CN116395821A - Catalytic oxidation integrated material for treating high-salt-content antibiotic wastewater - Google Patents
Catalytic oxidation integrated material for treating high-salt-content antibiotic wastewater Download PDFInfo
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- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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Abstract
The invention provides a catalytic oxidation integrated material for treating high-salt-content antibiotic wastewater, which comprises a carbon material and persulfate, wherein the mass ratio of the carbon material to the persulfate is 1:1-1:10, and the carbon material and the persulfate are mechanically ball-milled, activated and compounded. The invention adopts the development of the method that the carbon material catalyst and the solid Persulfate (PS) oxidant are mechanically activated together, and the activation effect is generated between the solid and the solid by physical and mechanical mixing in the ball milling process, so that the activated carbon catalytic material is not required to be added into the oxidant PS solution to generate oxide species; the advanced oxidation treatment process of the refractory organic pollutants, which is convenient to use, has high yield and high efficiency, can be obtained. The catalytic oxidation integrated material prepared by the invention has high-efficiency treatment effect on antibiotic wastewater, can still keep degradation performance in a high-salt environment, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a catalytic oxidation integrated material for treating high-salt-content antibiotic wastewater.
Background
Antibiotics, which are highly water-soluble and difficult to biodegrade, have become an emerging organic contaminant widely existing in water environments, and their use in large quantities severely threatens public health and natural environments. Among them, the tetracycline antibiotic is a broad-spectrum synthetic antibiotic, and is widely used in aquaculture, animal husbandry, agricultural production and medical industry due to its low price and effective sterilization performance, and as one of the most used antibiotic types in various countries, the overuse and incomplete degradation process of Tetracycline (TC) may cause serious harm to human health and environment. Because of its antibacterial properties and stable chemical structure, conventional methods such as biodegradation are difficult to treat, and development of a low-cost and efficient TC treatment technology is an urgent need.
Advanced Oxidation Processes (AOPs) can better remove these refractory organic contaminants. Wherein the Persulfate (PS) -based AOPs produce higher activity sulfate radicals (SO 4 · - ) Compared with hydroxyl radical (. OH) (1.8-2.7V,<1 mus) has higher oxidation-reduction potential and longer half-life (2.5-3.1V, 30-40 mus), and the advantages of easy storage and transportation, etc., so that the method has great development potential in the treatment of wastewater containing antibiotics. In addition to high energy consumption activation methods such as heat, UV radiation, ultrasound/microwave, and the like, the transition metals (such as Fe, cu, co, ni, mn, and the like) and metal oxides widely used at present can efficiently activate PS to form SO 4 · - . However, the metal ions tend to precipitate at high pH (e.g., fe at pH 4 or above) 3+ Iron hydroxide precipitate is formed) and PS can only be activated effectively under acidic conditions, and the large amount of metal-containing sludge produced after the reaction causes additional treatment costs. There is therefore a great need for new materials for the treatment of antibiotic wastewater.
Disclosure of Invention
In view of the above, the invention aims to provide a catalytic oxidation integrated material for treating high-salt-content antibiotic wastewater, which overcomes the defects of the prior art and is used for treating the high-salt-content refractory antibiotic wastewater; the invention can produce activation effect in solid-solid phase by physical and mechanical mixing and gradually increasing pressure and temperature in a closed ball milling tank in the ball milling process, so that surface crystal lattice is changed, solid solution is formed or synthesis or decomposition reaction is produced, carbon material and solid persulfate oxidizer are jointly and mechanically activated, and the catalytic oxidation integrated material is obtained by one-step mechanical treatment.
Carbon material as SO-based 4 · - Is an effective catalyst in advanced oxidation processes. The carbon material can activate PS oxidant to generate HO and SO 4 · - 、O 2 - And 1O 2 And the like, thereby effectively degrading various organic pollutants in the water phase.
In the prior art, solid carbon materials are generally added into PS solution, and the solid carbon materials and PS solution react at a solid-liquid interface to generate sulfate radical, hydroxyl radical and other oxidation species. The invention directly uses solid PS and carbon to form solid compound through ball milling, and the solid reacts with little PS dissolution when the solid compound is put into aqueous solution.
According to the invention, the carbon material is used as a catalyst, the PS is used as an oxidant, and the solid catalyst and the oxidant are directly combined by mechanical ball milling activation, so that the catalytic oxidation integrated material is obtained, the problems of high cost and low yield of the carbon catalytic material prepared by chemical activation are solved, and the process of adding the solid catalyst and the liquid oxidant respectively in the traditional AOPs reaction process can be simplified.
Compared with the prior art, the catalytic oxidation integrated material for treating the high-salt-content antibiotic wastewater has the following advantages:
1) According to the invention, the carbon material is used as a catalyst, the PS is used as an oxidant, and the solid catalyst and the oxidant are directly activated and simultaneously compounded through mechanical action, so that the catalytic oxidation integrated material is obtained by a green, economical, simple and efficient method.
2) Activating the carbon material by mechanochemical action to obtain a nonmetallic AOPs catalyst, and generating surface functional groups and defects which can be used as catalytic sites; but also initiates lattice deformation of PS to promote electron transfer and oxidant activation, and co-oxidizes and degrades contaminants by free and non-free radical mechanisms. The composite material has the adsorption, catalysis and oxidation capabilities, and is an advanced oxidation treatment material with excellent performance and convenient use.
3) The invention efficiently utilizes the carbon material and the oxidant, and obtains the high-performance composite catalytic oxidation material by a simple and low-consumption one-step mechanical synthesis method, thereby not only solving the problems of easy dissolution, narrow applicable pH range and the like of the traditional metal AOPs catalyst, but also improving the activation efficiency of the oxidant, being capable of rapidly and efficiently degrading the novel organic pollutants of antibiotics, keeping excellent treatment performance even in high-salt wastewater, and having wide application prospect in wastewater treatment in chemical industry, medicine industry and the like.
Drawings
Figure 1 is an XRD pattern of the different catalytic oxidation materials in the examples. Wherein, (ac@ps) -M is the catalytic oxidation monolith obtained in example 2; AC-M is a carbon material after ball milling; PS-M is persulfate after ball milling; PS is a persulfate that has not been ball milled.
FIG. 2 is a graph showing the comparison of TC removal by different catalytic oxidation materials in an example.
FIG. 3 shows the degradation performance of the catalytic oxidation monolith to TC at different pH conditions in the examples.
FIG. 4 shows the degradation performance of the catalytic oxidation monolith to TC in a high salt environment in the examples.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
A preparation method of a catalytic oxidation integrated material for treating high-salt antibiotic wastewater, which comprises the following steps,
10g of potassium persulfate is weighed, added with Active Carbon (AC) with a certain mass ratio and placed in a zirconia ball mill. The ball milling medium consists of 120g of zirconia balls with the diameters of 3, 5 and 15mm respectively, and the mass ratio of the three zirconia balls is 3:5:2. then, after purging the mixed material with nitrogen gas for 15 minutes, the ball mill was operated at a speed of 300 rpm. The composite material is ground for 12 hours, the rotation direction is changed every 3 hours, and the rest is continued for 5 minutes. After ball milling, the resulting composite material was collected and stored in a dry oxygen free glass bottle for use.
Example 1:
the mass ratio of the carbon material to PS added into the ball mill was 1:1, and after nitrogen purging the mixed material for 15min, the ball mill was operated at 300rpm and ground for 12h.
Example 2:
the mass ratio of carbon material to PS added to the ball mill was 1:2.5, and after nitrogen purging the mixed material for 15min, the ball mill was operated at 300rpm and ground for 12h.
The XRD pattern of the resulting catalytic oxidation monolith is shown in FIG. 1.
Example 3:
the mass ratio of the carbon material to PS added into the ball mill was 1:5, and after nitrogen purging the mixed material for 15min, the ball mill was operated at 300rpm and ground for 12h.
Example 4:
the mass ratio of the carbon material to PS added into the ball mill was 1:8, and after nitrogen purging the mixed material for 15min, the ball mill was operated at 300rpm and ground for 12h.
Example 5:
the mass ratio of the carbon material to PS added into the ball mill was 1:10, and after nitrogen purging the mixed material for 15min, the ball mill was operated at 300rpm and ground for 12h.
Comparative example:
the carbon material (activated carbon AC) was not mixed with PS and ball-milled separately. After nitrogen purging the carbon material/PS for 15min, the ball mill was operated at 300rpm and ground for 12h, after which the carbon material and PS were mixed uniformly in a mass ratio of 1:2.5.
From the XRD pattern in FIG. 1, it can be observed thatPS was changed after ball milling. Appears in the PS map to correspond to K 2 S 2 O 8 A peak of a main crystal plane, such as a peak belonging to a (020) crystal plane at 27.576 °; ball-milled PS-M has more K 2 S 2 O 8 The characteristic peak, such as 35.193 deg., corresponds in position to the (012) plane. And the composite material AC@PS-M is subjected to common ball milling except K 2 S 2 O 8 Besides the characteristic peak of (2), the crystal face of (002) is provided with a sharp peak corresponding to carbon, which shows that the crystallization degree of carbon is obviously improved. It can be seen that both the carbon material and PS are activated under mechanical action, have higher crystallinity and more exposed crystal planes, and combine successfully to form a composite.
The prepared catalytic oxidation integrated material has the following TC removal performance:
antibiotic TC oxidative degradation experiments: 100ml of tetracycline hydrochloride solution with the concentration of 20mg/L is prepared by deionized water, 35mg of prepared material is added, a reaction bottle is closed (oxygen removal is not needed), the reaction bottle is placed in a constant-temperature oscillator to react at the room temperature (about 25 ℃) and the rotating speed of 250r/min, sampling is carried out at certain time intervals, the sampling amount is 0.5ml each time, and the TC concentration is detected by a liquid chromatograph after the sample is filtered by a 0.22 mu m filter membrane.
The experimental results of treating TC with different kinds of catalytic/oxidation materials are shown in fig. 2. The amount of carbon material used in the reaction was 10mg and the amount of PS was 25mg, and the catalytic/oxidation material used was prepared in example 2.
The non-ball-milled PS has almost no degradation effect on TC, and the mechanical effect of ball milling directly realizes the activation of PS, so that the degradation efficiency of the ball-milled PS is improved to 36% after 40 min.
The adsorption capacity of the ball-milling carbon material is 26%, the degradation efficiency of the ball-milling carbon material for catalyzing the non-ball-milling PS is 39%, and the degradation efficiency of the ball-milling carbon material for catalyzing the ball-milling PS is 53%;
and the composite material obtained by ball milling the carbon material and PS can almost completely remove TC in 40min of reaction.
The experimental result shows that the simple ball milling treatment can improve the oxidation effect of PS and the activation effect of the carbon material, and the carbon material obtained by the mechanical ball milling of the two materials has obviously stronger activation effect on PS and can efficiently degrade antibiotics TC.
Examples 1-5 preparation the TC treatment effect of the catalytic/oxidation material at 40min of reaction was 98%, 84%, 48% and 47%, respectively.
Experiments examine the influence of pH and anions on the degradation of TC of the catalytic oxidation integrated material obtained by ball milling. The influence of pH change on TC degradation efficiency is not great (in figure 3, the material prepared in example 2 is used, TC is 20mg/L, the rotating speed is 220r/min, T is 25 ℃, AC is 100 mg/L), the TC degradation rate is not obviously changed within the range of 3-7, the TC degradation rate is 96-98%, and the TC degradation rate can still reach approximately 80% in the strongly alkaline pH11 environment.
Common anions SO in water 4 2- 、Cl - And HCO 3 - The degradation of TC in the presence of the catalyst is shown in FIG. 4, (using the material prepared in example 2, TC:20mg/L, pH 4, rotation speed: 220r/min, T:25 ℃, AC:100 mg/L), the content of each ion was 100mM, namely SO 4 2- 、Cl - And HCO 3 - The mass concentration of (C) is 9600mg/L, 3550mg/L and 6100mg/L respectively. In the presence of these three anions, the 40min degradation rate of TC was 92%, 91% and 88%, respectively. PS also produces SO during the reaction 4 2- ；Cl - Can react with OH in the reaction process to generate ClOH with oxidizing property - 、Cl 2 · - Iso-radicals; HCO (hydrogen chloride) 3 - Hydrolysis occurs to raise the pH of the reaction system, thereby reducing the survival rate of free radicals and reducing the degradation rate of TC. But in general, in the high-salt antibiotic wastewater, the mechanically-prepared catalytic oxidation integrated material still maintains higher degradation performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A catalytic oxidation integrated material for treating high-salt antibiotic wastewater is characterized in that: the composite material comprises a carbon material and persulfate, wherein the mass ratio of the carbon material to the persulfate is 1:1-1:10, and the carbon material and the persulfate are subjected to mechanical ball milling, activation and compounding.
2. The catalytic oxidation integrated material for treating high-salt antibiotic wastewater according to claim 1, wherein: the carbon material is one or more of active carbon, graphite and biochar, and the persulfate is potassium peroxodisulfate K 2 S 2 O 8 。
3. A method for preparing the catalytic oxidation integrated material for treating high-salt antibiotic wastewater according to claim 1 or 2, which is characterized in that: comprises the following steps of the method,
1) Uniformly mixing a carbon material and persulfate, and placing the mixture in a ball mill;
2) Adding a ball milling medium into the mixed material obtained in the step 1), wherein the ball milling medium is zirconia balls, and the diameter of the zirconia balls is 1-20 mm;
3) After the mixture obtained in the step 2) is purged for 5 to 20 minutes by nitrogen, the ball mill is operated at a speed of 100 to 500rpm, the mixed material is ground for 8 to 20 hours, the rotation direction is changed every 1 to 5 hours, and the grinding is stopped for 2 to 10 minutes in the middle.
4. The method for preparing the catalytic oxidation integrated material for treating high-salt antibiotic wastewater according to claim 3, wherein the method comprises the following steps: in the step 2), adding a carbon material and zirconia balls in a mass ratio of 1:10-1:200; preferably, 1:10-120.
5. The method for preparing the catalytic oxidation integrated material for treating high-salt antibiotic wastewater according to claim 3, wherein the method comprises the following steps: in the step 2), the diameters of the zirconia balls are divided into three types, namely 3, 5 and 15mm, and the mass ratio of the zirconia balls with the diameters is (2-6): 3-8): 1-5.
6. The use of a catalytic oxidation monolith for the treatment of highly salty antibiotic wastewater according to claim 1 or 2 or a catalytic oxidation monolith prepared by the method of any one of claims 3 to 5 in the treatment of antibiotic contaminated water.
7. The use according to claim 6, wherein the antibiotic is tetracycline hydrochloride.
8. The use according to claim 6, wherein the concentration of antibiotics in the sewage is in the range of 10-50 mg/L; the anion concentration of the high-salt-content wastewater is 50-200 mM, and the pH value is 3-11.
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