CN106632524A - Method for preparing high-content mannose - Google Patents
Method for preparing high-content mannose Download PDFInfo
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- CN106632524A CN106632524A CN201611189742.9A CN201611189742A CN106632524A CN 106632524 A CN106632524 A CN 106632524A CN 201611189742 A CN201611189742 A CN 201611189742A CN 106632524 A CN106632524 A CN 106632524A
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- 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
- C07H3/02—Monosaccharides
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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
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Abstract
The invention discloses a method for preparing high-content mannose. A current method for industrially preparing the mannose comprises the following steps: performing dissolution, chemical isomerization and refining on glucose, separating an isomerization solution to obtain a solution rich in the mannose and a solution rich in the glucose by virtue of a simulated moving bed chromatographic separation system, and enabling the solution rich in the glucose to return for re-isomerization. The method has the greatest shortcomings that heterogeneous sugar generated by isomerization cannot be removed and can be accumulated to influence subsequent separation and crystallization along with increase of the number of glucose recycling times; in addition, the content of the heterogeneous sugar is high, so that a chromatographic separation effect is influenced. According to the method, the isomerization solution is separated by virtue of a three-phase simulated moving bed chromatographic separation system, the heterogeneous sugar is discharged from the system at the same time of separation, and a high-content mannose extracting solution and high-content glucose raffinate are obtained; the glucose raffinate is returned for re-isomerization, and is mixed with a new glucose isomerization solution for entering the chromatographic separation system for separation.
Description
Technical field
The present invention relates to starch, the technical field of glucose deep processing, and in particular to a kind of preparation method of mannose.
Background technology
Mannose, C5H11O5CHO, is that, for saccharic nutrient clinically, medical value is high.
Mannose can be by the glycan rich in mannose（Dom nut, yeast mannans etc.）It is prepared by hydrolysis.Also can be by
PEARLITOL 25C（The byproduct of sea-tangle iodine industry）In the presence of ferrous ion, hydrogen peroxide oxidative synthesis are used.Can also be by grape
Sugared epimerization, or the preparation of the methods such as carbochain is increased by D-R.
At present the main method of industrial production mannose is extraction method and isomerate process.
Extraction method is mainly with dom nut or cocoanut shell etc. as raw material, has been waited until containing sweet by acidic hydrolysis
The mixed sugar liquid of dew sugar, then obtain crystallizing D-MANNOSE through processes such as desalination, separation, purifying, concentration, crystallizations.
Isomerate process is mainly with glucose as catalytic material isomery, by part glucose isomery into mannose, then to Portugal
The mixed liquor of grape sugar and mannose carries out the processes such as chromatographic isolation, purifying, concentration, crystallization and obtains crystallizing D-MANNOSE.Isomery is complete
Cheng Hou, obtains the isomery liquid of glucose, mannose and a small amount of miscellaneous sugar, and isomery liquid is separated, and obtains mannose solution and Portugal
Grape sugar juice, glucose solution returns recycling.
Crystallization mannose is to crystallize from mannose solution and obtain.The crystallization of mannose is relatively difficult, if sweet dew in solution
Sugared content is less than 90%, it is necessary to add organic solvent just can crystallize；If mannose content is more than 90% in solution, letter is can use
Single, easy-operating aqueous solution crystalgrowing method is crystallized, and mannose content is higher in solution, and it is easier to crystallize, and crystallization yield is got over
Height, crystal purity is also higher.
Chinese patent CN103387593B discloses a kind of coproduction D-Glucose alcohol-σ-lactone, mannose and mannitol
The isomery mixed liquor of glucose and mannose is carried out chromatographic isolation by method, the method, obtains two components：Rich in mannose component
With rich in glucose component.Rich in mannose component, mannose content only 65 ~ 75%, the yield of mannose is relatively low；Rich in Portugal
In grape sugar component, because mannose content is high, this part mannose returns isomery again with glucose, consumes the energy, reduces
The actual conversion of glucose, and it is also easy to produce miscellaneous sugar under high temperature isomerization conditions.It is topmost, repeatedly after circulation, high temperature isomery
The miscellaneous sugar of generation can accumulate in systems, can only pass through to reduce the mannose content rich in niannan component, increase miscellaneous sugar content,
Make part miscellaneous sugar from the backward operation transfer of mannose direction, follow crystalline mother solution discharge system, have lasting to whole production
Affect.
Chinese patent CN101851689 discloses a kind of preparation technology of D-MANNOSE, and glucose sugar isomery liquid Jing simulations are moved
Dynamic bed is isolated rich in niannan component B1 and rich in glucose component A1, and the latter returns isomery again.The technique and in
State's patent CN102807593 is similar with production method disclosed in Chinese patent CN103387593B, could not equally solve return and follow
The accumulation problem of miscellaneous sugar in the glucose that ring is utilized, the separation yield of mannose is not also high.
Comprehensively it is sayed, in the technique of current glucose isomerase method production mannose, crystal glucose Jing dissolvings, isomery obtain different
Structure liquid, by isomery liquid ion-exchange demineralization is carried out, and the isomery liquid after desalination is separated with separation system of simulated moving bed chromatography, point
The solution rich in mannose and the solution rich in glucose are not obtained, solution concentration, the crystallization of mannose is will be enriched in, sweet dew is obtained
Sugared crystalline product；Or will be enriched in the solution concentration of mannose, hydrogenate, crystallize, obtain crystallization of mannitol product.Will be enriched in glucose
Solution return mix with the new glucose for adding after isomery, isomery liquid is into chromatographic fractionation system separation.In this technique most
Big deficiency has at 2 points, and one is that the miscellaneous sugar that high temperature isomery is produced cannot be removed, and as glucose cycle-index increases, miscellaneous sugar can tire out
Product, accumulation to a certain amount, it will impact is produced on chromatographic isolation and follow-up hydrogenation, crystallization etc.；Two is due to entering chromatogram
The miscellaneous sugar content of piece-rate system is high, and chromatographic separation process causes mannose in the solution rich in mannose to contain without removal of impurities passage
Amount is not high, and the separation yield of mannose is not also high.Because these are not enough, balance in a relatively low receipts with causing whole production compromise
Carry out in the state of rate.
The content of the invention
Cannot exclude for miscellaneous sugar in existing mannose or mannitol production technology and accumulate and cause mannose content not high
Problem, the present invention propose a kind of method for producing high-load mannose, i.e., using three-phase simulation mobile bed chromatic segregative line
System separates isomery liquid, while separating, the miscellaneous sugar component discharge system that will be produced in high temperature isomery, and obtain high-load, height
The mannose extract of yield and the glucose raffinate of high-load.
It is an object of the invention to provide a kind of efficient method for preparing mannose.In chromatographic separation process, pass through
The continuously discharge system of the miscellaneous sugar in system, the circulation production process such as high temperature isomery, chromatographic isolation is set to be in high efficiency
Running status.
The technical scheme is that：Crystal glucose Jing dissolves, and high temeperature chemistry isomery is carried out in the presence of catalyst
Isomery liquid is obtained, the isomery liquid contains mannose, glucose and a small amount of miscellaneous sugar.The refined desalination of ion exchange is carried out to isomery liquid, will
Isomery liquid after desalination is separated with three-phase simulation moving bed chromatographic fractionation system, obtains the mannose that extract is high-load molten
Liquid, raffinate is the solution rich in glucose, and impurities removal liquid is the miscellaneous sugar weak solution of low concentration.The mannose of high-load is production knot
The raw material of brilliant mannose and crystallized mannitol ensures.By mannose solution concentration, crystallization, you can obtain Mannose crystallization product；
The mannose solution concentration of high-load, hydrogenation, crystallization, you can obtain crystallization of mannitol product.Solution rich in glucose is returned
Again after isomery, mix with new glucose isomerase liquid, separate into chromatographic fractionation system；Or will be enriched in the solution of glucose and be used for
The new solid glucose for adding of dissolving, then isomery, enters back into chromatographic fractionation system separation；The miscellaneous sugar weak solution of low concentration is discharged
System, collects discharge liquor, the mixing sugar juice containing maltose, glucose, polysaccharide etc. is obtained after concentration, by this mixed sugar liquid hydrogen
Change, that is, obtain the mixing alcoholic solution that food service industry is used in a large number.
The chromatographic isolation temperature of Simulation moving bed is 40 ~ 65 DEG C, and charging isomery liquid mass percent concentration is 40 ~ 60%；Inhale
Attached dose is that calcium type cation separation resin or calcium type cationic molecule are sieved, and eluant, eluent is purified water.
Described separation system of simulated moving bed chromatography is three phase separation, is different from traditional Simulation moving bed and separates, and is removed
One extracting liquid outlet and raffinate are produced outer, and it also provides the impurities removal liquid for discharging impurity and exports.
After isomery liquid is separated, while obtaining three components：Solution rich in mannose, the solution rich in glucose and low
The miscellaneous sugar weak solution of concentration.
Further, the solution rich in mannose, mannose content 90 ~ 95%；The solution rich in glucose,
Glucose content 90 ~ 95%, miscellaneous sugar content 1 ~ 3%；The miscellaneous sugar weak solution of the low concentration, mass percent concentration 2 ~ 5%, miscellaneous sugar
Content 10 ~ 20%, the part solution concentration is relatively low, and miscellaneous sugar content is high, is arranged by the impurities removal liquid passage of three-phase chromatographic fractionation system
Go out.
Invention introduces three-phase simulation moving bed piece-rate system, there is provided impurities removal liquid passage, in separating glucose and sweet
While dew sugar, the miscellaneous sugar component that will be produced in high temperature isomery, with the carrying out of chromatographic isolation, continuously discharge system,
After miscellaneous sugar discharge system in isomery liquid, the mannose extract of high-load and the glucose raffinate of high-load are obtained.
The present invention solves miscellaneous sugar accumulation in production system causes subsequent production difficult pure with chromatographic isolation mannose solution
The not high enough problem of degree, improves the yield of separative efficiency and mannose, therefore also improves conversion ratio of the glucose to mannose.
Into the glucose of system, a part is transformed into mannose, and small part is moved with mannose component toward subsequent handling, also more
Small part follows miscellaneous sugar weak solution discharge system, the mannose for obtaining to reach 80 ~ 90% to the yield of glucose.The present invention is one
Plant the method for efficiently producing mannose.
Description of the drawings
Fig. 1 is the chromatogram of isomery liquid after ion-exchange demineralization.
Fig. 2 is the high-efficient liquid phase chromatogram rich in mannose solution after chromatographic isolation.
Fig. 3 is the high-efficient liquid phase chromatogram rich in glucose solution after chromatographic isolation.
Fig. 4 is the high-efficient liquid phase chromatogram of low concentration miscellaneous sugar weak solution after chromatographic isolation.
It is embodied as case
Technical process and effect of the invention is illustrated with example is embodied as below in conjunction with accompanying drawing, but the present invention receives following reality
Apply the restriction of example.
Embodiment 1
1 isomery
It is 50% that solid glucose is dissolved to into mass percent concentration, and it is 3.0 to add hydrochloric acid to adjust pH value, adds glucose weight
The molybdate catalyst of amount 0.08%, is heated to 115 DEG C, high temperature isomerization reaction 1 hour, obtains containing glucose, mannose and miscellaneous
The isomery liquid of sugar.Jing after decolorizing with activated carbon, ion exchange desalination, the isomery liquid is entered using separation system of simulated moving bed chromatography
Row is separated.Use high performance liquid chromatograph（HPLC）Detection is consisted of into the isomery liquid of chromatographic fractionation system：Glucose 68.0%,
Mannose 27.5%, other miscellaneous sugars amount to 4.5%, HPLC analysis results as shown in Figure 1.
2 separate
SMBC separation condition is：60 DEG C of separation temperature, charge raw material mass percent concentration 50%；Adsorbent is
Calcium type molecular sieve, eluant, eluent is purified water.
Three kinds of components are obtained after SMBC is separated：
（1）Extract rich in mannose, wherein mass percent concentration 20.6%, mannose content 92.2%, glucose content
7.7%, miscellaneous sugar content 0.1%, HPLC analysis results are as shown in Figure 2.
By the concentration of the liquid glucose rich in mannose, the crystallization, highly purified Mannose crystallization product is obtained.
Or will be enriched in the solution concentration of mannose, hydrogenate, crystallize, obtain highly purified crystallization of mannitol product.
（2）Raffinate rich in glucose, wherein mass percent concentration 25.0%, glucose content 91.9%, mannose
Content 5.9%, miscellaneous sugar content 2.2%, HPLC analysis results are as shown in Figure 3.
The liquid glucose of glucose should be rich in Jing after decolorizing with activated carbon, ion exchange desalination, being concentrated into mass concentration 50%, returned
Again isomery obtains the isomery liquid after isomery again, and the isomery liquid mixes with new glucose isomerase liquid, into chromatographic fractionation system
Separate.
（3）The miscellaneous sugar weak solution of low concentration, mass percent concentration 3.5%, miscellaneous sugar content 14.6%, glucose content
85.4%, without mannose, HPLC analysis results are as shown in Figure 4.
The miscellaneous sugar weak solution of the part low concentration, concentration is relatively low, and miscellaneous sugar content is high, after being collected concentration, is contained
The mixing sugar juice of maltose, glucose, polysaccharide etc., by this mixed sugar liquid hydrogenation, that is, obtains mixed alcohol solution.
Embodiment 2
1 new glucose isomerase
It is 50% that solid glucose is dissolved to into mass percent concentration, and it is 3.0 to add hydrochloric acid to adjust pH value, adds glucose weight
The molybdate catalyst of amount 0.08%, is heated to 115 DEG C, high temperature isomerization reaction 1 hour, obtains containing glucose, mannose and miscellaneous
The new isomery liquid of sugar.
2 raffinate isomeries
The raffinate rich in glucose that SMBC is obtained after separating, wherein mass percent concentration 26.5%, sweet dew
Sugared content 4.5%, glucose content 93.5%, miscellaneous sugar content 2.0%, is concentrated into quality at Jing decolorizing with activated carbon, ion exchange desalination
After percent concentration 50%, the molybdate catalyst of grape sugar weight 0.08% is added, be heated to 115 DEG C, high temperature isomerization reaction 1 is little
When, obtain the circulation isomery liquid containing glucose, mannose and miscellaneous sugar.
3 mixing
The new isomery liquid of step 1 and step 2 gained is mixed with raffinate isomery liquid, isomery liquid must be mixed, consisting of, containing Portugal
Grape sugar 67.5%, mannose 27.4%, miscellaneous sugar summation 5.1%.
4 separate
As described in Example 1, the isomery liquid is separated using separation system of simulated moving bed chromatography, to separating obtained
Three kinds of components are processed.
Embodiment 3
1 dissolves new glucose with raffinate
By the raffinate rich in glucose, wherein mass percent concentration 27.3%, mannose Jing after SMBC is separated
Content 5.5%, glucose content 91.6%, miscellaneous sugar content 2.9% is new for dissolving Jing after decolorizing with activated carbon, ion exchange desalination
The solid glucose of addition, is subsequently adding pure water and allocates to solution quality percent concentration 50%.
2 isomeries
The molybdate catalyst of grape sugar weight 0.08% is added, 115 DEG C are heated to, high temperature isomerization reaction 1 hour is contained
The common isomery liquid of glucose, mannose and miscellaneous sugar, consisting of, containing glucose 67.9%, mannose 26.8%, miscellaneous sugar summation
5.3%。
3 separate
As described in Example 1, the isomery liquid is separated using separation system of simulated moving bed chromatography, to separating obtained
Three kinds of components are processed.
Claims (5)
1. a kind of method for producing high-load mannose, the method includes：Crystal glucose Jing dissolvings, high temeperature chemistry isomery obtain different
Structure liquid, by isomery liquid ion-exchange demineralization is carried out, it is characterised in that：Separated after desalination with separation system of simulated moving bed chromatography
Isomery liquid；Extract is the mannose solution of high-load, and raffinate is the solution rich in glucose, and impurities removal liquid is miscellaneous for low concentration
Malt sugar solution；Will be enriched in the solution return system of glucose；By the miscellaneous sugar weak solution discharge system of low concentration.
2. according to a kind of method for producing high-load mannose described in claim 1, it is characterised in that：Simulation moving bed color
Detached temperature is composed for 40 ~ 65 DEG C, charging isomery liquid mass percent concentration is 30 ~ 60%, adsorbent is calcium type cation separation
Resin or calcium type molecular sieve, eluant, eluent is purified water.
3. according to a kind of method for producing high-load mannose described in claim 1, it is characterised in that：Described extract
It is the solution rich in mannose, mass percent concentration 18.0 ~ 25.0%, mannose content 90 ~ 95%.
4. according to a kind of method for producing high-load mannose described in claim 1, it is characterised in that：Described raffinate
It is the solution rich in glucose, mass percent concentration 20.0 ~ 30.0%, glucose content 90 ~ 95%；This part solution is returned
Utilize, for after the crystal glucose for dissolving new addition, carrying out high temeperature chemistry isomery.
5. according to a kind of method for producing high-load mannose described in claim 1, it is characterised in that：Described impurities removal liquid
For miscellaneous sugar mass percent concentration 2 ~ 5%, the solution of miscellaneous sugar content 10 ~ 20%；This part solution is the miscellaneous sugar weak solution of low concentration,
System is discharged it by the impurity discharging passage of piece-rate system, and is collected after concentration, obtained containing maltose, glucose, polysaccharide etc.
Mixed sugar liquid；By this mixed sugar liquid hydrogenation, mixed alcohol liquid is obtained.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611189742.9A CN106632524A (en) | 2016-12-21 | 2016-12-21 | Method for preparing high-content mannose |
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| CN201611189742.9A CN106632524A (en) | 2016-12-21 | 2016-12-21 | Method for preparing high-content mannose |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389846A (en) * | 2017-09-05 | 2017-11-24 | 南京凯通粮食生化研究设计有限公司 | A kind of quick determination method of inulin content |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101554540A (en) * | 2009-04-22 | 2009-10-14 | 南京凯通粮食生化研究设计有限公司 | Method for separating glucose, seminose and oligosaccharide by simulated moving bed |
| CN102329340A (en) * | 2011-11-01 | 2012-01-25 | 青岛明月海藻集团有限公司 | Method for preparing D-mannose |
| CN103387593A (en) * | 2013-08-20 | 2013-11-13 | 青岛明月海藻集团有限公司 | High-yield co-production method of D-gluconic acid-delta-lactone, mannose and mannitol |
-
2016
- 2016-12-21 CN CN201611189742.9A patent/CN106632524A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101554540A (en) * | 2009-04-22 | 2009-10-14 | 南京凯通粮食生化研究设计有限公司 | Method for separating glucose, seminose and oligosaccharide by simulated moving bed |
| CN102329340A (en) * | 2011-11-01 | 2012-01-25 | 青岛明月海藻集团有限公司 | Method for preparing D-mannose |
| CN103387593A (en) * | 2013-08-20 | 2013-11-13 | 青岛明月海藻集团有限公司 | High-yield co-production method of D-gluconic acid-delta-lactone, mannose and mannitol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107389846A (en) * | 2017-09-05 | 2017-11-24 | 南京凯通粮食生化研究设计有限公司 | A kind of quick determination method of inulin content |
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Application publication date: 20170510 |