EP1468121B1 - Method for the recovery of sugars - Google Patents
Method for the recovery of sugars Download PDFInfo
- Publication number
- EP1468121B1 EP1468121B1 EP02788021A EP02788021A EP1468121B1 EP 1468121 B1 EP1468121 B1 EP 1468121B1 EP 02788021 A EP02788021 A EP 02788021A EP 02788021 A EP02788021 A EP 02788021A EP 1468121 B1 EP1468121 B1 EP 1468121B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mannose
- separation
- resin
- chromatographic
- fraction
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 101
- 235000000346 sugar Nutrition 0.000 title claims description 25
- 150000008163 sugars Chemical class 0.000 title claims description 23
- 238000011084 recovery Methods 0.000 title description 9
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims abstract description 165
- 239000011347 resin Substances 0.000 claims abstract description 98
- 229920005989 resin Polymers 0.000 claims abstract description 98
- 238000013375 chromatographic separation Methods 0.000 claims abstract description 69
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 130
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 120
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 119
- 238000000926 separation method Methods 0.000 claims description 101
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000002425 crystallisation Methods 0.000 claims description 37
- 230000008025 crystallization Effects 0.000 claims description 37
- 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 claims description 36
- 239000003729 cation exchange resin Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- 239000002028 Biomass Substances 0.000 claims description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 22
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 claims description 19
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 claims description 19
- 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 claims description 18
- 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 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000005185 salting out Methods 0.000 claims description 14
- 239000003265 pulping liquor Substances 0.000 claims description 13
- 229930091371 Fructose Natural products 0.000 claims description 10
- 239000005715 Fructose Substances 0.000 claims description 10
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 10
- 229930182830 galactose Natural products 0.000 claims description 10
- 239000000413 hydrolysate Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- -1 alkali metal cations Chemical class 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000011097 chromatography purification Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 150000002703 mannose derivatives Chemical class 0.000 claims description 5
- LKZGXPMJCWRGTC-IKQSSVLVSA-N (3s,4s,5s,6r)-2-anilino-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)OC1NC1=CC=CC=C1 LKZGXPMJCWRGTC-IKQSSVLVSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 238000001212 derivatisation Methods 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000012978 lignocellulosic material Substances 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- 239000005418 vegetable material Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims description 2
- 125000003423 D-mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 229960003487 xylose Drugs 0.000 description 59
- 239000008186 active pharmaceutical agent Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 16
- 238000004537 pulping Methods 0.000 description 10
- 150000001720 carbohydrates Chemical class 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 235000014633 carbohydrates Nutrition 0.000 description 8
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000006188 syrup Substances 0.000 description 8
- 235000020357 syrup Nutrition 0.000 description 8
- 229920001732 Lignosulfonate Polymers 0.000 description 7
- 239000004117 Lignosulphonate Substances 0.000 description 7
- 235000019357 lignosulphonate Nutrition 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002772 monosaccharides Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003109 Karl Fischer titration Methods 0.000 description 2
- SRBFZHDQGSBBOR-HWQSCIPKSA-N L-arabinopyranose Chemical compound O[C@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-HWQSCIPKSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000021536 Sugar beet Nutrition 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000001032 ion-exclusion chromatography Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YAHHFDSODKFKOV-OTEWLTGOSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;(2r,3r,4s,5s)-2,3,4,5-tetrahydroxyhexanal Chemical compound C[C@H](O)[C@H](O)[C@@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O YAHHFDSODKFKOV-OTEWLTGOSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229920002324 Galactoglucomannan Polymers 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 241001019674 Phytelephas schottii Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 150000002016 disaccharides Chemical class 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LUEWUZLMQUOBSB-GFVSVBBRSA-N mannan Chemical class O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-GFVSVBBRSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004810 partition chromatography Methods 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 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
- 239000010902 straw Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/14—Purification of sugar juices using ion-exchange materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/14—Purification of sugar juices using ion-exchange materials
- C13B20/144—Purification of sugar juices using ion-exchange materials using only cationic ion-exchange material
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/007—Separation of sugars provided for in subclass C13K
Definitions
- the present invention relates to a chromatographic separation method of separating carbohydrates, especially sugars, from a mixture including the same.
- the mixture to be treated in accordance with the present invention is typically a biomass-derived solution including carbohydrates/sugars.
- the invention provides a chromatographic separation method of recovering mannose with high purity from biomass-derived solutions, such as spent sulphite pulping liquors.
- Mannose can be recovered in a crystalline form or in the form of a solution.
- the claimed process of recovering mannose is based on the use of a combination of a Ba 2+ form resin and a resin in other than Ba 2+ form as the separation resin, whereafter mannose is crystallized, if desired.
- xylose and arabinose products can also be obtained as by-products, depending on the composition of the starting biomass-derived solution.
- Mannose is useful e.g. for various pharmaceutical applications. It can be used as a starting material or raw material for various pharmaceutical products. Mannose is also therapeutically useful in the treatment of urine infections and intravenous inflammation conditions. In food technology, mannose is useful e.g. for so-called Positech applications (GMO-testing of food products).
- Mannose is also useful as the raw material for the production of mannitol, which has various pharmaceutical applications.
- Mannose can be recovered from wood resources, where mannose is present as a mixture with other carbohydrates and lignin components.
- mannose typically occurs in polymeric form, such as hemicellulose, most frequently as a heteropolymer with glucose and/or galactose in glucomannans, galactoglucomannans and galactomannans. Spent liquors obtained from conifer wood-pulping processes are especially rich in mannose.
- Mannose has also been recovered from vegetable ivory nuts and specific seaweeds.
- Herrick, F.W., Casebier, R.L., Hamilton, J.K. & Wilson, J.D. disclose a study relating to the development of an economic process for recovering mannose or its derivatives from wood resources, such as a spent sulphite liquor, where mannose is a major component of mixtures containing other carbohydrates and lignin fragments.
- the main achievement of this work was the development of processes for recovering sodium mannose bisulphite and methyl mannoside from several raw materials.
- Processes were developed for recovering mannose from crude mixtures via two routes: (1) formation of the sodium bisulphite adducts of monomeric wood sugar mixtures, crystallization and separation of sodium mannose bisulphite and regeneration of mannose from this intermediate, and (2) anhydrous methanolysis concurrent with glycosidation of crude mixed-sugar polymers or monomers, crystallization and separation of methyl ⁇ -D mannoside and regeneration of mannose from this intermediate.
- These procedures for recovering mannose have the drawback that they are very cumbersome to carry out in practice.
- GB 1 540 556 (ICI Americas, publ. 14 February 1979) relates to a method of separating mannose from glucose present in aqueous solutions.
- the starting mixture of glucose and mannose is typically obtained by epimerization of glucose in an aqueous solution.
- the separation of mannose from glucose is typically carried out using a cation exchange resin in the form of an alkaline earth metal salt, such as in Ca 2+ , Sr 2+ or 8a 2+ form.
- the cation exchange resin is preferably a strongly acid cation exchange resin, typically a resin based on styrene divinylbenzene.
- Finnish Patent 78734 (Suomen Sokeri Oy, publ. 5 April 1987) relates to a multi-step process of separating sugars and lignosulphonates from a spent sulphite pulping liquor.
- This process comprises introducing a spent sulphite pulping liquor into a chromatographic column including a separation resin in a metal salt form, typically a strongly acid cation exchange resin in a Ca 2+ form, eluting the column with water to recover a fraction rich in lignosulphonates and a fraction rich in sugars, introducing the fraction rich in sugars thus obtained into another chromatographic column including a separation resin in a monovalent metal salt form, typically in Na + form.
- a sugar fraction free from lignosulphonates is obtained.
- WO 96/27029 (Xyrofin Oy, publ. 6 September 1996) relates to a method of recovering an organic compound, such as sugars, from solutions by crystallizing the compound substantially by way of nucleation. It is proposed that mannose can be recovered by the nucleation crystallization process, for example.
- Finnish Patent 97 625 (Xyrofin Oy, publ. 5 March 1996) discloses a process for crystallizing xylose.
- xylose is recovered by crystallization from solutions in which the xylose purity is relatively low.
- this process concerns recovering xylose from biomass-derived solutions.
- WO 99/10542 discloses a process of recovering L-arabinose from sugar beet pulp by a chromatographic separation method using a cation exchanger in a monovalent metal form as the separation resin.
- the L-arabinose solution thus obtained is purified by means of cation and anion exchangers and adsorbent resins.
- WO 01/21271 A1 discloses a method of recovering pectin, arabinose and salts from vegetable material using a cation exchange resin, which is preferably in the form of a multivalent metal.
- EP-A2-0104911 discloses porous styrene-divinylbenzene copolymer particles having SO3 - groups and counter ions for SO3 - groups, said counter ions being (a) at least one of Ca ++ and Sr ++ and (b) at least one of Pb ++ and Ba ++ and the equivalent ratio of (a)/(b) being 1/2 to 2/1.
- the particles are an excellent liquid chromatographic column packing material suited for separating sugars different in kind but the same in molecular weight.
- Biomass-derived raw materials used for the recovery of mannose are typically complex multicomponent mixtures. Separation of mannose with sufficient purity from these complex mixtures has presented a problem.
- One of the problems associated with the above-described known processes is that they provide mannose as a mixture with other closely-related sugars or that they do not provide mannose with a sufficient degree of purity.
- the production of mannose from mannans and other mannose derivatives is technically very cumbersome.
- mannose with high purity can be effectively recovered from biomass-derived carbohydrate-containing solutions using a novel chromatographic separation method.
- a mannose fraction having a purity of 45 to 80% or more can be obtained.
- the mannose fraction obtained from the chromatographic separation can then be further purified by crystallization.
- the crystallization provides a crystalline mannose product having a purity of up to 99% or more.
- various other sugars, such as xylose and arabinose can be recovered as by-products, depending on the composition of the starting biomass-derived raw material.
- the invention is based on the idea of purifying the mannose-containing carbohydrate mixture chromatographically using at least a resin in a Ba 2+ form and a resin in a Ca 2+ or NA + form.
- the invention relates to a method of recovering mannose from a solution containing the same.
- the method of the invention is characterized in that said mixture is subjected to a chromatographic separation process using at least one chromatographic separation resin bed where the resin is a cation exchange resin in a Ba 2+ form and at least one chromatographic separation resin bed where the resin is a cation exchange resin in a Ca 2+ or Na + form and recovering at least one mannose fraction.
- the chromatographic separation process of the invention typically comprises at least two chromatographic separation steps, whereby at least one of these steps is carried out with a chromatographic separation resin bed where the resin is a cation exchange resin in a Ba 2+ form and at least one of these steps is carried out with a chromatographic separation resin bed where the resin is a cation exchange resin in a Ca 2+ or Na + form.
- One embodiment of the invention is typically carried out by feeding a solution containing mannose into a first chromatographic column including a chromatographic separation resin bed where the resin is a cation exchange resin in a Ba 2+ form, eluting said column with an eluant, recovering a first mannose fraction, and then feeding said first mannose fraction into a second chromatographic column including a chromatographic separation resin bed where the resin is a cation exchange resin in a Ca 2+ or Na + form, eluting said column with an eluant, and recovering a second mannose fraction.
- said chromatographic separation process comprises two separation steps with a chromatographic separation resin bed where the resin is a cation exchange resin in a Ba 2+ form and one separation step with a chromatographic separation resin bed where the resin is a cation exchange resin in a Ca 2+ or Na + form.
- This embodiment of the invention is typically carried out by feeding a solution containing mannose into a first chromatographic column including a chromatographic separation resin bed where the resin is a cation exchange resin in a Ba 2+ form, eluting said column with an eluant, recovering a first mannose fraction, feeding said first mannose fraction into a second chromatographic column including a chromatographic separation resin bed where the resin is a cation exchange resin in a Ba 2+ form, eluting said column with an eluant, recovering a second mannose fraction, and then feeding said second mannose fraction into a third chromatographic column including a chromatographic separation resin bed where the resin is a cation exchange resin in a Ca 2+ or Na + forum, eluting said column with an eluant, and recovering a third mannose fraction.
- some other separation may be carried out before the Ba 2+ separation. In the same way, some other separation may be carried out between the Ba 2+ separations. Furthermore, between two ion exchange operations, equilibration of the ions or the ion composition is typically carried out, for example by ion exchange.
- the cation exchange resin in a Ca 2+ or Na + form is in a Ca 2+ form.
- the chromatographic separation for obtaining mannose in accordance with the present invention is typically carried out with a strongly acid cation exchange resin.
- a preferred resin is a cross-linked styrene-divinylbenzene based resin.
- a suitable cross-linking degree of the resin is 1 to 20% by weight, preferably 3 to 8% by weight.
- the average particle size of the resin is normally 10 to 2000 ⁇ m, preferably 100 to 400 ⁇ m. Zeolite-based molecular sieves can also be used.
- the eluant used in the chromatographic separation according to the present invention is either water, a solvent, e.g. an alcohol, or a mixture thereof.
- a preferred eluant is water.
- the elution is preferably carried out at a temperature from 10 to 95°C, more preferably from 30 to 95°C, most preferably from 55 to 85°C.
- the chromatographic separation method of the invention provides a mannose fraction where mannose is in a solution form.
- the mannose product obtained from the chromatographic separation has a typical purity of 45 to 80% mannose on RDS.
- recycle fractions of the chromatographic separation can also be used.
- the chromatographic separation method of the invention may further comprise one of more purification steps selected from membrane filtration, ion exchange, evaporation, filtration and derivatization. These purification steps may be carried out before, after or between said chromatographic separation step/steps.
- Ion exchange is typically carried out to purify the mannose-containing solution from SO 4 - ions, for example.
- a mannose derivative is formed, whereafter mannose is regenerated from the derivative thus obtained.
- One example of useful mannose derivatives is N-phenyl-D-mannopyranosylamine.
- the mannose solution obtained from the chromatographic separation can be further purified by crystallization to obtain a crystalline mannose product.
- the crystallization is typically carried out using a solvent selected from water, alcohol and a mixture of water and alcohol. In a preferred embodiment of the invention, the crystallization is carried out with a mixture of ethanol and water.
- the crystallization is carried out by evaporating the mannose solution or mannose syrup obtained from the chromatographic separation to an appropriate dry substance content (e.g. to RDS of about 85%).
- the boiling syrup may be seeded with mannose seed crystals.
- the seeds, if used, are suspended in a crystallization solvent, which may be either water, a solvent , e.g. an alcohol, or a mixture thereof.
- a typical crystallization solvent is ethanol.
- the crystallization solvent is added.
- the crystallization mass may then be allowed to stand for a period of time, preferably for 3 to 6 days, typically at room temperature, whereafter the crystals are filtered off.
- the filtration cake is washed with the crystallization solvent.
- Mannose crystals with a high purity are obtained.
- the crystallization provides crystalline mannose having a purity of over 90%, preferably over 95% and most preferably over 99% on RDS.
- the method of the invention may also comprise separation of other sugars, such as xylose, rhamnose and arabinose, depending on the composition of the starting mannose-containing solution.
- separation of other sugars is typically carried out before the separation of mannose.
- the method of the invention may thus comprise separation of xylose as a pretreatment step.
- the recovery of xylose may be carried out by various methods, e.g. through precipitation crystallization.
- the xylose precipitation crystallization is preferably carried out immediately before the chromatographic separation of mannose.
- the solution containing mannose and some xylose is subjected to a crystallization step.
- the precipitation crystallization of xylose is typically carried out by evaporating the solution to a desired dry substance content, seeding the solution with xylose seed crystals, and then cooling the crystallization mass according to a desired cooling program.
- the crystallization mass is filtered to obtain a xylose cake and mannose-containing crystallization run-off.
- Xylose is recovered from the crystallization cake and the run-off containing mannose is subjected to the chromatographic purification described above for obtaining mannose with high purity in accordance with the present invention.
- the method of the invention may also comprise separation of arabinose, preferably as a pretreatment step.
- the separation of arabinose may be carried out before the precipitation crystallization of xylose.
- Chromatographic separation is typically used for the recovery of arabinose.
- the chromatographic separation of arabinose is preferably carried out using a chromatographic separation resin bed in the form of a monovalent cation, which is selected from hydrogen, ammonium and alkali metal cations. Said monovalent cation is typically selected from H + , Na + , K + and NH 4 + .
- An arabinose fraction is recovered.
- the chromatographic separation resin is preferably a strongly acid cation exchange resin.
- the arabinose fraction may be subjected to further chromatographic purification.
- the chromatographic purification of the arabinose fraction typically comprises at least one step using a chromatographic separation resin bed in the form of an alkaline earth metal, preferably Ca 2+ .
- the arabinose fraction thus obtained may also be crystallized.
- the method of the invention may also comprise separation of rhamnose as a pretreatment step.
- the separation of rhamnose is typically carried out before the separation of arabinose.
- the method of the invention may also comprise separation of xylose as a pretreatment step.
- the separation of xylose it typically carried out before the separation of arabinose.
- the method of the invention may also include further purification steps, such as membrane filtration, e.g. ultrafiltration and nanofiltration, ion exchange, evaporation and filtration to remove e.g. lignosulphonates, acids (organic acids and inorganic acids) and salts.
- membrane filtration e.g. ultrafiltration and nanofiltration
- ion exchange e.g. ion exchange
- evaporation and filtration to remove e.g. lignosulphonates, acids (organic acids and inorganic acids) and salts.
- the starting solution containing mannose is typically a mixture containing carbohydrates, such as sugars.
- the solution may contain, in addition to mannose, e.g. xylose, galactose, glucose, rhamnose, arabinose and fructose.
- the mixture may also contain disaccharides and higher saccharides.
- the material containing a mixture of carbohydrates is typically derived from a biomass, typically mannose-containing vegetable material, such as softwood or hardwood, straw, com husks, com cops, com fibers and sugar beet.
- the starting material is as a rule used in the form of a hydrolysate obtained e.g. by prehydrolysis, total hydrolysis, steam hydrolysis, enzymatic hydrolysis or acid hydrolysis.
- the biomass hydrolysate used for the recovery of mannose in accordance with the present invention is typically a spent liquor obtained from a pulping process.
- the spent liquor is especially a spent sulphite pulping liquor, which may be obtained by acid, basic or neutral sulphite pulping. If the biomass hydrolysate, e.g. the spent liquor contains mannose in polymeric form, the polymeric mannose can be hydrolysed by acids or enzymes before the chromatographic separation steps.
- a typical spent liquor useful in the present invention is a mannose-containing spent liquor, which is preferably obtained from acid sulphite pulping.
- the spent liquor may be obtained directly from sulphite pulping. It may also be a concentrated sulphite pulping liquor or a side-relief obtained from sulphite cooking. It may also be a mannose-containing fraction chromatographically obtained from a sulphite pulping liquor.
- the liquor to be treated may also be any other liquor obtained from the digestion or hydrolysis of biomass, typically a hydrolysate obtained from acid hydrolysis of lignocellulosic material.
- a hydrolysate may be obtained from lignocellulosic material for example by treatment with an inorganic acid, such as hydrochloric acid, sulphuric acid or sulphur dioxide, or by treatment with an organic acid, such as formic acid or acetic acid.
- a spent liquor obtained from solvent-based pulping, such as phenol-based pulping and ethanol-based pulping may also be used.
- the starting solution containing mannose may be e.g. a spent sulphite pulping liquor recovered after the separation of rhamnose.
- the starting solution may also be a spent sulphite pulping liquor recovered after the separation of xylose.
- the mannose product obtained in accordance with the present invention typically comprises D-mannose.
- the starting liquor used in the first step of the process was a mannose-containing side stream separated from Ca 2+ based sulphite spent liquor after the recovery of xylose and rhamnose. Birch had been used as raw material for the sulphite pulping.
- the mannose-containing side stream recovered after the separation of rhamnose was subjected to chromatographic separation to obtain a mannose fraction and an arabinose fraction (chromatographic separation A).
- the mannose fraction was subjected to separation B (xylose precipitation crystallization) to obtain a xylose cake and a crystallization run-off containing mannose.
- separation B xylose precipitation crystallization
- the mannose-containing run-off from the crystallization of xylose was subjected to three successive chromatographic separations (C.1), (C.2) and (C.3).
- the mannose fraction from the last chromatographic separation was subjected to mannose crystallization.
- the arabinose fraction from separation (A) was subjected to two successive chromatographic separations (E.1) and (E.2) for recovering purified arabinose.
- the starting mannose-containing liquor obtained after the separation of rhamnose had the following composition: Component Content (% on DS) Xylose 36 Mannose 15 Galactose 13 Glucose 4.8 Rhamnose 0.6 Arabinose 4.9 Fructose 1.4 Others 24.6
- a strongly acid cation exchange resin in Na + form was used to remove the salts from the feed and to collect arabinose from the end of the elution profile.
- the separation was done using the following separation conditions: Column diameter 0.6 m Bed height 5.3 m Feed size 108.5 l Feed RSD 35 g/100 g Temperature 65 °C Flow rate 170 l/h Resin Finex CS 11 GC, 5.5% DVB, average particle size 0.35 mm
- composition of the mannose and arabinose fractions collected from separation are set forth in Table 1.
- Table 1 Composition of the mannose and arabinose fractions in % on DS
- Component Mannose fraction Arabinose fraction Xylose 43 34 Mannose 19 13
- Galactose 16 10
- Glucose 6.3 0.2
- Rhamnose 1.1
- Fructose 1.2
- Others 8.9 23.5
- the mannose yield was 38% for mannose purity of 19 % on DS and xylose purity of 43 % on DS.
- the concentration profile of separation (A) is presented in Figure 1 .
- the mannose fraction obtained from separation (A) and having a xylose content of about 43 % on DS was subjected to precipitation crystallization to separate xylose.
- the precipitation crystallization of xylose was carried out in pilot scale with one crystallizer of about 200 liters.
- the feed liquor was evaporated to a final DS of 87.5%.
- the batch was seeded in a boiling pan with xylose seed crystals.
- the mass was cooled down from 60°C to 31°C in 48 hours and then the mass was held at 31°C for 24 hours. No dilutions were made.
- the mass was dropped down to a mingler and then filtrated.
- the results of the xylose precipitation crystallization are set forth in Table 2.
- the table shows the contents of various components in the crystallization feed, cake and run-off in % on DS. Table 2.
- Analysis results of the xylose precipitation crystallization Component Feed Cake Run-off 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
- the run-off fraction obtained from the xylose precipitation crystallization was subjected to chromatographic separation using a Ba 2+ form SAC resin.
- the separation was done using the following separation conditions: Column diameter 0.225 m Bed height 5.3 m Feed size 11.9 l Feed RSD 32 g/100 g Temperature 65°C Flow rate 25 l/h Resin Finex CS 08 GC, 4 % DVB, average particle size 0.38 mm
- Mannose fraction was collected with a mannose yield of 70% and the total purity of 49 % on DS was obtained.
- the composition of the mannose and xylose fractions is presented in Table 3. Table 3. Composition of the mannose and xylose fractions from the first separation with Ba 2+ form SAC resin in % on DS Component 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 Others 6.5 24.2
- a second Ba 2+ form SAC resin separation was used to purify the mannose fraction obtained from the previous step (separation C.1).
- the same separation conditions were used as in separation (C.1) above.
- the mannose fraction obtained from the separation had a purity of 63 % on DS with a mannose yield of 68%.
- the compositions of the mannose and xylose fractions in % on DS are set forth in Table 4. Table 4. Composition of the mannose and xylose fractions from the second separation with Ba 2+ form SAC resin Component 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 Others 13.9 24.3
- the xylose fraction still contained 40% mannose.
- the mannose fraction obtained from separation (C.2) was subjected to a further chromatographic separation using Ca 2+ form SAC resin.
- the separation was done using the following separation conditions: Column diameter 0.225 m Bed height 4.8 m Feed size 11 l Feed RSD 30.7 g/100 g Temperature 65 °C Flow rate 30 l/h Resin Finex CS 11 GC, 5.5 % DVB, average particle size 0.35 mm
- composition of the mannose fraction in % on DS is set forth in Table 5.
- Table 5 Composition of the mannose fraction obtained from the separation with a Ca 2+ form SAC resin
- Mannose 80 Galactose 5.1
- Mannose fraction purity of 80 % on DS was obtained with a mannose yield of 70%.
- concentration profile of separation (C.3) is presented in Figure 4 .
- the mass was cooled down from a temperature of 30°C to a temperature of 25°C. 800 g ethanol was added slowly to the mass.
- the crystals were filtrated with a pressure filter.
- the filtration gave a cake purity of 93.0% (including solvent ethanol as impurity) and a mother liquor purity of 52.5% (including solvent ethanol as impurity). This corresponds to a mannose yield of 41%.
- the crystal size was in the range of 10 to 20 ⁇ m.
- the filtration cake was washed twice with ethanol.
- the crystals were centrifuged and dried at 40°C for 24 hours.
- the crystals had a crystal water content of 0.3% and a mannose content of 99.9%.
- the mass was cooled down from a temperature of 30°C to a temperature of 20°C. 300 g ethanol was added slowly to the mass.
- the crystals were centrifuged. The centrifuging gave a cake purity of 96.0% (including solvent ethanol as impurity). The centrifuging result corresponds to a 50% mannose yield.
- the crystal size was in the range of 30 to 50 ⁇ m.
- the centrifuging cake was washed twice with ethanol.
- the crystals were centrifuged and dried at 40°C for 24 hours.
- the crystal water content was analyzed to be 0.2%, and the crystal mannose content to be 99.7%.
- the mass was cooled down from a temperature of 60°C to a temperature of 25°C. After 6 days from seeding, the centrifuging cake gave a purity of 99.5%. The centrifuging result corresponds to a mannose yield of 30%.
- the crystal size was in the range of 30 to 50 ⁇ m.
- the arabinose fraction obtained from separation (A) had a purity of 10 % on DS. This fraction was further purified with a Ca 2+ form SAC resin.
- compositions of the feed, xylose and arabinose fractions in % on DS are set forth in Table 6.
- Table 6 Composition of the feed, xylose and arabinose fractions from the first separation with Ca 2+ resin
- Component 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 Others 20.8 13 35.4
- the concentration profile of separation (E.1) is presented in Figure 5 .
- the arabinose fraction obtained from separation (E.1) was subjected to another purification with a Ca 2+ form resin.
- the separation was done using the following separation conditions: Column diameter 0.225 m Bed height 4.9 m Feed size 20 l Feed RSD 30.6 g/100g Temperature 65°C Flow rate 30 l/h Resin Finex CS 11 GC, 5.5% DVB, average particle size 0.40mm
- composition of the feed, xylose and arabinose fractions in % on DS is set forth in Table 7.
- Table 7. Composition of the feed and xylose and arabinose fractions from the second separation with a Ca 2+ form resin
- Component 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 Others 23.6 13.6 34.7
- the arabinose was collected with an 85% yield.
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Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20012605 | 2001-12-31 | ||
| FI20012605A FI114553B (sv) | 2001-12-31 | 2001-12-31 | Förfarande för tillvaratagande av socker |
| PCT/FI2002/001059 WO2003056038A1 (en) | 2001-12-31 | 2002-12-30 | Method for the recovery of sugars |
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| EP1468121A1 EP1468121A1 (en) | 2004-10-20 |
| EP1468121B1 true EP1468121B1 (en) | 2011-11-09 |
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| EP02788021A Expired - Lifetime EP1468121B1 (en) | 2001-12-31 | 2002-12-30 | Method for the recovery of sugars |
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| EP (1) | EP1468121B1 (sv) |
| JP (2) | JP5212761B2 (sv) |
| KR (1) | KR100943835B1 (sv) |
| CN (1) | CN100390301C (sv) |
| AT (1) | ATE532881T1 (sv) |
| AU (1) | AU2002352310A1 (sv) |
| CA (1) | CA2472246C (sv) |
| FI (1) | FI114553B (sv) |
| WO (1) | WO2003056038A1 (sv) |
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| US20050033045A1 (en) | 2003-06-27 | 2005-02-10 | Danisco Sweeteners Oy | Separation method |
| US20050096464A1 (en) | 2003-10-30 | 2005-05-05 | Heikki Heikkila | Separation process |
| JP4488750B2 (ja) * | 2004-01-21 | 2010-06-23 | ユニチカ株式会社 | Ｌ−アラビノース含有シロップ |
| FR2876693B1 (fr) * | 2004-10-15 | 2007-01-26 | Roquette Freres | Procede de preparation de l-iditol |
| DE102007034621A1 (de) | 2007-07-25 | 2009-01-29 | Lanxess Deutschland Gmbh | Polyolreinigung |
| US9068206B1 (en) * | 2009-03-03 | 2015-06-30 | Poet Research, Inc. | System for treatment of biomass to facilitate the production of ethanol |
| CN105803118B (zh) | 2010-06-26 | 2021-08-13 | 威尔迪亚有限责任公司 | 糖混合物及其生产和使用方法 |
| IL206678A0 (en) * | 2010-06-28 | 2010-12-30 | Hcl Cleantech Ltd | A method for the production of fermentable sugars |
| IL207945A0 (en) | 2010-09-02 | 2010-12-30 | Robert Jansen | Method for the production of carbohydrates |
| US9512495B2 (en) | 2011-04-07 | 2016-12-06 | Virdia, Inc. | Lignocellulose conversion processes and products |
| CN104093485B (zh) * | 2012-01-31 | 2017-03-29 | 赛罗尔比利时公司 | 从木质纤维素基质中提取戊糖的方法 |
| BR112014027476B1 (pt) | 2012-05-03 | 2019-12-10 | Virdia Ltd | métodos de processamento de materiais lingnocelulósicos |
| NZ706072A (en) * | 2013-03-08 | 2018-12-21 | Xyleco Inc | Equipment protecting enclosures |
| JP2016531584A (ja) * | 2013-09-05 | 2016-10-13 | ダウ グローバル テクノロジーズ エルエルシー | 陽イオン交換樹脂の配合物を使用する糖のクロマトグラフィー分離 |
| WO2016112134A1 (en) | 2015-01-07 | 2016-07-14 | Virdia, Inc. | Methods for extracting and converting hemicellulose sugars |
| EP3303639B1 (en) | 2015-05-27 | 2020-08-05 | Virdia, Inc. | Integrated methods for treating lignocellulosic material |
| US10732153B2 (en) * | 2015-08-24 | 2020-08-04 | Shimadzu Corporation | Separation/purification apparatus |
| EP3385271A1 (en) | 2017-04-04 | 2018-10-10 | Borregaard AS | Industrial-scale d-mannose extraction from d-mannose bisulfite adducts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3677818A (en) * | 1970-04-02 | 1972-07-18 | Itt | Processes for preparing mannose and mannose derivatives |
| CA1151644A (en) * | 1976-05-27 | 1983-08-09 | Richard W. Neuzil | Process for separating ketose-aldose mixtures by selective adsorption |
| GB1540556A (en) * | 1977-01-11 | 1979-02-14 | Ici America Inc | Separation of mannose from glucose |
| JPS5668696A (en) * | 1979-11-09 | 1981-06-09 | Towa Kasei Kogyo Kk | Preparation of d-mannose |
| JPS5956162A (ja) * | 1982-09-24 | 1984-03-31 | Hitachi Chem Co Ltd | カラム充てん剤およびその製造法 |
| US4471114A (en) * | 1982-12-30 | 1984-09-11 | Union Carbide Corporation | Separation of mannose by selective adsorption on zeolitic molecular sieves |
| JPS6186654A (ja) * | 1984-10-04 | 1986-05-02 | Hitachi Chem Co Ltd | 液体クロマトグラフイ−用カラム充填剤 |
| JPS6185397A (ja) * | 1984-10-04 | 1986-04-30 | Hitachi Chem Co Ltd | 糖類の分離方法 |
| US4631129A (en) * | 1985-10-04 | 1986-12-23 | Suomen Sokeri Oy | Production of pure sugars and lignosulfonates from sulfite spent liquor |
| JP2740780B2 (ja) * | 1987-09-21 | 1998-04-15 | オルガノ株式会社 | 擬似移動層装置 |
| JPH0783720B2 (ja) * | 1988-08-26 | 1995-09-13 | 株式会社ヤトロン | 解糖を阻止する方法及び解糖阻止剤の製造方法 |
| US5084104A (en) * | 1989-12-05 | 1992-01-28 | Cultor, Ltd. | Method for recovering xylose |
| JP2979442B2 (ja) * | 1991-06-18 | 1999-11-15 | 東和化成工業株式会社 | マンニット及びマンノースの製造方法 |
| JPH06237782A (ja) * | 1993-02-13 | 1994-08-30 | Amano Pharmaceut Co Ltd | マンノースの分離取得方法 |
| DE4341780A1 (de) * | 1993-12-08 | 1995-06-14 | Suedzucker Ag | Hydrierte Fructooligosaccharide |
| RU2065499C1 (ru) * | 1994-06-29 | 1996-08-20 | Институт биохимии им.А.Н.Баха РАН | Способ получения д-маннозы из семян растения рода гледичия |
| FI952065A0 (fi) * | 1995-03-01 | 1995-04-28 | Xyrofin Oy | Foerfarande foer tillvaratagande av en kristalliserbar organisk foerening |
| JP3991434B2 (ja) * | 1998-03-23 | 2007-10-17 | オルガノ株式会社 | クロマト分離方法 |
| JP3478325B2 (ja) * | 1997-12-25 | 2003-12-15 | オルガノ株式会社 | クロマト分離方法 |
| JP2000139490A (ja) * | 1998-11-05 | 2000-05-23 | Unitika Ltd | マンノースおよびマンノオリゴ糖の製造方法 |
| JP3553866B2 (ja) * | 1999-09-14 | 2004-08-11 | 味の素ゼネラルフーヅ株式会社 | マンノオリゴ糖類を主成分とする組成物 |
-
2001
- 2001-12-31 FI FI20012605A patent/FI114553B/sv not_active IP Right Cessation
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2002
- 2002-12-30 EP EP02788021A patent/EP1468121B1/en not_active Expired - Lifetime
- 2002-12-30 AT AT02788021T patent/ATE532881T1/de active
- 2002-12-30 CN CNB028276558A patent/CN100390301C/zh not_active Expired - Fee Related
- 2002-12-30 WO PCT/FI2002/001059 patent/WO2003056038A1/en not_active Ceased
- 2002-12-30 CA CA2472246A patent/CA2472246C/en not_active Expired - Lifetime
- 2002-12-30 AU AU2002352310A patent/AU2002352310A1/en not_active Abandoned
- 2002-12-30 JP JP2003556555A patent/JP5212761B2/ja not_active Expired - Fee Related
- 2002-12-30 KR KR1020047010359A patent/KR100943835B1/ko not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| FI20012605A0 (sv) | 2001-12-31 |
| FI20012605L (sv) | 2003-07-01 |
| KR20040096515A (ko) | 2004-11-16 |
| WO2003056038A1 (en) | 2003-07-10 |
| CA2472246A1 (en) | 2003-07-10 |
| JP5212761B2 (ja) | 2013-06-19 |
| CN1617939A (zh) | 2005-05-18 |
| EP1468121A1 (en) | 2004-10-20 |
| FI114553B (sv) | 2004-11-15 |
| AU2002352310A1 (en) | 2003-07-15 |
| ATE532881T1 (de) | 2011-11-15 |
| JP2013056946A (ja) | 2013-03-28 |
| CN100390301C (zh) | 2008-05-28 |
| JP2005513161A (ja) | 2005-05-12 |
| KR100943835B1 (ko) | 2010-02-24 |
| CA2472246C (en) | 2011-09-20 |
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