CN106632371A - Method using dehydrated sorbitol liquid to produce high-purity isosorbide solution - Google Patents
Method using dehydrated sorbitol liquid to produce high-purity isosorbide solution Download PDFInfo
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- CN106632371A CN106632371A CN201610728496.3A CN201610728496A CN106632371A CN 106632371 A CN106632371 A CN 106632371A CN 201610728496 A CN201610728496 A CN 201610728496A CN 106632371 A CN106632371 A CN 106632371A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a method using dehydrated sorbitol liquid to produce a high-purity isosorbide solution and belongs to the technical field of functional sugar purification. The method includes: preprocessing a raw material, to be more specific, performing decoloring and ion exchange treatment on the dehydrated sorbitol liquid; secondly, performing simulated moving bed separation, wherein DTF chromatographic separation resin is used as the absorbent of the simulated moving bed chromatography, deionized water is used as the eluent of the simulated moving bed chromatography, the particle size of the separation resin is 0.2-0.4mm, and the crosslinking degree of the separation resin is 2-8%. By the method which is simple to operate, high in product purity, low in cost, stable and efficient in equipment and applicable industrial production, the isosorbide solution with the purity being not smaller than 98% can be prepared.
Description
Technical field
The invention belongs to functional sugar purification technique field, more particularly to it is a kind of different using sorb dehydration of alcohols liquid production high-purity
The method of sorbitol solution.
Background technology
Isobide (English name isosorbitol, isosorbide), inherently a kind of effective permeability is oral
Dehydration and diuresis medicine.At present, isobide is mainly used as the preparing raw material of cardiovascular drugs Ismo 20 in China.
Because medical market is comparatively smaller, people are have impact on to a certain extent in isobide preparation field
Research.With the raising of the increasingly depleted and people of world energy sources resource to artificial polymer's quality requirement, grinding in autgmentability
It is found that isobide improves the unique effect of polymer property in studying carefully.In recent years, for the study hotspot of isobide
It is as comonomer, for the commercial polymer of synthesis modification, such as PET, polyethers, polyester, polyurethane, Merlon
Deng.Isobide is added in PET the vitrification point that can improve polymer, the intensity for increasing polymer.Can also be by
It is used for the encapsulation bottle of hot liquid or thick liquid, extends the application market of polymer.Isobide participates in polymerization can be improved
The high-temperature behavior and shock resistance of polymer, gives the materials optical transparency and biodegradability.E.I.Du Pont Company invents
A series of polyester containing isobide, the polyester using aromatic diacid and isobide condensation reaction, it is right to produce
Number reduced viscosity is at least the polyester of 0.15-0.35dL/g, and itself and other thermosetting polyester blendings are obtained more full-bodied
Polyester.Due to its excellent properties, the polyester can be used for optical plastic, the base material of high definition optical disc, lens, instrument board window
Mouth, prism reflector, film or optical fiber etc..Isobide Effect study in the polymer, has shown that its improvement is polymer
The unique effect of matter, once in the field application, its market demand will be at annual more than 5,000,000 tons.
Isobide purifying technique is all to utilize in patent CN103980286A, CN104788465A, CN204752581U
Pyrogenous mode is produced, and particular problem is as follows present in the technique：Using pyrogenous mode to different sorb
Alcohol is purified, 372.1 DEG C of isobide boiling point, although vacuumize, but remains a need for 200 DEG C or so of high temperature, is either operated
Security, or from from the aspect of energy-conservation, be all not suitable with the needs of current economic constructional transfer；And yield is low, cost compared with
It is prepared by height, the production for being not suitable for carrying out heavy industrialization.
The content of the invention
Purpose is to provide a kind of method that utilization sorb dehydration of alcohols liquid produces high-purity Ismotic.
A kind of method that utilization sorb dehydration of alcohols liquid produces high-purity Ismotic, step is as follows：
(1) pretreatment of raw material：Sorb dehydration of alcohols liquid Jing decolourizes, ion-exchange treatment；
(2) Simulation moving bed is separated：The adsorbent of SMBC adopts DTF (preferred sodium form) used in chromatograph tree
Fat, eluant, eluent adopts water, preferably：Deionized water.
DTF (preferred sodium form) the used in chromatograph resin, refers to DTF series starch sugar dedicated separation resins.
It is preferred that：Decolourize to be specially in the step (1)：Sorb dehydration of alcohols liquid is 120-90 by volume/quality of activated carbon：
1.5-2.5 is (preferably：100:2), ml：G ratios add activated carbon, and 20-40min is incubated under the conditions of 70 DEG C -80 DEG C (preferably：
30min)。
Advantage：Ismotic color prepared by sorbierite Jing dehydrations is in deep yellow or brown, and the presence of pigment can be to moving
Bed resin is polluted, and color sense organ is poor has a strong impact on product condition, can be obtained by above-mentioned desolventing technology
The colourless Ismotic of light >=99%.
It is preferred that：Step (1) intermediate ion is exchanged and is specially：Jing cationic ion-exchange resins, anion exchange resin desalination
The removal of impurity is gone, liquid is purified.
Advantage：By above-mentioned decolouring, ion-exchange treatment, scavenging solution printing opacity >=99.8%, pH value 4.5-5.5, conductance
Rate≤20us/cm, by scavenging solution refractive power 45%-55% is concentrated.
It is preferred that：Separation temperature in step (2) is：50-80 DEG C, preferably：70℃.
Advantage：The rising of temperature increases molecular kinetic energy, and adsorption rate is accelerated, and can effectively reduce solution viscosity, drops
Low-pressure suppresses bacteria breed, but while can accordingly increase the consumption of steam, 50-80 DEG C is optimal separation temperature.
It is preferred that：Separate in step (2) and use resin particle diameter 0.2-0.4mm.Advantage：The chromatographic isolation resin is that particle is equal
It is even, the homogeneous microballoon in aperture, particle diameter 0.2-0.4mm, it is to avoid particle diameter is too small to cause device interior pressure excessive；Particle diameter crosses conference
Cause easily to occur bias current and be unfavorable for that feed liquid uniform adsorption finally affects to separate pure problem.
It is preferred that：The separation resin's crosslinkage is 2%-8%.
Advantage：Cross-linkage of resin reduces can exchange area less than 2%, affect absorption affinity, screening effect to weaken, and affect
Separating effect, the degree of cross linking is more than 8%, and the duct of resin narrows, and is unfavorable for that glycan molecule effectively equally affects to separate through duct
Effect.
The separation resin ionic type is Na+、H+、K+In one kind, wherein it is preferred that Na+DTF chromatographic isolation resins.
It is preferred that：Moving bed imitation chromatogram separation facility is composed in series using 6-12 root chromatogram columns head and the tail in the step (2),
Each chromatographic column controls input and output material by 1 group of internally piloted valve, and the internally piloted valve is Pneumatic valve；All gas control valve control signals are by gas circuit control
Case control processed sends；Charging group internally piloted valve has 1 to enter feed valve, 1 water intaking valve, 1 high-load isobide outlet valve, 1
Miscellaneous component outlet valve；Resin is filled in by chromatogram single-column using wet stowage, the switching of operated pneumatic valve is controlled by PLC, by each
Chromatographic column is separated into charging, the discharging of high-load isobide, the discharging of miscellaneous component, four type intervals of wash-out, and four class areas
Between switch in cyclic switching between different single-columns with Air control valve.
It is preferred that：Step (2) the feedstock solution refractive power 45%-55%, printing opacity >=99.8%, pH value 4.5-5.5, electrical conductivity
≤20us/cm。
Advantage：Avoid excessive concentration meeting build-up of pressure too high, while affecting separating effect, concentration is too low to cause production
The low problem of efficiency.PH range intervals can be effectively protected the loss of resin intermediate ion, extend resin service life.Avoid simultaneously
Electrical conductivity is too high to be caused to adsorb metal ion impact adsorption effect in feed liquid in resin separation process, and long-play can be made
The problem of the generation of resin intoxicating phenomenon.Printing opacity belongs to feed liquid preprocessing process intermediate ion and exchanges the subsidiary effect for producing, no
As the Primary Reference foundation of charging.
The operating parameter of Simulation moving bed, single-column volume 7m3, single-column quantity 6-12 root, eluting water 1.2m2/h-1.8m2/ h,
Charging 0.5m2/h-0.7m2/ h, high-load isobide discharging 1.2m2/h-1.4m2/ h, miscellaneous component discharging 0.7m2/h-0.9m2/
H, switching time 80-110min.Switching time and turnover doses can be according to single-column volume, single-column diameter, height in actual production
And single-column quantity has differences.This parameter is only used as our unit's physical device operational factor, and with directive significance, but right is not
It is only limitted to this parameter area.
Beneficial effects of the present invention：
The present invention carries out purification operations using moving bed imitation chromatogram separation facility to sorb dehydration of alcohols liquid, obtains high-purity
Ismotic；Conventional espresso method of purification is compared, condition of the present invention is simple, is not required to high temperature, vacuum, greatly reduces electricity
Consumption, steam consumption；Resin used is repeatable utilization, and resin life, up to 5-8, greatly reduces operating cost；It is produced
Miscellaneous component liquid (predominant amount is an anhydro sorbitol) can carry out further dehydrating operations and prepare isobide, reduce the wave of raw material
Take raising target product yield；Relatively conventional distillation technique has consume energy low, high income, operating cost low, does not exist and separated
The bad reactions such as the charing of journey greatly reduce production cost.
But although simulation thermopnore isolation technics is separated it has been reported that currently without utilizing analog stream in function sugar product
Dynamic bed separates the report of isobide, because sorb dehydration of alcohols liquid complicated component, sorb dehydration of alcohols liquid (Ismotic) is main
That what is wanted consists of isobide (two anhydro sorbitols) and an anhydro sorbitol, differs only by a hydrone, and separating difficulty is big.
To affect Simulation moving bed that a difficult problem for application is purified in isobide, present invention research discovery utilizes DTF for the selection of separation resin
(preferred sodium form) chromatographic isolation resin, can occur chelation with the hydroxyl in isobide and an anhydro sorbitol molecule.Root
According in molecule hydroxyl number, produce the size difference of active force so that adsorption time of the glycan molecule on resin produce it is effective
Time difference, it is ensured that different component is efficiently separated.The chelating radius of different metal ions has differences and absorption affinity can be produced
Affect；Different degree of cross linking resin aperture differences can also affect adsorption effect.The particle diameter 0.2- of the separation resin that the present invention is used
0.4mm, it is to avoid particle diameter is too small to cause device interior pressure excessive；Particle diameter crosses conference and causes bias current easily occur to be unfavorable for feed liquid
Uniform adsorption finally affects to separate pure problem.The separation resin degree of cross linking is 2%-8%.Avoid the too small meeting of cross-linkage of resin
Reduce exchange area, affect absorption affinity, screening effect to weaken, affect separating effect, the duct of the excessive resin of the degree of cross linking to narrow,
It is unfavorable for that glycan molecule effectively equally affects the problem of separating effect through duct.
The present invention is separated using moving bed imitation chromatogram separation facility to sorb dehydration of alcohols liquid, and whole process is using automation control
System, material operation is closed to be carried out.Human cost is greatly saved, cleannes are high.
The resin that the present invention is selected, effectively solving usual resins cannot efficiently separate the technical difficulty of isobide
Topic, realizes that Simulation moving bed is effectively applied in the separation of isobide.
Specific embodiment
Embodiment 1
With Simulation moving bed separation and purification high-purity isobide method, operating procedure is as follows：
1. raw material decolourizes：
Sorb dehydration of alcohols liquid refractive power 40%, is warming up to 75 DEG C, by volume mass than 2% activated carbon of addition；Stirring insulation
30min；Using Filter Press；Obtain the destainer of printing opacity 99%%.
2. ion exchange：
Destainer is sequentially passed through into ion exchange column according to positive and negative, positive and negative order, printing opacity 99.8%, pH value 4.5- is obtained
5.5th, conductance≤20us/cm scavenging solutions；It is concentrated into refractive power 40%
3. Simulation moving bed is separated：
Using by the end to end moving bed imitation chromatogram separation facility being composed in series of 6 chromatography column Jing pipelines to dense
Contracting after-purification liquid is separated, with sodium form DTF chromatographic isolation resin as adsorbent, with deionized water as eluant, eluent, and separation temperature
70 DEG C, fed by programme-control, discharged, feed rate 0.7m2/ h, deionized water 1.2m2/ h, each cycle run time
100min obtains purity for 98.8% Ismotic；
Embodiment 2
1. raw material decolourizes：
Sorb dehydration of alcohols liquid refractive power 40%, is warming up to 70 DEG C, by volume mass than 3% activated carbon of addition；Stirring insulation
30min；Using Filter Press；Obtain the destainer of printing opacity 99%%.
2. ion exchange：
Destainer is sequentially passed through into ion exchange column according to positive and negative, positive and negative order, printing opacity 99.8%, pH value 4.5- is obtained
5.5th, conductance≤20us/cm scavenging solutions；It is concentrated into refractive power 40%
3. Simulation moving bed is separated：
Using by the end to end moving bed imitation chromatogram separation facility pair being composed in series of 12 chromatography column Jing pipelines
Concentration after-purification liquid is separated, and sodium form DTF chromatographic isolation resin is adsorbent, with deionized water as eluant, eluent, separation temperature
50 DEG C, fed by programme-control, discharged, feed rate 1.2m2/ h, deionized water 1.2m2/ h, each cycle run time
80min obtains purity for 98.1% Ismotic；
Although the above-mentioned specific embodiment to the present invention is described, not to the limit of the scope of the present invention
System, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not pay
The various modifications made by going out creative work or deformation are still within protection scope of the present invention.
Claims (10)
1. a kind of method that utilization sorb dehydration of alcohols liquid produces high-purity Ismotic, is characterized in that：Step is as follows：
(1) pretreatment of raw material：Sorb dehydration of alcohols liquid Jing decolourizes, ion-exchange treatment；
(2) Simulation moving bed is separated：The adsorbent of SMBC adopts DTF used in chromatograph resins, eluant, eluent to adopt
Water.
2. the method for claim 1, is characterized in that：Decolourize to be specially in the step (1)：Sorb dehydration of alcohols liquid presses body
Product/quality of activated carbon is 120-90：1.5-2.5, ml：G ratios add activated carbon, and under the conditions of 70 DEG C -80 DEG C 20-40min is incubated.
3. the method for claim 1, is characterized in that：Decolourize to be specially in the step (1)：Sorb dehydration of alcohols liquid presses body
Product/quality of activated carbon is 100:2, ml：G ratios add activated carbon, and under the conditions of 70 DEG C -80 DEG C 30min is incubated.
4. the method for claim 1, is characterized in that：Sodium form DTF used in chromatograph resin is adopted in the step (2).
5. the method for claim 1, is characterized in that：Feedstock solution refractive power 45%-55% in the step (2), pH value
4.5-5.5, electrical conductivity≤20us/cm.
6. the method for claim 1, is characterized in that：Separation temperature is in the step (2)：50-80℃.
7. the method for claim 1, is characterized in that：Separate in the step (2) and use resin particle diameter 0.2-0.4mm.
8. the method for claim 1, is characterized in that：Separation resin's crosslinkage is 2%- described in the step (2)
8%.
9. the method for claim 1, is characterized in that：6-12 root chromatogram column head and the tail series connection groups are utilized in the step (2)
Into moving bed imitation chromatogram separation facility, each chromatographic column controls input and output material by 1 group of internally piloted valve, and the internally piloted valve is Pneumatic valve；
All gas control valve control signals are sent by the control of gas circuit control cabinet；Charging group internally piloted valve has 1 to enter feed valve, 1 water intaking valve, and 1
Individual high-load isobide outlet valve, 1 miscellaneous component outlet valve；Resin is filled in by chromatogram single-column using wet stowage, by PLC
The switching of control operated pneumatic valve, by each chromatographic column charging, the discharging of high-load isobide, the discharging of miscellaneous component, wash-out are separated into
Four type intervals, and four type intervals switch in cyclic switching between different single-columns with Air control valve.
10. the method for claim 1, is characterized in that：The operating parameter of Simulation moving bed, single-column in the step (2)
Volume 7m2, single-column quantity 6-12 root, eluting water 1.2m2/h-1.8m2/ h, feeds 0.5m2/h-0.7m2/ h, high-load isobide
Discharging 1.2m2/h-1.4m2/ h, miscellaneous component discharging 0.7m2/h-0.9m2/ h, switching time 80-110min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610728496.3A CN106632371A (en) | 2016-08-26 | 2016-08-26 | Method using dehydrated sorbitol liquid to produce high-purity isosorbide solution |
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| CN201610728496.3A CN106632371A (en) | 2016-08-26 | 2016-08-26 | Method using dehydrated sorbitol liquid to produce high-purity isosorbide solution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141301A (en) * | 2017-05-19 | 2017-09-08 | 南京凯通粮食生化研究设计有限公司 | A kind of preparation method for crystallizing isobide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002039957A2 (en) * | 2000-11-06 | 2002-05-23 | E.I. Dupont De Nemours And Company | Chromatographic processes for recovery of isosorbide |
| CN1425637A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Process for catalytically synthesizing isosorbierte by strong acid ion exchanging resin |
| CN101665497A (en) * | 2009-09-22 | 2010-03-10 | 南京工业大学 | Method for refining isosorbide by distillation and melt crystallization coupling technology |
| CN102603760A (en) * | 2011-01-24 | 2012-07-25 | 华东理工大学 | Synthesis method of anti-angina drug isosorbide mononitrate |
| CN104788465A (en) * | 2015-02-10 | 2015-07-22 | 沈阳化工大学 | Method for continuous preparation of isosorbide from sorbitol |
| CN104822684A (en) * | 2012-10-31 | 2015-08-05 | 阿彻丹尼尔斯米德兰德公司 | Improved method of making internal dehydration products of sugar alcohols |
| CN105154477A (en) * | 2015-10-16 | 2015-12-16 | 成都连接流体分离科技有限公司 | Method for producing crystalline sorbitol from starch |
-
2016
- 2016-08-26 CN CN201610728496.3A patent/CN106632371A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002039957A2 (en) * | 2000-11-06 | 2002-05-23 | E.I. Dupont De Nemours And Company | Chromatographic processes for recovery of isosorbide |
| CN1425637A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Process for catalytically synthesizing isosorbierte by strong acid ion exchanging resin |
| CN101665497A (en) * | 2009-09-22 | 2010-03-10 | 南京工业大学 | Method for refining isosorbide by distillation and melt crystallization coupling technology |
| CN102603760A (en) * | 2011-01-24 | 2012-07-25 | 华东理工大学 | Synthesis method of anti-angina drug isosorbide mononitrate |
| CN104822684A (en) * | 2012-10-31 | 2015-08-05 | 阿彻丹尼尔斯米德兰德公司 | Improved method of making internal dehydration products of sugar alcohols |
| CN104788465A (en) * | 2015-02-10 | 2015-07-22 | 沈阳化工大学 | Method for continuous preparation of isosorbide from sorbitol |
| CN105154477A (en) * | 2015-10-16 | 2015-12-16 | 成都连接流体分离科技有限公司 | Method for producing crystalline sorbitol from starch |
Non-Patent Citations (1)
| Title |
|---|
| 王振宇 等: "《生物活性成分分离技术》", 31 May 2015, 哈尔滨工业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141301A (en) * | 2017-05-19 | 2017-09-08 | 南京凯通粮食生化研究设计有限公司 | A kind of preparation method for crystallizing isobide |
| CN107141301B (en) * | 2017-05-19 | 2019-05-07 | 南京凯通粮食生化研究设计有限公司 | A kind of preparation method crystallizing isobide |
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Inventor after: Xin Chengfu Inventor after: Liu Baochen Inventor after: Jing Wenli Inventor after: Yu Li Inventor after: Wang Bin Inventor after: Ren Shangmei Inventor after: Liu Jian Inventor before: Xin Chengfu Inventor before: Jing Wenli Inventor before: Yu Li Inventor before: Wang Bin Inventor before: Ren Shangmei Inventor before: Liu Jian |
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