WO2014080269A1 - Process for the production and separation of mannitol and sorbitol from a mixture which was obtained by hydrogenation of a precursor - Google Patents
Process for the production and separation of mannitol and sorbitol from a mixture which was obtained by hydrogenation of a precursor Download PDFInfo
- Publication number
- WO2014080269A1 WO2014080269A1 PCT/IB2013/002597 IB2013002597W WO2014080269A1 WO 2014080269 A1 WO2014080269 A1 WO 2014080269A1 IB 2013002597 W IB2013002597 W IB 2013002597W WO 2014080269 A1 WO2014080269 A1 WO 2014080269A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mannitol
- sorbitol
- fraction
- substrate
- syrup
- Prior art date
Links
- 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 title claims abstract description 101
- 235000010355 mannitol Nutrition 0.000 title claims abstract description 99
- 229930195725 Mannitol Natural products 0.000 title claims abstract description 97
- 239000000594 mannitol Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000002243 precursor Substances 0.000 title claims abstract description 12
- 239000000600 sorbitol Substances 0.000 title claims description 66
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 title claims description 64
- 239000000203 mixture Substances 0.000 title claims description 18
- 238000000926 separation method Methods 0.000 title claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 12
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 title description 56
- 238000004519 manufacturing process Methods 0.000 title description 20
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 239000006188 syrup Substances 0.000 claims description 67
- 235000020357 syrup Nutrition 0.000 claims description 67
- 238000013375 chromatographic separation Methods 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- 239000012452 mother liquor Substances 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 235000000346 sugar Nutrition 0.000 claims description 18
- 239000005715 Fructose Substances 0.000 claims description 16
- 229930091371 Fructose Natural products 0.000 claims description 15
- 150000008163 sugars Chemical class 0.000 claims description 15
- 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 description 14
- 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 14
- 229960004903 invert sugar Drugs 0.000 claims description 8
- 235000019534 high fructose corn syrup Nutrition 0.000 claims description 5
- 150000005846 sugar alcohols Chemical class 0.000 claims description 5
- 229920001202 Inulin Polymers 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 3
- 229940029339 inulin Drugs 0.000 claims description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 235000014633 carbohydrates Nutrition 0.000 claims description 2
- 239000007858 starting material Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 2
- 235000010356 sorbitol Nutrition 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- 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 14
- 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 13
- 239000000243 solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000008103 glucose Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000012527 feed solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 3
- 108010057081 Merozoite Surface Protein 1 Proteins 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011210 chromatographic step Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008121 dextrose Substances 0.000 description 2
- 235000021433 fructose syrup Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002231 fructose derivatives Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 235000021096 natural sweeteners Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
Definitions
- the present invention concerns an improved method for the processing of substrates containing a starting material (precursor) of mannitol, wherein all of the fractions obtained can be recovered, thus eliminating waste.
- Mannitol is a polyol (sugar alcohol) widely used as a natural sweetener, anti-caking agent, and/or filler. It is the hydrogenation product of fructose or mannose.
- mannitol During hydrogenation of fructose, only 50% of the substance is converted to mannitol, while the remainder is hydrogenated into sorbitol.
- Mannose is not commercially available per se, but can be produced from glucose by means of a chemical isomerisation process. A mixture of glucose and mannose is thus obtained that is then hydrogenated.
- Suitable and economically available substrates containing a mannitol precursor to be used for the production of mannitol may be selected among the following: sucrose, invert sugar (a mixture of roughly identical amounts of glucose and fructose), HFCS, fructose and glucose and/or polymers rich in fructose or mannose.
- Patent 3,864,406 a method is described for separating a mixture of sorbitol and mannitol obtained by hydrogenation of invert sugar.
- the mixture is subjected to chromatographic fractionation, yielding highly pure fractions of mannitol and sorbitol.
- the described method is non-continuous and results in considerable dilution of the various fractions.
- the fructose syrup can be separately hydrogenated and further processed in order to separate out the mannitol.
- Another method of using this fructose fraction consists of subjecting it to isomerisation to obtain an invert syrup, which can then be subjected in combination with the starting material to the chromatography step.
- WO 2012/045985 does not concern the simultaneous production of high-purity sorbitol and crystalline mannitol.
- a parallel hydrogenation step will be required. This can then be followed by a crystallisation step in which crystalline mannitol and a second sorbitol-rich fraction are obtained.
- An alternative method can comprise chromatographic separation of the hydrogenated material followed by crystallisation of the mannitol fraction.
- the production of high-purity sorbitol ( ⁇ 0.2% total reducing sugars) and crystalline mannitol from a source (substrate) containing a precursor (starting material) of mannitol comprises at least four steps, specifically at least one chromatographic separation, two hydrogenations, and a crystallisation step.
- total reducing sugars refers to the amount of reducing sugars as determined by Bertrand's gravimetric method after acidic treatment of the sorbitol fraction.
- German patent publication DE 196 12 826 describes an alternative method for the production of high-purity sorbitol.
- the high-purity sorbitol obtained via this process must contain at least 99.5% sorbitol and less than 0.15% total reducing sugars.
- a glucose syrup containing 97 to 99% glucose based on dry matter (DM) is used as a starting material.
- the described process comprises a chromatographic separation method in which a sorbitol solution containing 98-99% sorbitol is processed in a specified chromatographic column configuration in which three fractions are obtained. Conversion from one fraction to the next is performed depending on the refractive index of the eluates.
- the high-purity sorbitol obtained in DE 196 12 826 and WO 2012/045985 is particularly well-suited for use in chemical reactions requiring high thermal stability (such as the production of isosorbide, sorbitan esters, or polyether polyols).
- the object of the present invention can be defined as a technically feasible method for the simultaneous production of a high-purity sorbitol fraction and crystalline mannitol together with a second sorbitol-rich fraction using a substrate containing a precursor of mannitol.
- the method should comprise only a limited number of steps, it should be conducted using only simple, commonly- known production equipment, it should be applicable to various substrates, and all of the fractions obtained by the method should be recovered as high-added-value products.
- the object of the invention is achieved by providing a method for the separation of a substrate containing a mannitol precursor into several fractions comprising the following steps:
- a first sorbitol fraction of high purity containing less than 0.2% total reducing sugars, and preferably less than 0.15% total reducing sugars, and
- Step (b) specifically chromatographic separation of the hydrogenated substrate, takes place by means of a continuous process, i.e., chromatographic separation takes place by conducting repeated cycles of steps without interruption.
- mannitol-rich is to be understood as referring to a fraction containing at least 60% mannitol based on dry matter, preferably at least 64% mannitol DM, and more preferably at least 67% mannitol DM.
- the first sorbitol fraction (X) preferably contains at least 98% sorbitol.
- the first sorbitol fraction should contain ⁇ 0.2%, and more preferably ⁇ 0.15% total reducing sugars.
- at least two and at most six resin beds connected in series are used for chromatographic separation.
- one of the following separation protocols is used for chromatographic separation: SSMB, ISMB, MCI or NMCI. The choice of the specific protocol depends on the substrate.
- the substrate used for this method is preferably a carbohydrate composition containing fructose and/or mannose.
- the substrate is selected among one of the following compositions: invert sugar, glucose-fructose syrup, fructose- enriched syrups, inulin hydrolysate, or mannose-containing syrup.
- Mannose- containing syrup can be obtained by chemical isomerisation of glucose or by hydrolysis of glucomannans. After hydrogenation of these substrates, refining may be conducted prior to the chromatographic step (step b) in order to increase the stability of the chromatographic separation process.
- Typical resins used for chromatographic separation of polyols are sulphonated polystyrenes in calcium form, with a suitable degree of divinylbenzene (DVB) crosslinking that imparts physical stability to the resin.
- the sulphonic acid function of the resin particles causes swelling in aqueous media.
- the resulting microporous resin beads can absorb water and non-ionically dissolved substances.
- Typical ranges of crosslinking are 2-15%, with crosslinking of 3-8% being preferred.
- DIAION UBK 555 Mitsubishi Chemical Corporation
- DOWEX * MONOSPHERE * N279 Ca The Dow Chemical Company.
- hydrogenated compositions subjected to chromatographic separation contain, on a dry matter basis, approximately 20-60% mannitol, approximately 40-80%) sorbitol, and 0.1 -5% other sugar alcohols, with the total of the various components not exceeding 100%. More preferably, hydrogenated compositions subjected to chromatographic separation contain, on a dry matter basis, 23-30% mannitol, 70-78% sorbitol and 0.1-5% other sugar alcohols.
- steps (c) and (d) are omitted, and following step (a), the hydrogenated substrate is subjected to a crystallisation step in which a third fraction is formed with crystalline mannitol, and a mother liquor. Subsequently the mother liquor is subjected to chromatographic separation according to step (b), after which the mannitol-rich subtraction formed is recirculated to the hydrogenated substrate for crystallisation.
- fig. 1 is a schematic diagram of the method according to the invention.
- FIG. 2 is a schematic diagram of the alternative embodiment of the method according to the invention.
- fig. 3 is a schematic diagram of a device suitable for carrying out chromatographic separation according to the method of the invention.
- the method according to the present invention is suitable for processing a substrate (1) containing a mannitol precursor, such as invert sugar, glucose-fructose syrup, fructose-enriched syrups, hydrolysates of inulin, and mannose-containing syrup in such a manner that a high-purity sorbitol fraction (X), crystalline mannitol (Z), and a sorbitol-rich fraction (Y) can be produced simultaneously.
- the substrate (1) is first hydrogenated to obtain a hydrogenated substrate (2).
- this hydrogenated substrate (2) is subjected to a chromatographic separation step that yields a mannitol-rich fraction (zl), a high-purity sorbitol fraction (X) containing a minimum of 98% sorbitol and ⁇ 0.2%, and preferably ⁇ 0.15% total reducing sugars, and a second sorbitol-rich fraction (Y).
- the mannitol-rich fraction (zl) is then subjected to a crystallisation step. After this crystallisation step, the crystalline mannitol (Z) is separated from the mother liquor (3), which in turn is added to the hydrogenated substrate (2).
- This method is shown schematically in Fig. 1.
- the hydrogenated substrate (2) is first subjected to crystallisation, with a portion of the mannitol present being recovered in crystalline form, and the mother liquor is then subjected to chromatographic separation.
- This mother liquor (3) is thus separated into a high- purity sorbitol fraction (X) containing at least 98% sorbitol and ⁇ 0.2%, and preferably ⁇ 0.15% total reducing sugars, a second sorbitol-rich fraction (Y), and a mannitol-enriched fraction (zl) that is recirculated to the hydrogenated substrate for crystallisation.
- X high- purity sorbitol fraction
- Y second sorbitol-rich fraction
- zl mannitol-enriched fraction
- Chromatographic separation is conducted using equipment having a limited number of resin beds connected in series, with the number of beds varying from 2 to 6.
- Various separation protocols may be used in this process, such as SSMB, ISMB, MCI or NMCI, depending on which protocol is most suitable for the substrate used.
- the chromatographic separation process involves the use of two resin beds connected in series (4a and 4b), with the method comprising repetition of the following steps (cf. Fig. 3) :
- the column is now heated to 85 °C and fed with 40 Bx glucose syrup (96% dextrose DM) at 0.5 BV/hr.
- the effluent of the column is collected and simultaneously analysed for mannose content.
- the feeding rate of the molybdate-packed column is adjusted so as to maintain a mannose content of 26% ⁇ 1% DM at the outlet of the column.
- the syrup from Example 1 is purified by passage over a Dowex 88 resin bed in H+ form (a strongly acidic cation exchange resin manufactured by the Dow Chemical Company) and a Dowex 66 resin bed in free amine form (a weakly basic anion exchanger manufactured by the Dow Chemical Company) connected in series.
- a Dowex 88 resin bed in H+ form a strongly acidic cation exchange resin manufactured by the Dow Chemical Company
- a Dowex 66 resin bed in free amine form a weakly basic anion exchanger manufactured by the Dow Chemical Company
- the refined syrup is concentrated to 50 Bx, and 3% w/w of 5% Ru/CP catalyst 9017 (BASF) is added.
- the suspension is added to a reactor and heated to 105 °C while stirring at a pressure of 40 bar H 2 until consumption of H 2 stops.
- the reactor is cooled down, the catalyst is filtered off, and the clear syrup is introduced at 0.5 BV/hr over a Dowex MSA-1 resin bed (a macroporous, strongly basic anion exchange resin manufactured by the Dow Chemical Company) in OH- form at 60 °C in order to remove the remaining reducing sugars.
- Dowex MSA-1 resin bed a macroporous, strongly basic anion exchange resin manufactured by the Dow Chemical Company
- the syrup is further refined by being passed at 30 °C and 2 BV/hr over a Lewatit S8528 resin bed in H+ form (a weakly acidic cation exchange resin manufactured by Lanxess).
- the pH of the refined syrup is adjusted to 6.0 by adding 0.05 N NaOH.
- Isosweet 111 a high- fructose syrup produced by Syral Belgium NV, is diluted to 50 Bx and 3% w/w of 5% Ru/CP 9017 catalyst (BASF) is added.
- the suspension is added to a reactor and heated to 105 °C while stirring at an H 2 pressure of 40 bar until consumption of H 2 stops.
- the reactor is cooled down, the catalyst is filtered off, and the clear syrup is introduced at 0.5 BV/hr over a Dowex MSA-1 resin bed (a macroporous, strongly basic anion exchange resin manufactured by the Dow Chemical Company) in OH- form at 60 °C in order to remove the remaining reducing sugars.
- Dowex MSA-1 resin bed a macroporous, strongly basic anion exchange resin manufactured by the Dow Chemical Company
- the syrup is further refined by feeding at 30 °C and 2 BV/hr over a Lewatit S8528 resin bed in H+ form (a weakly acidic cation exchange resin manufactured by Lanxess).
- the pH of the refined syrup is adjusted to 6.0 by adding 0.05 N NaOH.
- the chromatographic separation equipment is shown schematically in Fig. 3 and comprises 2 double-walled columns (4a and 4b) in series, each 1 m in height, with a usable internal volume of 2.35 L, which are stored at 80 °C.
- the columns are filled with DIAION UBK 555 (Mitsubishi Chemical Corporation) separation resin.
- the system further comprises 3 tanks temperature-controlled to 80 °C: a 20 L syrup storage tank (8), a 2 L syrup feeding tank (5), and a 50 L demineralised water tank
- the system further comprises a syrup metering pump (6), a circulation pump
- the separation process comprises repetition of the following steps:
- 0.5 L of mannitol syrup from the syrup feeding tank is introduced at 1.4 L/hr at the top of column 1 (4a), while at the same time, 0.5 L of product fraction (zl) (mannitol fraction) is collected at the outlet port of column 2 (4b).
- 0.126 L of demineralised water from the demineralised water tank (9) is introduced at 1.4 L/hr at the top of column 2 (4b), and at the same time, 0.126 L of product from the outlet port of column 2 (4b) is recirculated to the syrup feeding tank (5) of the chromatographic separation system.
- the inlet port of column 1 and outlet port of column 2 are connected via the circulation pump, and the product is circulated via the outlet port of column 2 to the inlet port of column 1 for 26 minutes at a flow rate of 1.4 L/hr.
- the inlet port of column 1 and the discharge port of column 2 are connected via the circulation pump, and the product is circulated via the outlet port of column 2 to the inlet port of column 1 for 53 minutes at a flow rate of 1.4 L/hr.
- This syrup is placed in a 3 L lab crystalliser (brand name Labo Service Belgium) and heated to 80 °C for three h. After this, the crystalliser is cooled while gently stirring at a rate of 1 °C/hr. D-mannitol crystals (Merck 1.05980.9050) are added as a seed material when the temperature in the crystalliser reaches 72 °C. The content of seed material is 0.2% DM of the feed solution. Cooling is continued at 1 °C/hr to 30 °C. The crystallised mass is transferred to a Rousselet-Robatel RC30VxR centrifuge, and the crystals and mother liquor are separated. The crystal cake is washed three times at room temperature with 30 mL demineralised water per kg of crystals.
- the mother liquor and washing solution are collected and mixed at a ratio of 1/3.8 parts DM/DM with the mannitol syrup produced as in Example 2.
- the resulting syrup has a mannitol content of 29.3% and is concentrated to 55 Bx.
- This syrup is now used as feed solution for another process of 6-step chromatographic separation as described above.
- the mannitol fractions (no. 1 fractions) from the first 5 cycles are removed.
- the mannitol fractions of the following 25 cycles are collected and concentrated into a mannitol syrup with 71% purity and a content of 56% DM at a similar mannitol to water ratio as that of the mannitol syrup having a content of 57% DM and 67.9% purity.
- the new mannitol syrup is now subjected to the same cycle of crystallisation, crystal separation, and washing as described above.
- the mother liquor and washing solution are collected and mixed at a ratio of 1/3.8 parts DM/DM with the mannitol syrup produced in Example 2.
- the resulting syrup has a mannitol purity of 30.0% DM and is concentrated to 55 Bx.
- This process which comprises: a) production via chromatography of a mannitol fraction suitable for crystallisation, b) production during crystallisation, crystal separation, and washing of a combined mother liquor and washing solution fraction,
- the separation process comprises repetition of the following steps:
- 0.45 L of mannitol syrup from the syrup feeding tank is introduced at a flow rate of 1.4 L/hr at the top of column 1, while at the same time, 0.45 L of product fraction
- 0.176 L of demineralised water from the demineralised water tank is introduced at 1.4 L/hr at the top of column 2, and at the same time, 0.176 L of product from the outlet port of column 2 is recirculated to the syrup feeding tank (5) of the chromatographic separation system.
- the inlet port of column 1 and the discharge port of column 2 are connected via the circulation pump, and the product is circulated via outlet column 2 to the inlet port of column 1 for 26 minutes at a flow rate of 1.4 L/hr.
- This syrup is placed in a 3 L lab crystalliser (brand name Labo Service Belgium) and heated to 80 °C for three h. After this period, the crystalliser is cooled while gently stirring at a rate of 1 °C/hr. D-mannitol crystals (Merck 1.05980.9050) are added as a seed material when the temperature in the crystalliser reaches 72 °C. The content of seed material is 0.2% DM of the feed solution. Cooling is continued at 1 °C/hr to 30 °C. The crystallised mass is transferred to a Rousselet-Robatel RC30VxR centrifuge, and the crystals and mother liquor are separated.
- the crystal cake is washed three times at room temperature with 30 mL demineralised water per kg of crystals.
- the mother liquor and washing solution are collected and mixed at a ratio of 1/4 parts DM/DM with the mannitol syrup produced as in Example 3.
- the resulting syrup has a mannitol content of 23.9% and is concentrated to 55 Bx.
- This syrup is now used as feed solution for next 6-step chromatographic separation as described above.
- the mannitol fractions (zl fractions) of the first 5 cycles are removed.
- the mannitol fractions of the following 25 cycles are collected and concentrated to a mannitol syrup having a purity of 64.7% and content of 58% DM, with a similar ratio of mannitol to water as that of the mannitol syrup having a content of 59.3% DM and 61.3% purity.
- the new mannitol syrup is now subjected to the same cycle of crystallisation, crystal separation, and washing as described above.
- the mother liquor and washing solution are collected and mixed at a ratio of 1/4 parts DM with the mannitol syrup produced in Example 2.
- the resulting syrup, with a mannitol content of 24.5%, is concentrated to 55 Bx.
- This process which comprises the following: e) production by chromatography of a mannitol fraction suitable for crystallisation, f production during crystallisation, crystal separation, and washing of a combined mother liquor and washing solution fraction, g) mixing of this combined mother liquor and washing solution fraction at a ratio of 1/4 parts DM with a mannitol syrup produced as in Example 3, and h) concentration of the mixture obtained to 55 Bx before it is subjected to the chromatographic separation of step e) above, is repeated two more times until all of the fractions show a stable composition.
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380061055.7A CN104812728A (en) | 2012-11-22 | 2013-11-20 | Process for production and separation of mannitol and sorbitol from mixture which was obtained by hydrogenation of precursor |
BR112015011204A BR112015011204A8 (en) | 2012-11-22 | 2013-11-20 | process for the production and separation of mannitol and sorbitol from a mixture which was obtained by hydrogenation of a precursor |
US14/646,958 US20150307424A1 (en) | 2012-11-22 | 2013-11-20 | Process for the production and separation of mannitol and sorbitol from a mixture which was obtained by hydrogenation of a precursor |
EP13821932.4A EP2928853A1 (en) | 2012-11-22 | 2013-11-20 | Process for the production and separation of mannitol and sorbitol from a mixture which was obtained by hydrogenation of a precursor |
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BEBE-2012/0791 | 2012-11-22 | ||
BE2012/0791A BE1021455B1 (en) | 2012-11-22 | 2012-11-22 | METHOD FOR PROCESSING SUBSTRATES INCLUDING A MANNITOL BASE. |
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PCT/IB2013/002597 WO2014080269A1 (en) | 2012-11-22 | 2013-11-20 | Process for the production and separation of mannitol and sorbitol from a mixture which was obtained by hydrogenation of a precursor |
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US (1) | US20150307424A1 (en) |
EP (1) | EP2928853A1 (en) |
CN (2) | CN104812728A (en) |
BE (1) | BE1021455B1 (en) |
BR (1) | BR112015011204A8 (en) |
WO (1) | WO2014080269A1 (en) |
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CN105211673A (en) * | 2015-09-18 | 2016-01-06 | 南京理工大学 | For the compound anti-caking agent in food-grade potassium chloride |
CN115784838A (en) * | 2022-12-07 | 2023-03-14 | 浙江华康药业股份有限公司 | Method for co-producing mannitol crystal and sorbitol crystal by using crystalline glucose |
Citations (9)
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AU3771172A (en) | 1972-01-07 | 1973-07-12 | C S R Chemicals Ltd | Separation of sorbitol and mannitol |
US3864406A (en) | 1973-04-25 | 1975-02-04 | Suomen Sokeri Oy | Process for the production of mannitol and sorbitol |
US4456774A (en) * | 1981-12-10 | 1984-06-26 | Union Carbide Corporation | Bulk separation of polyhydric alcohols by selective adsorption on zeolitic molecular sieves |
EP0202168A1 (en) | 1985-05-15 | 1986-11-20 | Roquette Frˬres | Process and device for the crystallization of mannitol |
DE19612826A1 (en) | 1996-03-30 | 1997-10-02 | Dhw Deutsche Hydrierwerke Gmbh | Preparation of highly pure sorbitol for use in e.g. chemical synthesis and in food industry |
US6649754B1 (en) * | 1999-06-25 | 2003-11-18 | Merck Patent Gmbh | Method for producing mannitol |
JP2009036536A (en) * | 2007-07-31 | 2009-02-19 | Japan Organo Co Ltd | Method for separating sugar and alcohol |
WO2012045985A1 (en) | 2010-10-08 | 2012-04-12 | Roquette Freres | Method for manufacturing high-purity sorbitol syrups from sucrose and uses thereof |
Family Cites Families (6)
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CH444132A (en) * | 1965-04-01 | 1967-09-30 | Hefti Aktiengesellschaft Chem | Process for the production of mannitol |
US4029878A (en) * | 1975-05-19 | 1977-06-14 | Ici United States Inc. | Process for preparing mannitol from glucose |
JPS5277007A (en) * | 1975-12-19 | 1977-06-29 | Towa Kasei Kogyo Kk | Method of producing aqueous hexose and hexoseealcohol containing solution |
FR2694019B1 (en) * | 1992-07-22 | 1994-10-14 | Roquette Freres | Process for the production of mannitol. |
CN100540672C (en) * | 2006-12-27 | 2009-09-16 | 山东西王糖业有限公司 | A kind of method of utilizing glucose mother liquid to produce N.F,USP MANNITOL |
CN101066984B (en) * | 2007-05-28 | 2010-05-19 | 江门量子高科生物股份有限公司 | Preparation process of hydrogenated oligofructos |
-
2012
- 2012-11-22 BE BE2012/0791A patent/BE1021455B1/en not_active IP Right Cessation
-
2013
- 2013-11-20 BR BR112015011204A patent/BR112015011204A8/en not_active Application Discontinuation
- 2013-11-20 US US14/646,958 patent/US20150307424A1/en not_active Abandoned
- 2013-11-20 CN CN201380061055.7A patent/CN104812728A/en active Pending
- 2013-11-20 EP EP13821932.4A patent/EP2928853A1/en not_active Ceased
- 2013-11-20 WO PCT/IB2013/002597 patent/WO2014080269A1/en active Application Filing
- 2013-11-20 CN CN201910588395.4A patent/CN110256197A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3632656A (en) | 1967-04-13 | 1972-01-04 | Atlas Chem Ind | Crystallization of mannitol |
AU3771172A (en) | 1972-01-07 | 1973-07-12 | C S R Chemicals Ltd | Separation of sorbitol and mannitol |
US3864406A (en) | 1973-04-25 | 1975-02-04 | Suomen Sokeri Oy | Process for the production of mannitol and sorbitol |
US4456774A (en) * | 1981-12-10 | 1984-06-26 | Union Carbide Corporation | Bulk separation of polyhydric alcohols by selective adsorption on zeolitic molecular sieves |
EP0202168A1 (en) | 1985-05-15 | 1986-11-20 | Roquette Frˬres | Process and device for the crystallization of mannitol |
US4670611A (en) * | 1985-05-15 | 1987-06-02 | Roquette Freres | Method and installation for the crystallization of mannitol |
DE19612826A1 (en) | 1996-03-30 | 1997-10-02 | Dhw Deutsche Hydrierwerke Gmbh | Preparation of highly pure sorbitol for use in e.g. chemical synthesis and in food industry |
US6649754B1 (en) * | 1999-06-25 | 2003-11-18 | Merck Patent Gmbh | Method for producing mannitol |
JP2009036536A (en) * | 2007-07-31 | 2009-02-19 | Japan Organo Co Ltd | Method for separating sugar and alcohol |
WO2012045985A1 (en) | 2010-10-08 | 2012-04-12 | Roquette Freres | Method for manufacturing high-purity sorbitol syrups from sucrose and uses thereof |
Also Published As
Publication number | Publication date |
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BR112015011204A2 (en) | 2017-07-11 |
US20150307424A1 (en) | 2015-10-29 |
BR112015011204A8 (en) | 2019-10-01 |
EP2928853A1 (en) | 2015-10-14 |
CN104812728A (en) | 2015-07-29 |
CN110256197A (en) | 2019-09-20 |
BE1021455B1 (en) | 2015-11-26 |
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