CN101935294B - Method for recycling two main by-products in C acid production - Google Patents
Method for recycling two main by-products in C acid production Download PDFInfo
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- CN101935294B CN101935294B CN 201010261909 CN201010261909A CN101935294B CN 101935294 B CN101935294 B CN 101935294B CN 201010261909 CN201010261909 CN 201010261909 CN 201010261909 A CN201010261909 A CN 201010261909A CN 101935294 B CN101935294 B CN 101935294B
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Abstract
The invention relates to a processing method for recycling two main by-products in the production of C acid as pigment intermediates, including 2-amino-3-chloro p-toluenesulfonic acid and 3-chloro-5-amino p-toluenesulfonic acid, or relevant salts. The method comprises the following steps of: recovering the 2-amino-3-chloro p-toluenesulfonic acid and the 3-chloro-5-amino p-toluenesulfonic acid as isomer byproducts generated by nitrifying and reducing 3-chloro p-toluenesulfonic acid for manufacturing the C acid, converting the 2-amino-3-chloro p-toluenesulfonic acid and the 3-chloro-5-amino p-toluenesulfonic acid into 3-chloro p-toluenesulfonic acid as a nitrification precursor by using a diazotization deaminizing process, and then producing the C acid by using the 3-chloro p-toluenesulfonic acid, thereby realizing the recycling of the isomer byproducts. The process in the invention can ensure that about 40% of total organic by-products in the C acid production are recycled, and the qualities of the produced C acid products are not influenced.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to Pigment Intermediates C acid produce in main two kinds of by products, the treatment process of the recycling of the amino tosic acid of 2-amino-3-chlorine tosic acid and 3-chloro-5-or corresponding salt.
Background technology
C acid claims again CLT acid a plurality of chemical names are arranged, and such as 2-amino-5-chlorine tosic acid etc., is the key intermediate of synthetic organic red pigment such as P.R.53:1 etc.The main technique that domestic C acid is produced is the toluene sulfonation method, namely by toluene through the sulphonating agent sulfonation such as the vitriol oil, chlorinated with chlorine, concentrated nitric acid is nitrated and the operation such as iron powder reducing nitro is produced C acid.Except nitroreduction, front three-step reaction all can produce various isomer by products in above-mentioned operation, i.e. chlorine, methyl and the nitrobenzene-sulfonic acid of different positions replacement; But wherein the selectivity of sulfonation reaction principal product is in 90% left and right, the selectivity of chlorination reaction principal product also can reach more than 90%, and the selectivity of nitration reaction is relatively poor, principal product only has the selectivity of 70-75%, two nitration isomer by products account for 25-30% (accounting for the over half of total organic by-products), and be at the production technique back segment, be to cause the major cause that production cost raises and organic waste produce.Two isomer by products that nitrated operation produces, 2-nitro-3-chlorine tosic acid and 3-chloro-5-nitro tosic acid namely produce 2-amino-3-chlorine tosic acid and two main isomer by products of C acid of the amino tosic acid of 3-chloro-5-after the nitroreduction operation.Due to the difference of solubility property, these two isomer can with C acid easy separation.But the amino tosic acid of the 2-amino of after separating-3-chlorine tosic acid and 3-chloro-5-or corresponding sodium salt and ammonium salt are processed as refuse basically at present, and the research that even further utilizes is all carried out seldom.
Once the amino tosic acid of 3-chloro-5-was converted into medicine intermediate 2-chloro-6-halogenated methylbenzene (Chinese invention patent application, application number 201010159197.5) before us, for effective approach has been explored in the utilization of C acid by-product; But another one isomer by product 2-amino-3-chlorine tosic acid still has no the research report that recycles at present.
Summary of the invention
The object of the present invention is to provide and a kind ofly will have two main isomer by product 2-amino-3-chlorine tosic acid and the amino tosic acid of 3-chloro-5-or the corresponding salt of producing that Pigment Intermediates C acid produces now, change into again C acid through deaminizating and produce intermediate 3-chlorine tosic acid, and be applied to again the method for the production of C acid, thereby realize the recycling of the organic waste that C acid is produced, reduce the discharging of refuse, reduce production costs.
For achieving the above object, technical scheme of the present invention is as follows:
The recycling method of main two kinds of by products during C acid is produced, it will be produced the isomer by product 2-amino that Pigment Intermediates C acid produces-3-chlorine tosic acid and the amino tosic acid of 3-chloro-5-or corresponding salt and recycle, be converted into nitrated precursor 3-chlorine tosilate through diazotization deamination technique, and be used further to produce C acid, concrete steps are:
One. with the 2-amino of a weight-3-chlorine tosic acid or the amino tosic acid of 3-chloro-5-or both mixtures and corresponding sulfonate, be mixed in 3 to 5 parts of weight, alcohol concn is in ethanol water mixed solution between 75-99%, mix the suspension that forms with the inorganic acid aqueous solution of 0.5-1.2 times of molar weight, at 50 ℃ of sodium nitrite in aqueous solution that add 1.1 times of molar weights below degree, spend the left and right stirring reaction, remove amino for 70 ℃;
Two. after reaction finishes, regulate pH to neutral, separate out product, after filtration with the industrial alcohol flush cake, vacuum-drying gets product 3-chlorine p-methyl benzenesulfonic acid sodium;
Three. reaction mother liquor is through Distillation recovery ethanol, and mother liquor filters, and uses the alcohol flushing filter cake, and vacuum-drying gets the second batch product;
Four. above-mentioned 3-chlorine tosic acid or 3-chlorine tosilate are produced nitrated operation acquisition C acid itrated compound precursor as the intermediate direct reuse in normal C acid.
As to further improvement in the technical proposal, sulfonate described above is sodium sulfonate or ammonium salt.Mineral acid is sulfuric acid or hydrochloric acid.Normal C acid is produced nitrated operation and is used the vitriol oil-nitric acid mixed acid nitrification operation.
For reaching above-mentioned purpose, the present invention also provides following methods:
The recycling method of main two kinds of by products during C acid is produced, it will be produced the isomer by product 2-amino that Pigment Intermediates C acid produces-3-chlorine tosic acid and the amino tosic acid of 3-chloro-5-or corresponding salt and recycle, be converted into nitrated precursor 3-chlorine tosilate through diazotization deamination technique, and be used further to produce C acid, concrete steps are:
One, with the 2-amino of a weight-3-chlorine tosic acid or the amino tosic acid of 3-chloro-5-or both mixtures or corresponding salt suspension in 3-5 part weight 95% ethanol or industrial alcohol, add concentrated hydrochloric acid (37%) or 50% aqueous sulfuric acid of 0.5-1.2 times of molar weight under stirring at room, fully stir salify;
Two, slowly add the 38-40% sodium nitrite in aqueous solution of 1.1 times of molar weights to react, exothermic heat of reaction, and have a large amount of gases to emit, reinforced process holding temperature is below 50 ℃; After reinforced completing, be warming up to gradually 70 ℃, stirring reaction is to the raw material completely dissolve.Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through the industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium;
Three, reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filters to get filter cake, and through the alcohol flushing filter cake, vacuum-drying gets the second batch product;
Four, two batches of products merge, weight yield 89-110%, and content 87-91%, other 9-13% are the inorganic salt such as sodium-chlor;
Five, 3-chlorine p-methyl benzenesulfonic acid or the salt of gained is mixed with the vitriol oil of 1-2 times of weight, slowly add the concentrated nitric acid (68%) of 1.1 times of molar weights under 50 ℃, keep temperature of reaction to be no more than 65 ℃, stirring reaction to nitrated fully;
Six, be neutralized to neutrality with buck, filter to get filter cake, vacuum-drying gets itrated compound, weight yield is 107% left and right, wherein contain 2-nitro-5-chlorine paratoluenesulfonic acid sodium salt (C acid itrated compound precursor) 75% left and right and isomer 2-nitro-3-chlorine paratoluenesulfonic acid sodium salt 12% left and right and 3-chloro-5-nitro paratoluenesulfonic acid sodium salt 13% left and right, above-mentioned three component concentrations of the itrated compound that obtains through sulfonation, chlorination and nitrated operation with toluene are basically identical.
The present invention changes into common product 3-chlorine tosic acid with two main isomer by product 2-amino-3-chlorine tosic acid and the amino tosic acid of 3-chloro-5-of C acid through desamination reaction, and 3-chlorine tosic acid itself is exactly the raw material of nitrated operation in the production of C acid, therefore can directly return to the nitrated operation that C acid is produced, for the production of C acid.So not only can realize the recycling of the organic waste that C acid is produced, reduce the discharging of refuse, and can save the consumption of the raw materials such as toluene, chlorine and sulfuric acid in C acid production, reduce production costs.The reaction conditions mild process of the technology of the present invention and technique is simple, practicality.
Embodiment:
Following examples are to further illustrate of the present invention, but the invention is not restricted to this.
The amino of 2-amino-3-chlorine paratoluenesulfonic acid sodium salt removes
Embodiment 1
To being equipped with in churned mechanically 1 liter of there-necked flask, add 100g (0.41mole) 2-amino-3-chlorine paratoluenesulfonic acid sodium salt, 500ml 75% industrial alcohol, 27 milliliters of vitriol oils (0.5mole)-50 ml water, suspension stirs to get; Take 30g (0.43mole) Sodium Nitrite and be dissolved in 50ml water, slowly add in above-mentioned suspension, keep reacting liquid temperature below 50 ℃ in reinforced process.Be warming up to gradually 70 ℃ after adding, continue to stir 5 hours, reaction is completed.Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through 50 milliliters of industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium 82 grams.Reaction mother liquor Distillation recovery ethanol, when no longer including ethanol and distillate, be cooled to room temperature, then filter to get filter cake, through the alcohol flushing filter cake of 10 milliliters of recovery, vacuum-drying gets second batch product 15 grams, and twice product merges to get 97 grams, content 90%, the 10% left and right impurity of separately having an appointment is the inorganic salt such as sodium-chlor.
Embodiment 2
To being equipped with in churned mechanically 1 liter of there-necked flask, add 100g (0.41mole) 2-amino-3-chlorine paratoluenesulfonic acid sodium salt, 300ml 95% industrial alcohol, 50 milliliter of 37% concentrated hydrochloric acid (0.5mole), suspension stirs to get; Take 30g (0.43mole) Sodium Nitrite and be dissolved in 50ml water, slowly add in above-mentioned suspension, keep reacting liquid temperature below 50 ℃ in reinforced process.Be warming up to gradually 70 ℃ after adding, continue to stir 7 hours, reaction is completed.Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through 50 milliliters of industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium 90 grams.Reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filter to get filter cake, through 10 milliliters of recovery alcohol flushing filter cakes, vacuum-drying gets second batch product 9 grams, twice product merges to get 99 grams, content 90%, and it is inorganic salt that 10% left and right impurity is separately arranged.
Embodiment 3
To being equipped with in churned mechanically 1 liter of there-necked flask, add 100g (0.42mole) 2-amino-3-chlorine paratoluenesulfonic acid ammonium salt, 500ml 95% ethanol, 50 milliliter of 37% concentrated hydrochloric acid (0.5mole), suspension stirs to get; Take 31g (0.45mole) Sodium Nitrite and be dissolved in 50ml water, slowly add in above-mentioned suspension, keep reacting liquid temperature below 50 ℃ in reinforced process.Be warming up to gradually 70 ℃ after adding, continue to stir 8 hours, reaction is completed.Stopped heating is cooled to room temperature, regulates pH until neutrality is filtered to get filter cake, and through 50 milliliters of industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium 84 grams.Reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filter to get filter cake, through 10 milliliters of recovery alcohol flushing filter cakes, vacuum-drying gets second batch product 11 grams, twice product merges to get 95 grams, content 88%, and it is inorganic salt that 12% left and right impurity is separately arranged.
Embodiment 4
To being equipped with in churned mechanically 1 liter of there-necked flask, add 100g (0.45mole) 2-amino-3-chlorine tosic acid, 300ml reclaims ethanol, 25 milliliter of 37% concentrated hydrochloric acid (0.25mole), suspension stirs to get; Take 34g (0.49mole) Sodium Nitrite and be dissolved in 55ml water, slowly add in above-mentioned suspension, keep reacting liquid temperature below 50 ℃ in reinforced process.Be warming up to gradually 70 ℃ after adding, continue to stir 5 hours, reaction is completed.Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through 50 milliliters of recovery alcohol flushing filter cakes, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium 98 grams.Reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filter to get filter cake, through 10 milliliters of recovery alcohol flushing filter cakes, vacuum-drying gets second batch product 12 grams, twice product merges to get 110 grams, content 89%, and it is inorganic salt that 11% left and right impurity is separately arranged.
Embodiment 5
To being equipped with in churned mechanically 1 liter of there-necked flask, add the amino paratoluenesulfonic acid sodium salt of 100g (0.41mole) 3-chloro-5-, 400ml 99% industrial alcohol, 50 milliliter of 37% concentrated hydrochloric acid (0.5mole), suspension stirs to get; Take 30g (0.43mole) Sodium Nitrite and be dissolved in 50ml water, slowly add in above-mentioned suspension, keep reacting liquid temperature below 50 ℃ in reinforced process.Be warming up to gradually 70 ℃ after adding, continue to stir 12 hours, reaction is completed.Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through 50 milliliters of industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium 78 grams.Reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filter to get filter cake, through 10 milliliters of recovery alcohol flushing filter cakes, vacuum-drying gets second batch product 13 grams, twice product merges to get 91 grams, content 87%, and it is inorganic salt that 13% left and right impurity is separately arranged.
Embodiment 6
To being equipped with in churned mechanically 1 liter of there-necked flask, add the amino paratoluenesulfonic acid sodium salt mixture of 100g (0.41mole) 2-amino-3-chlorine paratoluenesulfonic acid sodium salt and 3-chloro-5-, 400ml reclaims ethanol, 50 milliliter of 37% concentrated hydrochloric acid (0.5mole), and suspension stirs to get; Take 30g (0.43mole) Sodium Nitrite and be dissolved in 50ml water, slowly add in above-mentioned suspension, keep reacting liquid temperature below 50 ℃ in reinforced process.Be warming up to gradually 70 ℃ after adding, continue to stir 8 hours, reaction is completed.Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through 50 milliliters of industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium 80 grams.Reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filter to get filter cake, through 10 milliliters of recovery alcohol flushing filter cakes, vacuum-drying gets second batch product 12 grams, twice product merges to get 92 grams, content 90%, and it is inorganic salt that 10% left and right impurity is separately arranged.
3-chlorine p-methyl benzenesulfonic acid sodium nitrated
Embodiment 7
3-chlorine p-methyl benzenesulfonic acid sodium 100 grams (content 90%) of front gained and the vitriol oil of 200 grams are mixed, 68% concentrated nitric acid (43 gram) that slowly adds 1.1 times of molar weights under 50 ℃, keep temperature of reaction system to be no more than 55 ℃, stirring reaction is to nitrated complete.Be neutralized to neutrality with dilute sodium hydroxide or saturated aqueous sodium carbonate, filter to get filter cake, vacuum-drying gets itrated compound 98 grams, weight yield is 108%, wherein contain principal product 2-nitro-5-chlorine paratoluenesulfonic acid sodium salt (C acid precursor) 74% left and right and isomer 2-nitro-3-chlorine paratoluenesulfonic acid sodium salt 10% left and right and 3-chloro-5-nitro paratoluenesulfonic acid sodium salt 12% left and right, above-mentioned three component concentrations of the itrated compound that obtains through sulfonation, chlorination and nitrated operation with toluene are consistent.
Embodiment 8
3-chlorine p-methyl benzenesulfonic acid sodium 100 grams (content 90%) of front gained and the vitriol oil of 100 grams are mixed, 68% concentrated nitric acid (43 gram) that slowly adds 1.1 times of molar weights under 50 ℃, keep temperature of reaction system to be no more than 65 ℃, stirring reaction is to nitrated complete.Be neutralized to neutrality with dilute sodium hydroxide or saturated aqueous sodium carbonate, filter to get filter cake, vacuum-drying gets itrated compound 97 grams, weight yield is 107%, wherein contain principal product 2-nitro-5-chlorine paratoluenesulfonic acid sodium salt (C acid precursor) 72% left and right and isomer 2-nitro-3-chlorine paratoluenesulfonic acid sodium salt 11% left and right and 3-chloro-5-nitro paratoluenesulfonic acid sodium salt 11% left and right, above-mentioned three component concentrations of the itrated compound that obtains through sulfonation, chlorination and nitrated operation with toluene are consistent.
Abovely in conjunction with several embodiment, the present invention has been done detailed description; can not think that protection scope of the present invention only is confined to above-mentioned embodiment; if there is no to produce in essence difference with the technical scheme of claim of the present invention, to the simple change of above-mentioned embodiment or replace and still will be regarded as within protection scope of the present invention.
Claims (5)
- The recycling method of main two kinds of by products during 1.C acid is produced, described C acid is 2-amino-5-chlorine tosic acid, it is characterized in that recycling producing the isomer by product 2-amino that Pigment Intermediates C acid produces-3-chlorine tosic acid and the amino tosic acid of 3-chloro-5-or corresponding salt, be converted into nitrated precursor 3-chlorine tosilate through diazotization deamination technique, and be used further to produce C acid, concrete steps are:One, with the 2-amino of a weight-3-chlorine tosic acid or the amino tosic acid of 3-chloro-5-or both mixtures and corresponding sulfonate, be mixed in 3 to 5 parts of weight, alcohol concn is in ethanol water mixed solution between 75-99%, mix the suspension that forms with the inorganic acid aqueous solution of 0.5-1.2 times of molar weight, at 50 ℃ of sodium nitrite in aqueous solution that add 1.1 times of molar weights below degree, spend the left and right stirring reaction, remove amino for 70 ℃;Two, after reaction finishes, regulate pH to neutral, separate out product, after filtration with the industrial alcohol flush cake, vacuum-drying gets product 3-chlorine p-methyl benzenesulfonic acid sodium;Three, reaction mother liquor is through Distillation recovery ethanol, and mother liquor filters, and uses the alcohol flushing filter cake, and vacuum-drying gets the second batch product;Four, above-mentioned 3-chlorine p-methyl benzenesulfonic acid sodium is produced nitrated operation as the intermediate direct reuse in normal C acid and obtain C acid itrated compound precursor, it is to use the vitriol oil-nitric acid mixed acid nitrification operation that nitrated operation is produced in described normal C acid, and described C acid itrated compound precursor is 2-nitro-5-chlorine paratoluenesulfonic acid sodium salt.
- 2. the recycling method of main two kinds of by products during C acid is produced as claimed in claim 1 is characterized in that the central corresponding sulfonate of step 1 is sodium sulfonate or ammonium salt.
- 3. during C acid is produced as claimed in claim 1, the recycling method of main two kinds of by products, is characterized in that described mineral acid is sulfuric acid or hydrochloric acid.
- 4. during C acid is produced as claimed in claim 3, the recycling method of main two kinds of by products, is characterized in that described mineral acid is 0.5-1.2 times of molar weight 37% concentrated hydrochloric acid or 50% aqueous sulfuric acid.
- The recycling method of main two kinds of by products during 5.C acid is produced, described C acid is 2-amino-5-chlorine tosic acid, it is characterized in that recycling producing the isomer by product 2-amino that Pigment Intermediates C acid produces-3-chlorine tosic acid and the amino tosic acid of 3-chloro-5-or corresponding salt, be converted into nitrated precursor 3-chlorine tosilate through diazotization deamination technique, and be used further to produce C acid, concrete steps are:One, with the 2-amino of a weight-3-chlorine tosic acid or the amino tosic acid of 3-chloro-5-or both mixtures or corresponding salt suspension in 3-5 part weight 95% ethanol or industrial alcohol, add 37% concentrated hydrochloric acid or 50% aqueous sulfuric acid of 0.5-1.2 times of molar weight under stirring at room, fully stir salify;Two, the 38-40% sodium nitrite in aqueous solution reaction that slowly adds 1.1 times of molar weights, exothermic heat of reaction, and have a large amount of gases to emit, reinforced process holding temperature is below 50 ℃; After reinforced completing, be warming up to gradually 70 ℃, stirring reaction is to the raw material completely dissolve; Stopped heating is cooled to room temperature, regulates pH to neutral, filters to get filter cake, and through the industrial alcohol flush cake, vacuum-drying gets firstling 3-chlorine p-methyl benzenesulfonic acid sodium;Three, reaction mother liquor Distillation recovery ethanol when no longer including ethanol and distillate, is cooled to room temperature, then filters to get filter cake, and through the alcohol flushing filter cake, vacuum-drying gets the second batch product;Four, two batches of products merge, weight yield 89-110%, and content 87-91%, other 9-13% are the inorganic salt such as sodium-chlor;Five, the 3-chlorine p-methyl benzenesulfonic acid sodium with gained mixes with the vitriol oil of 1-2 times of weight, slowly adds 68% concentrated nitric acid of 1.1 times of molar weights under 50 ℃, keeps temperature of reaction to be no more than 65 ℃, and stirring reaction is to nitrated complete;Six, be neutralized to neutrality with buck, filter to get filter cake, vacuum-drying gets itrated compound, weight yield is 107%, wherein containing 2-nitro-5-chlorine paratoluenesulfonic acid sodium salt is 75%, isomer 2-nitro-3-chlorine paratoluenesulfonic acid sodium salt is that 12%, 3-chloro-5-nitro paratoluenesulfonic acid sodium salt is 13%, and above-mentioned three component concentrations of the itrated compound that obtains through sulfonation, chlorination and nitrated operation with toluene are basically identical.
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| CN102352007B (en) * | 2011-07-26 | 2012-09-05 | 浙江秦燕化工有限公司 | Method for preparing amino aryl sulfonic acid series high-molecular dispersant utilizing organic component in waste water from CLT acid production |
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| Development》.1999,第3卷(第3期),196-200. * |
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