CA2179972A1 - Process for the production of xylitol - Google Patents
Process for the production of xylitolInfo
- Publication number
- CA2179972A1 CA2179972A1 CA002179972A CA2179972A CA2179972A1 CA 2179972 A1 CA2179972 A1 CA 2179972A1 CA 002179972 A CA002179972 A CA 002179972A CA 2179972 A CA2179972 A CA 2179972A CA 2179972 A1 CA2179972 A1 CA 2179972A1
- Authority
- CA
- Canada
- Prior art keywords
- pentitol
- xylitol
- arabinitol
- isomerisation
- glucose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/911—Microorganisms using fungi
- Y10S435/921—Candida
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/911—Microorganisms using fungi
- Y10S435/93—Hansenula
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/911—Microorganisms using fungi
- Y10S435/938—Pichia
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/911—Microorganisms using fungi
- Y10S435/94—Saccharomyces
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/911—Microorganisms using fungi
- Y10S435/944—Torulopsis
Abstract
The present invention relates to a process for the production of xylitol. Specifically the process comprises two reaction steps. The first step is the fermentative conversion of a hexose to a pentitol. The second step is the catalytic chemical isomerisation of the pentitol to xylitol. Optionally, the xylitol is separated from the other pentitols.
Description
;
21~9~72 I
Process for the production of xylitol The present invention discloses a method for producing a pentitol. The present invention relates to a method for producing pentitols from hexoses. Specifically, xylitol is obtained from glucose in a reaction comprising a sequence of only two separate steps.
Glucose is fermented to arabinitol and chemically isomerised to a pentitol mixture comprising xylitol.
Xylitol is produced on an industrial scale by l~ydlu~ d~ion of xylose. Xylose isnot available as such it is obtained from xylan-containing plant materials. In order to obtain xylose, xylan-containing plant materials such as almond shells, corn cobs or birch wood are hydrolysed in acidic medium at elevated ~ llLæla~L.~ This hydrolysis suffers from two major d;sad~ ' ,, a high load of waste material due to the low content of xylan in the above mentioned starting materia~s and a low product purity and yield due to considerable formation of by-products under the extreme hydrolysis conditions which are used. Extensive F~rifi~ n and refining is required to remove excess of acid and the ~)IUIIUUII,~I COlOUr. The subsequent crystallisation of the d~ ldlis~d xylose syrup suffers from the low purity of the xylose syrup. Other hemicellulosic sugars also formed during hydrolysis have similar physico-chemical properties and have to be removed ~UallLiLdLi~,ly. In an earlier stage to avoid the formation of galactitol, galactose has to be removed prior to the catalytic llyLu~e,_llaLiOI~. Application of xylitol in food and related products requires the complete removal of galactitol for reasons of human safety, e.g.
eye damage.
For every kilogram of crystalline xylitol 12 to 13 kg of almond shells have to be processed, resulting in about 11 to 12 kg of solid waste. Apart from a pollution problem there is also a logistic problem with this process in that large quantities of almond shells have to be transported. Finally, the âvailability of the xylan containing material may become a limiting factor.
21~9~72 I
Process for the production of xylitol The present invention discloses a method for producing a pentitol. The present invention relates to a method for producing pentitols from hexoses. Specifically, xylitol is obtained from glucose in a reaction comprising a sequence of only two separate steps.
Glucose is fermented to arabinitol and chemically isomerised to a pentitol mixture comprising xylitol.
Xylitol is produced on an industrial scale by l~ydlu~ d~ion of xylose. Xylose isnot available as such it is obtained from xylan-containing plant materials. In order to obtain xylose, xylan-containing plant materials such as almond shells, corn cobs or birch wood are hydrolysed in acidic medium at elevated ~ llLæla~L.~ This hydrolysis suffers from two major d;sad~ ' ,, a high load of waste material due to the low content of xylan in the above mentioned starting materia~s and a low product purity and yield due to considerable formation of by-products under the extreme hydrolysis conditions which are used. Extensive F~rifi~ n and refining is required to remove excess of acid and the ~)IUIIUUII,~I COlOUr. The subsequent crystallisation of the d~ ldlis~d xylose syrup suffers from the low purity of the xylose syrup. Other hemicellulosic sugars also formed during hydrolysis have similar physico-chemical properties and have to be removed ~UallLiLdLi~,ly. In an earlier stage to avoid the formation of galactitol, galactose has to be removed prior to the catalytic llyLu~e,_llaLiOI~. Application of xylitol in food and related products requires the complete removal of galactitol for reasons of human safety, e.g.
eye damage.
For every kilogram of crystalline xylitol 12 to 13 kg of almond shells have to be processed, resulting in about 11 to 12 kg of solid waste. Apart from a pollution problem there is also a logistic problem with this process in that large quantities of almond shells have to be transported. Finally, the âvailability of the xylan containing material may become a limiting factor.
2 17~972 It is therefore of interest to consider alternative processes for producing xylitol which do not suffer from the mentioned drawbacks. Chemical and microbial processes for producing xylitol have been described.
Recently, some reaction schemes to produce xylitol, starting from readily available hexoses, in particular D-glucose and D-galactose, have been published. All of these schemes comprise a sequence of more than two reaction steps. In a first step the hexose is submitted to a chain shortening reaction which yields a Cs-intermediate. This step is performed either r~ lLd~ively or chemically. The subsequent process relates to the conversion of the Cs-intenned~ate into xylitol, by using a sequence of at least two rtllllC;llLdLiVe andlor chemical conversion steps.
In EP 403 392 and EP 421 882 a four step process is disclosed in which glucose is fermented to D-arabinitol by an osmophilic yeast. S~ lly, the arabinitol (Cs-intermediate) is converted by bacteria (ArPtohs~rfpr~ . . or Klebsiella) into D-xylulose. In the third step xylulose is isomerised by glucose (xylose) isomerase into a xylose/xylulose mixture. In the final step either the xylose is enriched prior to llydlub_llu~ion by ~ ,ully, or the xyluloselxylose mixture is directly subjectedto hydrogenation followed by the separation of xylitol by chr ~m~t--~r:~rhy.
In WO 93119030 glucose, fructose or galactose or mixtures thereof (obtained by hydrolysis of the rlic~ h~ Pc sucrose and lactose) are oxidatively dc~,albO,.~ ,d into alkali metal ~ ull~lLe and Iyxonate, respectively. These ' are first converted to the aldonic acid form. S~ y, the aldonic acids which are the C5-intennedrates, are ~,~"~ru""td into xylitol. When ~sorbose is used, L-xylonate is obtained via the oxidative d~,a~l~O~ylu~iv~ and this is converted to the aldonic acid form before being I~Lu~ .t~,d to xylitol. This last pathway seems simple howéver one has to take into account the reaction steps required to obtain L-sorbose. L-Sorbose is mainly obtained via rt,lll~...alive oxidation of sorbitol, which in turn is obtained from glucose by catalytic llydlub~,lld~iull, resulting overall in five reaction steps to obtain the final xylitol.
2 1 7~972 Other chemical methods for xylitol preparation include elaborated reaction schemes involving the use of protection groups. Due to the lack of economic feasibility these reactions are not further considered here (Helv. Chim. Acta 58, 1975, 3 l l).
Several exclusively microbiological pathways have been published, however, none of them are cu~ c~iLivc because of the overall yield which is far too low.
There exists therefore a need for an ~ nomirAlly valuable method for producing pentitols, especially xylitol, with a low level of impurities, which is easily refinable, which comprises a short reaction sequence, and starting from readily available hexoses, such as glucose (anhydrous, monohydrate, or high dextrose syrups).
The present invention provides such a method. The present invention relates to amethod for producing a pentitol from a hexose clldla~,Lcli~cd in that the methodcomprises the following steps, a) r~" . ,~ , of a hexose to yield a C5- i"f ~ r consisting mainly of a pentitol, b) isu~ll.,lisdLiull of the pentitol of step a) in the presence of a chemical catalyst to yield a cullc~l u.llil.g pentitol mixture, c) optionally separation of the desired pentitol from the product of step b).
The present invention can be ~-".""- ;~ .1 as follows. The invention discloses the r~.l,.~"lnl;..,. of C6-~,dlbollydldlc~ which results in Cs-polyols, the ferm^-~^fi. n step is followed by chemical catalytic is~ The sta~ting material can be any easily available C5-carbohydrate, the preferred substrate is glucose, anhydous as monohydrate or in the form of a high dextrose syrup. Starting with glucose the frllllrl,l~l;..,~ yields mainly arabinitol. The fermr^n~tinn of the present invention is based on methods known in the art. In carrying out a process according to the present invention, any yeast which has an ability to produce D-arabinitol from glucose may be used. For example yeasts belonging to the genera Pichia, El~du~l~Y.,uusis. Hansenula, D~l>dly~llly.,cs, Zy~:u~ l-d.u~llY~. Sd~-,ll~ull-y~,.,s. Candida and other yeasts belonging to the genus Torulopsis are suitable for this particular r~
t 21~9972 The yield of D-arabinitol in the fermentation product is preferably larger than 20% (w/w) more preferably larger than 40% (w/w) based on the initial hexose content.
In general with the use of osmophylic yeasts D-arabinitol is the only pentitol which is produced.
The D-arabinitol is subjected to catalytic is~-mPri~t~fi--n by methods known in the art. D-arabinitol is treated at L~ alul~ between 70 and 250C, preferably at a UlCi above 100C, and at hydrogen gas pressures between 0.1 and 10 MPa, preferably between I and 8 MPa.
The catalytic iSr)mf ri~-~fi~n is performed in the presence of catalysts which are known in the art for perfoming hydlv~llaLil)l~l~llydltJ~ t~ion. Suitable catalysts include ruthenium, copper, palladium, platinum, rhodium, cobalt and nickel basedcatalysts, or their oxides and mixtures thereof.
The polyol i~)",. .;~,.l;.~,~ is performed at distinctly different pH levels, and the addition of alkali or acid has an influence on the ~ ,llllo-lylla~, equilibrium of the pentitol mixture. The isomerisation reaction results in a product containing xylitol, ribitol and DL-arabinitol. Xylitol is present in these mixtures in more than 10%preferably in more than 20%. The reaction product further contains some lower alditols, such as tetritols and triitols, adding up to a maximum of 10% preferably only to 5% of the total alditol content.
The iSulll~ aLiull mixture is optionally subjected tû chromatography on cationicresin material yielding purified xylitol with a purity in excess of 95%. Preferably the mixture is first demineralized and ,~ y submitted to chromatography. The refining is suitably performed using a strong cation exchange resin e.g. Duolite C 26 followed by a medium base anion exchange resin Duolite A 368. This process is preferably repeated once. On industrial scale chromatography is performed using suitable equipment obtainable for example from Mitsubishi with Diaion UBK-555 resin (in Ca~+ form).
Recently, some reaction schemes to produce xylitol, starting from readily available hexoses, in particular D-glucose and D-galactose, have been published. All of these schemes comprise a sequence of more than two reaction steps. In a first step the hexose is submitted to a chain shortening reaction which yields a Cs-intermediate. This step is performed either r~ lLd~ively or chemically. The subsequent process relates to the conversion of the Cs-intenned~ate into xylitol, by using a sequence of at least two rtllllC;llLdLiVe andlor chemical conversion steps.
In EP 403 392 and EP 421 882 a four step process is disclosed in which glucose is fermented to D-arabinitol by an osmophilic yeast. S~ lly, the arabinitol (Cs-intermediate) is converted by bacteria (ArPtohs~rfpr~ . . or Klebsiella) into D-xylulose. In the third step xylulose is isomerised by glucose (xylose) isomerase into a xylose/xylulose mixture. In the final step either the xylose is enriched prior to llydlub_llu~ion by ~ ,ully, or the xyluloselxylose mixture is directly subjectedto hydrogenation followed by the separation of xylitol by chr ~m~t--~r:~rhy.
In WO 93119030 glucose, fructose or galactose or mixtures thereof (obtained by hydrolysis of the rlic~ h~ Pc sucrose and lactose) are oxidatively dc~,albO,.~ ,d into alkali metal ~ ull~lLe and Iyxonate, respectively. These ' are first converted to the aldonic acid form. S~ y, the aldonic acids which are the C5-intennedrates, are ~,~"~ru""td into xylitol. When ~sorbose is used, L-xylonate is obtained via the oxidative d~,a~l~O~ylu~iv~ and this is converted to the aldonic acid form before being I~Lu~ .t~,d to xylitol. This last pathway seems simple howéver one has to take into account the reaction steps required to obtain L-sorbose. L-Sorbose is mainly obtained via rt,lll~...alive oxidation of sorbitol, which in turn is obtained from glucose by catalytic llydlub~,lld~iull, resulting overall in five reaction steps to obtain the final xylitol.
2 1 7~972 Other chemical methods for xylitol preparation include elaborated reaction schemes involving the use of protection groups. Due to the lack of economic feasibility these reactions are not further considered here (Helv. Chim. Acta 58, 1975, 3 l l).
Several exclusively microbiological pathways have been published, however, none of them are cu~ c~iLivc because of the overall yield which is far too low.
There exists therefore a need for an ~ nomirAlly valuable method for producing pentitols, especially xylitol, with a low level of impurities, which is easily refinable, which comprises a short reaction sequence, and starting from readily available hexoses, such as glucose (anhydrous, monohydrate, or high dextrose syrups).
The present invention provides such a method. The present invention relates to amethod for producing a pentitol from a hexose clldla~,Lcli~cd in that the methodcomprises the following steps, a) r~" . ,~ , of a hexose to yield a C5- i"f ~ r consisting mainly of a pentitol, b) isu~ll.,lisdLiull of the pentitol of step a) in the presence of a chemical catalyst to yield a cullc~l u.llil.g pentitol mixture, c) optionally separation of the desired pentitol from the product of step b).
The present invention can be ~-".""- ;~ .1 as follows. The invention discloses the r~.l,.~"lnl;..,. of C6-~,dlbollydldlc~ which results in Cs-polyols, the ferm^-~^fi. n step is followed by chemical catalytic is~ The sta~ting material can be any easily available C5-carbohydrate, the preferred substrate is glucose, anhydous as monohydrate or in the form of a high dextrose syrup. Starting with glucose the frllllrl,l~l;..,~ yields mainly arabinitol. The fermr^n~tinn of the present invention is based on methods known in the art. In carrying out a process according to the present invention, any yeast which has an ability to produce D-arabinitol from glucose may be used. For example yeasts belonging to the genera Pichia, El~du~l~Y.,uusis. Hansenula, D~l>dly~llly.,cs, Zy~:u~ l-d.u~llY~. Sd~-,ll~ull-y~,.,s. Candida and other yeasts belonging to the genus Torulopsis are suitable for this particular r~
t 21~9972 The yield of D-arabinitol in the fermentation product is preferably larger than 20% (w/w) more preferably larger than 40% (w/w) based on the initial hexose content.
In general with the use of osmophylic yeasts D-arabinitol is the only pentitol which is produced.
The D-arabinitol is subjected to catalytic is~-mPri~t~fi--n by methods known in the art. D-arabinitol is treated at L~ alul~ between 70 and 250C, preferably at a UlCi above 100C, and at hydrogen gas pressures between 0.1 and 10 MPa, preferably between I and 8 MPa.
The catalytic iSr)mf ri~-~fi~n is performed in the presence of catalysts which are known in the art for perfoming hydlv~llaLil)l~l~llydltJ~ t~ion. Suitable catalysts include ruthenium, copper, palladium, platinum, rhodium, cobalt and nickel basedcatalysts, or their oxides and mixtures thereof.
The polyol i~)",. .;~,.l;.~,~ is performed at distinctly different pH levels, and the addition of alkali or acid has an influence on the ~ ,llllo-lylla~, equilibrium of the pentitol mixture. The isomerisation reaction results in a product containing xylitol, ribitol and DL-arabinitol. Xylitol is present in these mixtures in more than 10%preferably in more than 20%. The reaction product further contains some lower alditols, such as tetritols and triitols, adding up to a maximum of 10% preferably only to 5% of the total alditol content.
The iSulll~ aLiull mixture is optionally subjected tû chromatography on cationicresin material yielding purified xylitol with a purity in excess of 95%. Preferably the mixture is first demineralized and ,~ y submitted to chromatography. The refining is suitably performed using a strong cation exchange resin e.g. Duolite C 26 followed by a medium base anion exchange resin Duolite A 368. This process is preferably repeated once. On industrial scale chromatography is performed using suitable equipment obtainable for example from Mitsubishi with Diaion UBK-555 resin (in Ca~+ form).
The other pentitols are optionally recycled to the polyol isomerisation step, resulting in increased overall yield. The xylitol can also be further purified by crystallisation.
The advantage of this process in ~,O~ ali~Oll with earlier described processes such as the process disclosed in WO 93/19030 is that well established unit operations can be used for the refining (classical syrup refining) and that known techniques and equipment for re""~ and catalytic isr~mPris~ m can be used. The main advantage compared with other methods such as described in EP 403 392 and EP 421 882 and WO
93/19030 is the much shorter overall reaction sequence. SrhP~o~i~lllly the method of the present invention is illustrated in Scheme 1, wherein the underlined steps are essential.
2 1~9972 6 Scheme 1 Hexose v Ferrn~t~tion Pen titol Ref ning v, T~...,.. ,~,.1,.".
Recycle Pentito~s ~, Separation Xyitol The invention is further illustrated by the following examples.
Example 1 Z~KO~aCC~ YC~ barkeri Y-222 is inoculated in a culture medium containing 30 %
(w/v) glucose, 4.0 % (wlv) corn steep liquor, 0.1 % (w/v) potassium phosphate, 0.05 %
(W/Y) IIIA~ IIII sulphate, 0.01 % (w/v) calcium chloride, 0.01 % (w/v) sodium chloride, and cultured at pH 6, ~pH-adjustment with sodium hydroxide) at 30C for 4 days. The following yield is obtained: 46.1% arabinitol, 2% residual glucose, and 10.5%
glycerol (as a percentage of glucose which has been converted). The reaction product is demineralized and refined on a double-pass ion exchange battery, followed by selective crystallisation of the arabinitol. This results in crystals with a purity of 99%.
Arabinitol was isomerised on ruthenium catalyst (4% catalyst on total dry substance), which is supported on silica (5% Ru on silica), by applying a hydrogen pressure of 4 MPa at a tf ~ d~ of 150C. Polyol iC~mf ric~ion is completed within 4 hours. Theobtained ~cllf..l~,lal;~,J i,ol~ has the following pentitol composition: arabinitol (60%), xylitol (22%), ribitol (18%).
The xylitol was separated by chromatography on cation exchange resin in the calcium form, yielding xylitol with a purity greater than 95%. The arabinitol and ribitol were recycled to is ." ,~ The xylitol was crystallised to obtain crystals of 99.9% purity.
Example 2 Pichia c~hmf~ri ATCC 20.209 was cultured at 30C in a medium containing 15 % (w/v) glucose, 0.2 % (w/v) yeast éxtract, 0.1 % (w/v) potassium hydrogen phosphate and 0.1 % (w/v) ,. .",~ ~;."" sulphate. After 6 days the reaction medium was filtered and f~ ,,f~ on ion exchange resins. A yield of 40.5% arabinitol was obtained, after cry~f~ c~ n Arabinitol was isomerised on ruthenium catalyst (6% catalyst on total drY substance), which is supported on active carbon (5% Ru on carbon). To isomerize the arabinitol syrup phosphoric acid (1% on total dry substance) was added. The reaction t~,lll~f~ldlUlC
was 150C at a hydrogen pressure of 4 MPa. Within 4 hours the isomerised syrup had 21~q72 8 the following composition: 90% total pentitols (of which: arabinitol (45%), xylitol (34%), ribitol (21%)) and 10% lower alditols.
The xylitol was recoYered in a similar way as described in example 1.
Example 3 Fermentation of glucose to arabinitol is performed by using a culture medium of 10 %
(w/v) glucose, 0.5 % (w/v) yeast extract and 0.1 % (w/v) urea. The medium is inoculated with a yeast strain of the genus ElldQ~y~,u~ chodati. After 72 hours fc~ m time 56% arabinitol was obtained without considerable amounts of glycerol (below 4%). After demineralisation and tefining the arabinitol syrup is directly used for polyol is-.m~ ticotirn in the presence of Raney-nickel (5% catalyst s~urry on total dry substance). The pH is increased to 11, by the addition of 0.5 M NaOH. A
hydrogen pressure of 4 MPa is applied at a ttllllJCldlUlt of 170C and the isnm~ri~fi-,n reaction is stopped after 4 hours, resulting in a pentitol mixture of the following c.. rnro~iti.-n arabinitol (90%), xylitol (6%), ribitol (4%).
Examl~le 4 r~llll~,llL~Liull of glucose to arabinitol is performed as described in example 1, except that a yeast strain belonging to the genus Candida. namely Candida ~olvmorPha ATCC
20 213 is used. 4.5 g of D-arabinitol was obtained per 100 ml fermentation liquor. The subsequent polyol is~mrtic~fion is performed on a rutbenium catalyst (4% catalyst on total dry substance) which is supported on zeolite material (5% Ru on zeolite). The reaction ~tlll~ Lul~ is 135C at a hydrogen pressure of 4 MPa. After 4 hours reaction the polyol mixture has the following pentitol nf~mrocirif~n arabinitol (73%), xylitol (13%), ribitol (14%).
The xylitol is recovered as in example 1.
The advantage of this process in ~,O~ ali~Oll with earlier described processes such as the process disclosed in WO 93/19030 is that well established unit operations can be used for the refining (classical syrup refining) and that known techniques and equipment for re""~ and catalytic isr~mPris~ m can be used. The main advantage compared with other methods such as described in EP 403 392 and EP 421 882 and WO
93/19030 is the much shorter overall reaction sequence. SrhP~o~i~lllly the method of the present invention is illustrated in Scheme 1, wherein the underlined steps are essential.
2 1~9972 6 Scheme 1 Hexose v Ferrn~t~tion Pen titol Ref ning v, T~...,.. ,~,.1,.".
Recycle Pentito~s ~, Separation Xyitol The invention is further illustrated by the following examples.
Example 1 Z~KO~aCC~ YC~ barkeri Y-222 is inoculated in a culture medium containing 30 %
(w/v) glucose, 4.0 % (wlv) corn steep liquor, 0.1 % (w/v) potassium phosphate, 0.05 %
(W/Y) IIIA~ IIII sulphate, 0.01 % (w/v) calcium chloride, 0.01 % (w/v) sodium chloride, and cultured at pH 6, ~pH-adjustment with sodium hydroxide) at 30C for 4 days. The following yield is obtained: 46.1% arabinitol, 2% residual glucose, and 10.5%
glycerol (as a percentage of glucose which has been converted). The reaction product is demineralized and refined on a double-pass ion exchange battery, followed by selective crystallisation of the arabinitol. This results in crystals with a purity of 99%.
Arabinitol was isomerised on ruthenium catalyst (4% catalyst on total dry substance), which is supported on silica (5% Ru on silica), by applying a hydrogen pressure of 4 MPa at a tf ~ d~ of 150C. Polyol iC~mf ric~ion is completed within 4 hours. Theobtained ~cllf..l~,lal;~,J i,ol~ has the following pentitol composition: arabinitol (60%), xylitol (22%), ribitol (18%).
The xylitol was separated by chromatography on cation exchange resin in the calcium form, yielding xylitol with a purity greater than 95%. The arabinitol and ribitol were recycled to is ." ,~ The xylitol was crystallised to obtain crystals of 99.9% purity.
Example 2 Pichia c~hmf~ri ATCC 20.209 was cultured at 30C in a medium containing 15 % (w/v) glucose, 0.2 % (w/v) yeast éxtract, 0.1 % (w/v) potassium hydrogen phosphate and 0.1 % (w/v) ,. .",~ ~;."" sulphate. After 6 days the reaction medium was filtered and f~ ,,f~ on ion exchange resins. A yield of 40.5% arabinitol was obtained, after cry~f~ c~ n Arabinitol was isomerised on ruthenium catalyst (6% catalyst on total drY substance), which is supported on active carbon (5% Ru on carbon). To isomerize the arabinitol syrup phosphoric acid (1% on total dry substance) was added. The reaction t~,lll~f~ldlUlC
was 150C at a hydrogen pressure of 4 MPa. Within 4 hours the isomerised syrup had 21~q72 8 the following composition: 90% total pentitols (of which: arabinitol (45%), xylitol (34%), ribitol (21%)) and 10% lower alditols.
The xylitol was recoYered in a similar way as described in example 1.
Example 3 Fermentation of glucose to arabinitol is performed by using a culture medium of 10 %
(w/v) glucose, 0.5 % (w/v) yeast extract and 0.1 % (w/v) urea. The medium is inoculated with a yeast strain of the genus ElldQ~y~,u~ chodati. After 72 hours fc~ m time 56% arabinitol was obtained without considerable amounts of glycerol (below 4%). After demineralisation and tefining the arabinitol syrup is directly used for polyol is-.m~ ticotirn in the presence of Raney-nickel (5% catalyst s~urry on total dry substance). The pH is increased to 11, by the addition of 0.5 M NaOH. A
hydrogen pressure of 4 MPa is applied at a ttllllJCldlUlt of 170C and the isnm~ri~fi-,n reaction is stopped after 4 hours, resulting in a pentitol mixture of the following c.. rnro~iti.-n arabinitol (90%), xylitol (6%), ribitol (4%).
Examl~le 4 r~llll~,llL~Liull of glucose to arabinitol is performed as described in example 1, except that a yeast strain belonging to the genus Candida. namely Candida ~olvmorPha ATCC
20 213 is used. 4.5 g of D-arabinitol was obtained per 100 ml fermentation liquor. The subsequent polyol is~mrtic~fion is performed on a rutbenium catalyst (4% catalyst on total dry substance) which is supported on zeolite material (5% Ru on zeolite). The reaction ~tlll~ Lul~ is 135C at a hydrogen pressure of 4 MPa. After 4 hours reaction the polyol mixture has the following pentitol nf~mrocirif~n arabinitol (73%), xylitol (13%), ribitol (14%).
The xylitol is recovered as in example 1.
Claims (10)
1. A method for producing a pentitol from a hexose characterized in that the method comprises the following steps, a) fermentation of a hexose to yield a C5- intermediate consisting mainly of a pentitol, b) isomerisation of the pentitol of step a) in the presence of a chemical catalyst to yield a corresponding pentitol mixture, c) optionally separation of the desired pentitol from the product of step b).
2. A method according to claim 1 characterized in that the pentitol is refined after fermentation and/or after isomerisation.
3. A method according to claim 1 characterized in that the hexose is a readily available C6-carbohydrate, preferably glucose (for example in anhydrous, monohydrate or high dextrose syrup form).
4. A method according to claim 1 characterized in that step a) is an aerobic fermentation of glucose syrup to arabinitol by an osmophilic yeast selected from the group consisting of the following genera: Pichia, Endomycopsis, Hansenula, Debaryomyces, Zygosaccharomyces, Saccharomyces, Candida and Torulopsis.
5. A method according to claim 1 characterized in that the pentitol is selected from the group consisting of xylitol, ribitol, and arabinitol.
6. A method according to claim 1 characterized in that the isomerisation is performed in the presence of a hydrogenation/dehydrogenation catalyst promoted by the addition of alkali or acid respectively.
7. A method according to anyone of the previous claims characterized in that the isomerisation is conducted at a hydrogen pressure between 0.1 and 10 MPa and a temperature between 70 and 250°C.
8. A method according to claim 7 characterized in that the hydrogen pressure ispreferably between 1 and 8 MPa.
9. A method according to claim 7 characterized in that the temperature is preferably between 100 and 200°C.
10. A method according to claim 1 characterized in that the separation of step c) is performed using a cation resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9514538.9A GB9514538D0 (en) | 1995-07-15 | 1995-07-15 | Process for the production of xylitol |
| GB9514538.9 | 1995-07-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2179972A1 true CA2179972A1 (en) | 1997-01-16 |
Family
ID=10777760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002179972A Abandoned CA2179972A1 (en) | 1995-07-15 | 1996-06-26 | Process for the production of xylitol |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6458570B1 (en) |
| EP (1) | EP0754758B1 (en) |
| JP (1) | JPH0965888A (en) |
| CN (1) | CN1058721C (en) |
| AT (1) | ATE204906T1 (en) |
| CA (1) | CA2179972A1 (en) |
| DE (1) | DE69614786D1 (en) |
| GB (1) | GB9514538D0 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2762011B1 (en) * | 1997-04-11 | 1999-06-25 | Roquette Freres | PROCESS FOR THE PREPARATION OF RIBITOL BY FERMENTATION AND A STRAIN OF MICROORGANISMS USED IN THIS PROCESS |
| JP2000210095A (en) * | 1999-01-20 | 2000-08-02 | Ajinomoto Co Inc | Production of xylitol or d-xylulose |
| DE60002020T2 (en) * | 1999-08-10 | 2004-02-12 | Ajinomoto Co., Inc. | Process for producing high purity xylitol |
| US7812153B2 (en) * | 2004-03-11 | 2010-10-12 | Rayonier Products And Financial Services Company | Process for manufacturing high purity xylose |
| EP2314560B1 (en) | 2004-03-26 | 2012-03-21 | Purdue Research Foundation | Processes for the production of xylitol |
| EP2386625A2 (en) | 2004-05-19 | 2011-11-16 | Biotech Research And Development Corporation | Methods for production of xylitol in microorganisms |
| CN101560142B (en) * | 2009-05-25 | 2012-05-23 | 山东福田药业有限公司 | Separating and refining method of arabitol in fermentation liquor |
| US20120021467A1 (en) * | 2010-07-22 | 2012-01-26 | Thomson Biotech (Xiamen) PTE. LTD. | Method of producing xylitol and arabinose at same time from hemicellulose hydrolysates |
| CN103184164A (en) * | 2011-12-30 | 2013-07-03 | 天津工业生物技术研究所 | Yeast capable of producing D- arabitol and xylitol simultaneously and application thereof |
| BR112018015184B1 (en) | 2016-02-19 | 2022-09-06 | Intercontinental Great Brands Llc | PROCESSES TO CREATE MULTIPLE VALUE CHAINS FROM BIOMASS SOURCES |
| AU2017383557A1 (en) | 2016-12-21 | 2019-08-08 | Creatus Biosciences Inc. | Xylitol producing Metschnikowia species |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS543949B1 (en) * | 1968-05-25 | 1979-02-28 | ||
| JPS6296090A (en) | 1986-10-22 | 1987-05-02 | Natl Food Res Inst | Production of polyhydric alcohol by fermentation using novel microorganism |
| FR2648474B1 (en) | 1989-06-16 | 1995-01-06 | Roquette Freres | NEW PROCESS FOR THE MANUFACTURE OF XYLOSE |
| FR2652589B1 (en) | 1989-10-04 | 1995-02-17 | Roquette Freres | PROCESS FOR THE MANUFACTURE OF XYLITOL AND XYLITOL-RICH PRODUCTS. |
| FI92051C (en) * | 1992-03-17 | 1994-09-26 | Amylum Nv | Process for the preparation of xylitol from D-glucose and mixtures of D-glucose and D-fructose and D-glucose and D-galactose |
| KR950704503A (en) * | 1992-11-05 | 1995-11-20 | 필립 프랑켄호이저, 주하 쿠르키넨 | Recombinant method and host for manufacture of xylitol |
| JPH06296090A (en) * | 1993-04-09 | 1994-10-21 | Mitsubishi Electric Corp | Module fixing apparatus |
| FR2708269B1 (en) * | 1993-07-26 | 1995-10-06 | Roquette Freres | Viscous liquid xylitol compositions and process for their preparation. |
| GB9424567D0 (en) * | 1994-12-06 | 1995-01-25 | Cerestar Holding Bv | Process for the production of xylitol |
| GB9424566D0 (en) * | 1994-12-06 | 1995-01-25 | Cerestar Holding Bv | Method for decarbonylation of sugars |
-
1995
- 1995-07-15 GB GBGB9514538.9A patent/GB9514538D0/en active Pending
-
1996
- 1996-06-26 DE DE69614786T patent/DE69614786D1/en not_active Expired - Lifetime
- 1996-06-26 CA CA002179972A patent/CA2179972A1/en not_active Abandoned
- 1996-06-26 AT AT96304727T patent/ATE204906T1/en not_active IP Right Cessation
- 1996-06-26 EP EP96304727A patent/EP0754758B1/en not_active Expired - Lifetime
- 1996-07-12 JP JP8183771A patent/JPH0965888A/en active Pending
- 1996-07-15 CN CN96106196A patent/CN1058721C/en not_active Expired - Fee Related
- 1996-07-15 US US08/680,139 patent/US6458570B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US6458570B1 (en) | 2002-10-01 |
| EP0754758A1 (en) | 1997-01-22 |
| CN1148597A (en) | 1997-04-30 |
| JPH0965888A (en) | 1997-03-11 |
| US20020076772A1 (en) | 2002-06-20 |
| EP0754758B1 (en) | 2001-08-29 |
| CN1058721C (en) | 2000-11-22 |
| DE69614786D1 (en) | 2001-10-04 |
| ATE204906T1 (en) | 2001-09-15 |
| GB9514538D0 (en) | 1995-09-13 |
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