CN100361957C - Tech. of preparing 2,4-di nitro methyl-phenoxide by nitro methyl-phenoxide continuous thermal insulating nitration - Google Patents
Tech. of preparing 2,4-di nitro methyl-phenoxide by nitro methyl-phenoxide continuous thermal insulating nitration Download PDFInfo
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- CN100361957C CN100361957C CNB2006100854924A CN200610085492A CN100361957C CN 100361957 C CN100361957 C CN 100361957C CN B2006100854924 A CNB2006100854924 A CN B2006100854924A CN 200610085492 A CN200610085492 A CN 200610085492A CN 100361957 C CN100361957 C CN 100361957C
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Abstract
The present invention relates to a process for nitrobenzene methyl ether to prepare 2, 4-nitrobenzene methyl ether through continuous heat insulation nitrification. The present invention has the process procedures of continuous heat insulation nitration, evaporation concentration, liquid-liquid separation, cooling crystallization, first solid-liquid separation, separation refining and second solid-liquid separation, wherein the continuous heat insulation nitration respectively uses 2-nitrobenzene methyl ether, 4-nitrobenzene methyl ether and mixtures of 2-nitrobenzene methyl ether and 4-nitrobenzene methyl ether as raw materials which generate continuous nitration with mixed acid after a preheating fusing state, oil phases are 2, 4-dinitro phenyl methyl ether mainly, the cooling crystallization can separate 2, 4-dinitro phenyl methyl ether coarse products out, solid phases are 2, 4-dinitro phenyl methyl ether mainly, the separation refining removes impurities, and the solid phases of the second solid-liquid separation are 2, 4-dinitro phenyl methyl ether products which are prepared out. The present invention has the advantages of low cost, simple process, short process flow, clean process, safety, high reliability, environment protection and economization.
Description
Technical field
The present invention relates to a kind of continuous thermal insulating nitration preparation 2 of Nitroanisole, 4-dinitrobenzene methyl ether technology belongs to field of fine chemical.
Background technology
2,4-dinitrobenzene methyl ether is important organic synthesis intermediate.At present, 2, the preparation technology of 4-dinitrobenzene methyl ether is by 2, and the 4-dinitrochlorobenzene gets through methoxylation, and this preparation technology drops into fused 2 in reactor, 4-dinitrochlorobenzene and sodium methylate, be heated to about 40 ℃, temperature is controlled at 58 ℃～60 ℃ methoxylation takes place, after reaction finishes, treated operation promptly gets 2,4-dinitrobenzene methyl ether product.The principal reaction structural formula is:
This 2, the preparation technology of 4-dinitrobenzene methyl ether exists following shortcoming: the cost height, consume big, quality product is relatively poor, especially waste water, waste sludge discharge amount are big, caused the serious environmental pollution, if the waste water, the waste residue that produce are handled, so just increase processing cost, but also existed the hidden danger of secondary pollution.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of continuous thermal insulating nitration preparation 2 of Nitroanisole, 4-dinitrobenzene methyl ether technology.Make this explained hereafter cost low, technological process cleaning, safety, reliability height, constant product quality.
The technical scheme that realizes above-mentioned purpose is: a kind of continuous thermal insulating nitration preparation 2 of Nitroanisole, and 4-dinitrobenzene methyl ether technology, described processing step is as follows:
(1). the continuous thermal insulating nitration reaction, be raw material with 2-Nitroanisole, 4-Nitroanisole, 2-Nitroanisole and 4-nitrobenzoyl ether mixture respectively, with the reaction of nitration mixture generation continuous nitrification, described nitration mixture is formed by 98% sulfuric acid, 95% nitric acid and the 65% nitric acid mixed preparing of technical grade after the preheating molten state;
(2). evaporation concentration, the material that previous step is produced is decompressed to 10.0KPa～100KPa, evaporation water outlet and the remaining a small amount of nitric acid of nitration reaction;
(3). liquid liquid separates, and after evaporation concentration finishes, carries out liquid liquid and separates, and water is mainly waste acid liquor, and oil phase is mainly 2,4-dinitrobenzene methyl ether;
(4). crystallisation by cooling, oil phase is carried out crystallisation by cooling under certain condition, separate out 2,4-dinitrobenzene methyl ether crude product;
(5). solid-liquid separation for the first time, solid phase is mainly 2,4-dinitrobenzene methyl ether;
(6). separation and purification, adopt organic solvent to carry out separation and purification, with Impurity removal;
(7). solid-liquid separation for the second time, solid phase be prepare 2,4-dinitrobenzene methyl ether product, liquid phase is an organic solvent.
Further, the dehydration value of nitration mixture is controlled at 2.0～4.8 in the described the first step continuous thermal insulating nitration reaction, and the mole proportioning of Nitroanisole and nitric acid is controlled at 1: 0.90～1.20, and the temperature of the control of nitration reaction is at 60 ℃～140 ℃.
Further, the solid-liquid separation temperature behind described the 5th step crystallisation by cooling is controlled at 20 ℃～80 ℃.
Further, separation and purification can adopt the recrystallization separation and purification in described the 6th step, also can adopt the washing separation and purification;
Further, described organic solvent can be alcohol organic solvent such as methyl alcohol, ethanol.
Further, carry out rectification process after described the 7th step solid-liquid separation, reclaim organic solvent.
Further, described continuous thermal insulating nitration is reflected in the nitrator and carries out, and nitrator is quick liquid liquid mixing equipment.
Further, described quick liquid liquid mixing equipment is the stirring tank mixing tank, perhaps is the jet jet mixer, perhaps is the percussion flow mixing tank, perhaps is static mixer, perhaps is dynamic mixer.
Realize that the main technique equipment that the present invention needs is: nitrator, Crystallization Separation device, solvent recovery unit etc.
Adopt the benefit of technique scheme to be: (1), production cost are low.The present invention is to be the nitration mixture generation continuous thermal insulating nitration reaction that raw material and nitric acid and sulfuric acid mix with 4-Nitroanisole, 2-Nitroanisole and 4-Nitroanisole and 2-nitrobenzoyl ether mixture, because Nitroanisole and mixture cost are lower, therefore prepare 2,4-dinitrobenzene methyl ether technology cost is low; (2), technology is simple, technical process is short.(3) technological process cleaning, safety, reliability height.Make full use of the nitration reaction characteristics of Nitroanisole, realize the reasonable utilization of material and energy.The nitration reaction of Nitroanisole is the heterogeneous fast response process of the liquid liquid of strong heat release, be the mass transfer control process, and the water dilution that the sulfuric acid in the nitration mixture is reacted generation the time also will produce the heat of dilution, these heats such as untimely shifting out, temperature of reaction is risen rapidly, speed of response is sharply accelerated, so that the too high and wild effect such as set off an explosion of temperature occurs.The present invention adopts Nitroanisole continuous thermal insulating nitration technology, broken through the traditional concept that nitration reaction must be operated under lower temperature, the cancellation refrigerating unit, make full use of mixture heat, reaction heat, make material carry out the non-isothermal nitration reaction, form to guarantee reaction safety, to carry out smoothly by the control nitration mixture, meanwhile can also utilize reaction heat that spent acid is carried out flash concentration, thereby significantly reduce spent acid and concentrate necessary energy, and spent acid can be recycled technological process cleaning, environmental protection; (4) can realize large-scale industrial production.The nitrator of continuous thermal insulating nitration reaction state need adopt quick liquid liquid mixing equipment, realize the short mix of liquid liquid, improve liquid liquid mass transfer process speed, shorten the reaction times greatly, the degree that the control reaction is carried out, this helps improving selectivity, optimization whole process of production, the reduction facility investment of product, and process is safe and reliable, can realize large-scale industrial production; (5) environmental protection, saving.Adopt solvent method separation and purification 2,4-dinitrobenzene methyl ether product, process safety, reliable, and can be recycled, can save cost greatly like this, and the spent acid that produces also can reclaim recycled again in nitration reaction, both save cost, avoided the pollution of spent acid etc. again, very environmental protection.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Major equipment: continuous static mixing tank thermal insulation nitration device, Crystallization Separation device, solvent recovery unit etc.
Embodiment one
A kind of Nitroanisole continuous thermal insulating nitration preparation 2,4-dinitrobenzene methyl ether technology, described processing step is as follows:
(1). with the 4-Nitroanisole as raw material, nitration mixture 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 2.0～3.2, the mole proportioning of 4-Nitroanisole and nitric acid is 1: 1.05, the continuous thermal insulating nitration reaction takes place in continuous static mixing tank thermal insulation nitration device, and the red-tape operati temperature is between 65 ℃～120 ℃.
(2). the material through the continuous thermal insulating nitration reaction is decompressed to 28.0KPa, steams the remaining a small amount of nitric acid of water and nitration reaction, carries out spent acid and concentrates.
(3). evaporation concentration leaves standstill 1.0h 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 2-Nitroanisole, and lower floor's water is sulfuric acid, water and a spot of salpeter solution, carries out can be recycled after the spent acid recycling.
(4). upper oil phase is cooled to separate out 2 about 60 ℃ 4-dinitrobenzene methyl ether crude product.
(5). at 60 ℃ of left and right sides heat filterings, filtrate is returned the continuous thermal insulating nitration reactive system for reaching unreacted raw material; Filter cake is 2, and 4-dinitrobenzene methyl ether and a spot of 2 impurity carry out separation and purification.
(6). it is refining to adopt ethanol to be that solvent carries out Crystallization Separation, obtains 2, the crystallization of 6-dinitrobenzene methyl ether.
(7). about 60 ℃, filter, filter cake is 2,4-dinitrobenzene methyl ether product, liquid phase is an ethanolic soln.
(8). ethanol reclaims, and after the employing rectificating method reclaims ethanol, can be recycled.
Embodiment two
A kind of Nitroanisole continuous thermal insulating nitration preparation 2,4-dinitrobenzene methyl ether technology, described processing step is as follows:
(1). with the 2-Nitroanisole as raw material, nitration mixture 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 2-Nitroanisole and nitric acid is 1: 1.05, the continuous thermal insulating nitration reaction takes place in continuous static mixing tank thermal insulation nitration device, and service temperature is between 65 ℃～140 ℃.
(2). the material of process continuous thermal insulating nitration reaction is decompressed to and steams water and nitration reaction residue nitric acid under the 78.0KPa, carries out spent acid and concentrates.
(3). 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 2-Nitroanisole, and lower floor's water is sulfuric acid, water and a spot of salpeter solution, carries out can be recycled after the spent acid recycling.
(4). layer oil phase is cooled to separate out 2 about 40 ℃ 4-dinitrobenzene methyl ether product.
(5). about 40 ℃, heat filtering, filtrate is returned the continuous thermal insulating nitration reactive system for reaching unreacted raw material; Filter cake is 2,4-dinitrobenzene methyl ether and trace 2, and 6-dinitrobenzene methyl ether and 2 impurity carry out separation and purification.
(6). adopting methyl alcohol is that solvent is pulled an oar, washed and carries out separation and purification.
(7). about 40 ℃, filter, filter cake is 2,4-dinitrobenzene methyl ether product, filtrate is methanol solution.
(8). methanol solvate reclaims, and adopts rectificating method to reclaim methyl alcohol, recycles.
Embodiment three
A kind of Nitroanisole continuous thermal insulating nitration preparation 2,4-dinitrobenzene methyl ether technology, described processing step is as follows:
(1). with 2-Nitroanisole and 4-nitrobenzoyl ether mixture as raw material, nitration mixture 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, the continuous thermal insulating nitration reaction takes place in continuous static mixing tank thermal insulation nitration device, and service temperature is between 65 ℃～140 ℃.
(2). the material of process continuous thermal insulating nitration reaction is decompressed to and steams water and nitration reaction residue nitric acid under 10.0KPa～100KPa, carries out spent acid and concentrates.
(3). 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, and 4-dinitrobenzene methyl ether and unreacted raw material, lower floor's water are sulfuric acid, water and a spot of salpeter solution, carries out can be recycled after the spent acid recycling.
(4). layer oil phase is cooled to separate out 2 about 60 ℃ 4-dinitrobenzene methyl ether product.
(5). about 60 ℃, heat filtering, filtrate is returned the continuous thermal insulating nitration reactive system for reaching unreacted raw material; Filter cake is 2,4-dinitrobenzene methyl ether and trace 2, and 6-dinitrobenzene methyl ether and 2 impurity carry out recrystallization and separate.
(6). it is refining to adopt ethanol to be that solvent carries out Crystallization Separation, obtains 2, the crystallization of 6-dinitrobenzene methyl ether.
(7). about 55 ℃, filter, filter cake is 2,4-dinitrobenzene methyl ether product, liquid phase is an ethanolic soln.
(8). ethanol reclaims, and adopts rectificating method to reclaim ethanol, recycles.
Claims (8)
1. Nitroanisole continuous thermal insulating nitration preparation 2,4-dinitrobenzene methyl ether technology is characterized in that described processing step is as follows:
(1). the continuous thermal insulating nitration reaction, be raw material with 2-Nitroanisole, 4-Nitroanisole, 2-Nitroanisole and 4-nitrobenzoyl ether mixture respectively, with the reaction of nitration mixture generation continuous nitrification, described nitration mixture is formed by 98% sulfuric acid, 95% nitric acid and the 65% nitric acid mixed preparing of technical grade after the preheating molten state;
(2). evaporation concentration, the material that previous step is produced is decompressed to 10.0KPa～100KPa, evaporation water outlet and the remaining a small amount of nitric acid of nitration reaction;
(3). liquid liquid separates, and after evaporation concentration finishes, carries out liquid liquid and separates, and water is mainly waste acid liquor, and oil phase is mainly 2,4-dinitrobenzene methyl ether;
(4). crystallisation by cooling, oil phase is carried out crystallisation by cooling under certain condition, separate out 2,4-dinitrobenzene methyl ether crude product;
(5). solid-liquid separation for the first time, solid phase is mainly 2,4-dinitrobenzene methyl ether;
(6). separation and purification, adopt organic solvent to carry out separation and purification, with Impurity removal;
(7). solid-liquid separation for the second time, solid phase be prepare 2,4-dinitrobenzene methyl ether product, liquid phase is an organic solvent.
2. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 1,4-dinitrobenzene methyl ether technology, it is characterized in that: the dehydration value of nitration mixture is controlled at 2.0～4.8 in the described the first step continuous thermal insulating nitration reaction, the mole proportioning of Nitroanisole and nitric acid is controlled at 1: 0.90～1.20, and the temperature of the control of nitration reaction is at 60 ℃～140 ℃.
3. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 1 and 2,4-dinitrobenzene methyl ether technology is characterized in that: the solid-liquid separation temperature behind described the 5th step crystallisation by cooling is controlled at 20 ℃～80 ℃.
4. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 1 and 2,4-dinitrobenzene methyl ether technology is characterized in that: separation and purification can adopt the recrystallization separation and purification in described the 6th step, also can adopt the washing separation and purification.
5. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 1 and 2,4-dinitrobenzene methyl ether technology is characterized in that: described organic solvent is methyl alcohol, ethanol.
6. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 1 and 2,4-dinitrobenzene methyl ether technology is characterized in that: carry out rectification process after described the 7th step solid-liquid separation, reclaim organic solvent.
7. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 1 and 2,4-dinitrobenzene methyl ether technology is characterized in that: described continuous thermal insulating nitration is reflected in the nitrator and carries out, and nitrator is quick liquid liquid mixing equipment.
8. Nitroanisole continuous thermal insulating nitration preparation 2 according to claim 7,4-dinitrobenzene methyl ether technology, it is characterized in that: described quick liquid liquid mixing equipment is the stirring tank mixing tank, it perhaps is the jet jet mixer, perhaps be the percussion flow mixing tank, perhaps being static mixer, perhaps is dynamic mixer.
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| CNB2006100854924A CN100361957C (en) | 2006-06-19 | 2006-06-19 | Tech. of preparing 2,4-di nitro methyl-phenoxide by nitro methyl-phenoxide continuous thermal insulating nitration |
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| CNB2006100854924A CN100361957C (en) | 2006-06-19 | 2006-06-19 | Tech. of preparing 2,4-di nitro methyl-phenoxide by nitro methyl-phenoxide continuous thermal insulating nitration |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001077062A1 (en) * | 2000-04-11 | 2001-10-18 | Bayer Aktiengesellschaft | Method for producing 4-bromo- and 4-chloro-2-nitro-1-trifluoromethoxybenzene |
| CN1203045C (en) * | 2003-06-18 | 2005-05-25 | 江苏扬子江药业集团有限公司 | Method for preparing 4-chlorine-3-nitroanisole |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001077062A1 (en) * | 2000-04-11 | 2001-10-18 | Bayer Aktiengesellschaft | Method for producing 4-bromo- and 4-chloro-2-nitro-1-trifluoromethoxybenzene |
| CN1203045C (en) * | 2003-06-18 | 2005-05-25 | 江苏扬子江药业集团有限公司 | Method for preparing 4-chlorine-3-nitroanisole |
Non-Patent Citations (1)
| Title |
|---|
| 芳环上亲核取代反应－2,4-二硝基氯苯醚化研究. 曹瑞军，梅冬.西安交通大学学报，第8卷. 1994 * |
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