CN114534772B - Catalyst for antibiotic wastewater treatment and application thereof - Google Patents
Catalyst for antibiotic wastewater treatment and application thereof Download PDFInfo
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- CN114534772B CN114534772B CN202210047444.5A CN202210047444A CN114534772B CN 114534772 B CN114534772 B CN 114534772B CN 202210047444 A CN202210047444 A CN 202210047444A CN 114534772 B CN114534772 B CN 114534772B
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- antibiotic wastewater
- wastewater treatment
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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
-
- 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
- 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
-
- 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
-
- 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
-
- 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
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 lithium slag to obtain a pretreated 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, crystallizing: crystallizing the mixed solution obtained in the step S2 to obtain a reaction product; s4, purifying: and (3) 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, low cost of 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 past several decades to treat and prevent bacterial infections. In an aqueous environment, antibiotics are frequently detected, and research reports of the world health organization (the world health organization) confirm that they are present in sewage, surface water and groundwater. Along with the continuous increase of the output and consumption of antibiotics in China, the antibiotics accounts for about 50% of the world, and become the country with the largest production and consumption of antibiotics. The wide application of antibiotics brings great convenience to human society and enters the 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 concentration of organic matters and the like, so that the conventional wastewater treatment method is difficult to degrade the antibiotic wastewater.
In the production of penicillin in the 40 s of countries such as europe and america, 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 wastewater, but the effect is not obvious, and since antibiotic wastewater is difficult to treat, the preparation of a large amount of antibiotic raw medicines is transferred to developing countries from the 70 s. Michael and Rizzo et al believe that municipal wastewater treatment plants may be hot spots where antibiotics and antibiotic resistance genes are released in the natural environment. It is important to clean the waste water from biological residues before it is discharged to the environment. Air floatation, membrane method and the like are common antibiotic wastewater treatment technologies, but the technologies are mainly used for treating the high-concentration antibiotic wastewater and are easy to cause secondary pollution. Oxidation methods such as ozone oxidation and chlorination are suitable for treating low concentration antibiotic wastewater, but have high cost and secondary pollution caused by byproducts. Adsorption has been used instead of oxidation, but has not been widely used. Its disadvantage is that new waste is produced and the activated carbon used for adsorption is very costly in many studies. The use of adsorption requires the search for inexpensive adsorbent materials to replace activated carbon. The biological treatment method has harsh conditions and is difficult to be applied to practical engineering. Wet catalytic oxidation of waste water is a new technology for water treatment developed in the 80 s of the 20 th century, and mainly uses an oxidant to oxidize organic matters, ammonia nitrogen and the like into harmless products such as carbon dioxide, nitrogen and the like at high temperature and high pressure in the presence of a catalyst, so that the removal efficiency is high, but the conditions are special, the equipment price is high, and the catalyst is mostly noble metal.
Thus, there is a need for a simple, efficient, cost effective and environmentally friendly method for antibiotic wastewater treatment.
The lithium slag is an industrial waste residue produced in the production process of lithium salt, and is a residue which is removed after spodumene is calcined at a high temperature of about 1200 ℃ and ground into fine powder, lithium carbonate clinker is extracted by a sulfuric acid method, and the lithium carbonate clinker is leached and washed by percolation. Chemical groupThe production process and technical conditions of the 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 clay, mainly SiO 2 、Al 2 O 3 And Fe (Fe) 2 O 3 Etc.
In the prior art, the utilization of lithium slag is mainly to develop a lithium slag molecular sieve series product by utilizing the pore structure of the lithium slag, or to prepare a catalyst by taking the lithium slag as a carrier to load metal or to modify the catalyst. The application of lithium slag as a catalyst directly has not been reported yet.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a catalyst for treating antibiotic wastewater and application thereof, and provides a simple, effective, low-cost and environment-friendly method for treating the antibiotic wastewater.
In one aspect of the invention, a catalyst for antibiotic wastewater treatment is provided, and the preparation method of the catalyst comprises the following steps:
s1, pretreatment: drying and sieving lithium slag to obtain a pretreated 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, crystallizing: crystallizing the mixed solution obtained in the step S2 to obtain a reaction product;
s4, purifying: and (3) filtering, washing and drying the reaction product obtained in the step (S3) to obtain the catalyst.
Further, in step S2, the alkaline solution is sodium hydroxide solution.
Further, in the step S2, the mass ratio of the pretreatment raw material to the sodium hydroxide is 1:1-6:1.
Further, in the step S2, the stirring rotation speed is 100-300r/min, the stirring time is 0.1-5h, and the aging time is 0-120h.
Further, in the step S3, the crystallization reaction temperature is 60-300 ℃ and the reaction time is 4-120h.
In another aspect of the invention, there is provided the use of a catalyst for antibiotic wastewater treatment in antibiotic wastewater treatment.
In yet another aspect of the invention, a method for antibiotic wastewater treatment is provided, comprising treating with the above catalyst.
Further, the method comprises the steps of:
s1: adding a catalyst into the antibiotic wastewater until adsorption equilibrium is reached;
s2: adding hydrogen peroxide salt to the catalytic system for reaction.
Further, in the step S1, the adding amount of the catalyst in the antibiotic wastewater is 0.05-5g/L.
Further, in step S2, the mass ratio of the catalyst to the persulfate is 0.5-10:1.
The technical principle of the invention is as follows:
the inventor finds that the zeolite catalyst prepared by one-step in-situ synthesis has both carrier property and catalytic performance, has good adsorption performance, has 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-fusible treatment is far higher than the catalytic effect of the lithium slag and the catalytic effect of the lithium slag after water-soluble or alkali-fusible treatment. This is probably due to the fact that the lithium slag is subjected to water-soluble or alkali-fusible treatment, and the internal structure and the active components of the transition metal are changed, for example, the content of the effective iron is reduced in the treatment process, so that the catalytic performance of the catalyst is reduced. During the treatment, the interaction between the carrier and the transition metal particles is affected, so that the transition metal particles in the catalyst migrate, agglomerate and run away, and the size, content or dispersibility of the transition metal particles are affected, so that the catalytic performance is reduced.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, industrial waste lithium slag is used as a raw material, and zeolite catalyst with carrier property and catalytic performance is prepared through in-situ synthesis in one step, and transition metal contained in the lithium slag activates persulfate/peroxymonosulfate to degrade antibiotics in water. The catalyst has the advantages of high catalytic activity, high catalytic efficiency, simple preparation method, low cost of 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 prepared in example 1 of the present invention for treating antibiotic sulfadiazine simulated wastewater, wherein (a) is the scheme A-C, and (b) is the scheme D-F;
FIG. 3 is a graph showing the results of comparison of the catalyst prepared in the scheme A of example 1 according to the present invention with comparative examples 1 to 3, wherein the lithium slag is comparative example 1, the water-washed lithium slag zeolite is comparative example 2, the baked lithium slag zeolite is comparative example 3, and the lithium slag zeolite (catalyst) is the scheme A of example 1.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples.
Example 1 preparation of a catalyst for antibiotic wastewater treatment
And drying the lithium slag, and sieving the dried lithium slag 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, 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 initial gel). The initial gel is put into a polytetrafluoroethylene lining, put into a reaction kettle for sealing, and then put into a blast drying box for crystallization for 12 hours at 110 ℃. And after crystallization, taking out the reaction kettle, cooling to room temperature, filtering to obtain a reaction product (or 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 addition amount of NaOH solids, and the addition amount of the pretreated lithium slag are shown in Table 1.
TABLE 1 aging time and addition of reactants
| Group of | Aging time (h) | NaOH solid addition (g) | Amount of pretreated lithium slag (g) |
| Scheme A | 0 | 2 | 5 |
| Scheme B | 5 | 2 | 5 |
| Scheme C | 12 | 2 | 5 |
| Scheme D | 0 | 1 | 6 |
| Scheme E | 0 | 4 | 6 |
| Scheme F | 0 | 6 | 6 |
Example 2 preparation of a catalyst for antibiotic wastewater treatment
Similar to scheme a of example 1, 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 4h.
Example 3 preparation of a catalyst for antibiotic wastewater treatment
Similar to scheme a of example 1, except that: the stirring speed is 300r/min, the stirring time is 0.1h, the crystallization temperature is 60 ℃, and the crystallization time is 120h.
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 ageing times and alkali amounts is not greatly changed and is relatively stable.
Test example 2 catalytic performance test
The catalyst was studied for Sulfadiazine (SULF) removal efficiency in 250ml Erlenmeyer flasks at room temperature. 100ml of SULF solution (20 mg/L) was added, followed by 0.1g/L of catalyst, and the reaction was shaken to reach adsorption equilibrium. 0.2g/L of hydrogen peroxide monosulfate was added and the reaction was shaken. Samples were taken at time intervals of 0min,0.5min,1min,2min,3min,5min,7min for determination of residual antibiotic concentration. The results are shown in FIG. 2.
From the results, it can be seen that: the prepared catalyst has better catalytic performance on sulfadiazine.
The catalysts prepared in examples 2-3 were tested for XRD structure and catalytic performance similar to those of example 1.
Comparative example 1
Similar to scheme A of example 1, except that S2-S4 are not included. The prepared lithium slag which is not subjected to ageing and crystallization treatment is used for detecting the catalytic performance. At room temperature in a 250ml Erlenmeyer flask. 100ml of SULF solution (20 mg/L) is added, then 5g/L of catalyst is added, and the adsorption and desorption equilibrium is reached by oscillation reaction. 0.5g/L of hydrogen peroxide monosulfate was added and the reaction was shaken. Samples were taken at time intervals of 0min,0.5min,1min,2min,3min,5min,7min for determination of residual antibiotic concentration.
Comparative example 2
Similar to embodiment 1, scheme a, except that step S11 is 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. The prepared water-washed lithium slag zeolite is used for detecting the catalytic performance. For specific detection methods see comparative example 1.
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 ℃. The prepared calcined lithium slag zeolite is used for detecting the catalytic performance. For specific detection methods see comparative example 1.
The test results obtained by comparing with the lithium slag zeolite (catalyst) prepared in the scheme A of example 1 are shown in FIG. 3. As can be seen from FIG. 3, the catalyst prepared in scheme A of example 1 has significantly higher catalytic performance than the catalyst prepared in comparative examples 1-3.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and 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 and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and it is intended to be covered by the scope of the claims of the present invention.
Claims (9)
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 lithium slag to obtain a pretreated 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, crystallizing: crystallizing the mixed solution obtained in the step S2 to obtain a reaction product;
s4, purifying: filtering, washing and drying the reaction product obtained in the step S3 to obtain a catalyst;
wherein the pretreated raw material obtained in the step S1 is not subjected to water-soluble or alkali-soluble treatment;
in the step S3, the crystallization reaction temperature is 60-300 ℃ and the reaction time is 4-120h.
2. A catalyst for antibiotic wastewater treatment according to claim 1, wherein: in step S2, the alkaline solution is sodium hydroxide solution.
3. A catalyst for antibiotic wastewater treatment according to claim 2, wherein: in the 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 according to claim 1, wherein: in the step S2, the stirring rotation speed is 100-300r/min, the stirring time is 0.1-5h, and the aging time is 0-120h.
5. Use of the catalyst for antibiotic wastewater treatment according to any one of claims 1 to 4 in antibiotic wastewater treatment.
6. A method for treating antibiotic wastewater, which is characterized in that: comprising treatment with the catalyst of any one of claims 1-4.
7. A method of antibiotic wastewater treatment according to claim 6 wherein: the method comprises the following steps:
s1: adding a catalyst into the antibiotic wastewater until adsorption equilibrium is reached;
s2: the hydrogen peroxide salt is added to the catalytic system for reaction.
8. A method of antibiotic wastewater treatment as claimed in claim 7, wherein: in the step S1, the adding amount of the catalyst in the antibiotic wastewater is 0.05-5g/L.
9. A method of antibiotic wastewater treatment as claimed in claim 7, wherein: in step S2, the mass ratio of the catalyst to the persulfate is 0.5-10:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398877A (en) * | 2021-06-23 | 2021-09-17 | 南京永成分子筛有限公司 | Lithium-based molecular sieve with nitrogen-oxygen separation function and preparation method and production equipment thereof |
| WO2021223251A1 (en) * | 2020-05-06 | 2021-11-11 | 青岛理工大学 | Metal oxide nano-confined catalytic film for catalytic treatment of wastewater and method for preparation thereof |
| CN113663706A (en) * | 2021-08-03 | 2021-11-19 | 中南大学 | Sludge-based biological carbon-manganese slag composite catalyst and preparation method and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624191B (en) * | 2009-08-03 | 2011-05-18 | 南京工业大学 | Method for preparing 13 X molecular sieve by using lithium slag as raw materials |
| CN103920494B (en) * | 2014-04-04 | 2016-01-13 | 西华大学 | The application of the catalyst of catalytic wet oxidation method for preparing catalyst and preparation |
| CN103979664B (en) * | 2014-06-03 | 2016-01-06 | 武汉纺织大学 | A kind of OMS-2 activates the method for persulphate degradation of organic waste water |
| CN105107510A (en) * | 2015-09-10 | 2015-12-02 | 广西大学 | Modified red mud and preparation method and application thereof |
| CN107983395A (en) * | 2017-11-30 | 2018-05-04 | 青岛科技大学 | Using flyash as silicon source and the class fenton catalyst of source of iron and application |
| CN110227534B (en) * | 2019-07-16 | 2022-03-22 | 河南省科学院化学研究所有限公司 | Magnetic nitrogen-doped biochar catalyst based on sludge and preparation method thereof |
| CN110606539B (en) * | 2019-10-16 | 2021-10-15 | 河南省科学院化学研究所有限公司 | Method for treating organic wastewater by utilizing sludge resource |
| CN110898825A (en) * | 2019-12-13 | 2020-03-24 | 南京农业大学 | Heavy metal super-enriched biomass charcoal catalyst and preparation method and application thereof |
| CN111744476B (en) * | 2020-07-08 | 2022-10-14 | 昆明理工大学 | Preparation method and application of red mud carbon-based catalyst |
| CN111790386A (en) * | 2020-08-03 | 2020-10-20 | 中国科学技术大学 | Method for preparing catalyst by utilizing coagulated sludge of waterworks and application |
| AU2020102183A4 (en) * | 2020-09-09 | 2020-10-15 | University Of Science And Technology Beijing | Preparation of zeolite 4a from tailings and method for treatment of pb-containing wastewater |
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- 2022-01-17 CN CN202210047444.5A patent/CN114534772B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021223251A1 (en) * | 2020-05-06 | 2021-11-11 | 青岛理工大学 | Metal oxide nano-confined catalytic film for catalytic treatment of wastewater and method for preparation thereof |
| CN113398877A (en) * | 2021-06-23 | 2021-09-17 | 南京永成分子筛有限公司 | Lithium-based molecular sieve with nitrogen-oxygen separation function and preparation method and production equipment thereof |
| CN113663706A (en) * | 2021-08-03 | 2021-11-19 | 中南大学 | Sludge-based biological carbon-manganese slag composite catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Densification and crystallization of Ba-exchanged zeolite A powders;F. Andreola et.al;《Ceramics International》;全文 * |
| 锂渣合成NaX分子筛结构表征和吸附特性研究;胡昕;庄强;陈丹;崔群;王海燕;;高校化学工程学报(第04期);全文 * |
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