CN115414911A - Fe-rich alloy x Pharmaceutical sludge biochar with N structure, preparation method and application - Google Patents
Fe-rich alloy x Pharmaceutical sludge biochar with N structure, preparation method and application Download PDFInfo
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- CN115414911A CN115414911A CN202210996097.0A CN202210996097A CN115414911A CN 115414911 A CN115414911 A CN 115414911A CN 202210996097 A CN202210996097 A CN 202210996097A CN 115414911 A CN115414911 A CN 115414911A
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- 239000010802 sludge Substances 0.000 title claims abstract description 197
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 181
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- 238000000034 method Methods 0.000 claims abstract description 34
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- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 1
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 1
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- NOCJXYPHIIZEHN-UHFFFAOYSA-N difloxacin Chemical compound C1CN(C)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1=CC=C(F)C=C1 NOCJXYPHIIZEHN-UHFFFAOYSA-N 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
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- 229960001699 ofloxacin Drugs 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/026—Treating water for medical or cosmetic purposes
Abstract
Fe-rich food x Pharmaceutical sludge biochar with N structure, preparation method and application thereof, belonging to pharmaceutical wasteThe technical field of object processing. The method comprises the steps of taking pharmaceutical sludge containing Fenton iron mud, carrying out filter pressing dehydration, drying and crushing, and then adding ZnCl 2 Carrying out activation pretreatment and drying to obtain pretreated pharmaceutical sludge; uniformly mixing the pretreated pharmaceutical sludge with urea solid with the mass of 3 times of that of the pretreated pharmaceutical sludge, and adding N 2 Pyrolyzing for 1-2 h under the protection of 750-850 ℃, cooling, washing with hydrochloric acid and adjusting the pH value to 7 with deionized water to obtain pharmaceutical sludge biochar; the pharmaceutical sludge biochar is used for activating the peroxymonosulfate to degrade the antibiotic pharmaceutical wastewater. According to the invention, the pharmaceutical sludge is subjected to iron-nitrogen co-doping modification pyrolysis treatment to obtain the pharmaceutical sludge biochar with excellent catalytic performance, and the biochar is reasonably applied to the antibiotic pharmaceutical wastewater to effectively realize the treatment of the antibiotic pharmaceutical wastewater.
Description
Technical Field
The invention relates to the technical field of pharmaceutical waste treatment, in particular to a method for treating pharmaceutical waste by utilizing rich Fe x A method for treating pharmaceutical wastewater by pharmaceutical sludge biochar with an N structure.
Background
The scale of treating high-concentration pharmaceutical wastewater caused by the rapid development of the pharmaceutical industry is huge. At present, the biological treatment unit is still an important way for removing antibiotics in pharmaceutical wastewater; but the biological inhibitory properties of antibiotics can greatly limit the removal capabilities of this technology. Because the traditional wastewater treatment system is difficult to effectively remove antibiotics in water, advanced treatment of pharmaceutical wastewater is considered by adding an advanced oxidation process.
In addition to the deep removal of antibiotics, the treatment and disposal of pharmaceutical sludge is another problem that plagues pharmaceutical wastewater treatment. A large amount of pharmaceutical sludge is generated in the pharmaceutical wastewater treatment process, and compared with other types of sludge, the pharmaceutical sludge is complex in composition, contains high-concentration salts, antibiotics, pharmaceutical active ingredients and the like, and is high in toxic and harmful substance types, high in concentration and huge in potential hazard. Therefore, pharmaceutical sludge must be safely disposed of to avoid environmental hazards.
The pyrolysis charcoal making technology is a process that biomass raw materials absorb heat energy under the condition of isolating oxygen, and a biomass structure is damaged to form pores so as to be converted into biochar. The pharmaceutical sludge contains a large amount of organic matter, which makes the pharmaceutical sludgeCan be utilized by a pyrolytic carbon-making technology. During pyrolysis, high temperatures of several hundred degrees can destroy high risk contaminants such as antibiotics adsorbed on pharmaceutical sludge. In addition, in order to improve the biodegradability of pharmaceutical wastewater, a wastewater treatment system generally pretreats pharmaceutical wastewater using a Fenton method. Iron sludge produced by Fenton pretreatment, referred to as Fenton iron sludge, is used by many pharmaceutical factories to replace commercial conditioners to promote dehydration of pharmaceutical sludge, so that dehydrated pharmaceutical sludge contains rich Fe (mainly Fe (OH) 3 )。
However, it is currently shown in the related art that Fe is used 2 O 3 And Fe 3 O 4 The municipal sludge which is the main iron source is difficult to form Fe in the process of nitrogen doping x N structure, even using commercially available FeCl 3 It is difficult to form Fe as an iron source x N structure, which often forms FeN x Structure of FeN x The catalytic performance of the structure is significantly reduced. Therefore, the demand for a method for preparing Fe-rich sludge by using pharmaceutical sludge effectively is high x The catalyst with the structure of N can also be used for deeply treating pharmaceutical wastewater.
Disclosure of Invention
To solve the problems of the related art, the present invention provides a method for utilizing Fe-rich x The method for treating pharmaceutical wastewater by using pharmaceutical sludge biochar with an N structure tries to contain Fe (OH) 3 The pharmaceutical sludge is subjected to anaerobic pyrolysis by combining with external nitrogen source doping to prepare the Fe-containing composite material x The biochar with the N structure is used as a catalyst, and persulfate is efficiently activated to degrade residual organic pollutants in the conventional treated effluent of pharmaceutical wastewater. The safe treatment of pharmaceutical sludge can be realized, the advanced treatment of pharmaceutical wastewater can be realized, the difficult problems that the antibiotic removal effect is poor and the pharmaceutical sludge is difficult to treat safely in the pharmaceutical wastewater of the existing pharmaceutical enterprises can be synchronously solved, and the new idea of treating waste with waste and realizing clean production is provided.
The specific technical scheme of the invention is as follows:
in one aspect, an Fe-rich alloy is provided x The preparation method of the pharmaceutical sludge biochar with the N structure comprises the following steps:
(1) Adding Fenton iron-containing mud into pharmaceutical sludge, filter-pressing, dehydrating, drying and crushing, and then adding ZnCl with the molar concentration of 5mol/L 2 Performing modification pretreatment in the aqueous solution, and drying to obtain pretreated pharmaceutical sludge;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid, and adding the mixture into N 2 Under the protection of the solution, the solution is pyrolyzed for 1 to 2 hours under the condition of 750 to 850 ℃, cooled and then washed by hydrochloric acid and deionized water to adjust the pH value to 7 to obtain the Fe-rich solution x The pharmaceutical sludge biochar with the N structure.
Optionally, in the step (1), the addition amount of the fenton iron mud is 5 to 20% of the total amount of the pharmaceutical sludge.
Further, in the step (1), the addition amount of the fenton iron mud is 10% of the total amount of the pharmaceutical sludge.
Optionally, in the step (2), the mass ratio of the pretreated pharmaceutical sludge to urea is 1: 1-1: 4.
Further, in the step (2), the mass ratio of the pretreated pharmaceutical sludge to the urea is 1: 3.
In another aspect, there is provided a pharmaceutical sludge biochar prepared by the above method.
In another aspect, there is provided an Fe-rich alloy obtained by the above-mentioned preparation method x The application of the pharmaceutical sludge biochar with the N structure in the treatment of pharmaceutical wastewater is to enrich the Fe x Adding pharmaceutical sludge biochar with an N structure into fluoroquinolone antibiotic pharmaceutical wastewater containing peroxymonosulfate, and performing a reaction of activating the peroxymonosulfate to degrade the antibiotic at the temperature of 25-45 ℃ to obtain treated effluent.
Optionally, the Fe-rich x The addition amount of the pharmaceutical sludge biochar with the N structure is 0.05-0.15 g/L.
Optionally, the peroxymonosulfate is added in an amount of 1 to 10mM.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the iron-nitrogen co-doping modified pyrolysis treatment of the pharmaceutical sludgeTo obtain a Fe-rich alloy x The pharmaceutical sludge biochar with the N structure and excellent catalytic performance is reasonably applied to the pharmaceutical wastewater of the fluoroquinolone antibiotics, and the treatment of the pharmaceutical wastewater of the fluoroquinolone antibiotics is effectively realized.
2. The raw material of the pharmaceutical sludge biochar prepared by the invention is the pharmaceutical sludge generated by a pharmaceutical wastewater treatment system, so that the purchase is not needed, and the transportation, storage and other costs generated by alternative raw materials are saved.
3. The iron source for carrying out iron doping modification on the sludge in the invention is Fe (OH) generated by a Fenton pretreatment system of pharmaceutical wastewater 3 Can effectively form Fe with doped nitrogen element x The N structure does not need to additionally purchase iron chemical agents, and the preparation cost is greatly saved.
4. The pharmaceutical sludge biochar has excellent performance of activating the peroxymonosulfate, and can activate 5mM of the peroxymonosulfate to completely degrade levofloxacin with the concentration of 80mg/L within 90min under the addition of 0.1 g/L.
5. The method uses the pharmaceutical sludge biochar to activate the peroxymonosulfate to treat the pharmaceutical wastewater, has simple operation and low cost, and can effectively solve the problem of unsatisfactory effect of the biological treatment process.
6. The invention utilizes the pharmaceutical wastewater treatment system to prepare the iron-nitrogen co-doped biochar from the pharmaceutical sludge and Fenton iron mud, which are the self-produced wastes of the pharmaceutical wastewater treatment system, to perform catalytic degradation treatment on the pharmaceutical wastewater, and realizes the treatment of wastes with processes of wastes against one another and clean production in the pharmaceutical industry.
Fe x N and FeN x The difference and the catalysis principle of (1):
Fe x n and FeN x All of them have Fe-N structure. Wherein Fe x N is formed by the gradual diffusion of N atoms into interstitial sites of the metallic Fe lattice, which creates two distinct layers in the process. The outermost layer of iron (the composite layer or "white" layer) contains iron nitride, and the diffusion layer below the composite layer contains an Fe lattice. Fe x N has high hardness and corrosion resistance, the composite layer can effectively protect the metal of the inner layer from being etched and dissolved, and simultaneously avoid the poisoning of adsorbed species,the durability of the catalyst can be improved. Meanwhile, the metal of the inner layer can provide free electrons, promote electron transfer and contribute to enhancing the catalytic performance. Thus Fe x N has strong reactivity and is very stable, is insensitive to the pH change of the solution, and has a wide pH value range of the pharmaceutical wastewater suitable for degradation. And FeN x It is often the case that the Fe atom is loaded between 4 coordinated N atoms, as opposed to it. In acidic medium, feN x The active sites are susceptible to protonation, reducing their intrinsic catalytic activity, and demetallization of the central Fe atom may reduce the number of active sites, leading to activity decay.
Drawings
Fig. 1 transmission electron micrograph of pharmaceutical sludge biochar catalyst of exemplary embodiment 1 of the present invention.
Fig. 2 is an XRD pattern of the biochar catalysts in exemplary example 1, example 5 and comparative examples 1-2 of the present invention.
FIG. 3 is a high resolution N1s spectrum of the biochar catalysts in exemplary example 1, example 5 and comparative examples 1-2 of the present invention.
Fig. 4 is an XRD pattern of the biochar catalyst in exemplary examples 1-4 of the present invention.
FIG. 5 is a high resolution N1s spectrum of a biochar catalyst in exemplary examples 1-4 of the invention.
FIG. 6 is Fe-rich in accordance with exemplary embodiment 1 of the present invention x The effect graph of the removal rate of the levofloxacin from the pharmaceutical sludge biochar with the N structure under different pH conditions is shown.
FIG. 7 is an exemplary comparative example 3 of the present invention to illustrate the pyrolysis temperature, pyrolysis time versus Fe-rich production x Influence of pharmaceutical sludge biochar of N structure.
Detailed Description
Utilization of the embodiments of the invention to enrich Fe x The method for treating pharmaceutical wastewater by using pharmaceutical sludge biochar with an N structure comprises the following steps:
(1) Adding Fenton iron mud into pharmaceutical sludge, performing filter pressing dehydration, drying and crushing, and mixing with ZnCl of 5mol/L 2 Mixing the aqueous solutions, carrying out modification pretreatment, drying,obtaining pretreated pharmaceutical sludge; in some specific embodiments, the mixing method may be a known mixing method such as mechanical stirring, shaking mixing, etc., the drying is generally performed by an oven, the drying temperature is generally below 100-200 ℃, and the temperature is too high to decompose the fenton iron mud into Fe 2 O 3 Or Fe 3 O 4 The temperature is too low to facilitate rapid drying.
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid, and adding into the mixture N 2 Under the protection, the temperature is raised to 750-850 ℃, the pyrolysis is carried out for 1-2 h, the mixture is cooled and then washed by hydrochloric acid and deionized water to adjust the pH value to 7, and the Fe-rich material is obtained x Pharmaceutical sludge biochar with an N structure; pyrolysis temperatures above 850 ℃ or below 750 ℃ are not conducive to the formation of Fe x And (4) an N structure.
(3) Enriching the Fe in the step (2) x Adding pharmaceutical sludge biochar with an N structure into fluoroquinolone antibiotic pharmaceutical wastewater containing peroxymonosulfate, and performing a reaction of activating the peroxymonosulfate to degrade the antibiotic at the temperature of 25-45 ℃ to obtain treated effluent.
The invention adopts a pair of Fe (OH) containing 3 The pharmaceutical sludge is modified by urea nitrogen doping to obtain Fe x The pharmaceutical sludge biochar catalyst with the N structure is reasonably used in an advanced oxidation process of the pharmaceutical wastewater of the fluoroquinolone antibiotics, and the advanced treatment of the pharmaceutical wastewater of the fluoroquinolone antibiotics is effectively realized. By the specific embodiment of the present invention, it is reasonable to presume that pure Fe (OH) is used 3 Instead of containing Fe (OH) 3 The pharmaceutical sludge of (1) can also be used for obtaining Fe x N, but it is understood that it will increase the cost and does not achieve the environmental protection of "treating waste with waste".
In addition, the Fe-rich obtained by the invention x The pharmaceutical sludge biochar with the N structure can also be applied to other organic wastewater treatment fields except the fluoroquinolone antibiotic wastewater.
The fluoroquinolone antibiotics related by the invention include but are not limited to ofloxacin, enrofloxacin, ciprofloxacin, norfloxacin, difloxacin, erythromycin, roxithromycin and the like.
The present invention will be further described with reference to the following specific examples, which are set forth merely to illustrate specific embodiments of the invention, but the scope of the invention is not limited thereto.
The pharmaceutical sludge used in the following examples is a fluoroquinolone antibiotic pharmaceutical corporation A 2 And discharging sludge from a secondary sedimentation tank behind the O wastewater treatment system, adding Fenton iron sludge serving as a sludge dewatering conditioner, wherein the water content of the sludge after filter pressing is 52.3%, the iron content is 244.69 +/-3.15 mg/g, the total solid is 476.9g/L, the volatile solid is 316.3g/L, and the VS/TS is 66.3%.
It is understood that the pharmaceutical sludge to which embodiments of the invention relate may also be derived from municipal sludge or other high organic matter waste.
Example 1
This example provides a method of using a Fe-rich alloy x The method for deeply treating the pharmaceutical wastewater of the fluoroquinolone antibiotics by using the pharmaceutical sludge biochar with the N structure comprises the following specific steps:
(1) Mixing the Fenton iron mud and the pharmaceutical sludge according to the mass of 10 percent of the pharmaceutical sludge, performing filter pressing dehydration to obtain sludge mud cakes, drying the sludge mud cakes to constant weight, grinding the sludge mud cakes, sieving the sludge mud cakes by a 60-mesh sieve, and then mixing the sludge mud cakes with ZnCl of 5mol/L 2 Mixing the aqueous solutions, performing modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge is mixed with ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1: 1, shaking is carried out for 24h to mix evenly, and the drying conditions are as follows: drying in a 105 ℃ oven to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid with the weight of 3 times of that of the pretreated pharmaceutical sludge, and adding N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is raised to 800 ℃, the pyrolysis is carried out for 1h, after cooling, hydrochloric acid with the volume fraction of 5 percent is used for cleaning, the pH value is adjusted to 7 by deionized water, and the Fe-rich material is obtained x Pharmaceutical sludge biochar of structure N (labeled: PZBC 800U);
(3) Taking 10mg of Fe-rich material prepared in the step (2) x Pharmaceutical sludge biochar (PZBC 800U) of N structure was added to 100mL of levofloxacin-containing pharmaceutical wastewater in the examples of the present inventionIn the method, the initial concentration C0 of the levofloxacin pharmaceutical wastewater is 80mg/L, the pH value is 6.5, and the addition amount of the peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, the conical flask with the plug is oscillated in the dark under the conditions of 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
Example 2
This comparative example provides a method of using a Fe-rich alloy x The method for deeply treating the pharmaceutical wastewater of the fluoroquinolone antibiotics by using the pharmaceutical sludge biochar with the N structure comprises the following specific steps:
(1) Mixing Fenton iron mud and pharmaceutical sludge according to the mass of 5 percent of the pharmaceutical sludge, performing filter pressing dehydration on the mixture to obtain a pharmaceutical sludge mud cake, drying the pharmaceutical sludge mud cake to constant weight, grinding the pharmaceutical sludge mud cake, sieving the dried pharmaceutical sludge cake with a 60-mesh sieve, and then mixing the pharmaceutical sludge mud cake with 5mol/L ZnCl 2 Mixing the aqueous solutions, performing modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge is mixed with ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1: 1, shaking is carried out for 24h to mix evenly, and the drying conditions are as follows: drying in a 105 ℃ oven to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid with the same weight, and adding N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is raised to 850 ℃, the pyrolysis is carried out for 2h, after cooling, the solution is washed by hydrochloric acid with the volume fraction of 5%, the pH value is adjusted to 7 by deionized water, and the Fe-rich material is obtained x Pharmaceutical sludge biochar with an N structure (marked as PZBC 800U-1);
(3) Taking 10mg of Fe-rich material prepared in the step (2) x Adding pharmaceutical sludge biochar (PZBC 800U-1) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater containing levofloxacin is 80mg/L, the pH value is 6.5, and the addition amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, the conical flask with the plug is oscillated in the dark under the conditions of 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
Example 3
This comparative example provides a method of using a Fe-rich alloy x The method for deeply treating the pharmaceutical wastewater of the fluoroquinolone antibiotics by using the pharmaceutical sludge biochar with the N structure comprises the following specific steps:
(1) Mixing the Fenton iron mud and the pharmaceutical sludge according to the mass of the Fenton iron mud being 10 percent of the mass of the pharmaceutical sludge, performing filter pressing dehydration on the mixture to obtain a pharmaceutical sludge mud cake, drying the pharmaceutical sludge mud cake to constant weight, grinding the pharmaceutical sludge cake, sieving the dried pharmaceutical sludge cake with a 60-mesh sieve, and then mixing the pharmaceutical sludge cake with 5mol/L ZnCl 2 Mixing the aqueous solutions, performing modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge is mixed with ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1: 1, shaking is carried out for 24h to mix evenly, and the drying conditions are as follows: drying in a 105 ℃ oven to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid 2 times of the weight of the pretreated pharmaceutical sludge, and adding N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is raised to 750 ℃, the pyrolysis is carried out for 1.5h, after cooling, the solution is washed by hydrochloric acid with the volume fraction of 5%, the pH value is adjusted to 7 by deionized water, and the Fe-rich material is obtained x Pharmaceutical sludge biochar of structure N (labeled: PZBC 800U-2);
(3) Taking 10mg of Fe-rich product prepared in the step (2) x Adding pharmaceutical sludge biochar (PZBC 800U-2) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater containing levofloxacin is 80mg/L, the pH value is 6.5, and the addition amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, the conical flask with the plug is oscillated in the dark under the conditions of 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
Example 4
This comparative example provides a method of using a Fe-rich alloy x The method for deeply treating the pharmaceutical wastewater of the fluoroquinolone antibiotics by using the pharmaceutical sludge biochar with the N structure comprises the following specific steps:
(1) Mixing Fenton iron mud and pharmaceutical sludge according to the mass of 15% of the pharmaceutical sludge, performing filter pressing dehydration on the mixture to obtain a pharmaceutical sludge cake, drying the cake to constant weight, and grinding the cakeCrushing, sieving with a 60-mesh sieve, and mixing with 5mol/L ZnCl 2 Mixing the aqueous solutions, performing modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge is mixed with ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1: 1, shaking is carried out for 24h to mix evenly, and the drying conditions are as follows: drying in a 105 ℃ oven to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid with the weight of 4 times that of the pharmaceutical sludge, and adding N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃, the pyrolysis is carried out for 1.5h, after cooling, hydrochloric acid with the volume fraction of 5% is used for cleaning, the pH value is adjusted to 7 by deionized water, and the Fe-rich material is obtained x Pharmaceutical sludge biochar of structure N (labeled: PZBC 800U-4);
(3) Taking 10mg of Fe-rich material prepared in the step (2) x Adding pharmaceutical sludge biochar (PZBC 800U-4) with an N structure into 100mL of pharmaceutical wastewater containing levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater containing levofloxacin is 80mg/L, the pH value is 6.5, and the addition amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, the conical flask with the plug is oscillated in the dark under the conditions of 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
Example 5
The comparative example provides a method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Mixing Fenton iron mud and pharmaceutical sludge according to the mass of which is 20 percent of the mass of the pharmaceutical sludge, performing filter pressing dehydration on the mixture to obtain a pharmaceutical sludge mud cake, drying the pharmaceutical sludge mud cake to a constant weight, grinding the pharmaceutical sludge mud cake and sieving the powder with a 60-mesh sieve, adding 35g of the pharmaceutical sludge mud cake into 500ml of ultrapure water, adjusting the pH to be =2.0, adding 15g of ferrous sulfate and 60ml of hydrogen peroxide into the sludge suspension, adjusting the pH to be about 7.0 after reacting for 1 hour, and performing dehydration and drying on the mixture to obtain the pharmaceutical sludge with increased endogenous iron, wherein the iron content of the sludge is 381.70 +/-6.82 mg/g;
(2) Adding the pharmaceutical sludge obtained in the step (1) and added with endogenous iron to ZnCl with the molar concentration of 5mol/L 2 Carrying out modification pretreatment in an aqueous solution; pharmaceutical sludge and ZnCl 2 Soaking in water solution at a ratio (w/v) of 1: 1, shaking for 24h, and oven drying at 105 deg.C to obtain pretreated pharmaceutical sludge;
(3) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (2) with urea solid of which the weight is 3 times that of the pharmaceutical sludge under the protection of N2 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the pyrolysis is carried out for 1.5h at the temperature of 800 ℃, the cooled product is washed by hydrochloric acid with the volume fraction of 5%, the pH value is adjusted to 7 by deionized water, and the pharmaceutical sludge biochar (PZBC 800U + Fe) with the increased endogenous iron is obtained.
(4) Adding 10mg of the biochar (PZBC 800U + Fe) catalyst prepared in the step (3) into 100mL of pharmaceutical wastewater containing levofloxacin, wherein the initial concentration C0 of the pharmaceutical wastewater containing levofloxacin is 80mg/L, the pH value is 6.5, and the addition amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, the conical flask with the plug is oscillated in the dark under the conditions of 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
The method is characterized in that the iron-nitrogen co-doped pharmaceutical sludge biochar (PZBC 800U) prepared in example 1 is subjected to characterization, and the obtained transmission electron microscope photo is shown in figure 1; as can be seen from figure 1, the morphology of the pharmaceutical sludge biochar and the spacing between the lattice fringes in example 1 and the Fe reported in the literature x N is consistent, which indicates that Fe is formed in the biochar during the preparation process x And (3) the structure of N.
Example 6
Wastewater treatment under different pH conditions:
five pH gradients of 3.0, 5.0, 6.5, 8.0 and 10.0 were set up for single variable experiments of pH. The obtained product is rich in Fe x The pharmaceutical sludge biochar with the structure of N is PZBC800U in example 1, and the conditions are the same as in example 1 except that the pH value of the levofloxacin pharmaceutical wastewater is different. Results for levofloxacin removal rates see figure 6:
example 7 Effect of treating wastewater with various fluoroquinolones
The treatment effect of the wastewater containing various antibiotics is as follows:
the biological carbon is used as PZBC800U in example 1, the waste water is used as secondary biological carbon of a waste water treatment system of a fluoroquinolone antibiotic production enterprise to treat the outlet water, and the water quality is pH 7.1, COD 410.1 +/-82.9 mg/L and ammonia nitrogen 2.8mg/L.
TABLE 2 removal effect of 7 antibiotics
It can be seen that the use of Fe-rich x The method for deeply treating the pharmaceutical wastewater of the fluoroquinolone antibiotics by using the pharmaceutical sludge biochar with the N structure has a good treatment effect on common pharmaceutical wastewater of the fluoroquinolone antibiotics.
Comparative example 1
The comparative example provides a method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Mixing the Fenton iron mud and the pharmaceutical sludge according to the mass of the Fenton iron mud being 10 percent of the mass of the pharmaceutical sludge, performing filter pressing dehydration on the mixture to obtain a pharmaceutical sludge mud cake, drying the pharmaceutical sludge mud cake to constant weight, grinding the pharmaceutical sludge cake, sieving the dried pharmaceutical sludge cake with a 60-mesh sieve, and then mixing the pharmaceutical sludge cake with 5mol/L ZnCl 2 Mixing the aqueous solutions, performing modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; then it is placed in N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is increased to 800 ℃ for pyrolysis for 1.5h, after cooling, the mixture is washed by hydrochloric acid with the volume fraction of 5%, and the pH value is adjusted to 7 by deionized water, so that pharmaceutical sludge biochar (marked as PZBC 800) without nitrogen doping is obtained.
(2) Adding 10mg of the biochar (PZBC 800) prepared in the step (1) into 100mL of pharmaceutical wastewater containing the levofloxacin, wherein in the embodiment of the invention, the initial concentration C0 of the pharmaceutical wastewater containing the levofloxacin is 80mg/L, the pH value is 6.5, and the addition amount of the peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask is placed in a constant-temperature oscillator and is oscillated in a dark place at 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
Comparative example 2
The comparative example provides a method for deeply treating fluoroquinolone antibiotic pharmaceutical wastewater by using pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Taking pharmaceutical sludge, performing filter pressing dehydration to obtain a pharmaceutical sludge cake, drying to constant weight, grinding, sieving with a 60-mesh sieve, soaking in a mixed solution of 1M HCl and 10% (v/v) HF for 24h, cleaning, and drying to obtain pharmaceutical sludge with reduced endogenous iron, wherein the iron content of the sludge is 82.53 +/-1.34 mg/g;
(2) Adding the pharmaceutical sludge obtained in the step (1) and removing endogenous iron to a molar concentration of 5mol/LZnCl 2 Carrying out modification pretreatment in an aqueous solution; pharmaceutical sludge and ZnCl 2 Soaking in water solution at a ratio (w/v) of 1: 1, shaking for 24h, and oven drying at 105 deg.C to obtain pretreated pharmaceutical sludge;
(3) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (2) with urea solid with the weight of 3 times of that of the pretreated pharmaceutical sludge in N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the pyrolysis is carried out for 1.5h at the temperature of 800 ℃, after cooling, the cooling is carried out, the volume fraction of hydrochloric acid is used for cleaning, the pH value is adjusted to be 7 by deionized water, and the pharmaceutical sludge biochar (PZBC 800U-Fe) with reduced iron source is obtained.
(4) Adding 10mg of the biochar catalyst prepared in the step (3) into 100mL of pharmaceutical wastewater containing levofloxacin, wherein the initial concentration C0 of the pharmaceutical wastewater containing levofloxacin is 80mg/L, the pH value is 6.5, and the addition amount of peroxymonosulfate in the wastewater is 5mM; in the embodiment of the invention, the catalytic degradation reaction is carried out in a 250mL conical flask with a plug, the conical flask with the plug is placed in a constant temperature oscillator, the conical flask with the plug is oscillated in the dark under the conditions of 25 ℃ and 220r/min, and treated effluent is obtained after the catalytic degradation reaction.
The pharmaceutical sludge biochar prepared in the examples 1-5 and the comparative examples 1-2 is characterized by XRD and high-resolution N1s spectrogram, and the obtained results are respectively shown in figures 2-5; FIG. 2 compares the crystal structures of several biochar typesXRD spectrum shows that the main crystal structure of the iron-nitrogen co-doped biochar is Fe x N (x =2,3,4), which is consistent with the results of transmission electron microscopy. Fe with increasing iron content in sludge x The peak intensity of the N characteristic peak is also increasing. Meanwhile, because the iron content in the sludge is low, no Fe appears in PZBC800U-Fe x And (4) an N structure. In addition, as can be seen from fig. 3, fe is not present in the biochar that is not nitrogen-doped x N peak and PZBC800U-Fe may be Fe due to low iron content in sludge x The N signal is also very weak, which indicates that the co-doping of iron and nitrogen is to form Fe x The important condition of N structure. Fe with increasing iron content in sludge x The intensity of the N peak increases with it. The results of FIGS. 4 and 5 show that the mass ratio of sludge to urea is 1: 3, which is the optimum doping ratio, and more Fe can be formed x And N is added. Fe in charcoal x The higher the content of the N structure, the more active sites of the catalyst are, namely the higher the catalytic performance of the catalyst is. XRD and XPS results prove that Fe in sludge forms Fe in biochar x The N structure improves the key function in the catalytic performance.
In addition, setting time, extracting 2mL of water samples at intervals from the conical flasks of the above examples 1-5 and comparative examples 1-2, and filtering to obtain filtrate; taking 1mL of filtrate, measuring the concentration of the treated levofloxacin through liquid chromatography, drawing a degradation curve and calculating a reaction rate constant of the catalytic reaction. The results are shown in Table 1.
TABLE 1 Performance of activated Peronosulfate-degrading antibiotics of charcoal catalysts prepared in examples and comparative examples
| Case(s) | Catalyst and process for preparing same | Removal Rate (60 min) (%) | Reaction Rate K obs (min -1 ) |
| Example 1 | PZBC800U | 92.03 | 0.034 |
| Example 2 | PZBC800U-1 | 66.94 | 0.009 |
| Example 3 | PZBC800U-2 | 68.24 | 0.010 |
| Example 4 | PZBC800U-4 | 73.43 | 0.015 |
| Example 5 | PZBC800U+ |
100 | 0.118 |
| Comparative example 1 | PZBC800 | 84.98 | 0.025 |
| Comparative example 2 | PZBC800U-Fe | 80.58 | 0.016 |
Note: in the above case, the other steps and parameter conditions are the same except for the difference in the above parameter indexes.
As can be seen from Table 1, in example 5, after increasing the iron content in the sludge, PZBC800U + Fe has higher catalytic performance, 100% LEV removal can be realized within 60min, and K is obs Reaches 0.118min -1 . As a comparison, K of PZBC800 and PZBC800U-Fe obs Respectively for 0.025min -1 And 0.016min -1 This indicates that endogenous Fe and exogenous N are co-doped to form Fe x N is a key catalytically active site of the catalyst.
Comparative example 3
The comparative example provides a preparation method of pharmaceutical sludge biochar, which comprises the following specific steps:
(1) Mixing the Fenton iron mud and the pharmaceutical sludge according to the mass of the Fenton iron mud being 10 percent of the mass of the pharmaceutical sludge, performing filter pressing dehydration on the mixture to obtain sludge mud cakes, drying the sludge mud cakes to constant weight, grinding the sludge mud cakes, sieving the sludge mud cakes with a 60-mesh sieve, and then mixing the sludge mud cakes with 5mol/L ZnCl 2 Mixing the aqueous solutions, performing modification pretreatment, and drying to obtain pretreated pharmaceutical sludge; in this example, pharmaceutical sludge is mixed with ZnCl 2 The dipping ratio (w/v) of the aqueous solution is 1: 1, shaking is carried out for 24 hours to mix evenly, and the drying conditions are as follows: drying in a 105 ℃ oven to constant weight;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid with the weight of 3 times of that of the pretreated pharmaceutical sludge, and adding N 2 Under protection, N 2 The flow rate is 0.1L/min, the heating rate is 10 ℃/min, the temperature is increased to 500 ℃, the pyrolysis is carried out for 2.5h, after cooling, the mixture is washed by hydrochloric acid with the volume fraction of 5%, and the pH value is adjusted to 7 by deionized water, so that the pharmaceutical sludge biochar (PZBC 500U) is obtained. XRD pattern of PZBC500U referring to FIG. 7, it can be seen that Fe is not formed x N structure, which indicates that when the pyrolysis temperature is lower than 750 ℃, fe-rich material cannot be obtained even if the pyrolysis time is prolonged x The pharmaceutical sludge biochar with the N structure.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. Fe-rich alloy x The preparation method of the pharmaceutical sludge biochar with the N structure is characterized by comprising the following steps:
(1) Adding Fenton iron mud into pharmaceutical sludge, filter-pressing, dehydrating, drying and crushing, and then adding ZnCl with the molar concentration of 5mol/L 2 Performing modification pretreatment in the aqueous solution, and drying to obtain pretreated pharmaceutical sludge;
(2) Uniformly mixing the pretreated pharmaceutical sludge obtained in the step (1) with urea solid, and adding the mixture into N 2 Under the protection of 750-850 ℃, the materials are pyrolyzed for 1-2 h together, and after cooling, the materials are washed by hydrochloric acid and deionized water to adjust the pH value to 7, thus obtaining the Fe-rich material x The pharmaceutical sludge biochar with the N structure.
2. The preparation method according to claim 2, wherein in the step (1), the Fenton iron mud is added in an amount of 5-20% of the total amount of the pharmaceutical sludge.
3. The preparation method according to claim 3, wherein in the step (1), the Fenton iron mud is added in an amount of 10% of the pharmaceutical sludge.
4. The preparation method according to claim 4, wherein in the step (2), the mass ratio of the pretreated pharmaceutical sludge to the urea is 1: 1-1: 4.
5. The preparation method according to claim 5, wherein in the step (2), the mass ratio of the pretreated pharmaceutical sludge to the urea is 1: 3.
6. Fe-rich alloy x The pharmaceutical sludge biochar with the N structure is characterized by being prepared by the method of any one of claims 1 to 5.
7. Fe-rich alloy obtained by the method according to any one of claims 1 to 5 x The application of the pharmaceutical sludge biochar with the N structure in the treatment of pharmaceutical wastewater is characterized in that the biochar is rich in Fe x Adding pharmaceutical sludge biochar with an N structure into fluoroquinolone antibiotic pharmaceutical wastewater containing peroxymonosulfate, and performing a reaction of activating the peroxymonosulfate to degrade the antibiotic at the temperature of 25-45 ℃ to obtain treated effluent.
8. Use according to claim 7, wherein said Fe-rich fraction is x The addition amount of the pharmaceutical sludge biochar with the N structure is 0.05-0.15 g/L.
9. Use according to claim 8, wherein the peroxymonosulfate is added in an amount of 1 to 10mM.
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| Title |
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| 孙洪伟;蒋福春;: "氮自掺杂污泥炭催化过一硫酸盐氧化去除水中苯酚", 中国给水排水, no. 05 * |
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