CN105777603A - Method for extracting L-hydroxyproline from L-hydroxyproline fermentation liquor - Google Patents
Method for extracting L-hydroxyproline from L-hydroxyproline fermentation liquor Download PDFInfo
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- CN105777603A CN105777603A CN201610205738.0A CN201610205738A CN105777603A CN 105777603 A CN105777603 A CN 105777603A CN 201610205738 A CN201610205738 A CN 201610205738A CN 105777603 A CN105777603 A CN 105777603A
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- hydroxyproline
- exchange resin
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- cation exchange
- storng
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a method for extracting L-hydroxyproline from L-hydroxyproline fermentation liquor. The method comprises the following steps: performing microfiltration on L-hydroxyproline fermentation liquor, adjusting the pH value of a microfiltration solution to be neutral, then performing cationic and anionic resin adsorption, performing nanofiltration to obtain a nanofiltration clear solution, and performing primary concentration crystallization after decolorization to obtain a final product. According to the method, a primary mother solution is delivered back to the process of cationic and anionic resin adsorption for recycling, the mode of direct adsorption of amino acid of the conventional ion adsorption exchange process is changed into a mode of adsorption of impurities, and then primary crystallization is performed after nanofiltration impurity removal to obtain a product, so that the purity, content, yield and separation efficiency of the L-hydroxyproline can be greatly improved, the wastewater quantity is reduced, and the generated wastes are used for preparing feeds to avoid environmental pollution.
Description
Technical field
The present invention relates to a kind of amino acid whose extraction process technology field, particularly relate to a kind of from L-hydroxyproline
The method extracting L-hydroxyproline in fermentation liquid.
Background technology
Hydroxyproline (Hydroxyproline, Hyp) is imino acid, is the product after L-PROLINE hydroxylating,
Its molecular formula is C5H9NO3.The white flaky crystal of hydroxyproline or crystalline powder, micro-sweet, fusing point is
274 DEG C, soluble in water, it is slightly soluble in ethanol.Hydroxyproline has 4 kinds of stereoisomers, trans-4-in nature
Hydroxyproline is relatively conventional, and trans-4-Hydroxyproline is found in animal collagen the earliest.Trans-4-hydroxyl
Proline is widely used in the aspects such as medicine, chemical industry, animal feed, nutrition and beauty culture.
At present, the separation and Extraction hydroxyproline in fermentation liquid of report, generally uses ion-exchange process both at home and abroad,
Fermentation liquid upper prop under the conditions of specific pH of thalline will be removed, allows hydroxyproline adsorb on ion exchange column,
With deionized water, ion exchange column is fully washed subsequently, remove impurity, then with eluent by hydroxyproline from
Eluting on ion exchange column, obtains hydroxyproline solution, then through crystallizing and being dried, obtains hydroxyproline product.
There is following defect in the method: 1. hydroxyproline is oxidizable, and yield is unstable；2. thick hydroxyproline impurity many,
Color and luster is deep, the refined yield of impact and product quality.3. water consumption is big, and soda acid consumption is big, in process of production can
Produce substantial amounts of waste residue and waste water, environment is caused the most serious pollution.These defects can be overcome, it is achieved
Extract the slag and effluent zero-emission of production process, thoroughly eradicate problem of environmental pollution in hydroxyproline production process
Refined raw production. art there is not yet any report both at home and abroad.
Summary of the invention
Present invention seek to address that the deficiencies in the prior art, and provide a kind of and extract from L-hydroxyproline fermentation liquid
The method of L-hydroxyproline, the method can be isolated finished product efficiently and improve purity and extraction ratio.
The present invention for achieving the above object, by the following technical solutions: a kind of from L-hydroxyproline fermentation liquid
The method extracting L-hydroxyproline, it is characterised in that include following operating procedure:
Step one, by L-hydroxyproline fermentation liquid microfiltration, obtain microfiltration clear liquid and microfiltration trapped fluid, regulate micro-
Cleaner liquid pH value is 6～8, then adsorbs with storng-acid cation exchange resin, then uses weakly-basic anion
Exchanger resin absorption obtains ion exchange liquid；
Step 2, ion exchange liquid is crossed the NF membrane that molecular weight is 800～1000Da obtain nanofiltration clear liquid and receive
Filter trapped fluid；
Step 3, regulation nanofiltration trapped fluid pH value are 6～8, then adsorb with storng-acid cation exchange resin,
Then obtaining ion exchange liquid with weak-base anion-exchange resin absorption, ion exchange liquid repeats step 2；
Step 4, by after nanofiltration clear liquid activated carbon decolorizing, 50～70 DEG C be concentrated into volume be concentrate before
1/8～1/6, lower the temperature 20～30 DEG C of centrifugal finished products obtaining L-hydroxyproline and a mother solution；
Step 5, a mother solution regulation pH value are 6～8, then adsorb with storng-acid cation exchange resin,
Then obtaining ion exchange liquid with weak-base anion-exchange resin absorption, ion exchange liquid repeats step 2.
Described step one middle strong acidity cation exchange resin is with sulfonic acid in styrene-divinylbenzene copolymer
The cation exchange resin of base.
It is preferably C100 with sulfonic cation exchange resin in described styrene-divinylbenzene copolymer
One in type storng-acid cation exchange resin, 732 type storng-acid cation exchange resins.
Regulating microfiltration clear liquid pH value in described step one is 7, makes fermentation liquid partial neutral, the most by force
Acid cation exchange resin and weak-base anion-exchange resin are more weak to the absorption of L-hydroxyproline, but right
Other inorganic salt impurities and a small amount of miscellaneous amino acid adsorbed effect are obvious, can go out the big portion in addition to L-PROLINE
Divide impurity.
In described step 3, weak-base anion-exchange resin is polyacrylic acid series anion exchange resin.
Described polyacrylic acid series anion exchange resin is preferably A830 weak-base anion-exchange resin.
Upper flow velocity during described step 3 middle strong acidity cationic exchange resin adsorption is 0.6～0.8 times per hour
Storng-acid cation exchange resin volume, storng-acid cation exchange resin and weak-base anion-exchange resin
Volume ratio is 3:4～3:5.
In described step 4, thickening temperature is preferably 55 DEG C, concentrates volume and is preferably concentrated into 1/7 before concentration,
The method of described decolouring is to add to account for the injection type activated carbon of nanofiltration clear liquid 0.3%～0.6% at temperature 20～40 DEG C
Decolouring 1～2h.
1/3 batch of mother solution mixing of acquisition in a collection of microfiltration trapped fluid obtained in described step one and described step 4,
It is dried, L-hydroxyproline feedstuff can be prepared.
The invention has the beneficial effects as follows: the present invention changes traditional handicraft ion exchange resin absorption L-hydroxyl dried meat ammonia
Acid is adsorbing contaminant, then extracts L-hydroxyproline by the method for condensing crystallizing, is not only effectively increased product
Produced refuse also effectively is used for producing feedstuff by the purity of product, yield, it is to avoid environmental pollution.Specifically
Have the beneficial effect that:
(1), for the low problem of traditional handicraft extraction ratio, the present invention is by by nanofiltration trapped fluid and once female
Liquid sends ion exchange resin absorption process back to, is effectively reduced the loss of raw material, the extraction of L-hydroxyproline
Rate is more than 80%.
(2), the present invention and traditional handicraft contrast, spent ion exchange resin absorption be a small amount of impurity rather than
Traditional absorption major part L-hydroxyproline, the consumption of resin greatly reduces, be greatly saved for eluting and
The deionized water of regeneration, decreases the generation of waste water.
(3), microfiltration trapped fluid COD high, traditional handicraft is the most untreated i.e. discharges, and pollutes environment,
The invention provides and microfiltration trapped fluid and partial mother liquid are mixed, are dried, make L-hydroxyproline feedstuff, with
Time solve the pollution problem of microfiltration trapped fluid and mother solution, it is achieved that the purpose of zero-emission.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart；
It is described in detail referring to the drawings below with reference to embodiments of the invention.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
The invention discloses a kind of method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid, this area skill
Art personnel can use for reference present disclosure, is suitably modified technological parameter and realizes.Special needs to be pointed out is, all classes
As replace and change and will be apparent from for a person skilled in the art, be considered as being included in the present invention
In.The method of the present invention is described by preferably case study on implementation, and those skilled in the art substantially can be not
Depart from present invention, spirit and scope are to the method for the present invention and utilization is modified or suitable change and group
Close, realize and apply the technology of the present invention.
Embodiment 1
Take the fermentation liquor 0.05 micron after the fermentation of L-hydroxyproline～0.1 micrometer ceramics film processes that to obtain 10L micro-
Cleaner liquid and microfiltration trapped fluid (giving over to stand-by), regulation pH is 6～7, then with the flow velocity of 12.5ml/min
First cross 1L C100 storng-acid cation exchange resin, after 1.5L A830 weak-base anion-exchange resin.
By ion exchange liquid, cross the NF membrane of molecular weight 800～1000Da, obtain nanofiltration clear liquid and nanofiltration trapped fluid.
Nanofiltration trapped fluid regulation pH is 6～7 to send back to ion exchange resin circulating process, and nanofiltration clear liquid adds its volume
The injection type activated carbon of 0.5% 25 DEG C decolouring 1.5h, is filtrated to get the clear liquid of light transmittance 96%.
Above-mentioned destaining solution is concentrated in vacuo to the 1/8 of its volume at 55 DEG C, is cooled to 20～30 DEG C, be incubated 1h,
Being filtrated to get wet product 352.1g, mother solution sends ion exchange resin circulating process back to.
By L-hydroxyproline wet product in 60 DEG C of drying, obtain dry product 322.3g, HPLC99.3%, yield 80.6%.
Product yield and the contrast test of purity
Utilizing traditional handicraft to extract: the fermentation liquid that source of fetching is identical with volume, adjusting pH is 3 through C100 strong acid
Property cationic exchange resin adsorption after, use ammonia eluting, twice condensing crystallizing after eluent decolouring, last total receive
Rate is 59.2%, HPLC97.3%.
Embodiment 2
Take the fermentation liquor 0.05 micron after the fermentation of L-hydroxyproline～0.1 micrometer ceramics film processes and obtains 99.6L
Microfiltration clear liquid and microfiltration trapped fluid (giving over to stand-by), regulation pH is 6～7, then with the flow velocity of 135ml/min
First cross 9L 732 type storng-acid cation exchange resin, after 15L A830 weak-base anion-exchange resin.
By ion exchange liquid, cross the NF membrane of molecular weight 800～1000Da, obtain nanofiltration clear liquid and nanofiltration trapped fluid.
Nanofiltration trapped fluid regulation pH is 6～7 to send back to ion exchange resin circulating process, and nanofiltration clear liquid adds its volume
The injection type activated carbon of 0.5% 25 DEG C decolouring 1.5h, is filtrated to get the clear liquid of light transmittance 95.7%.
Above-mentioned destaining solution is concentrated in vacuo to the 1/8 of its volume at 55 DEG C, is cooled to 20～30 DEG C, be incubated 1h,
Being filtrated to get wet product 3670.2g, mother solution sends ion exchange resin circulating process back to.
By L-hydroxyproline wet product in 60 DEG C of drying, obtain dry product 3310.8g, HPLC99.4%, yield 83.1%.
Embodiment 3
Prepared by the feedstuff of L-hydroxyproline
By a collection of standby microfiltration trapped fluid and 1/3 batch of mother solution mixing, it is spray-dried to obtain L-hydroxyproline feedstuff product
Product, L-hydroxyproline about 30%.
Above the present invention is exemplarily described, it is clear that the present invention implements and do not limited by aforesaid way
System, as long as have employed method design and the various improvement that carry out of technical scheme of the present invention, or the most improved directly
It is applied to other occasion, all within protection scope of the present invention.
Claims (9)
1. the method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid, it is characterised in that include
Following operating procedure:
Step one, by L-hydroxyproline fermentation liquid microfiltration, obtain microfiltration clear liquid and microfiltration trapped fluid, regulate micro-
Cleaner liquid pH value is 6～8, then adsorbs with storng-acid cation exchange resin, then uses weakly-basic anion
Exchanger resin absorption obtains ion exchange liquid；
Step 2, ion exchange liquid is crossed the NF membrane that molecular weight is 800～1000Da obtain nanofiltration clear liquid and receive
Filter trapped fluid；
Step 3, regulation nanofiltration trapped fluid pH value are 6～8, then adsorb with storng-acid cation exchange resin,
Then obtaining ion exchange liquid with weak-base anion-exchange resin absorption, ion exchange liquid repeats step 2；
Step 4, by after nanofiltration clear liquid activated carbon decolorizing, 50～70 DEG C be concentrated into volume be concentrate before
1/8～1/6, lower the temperature 20～30 DEG C of centrifugal finished products obtaining L-hydroxyproline and a mother solution；
Step 5, a mother solution regulation pH value are 6～8, then adsorb with storng-acid cation exchange resin,
Then obtaining ion exchange liquid with weak-base anion-exchange resin absorption, ion exchange liquid repeats step 2.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 1,
It is characterized in that, described step one middle strong acidity cation exchange resin is in styrene-divinylbenzene copolymer
With sulfonic cation exchange resin.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 2,
It is characterized in that, described styrene-divinylbenzene copolymer with sulfonic cation exchange resin is
One in C100 type storng-acid cation exchange resin, 732 type storng-acid cation exchange resins.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 1,
It is characterized in that, regulating microfiltration clear liquid pH value in described step one is 7.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 1,
It is characterized in that, in described step 3, weak-base anion-exchange resin is polyacrylic acid series anion exchange resin.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 5,
It is characterized in that, described polyacrylic acid series anion exchange resin is A830 weak-base anion-exchange resin.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 1,
It is characterized in that, upper flow velocity during described step 3 middle strong acidity cationic exchange resin adsorption is per hour
0.6～0.8 times of storng-acid cation exchange resin volume, storng-acid cation exchange resin and weakly-basic anion
The volume ratio of exchanger resin is 3:4～3:5.
The method extracting L-hydroxyproline from L-hydroxyproline fermentation liquid the most according to claim 1,
It is characterized in that, in described step 4, thickening temperature is 55 DEG C, before concentration volume is preferably concentrated into concentration
1/7, the method for described decolouring is to add to account for the injection type activated carbon of nanofiltration clear liquid 0.3%～0.6% temperature 20～40 DEG C
Lower decolouring 1～2h.
9. according to extracting from L-hydroxyproline fermentation liquid described in any claim in claim 1 to 8
The method of L-hydroxyproline, it is characterised in that a collection of microfiltration trapped fluid of described step one acquisition and described step
The 1/3 batch of mother solution obtained in four mixes, is dried, and can prepare L-hydroxyproline feedstuff.
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| CN201610205738.0A CN105777603B (en) | 2016-04-01 | 2016-04-01 | A method of extracting L- hydroxyproline from L- hydroxyproline fermentation liquid |
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| CN201610205738.0A CN105777603B (en) | 2016-04-01 | 2016-04-01 | A method of extracting L- hydroxyproline from L- hydroxyproline fermentation liquid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977442A (en) * | 2017-04-28 | 2017-07-25 | 天津科技大学 | A kind of extraction process of hydroxyproline |
| CN106995398A (en) * | 2017-05-10 | 2017-08-01 | 通辽梅花生物科技有限公司 | L proline novel technology for extracting |
| CN107435057A (en) * | 2017-08-12 | 2017-12-05 | 河南宏大生物医药有限公司 | Using the method for ETEC JL HYP fermenting and producing hydroxyprolines |
| CN107513030A (en) * | 2017-10-19 | 2017-12-26 | 福建师范大学 | A kind of method that L hydroxyprolines are isolated and purified in the hydroxyproline zymotic fluid from L |
| CN107827803A (en) * | 2017-11-28 | 2018-03-23 | 绍兴厚普生物科技有限责任公司 | A kind of method that L hydroxyprolines are extracted from zymotic fluid |
| CN109971800A (en) * | 2019-05-17 | 2019-07-05 | 南通普悦生物医药有限公司 | The method for digesting legal system L- hydroxy-proline |
| CN114105849A (en) * | 2021-12-02 | 2022-03-01 | 保定九孚生化有限公司 | Method for extracting L-hydroxyproline |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977442A (en) * | 2017-04-28 | 2017-07-25 | 天津科技大学 | A kind of extraction process of hydroxyproline |
| CN106995398A (en) * | 2017-05-10 | 2017-08-01 | 通辽梅花生物科技有限公司 | L proline novel technology for extracting |
| CN107435057A (en) * | 2017-08-12 | 2017-12-05 | 河南宏大生物医药有限公司 | Using the method for ETEC JL HYP fermenting and producing hydroxyprolines |
| CN107435057B (en) * | 2017-08-12 | 2020-12-04 | 河南巨龙生物医药有限公司 | Method for producing hydroxyproline by adopting escherichia coli JL-HYP fermentation |
| CN107513030A (en) * | 2017-10-19 | 2017-12-26 | 福建师范大学 | A kind of method that L hydroxyprolines are isolated and purified in the hydroxyproline zymotic fluid from L |
| CN107827803A (en) * | 2017-11-28 | 2018-03-23 | 绍兴厚普生物科技有限责任公司 | A kind of method that L hydroxyprolines are extracted from zymotic fluid |
| CN109971800A (en) * | 2019-05-17 | 2019-07-05 | 南通普悦生物医药有限公司 | The method for digesting legal system L- hydroxy-proline |
| CN114105849A (en) * | 2021-12-02 | 2022-03-01 | 保定九孚生化有限公司 | Method for extracting L-hydroxyproline |
| CN114105849B (en) * | 2021-12-02 | 2024-07-09 | 河北远大九孚生物科技有限公司 | Extraction method of L-hydroxyproline |
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