WO2023279277A1 - 有机锡蔗糖配合物的制备方法 - Google Patents

有机锡蔗糖配合物的制备方法 Download PDF

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WO2023279277A1
WO2023279277A1 PCT/CN2021/104938 CN2021104938W WO2023279277A1 WO 2023279277 A1 WO2023279277 A1 WO 2023279277A1 CN 2021104938 W CN2021104938 W CN 2021104938W WO 2023279277 A1 WO2023279277 A1 WO 2023279277A1
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dmf
sucrose
organotin
solid adsorbent
molecular sieve
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PCT/CN2021/104938
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English (en)
French (fr)
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张正颂
陈永乐
刘建
郭思雨
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安徽金禾实业股份有限公司
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Priority to PCT/CN2021/104938 priority Critical patent/WO2023279277A1/zh
Priority to CN202180002116.7A priority patent/CN113646318A/zh
Publication of WO2023279277A1 publication Critical patent/WO2023279277A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • 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

Definitions

  • the invention belongs to the technical field of fine chemicals, and in particular relates to a preparation method of an organotin-sucrose complex.
  • Sucrose-6-ethyl ester is one of the important precursors for the synthesis of sucralose.
  • the widely used process uses sucrose as raw material, organotin as catalyst, acetic anhydride as acylating agent, DMF (N,N-dimethyl formamide) as solvent and dehydrating agent for esterification.
  • the process mainly has three processes.
  • the first step is the preparation of catalyst organotin ester, which is the synthesis of organotin ester by organotin and acetic anhydride in the case of cyclohexane as solvent;
  • the second step is the acylation reaction process, which is organic Tin esters and sucrose form organotin-sucrose complexes when DMF is used as a solvent and dehydrating agent;
  • the third step is the esterification process, which is to add acetic anhydride to the organotin-sucrose complexes for phase separation to obtain sucralose- DMF solution of 6-ethyl ester and cyclohexane solution of organotin ester, the organotin ester is recovered and reused after being concentrated to remove cyclohexane.
  • the water content in the system is a key factor affecting the formation of organotin-sucrose complexes, which are easily decomposed in the presence of water, resulting in the third step of esterification During the reaction, the yield of the target product is low, and it is even difficult to form the target product.
  • a large amount of protic solvents such as DMF
  • the loss of solvent in the dehydration process and the recovery of solvent in the later stage have always been a difficult problem that plagues this section of the process, especially in recent years due to DMF This problem has become more serious due to the sharp rise in raw material prices.
  • Such as Chinese patent CN106349300A is a dehydration process based on a large amount of proton solvent DMF, and in this patent, 300kg sucrose needs 1900L DMF to do solvent, also needs 2100L DMF to remove the moisture in the system as water-carrying agent, the water in the last batch of collection DMF The content is 0.9-1.0% ppm. Although this method can achieve nearly complete dehydration, the amount of solvent DMF used is 13.33 times that of sucrose, which seriously increases the difficulty of subsequent solvent recovery.
  • Chinese patents CN200310106027, CN200710074157, CN201080054223 and CN201080054224, etc. all rely too much on the amount of solvent DMF used.
  • Patent CN112218874A adopts a circulating spray drying method for dehydration, which has high dehydration efficiency, low energy consumption, high product yield and good selectivity.
  • the number of spray drying cycles needs 2 to 10 times, the amount of solvent used is relatively large, which cannot fundamentally solve the problem of large solvent consumption.
  • part of DMF will be decomposed into dimethylamine, which brings very serious troubles for the aftertreatment of DMF.
  • the present application is proposed to provide a preparation method of an organotin-sucrose complex that overcomes the above problems or at least partially solves the above problems.
  • a method for preparing an organotin-sucrose complex comprising:
  • Acylation reaction step the DMF solution of sucrose and the organotin ester catalyst are subjected to acylation reaction under preset conditions to generate organotin-sucrose complex and DMF vapor;
  • Solvent dehydration step Condensate and absorb the DMF vapor with a condensation adsorption device preset with a solid adsorbent to remove the water in it to obtain regenerated DMF;
  • Solvent recovery step collecting regenerated DMF, and reclaiming the collected regenerated DMF into the DMF solution of sucrose entering the acylation reaction step;
  • Adsorbent regeneration step use hot dry air to purge the solid adsorbent to remove impurities adsorbed by the solid adsorbent and regenerate the solid adsorbent.
  • the solvent recovery step is performed simultaneously with the acylation reaction step, and the solvent dehydration step is performed using another set of condensation adsorption device, wherein, The preset solid adsorbent in another set of condensation adsorption device is fresh or has been regenerated.
  • the mass content of sucrose is 10-20%.
  • the organotin ester catalyst is dibutyltin oxide
  • the ratio of the mass dosage of the organotin ester catalyst to the mass dosage of sucrose is 1.95-2.05.
  • the preset conditions are: the preset temperature is set to 45-70° C., the preset vacuum degree is set to -0.1-0.08 MPa, and the preset time is set to 1-3 hours.
  • the solid adsorbent is molecular sieve, one or more selected from 4A molecular sieve, 5A molecular sieve, 10Z molecular sieve, 13Z molecular sieve and 13X molecular sieve, preferably 5A molecular sieve.
  • the physical properties of each molecular sieve are: Particle size 3-10mm, static water absorption ⁇ 20%, packaging moisture content ⁇ 1.5%.
  • the ratio of the loading mass of the solid adsorbent to the mass and dosage of sucrose is 0.5-2.
  • the condensation temperature of the condensation is 0-15°C.
  • purging the solid adsorbent with hot dry air includes:
  • the solid adsorbent is purged by using hot dry air at a temperature of 130-200°C, at a space velocity of 10-20m 3 /m 3 ⁇ h, and a drying time of 1-4h.
  • the beneficial effects of the present application are that the DMF vapor formed by the acylation reaction between the DMF solution of sucrose and the organotin ester catalyst adopts a condensation adsorption device preset with a solid adsorbent for adsorption and condensation treatment.
  • the solid adsorption The agent can effectively remove the moisture in the DMF vapor, and at the same time, the DMF vapor is condensed into a liquid, which can be returned to the DMF solution of sucrose to continue to participate in the reaction, and the solid adsorbent can be quickly regenerated and reused after being purged with hot dry air.
  • Figure 1 shows a schematic structural view of the preparation equipment of an organotin-sucrose complex according to an embodiment of the present application
  • Figure 2 shows a schematic flow diagram of a method for preparing an organotin-sucrose complex according to an embodiment of the present application
  • Fig. 3 shows a schematic structural diagram of an organotin-sucrose complex preparation device according to another embodiment of the present application.
  • the idea of the present application is that in the process of synthesizing sucrose-6-ester in view of the prior art, due to the existence of water in the reaction system, the generation of the precursor organotin-sucrose complex of sucrose-6-ester is seriously affected, and it is necessary to use A large amount of DMF is used to remove water, resulting in a large amount of DMF usage, high economic costs, and difficulties in subsequent solvent recovery.
  • a method for preparing a precursor organotin-sucrose complex for the preparation of sucrose-6-ester is proposed.
  • the preparation method of the organotin-sucrose complex provided by this application can be implemented on any device or equipment that can be embodied, and the application is not limited.
  • the preparation equipment of an organotin-sucrose complex according to an embodiment of the present application is shown.
  • the equipment 100 includes:
  • Reactor V-1 condensation adsorption device V-2, DMF collection tank V-4, valve Q-1, valve Q-3, valve Q-5 and delivery pump P-1.
  • the outlet of the gaseous substance of the reactor V-1 is respectively connected to the inlet of the condensation adsorption device V-2
  • the outlet of the liquid substance of the condensation adsorption device V-2 is connected to the inlet of the DMF collection tank V-4
  • the outlet of the DMF collection tank V-4 The reactor V-1 is connected through the transfer pump P-1, and the valves Q-1, Q-3 and Q-5 are installed in the positions shown in Figure 1.
  • connection relationship of the organotin-sucrose complex preparation device 100 the connection relationship of each component can be adjusted adaptively according to the needs, and the type of the reaction vessel can be selected according to the respective functional needs.
  • the application is not limited; in addition, the components in the above-mentioned device can also be added or deleted as needed.
  • Fig. 2 shows a schematic flow chart of a method for preparing an organotin-sucrose complex according to an embodiment of the present application. It can be seen from Fig. 2 that the present application includes at least steps S210 to S240:
  • Acylation reaction step S210 acylating the DMF solution of sucrose with the organotin ester catalyst under preset conditions to generate organotin-sucrose complex and DMF vapor.
  • the DMF solution of sucrose and the organotin ester catalyst are preset in advance.
  • Valve Q-1 and valve Q-3 are set to open device, valve Q-5 is set to closed state, the DMF solution of sucrose and organotin ester catalyst are transported in the reactor V-1, the environment of the reactor is set to The preset conditions make the acylation reaction between the DMF solution of sucrose and the organotin ester catalyst. During the acylation reaction, the sucrose and the organotin ester catalyst gradually generate organotin-sucrose complexes and remove small molecules of water ; DMF solution will undergo phase inversion under heating conditions to generate DMF vapor.
  • Solvent dehydration step S220 Condensing and adsorbing the DMF steam by using a condensation adsorption device pre-installed with a solid adsorbent to remove moisture therein to obtain regenerated DMF.
  • DMF steam can be sent from the upper outlet of the reactor V-1 to the upper inlet of the condensation adsorption device V-2, and the condensation adsorption device V-2 is equipped with a solid adsorbent, which has excellent adsorption of moisture Ability to adsorb water molecules in DMF vapor and repel DMF molecules, that is, to effectively separate DMF and water.
  • a solid adsorbent which has excellent adsorption of moisture Ability to adsorb water molecules in DMF vapor and repel DMF molecules, that is, to effectively separate DMF and water.
  • most of the water is adsorbed and fixed in the solid adsorbent, and DMF vapor is condensed from gaseous state to In liquid state, it is recorded as regenerated DMF.
  • the regenerated DMF flows out from the lower outlet along the inner wall of the condensation adsorption device V-2.
  • Solvent recovery step S230 collecting the regenerated DMF, and recycling the collected regenerated DMF into the sucrose DMF solution entering the acylation reaction step.
  • the regenerated DMF flows into the DMF collection tank V-4, and is recovered into the reactor V-1 through the delivery pump P-1, and continues to participate in the reaction.
  • a liquid level gauge can be set in the DMF collection tank V-4, and when the liquid level of the regenerated DMF reaches a preset value, the delivery pump P-1 is turned on to recover the regenerated DMF.
  • acylation reaction step S210 the solvent dehydration step S220 and the solvent recovery step S230 can be carried out simultaneously, that is, during the acylation reaction process, the DMF solution is continuously evaporating and continuously refluxed through condensation and adsorption.
  • adsorbent regeneration step S240 using hot dry air to purge the solid adsorbent to remove impurities adsorbed by the solid adsorbent, so as to regenerate the solid adsorbent.
  • the solid adsorbent During the process of the solid adsorbent adsorbing the DMF vapor, the solid adsorbent will not only basically completely absorb the moisture in the DMF vapor, but also adsorb a small part of the DMF molecules.
  • Hot dry air can be blown into the solid adsorbent in the condensation adsorption device V-2. Specifically, the hot dry air can enter from the gas inlet at the lower end of the condensation adsorption device V-2, and enter from the upper end of the condensation adsorption device V-2. Exit discharge.
  • the solid adsorbent is purged with hot dry air, so that the moisture and DMF that have been adsorbed by the solid adsorbent are removed from the solid adsorbent, mixed with hot dry air, and discharged from the upper outlet of the condensation adsorption device V-2.
  • the mixture formed by hot dry air, moisture, DMF and other impurities can be directly desolventized and recovered to recover DMF.
  • the regeneration of the solid adsorbent is completed, and the next round of organotin-sucrose complex preparation can be carried out.
  • the DMF vapor that the present application carries out the acylation reaction to the DMF solution of sucrose and organotin ester catalyst adopts the condensation adsorption device that is preset with solid adsorbent to carry out adsorption and condensation treatment, in this process, solid
  • the adsorbent can effectively remove the moisture in the DMF vapor, and at the same time, the DMF vapor is condensed into a liquid, which can be returned to the DMF solution of sucrose to continue to participate in the reaction, and the solid adsorbent can be quickly regenerated and reused after being purged with hot dry air.
  • the above-mentioned preparation method of organotin-sucrose complexes can be implemented continuously to achieve the purpose of improving reaction efficiency and saving reaction time.
  • two sets of condensation adsorption devices need to be arranged in parallel , using these two sets of condensation adsorption devices to alternately perform condensation adsorption to realize the continuous process of the preparation method of the organotin-sucrose complex.
  • the solvent recovery step and the acylation reaction step are carried out simultaneously, and the solvent dehydration step is carried out by another set of condensation adsorption device, wherein, the solid The sorbent is fresh or regenerated. It can be realized by using the equipment given in the following embodiments, or can also be implemented by using other available equipment, which is not limited in this application.
  • Fig. 3 shows the preparation equipment of organotin sucrose complex according to another embodiment of the present application, as can be seen from Fig. 3, this equipment 300 comprises:
  • Reactor V-1 condensation adsorption device V-2, condensation adsorption device V-3, DMF collection tank V-4, valves Q-1 ⁇ Q-8 and delivery pump P-1.
  • the gaseous substance outlet of the reactor V-1 is respectively connected to the inlets of the condensation adsorption device V-2 and the condensation adsorption device V-3, and the liquid substance outlets of the condensation adsorption device V-2 and the condensation adsorption device V-3 are connected to the DMF collection tank
  • the inlet of V-4 and the outlet of DMF collection tank V-4 are connected to reactor V-1 through delivery pump P-1, and valves Q-1 to Q-8 are installed at the positions shown in Figure 1.
  • the valves Q2 and Q4-Q-8 Before the reaction starts, close the valves Q2 and Q4-Q-8, and open the valves Q-1 and Q-3. Put the DMF solution in which sucrose is dissolved and the organotin ester catalyst into the reactor V-1, and react at a certain temperature and vacuum. 1. After the adsorption, the water-free liquid DMF enters the collection tank V-4 through the valve Q-3 from the lower end. Then use the transfer pump P-1 to input the non-aqueous liquid DMF in the collection tank V-4 into the reaction kettle V-1 to continue to participate in the reaction. After the reaction, the acylation solution can be discharged from the reactor V-1 to carry out the next step of esterification reaction.
  • the content of sucrose and DMF in the sucrose DMF solution is not limited, as long as the sucrose can be completely dissolved.
  • the mass content of DMF is 80-90%, and the mass content of sucrose is 10-20%. If the mass content of sucrose is greater than 20%, it will affect the dissolving effect of sucrose on the one hand, on the other hand, the solvent viscosity of formation is too large, is unfavorable for follow-up reaction; If the mass content of sucrose is less than 10%, DMF consumption is big, causes waste, No other beneficial effects were brought.
  • the amount of DMF used is about 4-9 times that of sucrose, significantly lower than the amount of DMF in the prior art, such as 13.33 times as disclosed in Chinese patent CN106349300A.
  • the type of organotin ester catalyst is not limited, such as 1,3-dihydrocarbyloxy-1,1,3,3-tetra-(hydrocarbyl) distannoxane, Di(hydrocarbyl)tin oxide, 1,3-diacyloxy-1,1,3,3-tetra-(hydrocarbyl)distannoxane and 1-diacyloxy-1,1,3,3-tetra - any one or more of (hydrocarbyl) distannoxanes, and some embodiments select 1,3-diacyloxy-1,1,3,3-tetra-(hydrocarbyl) distannoxanes, There are also some embodiments that use 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane; wherein, in some embodiments, the alkoxy group is an alkoxy group or a phenoxy group , the alkoxy group can be methoxy, ethoxy, n
  • the amount of organotin ester catalyst used there is no limit to the amount of organotin ester catalyst used, and prior art may be referred to.
  • the ratio of the mass amount of organotin ester catalyst to the mass amount of sucrose is 1.95-2.05 . That is to say, the amount of the organotin ester catalyst is relatively excessive relative to the sucrose, specifically, the amount of the sucrose is about 2 times that of the sucrose, and a relatively good effect can be obtained.
  • the conditions of the acylation reaction are not limited.
  • the preset condition is that the preset temperature of the acylation reaction is set at 45° C. to 70° C. under stirring conditions , the preset time is 1h ⁇ 3h, and the vacuum degree is set to -0.1 ⁇ -0.08MPa.
  • the reaction temperature of the acylation is lower than 45° C., and the reaction time is shorter than 1 h, the acylation condition is too passivated, and the time is too short, which makes the acylation reaction difficult to carry out, and the conversion rate of the reactant is too low, resulting in a waste of the reactant; If the acylation reaction temperature is higher than 70°C and the preset time is longer than 4 hours, the acylation temperature will be too high and the time will be too long, making the acylation conditions too intense, prone to side reactions, and even dehydration and coke-forming reactions; and the present application
  • the acylation reaction in the method is carried out under the condition of negative pressure, which is more conducive to the forward progress of the reaction.
  • the type of solid adsorbent is not limited, any adsorbent that can effectively separate water molecules and DMF molecules is sufficient.
  • the solid adsorbent is 4A molecular sieve, 5A molecular sieve, One or more of 10Z molecular sieve, 13Z molecular sieve and 13X molecular sieve, in some other embodiments, the solid adsorbent is 5A molecular sieve.
  • the van der Waals diameter of a water molecule is about The van der Waals diameter of the DMF molecule is about
  • the microcosmic average internal diameter of the 4A molecular sieve chosen by the present invention is The microscopic average inner diameter of 5A molecular sieve is The microscopic average inner diameter of 10Z molecular sieve, 13Z molecular sieve and 13X molecular sieve is The above-mentioned molecular sieves can absorb water molecules while repelling DMF. Among them, 4A molecular sieve and 5A molecular sieve are more targeted in the adsorption of water, and 10Z molecular sieve, 13Z molecular sieve and 13X molecular sieve are better in water absorption.
  • the above molecular sieves can be used alone or in combination. In some embodiments of this application, considering the combination of selectivity and water absorption, it is recommended to use 4A molecular sieve and/or 5A molecular sieve together with 10Z molecular sieve, 13Z molecular sieve and 13X molecular sieve Use at least one of them.
  • the performance of the above-mentioned molecular sieves is not limited, and commercially available products can be used.
  • the physical properties of the above-mentioned molecular sieves are: Particle size 3-10mm, static water absorption ⁇ 20%, packaging moisture content ⁇ 1.5%. Molecular sieves within the above properties can achieve a more ideal adsorption effect on moisture.
  • the loading amount of the solid adsorbent there is no limit to the loading amount of the solid adsorbent, which can be determined according to the model of the condensation adsorption device. In other embodiments, in consideration of economy, the loading quality of the solid adsorbent and the quality of sucrose The ratio of the amount used is 0.5-2.
  • the condition of the solvent dehydration is not limited. In other embodiments, in the solvent dehydration step, the condensing temperature is 0-15°C.
  • the regeneration conditions of the solid adsorbent are not limited.
  • purging the solid adsorbent with hot dry air includes: using hot dry air at a temperature of 130-200°C , under the condition that the space velocity is 10-20m 3 /m 3 ⁇ h and the drying time is 1-4h, the solid adsorbent is purged to regenerate the solid adsorbent.
  • the water absorption performance of the regenerated solid adsorbent is almost the same as that of the fresh solid adsorbent. It can be used repeatedly and does not need to be replaced frequently. Usually, the solid adsorbent can be replaced once a year.
  • the organotin sucrose complex can be used as a raw material for esterification reaction with carboxylic anhydride to prepare sucrose-6 ester, using carboxylic anhydride as acetic acid to prepare sucrose-6 ethyl ester as an example.
  • This step reaction is set up by this application for testing the reaction effect.
  • the reaction temperature of the esterification reaction is 0-50 ° C
  • the reaction time of the esterification reaction is 10 minutes to 10 minutes.
  • the reaction time for the esterification reaction is 5-20°C
  • the reaction time is 30min to 4h.
  • reaction temperature of the esterification reaction is lower than 0°C and the reaction time is shorter than 30min, the temperature is too low and the time is too short, which will cause incomplete esterification reaction, waste of raw materials, and low product yield; if the reaction temperature of the esterification reaction If the temperature is higher than 50°C and the reaction time is longer than 4 hours, the temperature is too high and the time is too long, which will cause excessive esterification and even coke.
  • the esterification reaction conditions of the organotin sucrose complex and acetic anhydride were the same, and the reaction temperature of the esterification reaction was set at 20° C., and the reaction time of the esterification reaction was 2 hours.
  • a conventional esterification reactor can be used for the reactor.
  • each material content adopts the high performance liquid chromatography (High Performance Liquid Chromatography, HPLC) method to adopt the external standard method to record under the following conditions, no longer repeat them in each embodiment.
  • HPLC High Performance Liquid Chromatography
  • This embodiment is carried out by using the device shown in Figure 1, opening valves Q-1 and Q-3, and closing valve Q-5.
  • DMF steam enters from the upper end of condensation adsorption device V-2 through valve Q-1, and 50kg of 4A molecular sieve is filled in the condensation tower.
  • the water-free DMF solvent condensed by the condensation tower enters the collection tank V-4 through the valve Q-3 from the lower end, and the condensation temperature is 0°C.
  • the delivery pump P-1 uses the delivery pump P-1 to input the non-aqueous DMF in the collection tank V-4 into the reaction kettle V-1 to continue to participate in the reaction.
  • the acylation liquid is subjected to the next esterification reaction, and the valves Q-1 and Q-3 are closed. Open the valves Q-5 and Q-7, and pass hot dry air at 130°C and a space velocity of 10m 3 /m 3 h into the used condensation adsorption device V-2 for 4 hours to dry and remove the adsorbent.
  • the water and DMF solvent, the tail gas is sent to the lower solvent recovery system to separate and recover DMF.
  • the DMF samples in the collection tank V-4 were taken every 0.5h, and the water content and other components were detected.
  • the specific results are shown in Table 1.
  • the completed acylation solution was subjected to esterification treatment, and samples were taken and analyzed for the content of sucrose-6-ethyl ester and other components in the esterification solution.
  • the specific results are shown in Table 2.
  • This embodiment is carried out by adopting the device shown in Fig. 3, closing the valves Q2 and Q4-Q-8, and opening the valves Q-1 and Q-3.
  • 2t of the mixed solution containing 20% sucrose and 80% DMF was input into reactor V-1, and 820kg of organotin ester catalyst was added to prepare the first batch of organotin-sucrose complexes. React at 45°C and vacuum -0.1MPa for 3 hours.
  • DMF steam enters from the upper end of condensation adsorption device V-2 through valve Q-1, and 800kg of 5A molecular sieves are filled in the condensation tower.
  • the water-free DMF solvent condensed by the condensation tower enters the collection tank V-4 through the valve Q-3 from the lower end, and the condensation temperature is 5°C. Then use the delivery pump P-1 to input the non-aqueous DMF in the collection tank V-4 into the reactor V-1 to continue to participate in the reaction. After the acylation reaction is completed, the acylation liquid is discharged from the lower outlet of the reactor V-1 Enter the esterification reactor (not shown in the figure) to carry out the esterification reaction. Close valves Q-1 and Q-3, open valve Q-2 and valve Q-4, input 2t of mixed solution containing 20% sucrose and 80% DMF into reactor V-1, and add 820kg of organotin ester catalyst .
  • DMF steam enters from the upper end of the condensation adsorption device V-3 through the valve Q-2, fill the condensation tower with 800kg of 5A molecular sieves, and proceed to the second batch of organic tin sucrose complexes preparation.
  • the delivery pump P-1 uses the delivery pump P-1 to input the non-aqueous DMF in the collection tank V-4 into the reactor V-1 to continue to participate in the reaction.
  • the acylation liquid is discharged from the lower outlet of the reactor V-1 Enter the esterification reactor (not shown in the figure) to carry out the esterification reaction.
  • valves Q-1 and Q-3 are opened and valves Q-2 and Q-4 are closed, valves Q-6 and Q-8 are opened at the same time, and 150°C is introduced into the used condensation adsorption device V-2.
  • the subsequent regeneration operations of condensation adsorption unit V-3 are the same as above.
  • Table 3 The data in Table 3, Table 5 and Table 7 measure whether the molecular sieve completely absorbs the water in the evaporated DMF. The lower the water content, the better the adsorption effect, and the higher the acetic acid content, the more complete the reaction , since in this example, the preparation methods of the three batches of organotin-sucrose complexes have exactly the same conditions, the data in Table 3-8 are almost the same, and some of them are even completely consistent, which means that molecular sieves absorb water better , the esterification is relatively complete, and the reaction is very stable.
  • This embodiment is carried out by adopting the device shown in Fig. 3, closing the valves Q2 and Q4-Q-8, and opening the valves Q-1 and Q-3.
  • 3 t of mixed solution containing 15% sucrose and 85% DMF was input into reactor V-1, and 913.5 kg of organotin ester catalyst was added to prepare the first batch of organotin-sucrose complexes. React for 1.5 hours at 60°C and a vacuum of -0.08MPa.
  • DMF steam enters from the upper end of the condensation adsorption device V-2 through the valve Q-1.
  • the condensation tower is filled with 100kg of 4A molecular sieves, 250kg of 5A molecular sieves, and 100kg of 13X molecular sieves.
  • the water-free DMF solvent condensed by the condensation tower enters the collection tank V-4 through the valve Q-3 from the lower end, and the condensation temperature is 15°C. Then use the delivery pump P-1 to input the non-aqueous DMF in the collection tank V-4 into the reaction kettle V-1 to continue to participate in the reaction. After the acylation reaction, the acylation liquid is discharged from the lower outlet of the reactor V-1 into the esterification reactor (not shown in the figure) to carry out the esterification reaction.
  • valve Q-1 and the valve Q-3 After the esterification reaction, close the valve Q-1 and the valve Q-3, and open the valve Q-2 and the valve Q-4, and continue the preparation of the second batch of organotin-sucrose complexes.
  • Simultaneously open valve Q-5 and valve Q-7 pass hot dry air at 180°C and space velocity 15m 3 /m 3 h into the used condensation adsorption device V-2, and ventilate for 1.5h, dry and remove The water and DMF solvent on the adsorbent, the tail gas is sent to the lower-level solvent recovery system to separate and recover DMF, and the dried condensation adsorption device V-2 is used for the preparation of the third batch of organotin-sucrose complexes.
  • the regeneration operation of the solid adsorbent of condensation adsorption unit V-3 is consistent with the above.
  • the DMF samples in the collection tank V-4 were taken every 0.5h, and the water content and other components were detected.
  • the specific results are shown in Table 9.
  • the completed acylation solution was subjected to esterification treatment, and samples were taken and analyzed for the content of sucrose-6-ethyl ester and other components in the esterification solution.
  • the specific results are shown in Table 10.
  • This embodiment is carried out by adopting the device shown in Fig. 3, closing the valves Q-2 and Q-4 to Q-8, and opening the valves Q-1 and Q-3.
  • DMF steam enters from the upper end of the condensation adsorption device V-2 through the valve Q-1.
  • the condensation tower is filled with 70kg of 5A molecular sieves, 80kg of 10Z molecular sieves, 100kg of 13Z molecular sieves, and 150kg of 13X molecular sieves.
  • the water-free DMF solvent condensed by the condensation tower enters the collection tank V-4 through the valve Q-3 from the lower end, and the condensation temperature is 10°C.
  • the delivery pump P-1 uses the delivery pump P-1 to input the non-aqueous DMF in the collection tank V-4 into the reactor V-1 to continue to participate in the reaction.
  • the acylation liquid is discharged from the lower outlet of the reactor V-1 Enter the esterification reactor (not shown in the figure) to carry out the esterification reaction.
  • valve Q-1 and the valve Q-3 After the esterification reaction, close the valve Q-1 and the valve Q-3, and open the valve Q-2 and the valve Q-4, and continue the preparation of the second batch of organotin-sucrose complexes.
  • Simultaneously open valve Q-5 and valve Q-7 pass hot dry air at 200°C and space velocity 20m 3 /m 3 h into the used condensation adsorption device V-2, and ventilate for 1 hour to dry and desorb The water and DMF solvent on the solvent, the tail gas is sent to the lower solvent recovery system to separate and recover DMF, and the dried condensation adsorption device V-2 is used for the preparation of the third batch of organotin sucrose complexes.
  • the regeneration operation of the solid adsorbent of condensation adsorption unit V-3 is consistent with the above.
  • the DMF samples in the collection tank V-4 were taken every 0.5h, and the water content and other components were detected.
  • the specific results are shown in Table 11.
  • the completed acylation solution was subjected to esterification treatment, and samples were taken to analyze the content of sucrose-6-ethyl ester and other components in the esterification solution.
  • the specific results are shown in Table 12.
  • This embodiment is carried out by using the device shown in Figure 3, closing valves Q-2 and Q-4 to Q-8, and opening valves Q-1 and Q-3.
  • 5 t of mixed solution containing 17% sucrose and 83% DMF was input into reactor V-1, and 1674.5 kg of organotin ester catalyst was added to prepare the first batch of organotin-sucrose complexes. React for 1.5h at 65°C and vacuum degree -0.08MPa.
  • DMF steam enters from the upper end of condensation adsorption device V-2 through valve Q-1.
  • the condensation tower is filled with 300kg of 4A molecular sieve, 350kg of 5A molecular sieve, 50kg of 10Z molecular sieve, and 50kg of 13Z molecular sieve.
  • valve Q-1 and the valve Q-3 After the esterification reaction, close the valve Q-1 and the valve Q-3, and open the valve Q-2 and the valve Q-4, and continue the preparation of the second batch of organotin-sucrose complexes.
  • Simultaneously open valve Q-5 and valve Q-7 pass hot dry air at 165°C and space velocity 13m 3 /m 3 h into the used condensation adsorption device V-2, and ventilate for 3.5h, then dry and remove The water and DMF solvent on the adsorbent, the tail gas is sent to the lower-level solvent recovery system to separate and recover DMF, and the dried condensation adsorption device V-2 is used for the preparation of the third batch of organotin-sucrose complexes.
  • the regeneration operation of the solid adsorbent of condensation adsorption unit V-3 is consistent with the above.
  • the DMF samples in the collection tank V-4 were taken every 0.5h, and the water content and other components were detected.
  • the specific results are shown in Table 13.
  • the completed acylation solution was subjected to esterification treatment, and samples were taken to analyze the content of sucrose-6-ethyl ester and other components in the esterification solution. The specific results are shown in Table 14.
  • This embodiment is carried out by using the device shown in Figure 3, closing valves Q-2 and Q-4 to Q-8, and opening valves Q-1 and Q-3.
  • 6t of a mixed solution containing 14% sucrose and 86% DMF was input into reactor V-1, and 1680 kg of organotin ester catalyst was added to prepare the first batch of organotin-sucrose complexes. React at 55°C and vacuum -0.09MPa for 2.5 hours.
  • DMF steam enters from the upper end of condensation adsorption device V-2 through valve Q-1.
  • the condensation tower is filled with 500kg of 13Z molecular sieve and 400kg of 13X molecular sieve.
  • the water-free DMF solvent condensed by the condensation tower enters the collection tank V-4 through the valve Q-3 from the lower end, and the condensation temperature is 13°C. Then use the delivery pump P-1 to input the non-aqueous DMF in the collection tank V-4 into the reactor V-1 to continue to participate in the reaction. After the acylation reaction is completed, the acylation liquid is discharged from the lower outlet of the reactor V-1 Enter the esterification reactor (not shown in the figure) to carry out the esterification reaction.
  • valve Q-1 and the valve Q-3 After the esterification reaction, close the valve Q-1 and the valve Q-3, and open the valve Q-2 and the valve Q-4, and continue the preparation of the second batch of organotin-sucrose complexes.
  • Simultaneously open valve Q-5 and valve Q-7 pass hot dry air at 185°C and space velocity 11m 3 /m 3 h into the used condensation adsorption device V-2, and ventilate for 1.5h, dry and remove The water and DMF solvent on the adsorbent, the tail gas is sent to the lower-level solvent recovery system to separate and recover DMF, and the dried condensation adsorption device V-2 is used for the preparation of the third batch of organotin-sucrose complexes.
  • the regeneration operation of the solid adsorbent of condensation adsorption unit V-3 is consistent with the above.
  • the DMF samples in the collection tank V-4 were taken every 0.5h, and the water content and other components were detected.
  • the specific results are shown in Table 15.
  • the completed acylation solution was subjected to esterification treatment, and samples were taken to analyze the content of sucrose-6-ethyl ester and other components in the esterification solution.
  • the specific results are shown in Table 16.
  • Example 6 6t of a mixed solution containing 14% sucrose and 86% DMF was input into the reactor, and 1680kg of organotin ester catalyst was added, and reacted at 55°C and a vacuum of -0.09MPa, and 2.4% was distilled every 1h.
  • m 3 DMF a mixture of acetic acid and water (test its water content and other components, see Table 17 for specific results), and then add 2.4m 3 DMF to continue the reaction for a total of 3 hours.
  • the materials enter the acylation reactor, and the acylation solution is esterified. Samples are taken and analyzed for the content of sucrose-6-ethyl ester and other components in the esterification solution. The specific results are shown in Table 18.
  • the present invention adopts molecular sieve to process the moisture in the DMF that reclaims, in the situation that reaches equivalent sucrose conversion rate, can shorten the acylation time of reaction (from 3h to 2.5h) ; It can also significantly reduce the usage of DMF (from 12.36m 3 to 5.16m 3 ).
  • the sucrose esterification and dehydration method of the present invention has remarkable effects.
  • the DMF vapor formed by the acylation reaction between the DMF solution of sucrose and the organotin ester catalyst is subjected to adsorption and condensation treatment with a condensation adsorption device preset with a solid adsorbent.
  • the solid adsorbent can Effectively remove the moisture in the DMF vapor, and at the same time, the DMF vapor is condensed into a liquid, which can be returned to the DMF solution of sucrose to continue to participate in the reaction, and the solid adsorbent can be quickly regenerated and reused after being purged with hot dry air.
  • connection should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection. Connected, or integrally connected; it may be mechanically connected or electrically connected; it may be directly connected or indirectly connected through an intermediary, and it may be the internal communication of two components. Those of ordinary skill in the art can understand the specific meanings of the above terms in this application in specific situations.

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Abstract

本申请提供了一种有机锡蔗糖配合物的制备方法，包括：使蔗糖的DMF溶液与有机锡酯催化剂在预设条件下进行酰化反应，生成有机锡蔗糖配合物和DMF蒸汽；对DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行冷凝和吸附，以除去其中的水分，得到再生DMF；收集再生DMF，并回收至进入酰化反应步骤的蔗糖的DMF溶液中；和采用热干空气对所述固体吸附剂吹扫，使固体吸附剂再生。本申请极大程度上节约了DMF的用量，减轻了DMF后处理的负担，且能够有效去除反应体系中的水分，促进有机锡蔗糖配合物的生成，提高有机锡蔗糖配合物的收率；且整体工艺简单、设备造价低、具有极高的应用价值和经济价值。

Description

有机锡蔗糖配合物的制备方法 技术领域
本发明属于精细化工技术领域，具体涉及一种有机锡蔗糖配合物的制备方法。
发明背景
蔗糖-6-乙酯是合成三氯蔗糖的重要前驱体之一，目前广泛采用的工艺是以蔗糖为原料，有机锡为催化剂，乙酸酐为酰化剂，DMF(N,N-二甲基甲酰胺)为溶剂和脱水剂进行酯化反应。该工艺主要有三个流程，第一步是催化剂有机锡酯的制备，是由有机锡与乙酸酐在环己烷做溶剂的情况下合成有机锡酯；第二步是酰化反应过程，是有机锡酯与蔗糖在DMF做溶剂和脱水剂的情况下形成有机锡蔗糖配合物；第三步是酯化反应过程，是在有机锡蔗糖配合物中加入乙酸酐反应，分相得到三氯蔗糖-6-乙酯的DMF溶液和有机锡酯环己烷溶液，有机锡酯经浓缩除去环己烷后回收再利用。
在第二步酰化过程中，体系中的水含量是影响有机锡蔗糖配合物形成的关键因素，该有机锡蔗糖配合物极易在有水存在的情况下分解，从而导致第三步酯化反应过程中目标产物收率低，甚至难以形成目标产物。为了控制体系中的水分，现有技术中，通常采用大量的质子溶剂(如DMF)进行脱水，脱水过程中溶剂的损耗以及后期溶剂回收一直是困扰该段工艺的难题，特别是近年来由于DMF等原材料价格的大幅上涨，该问题变得更加严峻。目前已有一些针对上述问题的报道，如中国专利CN111763703A和CN112029754A，均以酶法工艺进行蔗糖酯化，在溶剂使用量及损耗上低于目前的酯化工艺。但由于其效率低，反应时间长，不能大规模生产，因此产业化前景渺茫。
如中国专利CN106349300A是以大量质子溶剂DMF脱水工艺，而在该专利中，300kg蔗糖需要1900L DMF做溶剂，还需要2100L DMF作为带水剂脱除体系中的水分，最后一批收集的DMF中水含量在0.9～1.0％ppm。该方法虽能够实现接近完全的脱水，但所用溶剂DMF的量是蔗糖的13.33倍，这严重增加了后续溶剂回收的难度。其他诸如此类的专利颇多，又如中国专利CN200310106027、CN200710074157、CN201080054223和CN201080054224等等，均对溶剂DMF的使用量过分依赖。
专利CN112218874A采用了一种循环喷雾干燥的方式进行脱水，脱水效率高、能耗低、产品收率高、选择性好。但由于喷雾干燥循环次数需要2～10次，溶剂使 用量较大，并不能根本上解决溶剂消耗量大的问题。且在反应过程中，部分DMF会发生分解成二甲胺，为DMF的后处理带来很严重的困扰。
综上所述，亟待一种合适的替代溶剂和脱水剂，或采用新工艺降低质子溶剂的使用量，来改进三氯蔗糖的生成工艺。
发明内容
鉴于上述问题，提出了本申请以便提供一种克服上述问题或者至少部分地解决上述问题的有机锡蔗糖配合物的制备方法。
根据本申请的一方面，提供了一种有机锡蔗糖配合物的制备方法，该方法包括：
酰化反应步骤：使蔗糖的DMF溶液与有机锡酯催化剂在预设条件下进行酰化反应，生成有机锡蔗糖配合物和DMF蒸汽；
溶剂脱水步骤：对DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行冷凝和吸附，以除去其中的水分，得到再生DMF；
溶剂回收步骤：收集再生DMF，并将收集的再生DMF回收至进入酰化反应步骤的蔗糖的DMF溶液中；和
吸附剂再生步骤：采用热干空气对固体吸附剂吹扫，以脱除固体吸附剂吸附的杂质，使固体吸附剂再生。
可选的，在上述方法中，在连续实施所述有机锡蔗糖配合物的制备方法时，溶剂回收步骤与酰化反应步骤同时进行，且溶剂脱水步骤采用另一套冷凝吸附装置进行，其中，另一套冷凝吸附装置中预置的固体吸附剂是新鲜的或者经过再生处理。
可选的，在上述方法中，在蔗糖的DMF溶液中，蔗糖的质量含量为10～20％。
可选的，在上述方法中，有机锡酯催化剂为二丁基氧化锡酯；
有机锡酯催化剂的质量用量与蔗糖的质量用量的比为1.95～2.05。
可选的，在上述方法中，预设条件为：预设温度设为45～70℃，预设真空度设为-0.1～-0.08MPa，预设时间设为1～3h。
可选的，在上述方法中，固体吸附剂为分子筛，选自4A分子筛，5A分子筛，10Z分子筛，13Z分子筛和13X分子筛中的一种或多种，优选5A分子筛。
可选的，在上述方法中，各分子筛的物理性能为：
Figure PCTCN2021104938-appb-000001
粒径3-10mm，静态吸水率≥20％，包装含水率≤1.5％。
可选的，在上述方法中，固体吸附剂的装填质量与蔗糖的质量用量的比为0.5～2。
可选的，在上述方法中，在溶剂脱水步骤中，冷凝的冷凝温度为0～15℃。
可选的，在上述方法中，采用热干空气对固体吸附剂吹扫包括：
采用温度为130～200℃的热干空气，在空速为10～20m 3/m 3·h，干燥时间为1～4h的条件下，对固体吸附剂进行吹扫。
本申请的有益效果在于，本申请对于蔗糖的DMF溶液与有机锡酯催化剂进行酰化反应形成的DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行吸附冷凝处理，在这个过程中，固体吸附剂能够有效去除DMF蒸汽中的水分，同时DMF蒸汽被冷凝为液体，可回流至蔗糖的DMF溶液中继续参与反应，且固体吸附剂经过热干空气的吹扫能够很快再生，反复利用。在这个过程中，只有极少量的DMF蒸汽由于被固体吸附剂吸附而流失需要后处理，绝大部分DMF溶液均回流至蔗糖的DMF溶液中，可为后续有机锡蔗糖配合物与酸酐的反应提供反应环境。本申请相对于现有技术，极大程度上节约了DMF的用量，减轻了DMF后处理的负担，且能够有效去除反应体系中的水分，促进有机锡蔗糖配合物的生成，提高有机锡蔗糖配合物的收率；且整体工艺简单、设备造价低、具有极高的应用价值和经济价值。
上述说明仅是本申请技术方案的概述，为了能够更清楚了解本申请的技术手段，而可依照说明书的内容予以实施，并且为了让本申请的上述和其它目的、特征和优点能够更明显易懂，以下特举本申请的具体实施方式。
附图简要说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本申请的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1示出了根据本申请的一个实施例的有机锡蔗糖配合物的制备设备的结构示意图；
图2示出了根据本申请的一个实施例的有机锡蔗糖配合物的制备方法的流程示意图；
图3示出了根据本申请的另一个实施例的有机锡蔗糖配合物的制备设备的结构示意图。
实施本发明的方式
本申请的构思在于，针对现有技术在合成蔗糖-6-酯的过程中，由于反应体系中水的存在，严重影响蔗糖-6-酯的前驱体有机锡蔗糖配合物的生成，而需要采用大量DMF以脱除水分，造成DMF使用量大、经济成本高、后续溶剂回收困难等问题，提出了一种制备蔗糖-6-酯的前驱体有机锡蔗糖配合物的制备方法，在该方法中，采用固体吸附剂对蔗糖的DMF溶液与有机锡酯催化剂进行酰化反应形成的DMF蒸汽进行吸附，以除去其中的水分，并将冷凝为液体的DMF回流，在这个过程中，DMF的损耗量极小，且固体吸附剂经过简单处理即可再生并反复利用，整体工艺简单、设备造价低，显示出极高的应用价值和经济价值。
本申请提供的有机锡蔗糖配合物的制备方法可在任何可实施例的装置或设备上实施，本申请不作限制，下述仅提供一种示例以作参考，如图1所示，图1示出了根据本申请的一个实施例的有机锡蔗糖配合物的制备设备，从图1可以看出，该设备100包括：
反应釜V-1、冷凝吸附装置V-2、DMF收集罐V-4、阀门Q-1、阀门Q-3、阀门Q-5和输送泵P-1。
其中，反应釜V-1的气态物质出口分别连接冷凝吸附装置V-2的入口，冷凝吸附装置V-2的液态物质出口连接DMF收集罐V-4的入口，DMF收集罐V-4的出口通过输送泵P-1连接反应釜V-1，阀门Q-1、阀门Q-3、阀门Q-5安装在如图1所示的位置上。
需要说明的是，上述描述仅是有机锡蔗糖配合物的制备装置100的主要连接关系，各组件的连接关系可以根据需要进行适应性调整，反应釜的类型可以根据各自的功能需要进行选择，本申请不作限制；另外，也可以根据需要对上述装置中的组件等根据需要进行增加或删减。
图2示出了根据本申请的一个实施例的有机锡蔗糖配合物的制备方法的流程示意图，从图2可以看出，本申请至少包括步骤S210～步骤S240：
酰化反应步骤S210：使蔗糖的DMF溶液与有机锡酯催化剂在预设条件下进行酰化反应，生成有机锡蔗糖配合物和DMF蒸汽。
蔗糖的DMF溶液和有机锡酯催化剂是提前预置好的。
将阀门Q-1和阀门Q-3设置为开启装置、阀门Q-5设置为闭合状态，将蔗糖的DMF溶液和有机锡酯催化剂输送到反应釜V-1中，将反应釜的环境设置为预设条件，使得置于其中的蔗糖的DMF溶液和有机锡酯催化剂发生酰化反应，在酰化 反应过程中，蔗糖与有机锡酯催化剂逐渐生成有机锡蔗糖配合物，并脱除小分子水；DMF溶液在加热的条件下会发生相转化，生成DMF蒸汽。
溶剂脱水步骤S220：对DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行冷凝和吸附，以除去其中的水分，得到再生DMF。
对于DMF蒸汽可从反应釜V-1的上出口被送入冷凝吸附装置V-2的上入口，在冷凝吸附装置V-2中设置有固体吸附剂，固体吸附剂对水分有极佳的吸附能力，能够吸附DMF蒸汽中的水分子，且排斥DMF分子，即将DMF和水有效分离，在这个过程中，绝大部分的水分被吸附固定于固体吸附剂中，DMF蒸汽被冷凝由气态转化为液态，记为再生DMF。
再生DMF沿着冷凝吸附装置V-2内壁，从其下出口流出。
溶剂回收步骤S230：收集再生DMF，并将收集的再生DMF回收至进入酰化反应步骤的蔗糖的DMF溶液中。
再生DMF流入DMF收集罐V-4中，并通过输送泵P-1被回收至反应釜V-1中，继续参与反应。在本申请的一些实施例中，在DMF收集罐V-4可设置一个液位计，当再生DMF的液位达到预设值时，才开启输送泵P-1回收再生DMF。
需要说明的是，酰化反应步骤S210、溶剂脱水步骤S220和溶剂回收步骤S230是可以同时进行的，即在酰化反应过程中，DMF溶液不断在蒸发，不断通过冷凝吸附回流。
和吸附剂再生步骤S240：采用热干空气对固体吸附剂吹扫，以脱除固体吸附剂吸附的杂质，使固体吸附剂再生。
在完成了DMF蒸汽的回收后，然后关闭阀门Q-1和阀门Q-3，并开启阀门Q-5，然后对固体吸附剂进行再生处理，这时不会有DMF蒸汽再进入冷凝吸附装置V-2中。
在固体吸附剂对DMF蒸汽进行吸附的过程中，固体吸附剂不仅会基本完全吸附掉DMF蒸汽中的水分，还会吸附一少部分的DMF分子。
可通过向冷凝吸附装置V-2中的固体吸附剂鼓入热干空气，具体的，热干空气可从冷凝吸附装置V-2的下端的气体入口进入，从冷凝吸附装置V-2的上端出口排出。通过热干空气对固体吸附剂吹扫，使得固体吸附剂已经吸附的水分和DMF从固体吸附剂上脱除，与热干空气混合在一起，从冷凝吸附装置V-2的上端出口排出，排出的热干空气与水分、DMF等杂质形成的混合物可直接去溶剂回收处理，以回收DMF，至此，固体吸附剂完成再生，可进行下一轮有机锡蔗糖配合物的制备。 从图2所示的方法，本申请对于蔗糖的DMF溶液与有机锡酯催化剂进行酰化反应形成的DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行吸附冷凝处理，在这个过程中，固体吸附剂能够有效去除DMF蒸汽中的水分，同时DMF蒸汽被冷凝为液体，可回流至蔗糖的DMF溶液中继续参与反应，且固体吸附剂经过热干空气的吹扫能够很快再生，反复利用。在这个过程中，只有极少量的DMF蒸汽由于被固体吸附剂吸附而流失需要后处理，绝大部分DMF溶液均回流至蔗糖的DMF溶液中，可为后续有机锡蔗糖配合物与酸酐的反应提供溶剂。本申请相对于现有技术，极大程度上节约了DMF的用量，减轻了DMF后处理的负担，且能够有效去除反应体系中的水分，促进有机锡蔗糖配合物的生成，提高有机锡蔗糖配合物的收率；且整体工艺简单、设备造价低、具有极高的应用价值和经济价值。
在本申请的一些实施例中，上述的有机锡蔗糖配合物的制备方法是可以连续实施的，以达到提高反应效率，节约反应时间的目的，这种情况下，需要平行设置两套冷凝吸附装置，采用这两套冷凝吸附装置交替进行冷凝吸附，来实现有机锡蔗糖配合物的制备方法的连续进行。在连续实施有机锡蔗糖配合物的制备方法时，溶剂回收步骤与酰化反应步骤同时进行，且溶剂脱水步骤采用另一套冷凝吸附装置进行，其中，另一套冷凝吸附装置中预置的固体吸附剂是新鲜的或者经过再生处理。可采用下述实施例给出的设备实现，也可采用其他可用设备进行，本申请不做限制。
图3示出了根据本申请的另一个实施例的有机锡蔗糖配合物的制备设备，从图3可以看出，该设备300包括：
反应釜V-1、冷凝吸附装置V-2、冷凝吸附装置V-3、DMF收集罐V-4、阀门Q-1～Q-8和输送泵P-1。
其中，反应釜V-1的气态物质出口分别连接冷凝吸附装置V-2和冷凝吸附装置V-3的入口，冷凝吸附装置V-2和冷凝吸附装置V-3的液态物质出口连接DMF收集罐V-4的入口，DMF收集罐V-4的出口通过输送泵P-1连接反应釜V-1，阀门Q-1～阀门Q-8安装在如图1所示的位置上。
反应开始前，关闭阀门Q2和Q4～Q-8，开启阀门Q-1和Q-3。将溶解蔗糖的DMF溶液，有机锡酯催化剂一同输入反应釜V-1中，在一定温度、真空度下反应，生成的DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，经冷凝、吸附后的不含水的液态DMF从下端经阀门Q-3进入收集罐V-4。然后采用输送泵P-1将收集罐V-4中的不含水的液态DMF输入进反应釜V-1中继续参与反应。反应结束后，酰化液可以从反应釜V-1中排出进行下步酯化反应。然后关闭阀门Q-1和Q-3，开 启阀门Q-2和Q-4继续进行第二批次的有机锡蔗糖配合物的制备；同时开启阀门Q-5和Q-7，向使用过的冷凝吸附装置V-2中通入一定温度，风速的热干空气，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，同时干燥好的冷凝吸附装置V-3用于第二批次的有机锡蔗糖配合物的制备，反应结束后冷凝吸附装置V-3中固体吸附剂的再生方式与上述一致，关闭阀门Q-2和Q-4同时开启阀门Q-6和Q-8。
通过两个冷凝吸附装置的设置，可实现有机锡蔗糖配合物的制备的连续实施，极大程度上提高了反应效率，节约了反应时间。
蔗糖的DMF溶液中蔗糖的含量
在本申请的一些实施例中，对蔗糖的DMF溶液中蔗糖和DMF的含量不作限制，只要能够保证蔗糖溶解完全即可，在另一些实施例中，考虑到蔗糖溶解后具有一定的粘度，也考虑到动力学。因此，在蔗糖的DMF溶液中，DMF的质量含量为80～90％，蔗糖的质量含量为10～20％。若蔗糖的质量含量大于20％，一方面影响蔗糖的溶解效果，另一方面，形成的溶剂粘度过大，不利于后续反应；若蔗糖的质量含量小于10％，DMF使用量大，造成浪费，也没有带来其他有益效果。在本申请中，DMF使用量大概是蔗糖使用量的4-9倍，显著低于现有技术中DMF的用量，如中国专利CN106349300A披露的13.33倍。
有机锡酯催化剂的种类和用量
在本申请的一些实施例中，对有机锡酯催化剂的种类不做限制，如可采用1,3-二烃氧基-1,1,3,3-四-(烃基)二锡氧烷、氧化二(烃基)锡、1,3-二酰氧基-1,1,3,3-四-(烃基)二锡氧烷和1-二酰氧基-1,1,3,3-四-(烃基)二锡氧烷中的任一种或几种，还有一些实施例选用1,3-二酰氧基-1,1,3,3-四-(烃基)二锡氧烷，还有一些实施例选用1,3-二乙酰氧基-1,1,3,3-四丁基二锡氧烷；其中，在一些实施例中，烃氧基为烷氧基或苯氧基，烷氧基可为甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基或正己氧基，其中，当烷氧基为甲氧基时效果突出；在一些实施例中，烃基为烷基、环烷基、芳基或芳烷基，在另一些实施例中，烃基为烷基，其中，当烃基为正丁基时效果突出，在本申请的一些实施例中，有机锡酯催化剂为二丁基氧化锡酯。
在本申请的一些实施例中，对有机锡酯催化剂的用量不作限制，可参考现有技术，在另一些实施例中，有机锡酯催化剂的质量用量与蔗糖的质量用量的比为1.95～2.05。也就是说，有机锡酯催化剂的用量相对于蔗糖是相对过量的，具体的，在蔗糖的用量的2倍左右，能够取得比较好的效果。
酰化反应的预设条件
在本申请的一些实施例中，对酰化反应的条件不作限制，在另一些实施例中，预设条件为，在搅拌的条件下，酰化反应的预设温度设为45℃～70℃，预设时间为1h～3h，真空度设为-0.1～-0.08MPa。若酰化的反应温度低于45℃，反应时间短于1h，则酰化条件过于钝化，时间过短，使得酰化反应难于进行，反应物转化率过低，造成反应物的浪费；若酰化的反应温度高于70℃，预设时间长于4h，则酰化温度过高，时间过长，使得酰化条件过于激烈，容易发生副反应，甚至会发生脱水生焦反应；且本申请中的酰化反应在负压的条件下进行，更加有利于反应的正向进行。
固体吸附剂的种类、性能和用量
在本申请的一些实施例中，对固体吸附剂的种类不作限制，凡是能够有效分离水分子和DMF分子的吸附剂即可，在另一些实施例中，固体吸附剂为4A分子筛，5A分子筛，10Z分子筛，13Z分子筛和13X分子筛中的一种或多种，在又一些实施例中，固体吸附剂为5A分子筛。
水分子范德华直径约为
Figure PCTCN2021104938-appb-000002
DMF分子范德华直径约为
Figure PCTCN2021104938-appb-000003
本发明选取的4A分子筛微观平均内径为
Figure PCTCN2021104938-appb-000004
5A分子筛微观平均内径为
Figure PCTCN2021104938-appb-000005
10Z分子筛、13Z分子筛和13X分子筛的微观平均内径为
Figure PCTCN2021104938-appb-000006
上述各分子筛能够吸附水分子，而排斥DMF，其中，4A分子筛和5A分子筛对水分的吸附针对性更强，10Z分子筛、13Z分子筛和13X分子筛在吸水率上更优。上述分子筛可以单独使用，也可以配合使用，在本申请的一些实施例中，考虑选择性和吸水率两方面的配合上，推荐使用4A分子筛和/或5A分子筛与10Z分子筛、13Z分子筛和13X分子筛中的至少一种配合使用。
各分子筛的物理性能
在本申请的一些实施例中，对上述各分子筛的性能不作限制，采用市售产品均可，在另一些实施例中，上述各分子筛的物理性能为：
Figure PCTCN2021104938-appb-000007
粒径3-10mm，静态吸水率≥20％，包装含水率≤1.5％。在上述性能内的分子筛能够对水分达到更理想的吸附效果。
在本申请的一些实施例中，对固体吸附剂的装填量不作限制，可根据冷凝吸附装置的型号确定，在另一些实施例中，处于经济的考虑，固体吸附剂的装填质量与蔗糖的质量用量的比为0.5～2。
溶剂脱水的条件
在本申请的一些实施例中，在溶剂脱水步骤中，对溶剂脱水的条件不作限制， 在另一些实施例中，在溶剂脱水步骤中，冷凝的冷凝温度为0～15℃。
固体吸附剂的再生条件
在本申请的一些实施例中，在固体吸附剂的再生条件不作限制，在另一些实施中，采用热干空气对所述固体吸附剂吹扫包括：采用温度为130～200℃的热干空气，在空速为10～20m 3/m 3·h，干燥时间为1～4h的条件下，对固体吸附剂进行吹扫，以使固体吸附剂再生。再生后的固体吸附剂与新鲜的固体吸附剂的吸水性能相差无几，可反复使用多次，无需频繁更换，通常情况下，固体吸附剂一年更换一次即可。
在有机锡蔗糖配合物完成后，可将有机锡蔗糖配合物作为原料与羧酸酐进行酯化反应，制备蔗糖-6酯，以羧酸酐为乙酸，制备蔗糖-6乙酯为例。该步反应是本申请为测试反应效果设置，对于反应条件，可参考现有技术，如在一些实施例中，酯化反应的反应温度为0～50℃，酯化反应的反应时间为10min到24h，在另一些实施例中为酯化反应的反应时间为5～20℃，为30min到4h。若酯化反应的反应温度低于0℃、反应时间短于30min，则温度过低、时间过短，会造成酯化反应不完全，原料浪费，产物产率低；若酯化反应的反应温度高于50℃、反应时间长于4h，则温度过高、时间过长，会造成酯化过度的现象，甚至造成生焦现象。
在下述各实施例和对比例中，有机锡蔗糖配合物与乙酸酐的酯化反应条件均相同，均设置酯化反应的反应温度为20℃，酯化反应的反应时间为2h。对于反应器采用常规酯化反应釜即可。
本申请中涉及的测试方法
本申请中各实施例和对比例中各物质含量均采用高效液相色谱(High Performance Liquid Chromatography，HPLC)方法在下述条件下采用外标法测得，在各个实施例中不再赘述。
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：乙腈-水溶液(8:2)；柱温：40℃；流量：1.0mL/min。其中，需要乙腈(色谱纯)、超纯水等等，各标准物质，外标法测量含量。
实施例1
采用如图1所示的装置实施本实施例，开启阀门Q-1和Q-3，关闭阀门Q-5。将1t含有10％蔗糖、90％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂195kg，在各实施例中，有机锡蔗糖配合物均选用1,3-二乙酰氧基-1,1,3,3- 四丁基二锡甲氧基。在70℃、真空度-0.08MPa下反应1h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填4A分子筛50kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为0℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应。反应结束后，酰化液进行下步酯化反应，关闭阀门Q-1和Q-3。开启阀门Q-5和Q-7，向使用过的冷凝吸附装置V-2中通入130℃、空速10m 3/m 3·h的热干空气，通气时长4h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF。
每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表1。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表2。
表1收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000008
表2酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 20.104 172.388 1.252
实施例2
采用如图3所示的装置实施本实施例，关闭阀门Q2和Q4～Q-8，开启阀门Q-1和Q-3。将2t含有20％蔗糖、80％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂820kg，进行第一批次的有机锡蔗糖配合物的制备。在45℃、真空度-0.1MPa下反应3h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填5A分子筛800kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为5℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应，酰化反应结束后，酰化液从反应釜V-1的下出口排出进入酯化反应釜(图中未示出)进行酯化反应。关闭阀门Q-1和Q-3，开启阀门Q-2和阀门Q-4，将2t含有20％蔗糖、80％DMF 的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂820kg。在45℃、真空度-0.1MPa下反应3h，DMF蒸汽从冷凝吸附装置V-3上端经阀门Q-2进入，冷凝塔中装填5A分子筛800kg，继续进行第二批次的有机锡蔗糖配合物的制备。同时开启阀门Q-5和阀门Q-7，向使用过的冷凝吸附装置V-2中通入150℃、空速20m 3/m 3·h的热干空气，通气时长2.5h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，干燥好的冷凝吸附装置V-2可用于第三批次的有机锡蔗糖配合物的制备。
关闭阀门Q-2和Q-4，Q-5和Q-7，开启阀门Q-1和Q-3。将2t含有20％蔗糖、80％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂820kg，进行第三批次的有机锡蔗糖配合物的制备。在45℃、真空度-0.1MPa下反应3h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填5A分子筛800kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为5℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应，酰化反应结束后，酰化液从反应釜V-1的下出口排出进入酯化反应釜(图中未示出)进行酯化反应。
在打开阀门Q-1和Q-3，关闭阀门Q-2和阀门Q-4时，同时开启阀门Q-6和阀门Q-8，向使用过的冷凝吸附装置V-2中通入150℃、空速20m 3/m 3·h的热干空气，通气时长2.5h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，干燥好的冷凝吸附装置V-3可用于第四批次的有机锡蔗糖配合物的制备。冷凝吸附装置V-3以后的再生操作与上述一致。
在第一批次的有机锡蔗糖配合物的制备中，每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表3。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表4。
表3收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000009
Figure PCTCN2021104938-appb-000010
表4酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 22.035 168.976 2.314
在第二批次的有机锡蔗糖配合物的制备中，每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表5。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表6。
表5收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000011
表6酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 22.035 168.976 2.314
在第三批次的有机锡蔗糖配合物的制备中，每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表7。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表8。
表7收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000012
Figure PCTCN2021104938-appb-000013
表8酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 22.035 168.976 2.314
表3、表5和表7中的数据衡量的是分子筛是否将蒸发出的DMF中的水分吸收完全，水含量越低，说明吸附的效果越好，乙酸含量越高，说明反应进行的越完全，由于在本实施例中，三个批次的有机锡蔗糖配合物的制备方法的条件完全相同，所以表3-8中的数据相差无几，甚至部分完全一致，是说明分子筛吸收水分都比较好，酯化都进行的比较完全，且反应非常稳定。
实施例3
采用如图3所示的装置实施本实施例，关闭阀门Q2和Q4～Q-8，开启阀门Q-1和Q-3。将3t含有15％蔗糖、85％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂913.5kg，进行第一批次的有机锡蔗糖配合物的制备。在60℃、真空度-0.08MPa下反应1.5h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填4A分子筛100kg，5A分子筛250kg，13X分子筛100kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为15℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应。酰化反应结束后，酰化液从反应釜V-1的下出口排出进入酯化反应釜(图中未示出)进行酯化反应。
酯化反应结束后，关闭阀门Q-1和阀门Q-3，并开启阀门Q-2和阀门Q-4，继续进行第二批次的有机锡蔗糖配合物的制备。同时开启阀门Q-5和阀门Q-7，向使用过的冷凝吸附装置V-2中通入180℃、空速15m 3/m 3·h的热干空气，通气时长1.5h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，干燥好的冷凝吸附装置V-2用于第三批次的有机锡蔗糖配合物的制备。冷凝吸附装置V-3的固体吸附剂的再生操作与上述一致。
每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表9。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其 他组分含量，具体结果见表10。
表9收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000014
表10酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 18.213 170.431 1.377
实施例4
采用如图3所示的装置实施本实施例，关闭阀门Q-2和和Q-4～Q-8，开启阀门Q-1和Q-3。将4t含有12％蔗糖、88％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂955.2kg，进行第一批次的有机锡蔗糖配合物的制备。在50℃、真空度-0.09MPa下反应2h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填5A分子筛70kg，10Z分子筛80kg，13Z分子筛100kg，13X分子筛150kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为10℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应，酰化反应结束后，酰化液从反应釜V-1的下出口排出进入酯化反应釜(图中未示出)进行酯化反应。
酯化反应结束后，关闭阀门Q-1和阀门Q-3，并开启阀门Q-2和阀门Q-4，继续进行第二批次的有机锡蔗糖配合物的制备。同时开启阀门Q-5和阀门Q-7，向使用过的冷凝吸附装置V-2中通入200℃、空速20m 3/m 3·h的热干空气，通气时长1h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，干燥好的冷凝吸附装置V-2用于第三批次的有机锡蔗糖配合物的制备。冷凝吸附装置V-3的固体吸附剂的再生操作与上述一致。每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表11。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表12。
表11收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000015
表12酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 15.299 181.751 1.430
实施例5
采用如图3所示的装置实施本实施例，关闭阀门Q-2和Q-4～Q-8，开启阀门Q-1和Q-3。将5t含有17％蔗糖、83％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂1674.5kg，进行第一批次的有机锡蔗糖配合物的制备。在65℃、真空度-0.08MPa下反应1.5h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填4A分子筛300kg，5A分子筛350kg，10Z分子筛50kg，13Z分子筛50kg，13X分子筛150kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为7℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应，酰化反应结束后，酰化液从反应釜V-1的下出口排出进入酯化反应釜(图中未示出)进行酯化反应。
酯化反应结束后，关闭阀门Q-1和阀门Q-3，并开启阀门Q-2和阀门Q-4，继续进行第二批次的有机锡蔗糖配合物的制备。同时开启阀门Q-5和阀门Q-7，向使用过的冷凝吸附装置V-2中通入165℃、空速13m 3/m 3·h的热干空气，通气时长3.5h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，干燥好的冷凝吸附装置V-2用于第三批次的有机锡蔗糖配合物的制备。冷凝吸附装置V-3的固体吸附剂的再生操作与上述一致。每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表13。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表14。
表13收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000016
Figure PCTCN2021104938-appb-000017
表14酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 17.930 179.230 1.018
实施例6
采用如图3所示的装置实施本实施例，关闭阀门Q-2和Q-4～Q-8，开启阀门Q-1和Q-3。将6t含有14％蔗糖、86％DMF的混合溶液输入进反应釜V-1中，并加入有机锡酯催化剂1680kg，进行第一批次的有机锡蔗糖配合物的制备。在55℃、真空度-0.09MPa下反应2.5h，DMF蒸汽从冷凝吸附装置V-2上端经阀门Q-1进入，冷凝塔中装填13Z分子筛500kg，13X分子筛400kg。经冷凝塔冷凝后的不含水的DMF溶剂从下端经阀门Q-3进入收集罐V-4，冷凝温度为13℃。然后采用输送泵P-1将收集罐V-4中的不含水的DMF输入进反应釜V-1中继续参与反应，酰化反应结束后，酰化液从反应釜V-1的下出口排出进入酯化反应釜(图中未示出)进行酯化反应。
酯化反应结束后，关闭阀门Q-1和阀门Q-3，并开启阀门Q-2和阀门Q-4，继续进行第二批次的有机锡蔗糖配合物的制备。同时开启阀门Q-5和阀门Q-7，向使用过的冷凝吸附装置V-2中通入185℃、空速11m 3/m 3·h的热干空气，通气时长1.5h，干燥脱除吸附剂上的水和DMF溶剂，尾气送入下级溶剂回收系统分离回收DMF，干燥好的冷凝吸附装置V-2用于第三批次的有机锡蔗糖配合物的制备。冷凝吸附装置V-3的固体吸附剂的再生操作与上述一致。每隔0.5h取收集罐V-4中的DMF样品，检测其水含量及其他组分，具体结果见表15。将反应完成的酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表16。
表15收集罐V-4中DMF成分
Figure PCTCN2021104938-appb-000018
Figure PCTCN2021104938-appb-000019
表16酯化液成分表
组分 蔗糖双酯 蔗糖-6-乙酯 蔗糖
含量g/L 16.871 169.336 1.985
对比例1
根据实施例6，将6t含有14％蔗糖、86％DMF的混合溶液输入进反应釜中，并加入有机锡酯催化剂1680kg，在55℃、真空度-0.09MPa下反应，每隔1h蒸馏出2.4m 3DMF，乙酸和水的混合液(检测其水含量及其他组分，具体结果见表17)，然后补加2.4m 3DMF继续反应，一共反应3h。反应结束后物料进入酰化反应釜，将完成酰化液进行酯化处理，取样并分析酯化液中蔗糖-6-乙酯及其他组分含量，具体结果见表18。
表17收集罐中DMF成分
Figure PCTCN2021104938-appb-000020
表18酯化液成分表及DMF用量
实施例 蔗糖双酯/g/L 蔗糖-6-乙酯/g/L 蔗糖/g/L DMF用量/m 3
实施例6 16.871 169.336 1.985 5.16
对比例1 17.011 169.432 1.734 12.36
由表16，18结果可知，在同样反应条件下，本发明采用分子筛处理回收的DMF中的水分，在达到同等蔗糖转化率的情况，可缩短反应的酰化时间(从3h降低至2.5h)；还可显著降低DMF的使用量(从12.36m 3降低至5.16m 3)。与传统工艺相比，本发明的蔗糖酯化脱水方式具有显著的效果。
综上所述，本申请对于蔗糖的DMF溶液与有机锡酯催化剂进行酰化反应形成的DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行吸附冷凝处理，在这个过程中，固体吸附剂能够有效去除DMF蒸汽中的水分，同时DMF蒸汽被冷凝为液 体，可回流至蔗糖的DMF溶液中继续参与反应，且固体吸附剂经过热干空气的吹扫能够很快再生，反复利用。在这个过程中，只有极少量的DMF蒸汽由于被固体吸附剂吸附而流失需要后处理，绝大部分DMF溶液均回流至蔗糖的DMF溶液中，可为后续有机锡蔗糖配合物与酸酐的反应提供反应环境。本申请相对于现有技术，极大程度上节约了DMF的用量，减轻了DMF后处理的负担，且能够有效去除反应体系中的水分，促进有机锡蔗糖配合物的生成，提高有机锡蔗糖配合物的收率；且整体工艺简单、设备造价低、具有极高的应用价值和经济价值。
在本申请的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。此外，术语“第一”、“第二”、“第三”等仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本申请的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本申请中的具体含义。
以上所述，仅为本申请的具体实施方式，在本申请的上述教导下，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申请的目的，本申请的保护范围应以权利要求的保护范围为准。
此外，本领域的技术人员能够理解，尽管在此所述的一些实施例包括其它实施例中所包括的某些特征而不是其它特征，但是不同实施例的特征的组合意味着处于本申请的范围之内并且形成不同的实施例。例如，在下面的权利要求书中，所要求保护的实施例的任意之一都可以以任意的组合方式来使用。

Claims (10)

  1. 一种有机锡蔗糖配合物的制备方法，其特征在于，包括：
    酰化反应步骤：使蔗糖的DMF溶液与有机锡酯催化剂在预设条件下进行酰化反应，生成有机锡蔗糖配合物和DMF蒸汽；
    溶剂脱水步骤：对所述DMF蒸汽采用预置有固体吸附剂的冷凝吸附装置进行冷凝和吸附，以除去其中的水分，得到再生DMF；
    溶剂回收步骤：收集所述再生DMF，并将收集的再生DMF回收至进入所述酰化反应步骤的蔗糖的DMF溶液中；和
    吸附剂再生步骤：采用热干空气对所述固体吸附剂吹扫，以脱除所述固体吸附剂吸附的杂质，使所述固体吸附剂再生。
  2. 根据权利要求1所述的方法，其特征在于，在连续实施所述有机锡蔗糖配合物的制备方法时，所述溶剂回收步骤与所述酰化反应步骤同时进行，且所述溶剂脱水步骤采用另一套冷凝吸附装置进行，其中，所述另一套冷凝吸附装置中预置的固体吸附剂是新鲜的或者经过再生处理。
  3. 根据权利要求1所述的方法，其特征在于，在所述蔗糖的DMF溶液中，蔗糖的质量含量为10～20％。
  4. 根据权利要求1所述的方法，其特征在于，所述有机锡酯催化剂为二丁基氧化锡酯；
    所述有机锡酯催化剂的质量用量与蔗糖的质量用量的比为1.95～2.05。
  5. 根据权利要求1所述的方法，其特征在于，所述预设条件为：预设温度设为45～70℃，预设真空度设为-0.1～-0.08MPa，预设时间设为1～3h。
  6. 根据权利要求1所述的方法，其特征在于，所述固体吸附剂为分子筛，选自4A分子筛，5A分子筛，10Z分子筛，13Z分子筛和13X分子筛中的一种或多种，优选5A分子筛。
  7. 根据权利要求6所述的方法，其特征在于，所述分子筛的物理性能为：
    Figure PCTCN2021104938-appb-100001
    Figure PCTCN2021104938-appb-100002
    粒径3-10mm，静态吸水率≥20％，包装含水率≤1.5％。
  8. 根据权利要求6所述的方法，其特征在于，所述固体吸附剂的装填质量与蔗糖的质量用量的比为0.5～2。
  9. 根据权利要求1所述的方法，其特征在于，在所述溶剂脱水步骤中，所述冷凝的冷凝温度为0～15℃。
  10. 根据权利要求1所述的方法，其特征在于，所述采用热干空气对所述固体吸附剂吹扫包括：
    采用温度为130～200℃的热干空气，在空速为10～20m 3/m 3·h，干燥时间为1～4h的条件下，对所述固体吸附剂进行吹扫。
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