CN106188186B - A kind of kitasamycin cleaning extraction process - Google Patents
A kind of kitasamycin cleaning extraction process Download PDFInfo
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- CN106188186B CN106188186B CN201610610224.3A CN201610610224A CN106188186B CN 106188186 B CN106188186 B CN 106188186B CN 201610610224 A CN201610610224 A CN 201610610224A CN 106188186 B CN106188186 B CN 106188186B
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- raffinate
- kitasamycin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/08—Hetero rings containing eight or more ring members, e.g. erythromycins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
Abstract
This method belongs to antibiotics production technique, and in particular to a kind of cleaning extraction process of kitasamycin.The technique includes to fermentation liquid acidification, filtering, extraction, recycling raffinate.In existing production technology, as raffinate after extraction in the often direct emission after harmless treatment.The application is on the basis of to associated production technical study, it is believed that the main component of raffinate is water, and production technology use can be returned to after appropriately processed, while saving water resource use, cost of sewage disposal can be preferably reduced, to improve productivity effect.The application overcomes the technology prejudice of production direct discharging of waste water to a certain extent.Compared with existing production technology, production technology provided herein, improvement cost is lower, simple process, and since it more can significantly reduce discharge of wastewater ratio, reduce production cost, environmental benefit and productivity effect are more significant, thus have preferably practicability and application value.
Description
Technical field
This method belongs to antibiotics production technique, and in particular to a kind of cleaning extraction process of kitasamycin.
Background technique
In the prior art, preparing antibiotic by microbial fermentation is a kind of more universal and common production technology,
Main production process includes: the processes such as microbial fermentation, filtering, extractive crystallization, refinement, purification.Wherein solvent extraction is anti-
One of raw element extraction process common method, is most widely used.
In antibiotic preparation process, due to the needs of production technology, waited in Antibiotics separation, extraction, polishing purification
Cheng Zhong, often generates a large amount of high concentrated organic wastewaters, and these waste water include COD content it is high (COD generally all 5000~
Between 80000mg/L), the features such as SS concentration high (500~25000mg/L), coloration is high, pH fluctuation is big, intermittent discharge, thus nothing
Evilization processing cost is higher, and difficulty of governance is larger, thus it is necessary to production technology progress when antibiotic is prepared to fermentation method for pole
It is suitably modified, to reduce its pollution treatment cost.
Summary of the invention
It is an object of that present invention to provide a kind of cleaning extraction process of kitasamycin, which can preferably reduce guitar
Wastewater flow rate in mycin production process, while can also be offered reference for other using the production technology of the antibiotic of fermentation method preparation
And reference.
Details are as follows for the technical solution that the application is taken.
A kind of Kitasamycin cleaning extraction process, specifically comprises the following steps:
(1) fermentation liquid is acidified, specifically: the fermentation liquid containing Kitasamycin resulting after microbial fermentation is saturated
Oxalic acid aqueous solution adjust its pH=3.5 ~ 4.0;
(2) it filters, specifically: acidification post-fermentation liquid in step (1) is filtered, obtains acidified filtrate, i.e., containing Ji
The stoste to be extracted of its mycin, while obtaining filter cake, i.e., the insoluble solid substance after filtering fermentation liquor;The filtering can be
The modes such as plate-frame filtering, centrifuge separation, suction filtration or rotary drum filtering;
Further, filter cake is cleaned, specifically: above-mentioned gained filter cake is cleaned, cleaning solution, gained are obtained
Cleaning solution individually store it is spare, or after merging with gained acidified filtrate it is spare;
(3) it extracts, specifically: gained acidified filtrate and/or cleaning solution in step (2) are transferred in extractor, by existing
There is technology that extractant is added to be extracted after mixing evenly;
(4) separation and recycling of extract liquor, specifically: after extraction in step (3), stratification separation, pairing
The extract liquor of lattice enters the preparation section of subsequent antibiotic after extracting, and (also referred to as heavy-fluid is extracted and contains antibiosis to raffinate
Remaining liq after the target extract liquor of element), it is spare after collection.
The Kitasamycin cleans extraction process, is cleaned when cleaning in step (2) to filter cake using clear water, or adopt
It is cleaned with raffinate in step (4).
The Kitasamycin cleans extraction process, and extraction pH is advisable no more than 8.8 with pH=8.5 ~ 8.8 in step (3),
Gained raffinate is relatively easy to handle and have preferably to recycle value at this time.
The Kitasamycin cleans extraction process, and the raffinate regathers spare, the place of settling after precipitation process
Reason specifically: its pH=3.5 ~ 4.0 is adjusted to raffinate, flocculant is then added, after flocculation sedimentation, it is spare to collect supernatant;
The flocculant be zinc sulfate, potassium ferrocyanide, in polyacrylamide one or more of arbitrary proportions mixture;Flocculation
The preferable additional amount of agent is specifically, zinc sulfate 50 ~ 200 PPm, preferably 100PPm;Potassium ferrocyanide 50 ~ 200 PPm, preferably 100PPm;It is poly-
Acrylamide 1 ~ 10 PPm, preferably 2PPm, when polyacrylamide is added, time of repose is not shorter than 2h.
In existing production technology, as raffinate after extraction in the often direct emission after harmless treatment, thus it is certain
The promotion of cost of sewage disposal is caused in degree.The application is on the basis of to associated production technical study, it is believed that raffinate
Main component be water, production technology use can be returned to after appropriately processed, can be compared with while saving water resource and using
Cost of sewage disposal is reduced well, to improve productivity effect.
In general, Kitasamycin provided herein cleans extraction process, overcomes production waste water to a certain extent
The technology prejudice of direct emission.Compared with existing production technology, production technology provided herein, improvement cost is lower,
Simple process, and since it more can significantly reduce discharge of wastewater ratio, reduce production cost, environmental benefit and productivity effect
It is more significant, thus there is preferably practicability and application value.
Detailed description of the invention
Fig. 1 is the chemical structural formula of kitasamycin, and wherein R1, R2, V and U structure are specific as follows:
A1, R1=H、R2=COCH2CH(CH3)2;
A3, R1=COCH3、R2=COCH2CH(CH3)2;
A4, R1=COCH3、R2=COC3H7;
A5, R1=H、R2=COC3H7;
A6, R1=COCH3、R2=COC2H5;
A7, R1=H、R2=COC2H5;
A8, R1=COCH3、R2=COCH3;
A9, R1=H、R2=COCH3;
V, R1=H、R2=H;
U, R1=COCH3、R2=H。
Specific embodiment
Explanation is further explained to the application below with reference to embodiment.
Embodiment
Kitasamycin provided herein cleans extraction process, specifically comprises the following steps:
(1) fermentation liquid is acidified
Specifically: the fermentation liquid containing Kitasamycin resulting after microbial fermentation is added the oxalic acid aqueous solution of saturation,
Adjust its pH=3.5.
(2) it filters
Filtrate is obtained using suction filtration mode to acidification post-fermentation liquid in step (1) in the present embodiment, that is, contains Kitasamycin
Stoste to be extracted;
For the preferable experiment parameter of determination, to filter residue obtained (filter cake, i.e., insoluble solid kind after filtering fermentation liquor
Substance), the equal clear water of same fermentating liquid volume and raffinate is respectively adopted, and (i.e. heavy-fluid, used heavy-fluid are using above-mentioned steps
(1), the heavy-fluid that step (2) is obtained by prior art preparation afterwards) it cleans three times, merge cleaning solution respectively.
(3) extraction and crystallization, specifically: gained acidified filtrate or cleaning solution in step (2) are transferred to extractor respectively
It is interior, with 20% sodium hydroxide solution, slowly and diafiltration liquid pH is equably adjusted to 9.2;
Then solvent is added, is stirred, surveys pH, adding liquid alkaline makes final pH=8.5 ~ 8.8;
Continue to be stirred 30min, after standing 100min, puts raffinate phase, and the 50% of recovery total;
2% potassium phosphate buffer of 1/4 extract liquor volume is added, with 5% oxalic acid water tune pH 3.5 or so;Stirring
After 30min, stop stirring, static 50min;
Sour water is slowly put into crystallizing tank;
Kitasamycin finished product is obtained after crystallized and drying, calculated yield after weighing, and prepared by being detected with liquid chromatography mass spectrometric
Kitasamycin quality condition.
(4) separation and recycling of raffinate,
To being heavy-fluid after raffinate recycling in step (3), that is, can be directly used for rinsing filter residue use in step (2), but
As flushing liquor, should be closer in terms of filtering velocity with clear water in using priciple, to guarantee the consistency of using effect.
It is to be understood that the pure and impure of heavy-fluid has a certain impact to filtrate filtering velocity, it is however generally that, when heavy-fluid is more muddy
Show that the solvent contained in heavy-fluid is more, thus need appropriate flocculation sedimentation, in order to be used as flushing liquor after recycling.To obtain
The preferred process mode of heavy-fluid is obtained, associated technical parameters when inventor is to heavy-fluid processing are optimized, and related experiment is brief
It is described below.
1, the determination of zinc sulfate, potassium ferrocyanide dosage:
Filtering velocity measurement result is as shown in the table:
。
It can be seen that the additional amount of zinc sulfate, potassium ferrocyanide with 100 PPM from upper table result, at this time flocculation sedimentation effect
Preferably, filtering velocity is higher.
2, flocculant polyacrylamide additional amount and the parameter optimization of time of repose
It is each that 100 PPM zinc sulfate, 100 PPM potassium ferrocyanidees are added after heavy-fluid pH is adjusted to 3.5, not same amount is then added
Polyacrylamide and stand different time, the filtering velocity of supernatant is measured, concrete outcome is as shown in the table:
。
From upper table data and Germicidal efficacy it was determined that the poly- propionamide of 2 PPM is being added in heavy-fluid, and stands and be not less than 2h
Afterwards, heavy-fluid upper layer no suspended substance, it is whole relatively to clarify, visually observe no oil bloom, filtering velocity is also very close with water, and (filtering velocity of water is
82), thus has prospect as rinse water.
3, raffinate (heavy-fluid) is analyzed
To determine utilization feasibility after raffinate (heavy-fluid) processing, raffinate (heavy-fluid) component is detected first, is had
Body testing result is as follows:
。
(raffinate after optimal conditions processing when raffinate is said determination polyacrylamide additional amount after handling in table)
Data can be seen that the higher difference 35% and 20% of component that A9, A5 in jean-washing wastewater occupy from upper table, show to give up
Liquid has recovery value.
It should be noted that the chemical structure of kitasamycin is as shown in Figure 1, A9, A8, A7 etc. in upper table indicate different knots
The Kitasamycin of structure.
4, the influence after fermentation liquid to filtering velocity is added in raffinate (heavy-fluid) after handling
200mL fermentation liquid is respectively taken, (said determination after the clear water and above-mentioned optimal conditions for being separately added into its volume 20% optimize
Optimal conditions when polyacrylamide additional amount) processing after raffinate (heavy-fluid), according to step (1) to fermentation liquid acidification after measure
Filtering velocity (measurement is three times), measurement result is as follows:
。
It is smaller on the influence of the filtering velocity of fermentation liquid when can be seen that heavy-fluid after using processing from the statistical result of upper table, with
The conventional technical effect handled using clear water is suitable, thus heavy-fluid can be used for washing filter cake after can tentatively assert the processing
(filter residue).
5, influence of raffinate (heavy-fluid) processing mode (acidification front and back) to raffinate heavy-fluid potency
Heavy-fluid is acidified using oxalic acid, adjusts its pH=3.5, then respectively to the effect before heavy-fluid acidification and after acidification
Valence is measured, and measurement result is as follows:
。
(1,2,3,4,5 represent 5 groups of different data in table)
Potency increases by 200 U/mL or so before being acidified relatively after can be seen that heavy-fluid acidification from upper table data;But to heavy-fluid
Further liquid chromatography mass spectrometric detect discovery, before and after acidification, significant change does not occur for the potency of heavy-fluid.According to the analysis, sour
After change processing, heavy-fluid is more clarified, and disturbs the measurement of potency before being acidified in heavy-fluid containing part albumen.
6, the influence of raffinate (heavy-fluid) acidification pH
The poly- propionamide of flocculant of 100PPM zinc sulfate and 100PPM potassium ferrocyanide and 2 PPM is added in heavy-fluid, then
Different pH value are adjusted to oxalic acid, measure filtering velocity, measurement result is as shown in the table:
。
It can be seen that from upper table data when adjusting heavy-fluid pH=3.5, filtering velocity is best.
7, influence of the extraction pH of kitasamycin filtrate (stoste) to heavy-fluid potency
To under different extraction pH value conditions, heavy-fluid titration result is as shown in the table:
。
It can be seen that in the range of pH=8.0 ~ 9.3 from upper table data, with the raising of extraction pH value, the potency of heavy-fluid
Gradually decline, but when pH reaches 8.8 or more, the potency downward trend of heavy-fluid tends towards stability, but emulsion is increasingly heavier, contains
Oil mass increases, and brings difficulty to later separation, simultaneously because oil content is more, the filtering velocity of heavy-fluid is lower, also to the again sharp of heavy-fluid
With bringing difficulty, thus for combining the recycling demand of heavy-fluid, pH is extracted no more than 8.8, is advisable with pH=8.5 ~ 8.8.
8, heavy-fluid is compared as the flushing effect of rinse water and clear water
It is limited to the limitation of abstraction technique itself, on the basis of existing abstraction technique, is still contained as raffinate (heavy-fluid)
Have certain effective component, its after proper treatment be used as filter cake rinse water when, to its flushing effect obviously it is necessary to
It is detected and is determined.Inventor has carried out the experiment of different batches thus, and using clear water flushing effect as control, specifically
Testing result is as shown in the table:
。
Note: 302 tanks, 309 tanks are only that experiment numbers use in table, have no particular meaning;Raffinate after being handled in table simultaneously
Raffinate after optimal conditions processing when using said determination polyacrylamide additional amount.
It can be seen that for yield effect from upper table data, raffinate (heavy-fluid) is used as rinse water after processing
When, yield 3% or so can be increased, and weight yield averagely increases by 4.0%, 1,000,000,000 yields increase by 6%.
9, COD of sewage changes in contrast situation:
The COD value of waste water in different step is measured, as a result as follows:
。
Note: 1,2,3 representatives are the testing result of different batches in table, while raffinate processing is using said determination
Optimal conditions processing mode when polyacrylamide additional amount.
It can be seen that unprocessed raffinate (original weight liquid) COD value in 12000mg/L from upper table data, and pass through processing
Recycling utilizes about 8000mg/L when discharge again.This is the result shows that COD reduces about 33% or so when sewage discharge, by raffinate
The clear water largely used in the prior art can be substituted compared with good part after liquid (heavy-fluid) processing, while reducing water consumption, reduced
Quantity of wastewater effluent, while reducing cost of sewage disposal.
In conclusion when extracting pH below 8.8, emulsifying amount is less, extraction when extracting to Kitasamycin fermentation liquid
Extraction raffinate (heavy-fluid) is relatively clear, can preferably recycle.When recycling to heavy-fluid, its pH=3.5 ~ 4.0 first can be adjusted with oxalic acid, so
The polyacrylamide of 100 PPM zinc sulfate, 100 PPM potassium ferrocyanidees and 1 ~ 10PPM is added afterwards, after being uniformly mixed, stands not
Less than 2 hours, its supernatant is taken to can be used as rinse water, filtering velocity and water filtering velocity are quite (>=70mL/4min).And it is further
When fermentation liquid is added in the heavy-fluid of this processing mode by a certain percentage, the filtering velocity of fermentation liquid is had not significant impact, as punching
When scouring water washs filter cake, final products measurement shows that it averagely increases by 4.0% than clear water washing weight yield, and 1,000,000,000 yields increase
Add 6%.
Claims (3)
1. a kind of Kitasamycin cleans extraction process, which is characterized in that specifically comprise the following steps:
(1) fermentation liquid is acidified, specifically: the fermentation liquid containing Kitasamycin resulting after microbial fermentation is adjusted with oxalic acid
Its pH=3.5 ~ 4.0;
(2) it filters, specifically: acidification post-fermentation liquid in step (1) is filtered, acidified filtrate is obtained, i.e., it is mould containing guitar
The stoste to be extracted of element, while obtaining filter cake, i.e., the insoluble solid substance after filtering fermentation liquor;
It is described to be filtered into plate-frame filtering, centrifuge separation, suction filtration or rotary drum filtering;
Further, filter cake is cleaned, specifically: above-mentioned gained filter cake is cleaned, cleaning solution, gained washing are obtained
Liquid individually store it is spare, or after merging with gained acidified filtrate it is spare;
(3) extraction and crystallization, specifically: gained acidified filtrate and/or cleaning solution in step (2) are transferred in extractor, into
Row extraction and crystallization;
When extracting operation, with 20% sodium hydroxide solution, slowly and diafiltration liquid pH is equably adjusted to 9.2;Then solvent is added,
It is stirred, surveys pH, adding liquid alkaline makes final pH=8.5 ~ 8.8;Continue to be stirred 30min, after standing 100min, puts raffinate
Phase, and the 50% of recovery total;
When crystallization operation, 2% potassium phosphate buffer of 1/4 extract liquor volume is added, with 5% oxalic acid water tune pH to 3.5;Stirring
After 30min, stop stirring, sour water is slowly put into crystallizing tank and crystallizes by static 50min;
(4) separation and recycling of extract liquor, specifically: after extraction in step (3), stratification separation, to qualification
Extract liquor enters the preparation section of subsequent antibiotic after extracting, and to raffinate, after precipitation process, regather spare;
The precipitation process specifically: its pH=3.5 ~ 4.0 is adjusted to raffinate, flocculant is then added, after flocculation sedimentation,
It is spare to collect supernatant;
The flocculant be zinc sulfate, potassium ferrocyanide, in polyacrylamide one or more of arbitrary proportions mixture;
It is cleaned when being cleaned in step (2) to filter cake using raffinate in step (4).
2. Kitasamycin as described in claim 1 cleans extraction process, which is characterized in that flocculant addition is, zinc sulfate 50 ~
200 PPm, 50 ~ 200 PPm of potassium ferrocyanide, 1 ~ 10 PPm of polyacrylamide.
3. Kitasamycin as claimed in claim 2 cleans extraction process, which is characterized in that flocculant addition is zinc sulfate
100PPm, potassium ferrocyanide 100PPm, polyacrylamide 2PPm, after polyacrylamide is added, time of repose is not shorter than 2h.
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CN115385970A (en) * | 2022-03-24 | 2022-11-25 | 浙江普洛生物科技有限公司 | Extraction method of kitasamycin |
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2016
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CA1046438A (en) * | 1975-08-28 | 1979-01-16 | Claude Vezina | Production of kitasamycin (leucomycin) complex from streptomyces kitasatoensis |
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CN102351368A (en) * | 2011-07-01 | 2012-02-15 | 石家庄开发区德赛化工有限公司 | Loading flocculation pretreatment method of antibiotic fermentation wastewater |
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