GB2408262A - Preparation of L-arabinose from sugar beet - Google Patents
Preparation of L-arabinose from sugar beet Download PDFInfo
- Publication number
- GB2408262A GB2408262A GB0327327A GB0327327A GB2408262A GB 2408262 A GB2408262 A GB 2408262A GB 0327327 A GB0327327 A GB 0327327A GB 0327327 A GB0327327 A GB 0327327A GB 2408262 A GB2408262 A GB 2408262A
- Authority
- GB
- United Kingdom
- Prior art keywords
- arabinose
- solution
- araban
- extract
- filtration
- 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.)
- Granted
Links
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- SRBFZHDQGSBBOR-HWQSCIPKSA-N L-arabinopyranose Chemical compound O[C@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-HWQSCIPKSA-N 0.000 title claims abstract description 51
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 title claims abstract description 22
- 235000021536 Sugar beet Nutrition 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 239000012141 concentrate Substances 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 3
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 3
- 238000011097 chromatography purification Methods 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 238000011026 diafiltration Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000012465 retentate Substances 0.000 claims description 7
- 239000010802 sludge Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims 2
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 9
- 229930006000 Sucrose Natural products 0.000 description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 8
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 150000004676 glycans Chemical class 0.000 description 8
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 239000005720 sucrose Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PYMYPHUHKUWMLA-VAYJURFESA-N aldehydo-L-arabinose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-VAYJURFESA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000016068 Berberis vulgaris Nutrition 0.000 description 3
- 241000335053 Beta vulgaris Species 0.000 description 3
- 125000003599 L-arabinosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)CO1)* 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000013375 chromatographic separation Methods 0.000 description 3
- 238000011210 chromatographic step Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920001277 pectin Polymers 0.000 description 3
- 239000001814 pectin Substances 0.000 description 3
- 235000010987 pectin Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- 241001494501 Prosopis <angiosperm> Species 0.000 description 1
- 235000001560 Prosopis chilensis Nutrition 0.000 description 1
- 235000014460 Prosopis juliflora var juliflora Nutrition 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-KCDKBNATSA-N aldehydo-D-galactose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-KCDKBNATSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-KLVWXMOXSA-N beta-L-arabinopyranose Chemical compound O[C@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-KLVWXMOXSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 uranic acids Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/02—Purification of sugar juices using alkaline earth metal compounds
- C13B20/04—Purification of sugar juices using alkaline earth metal compounds followed by saturation
- C13B20/06—Purification of sugar juices using alkaline earth metal compounds followed by saturation with carbon dioxide or sulfur dioxide
-
- 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
- C13B20/16—Purification of sugar juices by physical means, e.g. osmosis or filtration
- C13B20/165—Purification of sugar juices by physical means, e.g. osmosis or filtration using membranes, e.g. osmosis, ultrafiltration
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A method of preparing L-arabinose from sugar beet pulp comprises the steps of (a) treating sugar beet pulp with aqueous alkali to provide a crude araban extract; (b) treating the extract with a precipitating agent, such as carbon dioxide, to precipitate an insoluble salt from the extract; (c) removing the insoluble salt; (d) ultra-filtration to remove impurities and concentrate the extract; (e) acid hydrolysis of the purified extract to provide a crude L-arabinose solution; (f) ultra-filtration and neutralisation (in any order) of the solution to provide a purified L-arabinose solution, and (g) concentration and crystallisation of pure L-arabinose. Preferably, the method does not comprise a chromatographic purification step. The L-arabinose solution may also undergo treatment with an anionic exchange resin to remove anionic impurities and may be contacted with a polymeric adsorption resin to decolourise the solution. The crystalline product typically comprises 97-99% L-arabinose.
Description
A METHOD OF PREPARATION OF L-ARABINOSE
The present invention relates to methods of preparation of purified Larabinose starting from sugar beet pulp.
L-(+)-arabinose is present in polysaccharide components of higher plants. For example, it is present in naturally occurring plant gums such as gum arable and mesquite gum. The polysaccharide araban, which comprises mainly L-arabinose units, is associated with pectin in the cell walls of many higher plants, and is lo abundant in sugar beet pulp.
L-arabinose is by far the most abundant naturally occurring L-pentose. It is therefore a useful starting point for the chemical synthesis of other L-pentoses and derivatives thereof. A need therefore exists for improved methods of preparing L arabinose from plant material, in particular from sugar beet pulp, with high purity and at low cost.
Sugar beet pulp is the name given to the residue remaining after conventional extraction of sucrose from sugar beet. Pressed pulp typically contains about 25% by weight of dry matter, most of which consists of plant polysaccharides. A component of the polysaccharides is araban, which consist of a chain of 1, 5-a- linked L-arabinose residues, to which other L-arabinose residues are linked (1,3)-a and/or (1,2)-a. Pure araban normally contains no more than 2-3% wt.% of non- arabinose residues.
GB-A-1182099 describes a method of preparation of L-arabinose from sugar beet by treating sugar beet slices with acid or alkali to hydrolyse the pectin and araban, filtering, and then fermenting the filtrate with yeasts to remove glucose and fructose. The remaining solution is concentrated, and the arabinose is then crystallized by addition of alcohol.
DD-C-143261 describes a process for the extraction of L-arabinose from sugar beet pulp comprising the steps of: treating sugar beet pulp with aqueous calcium hydroxide to dissolve the araban, filtering off the araban solution, treating the araban solution with sulfuric acid to hydrolyse the araban to its constituent monosaccharides, neutralising the solution and separating the L-arabinose by crystallization. The resulting L-arabinose has low purity.
US-A-4591388 describes a process for the purification of arabinose from a mixture of monosaccharides which comprises the selective adsorption of arabinose on barium-exchanged, type-X zeolite molecular sieves. This method results in some barium contamination of the arabinose, which is undesirable. Furthermore, the to method is not readily adaptable to continuous manufacture.
EP-A-0276702 describes a process for the production of crystalline Larabinose from sugar beet pulp. The process comprises treating the beet pulp with aqueous calcium hydroxide to extract crude aqueous araban, carrying out chromatography on a cationic exchanger to purify the araban extract, followed by hydrolyzing the purified araban fraction with sulfuric acid, neutralizing, and carrying out chromatography again on a cation exchanger to purify the L-arabinose. This process is similar to that of DD-C-143261, but with two additional chromatography steps. The resulting L-arabinose is pure, but the cost of carrying out two chromatography steps is high, and it is difficult to carry out chromatography steps in a continuous process unless relatively complex technology, such as a simulated moving bed, is used.
WO99/10542 describes a further method of preparing L-arabinose from sugar beet pulp. The claimed method comprises treatment of the pulp with aqueous lime to extract aqueous araban, hydrolysis of the crude araban extract with a strong acid, neutralization and filtration of the resulting solution, followed by chromatographic separation of the L- arabinose by using a cation exchanger in monovalent metal form, followed by final purification of the L-arabinose. It is alleged that the use of a cation exchange resin in monovalent metal ion form is especially effective for separation of L-arabinose, and that it is therefore unnecessary to carry out any purification on the crude araban extract before hydrolysis. However, this method still suffers from the drawbacks of the high cost and non-continuous nature of the chromatographic separation step.
The present inventors have found that L-arabinose can be prepared from sugar beet pulp with high purity, in a continuous process, without any need for a chromatographic separation step.
The present invention provides a method of preparing L-arabinose from sugar beet pulp comprising the steps of: (a) treatment of a sugar beet pulp with aqueous alkali to provide a crude aqueous araban extract; (b) treatment of the crude araban extract with a precipitating agent to precipitate an insoluble salt from the araban extract; (c) removal of the insoluble salt sludge; (d) ultra-filtration to remove low molecular weight impurities and concentrate the araban extract; (e) acid hydrolysis of the purified araban extract after ultra-filtration to provide a crude aqueous L-arabinose solution; (0 ultra-filtration of the crude L-arabinose solution to remove high molecular weight impurities and provide a purified L-arabinose solution; (g) neutralization of the L-arabinose solution; and (h) concentration and crystallization of the purified L-arabinose solution to provide a purified L-arabinose.
The steps are generally carried out in the order specified above, optionally with further steps inserted as discussed further below. In some embodiments, the order of steps (f) and (g) may be reversed.
Use of ultra-filtration stages on both the araban extract and the Larabinose solution after hydrolysis enables the preparation of high purity L-arabinose, without chromatography.
The starting material for the process according to the present invention may be any sugar beet pulp from which sucrose has already been extracted by diffusion.
The process can start from stored pulp, frozen pulp or dried shreds. The pulp is preferably washed with excess water at about 50 C to about 70 C, suitably for a period of from about 1 to about 2 hours. This step removes residual sucrose and soluble impurities. The pulp is then dewatered. The dewatered pulp typically has a solids content of from about 10% to about 30%, for example about 20% to about 25% by weight. This dewatered pulp is then fed to step (a) of the process.
Step (a) of the process is extraction of araban from the beet pulp into alkali solution. The alkali is usually hot aqueous lime. The lime may be added as calcium oxide or calcium hydroxide. The alkali is preferably added to hot aqueous beet pulp, preferably already heated to at least about 60 C, more preferably to at least about 80 C, since adding the lime to cold pulp can result in the precipitation of calcium pectinates and hydrolysis of pectins to uranic acids. Suitable conditions are: temperature about 80 C to about 100 C, preferably about 90 C to about 95 C; pH about 10 to about 12, preferably pH about 11; time about 45 minutes to about 3 hours, preferably about 1 hour; solids content about 2 wt.% to about 10 wt.%, suitably about 4 wt.% to about 6 wt.%.
Following step (a), the alkali solution of araban is separated from the pulp sludge, for example by decanting. The araban solution is then treated to neutralise the solution and precipitate an insoluble salt of the alkali. The treatment may for example be carried out by treatment with a phosphoric acid. Preferably, the neutralization and precipitation is carried out with carbon dioxide (carbonatation).
The CO2 reacts with calcium hydroxide to precipitate calcium carbonate. The calcium carbonate precipitate also contains a number of impurities. The carbonatation is suitably carried out in similar fashion to the wellknown carbonatation step used for the purification of sugar beet juice in the manufacture of sucrose. Typical conditions are: temperature about 70 C to about 90 C, preferably about 80 C; time about 10 minutes to about 60 minutes, suitably about minutes to about 40 minutes; pH (final) about 6 to about 9, suitably about 8 to about 9. s
The precipitation step (b) may be followed by conventional filtration and/or centrifugation steps to remove the insoluble salt precipitate sludge and other insoluble matter and entrained impurities. Preferably, the process comprises S centrifugation, for example with a disk-stack centrifuge, followed by filtration, for example a plate-filtration or cartridge filtration stage, for example through 8 micrometer plate, to remove small particles of insoluble matter from the araban solution.
to The crude aqueous araban extract is then further purified by ultrafiltration. The ultra-filtration is preferably carried out using a membrane having a nominal molecular weight cut off of from about 5,000 to about 50,000, suitably from about 5,000 to about 30,000, depending on the membrane type. The ultrafiltration is generally carried out with a cross-flow of the solution in order to minimise filter blocking. The ultra-filtration step has two important functions. Firstly, it concentrates the araban in the retentate from an initial concentration of from about 2% to about 4% by weight to a final concentration of from about 10% to about 20% araban by weight. The ultra-filtration also removes low molecular weight impurities into the permeate. In particular, it removes saccharides and soluble salts such as calcium acetate.
Preferably, the ultra-filtration step is followed by a diafiltration step. That is to say, the concentrated araban extract from the ultrafiltration step is diluted with water and then ultra-filtered again to concentrate the araban as above, and to achieve a further reduction in the concentration of low molecular weight impurities. The diafiltration step may be carried out using a diafiltration membrane having similar nominal molecular weight cut-off values as the ultrafiltration membrane.
Typically, the process according to the present invention does not comprise any concentration step on the araban solution other than the ultra-filtration step and optional diafiltration step. The process steps described above result in a solution comprising typically about 10% to about 20% araban by weight, together with some large anionic impurities, some large organic impurities and some polysaccharide impurities, in particular galactan. Overall, the purified araban extract typically comprises (mainly as polysaccharides) about 65-75 wt.% arabinose, about 815 wt.% D-galactose, about 3-6% ash, about 4-7wt.% proteins, and the balance comprising other saccharides such as uranic acids, S rhamnose Dxylose, D-glucose and D-fructose.
Preferably, without further concentration, and preferably without any chromatographic purification step, the araban extract then undergoes hydrolysis in step (e) of the process according to the present invention.
The purified araban extract is treated with sulfuric acid in conventional fashion to hydrolyse the polysaccharides. The hydrolysis is carried out with H2SO4 in an amount of about 5 to about 10wt.%, preferably about 7 to about 8wt.%, calculated as pure H2SO4 on total dry substance in the araban extract. The hydrolysis is carried out preferably at a temperature of from about 90 C to about 100 C, typically at from about 93 C to about 97 C, for a time of from about 10 minutes to about 2 hours, suitably 30 minutes to about 90 minutes, for example about 1 hour.
The conditions preferably result in hydrolysis of the araban, but not of the galactan.
The hydrolysed solution having dry solids content typically about 7 to 9 wt.%, of which about 60% is L-arabinose, is then subjected to ultrafiltration through a membrane, usually by cross-flow filtration. The membrane suitably has a nominal molecular weight cut-off in the range of 1000-30,000, for example about 5000 to 30,000. The galactan and other non-hydrolysed polysaccharides are retained, and the L-arabinose is removed in the permeate stream at a total solids content of about 6 to 8 wt.%, or which about 75% to about 90% is L-arabinose. The permeate is substantially free of saccharides other than L-arabinose.
Preferably, the retentate is subjected to little or no diafiltration, since the water added for diafiltration results in further dilution of the L-arabinose stream.
Neutralisation of the acidic L-arabinose solution is achieved by anion exchange, for example on a suitable, commercially available resin. In fact, this may take the pH above 9 and additional acid is required to bring the pH back to about 7.
Currently this step is carried out after the ultrafiltration but it may be preferable to carry out the neutralization before the ultrafiltration in order to minimise acid damage to the membranes. The anionic exchange resin also has the effect of removing anionic impurities such as acetate from the solution.
The purified L-arabinose solution from the ultra-filtration and optional diafiltration steps still contains some impurities, such as salts and colour impurities.
Therefore, the method of the invention preferably further comprises treating the L- arabinose solution with a polymeric adsorption resin to decolorise the solution.
Any of the decolorising resins used in the decolorising of sucrose juice in the manufacture of sucrose may be used for this purpose.
Finally, the L-arabinose solution is crystallized to yield pure, crystalline L- arabinose. The crystallization step (h) may comprise for example the stages of neutralizing the solution, concentrating the solution, cooling crystallization, centrifugation and drying. Multiple crystallization stages may be carried out.
The resulting crystalline product typically comprises L-arabinose 97-99%, D- galactose < 1%, Ash< 0.2 %, total dry solids> 99.5 %.
An embodiment of the invention will now be described further, by way of example.
Example 1
Sugar beet pulp from which the sucrose had been extracted by conventional diffusion methods was washed by soaking in a 5-fold volume excess of water at 62 C for 2 hours. The dirty water containing sucrose and other soluble impurities was removed by screw-pressing, and the pressed pulp having a dry matter content of about 25% by weight was passed to the alkali treatment step (a).
Water was added to the pressed pulp to form a mobile slurry. The amount of water added was 5 times the weight of the pressed pulp. The slurry was then heated to 95 C, and calcium hydroxide was added with stirring to raise the pH to pH 11. Suitably, the amount of calcium hydroxide added is approximately 50g/kg of pressed pulp.
Stirring was continued for 45 minutes, and the alkali solution containing the araban was then decanted from the pulp sludge. The crude araban extract was then passed to the carbonatation stage (b) as follows.
Carbonatation was carried out by passing CO2 through the crude araban extract maintained at 80 C with stirring for 30 minutes, to a final pH of 8.
The neutralised crude araban extract when then centrifuged (disk stack) to remove l 5 the lime sludge and other insoluble matter. The araban extract was then subjected to plate filtration ( 8 micrometer plate) to remove small particles of lime sludge and other insoluble matter.
The araban extract was then subjected to ultra-filtration using a membrane having a nominal molecular weight cut off of 30,000. This concentrated the araban retentate to approximately 12wt.% solids, and removed sugars and other low molecular weight soluble impurities in the permeate.
The purified retentate was then subjected to diafiltration as follows. 500 liters of the retentate was diluted with 300 liters of water, and then ultrafiltered through a membrane of the same type as for the first ultrafiltration until a retentate volume of 500 liters was again reached. The steps of dilution and ultrafiltration were then repeated three more times Finally, the purified araban solution was treated with a strong cation resin to remove calcium ions and lower the pH of the solution to approximately pH 4. At this point the solution contains approximately 12 wt.% araban, together with some l galactan and other large organic soluble species. This solution was then passed to hydrolysis step (e) as follows.
Hydrolysis was carried out by adding sulfuric acid in an amount of 7wt.% acid (as HANSON), based on the dry solids weight of the araban solution, and stirring for one hour at 97 C. These conditions result in hydrolysis of the araban to L-arabinose, without substantial hydrolysis of the galactan.
The crude L-arabinose solution was then purified by ultrafiltration through a MW l () 30,000 cut-off membrane. The resulting purified Larabinose solution was treated with an anionic exchange resin [XE583 Rohm and Hass (OH form)] to neutralise the solution and remove anionic impurities. The neutralized solution was then treated with an adsorption resin [XAD16, Rohm and Haas] to decolorize the solution. The pH of the solution was then adjusted to about 7 with sulfuric acid.
The resulting purified L-arabinose solution having a dry solids content of about 5 to 7wt.% was concentrated to 50-55bx at 35-40 C, followed by cooling crystallization at 20-35 C for 30 minutes to 2 hours, basket centrifuging and drying of the crystalline arabinose under vacuum at 60 C. The purity of the solution would be good enough to get a second and third crystallization, if desired.
The product arabinose comprised L-arabinose 97-99%, D-Galactose <1%, ash < 0.2%, dry solids > 99.5%. )
Claims (12)
1. A method of preparing L-arabinose from sugar beet pulp comprising the steps of: (a) treatment of a sugar beet pulp with aqueous alkali to provide a crude aqueous araban extract; (b) treatment of the crude araban extract with a precipitating agent to precipitate an insoluble calcium salt from the araban extract; (c) removal of the insoluble calcium salt sludge; JO (d) ultra-filtration to remove low molecular weight impurities and concentrate the araban extract; (e) acid hydrolysis of the purified araban extract after ultra-filtration to provide a crude aqueous L-arabinose solution; (0 ultra-filtration of the crude L-arabinose solution to remove high molecular weight impurities and provide a purified L-arabinose solution; (g) neutralization of the L-arabinose solution; and (h) concentration and crystallization of the purified L-arabinose solution to provide a purified L-arabinose.
2. A method according to claim 1, wherein the precipitating agent is carbon dioxide.
3. A method according to claim 1 or 2, wherein the method does not comprise a chromatographic purification step.
4. A method according to any preceding claim, wherein the ultrafiltration is carried out using a membrane having a nominal molecular weight cut off of from about 5000 to about 50,000.
5. A method according to any preceding claim, wherein the ultrafiltration step (d) is followed by a diafiltration step prior to the step (e) of hydrolyzing the araban.
I
6. A method according to any preceding claim, wherein the concentration of the araban in the retentate from the ultrafiltration step (d) and the optional diafiltration step is from about 10% to about 20% by weight.
S
7. A method according to any preceding claim, wherein the method does not comprise any substantial concentration step carried out on the araban solution before the hydrolysis step (e), other than the ultra-filtration step and optional diafiltration step.
]0
8. A method according to any preceding claim, wherein the ultrafiltration step (0 is carried out using a membrane having a nominal molecular weight cut off of from about 1000 to about 30,000.
9. A method according to any preceding claim, wherein the neutralization step (9) is carried out before the ultrafiltration step (f).
10. A method according to any preceding claim, wherein the L-arabinose solution undergoes treatment with an anionic exchange resin to remove anionic impurities and optionally also to neutralise the L-arabinose solution.
11. A method according to any preceding claim, wherein the L-arabinose solution further undergoes treatment with a polymeric adsorption resin to decolorise the solution.
12. A method according to any preceding claim for the preparation of crystalline L-arabinose comprising L-arabinose 97-99%, D-galactose < 1%, Ash< 0.2 %, total dry solids> 99.5 %.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0327327A GB2408262B (en) | 2003-11-24 | 2003-11-24 | A method of preparation of L-arabinose |
| PCT/GB2004/004955 WO2005052195A1 (en) | 2003-11-24 | 2004-11-24 | A method of preparation of l-arabinose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0327327A GB2408262B (en) | 2003-11-24 | 2003-11-24 | A method of preparation of L-arabinose |
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| Publication Number | Publication Date |
|---|---|
| GB0327327D0 GB0327327D0 (en) | 2003-12-31 |
| GB2408262A true GB2408262A (en) | 2005-05-25 |
| GB2408262B GB2408262B (en) | 2007-09-12 |
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|---|---|---|---|
| GB0327327A Expired - Fee Related GB2408262B (en) | 2003-11-24 | 2003-11-24 | A method of preparation of L-arabinose |
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| GB (1) | GB2408262B (en) |
| WO (1) | WO2005052195A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017058017A1 (en) * | 2015-10-02 | 2017-04-06 | Koninklijke Coöperatie Cosun U.A. | Methods of enriching arabinose fractions and products obtainable thereby |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1781116A4 (en) | 2004-06-04 | 2009-07-29 | Horizon Science Pty Ltd | Natural sweetener |
| WO2008034180A1 (en) | 2006-09-19 | 2008-03-27 | Horizon Science Pty Ltd | Extracts derived from sugar cane and a process for their manufacture |
| WO2012106761A1 (en) | 2011-02-08 | 2012-08-16 | Horizon Science Pty Ltd | Sugar extracts |
| JP6239622B2 (en) | 2012-08-28 | 2017-11-29 | ザ プロダクト メーカーズ （オーストラリア） プロプライエタリー リミテッド | Extraction method |
| CA2906917A1 (en) | 2013-03-15 | 2014-09-18 | Sweetwater Energy, Inc. | Carbon purification of concentrated sugar streams derived from pretreated biomass |
| EP3035949B1 (en) | 2013-08-16 | 2023-10-04 | Poly Gain Pte Ltd | Sugar cane derived extracts and uses |
| WO2015179243A1 (en) * | 2014-05-17 | 2015-11-26 | Sweetwater Energy, Inc. | Sugar separation and purification through filtration |
| RS63528B1 (en) | 2014-12-09 | 2022-09-30 | Sweetwater Energy Inc | Rapid pretreatment |
| CN104744525B (en) * | 2015-03-24 | 2017-03-01 | 浙江大学 | A kind of technique that preparation high-purity L arabinose is extracted for raw material with arabic gum |
| WO2018151833A1 (en) | 2017-02-16 | 2018-08-23 | Sweetwater Energy, Inc. | High pressure zone formation for pretreatment |
| CN108586036A (en) * | 2018-05-03 | 2018-09-28 | 山东胜伟旅游发展有限公司 | Utilize the method for saline and alkaline real estate beet sugar manufacture |
| BR112022012348A2 (en) | 2019-12-22 | 2022-09-13 | Sweetwater Energy Inc | METHODS OF MAKING SPECIALIZED LIGIN AND BIOMASS LIGIN PRODUCTS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD143261A1 (en) * | 1979-04-25 | 1980-08-13 | Bruno Tschiersch | PROCESS FOR OBTAINING L - (+) ARABINOSE |
| WO1990006343A1 (en) * | 1988-12-05 | 1990-06-14 | British Sugar Plc | Debranched araban and its use as a fat substitute |
| WO1999010542A1 (en) * | 1997-08-26 | 1999-03-04 | Danisco Finland Oy | Method of preparing l-arabinose from sugar beet pulp |
| WO1999010384A1 (en) * | 1997-08-26 | 1999-03-04 | Sohkar Oy | A raw material for use in the preparation of pectin and related compounds, and a method for the preparation of same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1182099A (en) * | 1967-04-06 | 1970-02-25 | Slovenska Akademia Vied | A Method of Preparation of L-Arabinose |
| DE3702653A1 (en) * | 1987-01-29 | 1988-08-11 | Sueddeutsche Zucker Ag | METHOD FOR PRODUCING CRYSTALLINE L-ARABINOSE |
| CZ2002570A3 (en) * | 1999-08-19 | 2002-11-13 | Tate & Lyle Sugar Holdings, Inc. | Sugar beet membrane filtration process |
| ATE544874T1 (en) * | 2000-12-28 | 2012-02-15 | Danisco | SEPARATION PROCESS |
-
2003
- 2003-11-24 GB GB0327327A patent/GB2408262B/en not_active Expired - Fee Related
-
2004
- 2004-11-24 WO PCT/GB2004/004955 patent/WO2005052195A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD143261A1 (en) * | 1979-04-25 | 1980-08-13 | Bruno Tschiersch | PROCESS FOR OBTAINING L - (+) ARABINOSE |
| WO1990006343A1 (en) * | 1988-12-05 | 1990-06-14 | British Sugar Plc | Debranched araban and its use as a fat substitute |
| WO1999010542A1 (en) * | 1997-08-26 | 1999-03-04 | Danisco Finland Oy | Method of preparing l-arabinose from sugar beet pulp |
| WO1999010384A1 (en) * | 1997-08-26 | 1999-03-04 | Sohkar Oy | A raw material for use in the preparation of pectin and related compounds, and a method for the preparation of same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017058017A1 (en) * | 2015-10-02 | 2017-04-06 | Koninklijke Coöperatie Cosun U.A. | Methods of enriching arabinose fractions and products obtainable thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2408262B (en) | 2007-09-12 |
| WO2005052195A1 (en) | 2005-06-09 |
| GB0327327D0 (en) | 2003-12-31 |
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