CN101337915B - Process for preparing 2,4-diamino benzenesulfonic acid and sodium salt thereof - Google Patents
Process for preparing 2,4-diamino benzenesulfonic acid and sodium salt thereof Download PDFInfo
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- CN101337915B CN101337915B CN2008100167409A CN200810016740A CN101337915B CN 101337915 B CN101337915 B CN 101337915B CN 2008100167409 A CN2008100167409 A CN 2008100167409A CN 200810016740 A CN200810016740 A CN 200810016740A CN 101337915 B CN101337915 B CN 101337915B
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- sulfonic acid
- benzene sulfonic
- diamino benzene
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Abstract
The invention discloses a preparation technology of 2, 4-diaminobenzene sulphonic acid and sodium salts thereof, which adopts 2, 4-dinitrobenzene sulfonate sodium as raw material, uses palladium-charcoal or nickel aluminum alloy as a catalyst, and uses water or a lower alcohol as a solvent. 2, 4-diaminobenzene sulfonate sodium solution is produced through hydrogenation; the catalyst is removed through filtration; the colour removal is performed through active carbon; 2, 4-diaminobenzene sulfonate sodium is separated by crystallization after part of the solvent is removed, or hydrochloric acidis utilized to adjust the pH value to be 2 so as to separate out 2, 4-diaminobenzene sulphonic acid by crystallization after part of the solvent is removed. The preparation technology reduces the manufacture cost, no wastewater is discharged during the whole manufacturing process, the problem of waste acid discharge does not exist, and the environmental requirements are better satisfied.
Description
Technical field:
The present invention relates to a kind ofly 2, the preparation technology of 4-diamino benzene sulfonic acid and sodium salt thereof belongs to the compound field.
Technical background:
2,4-diamino benzene sulfonic acid sodium is used as abutment because of containing three reactive groups in dyestuff is synthetic, is widely used in the production of reactive dyestuffs and matching stain.
2, the traditional working method of 4-diamino benzene sulfonic acid sodium has two kinds:
1,2,4-dinitrobenzene sulfonic acid sodium iron powder reducing method:
Product per ton is with 1.8～2 tons of iron powders, and because of iron powder price continuous rise, production environment is relatively poor, and also there is bigger problem in environmental protection and is eliminated gradually.
2, mphenylenediamine sulfuric acid sulfonation method:
This method technology is simple, is prone to go up output, and shortcoming is that the spent acid amount is big, and product per ton produces about 7 tons in 50%～55% spent acid.
Summary of the invention:
In order to overcome above-mentioned traditional technology preparing method's shortcoming, the invention provides a kind of 2,4-dinitrobenzene sulfonic acid sodium hydrogenation preparing 2, the technology of 4-diamino benzene sulfonic acid sodium is to realize above-mentioned purpose, the present invention adopts following scheme:
2,4-dinitrobenzene sulfonic acid sodium is dissolved in the solvent, and solvent is water or low-carbon alcohol; Add catalyzer, hydrogenation reaction, when adding hydrogen in the reaction kettle hydrogen pressure be controlled at 0.1～2.5MPa; Temperature of reaction kettle is controlled at 35 ℃～150 ℃ when adding hydrogen; Catalyzer is palladium charcoal or Ni-Al alloy catalyst, and catalyst levels is the 1-10% of the quality of reactant, and reaction equation is following:
Generate 2 earlier, 4-diamino benzene sulfonic acid sodium reaction solution removes by filter catalyzer, and activated carbon decolorizing is removed impurity, and concentrated post crystallization separates out 2, and 4-diamino benzene sulfonic acid sodium is produced sour body like need, and then using hydrochloric acid to transfer PH is 2, and crystallization separates out 2, the 4-diamino benzene sulfonic acid.
According to the invention a kind of 2, the preparation technology of 4-diamino benzene sulfonic acid sodium has following effect or advantage:
1. reduced production cost;
2. whole process of production does not have waste water discharge, no spent acid emission problem, more compliance with environmental protection requirements.
Embodiment
Embodiment 1: in the 1000ml autoclave, add entry 500ml, and 2,4-dinitrobenzene sulfonic acid sodium 176.5g (content 85%), palladium carbon catalyst 5g; Airtight autoclave is evacuated down to earlier-0.095MPa, charges into nitrogen 1MPa. again and repeats 3 ~ 5 times, at last system is evacuated; Reaction solution is heated to 50 ℃, begins logical hydrogen, and pressure is 1 ~ 1.6MPa, and control reaction temperature is at 50 ~ 100 ℃; Hydrogen pressure no longer reduces in reaction kettle, and autoclave is opened in cooling after the emptying, remove by filter the palladium charcoal; Use the 10g activated carbon decolorizing, be concentrated to original volume 1/3rd, the cooling post crystallization goes out 2,4-diamino benzene sulfonic acid sodium 115g.Content 82.6%, yield 81.42%.
Embodiment 2: in the 1000ml autoclave, add entry 500ml, and 2,4-dinitrobenzene sulfonic acid sodium 176.5g (content 85%), palladium carbon catalyst 2g; Airtight autoclave is evacuated down to earlier-0.095MPa, charges into nitrogen 1MPa. again and repeats 3 ~ 5 times, at last system is evacuated, and reaction solution is heated to 50 ℃; Begin logical hydrogen, pressure is 1 ~ 1.6MPa, and control reaction temperature is at 50 ~ 100 ℃, and hydrogen pressure no longer reduces in reaction kettle; Autoclave is opened in cooling after the emptying, remove by filter the palladium charcoal, and the mother liquor after filtering among the embodiment 1 is poured into; Add the 10g activated carbon decolorizing, solution concentration to original volume 1/3rd, the cooling post crystallization goes out 2,4-diamino benzene sulfonic acid sodium 133g.Content 82.3%, yield 93.82%.
Embodiment 3: feed intake reaction and aftertreatment be with embodiment 2, be concentrated to original volume 1/3rd after, transfer about PH=2 with 30% hydrochloric acid, decrease temperature crystalline goes out 2,4-diamino benzene sulfonic acid, weight 106g behind the suction filtration.Content 92.4%, yield 94.18%.
Embodiment 4: in the 1000ml autoclave, add entry 150ml, ethanol 400ml, 2,4-dinitrobenzene sulfonic acid sodium 176.5g (content 85%); Palladium carbon catalyst 3g, airtight autoclave, reaction solution are heated to 50 ℃, begin logical hydrogen; Pressure is 0.8MPa, exothermic heat of reaction, 80 ℃ of temperature controls, pressure 1 ~ 1.2MPa; Inhale hydrogen and no longer change, cool to below 50 ℃, emit reaction solution, filter to pressure; Remove catalyzer, be concentrated to 1/3rd of original volume after the decolouring, the cooling post crystallization goes out 2,4-diamino benzene sulfonic acid sodium 136g.Content 82.6%, yield 96.28%.
Embodiment 5: in the 1000ml autoclave, and ethanol 520ml, 2,4-dinitrobenzene sulfonic acid sodium 176.5g (content 85%), palladium carbon catalyst 4g; Airtight autoclave, reaction solution are heated to 50 ℃, begin logical hydrogen, and pressure is 0.8MPa, exothermic heat of reaction; 80 ℃ of temperature controls, pressure 1.6 ~ 1.8MPa inhales hydrogen and no longer changes to pressure, cools to below 50 ℃, emits reaction solution; Filter, remove catalyzer, be concentrated to 1/3rd of original volume after the decolouring, the cooling post crystallization goes out 2,4-diamino benzene sulfonic acid sodium 138g.Content 82.2%, yield 97.21%.
Embodiment 6: in the 1000ml autoclave, and methyl alcohol 460ml, 2,4-dinitrobenzene sulfonic acid sodium 176.5g (content 85%), Ni-Al alloy catalyst 4.5g; Airtight autoclave, reaction solution are heated to 50 ℃, begin logical hydrogen, and pressure is 0.8MPa, exothermic heat of reaction; 80 ℃ of temperature controls, pressure 2 ~ 2.2MPa inhales hydrogen and no longer changes to pressure, cools to below 50 ℃, emits reaction solution; Filter, remove catalyzer, be concentrated to 1/3rd of original volume after the decolouring, the cooling post crystallization goes out 2,4-diamino benzene sulfonic acid sodium 132g.Content 82.4%, yield 93.22%.
Embodiment 7: in the 1000ml autoclave, and Virahol 400ml, 2,4-dinitrobenzene sulfonic acid sodium 176.5g (content 85%); Ni-Al alloy catalyst 3g, airtight autoclave, reaction solution are heated to 50 ℃, begin logical hydrogen; Pressure is 0.8MPa, exothermic heat of reaction, 80 ℃ of temperature controls, pressure 2.2 ~ 2.5MPa; Inhale hydrogen and no longer change, cool to below 50 ℃, emit reaction solution, filter to pressure; Remove catalyzer, be concentrated to 1/3rd of original volume after the decolouring, the cooling post crystallization goes out 2,4-diamino benzene sulfonic acid sodium 135g.Content 83.2%, yield 96.25%.
Explain: palladium carbon catalyst is applied mechanically 50 times continuously, and its activity does not descend basically.
Claims (2)
1. one kind 2, the preparation technology of 4-diamino benzene sulfonic acid and sodium salt thereof is characterized in that, 2; 4-dinitrobenzene sulfonic acid sodium is catalyzer with the metalloid in solvent, under certain temperature and pressure, produces 2 through the mode of hydrogenation; 4-diamino benzene sulfonic acid sodium solution removes by filter catalyzer, through activated carbon decolorizing, removes the partial solvent post crystallization and separates out 2; 4-diamino benzene sulfonic acid sodium, or transfer pH value with hydrochloric acid after removing partial solvent, crystallization separates out 2, the 4-diamino benzene sulfonic acid; Used solvent is water or low-carbon alcohol; Catalyst system therefor is palladium charcoal or Ni-Al alloy catalyst, and catalyst levels is the 1-10% of the quality of reactant; When being to add hydrogen in the reaction kettle hydrogen pressure be controlled at 0.1～2.5MPa, temperature of reaction kettle is controlled at 35 ℃～150 ℃ when adding hydrogen; Using hydrochloric acid to transfer pH value is 2, and crystallization separates out 2, the 4-diamino benzene sulfonic acid.
2. according to claim 1 a kind of 2, the preparation technology of 4-diamino benzene sulfonic acid sodium is characterized in that, used low-carbon alcohol be in methyl alcohol, ethanol and the Virahol any.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100167409A CN101337915B (en) | 2008-06-05 | 2008-06-05 | Process for preparing 2,4-diamino benzenesulfonic acid and sodium salt thereof |
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| CN2008100167409A CN101337915B (en) | 2008-06-05 | 2008-06-05 | Process for preparing 2,4-diamino benzenesulfonic acid and sodium salt thereof |
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| CN101337915A CN101337915A (en) | 2009-01-07 |
| CN101337915B true CN101337915B (en) | 2012-01-11 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120203031A1 (en) | 2009-10-19 | 2012-08-09 | Newreka Chemicals Private Limited | Sustainable chemical process for reduction of nitro compounds (R-NO2) or nitroso compounds (R-NO) containing sulphonic or carboxylic group into corresponding amino compounds (R-NH2) with inherent recycle of all acidic streams generated in synthesis |
| CN102516136A (en) * | 2011-10-31 | 2012-06-27 | 天津大学 | Method for preparing 4,4 '- diaminostilbene- 2,2' - disulfonic acid by using DNS sodium salt(4,4 '- dinitrostilbene-2,2' - disulfonic acid sodium salt) |
| CN115572246A (en) * | 2022-09-30 | 2023-01-06 | 湖北源洹实业投资有限公司 | Process for preparing benzenesulfonic acid by taking hydrogen chloride gas as acidification reagent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721398A (en) * | 2005-06-24 | 2006-01-18 | 上海世景国际贸易有限公司 | Process for synthesis of 2,4-diamino benzene sulfonic acid and its sodium salts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721398A (en) * | 2005-06-24 | 2006-01-18 | 上海世景国际贸易有限公司 | Process for synthesis of 2,4-diamino benzene sulfonic acid and its sodium salts |
Non-Patent Citations (3)
| Title |
|---|
| 宋东明 等.邻氨基苯磺酸合成工艺改进.《精细化工》.1995,第12卷(第12期),61-63. * |
| 李玉昌.利用硝基氯苯焦油状废液制备2 4 —二氨基苯磺酸钠.《河南城建高等专科学校学报》.2002 |
| 李玉昌.利用硝基氯苯焦油状废液制备2,4 —二氨基苯磺酸钠.《河南城建高等专科学校学报》.2002,第11卷(第2期),40-41. * |
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