CN105712907A - Cleaning sulfonation technology adopted in H acid production process - Google Patents
Cleaning sulfonation technology adopted in H acid production process Download PDFInfo
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- CN105712907A CN105712907A CN201610138415.4A CN201610138415A CN105712907A CN 105712907 A CN105712907 A CN 105712907A CN 201610138415 A CN201610138415 A CN 201610138415A CN 105712907 A CN105712907 A CN 105712907A
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- acid
- naphthalenedisulfonic
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- sulfonation
- naphthalenedisulfonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a cleaning sulfonation technology adopted in the H acid production process and belongs to the technical field of organic chemistry. According to the technology, a 2.7-naphthalene disulfonic acid damp product is subjected to decompression concentration so that the concentration of sulfuric acid in the 2.7-naphthalene disulfonic acid damp product can be increased to 90%, then, anhydrous slufuric acid is added for tri-sulfonation so that high-quality 1.3.6-naphthalene trisulfonic acid can be obtained, and finally, the obtained 1.3.6-naphthalene trisulfonic acid is subjected to conventional continuous nitration denitration, extraction, hydrogenation reduction, concentration, alkali fusion, H acid separation and other procedures so that high-quality H acid can be obtained. By means of the technology, the yield of 1.3.6-naphthalene trisulfonic acid is increased to 88% or above from the original 78%, the single-step yield is increased by 10%, and meanwhile the problem that in the prior art, the low alkali fusion yield caused by large impurity content after concentration is solved.
Description
Technical field
The present invention relates to the cleaning process for sulfonation in a kind of H-acid production process；Belong to technical field of organic chemistry.
Background technology
H-acid is the intermediate that a kind of dye industry is important, and H-acid is mainly for the production of acidity, directly and reactive dye, and these
Dyestuff is used for wool spinning, the dyeing of bafta.Also can be used for producing medicine.
In H-acid produces, sulfonation is significant element therein reaction, and the process for sulfonation in H-acid Conventional process uses
After naphthalene and anhydrous slufuric acid reaction obtain a LOMAR PWA EINECS 246-676-2, the oleum of 65% is then used to carry out two sulfonation and three sulfonation, final
To target product 1.3.6-naphthalene trisulfonic acid.Above process for sulfonation must be added to substantial amounts of anhydrous slufuric acid to reduce material viscosity, carries
High heat transfer efficiency, and be that the oleum being smoothed out adding excess guaranteeing reaction carries when two sulfonation and three sulfonation
The sulfuric acid concentration of high reaction system so that the later stage need to add substantial amounts of liquefied ammonia to neutralize in reaction system the sulphuric acid of excess, thus
Cause in end processing sequences, create a large amount of reluctant efflux wastewater.
The problem producing a large amount of difficult efflux wastewaters for solving conventionally produced H-acid, in 1984, first has Japan
Expert proposes diamine method and produces the synthetic route of H-acid: refined naphthalene generates 2.7-naphthalenedisulfonic acid under conditions of excess sulfuric acid exists, so
Afterwards by double nitrifications, reduce, the step synthesis H-acid such as hydrolysis.This process route is after the later stage improves in a large number, to a certain extent
Decrease the wastewater discharge in H-acid production process, but the acidity that the highly acid mother solution produced for double nitrifications and hydrolysis produce
Mother solution does not provide process or Utilization plan, and nearest Shenyang Chemical Engineering Inst discloses to enter both the above mother solution in its patent
Gone extraction rear enclosure scheme, but the most fundamentally solve mother solution produce problem.
Summary of the invention
It is an object of the invention to: provide a kind of diamine method that not only overcomes to produce the nitrification mother solution existing for H-acid and water
Hydrolysis mother liquor cannot Appropriate application or need the problem of extra process, solve the sulfonation in the presence of existing production H-acid simultaneously and receive
Rate is low, concentrates impurity content height in material and causes the cleaning sulfonation work in the H-acid production process of the later stage low problem of alkali fusion yield
Skill.
The technical scheme is that
Cleaning process for sulfonation in a kind of H-acid production process, it is characterised in that it comprises the following steps:
1), according to diamine method synthesis H-acid technique, synthesize 2.7-naphthalenedisulfonic acid tide product, 2.7-naphthalenedisulfonic acid tide product are put into
In the reactor of belt stirrer, and it is warmed up to 120 DEG C, then starts stirring, under conditions of rotating speed 30 revs/min, stir 10 points
Clock, then samples, utilize high performance liquid chromatography by external standard method detect wherein 1.3.6-naphthalene trisulfonic acid, 2.6-naphthalenedisulfonic acid,
2.7-naphthalenedisulfonic acid and the chromatographic content of other disulfonic acid and percetage by weight, detect the total acidity of material simultaneously；
2) the 2.7-naphthalenedisulfonic acid tide product after step 1) having been detected reduce pressure under conditions of negative pressure is more than-0.095Mpa
Concentrate so that its sulfuric acid concentration reaches 90%；
3) by step 2) the concentration qualified material of gained cools to 60 DEG C, drips 2.5 times according to step 1) gained testing result
The anhydrous slufuric acid of 2.7-naphthalenedisulfonic acid molal quantity, during acid adding, control temperature is below 80 DEG C, and time-consuming 23 hours of acid adding adds
It is warmed up to 165 DEG C after complete anhydrous slufuric acid, maintains sampling in 0.5 hour, detect wherein 2.7-naphthalenedisulfonic acid chromatographic content and be less than 0.5%
For qualified；
4) after reaction terminates, cooling to 80 ~ 90 DEG C, add appropriate water and terminate reaction, the total acidity simultaneously regulating material is
67.6-68.6%(is with sulphur acid meter), the process control temp that adds water is less than 115 DEG C, and adding water is time-consumingly 10 30 minutes；
5) after having added water, material is turned to continuous nitrification denitrating post, according to existing continuous nitrification denitrating, extraction, hydrogenating reduction, dense
Contracting, alkali fusion, H-acid isolation common process can be prepared by high-quality H-acid.
The invention have the advantage that
The present invention be by 2.7-naphthalenedisulfonic acid by concentrate after, carry out three sulfonation and obtain the 1.3.6-naphthalene that chromatographic content is 96 ~ 98%
Trisulfonic acid, is brought up to present more than 88% by the yield of 1.3.6-naphthalene trisulfonic acid by original 78%, and single step yield improves
10%, solve the problem that rear impurity content caused alkali fusion yield low more that concentrates present in prior art simultaneously.
Detailed description of the invention
Embodiment 1:
Take 2.7-naphthalenedisulfonic acid tide product 810Kg, put in the reactor of belt stirrer, and be warmed up to 120 DEG C, then start and stir
Mixing, stir 10 minutes, then sample under conditions of rotating speed 30 revs/min, the chromatograph recording wherein 1.3.6-naphthalene trisulfonic acid contains
Amount is 1.61%, and mass percent is 1.38%, and the chromatographic content of 2.6-naphthalenedisulfonic acid is 1.05%, and mass percent is 1.32%,
2.7-naphthalenedisulfonic acid is 96.91%, and mass percent is 56.57%, and 1.6-naphthalenedisulfonic acid is 0.07%, and mass percent is
0.04%, unknown material is 0.36%, and material total acidity is that 33.81%(is with sulphur acid meter), under conditions of negative pressure is-0.096Mpa, enter
Leftover materials, after concentrating water outlet 147.78Kg, are cooled to 60 DEG C by row concentrating under reduced pressure, the anhydrous slufuric acid of dropping 390Kg, drip
Cheng Zhong, control temperature, below 80 DEG C, drips sulphuric acid time-consuming 2 hours, after adding anhydrous slufuric acid, material is warmed up to 165 DEG C, dimension
Holding 30 minutes, sampling detection, recording wherein 1.3.6-naphthalene trisulfonic acid chromatographic content is 98.10%, 2.7-naphthalenedisulfonic acid chromatographic content
Being 0.4%, material cools to 60 DEG C, dropping 60Kg clear water terminates reaction, and the process maximum temperature of adding water is 108 DEG C, time-consuming 10 points
Clock, recording material total acidity after adding water is that 67.8%(is with sulphur acid meter), turn and expect to continuous nitrification denitrating post, according to
Technical scheme disclosed by CN200810169724.3 carries out follow-up continuous nitrification denitrating, extraction, hydrogenating reduction, concentration, alkali
The high-quality H-acid of the operations such as molten, H-acid isolation.
Embodiment 2:
Take 2.7-naphthalenedisulfonic acid tide product 1000Kg, put in the reactor of belt stirrer, and be warmed up to 120 DEG C, then start
Stirring, stirs 10 minutes under conditions of rotating speed 30 revs/min, then samples, record the chromatograph of wherein 1.3.6-naphthalene trisulfonic acid
Content is 1.61%, and mass percent is 1.38%, and the chromatographic content of 2.6-naphthalenedisulfonic acid is 1.05%, and mass percent is
1.32%, 2.7-naphthalenedisulfonic acid is 96.91%, and mass percent is 56.57%, and 1.6-naphthalenedisulfonic acid is 0.07%, mass percent
Being 0.04%, unknown material is 0.36%, and material total acidity is that 33.81%(is with sulphur acid meter), under conditions of negative pressure is-0.095Mpa,
Carry out concentrating under reduced pressure, after concentrating water outlet 182.4Kg, leftover materials are cooled to 60 DEG C, the anhydrous slufuric acid of dropping 481.24Kg, drips
During adding, control temperature, below 80 DEG C, drips sulphuric acid time-consuming 2 hours, after adding anhydrous slufuric acid, material is warmed up to 165
DEG C, maintaining 30 minutes, sampling detection, recording wherein 1.3.6-naphthalene trisulfonic acid chromatographic content is 98.25%, 2.7-naphthalenedisulfonic acid color
Spectrum content is 0.3%, and material cools to 60 DEG C, and dropping 74Kg clear water terminates reaction, and the process maximum temperature of adding water is 112 DEG C, consumption
Time 12 minutes, recording material total acidity after adding water is that 68.1 %(are with sulphur acid meter), turn material to continuous nitrification denitrating post, according to
Technical scheme disclosed by CN200810169724.3 carries out follow-up continuous nitrification denitrating, extraction, hydrogenating reduction, concentration, alkali
The high-quality H-acid of the operations such as molten, H-acid isolation.
Embodiment 3:
Take 2.7-naphthalenedisulfonic acid tide product 1500Kg, put in the reactor of belt stirrer, and be warmed up to 120 DEG C, then start
Stirring, stirs 10 minutes under conditions of rotating speed 30 revs/min, then samples, record the chromatograph of wherein 1.3.6-naphthalene trisulfonic acid
Content is 1.61%, and mass percent is 1.38%, and the chromatographic content of 2.6-naphthalenedisulfonic acid is 1.05%, and mass percent is
1.32%, 2.7-naphthalenedisulfonic acid is 96.91%, and mass percent is 56.57%, and 1.6-naphthalenedisulfonic acid is 0.07%, mass percent
Being 0.04%, unknown material is 0.36%, and material total acidity is that 33.81%(is with sulphur acid meter), under conditions of negative pressure is-0.097Mpa,
Carry out concentrating under reduced pressure, after concentrating water outlet 273.6Kg, leftover materials are cooled to 60 DEG C, the anhydrous slufuric acid of dropping 721.86Kg, drips
During adding, control temperature, below 80 DEG C, drips sulphuric acid time-consuming 2 hours, after adding anhydrous slufuric acid, material is warmed up to 165
DEG C, maintaining 30 minutes, sampling detection, recording wherein 1.3.6-naphthalene trisulfonic acid chromatographic content is 98.25%, 2.7-naphthalenedisulfonic acid color
Spectrum content is 0.3%, and material cools to 60 DEG C, and dropping 111Kg clear water terminates reaction, and the process maximum temperature of adding water is 106 DEG C,
Time-consuming 15 minutes, recording material total acidity after adding water was that 68.5%(is with sulphur acid meter), turn and expect to continuous nitrification denitrating post, according to
Technical scheme disclosed by CN200810169724.3 carries out follow-up continuous nitrification denitrating, extraction, hydrogenating reduction, concentration, alkali
The high-quality H-acid of the operations such as molten, H-acid isolation.
Claims (1)
1. the cleaning process for sulfonation in a H-acid production process, it is characterised in that it comprises the following steps:
1), according to diamine method synthesis H-acid technique, synthesize 2.7-naphthalenedisulfonic acid tide product, 2.7-naphthalenedisulfonic acid tide product are put into
In the reactor of belt stirrer, and it is warmed up to 120 DEG C, starts stirring simultaneously, under conditions of rotating speed 30 revs/min, stir 10 points
Clock, then samples, utilize high performance liquid chromatography by external standard method detect wherein 1.3.6-naphthalene trisulfonic acid, 2.6-naphthalenedisulfonic acid,
2.7-naphthalenedisulfonic acid and the chromatographic content of other disulfonic acid and percetage by weight, detect the total acidity of material simultaneously；
2) the 2.7-naphthalenedisulfonic acid tide product after step 1) having been detected reduce pressure under conditions of negative pressure is more than-0.095Mpa
Concentrate so that its sulfuric acid concentration reaches 90%；
3) by step 2) the concentration qualified material of gained cools to 60 DEG C, drips 2.5 times according to step 1) gained testing result
The anhydrous slufuric acid of 2.7-naphthalenedisulfonic acid molal quantity, during acid adding, control temperature is below 80 DEG C, and time-consuming 23 hours of acid adding adds
It is warmed up to 165 DEG C after complete anhydrous slufuric acid, maintains sampling in 0.5 hour, detect wherein 2.7-naphthalenedisulfonic acid chromatographic content and be less than 0.5%
For qualified；
4) after reaction terminates, cooling to 80 ~ 90 DEG C, add appropriate water and terminate reaction, the total acidity simultaneously regulating material is
67.6-68.6%(, the process control temp that adds water is less than 115 DEG C, and adding water is time-consumingly 10 30 minutes；
5) after having added water, material is turned to continuous nitrification denitrating post, according to existing continuous nitrification denitrating, extraction, hydrogenating reduction, dense
Contracting, alkali fusion, H-acid isolation common process can be prepared by high-quality H-acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610138415.4A CN105712907B (en) | 2016-03-11 | 2016-03-11 | A kind of cleaning process for sulfonation in the sour production processes of H |
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| CN201610138415.4A CN105712907B (en) | 2016-03-11 | 2016-03-11 | A kind of cleaning process for sulfonation in the sour production processes of H |
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| CN105712907A true CN105712907A (en) | 2016-06-29 |
| CN105712907B CN105712907B (en) | 2017-10-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759496A (en) * | 2016-08-18 | 2018-03-06 | 北京旭阳科技有限公司 | A kind of H acid synthetic method |
| CN108088917A (en) * | 2017-11-15 | 2018-05-29 | 北京工业大学 | The detection method of naphthalenedisulfonic acid isomer |
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|---|---|---|---|---|
| CN101161640A (en) * | 2007-11-16 | 2008-04-16 | 王在军 | Preparation technique of 2-amido-3,6,8-naphthalenetrisulphonic acid |
| CN101367753A (en) * | 2008-10-15 | 2009-02-18 | 湖北楚源高新科技股份有限公司 | Novel continuous nitrification denitrating, abstraction, hydrogenation reduction production process for H acid |
| 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 |
| CN102320635A (en) * | 2011-06-16 | 2012-01-18 | 青岛奥盖克化工有限公司 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
| CN102936214A (en) * | 2011-08-15 | 2013-02-20 | 中国中化股份有限公司 | Method for clean preparation H acid |
| CN105130853A (en) * | 2015-08-18 | 2015-12-09 | 楚源高新科技集团股份有限公司 | Novel nitration method used for industrial synthesis of H acid via diamine method |
-
2016
- 2016-03-11 CN CN201610138415.4A patent/CN105712907B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161640A (en) * | 2007-11-16 | 2008-04-16 | 王在军 | Preparation technique of 2-amido-3,6,8-naphthalenetrisulphonic acid |
| CN101367753A (en) * | 2008-10-15 | 2009-02-18 | 湖北楚源高新科技股份有限公司 | Novel continuous nitrification denitrating, abstraction, hydrogenation reduction production process for H acid |
| 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 |
| CN102320635A (en) * | 2011-06-16 | 2012-01-18 | 青岛奥盖克化工有限公司 | Comprehensive utilization method of waste sulfuric acid of sulfonated products |
| CN102936214A (en) * | 2011-08-15 | 2013-02-20 | 中国中化股份有限公司 | Method for clean preparation H acid |
| CN105130853A (en) * | 2015-08-18 | 2015-12-09 | 楚源高新科技集团股份有限公司 | Novel nitration method used for industrial synthesis of H acid via diamine method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759496A (en) * | 2016-08-18 | 2018-03-06 | 北京旭阳科技有限公司 | A kind of H acid synthetic method |
| CN107759496B (en) * | 2016-08-18 | 2020-06-12 | 北京旭阳科技有限公司 | H acid synthesis method |
| CN108088917A (en) * | 2017-11-15 | 2018-05-29 | 北京工业大学 | The detection method of naphthalenedisulfonic acid isomer |
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| Publication number | Publication date |
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| CN105712907B (en) | 2017-10-27 |
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