CN101851156B - Method for recovering fumaric acid from tiamulin production mother solution - Google Patents
Method for recovering fumaric acid from tiamulin production mother solution Download PDFInfo
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- CN101851156B CN101851156B CN 201010200659 CN201010200659A CN101851156B CN 101851156 B CN101851156 B CN 101851156B CN 201010200659 CN201010200659 CN 201010200659 CN 201010200659 A CN201010200659 A CN 201010200659A CN 101851156 B CN101851156 B CN 101851156B
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- fumaric acid
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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 succeeded 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 large animal doctors, be mainly used in the acute and chronic respiratory tract disease of livestock and poultry, to pneumonia, bronchitis, breathe, the treatment of the 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, up to the present there is no the report of synthetic.At present, producing the method that fumaric acid tiamulin adopts both at home and abroad, 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 about 6～10% fumaric acid 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, so that the production cost of product Tiamulin improves, and has increased the load of wastewater treatment.Therefore, in the urgent need to a kind of fumaric acid recovery technology of simple economy.
Summary of the invention
The objective of the invention is for 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 to get precipitation liquid;
(2), to add volume in the precipitation liquid be 0.5～2.0 times water of precipitation liquid and 0.3～1.0 times the organic extractant that volume is precipitation liquid, fully stir;
(3), with the PH of alkali regulating step (2) gained mixed solution＞10, after stirring, standing demix is removed oil reservoir, keeps water layer;
(4), to the water layer acid adding with the PH that regulates water layer at 1-2, separate out fumaric acid, filter to get fumaric acid.
Usually need to 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 usually condition below pressure-0.08Mpa is 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.
Organic extractant described above 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 technique is simple, and is workable, and the Working environment toxic is little, and the fumaric acid rate of recovery is high, and fumaric acid content reaches 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, substantially pollution-free to peripheral river etc., saved environmental pollution improvement's expense.Treatment process of the present invention reclaims approximately 3.2 yuan of per kilogram fumaric acid costs, after the fumaric acid that reclaims cover is used for producing, so that the production cost of Tiamulin per kilogram descends approximately 5～7%.
Embodiment
Embodiment below in conjunction with indefiniteness describes, and further specifies technique 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 the 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, adding approximately, 120ml40%NaOH transfers PH＞10, stir 10min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% sulfuric acid, stirs 30min, all separates out rear filtration until fumaric acid, with dilute sulphuric acid washing fumaric acid crystal, then with the crystal oven dry, gets fumaric acid 30g, and 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 approximately 150ml40%NaOH accent PH＞10, stir 30min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% hydrochloric acid, stirs 30min, all separates out rear filtration until fumaric acid, with dilute hydrochloric acid washing fumaric acid crystal, then with the crystal oven dry, gets fumaric acid 33g, and 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 approximately 105ml40%NaOH accent PH＞10, stir 30min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% hydrochloric acid, stirs 30min, all separates out rear filtration until fumaric acid, with dilute hydrochloric acid washing fumaric acid crystal, then with the crystal oven dry, gets fumaric acid 27g, and 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 approximately 170L 40%NaOH accent PH＞10, stir 60min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% hydrochloric acid, stirs 60min, all separates out rear centrifugally until fumaric acid, with dilute hydrochloric acid washing fumaric acid crystal, then with the crystal oven dry, gets fumaric acid 39kg, 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 approximately 135L40%NaOH accent PH＞10, stir 60min, standing demix.Oil reservoir recycles separately.Water layer transfers PH at 1-2 with 15% hydrochloric acid, stirs 60min, all separates out rear centrifugally until fumaric acid, with dilute hydrochloric acid washing fumaric acid crystal, then with the crystal oven dry, gets fumaric acid 32kg, and its purity is 99.0%, yield 84.3%.
Claims (8)
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 to get precipitation liquid;
(2), to add volume in the precipitation liquid be 0.5～2.0 times water of precipitation liquid and 0.3～1.0 times the organic extractant that volume is precipitation liquid, fully stir;
(3), with the pH of alkali regulating step (2) gained mixed solution 10, after stirring, standing demix is removed oil reservoir, keeps water layer;
(4), to the water layer acid adding with the pH that regulates water layer at 1-2, separate out fumaric acid, filter to get fumaric acid.
2. the method that reclaims fumaric acid from tiamulin production mother solution according to claim 1 is characterized in that: also comprise the 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 and 2, it is characterized in that: described alkali is one or more in sodium hydroxide, potassium hydroxide and their solution.
4. the method that reclaims fumaric acid from tiamulin production mother solution according to claim 1 and 2, it is characterized in that: the acid described in the step (4) is one or more in sulfuric acid, hydrochloric acid, the phosphoric acid.
5. the method that reclaims fumaric acid from tiamulin production mother solution according to claim 1 and 2 is characterized in that: described organic extractant is a kind of in methyl iso-butyl ketone (MIBK), methyl ethyl ketone, pimelinketone, methyl isopropyl Ketone, butylacetate, the isobutyl acetate.
6. the method that from tiamulin production mother solution, reclaims fumaric acid according to claim 1 and 2, it is characterized in that: the alkali in the step (3) is NaOH solution, its concentration is 20～40%.
7. the method that reclaims fumaric acid from tiamulin production mother solution according to claim 1 and 2, it is characterized in that: the acid described in the step (4) is 10～20% hydrochloric acid soln.
8. the method that from tiamulin production mother solution, reclaims fumaric acid according to claim 1 and 2, 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.
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| 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 |
| 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 |
| 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 |
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 |
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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 |
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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. |