CN103130843A - Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester - Google Patents
Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester Download PDFInfo
- Publication number
- CN103130843A CN103130843A CN2013100211614A CN201310021161A CN103130843A CN 103130843 A CN103130843 A CN 103130843A CN 2013100211614 A CN2013100211614 A CN 2013100211614A CN 201310021161 A CN201310021161 A CN 201310021161A CN 103130843 A CN103130843 A CN 103130843A
- Authority
- CN
- China
- Prior art keywords
- dibutyltin oxide
- sucrose
- ethyl ester
- cane
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method of recycling and reusing of dibutyltin oxide in the process of cane sugars manufacturing cane suger-6-ethyl ester. The method of recycling and reusing of the dibutyltin oxide in the process of the cane sugars manufacturing the cane suger-6-ethyl ester comprises the following steps: (1), carrying out the cane sugars manufacturing the cane suger-6-ethyl ester; (2), recycling cyclochexane liquor which contains the dibutyltin oxide; (3), using the recycled and obtained dibutyltin oxide with a moisture percentage of 10%-20% for the step (1) of manufacturing the cane suger-6-ethyl ester. The method of recycling and reusing of the dibutyltin oxide in the process of the cane sugars manufacturing the cane suger-6-ethyl ester is concise, operation is easy, and the obtained dibutyltin oxide which contains water can be directly used for manufacturing the cane suger-6-ethyl ester again. A step of drying the dibutyltin oxide can be saved. Under conditions of not affecting yields generally, production cost is reduced. Safe hidden dangers which exist in the process of drying and dewatering the dibutyltin oxide are completely prevented. The method of recycling and reusing of the dibutyltin oxide in process of the cane sugars manufacturing the cane suger-6-ethyl ester can be suitable for industrial production.
Description
Technical field
The present invention relates to the Sucralose intermediate and synthesize the field, be specifically related to the method that sucrose prepares the recycling of Dibutyltin oxide in the sucrose-6-ethyl ester process.
Background technology
Sucralose is a kind of in chloro sucrose, is a kind of novel sweetener, and sugariness is 600 times of sucrose, and it does not participate in body metabolism, and is safe, and antagonism acid hydrolysis ability is strong, and plurality of advantages makes him become the market preferred product.Sucralose esterification reaction is ripe at present triethly orthoacetate esterification process, dibutyl tin oxidation style and a diacetyl oxide esterification process, wherein adding diacetyl oxide esterification process part material and organic solvent with Dibutyltin oxide can recycling, and the rate of recovery is very high, greatly reduces cost.because the reaction of Dibutyltin oxide and sucrose is that the water process is adopted in a backflow, moisture Dibutyltin oxide is all influential to reaction times and speed of response, if generally believe that therefore the Dibutyltin oxide that adds contains this reaction of moisture and is not easy to realize, therefore the wet Dibutyltin oxide that contains that obtains in the recycling method of existing production technique to Dibutyltin oxide all needs through super-dry, and Dibutyltin oxide is a kind of white powder, water insoluble, and inflammable have a severe toxicity, make it dehydrate difficulty very large, production is put to no little inconvenience, and dehydrate and have potential safety hazard in process.
Summary of the invention
The object of the present invention is to provide the sucrose that a kind of method is simple, cost is low, the Dibutyltin oxide utilization ratio is high to prepare the method for the recycling of Dibutyltin oxide in the sucrose-6-ethyl ester process.
Concrete technical scheme of the present invention is as follows:
A kind of sucrose prepares the method for the recycling of Dibutyltin oxide in the sucrose-6-ethyl ester process, comprises the steps:
(1) sucrose prepares sucrose-6-ethyl ester
1. sucrose and Dibutyltin oxide are joined in the mixing solutions of dimethyl formamide and hexanaphthene formation, the sucrose that adds and the mol ratio of Dibutyltin oxide are 1:1.1-1.2, then heat up, and the insulation back flow reaction; In this step, mixing solutions is used for dissolving saccharose and Dibutyltin oxide, thus its add-on is not had special requirement, as long as reach the purpose of dissolving;
2. then be cooled to-2 ℃-0 ℃, then add diacetyl oxide, the mol ratio of the sucrose that the add-on of diacetyl oxide and step add in 1. is 1.1-1.2:1, add entry, stir, add hexanaphthene to extract, upper strata liquid is the cyclohexane solution that contains Dibutyltin oxide, subnatant through concentrated except anhydrate and dimethyl formamide after obtain sucrose-6-ethyl ester; The purpose that adds entry in this step is the diacetyl oxide of not participating in acylation reaction in order to remove, and its add-on is little on impact of the present invention, so there is no special requirement;
(2) contain the recovery of the cyclohexane solution of Dibutyltin oxide
(a) sodium hydroxide solution is heated up, insulated and stirred, the cyclohexane solution that contains Dibutyltin oxide that step is obtained in 2. joins in sodium hydroxide solution;
(b) then cooling adds the water with the quality such as sodium hydroxide solution, stirs, and then through whizzer filter dehydration 0.5 hour-1 hour, the rotating speed of whizzer was 800-1500rpm, and the moisture percentage that obtains is the Dibutyltin oxide of 10%-20%;
(3) moisture percentage that step (b) is obtained is that the Dibutyltin oxide of 10%-20% is used for step (1) preparation sucrose-6-ethyl ester.
Step is warming up to 82 ℃-90 ℃ in 1., insulation back flow reaction 6-12 hour.
Step 1., in the mixing solutions of dimethyl formamide and hexanaphthene, the volume ratio of dimethyl formamide and hexanaphthene is 6:4-7:3.
Be warming up to 90 ℃-95 ℃ in step (a), the stirring velocity of insulated and stirred is 60-70rpm.
The mass concentration of sodium hydroxide solution is 10%-20% in step (a), and the mol ratio of the Dibutyltin oxide that the sodium hydroxide in sodium hydroxide solution and step add in 1. is 1.1:1; The sodium hydroxide that adds words very little can affect the rate of recovery of Dibutyltin oxide; If excessive, as can to cause waste and increase subsequent disposal difficulty; So the amount that sodium hydroxide adds is the most suitable in above-mentioned scope.
Step (b) is cooled to 40 ℃-50 ℃, and churning time is 1-2 hour.
It is succinctly easy to operate that sucrose of the present invention prepares in the sucrose-6-ethyl ester process Dibutyltin oxide recycling method, resulting moisture Dibutyltin oxide is directly again for the preparation of sucrose-6-ethyl ester, save the Dibutyltin oxide drying step, in the situation that substantially do not affect yield, reduced production cost, stop Dibutyltin oxide and dehydrated the potential safety hazard that exists in process, suitability for industrialized production.
Embodiment
The purity of sucrose-6-ethyl ester of the present invention adopts liquid chromatograph to detect and obtains.
The measuring method of Dibutyltin oxide moisture percentage of the present invention is as follows:
Take in the constant temperature oven that the wet Dibutyltin oxide of 100g is placed in 60 ℃ dry 12 hours; Taking-up is weighed and is G; The moisture percentage that calculates Dibutyltin oxide is (100-G)
/100.
Preparation example 1
(1) sucrose prepares sucrose-6-ethyl ester
Take sucrose 72g, Dibutyltin oxide (doing) 58g puts into flask, adds organic solvent dimethyl formamide 280ml, hexanaphthene 120ml is warming up to 85 ℃ and begins to reflux, and is incubated 87 ℃ of-90 ℃ of backflows and adopts water 6 hours, be cooled to 0 ℃ and drip diacetyl oxide 23ml, stirring reaction 1 hour; Add 15ml water, stirred 1 hour; Add hexanaphthene 250ml extraction Dibutyltin oxide, upper strata liquid is the cyclohexane solution that contains Dibutyltin oxide, subnatant through concentrated except anhydrate with dimethyl formamide after obtain sucrose-6-ethyl ester (purity 87.77%).
(2) contain the recovery of the cyclohexane solution of Dibutyltin oxide
(a) be that 10% sodium hydroxide solution is warming up to 90 ℃-95 ℃ with the 102.55g mass concentration, insulated and stirred, stirring velocity are 60-70rpm, and the cyclohexane solution that contains Dibutyltin oxide that above-mentioned extraction is obtained joins in sodium hydroxide solution;
(b) then be cooled to 40 ℃-50 ℃, add 102.55g water, stirred 1-2 hour, then through whizzer filter dehydration 0.5 hour-1 hour, the rotating speed of whizzer was 800-1500rpm, and the moisture percentage that obtains is the Dibutyltin oxide of 10%-20%;
With adopt aforesaid method reclaim the moisture percentage that obtains be the Dibutyltin oxide of 10%-20% for the preparation of sucrose-6-ethyl ester, concrete grammar is as described in embodiment 1 to embodiment 3.
Embodiment 1
Take sucrose 72g, the method of employing preparation example 1 reclaims Dibutyltin oxide (moisture percentage 10%) 65g that obtains and puts into flask, add organic solvent dimethyl formamide 280ml, hexanaphthene 120ml, being warming up to 85 ℃ begins to reflux, be incubated 87 ℃ of-90 ℃ of backflows and adopted water 6 hours, be cooled to 0 ℃ and drip diacetyl oxide 23ml, stirring reaction 1 hour; Add 15ml water, stirred 1 hour; Add hexanaphthene 250ml extraction Dibutyltin oxide,
Upper strata liquid is the cyclohexane solution that contains Dibutyltin oxide, subnatant through concentrated except anhydrate and dimethyl formamide after obtain sucrose-6-ethyl ester (purity 86.85%).
Embodiment 2
Take sucrose 180kg, the method of employing preparation example 1 reclaims Dibutyltin oxide (moisture percentage 10%) 160kg that obtains and puts into flask, add organic solvent dimethyl formamide 500L, hexanaphthene 300L heats up, 83 ℃ begin to reflux, be incubated 87 ℃ of-90 ℃ of backflows and adopted water 12 hours, be cooled to 0 ℃ and drip diacetyl oxide 57.5L, stirring reaction 1 hour; Add 37.5L water, stirred 1 hour; Add hexanaphthene 500L extraction Dibutyltin oxide, upper strata liquid is the cyclohexane solution that contains Dibutyltin oxide, subnatant through concentrated except anhydrate with dimethyl formamide after obtain sucrose-6-ethyl ester (purity 88.06%).
Embodiment 3
Take sucrose 180kg, the method of employing preparation example 1 reclaims Dibutyltin oxide (moisture percentage 20%) 180kg that obtains and puts into flask, add organic solvent dimethyl formamide 700L, hexanaphthene 300L heats up, 83 ℃ begin to reflux, be incubated 87 ℃ of-90 ℃ of backflows and adopted water 12 hours, be cooled to 0 ℃ and drip diacetyl oxide 57.5L, stirring reaction 1 hour; Add 37.5L water, stirred 1 hour; Add hexanaphthene 500L extraction Dibutyltin oxide, upper strata liquid is the cyclohexane solution that contains Dibutyltin oxide, subnatant through concentrated except anhydrate with dimethyl formamide after obtain sucrose-6-ethyl ester (purity 86.6%).
Claims (6)
1. a sucrose prepares the method for the recycling of Dibutyltin oxide in the sucrose-6-ethyl ester process, it is characterized in that comprising the steps:
(1) sucrose prepares sucrose-6-ethyl ester
1. sucrose and Dibutyltin oxide are joined in the mixing solutions of dimethyl formamide and hexanaphthene formation, the sucrose that adds and the mol ratio of Dibutyltin oxide are 1:1.1-1.2, then heat up, and the insulation back flow reaction;
2. then be cooled to-2 ℃-0 ℃, add diacetyl oxide, the mol ratio of the sucrose that the add-on of diacetyl oxide and step add in 1. is 1.1-1.2:1, add entry, stir, add hexanaphthene to extract, upper strata liquid is the cyclohexane solution that contains Dibutyltin oxide, subnatant through concentrated except anhydrate and dimethyl formamide after obtain sucrose-6-ethyl ester;
(2) contain the recovery of the cyclohexane solution of Dibutyltin oxide
(a) sodium hydroxide solution is heated up, insulated and stirred, the cyclohexane solution that contains Dibutyltin oxide that step is obtained in 2. joins in sodium hydroxide solution;
(b) then cooling adds the water with the quality such as sodium hydroxide solution, stirs, and then through whizzer filter dehydration 0.5 hour-1 hour, the rotating speed of whizzer was 800-1500rpm, and the moisture percentage that obtains is the Dibutyltin oxide of 10%-20%;
(3) moisture percentage that step (b) is obtained is that the Dibutyltin oxide of 10%-20% is used for step (1) preparation sucrose-6-ethyl ester.
2. method according to claim 1, is characterized in that being warming up to 82 ℃-90 ℃ during step 1., insulation back flow reaction 6-12 hour.
3. 1. method according to claim 1 and 2, is characterized in that step, and in the mixing solutions of dimethyl formamide and hexanaphthene, the volume ratio of dimethyl formamide and hexanaphthene is 6:4-7:3.
4. method according to claim 1, is characterized in that being warming up to 90 ℃-95 ℃ in step (a), and the stirring velocity of insulated and stirred is 60-70rpm.
5. according to claim 1 or 4 described methods is characterized in that the mass concentration of sodium hydroxide solution in step (a) is 10%-20%, and the mol ratio of the Dibutyltin oxide that the sodium hydroxide in sodium hydroxide solution and step add in 1. is 1.1:1.
6. method according to claim 1, is characterized in that step (b) is cooled to 40 ℃-50 ℃, and churning time is 1-2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100211614A CN103130843A (en) | 2013-01-21 | 2013-01-21 | Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100211614A CN103130843A (en) | 2013-01-21 | 2013-01-21 | Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103130843A true CN103130843A (en) | 2013-06-05 |
Family
ID=48491340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100211614A Pending CN103130843A (en) | 2013-01-21 | 2013-01-21 | Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103130843A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601689A (en) * | 2016-03-04 | 2016-05-25 | 李云军 | Cane sugar stanizing method |
| CN105601665A (en) * | 2015-12-30 | 2016-05-25 | 浙江新和成股份有限公司 | Treatment method of dibutyltin oxide and application of treatment method to synthesis of cane sugar-6-ethyl ester |
| CN105646605A (en) * | 2016-03-04 | 2016-06-08 | 李云军 | Esterification method of cane sugar |
| CN109503361A (en) * | 2018-12-10 | 2019-03-22 | 安徽金禾实业股份有限公司 | Organotin extracting method and device in the attached production sodium acetate of Sucralose |
| CN109575069A (en) * | 2018-12-10 | 2019-04-05 | 安徽金禾实业股份有限公司 | The recovery method of catalyst in a kind of production of Sucralose |
| CN109734755A (en) * | 2018-12-28 | 2019-05-10 | 山东三和维信生物科技有限公司 | A kind of Sucralose crystallization processes |
| CN112495442A (en) * | 2020-12-02 | 2021-03-16 | 安徽金禾实业股份有限公司 | Method for recycling and preparing organic tin catalyst in sucrose-6-ethyl ester production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034551A (en) * | 1990-04-23 | 1991-07-23 | Noramco, Inc. | Process for recovery of organotin esters from reaction mixtures containing the same and re-use of the recovered organotin compounds |
| EP0454386A1 (en) * | 1990-04-23 | 1991-10-30 | McNEIL-PPC, INC. | Sucrose-6-ester production process |
| CN1528772A (en) * | 2003-10-01 | 2004-09-15 | 常州市牛塘化工厂 | Method for preparing sucrose-6-ethyl ester |
| US20060205936A1 (en) * | 2005-03-14 | 2006-09-14 | Sl Laboratories, Llc | Chlorination of Sucrose-6-esters |
-
2013
- 2013-01-21 CN CN2013100211614A patent/CN103130843A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034551A (en) * | 1990-04-23 | 1991-07-23 | Noramco, Inc. | Process for recovery of organotin esters from reaction mixtures containing the same and re-use of the recovered organotin compounds |
| EP0454386A1 (en) * | 1990-04-23 | 1991-10-30 | McNEIL-PPC, INC. | Sucrose-6-ester production process |
| CN1528772A (en) * | 2003-10-01 | 2004-09-15 | 常州市牛塘化工厂 | Method for preparing sucrose-6-ethyl ester |
| US20060205936A1 (en) * | 2005-03-14 | 2006-09-14 | Sl Laboratories, Llc | Chlorination of Sucrose-6-esters |
Non-Patent Citations (2)
| Title |
|---|
| 王小玲，王健祥: "有机锡酯化合成三氯蔗糖研究", 《天津化工》, vol. 22, no. 3, 31 May 2008 (2008-05-31), pages 32 - 34 * |
| 韦异，等: "蔗糖-6-乙酸酯的合成方法研究", 《化学世界》, no. 10, 31 December 2002 (2002-12-31), pages 551 - 555 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601665A (en) * | 2015-12-30 | 2016-05-25 | 浙江新和成股份有限公司 | Treatment method of dibutyltin oxide and application of treatment method to synthesis of cane sugar-6-ethyl ester |
| CN105601665B (en) * | 2015-12-30 | 2018-07-17 | 浙江新和成股份有限公司 | A kind of processing method of Dibutyltin oxide and its application in sucrose-6-ethyl ester synthesis |
| CN105601689A (en) * | 2016-03-04 | 2016-05-25 | 李云军 | Cane sugar stanizing method |
| CN105646605A (en) * | 2016-03-04 | 2016-06-08 | 李云军 | Esterification method of cane sugar |
| CN109503361A (en) * | 2018-12-10 | 2019-03-22 | 安徽金禾实业股份有限公司 | Organotin extracting method and device in the attached production sodium acetate of Sucralose |
| CN109575069A (en) * | 2018-12-10 | 2019-04-05 | 安徽金禾实业股份有限公司 | The recovery method of catalyst in a kind of production of Sucralose |
| CN109503361B (en) * | 2018-12-10 | 2022-03-29 | 安徽金禾实业股份有限公司 | Method and device for extracting organic tin from sodium acetate as byproduct of sucralose |
| CN109734755A (en) * | 2018-12-28 | 2019-05-10 | 山东三和维信生物科技有限公司 | A kind of Sucralose crystallization processes |
| CN112495442A (en) * | 2020-12-02 | 2021-03-16 | 安徽金禾实业股份有限公司 | Method for recycling and preparing organic tin catalyst in sucrose-6-ethyl ester production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130843A (en) | Method of recycling and reusing of dibutyltin oxide in process of cane sugars manufacturing cane suger-6-ethyl ester | |
| CN102875493B (en) | The method of epoxy aliphatic acid methyl ester is prepared in Continuous Flow micro passage reaction | |
| CN103044329B (en) | Preparation method of high-yield and high-purity celecoxib | |
| CN103570568A (en) | Clean production process of glycine in coproduction with ammonium chloride | |
| CN104725315A (en) | Method used for preparing solvent red 149 | |
| CN104649970A (en) | Method for directly synthesizing organic luminous material, namely 8-hydroxyquinoline zinc | |
| CN103539747A (en) | Preparation method of 4,6-dichloropyrimidine | |
| CN104086466A (en) | Preparation method of 2-chloro-4-methylsulfonylbenzoic acid | |
| CN204303239U (en) | A kind ofly promote the chemical experiment device that Synthesis Diethyl ether reaction forward is carried out | |
| CN102659088A (en) | Water-phase synthesis method of sodium azide | |
| CN102992949B (en) | Industrialized recycling method for o-chlorobenzaldehyde residual liquor | |
| CN105481717A (en) | Preparation method for cyanoacetic acid and derivatives thereof | |
| CN107118088A (en) | A kind of preparation method of m-hydroxy acetophenone | |
| CN104829525B (en) | A kind of continuous reaction produces the method for the chloro-nicotinonitrile of 2- | |
| CN103626791B (en) | A kind of method of synthesizing 3-amino-4-fluorobenzoic boric acid | |
| CN104230764A (en) | Preparation method of 2-acrylamide-2-methyl propanesulfonic acid | |
| CN112239415B (en) | Synthesis method of alpha-cyano-sodium benzoate | |
| CN104693019B (en) | Method for preparing 2, 5-dibromo-benzene acetic acid | |
| CN102766054B (en) | Industrial synthesizing and purifying method of bis (4-nitrophenyl) carbonate | |
| CN103772151A (en) | Preparation method of 2-methyl-3-phenyl benzyl alcohol | |
| CN103304405B (en) | A kind of method of selective chlorination | |
| CN103435464B (en) | Preparation method of diphenylethanone | |
| CN103739494B (en) | The method of High-efficient Production triethylene glycol dibenzoate | |
| CN102766053A (en) | Production method of 3-fluoro-4-nitrophenol | |
| CN110845352A (en) | Synthetic method of p-acetamido benzoic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130605 |