WO2015157617A1 - Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography - Google Patents
Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography Download PDFInfo
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- WO2015157617A1 WO2015157617A1 PCT/US2015/025271 US2015025271W WO2015157617A1 WO 2015157617 A1 WO2015157617 A1 WO 2015157617A1 US 2015025271 W US2015025271 W US 2015025271W WO 2015157617 A1 WO2015157617 A1 WO 2015157617A1
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- WIPO (PCT)
- Prior art keywords
- resin
- hto
- mixture
- sorbitol
- resin material
- Prior art date
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- 230000005661 hydrophobic surface Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 101150068863 ispE gene Proteins 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 description 1
- XLMFDCKSFJWJTP-UHFFFAOYSA-N pentane-2,3-diol Chemical compound CCC(O)C(C)O XLMFDCKSFJWJTP-UHFFFAOYSA-N 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
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- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
- B01D15/1821—Simulated moving beds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/10—Vacuum distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- B01J35/19—
-
- 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
- C07C29/15—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 oxides of carbon exclusively
- C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/007—Promoter-type Additives
Definitions
- the present invention relates to the synthesis and recovery of a hydrogenolysis product using chromatographic techniques.
- the invention pertains to the separation and purification of polyols derived from the hydrogenolysis of e sugar alcohols.
- Biomass contains carbohydrates or sugars (i.e., hexoses and pentoses) that can be converted into value added products from renewable hydrocarbon sources.
- Sugar alcohols such as sorbitol, mannitol, iditol, arbitol or xylitol, are one kind of sugar-derived compounds that can be further transformed into various kinds of materials, which in turn can be further modified.
- HTO 1 ,2,5,6-hexanetetrol
- Urbas claimed the synthesis of "3,4- dideoxyhexitol" (1 ,2,5,6-hexanetetrol) via the catalytic hydrogenolysis of sorbitol, in a stirred batch reaction using 85% CuO and 15%o Cr203 under 184-150atm H 2 at 200°C for 3 hrs and the subsequent acid catalyzed dehydration of 1,2,5,6-HTO to 2,5-bis(hydroxymethy)tetrahydrofuran (U.S. Patent No. 4,820,880).
- Montassier describes a heterogeneous catalysis of sorbitol by a retro-Michael reaction to selectively yield glycerol from sorbitol favored on certain copper-based catalysts.
- Ludwig mentions 1 ,2,5,6-HTO as a nearly 4% wt by-product in the synthesis of diols from sucrose, in a batch reaction, using CoO, CuO, Mn304, H3PO4, and M0O3 at 160C, under 280 bar H 2 , for three hours but does not claim any methods for purification of the 1,2,5,6-HTO (DE 3928285 Al).
- 1 ,2,5,6-HTO and other polyols having fewer oxygen atoms than carbon atoms may be considered a "reduced polyols.”
- Corma et al. disclose generally that higher molecular weight polyols containing at least four carbon atoms can be used to manufacture polyesters, alkyd resins, and polyurethanes. (Corma et al., "Chemical Routes for the Transformation of Biomass into Chemicals," 107 Chem. Rev. 2443 (2007)). 1,2,5,6-HTO is mentioned, for example, as a starting material for the synthesis of diols (International Patent Application No.
- 1,2,5,6-HTO is of primary commercial interest as a feedstock for the synthesis of adipic acid via continuous, selective oxidation.
- Adipic acid is used industrially to produce polyurethanes, plasticizers, lubricant components, polyester, and as food ingredient.
- Adipic acid's primary industrial outlet is in the production of Nylon-6,6 fibers and resins which, in 2010, accounted for 65% of the di-carboxylic acid's total 2.6MM tons produced globally (See, e.g., Polen, T., et al., Journal of Biotechnology 167 (2013) 75- 84).
- the present disclosure describes, in part, a method for the isolation and purification of 1 ,2,5,6-hexanetetrol (HTO) (C6H14O4) from a reaction mixture derived from hydrogenolysis of sugar alcohols.
- the method involves: contacting a mixture comprising HTO and other O-C6 alcohols and polyols with a resin adapted for chromatographic use, under conditions where HTO preferentially associates with the resin relative to other components in the mixture, and eluting HTO from the resin with a solvent.
- the resin employed is a non-functionalized material although other functionalized resin may also be used.
- SMB simulated-moving-bed
- FIG. 1 A is a flow chart representing conventional process for preparing and separating polyols from a hydrogenolysis reaction of sorbitol.
- FIG IB is a flow chart showing an alternative conventional process for preparing and separating polyols from a hydrogenolysis reaction of sorbitol.
- FIG. 1C is a flow chart illustrating another conventional process for preparing and separating polyols from a hydrogenolysis reaction of sorbitol.
- FIG. 2 is a flow chart showing a process for preparing and purifying 1 ,2,5,6-HTO from a hydrogenolysis reaction of sorbitol showing differences according to an embodiment of the present invention.
- FIG. 3 is a graph showing pulse test results for the chromatographic separation of processed sorbitol hydrogenolysis reaction mixture.
- FIG. 4 is a graph showing pulse test results with zones dividing analytes.
- FIG. 5 is a diagram of a 500cc simulated moving bed (SMB) system configured according to an embodiment of the present invention.
- FIG. 6 is a graph showing the percent adsorption vs resin loading for sorbitol from thin-film evaporative (TFE) distillate bottoms.
- FIG. 7 is a graph showing the percent adsorption vs resin loading for 1 ,2,5,6-HTO from thin- film evaporative (TFE) distillate bottoms.
- FIG. 8 is a graph showing the relative selectivity of a chromatographic resin (e.g., V493) according to an embodiment of the present invention for 1,2,5,6-HTO from sorbitol.
- a chromatographic resin e.g., V493
- FIG. 9 is a graph showing the capacity of a non-functionalized resin (V493) according to an embodiment of the present invention for 1 ,2,5,6-HTO separation.
- bed volume or "column volume” refers to the total volume of the packing material and interstitial liquid.
- the minimum volume of solvent necessary to wet the defined quantity of sorbent within the column can vary on the nature of the sorbent (e.g., -120 ⁇ per 100 mg of silica gel sorbent 6 ⁇ , compared to -600 ⁇ per 500 mg of silica gel sorbent 6 ⁇ ).
- chromatographic resolution refers to the degree of separation between consecutive analytes emerging from a chromatographic column.
- step-time refers to the interval or dwelling time that a chromatographic columns in a simulated-moving bed chromatographic device remains at a particular position before the position rotates.
- the present invention describes, in part, a process for the separation and purification of chemicals derived from hydrogenolysis of sugar alcohols.
- Sorbitol hydrogenolysis is known to produce 1,2,5,6-hexanetetrol (HTO) and other polyols, although typically the reaction conditions are harsh and not economical.
- HTO 1,2,5,6-hexanetetrol
- Various approaches can be used to make HTO.
- U.S. Patent No. 4,820,880 discloses a method for producing HTO that involves heating a solution of a hexitol in an organic solvent with hydrogen at an elevated temperature and pressure in the presence of a copper chromite catalyst.
- Exemplary starting hexitols include sorbitol and mannitol.
- 6,841,085 discloses methods for the hydrogenolysis of 6-carbon sugar alcohols, including sorbitol, involving reacting the starting material with hydrogen at a temperature of at least 120°C in the presence of a rhenium-containing multi-metallic solid catalyst.
- Nickel and ruthenium catalysts were disclosed as traditional catalysts for sorbitol hydrogenolysis, however these catalyst predominantly produced lower level polyols such as glycerol and propylene glycol and were not shown to detectably produce HTO or hexanetriols. (The contents of U.S. Patent Nos. 4,820,880, and 6,841 ,085, are incorporated herein by reference.)
- PCT/US2014/033580 and PCT/US2014/033581 the relevant contents of which are incorporated herein by reference.
- the processes described in these application involve contacting a solution comprising water and at least 20% wt/wt of a starting compound selected from the group consisting of a C(, sugar alcohol and a R-glycoside of a Ce sugar, wherein R is a methyl or ethyl group, with hydrogen and a Raney copper catalyst for a time and at a temperature and pressure sufficient to produce a mixture containing one or more of the reduced sugar alcohols with a combined selectively yield of at least 50%o mol/mol.
- the reaction solution comprises 20-30%o wt./wt.
- the solution comprises 20-30%o wt./wt. water and 50-55%o wt./wt. propylene glycol.
- These methods provide a combined selectivity yield for the reduced sugar alcohols of at least 70%o mol/mol.
- a specific embodiment for making 1 ,2,5,6-hexanetetrol involved contacting a solution comprising 20-30%o wt./wt. water, 45-55%o of propylene glycol and at least 20%o wt./wt.
- the selectivity yield for 1 ,2,5,6-hexanetetrol is at least 40%o wt./wt.
- Figure 1 A is a flow chart that illustrates typical standard purification methods. The protocol involves first reacting sorbitol solution 7 in a hydrogenolysis reactor 2, transferring the hydrogenolysis-reaction, polyol-product mixture 3 to an evaporator 4 to drive off water and low- boiling alcohols 4a (e.g., methanol and ethanol), then subjecting the resulting dewatered polyol reaction mixture 5 to one or more distillations 6 and collecting the high-boiling polyols 6a (e.g., propylyene glycol (PG), ethylene glycol (EG), glycerol).
- PG propylyene glycol
- EG ethylene glycol
- glycerol e.g., glycerol
- the remaining crude bottoms products 7 are subjected to one or more rounds of crystallization 8 to remove any residual higher- boiling polyols and unreacted sugar alcohols 8a (e.g., Ce triols, sorbitol), and produce a concentrated and purified HTO product 9.
- the evaporator or distillations
- Figure 1C illustrates an alternative protocol that does not use an evaporator but involves solvent or liquid-liquid extraction (LLE) technique, in one or more solute contained in a feed solution is transferred to another immiscible liquid solvent.
- the present purification process is simpler involving less steps or more cost efficient techniques.
- the present process employs a resin adapted for chromatographic purposes to separate and purify HTO from hydrogenolysis reaction mixtures.
- the present method involves a combination of evaporation and simulated-moving bed
- FIG. 2 presents a flow chart according to an embodiment of the present invention.
- sorbitol solution 7 in a hydrogenolysis reactor 2
- polyol-product mixture 3 to an evaporator 4 to drive off water, low-boiling alcohols, and O- C 5 diols 4a (e.g., MeOH, EtOH, PG, EG, 2,3-PeDO)
- de-ionized water (DI) 4b is added to dilute the polyol mixture 5, which is then subjected to chromatographic separation 6 using either non- functionalized or functionalized resins.
- the separation is performed with a non- functionalized resin in a simulated-moving bed (SMB) chromatographic device.
- SMB simulated-moving bed
- the de-ionized water serves to dissolve the mixture and make the solution less viscous.
- the evaporator in the present purification does not need to remove glycerol, only the lower boiling diols. This is because these lower boiling diols tend to retain on the SMB chromatographic resin, eluting along with the HTO, hence causing purity problems.
- Isolation and purification of 1 ,2,5,6-hexanetetrol (HTO) by means of a combined process of evaporation and simulated-moving bed chromatography (SMBC) using an industrial grade resin has advantages over conventional processes.
- the present invention contributes to a refinement of chromatographic separation techniques for difficult to purify organic species. These advantages include, for examples, cost savings and process efficiency associated with a continuous single-step separation method which more easily lends itself to high throughput automation, in contrast to the conventional need to employ multiple batch or semi-batch distillations.
- Another advantage is the ability to collect HTO product at a greater yield and purity.
- the inventive approach compares favorably to conventional approaches, in that it can be more efficient and cost effective than current processes.
- LC liquid chromatography
- LC typically utilizes different types of stationary phases (i.e. sorbents) contained in columns, a pump that moves the mobile phase and sample components through the column, and a detector capable of providing characteristic retention times for the sample components and area counts reflecting the amount of each analyte passing through the detector.
- Analyte retention time varies depending on the strength of its interactions with the stationary phase, the composition and flow rate of mobile phase used, and on the column dimensions.
- relatively large diameter columns and large particle sizes are employed to avoid pressure.
- DI deionized
- the elution is with DI water alone.
- the water and alcohol may be present respectively in a ratio in a range from about 50:1 to 1 :50 (e.g., 40:1, 35:1, 25:1, 20:1 , 12:1, 10:1, 5:1, or 1 :30, 1 :25, 1 :20, 1 :10, 1 :8, etc.).
- the particular yields and purity of the separated 1,2,5,6-HTO can vary depending on the operational conditions. Nonetheless, according to embodiments of the present process, one can achieve about at least 40-45% wt./wt. yield, and about 70-75% purity. Typically, the yield is much higher, such as reported in Table 4, below. In general, examples of yield can range from about 50%o or 55%o wt./wt. to about 92% or 95%> wt./wt., inclusive.
- the yield is in a range from about 60%> or 65%> wt./wt. to about 88%o or 92% wt./wt. (e.g., 63%, 68%, 70%, 75%, 80%, 85%, 90% wt/wt).
- the level of purity is about 80% or 85% to about 97% or 99.9%. More typically, the level of purity is about 86% or 87% to about 96% or 98%.
- the present invention can employ either functionalized or non-functionalized resins.
- the non-functionalized resins appear to perform better.
- Non-functionalized resins do not bind the different species by means of an ionic charge; rather, non-functionalized resins work by a balance of hydrophilic and hydrophobic affinities.
- the adsorbent resins are unmodified and considered to be hydrophobic resins. Thus, hydrophobic organic species can bind to them and be retained in aqueous systems.
- the pH range of the input material can be in a range from about 0 to about 14.
- the pH is about 5 to about 8, and desirably about 6.5 to about 7.5.
- the post-evaporative hydrogenolysis reaction mixture should be acidic, with a pH value of less than 7.
- the reaction mixture typically will have a pH of about 2.5 to about 5.8 or 6.5, more typically about 5.5 - 6.0.
- an adjustment of the pH of the input material may be needed for base functionalized resins.
- the post-evaporative reaction mixture will have a pH in a range of about 7 to about 14. Typically, this pH range is about 7 to about 9.5, and desirably about 7 to about 7.5.
- a type of resin employed in the separation of HTO can be classified as adsorbent poly(styrene-divinyl benzene) (PS-DVB) resins.
- PS-DVB resins are an attractive adsorbent for extraction and separation of various types of compounds due to its stability over the pH range of 1 -14.
- PS-DVB resins are known to have hydrophobic surfaces that highly retain non-polar compounds while poorly retaining polar compounds .
- Hydrophobic -type PS-DVB resins are commercially available from a variety of vendors (e.g., Dow Chemical Company, Rohm & Haas Co., Mitsubishi Chemical Corporation, Purolite Corporation, Lanxess Corporation, etc.). Depending on the manufacturer and the particular specifications of each type of resin, the resin can have a variety of different pore sizes and surface areas, which can affect the physical and chemical nature of the resins, the quality of the separation and therefore the temperatures required for the different protocols. One can use a resin that has a surface area in the range between about 120 m 2 /g or 150 m 2 /g up to about 1 100 m 2 /g or 1200 m 2 /g.
- the surface area of the resin is in between about 150 m 2 /g or 200 m 2 /g to about 800 m 2 /g or 1000 m 2 /g.
- the resin has a surface area of about 250 or 300 m 2 /g to about 600 or 750 m 2 /g.
- the average pore diameter can range between about 50 A or 100 A to about 600 A or 700 A; typically between about 100 A or 150 A to about 450 A or 500 A.
- the mean diameter of the resin particles may range between about 300 ⁇ or 350 ⁇ to about 750 ⁇ or 800 ⁇ ; typically, between about 400 ⁇ or 500 ⁇ to about 650 ⁇ or 700 ⁇ .
- the resins exhibit porosity in the range of about 0.90 or 0.95 ml/g to about 1.40 or 1.52 ml/g; typically about 0.97 ml/g to about 1.18 or 1.25 ml/g.
- adsorbent resins exhibit non-polar or hydrophobic tendencies, this means that they preferentially adsorb the more hydrophobic organic compounds that are dissolved in water relative to polar compounds.
- a class of commercial ion-exchange resins from Rohm & Haas is AMBERLITETM XADTM polymeric adsorbents, which are very porous spherical polymers based on highly crosslinked, macroreticular polystyrene polymers. Their high internal surface areas can adsorb and then desorb a wide variety of different species depending on the environment in which they are used. For example, in polar solvents such as water, polymeric adsorbents exhibit non-polar or hydrophobic behavior and can adsorb organic species that are sparingly soluble. This
- hydrophobicity is most pronounced with the styrenic adsorbents.
- non-polar solvents such as hydrocarbons, etc.
- most adsorbents exhibit slightly polar or hydrophilic properties and so will adsorb species with some degree of polarity. This polarity is most pronounced with the acrylic adsorbents and the phenolic adsorbents.
- the mean diameter particle size of the resins can range from about 200 ⁇ to about 850 ⁇ . Typically, the particles are in a range from about 250 ⁇ to about 500 ⁇ , and desirably about 300 ⁇ to about 450 ⁇ .
- SMB chromatography utilizes a column bed containing the stationary phase resin segmented into a plurality of column segments, which are moved in a countercurrent direction relative to the input flow of the moving phase sample and eluent.
- the segments of the column in the SMB apparatus are typically mounted on a carousel beneath input ports for sample and eluent and output ports for raffmate and product.
- a SMB chromatographic separation can be run continuously with a constant flow of feed being input into one port, a constant flow eluent entering a second port, a constant flow of raffmate being withdrawn from a third port, and a constant flow of product being withdrawn from a fourth port.
- SMB chromatography can thus be optimized to purify a stream of 1 ,2,5,6-HTO in a continuous fashion. Pulse tests discussed in the following section provide a basis to evaluate different conditions and resins for application in SMB chromatography.
- Figure 3 shows the results of a typical pulse test for the separation of 1,2,5,6-HTO and sorbitol, and the relative effectiveness of the present process to separate various different kinds of polyols or organic materials.
- the resolution for unreacted sorbitol, glycerol, erythitol, and threitol from 1 ,2,5,6 HTO in the hydrogenolysis reaction mixture can be achieved in a continuous chromatographic system.
- Persons of skill in the art understand that the separation performance of other particular resins may be either better or worse than that which is shown in the present illustrative results, and should be adjusted in each individual case may dictate.
- a pulse test result is divided into zones in order to translate the pulse test separation to a continuous simulated moving bed system (SMB).
- Theoretical zone flow rates for adaptation to a SMB separation method are determined from the pulse test, as detailed in Table 2.
- Table 3 shows the actual flow rates for zones adapted to a 12 column, combined 500 cc, carousel- type, SMB chromatography system, loaded with a Gaussian non-functionalized resin (V493), configured according to the diagram in Figure 5.
- V493 Gaussian non-functionalized resin
- V493 Gaussian non-functionalized resin
- the sorbitol hydrogenolysis reaction mixture thin-film evaporative (TFE) distillate bottoms processed according to the method detailed above, were diluted to approximately 30% wt.
- the resin materials may be subject to an operational temperature that ranges from about 10°C or 15°C to about 95°C or 100°C, so long as the mechanism of chromatography is not adversely interfered with to impede flow.
- the temperature is at about ambient room temperature or in a range from about 18°C or 20°C to about 75°C or 90°C (e.g., 22°C, 27°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 78°C, 80°C, 85°C).
- the temperature range can be from about 15°C or 20°C to about 88°C or 100°C for the non-functionalized resins.
- the temperature range can be from about 17°C or 20°C to about 50°C or 60°C for the functionalized resins.
- Table 5 presents operational ranges flow rates as prescribed according to certain embodiments, but which may vary and can influence the operational parameters of the SMB chromatography.
- Table 6 shows the flow rate for an amount of material that can be processed when constant bed volume (BV) and column volume is used, and step-time (ST) is variable.
- ST step-time
- the flow can be expressed in terms of bed volumes (BV) for use in potential industrial scale operations.
- Table 7 shows the parameters for flow rate range when the step time (ST) and column volume are constant and BV is variable - Low (0 to 3 BV), Medium (>3 to 8 BV), and High (>8 to >10 BV).
- Sorbitol solution was fed into the 165°C - 200°C reactor at 0.5-1.0 hr "1 , under 1800 psi 3 ⁇ 4 flowing at 20 SCFM.
- the reactor product was sampled and prepared by derivatizing with pyridine and acetic anhydride at 70°C and analyzed using a J&W DB-5 MS UI column (30m x 0.25mm x 0.25um) on an Agilent 7890 equipped with an FID detector. Samples were analyzed for water using a Mettler Toledo volumetric Karl Fischer auto-titrator. Carboxylate analysis was performed with a Showdex SH-1011 strong acid ion exchange analytical column (300 x 7.8mm) on an Agilent 1260 HPLC equipped with a diode array detector at 210 nm.
- the method of purifying 1 ,2,5,6 hexanetetrol from a reaction mixture containing HTO and other byproducts of a hydrogenation reaction of a sugar alcohol and/or a mono- or di-dehydrative product of a sugar alcohol involves:
- the sugar alcohol can be for example: sorbitol, mannitol, galactitol, fucitol, iditol, inositol, maltitol, and mixtures thereof.
- the hydrogenolysis product mixture was contacted with an ion exchange (IX) resin before contacting the effluent with a resin material adapted for chromatography because the sorbitol hydrogenolysis reaction employed sodium hydroxide as a homogeneous co- catalyst along with the heterogeneous NiRe on carbon catalyst.
- the IX resin is used to purify the reaction mixture by removing ionic organic and inorganic species before the mixture is fed into the chromatographic separation columns.
- the ion exchange reaction can be either 1) a single-step mixed-bed reaction, or 2) a two-step acid-first, base-second reaction or the reverse base-first, acid- second reaction.
- the fraction of the ion exchange reactions can be concentrated by evaporation.
- the evaporation method can be selected from the group consisting of vacuum evaporation, thin film evaporation (TFE), and a combination of both vacuum and TFE.
- vacuum evaporation can be performed at a temperature between about 1 10°C to about 160°C, and under a pressure in a range from about 100 Torr to about 10 Torr.
- TFE can be performed at a temperature in a range from about 150°C to about 175°C or 180°C, under a pressure from about 10 Torr to less than 1 Torr (e.g., 0.1 Torr).
- Table A summarizes the analyte distribution from the hydrogenolysis reaction.
- the reaction mixture was then passed over strong acid (Dowex 88) and strong base (Dowex 22) ion exchange resins to remove sodium and carboxylates respectively.
- the ion exchanged reaction mixture was heated, under vacuum, to remove water, volatile alcohols (methanol, ethanol, propanol) and finally propylene and ethylene glycols.
- the bottoms from the evaporation comprised primarily of sorbitol, glycerol, C Cs-sugar alcohols, 1 ,2,5,6-HTO other triols and trace diols, was then fed into a 2-inch Pope thin film evaporator (TFE) in the molecular still (internal condenser) configuration to remove glycerol.
- TFE thin film evaporator
- the hydrogenolysis reaction mixture was preheated to 75°C and fed at a rate of 3.87 g/min, into the Pope still.
- the TFE skin temp was set at 160°C
- the bottoms temp was 95°C
- the blade speed was 505 rpm
- the internal condenser was kept at 63°C
- the vacuum was held at 9.7 Torr.
- the final distillate fractions were pooled and bottoms and distillate analyzed.
- the bottoms fraction from the TFE was used for resin experiments detailed below.
- Carboxylic Acids include: Glyceric, Glycolic, Lactic, Formic, Acetic, Levulinic, Propionic; C4-Sugar Alcohols include: Erythritol, Threitol;
- C5-Sugar Alcohols include: Xylitol, Arabitol;
- Triols include: 1 ,2,3-Butanetriol, 1 ,2,4-Butanetriol, 1,2,5-Pentanetriol, 1,2,6- Hexanetriol, 1,4,5-Hexanetriol, 1,2,5-Hexanetriol.
- Figures 6 and 7 show the percent (%) adsorption for each of the four resins described in the foregoing, at increasing loading, for sorbitol and 1,2,5,6-HTO respectively.
- the figures contrast adsorbency and capacity of the resins.
- the Type I strong base anion resin (Dowex 1X8) demonstrated the best performance of the four kinds of sample resin materials for adsorbing sorbitol at about 32-78% per resin/sorbitol (g/g). This amount of sorbitol adsorbed is about 10%> to about 20-28%> greater than the next best performing resin material (AMBERLITETM XAD1600N), which is a non-functionalized resin and it adsorbed about at about 17%>-50%>. The two other remaining resins - non-functionalized (Optipore V493) and strong acid-functionalized (Dowex Monosphere 99/310) - performed comparable to the XAD1600N material.
- the material that performed the best for adsorbing 1,2,5,6-HTO appears to be a Gaussian non-functionalized resin (Optipore V493), which adsorbed about 20% to about 65%> of the HTO per amount resin/HTO (g/g).
- This non-functionalized resin adsorbed about 5-7%> more than the next best performing material which is a mono-dispersed non-functionalized resin material (AMBERLITE XAD1600N).
- the performance of the two remaining acid and base functionalized resins were comparable but at a little less (e.g., difference of ⁇ 5-10%) absorbency than that of the non-functionalized resins.
- Table B summarizes the data for each of the beaker tests.
- the results of these beaker tests suggested, surprisingly, that the Gaussian non-functionalized resin (V493) had the best selectivity for 1 ,2,5,6-HTO and was selected for use in subsequent pulse tests.
- a slurry of non-functionalized adsorptive resin (V493), in deionized water was added to a #11 Ace Glass jacketed chromatography column (1.10 cm ID x 45 cm L) to the 43 cc mark.
- the column was capped with Teflon adapters and connected using 0.0625" Teflon tubing and Swagelok fittings to a peristaltic pump at the influent and an automatic fraction collector at the effluent.
Abstract
Description
Claims
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MX2016013208A MX2016013208A (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography. |
CA2945144A CA2945144A1 (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromatography |
AU2015243402A AU2015243402B2 (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography |
US15/302,411 US9732020B2 (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromatography |
BR112016023499A BR112016023499A2 (en) | 2014-04-10 | 2015-04-10 | Methods for Purifying 1,2,5,6-Hexanotetrol |
EP15776787.2A EP3129342A4 (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography |
CN201580028097.XA CN106414384B (en) | 2014-04-10 | 2015-04-10 | The method of the own tetrol of 1,2,5,6- is separated from D-sorbite hydrogenolysis mixture using Simulated Moving Bed Chromatography method |
KR1020167030817A KR20160146780A (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography |
JP2016561730A JP2017515803A (en) | 2014-04-10 | 2015-04-10 | Process for isolating 1,2,5,6-hexanetetraol from a sorbitol hydrocracking reaction mixture using simulated moving bed chromatography |
US15/649,106 US10017439B2 (en) | 2014-04-10 | 2017-07-13 | Process for the isolation of reaction products from sugar alcohol or anhydrosugar alcohol hydrogenolysis reaction mixtures using simulated moving bed chromatography |
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US15/649,106 Continuation-In-Part US10017439B2 (en) | 2014-04-10 | 2017-07-13 | Process for the isolation of reaction products from sugar alcohol or anhydrosugar alcohol hydrogenolysis reaction mixtures using simulated moving bed chromatography |
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PCT/US2015/025369 WO2015157671A1 (en) | 2014-04-10 | 2015-04-10 | Synthesis of shorter chain polyols |
PCT/US2015/025271 WO2015157617A1 (en) | 2014-04-10 | 2015-04-10 | Process for the isolation of 1,2,5,6-hexanetetrol from sorbitol hydrogenolysis reaction mixtures using simulated moving bed chromotography |
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EP (3) | EP3129363B1 (en) |
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CN106279197A (en) * | 2016-08-04 | 2017-01-04 | 山东福田药业有限公司 | The purification of isosorbide reaction solution and crystallization processes |
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US11247956B2 (en) | 2018-04-20 | 2022-02-15 | Wisconsin Alumni Research Foundation | Catalytic production of 1,2,5,6-hexanetetrol from levoglucosenone |
CN109734756A (en) * | 2019-02-28 | 2019-05-10 | 山东兆光色谱分离技术有限公司 | A kind of method of chromatographic isolation maltitol |
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- 2015-04-10 CA CA2945327A patent/CA2945327A1/en not_active Abandoned
- 2015-04-10 RU RU2016141812A patent/RU2016141812A/en unknown
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US20090120878A1 (en) * | 2007-11-09 | 2009-05-14 | Archer-Daniels-Midland Company | Separation of a mixture of polyhydric alcohols |
US20130172586A1 (en) * | 2011-12-30 | 2013-07-04 | E I Du Pont De Nemours And Company | Production of tetrahydrofuran-2, 5-dimethanol from isosorbide |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106279197A (en) * | 2016-08-04 | 2017-01-04 | 山东福田药业有限公司 | The purification of isosorbide reaction solution and crystallization processes |
CN106279197B (en) * | 2016-08-04 | 2018-06-15 | 山东福田药业有限公司 | The purifying of isobide reaction solution and crystallization processes |
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