CN104611476A - Xylose and arabinose separating method - Google Patents

Xylose and arabinose separating method Download PDF

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Publication number
CN104611476A
CN104611476A CN201310539010.8A CN201310539010A CN104611476A CN 104611476 A CN104611476 A CN 104611476A CN 201310539010 A CN201310539010 A CN 201310539010A CN 104611476 A CN104611476 A CN 104611476A
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ion
exchange fiber
pectinose
xylose
fiber
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CN201310539010.8A
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CN104611476B (en
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林晓
陆剑鸣
张丽方
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Nanjing Tech University
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Nanjing Tech University
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    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13KSACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00Sugars not otherwise provided for in this class
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08Selective adsorption, e.g. chromatography
    • B01D15/26Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361Ion-exchange
    • B01D15/362Cation-exchange
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13KSACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00Sugars not otherwise provided for in this class
    • C13K13/002Xylose
    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13KSACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00Sugars not otherwise provided for in this class
    • C13K13/007Separation of sugars provided for in subclass C13K

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

The invention relates to a xylose and arabinose separating method using ion exchange fiber as chromatographic packing, the ion exchange fiber is used as the chromatographic separation packing for separation and preparation of high purity xylose and arabinose from xylose crystallization mother liquor, the ion exchange fiber is strong acidic ion exchange fiber, the diameter at dry state is 8-170 mum, cation exchange capacity is 2.0-4.3mmol / g, and before being used for separation of the xylose crystallization mother liquor, the replacement of calcium ions is performed in advance for the conversion from hydrogen type to calcium type. Compared with the ion exchange granular resin chromatographic column, the strong acid ion exchange fiber shows more excellent separation precision and higher production efficiency.

Description

A kind of method that wood sugar is separated with pectinose
Technical field
The present invention relates to a kind of strong acidic ion-exchange fiber that uses as chromatogram new packing, from xylose crystallization mother liquor, be separated the processing method of high-purity wood sugar and pectinose, belong to technical field of chromatography separation.
Background technology
Current domestic xylose production process under acid hydrolysis conditions, obtains Xylose with corn cob or bagasse, in xylose crystalline process, because assorted sugared content is high, a large amount of wood sugars in crystalline mother solution are difficult to crystallize out, final xylose crystallization mother liquor major part is used as pigment raw material process at a low price, and utility value is very low.Because several monose physicochemical property in xylose crystallization mother liquor are very close, therefore separation and purification difficulty is larger.Monose separating and purifying method common at present mainly contains: chemical method, membrane separation process, biological fermentation process and chromatography.Chemical method can effectively separating xylose and pectinose, but carries out derivative reaction to monose due to needs, and technique is loaded down with trivial details, and needs in mother liquor to add a large amount of organic solvents, is not suitable for the production of food grade carbohydrate.Membrane separation process utilizes the selective penetrated property of film to be separated monose, is applicable to the liquid glucose system that molecular weight difference is larger.In xylose crystallization mother liquor, glucose and semi-lactosi are aldohexose, and wood sugar and pectinose are aldopentose, molecular weight difference is little, although therefore adopt membrane sepn to have certain inrichment to five-carbon sugar, be difficult to realize thorough separation, still need to be further separated permeate.Microbial method is the direction of current green chemistry, but the important restriction factor being this method always and promoting on the high side of microorganism and enzyme.In current medicine and food grade carbohydrate industrial production, adopt chromatographic separation technology, separating xylose from xylose crystallization mother liquor.The special chromatograph packing material used is mainly from Europe, the U.S. and Japanese import.
Spheroidal particle resin due to its material specific surface area and loading capacity limited, chromatographic column ubiquity loadings in industrial production is large and material containing amount is little, the absorb-elute cycle long, cylinder length-to-diameter ratio requires the shortcomings such as high, and then causes production equipment as simulation moving-bed efficiency is not high and flow process is complicated.On the other hand, with spheroidal particle Ion Exchange Resin Phase ratio, from the extensive accreditation of handing over many advantages of fiber to obtain scientific research technician, comprise specific surface area large, loading capacity is large, exchange velocity and elution speed fast, easy regeneration, it is better etc. to fill out bed body uniformity coefficient and Flow Field Distribution after post.But up to the present, the technology using ion-exchange fiber to be separated with pectinose for wood sugar as chromatograph packing material is applied, and does not still have disclosed document and patent report.
Summary of the invention
The object of the invention is to, provide a kind of novel chromatographic separation to produce wood sugar and pectinose method, especially adopt ion-exchange fiber as chromatographic separation filler, from xylose crystallization mother liquor, be separated the method preparing high purity wood sugar and pectinose.
The described ion-exchange fiber for xylose crystallization mother liquor separation is strongly-acid, and exchange capacity is 2.0 ~ 4.3mmol/g, and fiber in the dry state diameter is 8 ~ 170 μm.
Described ion-exchange fiber is as filler, and the short fiber form of can be length be 5 ~ 100mm, also can be pre-formed as volume density in the non-woven fabrics of 100 ~ 500g/mL or felt form.
Described ion-exchange fiber, as filler, before being separated for xylose crystallization mother liquor, needing the displacement carrying out calcium ion in advance, completes the conversion from Hydrogen to calcium type.
Employing ion-exchange fiber provided by the invention, as the xylose crystallization mother liquor separation method of chromatograph packing material, is characterized in that implementation process comprises following key step:
A) ion-exchange fiber post filling: the short fiber being converted into calcium type by above-mentioned or non-woven fabrics form from friendship fiber, fill post with adopting column length compress mode after pure water complete wetting.Packing density is 200 ~ 600g/L, and filling blade diameter length ratio is 1:5 ~ 70.
B) material containing absorption: by xylose crystallization mother liquor with 2.2 ~ 8% volumes of packing volume, maintain constant separation temperature, by 0.35 ~ 2.5BV/h flow velocity, inject water-filled chromatographic column from cylinder opening for feed constant speed.
C) wash-out: after stopping injecting liquid glucose, do moving phase at cylinder charging saliva immediately, according to 0.5 ~ 1.3 times of water yield of packing volume, 0.35 ~ 3.5BV/h flow velocity carries out wash-out to filler, obtains being rich in Xylose and being rich in Arabic liquid glucose.
D) above-mentioned steps a) ~ c) be a material containing wash-out cycle, calculate according to planimetry in one-period, when getting pectinose purity 61% as cut-point, the rate of recovery of pectinose is 70 ~ 85%, the purity being rich in wood sugar in Xylose is 86 ~ 95%, and the rate of recovery is 85 ~ 92%.
Above-mentioned steps provided by the invention a) ~ c), the mode that multicolumn series-parallel connection can be adopted to combine is run continuously, and simulation moving-bed mode also can be adopted to run continuously.
Preferred steps a) in packing density be 250 ~ 550g/L.
Preferred steps b) in separation temperature be 35 ~ 60 DEG C.
Preferred steps c) in elution speed be 0.5 ~ 1.5BV/h.
Beneficial effect of the present invention: compare with ion-exchange resins method, proposes first from friendship fibre method, can significantly promote sugar from the efficiency of production, under the condition that processing load is identical, chromatographic bed packing volume can be reduced, reduce equipment manufacturing cost; Under identical bed body size and technical process condition, can improve treatment capacity, product purity is better.Especially the processing condition adopting the present invention to limit are wider, and work-ing life obviously extends, better effects if.
Embodiment
Following not form restriction to the claims in the present invention scope to embodiment, but the present invention is conducted further description.
Embodiment 1
1) ion-exchange fiber prepares: select that diameter under drying regime is 33 ~ 40 μm, exchange capacity is the strong acidic ion-exchange fiber of 3.3mmol/g, is cut into the short fiber of about 3 ~ 10mm, soaks into pure water.Adopt excessive calcium ion to make it displacement, complete the conversion from Hydrogen to calcium type.Especially the functional fibre base material after the polystyrene-based process adopting Chinese patent 201310533240.3 to propose, prepares ion-exchange fiber through crosslinking reaction and functional modification, also can if other reaches this functional fibre material.Treating processes can with reference to prior art, and typical bibliography is as F. and J. homogeneous and Heterogeneous Sulfonation of Polymers:A Review.Polym.Eng.Sci.1998,38 (5), 783-792.
2) ion-exchange fiber filling: soak the ion-exchange fiber being converted into calcium type with pure water, adopt column length compress mode dress post, fiber packing density is 500g/L, and filling blade diameter length ratio is 1:70.
3) xylose mother liquid is separated: the xylose mother liquid of 60 ° of Bx, wherein the concentration of wood sugar and pectinose is respectively 31.1% and 14.1%.Get the liquid glucose of packing volume 2.2%, adsorb through 26 DEG C of ion-exchange fiber posts with flow velocity 1BV/h, use the water elution of liquid glucose 17 times of volumes immediately.Treat that liquid glucose flows out and collect elution samples, analyze elutriant composition with HPLC.Obtain being rich in Xylose and being rich in Arabic liquid glucose, resolution is 0.76, and when getting pectinose purity 61% as cut-point, the rate of recovery of pectinose is 76%, and the purity being rich in wood sugar in Xylose is 93%, and the rate of recovery is 86%.
4) with the contrast of spheroidal particle resin: the calcium type particulate resin fibrous packing in chromatographic column being replaced by same volume, resin mean diameter is about 300 μm, exchange capacity 1.5mol/L, wet method dress post after soaking with pure water.Resin packing density is 790g/L, and filling blade diameter length ratio is 1:70.In parameters with under the identical condition of filling ion-exchange fiber, the wash-out water yield is 23 times of liquid glucose volume, analyzes elutriant composition with HPLC.Obtain being rich in Xylose and being rich in Arabic liquid glucose, resolution is 0.49, and when getting pectinose purity 61% as cut-point, the rate of recovery of pectinose is 46%, and the purity of wood sugar is 81%, and the rate of recovery of wood sugar is 88%.
Embodiment 2
1) ion-exchange fiber prepares: select that diameter under drying regime is 33 ~ 40 μm, exchange capacity is the strong acidic ion-exchange fiber of 3.3mmol/g, is cut into the short fiber of about 3 ~ 10mm, soaks into pure water.Adopt excessive calcium ion to make it displacement, complete the conversion from Hydrogen to calcium type.Adopt embodiment 1 ion exchange fiber material.
2) ion-exchange fiber filling: soak the ion-exchange fiber being converted into calcium type with pure water, adopt column length compress mode dress post, fiber packing density is 500g/L, and filling blade diameter length ratio is 1:70.
3) xylose mother liquid is separated: the xylose mother liquid of 60 ° of Bx, wherein the concentration of wood sugar and pectinose is respectively 31.1% and 14.1%.Get the liquid glucose of packing volume 3.5%, adsorb through 26 DEG C of ion-exchange fiber posts with flow velocity 1BV/h, use the water elution of liquid glucose 12.5 times of volumes immediately.Treat that liquid glucose flows out and collect elution samples, analyze elutriant composition with HPLC.Obtain wood sugar and pectinose resolution is 0.67, when getting pectinose purity 61% as cut-point, the rate of recovery of pectinose is 72%, and the purity being rich in wood sugar in Xylose is 87%, and the rate of recovery is 80%.
4) with the contrast of spheroidal particle resin: the calcium type particulate resin fibrous packing in chromatographic column being replaced by same volume, resin mean diameter is about 300 μm, exchange capacity 1.5mol/L, wet method dress post after soaking with pure water.Resin packing density is 790g/L, and filling blade diameter length ratio is 1:70.In parameters with under the identical condition of filling ion-exchange fiber, the wash-out water yield is 15 times of liquid glucose volume, analyzes elutriant composition with HPLC.Obtain being rich in Xylose and being rich in Arabic liquid glucose, resolution is 0.52, and when getting pectinose purity 61% as cut-point, the rate of recovery of pectinose is 43%, and the purity of wood sugar is 79%, and the rate of recovery of wood sugar is 89%.
5) by the comparative analysis to result, in order to obtain identical separating effect, particulate resin filler is used for the chromatographic separation of xylose crystallization mother liquor, needs larger length-to-diameter ratio and slower elution speed.Visible, adopt ion-exchange fiber as chromatograph packing material, higher separation accuracy can be obtained in xylose crystallization mother liquor is separated, and the separation efficiency under the same terms is far above particulate resin filler.
Although the present invention with preferred embodiment disclose as above, so itself and be not used to limit the present invention.Persond having ordinary knowledge in the technical field of the present invention, without departing from the spirit and scope of the present invention, when being used for a variety of modifications and variations.Therefore, protection scope of the present invention is when being as the criterion depending on those as defined in claim.

Claims (7)

1. ion-exchange fiber is used for the method that is separated with pectinose of wood sugar as chromatograph packing material, it is characterized in that adopting ion-exchange fiber as chromatographic separation filler, for being separated the method preparing high purity wood sugar and pectinose in xylose crystallization mother liquor; Described ion-exchange fiber is strong acidic ion-exchange fiber, under drying regime, diameter is 8 ~ 170 μm, and cation exchange capacity is 2.0 ~ 4.3mmol/g, before being separated for xylose crystallization mother liquor, need the displacement carrying out calcium ion in advance, complete the conversion from Hydrogen to calcium type.
2. ion-exchange fiber as claimed in claim 1 is as filler, it is characterized in that adopting length to be that the short fiber form of 5 ~ 100mm is loaded, or adopts and be pre-formed as volume density in the non-woven fabrics of 100 ~ 500g/L or felt form, then loads.
3. ion-exchange fiber as claimed in claim 1 is used for as chromatograph packing material the method that wood sugar is separated with pectinose, it is characterized in that implementation process comprises following key step:
A) ion-exchange fiber post filling: by the short fiber described in claim 2 ~ 4 or non-woven fabrics form from friendship fiber, fill post with adopting column length compress mode after pure water complete wetting.Packing density is 200 ~ 600g/L, and filling blade diameter length ratio is 1:5 ~ 70;
B) material containing absorption: by the xylose crystallization mother liquor of above-mentioned 25 ~ 60 DEG C with 2.2 ~ 8% volumes of packing volume, by 0.35 ~ 2.5BV/h flow velocity, inject water-filled chromatographic column from cylinder opening for feed constant speed;
C) wash-out: after stopping injecting liquid glucose, do moving phase at cylinder opening for feed water immediately, according to 0.5 ~ 1.3 times of water yield of packing volume, 0.35 ~ 3.5BV/h flow velocity carries out wash-out to filler, obtains being rich in Xylose and being rich in Arabic liquid glucose.
D) above-mentioned steps a) ~ c) be a material containing wash-out cycle, calculate according to planimetry in one-period, when getting pectinose purity 61% as cut-point, the rate of recovery of pectinose is 70 ~ 85%, the purity being rich in wood sugar in Xylose is 86 ~ 95%, and the rate of recovery is 85 ~ 92%.
4. ion-exchange fiber as claimed in claim 3 is used for as chromatograph packing material the method that wood sugar is separated with pectinose, it is characterized in that above-mentioned steps a) ~ c) mode that multicolumn series-parallel connection can be adopted to combine runs continuously, and simulation moving-bed mode also can be adopted to run continuously.
5. ion-exchange fiber as claimed in claim 3 is used for as chromatograph packing material the method that wood sugar is separated with pectinose, it is characterized in that the packing density during preferred steps a) is 250 ~ 550g/L.
6. ion-exchange fiber as claimed in claim 3 is used for as chromatograph packing material the method that wood sugar is separated with pectinose, it is characterized in that step b) in separation temperature be 35 ~ 60 DEG C.
7. ion-exchange fiber as claimed in claim 3 is used for as chromatograph packing material the method that wood sugar is separated with pectinose, it is characterized in that step c) in elution speed be 1 ~ 2BV/h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107849589A (en) * 2015-07-24 2018-03-27 安尼基有限责任公司 The method that the oxidation product and reduzate of mixed sugar are prepared for enzymatic
US11198702B2 (en) 2016-02-04 2021-12-14 Industrial Technology Research Institute Method for separating hydrolyzed product of biomass

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Publication number Priority date Publication date Assignee Title
CN107849589A (en) * 2015-07-24 2018-03-27 安尼基有限责任公司 The method that the oxidation product and reduzate of mixed sugar are prepared for enzymatic
US11198702B2 (en) 2016-02-04 2021-12-14 Industrial Technology Research Institute Method for separating hydrolyzed product of biomass

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