CN1869246A - Method of filtering transparent protonic acid fermentation liquid using magnetic field fortified membrane - Google Patents
Method of filtering transparent protonic acid fermentation liquid using magnetic field fortified membrane Download PDFInfo
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- CN1869246A CN1869246A CN 200610090586 CN200610090586A CN1869246A CN 1869246 A CN1869246 A CN 1869246A CN 200610090586 CN200610090586 CN 200610090586 CN 200610090586 A CN200610090586 A CN 200610090586A CN 1869246 A CN1869246 A CN 1869246A
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Abstract
The invention relates to a method to filter hyaluronic acid fermenting liquid by magnetic field intensified film. It could improve the flux over 20% in film stable state and decrease the film pollution. Comparing with the existing technology, the thickness of the fermenting liquid would increase 50% and could keep long time stable using. The invention could be used not only in hyaluronic acid, but also could used to purify macromolecule mucopolysaccharide matter.
Description
Technical field
The present invention relates to a kind of method of membrane filtration material, specifically relate to the be coupled method of reinforced film filtration hyaluronic acid fermentation liquid of magnetization this physical technique and membrane separation technique.
Background technology
Hyaluronic acid (Hyaluronic Acid, HA) be the linear polymeric mucopolysaccharide that forms by the repeating unit that glucuronic acid and acetylglucosamine are constituted by β 1-3 and β 1-4 glycosidic link, in bovine vitreous body, found first by Meyer and Palmer in 1934.The length of its molecular chain and molecular weight heterogeneity, disaccharide units are 300~1100 pairs, molecular weight ranges 10
5~10
7Da.HA is water-soluble, is insoluble to organic solvents such as alcohol, ketone, ether.The aqueous solution is electronegative, shifts to negative pole during electrophoresis.Because its solution has superpower retentiveness, visco-elasticity and biological easily absorptivity, all have a wide range of applications in fields such as superior cosmetics, medical science, food and study.
Preparation hyaluronic acid commonly used at present mainly contains two kinds of approach: a kind of is to extract from animal tissues; A kind of is to extract from microbial fermentation solution.The Production by Microorganism Fermentation hyaluronic acid has solved the raw material sources problem for animal tissues's extraction method, and can obtain the HA of macromolecule, high yield.Remove in the fermented liquid and contain HA, also have materials such as protein and lactic acid.Usually adopt organic solvent such as CPC, ethanol, acetone etc. through repeatedly purify the HA finished product, as patent CN1195027, CN1597704 etc.The common operational path of this method is long, complicated, time-consuming, the cost height; Adopt more organic solvent, easily cause secondary pollution.Though membrane technique has application in the HA fermented liquid separates, generally all be as a kind of auxiliary separation means, be used for thalline or small molecular weight and remove, still need organic solvent to separate.As patent USA4517295, US4801539 etc., adopt MWCO 10 000, small-molecule substance is removed in 20 000,30 000Da ultra-filtration membrane diafiltrations.
The present invention is to realize that membrane technique is an agent technology, and separating the HA fermented liquid is ultimate aim.Yet unavoidably have membrane pollution problem in the membrane filtration HA fermented liquid process, this is a most important reason that hinders application of membrane.Film pollute to shorten film work-ing life, makes people form the consciousness of a kind of " the film cost is too high " for a long time, and this has influenced the popularization and the application of membrane technique greatly.Therefore, take the efficient hardening measure to alleviate film and pollute, improving membrane sepn efficient is the key of application of membrane.
Magnetization technology is a kind of technology of material being carried out magnetic field treatment, and this technology all is widely used in that chemical industry, environment, medical science, water treatment etc. are multi-field.Because magnetic field is an energy field, magnetization exerts an influence to many physicochemical property of handled solution system.Can reduce the surface tension and the solid surface potential energy of solution as the effect in magnetic field, thereby the adsorption layer that causes solid surface thickens; Magnetization can also reduce the viscosity of solution, makes it be easier to carry and next step processing.Magnetic field also exerts an influence to pH, specific conductivity, the specific inductivity of solution in addition.The effect of magnetic field treatment and magneticstrength, magnetizing time, solution are relevant in the chemical property of the flow velocity of field regions, magnetization water temperature, solution etc.That magnetization technology has is easy for operation, less investment, low, simple and easy to do, nontoxic, the non-secondary pollution of working cost, saves human and material resources, and advantages such as save energy are very promising technology.
Magnetization technology is applied to membrane filtration HA fermented liquid process, utilizes magnetic field to the physical chemistry influence that filtration procedure produces, and will produce some and help filtering effect a bit, and the reinforced film strainability reduces film and pollutes.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and provide a kind of magnetization-high performance tangential flow membrane filtration integrated technique to filter the method for hyaluronic acid fermentation liquid.
For achieving the above object, technical scheme of the present invention is as follows: with the method for magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid, by applying the external static stabilizing magnetic field, adopt magnetization-high performance tangential flow membrane filtration integrated technique, under magneticstrength, HYDRODYNAMIC CONDITION RELATING TO and solution chemistry condition, reinforced film is filtered.
The external static stabilizing magnetic field is provided permanent magnetic field or is adopted electromagnetic field by the adjustable magnetizing apparatus that adopts NdFeB permanent magnet material processing and fabricating, membrane module is placed magnetic field, determine optimum magnetic field intensity and determine best filtration HA fermented liquid operational condition by the high performance tangential flow filtration know-why, develop magnetization-high performance tangential flow membrane filtration integrated technique, the reinforced film strainability.
Press such scheme, the magneticstrength of external static stabilizing magnetic field is 0.08~0.35T, and definite optimum magnetic field intensity is 0.11T.
Membrane module of the present invention is flat, rolling, tubular type, tubular fibre formula; Membrane module places magnetizing apparatus, and liquid flow direction is vertical with field direction; The separatory membrane material is PVDF (polyvinylidene difluoride (PVDF)); Separatory membrane is a microfiltration membrane: 0.20 μ m~0.45 μ m, ultra-filtration membrane: MWCO 100kDa~300kDa.
Press such scheme, definite optimum filtration operational condition: during micro-filtration, best saturating film pressure is 0.1MPa, best cross-flow velocity 1.25m/s, best solution chemistry condition pH 3.0, the ionic strength 0.25mol/L of reinforcement; During the ultra-filtration membrane operation, best saturating film pressure is 0.15MPa, best cross-flow velocity 1.25m/s, best solution chemistry condition pH 3.0, the ionic strength 0.15mol/L of reinforcement.
One aspect of the present invention, fermented liquid pH utilize 6mol/L HCl to regulate, and the ionic strength of reinforcement utilizes NaCl to regulate.
Another aspect of the present invention, the transmitance of HA in microfiltration membrane is more than 85%, thalline can be held back fully; The transmitance of protein in ultra-filtration membrane is more than 75%, and protein is more than 13 with respect to the screening efficiency of HA, has well the ability that protein and HA are separated.
Of the present invention more on the one hand, the application provide a kind of from fermented liquid the method for separation and Extraction HA, promptly adopt two stage micro-filtration-ultrafiltration technology, separablely go out high-quality HA.The micro-filtration stage removes thalline and makes HA pass through, and enters in the penetrating fluid.Ultra-filtration stage utilizes the penetrating fluid in micro-filtration stage as feed flow, and impurities such as wherein HA and protein are separated.
The present invention compares with membrane technique under the unmagnetized, has following advantage:
For same HA fermented liquid, to compare with the high performance tangential flow membrane technique, magnetization-high performance tangential flow membrane filtration integrated technique makes membrane flux improve more than 20%, has strengthened membrane filtration characteristic, has alleviated the film pollution, saves the displacement expense of film.
Under the identical filter effect of acquisition, compare with the high performance tangential flow membrane technique, make separable HA fermented liquid concentration improve and be about 50%, accelerate the separation purifying velocity of HA, raise the efficiency.
Magnetization-high performance tangential flow membrane filtration integrated technique technology can keep long-time stable operation.
Description of drawings
Fig. 1 is magnetization of the present invention-high performance tangential flow membrane filtration integral system figure.-
This system can adopt and concentrate and the filtration operation mode operation.
Numeral is described as follows among Fig. 1: 1,2, and the 3-valve; 4, the 5-tensimeter; The 6-under meter; The 7-membrane module; The 8-heat exchanger; The 9-liquid supply box; The 10-agitator; The 11-water pump; The 12-magnetizing apparatus
Embodiment
Below in conjunction with Fig. 1, enumerate 2 embodiment, the present invention is further specified, but the present invention is not only limited to these embodiment.
Embodiment 1
In membrane module 7, be 0.45 μ m microfiltration membrane and membrane module placed magnetizing apparatus 12 by the dress aperture, the fermented liquid that will contain HA concentration and be 1650mg/L places liquid supply box 9, be adjusted to best solution chemistry condition with 6mol/L HCl and NaCl, offer and open water pump 11, in best HYDRODYNAMIC CONDITION RELATING TO and holding temperature is 25 ℃ of filtrations down, system reaches stable state (or quasi-steady state) substantially behind about 120min, and flux is about 32L/m
2H.And under the non-magnetic field effect, when optimal operation conditions and holding temperature were 25 ℃, for identical fermented liquid, the flux during the membrane filtration stable state was 21.6L/m
2H.It is about 48% that magnetic field makes that flux improves, and the HA transmitance increases.Because under the constant situation of optimum operation condition, the variation of flux is directly related with the effect of film pollution, thus magnetic field-intensification membrane filtration characteristic, alleviated the film pollution.
Embodiment 2
In membrane module 7, place magnetizing apparatus 12 by dress MWCO 100kDa ultra-filtration membrane and with membrane module, the fermented liquid that will contain HA concentration and be 1480mg/L places liquid supply box 9, be adjusted to best solution chemistry condition with 6mol/L HCl and NaCl, offer and open water pump 11, in best HYDRODYNAMIC CONDITION RELATING TO and holding temperature is 25 ℃ of filtrations down, system is reaching stable state (or quasi-steady state) substantially behind about 120min, and flux is about 25.8L/m
2H.And under the non-magnetic field effect, when optimal operation conditions and holding temperature are 25 ℃, the flux when obtaining same film and filter stable state, the HA concentration that must adopt is about 950mg/L.Magnetic field makes increases by 55% in the supply concentration that obtains HA fermented liquid under the close filter effect.
Claims (7)
1, uses the method for magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid, it is characterized in that by applying the external static stabilizing magnetic field, adopt magnetization-high performance tangential flow membrane filtration integrated technique, under magneticstrength, HYDRODYNAMIC CONDITION RELATING TO and solution chemistry condition, the filtering method of reinforced film.
2, by the described method with magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid of claim 1, the magneticstrength that it is characterized in that the external static stabilizing magnetic field is 0.08~0.35T.
3, by the described method of claim 1, it is characterized in that the external static stabilizing magnetic field adopts permanent magnetic field, electromagnetic field with magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid.
4, by the described method with magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid of claim 1, it is characterized in that membrane module places magnetizing apparatus, liquid flow direction is vertical with field direction.
5, by the described method with magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid of claim 4, it is characterized in that the separatory membrane material is PVDF, membrane module is flat, rolling, tubular type, tubular fibre formula.
6, by the described method of claim 4, it is characterized in that separatory membrane is a microfiltration membrane: 0.20 μ m~0.45 μ m with magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid; Ultra-filtration membrane: MWCO 100kDa~300kDa.
7, by the described method of claim 1, it is characterized in that magneticstrength 0.11T with magnetic field-intensification membrane filtration hyaluronic acid fermentation liquid; During the microfiltration membrane operation, saturating film pressure is 0.1MPa, cross-flow velocity 1.25m/s, solution chemistry condition pH3.0, the ionic strength 0.25mol/L of reinforcement; During the ultra-filtration membrane operation, saturating film pressure is 0.15MPa, cross-flow velocity 1.25m/s, solution chemistry condition pH3.0, the ionic strength 0.15mol/L of reinforcement.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106589164A (en) * | 2016-12-02 | 2017-04-26 | 天津市康婷生物工程有限公司 | Method for increasing yield of hyaluronic acid |
CN106632728A (en) * | 2016-12-02 | 2017-05-10 | 天津市康婷生物工程有限公司 | Method for improving yield of hyaluronic acid with high molecular weight |
CN108706813A (en) * | 2018-04-25 | 2018-10-26 | 同济大学 | A kind of method of magnetic nano-particle coupling membrane separation emulsion |
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CN2447330Y (en) * | 2000-06-15 | 2001-09-12 | 郑正 | Device for treatment of water |
CN1330044A (en) * | 2000-06-15 | 2002-01-09 | 郑正 | Water treating equipment |
CN2507852Y (en) * | 2001-08-22 | 2002-08-28 | 杨义方 | Rareearth microporous magnetizing flowing water treatment device |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106589164A (en) * | 2016-12-02 | 2017-04-26 | 天津市康婷生物工程有限公司 | Method for increasing yield of hyaluronic acid |
CN106632728A (en) * | 2016-12-02 | 2017-05-10 | 天津市康婷生物工程有限公司 | Method for improving yield of hyaluronic acid with high molecular weight |
CN108706813A (en) * | 2018-04-25 | 2018-10-26 | 同济大学 | A kind of method of magnetic nano-particle coupling membrane separation emulsion |
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