CN108866247A - The method and apparatus that continuous large-scale separation prepares D-Psicose - Google Patents
The method and apparatus that continuous large-scale separation prepares D-Psicose Download PDFInfo
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- CN108866247A CN108866247A CN201811086450.1A CN201811086450A CN108866247A CN 108866247 A CN108866247 A CN 108866247A CN 201811086450 A CN201811086450 A CN 201811086450A CN 108866247 A CN108866247 A CN 108866247A
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/007—Separation of sugars provided for in subclass C13K
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Abstract
The present invention relates to the methods and apparatus that continuous large-scale separation prepares D-Psicose.Specifically, the method for the present invention includes：(1) it provides and is used as charging F containing sugared mixed liquor containing glucide, wherein is described to include containing sugared mixed liquor：Psicose, fructose, glucose and oligosaccharide；And (2) chromatographic isolation：It is separated to described containing sugared mixed liquor by the chromatographic isolation equipment based on mobile bed chromatic, obtains the solution containing psicose, wherein the purity of the psicose in the solution containing psicose>80wt%, on the basis of the quality of dry matter in solution.
Description
Technical field
The invention belongs to raw-food material manufacture fields, and in particular to a kind of continuous large-scale separation prepares D-Psicose
Method and apparatus.
Background technique
D-Psicose is a kind of rare sugar existing for nature, and according to research reports, D-Psicose is a kind of novel function
Can property monosaccharide compared with sucrose, heat is low, pure taste, will not can be very good control blood glucose by body metabolism.2011
Year, U.S. FDA approved D-Psicose is considered safety food as raw-food material；So D-Psicose is expected into
Diet, health care and medicine and other fields are widely used in as food or food additives for the substitute of sucrose.
The production cost of D-Psicose is also relatively high at present, as a kind of novel sweetener, to obtain universal push away
Wide and use, also needs to further decrease production cost.The separating and purifying technology needs of especially psicose are solved perfectly, ability
Enough further industrial applications.Having many patent reports all is to produce A Luo ketone by substrate of fructose, glucose or sucrose
Sugar, if Chinese patent CN101177672 discloses the method for preparing psicose by bioenzymatic conversion as raw material using fructose,
It is the raw material method that continuously conversion prepares psicose that CN102869783, which is then disclosed with glucose, and CN103333935A is disclosed
Psicose is prepared by bioconversion as raw material using sucrose method.Starch than glucose, fructose and sucrose price all
The solution composition complexity containing D-Psicose that is lower, however being obtained using starch as the preparation method of raw material, this field is not yet
There is the solution for purifying this complicated component to obtain the separation method of the industrial-scale of D-Psicose.
In conclusion there is an urgent need in the art to develop it is a kind of can continuous, large-scale separation prepare the side of D-Psicose
Method, and this method can be used for separating the solution containing D-Psicose with complex component prepared by carbohydrates such as starch；And phase
The separation equipment answered.
Summary of the invention
It is an object of the invention to provide it is a kind of can continuous, the large-scale separation method for preparing D-Psicose, and should
Method can be used for separating the solution containing D-Psicose with complex component prepared by carbohydrates such as starch；And corresponding separation
Equipment.
In the first aspect of the present invention, a kind of method that continuous, large-scale separation prepares D-Psicose is provided,
In, the method includes the following steps：
(1) it provides and is used as charging F containing sugared mixed liquor containing glucide；
Wherein, described to include containing sugared mixed liquor：Psicose, fructose, glucose and oligosaccharide；
The oligosaccharide is sugar selected from the group below：Maltose, isomaltose, maltotriose, maltotetraose, polysaccharide or its
Combination；And
(2) chromatographic isolation：It is separated to described containing sugared mixed liquor by the chromatographic isolation equipment based on mobile bed chromatic,
Obtain the solution containing psicose, wherein the purity of the psicose in the solution containing psicose>80wt%, with molten
In liquid on the basis of the quality of dry matter；
The chromatographic isolation includes：
(2.1) feed step：It will be in the chromatographic column that be passed through containing sugared mixed liquor；
(2.2) elution step：Eluent D is passed through in chromatographic column and is eluted, and the eluent D is water；
(2.3) discharge step：Collect out-feed liquid, wherein the out-feed liquid includes the first out-feed liquid, and described first discharges
Liquid is the solution containing psicose；
Wherein, the chromatographic isolation equipment includes 2-20 chromatographic columns and/or chromatography shell of column, and the chromatographic column
And/or the filler of chromatography shell of column is resin cation, each chromatographic column and/or chromatography shell of column are connected in series.
In another preferred example, the 2-20 chromatography shell of column is that chromatographic column is divided into several segments, can be real between every section
Existing input and output material, and be connected in series between section and section, liquid can flow successively through each section；And/or
The 2-20 chromatographic column refers to each Coupled columns, input and output material may be implemented between each column, liquid can
To flow successively through each chromatographic column.
In another preferred example, it on the flow direction of mobile phase, is successively arranged the feed inlet containing sugared mixed liquor, second goes out
The discharge port of the discharge port of feed liquid, eluant, eluent import and the first out-feed liquid.
In another preferred example, material-water ratio 1:(0.5-3.0)；Wherein, the material-water ratio is charging F:The matter of eluent D
Amount ratio；Preferably, material-water ratio 1:(0.8-2.5)；It preferably, is 1:(1.0-2.0).
In another preferred example, the switching time of the chromatographic column of the method and/or chromatography shell of column is 3~15min；It is preferred that
Ground is 5-8min.
In another preferred example, in step (2.3), the out-feed liquid further includes the second out-feed liquid, second out-feed liquid
Include glucose and fructose.
In another preferred example, first out-feed liquid refers to the feed liquid for collecting that slow component obtains in chromatographic isolation；And
Second out-feed liquid refers to the feed liquid for collecting that fast component obtains in chromatographic isolation.
In another preferred example, step (2.1), (2.2) and (2.3) is carried out in order or is carried out each independently.
In another preferred example, step (2.1) and (2.2) carry out in order or carry out each independently.
In another preferred example, step (2.1) and step (2.2) interval carry out；And/or step (2.3) is carried out continuously.
In another preferred example, the first out-feed liquid of collection and the mass ratio of charging F total amount are (0.9~1.5):1；It is preferred that
Ground, (1.0~1.3):1.
In another preferred example, the second out-feed liquid of collection and the mass ratio of charging F total amount are (1~3):1；Preferably,
(1~2.4):1.
In another preferred example, the mass ratio of the first out-feed liquid and the second out-feed liquid is 1:(1.0~3.0).
In another preferred example, in step (2.1), the flow of the charging of the method is 0.002-0.150BV (bed body
Product)/h；Preferably, the flow of the charging of the method is 0.005-0.10BV/h；It is highly preferred that being 0.01-0.05BV/h.
In another preferred example, in step (2.2), the flow of eluent is 0.005-0.375BV (bed volume)/h,；It is excellent
Selection of land, the flow of the charging of the method are 0.0125-0.10BV/h；It is highly preferred that being 0.025-0.125BV/h.
In another preferred example, in step (2.3), the flow of the out-feed liquid is 0.002-0.150BV (bed volume)/h.
In another preferred example, the column temperature of the chromatographic column of the method and/or chromatography shell of column is 20-80 DEG C；Preferably, it is
30-70℃；It is highly preferred that being 50-65 DEG C.
In another preferred example, the method has following one or more features：
The partial size of the resin cation is：50-500um；
The single chromatographic column and/or the density of the resin cation of chromatography shell of column filling are 0.85~0.95g/
cm3；
The single-column of the chromatographic column and/or the single long length of chromatography shell of column are 50-200cm；
The single-column of the chromatographic column and/or the single hop diameter height ratio 1/20-1/0.4 of chromatography shell of column；
The mobile bed chromatic includes 4-12 chromatographic column and/or chromatography shell of column；And/or
The resin cation is selected from：Calcium cation resin, sodium form resin cation, potassium type resin cation, magnesium
Type resin cation, lithium type resin cation, or combinations thereof；It preferably, is calcium cation resin, magnesium types resin cation,
Or combinations thereof.
In another preferred example, the diameter height compares for 1/15-1/1.
In another preferred example, 5-10 chromatographic column and/or chromatography shell of column.
In another preferred example, the filler of each chromatographic column and/or chromatography shell of column is identical or different, and length is identical or not
Together and/or diameter height is than identical or different.
In another preferred example, the filler of each chromatographic column and/or chromatography shell of column, length and diameter height are than identical.
In another preferred example, described is as made from starch containing sugared mixed liquor containing sugared mixed liquor；Preferably, described
Saccharified liquid is obtained by starch through amylase liquefaction, saccharification enzymatic conversion containing sugared mixed liquor；The saccharified liquid by glucose isomerase and
After C-3 epimerase catalyzed conversion, obtains and contain sugared mixed liquor containing psicose mixed liquor.
In another preferred example, the total concentration containing glucide in sugared mixed liquor is 20-70wt%；To contain mixed liquor
On the basis of gross mass；Preferably, total concentration 30-68wt%；It is highly preferred that being 50-65wt%.
In another preferred example, described to be greater than 5wt% containing psicose purity in sugared mixed liquor, the purity, which refers to, to be accounted for
The percentage of dry matter gross mass；It is preferably greater than 11wt%；It is more preferably, greater than 14wt%.
In another preferred example, described to include containing sugared mixed liquor：Psicose, the 8.6~10.5wt% of 5~7.5wt%
Fructose, 25~29wt% glucose and 2.7~6.2wt%, on the basis of the gross mass containing sugared mixed liquor.
In another preferred example, it described second discharges after glucose isomerase and C-3 epimerase catalyzed conversion,
It can be obtained described containing sugared mixed liquor.
In another preferred example, the purity of the psicose separated by the method is greater than 85wt%；It is highly preferred that big
In 90wt%；It is most preferably more than 95wt%.
In another preferred example, the rate of recovery of the psicose of the method is greater than 85wt%；It is more preferably, greater than
90wt%.
In another preferred example, the resin cation is not required to regeneration treatment；For physical adsorption process.
It in another preferred example, further include desalting steps in step (1)；Preferably, the desalting steps are to make described contain
Sugared mixed liquor is sloughed described containing the metal ion in sugared mixed liquor by cation exchange resin.
In another preferred example, the metal ion removed in recycling and reusing desalting steps.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is continuous chromatography separation process schematic diagram of the invention.
Specific embodiment
Inventor develops a kind of psicose separation method by extensive and in-depth research, and this method is based on movement
Bed chromatography realizes continuous, big from the sugary soln of the complicated component generated when preparing psicose by starch etc. for raw material
Scale discretely separates psicose, and the psicose that this method is isolated has high-purity, high concentration, returns to psicose
High income, and the amount of mobile phase needed for the psicose of this method acquisition unit mass is few.This is completed based on the invention people
Invention.
Term
As used herein, term " dry matter " refers to the summation for removing all substances other than water.
As used herein, term " concentration " refers to that predetermined substance quality accounts for the percentage of solution gross mass, for example, A Luo ketone
The concentration of sugar is psicose quality/solution gross mass * 100%.
As used herein, term " purity " refers to that predetermined substance quality accounts for the percentage of substance gross mass than water, example
Such as, the purity of psicose is the quality * 100% of dry matter in psicose quality/solution.
As used herein, the molecular compound that term " glucide " is made of tri- kinds of elements of C, H, O, in this application institute
Stating glucide is psicose, fructose, glucose etc..
As used herein, term " mass ratio " is within a certain period of time or when separating a certain amount of material between each substance
Average quality ratio.
The purpose of the invention is to which the production cost of D-Psicose can be further decreased, and push psicose
Industrialization, we have developed the methods for preparing D-Psicose by chromatography separation.
1. waste：Starch obtains saccharified liquid (ingredient by amylase liquefaction, saccharification enzymatic conversion：Glucose is about
95.4%, maltose about 1.9%, isomaltose about 0.9%, maltotriose about 0.5%, the above polysaccharide of maltotetraose be about
1.4%)；
The saccharified liquid is directly used into glucose isomerase and C-3 difference phase isomerase isomerization, starch saccharificating liquid is through glucose
Mixed liquor containing psicose after isomerase and C-3 epimerism enzymatic conversion (uses enzyme immobilization technology, or produces from reaction
Go to dezymotize in object), wherein the C-3 epimerase is D-Psicose -3- epimerase, and the mixed liquor is specially：
1) dry (predominantly glucide) concentration 50-60wt% of mixed liquor, based on the gross mass of mixed liquor；
2) component of mixed liquor：5.5~7.5wt% of psicose, 18.6~20.5wt% of fructose, glucose 20.5~
25.9wt%, 1.5~2.0wt% of maltose, 0.5~1.2wt% of isomaltose, 0.1~1.0wt% of maltotriose, malt four
Above 0.6~the 2.0wt% of polysaccharide of sugar, in terms of the gross mass of mixed liquor；
2. entering chromatographic isolation, three parts solution is mainly obtained after separation, it is as follows：
1) psicose, purity reach 95% or more (on the basis of dry matter gross mass in solution), 90% or more yield,
Concentration 4~7.2% (on the basis of solution gross mass).Psicose product is processed by the techniques such as being concentrated, crystallizing；
2) fructose 2.8~5.3%, glucose 8.0~14.5%, on the basis of solution gross mass；
3) maltose 0.6~1.0%, isomaltose 0.3~0.5%, maltotriose 0.13~0.3%, maltotetraose with
Upper polysaccharide 0.4~0.7%, psicose 0.05~0.3%, glucose 0.05-2.0%, fructose 0.05-1.0% are (total with solution
On the basis of quality).
Concrete operation step：
1) starch liquefacation and saccharification：(concentration 25-35% (concentration of the starch in water), starch is added in starch and water for mixing
10~25U/g of enzyme starch adjusts pH), liquefaction (100-130 DEG C liquefies and maintain 30-60 minute), neutralize (adjust pH), saccharification (addition
Carbohydrase 80-150U/g starch, 58-62 DEG C of saccharification) it obtains " saccharified liquid " ingredient and is：Glucose about 90.0-96.0%, maltose
The above polysaccharide 1.4-2.0% of 1.5-2.0%, isomaltose 0.5-1.5%, maltotriose 0.1-1.0%, maltotetraose.
2) above-mentioned saccharified liquid (using MVR or other evaporators) is concentrated to dry matter concentration as 45-55% and metal is added
Ion；Pass through the enzyme immobilization pillar equipped with " glucose isomerase " and " C-3 fructose difference phase isomerase " according to certain flow rate.
The mixed liquor containing psicose is obtained after crossing column conversion, material component is：Psicose 5.5~7.5%, fruit
Sugared 18.6~20.5%, glucose 20.5~25.9%, maltose 1.5~2.0%, isomaltose 0.5~1.2%, malt three
Sugared 0.1~1.0%, the above polysaccharide 0.6~2.0% of maltotetraose.
3) desalination：Desalination uses cation exchange column, and the material that above-mentioned column excessively has converted (is mixed containing psicose
Liquid) cation exchange column is flowed through, it can remove the metal ion being added in reaction process, this can be recycled by ion exchange
Metal ion simultaneously is recycled and reused for reacting, to complete desalination or the Recycling process of the metal ion.
4) chromatographic isolation：The pillar of dedicated chromatography separation resin is housed using 2-20, process signal is as shown in Figure 1 (with 4
For column).
If Fig. 1 is the schematic diagram for isolating and purifying psicose (Psi) and recycling glucose and fructose, as shown in Figure 1, discharging
It is carried out continuously and (is divided into fast component discharging stage and slow component discharging stage, component discharging discharges alternately with slow component out),
It carries out intermittent charging (feeding interval time such as 30-60min, related with the amount of resin and packed density etc.) and elution (is washed
Such as 30-60min of de- interval time, related with the amount of resin and packed density etc.), fast component (the i.e. second discharging is collected respectively
Liquid, main component are glucose and fructose) and slow component (i.e. the first out-feed liquid, main component are psicoses).
Specifically, 4 Coupled columns connections, mobile phase flow successively through (flow velocity 0.002-0.150BV/h, wherein 4
Whether flow velocity is identical or different in a pillar) this 4 chromatographic columns, while chromatographic column can be mobile to mobile phase flow direction.
(feed rate 0.002-0.150BV/h) is fed first, feeds the laggard water elution of 0.01-0.02BV, and pass through shifting
Dynamic chromatographic column makes the water entry position of eluant, eluent (be added) between fast component unloading position and slow component unloading position, color
The switching time t for composing column is 5-8min.Wherein, the switching time refers to, chromatographic column is in a certain position, in the t time, chromatography
Column starts that next position on mobile phase flow direction is moved and be moved to along mobile phase flow direction；For example, as shown in Figure 1,
After a certain chromatographic column is moved to 1 position of chromatographic column, after the t time, which is moved quickly by 1 position of chromatographic column
The position of chromatographic column 2 in figure.
In another preferred example, chromatographic isolation operating condition：Setting charging F=0.4Kg/h (it is related with amount of resin, herein
Resin total amount used is 8.0Kg), experimental temperature be 60-65 degrees Celsius, processing feed concentration 60wt% (solute (i.e. dry matter)
Total content), the purity of psicose be 14% (mass ratio of psicose and total soluble matters, following Reinheitszahl meaning are identical),
Eluant, eluent (water) D=0.6Kg/h, discharging AD (slow component)=0.33Kg/h, BD (fast component)=0.66Kg/h, treating capacity
0.240Kg feed liquid (containing fructose+glucose+other sugar 0.115Kg, contain psicose 0.020Kg), material-water ratio 1:1.5,BD/AD
=2；Momentary operation condition：F → B=33ml/min (fast component discharges when charging), D → A (slow component discharges when elution)=
33ml/min, D → B=33ml/min (fast component discharges when elution), rate of circulating flow 33ml/min (or flow rate of mobile phase in column
33ml/min), switching time 5-8min.
As a result：
(1) obtaining psicose solution (the first out-feed liquid) gross mass is 0.25Kg, and purity is greater than 95%, contains psicose
0.018Kg or more, yield are greater than 90%；
(2) obtaining " fructose+glucose " mixed liquor (the second out-feed liquid) gross mass is 0.31-0.54Kg, (contains fructose and Portugal
Grape sugar is total to about 0.11Kg, and 90%) rate of recovery is greater than, wherein fructose purity 30~55%, glucose purity 40~70%；It can also be with
Separate collection fructose and glucose.
(3) residual solution in addition to psicose solution and " fructose+glucose " mixed liquor, gross mass be 0.16~
0.32Kg includes：Maltose, isomaltose, maltotriose, polysaccharide, psicose, glucose and fructose, dry matter concentration 5.0~
10.0% (total soluble matters about 0.016Kg), wherein：Maltose purity 3.0~10.0% (0.0005-0.0016Kg), isomaltose
It is purity 3.0~10.0% (0.0005-0.0016Kg), maltotriose purity 1.0~5.0% (0.00016~0.001Kg), more
Sugared purity of 50 percent .5~5.0% (0.0001~0.001Kg), psicose purity 1.0~6.0% (0.00016~0.001Kg), Portugal
Grape sugar purity 1.0-5.0% (0.00016~0.001Kg), fructose purity 1.0-5.0% (0.00016-0.001Kg).
In more massive production, equally can using the material (starch saccharificating liquid through glucose isomerase and C-3 difference to
Mixed liquor after isomery), psicose, material-water ratio 1.0 are separated using chromatography separating method:0.5~1.0：3.0, fast component (grape
Sugar+fructose)/slow component (psicose) be 1.0~3.0 (quality).
In another preferred example, the parameter of chromatographic isolation：
The length of single-column：50-200cm；
The high ratio of diameter：1/20-1/0.4, preferably 1/15-1/1；
Resin type：Cation chromatography resin (for example, calcium type, sodium form, potassium type, magnesium types, lithium type cation chromatography resin)；
In another preferred example, the particle size range of resin used in chromatographic isolation is：50-500um.
Temperature：20-80 DEG C, preferably 30-70 DEG C, more preferably 50-65 DEG C；
Feed rate is 0.002-0.150BV/h, preferably 0.005-0.10BV/h, more preferably 0.01-0.05BV (bed body
Product)/h；
Eluant, eluent：Deionized water (including various forms of deionized waters, such as desalted water, distilled water or reverse osmosis water)；
Material-water ratio：1:(0.5-3.0), preferably 1:(0.8-2.5), more preferably 1:(1.0-2.0)；
Dry matter concentration：20-70%, preferably 30-68%, more preferably 50-65%；
Merogenesis：3-20 can be divided into using chromatographic column to save, preferably 4-12 is saved, more preferably 5-10 section.
In another preferred example, chromatographic isolation is using resin column 3 or more (containing 3).
In another preferred example, form used by chromatographic isolation includes true mobile bed chromatic, Simulated Moving Bed Chromatography,
Or the chromatographic column of batch-type chromatographic.
In another preferred example, it can be generalized to production amplification.
The chromatography separating method of psicose
A kind of chromatography separating method of psicose, carries out as steps described below：
1) raw material being done with starch and preparing psicose mixed liquor (i.e. containing sugared mixed liquor), which is：A Luo ketone
Sugar 5~14.5%, fructose 8.6~10.5%, glucose 25~29%, maltose 1.5~2.0%, isomaltose 0.5~
1.2%, the above polysaccharide 0.6~2.0% of maltotriose 0.1~1.0%, maltotetraose.
2) by the above psicose mixed liquor, under the conditions of 30-80 degree, injection is equipped with the chromatographic column of dedicated chromatograph packing material,
Eluant, eluent is made with water, collects the eluent for containing different components respectively；The column temperature of chromatographic column is 30-80 degree, column diameter height ratio is 1:
(0.4~15), inlet amount are 0.01BV/h~1.0BV/h, elution speed is 0.02BV/h~3.0BV/h and material-water ratio is 1:
(0.5-3.0).The dedicated chromatograph packing material of chromatographic column be strong type resin cation, calcium cation resin, magnesium types resin cation,
Sodium form resin cation, potassium type resin cation or ammonium type resin cation.
Ingredient after separation
First out-feed liquid：Psicose purity reaches 95% or more, 90% or more yield, concentration 4~7.2%；Through overrich
The techniques such as contracting, crystallization are processed into psicose product；
Second out-feed liquid：Fructose 2.8~5.3%, glucose 8.0~14.5%；
Third component：Maltose 0.6~1.0%, isomaltose 0.3~0.5%, maltotriose 0.13~0.3%, malt
The above polysaccharide 0.4~0.7% of tetrose, psicose 0.05~0.3%.
In another preferred example, the psicose mixed liquor preparation before chromatographic isolation includes step：Starch passes through amylase
Liquefaction, obtains saccharified liquid at saccharification enzymatic conversion；Saccharified liquid is contained by being made after glucose isomerase and C-3 epimerase catalyzed conversion
There is psicose mixed liquor；The mixed liquor ingredient is：Psicose 5~14.5%, fructose 8.6~10.5%, glucose 25~
29%, maltose 1.5~2.0%, isomaltose 0.5~1.2%, maltotriose 0.1~1.0%, the above polysaccharide of maltotetraose
0.6~2.0%.
In another preferred example, in the mixed liquor of obtained D-Psicose, the purity of D-Psicose is greater than 5%, leads to
Often 11% or more, preferably 14% or more.
Main advantages of the present invention include
(a) technique of the invention can be used for the solution containing psicose of separated component complexity.
(b) technique of the invention is suitble to be mass produced.
(c) isolated glucose and fructose can be recycled, and the resin of chromatographic isolation does not need to carry out again
Raw processing (belonging to physical absorption), can be directly recycled for the separation of next batch.
(d) technique of the invention uses relatively closed, high temperature (55-65 degrees Celsius), high concentration (50-70%) operation,
It is not likely to produce the pollution of microorganism.
(e) the concentration height for obtaining psicose in psicose solution is produced by this method, and it is (such as dense to be conducive to subsequent processing
Contracting, crystallization etc.)
Technique of the invention is suitble to be mass produced, and isolated glucose and fructose can be recycled, and color
It composes isolated resin not needing to carry out regeneration treatment (belonging to physical absorption), the separation of next batch can be directly recycled for.
Since the technique uses relatively closed, high temperature (55-65 degrees Celsius), high concentration (50-70%) operation, so being not easy on the whole
Generate the pollution of microorganism.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are mass percent and quality
Number.
Embodiment 1
The psicose aqueous solution that raw material is obtained by enzymatic conversion will be done by starch, through ion exchange resin desalination
Afterwards, 60 DEG C are preheated to, it is 1 that injection diameter height, which compares,:10, fill chromatographic column (column length 100cm, the diameter of calcium cation chromatography resin
10.0cm, totally 6), resin total amount is 4Kg, and total feed is 1Kg (wherein 0.084Kg containing psicose, glucose
0.252Kg, fructose 0.246Kg, other sugar 0.018Kg), column temperature is controlled at 60 DEG C, and feed rate 0.020BV/h is spent
Ion water elution, material-water ratio 1.0:2.0, elution flow rate 0.050BV/h collect eluent and Liquid Residue respectively, obtain respectively
Psicose (the first out-feed liquid, slow component, 0.076Kg), fructose+glucose (the second out-feed liquid, fast component, 0.48Kg)
With residual solution (maltose+isomaltose+maltotriose+polysaccharide+psicose aqueous solution 0.034Kg).
The psicose aqueous solution concentration with higher obtained by this method is conducive to carry out subsequent concentration crystallization etc.
Operation.
It separates 1Kg material (other sugar impurity containing 84gPsi, 498gGlu+Fru and 18g)
In embodiment 1, the separative efficiency of the method for the present invention is 76g Psi/ (8h*4Kg resin), i.e. 2.38g Psi/ (h*
Kg resin)；76g Psi/ (8h*2Kg water * 1Kg material), 1Kg material wherein contains 84g Psi, i.e. 4.75g Psi/ (h*Kg water),
1kg water separates obtain 4.75g Psi per hour.
In this experiment, institute's water consumption and inlet amount are all far beyond the separating capacity of efficient liquid phase.It compares, water and charging
Ratio greatly reduce that (efficient liquid phase sample introduction 20uL, needs mobile phase 9mL, 450) ratio of water to material is up to.
Embodiment 2 to 11
According to the operation of example 1, feed 1.0Kg, chromatogram column length 100cm, adjustment feeding temperature, column temperature, charging rate,
The factors such as elution speed and chromatographic column diameter height ratio, the results are shown in Table 1, and the resin partial size of chromatographic isolation is in table 1：50-
500um。
Table 1
Comparative example list separates post separation
0.2Kg material (contain 16gPsi), 1Kg resin single-unit resin post separation can only isolated about 1g with the water of 5Kg
Psi。
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of method that continuous, large-scale separation prepares D-Psicose, which is characterized in that the method includes following steps
Suddenly：
(1) it provides and is used as charging F containing sugared mixed liquor containing glucide；
Wherein, described to include containing sugared mixed liquor：Psicose, fructose, glucose and oligosaccharide；
The oligosaccharide is sugar selected from the group below：Maltose, isomaltose, maltotriose, maltotetraose, polysaccharide, or combinations thereof；
And
(2) chromatographic isolation：It is separated, is obtained containing sugared mixed liquor to described by the chromatographic isolation equipment based on mobile bed chromatic
Solution containing psicose, wherein the purity of the psicose in the solution containing psicose>80wt%, in solution
On the basis of the quality of dry matter；
The chromatographic isolation includes：
(2.1) feed step：It will be in the chromatographic column that be passed through containing sugared mixed liquor；
(2.2) elution step：Eluent D is passed through in chromatographic column and is eluted, and the eluent D is water；
(2.3) discharge step：Collect out-feed liquid, wherein the out-feed liquid includes the first out-feed liquid, and first out-feed liquid is
The solution containing psicose；
Wherein, the chromatographic isolation equipment includes 2-20 chromatographic columns and/or chromatography shell of column, and the chromatographic column and/or
The filler of chromatography shell of column is resin cation, and each chromatographic column and/or chromatography shell of column are connected in series.
2. the method as described in claim 1, which is characterized in that material-water ratio 1:(0.5-3.0)；Wherein, the material-water ratio is
Feed F:The mass ratio of eluent D.
3. method described in claim 1, which is characterized in that the chromatographic column of the method and/or the switching time of chromatography shell of column
For 3~15min.
4. the method as described in claim 1, which is characterized in that in step (2.3), the out-feed liquid further includes the second discharging
Liquid, and second out-feed liquid includes glucose and fructose.
5. method as claimed in claim 4, which is characterized in that in step (2.3), the matter of the first out-feed liquid and the second out-feed liquid
Amount is than being 1:(1.5~3).
6. the method as described in claim 1, which is characterized in that step (2.1) and step (2.2) interval carry out；And/or step
(2.3) it is carried out continuously.
7. the method as described in claim 1, which is characterized in that in step (2.1), the flow of the charging of the method is
0.002-0.150BV/h；
In step (2.2), the flow of eluent is 0.005-0.375BV/h；And/or
In step (2.3), the flow of the out-feed liquid is 0.002-0.150BV/h.
8. the method as described in claim 1, which is characterized in that the chromatographic column of the method and/or the column temperature of chromatography shell of column are
20-80℃。
9. the method as described in claim 1, which is characterized in that the method has following one or more features：
The partial size of the resin cation is：50-500um；
The single chromatographic column and/or the density of the resin cation of chromatography shell of column filling are 0.85~0.95g/cm3；
The single-column of the chromatographic column and/or the single long length of chromatography shell of column are 50-200cm；
The single-column of the chromatographic column and/or the single hop diameter height ratio 1/20-1/0.4 of chromatography shell of column；
The mobile bed chromatic includes 4-12 chromatographic column and/or chromatography shell of column；And/or
The resin cation is selected from：Calcium cation resin, sodium form resin cation, potassium type resin cation, magnesium types sun
Ion exchange resin, lithium type resin cation, or combinations thereof.
10. the method as described in claim 1, which is characterized in that described to have following one or more special containing sugared mixed liquor
Sign：
The total concentration of the glucide containing sugared mixed liquor is 20-70wt%, on the basis of containing sugared mixed liquor gross mass；
The purity containing psicose in sugared mixed liquor is greater than 5wt%
The mixed liquor containing sugar is as made from starch containing sugared mixed liquor；And/or
It is described to include containing sugared mixed liquor：The psicose of 5~7.5wt%, the fructose of 8.6~10.5wt%, 25~29wt%
Glucose and 2.7~6.2wt%, on the basis of the gross mass containing sugared mixed liquor.
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| PCT/CN2019/106472 WO2020057555A1 (en) | 2018-09-18 | 2019-09-18 | Method and device for continuous large-scale separation and preparation of d-psicose |
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|---|---|---|---|---|
| WO2020057555A1 (en) * | 2018-09-18 | 2020-03-26 | 上海立足生物科技有限公司 | Method and device for continuous large-scale separation and preparation of d-psicose |
| CN113912655A (en) * | 2021-09-30 | 2022-01-11 | 中粮营养健康研究院有限公司 | Method for separating psicose from mixed syrup by using simulated moving bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118076423A (en) | 2021-09-16 | 2024-05-24 | Ddp特种电子材料美国第八有限公司 | Mixed ion form sugar chromatography |
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| CN113912655A (en) * | 2021-09-30 | 2022-01-11 | 中粮营养健康研究院有限公司 | Method for separating psicose from mixed syrup by using simulated moving bed |
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