CN106083596A - A kind of continuous nitrification prepares the method for 2,5 dichloronitrobenzenes - Google Patents
A kind of continuous nitrification prepares the method for 2,5 dichloronitrobenzenes Download PDFInfo
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- CN106083596A CN106083596A CN201610408055.5A CN201610408055A CN106083596A CN 106083596 A CN106083596 A CN 106083596A CN 201610408055 A CN201610408055 A CN 201610408055A CN 106083596 A CN106083596 A CN 106083596A
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- acid
- nitrating pot
- paracide
- extraction
- dichloronitrobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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Abstract
The invention discloses a kind of continuous nitrification and prepare 2, the method of 5 dichloronitrobenzenes, comprise the following steps: use three grades of kettle-type continuous reactions, sulphuric acid, paracide in nitric acid and extraction kettle is simultaneously introduced in first order nitrating pot and carries out nitration reaction, nitrification liquid is sequentially entered in next stage nitrating pot by the lifter that each nitrating pot carries and reacts, after third level nitrating pot completes reaction, separate oil phase and acid phase, oil phase is neutralized, washing and dehydration obtain 2, 5 dichloronitrobenzenes, first order nitrating pot is looped back in part spent acid in acid mutually, residue spent acid enters extraction kettle, isolated acidity paracide and extraction spent acid after paracide extracts, extraction spent acid concentrated one-tenth concentrated vitriol and acid paracide enter recycled in first order nitrating pot.The present invention uses Automated condtrol, eliminates nitration mixture process for preparation, simplifies technological process, it is possible to achieve nitration reaction serialization, nitrification liquid separation serialization and spent acid extraction serialization.
Description
Technical field
The invention belongs to 2, the synthesis field of 5-dichloronitrobenzene, relate to a kind of continuous nitrification and prepare 2,5-dichloronitrobenzene
Method.
Background technology
2,5-dichloronitrobenzenes are important chemical intermediates, mainly for the production of 2,5-dichloroaniline, large red-based g G,
Red base 3GL, fast red rl and triclosan (2,4,4-tri-chloro-2-dihydroxy diphenyl ether) etc., additionally, be alternatively arranged as nitrogen fertilizer potentiating agent
In order to improve rice yield.
Industrialized production 2 at present, 5-dichloronitrobenzene all uses batch production process, makees end acid with sulphuric acid, adds two
Chlorobenzene, then drip nitric acid, sulphuric acid preparation mixed acid nitrification, neutralize, wash, be dehydrated 2,5-dichloronitrobenzene product.Intermittently
Production technology exists that production capacity is low, labor intensity big, poor working environment, consumption of raw materials are high, production cost is high, three-protection design amount
Wait greatly series of problems.Use continuous process, in conjunction with Automated condtrol means, can effectively solve the problems referred to above.Chinese patent
Application 201310601213.5 discloses a kind of acid and applies mechanically serialization nitrification and prepare 2, and the method for 5-dichloronitrobenzene, the method is protected
Nitration mixture preparation process, nitration mixture and paracide has been stayed to simultaneously enter three grades of kettle-type continuous reactor part serializations, by nitrification
A large amount of spent acid that reaction produces after terminating layering all extract concentration, and then set gives up for the mixed acid nitrification of lower batch, the method
Acid treatment amount is big, adds spent acid processing cost.Additionally, in traditional handicraft, oil phase acid boundary there will be emulsion layer, patent
Though CN104649910A is by controlling dehydrating value of sulfuric acid and reaction temperature, only produces a small amount of emulsion layer, but emulsion does not obtain
Control to basic.
Accordingly, it would be desirable to develop new technique, simplification 2, continuous process prepared by 5-dichloronitrobenzene, farthest subtract
The generation of few emulsion layer, improves the utilization rate of raw material, reduces spent acid processing cost.
Summary of the invention
There is no for current 2,5-dichloronitrobenzene production technology that whole serialization, spent acid circulating load be big, the sour phase boundary of oil phase
There is the problem of emulsion layer in face, the invention provides a kind of continuous nitrification and prepare 2, and the method for 5-dichloronitrobenzene, employing is continuously
Nitrification prepares 2, and 5-dichloronitrobenzene, the method uses Automated condtrol, eliminates nitration mixture process for preparation, simplify technique stream
Journey, it is possible to achieve nitration reaction serialization, nitrification liquid separation serialization and spent acid extraction serialization.
Technical scheme is as follows:
A kind of continuous nitrification prepares 2, and the method for 5-dichloronitrobenzene specifically comprises the following steps that employing three grades is kettle-type continuous
Reaction, the paracide in sulphuric acid, nitric acid and extraction kettle is simultaneously introduced in first order nitrating pot and carries out nitration reaction, and nitrification liquid leads to
Crossing the lifter that each nitrating pot carries to sequentially enter in next stage nitrating pot and react, controlling nitration reaction temperature is 58~68 DEG C,
Reacting modulus in nitrating pots at different levels is 3~4, and sulfuric acid concentration is 82~83%, after third level nitrating pot completes reaction, separates oil
Mutually and acid phase, oil phase is neutralized, wash and dehydration obtains 2,5-dichloronitrobenzene, loops back first in the part spent acid in acid mutually
Level nitrating pot, residue spent acid enters extraction kettle, isolated acidity paracide and extraction spent acid, extraction after paracide extracts
Take spent acid under vacuum, still temperature control be condensed into the concentrated vitriol of content >=97% at 290~320 DEG C, concentrated vitriol and
Acid paracide enters recycled in first order nitrating pot.
In the present invention, described reaction modulus refers to acid phase and the volume ratio of oil phase.
In the present invention, the sulphuric acid using mass fraction to be 97% and nitric acid that mass fraction is 98% are as raw material.
The present invention uses three grades of kettle-type continuous reactions, and the mol ratio controlling nitric acid and paracide is 1.00~1.05:
1, sulphuric acid is 1.08~1.35:1 with the mol ratio of nitric acid.
In a particular embodiment of the present invention, after third level nitrating pot completes reaction, separate oil phase and acid phase, in acid mutually
Looping back first order nitrating pot in 80% spent acid to apply mechanically, 20% spent acid enters extraction kettle.
In three grades of autoclave continuous nitrification courses of reaction, normal in order to ensure reaction, control di-nitrated wait side reaction and
Suppression emulsion, the temperature controlling first order nitrating pot is 58~62 DEG C, and the temperature of second level nitrating pot is 65~68 DEG C, the
The temperature of three grades of nitrating pots is 65~68 DEG C, and the temperature of extraction kettle is 68~70 DEG C.
In the present invention, oil phase neutralizes, washes and be dehydrated method particularly includes: drip in oil phase 65~70 DEG C, quality
Mark is the sodium carbonate hydrothermal solution of 8%, neutralizes pH to 8~9, stratification, and it is 7~8 that oil reservoir adds hot wash to pH, distillation
It is dehydrated to obtain 2,5-dichloronitrobenzene.
In the present invention, extraction waste acid concentration method particularly includes: extraction spent acid is evacuated to-0.090Mpa, is warming up to 290
~320 DEG C distilled, obtain the concentrated vitriol of content >=97%.
Nitrating pot in the present invention is all from tape lifter, and third level nitrating pot is reaction, separating one-piece, and extraction kettle is
Extraction, separating one-piece.
Compared with prior art, the present invention has a following remarkable result:
1, cancelling acid preparing device, sulphuric acid, nitric acid are simultaneously introduced first order nitrating pot, and paracide adds extraction kettle, optimize
Technological process;
2, the equal tape lifter of nitrating pots at different levels, possesses reaction, enhanced feature, and third level nitrating pot and extraction kettle are also with dividing
From device, possessing automatic separation, compact equipment, floor space is little;
The spent acid of 80% after 3, third level nitrating pot nitrification liquid separates enters recycled in first order nitrating pot, improves
Reaction modulus in nitrating pot, improves mass transfer condition, is conducive to controlling di-nitrated side reaction of Denging, eliminates emulsion;
4, by controlling reaction modulus, sulfuric acid concentration and the reaction temperature of each nitrating pot, di-nitrated side reaction of Denging is reduced,
And suppress the generation of emulsion, 2 obtained, 5-dichloronitrobenzene constant product quality.
Accompanying drawing explanation
Fig. 1 is the process chart that the continuous nitrification of the present invention prepares the method for 2,5-dichloronitrobenzene.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
1, process units uses 3 nitrating pots and 1 extraction kettle to combine, and 3 nitrating pot total volumies are respectively
2.5m3、1.5m3、1.5m3, dischargeable capacity is respectively as follows: 1.2m3、1.1m3、1.1m3;Extraction kettle total volume is 1.5m3, dischargeable capacity
For 1.1m31 is controlled during,#Nitrating pot temperature 58~62 DEG C, 2#Nitrating pot temperature 65~68 DEG C;3#Nitrating pot temperature 65~68
℃;Extraction kettle temperature 68~70 DEG C;Reaction modulus 3~4, sulfuric acid concentration 82~83%.320L/h paracide is entered to extraction kettle,
Still to be extracted has acid paracide to flow into 1#Nitrating pot, to 1#Nitrating pot throws 97% sulphuric acid of 175L/h, 98% nitre of 120L/h
Acid, nitrification liquid is promoted to next stage nitrating pot, finally 3 successively by each still lifter#Complete reaction in nitrating pot, separate,
Obtaining oil phase itrated compound and spent acid, 80% spent acid returns 1#Nitrating pot recycled, 20% flow to extraction kettle.
2, washing is neutralized: with PH to 8~9, standing point in oil phase itrated compound 65~70 DEG C of 8% sodium carbonate hydrothermal solution of dropping
Layer, oil reservoir adds hot wash twice PH to 7~8, and oil reservoir distillation dehydration obtains 2, and 5-dichloronitrobenzene, gas chromatographic analysis is contained
The 2,5-dichloronitrobenzene finished product of amount >=99.5%.
3, during nitrating wasting acid goes to distillating still, being evacuated to-0.090Mpa, distillation to the still temperature 290~320 DEG C that heat up obtains
The concentrated vitriol of content >=97%.
4, gelled acid is applied mechanically: enter 320L/h paracide to extraction kettle, and still to be extracted has acid paracide to flow into 1#Nitre
Change still, to 1#Nitrating pot throws 175L/h concentrated vitriol, 120L/h98% nitric acid, and nitrification liquid is promoted to successively by each still lifter
Next stage nitrating pot, finally 3#Completing reaction in nitrating pot, separate, obtain oil phase itrated compound and spent acid, 80% spent acid returns 1#Nitre
Changing still recycled, 20% flow to extraction kettle, applies mechanically 5 batches, result such as table 1.
Continuous nitrification and spent acid are applied mechanically the impact of rear product quality by table 1 acid-spending strength and reaction modulus
As known from Table 1, by controlling nitrating pot reacts modulus between 3~4, sulfuric acid concentration between 82~83%,
2 prepared, 5-dichloronitrobenzene content is more than 99.5%, and dinitro class by-products content is few, after continuous nitrification reaction
There is not emulsion.
Claims (7)
1. a continuous nitrification prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that specifically comprise the following steps that three grades of stills of employing
Formula continuous reaction, the paracide in sulphuric acid, nitric acid and extraction kettle is simultaneously introduced in first order nitrating pot and carries out nitration reaction,
Nitrification liquid is sequentially entered in next stage nitrating pot by the lifter that each nitrating pot carries and reacts, and controlling nitration reaction temperature is 58
~68 DEG C, reacting modulus in nitrating pots at different levels is 3~4, and sulfuric acid concentration is 82~83%, completes reaction at third level nitrating pot
After, separating oil phase and acid phase, oil phase is neutralized, wash and dehydration obtains 2, and 5-dichloronitrobenzene, in the part spent acid in acid mutually
Looping back first order nitrating pot, residue spent acid enters extraction kettle, after paracide extracts isolated acidity paracide and
Extraction spent acid, extraction spent acid under vacuum, still temperature control be condensed into the concentrated vitriol of content >=97% at 290~320 DEG C,
Concentrated vitriol and acid paracide enter recycled in first order nitrating pot.
Continuous nitrification the most according to claim 1 prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that described
The temperature of one-level nitrating pot is 58~62 DEG C, and the temperature of second level nitrating pot is 65~68 DEG C, and the temperature of third level nitrating pot is
65~68 DEG C, the temperature of extraction kettle is 68~70 DEG C.
Continuous nitrification the most according to claim 1 prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that use quality
Mark be 97% sulphuric acid and nitric acid that mass fraction is 98% as raw material.
Continuous nitrification the most according to claim 1 prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that control nitric acid
Being 1.00~1.05:1 with the mol ratio of paracide, sulphuric acid is 1.08~1.35:1 with the mol ratio of nitric acid.
Continuous nitrification the most according to claim 1 prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that third level nitre
Changing after still completes reaction, separate oil phase and acid phase, loop back first order nitrating pot and apply mechanically in 80% spent acid in acid mutually, 20% gives up
Acid enters extraction kettle.
Continuous nitrification the most according to claim 1 prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that described oil
Neutralize mutually, wash and be dehydrated method particularly includes: in oil phase drip 65~70 DEG C, mass fraction be 8% sodium carbonate heat
Aqueous solution, neutralizes pH to 8~9, and stratification, it is 7~8 that oil reservoir adds hot wash to pH, and distillation dehydration obtains 2,5-dichloro nitro
Benzene.
Continuous nitrification the most according to claim 1 prepares 2, the method for 5-dichloronitrobenzene, it is characterised in that described extraction
Take waste acid concentration method particularly includes: extraction spent acid is evacuated to-0.090Mpa, is warming up to 290~320 DEG C and distills,
Concentrated vitriol to content >=97%.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107417536A (en) * | 2017-04-10 | 2017-12-01 | 浙江工业大学 | Method and special device for continuous mono-nitration reaction of o-dichlorobenzene |
CN110054566A (en) * | 2019-04-08 | 2019-07-26 | 淮海工学院 | The method of mesitylene continuous nitrification production 2,4,6- trimethyl nitrobenzene |
CN110845338A (en) * | 2018-08-21 | 2020-02-28 | 中国石油化工股份有限公司 | Method for extracting and separating 2, 5-dichloronitrobenzene by adopting composite ionic liquid |
CN111929375A (en) * | 2020-07-20 | 2020-11-13 | 江苏云阳集团药业有限公司 | Method for detecting and analyzing content of 2, 5-dichloronitrobenzene in clozapine bulk drug and methodological verification |
CN112778136A (en) * | 2021-01-11 | 2021-05-11 | 南通江山农药化工股份有限公司 | 2, 5-dichloronitrobenzene and micro-channel continuous synthesis process thereof |
CN113861033A (en) * | 2021-11-03 | 2021-12-31 | 江苏海洋大学 | Process for preparing 1-nitronaphthalene by continuous low-temperature nitration |
CN115433091A (en) * | 2021-10-18 | 2022-12-06 | 江苏隆昌化工有限公司 | Method for synthesizing 2, 5-dichloronitrobenzene through continuous flow tubular reaction |
CN115521207A (en) * | 2022-10-08 | 2022-12-27 | 中建安装集团有限公司 | Continuous production C 9 H 3 Cl 2 F 6 NO 3 Process and apparatus for |
CN115611745A (en) * | 2022-09-26 | 2023-01-17 | 浙江闰土股份有限公司 | Method for continuously producing 3, 4-dichloronitrobenzene |
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Cited By (12)
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CN107417536A (en) * | 2017-04-10 | 2017-12-01 | 浙江工业大学 | Method and special device for continuous mono-nitration reaction of o-dichlorobenzene |
CN110845338A (en) * | 2018-08-21 | 2020-02-28 | 中国石油化工股份有限公司 | Method for extracting and separating 2, 5-dichloronitrobenzene by adopting composite ionic liquid |
CN110845338B (en) * | 2018-08-21 | 2022-09-06 | 中国石油化工股份有限公司 | Method for extracting and separating 2, 5-dichloronitrobenzene by adopting composite ionic liquid |
CN110054566A (en) * | 2019-04-08 | 2019-07-26 | 淮海工学院 | The method of mesitylene continuous nitrification production 2,4,6- trimethyl nitrobenzene |
CN111929375A (en) * | 2020-07-20 | 2020-11-13 | 江苏云阳集团药业有限公司 | Method for detecting and analyzing content of 2, 5-dichloronitrobenzene in clozapine bulk drug and methodological verification |
CN112778136A (en) * | 2021-01-11 | 2021-05-11 | 南通江山农药化工股份有限公司 | 2, 5-dichloronitrobenzene and micro-channel continuous synthesis process thereof |
CN112778136B (en) * | 2021-01-11 | 2023-07-14 | 南通江山农药化工股份有限公司 | 2, 5-dichloronitrobenzene and microchannel continuous synthesis process thereof |
CN115433091A (en) * | 2021-10-18 | 2022-12-06 | 江苏隆昌化工有限公司 | Method for synthesizing 2, 5-dichloronitrobenzene through continuous flow tubular reaction |
CN113861033A (en) * | 2021-11-03 | 2021-12-31 | 江苏海洋大学 | Process for preparing 1-nitronaphthalene by continuous low-temperature nitration |
CN115611745A (en) * | 2022-09-26 | 2023-01-17 | 浙江闰土股份有限公司 | Method for continuously producing 3, 4-dichloronitrobenzene |
CN115521207A (en) * | 2022-10-08 | 2022-12-27 | 中建安装集团有限公司 | Continuous production C 9 H 3 Cl 2 F 6 NO 3 Process and apparatus for |
CN115521207B (en) * | 2022-10-08 | 2023-10-13 | 中建安装集团有限公司 | Continuous production C 9 H 3 Cl 2 F 6 NO 3 Is a process and device for the production of a metal product |
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