CN106748901A - A kind of alkali fusion and aftertreatment technology of H acid - Google Patents
A kind of alkali fusion and aftertreatment technology of H acid Download PDFInfo
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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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Abstract
It is an object of the invention to provide a kind of H acid normal pressure alkali fusions and the technique of post processing, reaction condition is gentle, and recovery after excessive alkali can be separated after reaction significantly reduces the growing amount of brine waste.By normal pressure alkali fusion and the method for post processing; the dried powder for using T acid sodium-salts is raw material; it is solvent to use high boiling alcohols; using under alcohols solvent high temperature to the excellent solubility of alkali; realize that normal pressure alkali fusion reacts under nitrogen protection, reaction can be by separation of solid and liquid after simple filtration and alcohol are washed after terminating, and liquid contains alkali and solvent can be with recovery; it is mainly the sodium phenolate and inorganic salts of H acid in solid, it is acidified to finally give H acid finished products.Because excessive alkali is reclaimed, therefore the brine waste of acidization generation is greatly reduced.
Description
Technical field
The present invention relates to alkali fusion and aftertreatment technology in color-forming intermediate H acids production process.
Background technology
At present both at home and abroad generally using the production H acid of three sulfonation methods, process be by naphthalene and oleum at high temperature
Three sulfonation are carried out, 1,3,6- naphthalene trisulfonic acids is obtained, then T acid is obtained through mixed acid nitrification, extraction, iron powder reducing
Solution, then obtain H acid monosodium salt through high pressure alkali fusion, acidifying.Wherein alkali fusion process is typically all high in high temperature
Carried out under conditions of pressure, such as CN200610086202.8, its alkali fusion process is：48-50% is added in reducing solution
NaOH and primary alconol, are warming up to 150-170 DEG C, insulation reaction 2hr under pressure 2-2.4MPa；
CN200810155316.2, its alkali fusion process is：Concentrated to liquid caustic soda is added in reducing solution, it is ensured that basicity
25-30%, adds methyl alcohol, and being warming up to 185-200 DEG C carries out insulation reaction 3hr；CN200810169723.9,
Its alkali fusion process is：To adding liquid caustic soda to be concentrated in reducing solution, add methyl alcohol and be warming up to 150-180 DEG C,
Pressure about 2-3MPa, insulation reaction 1hr.The alkali fusion process of three patents of the above is more similar, is all in height
The alkali fusion reaction carried out under warm high pressure.
Alkali fusion reaction is carried out at high temperature under high pressure to have the following disadvantages：1., equipment requirement is higher：Should be in height
The lower alkali corrosion resistance of temperature also wants compression resistance；2., easily there is side reaction during alkali fusion：Generation chromotropic acid, W acid,
The impurity such as K acid, influence reaction selectivity and product quality；3., alkali fusion thing cannot be efficiently separated with the alkali of excess,
Produce a large amount of brine wastes：The alkali fusion thing and excess in alkali fusion liquid are caused due to the presence of alkali fusion system reclaimed water
Alkali cannot be efficiently separated (have larger solubility in alkaline water), what final excessive alkali was neutralized by acid
Method becomes the inorganic salts such as sodium sulphate, produces a large amount of brine wastes (15t/tH acid), the improvement of high slat-containing wastewater
High cost and difficulty of governance is big.In the case where green, the overall situation of environment-protective process is advocated, an environmental protection is developed
Alkali fusion and post-treatment new process seem extremely urgent.
The content of the invention
It is an object of the invention to provide a kind of H acid normal pressure alkali fusions and the technique of post processing, reaction condition is gentle,
Recovery after excessive alkali can be separated after reaction, significantly reduces the growing amount of brine waste.
A kind of method that the present invention provides normal pressure alkali fusion and post processing, it is characterised in that using the dry of T acid sodium-salts
Dry powder be raw material (anhydrous), it is solvent to use high boiling alcohols, using under alcohols solvent high temperature to alkali
Excellent solubility, realizes that normal pressure alkali fusion reacts under nitrogen protection, reacts after terminating by simple filtration and alcohol
Separation of solid and liquid, liquid can be contained alkali after washing (purpose that alcohol is washed is by the dihydroxylic alcohols washes clean in filter cake)
The sodium phenolate and inorganic salts of H acid can be mainly with recovery in solid with solvent, it is acidified final
To H acid finished products.Because excessive alkali is reclaimed, therefore it is useless that the saliferous of acidization generation is greatly reduced
Water.
Described higher boiling alcohols solvent can be more for low-carbon (LC)s such as ethylene glycol, propane diols, glycerine, butanediols
First alcohol.
The preparation flow is that about 100g T acid sodium-salt powder is added in four-hole boiling flask, 160-360g solid caustic soda and
300-500g higher boiling alcohols solvents, stirred under nitrogen atmosphere is warming up to 180-280 DEG C, and system is solid-liquid two
Phase, insulation reaction about 12-24hr, does not lower the temperature, and directly pours into pressure-resistant stainless steel pressure-filtering tank material, fills
Entering about 0.1-0.5MPa nitrogen carries out press filtration, obtains press filtration filter cake and press filtration filtrate, and alkali and second are contained in filtrate
Glycol and a small amount of salt, are back to next batch reaction；And filter cake is washed with 50-150g methyl alcohol, washing
Contain methyl alcohol and ethylene glycol and a small amount of alkali in liquid, cleaning solution carries out air-distillation, and the methyl alcohol of abjection is covered for filter cake
Wash, covered more than kettle for alkali fusion reaction.Filter cake after washing, is first dissolved with water, then molten with 50% sulfuric acid
Solution is acidified to pH=1-2, obtain H acid crude product, mother liquor (sulfur acid sodium 25-30%), crude product by washing,
Drying, finally gives H acid finished products.
In described alkali fusion technique temperature can be 180-280 DEG C, preferably 190-250 DEG C, most preferably
190-230℃；Alkali can be 1-40 with the mol ratio of T acid:1, preferably 5-30:1, most preferably 5-15:1；T
The concentration of acid can be 5-30%, most preferably preferably 10-25%, 15-20%；The concentration of alcohols solvent can be
20-80%, preferably 30-70%, most preferably 40-60%.Described T acid starting materials are dry white powder, its
Aqueous can be 0-1%, most preferably preferably 0-0.5%, 0-0.2%.
The present invention has advantages below：
1st, alkali fusion mild condition, lectotype selection is simple：Pressurization alkali fusion reacts general 150-250 DEG C of temperature, pressure
Power 2-4MPa, material requirement of the HTHP to equipment is very high, and normal pressure alkali fusion condition is relatively mild, if
Alternative type is easy；
2nd, realize that alkali is separated with material, reduce alkaline consumption, wastewater flow rate is reduced：Traditional alkali fusion reaction excess
Alkali is substantially and is neutralized with acid, produces substantial amounts of brine waste, and normal pressure alkali fusion is anhydrous due to system,
Excessive alkali is dissolved in alcohols solvent, and the H acid products for generating do not dissolve in alcohols solvent, therefore simple filtration
Alkali can just be separated with product, that isolates can also be back to next batch reaction containing alkali alcosol,
Both reduce alkaline consumption or significantly reduce wastewater flow rate.
Brief description of the drawings
Fig. 1 is pressurization alkali fusion flow chart (alkali cannot be separated with product).
Fig. 2 is normal pressure alkali fusion flow chart (alkali is separated with product and carries out reuse).
Specific embodiment
Example below is intended to explain prominent effect of the invention, rather than to further limit of the invention
It is fixed.
Embodiment 1
About 103.3gT acid sodium-salts powder (Mw=405, content 98%) is added in 1000ml four-hole boiling flasks,
156.25g solid caustic soda and 385g ethylene glycol, stirred under nitrogen atmosphere are warming up to 190 DEG C, and system is solid-liquid two-phase,
Insulation reaction 24hr, does not lower the temperature, and directly pours into pressure-resistant stainless steel pressure-filtering tank material, is filled with about 0.2MPa
Nitrogen carries out press filtration, obtains press filtration filter cake 182g and press filtration filtrate 452g, in filtrate containing alkali and ethylene glycol and
A small amount of salt, is back to next batch reaction；And filter cake is washed with 100g methyl alcohol, methyl alcohol is contained in cleaning solution
With ethylene glycol and a small amount of alkali, cleaning solution carries out air-distillation, and the methyl alcohol 95.2g of abjection is covered for Washing of Filter Cake,
36g is covered for alkali fusion reaction more than kettle.Filter cake 150g after washing, is first dissolved, then use with 150g water
The sulfuric acid dissolutions of 100g 50% are acidified to pH=1-2, obtain the crude product 170g of H acid, mother liquor 225g (sulfur acid sodium
28.5%), crude product finally gives H acid finished product 79.7g, amino value 86.1%, yield by washing, drying
80.5%.
Embodiment 2
About 103.3gT acid sodium-salts powder (Mw=405, content 98%), 364.6g are added in 1000ml four-hole boiling flasks
Solid caustic soda and 449.2g glycerine, stirred under nitrogen atmosphere are warming up to 240 DEG C, and system is solid-liquid two-phase, insulation
Reaction 16hr, does not lower the temperature, and directly pours into pressure-resistant stainless steel pressure-filtering tank material, is filled with about 0.2MPa nitrogen
Gas carries out press filtration, obtains press filtration filter cake 173g and press filtration filtrate 731g, alkali and glycerine is contained in filtrate and is lacked
The salt of amount, is back to next batch reaction；And filter cake is washed with 100g methyl alcohol, in cleaning solution containing methyl alcohol and
Glycerine and a small amount of alkali, cleaning solution carry out air-distillation, and the methyl alcohol 95.9g of abjection is covered for Washing of Filter Cake,
35.7g is covered for alkali fusion reaction more than kettle.Filter cake 141g after washing, is first dissolved, then use with 150g water
The sulfuric acid dissolutions of 90g 60% are acidified to pH=1-2, obtain the crude product 151g of H acid, mother liquor 223g (sulfur acid sodium
29%), crude product finally gives H acid finished product 80.9g, amino value 85.4%, yield 81% by washing, drying.
Embodiment 3
About 103.3gT acid sodium-salts powder (Mw=405, content 98%), 260.4g are added in 1000ml four-hole boiling flasks
Solid caustic soda and 293.2g propane diols, stirred under nitrogen atmosphere are warming up to 185 DEG C, and system is solid-liquid two-phase, insulation
Reaction 24hr, does not lower the temperature, and directly pours into pressure-resistant stainless steel pressure-filtering tank material, is filled with about 0.2MPa nitrogen
Gas carries out press filtration, obtains press filtration filter cake 171g and press filtration filtrate 476g, alkali and propane diols is contained in filtrate and is lacked
The salt of amount, is back to next batch reaction；And filter cake is washed with 100g methyl alcohol, in cleaning solution containing methyl alcohol and
Propane diols and a small amount of alkali, cleaning solution carry out air-distillation, and the methyl alcohol 95.4g of abjection is covered for Washing of Filter Cake,
30.1g is covered for alkali fusion reaction more than kettle.Filter cake 145g after washing, is first dissolved, then use with 150g water
The sulfuric acid dissolutions of 94g 60% are acidified to pH=1-2, obtain the crude product 153g of H acid, mother liquor 232g (sulfur acid sodium
27.9%), crude product finally gives H acid finished product 80.7g, amino value 85.7%, yield by washing, drying
81.1%.
Embodiment 4
About 103.3gT acid sodium-salts powder (Mw=405, content 98%), 260.4g are added in 1000ml four-hole boiling flasks
Solid caustic soda and 293.2g butanediols, stirred under nitrogen atmosphere are warming up to 185 DEG C, and system is solid-liquid two-phase, insulation
Reaction 24hr, does not lower the temperature, and directly pours into pressure-resistant stainless steel pressure-filtering tank material, is filled with about 0.2MPa nitrogen
Gas carries out press filtration, obtains press filtration filter cake 169g and press filtration filtrate 477g, alkali and propane diols is contained in filtrate and is lacked
The salt of amount, is back to next batch reaction；And filter cake is washed with 100g methyl alcohol, in cleaning solution containing methyl alcohol and
Butanediol and a small amount of alkali, cleaning solution carry out air-distillation, and the methyl alcohol 95.3g of abjection is covered for Washing of Filter Cake,
25g is covered for alkali fusion reaction more than kettle.Filter cake 148g after washing, is first dissolved, then use with 150g water
The sulfuric acid dissolutions of 104g 50% are acidified to pH=1-2, obtain the crude product 147g of H acid, mother liquor 249g (sulfur acid sodium
27.1%), crude product finally gives H acid finished product 79.4g, amino value 86.2%, yield by washing, drying
80.3%.
Embodiment 5-8
The recovery of alkali is carried out on the basis of embodiment 1, below as a example by covering 1 (embodiment 5)
About 103.3gT acid sodium-salts powder (Mw=405, content 98%) is added in 1000ml four-hole boiling flasks, is covered
With the filtrate 512g (36g more than press filtration filtrate 476g and alcohol washing lotion distillation still) of embodiment 1, wherein 114g containing alkali；
377g containing ethylene glycol, adds 37.5g solid caustic soda and 8g ethylene glycol, and stirred under nitrogen atmosphere is warming up to 190 DEG C,
System is solid-liquid two-phase, and insulation reaction 24hr does not lower the temperature, and material directly is poured into pressure-resistant stainless steel press filtration
In tank, being filled with about 0.2MPa nitrogen carries out press filtration, obtains press filtration filter cake 172g and press filtration filtrate 468g, filter
Containing alkali and ethylene glycol and a small amount of salt in liquid, next batch reaction is back to；And filter cake is carried out with 100g methyl alcohol
Washing, contains methyl alcohol and ethylene glycol and a small amount of alkali in cleaning solution, cleaning solution carries out air-distillation, the methyl alcohol of abjection
96.7g is covered for Washing of Filter Cake, and 32g is covered for alkali fusion reaction more than kettle.Filter cake 143g after washing, first uses
150g water is dissolved, then is acidified to pH=1-2 with the sulfuric acid dissolutions of 105g 50%, obtains the crude product 168g of H acid,
Mother liquor 228g (sulfur acid sodium 29.3%), crude product finally gives H acid finished product 79.7g by washing, drying,
Amino value 85.8%, yield 80.2%.
Claims (5)
1. the method for a kind of H acid normal pressure alkali fusion, it is characterised in that about T acid sodium-salts are added in four-hole boiling flask
Powder, solid caustic soda and higher boiling alcohols solvent, stirred under nitrogen atmosphere react after heating up, directly by thing after reaction
Material is poured into pressure-resistant stainless steel pressure-filtering tank, and being filled with about 0.1-0.5MPa nitrogen carries out press filtration, obtains press filtration filter
Cake and press filtration filtrate, containing alkali and ethylene glycol and a small amount of salt in filtrate, are back to next batch reaction；And filter
Cake is washed with methyl alcohol, and methyl alcohol and ethylene glycol and a small amount of alkali are contained in cleaning solution, and cleaning solution carries out air-distillation,
The methyl alcohol of abjection is covered for Washing of Filter Cake, is covered more than kettle for alkali fusion reaction；Filter cake after washing, is first entered with water
Row dissolving, then is acidified to pH=1-2 with 50% sulfuric acid dissolution, obtains the crude product of H acid, crude product by washing,
Drying, finally gives H acid finished products.
2. the method for H according to claim 1 acid normal pressure alkali fusion, it is characterised in that described alkali fusion work
Temperature can be 180-280 DEG C in skill；Reaction time is 12-24h；The mol ratio of alkali and T acid can be
1-40:1；The concentration of T acid can be 5-30%；The concentration of alcohols solvent can be 20-80%；Described T acid
Raw material is dry white powder, and it can be 0-1% that its is aqueous.
3. the method for H according to claim 2 acid normal pressure alkali fusion, it is characterised in that described alkali fusion work
Temperature can be 190-250 DEG C in skill；Alkali can be 5-30 with the mol ratio of T acid:1；The concentration of T acid can be with
It is 10-25%；The concentration of alcohols solvent can be 30-70%；Described T acid starting materials are dry white powder,
It can be 0-0.5% that its is aqueous.
4. the method for H according to claim 3 acid normal pressure alkali fusion, it is characterised in that described alkali fusion work
Temperature can be 190-230 DEG C in skill；Alkali can be 5-15 with the mol ratio of T acid:1；The concentration of T acid can be with
It is 15-20%；The concentration of alcohols solvent can be 40-60%；Described T acid starting materials are dry white powder,
It can be 0-0.2% that its is aqueous.
5. the method for H according to claim 1 acid normal pressure alkali fusion, it is characterised in that described higher boiling
Alcohols solvent can be the low-carbon polyols such as ethylene glycol, propane diols, glycerine, butanediol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986997A (en) * | 2017-12-08 | 2018-05-04 | 荆门市熊兴化工有限公司 | A kind of alkali fusion method being used in H acid production processes |
| CN108003071A (en) * | 2017-12-04 | 2018-05-08 | 大柴旦乐青科技化学有限公司 | A kind of H acid high pressure alkali fusion technique |
| CN108191715A (en) * | 2017-11-27 | 2018-06-22 | 江苏力禾颜料有限公司 | High pressure alkali fusion preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108191715A (en) * | 2017-11-27 | 2018-06-22 | 江苏力禾颜料有限公司 | High pressure alkali fusion preparation process |
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| CN107986997A (en) * | 2017-12-08 | 2018-05-04 | 荆门市熊兴化工有限公司 | A kind of alkali fusion method being used in H acid production processes |
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