CN103113334B - Method for separating mycelium in vitamin C fermentation broth by environment-friendly montmorillonite flocculant - Google Patents
Method for separating mycelium in vitamin C fermentation broth by environment-friendly montmorillonite flocculant Download PDFInfo
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Abstract
The invention relates to a method for separating mycelium in vitamin C fermentation broth by an environment-friendly montmorillonite flocculant. The method comprises the following steps of: (1) drying and soaking montmorillonite by water, and carrying out ultrasonic dispersion, (2) adjusting pH, standing, separating moisture at the upper layer, supplementing purified water and washing by water, wherein the supplementary addition amount is as same as the separation amount, carrying out washing by water for 3 to 5 times repeatedly, filtering, collecting filter cakes and drying, (3) crushing and sieving the filter cakes to obtain the montmorillonite flocculant, and (4) adding the montmorillonite flocculant to the fermentation broth of vitamin C, stirring and dropwise adding NaOH (sodium hydroxide) to adjust the pH value to be 7.1 to 7.8, then stopping stirring, standing, separating a supernatant, and carrying out pressure filtration on lower-layer materials, wherein the filter cakes are the materials rich in mycelium. The vitamin C fermentation broth from which the mycelium is separated by the environment-friendly montmorillonite flocculant has good clarity, facilitates the subsequent production process of vitamin C and provides good conditions for the clean production of vitamin C.
Description
Technical field
The present invention relates to one environment-friendlymontmorillonite montmorillonite flocculant and be separated mycelial method in vitamin c fermenting liquid, belong to the technical field of medicine fermentation.
Background technology
Vitamins C, its common name is xitix (ascorbic acid), and being the common name of ascorbic acid bio active compound, is a kind of water-soluble vitamins, rich content in fruits and vegetables.Play regulatory role in redox metabolism reaction, lacking it can cause vitamin C deficiency.Ascorbic main Physiological Function has: the biosynthesizing 1, promoting osso-albumin, is beneficial to healing sooner of tissue injury mouth; 2, promote the metabolism of tyrosine and tryptophane in amino acid, extend the human body life-span; 3, the utilization of iron, calcium and folic acid is improved; 4, the metabolism of fat and lipoid particularly cholesterol is improved, prevention cardiovascular diseases; 5, promote the growth of tooth and bone, prevent gum hemorrhage; 6, the human body anti-stress ability of environment and immunizing power is to external world strengthened; 7, gingival atrophy, hemorrhage etc. is prevented.The aftertreatment of vitamin c fermenting liquid and recovery technology are the important factors being related to vitamins C pharmaceutical industry development prospect, are the effective ways solving environmental pollution.By vitamin c fermenting liquid aftertreatment technology reform, be determine that vitamins C industry realizes the major objective of scientific and technical innovation; With regard to China's vitamins C industry, due to restraining factors such as technology, equipment, methods, conventional vitamin C production technique does not obtain breakthrough change for many years, particularly in the face of day by day fierce environmental pollution factors, speed technology progress, transformation fall behind technique, have become that production of vitamin C enterprise participation is competed, won the market, the important guarantee of development.And just at present, vitamins C product is the kind that vitamins uses the most extensively, production capacity is maximum; Past, because Environmental Protection in China cost drops into lower, attract the leading enterprise of the medicinal chemicals that global vitamins etc. is representative one after another to China's transfer production capacity, but along with expanding economy, China promotes the attention degree of environmental protection, and VITAMIN manufacturing enterprise is also faced with great environmental protection pressure.In vitamin C producing process, discharge is containing a large amount of albumen organic waste water, and the COD in waste water is up to about 10000mg/L, and biology is difficult to degraded, if do not administered, discharges arbitrarily, will cause serious pollution to environment.Chinese patent literature CN102491560A(application number 201110423558.7) disclose method and system for the process of vitamins C secondary biochemical effluent and reuse.This method describing ascorbic discharge adopts sand filtration, ozonization, activated carbon adsorption, resin cation exchange and filtration as pretreatment unit, and sodium filter, first-stage reverse osmosis and two-pass reverse osmosis are as processing unit.But there is certain defect in the method, containing a large amount of protein, thalline and colors in vitamin c fermenting liquid, adopt the treatment processs such as filtration, absorption and reverse osmosis cannot realize in the large production of vitamins C, filter membrane in particularly sodium filter, first-stage reverse osmosis and second-level reverse osmosis device is poisoning, replacing of losing efficacy often, and processing cost is very high, process fermentation liquid measure is minimum, cannot realize industrialization scale operation at all.
Montmorillonite (Montmorillonite) is the layer mineral be made up of the hydrous alumino silicates that particle is superfine, belongs to one of smectite race (smectite) mineral, is important clay mineral.The molecular formula of montmorillonite is (Al, Mg)
2[Si
4o
10] (OH)
2nH
2o, centre is alumina octahedral, the clay mineral of the three-layer tablet shape structure formed for silicon-oxy tetrahedron up and down, Montmorillonite Crystal belongs to monoclinic moisture layer silicate mineral, moisture and some exchange cations at crystal structure interlayer, have higher loading capacity and have larger water-swelling ability.Utilize its absorption property at present, be widely used in edible oil refinery decolorization except aspects such as poison, sewage disposals; Montmorillonite is widely used in medicine, can do medical carrier, play control-released agent, and have antidiarrheal efficacy.In view of the characteristic of montmorillonite, mould dose can also be taken off as classic feed.Montmorillonite is respectively to give the administration of small white mouse bowel lavage continuously in the dose one day of peak concentration, maximum volume, after every day three times, there is not poisoning manifestations in the acute toxicity of small white mouse, maximum tolerated dose, none routine mice dying, illustrates that montmorillonite is substantially nontoxic material as flocculation agent.
Ascorbic production method mainly contains 2 kinds: Lai Shi method and two-step fermenting.Lai Shi method is researched and developed by Reichstein and Grussner, obtain D-glucitol (having another name called D-Sorbitol Powder) using glucose as starting raw material through shortening, again through the obtained L-sorbose of acetobacter submerged fermentation oxidation, L-sorbose generates diacetone-l-sorbose through acetone and vitriolization, again with benzene or methylbenzene extraction, extracting solution is separated remove solvent after water law removing single ketones sorbose after, just obtains vitamins C with sodium permanganate oxidation, hydrolysis, esterification, conversion and neutralization.Lai Shi method complex steps, seldom adopts in ascorbic industrial production now.Two-step fermenting is that after D-glucitol fermentation generates L-sorbose, directly generate KGA (sodium) through second step bacterial oxidation again, prepared KGA (sodium) is converted into vitamins C through peracid conversion method or alkali conversion method.The name of University Of Tianjin's honest and just sea justice in 2003 is called that the Master's thesis of " research of vitamin c fermenting technique " has studied Vitamin C Two-step Fermentation method in great detail; Chinese patent literature CN1257127A (application number: 99110472.2) disclose a kind of process fermentable is become to produce KGA or its salt continuously production technique by D-Sorbitol Powder.Two-step fermenting after two-step fermentation in fermentation liquid except containing except KGA (sodium), also containing impurity such as mycelium, protein, substratum, need KGA (sodium) separating-purifying.Mainly contain thermal precipitation method, chemical flocculation and ultrafiltration process to the method for KGA (sodium) separating-purifying at present, thermal precipitation method energy consumption is comparatively large, and there be limited evidence currently of adopts; Chemical flocculation removes the impurity such as mycelium, protein by chemical floc, but the refuse environmental pollution that in operating process, easily generation is more is more serious; Ultrafiltration process is a kind of emerging membrane technology, and this method is simple to operate, pollute few, but cost is higher.
Many VITAMIN manufacturers drop into a large amount of improvement and working cost is administered the three wastes, have received certain effect, but be only conceived to the improvement of production process end contamination thing, there is many drawbacks, such as: (1) difficulty of governance is larger, (2) environmental protection investments increase, and (3) product cost improves, and the performance of enterprises reduces.In order to improve enterprise's productivity effect better, reducing the pollution to environment, must start with from production process, industrial pollution control is extended through the whole process of whole production, cleaner production is the key factor and the main path that realize sustainable development.And the key factor of vitamins cleaner production finds the flocculation agent of low cost, high efficiency environmental type.Succeeding in developing of montmorillonite flocculant, makes vitamin c fermenting liquid isolation of purified process application montmorillonite flocculant new technology, sets up new vitamins C aftertreatment production technique pattern, traditional processing technology is transformed and realizes breakthrough.
Utilize montmorillonite flocculant to carry out separation to mycelium in vitamin c fermenting liquid at present and have no report.
Summary of the invention
For the deficiencies in the prior art, the invention provides one environment-friendlymontmorillonite montmorillonite flocculant and be separated mycelial method in vitamin c fermenting liquid.
Summary of the invention:
It is a principal object of the present invention to, by application montmorillonite flocculant, set up new vitamins C aftertreatment production technique pattern, transformation traditional processing technology also realizes breakthrough.The present invention is based upon on domestic production vitamins C Process ba-sis, is effectively separated vitamin c fermenting liquid mycelium, albumen etc.The vitamin c fermenting liquor clarified is obtained, for the follow-up conversion extraction of vitamins C, Refining process are provided convenience after vitamin c fermenting liquid removing mycelium.The present invention saves energy and reduce the cost, the yield of vitamin c solution and quality are greatly improved, and does not cause new environmental pollution.
Term illustrates:
Vitamin c fermenting liquid: vitamin c fermenting liquid of the present invention refer to D-glucitol (having another name called D-Sorbitol Powder) for raw material conventionally in the fermentation liquid that obtains through two step bacterial oxidation fermentation of Vitamin C Two-step Fermentation method, containing 2KGA-Na in this fermentation liquid, also containing mycelium, protein, substratum etc.
The operational path of Vitamin C Two-step Fermentation method is:
Montmorillonite raw material: the ca-montmorillonite referring to pharmaceutical grade, commercially available prod.
Purified water: the water of the hyoscine that tap water obtains through distillation method, ion exchange method, reverse osmosis method or other suitable methods.
Technical scheme of the present invention is as follows:
One environment-friendlymontmorillonite montmorillonite flocculant is separated mycelial method in vitamin c fermenting liquid, and the method step is as follows:
(1) montmorillonite raw material 130 ~ 160 DEG C being dried to water content is 2 ~ 10wt%, and add after soaking 5 ~ 10h in purified water and fully stir, at 20 ~ 60 DEG C of ultrasonic disperse 10 ~ 50min, ultrasonic frequency is 15 ~ 40KHz, obtains suspended emulsion; Described montmorillonite raw material: the mass volume ratio of purified water is 1:5 ~ 10g/ml;
(2) adjust pH to 2.0 ~ 4.0 with medicinal hydrochloric acid under agitation, leave standstill 2 ~ 5h, separate upper strata moisture, and then add purified water washing, the amount adding purified water is identical with the water yield separated, and continues stirring 10 ~ 40min, after leaving standstill 10 ~ 20h, separate upper strata moisture again, and then add purified water washing, the amount adding purified water is identical with the water yield separated, repeatedly carry out 3 ~ 5 washings, then filter, collect filter cake, 90 ~ 160 DEG C are dried to water content≤10wt%;
(3) carry out micronizing again by after dried filter cake coarse reduction to mean particle size≤5mm, cross 400 ~ 600 mesh sieves, obtain montmorillonite flocculant;
(4) under agitation, mixing speed is 15 ~ 30 turns/min, be that 0.01 ~ 0.02:1g/ml slowly joins in vitamin c fermenting liquid by montmorillonite flocculant by mass volume ratio, continue to stir and use the NaOH of 10 ~ 20wt% concentration to drip adjust ph and stop stirring after 7.1 ~ 7.8, leave standstill 2 ~ 5h, separate supernatant liquid, press filtration lower floor material, filter cake is and is rich in mycelial material, supernatant liquid and filtrate mixing is the clarification vitamin c fermenting liquor after separation of mycelial.
According to the present invention, preferably, in described step (1), the ultrasonic disperse time is 30 ~ 50min, and ultrasonic disperse temperature is at 40 ~ 60 DEG C, and ultrasonic frequency is 30 ~ 40KHz.
According to the present invention, preferably, in described step (2), filter type is for adopting plate-and-frame filter press press filtration.
According to the present invention, preferably, 550 ~ 600 mesh sieves are crossed after micronizing in described step (3).
According to the present invention, preferably, in described step (4), the mass volume ratio of montmorillonite flocculant and vitamin c fermenting liquid is 0.01 ~ 0.012:1g/ml; The concentration of described NaOH solution is 15 ~ 20wt%; Preferred, described pH value range controls 7.2 ~ 7.5.
In order to reach better effect of settling, find the best sedimentation pH value of vitamin c fermenting liquid, more be conducive to industrialized production, preferably, after step of the present invention (3), carry out flocculation lab scale preliminary experiment before step (4), be specially: be that 0.01 ~ 0.02:1g/mL mix with vitamin c fermenting liquid by mass volume ratio by montmorillonite flocculant, 30 ~ 35 DEG C stir; Continue to stir, controlling stirrer rotating speed is 90 ~ 100 turns/min, drip with the NaOH aqueous solution of 10 ~ 20wt% concentration, observe mycelial separating effect, work as solid-liquid separation, during liquid clarification, stop dripping the NaOH aqueous solution and stop stirring, measure pH value now, be flocculation lab scale preliminary experiment pH value; Then carry out the operation of step (4), under agitation condition, drip adjust ph with the NaOH of 10 ~ 20wt% concentration, when mensuration pH value is consistent with flocculation lab scale preliminary experiment pH value, stop stirring.
Vitamins C material after the separation of mycelial that the present invention obtains can directly carry out follow-up conversion leaching process, and being rich in after mycelial dry materials is pulverized of obtaining can directly use as protein fodder.
First the present invention carries out process preparation montmorillonite flocculant to montmorillonite raw material, and utilize the montmorillonite flocculant of preparation to be separated mycelium in vitamin c fermenting liquid, method environmental protection, decreases the generation of refuse in vitamins C subsequent production process.
The chemical structure of montmorillonite itself determines that it has good adsorption, and increase several times to tens times when its volumetric expansion after montmorillonite water suction, after montmorillonite, its interlamellar spacing is opened.The present invention utilizes the adsorptivity of montmorillonite, recycling ultrasonic wave agglomerated montmorillonite Granular composite after soaking by purified water also forms suspension, ultrasonic wave produces sound wave cavatition between water and montmorillonite, cause the formation of bubble in montmorillonite mud, growth and explosion compression, solid montmorillonite is disperseed, thus its montmorillonite is pulverized in the liquid phase, dispersion.
The present invention has following beneficial effect:
1, the present invention is the adsorptivity utilizing montmorillonite, utilizes ultrasonic wave agglomerated montmorillonite Granular composite, and has higher loading capacity; Then exchange the metallic cation between montmorillonite layer with the hydrogen ion of hydrochloric acid, remove the metal ion in montmorillonite, avoid bringing exogenous metal ions in vitamins C.
2, the present invention utilizes the uneven charging property of montmorillonite to make it can adsorb mycelium in various fermented liquid and protein, realize vitamin c fermenting liquid mycelium, effective separation of protein, the internal medium of purification vitamin c fermenting liquid, break and hinder the bottleneck that vitamins C subsequent transformation extracts, process for refining improves, simplify treating processes comparatively loaded down with trivial details in vitamins C aftertreatment.
3, the situation to severe environmental pollution that current vitamins C production technique causes is fully taken into account, method environmental protection of the present invention, the impurity of montmorillonite flocculant to vitamin c fermenting liquid has good adsorption, vitamins C material clarity after separation of mycelial is better, facilitates ascorbic subsequent production process and decreases the refuse amount of subsequent production.
4, invention increases the quality of vitamins C product, reduce energy consumption, production cost is low.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of montmorillonite flocculant prepared by the embodiment of the present invention 3, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Fig. 2 is the X-ray diffracting spectrum of montmorillonite standard substance, and X-coordinate is 2 θ (°), and ordinate zou is intensity (arbitrary unit).
Embodiment
Below by specific embodiment, also the present invention will be further described by reference to the accompanying drawings, but be not limited thereto.
The equipment used in embodiment and experimental example is conventional equipment, commercial products; Montmorillonite raw material is the ca-montmorillonite of pharmaceutical grade, and Shandong Xianhe Pharmaceutical Co., Ltd. is on sale; Purified water is conventional pharmaceutical water, and Shandong Sibangde Pharmaceutical Co., Ltd. provides; Vitamin c fermenting liquid be with D-glucitol (having another name called D-Sorbitol Powder) for raw material conventionally in the fermentation liquid that obtains through two step bacterial oxidation fermentation of Vitamin C Two-step Fermentation method, Shandong Luwei Pharmaceutical Co., Ltd provides.Embodiment and the raw materials used source of experimental example are specially:
| Supplementary material title | Manufacturing enterprise | Operative norm |
| Montmorillonite raw material | Shandong Xianhe Pharmaceutical Co., Ltd. | China drug standard WS1-(X-165)-2004Z |
| Vitamin c fermenting liquid | Shandong Luwei Pharmaceutical Co., Ltd | Shandong Luwei Pharmaceutical Co., Ltd's company standard |
| Hydrochloric acid | Hunan Er Kang pharmaceutical excipient company limited | Chinese Pharmacopoeia 2010 editions two |
| Sodium hydroxide | Hunan Er Kang pharmaceutical excipient company limited | Chinese Pharmacopoeia 2010 editions two |
| Purified water | Shandong Sibangde Pharmaceutical Co., Ltd. | Chinese Pharmacopoeia 2010 editions two |
Embodiment 1, one environment-friendlymontmorillonite montmorillonite flocculant are separated mycelial method in vitamin c fermenting liquid, and the method step is as follows:
(1) montmorillonite raw material 130 DEG C is dried to water content 10wt%, adds in purified water after soaking 10h and fully stir, at 20 DEG C of ultrasonic disperse 50min, ultrasonic frequency is 15KHz, obtains suspended emulsion; Described montmorillonite raw material: the mass volume ratio of purified water is 1:5g/ml;
(2) 3N(3 equivalent is used under agitation) medicinal hydrochloric acid tune pH to 2.0, leave standstill 2h, separate upper strata moisture, and then add purified water washing, the amount adding purified water is identical with the water yield separated, and continues to stir 10min, after leaving standstill 10h, separate upper strata moisture again, and then add purified water washing, the amount adding purified water is identical with the water yield separated, repeatedly carry out 5 washings, then use plate-and-frame filter press press filtration, collect filter cake, 90 DEG C are dried to water content≤10wt%;
(3) carry out micronizing again by after dried filter cake coarse reduction to mean particle size≤5mm, cross 400 mesh sieves, obtain montmorillonite flocculant;
(4) carry out flocculation lab scale preliminary experiment, be that 0.01:1g/mL mix with vitamin c fermenting liquid by mass volume ratio by montmorillonite flocculant, 30 DEG C stir; Continue to stir with the rotating speed of 100 turns/min, drip with the NaOH aqueous solution of 10wt% concentration, observe mycelial separating effect, work as solid-liquid separation, during liquid clarification, stop dripping the NaOH aqueous solution and stop stirring, measuring pH value now, lab scale preliminary experiment pH value of must flocculating (this pH value is 7.2);
(5) under agitation, be that 0.01:1g/ml slowly joins in vitamin c fermenting liquid by montmorillonite flocculant by mass volume ratio, continue to stir with the rotating speed of 30 turns/min and use the NaOH of 10wt% concentration to drip adjust ph, stop dripping NaOH solution after there is obvious pure and impure layering, when mensuration pH is consistent with flocculation lab scale preliminary experiment pH value, stop stirring, leave standstill 5h, separate supernatant liquid, press filtration lower floor material, filter cake is and is rich in mycelial material, supernatant liquid and filtrate mixing is the clarification vitamin c fermenting liquor after separation of mycelial.
Embodiment 2, one environment-friendlymontmorillonite montmorillonite flocculant are separated mycelial method in vitamin c fermenting liquid, and the method step is as follows:
(1) montmorillonite raw material 160 DEG C is dried to water content 2wt%, adds in purified water after soaking 5h and fully stir, at 60 DEG C of ultrasonic disperse 10min, ultrasonic frequency is 40KHz, obtains suspended emulsion; Described montmorillonite raw material: the mass volume ratio of purified water is 1:10g/ml;
(2) 3N(3 equivalent is used under agitation) medicinal hydrochloric acid tune pH to 4.0, leave standstill 5h, separate upper strata moisture, and then add purified water washing, the amount adding purified water is identical with the water yield separated, and continues to stir 40min, after leaving standstill 20h, separate upper strata moisture again, and then add purified water washing, the amount adding purified water is identical with the water yield separated, repeatedly carry out 3 washings, then use plate-and-frame filter press press filtration, collect filter cake, 160 DEG C are dried to water content≤10wt%;
(3) carry out micronizing again by after dried filter cake coarse reduction to mean particle size≤5mm, cross 600 mesh sieves, obtain montmorillonite flocculant;
(4) carry out flocculation lab scale preliminary experiment, be that 0.02:1g/mL mix with vitamin c fermenting liquid by mass volume ratio by montmorillonite flocculant, 35 DEG C stir; Continue to stir with the rotating speed of 90 turns/min, drip with the NaOH aqueous solution of 20wt% concentration, observe mycelial separating effect, work as solid-liquid separation, during liquid clarification, stop dripping the NaOH aqueous solution and stop stirring, measuring pH value now, lab scale preliminary experiment pH value of must flocculating (this pH value is 7.3);
(5) under agitation, be that 0.02:1g/ml slowly joins in vitamin c fermenting liquid by montmorillonite flocculant by mass volume ratio, continue to stir with the rotating speed of 15 turns/min and use the NaOH of 10wt% concentration to drip adjust ph, stop dripping NaOH solution after there is obvious pure and impure layering, when mensuration pH is consistent with flocculation lab scale preliminary experiment pH value, stop stirring, leave standstill 5h, separate supernatant liquid, press filtration lower floor material, filter cake is and is rich in mycelial material, supernatant liquid and filtrate mixing is the clarification vitamin c fermenting liquor after separation of mycelial.
Embodiment 3, one environment-friendlymontmorillonite montmorillonite flocculant are separated mycelial method in vitamin c fermenting liquid, and the method step is as follows:
(1) montmorillonite raw material 160 DEG C is dried to water content 2wt%, adds in purified water after soaking 5h and fully stir, at 40 DEG C of ultrasonic disperse 30min, ultrasonic frequency is 30KHz, obtains suspended emulsion; Described montmorillonite raw material: the mass volume ratio of purified water is 1:8g/ml;
(2) 3N(3 equivalent is used under agitation) medicinal hydrochloric acid tune pH to 3.0, leave standstill 4h, separate upper strata moisture, and then add purified water washing, the amount adding purified water is identical with the water yield separated, and continues to stir 30min, after leaving standstill 20h, separate upper strata moisture again, and then add purified water washing, the amount adding purified water is identical with the water yield separated, repeatedly carry out 3 washings, then use plate-and-frame filter press press filtration, collect filter cake, 120 DEG C are dried to water content≤10wt%;
Get the filter cake 0.2g after oven dry to add water 25ml drip SILVER REAGENT dust technology 1, boil 5 minutes, filter, get filtrate according to the chloride content in " Chinese Pharmacopoeia 2010 editions two annex VIII A " muriate test procedure inspection filtrate, compare with standard chlorination sodium solution 5.0ml, chloride concentration≤0.025wt% in filtrate;
(3) carry out micronizing again by after dried filter cake coarse reduction to mean particle size≤5mm, cross 500 mesh sieves, obtain montmorillonite flocculant;
Get montmorillonite flocculant sample obtained above and carry out the experiment of X-ray powder diffraction, get 4g montmorillonite flocculant obtained above and grind to form fine powder; Get fine powder appropriate, be placed on load sample frame, load sample frame is put into moisture eliminator (containing saturated nacl aqueous solution, relative humidity about 75% when 20 DEG C) in after about 12 hours take out, sample on load sample frame is flattened, measure according to x-ray powder diffraction (Chinese Pharmacopoeia version in 2010 two annex IX F), in the scope interscan of diffraction angle (2 θ) 2 ° to 80 °, Fig. 1 is the X-ray diffraction spectrogram of montmorillonite flocculant prepared by the present embodiment; Consistent with the montmorillonite characteristic peak (diffraction angle (2 θ) is about 5.8 °, 19.8 ° and 61.9 ° respectively) in montmorillonite standard substance X-ray diffracting spectrum (Fig. 2), show not destroy montmorillonite chemical structure under adjusting pH to 3.0 condition with medicinal hydrochloric acid;
(4) carry out flocculation lab scale preliminary experiment, be that 0.012:1g/mL mix with vitamin c fermenting liquid by mass volume ratio by montmorillonite flocculant, 30 DEG C stir; Continue to stir with the rotating speed of 100 turns/min, drip with the NaOH aqueous solution of 15wt% concentration, observe mycelial separating effect, work as solid-liquid separation, during liquid clarification, stop dripping the NaOH aqueous solution and stop stirring, measuring pH value now, lab scale preliminary experiment pH value of must flocculating (this pH value is 7.4);
(5) under agitation, be that 0.012:1g/ml slowly joins in vitamin c fermenting liquid by montmorillonite flocculant by mass volume ratio, continue to stir with the rotating speed of 20 turns/min and use the NaOH of 10wt% concentration to drip adjust ph, stop dripping NaOH solution after there is obvious pure and impure layering, when mensuration pH is consistent with flocculation lab scale preliminary experiment pH value, stop stirring, leave standstill 2h, separate supernatant liquid, press filtration lower floor material, filter cake is and is rich in mycelial material, supernatant liquid and filtrate mixing is the clarification vitamin c fermenting liquor after separation of mycelial.
Embodiment 4, one environment-friendlymontmorillonite montmorillonite flocculant are separated mycelial method in vitamin c fermenting liquid, and the method step is as follows:
(1) montmorillonite raw material 130 DEG C is dried to water content 5wt%, adds in purified water after soaking 5h and fully stir, at 40 DEG C of ultrasonic disperse 30min, ultrasonic frequency is 30KHz, obtains suspended emulsion; Described montmorillonite raw material: the mass volume ratio of purified water is 1:8g/ml;
(2) 3N(3 equivalent is used under agitation) medicinal hydrochloric acid tune pH to 4.0, leave standstill 5h, separate upper strata moisture, and then add purified water washing, the amount adding purified water is identical with the water yield separated, and continues to stir 40min, after leaving standstill 20h, separate upper strata moisture again, and then add purified water washing, the amount adding purified water is identical with the water yield separated, repeatedly carry out 4 washings, then use plate-and-frame filter press press filtration, collect filter cake, 120 DEG C are dried to water content≤10wt%;
(3) carry out micronizing again by after dried filter cake coarse reduction to mean particle size≤5mm, cross 600 mesh sieves, obtain montmorillonite flocculant;
(4) carry out flocculation lab scale preliminary experiment, be that 0.012:1g/mL mix with vitamin c fermenting liquid by mass volume ratio by montmorillonite flocculant, 32 DEG C stir; Continue to stir with the rotating speed of 100 turns/min, drip with the NaOH aqueous solution of 15wt% concentration, observe mycelial separating effect, work as solid-liquid separation, during liquid clarification, stop dripping the NaOH aqueous solution and stop stirring, measuring pH value now, lab scale preliminary experiment pH value of must flocculating (this pH value is 7.5);
(5) under agitation, be that 0.012:1g/ml slowly joins in vitamin c fermenting liquid by montmorillonite flocculant by mass volume ratio, continue to stir with the rotating speed of 15 turns/min and use the NaOH of 15wt% concentration to drip adjust ph, stop dripping NaOH solution after there is obvious pure and impure layering, when mensuration pH is consistent with flocculation lab scale preliminary experiment pH value, stop stirring, leave standstill 4h, separate supernatant liquid, press filtration lower floor material, filter cake is and is rich in mycelial material, supernatant liquid and filtrate mixing is the clarification vitamin c fermenting liquor after separation of mycelial.
Experimental example 1, this experimental example investigate montmorillonite flocculant to the impact of vitamins C quality product.
Get lot number and be respectively 301,302,303,304, the each 1000ml of 305 vitamin c fermenting liquid, separately according to the operation of embodiment 1 step, wherein 305 batches in fermentation production process by microbiological contamination, the mass volume ratio of this batch of montmorillonite flocculant and vitamin c fermenting liquid is 0.02:1g/ml.
Vitamins C material after the separation of mycelial obtained carries out conversion according to production of vitamin C method and extracts, refines, and obtains vitamins C product.Detect vitamins C according to " Chinese Pharmacopoeia 2010 editions two ", detected result is as shown in table 1.
Table 1
Interpretation of result: wherein 301 ~ 304 4 batch products quality all meet state-promulgated pharmacopoeia standard, 305 batches are passed through to strengthen montmorillonite flocculant amount, and its quality product meets state-promulgated pharmacopoeia standard.
In order to investigate ascorbic quality further, increasing lot number is again 306,307,308 3 batches of vitamin c fermenting liquid, according to the step separation of mycelial of embodiment 1, vitamins C material after the separation of mycelial obtained carries out conversion according to production of vitamin C method and extracts, refines, and obtains vitamins C product.Carry out the study on the stability of influence factor test, accelerated test, test of long duration according to Chinese Pharmacopoeia version two in 2010, the results are shown in Table 2.
Table 2
Interpretation of result: the montmorillonite flocculant prepared of the present embodiment can not only effective separation of mycelial albumen in the large production of vitamins C, and do not produce any impact to vitamins C quality.
Experimental example 2, this experimental example investigate montmorillonite flocculant to the impact of vitamin c fermenting liquid clarity.
Get each 400ml of vitamin c fermenting liquid 301,302,303,304,305 of different lot number, wherein 305 batches in fermentation production process by microbiological contamination, separately according to the operation of embodiment 1 step, the mass volume ratio of 301 ~ 304 batches of montmorillonite flocculant and vitamin c fermenting liquid is 0.01:1g/ml; The mass volume ratio of 305 batches of montmorillonite flocculant and vitamin c fermenting liquid is 0.02:1g/ml, sets up 301 batches of fermenation raw liquids not adding montmorillonite flocculant and tests as a comparison.
The vitamin c fermenting liquid got the vitamins C material after the separation of mycelial of same volume respectively and do not add montmorillonite flocculant carries out clarity inspection according to " Chinese Pharmacopoeia 2010 editions two annex IV B " clarity test procedure, and measurement result is as shown in table 3.
The preparation of turbidity standard stock solution: take the hydrazonium sulfate 1.00g being dried to constant weight in 105 DEG C, put in 100ml volumetric flask, add water and make dissolving in right amount, if desired can warm dissolving in the water-bath of 40 DEG C, and is diluted with water to scale, shakes up, places 4 ~ 6 hours; Get this solution to mix with the 10wt% urotropine solution of the capacity of grade, shake up, leave standstill 24 hours in 25 DEG C of lucifuges, to obtain final product; This solution is put cold place and is kept in Dark Place, and can use, with front shaking up in 2 months.
The preparation of turbidity standard stoste: get turbidity standard stock solution 15.0ml, put in 1000ml volumetric flask, be diluted with water to scale, shake up, get appropriate, put in 1cm cuvette, according to ultraviolet visible spectrophotometry (Chinese Pharmacopoeia two annex IV A in 2010), measure at the wavelength place of 550nm, its absorbancy should in 0.12 ~ 0.15 scope; This solution should use, with front shaking up in 48 hours.
The preparation of turbidity standard: get turbidity standard stoste and water, configure by table 3, to obtain final product; Turbidity standard should face used time preparation, fully shakes up before using.
Interpretation of result: montmorillonite flocculant is removed in pigment at fermented liquid and played a role, 301 ~ 304 4 batches, clarity is between rank 1 ~ 2,305 batches because of microbiological contamination during the fermentation, fermented liquid environment is comparatively complicated, increase montmorillonite flocculant consumption, its clarity has greatly improved, and is increased to 2 from rank 4.The fermenation raw liquid not adding flocculation agent cannot detect according to " Chinese Pharmacopoeia 2010 editions two annex IV B " clarity test procedure, and ultraviolet-visible spectrophotometer cannot reading.
Claims (6)
1. be separated a mycelial method in vitamin c fermenting liquid by environment-friendlymontmorillonite montmorillonite flocculant, it is characterized in that, the method step is as follows:
(1) montmorillonite raw material 130 ~ 160 DEG C being dried to water content is 2 ~ 10wt%, and add after soaking 5 ~ 10h in purified water and fully stir, at 20 ~ 60 DEG C of ultrasonic disperse 10 ~ 50min, ultrasonic frequency is 15 ~ 40KHz, obtains suspended emulsion; Described montmorillonite raw material: the mass volume ratio of purified water is 1:5 ~ 10g/ml;
(2) adjust pH to 2.0 ~ 4.0 with medicinal hydrochloric acid under agitation, leave standstill 2 ~ 5h, separate upper strata moisture, and then add purified water washing, the amount adding purified water is identical with the water yield separated, and continues stirring 10 ~ 40min, after leaving standstill 10 ~ 20h, separate upper strata moisture again, and then add purified water washing, the amount adding purified water is identical with the water yield separated, repeatedly carry out 3 ~ 5 washings, then filter, collect filter cake, 90 ~ 160 DEG C are dried to water content≤10wt%;
(3) carry out micronizing again by after dried filter cake coarse reduction to mean particle size≤5mm, cross 400 ~ 600 mesh sieves, obtain montmorillonite flocculant;
(4) under agitation, mixing speed is 15 ~ 30 turns/min, be that 0.01 ~ 0.02:1g/ml slowly joins in vitamin c fermenting liquid by montmorillonite flocculant by mass volume ratio, continue to stir and use the NaOH of 10 ~ 20wt% concentration to drip adjust ph and stop stirring after 7.1 ~ 7.8, leave standstill 2 ~ 5h, separate supernatant liquid, press filtration lower floor material, filter cake is and is rich in mycelial material, supernatant liquid and filtrate mixing is the clarification vitamin c fermenting liquor after separation of mycelial.
2. environment-friendlymontmorillonite montmorillonite flocculant according to claim 1 is separated mycelial method in vitamin c fermenting liquid, it is characterized in that, in described step (1), the ultrasonic disperse time is 30 ~ 50min, and ultrasonic disperse temperature is at 40 ~ 60 DEG C, and ultrasonic frequency is 30 ~ 40KHz.
3. environment-friendlymontmorillonite montmorillonite flocculant according to claim 1 is separated mycelial method in vitamin c fermenting liquid, it is characterized in that, in described step (2), filter type is for adopting plate-and-frame filter press press filtration.
4. environment-friendlymontmorillonite montmorillonite flocculant according to claim 1 is separated mycelial method in vitamin c fermenting liquid, it is characterized in that, crosses 550 ~ 600 mesh sieves in described step (3) after micronizing.
5. environment-friendlymontmorillonite montmorillonite flocculant according to claim 1 is separated mycelial method in vitamin c fermenting liquid, it is characterized in that, in described step (4), the mass volume ratio of montmorillonite flocculant and vitamin c fermenting liquid is 0.01 ~ 0.012:1g/ml; The concentration of described NaOH solution is 15 ~ 20wt%; Preferred, described pH value range controls 7.2 ~ 7.5.
6. environment-friendlymontmorillonite montmorillonite flocculant according to claim 1 is separated mycelial method in vitamin c fermenting liquid, it is characterized in that, after step (3), flocculation lab scale preliminary experiment is carried out before step (4), be specially: be that 0.01 ~ 0.02:1g/mL mix with vitamin c fermenting liquid by mass volume ratio by montmorillonite flocculant, 30 ~ 35 DEG C stir; Continue to stir, controlling stirrer rotating speed is 90 ~ 100 turns/min, drip with the NaOH aqueous solution of 10 ~ 20wt% concentration, observe mycelial separating effect, work as solid-liquid separation, during liquid clarification, stop dripping the NaOH aqueous solution and stop stirring, measure pH value now, be flocculation lab scale preliminary experiment pH value; Then carry out the operation of step (4), under agitation condition, drip adjust ph with the NaOH of 10 ~ 20wt% concentration, when mensuration pH value is consistent with flocculation lab scale preliminary experiment pH value, stop stirring.
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