CN85101615A - Inexpensive and continuous production of saccharin - Google Patents
Inexpensive and continuous production of saccharin Download PDFInfo
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- CN85101615A CN85101615A CN198585101615A CN85101615A CN85101615A CN 85101615 A CN85101615 A CN 85101615A CN 198585101615 A CN198585101615 A CN 198585101615A CN 85101615 A CN85101615 A CN 85101615A CN 85101615 A CN85101615 A CN 85101615A
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- oxidation
- electrolysis
- asccharin
- reaction
- orthotoluene sulfonamide
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Abstract
About the oxidation of orthotoluene sulfonamide, the improvement technology of pass ring preparation asccharin.The oxidation and the electrolysis that comprise orthotoluene sulfonamide make two processes of oxygenant regeneration.With the chromic anhydride is oxygenant, in aqueous sulfuric acid, add the orthotoluene sulfonamide reaction and make asccharin, by changing reaction conditions, removed this operation of numerous and diverse low-pressure distillation from, avoided bulky structure and plant and equipments such as acid resistance distillation equipment and boiler house, providing realization " oxidation " and " electrolysis " whole flow process continuous and automatic round-robin to implement may.Reaction conditions is as follows: H
2SO
4Concentration is 50-58%, temperature of reaction 40-60 ℃, and reaction times 8-12 hour.
Description
The oxidation of orthotoluene sulfonamide, pass ring are produced asccharin.
Industrial production asccharin main technological route has at present: phthalic anhydride method and toluene method.But because phthalic anhydride belongs to industrial chemicals in short supply, therefore, the toluene route reformed be still very significant.Produce asccharin by orthotoluene sulfonamide,, mainly contain following three kinds of technical matters with oxidation style:
One, the oxidation style of potassium permanganate (sodium): the domestic and Soviet Union etc. still has adopts this method to produce.
Two, with the sexavalent chrome oxidation style:
1. with the chromic anhydride oxygenant continuous production asccharin, referring to u, s, 3.899.501
2. be oxygenant with the chromic anhydride, adopt electrolysis that chromic anhydride and sulfuric acid are recycled, negative electrode gets the by product electrolytic zinc, referring to J74040232.
3. be oxygenant with oxygen one air, acetic acid is solvent, is the Preparation of Catalyst asccharin with cobalt, manganese, bromine salt, referring to J58219170.
We think that " oxidation " cost that potassium permanganate (sodium) method is spent is higher, belongs to early stage industrial production method; With oxygen one air is oxidation style, and " oxidation " yield is lower on the one hand, and " oxidation " cost also fails to reach best economic benefit, and the chromic anhydride method is the comparatively sophisticated industrialization method that advanced country adopted in the world at present.But, " chromic anhydride " method that the U.S. adopted " oxidation " and " electrolysis " continuous automatic production that still is unrealized, " chromic anhydride " oxidation style that Japan is reported, though realize the circulation of " oxidation " and " electrolysis ", yet, produce one ton of asccharin and need low-pressure distillation water outlet 12-15 ton, and, can not realize the continuous and automatic circulation of whole process flow.
Based on above-mentioned " technical background ", asccharin is made in oxidation for orthotoluene sulfonamide, and we adopt the chromic anhydride oxidation, and electrolysis reaches chromic anhydride and sulfuric acid and recycles.Solve emphatically, remove the operation of low-pressure distillation water outlet 12-15 ton from, and provide realization " oxidation " and " electrolysis " whole flow process continuous and automatic round-robin to implement possibility, reach solution three wastes problem, avoid polluting.
Present technique technology comprises oxidation and two parts of electrolysis:
At sulfuric acid concentration is 50-58%, in the aqueous sulfuric acid of 700-800ml, adds chromic anhydride 160-200 gram, in temperature is under 40-60 ℃, constantly stirs down, adds the above orthotoluene sulfonamide of 100 orders 100 grams (oven dry 97 grams), constant temperature 8-12 hour, can the stop reaction.Take out the Lu and get the chromium sulphate mother liquor and can be used for electrolysis, the Lu cake is put into water through the aqueous sulfuric acid washed twice of PH=2, adds 20% the about 100ml of NaOH solution, and about PH=6 extremely is after the Lu.In its Lu liquid, add the about 35ml of hydrochloric acid, make PH=1-2, take out Lu, oven dry, promptly get saccharin insoluble.
Electrolysis process: the mother liquor that will prepare the asccharin gained carries out electrolysis, can adopt the single chamber undivided cell, chromic anhydride and regeneration of sulfuric acid are recycled, also can adopt two chamber diaphragm types or the dual-purpose diaphragm electrolytic cell in three Room to carry out electrolysis, make it to recycle, and can get the by product electrolytic zinc at negative electrode.
Carry out electrolysis at 30-50 ℃, behind appropriate time, anolyte can be directly used in oxidation and prepare asccharin.
Faradaic current efficient is calculated by following formula:
a＝ (26.8×m×100)/(A.t.E)
M: electrolysis gained weight metal (quality, gram)
A: electrolysis total current (ampere)
T: electrolysis time (hour); E: electricity gram equivalent.
Present technique technology, because we have removed this operation of low-pressure distillation from, the mother liquor of oxidation trough gained directly can be squeezed into electrolyzer and carried out electrolysis by filtering, and electrolyzer can be directly used in the possibility that oxidation trough prepares asccharin thereby enforcement is provided for the continuous and automatic industrial production in the whole flow process after the electrolytic solution after the electrolysis (is used nylon cloth or glasscloth) after filtration.Simultaneously, owing to exempted low-pressure distillation (distilling out 12-15 ton water/asccharin per ton) and centrifugation operations such as (centrifugation go out chromic anhydride from sulfuric acid and chromium sulphate mother liquor), thereby, just avoided the equipment of acid resistance low-pressure distillation, bulky structure such as boiler house, whizzer and factory building again can be energy-conservation well; If adopt the single chamber diaphragm-free electrolysis, can save diaphragm apparatus, if adopt three Room double-purpose diaphragm electrolytic cells also can obtain highly purified electrolytic zinc from zinc oxide.Because adopt this law, equipment is simple, operation reduces, and cost reduces, and causes " oxidation " cost of making asccharin per ton by the orthotoluene sulfonamide oxidation to be reduced to about 1000 yuan.
The embodiment I:
(1) oxidation:
In 50-58% aqueous sulfuric acid (700-800ml), add chromic anhydride 160-200 gram, under constantly stirring, slowly add the above orthotoluene sulfonamide of 100 orders 100 grams (oven dry is 97 grams), temperature of reaction is at 40-60 ℃, and the reaction times is 8-12 hour, can the stop reaction.
With sand core funnel or chemical fiber cloth, take out the Lu or cross the Lu, Lu liquid is directly used in electrolysis, the Lu cake is put into the PH=2(sulfuric acid of about 100ml) water, wash, take out the Lu, Lu liquid is incorporated in mother liquor and is used for electrolysis, this washs once for another example.The Lu cake is put into 300ml water, add the about 100ml of the 20%NaOH aqueous solution, make it PH6-7 and cross the Lu, oxyhydroxide and unreacted ortho position amine such as iron (zinc), chromium are arranged in its Lu cake.In its Lu liquid, add the about 35ml of hydrochloric acid, make it PH=1-2.Cross the Lu, dry by the fire its Lu cake, promptly get saccharin insoluble 80-90 ℃ of baking 15 hours.
Experimental result: get asccharin 98 grams, its theoretical oxidation ratio reaches 94.4%.
Get unreacted ortho position amine 0.5 gram, its theoretical total yield is 94.9%.
Through ultimate analysis: C
7H
5SO
3N
C????H????N????S
Theoretical value: 45.90% 2.93% 7.65% 17.5%
Analytical value: 45.2% 2.84% 7.25% 17.5%
By Infrared spectroscopy, the infrared spectrum of products therefrom and asccharin spectrogram are in full accord.
By nuclear magnetic resonance spectroscopy, its purity reaches more than 97%, and all the other are raw material, and orthotoluene sulfonamide is by atomic absorption spectrochemical analysis, and its chromium and plumbous residual quantity are:
Chromium: 0.03-2.5ppm;
Plumbous: 0.5-0.7ppm.
(2) electrolytic regeneration process:
Carry out electrolysis with the single chamber undivided cell:
About 800ml mother liquor is poured electrolyzer into, and electrolyzer is put into 50 ℃ of constant temperature water bath grooves and carried out electrolysis.Stereotype or lead rod with special processing are anode, are negative electrode with the platinum filament.
Current density: anode 2-4A/dm
2;
Negative electrode: 20-40A/dm
2
Electrolysis temperature: 40-60 ℃.
Groove is pressed: the 2.5-3.0 volt.
Faradaic current is about the 5A(ampere), electrolysis time 30-40 hour, this used for electrolyte can be prepared asccharin in oxidation.
Electrolysis result: electrolysis 122 ampere-hours.
Electrolysis gets C
rO
3: 61.6 grams, Faradaic current efficient: 40.6%.
Embodiment 2:
(1) asccharin is made in the orthotoluene sulfonamide oxidation: with embodiment 1;
(2) electrolytic regeneration process:
Adopt three Room double-purpose diaphragm electrolytic cells to carry out electrolysis:
Electrolytic solution: anode is with mother liquor (1600ml); Negative electrode: 200 gram Z
nO is dissolved in the 1600ml aqueous sulfuric acid, and PH is about 2-3; Intermediate chamber: 1NH
2SO
4
Anode: the lead rod (plate) through special processing is an anode;
Current density 3-5A/dm
2;
Temperature 30-50 ℃.
Negative electrode: aluminium sheet is a negative electrode;
Current density 4-6A/dm
2;
Temperature 30-50 ℃.
Groove is pressed: the 3.5-4.7 volt;
Barrier film: F101 ion exchange resin type barrier film.
Add about 0.5 gram of gelatin at cathode compartment.
Faradaic current is 5-8A, after electrolysis is carried out 20-24 hour, cathode compartment electrolytic solution is taken out, and is folded down electrolytic zinc on aluminium sheet, pours above-mentioned catholyte 1600ml again into, continues electrolysis 20-24 hour, gets final product stop.Electrolytic solution can be used for oxidation and prepares asccharin.
Electrolysis result: electrolysis 161 ampere-hours;
Get Zn:161g, current efficiency is 81.9%;
C
rO
3: 180g, current efficiency 90%.
Electrolytic zinc purity is measured as 99.9% by emmission spectrum, or more than 99.9%.
Claims (1)
- The technology that ring prepares asccharin is closed in the oxidation of orthotoluene sulfonamide, and it comprises the oxidation and the electrolysis of orthotoluene sulfonamide, makes two processes of oxygenant regeneration.With the junket acid anhydride is oxygenant, and in aqueous sulfuric acid, the adding orthotoluene sulfonamide reacts and gets.The invention is characterized in that the concentration of the aqueous sulfuric acid that oxidising process is used is 50-58%, temperature of reaction is at 40-60 ℃, and the reaction times is 8-12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585101615A CN85101615A (en) | 1985-04-01 | 1985-04-01 | Inexpensive and continuous production of saccharin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585101615A CN85101615A (en) | 1985-04-01 | 1985-04-01 | Inexpensive and continuous production of saccharin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85101615A true CN85101615A (en) | 1986-08-13 |
Family
ID=4791942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198585101615A Withdrawn CN85101615A (en) | 1985-04-01 | 1985-04-01 | Inexpensive and continuous production of saccharin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85101615A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130524B (en) * | 2006-08-23 | 2011-03-30 | 上海港福化工技术咨询有限公司 | Method for producing saccharin |
| KR101877778B1 (en) * | 2017-12-26 | 2018-07-12 | 한국화학연구원 | Preparation method of saccharin by using enhanced oxidation process of o-toluene sulfonamide |
-
1985
- 1985-04-01 CN CN198585101615A patent/CN85101615A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130524B (en) * | 2006-08-23 | 2011-03-30 | 上海港福化工技术咨询有限公司 | Method for producing saccharin |
| KR101877778B1 (en) * | 2017-12-26 | 2018-07-12 | 한국화학연구원 | Preparation method of saccharin by using enhanced oxidation process of o-toluene sulfonamide |
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