CN104611475A - Fructose separation method - Google Patents

Fructose separation method Download PDF

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Publication number
CN104611475A
CN104611475A CN201310538665.3A CN201310538665A CN104611475A CN 104611475 A CN104611475 A CN 104611475A CN 201310538665 A CN201310538665 A CN 201310538665A CN 104611475 A CN104611475 A CN 104611475A
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Prior art keywords
fructose
ion
exchange fiber
fiber
ion exchange
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CN201310538665.3A
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CN104611475B (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
    • C13K11/00Fructose
    • 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
    • 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

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

Abstract

The invention relates to a method for separating fructose by taking ion exchange fiber as chromatographic packing, which adopts the ion exchange fiber as the chromatographic packing and is used for separating and preparing high-purity fructose from mixed sugar liquid such as fructose-glucose syrup and the like; the mixed sugar solution is a mixed solution containing fructose glucose syrup F42 or fructose with other concentration; the ion exchange fiber is a strong acid ion exchange fiber, the diameter of the ion exchange fiber is 8-170 mu m in a dry state, the cation exchange capacity is 2.0-4.3 mmol/g, and calcium ions need to be replaced in advance before the ion exchange fiber is used for fructose separation, so that the conversion from a hydrogen type to a calcium type is completed. Compared with ion exchange particle resin chromatographic columns, the strong acid ion exchange fibers show more excellent separation precision and higher production efficiency.

Description

A kind of method that fructose is separated
Technical field
The present invention relates to a kind of strong acidic ion-exchange fiber that uses as chromatogram new packing, from high fructose syrup, be separated the processing method of high-purity fructose, belong to technical field of chromatography separation.
Background technology
Fructose has that sugariness is high, mouthfeel good, anti-dental caries, edible after do not cause the good characteristics such as blood glucose fluctuation, be widely used in the production of food, medicine and healthcare products, the market requirement increases day by day.Because fructose and glucose are isomerss, physico-chemical property is close, is separated very difficult, and the high efficiency separation how realizing fructose and glucose needs the problem of solution during fructose is produced badly.The separation method of fructose and glucose mainly contains crystallization process, double salt method, chromatography, fractionation, reverse osmosis method, liquid ~ liquid extraction separation method and Exchange Resin by Adsorption etc., most enterprises mainly adopts chromatography both at home and abroad at present, with spherical calcium type ion exchange resin as chromatograph packing material, from high fructose syrup, isolate fructose.
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, use ion-exchange fiber to be used for the technology application of fructose separation as chromatograph packing material, still there is no 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 fructose method, especially adopt ion-exchange fiber as chromatographic separation filler, for being separated the method preparing high-purity fructose in the mixed sugar liquid such as high fructose syrup.
Technical scheme of the present invention is: a kind of chromatographic separation fructose method, adopts ion-exchange fiber as chromatographic separation filler, for being separated the method preparing high-purity fructose in the mixed sugar liquid such as high fructose syrup.Described mixed sugar liquid is the mixed solution of the fructose comprising high fructose syrup F42 or other concentration; Described ion-exchange fiber, is characterized in that a kind of strong acidic ion-exchange fiber, and under drying regime, diameter is 8 ~ 170 μm, cation exchange capacity is 2.0 ~ 4.3mmol/g, before being separated for fructose, needing the displacement carrying out calcium ion in advance, complete the conversion from Hydrogen to calcium type.
Employing ion-exchange fiber provided by the invention is as the fructose separation method of chromatograph packing material, and its 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 above-mentioned mixed sugar liquid with 0.1 ~ 0.4 times amount 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 4 ~ 8 times of water yields of liquid glucose volume, 0.35 ~ 3.5BV/h flow velocity carries out wash-out to filler.
D) above-mentioned steps a) ~ c) be a material containing wash-out cycle, in one-period according to planimetry calculate, during fructose purity 90%, the rate of recovery of fructose is 40 ~ 70%.
Above-mentioned steps 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 1 ~ 2BV/h.
Beneficial effect of the present invention: by enforcement of the present invention, the chromatographic separation of high-purity fructose is separated from high fructose syrup, compare with ion-exchange resins method, propose first from friendship fibre method, in particular, provide and adopt strong acidic ion-exchange fiber as chromatograph packing material, significantly can promote the efficiency of the production that fructose is separated with glucose, 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.High fructose syrup is injected the cation exchange fibre chromatographic column of transition for calcium type, washes with water, may be used for the fructose that production purity is more than 90%.Processing condition of the present invention are wider, and work-ing life 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) high fructose syrup is separated: high fructose syrup total sugar concentration is 50%, fructose content 42%, glucose content 58%.Get the liquid glucose of packing volume 8.5%, adsorb through 26 DEG C of ion-exchange fiber posts with flow velocity 0.5BV/h, use the water elution of liquid glucose 5.8 times of volumes immediately.Treat that liquid glucose flows out and collect elution samples, analyze elutriant composition with HPLC.Fructose and glucose resolution are 0.89, and during fructose purity 90%, the rate of recovery of fructose is 67%.
4) above-mentioned steps 3) be adsorbed in elution process, the mode that multicolumn series-parallel connection can be adopted to combine is carried out continuously, and simulation moving-bed mode also can be adopted to carry out continuously.
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) high fructose syrup is separated: high fructose syrup total sugar concentration is 50%, fructose content 42%, glucose content 58%.The liquid glucose getting filling body accumulated amount 8.5%, with flow velocity 1.5BV/h, adsorbs through 26 DEG C of ion-exchange fiber posts, uses the water elution of liquid glucose 6.7 times of volumes immediately.Treat that liquid glucose flows out and collect elution samples, analyze elutriant composition with HPLC.Fructose and glucose resolution are 0.91, and during fructose purity 90%, the rate of recovery of fructose is 53%.
4) above-mentioned steps 3) be adsorbed in elution process, the mode that multicolumn series-parallel connection can be adopted to combine is carried out continuously, and simulation moving-bed mode also can be adopted to carry out continuously.
Embodiment 3
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) high fructose syrup is separated: get the commodity F42 high fructose syrup being diluted to total sugar concentration 50%, volume is filling body accumulated amount 8.5%, adsorbs, use the water elution of liquid glucose 7.2 times of volumes immediately with flow velocity 1.5BV/h through 26 DEG C of ion-exchange fiber posts.Treat that liquid glucose flows out and collect elution samples, analyze elutriant composition with HPLC.Fructose and glucose resolution are 0.88, and during fructose purity 90%, the rate of recovery of fructose is 61%.
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 8 times of liquid glucose volume.Elutriant composition is analyzed with HPLC.Fructose and glucose resolution are 0.52, and during fructose purity 90%, the rate of recovery of fructose is 23%.
By finding the comparative analysis from the particulate resin separating resulting handing over fiber, in order to obtain identical separating effect, particulate resin filler is used for the chromatographic separation of fructose, needs larger length-to-diameter ratio and slower elution speed.And adopt ion-exchange fiber as chromatograph packing material, higher separation accuracy can be obtained in fructose 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 a method for fructose separation as chromatograph packing material, it is characterized in that adopting ion-exchange fiber as chromatographic separation filler, prepares high-purity fructose for being separated in the mixed sugar liquid such as high fructose syrup; Described mixed sugar liquid is the mixed solution of the fructose comprising high fructose syrup F42 or other concentration; Described ion-exchange fiber is a kind of strong acidic ion-exchange fiber, and under drying regime, diameter is 8 ~ 170 μm, cation exchange capacity is 2.0 ~ 4.3mmol/g, before being separated for fructose, needing the displacement carrying out calcium ion in advance, complete the conversion from Hydrogen to calcium type.
2. a kind of ion-exchange fiber as claimed in claim 1 is used for the method for fructose separation as chromatograph packing material, it is characterized in that ion-exchange fiber is as filler, ion-exchange fiber employing length is that the short fiber form of 5 ~ 100mm is loaded, or be pre-formed as volume density in the non-woven fabrics of 100 ~ 500g/L or felt form, then load.
3. ion-exchange fiber as claimed in claim 1 or 2 is used for the method for fructose separation as chromatograph packing material, it is characterized in that implementation process comprises the following steps:
A) ion-exchange fiber post filling: by described short fiber 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 mixed sugar liquid of above-mentioned 25 ~ 60 DEG C with 0.1 ~ 0.4 times amount 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 4 ~ 8 times of water yields of liquid glucose volume, 0.35 ~ 3.5BV/h flow velocity carries out wash-out to filler.
4. ion-exchange fiber as claimed in claim 3 is used for as chromatograph packing material the method that fructose is separated, it is characterized in that above-mentioned steps a) ~ c) mode that adopts multicolumn series-parallel connection to combine runs continuously, or adopts simulation moving-bed mode to run continuously.
5. ion-exchange fiber as claimed in claim 3 is used for the method for fructose separation as chromatograph packing material, it is characterized in that the packing density during step a) is 250 ~ 550g/L.
6. ion-exchange fiber as claimed in claim 3 is used for as chromatograph packing material the method that fructose is separated, and 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 fructose is separated, and it is characterized in that step c) in elution speed be 1 ~ 2BV/h.
CN201310538665.3A 2013-11-04 2013-11-04 Fructose separation method Active CN104611475B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110387442A (en) * 2018-04-23 2019-10-29 诺瓦塞普工艺公司 The method for purifying fructose
CN111346622A (en) * 2018-12-24 2020-06-30 内蒙古蒙牛乳业(集团)股份有限公司 Chromatographic packing and preparation method and application thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1753952A (en) * 2003-02-24 2006-03-29 兰爱克谢斯德国有限责任公司 Mixture
CN101177716A (en) * 2007-12-12 2008-05-14 江南大学 Method for separating and purifying glucose, fructose and oligomeric polysaccharide from high fructose syrup
CN101766289A (en) * 2010-01-29 2010-07-07 安徽丰原发酵技术工程研究有限公司 Method for preparing high fructose corn syrup
CN102205039A (en) * 2011-05-25 2011-10-05 北京服装学院 Method for extracting purified saponin with ion exchange fiber

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1753952A (en) * 2003-02-24 2006-03-29 兰爱克谢斯德国有限责任公司 Mixture
CN101177716A (en) * 2007-12-12 2008-05-14 江南大学 Method for separating and purifying glucose, fructose and oligomeric polysaccharide from high fructose syrup
CN101766289A (en) * 2010-01-29 2010-07-07 安徽丰原发酵技术工程研究有限公司 Method for preparing high fructose corn syrup
CN102205039A (en) * 2011-05-25 2011-10-05 北京服装学院 Method for extracting purified saponin with ion exchange fiber

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宗亚宁: "《新型纺织材料及应用》", 31 October 2009 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110387442A (en) * 2018-04-23 2019-10-29 诺瓦塞普工艺公司 The method for purifying fructose
CN111346622A (en) * 2018-12-24 2020-06-30 内蒙古蒙牛乳业(集团)股份有限公司 Chromatographic packing and preparation method and application thereof
CN111346622B (en) * 2018-12-24 2023-05-09 内蒙古蒙牛乳业(集团)股份有限公司 Chromatographic packing and preparation method and application thereof

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