CN105461572A - Clean technology for continuously synthesizing 2,4-dinitro-6-chloroaniline - Google Patents
Clean technology for continuously synthesizing 2,4-dinitro-6-chloroaniline Download PDFInfo
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Abstract
A clean technology for continuously synthesizing 2,4-dinitro-6-chloroaniline adopts multistage serially connected reaction kettles and comprises the following steps: continuously adding 2,4-dinitroaniline, hydrochloric acid and chlorine to a first stage reaction kettle, carrying out a chlorination reaction under stirring, allowing parts of a material in a previous reaction kettle to enter a self reaction kettle through a pump and to circulate, allowing parts of the material in the previous reaction kettle to enter a next reaction kettle, continuously carrying out the chlorination reaction, allowing tail gas generated in the previous reaction kettle to enter the next reaction kettle, continuously carrying out the chlorination reaction, allowing parts of a material in a final stage reaction kettle to enter the self reaction kettle through a pump and to circulate, continuously discharging and filtering parts of the final obtained material after a detection result shows the reaction is completed to obtain a filter cake which is a 2,4-dinitro-6-chloroaniline product, allowing a mother liquor obtained after filtration to enter a mother liquor recovery tank, blowing air to the mother liquor in the mother liquor recovery tank, reusing hydrogen chloride tail gas obtained after blowing, pumping the blown mother liquor with certain acidity into a mother liquor storage tank, and recycling the mother liquor in the mother liquor storage tank to substitute hydrochloric acid.
Description
(1) technical field
The present invention relates to the cleaning procedure of a kind of synthesis 2,4-dinitrobenzene-6-chloroaniline, the cleaning procedure of especially a kind of serialization synthesis 2,4-dinitrobenzene-6-chloroaniline.
(2) background technology
2,4-dinitrobenzene-6-chloroaniline is the important intermediate of dispersed dye, and domestic and international consumption is all larger.Its production method generally with 2,4-dinitraniline for raw material, obtain through chlorination.Chlorizating agent mainly contains: (1) clorox; (2) sodium chlorate; (3) chlorine.
(1) use clorox as chlorizating agent, in hydrochloric acid medium, carry out chlorination reaction, the method production process is more numerous and diverse, reaction process has by product to produce, poor product quality, and color and luster is dark, time of chlorinating is longer, and equipment productivity is lower, and aftertreatment is cumbersome.
(2) use sodium chlorate as chlorizating agent, in hydrochloric acid medium, carry out chlorination reaction, the method product purity is more than 98%, and the reaction times is shorter, and yield in unit time is high, stable processing technique, is a kind of reasonable production method.But need a large amount of hydrochloric acid, and mother liquor acidity is lower can not apply mechanically production continuously, produces a large amount of waste water.
(3) use chlorine as chlorizating agent, pass into chlorine under iron(ic) chloride can be had in water medium to exist and carry out chlorination reaction, or in acetic aid medium, pass into chlorine carries out chlorination reaction.Pass into chlorine under having iron(ic) chloride to exist in water medium and carry out chlorination reaction, the method raw materials for production cost is lower, but product foreign matter content high-melting-point is low, product content is low, and require 2,4-dinitraniline to grind very thin, long reaction time, equipment productivity is not high; In acetic aid medium, pass into chlorine carry out chlorination reaction, the method technological process is fairly simple, and product crystalline form is better, and color and luster is good, and product purity is high, and yield is also better, but needs Dichlorodiphenyl Acetate to regenerate, and relatively needs to increase larger production cost.
Introduce a kind of process for cleanly preparing in patent CN103539680A, be that 2,4-dinitraniline is first carried out chlorination reaction with chlorine, then carry out chlorination reaction with sodium chlorate, Recycling Mother Solution is applied mechanically.Owing to can produce the mother liquor of sodium chloride-containing with sodium chlorate chlorination reaction, after mother liquid recycle to certain number of times, in mother liquor, sodium chloride content is too high and can not apply mechanically again, and is difficult to process containing the sodium-chlor mother liquor of high density, really can not accomplish cleaner production.
(3) summary of the invention
In order to solve the problem, the invention provides the cleaning procedure of a kind of serialization synthesis 2,4-dinitrobenzene-6-chloroaniline, this process recovery ratio is high, and the product purity obtained is high, and produces without waste water, really realizes the cleaner production of wastewater zero discharge.
The technical solution used in the present invention is as follows:
A kind of serialization synthesis 2, the cleaning procedure of 4-dinitrobenzene-6-chloroaniline, described technique is as follows: the reactor adopting plural serial stage, according to 2, 4-dinitraniline, hydrochloric acid, the raw materials components mole ratio of chlorine is 1:(4 ~ 12): the proportioning of (0.94 ~ 1.00), continuously by 2, 4-dinitraniline, hydrochloric acid and chlorine addition are in first order reaction still, chlorination reaction is carried out under stirring, material in upper level reactor enters id reaction still internal recycle by a pump part, a part enters in next stage reactor and continues chlorination reaction, the tail gas (hydrogenchloride and the complete chlorine of unreacted) that upper level reactor produces enters in next stage reactor and continues chlorination reaction, control the chlorination reaction temperature of reactor at different levels at 30 DEG C ~ 60 DEG C, material in final stage reactor enters id reaction still internal recycle by a pump part, after reacting completely after testing, part continuous discharge, after filtration or centrifugation, obtain 2, the thick product of 4-dinitrobenzene-6-chloroaniline and mother liquor mother liquor enter disposing mother liquor groove, to the mother liquor drum air in disposing mother liquor groove, bloat the hydrogen chloride tail gas reuse come, mother liquor drum air is to being driven in mother liquor storage tank during certain acidity, mother liquor in mother liquor storage tank substitutes hydrochloric acid recycled.
Further, the mol ratio of 2,4-described dinitranilines, hydrochloric acid, chlorine is preferably 1:(7 ~ 12): (0.95 ~ 0.97).
Further, the massfraction of hydrochloric acid is 28 ~ 35%, preferably 28% ~ 33%.
Further, described chlorination reaction temperature is preferably 35 DEG C ~ 50 DEG C.
Further, 2,4-dinitraniline and hydrochloric acid are first added in making beating still and mix, then are added to continuously in first order reaction still by pump.
Further, can add anion surfactant in described making beating still, as Dispersant MF, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate etc., anion surfactant input amount is 0.2% ~ 2% of 2,4-dinitraniline quality.
Further, to the mother liquor drum air in disposing mother liquor groove, when the hydrochloric acid massfraction in mother liquor is 28% ~ 35% (being preferably 28% ~ 33%), stop air-blowing, mother liquor enters mother liquor storage tank.
Further, reactor at different levels all connects an injector, in reactor, a part of material carries out id reaction still internal recycle by pump via injector, the negative pressure simultaneously produced in injector can suck the tail gas of chlorine or upper level generation, thus fluid and gas enter reactor after can fully mixing in injector, are conducive to the carrying out of chlorination reaction in reactor.
Further, described reactor preferably 2 ~ 4 grades of series connection.
Further, final stage reactor is provided with detection mouth, then judges to react completely without colour-change by KI detection paper.
Further, described filtration or the general physical filtering of separation finger or mechanical separation, as being separated with Filter Press or whizzer, for reaching being continuously removed of material, preferred pressure filter or whizzer are multiple parallel connection, namely final stage reactor material out enters in pressure filter in parallel or whizzer, when pressure filter or whizzer saturated after, switch to other pressure filter or whizzer to ensure being continuously removed of material.Described pressure filter or whizzer be 3 ~ 5 parallel connections preferably.
Further, for reaching being continuously removed of mother liquor, described disposing mother liquor groove can be multiple parallel connection, pressure filter leaches or the isolated mother liquor of whizzer enters in disposing mother liquor groove in parallel continuously one, when reaching setting liquid level, switch to other dead slots to ensure being continuously removed of mother liquor.Described disposing mother liquor groove is 2 or 3 parallel connections preferably.
Further, the hydrogen chloride tail gas that described final stage reactor produces also can reuse.
Further, the reuse of hydrogen chloride tail gas come is bloated in the hydrogen chloride tail gas that final stage reactor produces and disposing mother liquor groove, specifically refer to the synthesis that hydrogen chloride tail gas can be used for 3-acetylaminoaniline, as synthesized according to the method described in publication CN101328133A or similar approach, or hydrogen chloride tail gas enters exhaust treatment system recovery hydrochloric acid, described exhaust treatment system is the tail gas absorber adopting plural serial stage, hydrogen chloride tail gas enters first grade absorption tower and is absorbed by Water spray, in previous stage absorption tower unabsorbed hydrogen chloride tail gas enter next stage absorption tower continue absorbed by Water spray, absorption liquid enters own absorption tower internal recycle by pump and continues absorbing hydrogen chloride tail gas, final stage absorption tower hydrogen chloride tail gas of escaping a small amount of in absorbing by liquid caustic soda previous stage absorption tower, absorption liquid enters own absorption tower internal recycle by pump, the tail gas qualified rear discharge after testing on final stage absorption tower, when in first grade absorption tower, the massfraction of hydrochloric acid reaches set(ting)value, reclaim hydrochloric acid, absorption liquid in next stage absorption tower (except final stage absorption tower) is pumped in previous stage absorption tower, and to penultimate stage absorption tower make up water, when absorption liquid pH value≤10 on final stage absorption tower, enter Waste Water Treatment, and supplement liquid caustic soda to final stage absorption tower.
Further, described tail gas absorber is preferably 3 ~ 5 grades of series connection.
Further, in described first step absorption tower, the massfraction of hydrochloric acid reaches set(ting)value, and set(ting)value is generally be more than or equal to 25%.Further, described liquid caustic soda massfraction is preferably 5 ~ 15%.
Compared with prior art, serialization synthesis 2 of the present invention, the cleaning procedure of 4-dinitrobenzene-6-chloroaniline, its beneficial effect is embodied in: the reactor 1, adopting plural serial stage, partial material in upper level reactor and tail gas enter in next stage reactor and continue chlorination reaction, realize continuous prodution and it also avoid exhaust emissions simultaneously; 2, the hydrogen chloride tail gas that produces of final stage reactor and disposing mother liquor groove bloat the hydrogen chloride tail gas that comes for the synthesis of 3-acetylaminoaniline or reclaim hydrochloric acid after exhaust treatment system process, mother liquor substitutes hydrochloric acid recycled, non-wastewater discharge decreases hydrochloric acid consumption simultaneously, realizes effective process and the comprehensive utilization of resources of tail gas and waste water; 3, with 2,4-dinitrobenzene-6-chloroaniline purity >=98%, yield >=96% prepared by the method for the invention.
In sum, the cleaning procedure of serialization synthesis of the present invention 2,4-dinitrobenzene-6-chloroaniline, realize effective process and the comprehensive utilization of resources of tail gas and waste water, emission-free and waste water produces, and is a kind of real serialization process for cleanly preparing, has significant economic benefit and social benefit.
(4) accompanying drawing explanation
Fig. 1 is a kind of serialization synthesis process flow diagram that the embodiment of the present invention adopts, and wherein 1 is making beating still, and 2,3,4 are respectively one-level, secondary, third order reaction still, 5,6,7 injector is, 8,9,10 is pressure filter, and 11,12 are disposing mother liquor groove, and 13 is mother liquor storage tank;
Fig. 2 is the another kind of serialization synthesis process flow diagram that the embodiment of the present invention adopts, and wherein 1 is making beating still, and 2,3,4 are respectively one-level, secondary, third order reaction still, 5,6,7 injector is, 8,9,10 is pressure filter, and 11,12 are disposing mother liquor groove, and 13 is mother liquor storage tank;
Fig. 3 is the exhaust treatment system schema that the embodiment of the present invention 7,8 adopts, and wherein 14,15,16,17 is respectively one-level, secondary, three grades, level Four tail gas absorber.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1
Serialization is synthesized:
As Fig. 1, adopt the reactor (2,3,4) of thtee-stage shiplock, three pressure filter (8,9,10) in parallel and two disposing mother liquor grooves (11,12) in parallel, the volume of one, two, three reactor is 50m
3, control chlorination temperature 35 ~ 40 DEG C, disposing mother liquor groove volume is 50m
3, pressure filter volume is 500m
3, mother liquor storage tank volume is 100m
3, disposing mother liquor tank liquor position is set as 90% of volume.
Squeeze into raw material toward the middle continuous print simultaneously of making beating still (1) to pull an oar, control 2, the input speed of 4-dinitraniline is 915kg/h, the input speed of 31% hydrochloric acid is 4502kg/h, the input speed of 38% Dispersant MF is 24kg/h, and the material in making beating still enters first order reaction still (1) with the speed of 5441kg/h again; Chlorine passes in first order reaction still (2) by injector (5) with the flow velocity of 340kg/h, material in first order reaction still (2) is by the self-circulation of a pump part, a part enters second order reaction still (3) with the flow velocity of 5781kg/h, and the injected device of tail gas (6) of first order reaction still (3) is drawn onto in second order reaction still (3) and continues chlorination reaction; Material in second order reaction still (3) is by the self-circulation of a pump part, a part enters third order reaction still (4) with the flow velocity of 5781kg/h, and the injected device of tail gas (7) of second order reaction still (3) is drawn onto in third order reaction still (4) and continues chlorination reaction; Material in third order reaction still (4) is by the self-circulation of a pump part, (then judge to react completely without colour-change by KI detection paper) after reacting completely after testing, a part squeezes into Filter Press (the advanced pressure filter (8) of material with the flow velocity of 5781kg/h, pressure filter (9) is switched to after pressure filter (8) is saturated, pressure filter (8) shifts out filter cake simultaneously, for subsequent use; Switch to pressure filter (10) after pressure filter (9) is saturated, pressure filter (9) shifts out filter cake simultaneously, for subsequent use; Switch to pressure filter (8) after pressure filter (10) is saturated, pressure filter (10) shifts out filter cake simultaneously, for subsequent use; Circulation is gone down successively); Pressure filter mother liquor out enters in disposing mother liquor groove with the flow velocity of 5781kg/h that (mother liquor is introduced into disposing mother liquor groove (11), when liquid level is to switching to disposing mother liquor groove (12) during set(ting)value, drum air in disposing mother liquor groove (11) simultaneously, bloat the synthesis being directly used in 3-acetylaminoaniline after the hydrogen chloride gas come is collected, stop drum air when drum is 31% to concentration of hydrochloric acid, mother liquor enters mother liquor storage tank (13); The liquid level of disposing mother liquor groove (12) is to switching to disposing mother liquor groove (11) during set(ting)value again, drum air in disposing mother liquor groove (12) simultaneously, bloat the synthesis being directly used in 3-acetylaminoaniline after the hydrogen chloride gas come is collected, stop drum air when drum is 31% to concentration of hydrochloric acid, mother liquor enters mother liquor storage tank (13); Circulation is gone down successively); The alternative hydrochloric acid of mother liquor in mother liquor storage tank (13), recycled.
Pressure filter filter cake out, after washing and drying, obtains 2,4-dinitrobenzene-6-chloroanilines of the present invention, records purity (HPLC) 98.6%, yield 97.1%.
Recycling tail gas:
Get m-acetamidoaniline mother liquor 660Kg, wherein contain: hydrochloric acid 33Kg, acetic acid 59.4Kg, m-acetamidoaniline 30Kg, mphenylenediamine 50Kg, a diacetylamino aniline 60Kg, the HCl gas 30Kg of above-mentioned collection is passed at normal temperatures by difference assay, add mphenylenediamine 88g and Glacial acetic acid 56Kg (folding hundred amounts), after being warming up to 96 ~ 104 DEG C of reaction 20h, be cooled to less than 35 DEG C filtrations, after the filter cake obtained is drained, add 20Kg water washing, obtain the m-acetamidoaniline that purity is (HPLC) 99%.
Embodiment 2
By the working method described in embodiment 1, just hydrochloric acid is changed into the mother liquor in mother liquor storage tank, pressure filter filter cake out, after washing and drying, obtains of the present invention 2,4-dinitrobenzene-6-chloroaniline, records purity (HPLC) 98.2%, yield 96.8%.The HCl gas collected is used for the synthesis of m-acetamidoaniline, and can obtain purity (HPLC) is the m-acetamidoaniline of 99%.
Embodiment 3
Serialization is synthesized:
By the working method described in embodiment 1, flow velocity unlike raw material: 2, the input speed of 4-dinitraniline is 732kg/h, the input speed of 30% hydrochloric acid is 3893kg/h, the input speed of 38% Dispersant MF is 20kg/h, and the material in making beating still enters first order reaction still with the speed of 4918kg/h again; Chlorine passes in first order reaction still by injector with the flow velocity of 273kg/h, and the material of upper level reactor passes into next stage reactor with the flow velocity of 5191kg/h; Squeeze into Filter Press with the flow velocity of 5191kg/h again, pressure filter also enters disposing mother liquor groove with the flow velocity of 5191kg/h; Drum air in disposing mother liquor groove, stop drum air when drum is 30% to concentration of hydrochloric acid, mother liquor enters mother liquor storage tank, collects hydrogen chloride tail gas simultaneously; The alternative hydrochloric acid of mother liquor in mother liquor storage tank, recycled.
Pressure filter filter cake out, after washing and drying, obtains 2,4-dinitrobenzene-6-chloroanilines of the present invention, records purity (HPLC) 98.8%, yield 97.0%.
Recycling tail gas:
Get m-acetamidoaniline mother liquor 660Kg, wherein contain: hydrochloric acid 59.4Kg, acetic acid 105Kg, m-acetamidoaniline 44Kg, mphenylenediamine 63Kg, a diacetylamino aniline 80Kg, the HCl gas 25Kg of above-mentioned collection is passed at normal temperatures by difference assay, add mphenylenediamine 88Kg and Glacial acetic acid 56Kg (folding hundred amounts), after being warming up to 96 ~ 104 DEG C of reaction 20h, be cooled to less than 35 DEG C filtrations, after the filter cake obtained is drained, add 30Kg water washing, obtaining purity (HPLC) is the m-acetamidoaniline of 99%.
Embodiment 4
By the serialization synthetic operation method described in embodiment 3, just hydrochloric acid is changed into the mother liquor in mother liquor storage tank, pressure filter filter cake out, after washing and drying, obtains of the present invention 2,4-dinitrobenzene-6-chloroaniline, records purity 98.3%, yield 96.5%.
The HCl gas collected is used for the synthesis of m-acetamidoaniline, and can obtain purity (HPLC) is the m-acetamidoaniline of 99%.
Embodiment 5
Serialization is synthesized:
As Fig. 2, adopt the reactor (2,3,4) of thtee-stage shiplock, three pressure filter (8,9,10) in parallel and two disposing mother liquor grooves (11,12) in parallel, the volume of one, two, three reactor is 50m
3, control chlorination temperature 35 ~ 40 DEG C, disposing mother liquor groove volume is 50m
3, pressure filter volume is 500m
3, mother liquor storage tank volume is 100m
3, disposing mother liquor tank liquor position is set as 75% of volume.
Squeeze into raw material toward the middle continuous print simultaneously of making beating still (1) to pull an oar, control 2, the input speed of 4-dinitraniline is 915kg/h, the input speed of 31% hydrochloric acid is 4502kg/h, the input speed of 38% Dispersant MF is 24kg/h, and the material in making beating still enters first order reaction still (1) with the speed of 5441kg/h again; Chlorine passes in first order reaction still (2) by injector (5) with the flow velocity of 340kg/h, material in first order reaction still (2) is by the self-circulation of a pump part, a part enters second order reaction still (3) with the flow velocity of 5781kg/h, and the injected device of tail gas (6) of first order reaction still (3) is drawn onto in second order reaction still (3) and continues chlorination reaction; Material in second order reaction still (3) is by the self-circulation of a pump part, a part enters third order reaction still (4) with the flow velocity of 5781kg/h, and the injected device of tail gas (7) of second order reaction still (3) is drawn onto in third order reaction still (4) and continues chlorination reaction; Material in third order reaction still (4) is by the self-circulation of a pump part, (then judge to react completely without colour-change by KI detection paper) after reacting completely after testing, a part squeezes into Filter Press (the advanced pressure filter (8) of material with the flow velocity of 5781kg/h, pressure filter (9) is switched to after pressure filter (8) is saturated, pressure filter (8) shifts out filter cake simultaneously, for subsequent use, collect the hydrogen chloride gas produced in third order reaction still (4); Switch to pressure filter (10) after pressure filter (9) is saturated, pressure filter (9) shifts out filter cake simultaneously, for subsequent use; Switch to pressure filter (8) after pressure filter (10) is saturated, pressure filter (10) shifts out filter cake simultaneously, for subsequent use; Circulation is gone down successively); Pressure filter mother liquor out enters in disposing mother liquor groove with the flow velocity of 5781kg/h that (mother liquor is introduced into disposing mother liquor groove (11), when liquid level is to switching to disposing mother liquor groove (12) during set(ting)value, drum air in disposing mother liquor groove (11) simultaneously, bloat the synthesis being directly used in 3-acetylaminoaniline after the hydrogen chloride gas come is collected, stop drum air when drum is 31% to concentration of hydrochloric acid, mother liquor enters mother liquor storage tank (13); The liquid level of disposing mother liquor groove (12) is to switching to disposing mother liquor groove (11) during set(ting)value again, drum air in disposing mother liquor groove (12) simultaneously, stop drum air when the hydrogen chloride gas drum that collection bloats is 31% to concentration of hydrochloric acid, mother liquor enters mother liquor storage tank (13); Circulation is gone down successively); The alternative hydrochloric acid of mother liquor in mother liquor storage tank (13), recycled.
Pressure filter filter cake out, after washing and drying, obtains 2,4-dinitrobenzene-6-chloroanilines of the present invention, records purity (HPLC) 98.6%, yield 97.1%.
Recycling tail gas:
Get m-acetamidoaniline mother liquor 660Kg, wherein contain: hydrochloric acid 33Kg, acetic acid 59.4Kg, m-acetamidoaniline 30Kg, mphenylenediamine 50Kg, a diacetylamino aniline 60Kg, the HCl gas 30Kg of above-mentioned collection is passed at normal temperatures by difference assay, add mphenylenediamine 88g and Glacial acetic acid 56Kg (folding hundred amounts), after being warming up to 96 ~ 104 DEG C of reaction 20h, be cooled to less than 35 DEG C filtrations, after the filter cake obtained is drained, add 20Kg water washing, obtain the m-acetamidoaniline that purity is (HPLC) 99%.
Embodiment 6
By the working method described in embodiment 5, just hydrochloric acid is changed into the mother liquor in mother liquor storage tank, pressure filter filter cake out, after washing and drying, obtains of the present invention 2,4-dinitrobenzene-6-chloroaniline, records purity (HPLC) 98.2%, yield 96.8%.The HCl gas collected is used for the synthesis of m-acetamidoaniline, and can obtain purity (HPLC) is the m-acetamidoaniline of 99%.
Embodiment 7
Serialization is synthesized:
By the serialization synthetic operation method described in embodiment 1, flow velocity unlike raw material: 2, the input speed of 4-dinitraniline is 732kg/h, the input speed of 30% hydrochloric acid is 3893kg/h, the input speed of 38% Dispersant MF is 20kg/h, and the material in making beating still enters first order reaction still with the speed of 4918kg/h again; Chlorine passes in first order reaction still by injector with the flow velocity of 273kg/h, and the material of upper level reactor passes into next stage reactor with the flow velocity of 5191kg/h, collects the hydrogen chloride tail gas produced in third order reaction still (4); Squeeze into Filter Press with the flow velocity of 5191kg/h again, pressure filter also enters disposing mother liquor groove with the flow velocity of 5191kg/h; Drum air in disposing mother liquor groove, stop drum air when drum is 30% to concentration of hydrochloric acid, mother liquor enters mother liquor storage tank, collects hydrogen chloride tail gas simultaneously; The alternative hydrochloric acid of mother liquor in mother liquor storage tank, recycled.
Pressure filter filter cake out, after washing and drying, obtains 2,4-dinitrobenzene-6-chloroanilines of the present invention, records purity (HPLC) 98.8%, yield 97.0%.
Recycling tail gas:
Exhaust treatment system as shown in Figure 3, adopt 4 grades of tail gas absorbers (14 of connecting, 15, 16, 17), absorption tower diameter 1m, height 7.8m, first grade absorption tower (14), two-level absorption tower (15) and three grades of absorption towers (16) add water to 75% of volume, level Four absorption tower (17) adds 10% liquid caustic soda to 75% of volume: the hydrogen chloride tail gas continuous print of above-mentioned collection is entered first grade absorption tower (14) and is absorbed by Water spray, absorption liquid carries out self-circulation by pump and continues absorbing hydrogen chloride tail gas, in first grade absorption tower (14), unabsorbed hydrogen chloride tail gas enters two-level absorption tower (15) by Water spray continuation absorption, absorption liquid carries out self-circulation by pump, in two-level absorption tower (15), unabsorbed hydrogen chloride tail gas enters three grades of absorption towers (16) by Water spray continuation absorption, absorption liquid carries out self-circulation by pump, in three grades of absorption towers (16), a small amount of hydrogen chloride tail gas of escaping enters level Four absorption tower (17) by liquid caustic soda spray-absorption, air is entered through blower fan after tail gas in level Four absorption tower (17) is qualified after testing.When in first grade absorption tower (14), the hydrochloric acid massfraction of absorption liquid is reached for 28%, reclaim hydrochloric acid, and the absorption liquid of two-level absorption tower (15) is pumped in first grade absorption tower (14), the absorption liquid of three grades of absorption towers (16) pumps in two-level absorption tower (15), adds water to 75% of volume in three grades of absorption towers (16) simultaneously; As absorption liquid pH value < 10 in level Four absorption tower (17), pump into company's Waste Water Treatment, add 10% liquid caustic soda to 75% of volume simultaneously.
Embodiment 8
By the serialization synthetic operation method described in embodiment 7, just hydrochloric acid is changed into the mother liquor in mother liquor storage tank, pressure filter filter cake out, after washing and drying, obtains of the present invention 2,4-dinitrobenzene-6-chloroaniline, records purity 98.3%, yield 96.5%.
The liquid caustic soda of 10%, also by the recycling tail gas working method described in embodiment 7, is just changed into the liquid caustic soda of 8% by the HCl gas collected, and when the hydrochloric acid massfraction of absorption liquid is reached for 31% in first grade absorption tower (14), reclaims hydrochloric acid.
Claims (14)
1. a serialization synthesis 2, the cleaning procedure of 4-dinitrobenzene-6-chloroaniline, described technique is as follows: the reactor adopting plural serial stage, according to 2, 4-dinitraniline, hydrochloric acid, the raw materials components mole ratio of chlorine is 1:(4 ~ 12): the proportioning of (0.94 ~ 1.00), continuously by 2, 4-dinitraniline, hydrochloric acid and chlorine addition are in first order reaction still, chlorination reaction is carried out under stirring, material in upper level reactor enters id reaction still internal recycle by a pump part, a part enters in next stage reactor and continues chlorination reaction, the tail gas that upper level reactor produces enters in next stage reactor and continues chlorination reaction, control the chlorination reaction temperature of reactor at different levels at 30 DEG C ~ 60 DEG C, material in final stage reactor enters id reaction still internal recycle by a pump part, after reacting completely after testing, part continuous discharge filters, the filter cake of gained is 2, 4-dinitrobenzene-6-chloroaniline product, filter and mother liquid obtainedly enter disposing mother liquor groove, to the mother liquor drum air in disposing mother liquor groove, bloat the hydrogen chloride tail gas reuse come, mother liquor drum air is to being driven in mother liquor storage tank during certain acidity, mother liquor in mother liquor storage tank substitutes hydrochloric acid recycled.
2. a serialization synthesis 2, the cleaning procedure of 4-dinitrobenzene-6-chloroaniline, described technique is as follows: the reactor adopting plural serial stage, according to 2, 4-dinitraniline, hydrochloric acid, the raw materials components mole ratio of chlorine is 1:(4 ~ 12): the proportioning of (0.94 ~ 1.00), continuously by 2, 4-dinitraniline, hydrochloric acid and chlorine addition are in first order reaction still, chlorination reaction is carried out under stirring, material in upper level reactor enters id reaction still internal recycle by a pump part, a part enters in next stage reactor and continues chlorination reaction, the tail gas that upper level reactor produces enters in next stage reactor and continues chlorination reaction, control the chlorination reaction temperature of reactor at different levels at 30 DEG C ~ 60 DEG C, material in final stage reactor enters id reaction still internal recycle by a pump part, after reacting completely after testing, part continuous discharge carries out centrifugation, the isolated decorating film of gained is 2, 4-dinitrobenzene-6-chloroaniline product, centrifugation is mother liquid obtained enters disposing mother liquor groove, to the mother liquor drum air in disposing mother liquor groove, bloat the hydrogen chloride tail gas reuse come, mother liquor drum air is to being driven in mother liquor storage tank during certain acidity, mother liquor in mother liquor storage tank substitutes hydrochloric acid recycled.
3. cleaning procedure as claimed in claim 1 or 2, is characterized in that: 2,4-dinitraniline and hydrochloric acid are first added in making beating still and mix, then are added to continuously in first order reaction still by pump.
4. cleaning procedure as claimed in claim 3, is characterized in that: add anion surfactant in described making beating still, and it is 0.2% ~ 2% of 2,4-dinitraniline quality that anion surfactant drops into quality.
5. cleaning procedure as claimed in claim 4, is characterized in that: described anion surfactant is selected from one or more combination following: Dispersant MF, sodium laurylsulfonate, sodium dodecylbenzenesulfonate.
6. the cleaning procedure as described in one of Claims 1 to 5, is characterized in that: the molar ratio of 2,4-described dinitranilines, hydrochloric acid, chlorine is 1:(7 ~ 12): (0.95 ~ 0.97).
7. the cleaning procedure as described in one of Claims 1 to 5, is characterized in that: chlorination reaction temperature is 35 DEG C ~ 50 DEG C.
8. the cleaning procedure as described in one of Claims 1 to 5, is characterized in that: hydrochloric acid massfraction is 28 ~ 35%; To the mother liquor drum air in disposing mother liquor groove, stop air-blowing when being 28% ~ 35% to the hydrochloric acid massfraction in mother liquor, mother liquor enters mother liquor storage tank.
9. the cleaning procedure as described in one of Claims 1 to 5, it is characterized in that: reactor at different levels all connects an injector, in reactor, a part of material carries out id reaction still internal recycle by pump via injector, and the negative pressure simultaneously produced in injector can suck the tail gas of chlorine or upper level generation.
10. the cleaning procedure as described in one of Claims 1 to 5, is characterized in that: described reactor adopts 2 ~ 4 grades of series connection.
11. cleaning procedures as described in one of Claims 1 to 5, is characterized in that: described filtration adopts the pressure filter of multiple parallel connection; Described centrifugation adopts the whizzer of multiple parallel connection; Described disposing mother liquor groove adopts multiple parallel connection.
12. cleaning procedures as claimed in claim 1 or 2, is characterized in that: the hydrogen chloride tail gas reuse that final stage reactor produces.
13. cleaning procedures as claimed in claim 12, is characterized in that: bloat the synthesis of next hydrogen chloride tail gas for 3-acetylaminoaniline in the hydrogen chloride tail gas that final stage reactor produces and disposing mother liquor groove.
14. cleaning procedures as claimed in claim 12, is characterized in that: final stage reactor produce hydrogen chloride tail gas and disposing mother liquor groove in bloat come hydrogen chloride tail gas enter exhaust treatment system reclaim hydrochloric acid;
Described exhaust treatment system is the tail gas absorber adopting plural serial stage, hydrogen chloride tail gas enters first grade absorption tower and is absorbed by Water spray, in previous stage absorption tower unabsorbed hydrogen chloride tail gas enter next stage absorption tower continue absorbed by Water spray, absorption liquid enters own absorption tower internal recycle by pump and continues absorbing hydrogen chloride tail gas, final stage absorption tower hydrogen chloride tail gas of escaping a small amount of in absorbing by liquid caustic soda previous stage absorption tower, absorption liquid enters own absorption tower internal recycle by pump, the tail gas qualified rear discharge after testing on final stage absorption tower, when in first grade absorption tower, the massfraction of hydrochloric acid reaches set(ting)value, reclaim hydrochloric acid, absorption liquid in next stage absorption tower except final stage absorption tower is pumped in previous stage absorption tower, and to penultimate stage absorption tower make up water, when absorption liquid pH value≤10 on final stage absorption tower, enter Waste Water Treatment, and supplement liquid caustic soda to final stage absorption tower.
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| CN201510578028.8A Active CN105461572B (en) | 2014-12-29 | 2015-09-11 | A kind of cleaning procedure for being continuously synthesizing to the chloroaniline of 2,4 dinitro 6 |
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| CN107739315A (en) * | 2017-10-13 | 2018-02-27 | 烟台安诺其精细化工有限公司 | The processing method of 3-acetylaminoaniline hydrochloride mother liquor |
| CN108191672A (en) * | 2017-12-19 | 2018-06-22 | 浙江龙盛集团股份有限公司 | A kind of synthetic method of 2,4- dinitros -6- chloroanilines |
| CN109369469A (en) * | 2018-11-29 | 2019-02-22 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid chloride |
| CN109608353A (en) * | 2019-01-15 | 2019-04-12 | 浙江迪邦化工有限公司 | A kind of continuous production technology and device of 3-acetylaminoaniline |
| CN110981735A (en) * | 2019-12-30 | 2020-04-10 | 河南洛染股份有限公司 | 6-chloro-2, 4-dinitroaniline mother liquor recycling method |
| CN111056952A (en) * | 2019-12-30 | 2020-04-24 | 河南洛染股份有限公司 | Environment-friendly production process of 6-chloro-2, 4-dinitroaniline |
| CN113429298A (en) * | 2021-07-12 | 2021-09-24 | 翱华工程技术股份有限公司 | Preparation method, production equipment and use method of 2,4, 6-trichloroaniline |
| CN113816859A (en) * | 2021-08-23 | 2021-12-21 | 浙江迪邦化工有限公司 | Method for continuously producing 6-chloro-2, 4-dinitroaniline and diazonium salt thereof |
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| CN105367428B (en) * | 2015-11-10 | 2018-05-11 | 浙江龙盛集团股份有限公司 | A kind of synthesis technique of 2,4- dinitros -6- chloroanilines |
| CN111620785B (en) * | 2020-06-22 | 2023-03-28 | 浙江迪邦化工有限公司 | Continuous chlorination method of nitroaniline |
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| CN107739315A (en) * | 2017-10-13 | 2018-02-27 | 烟台安诺其精细化工有限公司 | The processing method of 3-acetylaminoaniline hydrochloride mother liquor |
| CN108191672A (en) * | 2017-12-19 | 2018-06-22 | 浙江龙盛集团股份有限公司 | A kind of synthetic method of 2,4- dinitros -6- chloroanilines |
| CN108191672B (en) * | 2017-12-19 | 2021-06-11 | 浙江龙盛集团股份有限公司 | Synthetic method of 2, 4-dinitro-6-chloroaniline |
| CN109369469A (en) * | 2018-11-29 | 2019-02-22 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid chloride |
| CN109608353A (en) * | 2019-01-15 | 2019-04-12 | 浙江迪邦化工有限公司 | A kind of continuous production technology and device of 3-acetylaminoaniline |
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| CN110981735A (en) * | 2019-12-30 | 2020-04-10 | 河南洛染股份有限公司 | 6-chloro-2, 4-dinitroaniline mother liquor recycling method |
| CN111056952A (en) * | 2019-12-30 | 2020-04-24 | 河南洛染股份有限公司 | Environment-friendly production process of 6-chloro-2, 4-dinitroaniline |
| CN113429298A (en) * | 2021-07-12 | 2021-09-24 | 翱华工程技术股份有限公司 | Preparation method, production equipment and use method of 2,4, 6-trichloroaniline |
| CN113816859A (en) * | 2021-08-23 | 2021-12-21 | 浙江迪邦化工有限公司 | Method for continuously producing 6-chloro-2, 4-dinitroaniline and diazonium salt thereof |
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|---|---|
| CN104592042A (en) | 2015-05-06 |
| CN105461572B (en) | 2018-02-13 |
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