WO2018116272A1 - Procédé de séparation de cétoses - Google Patents

Procédé de séparation de cétoses Download PDF

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Publication number
WO2018116272A1
WO2018116272A1 PCT/IB2017/058352 IB2017058352W WO2018116272A1 WO 2018116272 A1 WO2018116272 A1 WO 2018116272A1 IB 2017058352 W IB2017058352 W IB 2017058352W WO 2018116272 A1 WO2018116272 A1 WO 2018116272A1
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WIPO (PCT)
Prior art keywords
fructose
allulose
solution
filtrate
mixture
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PCT/IB2017/058352
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English (en)
Inventor
Sibnath RAY
Anindya SIL
Banibrata Pandey
Original Assignee
Petiva Private Ltd.
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Filing date
Publication date
Application filed by Petiva Private Ltd. filed Critical Petiva Private Ltd.
Publication of WO2018116272A1 publication Critical patent/WO2018116272A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K11/00—Fructose
    • 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

Definitions

  • the present invention relates to a process for separating ketoses. More specifically, the invention relates to a process for separating D-Allulose from an aqueous feed mixture comprising D-Allulose and at least one other ketose.
  • the known processes for production of D-Allulose (earlier known as psicose), on a commercial scale have one or more disadvantages due to absence of economical methods for separating D-Allulose and fructose.
  • the widely-used processes are: 1) Removal of fructose by yeast fermentation; and 2) Simulated Moving Bed (SMB) method using phenol- formaldehyde resin with Ca 2+ .
  • the present invention provides a process for separating D-Allulose from an aqueous feed mixture comprising D-Allulose and at least one other ketose, particularly, fructose.
  • the process comprises: adding calcium chloride to the solution comprising D-Allulose and fructose to get a mixture; drying the mixture obtained in the above step; adding aqueous ethanol to the dried mixture to precipitate the fructose as a hydrated addition compound of said calcium chloride; filtering the precipitate formed and recovering the fructose from the precipitate; collecting the filtrate comprising calcium addition D-Allulose and recovering the D-Allulose from the filtrate.
  • FIG. 1 shows chromatogram of bio-converted fructose D-Allulose mixture by DPEase enzyme
  • FIG. 2 shows chromatogram of fructose-D-Allulose mixture after spray drying
  • FIG. 3 shows chromatogram of calcium addition fructose dehydrate solid compound after 95% aqueous ethanol extraction
  • FIG. 4 shows chromatogram of calcium addition D-Allulose compound in 95% aqueous ethanol extract
  • FIG. 5 shows chromatogram of fructose after crystallization
  • FIG. 6 shows chromatogram of D-Allulose after crystallization.
  • the present disclosure provides a process for separating D-Allulose from an aqueous feed mixture comprising D-Allulose and at least one other ketose.
  • the process comprises:
  • alkaline earth metal salt to the solution comprising D-Allulose and at least one other ketose
  • ketoses include, but are not limited to, ketohexose (all six- carbon, ketone-containing sugars, including fructose), ketopentose (all five-carbon ketone containing sugars, including xylulose and ribulose), ketotetrose (all four-carbon, ketose containing sugars, including erythrulose), and ketotriose (all three-carbon ketose containing sugars, including dihydroxyacetone).
  • the alkaline-earth metal salt may be halide of alkaline- earth metal. In certain embodiments, the alkaline-earth metal salt is calcium chloride.
  • fructose and D-Allulose have similar solubility in anhydrous ethanol and the solubility of both sugar fructose and D- Allulose is enhanced in anhydrous ethanol in the presence of calcium chloride.
  • a large amount of white crystalline precipitate is formed at room temperature. The precipitate is not dissolved even after temperature is raised to 50 °C.
  • D-Allulose-Ca complex is completely soluble in anhydrous ethanol at the same temperature and even at 0 °C.
  • the present disclosure provides a process for separating D-Allulose from a solution comprising a mixture of pscicose and fructose.
  • the process comprises the steps of:
  • the sugar and salt mixtures of different final concentrations (30-90 % w/v) are concentrated by rotary evaporation to obtain different molality mixture with respect to total solutes.
  • the molality range may be from about 70 to about 90 molal with respect to total solute.
  • the sugar concentration is from about is 40-50% w/v.
  • the total sugar to calcium chloride mole ratio is from about 1:0.5 to 1:2. In a further embodiment, the total sugar to calcium chloride mole ratio is 1: 1.
  • the resultant mixture may be filtered to remove any undesired and insoluble materials present in the mixture. Any method known in the art can be used for the filtration. In certain embodiments, the mixture is filtered through a micro filtration device.
  • the resulting solution may be dried to achieve desired moisture values. Any known method for drying the filtrate can be employed.
  • the resulting solution is dried to get powder using spray drying technique in which a spray drier is used.
  • the inlet and outlet temperature of the spray drier is maintained in the range of 100 °C to 200 °C and 40 °C to 90 °C, respectively.
  • the inlet and outlet temperature of the spray drier is typically maintained in the range of 100 °C to 150 °C and 40 °C to 50 °C, respectively.
  • the inlet and outlet temperature of the spray drier is about 130 °C and about 40 °C, respectively.
  • the spray drying can be carried out with a feed rate of about 15 RPM, aspirator speed varying from about 1350 RPM to about 2000 RPM, and under vacuum varying from about -100 mmWC to about -200 mmWC.
  • Other process conditions during the spray drying may be maintained as follows: feed concentration: 30-70%; and vacuum: pumping speed: from about 5 RPM to about 200 RPM.
  • the moisture content of resultant dried powder is from about 0% to about 30%. In certain embodiments, it is from about 2% to about 5%. In a further embodiment, it is about 4%.
  • the dried powder is then extracted with ethanol containing 0-30% water.
  • the dried powder is extracted with about 95 % ethanol water system (ethanol 95% + water 5%).
  • the amount of 95% ethanol can be used is one part to five parts, preferably, two parts with respect to sugar-salt powder produced.
  • the temperature employed for the extraction is from about 0° to 35° C, preferably 10-25° C. At elevated temperature fructose also enters solution rendering its separation from D-Allulose incomplete.
  • the optimum extraction time of D-Allulose-calcium complex from the fructose-calcium complex can be done for 1-6 h. In certain embodiments, it is 2-3 h.
  • the precipitate dehydrated calcium salt of fructose
  • the precipitate is very stable, nonhygroscopic, and readily filterable. Further, it is not very much contaminated with D-Allulose.
  • the calcium chloride used in the process may be any commercial product. Although, commercial products of calcium chloride contain various impurities such as iron chloride, aluminum chloride, zinc chloride and sodium chloride, these impurities are harmless in the practice of the present process. Even when 3-5% of these impurities are admixed with calcium chloride purposed no obstacle is experienced.
  • the ethanol used in the process may be any commercial ethanol or recovered ethanol which contains no water or at most a few percent of water.
  • the dehydrated fructose-Ca salt (precipitate obtained) can be isolated using any filtration method known in the art. In certain embodiments, it is filtered using 10-11 micron filter under vacuum. The solid is washed with ethanol to get rid of the absorbed D-Allulose-Ca complex in solid, if any. The purity of the solid obtained is about 97% to about 99%.
  • the ethanoic filtrate contains predominantly D-Allulose-Ca salt ranging from about 75-90%, fructose about 10-15% and glucose about 4-5%. The conversion of fructose to glucose is observed depending on the temperature of extraction and duration of extraction.
  • the fructose from the addition compound (precipitate, dehydrated fructose-Ca salt) obtained as above is dissolved in equal parts of water and calcium content.
  • the calcium is removed by treating with equimoles of sulfates such as sodium sulphate and ammonium sulfate, followed by filtration of said calcium sulfate.
  • sodium sulfate is used for double decomposition of calcium sulfate.
  • the filtrate is concentrated to remove water and then it is made about 95% solution with respect to ethanol to remove the other salt from the solution.
  • the remaining salt is removed by using ion exchange resin (cation and anion exchange resin).
  • aqueous solution of fructose solution is concentrated to about 85-90 molal by vacuum evaporation and two parts of absolute ethanol is added with respect to the syrup weight and heated to about 50-70°C to dissolve the fructose.
  • fructose seed of about 1% is added to the solution and the temperature is decreased to about 15-25 °C, at a decreasing rate of 1 °C per hour with constant stirring.
  • crystallization is performed at a temperature of about 15-25°C with gentle agitation and recovered the fructose crystals.
  • the crystallization yield obtained is about 80-85% of total sugar and purity of fructose obtained is about 99.7%.
  • D-Allulose In order to recover the D-Allulose from alcoholic solution, equimolar saturated sodium sulfate solution is added to alcoholic solution of calcium adduct D-Allulose compound with constant stirring at room temperature and incubated for 1-2 h for calcium sulfate and sodium chloride precipitation. The precipitates are separated by filtration. Ethanol is recovered by vacuum distillation. Then, the D-Allulose enriched syrup is diluted to equal amount of water and remaining salt is removed passing aqueous solution of D-Allulose through cation and anion exchange column simultaneously. The color is removed passing the active charcoal column.
  • ion free solution is filtered through the micron filter to remove the contaminant particles and aqueous solution of D-Allulose solution is concentrated to 85-90 molal by vacuum evaporation and two parts of absolute ethanol is added with respect to syrup weight and heated to about 50-70°C to dissolve the fructose into alcohol.
  • the D-Allulose seed upto 1% is added to solution and the temperature is reduced to about 15-25°C at a decreasing rate of 1 °C per hour with constant stirring.
  • the crystallization is initiated at a temperature of about 15-25 °C with gentle agitation.
  • the crystallization yield obtained is about 70-85% of total sugar and purity of the D-Allulose obtained is about 99.7%.
  • calcium chloride is particularly referred to as the inorganic compound which is capable of information of an addition compound with fructose in the process of this invention.
  • other form of calcium salt like calcium bromide and iodide deposited with fructose in presence of ethanol.
  • strontium chloride is the only compound which exhibits the same behavior as calcium chloride among the compounds of the other members of the same alkaline earth metal group as calcium, because no magnesium compounds and barium compounds proved to deposit the addition compound under similar conditions.
  • strontium chloride is employed in place of calcium chloride for the formation of the addition compound with fructose in the process of the invention, the removal of strontium chloride from the addition compound may be carried out in the same manner as that for calcium chloride as previously described.
  • the present process is very advantageous to separate D-Allulose from fructose with any distribution proportion in their mixture.
  • This separation process can be applicable for any monosaccharide, di-saccharide and oligosaccharide preferably to their structural differences.
  • this process is advantageous to separate any sugar mixture containing pyranose and furnanose form.
  • Calcium complex with furanose sugar forms stable complex in their mono- or di-hydrated forms, which is less soluble in anhydrous ethanol.
  • calcium complex of pyranose sugars forms is highly soluble in anhydrous ethanol.
  • the ethanol used in the present process can be reused for extraction and crystallization process.
  • Adsorbed ion in ion exchange resin can be regenerated to the raw material and reused for this separation process and thus the less effluent generated in this current inventive process
  • an element means one element or more than one element.
  • feed mixture refers to a mixture containing one or more extract components and one or more raffinate components to be separated by this process.
  • raffinate refers to liquid phase which is recovered after separating the insoluble matrix or compound.
  • solubility of fructose, D-Allulose and their mixture in anhydrous ethanol in the presence of anhydrous calcium chloride was tested. Fructose and D-Allulose and mixture thereof were treated with calcium chloride. Then, small quantity of water was added and stirred at room temperature for few hours for calcium sugar complex formation and precipitation. The precipitate was filtered. The sugar composition and yield were analyzed by HPLC. Precisely, to 2 gm of fructose, 2 gm of D-Allulose and lgm each of fructose and D-Allulose was added 0.5 ml of water to make 80 molal syrup concentrations separately in beaker.
  • FIG. 1 shows the chromatogram of bio-converted fructose D-Allulose mixture as starting material.
  • Anhydrous calcium chloride used was 11.25 gm and 16.87 gm to 22.5 gm based on the fructose content on fructose-D-Allulose mixture.
  • Different fructose to calcium mole ratios (1 :0.5, 1 :0.75 and 1: 1) were used.
  • Aqueous solution of the sugar and calcium chloride mixture were spray dried to make as free flowing powder. Spray drying condition was used for this purpose are as follows:
  • fructose-D-Allulose (80:20) mixture brix of the sugar solution 45%
  • anhydrous calcium chloride solution in such a way that fructoseiCaCh mole ratio is 1: 1.
  • the sugar and salt solution was prepared by constant stirring at room temperature for an hour and filtered through micron filtered to remove the dust particle.
  • the filtered solution fed in spray dryer with pump speed of 5 RPM, inlet and outlet temperature was set to 130 °C and 40 °C, respectively. Vacuum applied -100 mmWC with Aspiration RPM 1350.
  • the free- flowing powder obtained in this process was 1184 gm with recovery yield of 88 %.
  • the powder as prepared in example 3 with the sugar composition (D-Allulose 20.47%, fructose 78.28% and glucose 1.25%) was used for separation of calcium addition compound of fructose by 5% aqueous content ethanol extraction.
  • 1 kg of spray dried powder extracted with 2 L of 95% aqueous ethanol with constant stirring by overhead stirrer setting RPM 250 at 25 °C for three hours.
  • the resultant precipitate was filtered under vacuum and washed with 200 ml of anhydrous ethanol and dried under vacuum.
  • the weight of the solid obtained was 788 gm and purity of fructose obtained was 98.5 % and D-Allulose content is 1.5%.
  • the calcium and sugar composition were analyzed by ICP-OES and HPLC methods, respectively.
  • Figure 3 shows the sugar composition of solid material obtained after aqueous ethanol extraction. The analysis results are depicted in Table 4 below.
  • Table 4 Material analysis data of calcium addition fructose dehydrate compound after aqueous ethanol (95 % ethanol content):
  • Example 4 The solid obtained in Example 4 was used for recovery of fructose from its calcium complex compound.
  • calcium equimolar sodium sulfate (Na 2 S04) (148 gm) was dissolved in 1.2 L of water by setting overhead stirrer at a speed of 250 rpm at room temperature.
  • 500 gm of calcium-fructosate solid (as described in example 4) was added slowly with constant stirring for one hour.
  • the precipitate thus obtained was filtered under vacuum and washed with 250 ml of water spraying on top.
  • Filtrate containing fructose and sodium chloride passed sequentially through one set of cation exchange, followed by two sets of anion exchange and one set of charcoal column with each column dimension of (100 cmx 5 cm) with feed flow rate of 10 ml per minute at 40 °C. Then, pH and conductivity were adjusted to 6.5 and 10 ⁇ 8/ ⁇ , respectively using 100 gm of cation and anion exchange mixed resin and filtered through micron filtered to remove undesired particles.
  • Example 4 2.2 L of ethanoic filtrate obtained from Example 4 was processed for recovery of D- Allulose from its calcium addition compound. The total sugar content in this mixture was 156 gm. HPLC analysis (as shown in FIG. 5) showed that composition is having D- Allulose (85.8%), fructose (11.5%), and glucose (2.6%),
  • the 2.2 L of ethanoic solution was treated with saturated aqueous solution of sodium sulfate.
  • the saturated solution was prepared by dissolving 98.2 gm Na 2 S0 4 in 700 ml water at room temperature. Removal calcium from D-Allulose containing sugar solution was done by slow addition of saturated solution of Na 2 S0 4 with constant stirring at a speed of 200 RPM. The solution was incubated at room temperature for one hour for complete decomposition of sodium sulfate to calcium sulfate (CaS0 4 ) and sodium chloride (NaCl).
  • the ion free aqueous D-Allulose rich solution was concentrated to 85 % (w/w) by vacuum evaporation for crystallization.
  • the weight of the syrup obtained was 183 gm.
  • 450 ml absolute ethanol was added to the 85 molal sugar solutions and incubated at 60°C for 2 hours at constant stirring until D-Allulose rich syrup dissolved completely.
  • the D-Allulose seed up to 1% of total sugar's weight was added to the solution and the temperature was slowly reduced to 16 °C, at a decreasing rate of 1°C per hour with constant stirring. Then, the crystallization was initiated at 16 °C with gentle agitation for 16 hours.
  • the crystallization yield obtained was 80 % of total sugar and purity of the D-Allulose obtained was 97.1% and fructose was 2.1% (shown in Figure 6). The remaining liquid mixed with main stream of crystallization.
  • Calcium-fructose (1:2) and calcium-D-Allulose (1: 1) complex produced by the present process can be used as food supplement for osteoporosis and calcium deficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un procédé de séparation de D-Allulose à partir d'un mélange d'alimentation aqueux comprenant du D-Allulose et au moins un autre cétose, en particulier, du fructose. Le procédé, selon l'invention consiste à : ajouter du chlorure de calcium à la solution comprenant du D-Allulose et du fructose pour obtenir un mélange ; sécher le mélange obtenu dans l'étape ci-dessus ; ajouter l'éthanol aqueux au mélange séché pour précipiter le fructose en tant que composé d'addition hydraté dudit chlorure de calcium ; filtrer le précipité formé et récupérer le fructose à partir du précipité ; collecter le filtrat comprenant le calcium et le D-Allulose et récupérer le D-Allulose à partir du filtrat.
PCT/IB2017/058352 2016-12-23 2017-12-22 Procédé de séparation de cétoses WO2018116272A1 (fr)

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IN201641044094 2016-12-23
IN201641044094 2016-12-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109748940A (zh) * 2018-12-04 2019-05-14 吉林中粮生化有限公司 一种从乙醇溶液中结晶阿洛酮糖的方法
CN114210101A (zh) * 2021-11-19 2022-03-22 山东润德生物科技有限公司 一种氨基葡萄糖水解液中产物的分离系统
CN115219628A (zh) * 2022-07-19 2022-10-21 东阿阿胶股份有限公司 一种复方阿胶浆的前处理方法和复方阿胶浆中低聚糖的检测方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3533839A (en) * 1966-02-16 1970-10-13 Kazuo Hara Process for separating fructose from glucose
US4692514A (en) * 1985-12-20 1987-09-08 Uop Inc. Process for separating ketoses from alkaline- or pyridine-catalyzed isomerization products
US4785794A (en) * 1986-01-17 1988-11-22 Institut National Polytechnique De Toulouse Method for processing aqueous sugar juice for separating ketose
CA1292988C (fr) * 1987-08-11 1991-12-10 Chin-Hsiung Chang Procede de separation de la psicose d'autres cetoses
FI84839C (fi) * 1987-08-12 1992-01-27 Uop Inc Foerfarande foer separering av psicos fraon andra ketoser.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3533839A (en) * 1966-02-16 1970-10-13 Kazuo Hara Process for separating fructose from glucose
US4692514A (en) * 1985-12-20 1987-09-08 Uop Inc. Process for separating ketoses from alkaline- or pyridine-catalyzed isomerization products
US4785794A (en) * 1986-01-17 1988-11-22 Institut National Polytechnique De Toulouse Method for processing aqueous sugar juice for separating ketose
CA1292988C (fr) * 1987-08-11 1991-12-10 Chin-Hsiung Chang Procede de separation de la psicose d'autres cetoses
FI84839C (fi) * 1987-08-12 1992-01-27 Uop Inc Foerfarande foer separering av psicos fraon andra ketoser.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109748940A (zh) * 2018-12-04 2019-05-14 吉林中粮生化有限公司 一种从乙醇溶液中结晶阿洛酮糖的方法
CN114210101A (zh) * 2021-11-19 2022-03-22 山东润德生物科技有限公司 一种氨基葡萄糖水解液中产物的分离系统
CN115219628A (zh) * 2022-07-19 2022-10-21 东阿阿胶股份有限公司 一种复方阿胶浆的前处理方法和复方阿胶浆中低聚糖的检测方法

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