CN1617939A - Method for the recovery of sugars - Google Patents

Method for the recovery of sugars Download PDF

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Publication number
CN1617939A
CN1617939A CNA028276558A CN02827655A CN1617939A CN 1617939 A CN1617939 A CN 1617939A CN A028276558 A CNA028276558 A CN A028276558A CN 02827655 A CN02827655 A CN 02827655A CN 1617939 A CN1617939 A CN 1617939A
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China
Prior art keywords
seminose
described method
fraction
separation
resin bed
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CN100390301C (en
Inventor
A·恩内林
J·云帕宁
V·拉万卡
J·努尔米
M·凯拉
H·海基莱
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Danisco Sweeteners Oy
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Danisco Sweeteners Oy
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/14—Purification of sugar juices using ion-exchange materials
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/14—Purification of sugar juices using ion-exchange materials
    • C13B20/144—Purification of sugar juices using ion-exchange materials using only cationic ion-exchange material
    • 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

Abstract

The invention relates to a chromatographic separation process of recovering mannose with high purity. The invention is based on the use of a chromatographic separation resin including a resin which is at least partly in a Ba<2+> form resin and a resin which is in other than Ba<2+> form.

Description

Reclaim the method for sugar
Background of invention
The present invention relates to separate in the mixture by carbohydrate containing carbohydrate, the particularly chromatography separating method of sugar.Handled mixture normally comprises the solution of the biomass derived of carbohydrate/sugar according to the present invention.Particularly, the invention provides by the chromatography separating method that reclaims the high purity seminose in the solution of biomass derived such as the useless slurry of sulphite.Seminose can be recovered with crystallized form or with the solution form.The method of claimed recovery seminose is based on Ba 2+The resin of form and non-Ba 2+The resin coupling of form is as separation resin, if desired, and afterwards with the seminose crystallization.For separation method of the present invention, also can obtain wood sugar and arabinose product as by product, this depends on the composition of the solution of initial biomass derived.
Seminose can be used for for example multiple pharmaceutical application.It can be used as the parent material of multiple medicament production, i.e. starting material.Seminose also can be used for the treatment of urine and infect (urine infection) and inflammation of vein disease in treatment.In food technology, seminose can be used for for example so-called Positech and uses (the GMO-test of edible product).
Seminose also can make to prepare the starting material of N.F,USP MANNITOL, and N.F,USP MANNITOL has multiple pharmaceutical use.
Seminose can be by reclaiming in the timber resources, and wherein seminose is to exist with other carbohydrate and lignin mixture of ingredients form.In timber and other material based on plant, seminose exists with polymer form usually, as hemicellulose, modal as with the heteropolymer of glucose and/or semi-lactosi, glucomannan, galactoglucomannan (galactoglucomannan) and polygalactomannan are arranged.The waste liquid that is obtained by conifer wood pulp technology is rich in seminose especially.Also by being recovered to seminose in vegetable ivory fruit and the special marine alga.
By a difficult problem that has become based on the highly purified seminose of recovery in the material of plant in the art technology.
Jones, J.K.N ﹠amp; Wall, R.A. (Canadian Journal of Organic Chemistry 38 (1960), 2290-2294 page or leaf) have described and have utilized ion exchange resin to separate sugared method by in synthetic sugar mixture and the plant milk extract.This method relates to separating with the sulfonic acid ion exchange resin of neutral salt form and comprises D-seminose and D-N.F,USP MANNITOL in interior mixture of monosaccharides.Adopt Ba 2+The resin Dowex50W X8 of form is as separation resin.
Larsson, L.I﹠amp; Samuelsson, O. (Acta Chemica Scandinavica 19 (1965), 1357-1364 page or leaf) have described and have utilized ion exchange resin to separate the automated method that is present in the monose in the wood saccharification product.On the strong basic type anion-exchange resin of sulphate form, with ethanol,, studied the separation of 16 kinds of monose that comprise the D-seminose with partition chromatography as eluent.
In addition, study ion exchange resin being used to separate monose, purpose is to observe the behavior of sugar on the post of the saturated resin of sulfur acid hydrogen salt.For example, the anion exchanger (Amberlite IRA-400) with the hydrosulfate form is used for separating levulose, glucose and seminose.As the practical result of this research, suggestion is used for improved method to measure the reducing sugar of sulfite waste lye.
To aluminum oxide with comprise the interaction that the D-seminose occurs also study between the interior monose aqueous solution.Show suitable selection, can on preparative-scale and analytical scale, easily and promptly realize sugared separation by aluminum oxide.
Also is known by mannose derivative by reclaiming seminose in the various sources.Fujita, T﹠amp; Sato, T disclose the method that reclaims the D-seminose by N-phenyl-D-mannopyranose amine in Bull.Chem.Soc. Japan 33 (1960) 353.To such an extent as to it is said that N-phenyl-D-mannopyranose amine is highly stable and water insoluble suggestion is used it for even by separating the D-seminose in the very impure starting material.
Herrick, F.W., Casebier, R.L., Hamilton, J.K.﹠amp; Wilson, J.D. (" seminose chemistry medicine ", Applied Polymer Symposium 28 phases (1975), the 93-108 page or leaf) disclose and relate to the research of foundation by the economic means that reclaims the seminose or derivatives thereof in timber resources such as the sulfite waste lye, wherein seminose is the main component that contains the mixture of other carbohydrate and lignin fragment.The Main Achievements of this work is to have set up the method that is used for being reclaimed by several starting material seminose sodium bisulfite (sodium mannose bisuphite) and methyl mannoside.Set up the method that reclaims seminose through two kinds of approach in by crude mixture: (1) forms bisulfite adduct, the crystallization of monomer wood sugar mixture and separates the seminose sodium bisulfite and by this intermediate seminose of regenerating, (2) carry out anhydrous methanol simultaneously with thick mixing sugar polymkeric substance or monomeric glycosidation and decompose, crystallization also separates methyl α-D mannoside and by this intermediate regeneration seminose.These methods that are used to reclaim seminose have the very defective of trouble of operation in practice.
Sinner, M, Simatupang, M.H.﹠amp; Dietrichs, H.H. (" the timber carbohydrate being carried out the automatization quantitative analysis " with the borate complex ion exchange chromatography, Wood Science andTechnology, 1975,307-322 page or leaf) described by the borate complex ion exchange chromatography and has separated the also simple automated analysis method of quantitative assay sugar with enzymic hydrolysate by the acid hydrolysis product of timber polysaccharide.Draw together seminose, fructose, arabinose, semi-lactosi, wood sugar, glucose and disaccharides such as xylo-bioses, cellobiose and sucrose with the isolating steamed bun stuffed with sugar of this method.
GB 1540556 (ICI Americas, on February 14th, 1979 open) relates to and separates the glucose that is present in the aqueous solution and the method for seminose.Initial glucose and seminose mixture obtain by the epimerization of glucose in the aqueous solution usually.Usually utilize alkaline-earth metal salt form such as Ca 2+, Sr 2+Or Ba 2+The Zeo-karb of form carries out separating of seminose and glucose.Zeo-karb is preferably strongly acidic cation-exchange, normally the resin of styrene-based-divinylbenzene.
Hassi, R., Tikka, P.﹠amp; Sj str m, E. (" by the ion exclusion chromatography by reclaiming Sulfite lignin and sugar in the sulfite waste lye ", the meeting (InternationalSulfite Pulping Conference) of the useless slurry of 1982 international sulphite, Sheraton Centre Hotel, Toronto, Ontario, October, 20-22 day, the 165-170 page or leaf) described separating of sugar and Sulfite lignin.The ion exclusion chromatography that to carry out on strongly acidic cation-exchange is used for separating Sulfite lignin that are present in sulfite waste lye and the sugar that comprises seminose.Used resin is strong acid type gel type polystyrene Zeo-karb (Amberlite IR-120, Ca in described test 2+Form).Suggestion can be with the raw material source of sugared fraction as preparation N.F,USP MANNITOL.
Finnish patent 78734 (Suomen Sokeri Oy, on April 5th, 1987 is open) relates to the rapid method of multistep of separating sugar and Sulfite lignin by in the useless slurry of sulphite.This method comprises to be introduced the useless slurry of sulphite the separation resin that comprises metallic salt form, is generally Ca 2+In the chromatographic column of the strongly acidic cation-exchange of form, water elution chromatography post is rich in the fraction and the rich sacchariferous fraction of Sulfite lignin with recovery, the sacchariferous fraction of thus obtained richness is introduced comprise the monovalent metal salt form, be generally Na +In another chromatographic column of isolated in form resin.Obtain not contain the sugared fraction of Sulfite lignin.
WO 96/27029 (Xyrofin Oy, on September 6th, 1996 open) relates to by mainly utilizing the nucleogenesis crystalline compounds by the method that reclaims organic compound such as sugar in the solution, and suggestion is for example reclaimed seminose by the nucleation crystallization method.
Finnish patent 97625 (Xyrofin Oy, on March 5th, 1996 is open) discloses the method for crystalline xylose.In the method, reclaim wood sugar by crystallization by the solution that wherein wood sugar purity is lower.Particularly, this method relates in the solution by biomass derived and reclaims wood sugar.
WO 99/10542 (Cultor company, on March 4th, 1999 open) disclose cationite by utilizing the monovalent metal form as the chromatography separating method of separation resin by the method that reclaims the L-arabinose in the sugar beet slurry.So the L-arabinose solution that obtains carries out purifying with positively charged ion and anionite and polymeric adsorbent.
WO 01/21271 A1 (Sohkar Oy, March 29 calendar year 2001 is open) discloses and has utilized Zeo-karb by the method that reclaims pectin, arabinose and salt in the vegetable material, and described Zeo-karb is preferably the polyvalent metal form.
Be used to reclaim the starting material complex compound multicomponent mixture normally of the biomass derived of seminose.Become a difficult problem by separating seminose in these complex compound mixtures with enough purity.One of problem relevant with above-mentioned currently known methods is that the seminose that they provide is and the mixture of other closely-related sugar that promptly they can not provide the seminose with enough purity.On the other hand, prepare seminose by mannosans and other mannose derivative bothers technically very much.In addition, preparation is used for the crystallization seminose also has problem with the suitable initial mannose solution that obtains crystallinity seminose product.
Have now found that and utilize the new chromatography separating method can be by reclaiming highly purified seminose in the carbohydrate containing solution of biomass derived effectively.Use chromatographic process of the present invention, can obtain purity and be 45 to 80% or higher seminose fraction.Then, can further carry out purifying by the seminose fraction that chromatographic separation obtains by crystallization.Crystallization can provide purity up to 99% or higher crystallinity seminose product.As for method of the present invention, as recyclable multiple other sugar such as wood sugar and the arabinose of by product, these starting material that depend on initial biomass derived are formed.
Summary of the invention
Therefore, the purpose of this invention is to provide by the method that reclaims high purity seminose product in the carbohydrate mixture that contains seminose.As by product, recyclable multiple other sugar is as wood sugar and arabinose.By being that the method for feature realizes purpose of the present invention with content described in the independent claim.The preferred embodiments of the invention are disclosed in the dependent claims.
The present invention is based on following design: with at least two kinds of separation resins, one of them is based on Ba 2+The chromatography purification of resin contain the carbohydrate mixture of seminose.
Use method of the present invention, can obtain highly purified seminose product.
The definition relevant with the present invention
In specification sheets and whole embodiment and claims, used to give a definition:
SAC is meant strongly acidic cation-exchange.
DS is meant the dry matter content of measuring with the Ka Er Karl Fischer titration, represent with weight percentage.
RDS is meant the dry matter content of measuring with refractometry, represent with weight percentage.
Brief Description Of Drawings
The following drawings is an illustrative embodiment of the present invention, is not to be intended to limit by any way defined scope of the present invention in claims.
Fig. 1 uses Na among the embodiment 1 +The diagrammatic representation of the concentration curve of the SAC resin isolation seminose-arabinose of form (separating A).
Fig. 2 uses Ba among the embodiment 1 2+The diagrammatic representation of the concentration curve of the SAC resin isolation seminose (separation of C .1) of form.
Fig. 3 uses Ba among the embodiment 1 2+The diagrammatic representation of the concentration curve of the SAC resin separating for several times seminose (separation of C .2) of form.
Fig. 4 uses Ca among the embodiment 1 2+The diagrammatic representation of the concentration curve of the SAC resin isolation seminose (separation of C .3) of form.
Fig. 5 uses Ca among the embodiment 1 2+The diagrammatic representation of the concentration curve of the SAC resin isolation arabinose of form (separating E.1).
Fig. 6 uses Ca among the embodiment 1 2+The diagrammatic representation of the concentration curve of the SAC resin separating for several times arabinose of form (separating E.2).
Fig. 7 describes the method diagram that the present invention reclaims an embodiment of seminose and wood sugar.As pre-treatment step, this method also comprises the separation of arabinose.
Detailed Description Of The Invention
The present invention relates to by the method that reclaims seminose in the solution that contains same substance.Method feature of the present invention is: to described mixture use at least a to small part be Ba 2+The chromatographic separation resin bed of form and at least a non-Ba 2+The chromatography separating method of the chromatographic separation resin bed of form, and reclaim a at least seminose fraction.
Chromatography separating method of the present invention generally includes at least two chromatrographic separation step, in these steps at least one step use to small part be Ba 2+The chromatographic separation resin bed of form carries out, and the non-Ba of at least one step in these steps 2+The chromatographic separation resin bed of form carries out.
An embodiment of the present invention is following carrying out usually: the solution feed that will contain seminose in comprise to small part be Ba 2+In first chromatographic column of the chromatographic separation resin bed of form,, reclaim first part of seminose fraction with eluent wash-out described chromatographic column, then with the charging of described first part of seminose fraction in comprising non-Ba 2+In second chromatographic column of the chromatographic separation resin bed of form,, and reclaim second part of seminose fraction with the described chromatographic column of eluent wash-out.
In another embodiment of the present invention, described chromatography separating method comprise use to small part be Ba 2+Two separating steps that the chromatographic separation resin bed of form carries out and use non-Ba 2+The separating step that the chromatographic separation resin bed of form carries out.
This embodiment of the present invention is following carrying out usually: the solution feed that will contain seminose in comprise to small part be Ba 2+In first chromatographic column of the chromatographic separation resin bed of form,, reclaim first part of seminose fraction with eluent wash-out described chromatographic column, with the charging of described first part of seminose fraction in comprise to small part be Ba 2+In second chromatographic column of the chromatographic separation resin bed of form,, reclaim second part of seminose fraction with eluent wash-out described chromatographic column, then with the charging of described second part of seminose fraction in comprising non-Ba 2+In the 3rd chromatographic column of the chromatographic separation resin bed of form,, and reclaim the 3rd part of seminose fraction with the described chromatographic column of eluent wash-out.
In above-mentioned embodiment of the present invention, can be at Ba 2+Carry out some other separation before separating.In the same way, some other separation can be at Ba 2+Carry out between the separation.In addition, between twice exchange operations, to carry out the balance of ion or ionic composition usually, for example be undertaken by ion-exchange.
In an embodiment of the present invention, described to small part be Ba 2+The resin of form (resin bed) is Ba basically 2+Form.In the method for separating resin process, carry out the chromatographic column balance, wherein said to small part be Ba 2+The chromatographic bed of form even can contain other ion is as H +, alkali metal cation such as Na +And K +, and alkali metal cation such as Ca 2+And Mg 2+
Described to small part be Ba 2+The resin of form is meant Zeo-karb.
Described non-Ba 2+The resin of form (resin bed) is meant Ba 2+The resin of cationic form in addition.Described resin is Zeo-karb normally, and positively charged ion wherein is hydrogen form (H +), NH 4 +Form or be selected from basic metal or alkaline-earth metal such as Na +, K +, Mg 2+And Ca 2+Form.Particularly preferred metal is Ca 2+
The chromatographic separation that is used to obtain seminose of the present invention is carried out with strongly acidic cation-exchange usually.Preferred resin is based on the resin of cross-linked styrene-divinylbenzene.The suitable degree of crosslinking of resin is by weight 1 to 20%, preferably by weight 3 to 8%.The mean particle size of resin is generally 10 to 2000 μ m, preferred 100 to 400 μ m.Also can use molecular sieve based on zeolite.
Used eluent is a for example alcohol of water, solvent in the chromatographic separation of the present invention, or its mixture.Preferred eluent is a water.
The temperature of carrying out wash-out is preferably 10 to 95 ℃, and more preferably 30 to 95 ℃, most preferably 55 to 85 ℃.
Chromatography separating method of the present invention provides wherein, and seminose is the seminose fraction of solution form.Represent that with RDS the typical purity of the seminose product that is obtained by chromatographic separation is 45 to 80% seminoses.
In order to improve the productive rate of chromatographic separation, also can use the recovery fraction of chromatographic separation.
Chromatography separating method of the present invention can also comprise one of a plurality of purification steps that are selected from membrane filtration, ion-exchange, evaporation, filtration and derivatize.These purification steps can before described one/a plurality of chromatrographic separation step, afterwards or between carry out.
For purifying contains the solution of seminose, for example remove SO 4 -Ion carries out ion-exchange usually.
In derivatization method, form mannose derivative, the derivates regeneration by acquisition like this becomes seminose afterwards.An example of available mannose derivative is N-phenyl-D-mannopyranose amine.
The mannose solution that is obtained by chromatographic separation can be further purified to obtain crystallinity seminose product by crystallization.Crystallization is carried out with the solvent of the mixture that is selected from water, alcohol and water and alcohol usually.In a preferred embodiment of the invention, crystallization is carried out with the mixture of second alcohol and water.
Crystallization can be carried out until the dry matter content that obtains being fit to (for example RDS about 85%) by evaporation by mannose solution or seminose syrup that chromatographic separation obtains.Can in the ebullient syrup, introduce the seminose crystal seed with the seminose crystal seed.If the use crystal seed is suspended in it in recrystallisation solvent, this solvent is a for example alcohol of water, solvent, or its mixture.Typical recrystallisation solvent is an ethanol.After crystallized stock is cooled to room temperature, add recrystallisation solvent.Material can be placed for some time then, preferred 3 to 6 days, at room temperature place usually, leach crystallization afterwards.Use the recrystallisation solvent washing leaching cake.Obtain highly purified seminose crystallization.
Crystallization provides with RDS represents that purity is higher than 90%, preferably is higher than 95%, most preferably is higher than 99% crystallinity seminose.
Method of the present invention also can comprise other sugar as the separating of wood sugar, rhamnosyl and arabinose, and this depends on the starting soln composition that contains seminose.The separation of other sugar was carried out before separating seminose usually.
Therefore, as pre-treatment step, method of the present invention can comprise the separation of wood sugar.The recovery of wood sugar can for example be undertaken by precipitated crystal by several different methods.
The precipitated crystal of wood sugar preferably carried out before the chromatographic separation of seminose just.
In the precipitated crystal of wood sugar, the solution that will contain seminose and some wood sugars carries out crystallisation step.The precipitated crystal of wood sugar is following carrying out usually: evaporating solns adds the wood sugar crystal seed, then according to required cooling program crystallisation by cooling material to required dry matter content in solution.Crystallized stock is filtered to obtain wood sugar filter cake and the crystallization filtrate that contains seminose.Reclaim wood sugar by the crystallization filter cake, and the filtrate that will contain seminose carries out above-mentioned chromatogram purification, to obtain highly purified seminose of the present invention.
Method of the present invention also can comprise the separation of arabinose, preferably as pre-treatment step.The separation of arabinose can be carried out before the precipitated crystal wood sugar.Usually reclaim arabinose with chromatographic separation.The chromatographic separation of arabinose is preferably carried out with the chromatographic separation resin bed of the univalent cation form that is selected from hydrogen, ammonium and alkali metal cation.Described univalent cation is selected from H usually +, Na +, K +And NH 4 +Reclaim the arabinose fraction.The chromatographic separation resin is preferably strongly acidic cation-exchange.
The arabinose fraction can be carried out further chromatogram purification.The chromatogram purification of arabinose fraction generally includes at least one and uses alkaline-earth metal, preferred Ca 2+The step of the chromatographic separation resin bed of form.Also thus obtained arabinose fraction can be carried out crystallization.
As pre-treatment step, method of the present invention can also comprise the separation of rhamnosyl.The separation of rhamnosyl was preferably carried out before separating arabinose.
For the starting material that are rich in wood sugar, as pre-treatment step, method of the present invention can also comprise the separation of wood sugar.The separation of wood sugar was carried out before separating arabinose usually.
Method of the present invention can also comprise further purification step, and for example ultrafiltration and millimicro are filtered (nanofiltration), ion-exchange, evaporate and remove by filter for example Sulfite lignin, acid (organic acid and mineral acid) and salt as membrane filtration.
The starting soln that contains seminose is generally the mixture of carbohydrate containing such as sugar.Except that seminose, solution also can contain for example wood sugar, semi-lactosi, glucose, rhamnosyl, arabinose and fructose.Mixture also can contain disaccharides and high-grade sugar.
The material of carbohydrate containing mixture is usually derived from biomass, normally contain the vegetable material of seminose such as softwood or hard material, grass, corn husk, Stigma Maydis (corn cops), corn fibre and sugar beet.Parent material uses with the hydrolysate form usually, for example the hydrolysate that obtains by prehydrolysis, complete hydrolysis (total hydrolysis), steam hydrolysis, enzymic hydrolysis or acid hydrolysis.
Be used to reclaim the waste liquid that the biomass by hydrolyzation product of seminose of the present invention is normally obtained by pulping technology.Described waste liquid is the useless slurry of sulphite particularly, and it can obtain by the useless slurry of acidity, alkalescence or neutral sulphite.If biomass by hydrolyzation product for example waste liquid contains the seminose of polymerized form, can before chromatrographic separation step, the polymerization seminose be hydrolyzed with acid or enzyme.
Can be used for typical waste liquid of the present invention is the waste liquid that contains seminose, and it is preferably obtained by the useless slurry of acid accumulator sulfite.Waste liquid can directly be obtained by the useless slurry of sulphite.Also can be spissated sulphite waste pulp or the effluent (side-relief) that obtains by sulfite waste lye.It can also be the fraction that contains seminose that is obtained through chromatographic separation by the sulphite waste pulp.
In the present invention, pending solution also can be any other solution that is obtained by biomass digestion or hydrolysis, the normally hydrolysate that is obtained by the lignocellulosic material acid hydrolysis.Described hydrolysate can be obtained by lignocellulosic material, for example by using mineral acid example hydrochloric acid, sulfuric acid or sulfur dioxide treatment or passing through with organic acid such as formic acid or acetic acid treatment acquisition.Also can use by based on the slurries of solvent as based on the slurries of phenol and the waste liquid that obtains based on the alcoholic acid slurries.
The starting soln that contains seminose can be for example to separate the useless slurry of the sulphite that reclaims behind the rhamnosyl.Starting soln also can be to separate the useless slurry of the sulphite that reclaims behind the wood sugar.
The seminose product that obtains according to the present invention comprises the D-seminose usually.
Following examples are used to set forth the present invention.Embodiment should be misinterpreted as and limit claim by any way.
In following examples, used to give a definition:
Unless otherwise indicated, DS is meant the dry matter content of measuring with the Ka Er Karl Fischer titration, represent with weight percentage.
Measured the content (representing) that separates the various compositions in the fraction that obtains by chromatographic separation with other with DS percentage ratio with the HPLC method.
Embodiment 1
The method of describing the rapid separation method of multistep among the embodiment 1 illustrates as shown in Figure 7.
In this method the first step used starting soln by reclaimed after wood sugar and the rhamnosyl, based on Ca 2+The isolated effluent (side stream) that contains seminose of sulfite waste lye.Use the starting material of birch as the useless slurry of sulphite.
Carry out chromatographic separation to obtain seminose fraction and arabinose fraction (chromatographic separation A) with separating the effluent that contains seminose that reclaims behind the rhamnosyl.The seminose fraction is separated B (wood sugar precipitated crystal) to obtain wood sugar filter cake and the crystallization filtrate that contains seminose.To carry out three successive chromatographic separation (C.1), (C.2) and (C.3) by the filtrate that contains seminose that crystalline xylose obtains.To carry out the seminose crystallization by the seminose fraction that the last chromatographic separation obtains.
To carry out twice successive chromatographic separation (E.1) and (E.2) arabinose by separating arabinose fraction that (A) obtain with the recovery purifying.
Separate the starting soln that contains seminose that obtains behind the rhamnosyl and have following composition:
Composition Content (DS percentage ratio)
Wood sugar 36
Seminose 15
Semi-lactosi ??13
Glucose ??4.8
Rhamnosyl ??0.6
Arabinose ??4.9
Fructose ??1.4
Other composition ??24.6
(A) useNa + The SAC resin isolation arabinose of form
Use Na +The strongly acidic cation-exchange of form is removed the salt in the charging and is collected the arabinose of elution curve end.Separate with following separation condition:
Column diameter 0.6m
The height of bed 5.3m
Feed volume 108.5l
Charging RSD 35g/100g
Temperature 65℃
Flow velocity 170l/h
Resin Finex CS 11 GC, 5.5%DVB, mean particle size 0.35mm
By listing in the table 1 seminose and the forming of arabinose fraction of separating (A) collection.
Table 1.
Seminose and the arabinose level represented with DS percentage ratio are grouped into
Composition The seminose fraction The arabinose fraction
Wood sugar 43 34
Seminose 19 13
Semi-lactosi 16 ??10
Glucose 6.3 ??0.2
Rhamnosyl 1.1 ??0.1
Arabinose 1.8 ??17
Fructose 1.2 ??2.2
Other composition 8.9 ??23.5
The seminose productive rate is 38%, represents that with DS seminose purity is 19%, represents that with DS wood sugar purity is 43%.
The concentration curve of separation (A) as shown in Figure 1.
(B) precipitated crystal of wood sugar
Will by separate that (A) obtain, represent that with DS wood sugar content is that about 43% seminose fraction is carried out precipitated crystal to separate wood sugar.
Carry out the precipitated crystal of wood sugar with pilot scale, about 200 liters of crystallizer.It is 87.5% that feedstock solution is evaporated to whole DS.In steam cooker, each batch introduced crystal seed with the wood sugar crystal seed.In 48 hours, material is cooled to 31 ℃ by 60 ℃, then it was kept 24 hours down at 31 ℃.Do not dilute.Material is splashed in the mixing machine, filter then.
The results are shown in Table 2 for the wood sugar precipitated crystal.This table has shown the content of various compositions in crystallization charging, filter cake and the filtrate of representing with DS percentage ratio.
Table 2.
The analytical results of wood sugar precipitated crystal
Composition Charging Filter cake Filtrate
Glucose 5.9 2.9 7.0
Wood sugar 42.7 73.8 29.8
Arabinose 3.5 1.0 2.9
Seminose 19.5 7.2 23.7
Represent that with DS it is about 24% that the seminose purity of crystallization filtrate increases to, wood sugar purity reduces to about 30%.
(C) separation of seminose
(C.1) useBa 2+ The SAC resin isolation seminose of form
Use Ba 2+The SAC resin of form partly carries out chromatographic separation to the filtrate that is obtained by the wood sugar precipitated crystal.Separate with following separation condition:
Column diameter 0.225m
The height of bed 5.3m
Feed volume 11.9l
Charging RSD 32g/100g
Temperature 65℃
Flow velocity 25l/h
Resin Finex CS 08 GC, 4%DVB, mean particle size 0.38mm
Collect the seminose productive rate and be 70% and represent that with DS total purity is 49% seminose fraction.The composition of seminose and wood sugar fraction is as shown in table 3.
Table 3.
Represent with DS percentage ratio, use Ba 2+The SAC resin of form carries out first time, isolating seminose and wood sugar level were grouped into
Composition The wood sugar fraction The seminose fraction
Wood sugar 47 9.2
Seminose 9.6 49
Semi-lactosi 23 13
Glucose 12 ?0.2
Rhamnosyl 1.8 ?0.8
Fructose 0.1 ?4.0
Other composition 6.5 ?24.2
The concentration curve of separation (C.1) as shown in Figure 2.
(C.2)Ba 2+ The SAC resin isolation of form
Use the Ba second time 2+The seminose fraction that the SAC resin separation purification of form is obtained by previous step (separation of C .1).Use and the identical separation condition of above separating (C.1).
Had by the seminose fraction that separate to obtain and to represent 63% purity with DS, the productive rate of seminose is 68%.The seminose of representing with DS percentage ratio and the composition of wood sugar fraction are listed in the table 4.
Table 4.
Use Ba 2+The SAC resin of form carries out second time, isolating seminose and wood sugar level were grouped into
Composition The wood sugar fraction The seminose fraction
Wood sugar 19 1.1
Seminose 41 63
Semi-lactosi 24 3.5
Glucose 0.5 -
Rhamnosyl 1.4 0.2
Fructose 0.7 7.8
Other composition 13.9 24.3
The wood sugar fraction also contains 40% seminose.
The concentration curve of separation (C.2) as shown in Figure 3.
(C.3) useCa 2+ The separation that the SAC resin of form carries out
Use Ca 2+The SAC resin of form is to carrying out further chromatographic separation by the seminose fraction of separating (C.2) acquisition.Use following separation condition to separate:
Column diameter 0.225m
The height of bed 4.8m
Feed volume 11l
Charging RSD 30.7g/100g
Temperature 65℃
Flow velocity 30l/h
Resin Finex CS 11 GC, 5.5%DVB, mean particle size 0.38mm
The composition of the seminose fraction of representing with DS percentage ratio is listed in the table 5.
Table 5.
By using Ca 2+The seminose level that the SAC resin of form separates acquisition is grouped into
Composition The seminose fraction
Wood sugar 1.8
Seminose 80
Semi-lactosi 5.1
Glucose -
Rhamnosyl 0.2
Fructose 2.6
Other composition 10.3
Obtained to represent that with DS purity is 80% seminose fraction, the seminose productive rate is 70%.Separate (C.3) concentration curve as shown in Figure 4.
D. seminose crystallization
(D.1.) the seminose crystallization carried out of water-alcohol solvent (batch 1)
Under 30 ℃ temperature, with DS be 51% and based on the mannose content that the pure seminose that refractometry is measured is done solids content be 78% 2924g seminose syrup to be evaporated to RDS be 86.2%, and be transferred in 2 liters the reaction vessel.Represent that in order to DS 0.03% crystal seed introduces crystal seed (30 ℃, RSD 86.2%) in the ebullient syrup.Crystal seed 10ml ethanol suspendible.
Material is cooled to 25 ℃ by 30 ℃.In material, slowly add 800g ethanol.
Introduce crystal seed after 5 days, use the pressure filter filtering for crystallizing.The filter cake purity that filtration obtains was 93.0% (comprising etoh solvent as impurity), and mother liquor purity was 52.5% (comprising etoh solvent as impurity).This is equivalent to the N.F,USP MANNITOL productive rate is 41%.Crystallite size is between 10 to 20 μ m.
Twice of washing with alcohol of filter cake.Crystallization is centrifugal and 40 ℃ of dryings 24 hours.It is that 0.3% crystal water and content are 99.9% seminose that crystallization contains content.
(D.2). water-alcohol solvent carries out seminose crystallization (criticizing 2)
Under 30 ℃ temperature, with DS be 50% and based on the mannose content that the pure seminose that refractometry is measured is done solids content be 93% 1230g seminose syrup to be evaporated to RDS be 84.1%, and be transferred in 2 liters the reaction vessel.Represent that in order to DS 0.03% crystal seed introduces crystal seed (30 ℃, RSD 84.1%) in the ebullient syrup.Crystal seed 10ml ethanol suspendible.
Material is cooled to 20 ℃ by 30 ℃.In material, slowly add 300g ethanol.
Introduce crystal seed after 3 days, crystallization is centrifugal.The centrifugal cake purity that obtains was 96.0% (comprising etoh solvent as impurity).It is 50% that centrifugal result is equivalent to the N.F,USP MANNITOL productive rate.Crystallite size is between 30 to 50 μ m.
Twice of washing with alcohol of centrifugal cake.Crystallization is centrifugal and following dry 24 hours at 40 ℃.Crystal water content is 0.2% by analysis, and the crystalline mannose content is 99.7%.
(D.3.) water carries out the seminose crystallization as solvent
Under 60 ℃ temperature, with DS be 50% and based on the mannose content that the pure seminose that refractometry is measured is done solids content be 80% 1552g seminose syrup to be evaporated to RDS be 86.7%, and be transferred in 1 liter the reaction vessel.Represent in order to DS 0.07% crystal seed in the ebullient syrup, introduce crystal seed (60 ℃, RSD86.7%).
Material is cooled to 25 ℃ by 60 ℃.Introduce crystal seed after 6 days, crystallization is centrifugal.Centrifugal cake purity is 99.5%.It is 30% that centrifugal result is equivalent to the N.F,USP MANNITOL productive rate.Crystallite size is between 30 to 50 μ m.
(E) purifying of arabinose fraction
Have and represent 10% purity with DS by separating arabinose fraction that (A) obtain.With this fraction Ca 2+The SAC resin of form is further purified.
(E.1.) useCa 2+ The SAC resin purification arabinose fraction of form
Under following separation condition, separate:
Column diameter 0.225m
The height of bed 4.9m
Feed volume 18.8l
Charging RSD 30.2g/100g
Temperature 65℃
Flow velocity 30l/h
Resin Finex CS 11 GC, 5.5%DVB, mean particle size 0.40mm
The composition of charging, wood sugar fraction and the seminose fraction of representing with DS percentage ratio is listed in the table 6.
Table 6.
Use Ca 2+The isolating charging first time that resin carries out, wood sugar fraction and arabinose level are grouped into
Composition Charging The wood sugar fraction The arabinose fraction
Wood sugar 39 50 21
Seminose 16 16 14
Semi-lactosi 13 15 9.2
Glucose 1.1 1.5 0.3
Rhamnosyl 0.3 0.3 0.3
Arabinose 9.7 3.5 19
Fructose 0.1 0.6 1.3
Other composition 20.8 13 35.4
The concentration curve of separation (E.1) as shown in Figure 5.
(E.2.) useCa 2+ The SAC resin of form carries out repeatedly purifying to the arabinose fraction
Will be by separating the arabinose fraction Ca that (E.1) obtains 2+The resin of form carries out another time purifying.Separate with following separation condition:
Column diameter 0.225m
The height of bed 4.9m
Feed volume 20l
Charging RSD 30.6g/100g
Temperature 65℃
Flow velocity 30l/h
Resin Finex CS 11 GC, 5.5%DVB, mean particle size 0.40mm
Charging, wood sugar fraction and the arabinose level represented with DS percentage ratio are grouped into lists in the table 7.
Table 7.
Use Ca 2+The isolating charging second time that the resin of form carries out and wood sugar fraction and arabinose level are grouped into
Composition Charging The wood sugar fraction The arabinose fraction
Wood sugar 27 43 14
Seminose 16 20 13
Semi-lactosi 11 15 7
Glucose 0.2 0.6 0.0
Rhamnosyl 0.4 0.4 0.3
Arabinose 18 6.2 26
Fructose 3.8 1.5 5.3
Other composition 23.6 13.6 34.7
The arabinose productive rate of collecting is 85%.
The concentration curve of separation (E.2) as shown in Figure 6.
It is apparent that for those skilled in the art: along with technical progress, design of the present invention can be implemented in many ways.The present invention and embodiment thereof are not limited to the foregoing description, but change in the claim scope.

Claims (36)

1. by the method that reclaims seminose derived from the solution of biomass, it comprise utilize at least a to small part be Ba 2+The chromatographic separation resin bed of form and at least a non-Ba 2+The chromatographic separation resin bed of form is handled described solution with chromatography separating method, and reclaims a at least seminose fraction.
2. the described method of claim 1, wherein said chromatography separating method comprises at least two chromatrographic separation step, wherein in these steps at least one step use to small part be Ba 2+The chromatographic separation resin bed of form carries out, and the non-Ba of at least one step in these steps 2+The chromatographic separation resin bed of form carries out.
3. the described method of claim 2, it comprise with derived from the solution feed of biomass in comprise to small part be Ba 2+In first chromatographic column of the chromatographic separation resin bed of form,, reclaim first part of seminose fraction with eluent wash-out described chromatographic column, then with the charging of described first part of seminose fraction in comprising non-Ba 2+In second chromatographic column of the chromatographic separation resin bed of form,, and reclaim second part of seminose fraction with the described chromatographic column of eluent wash-out.
4. the described method of claim 2, wherein said chromatography separating method comprise use to small part be Ba 2+Two separating steps that the chromatographic separation resin bed of form carries out and use non-Ba 2+The separating step that the chromatographic separation resin bed of form carries out.
5. the described method of claim 4, it comprises: will derived from the solution feed of biomass in comprise to small part be Ba 2+In first chromatographic column of the chromatographic separation resin bed of form,, reclaim first part of seminose fraction with eluent wash-out described chromatographic column, with the charging of described first part of seminose fraction in comprise to small part be Ba 2+In second chromatographic column of the chromatographic separation resin bed of form,, reclaim second part of seminose fraction with eluent wash-out described chromatographic column, then with the charging of described second part of seminose fraction in comprising non-Ba 2+In the 3rd chromatographic column of the chromatographic separation resin bed of form,, and reclaim the 3rd part of seminose fraction with the described chromatographic column of eluent wash-out.
6. the described method of claim 1, wherein said to small part be Ba 2+The resin of form is Ba basically 2+Form.
7. the described method of claim 1, wherein said non-Ba 2+The resin bed of form is to be selected from hydrogen, NH 4 +, alkali metal cation and alkaline earth metal cation cationic form.
8. the described method of claim 7, wherein said positively charged ion is selected from NH 4 +, Na +, K +, Mg 2+And Ca 2+
9. the described method of claim 1, wherein said chromatography separating method carries out with strongly acidic cation-exchange.
10. the described method of claim 1, method wherein also comprises the one or more purification steps that are selected from membrane filtration, ion-exchange, evaporation, filtration and derivatize, can before described one/a plurality of chromatrographic separation step, afterwards or between carry out.
11. comprising, the described method of claim 10, wherein said derivatize form N-phenyl-D-mannopyranose amine as mannose derivative.
12. the described method of claim 1, method wherein comprise that also the crystallization of seminose is to obtain crystallinity seminose product.
13. the described method of claim 12, wherein said crystallization is carried out with the solvent of the mixture that is selected from water, alcohol and alcohol and water.
14. the described method of claim 13, wherein said crystallization is carried out with the mixture of second alcohol and water.
15. the described method of claim 1, method wherein also comprises the separation of other sugar.
16. the described method of claim 15, method wherein comprise that the separation of wood sugar is as pre-treatment step.
17. the described method of claim 16, wherein the separation of wood sugar is undertaken by precipitated crystal.
18. the described method of claim 15, method wherein comprise that also the separation of arabinose is as pre-treatment step.
19. the described method of claim 18, wherein the precipitated crystal wood sugar that is separated in of arabinose carries out before.
20. claim 18 or 19 described methods, wherein the separation of arabinose is carried out to reclaim the arabinose fraction with chromatography separating method.
21. the described method of claim 20, the chromatographic separation resin bed of wherein said used in chromatograph univalent cation form carries out.
22. the described method of claim 21, wherein said univalent cation is selected from hydrogen, ammonium and alkali metal cation.
23. the described method of claim 22, wherein said positively charged ion is selected from H +, NH 4 +, Na +And K +
24. the described method of claim 20, method wherein also comprises the chromatogram purification of described arabinose fraction.
25. the described method of claim 24, the chromatogram purification of wherein said arabinose fraction comprise the step that at least one carries out with the chromatographic separation resin bed of alkaline earth metal cation form.
26. the described method of claim 25, wherein said alkaline-earth metal is Ca 2+
27. the described method of claim 20, the separation of wherein said arabinose is carried out with strongly acidic cation-exchange.
28. the described method of claim 15, method wherein comprise that also the separation of rhamnosyl is as pre-treatment step.
29. the described method of claim 28, wherein the separation arabinose that is separated in of rhamnosyl carries out before.
30. the described method of claim 1, wherein said solution derived from biomass are the mixtures of carbohydrate containing.
31. the described method of claim 30, wherein said carbohydrate comprises sugar.
32. the described method of claim 1, wherein said solution derived from biomass is the biomass by hydrolyzation product.
33. the described method of claim 1, the wherein said solution useless slurry that is sulphite derived from biomass.
34. the described method of claim 33, the useless slurry of wherein said sulphite are to separate the useless slurry of the sulphite that reclaims behind the rhamnosyl.
35. the described method of claim 33, the useless slurry of wherein said sulphite are to separate the useless slurry of the sulphite that reclaims behind the wood sugar.
36. the described method of claim 1, wherein said seminose are the D-seminoses.
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