CN102936213B - Clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid - Google Patents
Clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid Download PDFInfo
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Abstract
The invention provides a clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid. A reaction formula is shown in the description. The method includes: taking 2, 7-naphthalenedisulfonic acid as a reaction raw material, adopting sulfuric acid as a solvent, and adding fuming nitric acid with a content of 98% dropwisely to prepare 1, 8-dinitro-3, 6-naphthalenedisulfonic acid; and after the end of the reaction, adding water to conduct dilution and isolating the product, subjecting the remaining nitrification mother solution to flocculation treatment so as to remove impurities, and then carrying out pressure reduction concentrating to recover the sulfuric acid as the solvent for next reaction. The method provided in the invention has the advantages of short technological process, simple operation, good quality product, and no wastewater discharge, thus being suitable for industrialized production.
Description
Technical field
The invention belongs to organic synthesis field, relate to 1,8-dinitrobenzene-3, the clean method for preparing of 6-naphthalene disulfonic acid.
Background technology
1,8-dinitrobenzene-3, the main using value of 6-naphthalene disulfonic acid is synthetic H acid.The traditional processing technology of H acid is by naphthalidine-3, and 6,8-trisulfonic acid adds that thermokalite melts, acid out makes again.Last century the eighties, Japanese Patent JP8451253 and JP4210954 reported a kind of with 2,7-naphthalene disulfonic acid for raw material, prepare intermediate 1,8-dinitrobenzene-3,6-naphthalene disulfonic acid, the more further novel process of reduction, hydrolysis H acid.In recent years, Chinese patent CN101717355 has also reported that one is starting raw material by refined naphthalene, by intermediate 1, and 8-dinitrobenzene-3, the method for the synthetic H acid of 6-naphthalene disulfonic acid.Compared with traditional technology, above-mentioned novel process yield improves a lot, and technical superiority is obvious.
But, the preparation 1 that prior art provides, 8-dinitrobenzene-3, can produce a large amount of high density spent acid in the production process of the method for 6-naphthalene disulfonic acid, and this gives and promotes the use of the method and prepare H acid and cause very large obstacle, becomes a problem demanding prompt solution.
In field of waste water treatment, flocculation has a wide range of applications as a kind of important treatment process.For example, CN200410020218 reported the method for processing DSD acid reduction spent acid taking iron vitriol or ferric sulfate as flocculation agent; Flocculation agent aluminium silicate polymer zinc and zinc polysilicate magnesium have been prepared in " inorganic polymer flocculant is processed the research of H-acid waste water " (Northwest University's papers written by postgraduates, in August, 2008) research, in order to H Acid from Wastewater, have obtained certain effect.But up to the present,, about 1,8-dinitrobenzene-3, the clean method for preparing of 6-naphthalene disulfonic acid has no report.
Summary of the invention
The object of the present invention is to provide a kind of 1,8-dinitrobenzene-3, the clean method for preparing of 6-naphthalene disulfonic acid, to solve the problem of a large amount of discharges of nitration waste water.
In order to realize object of the present invention, contriver adopts and a kind ofly makes to prepare 1,8-dinitrobenzene-3 by nitrated mother liquor being carried out to the mode of flocculation treatment, recovery sulfuric acid, and the process non-wastewater discharge of 6-naphthalene disulfonic acid, realizes cleaner production.
The technical scheme adopting is as follows:
A kind of 1,8-dinitrobenzene-3, the clean method for preparing of 6-naphthalene disulfonic acid, reaction formula is as follows:
Reaction is with 2,7-naphthalene disulfonic acid for raw material, and sulfuric acid is made solvent, and the nitrosonitric acid that dropping content is 98% is prepared 1,8-dinitrobenzene-3,6-naphthalene disulfonic acid; After having reacted, thin up is also isolated product, and remaining nitrated mother liquor is removed impurity, reduced after mother solution C OD value through flocculation treatment, then concentrating under reduced pressure reclaim(ed) sulfuric acid is as lower batch reaction solvent.
The pH value narrow range that most of flocculation agents are applicable cannot be applied under strong acidic condition.The present invention finds by lot of experiments, although polyacrylamide flocculating effect under strongly-acid is not so good as ideal under weak acid or neutrallty condition, but still can play throwing out, can reach the processing requirements of the present invention to nitrated mother liquor completely.Therefore, the present invention selects the flocculation agent of polyacrylamide as nitrated mother liquor.The preferred non-ionic polyacrylamide of flocculation agent or cationic-type polyacrylamide that the present invention is used, both treatment effects are close; And anion-polyacrylamide effect is slightly poor.Suitable Molecular Weight for Polyacrylamide, 8,000,000～1,000 ten thousand, has commercial goods; The Optimum of flocculation agent uses 0.1～1mg for processing every liter of nitrated mother liquor; The consumption that continues increase flocculation agent does not have clear improvement to the treatment effect of mother liquor.Suitable flocculation temperature is 10～40 DEG C, and flocculation operation can at room temperature be carried out under normal circumstances, and the operation of for example directly flocculating under 15～30 DEG C of envrionment temperatures can reach promising result; Flocculation time is 0.5 hour to 2 hours.
In nitrated mother liquid disposal process, first flocculation agent is dissolved in pure water, is mixed with the aqueous solution of massfraction 0.1%.Nitrated mother liquor (for example 300～400r/min) under rapid stirring adds appropriate flocculation agent in 10～40 DEG C, is incubated 0.5 hour to 2 hours at 10～40 DEG C.Add after flocculation agent 5-15 minute and reduce stirring velocity (for example 60～70r/min), be beneficial to Precipitation.Flocculation operation is appreciated by those skilled in the art.Flocculation finishes rear filtering organic impurity.Reduce the COD value of nitrated mother liquor and its outward appearance is improved by flocculation treatment.Experiment shows, coagulating/flocculating method for processing provided by the invention can be down to the COD value of nitrated mother liquor below 4000mg/L, and then nitrated mother liquor concentrating under reduced pressure is obtained to the vitriol oil of massfraction >=93%, can be as the qualified solvent of nitration reaction.
5～20 times of moles of multiples that are raw material as the sulfuric acid consumption of solvent in reaction.Within the scope of this, reaction later stage material dispersion state is better, and yield is higher; Nitration reaction temperature is 0～70 DEG C; It is 98% nitrosonitric acid that nitrating agent is selected content, 2.2～3 moles of multiples that consumption is raw material.
The concrete operations of nitration reaction are: by 2, in 7-naphthalene disulfonic acid vitriolization (sulfuric acid new or that reclaim according to the method described above), drip nitrosonitric acid at 0～70 DEG C, time for adding is 1～2 hour, dropwise rear insulation 1～2 hour, liquid-phase chromatographic analysis raw material and single nitro-compound disappear and arrive reaction end.After nitration reaction finishes, adopt ordinary method to separate and obtain product (for example, be diluted with water to sulfuric acid concentration and approximately reach 50%, product is separated out completely).Being warmed up to 80～120 DEG C of insulation denitrations lowered the temperature after 3 hours.Room temperature is filtered, and what obtain is flaxen 1,8-dinitrobenzene-3,6-naphthalene disulfonic acid filter cake.
Nitrated mother liquor outward appearance is reddish-brown, COD value 40000～50000mg/L, and after impurity is removed in flocculation according to the method described above, nitrated mother liquor outward appearance becomes yellow from reddish-brown, and COD value drops to below 4000mg/L.Then concentrating under reduced pressure (for example control still internal pressure and be less than 60mmHg) obtains content >=93% sulfuric acid, as the solvent of lower batch of nitration reaction, still can obtain the product up-to-standard, yield is higher 1,8-dinitrobenzene-3, (reaction conditions is the same, product appearance: faint yellow, purity more than 98% (measure by liquid chromatography area normalization method for 6-naphthalene disulfonic acid, lower same), yield is more than 90%).Meet the requirement of further hydrogenating reduction, preparation H acid.
Preparation method of the present invention has the following advantages:
1, nitrated mother liquor can be realized recycled after treatment, solved the problems of a large amount of discharges of nitration waste water, has realized the object of cleaner production, environmental protection.
2, nitrated mother liquid disposal process is simple and practical.
3, application recovery solvent carries out nitration reaction, still can obtain 1 of high-quality, high yield, 8-dinitrobenzene-3, and 6-naphthalene disulfonic acid, meets the requirement of further hydrogenating reduction, preparation H acid completely.
Embodiment
By following examples, the present invention is further described in detail.But the present invention only limits to absolutely not this.In embodiment, flocculation agent used is molecular weight at 8,000,000～1,000 ten thousand cationic-type polyacrylamide (having commercially available), and is mixed with the aqueous solution of massfraction 0.1% with clear water.Raw material 2,7-naphthalene disulfonic acid self-control (with reference to the disclosed method of JP4210954).
Embodiment 1
By 1008 gram 2, it is 93% industrial sulphuric acid that 7-naphthalene disulfonic acid is dissolved in 3L massfraction, maintains the temperature at 0～5 DEG C, drips 630 grams of 98% nitrosonitric acids in 2 hours, and insulation reaction 2 hours to nitration reaction completes.In reactant, drip 4600ml water, then be warmed up to 95～100 DEG C, under stirring, continue to pass into air, be incubated cooling after 3 hours.Room temperature is filtered, obtain faint yellow 1,8-dinitrobenzene-3,1976 grams of 6-naphthalene disulfonic acid filter cakes, purity 98.83%, solid content 60.87%, yield 90.91%.Obtain the nitrated mother liquor 6.87L of reddish-brown, COD value 47000mg/L, for subsequent disposal.
Embodiment 2
Get the nitrated mother liquor 1L that embodiment 1 obtains, rapid stirring under room temperature (360r/min, lower same) adds 0.5 gram of aforementioned flocculation agent preparing, and reduces stirring velocity (60r/min, lower same) after ten minutes.After 1 hour, filter, mother liquor color is become faint yellow from reddish-brown.COD value 2200mg/L.
Embodiment 3
The nitrated mother liquor of 1L, rapid stirring adds 0.1 gram of aforementioned flocculation agent preparing at 10 DEG C, after ten minutes, reduces stirring velocity.After 2 hours, filter, filtrate is faint yellow, COD value 3700mg/L.
Embodiment 4
The nitrated mother liquor of 1L, keeps 40 DEG C of temperature, and rapid stirring adds 1 gram of aforementioned flocculation agent preparing, and after ten minutes, reduces stirring velocity.After half an hour, filter the faint yellow COD value of filtrate 2100mg/L.
Comparative example 1
The nitrated mother liquor of 1L, under room temperature, rapid stirring adds 0.05 gram of aforementioned flocculation agent preparing, and after ten minutes, reduces stirring velocity.After 1 hour, filter, filtrate color is dark (yellow), COD value higher (7400mg/L).
Embodiment 5
Embodiment 2 is processed to nitrated mother liquor (the COD value 2200mg/L) underpressure distillation under 50～60mmHg pressure obtaining, when still temperature to 190 DEG C, stop distillation, obtain 406ml gelled acid, record acid concentration 93.12% (massfraction), reclaim and make nitration reaction solvent.
By 101 gram 2,7-naphthalene disulfonic acid is dissolved in the above-mentioned reclaim(ed) sulfuric acid of 400ml, maintains the temperature at 25～30 DEG C, drips 67.5 grams of nitrosonitric acids in 1～2 hour, is incubated 1 hour and completes to nitration reaction.In reactant, drip 615 grams of water, then be warmed up to 80～85 DEG C, under stirring, continue to pass into air, be incubated cooling after 3 hours.Room temperature is filtered, obtain faint yellow 1,8-dinitrobenzene-3,193 grams of 6-naphthalene disulfonic acid filter cakes, purity 98.72%, solid content 62.15%, yield 90.66%.
Embodiment 6
Embodiment 3 is processed to the method that the nitrated mother liquor (COD value 3700mg/L) that obtains provides according to embodiment 5 concentrated, reclaim as nitration reaction solvent.
By 101 gram 2,7-naphthalene disulfonic acid is dissolved in the reclaim(ed) sulfuric acid of 250ml content 93%, maintains the temperature at 40～45 DEG C, drips 56.3 grams of nitrosonitric acids in 1～2 hour, is incubated 1 hour and completes to nitration reaction.In reactant, drip 380 grams of water, then be warmed up to 115～120 DEG C, under stirring, continue to pass into air denitration, cooling after 3 hours, room temperature is filtered, obtain faint yellow 1,8-dinitrobenzene-3,186 grams of 6-naphthalene disulfonic acid filter cakes, purity 98.64%, solid content 64.19%, yield 90.25%.
Comparative example 2
Preparation 1,8-dinitrobenzene-3, the reinforced and operational condition of 6-naphthalene disulfonic acid is all same as embodiment 5.Only change solvent, the method that the nitrated mother liquor (COD value 7400mg/L) that comparative example 1 is obtained provides according to embodiment 5 is concentrated, reclaims as nitration reaction solvent.Now quality product and yield all obviously reduce, and obtain dark yellow 1,8-dinitrobenzene-3,189 grams of 6-naphthalene disulfonic acid filter cakes, purity 95.26%, solid content 61.05%, yield 87.21%.The product obtaining can not meet the requirement of further hydrogenating reduction, preparation H acid.
Claims (3)
1. one kind 1,8-dinitrobenzene-3, the clean method for preparing of 6-naphthalene disulfonic acid, reaction formula is as follows:
Reaction is with 2,7-naphthalene disulfonic acid for raw material, and sulfuric acid is made solvent, and the nitrosonitric acid that dropping content is 98% is prepared 1,8-dinitrobenzene-3,6-naphthalene disulfonic acid; After having reacted, thin up is also isolated product, and remaining nitrated mother liquor is removed impurity, reduced after mother solution C OD value through flocculation treatment, then concentrating under reduced pressure reclaim(ed) sulfuric acid is as lower batch reaction solvent;
Flocculation treatment flocculation agent used is cationic polyacrylamide, and suitable consumption uses 0.1～1 milligram of flocculation agent for processing every liter of nitrated mother liquor, and flocculation temperature is 10～40 DEG C, and flocculation time is 0.5 hour to 2 hours.
2. preparation method according to claim 1, is characterized in that: the nitrated mother liquor after flocculation treatment is greater than 93% retrieval of sulfuric acid and applies mechanically being less than under 60mmHg pressure the concentrated mass concentration that obtains.
3. preparation method according to claim 1, it is characterized in that: use the sulfuric acid reclaiming in nitrated mother liquor as solvent, sulfuric acid consumption is 5～20 moles of multiples of raw material, 2.2～3 moles of multiples that nitrosonitric acid consumption is raw material, 0～70 DEG C of nitration reaction temperature.
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| CN104569278B (en) * | 2015-02-03 | 2016-02-03 | 枣庄学院 | A kind of HPLC analytical method of intermediate 4,5-dinitro-2,7-naphthalenedisulfonic acid content |
| CN106928100B (en) * | 2015-12-29 | 2018-11-13 | 沈阳化工研究院有限公司 | A kind of continuous nitrification method of naphthalene sulfonic acids class compound |
| CN111573811A (en) * | 2020-05-22 | 2020-08-25 | 中科乐美环保科技有限公司 | Composite cationic polyacrylamide flocculant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4534905A (en) * | 1980-05-29 | 1985-08-13 | Bayer Aktiengesellschaft | Process for the preparation of nitronaphthalene-sulphonic acids |
| JP4210954B2 (en) * | 2006-08-22 | 2009-01-21 | ソニー株式会社 | Image processing method, image processing method program, recording medium storing image processing method program, and image processing apparatus |
| CN101717355A (en) * | 2009-11-25 | 2010-06-02 | 泰兴市锦鸡染料有限公司 | Method for synthesizing dyestuff intermediate H acid by naphthalene |
| CN101941769A (en) * | 2010-09-10 | 2011-01-12 | 常州大学 | Method for pre-treating alkali PTA wastewater by using combined flocculating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04210954A (en) * | 1991-02-25 | 1992-08-03 | Sugai Kagaku Kogyo Kk | Production of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4534905A (en) * | 1980-05-29 | 1985-08-13 | Bayer Aktiengesellschaft | Process for the preparation of nitronaphthalene-sulphonic acids |
| JP4210954B2 (en) * | 2006-08-22 | 2009-01-21 | ソニー株式会社 | Image processing method, image processing method program, recording medium storing image processing method program, and image processing apparatus |
| CN101717355A (en) * | 2009-11-25 | 2010-06-02 | 泰兴市锦鸡染料有限公司 | Method for synthesizing dyestuff intermediate H acid by naphthalene |
| CN101941769A (en) * | 2010-09-10 | 2011-01-12 | 常州大学 | Method for pre-treating alkali PTA wastewater by using combined flocculating agent |
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