CN110227416B - Preparation of iron zinc and phosphoric acid modified sludge biochar and application of iron zinc and phosphoric acid modified sludge biochar in removal of fluoroquinolone antibiotics in water - Google Patents
Preparation of iron zinc and phosphoric acid modified sludge biochar and application of iron zinc and phosphoric acid modified sludge biochar in removal of fluoroquinolone antibiotics in water Download PDFInfo
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Abstract
The invention discloses preparation of sludge biochar modified by iron and zinc and phosphoric acid and application of the sludge biochar in removing fluoroquinolone antibiotics in water, and belongs to the technical field of biochar preparation. The preparation method comprises the steps of dehydrating and drying sludge in a secondary sedimentation tank of a municipal sewage treatment plant, pyrolyzing the sludge by using a high-temperature tubular furnace, modifying the sludge by using iron and zinc and phosphoric acid, and finally performing secondary calcination to obtain Fe/Zn + H3PO4-an SBC. Fe/Zn + H prepared by the invention3PO4The adsorption capacity of SBC on fluoroquinolone antibiotics ciprofloxacin, norfloxacin and ofloxacin in water can reach 25.43-88.73 mg/g. The municipal sludge is used as a raw material, so that the production cost is reduced, the resource utilization of the municipal sludge and the efficient removal of antibiotics in water are realized, and the method has the advantages of simplicity in operation, low cost and the like, and has great potential on the fluoroquinolone antibiotics in water.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing antibiotics in water by using sludge biochar modified by iron, zinc and phosphoric acid as an adsorbent.
Background
Since the advent of penicillin in 1929, there was an explosive increase in the use of antibiotics in order to improve and safeguard human and animal health. Antibiotics have the characteristics of broad-spectrum antibacterial activity and good bactericidal effect and are widely used for treating bacterial infection. According to market research results, China has become the world's largest antibiotic producing and consuming country. Antibiotics ingested by humans and animals are not completely metabolized and absorbed, about 50% to 90% are excreted as original compounds or metabolites through urine and feces, and are difficult to be effectively and completely removed into the environment by natural decay and conventional sewage treatment techniques. Even if the concentration of the antibiotics in the water is extremely low, the antibiotics can inhibit the growth of the algae, influence the photosynthesis and the growth metabolism of the algae and have potential endocrine disrupting effects on aquatic organisms. Irrigation with antibiotic-containing wastewater results in the enrichment of plants with antibiotics into the food chain. Antibiotics in the environment can enhance the resistance of bacteria, enhance the transmissibility of the bacteria, cause the drug resistance of the bacteria and the generation of super bacteria, and form great threats to the health of animals and human bodies, wherein Ciprofloxacin (CIP) and the like are listed in the European water environment quality observation list.
The antibiotic in traditional sewage treatment technique can not effectively get rid of aquatic, and present novel technique of getting rid of includes: advanced oxidation, biodegradation and adsorption techniques. A large amount of energy consumption and high treatment cost are generated in the advanced oxidative degradation process, and the environment can be seriously polluted secondarily due to uncertainty of byproducts generated by degradation; and biodegradation may have the disadvantages of long time consumption, low removal efficiency, strict requirements on operating conditions and the like. Adsorption is an economical, efficient and large-scale applicable process.
Municipal sludge is a main byproduct of a municipal sewage treatment plant, the growing and huge yield problem of the municipal sludge brings great pressure to the environment, research and prediction are carried out, the sludge yield of China reaches 4547 ten thousand tons/year by the end of 2020, and the resource utilization of the municipal sludge is an environmental problem which needs to be solved urgently and becomes a hotspot of the current international related research field. The municipal sludge is rich in organic matters, so that the municipal sludge is beneficial to preparing a biochar product, and researches show that the biochar has certain surface area and porosity and has certain adsorption capacity on organic pollutants in the environment. However, the antibiotics have larger molecular weight and molecular structure, so that the adsorption capacity of the sludge-based biochar is limited, and the adsorption capacity can be improved by a proper modification mode. Researches show that the iron-zinc and phosphoric acid modification can obviously improve the physicochemical characteristics of the biochar and enhance the adsorption capacity of the biochar, but researches on the combination of the iron-zinc and phosphoric acid modification and the modified sludge biochar system for exploring antibiotic adsorption have not been reported.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the method for modifying the sludge biochar by using the iron, the zinc and the phosphoric acid, which has a good treatment effect, can realize the resource utilization of municipal sludge and can efficiently remove antibiotics in water.
In order to solve the technical problems, the invention provides a preparation method of sludge biochar modified by iron and zinc and phosphoric acid, which comprises the following steps:
(1) preparing the sludge biochar modified by iron zinc and phosphoric acid: performing centrifugal dehydration on municipal sludge in the secondary sedimentation tank, drying to constant weight, grinding, performing pyrolysis, grinding, and sieving with a 200-mesh sieve of 100 meshes to obtain sludge biochar SBC;
(2) adding SBC obtained in the step (1) into FeCl with the volume ratio of 2:1-4:13·6H2Aqueous O solution and ZnCl2In a mixed solution of an aqueous solution, the FeCl3·6H2The mass concentration of O is 4.8-9.6g/L, and the ZnCl2The mass concentration of the aqueous solution is 2.4 g/L; the SBC and the mixed solution are vibrated for 24 hours at the ratio of 1Kg to 10L-1Kg to 20L, dried at 100 ℃, and the loading process is repeated for at least 3 times to improve the loading capacity of iron and zinc; then calcining to obtain the iron-zinc modified sludge biochar Fe/Zn-SBC;
(3) adding 10.6-15mol/L H into SBC obtained in the step (1)3PO4Performing the following steps; the SBC and H3PO4Shaking and soaking for 8-10H at a ratio of 1Kg to 2.5L-1Kg to 10L, filtering, drying, activating at high temperature, washing the sample with deionized water until the pH of the filtrate is constant, drying at 60-80 ℃, grinding and sieving with a 100-mesh and 200-mesh sieve to obtain H3PO4Modified sludge biochar H3PO4-SBC；
(4) Sequentially operating the SBC obtained in the step (1) according to the preparation processes of the step (2) and the step (3), and obtaining the biochar which is iron, zinc and H3PO4Modified sludge biochar Fe/Zn + H3PO4SBC, stored in desiccators protected from light.
As a preferred aspect of the above technical solution, the method for preparing iron-zinc and phosphoric acid modified sludge biochar provided by the present invention further includes part or all of the following technical features:
as an improvement of the technical scheme, in the step (1), the drying condition is blast drying at 60-80 ℃; the pyrolysis condition is N2Under protective conditions, N2The flow rate is 0.5-1L/min, the temperature rising rate is 10-20 ℃/min, and the pyrolysis is carried out for 1.5-2h under the conditions of 300 ℃ and 700 ℃.
As an improvement of the technical scheme, in the step (2), the calcining condition is N2Under protective conditions, N2The flow rate is 0.5-1L/min, the temperature rising rate is 10-20 ℃/min, and the pyrolysis is carried out for 1.5-2h under the conditions of 300 ℃ and 700 ℃.
As an improvement of the technical scheme, in the step (3), the high-temperature activation is carried out in a muffle furnace, the temperature rising rate is 10-20 ℃/min, and the temperature is kept at 400-450 ℃ for 1-2 h.
The iron-zinc and phosphoric acid modified sludge biochar is prepared according to any method.
The application of the sludge biochar SBC, the sludge biochar Fe/Zn-SBC and the sludge biochar H modified by iron and zinc in removing the fluoroquinolone antibiotics in water3PO4Modified sludge biochar H3PO4SBC and Fe-Zn and H3PO4Modified sludge biochar Fe/Zn + H3PO4SBC as adsorbent to fluorine-containing compoundsAnd (3) filtering the water containing the quinolone antibiotics after adsorption balance to obtain the water without the fluoroquinolone antibiotics.
Preferably, the application of the sludge biochar modified by iron and zinc and phosphoric acid in the removal of fluoroquinolone antibiotics in water further comprises part or all of the following technical characteristics:
as an improvement of the technical scheme, the fluoroquinolone antibiotic is one or more of Ciprofloxacin (CIP), Norfloxacin (NOR) and Ofloxacin (OFL).
As an improvement of the technical scheme, the solubility of the antibiotics in water of the fluoroquinolone antibiotics is 5-100mg/L, and the adding amount of the adsorbent is 0.2-1.0 g/L.
As an improvement of the technical scheme, the pH of the solution is adjusted to 2-10 after the adsorbent is added into water containing the fluoroquinolone antibiotics.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects: the method for effectively removing the antibiotics in the water by using the iron-zinc and phosphoric acid modified sludge biochar as the adsorbent is provided, so that the antibiotics in the water can be effectively removed, the harm of the antibiotics to the environment is reduced, the resource utilization of the municipal sludge can be realized, and the method has the advantages of low cost, simplicity in operation and the like.
(1) Fe/Zn + H of the invention3PO4SBC has optimum adsorption properties, adsorbent Fe/Zn + H3PO4SBC (0.5g/L) has removal rate of 60.29-94.81% for CIP, NOR and OFL with concentration of 10 mg/L. Meanwhile, the maximum adsorption capacity of the adsorbent to CIP, NOR and OFL can reach 25.43-83.73mg/g according to the adsorption isotherm.
(2) Compared with advanced oxidation, biodegradation and other methods, the method for removing antibiotics in water by adsorption of the modified sludge biochar has the advantages of simple operation, low cost and large-scale application prospect.
(3) The adsorbent prepared by the invention is Fe/Zn + H3PO4The SBC can effectively promote the resource utilization of municipal sludge, reduce the harm to the environment and simultaneously realize the removal of antibiotics in water.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a graph showing the relationship between the reaction time and the adsorption amounts and removal rates of CIP, NOR and OFL when SBC is used as an adsorbent;
FIG. 2 is a graph showing the relationship between the reaction time and the adsorption amounts and removal rates of CIP, NOR and OFL when Fe/Zn-SBC is used as an adsorbent;
FIG. 3 is H3PO4Curves of reaction time with SBC as adsorbent, adsorption amounts and removal rates of CIP, NOR, OFL;
FIG. 4 shows Fe/Zn + H3PO4Curves of reaction time with SBC as adsorbent, adsorption amounts and removal rates of CIP, NOR, OFL;
FIG. 5 shows Fe/Zn + H3PO4-pH of the solution as adsorbent versus adsorption and removal of CIP, NOR, OFL for SBC;
FIG. 6 shows Fe/Zn + H3PO4-CIP, NOR, OFL concentration as a function of adsorption and removal rate for SBC as adsorbent;
figure 7(a) is SBC and H3PO4-XRD pattern of SBC;
FIG. 7(b) shows Fe/Zn-SBC and Fe/Zn + H3PO4-XRD pattern of SBC;
figure 8(a) is an SEM image of an SBC;
FIG. 8(b) is an SEM image of Fe/Zn-SBC;
FIG. 8(c) is H3PO4-SEM spectra of SBC;
FIG. 8(d) shows Fe/Zn + H3PO4-SEM spectra of SBC;
figure 9(a) is a pore distribution map of an SBC;
FIG. 9(b) is a pore distribution map of Fe/Zn-SBC;
FIG. 9(c) is H3PO4-a pore distribution pattern of the SBC;
FIG. 9(d) shows Fe/Zn + H3PO4Pore distribution Pattern of SBC
FIG. 10(a) shows SBC, Fe/Zn-SBC, H3PO4SBC and Fe/Zn + H3PO4-FTIR spectrum before SBC adsorption;
FIG. 10(b) shows SBC, Fe/Zn-SBC, H3PO4SBC and Fe/Zn + H3PO4-FTIR spectra after SBC adsorption;
FIG. 11 shows SBC, Fe/Zn-SBC, H3PO4SBC and Fe/Zn + H3PO4Zeta potential profile of SBC.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example one: centrifuging and dehydrating municipal sludge in a secondary sedimentation tank, drying in a blast drying oven at 70 ℃ to constant weight, grinding, and placing in N2Pyrolyzing at 500 deg.C for 2h in a tubular furnace with flow rate of 1L/min and temperature rise rate of 10 deg.C/min, grinding and sieving (0.15mm) to obtain SBC. SBC with dissolved FeCl3·6H2O：ZnCl2Shaking the solution at a ratio of 3:1 for 24h, drying at 100 ℃, repeating the loading process for 3 times to improve the loading of iron and zinc, transferring the solution into a tube furnace, and calcining the solution for 2h under the conditions to obtain Fe/Zn-SBC. Adding the Fe/Zn-SBC into H3PO4Middle (SBC: H)3PO4Soaking for 10H at a rate of 10 ℃/min ═ 1:5), activating at 450 ℃ for 1H in a muffle furnace at a temperature rise rate of 10 ℃/min, washing with deionized water until the pH of the filtrate is constant, drying at 70 ℃, grinding and sieving (0.15mm) to obtain Fe/Zn + H3PO4SBC, stored in desiccators protected from light.
Example two: SBC is added into an antibiotic solution with the concentration of 10mg/L, the adding amount of the SBC is 0.5g/L, the reaction is carried out in a constant temperature oscillation box at the temperature of 25 ℃, the residual concentrations of CIP, NOR and OFL are sampled and measured at set time, and the adsorption amount and the removal rate are calculated.
As is clear from FIG. 1, SBC, which is an adsorbent, has an adsorption amount of 0.60 to 11.27mg/g for CIP, NOR and OFL at the time of equilibrium of the reaction, a removal rate of 1.32 to 55.87%, and the highest removal ability for CIP.
Example three: adding Fe/Zn-SBC into an antibiotic solution with the concentration of 10mg/L, wherein the adding amount of the Fe/Zn-SBC is 0.5g/L, reacting in a constant temperature oscillation box at 25 ℃, sampling and measuring the residual concentrations of CIP, NOR and OFL at set time, and calculating the adsorption amount and the removal rate.
As can be seen from FIG. 2, Fe/Zn-SBC as the adsorbent shows a higher adsorption amount and removal rate for CIP, NOR and OFL with time, and the adsorption amount is 7.29-13.35mg/g and the removal rate is 36.43-67.81% at the equilibrium of the reaction, and the adsorption capacity is significantly higher than that of SBC and the removal capacity for CIP is strongest.
Example four: h is to be3PO4SBC added to an antibiotic solution at a concentration of 10mg/L, H3PO4SBC was added in an amount of 0.5g/L, the reaction was carried out in a 25 ℃ incubator, the residual concentrations of CIP, NOR and OFL were measured by sampling at a set time, and the adsorption amount and removal rate were calculated.
As can be seen from FIG. 3, the number H3PO4SBC is used as an adsorbent, the adsorption quantity and the removal rate of the SBC to CIP, NOR and OFL are increased along with time, the adsorption quantity of the SBC is 10.58-15.03mg/g when the reaction is balanced, the removal rate is 52.91-76.90%, the adsorption capacity of the SBC is obviously higher than that of the SBC, and the removal capacity of the SBC to CIP is strongest.
Example five: Fe/Zn + H3PO4SBC added to an antibiotic solution at a concentration of 10mg/L, H3PO4SBC was dosed at 0.5g/L, the reaction was carried out in a 25 ℃ incubator, the residual concentrations of CIP, NOR and OFL were measured by sampling at set times, and the adsorption amount and removal rate were calculated.
As shown in FIG. 4, the formula is Fe/Zn + H3PO4SBC is an adsorbent whose adsorption capacity and removal rate for CIP, NOR and OFL are significantly higher than SBC, Fe/Zn-SBC and H3PO4SBC, the removal rate is improved along with the increase of time, the adsorption quantity of SBC to antibiotics can reach 12.04-19.12mg/g in equilibrium, and the removal rate can reach 60.29-94.81%.
Example five: with Fe/Zn + H3PO4SBC as an adsorbent was added to CIP, NOR and OFL solutions at a concentration of 10mg/L (solution pH adjusted to 2-10, addition amount 0.5g/L), the reaction was carried out in a 25 ℃ incubator, and the residual concentration of antibiotics was measured at equilibrium to calculate the adsorption amount and removal rate.
As can be seen from FIG. 5, the formula of Fe/Zn + H3PO4SBC is an adsorbent whose adsorption capacity for CIP, NOR and OFL is influenced by the pH of the solution. Fe/Zn + H3PO4The pH value of the solution of SBC with the best removal rate to CIP, NOR and OFL is 8, 7 and 7 respectively, the adsorption capacity can reach 15.99-19.12mg/g, the highest removal rate can reach 79.93-97.10%,
example six: with Fe/Zn + H3PO4SBC is an adsorbent, added to CIP, NOR and OFL solutions of 5, 10, 20, 40, 80, 100mg/L, respectively, in an amount of 0.5g/L, and the pH of the solution is adjusted to an optimum value, and the residual concentration of the antibiotic is determined at equilibrium.
As can be seen from FIG. 6, the formula of Fe/Zn + H3PO4SBC is an adsorbent whose adsorption capacity to CIP, NOR and OFL increases with increasing antibiotic concentration, and whose maximum adsorption capacity to antibiotics can reach 25.43-88.73 mg/g.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (4)
1. The application of the sludge biochar modified by iron and zinc and phosphoric acid in removing fluoroquinolone antibiotics in water is characterized in that:
SBC (sludge biochar), Fe/Zn-SBC and H (iron-zinc modified sludge biochar)3PO4Modified sludge biochar H3PO4SBC and iron Zinc and H3PO4Modified sludge biochar Fe/Zn + H3PO4Adding SBC serving as an adsorbent into water containing fluoroquinolone antibiotics, and filtering after adsorption balance to obtain water without fluoroquinolone antibiotics;
the iron-zinc and phosphoric acid modified sludge biochar is prepared by the following method:
(1) preparing the sludge biochar modified by iron and zinc and phosphoric acid: performing centrifugal dehydration on municipal sludge in the secondary sedimentation tank, drying to constant weight, grinding, performing pyrolysis, grinding, and sieving with a 200-mesh sieve of 100 meshes to obtain sludge biochar SBC; the drying condition is blast drying at 60-80 ℃; the pyrolysis condition is N2Under protective conditions, N2The flow rate is 0.5-1L/min, the temperature rising rate is 10-20 ℃/min, and the pyrolysis is carried out for 1.5-2h under the conditions of 300 ℃ and 700 ℃;
(2) adding SBC obtained in the step (1) into FeCl with the volume ratio of 2:1-4:13·6H2Aqueous O solution and ZnCl2In a mixed solution of an aqueous solution, the FeCl3·6H2The mass concentration of O is 4.8-9.6g/L, and the ZnCl is2The mass concentration of the aqueous solution is 2.4 g/L; the SBC and the mixed solution are vibrated for 24 hours at the ratio of 1Kg to 10L-1Kg to 20L, dried at 100 ℃, and the loading process is repeated for at least 3 times to improve the loading capacity of iron and zinc; then calcining to obtain Fe-Zn modified sludge biochar Fe/Zn-SBC; calcination conditions are N2Under protective conditions, N2The flow rate is 0.5-1L/min, the temperature rising rate is 10-20 ℃/min, and the pyrolysis is carried out for 1.5-2h under the conditions of 300 ℃ and 700 ℃;
(3) adding 10.6-15mol/L H into SBC obtained in the step (1)3PO4Performing the following steps; the SBC and H3PO4Shaking and soaking for 8-10H at a ratio of 1Kg to 2.5L-1Kg to 10L, filtering, drying, activating at high temperature, washing the sample with deionized water until the pH of the filtrate is constant, drying at 60-80 ℃, grinding and sieving with a 100-mesh and 200-mesh sieve to obtain H3PO4Modified sludge biochar H3PO4-an SBC; in the step (3), the high-temperature activation is carried out by placing the mixture in a muffle furnace, wherein the temperature rise rate is 10-20 ℃/min, and the temperature is kept at 400-450 ℃ for 1-1.5 h;
(4) sequentially operating the SBC obtained in the step (1) according to the preparation processes of the step (2) and the step (3), and obtaining the biochar which is iron, zinc and H3PO4Modified sludge biochar Fe/Zn + H3PO4SBC, stored in desiccators protected from light.
2. The use of the iron zinc and phosphoric acid modified sludge biochar in removing fluoroquinolone antibiotics in water as claimed in claim 1, wherein: the fluoroquinolone antibiotics are one or more of ciprofloxacin, norfloxacin and ofloxacin.
3. The use of the iron zinc and phosphoric acid modified sludge biochar in removing fluoroquinolone antibiotics in water as claimed in claim 1, wherein: the solubility of the antibiotic in water of the fluoroquinolone antibiotic is 5-100mg/L, and the dosage of the adsorbent is 0.2-1.0 g/L.
4. The use of the iron zinc and phosphoric acid modified sludge biochar in removing fluoroquinolone antibiotics in water as claimed in claim 1, wherein: after the adsorbent is added into water containing fluoroquinolone antibiotics, the pH value of the solution is adjusted to 2-10.
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| CN111018291A (en) * | 2019-11-25 | 2020-04-17 | 北京林业大学 | Method for preparing soluble black carbon from sludge, soluble black carbon and application of soluble black carbon |
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