KR100943835B1 - Method for the recovery of sugars - Google Patents

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

{Method for the recovery of sugars}             

The present invention relates to a chromatographic separation method for separating carbohydrates, in particular sugars, from a mixture comprising carbohydrates, in particular sugars. The mixture treated according to the invention is typically a solution from biomass comprising carbohydrates / sugars. In particular, the present invention provides a chromatographic separation method for recovering high purity mannose from a solution derived from biomass such as sulfite pulp waste liquor. Mannose can be recovered in crystalline form or in solution form. The claimed method of recovering mannose is based on the use of a combination of a resin in the form of Ba ²⁺ and a resin other than the Ba ²⁺ form as a separation resin, which then crystallizes the mannose as necessary. In connection with the separation process of the present invention, xylose and arabinose products may also be obtained as by-products depending on the composition of the starting solution from the biomass.

Mannose is useful, for example, for various pharmaceutical uses. It can be used as starting material or raw material for various pharmaceutical products. Mannose is also therapeutically useful in the treatment of urinary infections and intravenous inflammatory conditions. In food technology, mannose is useful, for example, in so-called Positech applications (GMO testing of food products).

Mannose is also useful as a raw material for the production of mannitol with various pharmaceutical uses.

Mannose can be recovered from a wood source where mannose is present in a mixture with other carbohydrate and lignin components. In wood and other plant-based materials, mannose is typically found as heterogeneous polymers with polymer forms such as hemicellulose, most often glucose and / or galactose in glucomannan, galactoglucomannan and galactomannan. The waste liquor obtained from the softwood pulping process is particularly rich in mannose. Mannose is also recovered from vegetable palm fruit and certain seaweeds.

Recovery of high purity mannose from plant based materials has been a problem in the art.

Jones, JKN and Wall, RA, Canadian Journal of Organic Chemistry 38 (1960), pp. 2290 to 2294 disclose a method of separating sugars from synthetic sugar mixtures and plant extracts using ion exchange resins. This method relates to the separation of a monosaccharide mixture comprising D-mannose and D-mannitol using an ion exchange resin in the form of a neutral salt of sulfonic acid. As the separation resin, Dowex 50W X8 resin of the Ba ²⁺ form is used.

Larsson, L.I and Samuelsson, O., Acta Chemica Scandinavica 19 (1965), pp. 1357 to 1364 discloses a method for automatically separating monosaccharides present in wood hydrolysates using ion exchange resins. Separation of 16 monosaccharides including D-mannose by partition chromatography on sulfate-based strong basic anion exchange resin using ethanol as eluent was studied.

In addition, the use of ion exchangers for the isolation of monosaccharides has been studied for the purpose of investigating the behavior of sugars on columns containing nonsulfite saturated resins. For example, a nonsulfite type ion exchanger (Amberlite IRA-400) was used to separate fructose, glucose and mannose. As a practical result of this study, an improved method of measuring the reduced sugar in sulfite waste liquor is proposed.

The interactions found between aqueous solutions of monosaccharides including aluminum oxide and D-mannose have also been studied. By suitable selection of alumina it is proposed that the separation of sugars can be easily and quickly achieved on a preliminary and analytical scale.

It is also known to recover mannose from various sources via mannose derivatives. Fujita, T and Sato, T [see Bull. Chem. Soc. Japan 33 (1960) 353 discloses the recovery of D-mannose through N-phenyl-D-mannopyranosylamine. N-phenyl-D-mannopyranosylamine is disclosed to be highly stable and water insoluble and therefore even recommended for isolating D-mannose from very impure raw materials.

Herrick, F.W., Casebier, R.L., Hamilton, J.K. And Wilson, J.D., "Mannose chemicals", Applied Polymer Symposium No. 28 (1975), pp. 93 to 108 discloses the development of a method for the economic recovery of mannose or its derivatives from a wood source such as sulfite waste liquor (mannose is a major component of a mixture containing other carbohydrates and lignin fractions). The main achievement of this study was the development of recovery methods for sodium mannose bisulfite and methyl mannosides from several raw materials. Recovery processes of mannose from coarse mixtures have been developed through two routes: (1) formation of sodium bisulfite adducts of the mixture of monomeric wood sugars, crystallization and separation of sodium mannose bisulfite, and of mannose from this intermediate Regeneration, and (2) anhydrous methanolysis with glycosidation of coarse mixed sugar polymers or monomers, crystallization and separation of methyl α-D mannosides, and regeneration of mannose from this intermediate. These mannose recovery processes have the disadvantage of being very cumbersome to carry out in practice.

Sinner, M, Simatupang, M.H. And Dietrichs, H.H., “Automated Quantitative Analysis of Wood Carbohydrates by Borate Complex Ion Exchange Cromatography,” Wood Science and Technology, 1975, pp. 307 to 322 disclose a method for automated and simple analytical separation and quantitative determination of sugars from acidic and enzymatic hydrolysates of wood polysaccharides via borate complex ion exchange chromatography. Sugars separated in this way include mannose, fructose, arabinose, galactose, xylose, glucose, and disaccharides such as xylobiose, cellobiose and sucrose.

British Patent 1 540 556 (ICI Americas, published February 14, 1979) relates to a process for separating mannose from glucose present in an aqueous solution. Starting mixtures of glucose and mannose are typically obtained by epimerization of glucose in aqueous solution. Separation of mannose from glucose is typically carried out using cation exchange resins in the form of alkaline earth metal salts, such as Ca ²⁺ , Sr ²⁺ or Ba ²⁺ forms. Cation exchange resins are preferably cation exchange resins of strong acids, typically based on styrene divinylbenzene.

Hassi, R., Tikka, P. and Sjostrom, E. [Note: "Recovery of Lignosulphonates and Sugars from Spent Sulphite Liquors by Ion Exclusion Chromatography", 1982 International Sulfite Pulping Conference, Sheraton Center Hotel, Toronto, Ontario, October 20-- 22, pp. 165 to 170, the separation of sugars from lignosulfonates is disclosed. Ion exchange chromatography on strong acid cation exchange resins was applied to fractionation of lignosulfonates and sugars, including mannose present in the sulfite waste liquor. The resin used in the test was a strong acid gel type polystyrene cation exchange resin (Amberlite IR-120, Ca ²⁺ form). It has been suggested that the sugar fraction can be used as a source of raw material for the production of mannitol.

Finnish patent No. 78734 (Sumen Sokeri Oy, published April 5, 1987) relates to a multistage separation process of sugar and lignosulfonate from sulfite pulp waste liquor. The process involves the introduction of a sulfite pulp waste solution into a chromatography column comprising a separation resin in the form of a metal salt, typically a strong acid cation exchange resin in the form of Ca ²⁺ , eluting the column with water to give a lignosulfonate rich fraction and a sugar rich fraction. Recovering, and introducing the obtained sugar rich fraction into another chromatography column comprising a separation resin in the form of a monovalent metal salt, typically in the form of Na ⁺ . A sugar fraction is obtained that does not contain lignosulfonate.

WO 96/27029 (Xyrofin Oy, published 6 September 1996) relates to a method for recovering organic compounds from solution by crystallizing organic compounds such as sugars substantially by nucleation. Mannose suggests that it can be recovered by, for example, a nucleation crystallization method.

Finnish patent 97 625 (Xyrofin Oy, published March 5, 1996) discloses a method for crystallization of xylose. In this method, xylose is recovered from the solution by crystallization, with xylose purity being relatively low. In particular, this method relates to the recovery of xylose from biomass derived solutions.

International Patent Publication No. 99/10542 (Cultor Corporation, published March 4, 1999) discloses L-Arabinose from beet pulp by chromatographic separation using a cation exchanger in the form of a monovalent metal as a separation resin. Disclosed is a recovery method of. The L-arabinose solution thus obtained is purified by cation and anion exchanger and adsorptive resin.

International Patent Publication No. 01/21271 A1 (Sohkar Oy, published March 29, 2001) discloses a process for the recovery of pectin, arabinose and salts from vegetable materials using cation exchange resins, preferably polyvalent metal forms. do.

The biomass derived raw materials used for the recovery of mannose are typically multicomponent complex mixtures. The separation of mannose with sufficient purity from these complex mixtures is problematic. One of the problems associated with the known methods described above is that it does not provide mannose as a mixture with other closely related sugars, or does not provide mannose with sufficient purity. On the other hand, generating mannose from mannan and other mannose derivatives is technically very cumbersome. Moreover, it is problematic to prepare a mannose starting solution suitable for crystallizing mannose to give crystalline mannose products.

In the present invention, it has been found that high purity mannose can be efficiently recovered from a carbohydrate-containing solution derived from biomass using a novel chromatographic separation method. With the chromatographic process of the invention, mannose fractions of purity 45-80% or more can be obtained. The mannose fraction obtained by chromatographic separation can be further purified by crystallization. Crystallization provides a crystalline mannose product of at least 99% purity. In connection with the process of the invention, other various sugars, such as xylose and arabinose, can be recovered as by-products depending on the composition of the starting raw material derived from the biomass.

Brief description of the invention

It is therefore an object of the present invention to provide a method for recovering high purity mannose products from carbohydrate mixtures containing mannose. Various other sugars can be recovered as by-products such as xylose and arabinose. The object of the present invention is achieved by a method having the features described in the independent claims. Preferred embodiments of the invention are described in the dependent claims.

The present invention is based on the purification of mannose containing carbohydrate mixtures by chromatography using two or more separation resins, one of which is a Ba ²⁺ based resin.

By the process of the present invention, high purity mannose products can be obtained.

[Note: Definition]

The following definitions are used throughout the specification and examples and claims:

SAC means cation exchange resin of strong acid.

DS refers to dry matter content as measured by Karl Fischer titration, expressed in weight percent.

RDS means refractometer dry matter content and is expressed in weight percent.

The following figures are exemplary aspects of the invention and do not in any way limit the scope of the invention as defined in the claims.

1 is a graph showing the concentration profile of mannose-arabinose separation (separation A) using the Na ⁺ form SAC resin of Example 1. FIG.

FIG. 2 is a graph showing the concentration profile of mannose separation (separation C.1) using Ba ²⁺ form SAC resin of Example 1. FIG.

3 is a graph showing the concentration profile of repeated mannose separation (Separation C.2) using Ba ²⁺ form SAC resin of Example 1. FIG.

4 is a graph showing the concentration profile of mannose separation (separation C.3) using the Ca ²⁺ type SAC resin of Example 1. FIG.

5 is a graph showing a concentration profile of arabinose separation (separation E.1) using the Ca ²⁺ form SAC resin of Example 1. FIG.

FIG. 6 is a graph showing the concentration profile of repeated arabinose separation (separation E.2) using the Ca ²⁺ form SAC resin of Example 1. FIG.

7 is a process diagram describing one aspect of the present invention for recovering mannose and xylose. This process also includes the separation of arabinose as a pretreatment step.

The present invention relates to a method for recovering mannose from a solution containing mannose. The process of the present invention utilizes one or more chromatographic separation resin layers, at least partially in the form of Ba ²⁺ , and one or more chromatographic separation resin layers other than Ba ²⁺ form, to treat the mixture in a chromatographic separation process and Recovering the nose fraction.

The chromatographic separation methods of the present invention typically comprise two or more chromatographic separation steps, wherein one or more of these steps is performed with a chromatography separation resin layer that is at least partially in the form of Ba ²⁺ , and one or more of these steps Is performed with a chromatographic separation resin layer other than the Ba ²⁺ form.

One aspect of the present invention provides a method comprising the steps of: feeding a mannose containing solution into a first chromatography column comprising a chromatography separation resin layer, at least partially in the form of Ba ²⁺ , eluting the column with an eluent, first bay Recovering the nose fraction, feeding the first mannose fraction into a second chromatography column comprising a chromatography separation resin layer other than Ba ²⁺ form, eluting the column with an eluent, and second bay Recovering the nose fraction.

In another aspect of the invention, the chromatographic separation method is a one-to use at least in part, Ba ²⁺ form of a chromatographic separation can be two separate chromatography other than the one separating step, and Ba ²⁺ form resin layer using the resin layer A separation step.

This aspect of the invention typically comprises feeding a mannose containing solution into a first chromatography column comprising a chromatography separation resin layer at least partially in the form of Ba ²⁺ , eluting the column with an eluent, first only Recovering the nose fraction, feeding the first mannose fraction into a second chromatography column comprising a chromatography separation resin layer at least partially in the form of Ba ²⁺ , eluting the column with an eluent, and second Recovering the mannose fraction, feeding the second mannose fraction into a third chromatography column comprising a chromatographic separation resin layer other than Ba ²⁺ form, eluting the column with an eluent, and a third Recovering the mannose fraction.

In the above-mentioned embodiments of the present invention, some other separation may be performed before Ba ²⁺ separation. In the same way, some other separation can be performed between Ba ²⁺ separations. In addition, equilibrium of ions or ionic compositions is typically performed between two ion exchange operations, for example by ion exchange.

In one aspect of the invention, the resin (resin layer) in at least partially Ba ²⁺ form is substantially Ba ²⁺ form. As a result of the balancing of the chromatographic columns during the chromatographic separation process, the resin layer, at least partially in the form of Ba ²⁺ , contains other ions such as H ⁺ , alkali metal cations such as Na ⁺ and Ka ⁺ , and Ca ²⁺ and Alkaline earth metal cations such as Mg ²⁺ and the like.

The resin in at least partially Ba ²⁺ form refers to a cation exchange resin.

Form of the resin (resin layer) other than the Ba ^2+; refers to a cationic form of the resin other than Ba ^2+. The resin is typically a cation exchange resin, wherein the cation is in hydrogen form (H ⁺ ), NH ₄ ⁺ form or metal form selected from alkali metals and alkaline earth metals such as Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ . Particularly preferred metal is Ca ²⁺ .

Chromatographic separation to obtain mannose in accordance with the invention is typically carried out with a cation exchange resin of strong acid. Preferred resins are resins based on styrene-divinylbenzene crosslinked. Suitable crosslinking degree of the resin is 1 to 20% by weight, preferably 3 to 8% by weight. The average particle size of the resin is usually 10 to 2000 mu m, preferably 100 to 400 mu m. Zeolite based molecular sieves may also be used.

The eluent used for the chromatographic separation according to the invention is water, a solvent, for example an alcohol, or a mixture thereof. Preferred eluent is water.

Elution is preferably carried out at a temperature of 10 to 95 ° C, more preferably 30 to 95 ° C, most preferably 55 to 85 ° C.

The chromatographic separation method of the present invention provides a mannose fraction in which the mannose is in solution. The mannose product obtained from the chromatographic separation has a typical purity of 45-80% mannose based on RDS.

In order to improve the yield of the chromatographic separation, a recycle fraction of the chromatographic separation may be used.                 

The chromatographic separation methods of the present invention may further comprise one or more purification steps selected from membrane filtration, ion exchange, evaporation, filtration and derivatization. These purification steps can be performed before, after or between the chromatographic separation steps / steps.

Ion exchange is typically performed to purify the mannose containing solution, for example from SO ₄ ⁻ ions.

In the derivatization method, mannose derivatives are formed and then mannose is regenerated from the obtained derivatives. One example of a useful mannose derivative is N-phenyl-D-mannopyranosylamine.

The mannose solution obtained from the chromatographic separation can be further purified by crystallization to obtain crystalline mannose product. Crystallization is typically carried out using a solvent selected from water, alcohols and mixtures of water and alcohols. In a preferred embodiment of the invention, the crystallization is carried out with a mixture of ethanol and water.

Crystallization is carried out by evaporating the mannose solution or mannose syrup obtained from the chromatographic separation to a suitable dry matter content (eg RDS of about 85%). Boiling syrup can be inoculated with mannose seed crystals. Seeds, if used, are suspended in crystallization solvents which may be water, solvents such as alcohols or mixtures thereof. Typical crystallization solvent is ethanol. The crystallized mass is cooled to room temperature before the crystallization solvent is added. The crystallization mass can then be left at room temperature for a period of time, preferably 3 to 6 days, after which the crystals can be filtered off. The filtrate cake is washed with crystallization solvent. High purity mannose crystals are obtained.

Crystallization provides crystalline mannose having a purity of at least 90%, preferably at least 95%, and most preferably at least 99%, based on RDS.

The process of the present invention may also include separation of other sugars, such as xylose, rhamnose and arabinose, depending on the composition of the mannose containing starting solution. Separation of other sugars is typically performed prior to mannose separation.

The process of the present invention may thus comprise separation of xylose as a pretreatment step. Recovery of xylose can be carried out by various methods, for example by precipitation crystallization.

Xylose precipitation crystallization is preferably performed immediately before chromatographic separation of mannose.

In xylose precipitation crystallization, a solution containing mannose and some xylose is subjected to a crystallization step. Precipitation crystallization of xylose is typically performed by evaporating the solution to the desired dry matter content, inoculating the solution with xylose seed crystals and then cooling the crystallization mass according to the desired cooling program. The crystallized mass is filtered to give xylose cake and mannose-containing crystallization effluent. Xylose is recovered from the crystallized cake and the mannose containing effluent is subjected to the chromatographic purification described above to obtain high purity mannose in accordance with the present invention.

The process of the present invention may also preferably include the separation of arabinose as a pretreatment step. Separation of arabinose can be carried out prior to precipitation crystallization of xylose. Typically chromatographic separation is used to recover the arabinose. Chromatographic separation of arabinose is preferably carried out using a chromatographic separation resin layer in monovalent cation form selected from hydrogen, ammonium and alkali metal cations. The monovalent cation is typically selected from H ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ . Recover the arabinose fraction. The chromatographic separation resin is preferably a strong acid cation exchange resin.

The arabinose fraction can be further purified by chromatography. Chromatographic purification of the arabinose fraction typically involves one or more steps using a chromatography separation resin layer in the form of an alkaline earth metal, preferably Ca ²⁺ . The arabinose fraction thus obtained may also be crystallized.

The process of the present invention may also include separation of rhamnose as a pretreatment step. The separation of rhamnose is typically performed before the separation of arabinose.

For xylose-rich raw materials, the process of the present invention may also include separation of xylose as a pretreatment step. Separation of xylose is typically performed prior to separation of arabinose.

The process of the present invention further comprises purification steps such as membrane filtration, for example ultrafiltration and nanofiltration, ion exchange, evaporation and filtration, for example to remove lignosulfonates, acids (organic and inorganic acids) and salts. It may also include.

Starting solutions containing mannose are typically mixtures containing carbohydrates such as sugars. The solution may contain, in addition to mannose, for example xylose, galactose, glucose, rhamnose, arabinose and fructose. The mixture may contain disaccharides and more sugars.

Materials containing a mixture of carbohydrates are typically derived from mannose containing vegetable materials such as biomass, typically softwood or hardwood, straw, corn husk, corn sills, corn fiber and sugar beet. Starting materials are generally used in the form of hydrolysates obtained by, for example, prehydrolysis, total hydrolysis, steam hydrolysis, enzymatic hydrolysis or acid hydrolysis.

The biomass hydrolysates used for the recovery of mannose in accordance with the invention are typically waste liquors obtained from the pulping process. The waste liquor is in particular a sulfite pulp waste liquor obtainable by acidic, basic or neutral sulfite pulping. If the biomass hydrolyzate, such as the waste liquor, contains mannose in polymer form, the polymer mannose may be hydrolyzed by acid or enzyme prior to the chromatographic separation step.

Typical waste liquors useful in the present invention are mannose-containing waste liquors, preferably obtained from acid sulfite pulping. Waste liquor can be obtained directly from sulfite pulping. It may also be a side-relief obtained from concentrated sulfite pulp liquor or sulfite cooking. It may also be a mannose-containing fraction obtained by chromatography from a sulfite pulp solution.

In the present invention, the liquid to be treated may also be any other liquid obtained from decomposition or hydrolysis of biomass, typically a hydrolyzate obtained from acid hydrolysis of lignocellulosic material. Such hydrolyzate can be obtained by treating the lignocellulosic material with, for example, an inorganic acid such as hydrochloric acid, sulfuric acid or sulfur dioxide, or an organic acid such as formic acid or acetic acid. Waste liquors obtained from solvent-based pulping, such as phenol-based pulping and ethanol-based pulping, may also be used.

The starting solution containing mannose can be, for example, sulfite pulp waste liquor recovered after separation of the ramnose. The starting solution may also be the sulfite pulp waste liquid recovered after xylose separation.

Mannose products obtained according to the present invention typically comprise D-mannose.

The following examples illustrate the invention. The examples do not limit the claims in any way.

In the following examples the following definitions are used:

DS refers to dry matter content as measured by Karl Fischer titration, expressed in weight percent unless otherwise noted.

The contents of the various components of the fraction (expressed in% based on DS) obtained from chromatography and other separation methods are measured using HPLC method.

Example 1

7 is a flowchart illustrating the multi-stage separation process of Example 1. FIG.                 

The starting liquid used in the first step of the process was mannose-containing side vapor separated from the sulfite waste liquor based on Ca ²⁺ after the recovery of xylose and rhamnose. Birch was used as raw material for sulfite pulping.

The mannose-containing side vapor recovered after separation of the rhamnose was chromatographically separated to give the mannose fraction and the arabinose fraction (chromatographic separation A). The mannose fraction was treated with Separation B (xylose precipitated crystallization) to yield a xylose cake and mannose-containing crystallization effluent. Mannose-containing effluent from the crystallization of xylose was treated with three successive chromatographic separations (C.1), (C.2) and (C.3). Mannose fractions were mannose crystallized from the final chromatographic separation.

The arabinose fraction from separation (A) was treated with two successive chromatographic separations (E.1) and (E.2) to recover pure arabinose.

The mannose-containing starting liquid obtained after separation of the ramnose has the following composition:

ingredient Content (% based on DS) Xylose 36 Mannose 15 Galactose 13 Glucose 4.8 Rhamnose 0.6 Arabinose 4.9 Fructose 1.4 Etc 24.6

(A) Na ⁺ Separation of Arabinoses Using A-Type SAC Resin

A strong acid cation exchange resin in Na ⁺ form was used to remove salt from the feed and arabinose was collected at the final stage of the elution profile. Separation was carried out using the following separation states:

Column diameter 0.6 m Floor height 5.3 m Feed volume 108.51 Feed RSD 35g / 100g Temperature 65 ℃ Flow rate 170 ℓ / h Suzy Fineex CS 11 GC, 5.5% DVB, Average Particle Size 0.35 mm

The composition of the mannose and arabinose fractions collected from isolate (A) is shown in Table 1.

Composition of mannose and arabinose fractions (% based on DS) ingredient Mannose fraction Arabinose fraction Xylose 43 34 Mannose 19 13 Galactose 16 10 Glucose 6.3 0.2 Rhamnose 1.1 0.1 Arabinose 1.8 17 Fructose 1.2 2.2 Etc 8.9 23.5

Mannose yield was 38% for 19% mannose purity based on DS and 43% xylose purity based on DS.

The concentration profile of the isolate (A) is shown in FIG. 1.

(B) xylose precipitation crystallization

Xylose was isolated by subjecting the mannose fraction obtained from separation (A) with a xylose content of about 43% based on DS to precipitation crystallization.

Precipitation crystallization of xylose was carried out on a pilot scale using about 200 liters of one crystallizer. The feed was evaporated to a final DS of 87.5%. The batch was inoculated with xylose seed crystals in a boiling pan. The mass was cooled from 60 ° C. to 31 ° C. within 48 hours and then maintained at 31 ° C. for 24 hours. No dilution was done. The mass was added dropwise to a mingler and filtered.

The results of xylose precipitation crystallization are listed in Table 2. The table shows the content of various components in the crystallization feed, cake and effluent in% on a DS basis.

Assay of xylose precipitation crystallization ingredient Feed cake Effluent Glucose 5.9 2.9 7.0 Xylose 42.7 73.8 29.8 Arabinose 3.5 1.0 2.9 Mannose 19.5 7.2 23.7

Mannose purity of the crystallization effluent increased to about 24% based on DS and xylose purity decreased to about 30%.

(C) mannose separation

(C.1) Ba ²⁺ Mannose Separation Using SAC Resin

The effluent fraction obtained from xylose precipitation crystallization was separated by chromatography using SAC resin in the form of Ba ²⁺ . Separation was carried out using the following separation states:

Column diameter 0.225 m Floor height 5.3 m Feed volume 11.9 ℓ Feed RSD 32 g / 100 g Temperature 65 ℃ Flow rate 25 ℓ / h Suzy Finex CS 08 GC, 4% DVB, average particle size 0.38 mm

Mannose fractions were harvested with a mannose yield of 70% and a total purity of 49% based on DS. The composition of the mannose and xylose fractions is shown in Table 3.

Composition of mannose and xylose fractions from first separation using SAC resin in the form of Ba ²⁺ (% based on DS) ingredient Xylose fraction Mannose fraction Xylose 47 9.2 Mannose 9.6 49 Galactose 23 13 Glucose 12 0.2 Rhamnose 1.8 0.8 Fructose 0.1 4.0 Etc 6.5 24.2

The concentration profile of the separation (C.1) is shown in FIG.

(C.2) Ba ²⁺ SAC resin separation

SAC resin separation in the form of a second Ba ²⁺ was used to purify the mannose fraction obtained in the previous step (separation C.1). The same separation was used as for separation (C.1).

The mannose fraction obtained by separation had a purity of 63% and a mannose yield of 68% based on DS. The composition of the mannose and xylose fractions is listed in Table 4 in% based on DS.

Composition of Mannose and Xylose Fractions Obtained from Second Separation Using SAC Resin with Ba ²⁺ Form ingredient Xylose fraction Mannose fraction Xylose 19 1.1 Mannose 41 63 Galactose 24 3.5 Glucose 0.5 - Rhamnose 1.4 0.2 Fructose 0.7 7.8 Etc 13.9 24.3

The xylose fraction still contained 40% mannose.

The concentration profile of the separation (C.2) is shown in FIG. 3.

(C.3) Ca ²⁺ Separation using SAC resin

The mannose fraction obtained in separation (C.2) was separated by further chromatography using SAC resin in the form of Ca ²⁺ . Separation was carried out using the following separation states:

Column diameter 0.225 m Floor height 4.8 m Feed volume 11 ℓ Feed RSD 30.7 g / 100 g Temperature 65 ℃ Flow rate 30 ℓ / h Suzy Finex CS 11 GC, 5.5% DVB, Average Particle Size 0.38 mm

The composition of the mannose fraction is listed in Table 5 in% based on DS.

Composition of Mannose Fraction Obtained from Separation with SAC Resin of Ca ²⁺ Form ingredient Mannose fraction Xylose 1.8 Mannose 80 Galactose 5.1 Glucose - Rhamnose 0.2 Fructose 2.6 Etc 10.3

80% mannose fraction purity was obtained with 70% mannose yield based on DS. The concentration profile of the separation (C.3) is shown in FIG. 4.

D. Mannose Crystallization

(D.1) Mannose Crystallization Using Water-Ethanol Solvent (Batch 1)

2924 g of mannose syrup having 51% DS and 78% mannose content (based on pure mannose refractometer dry solids content) was evaporated to 86.2% RDS and transferred to a 2 liter reaction vessel at a temperature of 30 ° C. The boiling syrup is inoculated with 0.03% seed based on DS (30 ° C., RDS 86.2%). Seeds were suspended with 10 ml of ethanol.

The mass was cooled from 30 ° C. to 25 ° C. 800 g of ethanol was slowly added to the mass.

Five days after inoculation, the crystals were filtered through a compression filter. Filtration gave 93.0% cake purity (including solvent ethanol as impurities) and 52.5% mother liquor purity (including solvent ethanol as impurities). This corresponds to a 41% mannose yield. The crystal size ranged from 10-20 μm.

The filter cake was washed twice with ethanol. The crystals were centrifuged and dried at 40 ° C. for 24 hours. The crystal had a crystalline moisture content of 0.3% and a mannose content of 99.9%.

(D.2) Mannose Crystallization Using Water-Ethanol Solvent (Batch 2)

1230 g of mannose syrup with 50% DS and 93% mannose content (based on pure mannose refractometer dry solids content) was evaporated to 84.1% RDS and transferred to a 2 liter reaction vessel at a temperature of 30 ° C. Boiling syrup was inoculated with 0.03% of seed based on DS (30 ° C., RDS 84.1%). Seeds were suspended with 10 ml of ethanol.

The mass was cooled from 30 ° C. to 20 ° C. 300 g of ethanol was added slowly to the mass.

Three days after inoculation, the crystals were centrifuged. Centrifugation yielded 96.0% cake purity (including solvent ethanol as impurities). The centrifugation result corresponds to 50% mannose yield. The crystal size ranged from 30 to 50 μm.

The centrifugal cake was washed twice with ethanol. The crystals were centrifuged and dried at 40 ° C. for 24 hours. The moisture content of the crystal was 0.2% and the mannose content of the crystal was analyzed to 99.7%.

(D.3) Mannose Crystallization Using Water as Solvent

1552 g of mannose syrup with 50% DS and 80% mannose content (based on pure mannose refractometer dry solids content) was evaporated to 86.7% RDS and transferred to a 1 liter reaction vessel at a temperature of 60 ° C. Boiling syrup was inoculated with 0.07% seed based on DS (60 ° C., RDS 86.7%).

The mass was cooled from 60 ° C. to 25 ° C. Six days after the inoculation, the cake was centrifuged to yield 99.5% purity. The centrifugation result corresponds to 30% mannose yield. The crystal size ranged from 30 to 50 μm.

(E) Purification of arabinose fraction

The purity of the arabinose fraction obtained in separation (A) was 10% based on DS. This fraction was further purified using SAC resin in the form of Ca ²⁺ .

(E.1) Ca ²⁺  Purification of the Arabinose Fraction Using SAC Resin in the Form

Separation was carried out using the following separation states:

Column diameter 0.225 m Floor height 4.9 m Feed volume 18.8 ℓ Feed RSD 30.2 g / 100 g Temperature 65 ℃ Flow rate 30 ℓ / h Suzy Finex CS 11 GC, 5.5% DVB, 0.40 mm average particle size

The composition of the seed, xylose and arabinose fractions is listed in Table 6 in% based on DS.

Composition of xylose and arabinose fractions and seeds obtained from first separation with Ca ²⁺ resin ingredient Feed Xylose fraction Arabinose fraction Xylose 39 50 21 Mannose 16 16 14 Galactose 13 15 9.2 Glucose 1.1 1.5 0.3 Rhamnose 0.3 0.3 0.3 Arabinose 9.7 3.5 19 Fructose 0.1 0.6 1.3 Etc 20.8 13 35.4

The concentration profile of the separation (E.1) is shown in FIG. 5.

(E.2) Ca ²⁺  Purification of the Arabinose Fraction Using SAC Resin in the Form

The arabinose fraction obtained from separation (E.1) was further purified using a resin in the form of Ca ²⁺ . Separation was carried out using the following separation states:

Column diameter 0.225 m Floor height 4.9 m Feed volume 20 ℓ Feed RSD 30.6 g / 100 g Temperature 65 ℃ Flow rate 30 ℓ / h Suzy Finex CS 11 GC, 5.5% DVB, 0.40 mm average particle size

The composition of the seed, xylose and arabinose fractions is listed in Table 7 in% based on DS.

Composition of xylose and arabinose fractions and seeds obtained from second separation using Ca ²⁺ form resin ingredient Feed Xylose fraction Arabinose fraction Xylose 27 43 14 Mannose 16 20 13 Galactose 11 15 7 Glucose 0.2 0.6 0.0 Rhamnose 0.4 0.4 0.3 Arabinose 18 6.2 26 Fructose 3.8 1.5 5.3 Etc 23.6 13.6 34.7

Arabinose was harvested in 85% yield.

The concentration profile of the separation (E.2) is shown in FIG. 6.

Those skilled in the art will clearly appreciate that the present invention may be used in various ways as a technical advance. The invention and its aspects are not limited to the embodiments described above but will vary within the scope of the claims.

Claims (36)

Chromatographic separation of hydrolyzate of mannose-containing vegetable material using at least one cation exchange chromatography separation resin layer having a cation of Ba ²⁺ and at least one cation exchange chromatography separation resin layer of a cation other than Ba ^2+. A process for recovering mannose from a hydrolyzate of mannose-containing vegetable material comprising performing a process and recovering one or more mannose fractions. The method of claim 1 wherein the chromatographic separation process, one or more of the steps, the cation exchange chromatography is carried out in one or more of the number of cation exchange chromatography separation is Ba ²⁺ cationic resin phase is other than a cation Ba ²⁺ A method comprising two or more chromatographic separation steps performed with a chromatography separation resin layer. The method of claim 2, wherein the hydrolyzate of the mannose-containing vegetable material is fed into a first chromatography column comprising a cation exchange chromatography separation resin layer having a cation of Ba ²⁺ , eluting the column with an eluent, Recovering a first mannose fraction, feeding the first mannose fraction into a second chromatography column comprising a cation exchange chromatography separation resin layer wherein the cation is other than Ba ^2+; Eluting, and recovering the second mannose fraction. The first, chromatographic separation process, the cation can be the cation exchange chromatography separated the two separate steps and the cation used to Ba ²⁺ cation exchange chromatographic separation resin is other than Ba ²⁺ resin according to 2, wherein A method comprising one separation step of use. The method of claim 4, wherein the hydrolyzate of the mannose-containing vegetable material is fed into a first chromatography column comprising a cation exchange chromatography separation resin layer having a cation of Ba ²⁺ , eluting the column with an eluent, Recovering a first mannose fraction, feeding the first mannose fraction into a second chromatography column comprising a cation exchange chromatography separation resin layer with a cation of Ba ²⁺ , eluting the column with an eluent. Recovering a second mannose fraction, feeding the second mannose fraction into a third chromatography column comprising a cation exchange chromatography separation resin layer with a cation other than Ba ²⁺ , the column as an eluent Eluting and recovering the third mannose fraction. The method of claim 1 wherein the cations other than Ba ²⁺ are selected from hydrogen, NH ₄ ⁺ , alkali metal cations and alkaline earth metal cations. The method of claim 6, wherein the cation is selected from NH ₄ ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ . The method of claim 1, wherein the chromatographic separation process is performed with a strong acid cation exchange resin. The method of claim 1, wherein the chromatographic separation process provides a mannose fraction having a purity of 45 to 80% based on the refractive system dry matter content (RDS). The method of claim 1, wherein the chromatographic separation process provides a mannose fraction having a purity of at least 80% based on RDS. The method of claim 1, wherein the chromatographic separation process provides mannose and mannose fractions containing additional sugars selected from arabinose, xylose, galactose, rhamnose, and fructose. The method of claim 1, further comprising one or more purification steps selected from membrane filtration, ion exchange, evaporation, filtration and derivatization performed before, after or between chromatographic separation steps / steps. The method of claim 12, wherein the derivatization comprises forming N-phenyl-D-mannopyranosylamine as the mannose derivative. The method of claim 1 further comprising crystallizing the mannose to obtain a crystalline mannose product. 15. The process of claim 14 wherein the crystallization is performed with a solvent selected from water, alcohols and mixtures of water and alcohols.  The method of claim 14, wherein the crystallization provides crystalline mannose having a purity of at least 95% based on RDS.  The method of claim 14, wherein the crystallization provides crystalline mannose having a purity of at least 99% based on RDS.  The method of claim 14, wherein the crystallization provides crystalline mannose having a purity of 90% to 99.9% based on RDS. The method of claim 1, further comprising the separation of other sugars selected from arabinose, xylose, galactose, rhamnose and fructose. The method of claim 19, comprising separating xylose as a pretreatment step. The method of claim 19, further comprising the separation of arabinose as a pretreatment step. The method of claim 19, further comprising the separation of rhamnose as a pretreatment step. The method of claim 1 wherein the hydrolyzate of the mannose-containing vegetable material contains mannose and an additional sugar selected from xylose, arabinose, rhamnose, galactose, glucose and fructose. The method of claim 1 wherein the hydrolyzate of the mannose-containing vegetable material is a hydrolyzate of lignocellulosic material, softwood or hardwood. The method of claim 23, wherein the hydrolyzate of the mannose-containing vegetable material is a sulfite pulp waste liquor. The method of claim 1, wherein the mannose is D-mannose. delete delete delete delete delete delete delete delete delete delete

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