CN103613160A - Method for removing ciprofloxacin in water body through bamboo charcoal adsorption - Google Patents
Method for removing ciprofloxacin in water body through bamboo charcoal adsorption Download PDFInfo
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- CN103613160A CN103613160A CN201310609293.9A CN201310609293A CN103613160A CN 103613160 A CN103613160 A CN 103613160A CN 201310609293 A CN201310609293 A CN 201310609293A CN 103613160 A CN103613160 A CN 103613160A
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Abstract
The invention discloses a method for removing ciprofloxacin in a water body through bamboo charcoal adsorption, belonging to the technical field of water treatment. The method comprises the steps of (1) firing a bamboo wood into bamboo charcoal at a high temperature; (2) crushing the bamboo charcoal obtained in the step (1), and screening; (3) adding the bamboo charcoal powder obtained in the step (2) into wastewater containing ciprofloxacin, and performing continuous oscillation treatment; (4) removing the bamboo charcoal powder from the wastewater. Compared with the prior art, the method disclosed by the invention has the advantages and effects as follows: ciprofloxacin antibiotics in the water body can be adsorbed, and the adsorption efficiency of adsorbing ciprofloxacin of which the initial concentration is 25mg/L is 99.6% under an optimum adsorption condition; the method disclosed by the invention is simple in preparation of an adsorbent, simple and convenient in operation and low in energy consumption; according to the method disclosed by the invention, bamboo wood leftovers can be used for firing, so that the aim of effective utilization of resources is achieved; the method disclosed by the invention also can be applied to removal of antibiotics in livestock and fowl urine and wastewater, and then the livestock and fowl urine is returned to fields, wherein the bamboo charcoal can keep soil nutrients and adjust the soil pH value.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body.
Background technology
Quinolone antibiotic is widely used in mankind's medical treatment and livestock and poultry breeding industry as a kind of extensive pedigree antibiotic, and a large amount of microbiotic are made an addition to the growth that promotes animal in feed for a long time.Research shows, most of microbiotic enters after body, can not be completely absorbed, and wherein with the form of parent and metabolite, gets rid of external 30%～90% of the total dosage that accounts for, and farm animal excrement enters water surrounding and edatope through different approach.In at present existing a lot of countries and regions surface water, underground water and tap water, have microbiotic in various degree to detect, these microbiotic that residue in water body can threaten to biology, bring out microorganisms resistance and resistant gene.Therefore, in water body, antibiotic remains removal has become the global focus of attention.
Utilizing absorption method to remove pollutent in water body is a kind of conventional water technology.At present, mostly adopt activated carbon as sorbing material, yet activated carbon contain a large amount of irregular microvoid structures, causes the adsorption effect of larger molecular organics pollutent poor.Bamboo charcoal is the main products that bamboo wood pyrolysis obtains, there is abundant porosity distribution and high-specific surface area, and its surface exists the surface functional group of other elements such as the oxygen-containing functional groups such as carboxyl, phenolic hydroxyl group and a small amount of sulfur-bearing, hydrogen, chlorine, and there is stronger characterization of adsorption.Bamboo charcoal is a kind of of biomass charcoal, has utmost point stable in properties, the feature of hard degradation.Bamboo charcoal is as a kind of good sorbent material, and cost is lower, and preparation is simple, and environmental protection and economy and adsorption efficiency are high, in adsorbing domain, have great application prospect.
The present invention utilizes the distinctive constitutional features of bamboo charcoal absorption target contaminant microbiotic, and the characteristic of its absorption is studied, for the improvement of microbiotic pollutant effluents provides reference value.
Summary of the invention
The problem existing for prior art, the object of the invention is to design provides a kind of technical scheme of utilizing bamboo Charcoal Adsorption to remove the method for Ciprofloxacin in water body.The method is utilized cheap, easily the bamboo charcoal of preparation is as sorbing material, Ciprofloxacin microbiotic pollutent in water body is carried out to Adsorption, for the toxicological harmlessization of microbiotic pollutant effluents, process a kind of simple economy effective means is provided, environmental improvement is had to potential using value.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that comprising the following steps:
1) bamboo wood is generated to bamboo charcoal through high-temperature firing;
2) bamboo charcoal step 1) being obtained is pulverized, and sieves;
3) by step 2) the powder bamboo charcoal that obtains is added in the waste water that contains Ciprofloxacin, carries out continuous oscillation processing;
4) powder bamboo charcoal is removed from waste water.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that in described step 1), bamboo wood is 3～6 years raw bamboos.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that in described step 1), firing temperature is 800～1000 ℃.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that described step 2) in bamboo charcoal after pulverizing, sieving, to obtain particle diameter be 100～200 object powder bamboo charcoals.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that it is 200～300 r/min that rotating speed is processed in described step 3) continuous oscillation.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, the condition that it is characterized in that powder bamboo Charcoal Adsorption Ciprofloxacin in described step 3) is: adsorption temp is 20～30 ℃, the continuous oscillation time is 12～24 h, and the pH of solution is 5.5～6.5.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that the starting point concentration of Ciprofloxacin in described step 3) is 5～25 mg/L, and powder bamboo charcoal is 1:500～1:2500 with the mass ratio that contains the waste water of Ciprofloxacin.
A kind of described method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body, is characterized in that adopting the method for filtering that waste water is carried out separated with powder bamboo charcoal in described step 4).
The present invention compared with prior art, has the following advantages and effect:
1, the Ciprofloxacin microbiotic in adsorbable water body, under its optimum adsorption conditions, absorption starting point concentration is that the adsorption efficiency of the Ciprofloxacin of 25 mg/L is 99.6%;
2, absorbent preparation of the present invention is simple, easy and simple to handle, consumes energy low;
3, the present invention can utilize bamboo wood scrap stock to fire, and has reached the object of utilization of resources;
4, the present invention also can be applicable to antibiotic removal in livestock and poultry urine and waste water, then goes back field, and wherein bamboo charcoal can keep soil nutrient, regulates soil pH.
Accompanying drawing explanation
Fig. 1 is the affect figure of sorbent material consumption on adsorption effect in embodiment 1;
Fig. 2 is the affect figure of pH on adsorption effect in embodiment 2;
Fig. 3 is the affect figure of adsorption time on adsorption effect in embodiment 3.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1: the impact of sorbent material consumption on adsorption effect
Taking 0.005,0.0100,0.0200,0.0500,0.1000,0.2000,0.5000 g(0.0005g) bamboo charcoal particles of different amounts are in 50 ml vials, add 25 mL, the solution of concentration 25 mg/L Ciprofloxacins, contains 0.01 mol/L CaC1 in this solution
2with 0.01 mol/L NaN
3(0.01 mol/L CaC1
2: solution is supporting electrolyte, 0.01 mol/L NaN
3: to suppress bacterial activity in soil).
At 25 ℃, 220 r/min lucifuges, 12 h that vibrate, respectively sampling, supernatant liquor is crossed after 0.22 μ m filter membrane, with the content of Ciprofloxacin in liquid chromatogram measuring sample, and calculate clearance, draw the optimum amount of bamboo charcoal, as shown in Figure 1, when the input amount of sorbent material is during at 0.005～0.0500 g, the eliminating rate of absorption of Ciprofloxacin raises with the increase of sorbent material, when the input amount of sorbent material is 0.1 g, removal effect to Ciprofloxacin is best, and clearance has reached 99.6%.When input amount superelevation 0.1 g of sorbent material, sorbent material remains unchanged substantially to the clearance of Ciprofloxacin.Therefore, in tool plug Glass tubing, add 0.1 g bamboo charcoal as sorbing material, to remove the best Static Adsorption agent consumption of Ciprofloxacin.
The impact of embodiment 2:pH on adsorption effect
Accurately take the bamboo charcoal (being accurate to ± 0.0005 g) of 0.1 g in 50 mL vials, get ciprofloxacin solution (the 0.01 mol/L CaC1 of 25 mg/l
2, 0.01 mol/L NaN
3), by the pH value of HCl and NaOH regulator solution, be 2.5,3.5,4.5,5.5,6.5,7.5,8.5,9.5, the solution that adds the different pH values of 25 mL, at 25 ℃, under 220 r/min, lucifuge is vibrated after 12 h, cross after 0.22 μ m filter membrane the concentration of Ciprofloxacin in working sample, the adsorptive capacity of calculating Ciprofloxacin.As shown in Figure 2, when water pH value is between 2.5～4.5, bamboo charcoal is relatively low to the saturated adsorption capacity of Ciprofloxacin, when pH=5.5, bamboo charcoal is maximum to the saturated adsorption capacity of Ciprofloxacin, be 6148.32 mg/kg, when water pH value is greater than 5.5, bamboo charcoal reduces along with the rising of pH value the saturated adsorption capacity of Ciprofloxacin, in pH value, is that 8.5～9.5 o'clock bamboo charcoals remain unchanged substantially to the saturated adsorption capacity of Ciprofloxacin.
Embodiment 3: the impact of adsorption time on adsorption effect
Accurately take the bamboo charcoal (being accurate to 0.0005 g) of 0.1 g in 50 mL vials, regulating the pH value of background solution is 5.5, adds 25 mL, 0.01 mol/L CaC1 of 25 mg/l Ciprofloxacins
2solution (0.01 mol/L CaC1
2: solution is supporting electrolyte, wherein adds NaN
3making its concentration is 0.01 mol/L,), at 25 ℃, 48 h that vibrate under 220 r/min, at 0,1/6,1/3,0.5,1,1.5,2,4,6,8,10,12,16,24,36,48 h, get supernatant liquor, cross after 0.22 μ m filter membrane, adopt the Ciprofloxacin Concentration in liquid chromatogram measuring sample, calculate the adsorptive capacity of Ciprofloxacin, determine the absorption Best Times of Ciprofloxacin on bamboo charcoal.As shown in Figure 3, when adsorption time is in 0.5 h the most, bamboo charcoal is very fast to the absorption of Ciprofloxacin, in water body, the concentration of Ciprofloxacin sharply declines, bamboo charcoal is 80% to the eliminating rate of absorption of Ciprofloxacin, and adsorption time is about 12 h left and right, and bamboo charcoal is 99.6% to the eliminating rate of absorption of Ciprofloxacin, the absorption kept stable of bamboo charcoal to Ciprofloxacin in 24 h subsequently, shows that 12 h are the shortest adsorption time that bamboo Charcoal Adsorption agent reaches maximum adsorption capacity.
Application examples 1:
1) by bamboo wood, be that 5 years raw bamboos are fired generation bamboo charcoal through 800 ℃;
2) bamboo charcoal step 1) being obtained is pulverized, and sieves, and obtaining particle diameter is 100 object powder bamboo charcoals;
3) regulating the wastewater pH to 6 contain 5% Ciprofloxacin, by step 2) the powder bamboo charcoal that obtains is added in this waste water, and the mass ratio of powder bamboo charcoal and waste water is 1:2000, then 25 ℃ of temperature, continuous oscillation 18 h under rotating speed 250 r/min;
4) powder bamboo charcoal is filtered and removed from waste water.
5) the Ciprofloxacin content finally detecting in waste water is 0.10 mg/kg, and clearance reaches 97.97%.
Application examples 2:
1) by bamboo wood, be that 6 years raw bamboos are fired generation bamboo charcoal through 1000 ℃;
2) bamboo charcoal step 1) being obtained is pulverized, and sieves, and obtaining particle diameter is 200 object powder bamboo charcoals;
3) regulating the wastewater pH to 5.5 contain 15% Ciprofloxacin, by step 2) the powder bamboo charcoal that obtains is added in this waste water, and the mass ratio of powder bamboo charcoal and waste water is 1:1000, then 20 ℃ of temperature, continuous oscillation 12 h under rotating speed 200 r/min;
4) powder bamboo charcoal is filtered and removed from waste water.
5) the Ciprofloxacin content finally detecting in waste water is 0.12 mg/kg, and clearance reaches 99.17%.
Application examples 3:
1) by bamboo wood, be that 3 years raw bamboos are fired generation bamboo charcoal through 900 ℃;
2) bamboo charcoal step 1) being obtained is pulverized, and sieves, and obtaining particle diameter is 200 object powder bamboo charcoals;
3) regulating the wastewater pH to 6 contain 25% Ciprofloxacin, by step 2) the powder bamboo charcoal that obtains is added in this waste water, and the mass ratio of powder bamboo charcoal and waste water is 1:2500, then 30 ℃ of temperature, continuous oscillation 24 h under rotating speed 300 r/min;
4) powder bamboo charcoal is filtered and removed from waste water.
5) the Ciprofloxacin content finally detecting in waste water is 0.19 mg/kg, and clearance reaches 99.24%.
Claims (8)
1. utilize bamboo Charcoal Adsorption to remove a method for Ciprofloxacin in water body, it is characterized in that comprising the following steps:
1) bamboo wood is generated to bamboo charcoal through high-temperature firing;
2) bamboo charcoal step 1) being obtained is pulverized, and sieves;
3) by step 2) the powder bamboo charcoal that obtains is added in the waste water that contains Ciprofloxacin, carries out continuous oscillation processing;
4) powder bamboo charcoal is removed from waste water.
2. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, is characterized in that in described step 1), bamboo wood is 3～6 years raw bamboos.
3. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, is characterized in that in described step 1), firing temperature is 800～1000 ℃.
4. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, is characterized in that described step 2) in bamboo charcoal after pulverizing, sieving, to obtain particle diameter be 100～200 object powder bamboo charcoals.
5. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, is characterized in that it is 200～300 r/min that rotating speed is processed in described step 3) continuous oscillation.
6. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, the condition that it is characterized in that powder bamboo Charcoal Adsorption Ciprofloxacin in described step 3) is: adsorption temp is 20～30 ℃, the continuous oscillation time is 12～24 h, and the pH of solution is 5.5～6.5.
7. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, the starting point concentration that it is characterized in that Ciprofloxacin in described step 3) is 5～25 mg/L, and powder bamboo charcoal is 1:500～1:2500 with the mass ratio that contains the waste water of Ciprofloxacin.
8. a kind of method of utilizing bamboo Charcoal Adsorption to remove Ciprofloxacin in water body as claimed in claim 1, is characterized in that adopting the method for filtering that waste water is carried out separated with powder bamboo charcoal in described step 4).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108764A (en) * | 2014-07-09 | 2014-10-22 | 山东大学 | Method for restoring antibiotics-polluted wastewater |
| CN105668684A (en) * | 2016-03-01 | 2016-06-15 | 同济大学 | Application of phoenix tree leaf as adsorbent for antibiotic and/or organic pollutants |
| CN106542686A (en) * | 2016-11-25 | 2017-03-29 | 东莞市联洲知识产权运营管理有限公司 | A kind of effective method for removing Ciprofloxacin in waste water |
| CN107081160A (en) * | 2017-03-21 | 2017-08-22 | 江苏大学 | CdSe quantum dot is embedded in the preparation and its application of culm charcoal composite photo-catalyst |
| CN107224987A (en) * | 2017-05-08 | 2017-10-03 | 江苏大学 | CdSe quantum dot is embedded in culm charcoal and Bi12TiO20The preparation and its application of composite photo-catalyst |
| CN113042018A (en) * | 2021-03-12 | 2021-06-29 | 重庆大学 | Preparation method and application of calcium-rich biochar |
| CN114082400A (en) * | 2021-11-09 | 2022-02-25 | 陇东学院 | Method for preparing biochar by co-pyrolysis of rubber and ginkgo leaves and application of biochar in removal of antibiotics in water body |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108764A (en) * | 2014-07-09 | 2014-10-22 | 山东大学 | Method for restoring antibiotics-polluted wastewater |
| CN104108764B (en) * | 2014-07-09 | 2016-02-03 | 山东大学 | A kind of restorative procedure to microbiotic drug contamination waste water |
| CN105668684A (en) * | 2016-03-01 | 2016-06-15 | 同济大学 | Application of phoenix tree leaf as adsorbent for antibiotic and/or organic pollutants |
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| CN107224987A (en) * | 2017-05-08 | 2017-10-03 | 江苏大学 | CdSe quantum dot is embedded in culm charcoal and Bi12TiO20The preparation and its application of composite photo-catalyst |
| CN113042018A (en) * | 2021-03-12 | 2021-06-29 | 重庆大学 | Preparation method and application of calcium-rich biochar |
| CN114082400A (en) * | 2021-11-09 | 2022-02-25 | 陇东学院 | Method for preparing biochar by co-pyrolysis of rubber and ginkgo leaves and application of biochar in removal of antibiotics in water body |
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Application publication date: 20140305 |