A manganese-resistant bacterial strain-loaded iron-manganese catalyst and its preparation method and application
By loading iron-manganese catalysts on manganese-resistant strains, the problems of poor biochemical properties of biological methods, high physical costs and difficult selection of advanced oxidation catalyst materials in coking wastewater treatment in the prior art are solved, and efficient and environmentally friendly catalytic ozone oxidation and degradation effects are achieved.
Patent Information
- Application Number
- CN202410748679.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-12
- Publication Date
- 2025-05-23
- Estimated Expiration
- 2044-06-12
AI Technical Summary
When treating coking wastewater in the prior art, biological methods have poor biochemical properties and are difficult to meet emission standards. Physical methods are costly and difficult to operate. Although advanced oxidation methods such as ozone oxidation methods are effective, there are dangers in the selection of catalyst materials and the use of expensive chemicals.
A catalyst with high catalytic properties in the catalytic ozone oxidation process was prepared by cultured iron and manganese salts with Enterobacteria oxidation by manganese.
The catalyst has higher catalytic performance, can effectively degrade organic pollutants in coking wastewater, and the preparation process does not require dangerous and expensive chemicals, avoids the use of high temperature and high pressure conditions, reduces the demand for rare metals, and improves the environmental protection and sustainability of the catalyst.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of biomaterials and water purification environment, and in particular to a manganese-resistant bacterial strain-loaded iron-manganese catalyst and a preparation method and application thereof. Background Art
[0002] In view of the water quality pollution and human health hazards caused by refractory organic substances such as phenols and polycyclic aromatic hydrocarbons in the secondary effluent of coking wastewater, it is urgent to develop efficient methods for degrading such substances. At present, the main methods for degrading phenolic substances are physical method, biological method and advanced oxidation method. Among them, the biological method is easily affected by water quality and produces a large amount of sludge. Especially when treating coking wastewater, the biodegradability is poor and it is difficult to meet the discharge standards. The physical method has high cost and the regeneration system is difficult to operate. If the biochemical treatment of the previous process is not thorough, the organic pollutants remaining in the coking wastewater will be deposited or adsorbed on the membrane surface, blocking the membrane pores, causing membrane pollution, and the replacement and backwashing of the membrane increase the treatment cost. As one of the advanced oxidation methods, the ozone oxidation method has the advantages of strong oxidizing ability, no introduction of other substances, and no secondary pollution compared with other advanced oxidation methods. It is widely used in the treatment of coking wastewater. Adding a catalyst can promote the decomposition of ozone, produce a large amount of ·OH, and improve the removal rate of pollutants in coking wastewater.
[0003] The material of the catalyst in the catalytic ozone oxidation process is very important. In recent years, a lot of research has been done on the development of heterogeneous catalytic ozone oxidation technology. Metal oxides have more active centers and better stability. Among them, Fe and Mn have become research hotspots because of their good catalytic activity in nature. They can have variable valence states in their oxides and can produce electron transfer pathways in the catalytic ozone oxidation process. The physical and chemical synthesis method usually requires dangerous and expensive chemicals as reducing agents or stabilizers, as well as extreme conditions such as high temperature and high pressure to prepare metal oxides. The biosynthesis method can effectively avoid these drawbacks because microorganisms can mediate the oxidation of metal ions, and the biosynthesized catalysts have a higher specific surface area, more crystal defects and unique crystal structures compared to similar products generated by chemicals. Summary of the invention
[0004] Based on the above content, the purpose of the present invention is to provide a manganese-resistant bacterial strain-loaded iron-manganese catalyst and its preparation method and application. The preparation process of the manganese-resistant bacterial strain-loaded iron-manganese catalyst provided by the present invention is relatively simple, safe and low-cost. This method can improve the catalytic performance of the catalyst and provide a feasible solution for the application of catalytic ozone oxidation process.
[0005] In order to achieve the above-mentioned purpose, the present invention provides the following technical scheme: a manganese-resistant Enterobacter (Enterobacter sp.) FM-500, which was deposited in the China Center for Type Culture Collection on April 22, 2024, with the deposit address being Wuhan University, Wuhan, China, and the deposit number being CCTCC NO: M2024737.
[0006] The present invention also provides a bacterial agent, comprising the manganese-resistant Enterobacter described in the above technical solution.
[0007] The present invention also provides the use of the manganese-resistant Enterobacter or the bacterial agent described in the above technical solution in the preparation of a catalyst.
[0008] In some embodiments, the catalyst is a catalyst that catalyzes ozone oxidation.
[0009] The present invention also provides a manganese-resistant bacterial strain-loaded iron-manganese catalyst, comprising iron element and / or manganese element and the manganese-resistant Enterobacter; the iron element and / or manganese element is adsorbed on the manganese-resistant Enterobacter.
[0010] The present invention also provides a method for preparing the manganese-resistant bacterial strain-loaded iron-manganese catalyst, which comprises culturing iron salt and / or manganese salt with the manganese-resistant Enterobacter.
[0011] In some embodiments, the iron salt is ammonium ferric citrate, and the dosage of the iron salt is 0-2000 mg / L; the manganese salt is manganese sulfate, and the dosage of the manganese salt is 0-500 mg / L.
[0012] In some embodiments, the culturing is performed at 30° C. with shaking at 170 rpm / min for 5 days.
[0013] In some embodiments, the catalyst medium used in the culture is formulated as follows: 0.22 g / L yeast extract powder, 0.89 g / L peptone, 0.14 g / L CaCl 2 ·2H 2 O, 0.14g / LK 2 HPO 4 ·3H 2 O, 0.22 g / L MgSO 4 7H 2 O, 0.22g / LNaNO 3 、0.11g / LNH 4 Cl.
[0014] In some embodiments, after the culturing is completed, the method further comprises collecting the precipitate, and washing and polishing the precipitate.
[0015] In some embodiments, the washing is performed by washing with sterile water for 4-8 times to remove surface impurities; and the polishing is performed by drying at 60° C. for 8 hours.
[0016] The invention also provides the use of the manganese-resistant bacterial strain loaded with an iron-manganese catalyst in catalyzing ozone oxidation and degradation of organic pollutants.
[0017] In some embodiments, the organic pollutants are organic pollutants in the secondary effluent of coking wastewater.
[0018] In some embodiments, the organic contaminant is phenol.
[0019] Beneficial technical effects:
[0020] 1. In the manganese-resistant bacterial strain-loaded iron-manganese catalyst prepared by the present invention, metal oxides are uniformly attached to the bacterial surface in the form of ions, wherein Mn(II) is oxidized to Mn(III / IV) by microorganisms through enzymes or other pathways, and its kinetic constant can be 105 times higher than that of non-biological oxidation. This makes the obtained catalyst have higher catalytic performance and effectively degrade organic pollutants in the secondary effluent of coking wastewater.
[0021] 2. The manganese-resistant strain-loaded iron-manganese catalyst prepared by the present invention has a higher specific surface area, more crystal defects and a unique crystal structure compared to similar products generated chemically.
[0022] 3. The preparation process of the manganese-resistant bacterial strain-loaded iron-manganese catalyst prepared by the present invention does not require dangerous and expensive chemicals as reducing agents or stabilizers, nor does it require extreme conditions such as high temperature and high pressure.
[0023] 4. The iron-manganese catalyst loaded with manganese-resistant bacteria prepared by the present invention uses iron-manganese oxides attached to the surface of bacteria, which is expected to reduce the demand for rare and expensive metals and make the catalyst more environmentally friendly and sustainable.
[0024] 5. The manganese-resistant bacterial strain-loaded iron-manganese catalyst prepared by the present invention has stable properties in an oxidation system and good repeatability. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0026] Figure 1 Bio-Fe in Example 1 500 Mn 500 X-ray diffraction (XRD) patterns of O catalysts.
[0027] Figure 2 Bio-Fe in Example 1 500 Mn 500 X-ray photoelectron spectroscopy (XPS) of O catalysts; (a) is Survey, (b) is Fe2p, and (c) is Mn2p.
[0028] Figure 3 This is a degradation efficiency diagram of phenol wastewater degradation in Example 2;
[0029] Figure 4 This is a morphological diagram of the strain of manganese-resistant Enterobacter in the present invention. DETAILED DESCRIPTION
[0030] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0031] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.
[0032] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.
[0033] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.
[0034] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.
[0035] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.
[0036] Example 1
[0037] 1. Strain origin, isolation and purification
[0038] The samples were collected from the drainage soil of a steel plant in Shijiazhuang, Hebei Province, China.
[0039] Screening for manganese-resistant Enterobacter sp. FM-500
[0040] 1-1. Take 5g of the sieved soil sample, add it to 45ml of 0.9% sterile saline, place it on a shaker for 1h, let it stand, take 5ml of the supernatant, and transfer it to MnSO 4 ·H 2 In 45 ml of culture medium with an O concentration of 50 mg / L, shake culture was performed at 30°C for 48 h;
[0041] 1-2. Take 0.1ml of bacterial solution and dilute it to 10 -1 , 10 -2 , 10 -3 , 10 -4 , 10 -5 , 10 -6 of bacterial suspension;
[0042] 1-3. 10 -4 , 10 -5 , 10 -6 0.2 ml of bacterial suspension was coated with MnSO 4 ·H 2 Solid culture medium with O concentration of 50 mg / L was placed in an incubator at 30°C to observe the bacterial growth;
[0043] 1-4. If the growth is good, take the colonies with 30-300 colonies in the solid medium and transfer them to MnSO 4 ·H 2 O concentrations of 100 mg / L, 200 mg / L, and 500 mg / L were added to fresh culture medium, cultured for 48 h, and then diluted to 10 -1 , 10 -2 , 10 -3 , 10 -4 , 10 -5 , 10 -6 of bacterial suspension;
[0044] 1-5. 10 -4 , 10 -5 , 10 -6The bacterial suspension was coated with MnSO 4 ·H 2 O concentration of 500mg / L plate, at 30 ℃ static culture for 48h, select the single colony with good growth and different colony morphology, separate and purify by plate streak method, repeatedly streak culture until a single clone colony is obtained. Figure 4 As shown, the colony morphology of the FM-500 strain on the Lb plate is light yellow, with regular edges, round and slightly convex, moist and smooth surface, and opaque.
[0045] PCR amplification was performed using universal primers for bacterial identification of 16S rDNA, and the sequencing results were submitted to NCBI for Blast comparison analysis. It was identified as Enterobacter sp. and manganese-resistant Enterobacter sp. FM-500 was obtained.
[0046] The manganese-resistant Enterobacter sp. FM-500 was deposited in the China Center for Type Culture Collection on April 22, 2024, with the deposit address being Wuhan University, Wuhan, China, and the deposit number being CCTCC NO: M2024737
[0047] 2. The preparation method of the manganese-resistant strain-loaded iron-manganese catalyst in this embodiment is:
[0048] S1. Prepare 0.22g / L yeast extract powder, 0.89g / L peptone, 0.14g / L CaCl 2 ·2H 2 O, 0.14g / LK 2 HPO 4 ·3H 2 O, 0.22g / LMgSO 4 7H 2 O, 0.22g / LNaNO 3 、0.11g / LNH 4 Cl catalyst medium.
[0049] S2. Use a sterile 0.22um membrane filter to filter ammonium ferric citrate and MnSO 4 ·H 2 O was added to 0.75L catalyst culture medium, and then bacteria were inoculated from the culture dish. The inoculated catalyst culture medium was placed at 30°C and shaken in an incubator at 170 rpm / min. After 5 days, the precipitate was collected, washed 8 times with sterile water, and gently dried at 60°C for 8 hours to obtain the manganese-resistant strain-loaded iron-manganese catalyst, which was labeled Bio-Fe x Mn y O catalyst, where x represents the dosage of ammonium ferric citrate, and y represents MnSO 4 ·H 2The dosage of O.
[0050] When the dosage of ammonium ferric citrate is 500 mg / L, MnSO 4 ·H 2 When the dosage of O is 500 mg / L, Bio-Fe 500 Mn 500 O catalyst.
[0051] When the dosage of ammonium ferric citrate is 1000 mg / L, MnSO 4 ·H 2 When the dosage of O is 200 mg / L, Bio-Fe 1000 Mn 200 O catalyst.
[0052] When the dosage of ammonium ferric citrate is 0 mg / L, MnSO 4 ·H 2 When the dosage of O is 500 mg / L, Bio-Mn 500 O catalyst.
[0053] When the dosage of ammonium ferric citrate is 2000 mg / L, MnSO 4 ·H 2 When the dosage of O is 0 mg / L, Bio-Fe 2000 O catalyst.
[0054] Figure 1 Bio-Fe provided by the present invention 500 Mn 500 O catalyst X-ray diffraction (XRD) pattern; Figure 2 Bio-Fe provided by the present invention 500 Mn 500 O catalyst X-ray photoelectron spectroscopy (XPS). Figure 1 , Figure 2 It can be seen that the high activity may come from its amorphous structure; the valence states of Fe and Mn are Fe(II, III) and Mn(III, IV), respectively, Fe(II) and Mn(IV) can react, and the multi-pathway redox reaction between metal and ozone is beneficial to the decomposition of ozone and the stability of the catalyst.
[0055] Example 2
[0056] The manganese-resistant strain provided in Example 1 supports the iron-manganese catalyst (Bio-Fe x Mn y O) is used for the degradation of COD in phenol wastewater.
[0057] Effect verification:
[0058] This experiment is a simulated application of the catalyst prepared in Example 1 and catalytic ozone oxidation to efficiently degrade phenol, an organic pollutant in the secondary effluent of coking wastewater. 200 mg of phenol was dissolved in 1 L of deionized water to obtain a phenol solution with a concentration of 200 mg / L, which was loaded into a catalytic ozone reaction device. The catalyst prepared in Example 1 was then respectively put into the catalytic ozone reaction device, and the catalyst dosage was 500 mg / L. Ozone was introduced into the reactor by aeration, and the ozone concentration was detected at the reactor outlet. Phenol wastewater in the reactor was taken every 15 minutes to detect its COD size.
[0059] The experimental results are as follows Figure 3 As shown, in Figure 3 middle, The connecting line represents the removal rate of COD in phenol wastewater without adding catalyst. The connecting line represents the addition of Bio-Fe prepared in Example 1 500 Mn 500 O catalyst COD removal rate, The connecting line represents the addition of Bio-Fe prepared in Example 1 1000 Mn 200 O catalyst COD removal rate, The connecting line represents the addition of Bio-Mn prepared in Example 1 500 O catalyst COD removal rate, The connecting line represents the addition of Bio-Fe prepared in Example 1 2000 O catalyst for COD removal. Figure 3 The results showed that after 90 minutes of reaction, the removal rate of COD by ozone oxidation without catalyst was 64%, while that by adding Bio-Fe 500 Mn 500 O. Bio-Fe 1000 Mn 200 O. Bio-Mn 500 O and Bio-Fe 2000 O catalyst, after 90 minutes of reaction, the COD removal rates were 92%, 70%, 83% and 78% respectively. It can be seen that the Bio-FeMnOx catalysts prepared by the present invention all show the performance of highly efficient catalytic ozone oxidation degradation of COD in phenol wastewater, among which Bio-Fe 500 Mn 500 The catalytic performance of O catalyst is the best.
[0060] The Bio-Fe after catalytic ozone oxidation reaction was tested by o-phenanthroline spectrophotometry. 500 Mn 500 The results show that after catalytic ozone oxidation reaction, Bio-Fe 500Mn 500 The amount of metal ions dissolved from the O catalyst was only 0.032 mg / L, indicating that Bio-Fe 500 Mn 500 O catalyst has high stability.
[0061] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A manganese-resistant Enterobacter ( Enterobacter sp. )FM-500, characterized in that, The manganese-resistant Enterobacter was deposited in the China Center for Type Culture Collection on April 22, 2024, with the deposit address being Wuhan University, Wuhan, China, and the deposit number being CCTCC NO: M2024737.
2. A bacterial agent, characterized in that It comprises the manganese-resistant Enterobacter as described in claim 1.
3. Use of the manganese-resistant Enterobacter according to claim 1 or the bacterial agent according to claim 2 in preparing a catalyst for ozone oxidation and decomposition of organic pollutants.
4. The use according to claim 3, characterized in that: The catalyst is a catalyst for catalyzing ozone oxidation.
5. A manganese-resistant bacterial strain loaded with iron-manganese catalyst, characterized in that: The manganese-resistant Enterobacter according to claim 1 comprises iron and / or manganese; the iron and / or manganese are adsorbed on the manganese-resistant Enterobacter; The preparation method of the manganese-resistant strain loaded iron-manganese catalyst is as follows: iron salt and / or manganese salt are added into the manganese-resistant Enterobacter culture medium as described in claim 1 for culturing, and after the culturing is completed, the steps of collecting the precipitate, washing and polishing the precipitate are further included; the polishing method is drying at 60° C. for 8 hours; the iron salt is ammonium ferric citrate; and the manganese salt is manganese sulfate.
6. A method for preparing the manganese-resistant bacterial strain-loaded iron-manganese catalyst according to claim 5, characterized in that: Iron salt and / or manganese salt are added to the manganese-resistant Enterobacter culture medium of claim 1 for culturing. After the culturing is completed, the steps of collecting the precipitate, washing and polishing the precipitate are also included; the polishing method is drying at 60°C for 8 hours; the iron salt is ammonium ferric citrate; and the manganese salt is manganese sulfate.
7. The preparation method according to claim 6, characterized in that: The dosage of the iron salt is 0-2000 mg / L; the dosage of the manganese salt is 0-500 mg / L; and at least one of the manganese salt and the iron salt is not zero.
8. The preparation method according to claim 6, characterized in that: The culture was carried out at 30°C with shaking at 170 rpm / min for 5 days.
9. Use of the manganese-resistant bacterial strain loaded with an iron-manganese catalyst as claimed in claim 5 in catalytic ozone oxidation degradation of organic pollutants.
10. The use of the manganese-resistant bacterial strain-loaded iron-manganese catalyst in catalytic ozone oxidation degradation of organic pollutants according to claim 9, characterized in that: The organic pollutants are organic pollutants in the secondary effluent of coking wastewater.