WO2022233040A1 - 一种三氯蔗糖-6-乙酯提纯方法 - Google Patents

一种三氯蔗糖-6-乙酯提纯方法 Download PDF

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WO2022233040A1
WO2022233040A1 PCT/CN2021/092168 CN2021092168W WO2022233040A1 WO 2022233040 A1 WO2022233040 A1 WO 2022233040A1 CN 2021092168 W CN2021092168 W CN 2021092168W WO 2022233040 A1 WO2022233040 A1 WO 2022233040A1
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sucralose
ethyl ester
extraction
mother liquor
water
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PCT/CN2021/092168
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English (en)
French (fr)
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郑学连
王东
陈永乐
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安徽金禾实业股份有限公司
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Priority to PCT/CN2021/092168 priority Critical patent/WO2022233040A1/zh
Priority to CN202180001115.0A priority patent/CN113366006B/zh
Priority to EP21939686.8A priority patent/EP4335857A4/en
Publication of WO2022233040A1 publication Critical patent/WO2022233040A1/zh
Priority to US18/386,643 priority patent/US20240067671A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/04—Disaccharides

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  • the invention relates to the technical field of sugar making industry, in particular to a method for purifying sucralose-6-ethyl ester.
  • the chlorinated neutralization liquid obtained in the chlorination section contains impurities such as trichloroethane and dimethylformamide (DMF), which need to be removed by extraction with white oil.
  • White oil is a mixture of liquid hydrocarbons, mainly a mixture of saturated naphthenes and saturated paraffins, obtained from petroleum refining, or obtained from crude oil by atmospheric and vacuum fractionation, solvent extraction, dewaxing, and hydrorefining.
  • Industrial standards such as "NB/SH/T 0006-2017 Industrial White Oil”.
  • sucralose-6-ethyl ester the product of the high-temperature chlorination section of sucralose, needs to be boiled once after the white oil extraction, and a small amount of residual trichloroethane is removed by negative pressure, and then ethyl acetate is used. Carry out multiple crystallizations, then dissolve, decolorize, deesterify, crystallize by cooling, and centrifuge to obtain sucralose-6-ethyl ester fine products, as described in Chinese patent CN109180748A.
  • Secondary boiling step taking the boiled and negative pressure treated sucralose-6-ethyl ester mother liquor, adding a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor, fully stirring and heating for boiling, After stirring for a preset time, solid-liquid separation is performed to obtain a secondary boiled mother liquor in which sucralose-6-ethyl ester is dissolved;
  • Phase separation extraction step the secondary boiled mother liquor is left to stand for phase separation, the upper phase after the phase separation is taken, and the alkane extractant is used for extraction at a preset temperature to remove the residual white oil in the upper phase;
  • Recrystallization and purification step the lower layer effluent obtained after extraction is evaporated to obtain a solid, and the solid is purified by recrystallization to obtain sucralose-6-ethyl ester;
  • Recovery cycle step separate the upper effluent after extraction, recover the alkane extractant and recycle it to the phase separation extraction step for use.
  • the heating temperature is 40-90° C.
  • the stirring rate is 200-400 r/min
  • the stirring time is 0.5-2 h.
  • adding a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor including:
  • the predetermined proportion of water is gradually added with stirring.
  • the water content in the obtained sucralose-6-ethyl ester mother liquor after boiling and negative pressure treatment is 30-90 wt%.
  • adding a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor including:
  • the alkane extractant used is one or more of cyclopentane, n-hexane, cyclohexane, isohexane, n-heptane, cycloheptane and isoheptane .
  • the feed volume ratio of the upper phase after separation of the mother liquor to the alkane extractant is 1:0.2-1, and the extraction temperature is 20-40°C.
  • the solid is purified by recrystallization to obtain sucralose-6-ethyl ester, including:
  • the solid was recrystallized using ethyl acetate to obtain sucralose-6-ethyl ester.
  • the upper phase after the phase-separation is taken, and the extraction is carried out using an alkane extractant at a preset temperature, including:
  • the upper phase after phase separation enters from the upper edge of the extraction column, and the alkane extractant enters from the lower edge of the extraction column to extract in the extraction column.
  • the method further includes:
  • the solid substance obtained by the solid-liquid separation in the secondary water boiling step is recovered, and used as a raw material to be subjected to secondary water boiling with the sucralose-6-ethyl ester mother liquor again.
  • the mother liquor of the chlorination section after the white oil extraction is subjected to secondary boiling with water, after solid-liquid separation, static phase separation is performed, and the upper phase is extracted with alkane.
  • the solid residue in the mother liquor is removed and impurities such as tar at the bottom are precipitated, and the trace amount of white oil remaining in the mother liquor is removed at the same time, and finally sucralose-6-ethyl ester crystals with higher purity are obtained by separation and recrystallization.
  • the method is simple and efficient, the obtained sucralose-6-ethyl ester crystals have almost no white oil residue, and the white oil removal process is only boiled and extracted, and does not involve the crystallization process, which can reduce the crystallization times of the later crystallization process and reduce The amount of solvent used can improve the quality of the final product sucralose, and has high industrial application value.
  • Fig. 1 is a kind of sucralose-6-ethyl ester purification method step flow chart provided for an embodiment of the application;
  • Fig. 2 is a kind of sucralose-6-ethyl ester purification method process flow diagram provided for an embodiment of the application;
  • E-1 mixing kettle
  • H-1 solid-liquid separator
  • E-2 liquid phase separator
  • E-3 extraction tower
  • E-4 evaporator
  • E-5 solvent recovery tower.
  • the final product is still mixed with a small amount of white oil, which may be caused by three reasons: 1. In the process of white oil extraction of trichloroethane and dimethylformamide , due to the coating of the solid, the trichloroethane and DMF contained in the undissolved sucralose-6-ethyl ester solid crude product entrained a trace amount of white oil; 2. During the phase separation process, it may be due to equipment or operational problems , causing part of the white oil to be mixed in the aqueous phase of sucralose-6-ethyl ester in the form of droplets; 3.
  • the present application proposes a method for purifying sucralose-6-ethyl ester.
  • the technical concept of the present application is: in the purification process, the mother liquor of the chlorination section after the white oil extraction is subjected to secondary boiling with water, after the solid-liquid separation, it is left to stand for phase separation, and the upper phase is subjected to alkane extraction, and after such treatment , which can remove the solid residue in the mother liquor and separate out impurities such as tar at the bottom, and at the same time remove the trace white oil remaining in the mother liquor, and finally obtain sucralose-6-ethyl ester crystals with higher purity through separation and recrystallization.
  • the sucralose-6-ethyl ester purification method of the present application is simple and efficient, the sucralose-6-ethyl ester crystals obtained by crystallization have almost no white oil residue, and the white oil removal process is only boiling and extraction, and does not involve crystallization
  • the process can reduce the crystallization times of the later crystallization process, reduce the use amount of the solvent, improve the quality of the final product sucralose, and has high industrial application value.
  • FIG. 1 shows a schematic embodiment of the method for purifying sucralose-6-ethyl ester of the present application, wherein, in the chlorination section of the preparation process of the sucralose-6-ethyl ester, white oil is used as the extractant, so
  • the methods described include:
  • Secondary boiling step S110 take the boiled and negative pressure treated sucralose-6-ethyl ester mother liquor, add a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor, fully stir and heat for boiling , after stirring for a preset time, solid-liquid separation is performed to obtain a secondary boiled mother liquor in which sucralose-6-ethyl ester is dissolved.
  • the sucralose-6-ethyl ester mother liquor obtained in the chlorination section is a solid-liquid mixture.
  • Phase-separation extraction step S120 the secondary boiled mother liquor is left to stand for phase separation, the upper phase after the phase separation is taken, and the alkane extractant is used for extraction at a preset temperature, and the residual white oil in the upper phase is removed to overcome the traditional process. Effects of medium and trace amounts of white oil.
  • Recrystallization and purification step S130 Evaporate the lower layer effluent obtained after extraction to obtain a solid, which is the crude sucralose-6-ethyl ester after removing the white oil impurities, and recrystallization and purification is performed on the solid to obtain three. Sucralose-6-ethyl ester.
  • Recycling step S140 separate the extracted upper effluent, recover the alkane extractant, and recycle it to the phase-separating extraction step for use. Through the recovery step, the present application realizes the recycling of the extraction agent, and further reduces the production cost and the environmental cost.
  • the boiling heating temperature is 40-90° C.
  • the stirring rate is 200-400 r/min
  • the stirring and boiling time is 0.5-2 h.
  • the adding a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor includes: gradually adding the predetermined proportion with stirring proportion of water.
  • adding a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor includes: adding a predetermined proportion of water to the sucralose-6-ethyl ester mother liquor Water whose mass is 5-90% of the mass of the sucralose-6-ethyl ester mother liquor is added.
  • the effective pretreatment of impurities in the sucralose-6-ethyl ester mother liquor can be realized, and the phase separation accuracy of the sucralose-6-ethyl ester mother liquor can be improved.
  • the degree of extraction and separation of white oil it provides a basis for removing trace white oil and preparing products with higher purity.
  • the water content in the obtained sucralose-6-ethyl ester mother liquor after boiling and negative pressure treatment is 30-90 wt%.
  • the alkane extraction agent used is cyclopentane, n-hexane, cyclohexane, isohexane, n-heptane, cycloheptane and isoheptane one or more of.
  • alkanes such as cyclopentane, n-hexane, cyclohexane, isohexane, n-heptane, cycloheptane and isoheptane can fully extract the trace white oil in the upper phase after phase separation, and do not introduce Updated impurities.
  • the feed volume ratio of the upper phase after separation of the mother liquor to the alkane extractant is 1:0.2-1, and the extraction temperature is 20-40 °C.
  • the extraction of the upper phase after the phase separation is carried out by using an alkane extractant at a preset temperature, including: entering the upper phase after the phase separation from the upper edge of the extraction column.
  • the alkane extractant enters from the lower edge of the extraction column and is extracted in the extraction column.
  • the solid in the recrystallization and purification step S130, is purified by recrystallization to obtain sucralose-6-ethyl ester, including: using ethyl acetate to recrystallize the solid, Obtain sucralose-6-ethyl ester.
  • the method further includes: recovering the solid substance obtained by the solid-liquid separation in the secondary boiling step S110, and using it as a raw material again with the sucralose-6-ethyl ester mother liquor. Boil twice. Because the solid is mainly undissolved sucralose-6-ethyl ester, it can be recovered as a raw material after filtration, so that the output of the final product can be improved.
  • Fig. 2 is the process flow diagram of the schematic embodiment of the purification method of sucralose-6-ethyl ester of the present application.
  • the solid-liquid separator H-1, the liquid phase separator E-2, the evaporator E-4 and the solvent recovery tower E-5 are all conventional towers, and the operating parameters of the above towers are not regarded as special features of the present invention. place.
  • Figure 2 a brief description of the process in the embodiment of the method of the present application is made:
  • the sucralose-6-ethyl ester mother liquor of boiling water and removing trichloroethane under negative pressure is selected as the raw material, and then,
  • the mother liquor is discharged into the lower phase brown tar after the liquid phase separator E-2 is left standing for stratification, and the upper phase enters the upper edge of the extraction tower E-3;
  • the extraction agent alkane enters from the lower edge of the extraction tower, and the two are in a certain proportion , extracting at a certain temperature, after the extraction is completed, the sucralose-6-ethyl ester aqueous solution without white oil is produced at the bottom of the tower, and the alkane mixed liquid (containing the extracted white oil) is produced at the top of the tower;
  • the purification method of the present application is beneficial to improve the purity of sucralose-6-ethyl ester, thereby facilitating the next step reaction and ensuring the quality of the final product sucralose; moreover, the purification method of the present application can effectively remove white oil, reduce The number of crystallization in the later stage can reduce solvent consumption and reduce production cost; at the same time, the method can also remove impurities such as high polymers in the raw materials at the same time, so as to improve product quality and recrystallization efficiency; Reduce the generation of waste water and effectively reduce the pressure on environmental protection.
  • sucralose-6-ethyl ester is obtained by sucralose esterification, chlorination and crystallization in the sucralose production process, and its purity is detected by high performance liquid chromatography (analysis and determination conditions of high performance liquid chromatography: Japan Island Jin high performance liquid chromatograph equipped with RID-10A differential refractive index detection, LC-10ADVP high pressure pump, CTO-10ASVP incubator; chromatographic column: Agilent XDB C18 column (250mm ⁇ 4.6mm, 5 ⁇ m); mobile phase: methanol-ultra pure Water (4.5:5.5); column temperature: 45°C; flow rate: 1.0 mL/min.
  • high performance liquid chromatography analysis and determination conditions of high performance liquid chromatography: Japan Island Jin high performance liquid chromatograph equipped with RID-10A differential refractive index detection, LC-10ADVP high pressure pump, CTO-10ASVP incubator; chromatographic column: Agilent XDB C18 column (250mm ⁇ 4.6mm, 5 ⁇ m); mobile phase: methanol-ultra pure Water (4.5
  • methanol chromatographically pure
  • ultrapure water each standard substance
  • external standard method are required to measure the content.
  • the raw materials such as cyclopentane, n-hexane, cyclohexane, isohexane, n-heptane, cycloheptane, and isoheptane used in each embodiment have a purity greater than 99% and are commercially available.
  • the untreated white oil used as a comparison in each embodiment is a blank comparison group that has not undergone the secondary boiling of the present invention and its subsequent phase-separation extraction steps, etc.
  • the sucralose-6-ethyl ester aqueous solution without white oil is extracted from the bottom of the tower, and the alkane mixed liquid is extracted from the top of the tower; the extracted liquid from the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained
  • the solid is cooled and recrystallized twice through ethyl acetate, and the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 1.
  • the white oil impurities are significantly reduced, which overcomes the influence of trace white oil on the subsequent sugar industry, and does not require
  • the use of more solvents for multiple recrystallizations effectively reduces the amount of solvent used and the number of times of crystallization, and reduces production costs and environmental costs.
  • the sucralose-6-ethyl ester aqueous solution without white oil is extracted from the bottom, and the alkane mixed liquid is extracted from the top of the tower; the extracted liquid from the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is passed through ethyl acetate twice. Cooling and recrystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 2.
  • the 3t sucralose-6-ethyl ester mother liquor with a water content of 50% was added to the mixing kettle E-1, heated and boiled at 55°C, and 65% of the mother liquor mass was added at a stirring speed of 250r/min, and stirred thoroughly. After stirring for 1.5h, it is separated by solid-liquid separator H-1, the solid is returned to mixing kettle E-1, and the mother liquor enters liquid phase separator E-2 to stand; The brown tar in the lower phase is removed, and the upper phase enters the upper edge of the extraction tower E-3; the extraction agent isoheptane enters from the lower edge of the extraction tower, and the ratio of the two is 1:0.8.
  • sucralose-6-ethyl ester aqueous solution without white oil is extracted from the bottom, and the alkane mixed liquid is extracted from the top of the tower; the extracted liquid from the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is passed through ethyl acetate twice. Cooling and recrystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 3.
  • sucralose-6-ethyl ester aqueous solution that does not contain white oil is produced, and the alkane mixed liquid is produced from the top of the tower; the produced liquid from the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is cooled twice by ethyl acetate. Crystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 4.
  • the 1.5t sucralose-6-ethyl ester mother liquor with a water content of 70% was added to the mixing kettle E-1, boiled at 85°C, and 25% of the mother liquor mass was added at a stirring rate of 350r/min, and stirred thoroughly. After stirring for 0.5h, it is separated by the solid-liquid separator H-1, the solid is returned to the mixing kettle E-1, and the mother liquor enters the liquid phase separator E-2 to stand; Drain the lower phase brown tar, the upper phase enters the upper edge of the extraction tower E-3; the extraction agent n-hexane enters from the lower edge of the extraction tower, the ratio of the two is 1:0.2, and the extraction is carried out at a temperature of 20 °C.
  • the sucralose-6-ethyl ester aqueous solution without white oil is produced, and the alkane mixed liquid is produced at the top of the tower; the produced liquid at the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is cooled twice by ethyl acetate Recrystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 5.
  • sucralose-6-ethyl ester mother liquor with a water content of 80% into mixing kettle E-1, heat and boil at 75°C, add 10% of the mother liquor mass at a stirring speed of 300r/min, and stir well. After stirring for 2h, it is separated by solid-liquid separator H-1, the solid is returned to mixing kettle E-1, and the mother liquor enters liquid phase separator E-2 to stand; The lower phase brown tar is removed, and the upper phase enters the upper edge of the extraction tower E-3; the extraction agent n-heptane enters from the lower edge of the extraction tower, and the ratio of the two is 1:0.3.
  • the sucralose-6-ethyl ester aqueous solution without white oil is produced, and the alkane mixed liquid is produced at the top of the tower; the produced liquid at the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is cooled twice by ethyl acetate Recrystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 6.
  • the 2.5t sucralose-6-ethyl ester mother liquor with a water content of 90% was added to the mixing kettle E-1, boiled at 60°C, and 5% of the mother liquor mass was added at a stirring speed of 400r/min, and stirred thoroughly. After stirring for 1 hour, it is separated by solid-liquid separator H-1, the solid is returned to mixing kettle E-1, and the mother liquor enters liquid phase separator E-2 to stand; The lower phase brown tar is removed, and the upper phase enters the upper edge of the extraction tower E-3; the extraction agent cyclopentane enters from the lower edge of the extraction tower, and the ratio of the two is 1:0.2.
  • the sucralose-6-ethyl ester aqueous solution without white oil is produced, and the alkane mixed liquid is produced at the top of the tower; the produced liquid at the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is cooled twice by ethyl acetate Recrystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 7.
  • the 3.5t sucralose-6-ethyl ester mother liquor with a water content of 55% was added to the mixing kettle E-1, heated and boiled at 80°C, and 25% of the mother liquor mass was added at a stirring speed of 200r/min, and stirred thoroughly. After stirring for 1.5h, it is separated by solid-liquid separator H-1, the solid is returned to mixing kettle E-1, and the mother liquor enters liquid phase separator E-2 to stand; The brown tar in the lower phase is removed, and the upper phase enters the upper edge of the extraction tower E-3; the extraction agent cycloheptane enters from the lower edge of the extraction tower, and the ratio of the two is 1:1.
  • the sucralose-6-ethyl ester aqueous solution without white oil is extracted from the bottom, and the alkane mixed liquid is extracted from the top of the tower; the extracted liquid from the bottom of the extraction tower enters the evaporator E-4 for evaporation, and the obtained solid is passed through ethyl acetate twice. Cooling and recrystallization, the obtained product detects the content of sucralose-6-ethyl ester, white oil and other components, and the specific results are shown in Table 8.
  • the method of the present application can significantly remove the white oil in the sucralose-6-ethyl ester product, effectively improve the purity of the sucralose-6-ethyl ester, thereby overcoming the effect of residual white oil on three
  • the influence of the sucralose sugar making process improves the quality of the final product sucralose, and the method is simple and efficient, it can be realized without large-scale changes to the original process and equipment, the production cost and environmental cost are low, and the subsequent crystallization can also be controlled.
  • the complexity of the process is very simple and efficient, it can be realized without large-scale changes to the original process and equipment, the production cost and environmental cost are low, and the subsequent crystallization can also be controlled. The complexity of the process.

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Abstract

本发明公开了一种三氯蔗糖-6-乙酯提纯方法，方法包括：二次水煮步骤：取水煮并负压处理后的三氯蔗糖-6-乙酯母液，向三氯蔗糖-6-乙酯母液中加入预定比例的水，充分搅拌并加热水煮，搅拌水煮预设时间后，固液分离获得溶有三氯蔗糖-6-乙酯的二次水煮母液；分相萃取步骤：将二次水煮母液静置分相，取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，去除上相中的残留白油；重结晶提纯步骤：将萃取后得到的下层流出物蒸发，得到固体，固体通过重结晶提纯，获取三氯蔗糖-6-乙酯；回收循环步骤：将萃取后的上层流出物进行分离，回收烷烃萃取剂并循环到分相萃取步骤使用。本方法简单高效，成本低，可以有效去除微量白油，提高三氯蔗糖-6-乙酯的纯度。

Description

一种三氯蔗糖-6-乙酯提纯方法 技术领域
本发明涉及制糖工业技术领域，特别涉及一种三氯蔗糖-6-乙酯提纯方法。
发明背景
在三氯蔗糖生产工艺中，氯化工段得到的氯化中和液含有三氯乙烷和二甲基甲酰胺(DMF)等杂质，需要用白油萃取去除。白油，是液态烃的混合物，主要为饱和环烷烃与饱和链烷烃的混合物，由石油精炼所得，或者由原油经常压和减压分馏、溶剂抽提、脱蜡、加氢精制而得，相关工业化标准如《NB/SH/T 0006-2017工业白油》。
传统工艺中，三氯蔗糖高温氯化工段的产品三氯蔗糖-6-乙酯在白油萃取后还需要进行一次水煮，并负压去除残留的少量三氯乙烷，再用乙酸乙酯进行多次结晶，继而溶解，脱色，脱酯，降温结晶，离心得到三氯蔗糖-6-乙酯精品，如中国专利CN109180748A所述。但是，生产中发现，经过白油萃取后，上述方法中加工制得的三氯蔗糖-6-乙酯精品中会残留微量的白油，影响了后续三氯蔗糖产品的质量，因而，还需要对三氯蔗糖-6-乙酯精品进行多次重结晶才能除去微量白油。从而，因氯代工段萃取引入的微量白油，造成了三氯蔗糖-6-乙酯产品提纯过程中增加了溶剂的使用量，并对生产及环境造成了一定的负担及影响。
目前，关于专门针对三氯蔗糖-6-乙酯产品中去除白油的方法鲜见报道，可见的关于提纯三氯蔗糖-6-乙酯的报道，如CN101328195、CN101709069等，通常只是使用酯等溶剂通过结晶提纯三氯蔗糖-6-乙酯，如常用的乙酸乙酯、乙酸丁酯等，在效果上始终无法避免白油的夹杂。
发明内容
鉴于现有技术三氯蔗糖制糖工艺中白油残留的问题，提出了本申请的一种三氯蔗糖-6-乙酯提纯方法，以便克服上述问题。
为了实现上述目的，本申请采用了如下技术方案：
一种三氯蔗糖-6-乙酯提纯方法，所述三氯蔗糖-6-乙酯的制备过程氯化工段使用白油作为萃取剂，所述方法包括：
二次水煮步骤：取水煮并负压处理后的三氯蔗糖-6-乙酯母液，向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，充分搅拌并加热水煮，搅拌预设时间后，固液分离获得溶有三氯蔗糖-6-乙酯的二次水煮母液；
分相萃取步骤：将二次水煮母液静置分相，取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，去除上相中的残留白油；
重结晶提纯步骤：将萃取后得到的下层流出物蒸发，得到固体，所述固体通过重结晶提纯，获取三氯蔗糖-6-乙酯；
回收循环步骤：将萃取后的上层流出物进行分离，回收烷烃萃取剂并循环到分相萃取步骤使用。
可选地，所述二次水煮步骤中，加热温度为40～90℃，搅拌速率为200～400r/min，搅拌时间为0.5～2h。
可选地，所述二次水煮步骤中，所述向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，包括：
随搅拌进行逐渐加入所述预定比例的水。
可选地，所述二次水煮步骤中，取得的水煮并负压处理后的三氯蔗糖-6-乙酯母液中，水含量为30～90wt％。
可选地，所述二次水煮步骤中，所述向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，包括：
向所述三氯蔗糖-6-乙酯母液中加入质量为所述三氯蔗糖-6-乙酯母液质量5～90％的水。
可选地，所述分相萃取步骤中，所用的烷烃萃取剂为环戊烷、正己烷、环己烷、异己烷、正庚烷、环庚烷和异庚烷中的一种或多种。
可选地，所述分相萃取步骤中，所述母液分离后的上相与所述烷烃萃取剂的进料体积比为1：0.2～1，萃取温度为20～40℃。
可选地，所述重结晶提纯步骤中，所述固体通过重结晶提纯，获取三氯蔗糖-6-乙酯，包括：
使用乙酸乙酯对所述固体进行重结晶，获取三氯蔗糖-6-乙酯。
可选地，所述分相萃取步骤中，所述取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，包括：
将分相后的上相从萃取塔的上沿进入，将烷烃萃取剂从萃取塔的下沿进入，在萃取塔内萃取。
可选地，所述方法还包括：
将所述二次水煮步骤中固液分离得到的固体物质回收，作为原料再次与所述三氯蔗糖-6-乙酯母液进行二次水煮。
综上所述，本申请的有益效果是：
本发明的提纯方法，在纯化过程中将白油萃取后的氯化工段母液进行加水二次水煮，固液分离后，静止分相，并对上相进行烷烃萃取，经过这样的处理，可去除母液中的固体残渣并析出底部焦油等杂质，同时去除母液中残留的微量白油，最终通过分离和重结晶，得到纯度更高的三氯蔗糖-6-乙酯晶体。该方法简单高效，获得的三氯蔗糖-6-乙酯晶体几乎无白油残留，且白油的去除过程仅为水煮和萃取，不涉及结晶过程，可以减少后期结晶工艺的结晶次数，降低溶剂的使用量，提高最终产品三氯蔗糖的品质，具有较高的工业应用价值。
附图简要说明
图1为本申请一个实施例提供的一种三氯蔗糖-6-乙酯提纯方法步骤流程图；
图2为本申请一个实施例提供的一种三氯蔗糖-6-乙酯提纯方法工艺流程图；
图中；E-1、混合釜；H-1、固液分离器；E-2、液相分离器；E-3、萃取塔；E-4、蒸发器；E-5、溶剂回收塔。
实施本发明的方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合附图对本申请实施方式作进一步地详细描述。
在传统的三氯蔗糖-6-乙酯纯化过程中，最终产品仍夹杂微量白油，可能是三个方面的原因导致：1、在白油萃取三氯乙烷及二甲基甲酰胺过程中，由于固体的包覆作用，未溶解的三氯蔗糖-6-乙酯固体粗品内含有的三氯乙烷和DMF夹带了微量的白油；2、在相分离过程中可能因设备或操作问题，导致部分白油以液滴形式夹杂在三氯蔗糖-6-乙酯水相中；3、前期处理后，三氯蔗糖-6-乙酯粗品中仍残留大量三氯乙烷与DMF，溶解白油后形成了两相分配。因此，传统制糖工艺中，对白油萃取后的母液进行精制，以制取三氯蔗糖-6-乙酯晶体的方法，不能克服微量白油的影响，因而需要较多的重结晶工艺，溶剂成本和环境成本较高。
由此，本申请提出了一种三氯蔗糖-6-乙酯提纯方法。本申请的技术构思是： 在纯化过程中将白油萃取后的氯化工段母液进行加水二次水煮，固液分离后，静置分相，并对上相进行烷烃萃取，经过这样的处理，可去除母液中的固体残渣并析出底部焦油等杂质，同时去除母液中残留的微量白油，最终通过分离和重结晶，得到纯度更高的三氯蔗糖-6-乙酯晶体。
本申请的三氯蔗糖-6-乙酯提纯方法简单高效，结晶获得的三氯蔗糖-6-乙酯晶体几乎无白油残留，且白油的去除过程仅为水煮和萃取，不涉及结晶过程，可以减少后期结晶工艺的结晶次数，降低溶剂的使用量，提高最终产品三氯蔗糖的品质，具有较高的工业应用价值。
图1示出了本申请三氯蔗糖-6-乙酯提纯方法的一个示意性实施例，其中，所述三氯蔗糖-6-乙酯的制备过程氯化工段使用白油作为萃取剂，所述方法包括：
二次水煮步骤S110：取水煮并负压处理后的三氯蔗糖-6-乙酯母液，向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，充分搅拌并加热水煮，搅拌预设时间后，固液分离获得溶有三氯蔗糖-6-乙酯的二次水煮母液。其中，氯代工段所得的三氯蔗糖-6-乙酯母液为固液混合物，本申请通过加水并加热，可以提高三氯蔗糖-6-乙酯在母液中的溶解度，以克服常温下三氯蔗糖-6-乙酯在水中溶解度不高的问题，同时，通过加热水煮，也能使焦油等杂质从母液中更好分离。
分相萃取步骤S120：将二次水煮母液静置分相，取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，去除上相中的残留白油，以克服传统工艺中微量白油的影响。
重结晶提纯步骤S130：将萃取后得到的下层流出物蒸发，得到固体，该固体即为去除白油杂质后的三氯蔗糖-6-乙酯粗品，对所述固体进行重结晶提纯，获取三氯蔗糖-6-乙酯。
回收循环步骤S140：将萃取后的上层流出物进行分离，回收烷烃萃取剂并循环到分相萃取步骤使用。通过回收步骤，本申请实现了萃取剂的循环使用，进一步降低了生产成本和环境成本。
在本申请的一些实施例中，所述二次水煮步骤S110中，水煮加热温度为40～90℃，搅拌速率为200～400r/min，搅拌水煮时间为0.5～2h。通过二次水煮，可以更好地析出底部焦油类杂质，并有利于后续步骤中对母液的分层分离和白油萃取。
在本申请的一些实施例中，所述二次水煮步骤S110中，所述向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，包括：随搅拌进行逐渐加入所述预定比例的水。
更优选地，所述二次水煮步骤S110中，所述向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，包括：向所述三氯蔗糖-6-乙酯母液中加入质量为所述三氯蔗糖-6-乙酯母液质量5～90％的水。
通过如上实施例对加热温度、用水量和水煮搅拌时间的控制，可以实现三氯蔗糖-6-乙酯母液中杂质的有效预处理，提高三氯蔗糖-6-乙酯母液的分相精度以及白油萃取分离程度，为去除微量白油、制备纯度更高的产品提供基础。
在本申请的一些实施例中，所述二次水煮步骤S110中，取得的水煮并负压处理后的三氯蔗糖-6-乙酯母液中，水含量为30～90wt％。
在本申请的一个实施例中，所述分相萃取步骤S120中，所用的烷烃萃取剂为环戊烷、正己烷、环己烷、异己烷、正庚烷、环庚烷和异庚烷中的一种或多种。其中，环戊烷、正己烷、环己烷、异己烷、正庚烷、环庚烷和异庚烷等烷烃，可以对分相后上相中的微量白油实现充分的萃取，且不引入更新的杂质。
在本申请的一些实施例中，所述分相萃取步骤S120中，所述母液分离后的上相与所述烷烃萃取剂的进料体积比为1：0.2～1，萃取温度为20～40℃。
具体地，所述分相萃取步骤S120中，所述取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，包括：将分相后的上相从萃取塔的上沿进入，将烷烃萃取剂从萃取塔的下沿进入，在萃取塔内萃取。
在本申请的一些实施例中，所述重结晶提纯步骤S130中，所述固体通过重结晶提纯，获取三氯蔗糖-6-乙酯，包括：使用乙酸乙酯对所述固体进行重结晶，获取三氯蔗糖-6-乙酯。
在本申请的一些实施例中，所述方法还包括：将所述二次水煮步骤S110中固液分离得到的固体物质回收，作为原料再次与所述三氯蔗糖-6-乙酯母液进行二次水煮。因所述固体主要为未溶解的三氯蔗糖-6-乙酯，通过过滤后重新作为原料回收，可以提高最终产品的产量。
图2为本申请三氯蔗糖-6-乙酯提纯方法示意性实施例的工艺流程图。其中，固液分离器H-1、液相分离器E-2、蒸发器E-4和溶剂回收塔E-5等均为常规塔器，以上塔器的操作参数不作为本发明的特殊之处。结合图2所示，对本申请方法实施例工艺做简要说明：
首先，在氯化工段使用白油作为萃取剂的传统制糖工艺中，选取水煮并负压去除三氯乙烷的三氯蔗糖-6-乙酯母液为原料，进而，
(1)将母液加入混合釜E-1中，并加入少量水，充分搅拌，加热水煮；搅拌 一定时间后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；
(2)将母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂烷烃从萃取塔下沿进入，两者按一定比例，一定温度进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液(含萃取出的白油)；
(3)萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体去乙酸乙酯重结晶工段，得三氯蔗糖-6-乙酯精品晶体，蒸发出的冷凝水去污水处理；
(4)萃取塔塔顶采出的烷烃混合液进入溶剂回收塔E-5，溶剂回收塔塔顶采出烷烃返回萃取塔，塔底采出白油等杂质去处理。
通过本申请的提纯方法，有利于提高三氯蔗糖-6-乙酯的纯度，从而有利于下一步反应，确保最终产品三氯蔗糖的品质；而且，本申请提纯方法能够有效去除白油，减少后期结晶的次数，以减少溶剂消耗，降低生产成本；同时，本方法还能够同时去除原料中的高聚物等杂质，提高产品品质和重结晶效率；最后，通过降低结晶次数以及萃取剂回收，减少废水的产生，有效降低环保压力。
下文示出了应用本申请方法的一些实施例。
其中，三氯蔗糖-6-乙酯由三氯蔗糖生产工艺中经蔗糖酯化、氯化、结晶后获得，其纯度采用高效液相色谱仪检测(高效液相色谱的分析测定条件：日本岛津高效液相色谱仪，配RID-10A示差折光检测，LC-10ADVP高压泵，CTO-10ASVP恒温箱；色谱柱：Agilent XDB C18柱(250mm×4.6mm，5μm)；流动相：甲醇-超纯水(4.5：5.5)；柱温：45℃；流量：1.0mL/min。其中，需要甲醇(色谱纯)、超纯水，各标准物质，外标法测量含量)。各实施例中使用的环戊烷、正己烷、环己烷、异己烷、正庚烷、环庚烷、异庚烷等原料，纯度均大于99％，市售获取。
各实施例中作为对比的未处理白油是未进行本发明的二次水煮及其后续分相萃取步骤等的空白对比组，其处理过程为：对于传统工艺中仅经过一次水煮并负压去除残留三氯乙烷的三氯蔗糖-6-乙酯母液，不经过本申请的二次水煮和分相萃取步骤，只进行与对应实施例同样次数的重结晶提纯。
实施例1
将水含量为30％的1t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在40℃加热水煮，具体为，在300r/min搅拌速率下加入母液质量90％的水，充分搅拌。搅拌0.5h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静 置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3的上沿；将萃取剂环戊烷从萃取塔E-3的下沿进入，两者比例为1：0.5，在30℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表1。
表1处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 89.11 4.32 3.32 0.013 3.237
实施例1 89.23 5.10 2.11 0.001 3.559
由上述数据可以看出，采用本申请方法实施例1处理后制得的三氯蔗糖-6-乙酯，其中的白油杂质显著减少，克服了微量白油对于后续制糖工业的影响，无需使用更多的溶剂进行多次重结晶，有效降低了溶剂使用量和结晶次数，降低了生成成本和环境成本。
实施例2
将水含量为40％的2t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在90℃加热水煮，400r/min搅拌速率下加入母液质量80％的水，充分搅拌。搅拌0.5h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂环己烷从萃取塔下沿进入，两者比例为1：0.6，在25℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表2。
表2处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 86.47 5.08 3.97 0.021 4.459
实施例1 87.23 5.75 3.23 0.002 3.788
实施例3
将水含量为50％的3t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在55℃加热水煮，250r/min搅拌速率下加入母液质量65％的水，充分搅拌。搅拌1.5h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂异庚烷从萃取塔下沿进入，两者比例为1：0.8，在40℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表3。
表3处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 88.89 4.99 4.21 0.028 1.882
实施例1 90.45 5.16 3.57 0.001 0.819
实施例4
将水含量为60％的4t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在70℃加热水煮，200r/min搅拌速率下加入母液质量45％的水，充分搅拌。搅拌2h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂异己烷从萃取塔下沿进入，两者比例为1：1，在35℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表4。
表4处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 88.65 5.87 4.16 0.034 1.286
实施例1 90.38 6.00 3.01 0.002 0.608
实施例5
将水含量为70％的1.5t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在85℃加热水煮，350r/min搅拌速率下加入母液质量25％的水，充分搅拌。搅拌0.5h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂正己烷从萃取塔下沿进入，两者比例为1：0.2，在20℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表5。
表5处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 89.74 3.98 4.55 0.015 1.715
实施例1 92.03 5.02 2.09 0.001 0.859
实施例6
将水含量为80％的4.5t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在75℃加热水煮，300r/min搅拌速率下加入母液质量10％的水，充分搅拌。搅拌2h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂正庚烷从萃取塔下沿进入，两者比例为1：0.3，在20℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表6。
表6处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 89.33 3.99 5.43 0.017 1.233
实施例1 91.11 6.29 2.11 0.001 0.489
实施例7
将水含量为90％的2.5t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在60℃加热水煮，400r/min搅拌速率下加入母液质量5％的水，充分搅拌。搅拌1h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂环戊烷从萃取塔下沿进入，两者比例为1：0.2，在25℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表7。
表7处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 87.37 6.70 2.12 0.009 3.801
实施例1 88.80 7.22 1.93 0.001 2.049
实施例8
将水含量为55％的3.5t三氯蔗糖-6-乙酯母液加入混合釜E-1中，在80℃加热水煮，200r/min搅拌速率下加入母液质量25％的水，充分搅拌。搅拌1.5h后，经固液分离器H-1分离，固体返回混合釜E-1中，母液进入液相分离器E-2静置；母液在液相分离器E-2静置分层后排去下相褐色焦油，上相进入萃取塔E-3上沿；萃取剂环庚烷从萃取塔下沿进入，两者比例为1：1，在25℃温度下进行萃取，萃取完成后，塔底采出不含白油的三氯蔗糖-6-乙酯水溶液，塔顶采出烷烃混合液；萃取塔塔底采出液进入蒸发器E-4蒸发，得到的固体经乙酸乙酯两次降温重结晶，获得的产品检测三氯蔗糖-6-乙酯、白油及其他组分的含量，具体结果见表8。
表8处理与未处理白油时三氯蔗糖-6-乙酯纯度对比
项目 三氯蔗糖-6-乙酯/％ 水/％ 三氯乙烷/％ 白油/％ 其他/％
未处理白油 85.21 7.16 2.37 0.032 5.228
实施例1 87.39 7.87 1.93 0.002 2.808
综合上述实施例可以看出，本申请的方法，可以显著去除三氯蔗糖-6-乙酯产品中的白油，有效提高三氯蔗糖-6-乙酯的纯度，从而克服残留白油对三氯蔗糖制 糖工艺的影响，提高最终产品三氯蔗糖的品质，且方法简单高效，不需要对原有工艺和设备进行大规模改变即可实现，生产成本和环境成本低，也能够控制后续结晶工艺的复杂程度。
以上所述，仅为本发明的具体实施方式，在本发明的上述教导下，本领域技术人员可以在上述实施例的基础上进行其他的改进或变形。本领域技术人员应该明白，上述的具体描述只是更好的解释本发明的目的，本发明的保护范围应以权利要求的保护范围为准。

Claims (10)

  1. 一种三氯蔗糖-6-乙酯提纯方法，所述三氯蔗糖-6-乙酯的制备过程的氯化工段使用白油作为萃取剂，其特征在于，所述方法包括：
    二次水煮步骤：取水煮并负压处理后的三氯蔗糖-6-乙酯母液，向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，充分搅拌并加热水煮，搅拌水煮预设时间后，固液分离获得溶有三氯蔗糖-6-乙酯的二次水煮母液；
    分相萃取步骤：将二次水煮母液静置分相，取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，去除上相中的残留白油；
    重结晶提纯步骤：将萃取后得到的下层流出物蒸发，得到固体，所述固体通过重结晶提纯，获取三氯蔗糖-6-乙酯；
    回收循环步骤：将萃取后的上层流出物进行分离，回收烷烃萃取剂并循环到分相萃取步骤使用。
  2. 根据权利要求1所述的提纯方法，其特征在于，所述二次水煮步骤中，加热温度为40～90℃，搅拌速率为200～400r/min，搅拌水煮时间为0.5～2h。
  3. 根据权利要求1所述的提纯方法，其特征在于，所述二次水煮步骤中，所述向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，包括：
    随搅拌进行逐渐加入所述预定比例的水。
  4. 根据权利要求1所述的提纯方法，其特征在于，所述二次水煮步骤中，取得的水煮并负压处理后的三氯蔗糖-6-乙酯母液中，水含量为30～90wt％。
  5. 根据权利要求1所述的提纯方法，其特征在于，所述二次水煮步骤中，所述向所述三氯蔗糖-6-乙酯母液中加入预定比例的水，包括：
    向所述三氯蔗糖-6-乙酯母液中加入质量为所述三氯蔗糖-6-乙酯母液质量5～90％的水。
  6. 根据权利要求1所述的提纯方法，其特征在于，所述分相萃取步骤中，所用的烷烃萃取剂为环戊烷、正己烷、环己烷、异己烷、正庚烷、环庚烷和异庚烷中的一种或多种。
  7. 根据权利要求1所述的提纯方法，其特征在于，所述分相萃取步骤中，所述母液分离后的上相与所述烷烃萃取剂的进料体积比为1：0.2～1，萃取温度为20～40℃。
  8. 根据权利要求1所述的提纯方法，其特征在于，所述重结晶提纯步骤中，所 述固体通过重结晶提纯，获取三氯蔗糖-6-乙酯，包括：
    使用乙酸乙酯对所述固体进行重结晶，获取三氯蔗糖-6-乙酯。
  9. 根据权利要求1所述的提纯方法，其特征在于，所述分相萃取步骤中，所述取分相后的上相，在预设温度下使用烷烃萃取剂进行萃取，包括：
    将分相后的上相从萃取塔的上沿进入，将烷烃萃取剂从萃取塔的下沿进入，在萃取塔内萃取。
  10. 根据权利要求1所述的提纯方法，其特征在于，所述方法还包括：
    将所述二次水煮步骤中固液分离得到的固体物质回收，作为原料再次与所述三氯蔗糖-6-乙酯母液进行二次水煮。
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