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WO2020062060A1 - Procédé de purification de xylose - Google Patents

Procédé de purification de xylose Download PDF

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Publication number
WO2020062060A1
WO2020062060A1 PCT/CN2018/108415 CN2018108415W WO2020062060A1 WO 2020062060 A1 WO2020062060 A1 WO 2020062060A1 CN 2018108415 W CN2018108415 W CN 2018108415W WO 2020062060 A1 WO2020062060 A1 WO 2020062060A1
Authority
WO
WIPO (PCT)
Prior art keywords
xylose
quaternary ammonium
ammonium compound
alkyl
benzyl
Prior art date
Application number
PCT/CN2018/108415
Other languages
English (en)
Inventor
Zhaofei Chen
Shujing Cheng
Original Assignee
Rhodia Operations
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Operations filed Critical Rhodia Operations
Priority to BR112021005502-9A priority Critical patent/BR112021005502B1/pt
Priority to CN201880098115.5A priority patent/CN113039291A/zh
Priority to PCT/CN2018/108415 priority patent/WO2020062060A1/fr
Publication of WO2020062060A1 publication Critical patent/WO2020062060A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/002—Xylose

Definitions

  • the present invention relates to a method for purifying xylose, wherein the xylose is purified by using a quaternary ammonium compound.
  • the present invention also relates to a xylose composition obtained by said method.
  • Xylose is a pentose sugar which is widely used for applications such as food additives and pharmaceutical products. It is prepared by the acid hydrolysis of ligno-cellulosic materials containing hemicelluloses having a high proportion of xylose units or xylans in their molecules. In addition to hemicelluloses, ligno-cellulosic material to contain lignin, cellulose and other carbohydrates. Furthermore, hemicellulose molecules contain, in addition to xylans, units of other sugars. Hemicelluloses derived from different ligno-cellulosic materials vary in structure, some containing a greater proportion of xylans in their molecules than are contained in the molecules of other hemicelluloses. In the production of xylose, it is necessary to separate lignin, cellulose and other materials from the product of the initial hydrolysis.
  • the manufacturing process of xylose generally comprises steps of (I) hydrolyzing plant-derived materials which contain xylose, such as sawdusts, straws, and cornstalks, so as to obtain a raw xylose-containing liquid, (II) purification, and (III) crystallization.
  • the raw xylose-containing liquid in (I) is normally very dark and contains impurities.
  • the impurities mainly include side products of Maillard reaction, lignins, and aromatic pigments. The impurities have to be removed so as to obtain xylose with high purity and good quality.
  • wastes from papermaking industry are also used as raw materials for making xylose.
  • the wastes from papermaking industry contain not only celluloses, lignins, but also impurities like chlorinated aromatic hydrocarbons, polycyclic aromatic hydrocarbons. In such case, purification becomes more difficult.
  • the wastes are processed into a xylose containing syrup, which is subsequently purified by using activated carbons, ion exchange resins or membrane filters.
  • US Patent No. US 5340403 B2 disclosed a process in which a xylose containing syrup is decolored by activated carbon.
  • activated carbon can absorb indiscriminately impurities as well as xylose which is the desired product. For this reason, adding large amount of activated carbon not only leads to high costs, but also cause reduced yield of xylose.
  • ion exchange resins can be used in decolorization of xylose syrup.
  • US Patent No. US3985815 B1 discloses a method using crosslinked polystyrene.
  • the purification process utilizing the ion exchange resin is time consuming and require use of water in large amount.
  • raw hydrolyzed xylose liquid or syrup generally has high temperature and strong acidity. It can thus damage the resin and generate large amount of liquid waste which can be hazardous to environment.
  • Membrane filter is also an option, however this method is expensive and the purification efficiency is not satisfactory.
  • the present invention aims at developing a method for purifying xylose, which has good purification efficiency and which is fast and cost efficient.
  • the present invention relates to a method for purifying xylose, comprising a step of adding to a raw xylose-containing liquid a quaternary ammonium compound.
  • the quaternary ammonium compound is according to the general formula (I) :
  • R 1 , R 2 , R 3 and R 4 which may be the same or different, is a C 1 -C 30 hydrocarbyl group, optionally containing a hetero atom, or an ester or amide group;
  • X is an anion
  • y is the valence of X.
  • the quaternary ammonium compound is according to the general formula (II)
  • R 1 , R 2 , R 3 and R 4 which may be the same or different, is a C 1 -C 30 hydrocarbyl group, wherein at least one of R 1 , R 2 , R 3 and R 4 is a C 10 -C 28 alkyl or hydroxyalkyl group;
  • X is an anion
  • y is the valence of X.
  • the quaternary ammonium compound is according to general formula (III)
  • R 1 is a C 10 -C 28 alkyl or hydroxyalkyl, each of R 2 and R 3 is methyl, R 4 is benzyl,
  • X is an anion
  • y is the valence of X.
  • the quaternary ammonium compound is according to general formula (IV)
  • R 1 and R 2 is independently a C 10 -C 28 alkyl or hydroxyalkyl, R 3 is methyl,
  • R 4 is methyl or benzyl
  • X is an anion
  • y is the valence of X.
  • the present invention also relates to a xylose composition, wherein the xylose composition contains a xylose obtained by using the method of the present invention.
  • any particular upper concentration, weight ratio or amount can be associated with any particular lower concentration, weight ratio or amount.
  • hydrocarbyl should be understand as including but not limited to saturated and unsaturated hydrocarbyl groups, straight, branched or cyclic hydrocarbyl groups, aliphatic or aromatic groups, substituted or unsubstituted hydrocarbyl groups, etc..
  • Hydrocarbyl group includes not only single species hydrocarbyl like methyl, ethyl and so on, but also mixed hydrocarbyls from natural sources (animal and plants) , for example, palmityl alkyl and tallow alkyl.
  • alkyl means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.
  • hydroxyalkyl means an alkyl radical, which is substituted with a hydroxyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.
  • aryl means a monovalent unsaturated hydrocarbon radical containing one or more six - membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted one or more of carbons of the ring with hydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, such as, for example, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl.
  • aralkyl means an alkyl group substituted with one or more aryl groups, such as, for example, phenylmethyl, phenylethyl, triphenylmethyl.
  • quaternary ammonium compound (also referred to as “quat” ) , as used herein, means a compound containing at least one quaternized nitrogen wherein the nitrogen atom is attached to four organic groups.
  • the quat may comprise one or more quaternized nitrogen atoms.
  • the quat comprises only one quaternized nitrogen atom.
  • xylose-containing liquid means a liquid or a liquid mixture which contains xylose, raw xylose, or other raw materiala from which xylose can be made.
  • the liquid here should include but not limited to aqueous solutions and melts containing xylose or raw xylose.
  • the method of the present invention comprises a step of adding a quaternary ammonium compound into a raw xylose-containing liquid.
  • the raw xylose-containing liquid may be obtained by hydrolysis of ligno-cellulosic materials containing hemicelluloses that have a high proportion of xylose units or xylans in their molecules.
  • the raw xylose-containing liquid may be obtained by hydrolysis of cornstalk, sawdust, waste of papermaking industry, or straw.
  • the raw xylose-containing liquid may be a direct product of the hydrolysis treatment.
  • the raw xylose-containing liquid may be a diluted solution, a diluted mixture, or a concentrated syrup.
  • raw materials can be hydrolyzed in presence of an acid or enzyme, and/or by heating.
  • acid or enzyme e.g., benzyl alcohol, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl ether, benzyl, naric acid, or hydrochloric acid are preferred for acid treatment.
  • a temperature below boiling point (of water or other solvent) is preferred, 95°C or below is more preferred.
  • the raw material can be mixed with the quaternary ammonium compound before hydrolyzation, during hydrolyzation or after hydrolyzation.
  • the raw material such as the raw xylose-containing liquid, may also be filtered before addition of the quaternary ammonium compound.
  • the quaternary ammonium compound, once added, can be mixed and/or stirred with the raw xylose–containing liquid.
  • the xylose-containing liquid can be heated to a predetermined temperature before adding the quaternary ammonium compound.
  • the heated solution can be mixed by stirring then.
  • the raw xylose-containing liquid can be heated after adding the quaternary ammonium compound. In this case, the solution can be stirred before or after being heated.
  • the raw xylose-containing liquid when the raw xylose-containing liquid is heated in the hydrolyzation step, it can be kept warm (preferably for a short period) till adding the quaternary ammonium compound, which is energy-efficient since the xylose-containing liquid need not to be heated again.
  • heating temperature There is no limit on heating temperature.
  • a temperature below boiling point of water or other solvent
  • 95°C or below is more preferred
  • the quat is preferably added in form of a diluted aqueous solution.
  • the quat may be added in form of a concentrated aqueous solution or a solid, for example a powder or cake.
  • the quat may also be added in form of non-aqueous solution, or solution of mixed solvent, for example, alcohol or water-alcohol can be used as solvent.
  • the solution may contain water, ethanol isopropanol or isopropanol as solvent.
  • the quat may also be added with other addictive like flocculant, activated carbon or other adsorbents.
  • Dosage of the quaternary ammonium compound may be from 200 to 5000 ppm, preferably from 200 to 3000 ppm, more preferably from 500 to 3000 ppm, even more preferably from 1000 to 2000 ppm.
  • the method of the present invention is characterized in that adding the quaternary ammonium compound, preferably into a raw xylose-containing liquid obtained by hydrolyzation of raw material.
  • the purified xylose can be subject to further steps which are known by a skilled person, such as seperration (for example, by filtration or centrifugalization) , concentration (for example, by evaporation, preferably at a reduced pressure and/or at a high temperature) , crystallization, washing and drying the crystallized xylose.
  • the purification method of the present invention can be used solely or can be used in combination with other purification methods, for example, purification by using membrane filter, activated carbon, or ion exchange resin.
  • the quaternary ammonium compound can be added before or after any one of the steps above.
  • the quaternary ammonium compound is preferably according to the general formula (I) :
  • R 1 , R 2 , R 3 and R 4 which may be the same or different, is a C 1 -C 30 hydrocarbyl group, typically an alkyl, hydroxyalkyl, aryl or aralkyl, optionally containing a heteroatom, or an ester or amide group;
  • X is an anion, for example halide, such as Cl or Br, sulphate, alkyl sulphate, nitrate or acetate;
  • y is the valence of X.
  • the quaternary ammonium compound is according to the general formula (II)
  • R 1 , R 2 , R 3 and R 4 which may be the same or different, is a C 1 -C 30 hydrocarbyl group, typically an alkyl, hydroxyalkyl, aryl or aralkyl, wherein at least one of R 1 , R 2 , R 3 and R 4 is a C 10 -C 28 alkyl or hydroxyalkyl group;
  • X is an anion, for example halide, such as Cl or Br, sulphate, alkyl sulphate, nitrate or acetate;
  • y is the valence of X.
  • R 1 ⁇ R 4 can be replaced by a heteroatom like O, S and N, preferably O.
  • number of carbon atoms being replaced by heteroatom is not limited, preferably 4 or less carbon atoms are replaced by heteroatom, more preferably two or three carbon atoms are replaced by heteroatom, most preferably one.
  • R 1 , R 2 , R 3 and R 4 may be an alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl, dodecyl, tetradecyl, cetyl, octadecyl, eicosyl.
  • R 1 , R 2 , R 3 and R 4 may be an hydroalkyl of the alkyls listed above.
  • R 1 , R 2 , R 3 and R 4 may be an aryl such as phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl.
  • R 1 , R 2 , R 3 and R 4 may be an alkylaryl, such as benzyl phenylethyl, phenyl-n-propyl, phenyl-iso-propyl, phenyl-n-butyl, phenyl-sec-butyl, phenyl-t-butyl, phenylpentyl, phenyl-n-hexyl, cyclohexyl, phenyldodecyl, phenyltetradecyl, phenylcetyl, phenyloctadecyl, phenyleicosyl.
  • alkylaryl such as benzyl phenylethyl, phenyl-n-propyl, phenyl-iso-propyl, phenyl-n-butyl, phenyl-sec-butyl, phenyl-t-butyl, phenylpentyl,
  • X may be anions like Cl - , Br - , F - , I - , SO 4 2- , HSO 4 - , PO 3 3- , HPO 3 2- , H 2 PO 3 - , CO 3 2- , HCO 3 - , NO 3 - , preferably halide ion, like Cl - or Br - .
  • the anion can also be the anion part of organic acids like acetic acid, maleic acid, fumaric acid, iconic acid.
  • the quaternary ammonium compound is according to general formula (III)
  • R 1 is a C 10 -C 28 alkyl or hydroxyalkyl, each of R 2 and R 3 is methyl, R 4 is benzyl,
  • X is an anion
  • y is the valence of X.
  • the quaternary ammonium compound is according to general formula (IV)
  • R 1 and R 2 is independently a C 10 -C 28 alkyl or hydroxyalkyl, R 3 is methyl, R 4 is methyl or benzyl
  • X is an anion
  • y is the valence of X.
  • Examples of the quaternary ammonium compound suitable for the invention include and are not limited to didecyl dimethyl ammonium chloride, C 12-16 -alkyldimethyl benzyl ammonium chloride, hydrogenated tallowdimethyl benzyl ammonium chloride, dihydrogenated tallow benzyl methyl ammonium chloride, and dihydrogenated tallowdimethylammonium chloride.
  • quaternary ammonium compound suitable for the invention include and are not limit to D1217S, 1831 and T05 (all from Solvay) .
  • the quaternary ammonium compound may comprise one or more of the compounds above. It can be used with other functional addictive
  • Step 1 Waste of papermaking industry was used as the raw material, to obtain a raw xylose liquid by acid hydroxylation (add sulfuric acid to pH ⁇ 1) , and heat the raw xylose liquid to 70 ⁇ 95°C.
  • Step 2 add calculated amount of the quaternary ammonium compound on the weight of raw xylose liquid and stir for approx. 1 min at 70 ⁇ 95°C.
  • Step 4 filter and test the color value.
  • Step 1 collect the clear filtrate (adjust pH to 4.5)
  • Step 2 check the brix with Abbe Refractometer (from ATAGO Company)
  • Step 3 check the adsorption at 420nm using 1 cm cuvette
  • color value (A420 /Brix*L) *10 5 , unit is IU 420
  • A420 is the adsorption at 420 nm
  • Brix is the brix of the xylose liquid measured by Abbe Refractometer
  • Color removal (%) [color value (raw liquid) –color value (clear liquid) ] /color value (raw liquid) *100
  • E1 refers to Example 1 and so on.
  • CE1 refers to Comparative Example 1 and so on.
  • the quaternary ammonium compound of the present invention provided higher color reduction compared to PAC or the tertiary amine.
  • the quat according to the invention provided reduced scaling. This is particular advantageous when the purified xylose is subject to concentration by heating. High scale will be harmful for the equipment used for concentration step and will require additional efforts to remove the scales in the concentration equipment from time to time.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de purification de xylose, comprenant une étape consistant à ajouter à un liquide brut contenant du xylose un composé d'ammonium quaternaire.
PCT/CN2018/108415 2018-09-28 2018-09-28 Procédé de purification de xylose WO2020062060A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR112021005502-9A BR112021005502B1 (pt) 2018-09-28 Método para purificar xilose
CN201880098115.5A CN113039291A (zh) 2018-09-28 2018-09-28 用于纯化木糖的方法
PCT/CN2018/108415 WO2020062060A1 (fr) 2018-09-28 2018-09-28 Procédé de purification de xylose

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/108415 WO2020062060A1 (fr) 2018-09-28 2018-09-28 Procédé de purification de xylose

Publications (1)

Publication Number Publication Date
WO2020062060A1 true WO2020062060A1 (fr) 2020-04-02

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Application Number Title Priority Date Filing Date
PCT/CN2018/108415 WO2020062060A1 (fr) 2018-09-28 2018-09-28 Procédé de purification de xylose

Country Status (2)

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CN (1) CN113039291A (fr)
WO (1) WO2020062060A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3698951A (en) * 1967-09-29 1972-10-17 Tate & Lyle Ltd Sugar refining
CN101092436A (zh) * 2007-04-06 2007-12-26 李来锁 物理爆碎法生产低聚木糖或木糖的工艺技术
CN101812546A (zh) * 2010-04-23 2010-08-25 广西大学 磷酸复合物脱色剂的制备及其应用方法
CN103210095A (zh) * 2009-11-11 2013-07-17 卡博Ua有限公司 用于改进糖液和糖浆的磷酸盐化澄清的组合物和方法
WO2017202240A1 (fr) * 2016-05-26 2017-11-30 Rhodia Operations Procédé pour réduire des impuretés de couleur dans un liquide sucré ou un sirop de sucre

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3698951A (en) * 1967-09-29 1972-10-17 Tate & Lyle Ltd Sugar refining
CN101092436A (zh) * 2007-04-06 2007-12-26 李来锁 物理爆碎法生产低聚木糖或木糖的工艺技术
CN103210095A (zh) * 2009-11-11 2013-07-17 卡博Ua有限公司 用于改进糖液和糖浆的磷酸盐化澄清的组合物和方法
CN101812546A (zh) * 2010-04-23 2010-08-25 广西大学 磷酸复合物脱色剂的制备及其应用方法
WO2017202240A1 (fr) * 2016-05-26 2017-11-30 Rhodia Operations Procédé pour réduire des impuretés de couleur dans un liquide sucré ou un sirop de sucre

Also Published As

Publication number Publication date
CN113039291A (zh) 2021-06-25
BR112021005502A2 (pt) 2021-06-15

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