Composite biochar catalyst, preparation method thereof and application of composite biochar catalyst in oxidative degradation of antibiotic wastewater
By preparing an iron-cobalt-loaded orange peel composite biochar catalyst and using it for the oxidative degradation of antibiotic wastewater, the problem of difficulty in removing tetracycline in the prior art is solved, and efficient antibiotic wastewater treatment is achieved.
Patent Information
- Application Number
- CN202510368656.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-26
- Publication Date
- 2025-05-30
AI Technical Summary
The prior art is difficult to effectively remove tetracycline in antibiotic wastewater, resulting in its enrichment in wastewater recycling and reuse, affecting the environment and health.
The catalyst is prepared by drying, crushing, mixing, and pyrolysis steps, and putting it into antibiotic wastewater, and reacting with oxidizing agents to achieve the degradation of tetracycline.
This method can significantly improve the degradation rate of tetracycline to more than 90%, and the catalyst has a large specific surface area and rich functional groups. It can efficiently activate a variety of oxidants and have excellent degradation effect.
Smart Images
Figure CN120054491A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical fields of modified biochar preparation and sewage treatment, and particularly relates to a composite biochar catalyst, a preparation method thereof, and an application thereof in the oxidative degradation of antibiotic wastewater. Background Art
[0002] Antibiotic wastewater has high toxicity and is difficult to degrade, and conventional treatment processes such as biodegradation, coagulation sedimentation, filtration and other methods are difficult to effectively remove it. Since most antibiotics have bioaccumulation properties, if antibiotics are not effectively removed, they are bound to be enriched in the recycling of wastewater, thereby posing a serious potential threat to human health and the safety of the water ecological environment. At the same time, for the recycling of industrial wastewater, the significant enrichment of antibiotics during the recycling process often affects the normal operation of the treatment system, thus severely limiting the improvement of the reuse rate of enterprise production wastewater.
[0003] In view of the above problems, developing more efficient and low-cost antibiotic treatment technologies is of great significance for promoting the recycling of sewage and wastewater. Summary of the Invention
[0004] The purpose of the present invention is to provide a composite biochar catalyst, a preparation method thereof, and an application thereof in the oxidative degradation of antibiotic wastewater, which can efficiently activate various oxidants for degrading tetracycline.
[0005] In order to achieve the above invention purpose, the present invention provides the following technical solutions:
[0006] The present invention provides a preparation method of a composite biochar catalyst, comprising the following steps:
[0007] (1) Drying and pulverizing a biochar raw material, and sieving to obtain a raw material powder;
[0008] (2) Mixing a soluble iron salt, a soluble cobalt salt, the raw material powder and water to obtain a mixture;
[0009] (3) Drying and pulverizing the mixture, and performing pyrolysis treatment to obtain a carbonized product;
[0010] (4) Washing, drying, pulverizing and sieving the carbonized product to obtain a composite biochar catalyst.
[0011] Preferably, in step (1), the biochar raw material is the peel of citrus, the drying temperature is 60-80 °C, the drying time is 5-7 h, and an 80-120 mesh sieve is used during sieving.
[0012] Preferably, the dosage ratio of the soluble iron salt, soluble cobalt salt, raw material powder and water in step (2) is 0.8 - 1.2 g: 1 - 1.3 g: 1.5 - 2.5 g: 45 - 55 mL.
[0013] Preferably, the mixing step in step (2) is as follows:
[0014] A. Dissolve the soluble iron salt and soluble cobalt salt in water to obtain a mixed solution;
[0015] B. Add the raw material powder to the mixed solution and stir.
[0016] In step A, the soluble iron salt and soluble cobalt salt are used in a ratio of Fe:Co molar ratio of 1:1 - 3:1; the soluble iron salt includes ferric chloride or ferric nitrate, and the soluble cobalt salt includes cobalt chloride or cobalt nitrate;
[0017] In step B, the stirring time is 6 - 10 h, and the stirring speed is 200 - 300 r / min.
[0018] Preferably, the drying temperature in step (3) is 60 - 80 °C, the drying time is 5 - 7 h, and the pyrolysis treatment method is: heating to 550 - 650 °C at a heating rate of 4 - 6 °C / min, maintaining for 40 - 80 min, and naturally cooling to room temperature; the pyrolysis treatment is carried out in a nitrogen atmosphere, and the nitrogen flow rate is 180 - 220 mL / min.
[0019] Preferably, the washing method in step (4) is: washing several times with water to remove ash, the drying temperature is 60 - 80 °C, and an 80 - 120 mesh sieve is used for sieving.
[0020] The present invention also provides a composite biochar catalyst prepared by the above preparation method.
[0021] The present invention also provides the application of the composite biochar catalyst in treating antibiotic wastewater.
[0022] The present invention also provides a method for treating antibiotic wastewater using the composite biochar catalyst, including the following steps: putting the composite biochar catalyst into the wastewater containing antibiotics, and then adding an oxidant, and obtaining the treated wastewater after the reaction.
[0023] Preferably, the concentration of the composite biochar catalyst in the wastewater is 100 - 600 mg / L, the concentration of the oxidant is 2 - 10 mM, the type of the oxidant is persulfate, peracetic acid or hydrogen peroxide, the temperature of the reaction is 20 - 30 °C, the time is 1 - 2 h, stirring is carried out during the reaction, the rotation speed of the stirring is 200 - 300 r / min, and the type of the antibiotic is tetracycline.
[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0025] (1) The preparation method of a supported iron-cobalt orange peel composite biochar catalyst provided by the present invention uses orange peel as a carrier to load bimetals to prepare an iron-cobalt orange peel composite biochar catalyst. The carbonization treatment makes the surface of the catalyst have a large specific surface area and abundant functional groups, which can effectively disperse metal particles and reduce metal ion leaching, and can efficiently activate various oxidants for degrading tetracycline.
[0026] (2) The copper-cobalt bimetal has double active sites, can provide higher catalytic activity, and obtain better degradation effects. The supported iron-cobalt orange peel composite biochar catalyst prepared by the present invention has the advantages of low raw material cost and high economic benefits, providing a new idea for the disposal and recycling of antibiotic wastewater.
[0027] (3) In the present invention, when the supported iron-cobalt orange peel composite biochar catalyst is used to degrade dyes in the presence of various anions, it can also exhibit high catalytic activity; at the same time, when the catalyst degrades antibiotic wastewater in the pH range of 3 - 10, it can all exhibit high catalytic activity, having the advantage of a wide adaptation range. Description of the Drawings
[0028] Figure 1 It is the change curve of the removal rate of tetracycline with time under different catalyst systems in Examples 1 - 4 of the present invention.
[0029] Figure 2 It is the change curve of the removal rate of tetracycline with time under different oxidant systems in Examples 8 - 10 of the present invention. Detailed Embodiments
[0030] The present invention provides a preparation method of a composite biochar catalyst, including the following steps:
[0031] (1) The biochar raw material is dried and then crushed, and the raw material powder is obtained after sieving;
[0032] (2) A soluble iron salt, a soluble cobalt salt, the raw material powder and water are mixed to obtain a mixture;
[0033] (3) The mixture is dried and then crushed, and a carbonized product is obtained after pyrolysis treatment;
[0034] (4) Wash the carbonized product, dry it, crush it, and then sieve it to obtain the composite biochar catalyst.
[0035] In the present invention, the biochar raw material in step (1) is preferably the peel of citrus fruits. The drying temperature is preferably 60 - 80 °C, more preferably 70 °C. The drying time is preferably 5 - 7 h, more preferably 6 h. When sieving, it is preferably carried out with a sieve of 80 - 120 mesh, more preferably with a 100 - mesh sieve.
[0036] In the present invention, the dosage ratio of the soluble iron salt, soluble cobalt salt, raw material powder, and water in step (2) is preferably 0.8 - 1.2 g : 1 - 1.3 g : 1.5 - 2.5 g : 45 - 55 mL, more preferably 1 g : 1.14 g : 2 g : 50 mL.
[0037] In the present invention, the mixing step in step (2) is preferably as follows:
[0038] A. Dissolve the soluble iron salt and soluble cobalt salt in water to obtain a mixed solution;
[0039] B. Add the raw material powder to the mixed solution and stir.
[0040] In step A, the soluble iron salt and soluble cobalt salt are preferably used in a ratio of Fe:Co molar ratio of 1:1 - 3:1, more preferably in a ratio of Fe:Co molar ratio of 2:1. The soluble iron salt preferably includes ferric chloride or ferric nitrate, and the soluble cobalt salt preferably includes cobalt chloride or cobalt nitrate.
[0041] In step B, the stirring time is preferably 6 - 10 h, more preferably 8 h, and the stirring speed is preferably 200 - 300 r / min, more preferably 250 r / min.
[0042] In the present invention, the drying temperature in step (3) is preferably 60 - 80 °C, more preferably 70 °C. The drying time is preferably 5 - 7 h, more preferably 6 h. The pyrolysis treatment method is preferably: heating to 550 - 650 °C at a heating rate of 4 - 6 °C / min, maintaining for 40 - 80 min, and then naturally cooling to room temperature. More preferably: heating to 600 °C at a heating rate of 5 °C / min, maintaining for 60 min, and then naturally cooling to room temperature. The pyrolysis treatment process is preferably carried out in a nitrogen atmosphere, and the nitrogen flow rate is preferably 180 - 220 mL / min, more preferably 200 mL / min.
[0043] In the present invention, the washing method in step (4) is preferably: washing several times with water to remove ash, the drying temperature is 60 - 80°C, more preferably 70°C, and when sieving, an 80 - 120 mesh sieve is used, more preferably a 100 mesh sieve.
[0044] The present invention also provides a composite biochar catalyst prepared by the above preparation method.
[0045] The present invention also provides the application of the composite biochar catalyst in treating antibiotic wastewater.
[0046] The present invention also provides a method for treating antibiotic wastewater using the composite biochar catalyst, comprising the following steps: putting the composite biochar catalyst into the wastewater containing antibiotics, then adding an oxidant, and obtaining the treated wastewater after the reaction.
[0047] In the present invention, the concentration of the composite biochar catalyst in the wastewater is preferably 100 - 600 mg / L, more preferably 200 - 300 mg / L, the concentration of the oxidant is preferably 2 - 10 mM, more preferably 5 - 6 mM, the type of the oxidant is preferably persulfate, peracetic acid or hydrogen peroxide, the reaction temperature is preferably 20 - 30°C, more preferably 25°C, the reaction time is preferably 1 - 2 h, more preferably 1.5 h, stirring is preferably carried out during the reaction, the stirring speed is preferably 200 - 300 r / min, more preferably 250 r / min, and the type of the antibiotic is preferably tetracycline.
[0048] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0049] Example 1
[0050] This example provides a preparation method of an iron-cobalt loaded orange peel composite biochar catalyst Fe-Co@OPC, comprising the following steps:
[0051] Step 1: After washing the citrus peel with water, it is dried, crushed, and sieved in sequence to obtain citrus peel powder.
[0052] Step 2: Take 1 g of FeCl 3 ·6H 2 O, 1.14 g of CoCl 2 ·6H 2 O and 2 g of citrus peel powder, and add them to 50 mL of deionized water in sequence, continuously stir for 6 h, and the stirring speed is 200 r / min.
[0053] Step 3: Dry the obtained solid at 60 °C, transfer it to a crucible, and place it in a tube furnace for calcination at 600 °C for 6 h. The heating rate of the tube furnace is 5 °C / min, and the nitrogen flow rate is 200 mL / min.
[0054] Step 4: Wash the calcined solid with deionized water, dry it, and grind it into a uniform powder to obtain Fe-Co@OPC for standby.
[0055] Example 2
[0056] This example provides a preparation method of an orange peel biochar catalyst OPC, including the following steps:
[0057] Step 1: Wash the peel of citrus fruits with water, and then dry, crush, and sieve it in sequence to obtain citrus peel powder.
[0058] Step 2: Transfer the citrus peel powder to a crucible, and place it in a tube furnace for calcination at 600 °C for 6 h. The heating rate of the tube furnace is 5 °C / min, and the nitrogen flow rate is 200 mL / min.
[0059] Step 3: Wash the calcined solid with deionized water, dry it, and grind it into a uniform powder to obtain OPC for standby.
[0060] Example 3
[0061] This example provides a preparation method of an iron-loaded orange peel composite biochar catalyst Fe@OPC, including the following steps:
[0062] Step 1: Wash the peel of citrus fruits with water, and then dry, crush, and sieve it in sequence to obtain citrus peel powder.
[0063] Step 2: Take 1 g of FeCl 3 ·6H 2 O and 2 g of citrus peel powder, and add them to 50 mL of deionized water in sequence, and continuously stir for 6 h at a stirring speed of 200 r / min.
[0064] Step 3: Dry the obtained solid at 60 °C, transfer it to a crucible, and place it in a tube furnace for calcination at 600 °C for 6 h. The heating rate of the tube furnace is 5 °C / min, and the nitrogen flow rate is 200 mL / min.
[0065] Step 4: Wash the calcined solid with deionized water, dry it, and grind it into a uniform powder to obtain Fe@OPC for standby.
[0066] Example 4
[0067] This example provides a preparation method of a cobalt-loaded orange peel composite biochar catalyst Co@OPC, including the following steps:
[0068] Step 1: After washing the citrus peel with water, dry it, crush it, and sieve it in sequence to obtain citrus peel powder.
[0069] Step 2: Take 1.14 g of CoCl 2 ·6H 2 O and 2 g of citrus peel powder, add them to 50 mL of deionized water in sequence, continuously stir for 6 h, and the stirring speed is 200 r / min.
[0070] Step 3: Dry the obtained solid at 60 °C, transfer it to a crucible, and place it in a tube furnace for calcination at 600 °C for 6 h. The heating rate of the tube furnace is 5 °C / min, and the nitrogen flow rate is 200 mL / min.
[0071] Step 4: Wash the calcined solid with deionized water, dry it, and grind it into a uniform powder to prepare Co@OPC for standby.
[0072] Example 5
[0073] Take 100 mL of tetracycline wastewater containing 20 mg / L, add 0.2 g / L of the catalyst in Example 1, add 2 mM of PMS, keep the temperature at 25 °C, and react for 60 min.
[0074] Example 6
[0075] Take 100 mL of tetracycline wastewater containing 20 mg / L, add 0.2 g / L of the catalyst in Example 2, add 2 mM of PMS, keep the temperature at 25 °C, and react for 60 min.
[0076] Example 7
[0077] Take 100 mL of tetracycline wastewater containing 20 mg / L, add 0.2 g / L of the catalyst in Example 3, add 2 mM of PMS, keep the temperature at 25 °C, and react for 60 min.
[0078] Example 8
[0079] Take 100 mL of tetracycline wastewater containing 20 mg / L, add 0.2 g / L of the catalyst in Example 4, add 2 mM of PMS, keep the temperature at 25 °C, and react for 60 min.
[0080] Example 9
[0081] Take 100 mL of tetracycline wastewater containing 20 mg / L, add 0.2 g / L of the catalyst in Example 1, add 2 mM of H2O2, keep the temperature at 25 °C, and react for 60 min.
[0082] Example 10
[0083] Take 100 mL of tetracycline wastewater containing 20 mg / L, add 0.2 g / L of the catalyst of Example 1, add 2 mM PAA, keep the temperature at 25 °C, and react for 60 min.
[0084] Application Example
[0085] Prepare multiple aqueous solutions with a tetracycline concentration of 20 mg / L. Take 20 mg of the catalysts prepared in Example 1 and Comparative Examples 1-3 respectively and add them to 100 mL of the above solution. Then add 2 mM of the oxidant respectively. Under the conditions of a temperature of 25 °C and a stirring speed of 200 r / min, the reaction time is 60 min. Test the change in the concentration of the tetracycline solution under different catalyst systems of Example 1 and Comparative Examples 4-6, and calculate the degradation rate of tetracycline.
[0086] Figure 1 This is the change curve of the removal rate of tetracycline with time under different catalyst systems of Examples 1-4 of the present invention. From Figure 1 It can be seen that in Example 2, the pure orange peel biochar OPC has poor catalytic degradation ability for tetracycline, and the degradation rate within 60 min is only 11.6%; in Example 3, the orange peel composite biochar catalyst Fe@OPC loaded with metal iron alone has a tetracycline degradation rate of 42.7% within 60 min; in Example 4, the orange peel composite biochar catalyst Co@OPC loaded with metal cobalt alone has a tetracycline degradation rate of 59.1% within 60 min. In contrast, Example 1 of the present application adopts a dual-metal loading scheme, and the prepared Fe-Co@OPC has significantly better catalytic degradation performance than Examples 2-4, and the degradation rate can reach more than 90% within 60 min.
[0087] Figure 2 This is the change curve of the removal rate of tetracycline with time under different oxidant systems of Examples 8-10 of the present invention. From Figure 2 It can be seen that in Example 8, Fe-Co@OPC activates PMS and degrades 96% of tetracycline within 60 min; in Example 9, Fe-Co@OPC activates H 2 O 2 and degrades 89% of tetracycline within 60 min; in Example 10, Fe-Co@OPC activates PAA and degrades 88% of tetracycline within 60 min.
[0088] The above experimental data show that metal modification significantly improves the catalytic activity, and Fe-Co@OPC can efficiently activate PMS, H 2 O 2 and PAA to degrade tetracycline, and the degradation rate reaches more than 85%.
[0089] As can be seen from the above embodiments, the present invention provides a composite biochar catalyst, a preparation method thereof, and an application in the oxidative degradation of antibiotic wastewater. The preparation method includes the following steps: (1) drying and pulverizing the raw materials for preparing biochar, and obtaining raw material powder after sieving; (2) mixing soluble iron salt, soluble cobalt salt, raw material powder and water to obtain a mixture; (3) drying and pulverizing the mixture, and obtaining a carbonized product after pyrolysis treatment; (4) washing and drying the carbonized product to obtain a composite biochar catalyst. The catalyst of the present invention uses waste citrus peel as raw material, impregnates and loads iron-cobalt bimetallic active components, and forms an Fe-Co / OPC composite biochar catalyst after high-temperature pyrolysis. It can efficiently activate three oxidants, namely persulfate, hydrogen peroxide and peroxyacetate, effectively degrade tetracycline pollutants, and its preparation method is simple, the raw material source is wide, the price is low, it is not easy to cause secondary pollution, realizes the resource utilization of agricultural waste, and provides a high-efficiency and low-cost technical solution for treating antibiotic wastewater.
[0090] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims
1. A method for preparing a composite biochar catalyst, characterized in that: The steps include: (1) drying the biochar raw material, crushing it, and sieving it to obtain raw material powder; (2) mixing a soluble iron salt, a soluble cobalt salt, a raw material powder and water to obtain a mixture; (3) drying the mixture, crushing it, and subjecting it to pyrolysis treatment to obtain a carbonized product; (4) The carbonized product is washed, dried, crushed, and sieved to obtain a composite biochar catalyst.
2. The method according to claim 1, characterized in that In step (1), the biochar raw material is citrus peel, the drying temperature is 60-80° C., the drying time is 5-7 hours, and an 80-120 mesh sieve is used for sieving.
3. The method according to claim 2, characterized in that The usage ratio of the soluble iron salt, the soluble cobalt salt, the raw material powder and the water in step (2) is 0.8-1.2 g: 1-1.3 g: 1.5-2.5 g: 45-55 mL.
4. The method according to claim 2, characterized in that: The mixing step in step (2) is: A. dissolving a soluble iron salt and a soluble cobalt salt in water to obtain a mixed solution; B. Add the raw material powder into the mixed solution and stir; The soluble iron salt and the soluble cobalt salt in step A are used in a Fe:Co molar ratio of 1:1 to 3:1; the soluble iron salt includes ferric chloride or ferric nitrate, and the soluble cobalt salt includes cobalt chloride or cobalt nitrate; The stirring time in step B is 6 to 10 hours, and the stirring speed is 200 to 300 r / min.
5. The method according to claim 4, characterized in that The drying temperature in step (3) is 60-80°C, the drying time is 5-7h, and the pyrolysis treatment method is: heating to 550-650°C at a heating rate of 4-6°C / min, maintaining for 40-80min, and naturally cooling to room temperature; the pyrolysis treatment is carried out under a nitrogen atmosphere, and the flow rate of the nitrogen is 180-220mL / min.
6. The method according to any one of claims 1 to 5, characterized in that: The washing method in step (4) is: washing with water for several times to remove ash, the drying temperature is 60-80°C, and the sieving is performed using a sieve of 80-120 meshes.
7. The composite biochar catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the composite biochar catalyst according to claim 7 in treating antibiotic wastewater.
9. A method for treating antibiotic wastewater using the composite biochar catalyst according to claim 7, characterized in that: The method comprises the following steps: adding the composite biochar catalyst according to claim 7 into wastewater containing antibiotics, then adding an oxidant, and obtaining treated wastewater after reaction.
10. The method according to claim 9, characterized in that The concentration of the composite biochar catalyst in the wastewater is 100-600 mg / L, the concentration of the oxidant is 2-10 mM, the type of the oxidant is persulfate, peracetic acid or hydrogen peroxide, the reaction temperature is 20-30° C., the time is 1-2 h, stirring is performed during the reaction, the stirring speed is 200-300 r / min, and the type of the antibiotic is tetracycline.