CN101219977A - CLT acid production method without acid waste liquid discharge - Google Patents
CLT acid production method without acid waste liquid discharge Download PDFInfo
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- CN101219977A CN101219977A CNA2008100090021A CN200810009002A CN101219977A CN 101219977 A CN101219977 A CN 101219977A CN A2008100090021 A CNA2008100090021 A CN A2008100090021A CN 200810009002 A CN200810009002 A CN 200810009002A CN 101219977 A CN101219977 A CN 101219977A
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Abstract
The invention relates to a manufacture method for 6-chlorine-3-aminotoluene-4-sulfonic acid (CLT acid for short in the followings). A method of toluene azeotropic dehydration is used in the process of manufacturing the CLT acid to prepare a toluene sulfonic acid with the toluene sulfonic acid as main products; the toluene sulfonic acid is chloro-substituted and nitrated, which abolishes the precipitation method of 45 to 60 percent of the sulfate in the prior art, thereby directly reducing nitration products; the reduction and after-processing method is that one molar toluene sulfonic acid is used as the standard to use 1000 to 2500ml water to dissolve the nitration products, 10 percent of the liquor of the nitration products is taken to activate the iron powder, and then the remained 90 percent of the liquor is adjusted by sodium carbonate to have the pH value of 5 to 7, which is dropped into the activated iron powder mixture to process reduction reaction. After the thorough reduction, the pH value is adjusted to be 9 to 11 by sodium carbonate, and after filtering, 500 to 2000ml thermal recovered liquor (I) is used for washing the iron mud. The filtering liquid and the washing liquid are combined (discoloration is necessary if the color is dark), the pH value is adjusted to be 1 to 1.5 by dilute sulfuric acid to precipitate the crude products of CLT acid and then the filtering liquid is cooled to be under 10 DEG C to filter the sodium bisulfate crystallization. The filter cake is washed by using the recovered liquor (II), the filtrate is combined with the filtrate which filters sodium bisulfate, and then the recovered liquor (I) can be gotten by the neutralization of sodium carbonate.
Description
[technical field] the present invention relates to the manufacture method of 6-chloro-3-phenylmethylamine-4-sulfonic acid (being designated hereinafter simply as CLT acid), refer to that particularly toluene and sulfuric acid carry out sulfonation reaction in the presence of excess toluene, continuation is carried out chloro, nitrated and reduction with toluenesulphonic acids, recycle the spent acid salts solution, make the method for CLT acid.Feature of the present invention is; CLT acid is made in no sulfur waste acid and the discharging of no spent acid salts solution under the close envrionment conditions.
[background technology] CLT acid synthetic route is more: toluene sulfonation route, meta-aminotoluene route, ortho-chlorotolu'ene route, m-xylene route etc.But the toluene sulfonation route has advantages such as raw material sources are wide, production cost is low, easy and simple to handle, low for equipment requirements.Shortcoming is that the generation isomer is many, and product yield is low, and sulfuric acid consumption is big, produces a large amount of sulfur wastes acid and a large amount of acid saline solns in the acid out process.If can further improve, reduce the three wastes, improve yield, the toluene sulfonation route still be can yet be regarded as and is produced the best process flow of CLT acid.
West Germany's BASF (BASF) EP57889 of house journal (1982) has used the 2.65-2.75 mole vitriol oil/mole toluene to carry out sulfonation at 105-110 ℃, at 60-80 ℃ of logical 1.1-1.3 mole chlorine, adding 98-100% nitric acid at 60-70 ℃ carries out nitrated, thin up makes sulfuric acid concentration become 50-60% and allows itrated compound separate out, reduce then and obtain target compound.People such as Sun Chunguang [dyestuffs industries, 1990,27 (3) 29-32) processing condition of toluene sulfonation route are improved, product yield is improved a lot, reduced the sulfuric acid consumption significantly simultaneously, got rid of and saltoutd, the three wastes are greatly reduced.But this method is used the 2.88 moles of vitriol oil/mole toluene, adopts and applies mechanically sulfur waste acid acid-precipitation method.
People such as Cui Yumin [chemical reaction engineering and technology, 2001,17 (1) 94-96] are in order to overcome CLT acid yield low (42.8%), purity low (96.7%), and the calcium sulfate residue is many, and with serious pollution problem is improved former technology.Replace neutralisation with acid out, make CLT acid lab scale yield reach 53.8%, purity reaches more than 98.0%, has reduced the vitriolic consumption significantly.
1 ton of CLT acid of every production will be discharged the salt bearing liquid wastes that 3-5 ton concentration is acid of 50-60% sulfur waste and 15-30 ton PH=1-1.5 in above-mentioned all methods, and environmental pollution is serious.One of reason that produces a large amount of sulfur waste acid and acidic salt solution is to have used big excessive sulfuric acid (the 2.64-3 mole vitriol oil/mole toluene) in sulfonation process; Former two is to use a large amount of water in reduction, acid out, water washing process therefore.Therefore the problem of a large amount of sulfur waste acid of discharging and acidic salt solution to be solved, the work of two aspects need be done:
(1) uses the technology of excess sulfuric acid to use the technology of excess toluene in the former sulfonation reaction instead, reduce the vitriolic consumption as far as possible, will abolish the sulfur waste acid acid-precipitation method that uses in above-mentioned all documents simultaneously; (2) after suitably handling, recycle the acid abraum salt solution that produces in the CLT acid production process.
About the existing document of preparation tosic acid hydrate under the excessive situation of toluene.For example, English Patent GB967874 uses excess toluene to carry out sulfonation, and sulfonated bodies is separated out with the form of hydrate, and hydrate is filtered in air, and drying obtains the tosic acid hydrate.Day disclosure is speciallyyed permit flat 2-1457 and is used 50-100% sulfuric acid to carry out sulfonation in the presence of excess toluene, adds suitable quantity of water in the toluenesulphonic acids mixture of generation, and the crystal of hydrate of separating out is at moisture content≤1g/m
3Dry air in filter, drying obtains highly purified tosic acid hydrate.But these method processing condition strictnesses will expect that anhydrous tosic acid operational path is longer, are not suitable for directly applying to CLT acid and produce.
Do not see the document record as yet about the technology of in CLT acid production process, recycling acid abraum salt solution.
[summary of the invention] the purpose of this invention is to provide a kind of improved CLT acid manufacture method, it is characterized in that yield height, no sulfur waste acid discharging, also do not have the discharging of the salt bearing liquid wastes of PH=1-1.5.
For achieving the above object, sulfonation reaction of the present invention is carried out in the presence of excess toluene.Toluene and vitriolic mol ratio are 1.5-3.0, and sulfonation temperature is 110-115 ℃, and dehydrating amount is water and the theoretical 70-100% that generates water yield sum of sulfonation reaction in the sulfuric acid, and dewatering time generally need be with 2-15 hour.Dehydration finishes, and reclaims toluene, adds a small amount of sulfuric acid, carries out chloro and nitrated by traditional method then.
Among the present invention, in order to reach the purpose of no sulfur waste acid and acid waste liquid discharging, the salts solution of the most of PH=1-1.5 after filtration, the washing CLT acid is recycled, a spot of residue acidic salt solution is handled, and reaches no discharging of waste liquid.For this purpose, 1 mole of toluenesulphonic acids is used 1000-2500 ml water dissolving nitration product as benchmark, 1/10 or the 100-200 milliliter of getting its solution reclaim liquid (I) and activate iron powder, remaining 9/10 solution or all the itrated compound aqueous solution transfer to splash into behind the PH=5-7 with yellow soda ash and carry out reduction reaction in the activatory iron mixture.Deng reduction fully, transfer PH=9-11 with yellow soda ash, filter, with 500-2000 milliliter neutral recovery of heat last time liquid (I) washed metal mud, merging filtrate and washing lotion (if color is faded more deeply) are transferred PH=1-1.5 deposit C LT acid crude with dilute sulphuric acid, filter, filtrate is cooled to remove by filter the sodium pyrosulfate crystallization below 20 ℃.CLT acidleach cake is washed with the hot recessed receipts liquid (II) of last time, and washing lotion and filter the filtrate that sodium pyrosulfate produces and merge obtains reclaiming liquid (I), uses when reduction and washed metal mud next time.Add 500-1000 milliliter hot water in the CLT acidleach cake of washing with the recovery of heat liquid (II) of last time, stir, filter, must reclaim liquid (II), cake is considered in resulting CLT acid carry out drying at 80 ℃.Direct or concentrated back of remaining recovery liquid (I) and coal are mixed together and are burnt.
Among the present invention, toluenesulphonic acids content, sulfuric acid content and the water content in the sulfonated bodies and the purity of the finished product etc. are that chemical analysis method is measured; The content of the isomer in sulfonated bodies, chloro thing and the itrated compound is measured with HPLC wavelength 214nm.
[embodiment]
Embodiment 1
Fill it up with toluene in the water trap, add 79.46g (0.75mol) 92.58% sulfuric acid in the dropping funnel, add 110g 98% toluene in the four-hole bottle that 250ml has weighed, heating makes refluxing toluene, at this moment splashes into the sulfuric acid in the dropping funnel between 1 hour, drips to finish, proceed azeotropic dehydration, until aquifer yield is 14.55ml, steams excess toluene then, obtains sulfonated bodies 127.9g.Chemical analysis results shows, sulfur acid 6.556g in the product, and moisture 3.64g, toluenesulphonic acids are 117.7g.The HPLC analysis revealed, the content of para-isomeride is 88.18% in toluenesulphonic acids, and the content of ortho isomer is 11.82%, and other product is that tracer level HPLC fails to detect.
Embodiment 2
Will by the sulfonated bodies of 0.3416mol toluenesulphonic acids through chloro and nitrated after the itrated compound that obtains be dissolved in 512 ml waters, getting its 1/10 volume is added in the four-hole bottle that the 70g cast iron powder is housed, be warmed up to 100-102 ℃ of activation 30 minutes, under 100-102 ℃, splash into the surplus solution of 9/10 volume that is neutralized to PH=5-7, drip and finish, continue stirring reaction to react completely (needing 3-5 hour approximately).Transfer PH=9-10 with yellow soda ash, filtered while hot, at every turn with twice of 200ml neutral recovery of heat last time liquid (I) washed metal mud, merge and consider liquid and washing lotion (if color is faded deeply), transfer PH=1.2-1.3 deposit C LT acid with dilute sulphuric acid, be cooled to 55 ℃ of filtrations, compacting, filtrate is cooled to remove by filter the sodium pyrosulfate crystallization below 10 ℃.CLT acidleach cake is washed with the recovery of heat liquid (II) of about 170 milliliters of last time, and this filtrate and the filtrate that removes by filter behind the sodium pyrosulfate are merged, and obtains reclaiming liquid (I) with the yellow soda ash neutralization, uses during washed metal mud next time.Add 170 milliliters of hot water in the CLT acidleach cake of washing with the recovery of heat liquid (II) of last time, stir, filter, must reclaim liquid (II), cake is considered in resulting CLT acid carry out drying, get the CLT acid 46.2-48.4g (yield that is calculated by toluenesulphonic acids is 59.8-62.6%) of purity 〉=98% at 80 ℃.Remaining recovery liquid (I) is the 100-270 milliliter, and direct or concentrated back and coal are burnt together.
Embodiment 3
Will by the sulfonated bodies of 0.3416mol toluenesulphonic acids through chloro and nitrated after the itrated compound that obtains be dissolved in 337 ml waters, transfer PH=5-7 with yellow soda ash.The recovery liquid (I) of 346ml last time is added in the four-hole bottle that the 70g cast iron powder is housed, be warmed up to 100-102 ℃ of activation 30 minutes, under 100-102 ℃, splash into the itrated compound solution that is neutralized to PH=5-7, drip and finish, continue stirring reaction to react completely (needing 3-5 hour approximately).Transfer PH=9-10 with yellow soda ash, filtered while hot, twice in recovery of heat last time liquid (I) the washed metal mud of each usefulness 116ml PH=8-10, merge and consider liquid and washing lotion (if color is faded deeply), transfer PH=1.2-1.3 deposit C LT acid with dilute sulphuric acid, be cooled to 55 ℃ of filtrations, compacting, filtrate is cooled to remove by filter the sodium pyrosulfate crystallization below 10 ℃.CLT acidleach cake is washed with the recovery of heat liquid (II) of about 170 milliliters of last time, and this filtrate and the filtrate that removes by filter behind the sodium pyrosulfate are merged, and obtains reclaiming liquid (I), uses when reduction and washed metal mud next time.Add 170 milliliters of hot water in the CLT acidleach cake of washing with the recovery of heat liquid (II) of last time, stir, filter, must reclaim liquid (II), cake is considered in resulting CLT acid carry out drying, get the CLT acid 47.1-49.3g (yield that is calculated by toluenesulphonic acids is 61.3-63.8%) of purity 〉=98% at 80 ℃.Remaining recovery liquid (I) is about the 80-120 milliliter, and direct or concentrated back and coal are burnt together.
Claims (4)
1. the method for toluene sulfonation manufactured 6-chloro-3-phenylmethylamine-4-sulfonic acid (being designated hereinafter simply as CLT acid), it is characterized in that toluene and sulfuric acid carry out sulfonation reaction under the existence of excess toluene, continuation is carried out chloro and nitrated with toluenesulphonic acids, directly itrated compound is reduced, under no discharging of waste liquid condition, make CLT acid.
2. the method for manufacturing CLT according to claim 1 acid, it is characterized in that process for sulfonation in the presence of the excess sulfuric acid discarded traditional in CLT acid is made and use methylbenzene azeotropic dehydration process for sulfonation, making with the tosic acid is the toluenesulphonic acids mixture of principal product.Toluene and vitriolic mol ratio are 1.5-3.0, and sulfonation temperature is 105-115 ℃, and dehydrating amount is water and the theoretical 70-100% that generates water yield sum of sulfonation reaction in the sulfuric acid.Dehydration finishes, and reclaims excess toluene, adds a small amount of sulfuric acid, carries out chloro and nitrated by traditional method then.
3. the method for manufacturing CLT according to claim 1 acid is characterized in that toluenesulphonic acids is carried out chloro and 45-60% sulfuric acid precipitation method in the former technology is abolished in nitrated back, directly itrated compound is reduced.
4. the method for manufacturing CLT according to claim 1 acid, it is characterized in that reducing and aftertreatment in recycle the waste liquid that 70-90% produces in reduced liquid preparation and last handling process, direct or the concentrated back of 10-30% residual waste solution is mixed together with coal and is burnt, thereby makes CLT acid under no discharging of waste liquid condition.
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| CNA2008100090021A CN101219977A (en) | 2008-01-25 | 2008-01-25 | CLT acid production method without acid waste liquid discharge |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698743A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same |
| CN103193411A (en) * | 2013-04-03 | 2013-07-10 | 上海固佳化工科技有限公司 | Modified aliphatic high-efficiency water reducing agent prepared from CLT acid production wastewater as raw material and preparation method of water reducing agent |
| CN104496860A (en) * | 2014-11-21 | 2015-04-08 | 浙江秦燕化工有限公司 | Reserve salt, preparation method and application thereof |
| CN105175289A (en) * | 2015-10-09 | 2015-12-23 | 江苏瑞燕橡塑助剂有限公司 | Aromatic hydrocarbon sulfonation method |
| CN105541668A (en) * | 2016-01-14 | 2016-05-04 | 浙江秦燕科技股份有限公司 | Method for achieving pipe-type continuous production of CLT acid chloride |
| CN109438295A (en) * | 2018-11-29 | 2019-03-08 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid sulfonated bodies |
| CN109651205A (en) * | 2018-12-18 | 2019-04-19 | 山东世纪阳光科技有限公司 | A kind of CLT acid synthetic method |
| CN110759831A (en) * | 2019-10-16 | 2020-02-07 | 浙江金伯士药业有限公司 | Method for preparing halofuginone intermediate 2-amino-4-bromo-5-chlorobenzoic acid |
| CN112500319A (en) * | 2020-10-30 | 2021-03-16 | 浙江秦燕科技股份有限公司 | Method for preparing CLT acid by continuous acidification |
-
2008
- 2008-01-25 CN CNA2008100090021A patent/CN101219977A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698743B (en) * | 2012-05-18 | 2015-01-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same |
| CN102698743A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same |
| CN103193411B (en) * | 2013-04-03 | 2016-08-03 | 上海固佳化工科技有限公司 | With modified aliphatic high efficiency water reducing agent that CLT acid production waste water is prepared for raw material and preparation method thereof |
| CN103193411A (en) * | 2013-04-03 | 2013-07-10 | 上海固佳化工科技有限公司 | Modified aliphatic high-efficiency water reducing agent prepared from CLT acid production wastewater as raw material and preparation method of water reducing agent |
| CN104496860A (en) * | 2014-11-21 | 2015-04-08 | 浙江秦燕化工有限公司 | Reserve salt, preparation method and application thereof |
| CN105175289A (en) * | 2015-10-09 | 2015-12-23 | 江苏瑞燕橡塑助剂有限公司 | Aromatic hydrocarbon sulfonation method |
| CN105541668A (en) * | 2016-01-14 | 2016-05-04 | 浙江秦燕科技股份有限公司 | Method for achieving pipe-type continuous production of CLT acid chloride |
| CN105541668B (en) * | 2016-01-14 | 2017-11-24 | 浙江秦燕科技股份有限公司 | A kind of method of duct type continuous production CLT acid chloride |
| CN109438295A (en) * | 2018-11-29 | 2019-03-08 | 浙江秦燕科技股份有限公司 | The method of successive reaction preparation CLT acid sulfonated bodies |
| CN109438295B (en) * | 2018-11-29 | 2021-05-28 | 浙江秦燕科技股份有限公司 | Method for preparing CLT acid sulfonate by continuous reaction |
| CN109651205A (en) * | 2018-12-18 | 2019-04-19 | 山东世纪阳光科技有限公司 | A kind of CLT acid synthetic method |
| CN110759831A (en) * | 2019-10-16 | 2020-02-07 | 浙江金伯士药业有限公司 | Method for preparing halofuginone intermediate 2-amino-4-bromo-5-chlorobenzoic acid |
| CN110759831B (en) * | 2019-10-16 | 2022-09-27 | 浙江金伯士药业有限公司 | Method for preparing halofuginone intermediate 2-amino-4-bromo-5-chlorobenzoic acid |
| CN112500319A (en) * | 2020-10-30 | 2021-03-16 | 浙江秦燕科技股份有限公司 | Method for preparing CLT acid by continuous acidification |
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Application publication date: 20080716 |