CN102583893A - Method for adsorbing and removing microscale antibiotic in livestock and poultry waste water by modified zeolite - Google Patents
Method for adsorbing and removing microscale antibiotic in livestock and poultry waste water by modified zeolite Download PDFInfo
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- CN102583893A CN102583893A CN2012100477153A CN201210047715A CN102583893A CN 102583893 A CN102583893 A CN 102583893A CN 2012100477153 A CN2012100477153 A CN 2012100477153A CN 201210047715 A CN201210047715 A CN 201210047715A CN 102583893 A CN102583893 A CN 102583893A
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Abstract
The invention discloses a method for adsorbing and removing microscale antibiotic in livestock and poultry waste water by modified zeolite, which belongs to the waste water treatment technical field. The method comprises the following steps: 1) biological pretreatment of livestock and poultry waste water; 2) zeolite modified treatment; and 3) adsorption and treatment of livestock and poultry waste water and the like. According to the invention, after the adsorption treatment by zeolite modified by nitric acid, hydrochloric acid and sulfuric acid, the removal rate of tetracycline antibiotics in livestock and poultry waste water can respectively reach 61.1%, 90.7% and 88.8%, but the removal rate of the natural zeolite are only 10.3%, 12.9% and 16.0% under the same condition, thereby the method of the invention has the characteristics of simple process flow, convenience, less investment, abundant material source, cheap and easily available material, low treatment cost and the like. The invention can be popularized and applied in large-scale livestock and poultry breeding enterprises.
Description
Technical field
The present invention relates to technical field of waste water processing, be specifically related to a kind of micro-antibiotic method in the modified zeolite absorption removal waste water of livestock poultry of utilizing.
Background technology
In recent years, along with the fast development of domestic intensification livestock and poultry breeding industry, in the waste water of livestock poultry microbiotic pollution problem serious day by day, the microbiotic in the water body has become a big obstacle of water resources recycling.Because TCs that in livestock and poultry breeding industry, is widely used such as tsiklomitsin, terramycin, duomycin etc.; Because it is water-soluble better, major part is still discharged with original shape behind internal metabolism; And in environment, be difficult for by reasons such as biological degradations; So in water surrounding, be prone to be stored and accumulate, therefore, become antibiotic primary pollution source in the present environment; Simultaneously, have also in this waste water that the water yield is big, water quality is complicated contains the higher concentration dissolved organic matter and contained antibiotic concentration is lower, generally only at ngL
-1-μ gL
-1Characteristics such as scope is interior.
At present, adopt multiple natural clay mineral sorbent materials such as kaolin, polynite, zeolite, antibiotic absorption method has received extensive concern in the removal water surrounding.Adsorption selectivity is weak, adsorption rate is low, defectives such as efficient difference are removed in absorption but they have, and therefore, mainly is used to handle concentration higher (10～10 in chemical industry and the pharmacy waste water
3MgL
-1) microbiotic, and seldom relate to micro-antibiotic removal in the waste water of livestock poultry.Because the antibiotic concentration in the waste water of livestock poultry itself is just lower, and its water quality is very complicated, and (COD is generally 10 even still contain the deliquescent organism of higher concentration in the water outlet after biological treatment
2～10
3MgL
-1), these organic existence will certainly have a strong impact on absorption method and remove antibiotic efficient.So micro-antibiotic removal has become the difficult point of polluted-water reparation research in the waste water of livestock poultry, does not have good solution so far.For reaching under complicated water quality background condition the micro-antibiotic target of absorption, to the screening of efficient selective sorbent material be prepared into for key.
The acid modification is a kind of method of modifying of natural zeolite, but relevant its report that ability is removed in micro-antibiotic selective adsorption in waste water of livestock poultry of sour modified zeolite raising that how to utilize was not met at present as yet.
Summary of the invention
The present invention seeks to; A little less than having an adsorption selectivity to the natural clay mineral sorbent material, low, the absorption of adsorption rate removes inefficient defective; A kind of cation exchange property that can strengthen zeolite is provided; Improve its selective adsorption capacity, improve efficient is removed in micro-microbiotic absorption in the waste water of livestock poultry, the antibiotic method of waste water of livestock poultry trace is removed in the modified zeolite absorption of water pollution and harm with effective control microbiotic.
The object of the invention realizes through following technical scheme and step:
The antibiotic method of waste water of livestock poultry trace is removed in modified zeolite absorption, and this method is carried out according to the following steps:
(1) Biological Pretreatment of waste water of livestock poultry: after the waste water that livestock and poultry farm is collected carries out the pre-treatment of anaerobic-aerobic two stage biological by routine, make COD≤100 mg/litre of water outlet, TCs concentration≤1.0 mg/litre, pH is 5.0-7.0, and is subsequent use;
(2) Zeolite modifying is handled: be 25～50% acids solution with natural zeolite and concentration by mass and size 1g: 10～20ml mixed; This mixture is placed on the shaking table, behind vibration 12h under room temperature, the 200 commentaries on classics/min conditions, vacuumizing filtration; With drying to constant weight in 105～120 ℃ in this treatment of zeolites 3-5 time of deionized water rinsing, the rearmounted baking oven of vacuum filtration, promptly get sour modified zeolite adsorbent, subsequent use;
(3) adsorption treatment of waste water of livestock poultry: with the sour modified zeolite adsorbent of step (2) and the pretreated waste water of livestock poultry of step (1) in mass and size 1g: 1000～2000ml ratio drops in the closed cell, whip attachment 3～5h under 20～30 ℃ of conditions.
The granularity of said zeolite was the 150-200 mesh sieve.
Described acids is choosing any one kind of them in nitric acid, hydrochloric acid and the sulfuric acid.
TCs in the said waste water of livestock poultry is tsiklomitsin, terramycin or duomycin.
The invention has the beneficial effects as follows:
1, the present invention adopts acids solution that natural zeolite is carried out modification and is prepared into the target sorbent material, and employed starting material mineral acid and natural zeolite source are abundant, and cheap and easy to get, processing cost is low.
2, the present invention adopts absorption method that the microbiotic in the waste water of livestock poultry is adsorbed removal, and required capital construction and facility investment economize, treatment process is convenient, technical process is simple, is convenient to actually operating.
3, the present invention adopts sour modified zeolite adsorbent, has improved its CEC and to the antibiotic selection adsorptivity of tetracyclines trace, adsorption rate and efficient all obtain bigger raising, and the microbiotic removal effect is remarkable; Wherein, After Nitric Acid Modified zeolite, hydrochloric acid modified zeolite and sulfuric acid modified zeolite adsorption are handled; The clearance of the TCs in the waste water of livestock poultry is respectively 61.1%, 90.7% and 88.8%, and only is respectively 10.3%, 12.9% and 16.0% at the eliminating rate of absorption with natural zeolite under the condition.
Embodiment
Through following examples the present invention is done further detailed description, but content of the present invention is not limited thereto.
Explanation to the related material of following examples:
Natural zeolite: granularity 150-200 order, the refreshing stone ore industry in Zhejiang ltd produces;
Nitric acid: product content 65～68%, Zhejiang three hawk chemical reagent ltds produce;
Hydrochloric acid: product content 36-38%, Chemical Reagent Co., Ltd., Sinopharm Group produces;
Sulfuric acid: product content 95-98%, hugeization reagent ltd in Quzhou, Zhejiang produces.
Embodiment 1: (the antibiotic method 1 of waste water of livestock poultry trace is removed in modified zeolite absorption)
This method is carried out according to the following steps:
(1) Biological Pretreatment of waste water of livestock poultry: after the waste water that livestock and poultry farm is collected carries out UASB (up-flow anaerobic sludge blanket)-MBR (aerobic membrane bioreactor) secondary combination process pre-treatment; The COD that makes water outlet is 82 mg/litre; TCs concentration is 0.18 mg/litre; PH is 5.0, and is subsequent use;
(2) Zeolite modifying is handled: be 25% salpeter solution with natural zeolite and concentration by mass and size 1g: the 10ml mixed; This mixture is placed on the shaking table, behind vibration 12h under room temperature, the 200 commentaries on classics/min conditions, vacuumizing filtration; Make the Nitric Acid Modified zeolite adsorbents with drying to constant weight in 120 ℃ in this treatment of zeolites 3-5 time of deionized water rinsing, the rearmounted baking oven of vacuum filtration, subsequent use;
(3) adsorption treatment of waste water of livestock poultry: with step (2) Nitric Acid Modified zeolite adsorbents and the pretreated waste water of livestock poultry of step (1) in mass and size 1g: the 1500ml ratio drops in the closed cell; Behind whip attachment 4h under 20 ℃ of conditions; TCs is reduced to 0.07 mg/litre through detectable level; Clearance is 61.1%, is merely 10.3% at the eliminating rate of absorption with natural zeolite under the condition.
Embodiment 2:
In this example, the Biological Pretreatment of step (1) waste water of livestock poultry: the COD of water outlet is 70 mg/litre after biological treatment, and TCs concentration is 0.97 mg/litre, and pH is 6.0, and is subsequent use; Step (2) Zeolite modifying is handled: be 50% hydrochloric acid soln with natural zeolite and concentration by mass and size 1g: the 20ml mixed; With drying to constant weight in 105 ℃ in the rearmounted baking oven of this mixture vacuum filtration, make the hydrochloric acid modified zeolite adsorbent; The adsorption treatment of step (3) waste water of livestock poultry: with hydrochloric acid modified zeolite adsorbent and pretreated waste water of livestock poultry in mass and size 1g: the 2000ml ratio drops in the closed cell; Behind whip attachment 5h under 30 ℃ of conditions; TCs is reduced to 0.09 mg/litre through detectable level; Clearance is 90.7%, is merely 12.9% at the eliminating rate of absorption with natural zeolite under the condition; All the other process are same as embodiment 1.
Embodiment 3:
In this example, the Biological Pretreatment of step (1) waste water of livestock poultry: the COD of water outlet is 99 mg/litre after biological treatment, and TCs concentration is 0.80 mg/litre, and pH is 7.0, and is subsequent use; Step (2) Zeolite modifying is handled: be 35% sulphuric acid soln with natural zeolite and concentration by mass and size 1g: the 16ml mixed; With drying to constant weight in 110 ℃ in the rearmounted baking oven of this mixture vacuum filtration, make sulfuric acid modified zeolite adsorbents; The adsorption treatment of step (3) waste water of livestock poultry: with sulfuric acid modified zeolite adsorbents and pretreated waste water of livestock poultry in mass and size 1g: the 1300ml ratio drops in the closed cell; Behind whip attachment 3h under 25 ℃ of conditions; TCs is reduced to 0.10 mg/litre through detectable level; Clearance is 88.8%, is merely 16.0% at the eliminating rate of absorption with natural zeolite under the condition; All the other process are same as embodiment 1.
Claims (4)
1. the antibiotic method of waste water of livestock poultry trace is removed in modified zeolite absorption, it is characterized in that carrying out according to the following steps:
(1) Biological Pretreatment of waste water of livestock poultry: the waste water that livestock and poultry farm is collected is undertaken after the anaerobic-aerobic two stage biological handles by routine, makes COD≤100 mg/litre of water outlet, TCs concentration≤1.0 mg/litre, and pH is 5.0-7.0, and is subsequent use;
(2) Zeolite modifying is handled: be 25～50% acids solution with natural zeolite and concentration by mass and size 1g: 10～20ml mixed; This mixture is placed on the shaking table, behind vibration 12h under room temperature, the 200 commentaries on classics/min conditions, vacuumizing filtration; With drying to constant weight in 105～120 ℃ in this treatment of zeolites 3-5 time of deionized water rinsing, the rearmounted baking oven of vacuum filtration, promptly get sour modified zeolite adsorbent, subsequent use;
(3) adsorption treatment of waste water of livestock poultry: with the sour modified zeolite adsorbent of step (2) and the pretreated livestock and poultry breeding industry waste water of step (1) in mass and size 1g: 1000～2000ml ratio drops in the closed cell, whip attachment 3～5h under 20～30 ℃ of conditions.
2. by the described method of claim 1, it is characterized in that the TCs in the said waste water of livestock poultry is tsiklomitsin, terramycin or duomycin.
3. by the described method of claim 1, the granularity that it is characterized in that said natural zeolite was the 150-200 mesh sieve.
4. by the described method of claim 1, it is characterized in that described acids is choosing any one kind of them in nitric acid, hydrochloric acid and the sulfuric acid.
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|---|---|---|---|
| CN 201210047715 CN102583893B (en) | 2012-02-24 | 2012-02-24 | Method for adsorbing and removing microscale antibiotic in livestock and poultry waste water by modified zeolite |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478454A (en) * | 2016-01-12 | 2016-04-13 | 宁夏大学 | Method for removing residual high-concentration tetracycline in pharmacy mushroom residues |
| CN107792911A (en) * | 2017-11-03 | 2018-03-13 | 宁夏大学 | A kind of method for going in water removal to remain tetracycline using absorption method |
| CN107857327A (en) * | 2017-10-19 | 2018-03-30 | 五邑大学 | A kind of method for the micro antibiotic that modified zeolite is gone in water removal |
| CN110550726A (en) * | 2019-09-04 | 2019-12-10 | 湖南宇山玉月农业科技有限公司 | Biological filler for treating livestock and poultry wastewater |
| CN110550724A (en) * | 2019-09-04 | 2019-12-10 | 湖南宇山玉月农业科技有限公司 | Biological filler for treating livestock and poultry wastewater |
| CN110550727A (en) * | 2019-09-04 | 2019-12-10 | 湖南宇山玉月农业科技有限公司 | biological filler for treating livestock and poultry wastewater |
| CN115445589A (en) * | 2022-09-28 | 2022-12-09 | 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 |
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| JP2003094090A (en) * | 2001-09-26 | 2003-04-02 | Tsuzuki Masatoshi | Purification and treatment system for pig urine |
| CN1587111A (en) * | 2004-09-10 | 2005-03-02 | 徐冰珍 | Discharging technology for livestock feces sewage treatment to reach standard |
| CN101544412A (en) * | 2009-05-11 | 2009-09-30 | 浙江皇冠科技有限公司 | Aquaculture water purifying agent and preparation method thereof |
| GB2464686A (en) * | 2008-10-21 | 2010-04-28 | Pisces Engineering Ltd | Filtration system |
| CN101781035A (en) * | 2009-12-14 | 2010-07-21 | 同济大学 | Method for recovering terramycin from terramycin production wastewater. |
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2012
- 2012-02-24 CN CN 201210047715 patent/CN102583893B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003094090A (en) * | 2001-09-26 | 2003-04-02 | Tsuzuki Masatoshi | Purification and treatment system for pig urine |
| CN1587111A (en) * | 2004-09-10 | 2005-03-02 | 徐冰珍 | Discharging technology for livestock feces sewage treatment to reach standard |
| GB2464686A (en) * | 2008-10-21 | 2010-04-28 | Pisces Engineering Ltd | Filtration system |
| CN101544412A (en) * | 2009-05-11 | 2009-09-30 | 浙江皇冠科技有限公司 | Aquaculture water purifying agent and preparation method thereof |
| CN101781035A (en) * | 2009-12-14 | 2010-07-21 | 同济大学 | Method for recovering terramycin from terramycin production wastewater. |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478454A (en) * | 2016-01-12 | 2016-04-13 | 宁夏大学 | Method for removing residual high-concentration tetracycline in pharmacy mushroom residues |
| CN107857327A (en) * | 2017-10-19 | 2018-03-30 | 五邑大学 | A kind of method for the micro antibiotic that modified zeolite is gone in water removal |
| CN107792911A (en) * | 2017-11-03 | 2018-03-13 | 宁夏大学 | A kind of method for going in water removal to remain tetracycline using absorption method |
| CN110550726A (en) * | 2019-09-04 | 2019-12-10 | 湖南宇山玉月农业科技有限公司 | Biological filler for treating livestock and poultry wastewater |
| CN110550724A (en) * | 2019-09-04 | 2019-12-10 | 湖南宇山玉月农业科技有限公司 | Biological filler for treating livestock and poultry wastewater |
| CN110550727A (en) * | 2019-09-04 | 2019-12-10 | 湖南宇山玉月农业科技有限公司 | biological filler for treating livestock and poultry wastewater |
| CN115445589A (en) * | 2022-09-28 | 2022-12-09 | 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 |
| 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 |
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| CN102583893B (en) | 2013-10-02 |
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