CN109651205A - A kind of CLT acid synthetic method - Google Patents
A kind of CLT acid synthetic method Download PDFInfo
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- CN109651205A CN109651205A CN201811547381.XA CN201811547381A CN109651205A CN 109651205 A CN109651205 A CN 109651205A CN 201811547381 A CN201811547381 A CN 201811547381A CN 109651205 A CN109651205 A CN 109651205A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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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
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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Abstract
The invention discloses a kind of CLT acid synthetic methods, it is characterized in that adding magnesia in the itrated compound being diluted with water before reduction reaction, the sulfuric acid in waste liquid is promoted to be converted into the magnesium sulfate of high concentration, and then effect of saltouing is reached, it realizes and the means of in addition addition saturated salt solution is not used to can be carried out the purpose saltoutd, waste water is significantly reduced in this way in the total amount of salt, alleviates the pressure of subsequent technique processing salt；Based on sulfuric acid is converted into magnesium sulfate, creativeness eliminates separation of solid and liquid after salting-out procedures, avoids in traditional handicraft waste liquid because carrying a large amount of materials in sulfuric acid waste after being separated by solid-liquid separation, causes product to be lost, improve product yield；Based on sulfuric acid is converted into magnesium sulfate, separation of solid and liquid is eliminated after salting-out procedures, direct iron reduction creatively is carried out to reaction system, avoid traditional handicraft causes sulfuric acid waste to consume a large amount of iron powder using the means of direct-reduction, and heavy metal in waste water content is caused to increase.
Description
Technical field:
The invention belongs to organic pigment synthesis technical fields, relate more specifically to a kind of CLT acid synthetic method.
Background technique:
The chloro- 3- amino toluene -4- sulfonic acid of the chemical name 6- of CLT acid, is the important intermediate for synthesizing organic red pigment, it is passed through
After diazotising with betanaphthol or 2,3- acid coupling, C.I. paratonere 53 and C.I. paratonere 52 can be respectively obtained, they are answered extensively
The coloring of unrestrained, rubber and school supply and stationery for oil.It is a variety of for the synthetic route of CLT acid at present, including toluene sulfonation method,
Toluidines method, ortho-chlorotolu'ene method, wherein toluene sulfonation method is the most mature, is widely used in pigment production enterprise.
The specific reaction principle of toluene sulfonation method are as follows: by toluene in 105 ~ 110 DEG C with excessive 2.04 times moles of dense sulphur
Acid carbonization is added 2.93 times moles of the concentrated sulfuric acid, is passed through chlorinated with chlorine again at 50 DEG C using anhydrous frerrous chloride as catalyst after carbonization
It is nitrified in 30 DEG C with 74% nitric acid of equivalent mole, is then placed in the saline solution being largely saturated and saltouts, filtered, washing obtains
To the chloro- 3- nitrotoleune -4- sulfonic acid of 6-.It by it with sulfuric acid activated iron powder reducing, neutralizes, filtering, test solution hydrochloric acid acid out is done
Dry sediment obtains finished product CLT acid.
Although many people improve toluene sulfonation method conventional production methods, such as: Cui Yumin, Shao Sichang are to traditional work
Skill is improved: using to the nitrification liquid after nitration reaction plus water acid-precipitation method subtracts instead of the quick lime neutralisation of original process
Lack pollution, and saves the expense of processing calcium sulfate residue；Chlorination is eliminated during adding water acid out, is nitrified, in carbonization
The problem of isomer impurities of generation improve the quality of CLT acid, but there are still produce a large amount of waste liquid；
Therefore, although there is the toluene sulfonation method produced in conventional processes CLT acid at low cost, technique to require simply, to produce
A large amount of sulfuric acid waste, especially:
It saltouts 1. being added in the saline solution being largely saturated using the means in addition added, a large amount of sodium ion and chloride ion is caused to draw
Enter, chloride ion has serious corrosivity for stainless steel, also exacerbates salt total amount in waste water；
2. the sour waste water of the solid containing CLT acid obtained after saltouing, needs through plate-frame filtering, after filter cake is dissolved also
Former and acidification, the sulfuric acid waste of a large amount of sodium chloride of content is discharged, but due to carry a large amount of CLT acid in sulfuric acid, is caused
CLT acid yield reduces；
3. washing step occupies multiple storage tanks for reaction and transfer, occupancy equipment is more, and occupied ground is larger.
A kind of high income of demand, waste water salt weight are low and simple process occupies the less CLT acid synthetic method of equipment and compels
The eyebrows and eyelashes.
Summary of the invention:
To solve the above problems, overcome the deficiencies in the prior art, the present invention provides CLT acid synthetic method,
First technical problem solved is: in addition means that the utilization of existing toluene sulfonation method production CLT acid is added are added big
It measures and saltouts in the saline solution of saturation, a large amount of sodium ion and chloride ion is caused to introduce, chloride ion has stainless steel serious
Corrosivity also exacerbates salt total amount in waste water；
Second technical problem solved is: the consolidating containing CLT acid obtained after the saltouing of existing toluene sulfonation method production CLT acid
The sour waste water of body, needs through plate-frame filtering, restores and is acidified after filter cake is dissolved, by the sulfuric acid of a large amount of sodium chloride of content
Discharging of waste liquid, but due to carry a large amount of CLT acid in sulfuric acid, lead to the reduction of CLT acid yield；
The present invention solve above-mentioned technical problem the specific technical proposal is: CLT acid synthetic method, prepared using toluene sulfonation method,
In the presence of with excessive sulfuric acid, itrated compound is obtained by sulfonation, chlorination and nitration reaction, it is characterised in that: by the nitre
Compound does not use the means of in addition addition saturated salt solution to carry out salting-out procedures, and carries out reduction process reaction, will be restored
Liquid filters after acid out process, will obtain CLT acid after the drying of obtained solid phase.
Further, the mass ratio of the toluene and sulfuric acid: 1:2-4.
Further, the reduction reaction is: bottom water and iron powder being added in reduction kettle, a small amount of sulfuric acid tune is then added
Saving pH in kettle is 4-5, activates iron powder, activation time 30-60min, the mixed solution after activation, after above-mentioned saltout is added
In, be warming up to: 90-120 DEG C is reacted, and reaction time 6-10h obtains reducing solution.
Further, the acid out process are as follows: the reducing solution enters acid out kettle, and sulfuric acid is added into acid out kettle, adjusts
Saving pH in kettle is 0.8-1, and the solid of precipitation is CLT acid, and liquid is Adlerika, and pH when acid out is 0.8-1.
Further, described to add magnesia in the itrated compound by being diluted with water before reduction reaction, by cold
Freeze salt water management reaction temperature, adds magnesia to neutrality, sulfuric acid is converted into magnesium sulfate；Then it is restored using the iron of activation
Reaction；And acid out is carried out by addition sulfuric acid to acidity, the suspension for the finished product that acid out is obtained passes through plate-frame filtering, obtains
Solid phase is CLT acid；It is MgSO4 mother liquor by the liquid phase that plate-frame filtering obtains.
Further, the MgSO4 mother liquor obtained carries out extraction process, after MgSO4 mother liquor is entered extractor, same to extractant
It is extracted in 1:5-10 ratio, removes the organic matter in mother liquor, then turned mother liquor extracted to enamel reactor and live
Property charcoal adsorption bleaching, solution becomes colorless transparent.
Further, the mother liquor after extracting, decolourizing enters multiple-effect evaporation, obtains MgSO4Finished product.
Further, extractant is tertiary amine kind of extractants.
The beneficial effects of the present invention are: the present invention creatively adds in the itrated compound being diluted with water before reduction reaction
Add magnesia, promotes the sulfuric acid in waste liquid to be converted into the magnesium sulfate of high concentration, and then reached effect of saltouing, realize and do not adopt
It can be carried out the purpose saltoutd with the means of other addition saturated salt solution, significantly reduce waste water in this way in the total of salt
Amount alleviates the pressure of subsequent technique processing salt；
Based on sulfuric acid is converted into magnesium sulfate, creativeness eliminates separation of solid and liquid after salting-out procedures, avoids traditional handicraft waste liquid
It is middle because carrying a large amount of materials in sulfuric acid waste after being separated by solid-liquid separation, cause product to be lost, improve product yield；
Based on sulfuric acid is converted into magnesium sulfate, separation of solid and liquid is eliminated after salting-out procedures, creatively reaction system is carried out straight
Iron reduction is connect, avoid traditional handicraft causes sulfuric acid waste to consume a large amount of iron powder using the means of direct-reduction, leads to waste water
Middle content of beary metal increases；
Traditional CLT acid technique is improved, elutriation and filter-pressing process are saved, save the cost is environmental-friendly, does not generate sulfur waste
Acid, sewage zero-discharge obtain magnesium sulfate byproduct, have use value, while CLT acid product yield can be improved, and reduce life
Produce cost.
Specific embodiment:
Detail is used for the purpose of to fully understand the embodiment of the present invention in the description of the present invention, but as ability
The technical staff in domain will be appreciated that implementation of the invention is not limited to these details.In addition, well known structure and function not by
Detailed description or displaying, to avoid the main points for having obscured the embodiment of the present invention.For those of ordinary skill in the art and
Speech, can understand the concrete meaning of above-mentioned term in the present invention with concrete condition.
A specific embodiment of the invention:
Embodiment one:
1. 8000L water is added in enamel reactor, 4300L nitrification liquid is then added, quality is added under agitation is
The MgO of 1.566t controls reaction temperature within the scope of 40 DEG C by chilled brine, counts observing response tank by ph in reaction process
Interior pH value reaches reaction end when pH value reaches neutrality, and solution is squeezed into reduction kettle with pump；
2. solution obtains the suspension of finished product by reduction, acid out, suspension is separated by filter press, and solid is finished product,
Mother liquor is MgSO4 solution, and mother liquor pump squeezes into extraction process；
3. after mother liquor enters extractor, being extracted with extractant in the ratio of 5:1, the organic matter in mother liquor is removed, then will
Mother liquor extracted is beaten to enamel reactor to be decolourized with activated carbon adsorption, and solution becomes colorless transparent；
4. the mother liquor after extraction, decoloration enters multiple-effect evaporation, MgSO4 finished product is produced, the water for evaporating generation is recycled, and realizes sewage
Zero-emission.
8000L water is added in enamel reactor embodiment two: 1., 4300L nitrification liquid is then added, under agitation
The MgO that quality is 1.566t is added, reaction temperature is controlled within the scope of 45 DEG C by chilled brine, is counted in reaction process by ph
PH value in observing response tank reaches reaction end when pH value reaches neutrality, and solution is squeezed into reduction kettle with pump；
2. solution obtains the suspension of finished product by reduction, acid out, suspension is separated by filter press, and solid is finished product,
Mother liquor is MgSO4 solution, and mother liquor pump squeezes into extraction process；
3. after mother liquor enters extractor, being extracted with extractant in the ratio of 10:1, the organic matter in mother liquor is removed, then will
Mother liquor extracted is beaten to enamel reactor to be decolourized with activated carbon adsorption, and solution becomes colorless transparent；
4. the mother liquor after extraction, decoloration enters multiple-effect evaporation, MgSO4 finished product is produced, the water for evaporating generation is recycled, and realizes sewage
Zero-emission.
8000L water is added in enamel reactor embodiment three: 1., 4300L nitrification liquid is then added, under agitation
The MgO that quality is 1.566t is added, reaction temperature is controlled within the scope of 50 DEG C by chilled brine, is counted in reaction process by ph
PH value in observing response tank reaches reaction end when pH value reaches neutrality, and solution is squeezed into reduction kettle with pump；
2. solution obtains the suspension of finished product by reduction, acid out, suspension is separated by filter press, and solid is finished product,
Mother liquor is MgSO4 solution, and mother liquor pump squeezes into extraction process；
3. after mother liquor enters extractor, being extracted with extractant in the ratio of 8:1, the organic matter in mother liquor is removed, then will
Mother liquor extracted is beaten to enamel reactor to be decolourized with activated carbon adsorption, and solution becomes colorless transparent；
4. the mother liquor after extraction, decoloration enters multiple-effect evaporation, MgSO4 finished product is produced, the water for evaporating generation is recycled, and realizes sewage
Zero-emission.
In order to which the more intuitive present invention that shows is in technologic advantage of saltouing, it is special with:
The present invention: in itrated compound after the reaction, adding magnesia and sulfuric acid be converted into magnesium sulfate, using generation magnesium sulfate into
It goes and saltouts, and abandon separation of solid and liquid, the iron powder of activation is directly added in reaction dissolvent, carry out acid out again after reduction and consolidate
Liquid separation；
Comparative example 1: CLT acid is prepared using traditional toluene sulfonation method, and carries out salt using the method for outer addition saturated sodium-chloride
Analysis, then according to traditional plate-frame filtering, rear acid out is hydrolyzed in solid phase；Waste liquid is due to containing chloride ion, sulfate ion, sodium
Ion, recovery difficult direct emission general greatly；
Comparative example 2: by the way of quoting, by the work using traditional toluene sulfonation method preparation CLT acid traditional in comparative example 1
Of the invention " is abandoned separation of solid and liquid, the directly addition activation in reaction dissolvent using the principle of unitary variant by skill after saltouing
Iron powder " technique introduce i.e.:
CLT acid is prepared using traditional toluene sulfonation method, and is saltoutd using the method for outer addition saturated sodium-chloride, and abandon
It is separated by solid-liquid separation, the iron powder of activation is directly added in reaction dissolvent, carry out acid out and solid-liquid analysis again after reduction；
And it is compared using the yield and quality of sewage total amount and CLT acid as test index, the wherein yield and product of CLT acid
The examination criteria of matter are as follows:
Table 1: the Experimental Comparison data that the present invention and traditional handicraft are saltoutd
| Group | Additive | Additive amount | Sewage discharge salt total amount | Iron powder consumption | CLT acid yield | CLT acid content | Waste water salt type |
| The present invention | Magnesia | 1.566t | 3.7t | 3.7t | 95 | 98% | Magnesium sulfate |
| Comparative example 1 | Saturated salt solution | 0.353t | 4.8t | 4.8t | 80 | 98% | Sodium sulphate, sodium chloride |
| Comparative example 2: | Saturated salt solution | 0.353t | 9.5t | 5.1t | —— | —— | Sodium sulphate, sodium chloride, ferrous sulfate |
It is analyzed from above data: on the basis of the content of excess sulfuric acid in reaction solution, being compared；
(1) present invention is known with the comparison of comparative example 1: being added magnesia in the itrated compound before reduction reaction of the present invention, is promoted to give up
Sulfuric acid in liquid is converted into the magnesium sulfate of high concentration, and then has reached effect of saltouing, and sewage discharge salt total amount is 3.7t, and right
For ratio 1 due in addition adding saturated salt solution, sewage discharge salt total amount is higher, be 4.8t, and the present invention pollution in salt type
Only magnesium sulfate, and salt type is there are sodium sulphate and sodium chloride in the pollution of comparative example 1, recovery difficult is big, recycling meaning is small, can only
Direct emission sewage treatment；
(2) present invention is known with the comparison of comparative example 1: the present invention is based on sulfuric acid is converted into magnesium sulfate, creativeness after elutriation process
Separation of solid and liquid is eliminated, due to being dissolved with partial material in sulfuric acid wastewater containing, CLT acid yield of the invention is 95%, and right
The CLT acid yield of ratio 1 only has 80%；
(3) present invention is known with the comparison of comparative example 2: iron powder consumption is 3.7t in the present invention；And the iron powder consumption of comparative example 2
For 5.1t, this is because in comparative example 2 sulfuric acid presence, cause iron powder to be converted to ferrous sulfate, consume a large amount of iron powders, generation
Ferrous sulfate is transferred in sewage, increases the content of the heavy metal of sewage；
Therefore the present invention carries out direct iron reduction to reaction system, and avoiding traditional handicraft using the means of direct-reduction leads to sulphur
Acid waste liquid consumes a large amount of iron powder, and heavy metal in waste water content is caused to increase.
In summary: the present invention creatively adds magnesia in the itrated compound before reduction reaction, promotes in waste liquid
Sulfuric acid be converted into the magnesium sulfate of high concentration, and then reached effect of saltouing, realize do not use in addition addition saturated salt it is molten
The means of liquid can be carried out the purpose saltoutd, and significantly reduces the total amount of salt in waste water in this way, alleviates at subsequent technique
Manage the pressure of salt；
Based on sulfuric acid is converted into magnesium sulfate, creativeness eliminates separation of solid and liquid after saltouing, avoid in traditional handicraft waste liquid because
A large amount of materials are carried after separation of solid and liquid in sulfuric acid waste, product is caused to be lost, improve product yield；
Based on sulfuric acid is converted into magnesium sulfate, separation of solid and liquid is eliminated after saltouing, and direct iron creatively is carried out to reaction system
Reduction, avoid traditional handicraft causes sulfuric acid waste to consume a large amount of iron powder using the means of direct-reduction, leads to weight in waste water
Tenor increases.
Claims (8)
1. a kind of CLT acid synthetic method is prepared using toluene sulfonation method, in the presence of with excessive sulfuric acid, by sulfonation, chlorine
Change and nitration reaction obtains itrated compound, it is characterised in that: the itrated compound is not used to the means of in addition addition saturated salt solution
Salting-out procedures are carried out, and carry out reduction process reaction, reducing solution will be obtained and filtered after acid out process, obtained solid phase is done
CLT acid is obtained after dry.
2. CLT acid synthetic method according to claim 1, it is characterised in that the mass ratio of the toluene and sulfuric acid: 1:
2-4。
3. CLT acid synthetic method according to claim 1, it is characterised in that the reduction reaction is: in reduction kettle
Bottom water and iron powder is added, it is 4-5 that a small amount of sulfuric acid, which is then added, and adjusts pH in kettle, activates iron powder, activation time 30-60min, activation
After, in the mixed solution after above-mentioned saltout is added, be warming up to: 90-120 DEG C is reacted, and reaction time 6-10h is obtained
Reducing solution.
4. CLT acid synthetic method according to claim 1, it is characterised in that the acid out process are as follows: the reducing solution
Into acid out kettle, sulfuric acid is added into acid out kettle, adjusting pH in kettle is 0.8-1, and the solid of precipitation is CLT acid, and liquid is sulfuric acid
Magnesium solution, pH when acid out are 0.8-1.
5. CLT acid synthetic method described in -4 any claims according to claim 1, it is characterised in that described in reduction reaction
Magnesia is added in the itrated compound by being diluted with water before, reaction temperature is controlled by chilled brine, adds magnesia into
Property, sulfuric acid is converted into magnesium sulfate；Then reduction reaction is carried out using the iron of activation；And acid is carried out by addition sulfuric acid to acidity
Analysis, the suspension for the finished product that acid out is obtained pass through plate-frame filtering, and obtained solid phase is CLT acid；It is obtained by plate-frame filtering
Liquid phase is MgSO4 mother liquor.
6. CLT acid synthetic method according to claim 5, it is characterised in that obtained MgSO4 mother liquor carries out extraction process,
It after MgSO4 mother liquor is entered extractor, is extracted with extractant in 1:5-10 ratio, removes the organic matter in mother liquor, then
It turns mother liquor extracted and is decolourized to enamel reactor with activated carbon adsorption, solution becomes colorless transparent.
7. CLT acid synthetic method according to claim 6, it is characterised in that the mother liquor after extraction, decoloration enters multiple-effect steaming
Hair, obtains MgSO4Finished product.
8. CLT acid synthetic method according to claim 6, it is characterised in that extractant is tertiary amine kind of extractants.
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Application publication date: 20190419 |
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