CN1062560C - Method for separating and refining dioxathiazine salts compound - Google Patents
Method for separating and refining dioxathiazine salts compound Download PDFInfo
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- CN1062560C CN1062560C CN96119015A CN96119015A CN1062560C CN 1062560 C CN1062560 C CN 1062560C CN 96119015 A CN96119015 A CN 96119015A CN 96119015 A CN96119015 A CN 96119015A CN 1062560 C CN1062560 C CN 1062560C
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Abstract
The present invention relates to a separation and refining method for preparing dioxygen and thiazine salt, which is characterized in that an extraction agent is added in a mixture which is synthesized so that an acid product and the extraction agent form an ionic associated substance which enters an organic phase; the organic phase is washed in water, and inorganic aqueous alkali is used as the extraction agent; thereby, the product is converted into corresponding salt and then returns a water phase, and a coarse product which is concentrated and precipitated is re-crystallized and refined in mixed solvent of ethanol and water. The separation and refining method of the present invention has the characteristics of smartness, high efficiency, economy and practicality, is capable of obtaining high-purity dioxygen and thiazine salt, and is suitable for the production of sweetener.
Description
Acesulfame has following structure:
Wherein the hydrogen on the nitrogen-atoms has very strong acidity, can be converted into salt when doing the time spent with alkali, as sodium salt, calcium salt, sylvite etc., particularly sylvite, is called for short AK sugar and has been widely accepted as edible low heat value non-nutritive sweetener and uses.At present, the existing several different methods of synthetic this compound or its salt:
1. fluosulfonic acid acyl group isocyanic acid and 2-butyne or tertiary butyl methyl aceto acetate reaction; generate 3-methyl-acetoacetic acid fluosulfonic acid acid amides earlier; cyclisation is acid acesulfame (Angewandle Chemie 85, lssue 22 (1973) pp 965-973) under alkaline condition then.
2. be raw material [DE 3410440] with aceto-acetamide, sulphur trioxide and potassium hydroxide, in inertia organic or inorganic solvent, SO3 fed carry out circulating condensing in the aceto-acetamide, reaction generates acetyl acetamide sulfonic, is converted into acesulfame again under alkaline condition.
3. be raw material with thionamic acid, triethylamine, diketene, sulphur trioxide and potassium hydroxide etc.[DE 3410439] are dissolved in thionamic acid and dienone in the inert solvent, drip triethylamine about 0 ℃, reaction back standing over night.Then, add SO3 at low temperatures, carry out the cyclization place to the acid acesulfame.
4. be that raw material [spy opens clear 61/47473] is with aceto-acetamide and K with aceto-acetamide, salt of wormwood, sulfur fluoride acyl fluorides and potassium hydroxide
2CO
3Be dissolved in the aqueous acetone solution; feed sulfur fluoride acyl fluorides gas while stirring; carry out the acetoacetyl reaction; after the filtration, filter residue is added 0 ℃ hydrochloric acid make it that cyclization take place to obtain the acid acesulfame, then by solvent evaporation; ethyl acetate extraction; drying, the revaporization ethyl acetate is settled out the sylvite of acesulfame at last with the methanol solution of KOH.
With thionamic acid acyl fluorides, diketene, salt of wormwood and potassium hydroxide be raw material [spy opens clear 60/215661] with diketene to containing H
2NSO
2F and K
2CO
3Acetone soln in, make the sylvite of acetoacetyl amido-N-sulfonic acid fluoride, the methanol solution with KOH makes it to be cyclized into sylvite again.
Though the raw material that these method for makings adopted is different with reaction conditions, the method that final step is adopted but is duplicate, promptly makes the sylvite that salt forming agent directly precipitates and isolates two oxygen Evil thiazines with the methanol solution of potassium hydroxide.Above-mentioned this direct salify partition method has following shortcoming: 1. owing to react the employed low boiling point solvent that is, the methyl alcohol of introducing with the salify separating step has close boiling point, so just must carry out the separation of the close solvent of two or more boiling points.Because used acetoacetyl reagent in the synthesis step; do not contain the material (as methyl alcohol) that has reactive hydrogen in these reagent general requirement reaction solvents; so will separate methyl alcohol fully, and the close component of industrial thorough separation boiling point is quite difficult.2. in the direct sedimentary product, not only contain a large amount of inorganic salt,, and contain other and can produce sedimentary by product and the residual bigger methyl alcohol of toxicity with KOH as Potassium monofluoride, vitriolate of tartar etc.Product purity is difficult to improve.The objective of the invention is to overcome the above-mentioned shortcoming that existing method exists, propose a kind of simple and direct efficient, economical and practical separation and process for purification that obtains high purity acesulfame salt.Method of the present invention can be realized by following steps:
By above-mentioned synthetic method; after carrying out acetoacetylization and cyclization; contain following component in the reaction mixture that obtains: primary product acid acesulfame; sulfuric acid that forms after the excessive sulphur trioxide hydrolysis and the inorganic salt that generate as the component of catalyzer and sulfuric acid, carbonic acid, fluorochemical etc., and contain the by product and the excessive reactant of multiple reaction.
Add extraction agent in the thing mixed containing in above-mentioned reaction, extraction between temperature-20～+ 35 ℃, wash organic phase with water, make strippant with inorganic base aqueous solution again, between temperature-20～+ 35 ℃, strip, the pH that makes the aqueous solution after the reextraction concentrates the crude product of separating out between 5～12, use ethanol: the mixed solvent of water=0%～50% (V/V) carries out recrystallizing and refining.
Extraction agent of the present invention comprises following a few class:
(1) acid organophosphorus extraction agent, general structure:
(wherein R1, R2 represent alkyl, alkoxyl group or the aromatic base of C2～12) (2) neutral phosphonic oxygen kind of extractants, general structure:
(wherein R1, R2, R3 represent alkyl, alkoxyl group or the aromatic base of C1～10) (3) neutral sulfur-bearing extraction agent, general structure:
(wherein R1, R2 represent the alkyl or the ether of C6～12) (4) amine extractant, general structure
Wherein R1, R2, R3 represent the alkyl or the acyl group of C5～12
The extraction agent of selecting for use should have following characteristics in principle: (1) can form ionic associate to the acid acesulfame and have very strong extracting power, promptly partition ratio help the acid product in organic phase content greater than its content at aqueous phase.But the metal-salt of acesulfame is not had an extracting power, and promptly the product of salt formula structure trends towards being distributed in aqueous phase.(2) has higher boiling point, general requirement than the boiling point of reaction solvent high more than 20 ℃ (if mixed solvent is adopted in reaction, then the component that the boiling point of extraction agent should be higher than its mid-boiling point is high more than 20 ℃), and do not form azeotrope with reaction solvent, thereby, can adopt simple distillating method to reclaim reaction solvent.(3) solubleness is little in water, preferably less than 1g/100ml, can avoid extraction agent significantly sacrificing in use itself like this.(4) good stability in acid, alkaline medium, and have good thermostability below 100 ℃ at least.Extraction agent with these characteristics comprises following a few class:
1. acid organophosphorus extraction agent: di-(2-ethylhexyl)phosphoric acid, two (diisobutyl methyl) phosphoric acid, dodecylphosphoric acid, 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester, dibutyl phosphate, phenyl-phosphonic acid list (2-ethylhexyl) ester, hexyl mono phosphoric acid ester (1-methylheptyl) ester etc.
2. neutral phosphonic oxygen kind of extractants: triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, THP triheptylphosphate, trioctyl phosphate, triphenylphosphate, dibutyl butylphosphonate, dihexyl methylphosphonate, methyl-phosphorous acid diformazan heptyl ester, dibutyl phosphonic acids butyl ester, tributylphosphine oxide, trioctylphosphine oxide (TOPO) etc.
3. neutral sulfur-bearing extraction agent: diheptyl sulfoxide, dioctylsulfoxide(DOSO), 3-hexyl thiophene sulfoxide etc.
4. amine extractant: trioctylphosphine amine, three heptyl amine, trilaurylamine (Tridodecylamine, secondary amine, N, N ＇ diformazan heptyl ethanamide, trialkylamine etc.
Above extraction agent can be used alone, but also also mix together.Under some extraction agent normal temperature is solid, and the then available high boiling organic solvent that is higher than 70 ℃ as sulfonated kerosene, methyl propyl ketone, 1, re-uses after the dissolvings such as 2-ethylene dichloride.The consumption of extraction agent is mainly according to extraction efficiency decision, and is relevant with multiple factor, and as pH, solution temperature, the type of reaction solvent and used extraction agent self character of water or the like, general consumption is preferably 0.1～5 times of reaction solvent.Extraction should be carried out at a lower temperature, to avoid the volatilization loss of reaction solvent, generally is controlled between-20～+ 35 ℃, is preferably between 0～+ 20 ℃.
Isolate the sour water phase after the extraction, and adopt the water that is equivalent to organic phase volume about 1/10 repeatedly to wash organic phase, up to the water BaCl that washes out
2Or AgNO
3Solution check, (do not produce till the white precipitate, illustrate promptly in the organic phase that sulfate radical or content of fluoride ion are below 0.1g/Kg) keeps organic phase and is used for next step operation.With the hydration of sour water and washing usefulness also, the extraction agent of the same race that adds with the first step same amount extracts, and contains a certain amount of acid product in the extraction agent after the extraction, is used for next cyclical operation.
The reextraction solutions employed is the alkali of respective metal or the aqueous solution of its carbonate.As prepare the sylvite of acesulfame, adopt the aqueous solution of potassium hydroxide or salt of wormwood.The consumption of alkali or carbonate, is preferably between the pH 7～9 between pH 5～12 with the acidity of the aqueous solution after stripping.
With the organic phase of potassium hydroxide aqueous solution reextraction previous step, make the acid product be converted into sylvite and transfer to aqueous phase.The concentration of potassium hydroxide aqueous solution can in very large range change, the upper limit with back extraction after water do not produce product and be precipitated as, otherwise need first precipitation separation, lower limit then is arbitrarily, but potassium hydroxide solution concentration is too low, the concentration of aqueous phase product also must be low after stripping, and need evaporate a large amount of water when next step is concentrated.The concentration of best potassium hydroxide solution is to make the water after the reextraction contain acesulfame sylvite near saturated.The pH of water is preferably between 5～12 after stripping, and is preferably between 7～9.Then, wash organic phase with less water, the water after the washing is incorporated the aqueous phase of stripping and obtaining into, as concentrating of next step.Organic phase then reclaims solvent and extraction agent with distillation method.
Method with reduction vaporization concentrates the resulting water of previous step.Vacuum tightness can be controlled in 200～720mm and adopts between the post during evaporation, preferably between 500～680mm mercury column.Control certain Heating temperature, balance the boiling to keep solution, till producing small amount of crystal.The crude product that the cooling back is drawn is used for next step and makes with extra care.
Adopting water and ethanol mixed solvent that crude product is carried out recrystallization handles.Solvent is heated to about 70 ℃, dissolves in crude product while stirring up to saturated, filtered while hot, filtrate naturally cools to room temperature.Separate out crystalline product.Can repeatedly repeat the operation of the 5th step on demand.Water and alcoholic acid ratio can be decided as the case may be.The solubleness of the sylvite of acesulfame in water is very big, and improve with temperature and to increase, solubleness in ethanol is then very little, so alcoholic acid content is high more in the mixed solvent, the crystal of separating out after the cooling is many more, but when heating treatment capacity more little, otherwise, treatment capacity is big, but residual quantity is also big in mother liquor.The situations such as temperature of the main purity according to crude product of both ratios, cooling back mother liquor decide.Ethanol: water (V/V) can be preferably 10%～30% between 0%～50%.
Embodiment one
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 100ml two-(2-ethylhexyl) phosphoric acid, temperature is controlled at 30 ℃, extracted 10 minutes, leave standstill and made the abundant layering of two-phase in about 5 minutes, isolate water, with the content in high-performance liquid chromatogram determination water and the organic phase, calculating the single extraction rate is 81.2%.In the organic phase of washing, adding 50ml water, then under intense stirring condition, gradation adds the potassium hydroxide solution of 5M, the pH value of water is reached about 6, tell water after leaving standstill, measure the content of acesulfame sylvite in water and the organic phase, calculating a stripping rate is 75.6%.
Embodiment two
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 100ml 2-ethylhexyl phosphonic acids list (2-ethylhexyl) ester, temperature is controlled at 18 ℃, extracted 10 minutes, leave standstill and make the abundant layering of two-phase, isolate water, with the content in high-performance liquid chromatogram determination water and the organic phase, calculating the single extraction rate is 86.4%.In the organic phase after the clear water washing, add 50ml water, then under intense stirring condition, gradation adds the potassium hydroxide solution of 5M, the pH value of water is reached about 9, measure the content of acesulfame sylvite in water and the organic phase after leaving standstill respectively, calculating a stripping rate is 99.0%.
Embodiment three
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add the 100ml dodecylphosphoric acid, temperature is controlled at 23 ℃, extracts 10 minutes, leaves standstill to make the abundant layering of two-phase in about 5 minutes, use routine method and measure, calculating the single extraction rate is 53.0%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the unsaturated carbonate potassium solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 98.0%.
Embodiment four
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 100ml two ylmethyl phosphonic acid ester, temperature is controlled at 23 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 74.5%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 99.0%.
Embodiment five
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 100ml diethyl decyl phosphoric acid ester, temperature is controlled at 20 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 83.6%.In in the organic phase of clear water washing, adding 50ml water, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 12, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 99.0%.
Embodiment six
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 100ml 20% trioctyl phosphine oxide-sulfonated kerosene, temperature is controlled at 22 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 78.5%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 98.0%.
Embodiment seven
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 50ml diethyl decyl phosphoric acid ester and 50ml 20% trioctyl phosphine oxide, temperature is controlled at 20 ℃, extracted 10 minutes, leave standstill and make the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 87.8%.In in the organic phase of clear water washing, adding 50ml water, under strong stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 12, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 99.0%.
Embodiment eight
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add the 100ml triphenylphosphate, temperature is controlled at 20 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 57.5%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 99.0%.Embodiment nine
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add 100ml 25% dioctylsulfoxide(DOSO)-methyl propyl ketone, temperature is controlled at 20 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 43%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 97.0%.
Embodiment ten
Add the 100ml trialkylamine in 100ml acesulfame acid reaction mixture (comprising organic phase and water), temperature is controlled at 20 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measures with embodiment two methods, and calculating the single extraction rate is 72.6%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 99.0%.
Embodiment 11
In 100ml acesulfame acid reaction mixture (comprising organic phase and water), add the basic thiophene sulfoxide-1 of 100ml3-, the 2-ethylene dichloride, temperature is controlled at 20 ℃, extracts 10 minutes.Leave standstill and make the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 39.5%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 97.0%.
Embodiment 12
Add the 100ml trioctylamine in 100ml acesulfame acid reaction mixture (comprising organic phase and water), temperature is controlled at 25 ℃, extracts 10 minutes, leaves standstill and makes the abundant layering of two-phase, measures with embodiment two methods, and calculating the single extraction rate is 77.0%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, make the pH value of water reach 7.5, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 98.5%.
Embodiment 13
Contain adding 100ml N in the acesulfame acid reaction mixture (comprising organic phase and water) at 100ml, N-diformazan heptyl ethanamide, temperature is controlled at 20 ℃, extracts 10 minutes.Leave standstill and make the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 63.5%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 98.5%.
Embodiment 14
Contain the mixed extractant that adds 50ml di-(2-ethylhexyl)phosphoric acid trialkylamine and 50ml phenyl-phosphonic acid in the acesulfame acid reaction mixture (comprising organic phase and water) at 100ml, temperature is controlled at 20 ℃, extracts 10 minutes.Leave standstill and make the abundant layering of two-phase, measure with embodiment two methods, calculating the single extraction rate is 90.3%.In add 50ml water in the organic phase of clear water washing, under intense stirring condition, gradation adds the 5M potassium hydroxide solution, the pH value of water is reached about 8, leave standstill the back layering, measure the content of acesulfame sylvite in water and the organic phase respectively, calculating a stripping rate is 99.0%.
Embodiment 15
The acesulfame potassium salt brine solution that after the processing of stripping, obtains, behind the available reduction vaporization, the thick acesulfame potassium crystal of separating out after the concentrated solution cooling that obtains, purity can reach more than 95%.It is refined products more than 99% that this crude product can obtain purity with the process for purification of this patent.Get the thick acesulfame sylvite crystal of 100 grams, gradation adds the mixing solutions dissolving that contains 10% (V/V) alcoholic acid ethanol and water, near boiling point the time crystal is all dissolved, filtered while hot.Separate out crystal after the mother liquor cooling, suction filtration gets refined products 84.5 grams, and refined yield is 88.9%.
Embodiment 16
Get the thick acesulfame sylvite crystal of 100 grams, gradation adds the mixing solutions dissolving that contains 10% (V/V) alcoholic acid ethanol and water, near boiling point the time crystal is all dissolved, filtered while hot.Separate out crystal after the mother liquor cooling, suction filtration gets refined products 89.4 grams.Refined yield is 94.1%.
Embodiment 17
Get the thick acesulfame sylvite crystal of 100 grams, gradation adds the mixing solutions dissolving that contains 50% (V/V) alcoholic acid ethanol and water, near boiling point the time crystal is all dissolved, filtered while hot.Separate out crystal after the mother liquor cooling, suction filtration gets refined products 93.8 grams.Refined yield is 98.7%.
Embodiment 18
Get the thick acesulfame sylvite crystal of 100 grams, gradation adds pure water, when boiling point crystal is all dissolved, filtered while hot.Separate out the crystal suction filtration after the mother liquor cooling and get refined products 74.6 grams.Refined yield is 78.5%.
Claims (16)
1. the separation of a dioxathiazine salts and process for purification, it is characterized in that comprising primary product acid acesulfame, the sulfuric acid that forms after the excessive sulphur trioxide hydrolysis and as the component and the sulfuric acid of catalyzer, carbonic acid, the inorganic salt that fluorochemical generates, and contain in the synthesis reaction mixture of acesulfame of multiple byproduct of reaction and excess reactant, add acid organophosphorus extraction agent, neutral phosphonic oxygen kind of extractants, neutral sulfur-bearing extraction agent or amine extractant, extraction between temperature-20～+ 35 ℃, wash organic phase with water, make strippant with inorganic base aqueous solution again, between temperature-20～+ 35 ℃, strip, the pH that makes the aqueous solution after the reextraction is between 5～12, concentrating the crude product separate out, is that 0～50% mixed solvent carries out recrystallizing and refining with the volume ratio of ethanol and water.
2. separation according to claim 1 and process for purification is characterized in that the general structure of described acid organophosphorus extraction agent is:
Wherein R1, R2 represent alkyl, alkoxyl group or the aromatic base of C2～12
3. separation according to claim 1 and process for purification is characterized in that the general structure of described neutral phosphonic oxygen kind of extractants is:
Wherein R1, R2, R3 represent alkyl, alkoxyl group or the aromatic base of C1～10
4. separation according to claim 1 and process for purification is characterized in that the general structure of described neutral sulfur-bearing extraction agent is:
Wherein R1, R2 represent the alkyl or the ether of C6～12
5. separation according to claim 1 and process for purification is characterized in that the general structure of described amine extractant is:
Wherein R1, R2, R3 represent the alkyl or the acyl group of C5～12
6. separation according to claim 1 and process for purification is characterized in that described acid organophosphorus extraction agent is di-(2-ethylhexyl)phosphoric acid, two (diisobutyl methyl) phosphoric acid, dodecylphosphoric acid, 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester, phenyl-phosphonic acid list (2-ethylhexyl) ester, hexyl phosphonic acids list (1-methylheptyl) ester.
7. separation according to claim 1 and process for purification is characterized in that described neutral phosphonic oxygen kind of extractants is triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, THP triheptylphosphate, trioctyl phosphate, triphenylphosphate, dibutyl butylphosphonate, dihexyl methylphosphonate, methyl-phosphorous acid diformazan heptyl ester, dibutyl phosphonic acids butyl ester, tributylphosphine oxide, trioctylphosphine oxide (TOPO).
8. separation according to claim 1 and process for purification is characterized in that described neutral sulfur-bearing extraction agent is diheptyl sulfoxide, dioctylsulfoxide(DOSO), 3-hexyl thiophene sulfoxide.
9. separation according to claim 1 and process for purification is characterized in that described amine extractant is three heptyl amine, trioctylphosphine amine, trilaurylamine (Tridodecylamine, N, N ＇-two (1-methylheptyl) ethanamide.
10. separation according to claim 1 and process for purification is characterized in that described extraction agent can be used alone, but also also mix together.
11. separation according to claim 1 and process for purification is characterized in that re-using after described extraction agent can dissolve with the high boiling organic solvent that is higher than 70 ℃.
12. separation according to claim 11 and process for purification, the organic solvent that it is characterized in that described extraction agent are sulfonated kerosene, methyl propyl ketone, 1, the 2-ethylene dichloride.
13. separation according to claim 1 and process for purification is characterized in that described extraction and reextraction temperature are 0～20 ℃.
14. separation according to claim 1 and process for purification is characterized in that described inorganic base aqueous solution strippant is potassium hydroxide or wet chemical.
15. separation according to claim 1 and process for purification is characterized in that the pH of the aqueous solution after the described reextraction is 7～9.
16. separation according to claim 1 and process for purification, the volume ratio that it is characterized in that the mixed solvent of described ethanol and water is 10～30%.
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| CN1062560C true CN1062560C (en) | 2001-02-28 |
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| CN107050924B (en) * | 2017-05-16 | 2020-10-27 | 郑州天一萃取科技有限公司 | Method for extracting citric acid by using centrifugal extractor |
| CN113636959A (en) * | 2021-07-05 | 2021-11-12 | 南通醋酸化工股份有限公司 | Quality control method in process of producing acesulfame potassium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077712A (en) * | 1992-03-17 | 1993-10-27 | 赫彻斯特股份公司 | thiazine-4-ketone-2 that preparation replaces, the method and the device of 2-dioxide non-toxic salt |
| CN1092066A (en) * | 1993-03-04 | 1994-09-14 | 商业部科学研究院 | The 6-methyl isophthalic acid, 2,3-Evil thiazine-4 (3H)-ketone-2, the synthetic method of 2-dioxide and salt thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077712A (en) * | 1992-03-17 | 1993-10-27 | 赫彻斯特股份公司 | thiazine-4-ketone-2 that preparation replaces, the method and the device of 2-dioxide non-toxic salt |
| CN1092066A (en) * | 1993-03-04 | 1994-09-14 | 商业部科学研究院 | The 6-methyl isophthalic acid, 2,3-Evil thiazine-4 (3H)-ketone-2, the synthetic method of 2-dioxide and salt thereof |
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