CN101851156A - Method for recovering fumaric acid from tiamulin production mother solution - Google Patents
Method for recovering fumaric acid from tiamulin production mother solution Download PDFInfo
- Publication number
- CN101851156A CN101851156A CN201010200659A CN201010200659A CN101851156A CN 101851156 A CN101851156 A CN 101851156A CN 201010200659 A CN201010200659 A CN 201010200659A CN 201010200659 A CN201010200659 A CN 201010200659A CN 101851156 A CN101851156 A CN 101851156A
- Authority
- CN
- China
- Prior art keywords
- fumaric acid
- acid
- mother solution
- solution
- tiamulin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of industrial sewage treatment, in particular to a method for recovering fumaric acid from liquid wastes containing the fumaric acid or fumarates, which are generated in tiamulin production mother solution. The method comprises the following steps: (1) carrying out decompression desolvation on the mother solution to remove an organic solvent to obtain a desolvation solution; (2) adding water the volume of which is 0.5-2.0 times of the desolvation solution and an organic extracting agent the volume of which is 0.3-1.0 time of the desolvation solution to the desolvation solution, and sufficiently stirring; (3) regulating the pH value of the mixed solution obtained in the step 2 to be greater than 10, evenly stirring and then standing for layering, removing an oil layer and preserving a water layer; and (4) adding acid to the water layer so as to regulate the pH value of the water layer to be 1-2 to separate out the fumaric acid and filtering to obtain the fumaric acid. The fumaric acid has high yield and low cost.
Description
Technical field
The invention belongs to the technology for treating industrial waste water field, be specifically related to a kind of method that contains recovery fumaric acid in fumaric acid or the fumarate class I liquid I waste that from tiamulin production mother solution, produces.
Background technology
Fumaric acid tiamulin is a kind of special-purpose microbiotic for animals, at first succeed in developing the seventies in last century by Switzerland Novartis Co.,Ltd, it have quick-acting, wide spectrum, antibiotic, relieving asthma, the high security characteristics.Independent or multiplicity of infection because of initiations such as mycoplasma, chlamydozoan, Salmonellas, staphylococcus there is extremely strong curative effect.Fumaric acid tiamulin is used one of microbiotic because its superior curative effect has become the world ten big animal doctors, be mainly used in the acute and chronic respiratory tract disease of livestock and poultry, to pneumonia, bronchitis, breathe, treatment of diseases such as phlegm is many, cough, bronchospasm, mycoplasmal arthritis, actinomyces bacillus pleuropneumoniae, ileitis, colitis, edema disease.Fumaric acid tiamulin is widely used all over the world having unrivaled effect aspect prevention and treatment porcine enzootic pneumonia (asthma) and the swine dysentery, and is recommended as the choice drug that the control porcine mycoplasmal infects by the expert that raises pigs.
Fumaric acid tiamulin belongs to the semi-synthetic antibiotic of biological fermentation class, does not up to the present still have artificial synthetic report.At present, the method for producing fumaric acid tiamulin both at home and abroad and being adopted is with fumaric acid and safe wonderful alkali reaction salify gained in organic solvent.More mother liquor be to produce inevitably in process of production, product fumaric acid tiamulin and about fumaric acid of about 6～10% wherein contained.To the processing of mother liquor, the used method of different producers is different to some extent, but all is therefrom to have reclaimed the major product fumaric acid tiamulin, and fumaric acid is not all recycled, and documents and materials do not see report yet.This treatment process has not only caused the waste of resource, makes the production cost of product Tiamulin improve, and has increased the load of wastewater treatment.Therefore, press for a kind of fumaric acid recovery technology of simple economy.
Summary of the invention
The objective of the invention is at problems of the prior art, a kind of method that reclaims fumaric acid from tiamulin production mother solution is provided, solved above-mentioned technical problem.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of method that from tiamulin production mother solution, reclaims fumaric acid, it may further comprise the steps:
(1), with the mother liquor precipitation that reduces pressure, remove behind the organic solvent precipitation liquid;
(2), the adding volume is 0.5～2.0 times water of precipitation liquid and 0.3～1.0 times the organic extractant that volume is precipitation liquid in precipitation liquid, fully stirring;
(3), with PH＞10 of alkali regulating step (2) gained mixed solution, after stirring, standing demix is removed oil reservoir, keeps water layer;
(4), to water layer add acid with the PH that regulates water layer at 1-2, separate out fumaric acid, filter fumaric acid.
Usually need measure the fumaric acid content in the mother liquor in the step (1), the purpose of measuring fumaric acid content is to calculate the yield that test obtains fumaric acid, and the decompression condition below pressure-0.08Mpa is usually carried out.
As preferably, the present invention also comprises a fumaric acid of separating out with the 1-5% weak acid scrubbing and the step of oven dry.
As preferably, described organic extractant is letones or Ester.
Above-mentioned described organic extractant comprises letones such as methyl iso-butyl ketone (MIBK), methyl ethyl ketone, pimelinketone, methyl isopropyl Ketone etc.; Ester such as butylacetate, isobutyl acetate etc.Described alkali comprises sodium hydroxide, potassium hydroxide etc.
As preferably, described alkali is one or more in sodium hydroxide, potassium hydroxide and their solution.
As preferably, the acid described in the step (4) is one or more in sulfuric acid, hydrochloric acid, the phosphoric acid.
As preferably, described organic extractant is that letones comprises methyl iso-butyl ketone (MIBK), methyl ethyl ketone, pimelinketone, methyl isopropyl Ketone etc.
As preferably, described organic extractant is that Ester comprises butylacetate, isobutyl acetate etc.
As preferably, the alkali in the step (3) is NaOH solution, and its concentration is 20-40%.
As preferably, the acid described in the step (4) is the hydrochloric acid soln of 10-20%.
The present invention is reasonable in design, and technology is simple, and is workable, and the Working environment toxic is little, and fumaric acid rate of recovery height, fumaric acid content reach the industrial application standard more than 98%; Make safe wonderful
RhzomorphProduction cost reduces.Present basic three-waste free discharge in liquid debris and the follow-up fumaric acid removal process, pollution-free substantially to peripheral river etc., saved environmental pollution improvement's expense.Treatment process of the present invention reclaims about 3.2 yuan of per kilogram fumaric acid cost, and the fumaric acid cover that is reclaimed makes the production cost of Tiamulin per kilogram descend about 5～7% after being used for producing.
Embodiment
Embodiment below in conjunction with indefiniteness describes, and further specifies technology of the present invention.
Fumaric acid in the liquid debris exists with fumaric acid and safe wonderful salt form, content detects with HPLC, liquid debris content is about 6～10% among the present invention through detecting, and the fumaric acid rate of recovery is calculated with qualified fumaric acid amount of output and the ratio that drops into fumaric acid amount in the liquid.
Embodiment 1
Dropping into 500ml in the 1000ml reaction flask detected the safe wonderful salt mother liquor of content (fumaric acid content was 7.1%, safe wonderful alkali content is 5%, under-0.08Mpa pressure, slough methyl alcohol, add 320ml water and 160ml butylacetate, add about 120ml40%NaOH and transfer PH＞10, stir 10min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% sulfuric acid, stirs 30min, treats that fumaric acid all separates out after-filtration, with dilute sulphuric acid washing fumaric acid crystal, then with the crystal oven dry, fumaric acid 30g, its purity is 98.1%, yield 82.6%.
Embodiment 2
(fumaric acid content is 8%, and safe wonderful alkali content is 5.5%, sloughs methyl alcohol under-0.08Mpa pressure to drop into the safe wonderful salt mother liquor that 500ml detected content in the 1000ml reaction flask, add 400ml water and 200mlMIBK, add about 150ml40%NaOH and transfer PH＞10, stir 30min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% hydrochloric acid, stirs 30min, treats that fumaric acid all separates out after-filtration, with dilute hydrochloric acid washing fumaric acid crystal, then with the crystal oven dry, fumaric acid 33g, its purity is 99.2%, yield 81.1%.
Embodiment 3
(fumaric acid content is 6.2%, and safe wonderful alkali content is 4.5%, sloughs methyl alcohol under-0.08Mpa pressure to drop into the safe wonderful salt mother liquor that 500ml detected content in the 1000ml reaction flask, add 280ml water and 350mlMIBK, add about 105ml40%NaOH and transfer PH＞10, stir 30min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% hydrochloric acid, stirs 30min, treats that fumaric acid all separates out after-filtration, with dilute hydrochloric acid washing fumaric acid crystal, then with the crystal oven dry, fumaric acid 27g, its purity is 98.9%, yield 86.1%.
Embodiment 4
(fumaric acid content is 9%, and safe wonderful alkali content is 6%, sloughs methyl alcohol under-0.08Mpa pressure to drop into the safe wonderful salt mother liquor that 500L detected content in the 1000L reactor, add 400L water and 350LMIBK, add about 170L40%NaOH and transfer PH＞10, stir 60min, standing demix.Oil reservoir recycles separately.Water layer at 1-2, stirs 60min with 15% hydrochloric acid accent PH, treats that fumaric acid is centrifugal after all separating out, and with dilute hydrochloric acid washing fumaric acid crystal, with the crystal oven dry, gets fumaric acid 39kg then, and its purity is 98.5%, yield 85.4%.
Embodiment 5
(fumaric acid content is 7.5%, and safe wonderful alkali content is 5%, sloughs methyl alcohol under-0.08Mpa pressure to drop into the safe wonderful salt mother liquor that 500L detected content in the 1000L reactor, add 400L water and 200LMIBK, add about 135L40%NaOH and transfer PH＞10, stir 60min, standing demix.Oil reservoir recycles separately.Water layer at 1-2, stirs 60min with 15% hydrochloric acid accent PH, treats that fumaric acid is centrifugal after all separating out, and with dilute hydrochloric acid washing fumaric acid crystal, with the crystal oven dry, gets fumaric acid 32kg then, and its purity is 99.0%, yield 84.3%.
Claims (10)
1. method that reclaims fumaric acid from tiamulin production mother solution is characterized in that may further comprise the steps:
(1), with the mother liquor precipitation that reduces pressure, remove behind the organic solvent precipitation liquid;
(2), the adding volume is 0.5～2.0 times water of precipitation liquid and 0.3～1.0 times the organic extractant that volume is precipitation liquid in precipitation liquid, fully stirring;
(3), with PH＞10 of alkali regulating step (2) gained mixed solution, after stirring, standing demix is removed oil reservoir, keeps water layer;
(4), to water layer add acid with the PH that regulates water layer at 1-2, separate out fumaric acid, filter fumaric acid.
2. the method that reclaims fumaric acid from tiamulin production mother solution according to claim 1 is characterized in that: also comprise fumaric acid that a dilute acid wash is separated out and the step of drying.
3. the method that reclaims fumaric acid from tiamulin production mother solution according to claim 1, it is characterized in that: described organic extractant is letones or Ester.
4. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: described alkali is one or more in sodium hydroxide, potassium hydroxide and their solution.
5. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: the acid described in the step (4) is one or more in sulfuric acid, hydrochloric acid, the phosphoric acid.
6. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: described organic extractant is that letones comprises methyl iso-butyl ketone (MIBK), methyl ethyl ketone, pimelinketone, methyl isopropyl Ketone etc.
7. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: described organic extractant is that Ester comprises butylacetate, isobutyl acetate etc.
8. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: the alkali in the step (3) is NaOH solution, and its concentration is 20-40%.
9. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: the acid described in the step (4) is the hydrochloric acid soln of 10-20%.
10. according to claim 1 or the 2 or 3 described methods that reclaim fumaric acid from tiamulin production mother solution, it is characterized in that: the alkali in the step (3) is NaOH solution, and its concentration is 40%, and the acid described in the step (4) is 15% hydrochloric acid soln.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010200659 CN101851156B (en) | 2010-06-13 | 2010-06-13 | Method for recovering fumaric acid from tiamulin production mother solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010200659 CN101851156B (en) | 2010-06-13 | 2010-06-13 | Method for recovering fumaric acid from tiamulin production mother solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101851156A true CN101851156A (en) | 2010-10-06 |
| CN101851156B CN101851156B (en) | 2013-01-16 |
Family
ID=42802871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010200659 Active CN101851156B (en) | 2010-06-13 | 2010-06-13 | Method for recovering fumaric acid from tiamulin production mother solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101851156B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642954A (en) * | 2012-05-11 | 2012-08-22 | 山东胜利生物工程有限公司 | Method for recovering 4-methyl-2-pentanone from tiamulin wastewater by acidification and wastewater treatment method |
| CN103006545A (en) * | 2012-12-28 | 2013-04-03 | 山东胜利生物工程有限公司 | Tiamulin alkali ointment and preparation method thereof |
| CN103450061A (en) * | 2012-05-29 | 2013-12-18 | 大英九合生物化工股份有限公司 | Purification method for tiamulin reaction solution in industrial production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417965A (en) * | 2008-12-01 | 2009-04-29 | 浙江升华拜克生物股份有限公司 | Method for recovering diethylamino ethanethiol from taimulin production waste water |
| CN101492366A (en) * | 2009-03-12 | 2009-07-29 | 常茂生物化学工程股份有限公司 | Method for extracting allomaleic acid from fermentation liquor |
| CN101492369A (en) * | 2008-12-12 | 2009-07-29 | 江苏工业学院 | Separation purification method for benzoic anhydride sour water and production process for allomaleic acid |
-
2010
- 2010-06-13 CN CN 201010200659 patent/CN101851156B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417965A (en) * | 2008-12-01 | 2009-04-29 | 浙江升华拜克生物股份有限公司 | Method for recovering diethylamino ethanethiol from taimulin production waste water |
| CN101492369A (en) * | 2008-12-12 | 2009-07-29 | 江苏工业学院 | Separation purification method for benzoic anhydride sour water and production process for allomaleic acid |
| CN101492366A (en) * | 2009-03-12 | 2009-07-29 | 常茂生物化学工程股份有限公司 | Method for extracting allomaleic acid from fermentation liquor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102642954A (en) * | 2012-05-11 | 2012-08-22 | 山东胜利生物工程有限公司 | Method for recovering 4-methyl-2-pentanone from tiamulin wastewater by acidification and wastewater treatment method |
| CN102642954B (en) * | 2012-05-11 | 2013-07-17 | 山东胜利生物工程有限公司 | Method for recovering 4-methyl-2-pentanone from tiamulin wastewater by acidification and wastewater treatment method |
| CN103450061A (en) * | 2012-05-29 | 2013-12-18 | 大英九合生物化工股份有限公司 | Purification method for tiamulin reaction solution in industrial production |
| CN103450061B (en) * | 2012-05-29 | 2014-10-22 | 大英九合生物化工股份有限公司 | Purification method for tiamulin reaction solution in industrial production |
| CN103006545A (en) * | 2012-12-28 | 2013-04-03 | 山东胜利生物工程有限公司 | Tiamulin alkali ointment and preparation method thereof |
| CN103006545B (en) * | 2012-12-28 | 2014-08-13 | 山东胜利生物工程有限公司 | Tiamulin alkali ointment and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101851156B (en) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102267890B (en) | Method for extracting and recovering acrylic acid from acrylic ester production wastewater | |
| CN101891842B (en) | Process for producing heparin sodium | |
| CN102417162B (en) | Recycling method of hydrochloric acid-acetic acid waste liquid | |
| CN102583684B (en) | Method for preparing flocculating agent from paper mill sludge | |
| CN101851156B (en) | Method for recovering fumaric acid from tiamulin production mother solution | |
| CN102730721A (en) | Recovering method of by-product sodium chloride in polyphenylene sulfide production | |
| CN106995398A (en) | L proline novel technology for extracting | |
| CN109205904A (en) | The producing wastewater treatment of sodium cellulose glycolate | |
| CN102746354A (en) | Method for extracting tylosin by tylosin fermentation broth | |
| CN1064680A (en) | The production technique of nicotine salt and pure nicotine products | |
| CN101708830B (en) | Method for purifying raffinate | |
| CN100497354C (en) | Technique for extracting and recovering wastewater of acephate pesticide | |
| CN102515106A (en) | Method for extracting iodine from blanching waste water of fresh kelp | |
| CN116425815A (en) | Cytidine acid production process | |
| CN104193065A (en) | Treatment method for wastewater containing fluorescent whitening agent | |
| CN102344397B (en) | Method for purifying valnemulin hydrochloride | |
| CN108658351A (en) | A method of recycling tannic acid from colophony wastewater | |
| CN111777151A (en) | Quaternary composite flocculant | |
| CN103146219A (en) | Process for preparing high-purity auramine O | |
| CN105621745A (en) | Method for recycling nicotine in tobacco processing wastewater | |
| CN112591784A (en) | Safe and energy-saving chemical agent production process | |
| CN102701963B (en) | Method for preparing potassium hydrogen terephthalate | |
| CN111393541A (en) | Enzymatic refining process of chitosan | |
| CN110200021A (en) | A kind of preparation method of ginkgo biloba leaf total organic salt | |
| CN110746061A (en) | Sludge treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171201 Address after: 313000 Zhejiang city of Huzhou province Deqing County Zhongguan town Hengtang Bridge No. 81 Patentee after: Zhejiang biok Biology Technology Co. Ltd. Address before: 313000 Huzhou City, Zhejiang Province, Deqing County Zhong Guan Town Industrial Zone Patentee before: Zhejiang Shenghua Biok Biology Co., Ltd. |
|
| TR01 | Transfer of patent right |