CN102070457A - Method for continuously preparing dinitrochlorobenzene - Google Patents
Method for continuously preparing dinitrochlorobenzene Download PDFInfo
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- CN102070457A CN102070457A CN2011100382799A CN201110038279A CN102070457A CN 102070457 A CN102070457 A CN 102070457A CN 2011100382799 A CN2011100382799 A CN 2011100382799A CN 201110038279 A CN201110038279 A CN 201110038279A CN 102070457 A CN102070457 A CN 102070457A
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Abstract
The invention discloses a method for continuously preparing dinitrochlorobenzene. Multiple dinitration reactors are connected in series for reaction, and mononitrochlorobenzene is continuously added to the first dinitration reactor, and continuously flows through all the dinitration reactors and flows out; a mixed acid nitrating agent is prepared from 75-85% of sulfuric acid, 2-7% of nitric acid and 5-15% of water; the reaction temperature is 40-95 DEG C; and each dinitration reactor is provided with a separation device for separating an organic phase from an inorganic phase, and the inorganic phase is returned into the reactor, thereby keeping the inorganic phase and the organic phase in the required proportion. In the invention, the dinitrochlorobenzene is prepared by continuous reactions, and the reactions are continuously carried out and sequentially completed; chlorobenzene is used for extracting nitrates and nitric acid in an acid phase, thereby lowering the content of the nitric acid in the acid phase and recycling the nitrates in the acid phase; by the invention, the dinitrochlorobenzene can be continuously prepared from two raw materials (chlorobenzene and p-nitrochlorobenzene) by using one set of devices; and the invention has the advantages of low raw material consumption and high production capacity.
Description
Technical field
The present invention relates to a kind of preparation method of dinitrochlorobenzene, particularly a kind of continuous method for preparing dinitrochlorobenzene.
Background technology
Dinitrochlorobenzene abbreviates DNCB as, mainly be used as preparation dyestuff, medicine with the intermediate of agricultural chemicals, help and gather auxiliary agent etc., molecular formula is C
6H
3Cl (NO
2)
2, it has six kinds of isomer, and what need production is 2, the dinitrochlorobenzene of 4-DNCB structure, be in the product of raw material production 2 with Benzene Chloride, 4-DNCB accounts for general about 96%, 2,6-DNCB accounts for about 3%, and not nitrated nitro-chlorobenzene accounts for 0.2%, and all the other are nitrated by product.With p-Nitrophenyl chloride is 2 of raw material production, and 4-DNCB generally accounts for 99.5%, and all the other itrated compounds and by product account for 0.5%.
Fs: by nitrated one-tenth one nitro-chlorobenzene of chlorobenzene, a nitro-chlorobenzene is called for short MNCB:
Subordinate phase: by the nitrated one-tenth dinitrochlorobenzene of a nitro-chlorobenzene:
Domestic existing dinitrochlorobenzene production technique all adopts be interrupted to produce, be interrupted explained hereafter ubiquity efficient low, consume high, security and quality product can not get guaranteeing.
At the above-mentioned defective that exists, scientific and technical personnel have carried out a large amount of research, have delivered a large amount of documents and have attempted to solve, and are not high but these methods all exist product purity, and the raw materials consumption height is difficult for realizing defectives such as large-scale industrialization continuous production.
Summary of the invention
Technical problem to be solved by this invention provides a kind of continuous method for preparing dinitrochlorobenzene, this method is fit to large-scale industrial production, can guarantee the safety and stability of producing and the quality of product, reduce the generation of raw-material consumption and waste water, enhance productivity, energy consumption reduces, and guarantees production safety and quality product.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
The present invention is a kind of continuous method for preparing dinitrochlorobenzene, comprise to contain a nitro-chlorobenzene mixed solution by the direct synthetic of chlorobenzene or a nitro-chlorobenzene is a raw material, use the dinitrobenzene reactor to carry out nitration reaction, it is characterized in that: described method is used many dinitrobenzene reactors in series reactions, to contain a nitro-chlorobenzene mixed solution or a nitro-chlorobenzene by the direct synthetic of chlorobenzene be the reaction of a too much platform reactor of Continuous Flow to the process of final generation dinitrochlorobenzene from adding, contain a nitro-chlorobenzene mixed solution or a nitro-chlorobenzene by the direct synthetic of chlorobenzene continuous the adding by first dinitrobenzene reactor, since first the too much platform dinitrobenzene of dinitrobenzene reactor Continuous Flow reactor, flow out continuously then by last platform dinitrobenzene reactor; The dinitro glycosylation reaction uses nitration mixture as nitrating agent, and the nitration mixture quality group becomes 75 ~ 85% sulfuric acid, 2 ~ 7% nitric acid, 5 ~ 15% water; The reaction time of mixed solution in every dinitrobenzene reactor that contains nitrating agent, a nitro-chlorobenzene is 15 ~ 60 minutes, and temperature of reaction is 40～95 ℃, and preferred temperature of reaction is 60～90 ℃, and preferred temperature of reaction is 75～90 ℃; Described dinitrobenzene reactor all has tripping device, the organic phase that produces in order to separating reaction is with mutually inorganic, inorganic phase circulation device is arranged in the separator, can turn back to mutually in the reactor, make inorganic phase and organic phase in the reactor keep the ratio of requirement inorganic.Described many dinitrobenzene reactors comprise first dinitrobenzene reactor and Mo Tai dinitrobenzene reactor at least, and when comprising two dinitrobenzene reactors, second dinitrobenzene reactor is last platform dinitrobenzene reactor.The above-mentioned continuous method for preparing dinitrochlorobenzene, preferred technical scheme is: the dinitrobenzene temperature of reaction is 60 ~ 90 ℃.In every reactor, organism and be 1:(4.0 ~ 5.0 as the nitration mixture mass ratio of nitrating agent) between.
A kind of continuous method for preparing dinitrochlorobenzene of the present invention, further concrete technical scheme can be: describedly contain a nitro-chlorobenzene mixed solution or a nitro-chlorobenzene is added by first dinitrobenzene reactor, the organic phase that reaction generates flows through successively and comprises first dinitrobenzene reactor, end platform dinitrobenzene reactor participates in reaction at each interior dinitrobenzene reactor, final generation contains the dinitrochlorobenzene organic phase and enters first step washed reaction device successively, the alkali cleaning reactor, second stage washed reaction device is handled, sulfuric acid is added by last platform dinitrobenzene reactor, nitric acid is added respectively by each dinitrobenzene reactor, the inorganic of reaction generation begins to flow through each dinitrobenzene reactor with the organic phase reverse direction from last platform dinitrobenzene reactor, arrive first dinitrobenzene reactor at last and participate in reaction successively, finally become the acid of lower concentration.The organic phase that reaction generates in the entire reaction device forms countercurrent flow mutually with inorganic like this, and the acid of lower concentration can participate in other reactions or be for further processing.Further, first step washed reaction device contains acid elution water and can some or all ofly return each dinitrobenzene reactor preparation nitration mixture.
A kind of continuous method for preparing dinitrochlorobenzene of the present invention, further concrete technical scheme can also be: the described continuous method for preparing dinitrochlorobenzene, with the chlorobenzene is starting raw material, at first carry out the mononitration reaction and generate a nitro-chlorobenzene by chlorobenzene, the detailed process and the condition of mononitration reaction are: reaction uses nitration mixture to be nitrating agent, and the nitration mixture quality group becomes 70 ~ 80% sulfuric acid, 0.2 ~ 5% nitric acid, 16 ~ 28% water; Preferred nitration mixture consists of 72 ~ 78% sulfuric acid, 3.8 ~ 4.0% nitric acid, 16 ~ 20% water; Temperature of reaction is 30 ~ 85 ℃; Described mononitration reactor has tripping device, the organic phase that produces in order to separating reaction is with mutually inorganic, inorganic phase circulation device is arranged in the separator, can turn back to mutually in the reactor, make inorganic phase and organic phase in the reactor keep the ratio of requirement inorganic.Further concrete condition can be: the temperature of reaction of a nitration reaction is 65 ~ 75 ℃.Further concrete condition can be: many mononitration reactors are used in described mononitration reaction, the mononitration reactor comprises first mononitration reactor and a last platform mononitration reactor at least, chlorobenzene is added by first mononitration reactor, react the organic phase that generates and flow through each mononitration reactor participation reaction successively, the organic phase mixed solution that final generation contains a nitro-chlorobenzene enters the dinitrobenzene reactor and carries out the dinitro glycosylation reaction; Inorganic phase flow direction is opposite with organic phase, reach first mononitration reactor from last platform mononitration reactor, finally become the inorganic phase of low acid concentration, be for further processing, the organic phase that reaction generates in the entire reaction device forms countercurrent flow mutually with inorganic; The mononitration reactor has tripping device, and the organic phase that produces in order to separating reaction has inorganic phase circulation device with mutually inorganic in the separator, can turn back to mutually in the reactor inorganic, makes inorganic phase in the reactor and organic phase keep the ratio that requires.Further concrete condition can also be: carry out nitration reaction by chlorobenzene and generate in the process of a nitro-chlorobenzene, before a nitroso reaction device, extraction reactor is set, inorganic itrated compound and the nitric acid mutually that in extraction reactor extraction mononitration reaction process, flows out by chlorobenzene at first from first mononitration reactor, in order to reduce inorganic nitric acid in mutually, reclaim inorganic itrated compound in mutually.
A kind of continuous method for preparing dinitrochlorobenzene of the present invention, further concrete technical scheme can also be: the described continuous method for preparing dinitrochlorobenzene, with right-nitro-chlorobenzene is that starting raw material carries out the dinitro glycosylation reaction, and the dinitrobenzene temperature of reaction is 60 ~ 90 ℃.Further concrete technical scheme can be: before first dinitrobenzene reactor extraction reactor is set, with right-nitro-chlorobenzene is before starting raw material carries out the dinitro glycosylation reaction, in extraction reactor, use right-inorganic dinitrochlorobenzene in mutually that first dinitrobenzene reactor of nitro-chlorobenzene extraction flows out, then organic phase is added first dinitrobenzene reactor.Further concrete technical scheme can also be: reaction generates contains the dinitrochlorobenzene organic phase and enters first step washed reaction device, alkali cleaning reactor, second stage washed reaction device successively and handle; With right-nitro-chlorobenzene is before starting raw material carries out the dinitro glycosylation reaction, inorganic dinitrochlorobenzene and the nitric acid in mutually that uses that first dinitrobenzene reactor of chlorobenzene extraction flow out.Acid chlorobenzene after the extraction can be stored, utilize again during with chlorobenzene continuous production dinitrochlorobenzene.Further concrete technical scheme can also be: reaction generates contains the dinitrochlorobenzene organic phase and enters first step washed reaction device, alkali cleaning reactor, second stage washed reaction device successively and handle; With right-nitro-chlorobenzene is before starting raw material carries out the dinitro glycosylation reaction, use right-inorganic dinitrochlorobenzene in mutually that first dinitrobenzene reactor of nitro-chlorobenzene extraction flows out, then organic phase is added first dinitrobenzene reactor, add the partly sour water of first step washed reaction device generation simultaneously, reduce vitriolic effective concentration in the acid mutually, with the sour phase after the chlorobenzene extraction dilution, the acid chlorobenzene after the extraction is stored again, utilize again during with chlorobenzene continuous production dinitrochlorobenzene.
A kind of continuous method for preparing dinitrochlorobenzene of the present invention, further concrete technical scheme can also be: enter first step washed reaction device, alkali cleaning reactor, second stage washed reaction device successively from the organic phase that contains dinitrochlorobenzene of last platform dinitrobenzene reactor made and handle, in first step washed reaction device, add hot water, add alkali lye in the alkali cleaning reactor, add hot water in the washed reaction device of the second stage; Containing finally becomes finished product after the dinitrochlorobenzene organic phase flows through first step washed reaction device, alkali cleaning reactor, second stage washed reaction device successively; Hot water flows into the alkali cleaning reactor by second stage washed reaction device, and the inorganic phase of alkaline waste water that final sum alkali cleaning reactor reaction produces flows out together; The inorganic dinitrobenzene reactor that can some or all ofly return mutually of acid elution water that contains in the first step washed reaction device is prepared nitration mixture; First step washed reaction device, alkali cleaning reactor and second stage washed reaction device all have tripping device, the organic phase that produces in order to separating reaction is with mutually inorganic, inorganic phase circulation device is arranged in the separator, inorganic phase can be turned back to as requested in the reactor or discharge.Further concrete technical scheme can also be: described one-level washed reaction device, alkali cleaning reactor, second stage washed reaction device are made up of 1 or many reactors in series.The hot water temperature of the hot water of first step washed reaction device, second stage washed reaction device is preferably 65 ~ 75 ℃.
A kind of continuous method for preparing dinitrochlorobenzene of the present invention, in each above-mentioned technical scheme, its method of adjusting the nitration mixture composition can be sulfuric acid, oleum, concentrated nitric acid, the rare nitric acid that adds various concentration, can satisfy the demand as long as make the nitration mixture composition reach specified requirement.
In each above-mentioned technical scheme, the extraction reactor of a chlorobenzene and a nitro-chlorobenzene, mononitration reactor, dinitrobenzene reactor, first step washed reaction device, alkali cleaning reactor, second stage washed reaction device all can be formed by 1 or many, and the concrete platform of each several part is several according to various situations such as throughput requirement, product purity and yield requirements and decide.
In each above-mentioned technical scheme, the reactor of chlorobenzene and nitro-chlorobenzene extraction is preferably one or two; The mononitration reactor is preferably two or three, and the dinitrobenzene reactor is preferably Liang Tai, three, four, five or six, and first step washed reaction device, alkali cleaning reactor, second stage washed reaction device are preferably one, two or three.
In each above-mentioned technical scheme, the mass concentration of the vitriol oil of adding is preferably more than 90%, and more preferably more than 92.5%, the nitric acid mass concentration is preferably more than 80%, more preferably more than 90%.
A kind of typically by chlorobenzene be starting raw material prepare dinitrochlorobenzene technology as shown in Figure 1, chlorobenzene is a dinitrochlorobenzene through extraction reactor, two mononitration reactors and two dinitrobenzene reactor made, makes finished product through two-stage washing, alkali cleaning.But in this technology, the mononitration reactor can be one, Liang Tai, three or four, the dinitrobenzene reactor can be Liang Tai, three, four, five or six, and first step washed reaction device, alkali cleaning reactor, second stage washed reaction device can be two or three.
By adopting technique scheme, a kind of continuous method for preparing dinitrochlorobenzene of the present invention has the characteristics of following several respects:
A) sulfuric acid directly adds dinitrobenzene reactor participation reaction, and the inorganic of Reaction Separation enters the mononitration reactor successively from the dinitrobenzene reactor; And the itrated compound organic phase that reaction produces enters each dinitrobenzene reactor successively from last platform mononitration reactor, and inorganic like this phase and organic phase form full counter flow in series continuous flow;
B) be provided with inorganic phase circulation device in the tripping device of mononitration reactor, the inorganic phase Returning reactor of a part can be recycled, redundance inorganic by after move forward.The mononitration reactor is finished the first step nitration reaction, by 2 above mononitration reactors in series with nitrated one-tenth one nitro-chlorobenzene of chlorobenzene; The dinitrobenzene reactor finish second the step nitration reaction, by 2 above dinitrobenzene reactors in series with the nitrated one-tenth dinitrochlorobenzene of a nitro-chlorobenzene;
C) chlorobenzene or a nitro-chlorobenzene add extraction reactor and extract after the first step Reaction Separation organism contained in the acid mutually and reduce sour nitric acid content in mutually, and then reduce raw-material consumption;
D) the dinitrobenzene reactor is by the device of 2 above reactors in series groups, the acid waste water that produces can continue on in the mononitration reactor, vitriolic effective concentration in the acid mutually of control mononitration reactor, the mononitration reaction is carried out fully, be unlikely making that reaction is too violent simultaneously again.
These technical schemes comprise concrete technical scheme, further concrete technical scheme and further concrete technical scheme also can be according to response situation combination or combinations mutually, thereby reach better technique effect.
A kind of continuous method for preparing dinitrochlorobenzene of the present invention, the dinitrochlorobenzene finished product of preparation consists of 2, and 6-DNCB is about 3%2, and 4-DNCB is about 96%, and MNCB 0.2%; After adopting two washed reaction devices, an alkali cleaning reactor to separate, dinitrochlorobenzene can reach purity 99.5%; Reaction process is carried out continuously, and sulfuric acid, nitric acid are utilized continuously, the raw material availability height; Adopt the continuous and automatic operation, reduced labour intensity, enlarged throughput; The sour water that reaction produces is used for the mononitration reaction, and the alkaline water of generation is used for the production of other products, and discharge of wastewater is few; Adopt itrated compound and nitric acid in the chlorobenzene extraction acid mutually in this method, reclaimed the itrated compound in the acid mutually, reduced raw materials consumption, improved the utilization ratio of nitric acid.Between produce 1310 kilograms of dinitrochlorobenzene sulfuric acid consumption per ton in the breaking process, nitric acid consumes 720 kilograms, dinitrochlorobenzene sulfuric acid consumption per ton is 950 kilograms in the production method of employing this patent, 700 kilograms of nitric acid consumptions, compare with the interruption production technique, adopt the sulfuric acid consumption of the method dinitrochlorobenzene per ton of this patent to descend about 27.5%, the nitric acid consumption descends about 2.8%, and throughput can reach 1.5 ~ 6 times an of breaking process.
Various content of the art of this patent scheme and ratio if no special instructions, are mass content and ratio.
The present invention has following beneficial effect:
A kind of continuous method for preparing dinitrochlorobenzene of the present invention prepares dinitrochlorobenzene with chlorobenzene or a nitro-chlorobenzene and nitric-sulfuric acid successive reaction under the certain temperature condition, and each reaction is carried out continuously, finishes successively; Also adopt itrated compound and nitric acid in the chlorobenzene extraction acid mutually in the method, in order to reducing the nitric acid in the acid mutually, the itrated compound of recovered acid in mutually; Can accomplish covering device chlorobenzene, two kinds of raw material continuous production of p-Nitrophenyl chloride dinitrochlorobenzene; Raw material consumption is few, the throughput height.
Description of drawings
Fig. 1 is a kind of schematic flow sheet of the nitrated one-tenth dinitrochlorobenzene of chlorobenzene.
This technology, chlorobenzene make finished product through one-level extraction reactor, two mononitration reactors and two dinitrobenzene reactor made through washing, alkali cleaning, washing.Among the figure, 1 is extraction reactor, and 2 and 3 are the mononitration reactor, and 4 and 5 is the dinitrobenzene reactor, and 6 and 8 is the washed reaction device, and 7 are the alkali cleaning reactor.
Fig. 2 is a kind of schematic flow sheet of the nitrated one-tenth dinitrochlorobenzene of p-Nitrophenyl chloride.
This flow process p-Nitrophenyl chloride is made dinitrochlorobenzene through two dinitrobenzene reactors, makes finished product through washing, alkali cleaning, washing.Among the figure, 1 is extraction reactor, and 4 and 5 is the dinitrobenzene reactor, and 6 and 8 is the washed reaction device, and 7 are the alkali cleaning reactor.
Fig. 3 is the another kind of schematic flow sheet of the nitrated one-tenth dinitrochlorobenzene of p-Nitrophenyl chloride.
This flow process chlorobenzene becomes dinitrochlorobenzene through two-stage extraction reactor, p-Nitrophenyl chloride through two dinitrobenzene reactor made, make finished product through washing, alkali cleaning, washing, inorganic dinitrochlorobenzene, the nitric acid in mutually that uses that first dinitrobenzene reactor of chlorobenzene extraction flow out.Among the figure, 1 and 11 is extraction reactor, and 4 and 5 is the dinitrobenzene reactor, and 6 and 8 is the washed reaction device, and 7 are the alkali cleaning reactor.
Fig. 4 is the another kind of schematic flow sheet of the nitrated one-tenth dinitrochlorobenzene of p-Nitrophenyl chloride.
That this flow process is used is right-inorganic dinitrochlorobenzene in mutually that first dinitrobenzene reactor of nitro-chlorobenzene extraction flows out, and p-Nitrophenyl chloride is made dinitrochlorobenzene through two dinitrobenzene reactors then, makes finished product through washing, alkali cleaning, washing.Among the figure, 1 is extraction reactor, and 4 and 5 is the dinitrobenzene reactor, and 6 and 8 is the washed reaction device, and 7 are the alkali cleaning reactor.
Embodiment
Below in conjunction with embodiment this patent is further detailed, the various content of embodiment and ratio are mass content and ratio if no special instructions.The technology of aftertreatment is handled according to common processing purifying technique, as long as reach the purification purpose.Other components in the form are meant that raw material contains or react the HCl of the sulfurous acid of generation, persulfuric acid, nitrous acid, oxynitride, hydrolysis generation, and this component does not participate in reaction substantially.The mean residence time that the organic phase stop reaction times in the form calculates according to organic content, input speed.
As shown in Figure 1, according to the method described in this patent, wherein on the reactor 1,2,3,4,5,6,7,8 tripping device is arranged all.Inorganic phase control condition of each reactor and organic phase on average stop reaction times such as following table 1.Chlorobenzene total amount, nitric acid total amount, sulfuric acid total amount additional proportion are chlorobenzene: nitric acid total amount: sulfuric acid total amount=1:1.2:1.5.
Table 1
The first step is that chlorobenzene and nitric acid reaction generate a nitro-chlorobenzene, and nitration mixture consists of 74% sulfuric acid, 4% nitric acid, 18% water in the reaction; Second step was that the nitro-chlorobenzene that reaction generates continues and nitric acid reaction generation dinitrochlorobenzene, and the nitration mixture standard group becomes 79% sulfuric acid, 5% nitric acid, 14% water in the reaction.
The requirement of washing is that the organic phase pH value that the first washed reaction still comes out is 3.3 ~ 4.5, and the organic phase pH value that the alkali cleaning reactor comes out is that the organic phase pH value that 6.5 ~ 7.5, the second washed reaction still comes out is 6.7 ~ 7.3.
Quality product such as following table 2:
Table 2
| |
2,4- |
2,6-DNCB | Isomer | MNCB |
| % | 96 | 3 | 0.8 | 0.2 |
Product yield: 97.0%.
As shown in Figure 2, according to the flow process described in this patent, wherein on the reactor 1,4,5 tripping device is arranged all.One nitro-chlorobenzene total amount, nitric acid total amount, sulfuric acid total amount additional proportion are a nitro-chlorobenzene: nitric acid total amount: sulfuric acid total amount=1:(0.4 ~ 0.5): (1.0 ~ 1.3).Inorganic phase control condition of each reactor and organic phase on average stop reaction times such as following table 3, and washing, alkali cleaning purification condition are with embodiment 1.
Table 3
Quality product such as following table 4, product yield: 96.5%.：
Table 4
| |
2,4-DNCB | MNCB | Other |
| % | 99.5 | 0.1 | 0.4 |
Shown in the technical process of Fig. 3, be raw material with the p-Nitrophenyl chloride, preparation 2,4 dinitrochlorobenzene are with inorganic itrated compound and the nitric acid in mutually of chlorobenzene extraction.The inorganic dinitrochlorobenzene in mutually that chlorobenzene flows out through first dinitrobenzene reactor of two placed in-line reactors extractions continuously, p-Nitrophenyl chloride is made dinitrochlorobenzene through two dinitrobenzene reactors then, makes finished product through washing, alkali cleaning, washing.On the reactor 1,11,4,5,6,7,8 tripping device is arranged all.One nitro-chlorobenzene: nitric acid total amount: sulfuric acid total amount mass ratio=1:0.41 ~ 0.45:0.9 ~ 1.2.It is as shown in table 5 that the parameter of the inorganic phase of each reactor and organic phase on average stop the reaction times, and washing, alkali cleaning purification condition are with embodiment 1.
Table 5
Quality product such as following table 6:
Table 6
| |
2,4-DNCB | MNCB? | Other |
| % | 99.6 | 0.1 | 0.3 |
Product yield: 97.5%.
Shown in the technical process of Fig. 4, be raw material with the p-Nitrophenyl chloride, the preparation dinitrochlorobenzene.Inorganic dinitrochlorobenzene in mutually that p-Nitrophenyl chloride extracts at first that first dinitrobenzene reactor flow out, p-Nitrophenyl chloride is made dinitrochlorobenzene through two dinitrobenzene reactors then, makes finished product through washing, alkali cleaning, washing.On the reactor 1,4,5,6,7,8 tripping device is arranged all.One nitro-chlorobenzene: nitric acid total amount: sulfuric acid total amount=1:0.43 ~ 0.45:0.8 ~ 0.9(mass ratio).It is as shown in table 7 that the inorganic phase parameter of each reactor and organic phase on average stop the reaction times, and washing, alkali cleaning purification condition are with embodiment 1.
Table 7
Quality product such as following table 8:
Table 8
| |
2,4-DNCB | MNCB? | Other |
| % | 99.7 | 0.1 | 0.2 |
Product yield: 96.0%.
As shown in Figure 1, according to the method described in this patent, wherein on the reactor 1,2,3,4,5,6,7,8 tripping device is arranged all.Inorganic phase control condition of each reactor and organic phase on average stop reaction times such as following table 9, and washing, alkali cleaning purification condition are with embodiment 1.
Table 9
Quality product such as following table 10:
Table 10
| |
2,4- |
2,6-DNCB | Isomer | MNCB |
| % | 96 | 3 | 0.8 | 0.2 |
Product yield: 95.70%.
Claims (10)
1. method for preparing continuously dinitrochlorobenzene, comprise to contain a nitro-chlorobenzene mixed solution by the direct synthetic of chlorobenzene or a nitro-chlorobenzene is a raw material, use the dinitrobenzene reactor to carry out nitration reaction, it is characterized in that: described method is used many dinitrobenzene reactors in series reactions, to contain a nitro-chlorobenzene mixed solution or a nitro-chlorobenzene by the direct synthetic of chlorobenzene be the reaction of a too much platform reactor of Continuous Flow to the process of final generation dinitrochlorobenzene from adding, contain a nitro-chlorobenzene mixed solution or a nitro-chlorobenzene by the direct synthetic of chlorobenzene continuous the adding by first dinitrobenzene reactor, since first the too much platform dinitrobenzene of dinitrobenzene reactor Continuous Flow reactor, flow out continuously then by last platform dinitrobenzene reactor; The dinitro glycosylation reaction uses nitration mixture as nitrating agent, and the nitration mixture quality group becomes 75 ~ 85% sulfuric acid, 2 ~ 7% nitric acid, 5 ~ 15% water; The reaction time of mixed solution in every dinitrobenzene reactor that contains nitrating agent, a nitro-chlorobenzene is 15 ~ 60 minutes, and temperature of reaction is 40～95 ℃; Described dinitrobenzene reactor all has tripping device, the organic phase that produces in order to separating reaction is with mutually inorganic, inorganic phase circulation device is arranged in the separator, can turn back to mutually in the reactor, make inorganic phase and organic phase in the reactor keep the ratio of requirement inorganic; Described many dinitrobenzene reactors comprise first dinitrobenzene reactor and Mo Tai dinitrobenzene reactor at least, and when comprising two dinitrobenzene reactors, second dinitrobenzene reactor is last platform dinitrobenzene reactor.
2. according to the described continuous method for preparing dinitrochlorobenzene of claim 1, it is characterized in that: described dinitrobenzene temperature of reaction is 60 ~ 90 ℃.
3. according to the described continuous method for preparing dinitrochlorobenzene of claim 1, it is characterized in that: described many dinitrobenzene reactors comprise first dinitrobenzene reactor and Mo Tai dinitrobenzene reactor at least, when comprising two dinitrobenzene reactors, second dinitrobenzene reactor is last platform dinitrobenzene reactor.
4. according to the described continuous method for preparing dinitrochlorobenzene of claim 1, it is characterized in that: describedly contain a nitro-chlorobenzene mixed solution or a nitro-chlorobenzene is added by first dinitrobenzene reactor, the organic phase that reaction generates flows through successively and comprises first dinitrobenzene reactor, end platform dinitrobenzene reactor participates in reaction at each interior dinitrobenzene reactor, final generation contains the dinitrochlorobenzene organic phase and enters first step washed reaction device successively, the alkali cleaning reactor, second stage washed reaction device is handled, sulfuric acid is added by last platform dinitrobenzene reactor, nitric acid is added respectively by each dinitrobenzene reactor, the inorganic of reaction generation begins to flow through each dinitrobenzene reactor with the organic phase reverse direction from last platform dinitrobenzene reactor, arrive first dinitrobenzene reactor at last and participate in reaction successively, finally become the acid of lower concentration.
5. according to the described continuous method for preparing dinitrochlorobenzene of claim 4, it is characterized in that: the containing the acid elution water section or all return each dinitrobenzene reactor preparation nitration mixture of first step washed reaction device.
6. according to the described continuous method for preparing dinitrochlorobenzene of claim 1, it is characterized in that: the described continuous method for preparing dinitrochlorobenzene, with the chlorobenzene is starting raw material, at first carry out nitration reaction and generate a nitro-chlorobenzene by chlorobenzene, the detailed process and the condition of mononitration reaction are: reaction uses nitration mixture to be nitrating agent, the nitration mixture quality group becomes 70 ~ 80% sulfuric acid, 0.2 ~ 5% nitric acid, 16 ~ 28% water, and temperature of reaction is 30 ~ 85 ℃; Described mononitration reactor has tripping device, the organic phase that produces in order to separating reaction is with mutually inorganic, inorganic phase circulation device is arranged in the separator, can turn back to mutually in the reactor, make inorganic phase and organic phase in the reactor keep the ratio of requirement inorganic.
7. according to the described continuous method for preparing dinitrochlorobenzene of claim 6, it is characterized in that: many mononitration reactors are used in described mononitration reaction, the mononitration reactor comprises first mononitration reactor and a last platform mononitration reactor at least, chlorobenzene is added by first mononitration reactor, react the organic phase that generates and flow through each mononitration reactor participation reaction successively, the organic phase mixed solution that final generation contains a nitro-chlorobenzene enters the dinitrobenzene reactor and carries out the dinitro glycosylation reaction; Inorganic phase flow direction is opposite with organic phase, reach first mononitration reactor from last platform mononitration reactor, finally become the inorganic phase of low acid concentration, be for further processing, the organic phase that reaction generates in the entire reaction device forms countercurrent flow mutually with inorganic; The mononitration reactor has tripping device, and the organic phase that produces in order to separating reaction has inorganic phase circulation device with mutually inorganic in the separator, can turn back to mutually in the reactor inorganic, makes inorganic phase in the reactor and organic phase keep the ratio that requires.
8. according to the described continuous method for preparing dinitrochlorobenzene of claim 6, it is characterized in that: carry out digestion reaction by chlorobenzene and generate in the process of a nitro-chlorobenzene, before a nitroso reaction device, extraction reactor is set, inorganic itrated compound and the nitric acid mutually that in extraction reactor extraction mononitration reaction process, flows out by chlorobenzene at first from first mononitration reactor, in order to reduce inorganic nitric acid in mutually, reclaim inorganic itrated compound in mutually.
9. according to the described continuous method for preparing dinitrochlorobenzene of claim 1, it is characterized in that: the described continuous method for preparing dinitrochlorobenzene is that starting raw material carries out the dinitro glycosylation reaction with right-nitro-chlorobenzene, and the dinitrobenzene temperature of reaction is 60 ~ 90 ℃.
10. according to the described continuous method for preparing dinitrochlorobenzene of claim 1, it is characterized in that: enter first step washed reaction device, alkali cleaning reactor, second stage washed reaction device successively from the organic phase that contains dinitrochlorobenzene of last platform dinitrobenzene reactor made and handle, in first step washed reaction device, add hot water, add alkali lye in the alkali cleaning reactor, add hot water in the washed reaction device of the second stage; Containing finally becomes finished product after the dinitrochlorobenzene organic phase flows through first step washed reaction device, alkali cleaning reactor, second stage washed reaction device successively; Hot water flows into the alkali cleaning reactor by second stage washed reaction device, and the inorganic phase of alkaline waste water that final sum alkali cleaning reactor reaction produces flows out together; The inorganic dinitrobenzene reactor that can some or all ofly return mutually of acid elution water that contains in the first step washed reaction device is prepared nitration mixture; First step washed reaction device, alkali cleaning reactor and second stage washed reaction device all have tripping device, the organic phase that produces in order to separating reaction is with mutually inorganic, inorganic phase circulation device is arranged in the separator, inorganic phase can be turned back to as requested in the reactor or discharge.
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