CN114534772A - Catalyst for antibiotic wastewater treatment and application thereof - Google Patents
Catalyst for antibiotic wastewater treatment and application thereof Download PDFInfo
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- CN114534772A CN114534772A CN202210047444.5A CN202210047444A CN114534772A CN 114534772 A CN114534772 A CN 114534772A CN 202210047444 A CN202210047444 A CN 202210047444A CN 114534772 A CN114534772 A CN 114534772A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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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
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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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- 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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Abstract
The invention provides a catalyst for antibiotic wastewater treatment and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: s1 pretreatment: drying and sieving the lithium slag to obtain a pretreatment raw material; s2 aging: adding the pretreated raw material obtained in the step S1 into an alkaline solution, stirring, standing and aging to obtain a mixed solution; s3 crystallization: crystallizing the mixed solution obtained in the step S2 to obtain a reaction product; s4 purification: and filtering, washing and drying the reaction product obtained in the step S3 to obtain the catalyst. The catalyst has the advantages of high catalytic activity, high catalytic efficiency, simple preparation method, cheap raw materials and environmental protection.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a catalyst for antibiotic wastewater treatment and application thereof.
Background
Antibiotics have been widely used in human and animal medicine for the treatment and prevention of bacterial infections over the past few decades. Antibiotics are frequently detected in water environments and their presence in sewage, surface water and groundwater is confirmed by the world health organization (world health organization) research report. With the increasing of the antibiotic yield and consumption of China, the antibiotic yield and consumption of China account for about 50% of the world and become the countries with the largest antibiotic production and consumption. The wide application of antibiotics brings great convenience to human society and simultaneously enters into ecological environment through various ways. Compared with other types of wastewater, the antibiotic wastewater has the characteristics of high toxicity, high solubility, low biodegradability, complex components, high organic matter concentration and the like, so that the antibiotic wastewater is difficult to degrade by the traditional sewage treatment method.
When penicillin is produced in countries such as Europe and America from 40 s, attention is paid to wastewater treatment, and an activated sludge method or a biological filter method is adopted to remove high-concentration organic matters in the penicillin, but the effect is not obvious, and due to the fact that antibiotic wastewater is difficult to treat, preparation of a large amount of original antibiotics is transferred to developing countries after 70 s. Michael and Rizzo et al believe that municipal sewage treatment plants may be a hotspot for release of antibiotics and antibiotic resistance genes in the natural environment. It is important to remove the bioresistant residues before the waste water is discharged into the environment. The air flotation method, the membrane method and the like are commonly used antibiotic wastewater treatment technologies, but the technologies are mainly used for treating antibiotic wastewater with higher concentration and are easy to cause secondary pollution. Oxidation methods such as ozone oxidation and chlorination are suitable for treating low-concentration antibiotic wastewater, but the cost is high and secondary pollution is caused by byproducts. Adsorption has been used in place of oxidation, but has not been widely used. Its disadvantage is that new waste is generated, and most of the activated carbon used in research is adsorbed, which is very costly. The adsorption method needs to search for cheap adsorption materials to replace the activated carbon. The biological treatment method has harsh conditions and is difficult to be applied to practical engineering. The wet catalytic oxidation of waste water is a new water treatment technology developed in the 80 th 20 th age, mainly utilizes oxidant to oxidize organic matter, ammonia nitrogen and the like into harmless products such as carbon dioxide, nitrogen and the like under high temperature and high pressure and in the presence of catalyst, the removal efficiency is high, but the conditions are special, the equipment price is high, and the catalyst is mostly noble metal.
Therefore, a simple, effective, low-cost and environmentally friendly method is needed for antibiotic wastewater treatment.
The lithium slag is an industrial waste slag generated in the production process of lithium salt, and is fine powder obtained by grinding spodumene after high-temperature calcination at about 1200 ℃, and residues discharged after lithium carbonate clinker is extracted by a sulfuric acid method and is leached and washed by percolation. The production process and technical conditions of the chemical composition lithium carbonate are relatively stable, so that the chemical composition and properties of the lithium slag are uniform and stable. The chemical composition of the lithium slag is similar to that of clayey slag, and the chemical composition is mainly SiO2、Al2O3And Fe2O3And the like.
In the prior art, the utilization of the lithium slag mainly utilizes the pore structure of the lithium slag to develop lithium slag molecular sieve series products, or uses the lithium slag as a carrier to load metal to prepare a catalyst or modify the catalyst. The application of the lithium slag directly as a catalyst is not reported yet.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst for antibiotic wastewater treatment and application thereof, and provides a simple, effective, low-cost and environment-friendly method for antibiotic wastewater treatment.
In one aspect of the present invention, there is provided a catalyst for antibiotic wastewater treatment, the preparation method of the catalyst comprising the steps of:
s1 pretreatment: drying and sieving the lithium slag to obtain a pretreatment raw material;
s2 aging: adding the pretreated raw material obtained in the step S1 into an alkaline solution, stirring, standing and aging to obtain a mixed solution;
s3 crystallization: crystallizing the mixed solution obtained in the step S2 to obtain a reaction product;
s4 purification: and filtering, washing and drying the reaction product obtained in the step S3 to obtain the catalyst.
Further, in step S2, the alkaline solution is a sodium hydroxide solution.
Further, in step S2, the mass ratio of the pretreatment raw material to the sodium hydroxide is 1:1 to 6: 1.
Further, in step S2, the stirring speed is 100-300r/min, the stirring time is 0.1-5h, and the aging time is 0-120 h.
Further, in step S3, the crystallization reaction temperature is 60-300 ℃, and the reaction time is 4-120 h.
In another aspect of the invention, the application of the catalyst for antibiotic wastewater treatment in antibiotic wastewater treatment is provided.
In another aspect of the invention, a method for treating antibiotic wastewater is provided, which comprises treating with the catalyst.
Further, the method comprises the steps of:
s1: adding a catalyst into the antibiotic wastewater until adsorption balance is achieved;
s2: adding hydrogen persulfate into the catalytic system for reaction.
Further, in step S1, the amount of the catalyst added to the antibiotic wastewater is 0.05-5 g/L.
Further, in step S2, the mass ratio of the catalyst to the peroxodisulfate is 0.5-10: 1.
The technical principle of the invention is as follows:
the inventor finds in research that the zeolite catalyst prepared by in-situ synthesis in one step has both carrier property and catalytic performance, has good adsorption performance and very good catalytic capability, and has good catalytic degradation effect on antibiotic wastewater. Further, the inventor finds that the catalytic effect of the catalyst directly prepared from the lithium slag without water-soluble or alkali-soluble treatment is far higher than that of the lithium slag and that of the lithium slag subjected to water-soluble or alkali-soluble treatment. This is probably because the internal structure and the transition metal active component of the lithium slag are changed after the water-soluble or alkali-soluble treatment, for example, the content of available iron is reduced during the treatment process, so that the catalytic performance of the catalyst is reduced. During the treatment process, the interaction between the carrier and the transition metal particles is influenced, so that the transition metal particles in the catalyst are migrated, agglomerated and lost, the size, content or dispersibility of the transition metal particles are influenced, and the catalytic performance is reduced.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes industrial waste lithium slag as a raw material, prepares the zeolite catalyst with carrier property and catalytic performance by one step of in-situ synthesis, and degrades antibiotics in water by the transition metal activated persulfate/peroxymonosulfate contained in the lithium slag. The catalyst has the advantages of high catalytic activity, high catalytic efficiency, simple preparation method, cheap raw materials and environmental protection.
Drawings
FIG. 1 is an X-ray diffraction pattern of the catalyst prepared in example 1 of the present invention, wherein (a) is schemes A-C and (b) is schemes D-F;
FIG. 2 is a graph showing the removal performance of the catalyst for treating antibiotic sulfadiazine simulated wastewater prepared in example 1 of the present invention, wherein (a) is schemes A to C and (b) is schemes D to F;
fig. 3 is a graph showing the results of comparing the catalyst prepared in the embodiment a of example 1 of the present invention with comparative examples 1 to 3, wherein the li slag is comparative example 1, the water-washed li slag zeolite is comparative example 2, the baked li slag zeolite is comparative example 3, and the li slag zeolite (catalyst) is embodiment a of example 1.
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Example 1 preparation of catalyst for antibiotic wastewater treatment
Drying the lithium slag, and sieving with a 200-mesh sieve to obtain a pretreated raw material (or called pretreated lithium slag).
20ml of ultrapure water was taken into a 100ml beaker, and NaOH solid was added and stirred until completely dissolved. Adding the pretreated lithium slag, magnetically stirring for 2 hours at 253r/min, and aging to obtain a mixed solution (or called as initial gel). And (3) filling the initial gel into a polytetrafluoroethylene lining, sealing the initial gel in a reaction kettle, and then placing the reaction kettle in a forced air drying oven for crystallization at 110 ℃ for 12 hours. And after crystallization is finished, taking out the reaction kettle, cooling to room temperature, filtering to obtain a reaction product (or called as a synthetic sample), repeatedly washing the synthetic sample with distilled water until the pH value is unchanged, and drying to constant weight to obtain the catalyst for treating the antibiotic wastewater. The aging time, the amount of NaOH solid added, and the amount of lithium slag added after pretreatment are shown in Table 1.
TABLE 1 ageing time and amount of reactants added
| Group of | Aging time (h) | NaOH solid addition amount (g) | Addition amount (g) of pretreated lithium |
| Scheme A | |||
| 0 | 2 | 5 | |
| Scheme B | 5 | 2 | 5 |
| Scheme C | 12 | 2 | 5 |
| |
0 | 1 | 6 |
| |
0 | 4 | 6 |
| |
0 | 6 | 6 |
Example 2 preparation of catalyst for antibiotic wastewater treatment
Similar to example 1, scheme a, except that: the stirring speed is 100r/min, the stirring time is 5h, the aging time is 120h, the crystallization temperature is 300 ℃, and the crystallization time is 4 h.
Example 3 preparation of catalyst for antibiotic wastewater treatment
Similar to example 1, scheme a, except that: the stirring speed is 300r/min, the stirring time is 0.1h, the crystallization temperature is 60 ℃, and the crystallization time is 120 h.
Test example 1X-ray diffraction analysis
The catalyst prepared in example 1 was subjected to X-ray diffraction analysis, and the results are shown in fig. 1.
From the results, it can be seen that: the XRD structure of the catalyst prepared under different aging times and alkali amounts has little change and is relatively stable.
Test example 2 detection of catalytic Performance
The catalyst was studied for Sulfadiazine (SULF) removal efficiency in 250ml Erlenmeyer flasks at room temperature. 100ml of SULF solution (20mg/L) was added, then 0.1g/L of catalyst was added, and the adsorption equilibrium was reached by shaking reaction. 0.2g/L of peroxymonosulfate was added and the reaction was shaken. Samples were collected at time intervals of 0min, 0.5min, 1min, 2min, 3min, 5min, and 7min for residual antibiotic concentration determination. The results are shown in FIG. 2.
From the results, it can be seen that: the prepared catalyst has better catalytic performance to sulfadiazine.
The catalysts prepared in examples 2-3 were tested to have similar XRD structures and catalytic properties as example 1.
Comparative example 1
Similar to example 1, version A, except that S2-S4 were not included. And (3) using the prepared lithium slag which is not aged and crystallized for catalytic performance detection. At room temperature, in a 250ml Erlenmeyer flask. 100ml of SULF solution (20mg/L) is added firstly, then 5g/L of catalyst is added, and the oscillation reaction is carried out to reach the adsorption and desorption equilibrium. 0.5g/L of peroxymonosulfate was added and the reaction was shaken. Samples were collected at time intervals of 0min, 0.5min, 1min, 2min, 3min, 5min, and 7min for residual antibiotic concentration determination.
Comparative example 2
Similar to embodiment 1, version a, except that step S11 was added between steps S1 and S2: mixing the lithium slag with a proper amount of water, stirring, standing for a certain time, filtering, and drying. And (3) using the prepared water-washed lithium slag zeolite for detecting catalytic performance. See comparative example 1 for a specific detection method.
Comparative example 3
Similar to embodiment 1, scheme a, except that step S22 is added between steps S1 and S2: mixing the lithium slag and solid sodium hydroxide according to a certain proportion, and roasting for 2-6h at 500 ℃. And (3) using the prepared calcined lithium slag zeolite for detecting catalytic performance. See comparative example 1 for a specific detection method.
The results of the tests performed in comparison with the lithium slag zeolite (catalyst) prepared in scheme a of example 1 are shown in fig. 3. As can be seen from fig. 3, the catalytic performance of the catalyst prepared in example 1, scheme a is significantly higher than that of the catalysts prepared in comparative examples 1-3.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, 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 modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A catalyst for antibiotic wastewater treatment, characterized in that: the preparation method of the catalyst comprises the following steps:
s1 pretreatment: drying and sieving the lithium slag to obtain a pretreatment raw material;
s2 aging: adding the pretreated raw material obtained in the step S1 into an alkaline solution, stirring, standing and aging to obtain a mixed solution;
s3 crystallization: crystallizing the mixed solution obtained in the step S2 to obtain a reaction product;
s4 purification: and filtering, washing and drying the reaction product obtained in the step S3 to obtain the catalyst.
2. A catalyst for antibiotic wastewater treatment in accordance with claim 1, wherein: in step S2, the alkaline solution is a sodium hydroxide solution.
3. A catalyst for antibiotic wastewater treatment in accordance with claim 2, wherein: in step S2, the mass ratio of the pretreatment raw material to the sodium hydroxide is 1:1-6: 1.
4. A catalyst for antibiotic wastewater treatment in accordance with claim 1, wherein: in step S2, the stirring speed is 100-300r/min, the stirring time is 0.1-5h, and the aging time is 0-120 h.
5. A catalyst for antibiotic wastewater treatment in accordance with claim 1, wherein: in step S3, the crystallization reaction temperature is 60-300 ℃, and the reaction time is 4-120 h.
6. Use of the catalyst for antibiotic wastewater treatment according to any one of claims 1 to 5 in antibiotic wastewater treatment.
7. A method for treating antibiotic wastewater is characterized by comprising the following steps: comprising treatment with a catalyst as claimed in any one of claims 1 to 5.
8. The method of antibiotic wastewater treatment as in claim 7, wherein: the method comprises the following steps:
s1: adding a catalyst into the antibiotic wastewater until adsorption balance is achieved;
s2: adding hydrogen persulfate into the catalytic system for reaction.
9. The method of antibiotic wastewater treatment as in claim 8, wherein: in step S1, the catalyst is added into the antibiotic wastewater in an amount of 0.05-5 g/L.
10. The method of antibiotic wastewater treatment as in claim 8, wherein: in step S2, the mass ratio of the catalyst to the peroxodisulfate is 0.5-10: 1.
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