CN101367847A - Crystallization preparation method for high purity raffinose - Google Patents
Crystallization preparation method for high purity raffinose Download PDFInfo
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Abstract
The present invention discloses a crystallization method for preparing high-purity raffinose. C1 to C3 alcohol aqueous solution is adopted as crystallizing solvent, raffinose in the form of small crystal particles is used as inoculating seeds to induce crystallization, and after two to twenty four hours of grain growing, the high-purity raffinose is obtained by filtration and drying. The purity of the obtained raffinose product can reach over 99 percent, and the crystallization yield can reach over 80 percent. The method has the advantages of simple technique, low production cost and easy industrialized production.
Description
Technical field
The present invention relates to a kind ofly prepare the method for high purity raffinose, belong to the industrial crystallization technical field by the crystallization of raffinose crude product.
Background technology
Raffinose (Raffinose) claims raffinose (Melitriose) again, by semi-lactosi, glucose and fructose be combined into, belongs to oligose, is non-reducing sugar, and its structural formula is as follows:
Raffinose extensively is present in beet, cottonseed, honey, Caulis et Folium Brassicae capitatae, yeast, potato, grape, wheat class, corn and the fabaceous seed, it is the widest oligose that distributes in plant except that sucrose, also is one of main component of soybean oligosaccharide.Wherein raffinose content is the highest in cottonseed, is about 4～9%; Be about 1.0% in the beet; Be about 1.3% in the soybean, these raw materials all are the important sources of extracting raffinose.Because the human digestive enzyme system lacks the alpha-galactosidase that can decompose raffinose, raffinose can waltz through stomach and enteron aisle and directly do not decomposed by human body and absorb.Find that after deliberation raffinose is the fabulous nutrition source of probiotics such as bifidus bacillus, Lactobacillus acidophilus in the human intestinal, can promote their propagation, thereby suppress the growth of spoilage organism in the enteron aisle, and reduce the formation of poisonous tunning.The bifidobacterium fermentation raffinose produces a large amount of short chain fatty acids, can stimulate intestines peristalsis, increases the ight soil degree of wetting and keep certain osmotic pressure, thereby prevent the generation of constipation.In addition, raffinose can improve the digestive function of human body, promotes the absorption of human body to calcium, thereby strengthens body immunity, to preventing disease with anti-ageingly have a positive effect.Raffinose also can be used as human body and animal lives organ transplantation with protecting the main component of carrying liquid and prolonging the viable bacteria body synergistic agent of survival time at normal temperatures.Acidproof, the good heat resistance of raffinose can not lump under 90% relative humidity in moisture absorption yet, itself can be used as foodstuff additive and use, and improve the processing characteristics of food, prevent the product brown stain, improve the quality of products, and prolong the quality guaranteed period of product.Because of raffinose has good physicochemical property and physiologically active, industries such as food, medicine and makeup have been widely used at present.
Raffinose is very wide in natural distribution, it is the widest oligose that except that sucrose, in plant, distributes, it extensively is present in beet, cottonseed, honey, Caulis et Folium Brassicae capitatae, yeast, potato, grape, wheat class, corn and the fabaceous seed, wherein the content in cottonseed is the highest, is about 4～9%.Cottonseed benevolence produces a large amount of byproducts---degreasing cottonseed meal after being extracted Oleum Gossypii semen, the content of raffinose remains unchanged substantially in the degreasing cottonseed meal, and therefore, degreasing cottonseed meal cake is the splendid raw material of industrial production raffinose.
In the prior art, produce raffinose from the degreasing cottonseed meal, will not containing behind the direct condensing crystal of raffinose raffinate of pigment repeatedly usually, recrystallization obtains.As magnify people such as illuminate (from no body of gland cottonseed, extract the research of raffinose, Chinese oil, 1996,5,7-9) disclosed from no body of gland cottonseed the technology of extraction raffinose, the extraction yield of raffinose is 58.8%, product purity is more than 97%.Chinese patent application 200710014172.4 disclosed a kind of methods of extracting raffinose in cottonseed meal, the raffinose product yield is also very low.Owing to comprise raffinose, albumen, salinity, gossypol pigment and monose and sucrose etc. in the degreasing cottonseed meal, after the solvent extraction, albumen wherein, salinity, gossypol pigment and impurity such as other monose or sucrose still exist, and the existence of these impurity can cause raffinose crystallization difficulty, if before the raffinose crystal refining, do not remove these impurity in advance, then must pass through repeatedly recrystallization and could obtain high purity raffinose, must cause lower raffinose yield like this.Also be lower than 60% even if extract the extraction yield of raffinose (not needing to handle through decolouring) from no body of gland absorbent cotton, the material waste seriously can not be used for commercial scale production in the production technique of this method.
Therefore, in order to realize suitability for industrialized production high purity raffinose from the degreasing cottonseed meal, need to reduce cost, improve yield, simplify flow process, can consider from the following aspects: (1) adopts the method for lower production cost, high raffinose extraction yield in leach the process that obtains raffinose raffinate from the degreasing cottonseed meal with organic solvent; (2) before to the raffinose crystal refining, raffinose raffinate is purified, promptly to raffinose raffinate decolour, deproteinated, desalination and remove monose and processing such as sucrose, and adopt the purifying technique of optimizing as far as possible; (3) adopt the raffinose process for refining of optimizing.
In the prior art, the extracting method that obtains raffinose from the degreasing cottonseed meal mainly contains water extraction, water-containing organic solvent extraction method and enzymolysis-alcoholic solution extraction method etc.At present, from the degreasing cottonseed meal, extract raffinose, the most frequently used method be with alcoholic solution as extracting solvent, adopt static leaching method to extract to the degreasing cottonseed meal.As people such as Wang Xingguo (research of raffinose extracting method in the degreasing cottonseed meal, Chinese oil, 2005,3,57-60) disclose raffinose extract technology in a kind of cottonseed meal, as extracting solvent, stirring is at a certain temperature isolated extraction solution after extracting with ethanolic soln.After the extracted many times, united extraction solution also filters, and obtains raffinose raffinate.Solvent load is big in this static state leaching method, cause difficulty and cause the solvent waste to solvent recuperation, the utilization ratio of solvent is low simultaneously, effective constituent leaches not exclusively, for guaranteeing to have higher extraction yield, generally needs the extraction of long-time and repeated multiple times, cause foreign matter content rising in the extract, composition complicates, and the later separation purification difficult is difficult to prepare high purity product.Therefore, adopt existing common technology, can not take into account high extraction and low cost, especially solvent consumption is huge, and the cost that reclaims solvent also increases.
In the prior art,, mainly be that single wherein certain class impurity is removed the report respectively of method to the relevant report that raffinose raffinate is purified.As: (1) removes pigment: the decoloring method of raffinose raffinate mainly is to use the powder activated carbon decolorizing.Beam stands the new people of grade, and (cottonseed double liquid phase extraction process methanol is the decolouring of middle raffinose extracting solution mutually, food and fermentation industries, 2007,4,73-76) and people such as Jin Qingzhe (decolouring of raffinose raffinate and gossypol removal, Chinese oil, 2005,4,47-49) a kind of method that Powdered Activated Carbon is added static decolouring in the tank reactor that raffinose raffinate is housed is disclosed, from solution, isolate gac after decolouring is finished and obtain destainer; (2) remove freshen: ion exchange resin and nanofiltration desalination (Lip river iron man etc., the application of ion exchange resin in the syrup desalination, Chinese beet sugar industry, 2000,1,3-5 are mainly adopted in desalination; Wang Xiaolin etc., the experimental study of using nanofiltration membrane sepn sugar and salt, membrane science and technology, 2001,1,44-48); (3) remove Deproteinization: mainly adopt ultra-filtration membrane to separate, (cottonseed double liquid phase extraction process methanol is the decolouring of middle raffinose extracting solution mutually as people such as Liang Lixin, food and fermentation industries, 2007,4,73-76) reported and a kind ofly made the protein denaturation precipitation, adopted ultra-filtration membrane to separate again and finish the method that raffinose extracting solution deproteinated is handled by adding plumbic acetate; (4) the common technology of removing monose and sucrose is finished in the crystalline process simultaneously.These methods can only be removed single impurity, and itself there is a such-and-such problem, mainly contain: use a large amount of Powdered Activated Carbons just can reach satisfied decolorizing effect as needing in (1), simultaneously Powdered Activated Carbon can not reuse, and easily residues in to be difficult to finish in the solution of decolouring back and remove; Can produce a large amount of spent acid and salkali waste during ion exchange resin column resin regeneration (2), cause environmental pollution, and the used facility investment of nanofiltration membrane separation is big, it is short that separatory membrane easily pollutes the life-span; (3) use of plumbic acetate can bring heavy-metal residual in, and it is big that ultra-filtration membrane separates used facility investment, and it is short that separatory membrane easily pollutes the life-span; (4) remove monose and sucrose in the crystallization in, mean that final acquisition high purity raffinose must be by repeatedly recrystallization realization, cause low raffinose yield, therefore, iff with removing these a series of operations such as pigment, salinity, albumen, monose and sucrose in the prior art, still can not obtain ideal raffinose yield simply in conjunction with purifying raffinose raffinate.The raffinose purification process is still needed and will further be optimized and simplify.
In the prior art, the raffinose process for refining adopts crystallization or precipitation to realize usually.Because the precipitator method can introduce new impurity, therefore adopt usually crystallization or repeatedly recrystallization to carry out raffinose refining.U.S. Pat 6224684 discloses with pure water as recrystallisation solvent, a kind of with the crystallizer of circulation device in the method and apparatus of crystallization raffinose.In this invention, adopt pure water as recrystallisation solvent, the mass percentage concentration of initial raffinose is 60%, in crystallisation process, because the solubleness of raffinose in pure water is big, makes that the viscosity of crystallization solution is excessive, cause crystallization rate to descend, only temperature fall time just needs 50 hours more than, and the yield of simultaneously final raffinose is also lower.
Generally speaking, under the prior art condition, realize industrialization from the degreasing cottonseed meal (low cost, high yield, quick-reading flow sheets) production high purity raffinose, need respectively or on the whole raffinose extracting method, raffinose raffinate purification process and raffinose process for refining to be improved, wherein the improvement of raffinose process for refining has direct influence to the yield and the purity of raffinose in the final product.In the existing purification techniques, though the circulation crystallization and repeatedly recrystallization can guarantee the purity of raffinose in the final product, the raffinose yield is very low, is not suitable for suitability for industrialized production.
Summary of the invention
The invention provides refining raffinose under a kind of situation that crystal seed exists in aqueous alcohol solutions and obtain the method for high yield high purity raffinose, the purity of the raffinose that obtains by this method can reach more than 99%, and yield can reach more than 80%.
A kind of crystallization preparation method of high purity raffinose comprises the steps:
(1) with raffinose crude product and concentration expressed in percentage by volume is 60～80% C
1～C
3The aqueous solution of alcohol is warming up to 50～85 ℃ with the mixed system that obtains and makes the raffinose dissolving crude product;
Add raffinose crystal grain when (2) the mixed system cooling being cooled to 30～50 ℃ and induce crystallization;
(3) crystal is separated out back system cooling and was cooled to 5～30 ℃ of growing the grains 2～24 hours;
(4) leach the crystal that obtains 30～40 ℃ of vacuum-dryings;
Described raffinose crude product obtains via following processing: extract with alcoholic solution from the degreasing cottonseed meal and obtain raffinose raffinate; Raffinose raffinate is removed the gossypol decolouring; Destainer is carried out the desalination deproteinated remove sugar processing back except that desolvating.
Prepare the process of raffinose crude product from the degreasing cottonseed meal, comprise that wherein each step can adopt existing techniques in realizing.The present invention specifically provides a kind of and has prepared the method for raffinose crude product from the degreasing cottonseed meal, and detailed step is as follows:
(a) diacolation extracts:
Raw material degreasing cottonseed meal is packed into the diacolation post, adds in the diacolation post and extract solvent, soaked 30～60 minutes at 50～70 ℃, the volume of the extraction solvent of adding is 0.6～1 times of degreasing cottonseed meal stacking volume.Under the keeping warm mode, carrying out diacolation operation in the diacolation post, add the extraction solvent continuously in the diacolation post when collecting percolate, is 3～5 times of degreasing cottonseed meal stacking volume until the volume of the percolate of collecting.
Described extraction solvent is that concentration expressed in percentage by volume is that 70～85% methanol aqueous solution or concentration expressed in percentage by volume are 70～85% aqueous ethanolic solution.
Degreasing cottonseed meal stacking volume: the degreasing cottonseed meal is packed into the diacolation post, and the degreasing cottonseed meal is in the volume under the free accumulation state, and its apparent density is a tap density; The tap density of degreasing cottonseed meal is about 0.77g/ml, i.e. per kilogram degreasing cottonseed meal stacking volume is about 1300ml.
(b) decolouring:
After the percolate that obtains in the step (a) carried out concentration, adding water, to be made into solid content be 10% solution, regulates pH value to 4～6, the aqueous solution that obtains preparing; 30～60 ℃, with the flow velocity of 0.5～3BV/h gained is prepared the aqueous solution join in the fixed bed that adsorbent A is housed, collecting the effluent liquid that obtains is destainer, is 5～10BV until the destainer volume of collecting.
Describedly add water to be made into solid content be in 10% the solution, quality when solid content is meant solution is dried to constant weight account for dry before the per-cent of solution quality, be the quality percentage composition sum of all solutes in the solution, because composition more complicated in the solution, also may occur suspending or precipitation, when calculating the solution total mass, refer to the total mass of mixed system, promptly also comprise the quality of foreign material such as suspension or precipitation.
BV: bed volume refers to the bed volume that adsorbent A is loaded in the ADSORPTION IN A FIXED BED post;
BV/h: the volume of moving phase that per hour flows through the bed of adsorbent A filling is the multiple of fixed bed volume BV;
Described adsorbent A is that granulated active carbon, nonpolar macroporous type polystyrene polymeric adsorbent, low-pole macroporous type polystyrene polymeric adsorbent, nonpolar macroporous type acrylic acid series polymeric adsorbent, low-pole macroporous type acrylic acid series polymeric adsorbent, nonpolar gel type polystyrene are that polymeric adsorbent, low-pole gel type polystyrene are polymeric adsorbent, nonpolar gel-type acrylic acid series polymeric adsorbent or low-pole gel-type acrylic acid series polymeric adsorbent.
(c) fractionation by adsorption:
The destainer that obtains by step (b) with 2～4B ' V ', feed with the flow velocity of 0.5～3B ' V '/h and to make raffinose be adsorbed agent B absorption in the fixed bed that adsorbent B is housed, use again deionized water with the flow velocity drip washing fixed bed of 0.5～3B ' V '/h to reclaim the destainer in the fixed bed space, leacheate that obtains and destainer merge to be applied mechanically, use 2～4B ' V ' desorbing agent adsorbent B to be carried out desorb at last with the flow velocity of 0.5～3B ' V '/h, obtain containing the elutriant of raffinose, the temperature of adsorption separation process is controlled at 40～80 ℃; Elutriant concentrates or drying obtains the raffinose crude product;
Described desorbing agent is that concentration expressed in percentage by volume is that 20～60% methanol aqueous solution or concentration expressed in percentage by volume are 20～60% aqueous ethanolic solution.
B ' V ': bed volume refers to the bed volume that adsorbent B is loaded in the ADSORPTION IN A FIXED BED post;
B ' V '/h: the volume of moving phase that per hour flows through the bed of adsorbent B filling is the multiple of fixed bed volume B ' V ';
Described adsorbent B is that nonpolar macroporous type polystyrene polymeric adsorbent, nonpolar macroporous type acrylic acid series polymeric adsorbent, nonpolar gel type polystyrene are that polymeric adsorbent, nonpolar gel-type acrylic acid series polymeric adsorbent, granulated active carbon, bonding have C
18Silica gel or bonding C is arranged
30Silica gel;
Among the present invention, utilize C
1～C
3The aqueous solution of alcohol can effectively accelerate crystallization velocity as recrystallisation solvent, raffinose is separated out fully; While C
1～C
3The aqueous solution of alcohol in the existence of lower alcohol, can effectively reduce the solubleness of raffinose in mother liquor, thereby improve the raffinose yield greatly.C
1～C
3Alcohol be preferably methyl alcohol, ethanol or Virahol.
In the preferred scheme, C
1～C
3The aqueous solution of alcoholic solution in C
1～C
3The volumetric concentration of alcohol be 60～80%.Above-mentioned solvent boiling point is moderate, toxicity is little, and raffinose solubility with temperature variation therein obviously, is suitable recrystallisation solvent.
In the preferred scheme, per kilogram raffinose crude product and 4～8 liters of C
1～C
3The aqueous solution of alcohol.Under the ratio of this optimization, can form the sufficiently high raffinose solution of degree of supersaturation, can guarantee that again raffinose can come out by rapid crystallization.
In the preferred scheme, the cooling cooling described in step (2) and the step (3) is slowly to carry out under the stirring condition, helping accelerate crystallisation.
In the preferred scheme, the cooling cooling described in step (2) and the step (3), its rate of temperature fall is 0.5～2 ℃/min, helps forming the crystal of homogeneous grain diameter.
The particle diameter of described raffinose crystal grain is 170～200 orders, and consumption is 0.5～1.0% of an employed raffinose crude product weight.Raffinose crystal grain can be so that the raffinose crystal size that arrives be bigger as the adding of crystal seed, and size distribution is more even.
In the preferred scheme, the mass percent of raffinose is 75% or higher in the raffinose crude product.With this raffinose crude product is raw material, with its dissolving C
1～C
3The aqueous solution of alcohol in, growing the grain under the condition that crystal seed exists, gained raffinose product is a raffinose pentahydrate white needle-like crystals after filtering, its purity is greater than 99%, yield is greater than 80%.
Compared to existing technology, the useful effect that has of the present invention is:
This method technology is simple, yield is high, and production cost is low, is easy to suitability for industrialized production.Greater than 98%, can directly be used as foodstuff additive by the prepared raffinose crystal purity of this method, add in the products such as various beverages, milk-product and healthcare products.
Embodiment
Below, describe content of the present invention in detail by embodiment, but the present invention is not limited thereto.
Embodiment 1: preparation raffinose crude product:
(a). the degreasing cottonseed meal is (wherein, the mass percentage content of raffinose is 3.9%) be the screening of 1.8mm sieve through sieve aperture, take by weighing 435 grams and be loaded to the diacolation post (in the Φ 3.5cm * 70cm), filling evenly its stacking volume of back is about 560 milliliters, adding 350 ml volumes percentage concentrations again in the diacolation post is 75% aqueous ethanolic solution, soak under 55 ℃ and made the abundant swelling of degreasing cottonseed meal in 30 minutes, open diacolation column outlet valve, simultaneously add the extraction solvent continuously from the diacolation column top, the control flow velocity is 168 milliliters/hour, is 1900 milliliters until the volume of collecting percolate.Percolate by analysis, solid content (quality when solid content is meant solution is dried to constant weight account for dry before the per-cent of solution quality, down with) be 4.2%; With butt (butt is meant the solid quality that obtains after the solution drying, and the quality summation of the whole solutes in the ie in solution is together following) meter, the mass percent of raffinose is 38.2%.
At last, add deionized water from the diacolation column top to replace residual ethanol in the degreasing cottonseed meal, the control flow velocity is 560 milliliters/hour, collects the ethanol of exit lower concentration, reclaims ethanol by modes such as concentrated and rectifying again.
(b). drill and make 1900 milliliters of percolates of gained and be concentrated into original volume 1/10, add water and be mixed with solution (wherein, solid content is 10%), add mass percentage concentration and be 5% salt acid for adjusting pH value to 5.
Granulated active carbon packed into to be of a size of in the adsorption column of Φ 5.6cm * 40cm, and post bed volume BV is 980mL, in about 230 grams of granulated active carbon (adsorbent A) are housed.
By the ADSORPTION IN A FIXED BED post of granulated active carbon is housed, temperature is controlled at 40 ℃ with the flow velocity of the 1.0BV/h aqueous solution after with above-mentioned adjusting pH value.Collect effluent liquid (the being destainer) 10BV of sample process on the ADSORPTION IN A FIXED BED post, its color more shallow (colour is less than 10% of last sample aqueous solution colour).In butt, cottonseed saccharic amount per-cent is 50.6% in the destainer.With the flow velocity flushing adsorption column of 1.5BV deionized water with 1.0BV/h, collect in the water lotion that obtains and also contain a spot of raffinose, can continue recycled.Whole process, adsorption column temperature are controlled at 40 ℃.The effusive destainer of last sample process is analyzed through HPLC, and the raffinose rate of recovery is 95%.
Be 60% the aqueous ethanolic solution flow velocity flushing adsorption column with 1.0BV/h with the concentration expressed in percentage by volume of 2BV at last, elutriant is a scarlet; With the ethanol in the deionized water displacement adsorption column, the decolouring that adsorption column regeneration can directly be entered is next time operated again.
(c). pretreated HZ816 resin (adsorbent B) packed into to be of a size of in the adsorption column of Φ 5.6cm * 97cm, and post bed volume B ' V ' is about 2400mL, in about 1700 grams of resin are housed.Last sample liquid is the raffinose destainer of step (b) gained, and wherein solid content is 10%.Flow velocity with 1.0B ' V '/h feeds above-mentioned raffinose destainer 2.5B ' V ' continuously in the ADSORPTION IN A FIXED BED post, also contain a small amount of raffinose in the effluent liquid that last sample process is collected, and can directly recycle.Last sample finishes, and earlier with the flow velocity flushing adsorption column of 2B ' V ' deionized water with 1.5B ' V '/h, removes the destainer of adsorption column internal adsorption agent voids left, and the water lotion that obtains can be recycled; Again with 2B ' V ' concentration expressed in percentage by volume be 40% aqueous ethanolic solution with 1.0B ' V '/h flow velocity flushing adsorption column, desorb HZ816 resin, the raffinose in the wash-out HZ816 resin is collected the elutriant that obtains containing raffinose.The adsorption column temperature is controlled at 60 ℃ in the whole process.The spray-dried raffinose crude product that obtains of elutriant, analyzing wherein through HPLC, the mass percent of raffinose is 80%.
Use 2B ' V ' deionized water to make the HZ816 resin regeneration at last with the ethanol in the flow velocity displacement adsorption column of 2B ' V '/h.
Embodiment 2: the preparation of high purity raffinose
In the there-necked flask of taking back the stream prolong of a cleaning, the purity that adding makes by embodiment 1 method is that 80% raffinose crude product, 100 grams and 500 ml volumes concentration are 70% methanol aqueous solution, open and stir, be warming up to 65 ℃, after treating to dissolve fully, slowly be cooled to 40 ℃, add 170～200 order raffinoses (being crystal seed), 0.5 gram and induces crystallization so that the speed of 0.5 ℃/min is first, continue slowly to be cooled to 10 ℃ with same speed again, growing the grain is 12 hours under this temperature.Then, be 70% methanol solution washing leaching cake again with the crystalline solid filtration, and with a little volume concentration, drying is 6 hours in 40 ℃ of vacuum drying ovens, makes white needles raffinose pentahydrate crystal 6 5.2 grams, analyzes through HPLC, its purity is 98.7%, yield 80.5%.
Embodiment 3: the preparation of high purity raffinose
In the there-necked flask of taking back the stream prolong of a cleaning, the purity that adding makes by embodiment 1 method is that 80% raffinose crude product, 100 grams and 400 ml volumes concentration are 60% aqueous ethanolic solution, open and stir, be warming up to 75 ℃, after treating to dissolve fully, slowly be cooled to 45 ℃, add 170～200 order raffinoses (being crystal seed), 0.6 gram and induces crystallization so that the speed of 1 ℃/min is first, continue slowly to be cooled to 20 ℃ with same speed again, growing the grain is 24 hours under this temperature.At last, crystalline solid is filtered, with a small amount of 70% ethanolic soln washing leaching cake, drying is 8 hours in 40 ℃ of vacuum drying ovens, makes white needles raffinose pentahydrate crystal 6 3.8 grams, analyzes through HPLC, and its purity is 98.2%, yield 78.4%.
Embodiment 4: the preparation of high purity raffinose
In the there-necked flask of taking back the stream prolong of a cleaning, add the purity that makes by embodiment 1 method and be 80% raffinose crude product 100 grams and 500 ml volumes concentration and be 70% isopropanol water solution, open stirring, be warming up to 85 ℃.After treating to dissolve fully, slowly be cooled to 25 ℃ so that the speed of 1.5 ℃/min is first, add 170～200 order raffinoses (being crystal seed), 1.0 grams and induces crystallization, continue slowly to be cooled to 5 ℃ with same speed again, growing the grain is 24 hours under this temperature.At last, crystalline solid is filtered, with a small amount of pure water washing leaching cake, drying is 8 hours in 60 ℃ of vacuum drying ovens, makes white needles raffinose pentahydrate crystal 6 0.5 gram, analyzes through HPLC, and its purity is 99.2%, yield 75%.
Embodiment 5: the preparation of high purity raffinose
In the there-necked flask of taking back the stream prolong of a cleaning, the purity that adding is made by embodiment 1 technology is that 80% raffinose crude product, 100 grams and 800 ml volumes percentage concentrations are 80% methanol aqueous solution, open and stir, be warming up to 65 ℃, after treating to dissolve fully, slowly be cooled to 30 ℃, add 170～200 order raffinoses (being crystal seed), 0.5 gram and induces crystallization so that the speed of 1.5 ℃/min is first, continue slowly to be cooled to 5 ℃ with same speed again, growing the grain is 24 hours under this temperature.Then, again crystalline solid is filtered, and with a small amount of 80% methanol solution washing leaching cake, in 40 ℃ of vacuum drying ovens dry 6 hours, make white needles raffinose pentahydrate crystal 6 1.1 grams, through the HPLC analysis, its purity is 99.3%, yield 75.9%.
Embodiment 6: the preparation of high purity raffinose
In the there-necked flask of taking back the stream prolong of a cleaning, the purity that adding is made by embodiment 1 technology is that 80% raffinose crude product, 100 grams and 400 ml volumes percentage concentrations are 60% methanol aqueous solution, open and stir, be warming up to 65 ℃, after treating to dissolve fully, slowly be cooled to 35 ℃, add 170～200 order raffinoses (being crystal seed), 1.0 grams and induces crystallization so that the speed of 1 ℃/min is first, continue slowly to be cooled to 10 ℃ with same speed again, growing the grain is 12 hours under this temperature.Then, again crystalline solid is filtered, and with a small amount of 60% methanol solution washing leaching cake, in 40 ℃ of vacuum drying ovens dry 6 hours, make white needles raffinose pentahydrate crystal 5 7.4 grams, through the HPLC analysis, its purity is 98.1%, yield 70.4%.
Claims (7)
1. the crystallization preparation method of a high purity raffinose comprises the steps:
(1) with raffinose crude product and concentration expressed in percentage by volume is 60～80% C
1～C
3The aqueous solution of alcohol is warming up to 50～85 ℃ with the mixed system that obtains and makes the raffinose dissolving crude product;
Add raffinose crystal grain when (2) the mixed system cooling being cooled to 30～50 ℃ and induce crystallization;
(3) crystal is separated out back system cooling and was cooled to 5～30 ℃ of growing the grains 2～24 hours;
(4) leach the crystal that obtains 30～40 ℃ of vacuum-dryings;
Described raffinose crude product obtains via following processing: extract with alcoholic solution from the degreasing cottonseed meal and obtain raffinose raffinate; Raffinose raffinate is removed the gossypol decolouring; Destainer is carried out the desalination deproteinated remove sugar processing back except that desolvating.
2. crystallization preparation method according to claim 1 is characterized in that: described C1～C
3Alcohol be methyl alcohol, ethanol or Virahol.
3. crystallization preparation method according to claim 1 is characterized in that: the described raffinose crude product of per kilogram and 4～8 liters of described C
1～C
3The aqueous solution of alcohol.
4. crystallization preparation method according to claim 1 is characterized in that: the cooling cooling described in step (2) and the step (3), under stirring condition, carry out.
5. crystallization preparation method according to claim 1 is characterized in that: the cooling cooling described in step (2) and the step (3), its rate of temperature fall is 0.5～2 ℃/min.
6. crystallization preparation method according to claim 1 is characterized in that: the particle diameter of described raffinose crystal grain is 170～200 orders, and consumption is 0.5～1.0% of a raffinose crude product weight used in the step (1).
7. crystallization preparation method according to claim 2 is characterized in that: the quality percentage composition of raffinose is 75% or higher in the described raffinose crude product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351917A (en) * | 2011-09-14 | 2012-02-15 | 北京科技大学 | Method for extracting raffinose from cotton seed meal |
| CN105017339A (en) * | 2015-07-01 | 2015-11-04 | 浙江大学 | Method for preparing raffinose and stachyose by simulated-moving-bed chromatographic separation |
| CN107936067A (en) * | 2017-12-01 | 2018-04-20 | 江南大学 | A kind of industrial method that raffinose is recycled from discarded object |
| CN110833115A (en) * | 2019-11-21 | 2020-02-25 | 南京胜昔实业有限公司 | Comprehensive utilization method of cotton production by-products by using biochemical fulvic acid as main product |
| CN113308513A (en) * | 2021-05-27 | 2021-08-27 | 宁波瑞源生物科技有限公司 | Small and dense low-density lipoprotein cholesterol detection kit and detection method thereof |
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2008
- 2008-09-27 CN CNA200810121283XA patent/CN101367847A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351917A (en) * | 2011-09-14 | 2012-02-15 | 北京科技大学 | Method for extracting raffinose from cotton seed meal |
| CN105017339A (en) * | 2015-07-01 | 2015-11-04 | 浙江大学 | Method for preparing raffinose and stachyose by simulated-moving-bed chromatographic separation |
| CN105017339B (en) * | 2015-07-01 | 2018-03-09 | 浙江大学 | A kind of method that SMBC separation prepares raffinose and stachyose |
| CN107936067A (en) * | 2017-12-01 | 2018-04-20 | 江南大学 | A kind of industrial method that raffinose is recycled from discarded object |
| CN107936067B (en) * | 2017-12-01 | 2020-12-01 | 江南大学 | Industrial method for recovering raffinose from waste |
| CN110833115A (en) * | 2019-11-21 | 2020-02-25 | 南京胜昔实业有限公司 | Comprehensive utilization method of cotton production by-products by using biochemical fulvic acid as main product |
| CN113308513A (en) * | 2021-05-27 | 2021-08-27 | 宁波瑞源生物科技有限公司 | Small and dense low-density lipoprotein cholesterol detection kit and detection method thereof |
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