CN105037669A - Preparation method for adsorbent for sugar liquor refining - Google Patents
Preparation method for adsorbent for sugar liquor refining Download PDFInfo
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- CN105037669A CN105037669A CN201510406041.5A CN201510406041A CN105037669A CN 105037669 A CN105037669 A CN 105037669A CN 201510406041 A CN201510406041 A CN 201510406041A CN 105037669 A CN105037669 A CN 105037669A
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- exchange resin
- tannin
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Abstract
The invention relates to a preparation method for adsorbent for sugar liquor refining. By adopting ion exchange resin grafting a tertiary amine group [-N(CH3)2] on a styrene-divinylbenzene copolymer in a porous structure as a raw material, a swelling agent, water, p-trifluoromethyl benzaldehyde C8H5F3O and tannin C76H52O46 are added; tannin resin is fixed on amino resin through condensation reaction and a grafting method; p-trifluoromethyl benzaldehyde plays a critical role in a Mannich reaction system; tannin can be fixed on the amino resin through a bridging effect of p-trifluoromethyl benzaldehyde; a lot of phenolic hydroxyl groups on the surface of cured tannin macroporous resin not only are donors of hydrogen bonds, but also receptors of hydrogen bonds, and impurities such as phenolic compounds, iron, furfural and the like in an xylose solution can be adsorbed by virtue of a relatively strong hydrogen bond action force, so that the sugar liquor refining effect is improved.
Description
Technical field
The present invention relates to a kind of preparation method of anionite-exchange resin, particularly a kind of preparation method of the sorbent material refined for liquid glucose.
Background technology
Wood sugar is a kind of non-caloric sweetener, and because its metabolism in vivo and Regular Insulin have nothing to do, do not cause carious tooth, the utilization ratio of metabolism is low, is widely used in the departments such as food, chemical industry, medicine.With the waste plant fiber such as corn cob, bagasse for raw material, through hydrolysis, decolouring, filter, produce from operations such as friendship, concentrated, crystallizations.Corn cob is in hydrolytic process, except generation wood sugar, also produce the materials such as assorted sugar, pigment, colloid, nitrogenous thing, ash content, mineral acid, activated carbon decolorizing is adopted to remove partial pigment, colloid, other foreign ion and partial pigment are removed not fall, and are mainly the protein in Xylose, phenolic compound, iron and furfural, for thoroughly removing foreign ion and pigment, Xylose generally adopts macropore weak basic anion exchange resin (as D301) to carry out primary ions exchange.
Softening, the desalination of a CN1760376 beet liquid glucose, dealkalize, decolouring and refining device.The rare liquid glucose of beet is made after beet raw sugar liquid being carried out the larger organism of pre-treatment removing molecular weight, then the rare liquid glucose of beet enters storng-acid cation exchange resin, and the positively charged ion in the rare liquid glucose of beet is carried out exchange adsorption by storng-acid cation exchange resin and completes softening; Filtration beet liquid glucose is made to enter H
+formula weakly acidic cation-exchange resin can remove residual positively charged ion (Na
+, K
+) and amino nitrogen compound after complete dealkalize; Complete decolouring after can removing pigment, ash and the residual organism in liquid glucose after making beet liquid glucose enter OH formula weak base anion-exchange resin afterwards, then can make beet refinery liquor.
CN102031315 discloses a kind of renovation process of decolouring decalcification resin of refining sugar, and comprises the steps: the decolouring of (1) syrup or clear juice, obtains decolorizing resin and decolour syrup or clear juice; (2) regeneration of decolorizing resin, obtains the decolorizing resin after regenerating and decolorizing resin regeneration waste liquid I; (3) decalcification of sugar juice processed, obtains decalcification resin and the clear juice of decalcification; (4) regeneration of decalcification resin, regenerates decalcification resin with regeneration waste liquid I, obtains the decalcification resin after regenerating and decalcification acid-basic regenerated waste liquids in water II.The invention also discloses the reuse method of regeneration waste liquid II, namely for the preparation of the rich calcichrome with anti-oxidant activity.The present invention is applicable to the peace and quiet or clarifying process of the syrup (juice) of beet or cane sugar factory, be particularly suitable for decolouring and the decalcification of sugar juice processed and syrup, principal feature is processing technology safety, reduces regenerant consumption and evaporating pot fouling, non-environmental-pollution, saving evaporating pot evaporation energy, has recycled the non-sugars such as pigment in syrup (juice) and calcium.
CN101249424 provides a kind of solidify tannin large hole adsorption resin, and it contains the vegatable tannin of 0.25 ~ 1% amount.Additionally provide the preparation method of solidify tannin large hole adsorption resin simultaneously, adopt mannich reaction, vegatable tannin is fixed on styrene-divinylbenzene copolymer, prepares a kind of new curing tannin large hole adsorption resin.Solidify tannin large hole adsorption resin of the present invention shows good absorption property to the aldehydes matter in the aqueous solution, easy zeolite regeneration, reuses effective, and enriching and recovering reality being contained to aldehydes matter waste water all obtains gratifying result.But also the toxic chemical substance of synthetic resins can be overcome.
Above prior art process flow is long, and yield is low, and cost is high, and the problem that after life-time service, mechanical strength of resin reduces, and have impact on the result of use in full scale plant.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of the sorbent material refined for liquid glucose.
For a preparation method for the sorbent material that liquid glucose is refined, grafting tertiary amine groups [-N (CH on the SDEB styrene diethylenebenzene interpolymer of employing macroporous structure
3)
2] ion exchange resin be raw material, add swelling agent, water, p-trifluoromethyl benzaldehyde C
8h
3f
3o, tannin C
76h
52o
46by condensation reaction with by the method for grafting, tannin resin is fixed on amine resin, p-trifluoromethyl benzaldehyde plays vital effect in Mannich reaction system, by the chain bridge effect to three ylmethyl phenyl aldehydes, tannin just can be fixed on amine resin, there is a large amount of phenolic hydroxyl groups on solidify tannin large hole adsorption resin surface, phenolic hydroxyl group be hydrogen bond give body, also be the acceptor of hydrogen bond, can with the phenolic compound in stronger Hyarogen-bonding absorption Xylose, the impurity such as iron and alditol, thus improve the refining effect of liquid glucose.
For the anionite-exchange resin that liquid glucose is refining, by the condenses of poly styrene polymer graft curing p-trifluoromethyl benzaldehyde and tannin, structural representation is as follows:
The integer of m, n=1-3000; R=C
70h
44o
41
For the anionite-exchange resin that liquid glucose is refining, comprise the following steps:
Grafting tertiary amine groups [-N (CH on the SDEB styrene diethylenebenzene interpolymer of macroporous structure
3)
2] ion exchange resin ball body swell in ion exchange resin ball body percent 10-50 (wt%) dimethyl sulfoxide (DMSO), be optimized for percent 20 (wt%), add ion exchange resin ball body percent 100-500 (wt%) water, be optimized for 300 (wt%) (weight ratio); Add the p-trifluoromethyl benzaldehyde of ion exchange resin ball body percent 10-50 (wt%), add the tannin of ion exchange resin ball body percent 2-10 (wt%), in 80 DEG C-120 DEG C (being optimized for 100 DEG C) stirring reaction 5-10h, (being optimized for 8h), reaction terminates obtained this patent product.
Grafting tertiary amine groups [-N (CH on the SDEB styrene diethylenebenzene interpolymer of described macroporous structure
3)
2] ion exchange resin ball body can use commercially available prod, as the D301 macroreticular weakly base styrene series anion exchange resin that Anhui Samsung resin Science and Technology Ltd. produces, the U.S. produces AmberliteIRA-93 anionite-exchange resin, West Germany produces LewacitMP-64 anionite-exchange resin etc., preferred D301 macroreticular weakly base styrene series anion exchange resin.
Described tannin molecular formula: C
76h
52o
46, commercially available prod.
Described p-trifluoromethyl benzaldehyde molecular formula is: C
8h
5f
3o, commercially available prod.
Beneficial effect of the present invention:
1) grafting tertiary amine groups [-N (CH on the SDEB styrene diethylenebenzene interpolymer of macroporous structure
3)
2] ion exchange resin to the impurity in liquid glucose, there is certain adsorption, for further strengthening this effect, on resin matrix, the tannin condenses of phenolic hydroxyl group is rich in grafting, p-trifluoromethyl benzaldehyde plays vital effect in Mannich reaction system, by the chain bridge effect of p-trifluoromethyl benzaldehyde, tannin just can be fixed on amine resin. and there is a large amount of phenolic hydroxyl groups on solidify tannin large hole adsorption resin surface, phenolic hydroxyl group be hydrogen bond give body, also be the acceptor of hydrogen bond, can with the phenolic compound in stronger Hyarogen-bonding absorption Xylose, the impurity such as iron and furfural, thus improve the refining effect of liquid glucose.
2) p-trifluoromethyl benzaldehyde participates in the fluoropolymer that condensation is formed, and due to the introducing of fluorine, rise significantly with the consistency in non-polar solvent and aromatic series kind solvent, the ability of the adsorbing contaminant in liquid glucose is also improved.The ability of resin absorption liquid glucose is improved.
Embodiment
Following examples are only further illustrate the present invention, are not restriction the scope of protection of the invention.
Embodiment 1
In 500L reactor, add 100KgD301 macroreticular weakly base styrene series anion exchange resin, swell in 20Kg dimethyl sulfoxide (DMSO), add 300Kg water, add 20Kg to three ylmethyl phenyl aldehydes, add the tannin of 5Kg, in 100 DEG C of stirring reaction 8h, reaction terminates obtained this patent product.Products obtained therefrom sucking is SX-1.
Embodiment 2
In 500L reactor, add 100KgD301 macroreticular weakly base styrene series anion exchange resin, swell in 10Kg methyl-sulphoxide, add 500Kg water, add the p-trifluoromethyl benzaldehyde of 20Kg, add the tannin of 5Kg, in 80 DEG C of stirring reaction 10h, reaction terminates obtained this patent product.Products obtained therefrom is numbered SX-2.
Embodiment 3
In 500L reactor, add 100KgD301 macroreticular weakly base styrene series anion exchange resin, swell in 50Kg methyl-sulphoxide, add 300Kg water, add the p-trifluoromethyl benzaldehyde of 20Kg, add the tannin of 5Kg, in 120 DEG C of stirring reaction 5h, reaction terminates obtained this patent product.Products obtained therefrom is numbered SX-3.
Embodiment 4
Add the p-trifluoromethyl benzaldehyde of 50Kg, the other the same as in Example 1.Products obtained therefrom is numbered SX-4.
Embodiment 5
Add the p-trifluoromethyl benzaldehyde of 10Kg, the other the same as in Example 1.Products obtained therefrom is numbered SX-5.
Embodiment 6
Add the tannin of 2Kg, the other the same as in Example 1.Products obtained therefrom is numbered SX-6.
Embodiment 7
Add the tannin of 2Kg, the other the same as in Example 2.Products obtained therefrom is numbered SX-7.
Embodiment 8
Add the tannin of 2Kg, the other the same as in Example 3.Products obtained therefrom is numbered SX-8.
Embodiment 9
Add the tannin of 10Kg, the other the same as in Example 1, products obtained therefrom is numbered SX-9
Embodiment 10
Add the tannin of 10Kg, the other the same as in Example 2, products obtained therefrom is numbered SX-10
Embodiment 11
Add the tannin of 10Kg, the other the same as in Example 3, products obtained therefrom is numbered SX-11
Comparative example 1
Do not add p-trifluoromethyl benzaldehyde, the other the same as in Example 1.Products obtained therefrom is numbered SX-12.
Comparative example 2
Do not add tannin, the other the same as in Example 1, products obtained therefrom is numbered SX-13.
Comparative example 3
The tannin do not added, other is with comparative example 1, and products obtained therefrom is numbered SX-14.
Comparative example 4
Use D301 macroreticular weakly base styrene series anion exchange resin to decolour, be numbered SX-15.
By Fourier transform infrared spectrometer, pressing potassium bromide troche does Infrared spectroscopy to synthesized each resin.Infrared spectra from reaction product: SX1-SX14 is at 1370cm
-1near there is C-N stretching vibration absorption peak, at 1640cm
-1near there is N-H symmetric vibration absorption peak, illustrate and introduce tertiary amine group in the skeleton of polystyrene resin; At 1720cm in the collection of illustrative plates of SX1-SX11 sample
-1near have the carbonyl peak of Weibull, 1320cm
-1near have the polyphenol hydroxyl absorption peak of Weibull, 760cm
-1near have the phenyl ring peak of Weibull; At 1235cm in the collection of illustrative plates of SX1-SX11, SX13 sample
-1near have CF
2, CF
3stretching vibration peak, at 2750cm
-1near have the stretching vibration peak of aldehyde radical C-H, illustrated that trifluoromethylated benzaldehyde exists, so can determine that this patent product generates the condenses by macroreticular weakly base styrene series anion exchange resin graft curing p-trifluoromethyl benzaldehyde and tannin.
Embodiment 12
Get the product of 200ml embodiment 1-9 and comparative example 1-2, put into 1000ml glass exchange column, 20L xylo-oligosaccharide liquid is crossed post with 200ml/h flow velocity, by the measure and calculation Sugarcane juice decolorization rate of B/T12496.9-1999 caramel decolorization rate.
| Production code member | Sugarcane juice decolorization rate % |
| SX-1 | 94 |
| SX-2 | 96 |
| SX-3 | 94 |
| SX-4 | 98 |
| SX-5 | 91 |
| SX-6 | 89 |
| SX-7 | 87 |
| SX-8 | 86 |
| SX-9 | 93 |
| SX-10 | 94 |
| SX-11 | 98 |
| SX-12 | 77 |
| SX-13 | 78 |
| SX-14 | 71 |
Claims (4)
1. a preparation method for the sorbent material refined for liquid glucose, is characterized in that comprising the following steps:
Grafting tertiary amine groups [-N (CH on the SDEB styrene diethylenebenzene interpolymer of macroporous structure
3)
2] ion exchange resin ball body swell in ion exchange resin ball body percent 10-50 (wt%) dimethyl sulfoxide (DMSO), add ion exchange resin ball body percent 100-500 (wt%) water, add the p-trifluoromethyl benzaldehyde of ion exchange resin ball body percent 10-50 (wt%), add the tannin of ion exchange resin ball body percent 2-10 (wt%), in 80 DEG C-120 DEG C stirring reaction 5-10h,, reaction terminates obtained this patent product.
2. a preparation method for the sorbent material refined for liquid glucose, is characterized in that, grafting tertiary amine groups [-N (CH on the SDEB styrene diethylenebenzene interpolymer of macroporous structure
3)
2] ion exchange resin as body material.As domestic D301 macroreticular weakly base styrene series anion exchange resin, the U.S. produces AmberliteIRA-93 anionite-exchange resin, and West Germany produces LewacitMP-64 anionite-exchange resin etc.
3. a preparation method for the sorbent material refined for liquid glucose, is characterized in that, tannin, by condensation reaction, is cured on body material according to claim 3 by p-trifluoromethyl benzaldehyde and tannin.
4. the preparation method of a kind of sorbent material refined for liquid glucose obtained according to the described preparation method of one of claim 1-4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859938A (en) * | 2016-06-13 | 2016-08-17 | 王金明 | Preparation of cobalt adsorbent |
| CN106902732A (en) * | 2015-12-22 | 2017-06-30 | 中粮集团有限公司 | Compound adsorbent and the method that beet sugar peculiar smell is removed using the compound adsorbent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1804025A (en) * | 2005-12-09 | 2006-07-19 | 山东省中协食品添加剂研究开发中心 | Production method for xylose by enzyme process |
| CN101249424A (en) * | 2008-03-31 | 2008-08-27 | 北京林业大学 | Solidify tannin large hole adsorption resin and method of preparing the same |
| CN102605108A (en) * | 2012-03-26 | 2012-07-25 | 山东福田药业有限公司 | Method for producing xylose by using eucalyptus pulp pre-hydrolyzing liquid |
| CN103088166A (en) * | 2013-01-28 | 2013-05-08 | 山东省食品发酵工业研究设计院 | Method for extracting xylose by strong-flavor solid white wine vinasse |
| CN103864989A (en) * | 2014-03-30 | 2014-06-18 | 吉首大学 | Preparation method of tannin-based adsorbent resin |
-
2015
- 2015-07-08 CN CN201510406041.5A patent/CN105037669B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1804025A (en) * | 2005-12-09 | 2006-07-19 | 山东省中协食品添加剂研究开发中心 | Production method for xylose by enzyme process |
| CN101249424A (en) * | 2008-03-31 | 2008-08-27 | 北京林业大学 | Solidify tannin large hole adsorption resin and method of preparing the same |
| CN102605108A (en) * | 2012-03-26 | 2012-07-25 | 山东福田药业有限公司 | Method for producing xylose by using eucalyptus pulp pre-hydrolyzing liquid |
| CN103088166A (en) * | 2013-01-28 | 2013-05-08 | 山东省食品发酵工业研究设计院 | Method for extracting xylose by strong-flavor solid white wine vinasse |
| CN103864989A (en) * | 2014-03-30 | 2014-06-18 | 吉首大学 | Preparation method of tannin-based adsorbent resin |
Non-Patent Citations (1)
| Title |
|---|
| 黄礼煌: "《化学选矿》", 30 April 2012 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902732A (en) * | 2015-12-22 | 2017-06-30 | 中粮集团有限公司 | Compound adsorbent and the method that beet sugar peculiar smell is removed using the compound adsorbent |
| CN106902732B (en) * | 2015-12-22 | 2019-12-06 | 中粮集团有限公司 | Composite adsorbent and method for removing beet sugar odor by using same |
| CN105859938A (en) * | 2016-06-13 | 2016-08-17 | 王金明 | Preparation of cobalt adsorbent |
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| CN105037669B (en) | 2017-05-31 |
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Address after: 322000 Zhejiang province Yiwu City Binwang zipper Street 5 District No. 3 room 602 Applicant after: Wang Jinming Address before: 315042 Zhejiang province Jiangdong District of Ningbo City Road 265 Lane 17 No. 104 Min'an room Applicant before: Wang Jinming |
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Effective date of registration: 20200831 Address after: 161500 Northwest New Street, Yi'an Town, Yi'an County, Qiqihar City, Heilongjiang Province Patentee after: Yian Dongfang Ruixue Sugar Industry Co., Ltd Address before: 322000 Zhejiang province Yiwu City Binwang zipper Street 5 District No. 3 room 602 Patentee before: Wang Jinming |
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