CN101781035B - Method for recovering terramycin from terramycin production wastewater. - Google Patents
Method for recovering terramycin from terramycin production wastewater. Download PDFInfo
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- CN101781035B CN101781035B CN2009102010505A CN200910201050A CN101781035B CN 101781035 B CN101781035 B CN 101781035B CN 2009102010505 A CN2009102010505 A CN 2009102010505A CN 200910201050 A CN200910201050 A CN 200910201050A CN 101781035 B CN101781035 B CN 101781035B
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- terramycin
- molecular sieve
- zeolite molecular
- waste liquid
- adsorption column
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Abstract
The invention relates to a method for recovering terramycin from terramycin c wastewater, in particular to a method for treating terramycin wastewater. The method comprises the following steps: first adjusting the PH value of the terramycin production wastewater and clarifying the wastewater by filtration; loading the absorption column with a hydrophilic zeolite molecular sieve (one of the 3A, 4A, 5A, 10 X, 13 X or Y types of molecular sieves); running the clarified terramycin wastewater through the absorption column, with the velocity of the flow between 1 to 12 BV/h under the temperature of 5-100 DEG C, the terramycin is absorbed by the absorption column; then desorbing the solution by alkali solution (Ammonia, sodium hydroxide solution or sodium carbonate solution) of 0.1 to 2.0 M under the temperature of 10 to 100 DEG C with the velocity of the flow between 1 to 4 BV/h to get high-concentration terramycin alkali solution; after the crystallization treatment, the crystal oxytetracycline dihyclorate obtained can directly be used as drug product. The recycle rate of the terramycin is 40-90 percent. The method of the invention is easy to operate and the zeolite molecular sieve can be repeatedly used. The treatment cost of the invention is lower than the treatment cost of methods of the same type. The method of the invention can be widely applied to recover terramycin from terramycin production wastewater.
Description
Technical field
The present invention relates to the treatment process of terramycin factory effluent, be specifically related to a kind of method that from the terramycin factory effluent, reclaims the lower concentration terramycin.
Background technology
At present, the terramycin concentration that terramycin is produced in the waste liquid is about 20-600mg/L, because terramycin is difficult to oxidation and biological degradation, and it has rejection to the mikrobe in the biological process of wastewater treatment, is unfavorable for the biochemical treatment of pharmacy waste water.Cause present terramycin wastewater to need to handle behind the Macrodilution, still, terramycin has suitable recovery value again.For the recovery that terramycin is produced the terramycin in the waste liquid, attempt through methods such as extraction, membrane sepn, ion exchange resin, use a difficult problem but all exist.When for example extraction was reclaimed, the extraction agent losing issue was serious, causes cost recovery higher, and flux is decayed fast because waste liquid middle and high concentration organism makes the film pollution and adopt the membrane sepn rule.Chinese invention patent 200710021381 and 200710021382 discloses two kinds of methods that make spent ion exchange resin from terramycin production mother liquid, reclaim terramycin; Advantages such as technology is simple though ion-exchange-resin process has, selection excellent adsorption; But owing to also contain amounts of protein, polyose organism in the terramycin wastewater; Can efficient reduce owing to the saturated of resin functional group behind the life-time service; And the organism characteristic of ion exchange resin itself, make it can receive oxygenolysis in use repeatedly, the puzzlement of problems such as organism stripping.In addition, the ion exchange resin regeneration process is not thorough, uses the soda acid reagent cost higher, thereby has restricted the industrial applications of ion-exchange-resin process in terramycin wastewater reclaims.
Summary of the invention
The objective of the invention is to disclose a kind of method of producing recovery terramycin the waste liquid from terramycin, it is low from terramycin production waste liquid, to reclaim the terramycin cost with method of the present invention, and technology is simple.
In order to achieve the above object; The present invention adopts the terramycin in the zeolite molecular sieve absorption waste liquid; Zeolite molecular sieve is any one of 3A, 4A, 5A, 10X, 13X or y-type zeolite molecular sieve; Under pH4-9,5-100 ℃, flow velocity 1-12BV/h, carry out, use sig water (ammoniacal liquor, NaOH solution or Na again
2CO
3Solution) desorption reclaims the terramycin alkali lye that obtains high density, through crystallization treatment, obtains the crystal Oxytetracycline Base BP (98) again, can directly use as the medicine finished product.
Concrete steps are following:
A with producing the waste liquid that contains the about 20-500mg/L of terramycin concentration that terramycin produces, adds acid or alkali and regulates pH to 5-9, through filtering, obtains clarifying terramycin waste liquid again;
B; The wetting ability of in adsorption column, packing into zeolite molecular sieve (any one of 3A, 4A, 5A, 10X, 13X or Y zeolite); The clarifying terramycin waste liquid of terramycin that steps A the is obtained adsorption column of flowing through; Controlled temperature is at 5-100 ℃ and flow velocity 1-12BV/h, and zeolite molecular sieve adsorbs terramycin, qualified discharge behind the waste water treatment process of absorption effluent process routine;
C, alkali lye (ammoniacal liquor, NaOH solution or the Na of configuration 0.1-2.0M
2CO
3Solution) be desorption liquid, controlled temperature 10-100 ℃ with flow velocity 1-4BV/h condition under carry out desorption, the desorption water outlet is a high density terramycin alkali lye; Pass through crystallization treatment; Obtain the crystal Oxytetracycline Base BP (98), can directly use as medicine, the terramycin recovery reaches 40-90%;
Above-mentioned zeolite molecular sieve be because long-term repeated use the and efficient when reducing, can make it holomorphosis through calcination, and calcination temperature is 300-800 ℃, and calcination time 3-5 hour, the efficient when returning to first the use fully.
Advantage of the present invention and effect are:
1. because the present invention has used zeolite molecular sieve, make the terramycin recovery reach 40-90%, wherein the 13X zeolite molecular sieve is because its bigger aperture; The terramycin molecule can get into its inner hole structure; Possess best rate of adsorption and loading capacity, so cost is low, technology is simple.
2. the zeolite molecular sieve of using owing to the present invention can be reused, so its use cost is than cheaper with class methods.
Embodiment
Below through embodiment the present invention is made further detailed description.
Embodiment 1
The terramycin waste liquid is added alkali regulate pH to 7, through removing the suspension particle in the water after the secondary filter, obtain terramycin clarification waste liquid with accurate filter, the mycin that fetches earth clarification waste liquid 200mL, terramycin concentration is 468mg/L; Get 13X type zeolite molecular sieve (with the 13X type molecule of Shanghai zeolite molecular sieve ltd production
Sieve is for example) 10ml adorn post, and the above-mentioned terramycin clarification waste liquid adsorption column of flowing through is adsorbed, and adsorption temp is 25 ℃, flow velocity 2BV/h, terramycin concentration is 59.3mg/L in the absorption effluent, the recovery 87.3%.Adsorbing saturated back use 0.5M ammonia soln is 25 ℃ in temperature, and flow velocity is to carry out desorption under the 1BV/h condition, obtains the terramycin ammonium solution, and terramycin concentration is 8010mg/L, and desorption rate is 98.0%.Foreign matter content is lower than 5% in the desorption liquid, through qualified discharge behind the conventional waste water treatment process.With the terramycin ammonium solution crystallization treatment that obtains, produce the terramycin crystal after the crystallization, these crystal can be used as medicine and directly use.Terramycin obtains reclaiming.
Embodiment 2
The terramycin waste liquid is added alkali regulate pH to 5, filter, obtain terramycin clarification waste liquid, the mycin that fetches earth clarification waste liquid 200mL, terramycin concentration is 468mg/L.Get 5A type zeolite molecular sieve (the 5A type molecular sieve of producing with Shanghai zeolite molecular sieve ltd is an example) 10ml and adorn post; With the adsorption column absorption of flowing through of above-mentioned terramycin clarification waste liquid, adsorption temp is 10 ℃, flow velocity 8BV/h; Absorption effluent terramycin concentration is 282mg/L, the recovery 39.7%.Adsorbing saturated back use 1M sodium hydroxide solution is 25 ℃ in temperature, and flow velocity is to carry out desorption under the 2BV/h condition, obtains Oxytetracycline Base BP (98) solution, and terramycin concentration is 1836mg/L, and desorption rate is 98.7%.Foreign matter content is lower than 8% in the desorption liquid, through qualified discharge behind the conventional waste water treatment process.The Oxytetracycline Base BP (98) solution crystallization that obtains is handled, and terramycin obtains reclaiming (produce the terramycin crystal after the crystallization, these crystal can be used as medicine and directly use).
Embodiment 3
The terramycin waste liquid is added alkali regulate pH to 9, filter, obtain terramycin clarification waste liquid, the mycin that fetches earth clarification waste liquid 200mL, terramycin concentration is 56mg/L; Get 10X type zeolite molecular sieve (the 10X type molecular sieve of producing with Shanghai zeolite molecular sieve ltd is an example) 10ml and adorn post; With the adsorption column absorption of flowing through of above-mentioned terramycin clarification waste liquid, adsorption temp is 20 ℃, flow velocity 1BV/h; Absorption effluent terramycin concentration is 14mg/L, the recovery 75.0%.Adsorbing saturated back use 1M ammonia soln is 25 ℃ in temperature, and flow velocity is to carry out desorption under the 1BV/h condition, obtains the terramycin ammonium solution, and terramycin concentration is 800mg/L, and desorption rate is 95.2%.Foreign matter content is lower than 5% in the desorption liquid.Through qualified discharge behind the conventional waste water treatment process.Crystallization treatment, terramycin obtain reclaiming (produce the terramycin crystal after the crystallization, these crystal can be used as medicine and directly use).
Claims (2)
1. produce the method that reclaims terramycin the waste liquid from terramycin for one kind, it is characterized in that:
A adds acid or alkali in the waste liquid of producing terramycin, make the waste liquor PH=5-9 of terramycin, refilters, and obtains the waste liquid of clarifying terramycin;
B; The terramycin clarification waste liquid that steps A the is obtained adsorption column absorption of flowing through, 5-100 ℃ with flow velocity 1-12BV/h, the terramycin in the waste liquid is adsorbed the zeolite molecular sieve absorption in the post; The adsorption column water outlet directly adopts biochemical process to handle, and discharges after reaching national grade one discharge standard;
Above-mentioned adsorption column is the adsorption column of interior dress wetting ability zeolite molecular sieve, and the wetting ability zeolite molecular sieve is selected from any one of 3A, 4A, 5A, 10X, 13X or Y zeolite;
C; The configuration 0.1-2.0M alkali lye as desorption liquid, with desorption liquid 10-100 ℃ with flow velocity 1-4BV/h condition under pump in the adsorption column, the terramycin that adsorbs on the zeolite molecular sieve is carried out desorption; The desorption water outlet is to contain the terramycin alkali lye that terramycin concentration is 500mg/L-9000mg/L; Terramycin alkali lye to desorption carries out crystallization treatment at last, obtains the crystal Oxytetracycline Base BP (98), and the terramycin recovery is 40-90%;
Above-mentioned alkali lye is ammoniacal liquor, NaOH solution or Na
2CO
3Solution.
2. a kind of method of producing recovery terramycin the waste liquid according to claim 1 from terramycin; It is characterized in that: when the built-in wetting ability zeolite molecular sieve of the adsorption column among the step B is reused back adsorptional earth mycin efficient reduction for a long time; Zeolite molecular sieve is taken out in adsorption column; At 300-800 ℃ of following calcination 3-5 hour, put in back adsorption column, the efficient when adsorption efficiency returns to first the use fully.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102010505A CN101781035B (en) | 2009-12-14 | 2009-12-14 | Method for recovering terramycin from terramycin production wastewater. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102010505A CN101781035B (en) | 2009-12-14 | 2009-12-14 | Method for recovering terramycin from terramycin production wastewater. |
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| Publication Number | Publication Date |
|---|---|
| CN101781035A CN101781035A (en) | 2010-07-21 |
| CN101781035B true CN101781035B (en) | 2012-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2009102010505A Expired - Fee Related CN101781035B (en) | 2009-12-14 | 2009-12-14 | Method for recovering terramycin from terramycin production wastewater. |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059102A (en) * | 2010-11-22 | 2011-05-18 | 周奇迪 | Filter medium for removing oxytetracycline in drinking water and preparation method thereof |
| CN102320990B (en) * | 2011-07-07 | 2013-07-17 | 赤峰制药股份有限公司 | Method for recovering oxytetracycline from oxytetracycline hydrochloride waste liquid |
| CN102583893B (en) * | 2012-02-24 | 2013-10-02 | 浙江省农业科学院 | Method for adsorbing and removing microscale antibiotic in livestock and poultry waste water by modified zeolite |
| CN104724891B (en) * | 2015-03-27 | 2016-09-07 | 上海赛奥分离技术工程有限公司 | A kind of processing method of oxytetracycline crystallization mother liquor waste water |
| CN115445589B (en) * | 2022-09-28 | 2024-03-15 | 中交上海航道勘察设计研究院有限公司 | Preparation method and application of molecular sieve/Fe-MIL-53 material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004313877A (en) * | 2003-04-14 | 2004-11-11 | Tokyo Electric Power Co Inc:The | Organic halide recovery system |
| CN101033199A (en) * | 2007-04-10 | 2007-09-12 | 南京大学 | Method of recovering terramycin from terramycin production mother liquid |
| CN101085749A (en) * | 2007-06-22 | 2007-12-12 | 南京大学 | Method for separating terramycin |
| CN101085731A (en) * | 2007-06-22 | 2007-12-12 | 南京大学 | Method for reclaiming oxalic acid from terramycin purification liquid |
-
2009
- 2009-12-14 CN CN2009102010505A patent/CN101781035B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004313877A (en) * | 2003-04-14 | 2004-11-11 | Tokyo Electric Power Co Inc:The | Organic halide recovery system |
| CN101033199A (en) * | 2007-04-10 | 2007-09-12 | 南京大学 | Method of recovering terramycin from terramycin production mother liquid |
| CN101085749A (en) * | 2007-06-22 | 2007-12-12 | 南京大学 | Method for separating terramycin |
| CN101085731A (en) * | 2007-06-22 | 2007-12-12 | 南京大学 | Method for reclaiming oxalic acid from terramycin purification liquid |
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| CN101781035A (en) | 2010-07-21 |
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Application publication date: 20100721 Assignee: Inner Mongolia Kaisheng Bio-Technology Co., Ltd. Assignor: Tongji University Contract record no.: 2013990000647 Denomination of invention: Method for recovering terramycin from terramycin production wastewater. Granted publication date: 20120321 License type: Exclusive License Record date: 20130930 |
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