EP3356563B1 - Verfahren zur anreicherung von arabinosefraktionen - Google Patents

Verfahren zur anreicherung von arabinosefraktionen Download PDF

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Publication number
EP3356563B1
EP3356563B1 EP16784983.5A EP16784983A EP3356563B1 EP 3356563 B1 EP3356563 B1 EP 3356563B1 EP 16784983 A EP16784983 A EP 16784983A EP 3356563 B1 EP3356563 B1 EP 3356563B1
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Prior art keywords
arabinose
liquid
acid
range
treatment
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French (fr)
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EP3356563A1 (de
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Henricus Wilhelmus Carolina Raaijmakers
Joannes Gerardus Maria Van Nispen
Jacobus Petrus Maria Bink
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Cooeperatie Koninklijke Cosun Ua
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Koninklijke Cooperatie Cosun UA
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    • 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 methods of processing arabinose fractions, especially to methods of enriching arabinose fractions containing, besides arabinose mineral acid and salt. These methods are particularly suitable in the (industrial-scale) production of high-purity crystalline arabinose from crude arabinose extracts produced from plant materials.
  • the present invention also pertains to the enriched arabinose fractions and the crystalline arabinose materials that can be obtained with these methods.
  • L-Arabinose is a non-caloric sweetener which has taste characteristics similar to sucrose and shows little absorbability.
  • the carbohydrate chemistry of the human body centers around sugars with 'D' configurations.
  • No human enzyme can synthesize or digest sugars of 'L' configurations.
  • the non-enzymatic chemistry and general properties of L- sugars should be essentially identical to their D-counterparts. This makes L-arabinose and the L-counterparts of common sugars such as L-fructose, L-glucose and L-sucrose interesting sweeteners; they should taste like D-sugars yet cannot be metabolized by human enzymes.
  • L-fructose, L-glucose and L-sucrose do not occur naturally.
  • L-arabinose on the other hand can be obtained from natural sources in substantial amounts, which make L-arabinose a very non-nutritive sweetener as well as an important starting material for synthesizing other non-nutritive sweeteners, in particular for synthesizing the L-counterparts of common sugars.
  • L-arabinose also has been proposed as a starting material for producing certain drug substances.
  • plant derived materials include mesquite gum, cherry gum, peach gum, rye and wheat bran, beet pulp and in the wood of coniferous trees.
  • the content of these hemicelluloses is substantial.
  • 20-30% of the pectic substance in sugar beet is araban.
  • the wood of genus Larix may contain 25% L-araban-D-galactan.
  • the present inventors have developed a process that meets this need.
  • the invention in one aspect, resides in the discovery that mineral acids can efficiently be removed from crude arabinose fractions obtained in 'conventional' extraction processes, using the subsequent steps of cation exchange treatment and nanofiltration.
  • Methods of the invention comprise the steps of treating an arabinose fraction containing arabinose, at least one mineral acid, and at least one metal cation containing compound, using cation exchange treatment, typically aimed at the replacement of metal cations for protons, followed by nanofiltration, typically aimed at the separation of arabinose and mineral acid (anions), yielding a retentate as the enriched arabinose fraction.
  • the invention provides processes of producing high-purity crystalline L-arabinose, comprising the step of producing an enriched arabinose fraction using the method of the invention, and treating it so as to induce crystallization of arabinose.
  • the invention provides processes of producing an arabinose fraction containing arabinose, at least one mineral acid, and at least one metal cation containing compound from crude arabinose extracts, typically derived from plant material, and subsequently subjecting it further enriching it using the method of the invention.
  • the invention pertains the intermediate and end-products obtainable by the methods described herein.
  • a first aspect of the invention concerns a method of enriching and/or purifying an arabinose fraction, said method comprising the consecutive steps of:
  • the term 'arabinose fraction' is used to refer to the arabinose containing fraction that is obtained in a respective step of the process.
  • the arabinose fraction will contain arabinose, optionally in combination with other solid constituents, as specified throughout this document.
  • the type and (relative) amount of any other constituent of the arabinose fraction may vary, depending on the step of the process in which it is produced, as will be understood by those skilled in the art.
  • a crude arabinose extract obtained from natural (plant) materials will typically contain, besides arabinose, mineral acids and metal cation containing compounds, other monosacharides, oligosaccharides, proteins, ash, etc.
  • Arabinose fractions in accordance with the invention will typically be dissolved/dispersed (as the case may be) in a liquid phase, typically it may be dissolved/dispersed in water or an aqueous liquid.
  • steps a)-d) as defined above are primarily aimed at separating arabinose from mineral acids and metal cation containing compounds, thereby obtaining an enriched or purified arabinose fraction dissolved in water, from which arabinose can be crystallized.
  • the arabinose fraction provided in step a) contains, besides arabinose, at least one mineral acid, preferably at least one mineral acid selected from the group of nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid, more preferably nitric acid.
  • the total amount of acid present in the arabinose fraction of step a) is within the range of 40-150 % (w/w), based on the total dry weight of the arabinose fraction, preferably within the range of 50-145 % (w/w), more preferably within the range of 60-140 % (w/w).
  • the arabinose fraction provided in step a) contains, besides arabinose, at least one metal cation containing compound, preferably at least one alkali metal cation containing compound or earth alkali metal cation containing compound, more preferably a Ca 2+ , Mg 2+ , Na + or K + containing compound.
  • the metal cation containing compound is water soluble. More preferably the metal cation containing compound has a water solubility of at least 100 g/l at a temperature of 20°C and a pH of 7.
  • the arabinose fraction contains a metal cation in nitrate salt form.
  • the total amount of metal cation containing compound in the arabinose fraction of step a) is within the range of 5-40 % (w/w), based on the total dry weight of the arabinose fraction, preferably within the range of 10-30 % (w/w), more preferably within the range of 15-25 % (w/w).
  • the (relative) amount of arabinose in the arabinose fraction provided in step a) is not particularly limited.
  • the present method will allow for the enrichment of the arabinose fraction regardless of the initial arabinose amount.
  • the amount of arabinose in the arabinose fraction is at least 10 % (w/w), based on the total dry weight of the arabinose fraction, more preferably at least 20 % (w/w), more preferably at least 25 % (w/w), more preferably at least 30 % (w/w), most preferably at least 35 % (w/w).
  • the arabinose fraction provided in step a) has a combined level of oligosaccharides of below 20 % (w/w), based on total dry weight of the arabinose fraction, more preferably below 15 % (w/w), more preferably below 10 % (w/w), more preferably below 7.5 % (w/w), more preferably below 6 % (w/w), most preferably below 5 % (w/w).
  • the arabinose provided in step a) fraction will be in the form of an aqueous liquid containing the solid constituents in the (relative) amounts as described herein, in combination with water.
  • the amount of water can vary, as will be understood by those of average skill in the art, depending on the processing steps applied to produce the arabinose fraction.
  • the aqueous liquid as provided in step a) contains a total level of dissolved solids within the range of 0.25-20 % (w/v), preferably within the range of within the range of 0.5-10 % (w/v), more preferably within within the range of 1-5 % (w/v).
  • step b) the aqueous liquid provided in step a) is subjected to cation exchange treatment by contacting it with a protonated cation exchange resin, in order to replace the metal cations present in said aqueous liquid with protons.
  • a protonated cation exchange resin as the stationary phase, in that the present method does not rely on on differential partitioning between a mobile phase and a stationary phase.
  • step b) is performed by combining in an open or closed system, typically in a batch-wise fashion, the aqueous liquid and the protonated cation exchange resin, resulting in displacement of protons initially bound to the resin with metal cations initially present in the aqueous liquid, thereby effectively converting the metal cation compounds to the corresponding acids.
  • the ion exchange (IE) treated liquid comprising the arabinose fraction, is also referred to herein as the IE-treated liquid or IE-treated extract.
  • step b) comprises:
  • the cation exchange resin is selected from the group consisting of strong acid cation exchange (SAC) resins.
  • SAC resins for example include sulfonic acid substituted polystyrene cross-linked with divinyl benzene.
  • Ion exchange resins are typically provided in the form of solid macroporous particles or beads.
  • Commercially available SAC exchange resins of the macroporous type include, for example, Lewatit SCP 118, Lewatit SCP 108, Amberlyst A15 and Amberlyst A35.
  • Other strong acid ion exchange resins include Duolite C20, Duolite C26, Amberlite IR-120, Amberlite 200, Dowex 50, Lewatit SPC 118, Lewatit SPC 108, K2611, K2621, OC 1501. Amberlyte, Amberlyst, Amberjet Duolite, and DOWEX are trademarks of the Dow Chemical Company. Lewatit is a trademark of the Lanxess Company.
  • step b) comprises producing a slurry by combining an amount of cation exchange resin in protonated form and the aqueous liquid and allowing for the exchange of metal cations between the SAC resin and the aqueous liquid to take place.
  • step b1) comprises providing a packed column of the ion exchange resin in protonated form, as defined herein, and passing the aqueous liquid over said column.
  • the aqueous liquid is passed over the column at a flow rate of 1-4 bed volumes per hour (BV/h), more preferably 2-3 BV/h.
  • the packed column has a height of at least 1 meter.
  • step b1) is performed at ambient temperature, preferably at 20-25°C, and ambient pressure.
  • step b1) is typically performed in a batch-wise fashion.
  • step b2) comprises collecting the IE treated liquid.
  • step b1) comprises producing a slurry by combining an amount of cation exchange material in protonated form and the aqueous liquid comprising the arabinose fraction, followed by a step of separating the solid ion exchange material from the liquid, using any suitable conventional solid-liquid separation technique.
  • step b1) comprises passing the aqueous liquid over a packed column of ion exchange material and step b2) comprises collecting the eluate.
  • the ion exchange material can be regenerated with a strong acid, such as hydrochloric acid so as to replace all metal cations bound to the resin with protons, following which the ion exchange material can be re-used to treat a subsequent batch of aqueous liquid containing an arabinose fraction.
  • a strong acid such as hydrochloric acid
  • the aqueous liquid provided in step a) is subjected to electrodialysis treatment.
  • Electrodialysis is a separation method for use with ionic solutions. It uses an electric field which generates a motive force for the migration of ions in solution and ion-permeable membranes which ensure the selectivity of the ion migration and which also allow part of the ionic charge of the solutions to be removed.
  • Suitable electrodialysis units that can be utilized in the method of the present invention are known to those of average skill in the art and it is within the normal capabilities of those skilled in the art to employ them in an effective manner.
  • the electrodialysis (ID) treated liquid comprising the arabinose fraction
  • ID-treated liquid or ID-treated extract is also referred to herein as the ID-treated liquid or ID-treated extract.
  • the IE- or ID-treated aqueous liquid is subjected to a nanofiltration treatment.
  • step c) of the present process comprises a nanofiltration treatment.
  • nanofiltration refers to a form of pressure driven filtration that uses semipermeable membranes of pore size typically in the 0.001-0.1 ⁇ m range, to separate different fluids or ions. Such methods are well-known in the art.
  • step c) comprises contacting the aqueous liquid with a semi-permeable membrane while applying a pressure difference across the membrane. A major portion of the mineral acids and salts pass through the membrane with a portion of the water in a permeate stream and are thereby concentrated in the permeate stream. The major part of the arabinose does not pass through the membrane (i.e.
  • the retentate stream from the nanofiltration step comprising the enriched and/or purified arabinose fraction, is also referred to herein as the enriched liquid/extract or purified extract/liquid.
  • Nanofiltration membranes are generally classified based on the molecular weight cut-offs. Generally, the largest pore size that will provide at least 95%, 96%, 97%, 98%, or 99% arabinose retention is preferred. Nanofiltration membranes suitable for the present invention typically have a molecular weight cut-off (MWCO) within the range of 150 to 250 Da, as defined herein before. In a preferred embodiment of the invention, step c) is performed using a nanofiltration membrane having a molecular weight cut-off value within the range of 160-225 Dalton, more preferably within the range of 170-200 Dalton, more preferably within the range of 175-190 Dalton, e.g. about 180 Dalton.
  • MWCO molecular weight cut-off
  • nanofiltration membranes are (commercially) available, made of ceramic, semi-conducting or polymeric materials, including for example aluminium-oxide, zirconium oxide, titanium oxide or mixtures thereof, siliciumnitride or other silicium based compounds or mixtures thereof, polysulphones, fluoropolymers, cellulose, polyolefin resins and polyethersulphones.
  • the porous nanofiltration membrane is a polymeric porous membrane, preferably and acid stable polymeric porous membranes.
  • Polymeric membranes with stability toward acids are known by those skilled in the art.
  • polymers that are relatively stable towards acids and can be used to prepare membranes include polyolefins such as, for example, polyethylene and polypropylene, polyvinylidene flouride, polysulfones, polyethersulfone, and polyether ketones.
  • the invention is not particularly limited. Both the direct Flow Filtration (DFF) mode and the Tangential Flow Filtration (TFF) mode may be suitable for the purposes of the invention.
  • DFF direct Flow Filtration
  • TFF Tangential Flow Filtration
  • Examples of different filter modules known in the art that may be used in one of these filtration modes include hollow fibre modules, spiral wound modules, tubular modules, and plate modules.
  • a spiral wound module is used, e.g. a spiral wound module Type AMS 3012 from AMS - Tel Aviv - Israel.
  • a flux of 5-50 l/m 2 h is applied, preferably 10-40 l/m 2 h, more preferably 20-30 l/m 2 h.
  • the pressures applied result in a transmembrane pressure within the range of 10-50 bar, preferably 15-45 bar, more preferably 20-40 bar.
  • the temperature is typically kept within the range of 10-60 °C, preferably within the range of 20-25 °C.
  • the nanofiltration is operated in diafiltration mode, to further reduce the level of mineral acids and salts in the arabinose fraction.
  • the arabinose fraction is first concentrated until a given optimal value of the concentration factor (CF), and then the nanofiltration proceeds with the addition of water to the retentate.
  • CF concentration factor
  • step c) comprises diafiltration in discontinuous mode.
  • step d) comprises the steps of c1) concentrating the sample by nanofiltration; c2) diluting the sample with water to a predetermined volume and c3) concentrating the sample by nanofiltration, e.g. back to the volume obtained in step c1).
  • Steps c2) and c3) may be repeated until the unwanted mineral acids and salts are removed to a sufficient degree. Each subsequent dilution removes more of the mineral acids and salts. It may be advantageous to perform multiple cycles of steps c2) and c3) to achieve the desired results, e.g. up to 15 cycles. In some embodiments, it is preferred to perform at least 1, at least 2, at least 3 or at least 4 cycles.
  • step c) comprises diafiltration in continuous mode.
  • Continuous diafiltration also referred to as constant volume diafiltration
  • continuous diafiltration involves washing out the original buffer salts (or other low molecular weight species) in the retentate (sample) by adding water or a new buffer to the retentate at the same rate as filtrate is being generated.
  • the retentate volume and product concentration does not change during the diafiltration process, while the mineral acids and salts will be washed out.
  • step c) comprises continuous mode diafiltration, typically comprising the addition of liquid, typically water, to the retentate side while forcing liquid through the nanofiltration membrane, thereby keeping the volume of liquid containing the arabinose fraction at a predetermined value, e.g. at the original volume.
  • the amount of mineral acids and salts removed is related to the filtrate volume generated, relative to the original retentate volume.
  • the filtrate volume generated is usually referred to in terms of "diafiltration volumes”.
  • a single diafiltration volume (DV) is the volume of retentate when diafiltration is started. For continuous diafiltration, liquid is typically added at the same rate as filtrate is generated.
  • step d) comprises diafiltration in continuous mode, as described herein, wherein at least 2 DV, at least 3 DV or at least 4 DV is processed.
  • the enriched or purified arabinose fraction can suitably be used for producing high-purity arabinose by crystallization.
  • the retentate obtained in step d) is subjected to one or more additional treatments before performing the crystallization step as defined herein, which additional treatments are typically aimed at the removal of (traces of) certain impurities, especially those that affect the arabinose crystallization.
  • additional treatments are herein collectively referred to as 'polishing treatments'.
  • Particularly advantageous polishing treatments include anion exchange treatment, yeast fermentation and treatment with active carbon.
  • the arabinose fraction obtained by polishing of the retentate obtained in step d) is also referred to herein as the polished retentate.
  • a method comprising the steps a)-d) as defined herein, said method further comprising the step of: e) subjecting the retentate obtained in step d) to one or more polishing treatments, preferably to one or more polishing treatments selected form (i) Anion exchange treatment; (ii) fermentative treatment; and (iii) active carbon treatment.
  • Anion exchange treatment in accordance with the invention, is primarily aimed at the removal of residual (mineral) acid and typically comprises contacting the liquid retentate with an OH - loaded anion exchange resin and can be performed by combining in an open or closed system, typically in a batch-wise fashion, the liquid retentate and the anion exchange resin, resulting in displacement of OH - initially bound to the resin with mineral acid anions initially present in the retentate, thereby effectively removing the mineral acids.
  • the anion exchange resin is selected from the group consisting of weak base, medium base and strong base anion exchange resins, preferably from the group of medium base anion exchange resins.
  • Suitable resins for example include polystyrene resins with bound tertiary and/or quaternary ammonium groups. These resins are typically provided in the form of solid macroporous particles or beads.
  • Anion exchange resin suitable for use in accordance with the invention are commercially available, such as Bayer type S 4268 type resin.
  • the anion exchange treatment can be performed in any suitable manner known those skilled in the art, such as by passing the retentate liquid over a packed column of the anion exchange resin material.
  • the retentate liquid is passed over the column at a flow rate of 1-4 bed volumes per hour (BV/h), more preferably 2-3 BV/h.
  • the packed column has a height of at least 0.5 meter.
  • anion exchange treatment is performed at ambient temperature, preferably at 20-25°C, and ambient pressure.
  • Fermentative treatment in accordance with the invention, is primarily aimed at the removal of residual monosaccharides such as glucose, mannose and galactose, in particular galactose, and typically comprises inoculating the retentate liquid, optionally after it has been subjected to anion exchange treatment, with a microorganism capable of consuming said monosccharides and incapable of consuming and/or converting arabinose, followed by incubation of the inoculated liquid retentate under conditions favorable to the growth and development of said microorganism, for a period sufficient to reduce the content of the aforementioned monosaccharides.
  • monosaccharides such as glucose, mannose and galactose, in particular galactose
  • the pH of the liquid retentate is adjusted to a value within the range of 4-5, preferably within the range of 4.3-4.7, before inoculation.
  • the mircroorganism is a yeast strain, preferably a strain selected from the genus Saccharomyces, preferably selected from S. cerevisae and S. uvarum most preferably S. cerevisae. Suitable commercially available preparations are also sometimes referred to as 'baker's yeast', 'brewer's yeast', 'distillers yeast'and 'wine yeast'.
  • the inoculated liquid retentate is incubated at a temperature within the range of 25-35 °C, preferably within the range of 27-33 °C, for a period of 24-60 hours, preferably 36-54 hours.
  • a standard solid-liquid separation step is typically applied in order to separate the solid biomass (mainly yeast cells) from the liquid, such as by microfiltration.
  • the ferment is also treated with active carbon, in which case the solid-liquid separation is conveniently done after said active carbon treatment.
  • Active carbon treatment in accordance with the invention, is primarily aimed at the removal of low MW organic substances that tend to affect the colour, taste and/or flavor of the products eventually produced.
  • Active carbon treatment typically involves the addition of an effective amount of active carbon, typically in particulate/powder form, to the liquid retentate, which may have undergone any further polishing treatment as described here above, and allowing the active carbon to absorb at least a fraction of the low MW organic substances.
  • An example of a commercially available active carbon product that may suitably be used in accordance with the invention is type CN1 from Norit.
  • the active carbon is typically applied in an amount within the range of 0.5-5 g/l, preferably 1-3 g/l.
  • the mixture is kept for a period of 0.5-2 hours, preferably 0.75-1.5 hours, typically under gentle agitation, such as stirring, at ambient temperature.
  • gentle agitation such as stirring
  • a standard solid-liquid separation step is typically applied in order to separate the active carbon particles from the liquid, such as by microfiltration
  • a method comprising the step of: e) subjecting the retentate obtained in step d) to the consecutive polishing treatments of (i) anion exchange treatment; (ii) fermentative treatment; and (iii) active carbon treatment.
  • the polished retentate obtained following step e) as described here above can suitably be used for producing high-purity arabinose by crystallization.
  • a method of producing crystalline arabinose comprising the steps a)-d) or a)-e), as defined herein, said method further comprising the step of: f) inducing crystallization of arabinose from the retentate obtained in step d) or the polished retentate obtained in step e).
  • crystallization refers to any process for the formation of solid crystals of a solute from a saturated or supersaturated solution.
  • the crystallization may be carried out by any conventional crystallization methods known in the art. Suitable examples of crystallization methods include: a cooling crystallization method, wherein the temperature of the arabinose-containing liquid is lowered whereby the arabinose precipitates; a concentration crystallization method in which the solvent is volatilized from the solution, for example, by heating and/or a pressure reduction, to heighten the arabinose concentration of the arabinose-containing liquid and thereby precipitate the arabinose; a poor-solvent crystallization method in which a third ingredient (poor solvent) which lowers the solubility of the arabinose is added to the arabinose-containing liquid to precipitate the arabinose; and a method which includes a combination of these.
  • a cooling crystallization method wherein the temperature of the arabinose-containing liquid is lowered whereby the arabinose precipitates
  • concentration crystallization method in which the solvent is volatilized from the solution, for example, by heating and/or a pressure reduction, to heighten the arab
  • step f) comprises processing the retentate into a saturated or supersaturated solution of arabinose, exposing the solution to conditions that permit crystallization, and harvesting the crystals so obtained.
  • step f) comprises the steps of:
  • the pressure is typically within the range of 0.05-0.5 bar, preferably 0.1-0.30bar, more preferably 0.18-0.22 bar.
  • the temperature is typically kept within the range of 50-85 °C, preferably within the range of 60-70 °C. more preferably within the range of 63-67 °C.
  • the temperature of the arabinose-containing liquid is subsequently lowered to induce crystallization (hereinafter, that temperature is often referred to as crystallization temperature).
  • the crystallization temperature during step f2) is typically within the range of 5-40 °C, preferably within the range of 10-30 °C. more preferably within the range of 15-25 °C.
  • the rate of cooling may also affect the result.
  • the arabinose-containing liquid is cooled to the crystallization temperature over 6-48 hours, more preferably 12-36 hours, morst preferably 18-24 hours and then aged at the crystallization temperature for 6-48 hours, more preferably 12-36 hours, most preferably 18-24 hours.
  • the rate of cooling the arabinose-containing liquid is usually preferably 0.05-2 °C/min, more preferably 0.1-1.5 °C/min, even more preferably 0.2-1 °C/min.
  • the solution may be seeded with seed crystals of arabinose.
  • pulverized crystals of arabinose in a dry form or suspended in a crystallization solvent are added to the saturated or supersaturated liquid, e.g. during step f2) as described above.
  • the arabinose crystals are collected, for example by filtering the crystallization liquid.
  • the filtration can be carried out with traditional centrifuges or filters.
  • the filtration cake may be washed with the crystallization solvent and dried. Drying can be carried out for example at a temperature between 30 and 90 °C by traditional methods.
  • Crystals of arabinose with a high purity are obtained.
  • the crystallization typically provides crystalline arabinose having a purity of over 99%.
  • the melting point of the obtained crystalline material is typically within the range of 155-163 °C.
  • the arabinose fraction treated in accordance with the invention preferably originates from a natural (plant) source.
  • Crude arabinose extracts obtained from natural (plant) sources will often contain, besides arabinose, mineral acids and salts, a number of other mono-saccharides, di-saccharides, tri-sacharides, oligosaccharides, polysaccharides, proteins, ashes, etc.
  • Such crude extracts are therefore preferably subjected to one or more pre-treatment steps.
  • Such pre-treatment steps may include, for example, ultrafiltration and/or nanofiltration.
  • step a) comprises:
  • a retentate comprising the olicho-saccarides and a permeate enriched in arabinose, typically also comprising the mineral acids and salts as well as other monosaccharides, disaccharides, trisaccharides and small oligosaccharides.
  • the permeate obtained after nanofiltration (NF) pre-treatment comprising the arabinose fraction, is also referred to herein as the NF-treated liquid or NF-treated extract.
  • Membranes suitable for the NF pre-treatment include nanofiltration membranes having a molecular weight cut-off (MWCO) of 500 to 3000 Da, more preferably 750-2000 Da, most preferably 900-1500, e.g. an MWCO or around 1000.
  • MWCO molecular weight cut-off
  • nanofiltration membranes are (commercially) available, made of ceramic, semi-conducting or polymeric materials, including for example aluminium-oxide, zirconium oxide, titanium oxide or mixtures thereof, siliciumnitride or other silicium based compounds or mixtures thereof, polysulphones, fluoropolymers, cellulose, polyolefin resins and polyethersulphones.
  • the nanofiltration membrane is a polymeric porous membrane, preferably and acid stable polymeric porous membranes.
  • Polymeric membranes with stability toward acids are known by those skilled in the art.
  • polymers that are relatively stable towards acids and can be used to prepare membranes include polyolefins such as, for example, polyethylene and polypropylene, polyvinylidene flouride, polysulfones, polyethersulfone, and polyether ketones.
  • the invention is not particularly limited. Both the direct Flow Filtration (DFF) mode and the Tangential Flow Filtration (TFF) mode may be suitable for the purposes of the invention.
  • DFF direct Flow Filtration
  • TFF Tangential Flow Filtration
  • Examples of different filter modules known in the art that may be used in one of these filtration modes include hollow fibre modules, spiral wound modules, tubular modules, and plate modules.
  • a tubular module is used, e.g. a multichannel ceramic type module from Tami-France having a hydraulic diameter of 3.5 mm and a length of 1200 mm.
  • Conditions to be applied during the nanofiltration pre-treatment will depend on a number of variables as will be understood by the skilled person. It is within the skills of the trained professionals to carry out and optimize the process depending on the specific circumstances.
  • a flux of 5-50 l/m 2 h is applied, preferably 10-40 l/m 2 h, more preferably 20-30 l/m 2 h.
  • the pressures applied result in a transmembrane pressure within the range of 2-30 bar, preferably 3-20 bar, more preferably 4-10 bar.
  • the temperature is typically kept within the range of 20-80 °C, preferably within the range of 40-60 °C.
  • the nanofiltration pre-treatment is operated in diafiltration mode in continuous or discontinuous mode.
  • the pre-treatment comprises diafiltration in discontinuous mode, wherein sequential cycles of dilution and concentration are performed.
  • the pre-treatment comprises the steps of concentrating the aqueous liquid by nanofiltration; diluting the retentate with water to a predetermined volume and concentrating the diluted retentate by nanofiltration, e.g. back to the original volume. It may be advantageous to perform multiple cycles to achieve the desired result, e.g. up to 15 cycles. In some embodiments, it is preferred to perform at least 1, at least 2, at least 3 or at least 4 cycles.
  • the pre-treatment comprises diafiltration in continuous mode, wherein water is added to the retentate side while forcing liquid through the nanofiltration membrane, thereby keeping the volume of liquid containing the arabinose fraction at a predetermined, preferably constant, value, e.g. at the original volume.
  • step d) comprises diafiltration in continuous mode, as described herein, wherein at least 2 DV, at least 3 DV or at least 4 DV is processed.
  • step a) comprises:
  • a retentate is obtained containing mainly pectin and a permeate enriched in arabinose, and typically also comprising mineral acids and salts as well as other monosaccharides, disaccharides, trisaccharides and oligosaccharides.
  • the permeate obtained after ultrafiltration (UF) pre-treatment comprising the arabinose fraction, is also referred to herein as the UF-treated liquid or UF-treated extract.
  • Ultrafiltration membranes suitable for the present invention typically have a molecular weight cut-off (MWCO) of 5 - 50 kDa, more preferably 10-30 kDa, most preferably 12-20, e.g. an MWCO of around 15 kDa.
  • MWCO molecular weight cut-off
  • ultrafiltration membranes are (commercially) available, made of ceramic, semi-conducting or polymeric materials, including for example aluminium-oxide, zirconium oxide, titanium oxide or mixtures thereof, siliciumnitride or other silicium based compounds or mixtures thereof, polysulphones, fluoropolymers, cellulose, polyolefin resins and polyethersulphones.
  • the porous ultrafiltration membrane is a polymeric porous membrane, preferably and acid stable polymeric porous membranes.
  • Polymeric membranes with stability toward acids are known by those skilled in the art.
  • polymers that are relatively stable towards acids and can be used to prepare membranes include polyolefins such as, for example, polyethylene and polypropylene, polyvinylidene flouride, polysulfones, polyethersulfone, and polyether ketones.
  • the invention is not particularly limited. Both the direct Flow Filtration (DFF) mode and the Tangential Flow Filtration (TFF) mode may be suitable for the purposes of the invention.
  • DFF direct Flow Filtration
  • TFF Tangential Flow Filtration
  • Examples of different filter modules known in the art that may be used in one of these filtration modes include hollow fibre modules, spiral wound modules, tubular modules, and plate modules.
  • a tubular module is used, e.g. a multichannel ceramic type module from Tami-France having a hydraulic diameter of 3.5 mm and a length of 1200 mm.
  • a flux of 5-50 l/m 2 h is applied, preferably 10-40 l/m 2 h, more preferably 20-30 l/m 2 h.
  • the pressures applied result in a transmembrane pressure within the range of 2-30 bar, preferably 3-20 bar, more preferably 4-10 bar.
  • the temperature is typically kept within the range of 20-80 °C, preferably within the range of 40-60 °C.
  • the ultrafiltration pre-treatment is operated in diafiltration mode in continuous or discontinuous mode.
  • the pre-treatment comprises diafiltration in discontinuous mode, wherein sequential cycles of dilution and concentration are performed.
  • the pre-treatment comprises the steps of concentrating the aqueous liquid by ultrafiltration; diluting the retentate with water to a predetermined volume and concentrating the diluted retentate by ultrafiltration, e.g. back to the original volume. It may be advantageous to perform multiple cycles to achieve the desired result, e.g. up to 15 cycles. In some embodiments, it is preferred to perform at least 1, at least 2, at least 3 or at least 4 cycles.
  • the pre-treatment comprises diafiltration in continuous mode, wherein water is added to the retentate side while forcing liquid through the ultrafiltration membrane, thereby keeping the volume of liquid containing the arabinose fraction at a predetermined, preferably constant, value, e.g. at the original volume.
  • step d) comprises diafiltration in continuous mode, as described herein, wherein at least 2 DV, at least 3 DV or at least 4 DV is processed.
  • step a) comprises the consecutive steps of:
  • the process of the invention is particularly suitable for the enrichment of arabinose fractions obtained from a natural source.
  • Arabinose can be obtained from a broad range of natural sources, including by-products obtained during processing of agricultural or forestry raw materials. Typical examples of such by-products are e.g. cereal straw, cereal bran, corn stover, corn cobs, bagasse, sugarbeet pulp, almond shells, coconut shells, chicory, gum arabic or other ligno-cellulosic by-products.
  • the respective by-products as well as the feedstock used in the respective processes, are collectively referred herein as 'arabinose containing plant material'.
  • sugar beet pulp is the production residuum from the sugar beet industry. More specifically, sugar beet pulp is the residue from the sugar beet after the extraction of sucrose there from. This material is also referred to as 'spent sugar beet pulp'. Sugar beet processors often dry the pulp.
  • the dry sugar beet pulp can be referred to as 'sugar beet shreds' or 'sugar beet cosettes'.
  • step a1) will comprise suspending the dry sugar beet pulp material in an aqueous liquid, typically to the afore-mentioned dry solids contents.
  • aqueous liquid typically to the afore-mentioned dry solids contents.
  • fresh wet sugar beet pulp is used as the staring material.
  • ensilaged vegetable pulp especially ensilaged sugar beet pulp.
  • the term "ensilage” refers to the process of storing vegetable materials in a moist state under conditions resulting in acidification caused by anaerobic fermentation of carbohydrates present in the materials being treated. Ensilage is carried out according to known methods with pulps preferably containing 15 to 35% of dry matter. Ensilage of sugar beets is continued until the pH is within the range of 3.5-5. It is known that pressed beet pulps may be ensilaged to protect them from unwanted decomposition. This process is most commonly used to protect this perishable product, the other alternative being drying to 90% dry matter. This drying has the disadvantage of being very energy-intensive. The fermentation process starts spontaneously under anaerobic conditions with the lactic acid bacteria being inherently present. These microorganisms convert the residual sucrose of the pressed beet pulp to lactic acid, causing a fall in the pH.
  • the arabinose containing plant material or pulp is washed in a flotation washer in order to remove sand and clay particles before subjecting it to the acid treatment.
  • step a2) of the method the water-soluble pectin material is extracted from the arabinose containing plant material by acid catalyzed hydrolysis.
  • the liquid obtained in accordance with step a2), comprising the plant material and an acid is also referred to herein as the hydrolysis mixture.
  • step a2) comprises placing the plant material in a reactor with an aqueous solution of a mineral acid selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid or phosphoric acid.
  • step a2) comprises placing the plant material in a reactor with an aqueous solution of nitric acid.
  • step a2) comprises placing the plant material in a reactor with an aqueous solution of a mineral acid in amounts resulting in an acid concentration of 0.5-4 % (w/v), preferably 0.75-3 % (w/v), more preferably 1-2 (w/v).
  • step a2) comprises placing the plant material in a reactor with an aqueous solution of a mineral acid in amounts resulting in a level of sugar beet solids of 5-25 wt.%, based on the total weight of the obtained slurry, preferably 7-15 wt.%, more preferably 8-10 wt.%.
  • the treatment according to step a2) comprises mixing the arabinose containing plant material with the aqueous solution of a mineral acid and heating the mixture accordingly obtained to a temperature within the range of 40-100 °C for a period of at least 10 minutes, preferably at least 20 minutes, more preferably at least 30 minutes.
  • the use of relatively low temperatures in the present chemical process allows the plant material to be processed with the use of less energy and therefore at a lower cost than methods known in the art employing higher temperatures.
  • the mixture may be heated to at least 60°C, at least 70°C, at least 80°C or at least 90°C.
  • the mixture is heated to less than 100°C, preferably less than 90°C, more preferably less than 85 °C.
  • step a2) comprises placing the spent plant material in a reactor with an aqueous mineral acid solution and heating the solution to a temperature within the range of 50-100 °C, for a period of time within the range of 30- 240 minutes, preferably under agitation.
  • step a2) comprises heating the mixture to a temperature of 70-90°C for 120-240 minutes, for example to a temperature of approximately 80 °C for 180 minutes.
  • the mixture is stirred or agitated during step a2).
  • Step a2) is followed by a step a3) of extracting an aqueous liquid containing the arabinose fraction.
  • the liquid obtained in accordance with step a3) comprising the arabinose fraction, is also referred to herein as the crude extract.
  • step a3) comprises taking the hydrolysis mixture obtained in step a2) from the reactor and subjecting it to a solid-liquid separation process, preferably filtration, centrifuging and/or decantation and collecting the extracted liquid as the arabinose fraction.
  • the hydrolysis mixture is subjected to filtration, e.g. in a chamber filter press, during which extracted liquid is collected as the arabinose fraction.
  • an embodiment is envisaged wherein the hydrolysis mixture is filtered, followed by the addition of water or liquid followed by an additional step of extracting the aqueous liquid, e.g. using a chamber filter press, and combining the extracts obtained in the respective cycles. This step may be repeated as many times as desired in order to achieve e.g. a higher yield.
  • the extracted liquid (or combined extract liquids) will typically contain the monosaccharides, including arabinose, pecto-oligosaccharides, pectin (fragments), hemicelluloses (fragments) and mineral acids and salts.
  • the fraction containing the solids may be used as a source of other valuable components.
  • the invention also entails embodiments wherein the extracted liquid is used to treat an additional quantity of fresh plant material.
  • This has the advantage that the amount of mineral acid relative to arabinose in the resulting extract is effectively reduced.
  • the amount of mineral acid relative to arabinose in the produced extract can effectively be reduced by as much as 50 %.
  • a method as defined herein comprising the steps of: a3) extracting liquid from the mixture obtained in step a2) by solid-liquid separation; a3') introducing the extracted liquid in a reactor together with a further quantity of the plant material provided in step a1), preferably under agitation and/or heating, optionally in combination with an additional quantity of an aqueous mineral solution; and a3") extracting liquid from the mixture obtained in step a3') by solid-liquid separation.
  • step a3' the techniques, equipment and conditions employed in step a3' will typically (but not necessarily) be the same as for step a2). Similarly, in step a3") the same techniques will typically be employed as what has been described here above for step a3).
  • Embodiments are also envisaged wherein the method comprises two or even more cycles of steps a3) - a3").
  • crysalline arabinose material having a melting point within the range of 155-163 °C and comprising more than 99 % (w/w) arabinose, preferably more than 99.5 % (w/w) more than 99.6 % (w/w), more than 99.7 % (w/w), more than 99.8 % (w/w), or more than 99.9 % (w/w), which is further typically characterized by the presence of detectable amounts of at least one component, at least two components, at least three components, at least four components or at least five components selected from the group consisting of galactose, xylose, rhamnose, glucose, disaccharides, trisaccharides and oligosaccharides.
  • a crystalline arabinose material as defined herein is provided, characterized in that it comprises 0.01-0.5 % (w/w) of galactose, e.g. 0.02-0.1 % (w/w); and/or 0.005-0.06 % (w/w) of xylose, e.g. 0.01-0.05 % (w/w).
  • the crystalline arabinose material obtainable by the method of the present invention may further contain residual amounts of water, e.g. amounts up to 1.0 or 0.5 % (w/w).
  • the acidic pulp slurry is pumped to a filter press (pump pressure of 0.6 bar overpressure).
  • Analysis of the acid extract Brix 4.83% Arabinose 1.22% Pectin 1.85% Nitrate 1.1%
  • the acid extract as produced in example 1 is subjected to ultrafiltration.
  • the total membrane surface is 4.9 m 2 .
  • the filtration process is performed at a temperature of 40-60°C and a transmembrane pressure (TMP) of 4-5 bar.
  • TMP transmembrane pressure
  • the dialysis is performed at a constant retentate volume.
  • the amount of permeate was 494 kg and had a brix value of 1.4%
  • the amount of retentate was 115 kg with a brix value of 3.2%
  • the UF 15 KD permeate as produced in example 2 is subjected to nanofiltration. installation.
  • the membrane elements are ceramic and have a MWCO of 1 kDa.
  • the total membrane surface is 2.45 m 2 .
  • Permeate was produced in an amount of 464 kg, which had a brix value of 1.3%.
  • Retentate was produced in an amount of 50kg, which had a Brix value of 2.82%
  • Cation exchange treatment is performed in order to exchange the cation in the NF 1 KD permeate, as produced in example 3, against H + ions.
  • a macroporous strong acid ion exchange resin is applied; type Lewatit S 1462 (Bayer). The resin is treated with HCl to become fully loaded with H + .
  • the permeate of the NF(IKD) is passed over a column packed with the cation exchange resin (2 bed volume an hour). The column height is approximately 1 meter. The temperature is 20-25°C. As total amount of 464 kg permeate UF 1 KD is passed over the column. Am amount of 486 kg eluate is collected.
  • a nanofiltration treatment is performed to enrich the cation exchange eluate as produced in example 4 in arabinose.
  • An organic membrane element is used having a MWCO of 180 Da.
  • the membrane configuration is spiral wound with a spacer of 46 mill (milliinches).
  • the membrane surface is 1.6 m 2 .
  • TMP transmembrane pressure
  • the process involves a batch-wise concentration of the retentate by withdrawal of the permeate and subsequent dialysis of the retentate (at a constant retentate volume).
  • the dialysis was done by diluting the retentate with a factor 3 (with demiwater).
  • J gradually decreases to 20-15 lmh.
  • the retentate comprises arabinose wit traces of oligosaccharides and anions of the extraction acid.
  • the purity of the de arabinose fraction is 68.6%.
  • Arabinose is crystallized from the NF retentate as produced in example 5.
  • the retentate is concentrated by evaporation to create a state of supersaturation so that cooling crystallization van be performed resulting in the formation of arabinose crystals that can be collected.
  • the mother liquor of the first crystallization is again concentrated to a state of supersaturation and subjected to cooling, thereby forming another quantity of arabinose crystals which are also collected.
  • the combined crystllization yield was 62% of the arabinose originally present.
  • the purity of the crystalls formed in the first crystallization was 99.2%; the purity of the crystalls formed in the second crystallization was 97.8%.
  • polishing treatment comprises:
  • the anion exchange treatment is performed to exchange the anions in the NF 180D retentate as produced in example 5, with OH - ions.
  • a macroporous medium base resin is used (Lewatit S 4268, Bayer). The resin is loaded with OH - using NaOH.
  • the NF 180D retentate is passed over a packed column of the resin, at a rate of 2 bed volumes per hour (BV/h.) The column height was approximately 1 meter. The temperature was kept at 20-25°C.
  • the eluate contains the initial content of sugars. The purity of the arabinose fraction increases from 69% (in the nanofiltration retentate) to 91.3% in the eluate.
  • the sugar fermentation is performed in order to convert the fermentable sugars still present in the arabinose fraction into other byproducts resulting in enhancement of the yield of the crystallization
  • baker's yeast Fermipan Brown, AB Mauri (UK) Ltd
  • AB Mauri UK
  • the fermentation is allowed to continue for 48 hours, while maintaining the temperature at 30°C and under constant stirring. Thereafter the liquid is separated from solid biomass.
  • Active carbon treatment is performed in order to remova color, flavor and/or taste imparting components.
  • active carbon powder type CN1, Norit
  • the mixture is kept at ambient temperature and is continuously stirred for one hour.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (14)

  1. Verfahren zum Anreichern einer Arabinosefraktion enthaltend, neben Arabinose, zumindest eine Mineralsäure, bevorzugt zumindest eine Mineralsäure ausgewählt aus der Gruppe von Salpetersäure, Salzsäure, Schwefelsäure und Phosphorsäure, sowie zumindest eine Metallkationenenthaltende Verbindung, bevorzugt zumindest eine Alkalimetall- oder Erdalkalimetallkationen-enthaltende Verbindung;
    das Verfahren umfassend die aufeinanderfolgenden Schritte von:
    a) Bereitstellen einer die Arabinosefraktion umfassenden wässrigen Flüssigkeit;
    b) Unterwerfen der wässrigen Flüssigkeit einer Behandlung resultierend in dem Ersatz von Metallkationen durch Protonen, bevorzugt einer Behandlung ausgewählt aus Kationenaustauschbehandlung und Elektrodialyse;
    c) Durchleiten der in Schritt b) erhaltenen wässrigen Flüssigkeit durch eine Nanofiltrationsmembran mit einem Molekulargewichtsgrenzwert innerhalb des Bereichs von 150-250 Da;
    d) Sammeln des Retentats als die angereicherte Arabinosefraktion.
  2. Verfahren nach Anspruch 1, wobei Schritt b) umfasst:
    b1) Kontaktieren der wässrigen Flüssigkeit mit einem protonierten Kationenaustauschharz;
    b2) Trennen der wässrigen Flüssigkeit von dem Kationenaustauschharz.
  3. Verfahren nach Anspruch 1, wobei die Arabinosefraktion einen kombinierten Gehalt von Oligosacchariden und Polysacchariden basierend auf dem Gesamttrockengewicht der Arabinosefraktion von unter 60% (w/w) aufweist.
  4. Verfahren nach Anspruch 1, wobei die Arabinosefraktion vorbehandelt wird durch Hindurchleiten einer die Arabinosefraktion umfassenden wässrigen Flüssigkeit durch eine Nanofiltrations- oder dichte Ultrafiltrationsmembran mit einem Molekulargewichtsgrenzwert innerhalb des Bereichs von 500-5000 Da und Sammeln des Permeats.
  5. Verfahren nach Anspruch 4, wobei die Arabinosefraktion vorbehandelt wird durch Hindurchleiten einer die Arabinosefraktion umfassenden wässrigen Flüssigkeit durch eine Ultrafiltrationsmembran mit einem Molekulargewichtsgrenzwert innerhalb des Bereichs von 10-100 KDa,
    vor der Vorbehandlung mit der Nanofiltrations- oder dichten Ultrafiltrationsmembran, und Sammeln des Permeats.
  6. Verfahren nach Anspruch 1, wobei die Arabinosefraktion hergestellt ist durch einen Prozess umfassend die aufeinanderfolgenden Schritte von:
    a1) Bereitstellen eines Arabinose-enthaltenden Pflanzenmaterials, bevorzugt einer Pflanzenpulpe, mehr bevorzugt verbrauchte Zuckerrübenpulpe;
    a2) Platzieren des Pflanzenmaterials in einem Reaktor mit einer wässrigen Mineralsäurelösung, bevorzugt unter Rühren und/oder Erwärmen;
    a3) Extrahieren von Flüssigkeit von dem Reaktor durch Fest-Flüssig-Trennung;
    a4) Behandeln der extrahierten Flüssigkeit durch Hindurchleiten durch eine Ultrafiltrationsmembran mit einem Molekulargewichtsgrenzwert innerhalb des Bereichs von 10-100 KDa und Sammeln des Permeats; und
    a5) Behandeln des Permeats durch Hindurchleiten durch eine Nanofiltrations- oder dichte Ultrafiltrationsmembran mit einem Molekulargewichtsgrenzwert innerhalb des Bereichs von 5-5000 Da und Sammeln des Permeats.
  7. Verfahren nach Anspruch 6, wobei Schritt a2) umfasst Platzieren des Pflanzenmaterials in einem Reaktor mit einer wässrigen Lösung einer Mineralsäure, bevorzugt einer wässrigen Lösung von Salpetersäure, Salzsäure, Schwefelsäure oder Phosphorsäure, mehr bevorzugt einer wässrigen Lösung umfassend Salpetersäure bei einer Konzentration von 1-3% (w/v).
  8. Verfahren nach einem der Ansprüche 6 oder 7, wobei Schritt a2) umfasst Platzieren des verbrauchten Pflanzenmaterials in einem Reaktor mit einer wässrigen Mineralsäurelösung und Erwärmen der Lösung auf eine Temperatur innerhalb des Bereichs von 50-100°C, für eine Zeitspanne innerhalb des Bereichs von 60-240 Minuten, bevorzugt unter Rühren.
  9. Verfahren nach einem der Ansprüche 6 bis 8, wobei Schritt a3) umfasst
    Extrahieren von Flüssigkeit aus dem Reaktor und Unterwerfen desselben einem Fest-Flüssig-Trennprozess, bevorzugt Makrofiltration, Zentrifugieren und/oder Dekantieren.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei Schritt b) unter Verwendung eines starken Säurekationenaustauschharzes (SRC) durchgeführt wird.
  11. Verfahren nach einem der Ansprüche 1 bis 10, wobei Schritt c) unter Verwendung einer Nanofiltrationsmembran mit einem Molekulargewichtsgrenzwert innerhalb des Bereichs von 170-200 Da durchgeführt wird.
  12. Verfahren nach Anspruch 11, wobei die Nanofiltrationsmembran ausgewählt ist aus der Gruppe bestehend aus säurestabilen organischen Membranen.
  13. Verfahren nach einem der vorstehenden Ansprüche, das Verfahren ferner umfassend die Schritte:
    e) Unterwerfen des in Schritt d) erhaltenen Retentats einer oder mehr Polierbehandlungen, bevorzugt ein oder mehr Polierbehandlungen ausgewählt aus (i) Anionenaustauschbehandlung; (ii) fermentativer Behandlung; und (iii) Aktivkohlebehandlung.
  14. Verfahren zum Herstellen von kristalliner Arabinose, das Verfahren umfassend die Schritte a) bis d) oder a) bis e), wie in einem der Ansprüche 1 bis 13 definiert, das Verfahren ferner umfassend den Schritt von:
    f) Induzieren der Kristallisation von Arabinose aus dem in Schritt d) erhaltenen Retentat oder dem in Schritt e) erhaltenen polierten Retentat.
EP16784983.5A 2015-10-02 2016-09-30 Verfahren zur anreicherung von arabinosefraktionen Active EP3356563B1 (de)

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DE3702653A1 (de) * 1987-01-29 1988-08-11 Sueddeutsche Zucker Ag Verfahren zur herstellung von kristalliner l-arabinose
FI104500B (fi) 1997-08-26 2000-02-15 Cultor Oyj Menetelmä L-arabinoosin valmistamiseksi sokerijuurikasleikkeestä
FI113453B (fi) * 1999-09-17 2004-04-30 Sohkar Oy Kasvimateriaalin kromatografinen fraktiointi
US20050096464A1 (en) * 2003-10-30 2005-05-05 Heikki Heikkila Separation process
GB2408262B (en) * 2003-11-24 2007-09-12 British Sugar Plc A method of preparation of L-arabinose
WO2013152493A1 (zh) * 2012-04-12 2013-10-17 淮北中润生物能源技术开发有限公司 联产多种产品的阿拉伯糖生产方法

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