CN102070677B - Method for refining raffinose - Google Patents
Method for refining raffinose Download PDFInfo
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- CN102070677B CN102070677B CN 201110031742 CN201110031742A CN102070677B CN 102070677 B CN102070677 B CN 102070677B CN 201110031742 CN201110031742 CN 201110031742 CN 201110031742 A CN201110031742 A CN 201110031742A CN 102070677 B CN102070677 B CN 102070677B
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Abstract
The invention discloses a method for refining raffinose from cottonseed meal subjected to oil extraction, which comprises the following steps of: 1) leaching the cottonseed meal subjected to oil extraction by using methanol or ethanol to obtain extract liquor containing phenol and raffinose, and concentrating to obtain paste; 2) dissolving the paste in hot water in an amount of 1 to 1.5 times weight of the paste to obtain slurry, cooling, standing for at least 5 hours, and removing solids or asphalt substances to obtain liquid; 3) filtering the liquid to obtain clear liquid, standing at the temperature of between 0 and 10 DEG C for at least 24 hours, and crystallizing to obtain a crystal I; 4) heating and dissolving the crystal I in more than 90 weight percent ethanol solution, cooling, standing at the temperature of between 0 and 10 DEG C for at least 24 hours, and crystallizing to obtain a crystal II; and 5) washing the crystal II by using more than 95 weight percent ethanol at the temperature of below 10 DEG C, and drying to obtain the raffinose. The method is easy to operate and low in cost, and the obtained raffinose has the purity of over 85 percent.
Description
Technical field
The invention belongs to the deep processing field of cottonseed, be specifically related to a kind of process for purification of cottonseed sugar.
Background technology
Cottonseed sugar is claimed raffinose again, is the most well-known a kind of trisaccharide of occurring in nature,, in most plant, all has the about 2-5wt% of content in cottonseed benevolence by semi-lactosi, fructose and glucose be combined into.Cottonseed sugar belongs to functional oligose; Has extensive use at protective foods and pharmaceutical industries; Its physiological function mainly contains: 1) cottonseed sugar promotes bifidus bacillus propagation, is the MF of bifidus bacillus, and bifidus bacillus can be in enteron aisle nutritive substances such as synthesise vitamins B1, B2, B6, B12, nicotinic acid, folic acid; Help enhancing body immunizing power, the opposing tumour; 2) cottonseed sugar can suppress the growth of spoilage organism such as intestinal bacteria and clostridium perfringens, thus objectionable impuritiess such as the phenol that the metabolism of inhibition spoilage organism produces, ammonia, earthworm diindyl, cadaverine; 3) cottonseed sugar is difficult to absorbed by human consumption, the energy that provides very low (6KJ/g), and have certain sugariness, can be used as functional food additives and in food, use; 4) can stimulate intestines peristalsis because the bifidobacterium fermentation cottonseed sugar produces a large amount of short chain fatty acids, increase the wettability of ight soil, and the raised growth through thalline to be keeping certain osmotic pressure, thereby improve bowel movement function, prevent the generation of constipation.
Chinese patent No.00134520.6 discloses a kind of treatment process of cottonseed, comprising from cotton benevolence, extracting Oleum Gossypii semen, from cotton dregs, remove gossypol and obtain cottonseed protein, and the methanol solution recovery evaporation that will extract behind the gossypol obtains sub product-bullion oligose.Yet; Contain more impurity, pigment owing to extract in the methanol solution behind the gossypol, the bullion oligosaccharide contg that obtains is low, impurity is big, and using value is little; This patented technology is in practice; Produce the sub product that obtains behind the dephenolization cottonseed protein and be dropped, not only environment is had pollution, and wasted natural cottonseed sugar resource owing to being not used.
In recent years, the comprehensive utilization of cottonseed resource comes into one's own gradually.Existing cottonseed sugar is purified has several different methods, comprises adopting Acid precipitation, centrifugal, resin absorption, millipore filtration, discoloring agent etc.Chinese patent No.200710098890.4 discloses a kind of working method of cottonseed oligosaccharide; The center is similar with the processing of patent No.00134520.6 cottonseed step by step; Use the method for three grades of dephenolizes; Institute's difference be the methanol concentration that uses of each extraction step all not to the utmost institute with, how will adjust methyl alcohol in the practical application and not adjust to suitable concentration also not fully not openly; From its disclosed technical parameter, the content of the oligomeric Icing Sugar middle cotton seed sugar for preparing has only about 30%, and protein content explains that then up to 20% impurity wherein is still more.
One Chinese patent application CN200810089636.2 discloses a kind of method of in cotton dregs, extracting cottonseed sugar; Wherein pay attention to the process of producing of cottonseed sugar coarse fodder; Only mention subsequent process simply to raffinose raffinate; Cottonseed sugar purified detailed step is not provided, through conventional means the cottonseed sugar crude extract of said preparation is handled and be difficult to obtain the higher cottonseed sugar of purity.
Therefore, the sub product that deep processing obtains from cotton dregs for cottonseed---bullion cottonseed sugar is necessary to make with extra care processing, to improve its economic worth and use value.
Summary of the invention
The method that the purpose of this invention is to provide a kind of refining cottonseed sugar can remove harmful gossypol and other impurity through this method, obtains the higher cottonseed sugar of purity, for cottonseed sugar has been opened up bright prospects in the application in food and medicine field.
To achieve these goals, the present invention provides following technical scheme:
A kind of method of refining cottonseed sugar comprises step:
1) will carry that to add concentration in the cotton dregs behind the oil be methyl alcohol or the ethanol of 65～95wt%, ℃ leaching is 0.5～1.5 hour in normal temperature～65, obtains containing the methyl alcohol or the alcohol extraction liquid of phenol and cottonseed sugar, and is concentrated, obtains paste;
2) paste is dissolved in the hot water of 1～1.5 times of weight obtains slurry, cooling was left standstill 5 hours at least, removed solids or pitch shape thing, obtained fraction;
3) with fraction through filtering, obtain clear liquid, clear liquid leaves standstill at least 24 hours crystallizatioies under 0～10 ℃ temperature, obtain crystallisate I;
4) with heating for dissolving in the ethanolic soln of crystallisate I more than concentration 90wt%, at least 24 hours crystallizatioies are left standstill in cooling under 0～10 ℃ temperature, obtain crystallisate II;
5) with crystallisate II with temperature less than 10 ℃, washing with alcohol more than the concentration 95wt%, drying obtains cottonseed sugar.
Wherein, cotton dregs described in the step 1) are to obtain after from cottonseed, extracting Oleum Gossypii semen through any means known in the art.For example, can be to carry the wet dregs of rice behind the oil through what disclosed method among the patent CN00134520.6 obtained.
The said methanol extraction liquid that contains phenol and cottonseed sugar is to concentrate being no more than under 100 ℃ the temperature, and methanol content is less than 500mg/kg in the paste product that obtains.Concentrate and to use modes such as single vaporization, falling film type evaporation, multiple-effect evaporation or thin film evaporation.
The temperature of hot water step 2) is any number in 50 ℃～100 ℃ scopes, for example 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃; Preferred 70～90 ℃, for example 70 ℃, 80 ℃ or 90 ℃; More preferably 70～80 ℃; The weight ratio of paste and hot water is 1: 1～1: the 1.5 any ratio in the scope, for example can be 1: 1,1: 1.1,1: 1.2,1: 1.3,1: 1.4 or 1: 1.5; Preferred 1.2～1.4; Said slurry leaves standstill and can carry out at normal temperatures.
Filter described in the step 3) and comprise coarse filtration and fine filtering.Coarse filtration is meant through the aperture of 0.04～0.1mm filters the aperture of preferred 0.05～0.08mm, the more preferably from about aperture of 0.06～0.07mm.For example, can preferably adopt the filtering material in 0.053mm, 0.063mm or 0.071mm aperture.Said filtering material is silk screen filter cloth, for example Stainless Steel Cloth or fibers material silk screen preferably.Coarse filtration can adopt technique known to carry out, for example centrifugation apparatus, pumping and filtering device, filtering equipment etc.
Filtrating after the coarse filtration is continued fine filtering, and coarse filtration is meant through the aperture of 0.015～0.02mm and filters that the filtering material in 0.02mm aperture for example can preferably be adopted in the aperture of preferred 0.018～0.02mm.Said filtering material can be band suede filter cloth or the essentially identical silk screen filter cloth in aperture, preferably is with the suede filter cloth.Fine filtering can adopt technique known to carry out, for example centrifugation apparatus, pumping and filtering device, filtering equipment etc., but be good with suction filtration or press filtration.Filtering number of times can be an one or many, and the liquid that obtains behind the fine filtering is the best with the solid shape impurity of transparent nothing.
Heating temperature when dissolving in the step 4) is more than 45 ℃, for example 45～75 ℃, and preferred 50～70 ℃, more preferably 55～65 ℃.The weight ratio of crystallisate I and ethanolic soln is 1: 1～1: 5.Dwell temperature can be a normal temperature.Said normal temperature is meant the envrionment temperature when leaving standstill, and when envrionment temperature was hanged down, crystallization effect was better, preferably in envrionment temperature less than 10 ℃, time of repose greater than 24 hours, obtain more crystallisate.Can adopt the freezing artificial hypothermia's method that waits, make envrionment temperature when leaving standstill between 0～10 ℃, for example can be 1 ℃, 2 ℃, 3 ℃, 5 ℃, 7 ℃, 9 ℃ or 10 ℃; Preferred 0～7 ℃, more preferably 0～3.
Consumption of ethanol when washing in the step 5) more than the said concentration 95wt% and 1～1.5 times of weight of crystallisate II for example can be 1.1,1.2,1.3,1.4,1.5 times of weight of crystallisate II.The washing post crystallization thing that finishes is dry through low temperature (less than 10 ℃) or vacuum or conventional known method such as freezing, obtains the crystallisate cottonseed sugar at last, and its purity can reach 85%.In addition, other cotton glycan such as clear liquid crystallization once more, last resistates simmer down to wood sugar that return capable of circulation of the mother liquor resistates after the crystallization.
Can remove a large amount of protein, tannin, phytic acid, gossypol pigment and lipid-soluble substance and insoluble solid matter in the cotton dregs through method of the present invention; The cottonseed sugar for preparing is faint yellow meal; Do not have or little hygroscopic effect arranged; Removed the purity of raffinose in the bullion and reached more than 85%, moisture is less than 5%, but the additive of food, medicine and other fields is made in widespread use.
The present invention has following beneficial effect:
1) adopt comparatively simple physics method, got rid of the interpolation chemical agent, like steps such as acid solution, discoloring agents, ethanolic soln is recyclable, makes whole technological operation easy, and cost reduces;
2) purification obtains highly purified cottonseed sugar the cotton dregs after cottonseed is carried oil, for bright prospects have been opened up in the application of cottonseed sugar; Solved the liquid waste disposal problem of producing behind Oleum Gossypii semen and the cottonseed protein simultaneously;
3) cotton dregs extract in the residue waste residue behind the cottonseed sugar and contain great deal of tannin and phytic acid etc., can further extract or as fermentation fertilizer, make cottonseed obtain comprehensively utilization rationally, for enterprise brings certain economic benefits.
Description of drawings
Fig. 1 is the process flow sheet of the refining cottonseed sugar of the present invention.
Embodiment
Following embodiment combines accompanying drawing to be used to further specify the present invention, but does not limit the scope of the present invention's protection.Unless stated otherwise, used reagent and other experiment materials of the present invention is common commercially available prod.
The preparation of embodiment 1 cottonseed sugar
Present embodiment uses the cotton dregs carry behind the oil as raw material, and said cotton dregs can be according to the method production among the Chinese patent No.001345206.Methyl alcohol is reclaimed in the methanol solution evaporation that Chinese patent No.001345206 produces behind the dephenolization cottonseed protein, concentrate, obtain paste, controlled temperature≤100 ℃ when concentrating.In system, recycle methanol content＜500mg/kg in the paste after the Methanol Recovery.With paste and hot water by weight 1: 1 in common vessel stirring and dissolving be soup compound, the temperature of hot water is 70 ℃.Soup compound left standstill 5 hours after being cooled to room temperature, removed the solids on upper strata or the throw out of pitch shape thing and lower floor, obtained fraction.
The filter cloth suction filtration (coarse filtration) of fraction through the 0.053mm aperture with after removing partial impurities, then through the band suede filter cloth suction filtration (fine filtering) in 0.015mm aperture, obtained the clear liquid of the solid shape impurity of transparent nothing.Place container to leave standstill the clear liquid behind the fine filtering and made its crystallization in 24 hours, cross and filter crystallisate I at 10 ℃.With crystallisate I and concentration is that the ethanolic soln of 95wt% mixes with weight ratio at 1: 1, is heated to 45 ℃～75 ℃ to dissolving fully, naturally cools to normal temperature, under 10 ℃, leaves standstill crystallization, filter, crystallisate II.Crystallisate II is used less than the alcohol immersion washing as 95wt% of 10 ℃ concentration, and consumption of ethanol is about 1 times of weight of crystallisate during washing.Crystallisate II after the washing is the dry crystallisate that obtains cottonseed sugar under low temperature (less than 10 ℃) condition, detects through HPLC (HPLC) method, and its purity is about 85.1%.
The preparation of embodiment 2 cottonseed sugars
Present embodiment uses the cotton dregs carry behind the oil as raw material, and said cotton dregs can be according to the method production among the Chinese patent No.001345206.Ethanol is reclaimed in the ethanol liquid evaporation that Chinese patent No.001345206 produces behind the dephenolization cottonseed protein, concentrate, obtain paste, controlled temperature≤100 ℃ when concentrating.Ethanol reclaims the back and in system, recycles ethanol content＜500mg/kg in the paste.With paste and hot water by weight 1: 1.5 in common vessel stirring and dissolving be soup compound, the temperature of hot water is 90 ℃.Soup compound is cooled to hold over night after the room temperature, removes the solids on upper strata or the throw out of pitch shape thing and lower floor, obtains fraction.
The filter cloth suction filtration (coarse filtration) of fraction through the 0.1mm aperture with after removing partial impurities, then through the band suede filter cloth suction filtration (fine filtering) in 0.02mm aperture, obtained the clear liquid of the solid shape impurity of transparent nothing.Place container to leave standstill the clear liquid behind the fine filtering and made its crystallization at least in 24 hours, cross and filter crystallisate I at 2 ℃.With crystallisate I and concentration is that the ethanolic soln of 95wt% mixes with weight ratio at 1: 1.5, is heated to 45 ℃～75 ℃ to dissolving fully, naturally cools to normal temperature, leaves standstill crystallization at 2 ℃, filter, crystallisate II.Crystallisate II is used less than after 10 ℃ the soaked in absolute ethyl alcohol washing, and lyophilize obtains the crystallisate of cottonseed sugar.Consumption of ethanol is about 1.4 times of crystallisate during washing.In the cottonseed sugar crystallisate that obtains, the content of cottonseed sugar about 85%.
The preparation of embodiment 3 cottonseed sugars
Present embodiment uses the cotton dregs carry behind the oil as raw material, and said cotton dregs can be common high temperature cotton dregs, perhaps according to the method production among the Chinese patent No.001345206; Obtain contain wet cake with 85% methyl alcohol 40 ℃ of extractions 1.5 hours down; The extraction liquid evaporation concentration, methyl alcohol is reclaimed in controlled temperature≤100 ℃ when concentrating; And obtain paste, methanol content＜500mg/kg in the paste.With paste and hot water by weight 1: 1.2 in common vessel stirring and dissolving be soup compound, the temperature of hot water is 80 ℃.Soup compound is cooled to hold over night after the room temperature, removes the solids on upper strata or the throw out of pitch shape thing and lower floor, obtains fraction.
The filter cloth suction filtration (coarse filtration) of fraction through the 0.071mm aperture with after removing partial impurities, then through the band suede filter cloth suction filtration (fine filtering) in 0.02mm aperture, obtained the clear liquid of the solid shape impurity of transparent nothing.Place container to leave standstill the clear liquid behind the fine filtering and made its crystallization in 24 hours, cross and filter crystallisate I at 5 ℃.With crystallisate I and concentration is that the ethanolic soln of 95wt% mixes with weight ratio at 1: 1.5, is heated to dissolving fully, naturally cools to normal temperature, leaves standstill the 24h crystallization at 5 ℃, filter, crystallisate II.Crystallisate II is used less than after 10 ℃ the soaked in absolute ethyl alcohol washing, and lyophilize obtains the crystallisate of cottonseed sugar.Consumption of ethanol is about 1.2 times of crystallisate during washing.The content about 85.3% of cottonseed sugar in the cottonseed oligose crystallisate that obtains at last.
Claims (6)
1. the method for a refining cottonseed sugar comprises step:
1) will carry that to add concentration in the cotton dregs behind the oil be methyl alcohol or the ethanol of 65～95wt%, ℃ leaching is 0.5～1.5 hour in normal temperature～65, obtains containing the methyl alcohol or the alcohol extraction liquid of phenol and cottonseed sugar, and is concentrated, obtains paste;
2) paste is dissolved in the hot water of 1～1.5 times of weight obtains slurry, cooling was left standstill 5 hours at least, removed solids or pitch shape thing, obtained fraction;
3) with fraction through filtering, obtain clear liquid, clear liquid leaves standstill at least 24 hours crystallizatioies under 0～10 ℃ temperature, obtain crystallisate I;
4) with heating for dissolving in the ethanolic soln of crystallisate I more than concentration 90wt%, at least 24 hours crystallizatioies are left standstill in cooling under 0～10 ℃ temperature, obtain crystallisate II;
5) with crystallisate II with temperature less than 10 ℃, washing with alcohol more than the concentration 95wt%, drying obtains cottonseed sugar;
Wherein filter on the filtering material that is included in 0.04～0.1mm aperture described in the step 3) and carry out coarse filtration, then on the filtering material in 0.015mm～0.02mm aperture, carry out fine filtering; The weight ratio of the ethanolic soln that I of crystallisate described in the step 4) and concentration 90wt% are above is 1: 1～1: 1.5; The temperature of said heating is 45～75 ℃.
2. method according to claim 1, wherein step 2) described in the temperature of hot water be 50～100 ℃.
3. method according to claim 1, wherein step 2) described in the temperature of hot water be 70～90 ℃.
4. method according to claim 1, wherein said coarse filtration are on the filtering material in 0.05～0.08mm aperture, to carry out.
5. method according to claim 1, the filtering material of wherein said coarse filtration are the silk screen filter cloth; The filtering material of said fine filtering is band suede filter cloth or silk screen filter cloth.
6. method according to claim 1, wherein the weight ratio of the ethanolic soln more than II of crystallisate described in the step 5) and the concentration 95wt% is 1: 1～1: 1.5.
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Families Citing this family (3)
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| CN102898486B (en) * | 2012-09-21 | 2015-07-22 | 晨光生物科技集团股份有限公司 | Comprehensive method for preparation of raffinose and gossypol from cottonseed meal |
| CN104140988A (en) * | 2013-05-07 | 2014-11-12 | 南京中医药大学 | Process of preparing D-galactose by extracting cottonseed meal |
| CN106349041B (en) * | 2016-08-26 | 2019-05-24 | 新疆泰昆集团股份有限公司 | A method of extracting gossypol and raffinose from high protein cotton dregs |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265280A (en) * | 2007-04-13 | 2008-09-17 | 北京中棉紫光生物科技有限公司 | Method for extracting raffinose from cottonseed scum |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265280A (en) * | 2007-04-13 | 2008-09-17 | 北京中棉紫光生物科技有限公司 | Method for extracting raffinose from cottonseed scum |
Non-Patent Citations (1)
| Title |
|---|
| I. A. Ivanova,et al.Isolation of raffinose from cottonseed meal..《Chemistry of natural compounds》.1985,第20卷(第6期),第659页第4段. * |
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