyl methyl ether and the p-Nitromethoxybenzene mixture is a raw material, the continuous thermal insulating nitration reaction takes place in continuous static mixing tank thermal insulation nitration device, nitration mixture in the reaction process is formed by 98% sulfuric acid, 95% nitric acid and the 65% nitric acid mixed preparing of technical grade, the dehydration value of nitration mixture is between 2.8-4.2, the mole proportioning of Nitroanisole and nitric acid is 1:1.05, and service temperature is between 65～140 ℃;
(14). evaporation concentration, the material of previous step reaction is decompressed to steams water and nitration reaction residue nitric acid under 10.0～100KPa, carry out spent acid and concentrate;
(15). liquid liquid separates, and evaporation concentration leaves standstill 0.5h after finishing, and carries out the layering of liquid liquid and separates.Lower floor's water is that sulfuric acid and a spot of aqueous nitric acid carry out the spent acid recycling; Upper oil phase is mainly 2,4-dinitrobenzene methyl ether and unreacted raw material, lower floor's water is sulfuric acid, water and a spot of salpeter solution, carry out can be recycled after the spent acid recycling, oil phase is mainly 2, and 4-dinitrobenzene methyl ether can enter next step and carry out catalytic hydrogenation reaction, also can get 2 by separation and purification, 4-dinitrobenzene methyl ether product P 6;
(16). catalytic hydrogenating reduction, with methyl alcohol is solvent, with 2, it is in three phase fixed bed catalyst chambers of catalyzer that 4 Nitroanisoles add Raney-Ni, and catalyst consumption is 1.0% of a nitro thing, and granules of catalyst is 9.0mm, feed the reaction of hydrogen generation catalytic hydrogenating reduction then, controlled temperature is 120 ℃ during reaction, and working pressure is 4.0MPa, and the reaction times is 4h;
(17). after the catalytic hydrogenating reduction reaction finishes, cooling, pressure release, carry out solid-liquid separation, reaction mass is transported to catalyst recovery devices reclaims catalyzer, the catalyzer that reclaims can be recycled, and the material of sloughing catalyzer enters next step, the material of sloughing catalyzer also can carry out liquid liquid to be separated, water carries out rectifying, reclaim methyl alcohol with solvent recovery unit, oil phase is 2,4-diamino anisole crude product is solvent with methyl alcohol, with 2,4-diamino anisole crude product carries out Crystallization Separation in Crystallization Separation device evaporative crystallization still refining, and 2, the amount ratio of 4-diamino anisole and methyl alcohol is 100g:250ml, be warmed up to reflux temperature, keep service temperature be 20 ℃ to the methyl alcohol boiling, working pressure is 0.2MPa, under refluxad keeps 30min, slowly drop to 20 ℃ then, 2, the crystallization of 4-diamino anisole is separated out, and filters, after isolated mother liquor methyl alcohol is reclaimed by solvent recovery unit, can be directly as 2, after the solvent of 4-dinitrobenzene methyl ether catalytic hydrogenation reaction, filter cake carry out the conventional drying processing, then for prepare 2,4-diamino anisole product P 7.
(18). add 5 ℃ of acetic anhydride solution in the acylation reaction device, add acylation reaction acid binding agent yellow soda ash, add the product 2 that previous step is sloughed catalyzer, the 4-diamino anisole carries out acylation reaction, and the operation temperature is 16 ℃, and the reaction times is 4h; After the acylation reaction; carrying out liquid liquid after acylation reaction separates; water evaporated use solvent recovery unit respectively; acetyl reclaims methyl alcohol; sodium acetate; oil phase is 2-amino-4-acetyl-anisidine crude product; 2-amino-4-acetyl-anisidine crude product is put into Crystallization Separation device evaporative crystallization still; add methyl alcohol as solvent; it is refining to carry out Crystallization Separation; the amount ratio of 2-amino-4-acetyl-anisidine and methyl alcohol is 100g:250ml; be warmed up to reflux temperature; keeping service temperature to be 20 ℃ seethes with excitement to methyl alcohol; working pressure is 0.2MPa; under refluxad keep 30min, slowly drop to 20 ℃ then, slowly drop to 30 ℃ then; after isolated mother liquor methyl alcohol is reclaimed by solvent recovery unit; can be directly as 2, the solvent of 4--dinitrobenzene methyl ether catalytic hydrogenation reaction then is the 2-amino-4-acetyl-anisidine product P 8 of preparation after the filter cake conventional drying is handled.
Claims (6)
1, a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate with chlorobenzene is characterized in that described processing step is as follows:
(1). nitration reaction is raw material and nitration mixture generation nitration reaction with the chlorobenzene, and the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water;
(2). evaporation concentration steams water and remaining a small amount of nitric acid under the material decompression of nitration reaction;
(3). liquid liquid separates, and the material of evaporation concentration carries out liquid liquid to be separated, and water is mainly waste acid liquor, separates through removal of impurities, and for recycling, organic phase is mainly o-Nitrochlorobenzene, p-Nitrophenyl chloride, m-nitrochlorobenzene and small amount of impurities;
(4). etherification reaction, under the acid binding agent existence condition, etherification reaction takes place and generates ortho-nitrophenyl ether and p-nitrophenyl ether in o-Nitrochlorobenzene in the nitro-chlorobenzene mixture and p-Nitrophenyl chloride in etherifying agent;
(5). distillation, after the recovery etherifying agent, separate through removal of impurities, etherifying agent is for recycling;
(6). vacuum distilling, obtain the m-nitrochlorobenzene crude product, the m-nitrochlorobenzene crude product obtains the m-nitrochlorobenzene product through adopt the crystallization method separation and purification in etherifying agent;
(7). solid-liquid separation, remove the salt that generates in the etherification reaction process, chlorate can be produced the chlorate product after separating, liquid phase is mainly p-nitrophenyl ether and ortho-nitrophenyl ether, it has two technologies, and the one, carry out Crystallization Separation, the 2nd, directly enter (13) step and carry out two nitrated reactions;
(8). Crystallization Separation, with p-nitrophenyl ether and the cooling of ortho-nitrophenyl ether mixture material, the crystallization of p-nitrophenyl ether is separated out, and filters, and filter cake enters p-nitrophenyl ether crystallizer, and filtrate enters ortho-nitrophenyl ether crystallizer;
(9). p-nitrophenyl ether is refining, in p-nitrophenyl ether crystallizer, adopts organic solvent to carry out the recrystallization separation and purification, filters, and filter cake is the p-nitrophenyl ether product;
(10). p-nitrophenyl ether catalytic hydrogenation reaction, in the presence of catalyzer, p-Nitromethoxybenzene carries out the p-aminophenyl ether that the catalytic hydrogenating reduction reaction makes in organic solvent, after the catalytic hydrogenating reduction reaction finishes, reclaim catalyzer through solid-liquid separation, adsorption bleaching obtains the p-aminophenyl ether product;
(11). ortho-nitrophenyl ether is refining, in ortho-nitrophenyl ether crystallizer, filtrate is continued cooling, and the crystallization of ortho-nitrophenyl ether is separated out, filtered, and filter cake carries out the recrystallization separation and purification, obtains the ortho-nitrophenyl ether product;
(12). ortho-nitrophenyl ether catalytic hydrogenation reaction, in the presence of catalyzer, o-Nitrophenyl methyl ether carries out the adjacent amino phenylate that the catalytic hydrogenating reduction reaction makes in organic solvent, after the catalytic hydrogenating reduction reaction finishes, reclaim catalyzer through solid-liquid separation, adsorption bleaching obtains adjacent amino-benzene ether product;
(13). two nitrated reactions, solid-liquid separation in the 7th step is got ortho-nitrophenyl ether and the p-nitrophenyl ether mixture is raw material and nitration mixture generation nitration reaction, the nitration mixture in the reaction process is to be mixed by nitric acid, sulfuric acid and water;
(14). evaporation concentration, with the material reduction vaporization that previous step produces, the water that the nitration reaction process produces is removed, concentrate nitration mixture;
(15). liquid liquid separates, and after evaporation concentration finishes, carries out liquid liquid and separates, and water is mainly waste acid liquor, can recycle, oil phase is mainly 2, the 4-dinitrodiphenyl ether, or enter next step and carry out catalytic hydrogenation reaction, or separation and purification gets 2,4-dinitrobenzene ether product;
(16). catalytic hydrogenating reduction is a solvent with the etherifying agent, in the presence of catalyzer, 2,4-dinitrodiphenyl ether and hydrogen generation catalytic hydrogenating reduction prepared in reaction 2,4-diamino phenylate;
(17). after catalytic hydrogenating reduction reaction finished, solid-liquid separation was carried out in cooling, pressure release, reaction mass is transported to catalyst recovery devices reclaims catalyzer, and the catalyzer of recovery can be recycled, and the material of sloughing catalyzer enters next step;
(18). at previous step catalytic hydrogenating reduction material 2; in the reactor of 4-diaminobenzene ethereal solution; the acid binding agent that adds acylation reaction; add solution of acetic anhydride, carry out acylation reaction, after the acylation reaction; crystallisation by cooling, filtration; filter cake is 2-amino-4-kharophen phenylate crude product, and the filter cake 2-amino-4-kharophen phenylate crude product of previous step is carried out separation and purification, prepares 2-amino-4-acetyl amino phenyl ether product.
2, according to claim 1 a kind of with chlorobenzene production nitro phenylate, amino phenylate and amido phenylate technology, it is characterized in that: described nitro phenylate is o-Nitrophenyl methyl ether or p-Nitromethoxybenzene or 2,4-dinitrobenzene methyl ether, or o-Nitrophenetole, p-Nitrophenetole, the ortho-nitrophenyl propyl ether, the p-nitrophenyl propyl ether, 2,4-dinitrobenzene ether and 2,4-dinitrobenzene propyl ether, described amino phenylate is an Ortho Anisidine, Para-Anisidine, 2, the 4-diamino anisole, or o-phenetidine, p-phenetidine, adjacent amino-benzene propyl ether, the p-aminophenyl propyl ether, 2,4-diaminophenetole and 2,4-diaminobenzene propyl ether, described amido phenylate are 2-amino-4-acetyl-anisidines, 2-amino-4-acetphenetidide and 2-amino-4-kharophen propyl phenyl ether.
3, according to claim 1 or the described a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate with chlorobenzene of claim 2, it is characterized in that: acid binding agent is a sodium hydroxide in described (4) step, or yellow soda ash, magnesiumcarbonate, volatile salt, lime carbonate, bicarbonate of ammonia, sodium bicarbonate, magnesium oxide, calcium oxide, acid binding agent is a volatile salt in (18) step, or yellow soda ash, magnesiumcarbonate, lime carbonate, bicarbonate of ammonia, sodium bicarbonate, magnesium oxide, calcium oxide.
4, according to claim 1 or the described a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate with chlorobenzene of claim 2, it is characterized in that: chlorobenzene and nitration mixture carry out the continuous thermal insulating nitration reaction in liquid liquid Fast Mixing Equipment.
5, according to claim 1 or the described a kind of technology of producing nitro phenylate, amino phenylate and amido phenylate with chlorobenzene of claim 2, it is characterized in that: behind the etherification reaction, an operational path wherein is that oil of mirbane ether mixture employing etherifying agent is that solvent adopts the Crystallization Separation method to produce ortho-nitrophenyl ether and p-nitrophenyl ether product, and ortho-nitrophenyl ether and p-nitrophenyl ether product are proceeded catalytic hydrogenating reduction and produced Ortho Anisidine and Para-Anisidine product; Wherein another operational path is that the etherificate mixture is directly proceeded two nitrated reactions.
6, according to claim 1 or claim 2 described a kind of be raw material cleaner production nitro phenylate, amino phenylate and amido phenylate technology with the chlorobenzene, it is characterized in that: after two nitrated reactions finish, after the evaporation concentration end, liquid liquid separates, and water is mainly waste acid liquor, oil phase is mainly 2, the 4-dinitrodiphenyl ether obtains 2,4-dinitrobenzene ether product through separation and purification, oil phase generates 2,4-diamino phenylate by directly carrying out the catalytic hydrogenating reduction reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101307001B (en) * | 2008-07-11 | 2011-05-11 | 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 |
| CN101307000B (en) * | 2008-07-11 | 2011-05-11 | 常州市佳森化工有限公司 | Process for preparing aminoanisol and aniline by using mixture of nitroanisole and nitro chlorobenzene as raw materials |
| 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 anisidine by mixed nitrochlorobenzene reacting in aqueous solvent |
| CN102391134A (en) * | 2011-09-22 | 2012-03-28 | 江苏康恒化工有限公司 | Method for preparing o-anisidine by catalytic hydrogenation |
| CN103524371B (en) * | 2013-07-22 | 2016-08-17 | 上海综星化工科技有限公司 | A kind of preparation technology of 2-amino-4-acetyl-anisidine |
| CN104844461A (en) * | 2015-03-24 | 2015-08-19 | 安徽生源化工有限公司 | Synthetic process for amino aromatic hydrocarbon compound |
| CN106608838A (en) * | 2015-11-22 | 2017-05-03 | 宁夏际华环境安全科技有限公司 | Production technology of 2-amino-4-acetyl amino phenyl methyl ether |
| CN106187786B (en) * | 2016-06-29 | 2019-01-22 | 浙江闰土研究院有限公司 | A kind of clean preparation method of paraphenetidine |
| 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 |
| CN106496039B (en) * | 2016-09-28 | 2019-04-05 | 连云港泰盛化工有限公司 | The separation method of nitrochlorobenzene meta-position oil intermediate nitro Benzene Chloride and para-nitrochloro-benzene, ortho-nitrochlorobenzene |
| CN106883129B (en) * | 2016-12-29 | 2021-05-14 | 安徽海华科技集团有限公司 | Method for preparing m-chloroaniline by using meta-oil |
| CN107417541A (en) * | 2017-05-17 | 2017-12-01 | 周龙根 | The preparation technology of para aminophenyl ethyl ether and aniline |
| CN111187168A (en) * | 2019-12-12 | 2020-05-22 | 中卫市鑫三元化工有限公司 | Clean production process for producing nitrobenzene alkoxy ether by using nitrohalogenated benzene |
| CN112479891A (en) * | 2020-12-10 | 2021-03-12 | 浙江鸿盛化工有限公司 | Synthetic method of p-nitroanisole |
| CN114874101A (en) * | 2022-03-30 | 2022-08-09 | 葫芦岛天启晟业化工有限公司 | Method for producing o-, p-and m-chloroaniline by directly hydrogenating chloronitrobenzene mixture |
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