Method for preparing magnetic filler using water supply sludge and application thereof

Abstract

The application discloses a method for preparing magnetic filler by using water supply sludge and application thereof, and comprises the following steps: after the purification of a water supply sludge carbon-based precursor material, a magnetic material precursor rich in Fe elements and a magnetic material precursor rich in Al elements are obtained; taking the precursors as intermediates, preparation of an iron-aluminum-carbon-based magnetic material S9 and preparation of a magnetic plastic matrix S 10 are completed; after the extrusion molding of the magnetic plastic, the magnetic material S9 is filled into the magnetic plastic matrix S 10 to obtain the magnetic filler. The raw material of the application is derived from the water supply sludge, and the magnetic filler is prepared by using the rich iron salt and aluminum salt of the water supply sludge. After the magnetization of the filler, the filler can be combined with a conventional wastewater treatment process, and the removal of COD and chroma in the refractory wastewater is strengthened, and the filler can also be used for the effective removal of antibiotics and antibiotic resistance genes in livestock manure fermentation biogas slurry.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of sludge treatment and disposal, and particularly relates to a method for preparing magnetic filler from water supply sludge and application thereof. BACKGROUND

[0002] Waterworks will produce a large amount of water supply sludge every day, and with the increase of water consumption, the production of sludge is also increasing. How to treat a large amount of water supply sludge has become a problem to be solved.

[0003] As a solid waste to be treated and disposed, water supply sludge is rich in a small amount of organic matter and a large amount of SiO2, iron salt and aluminum salt (iron and aluminum mainly exist in the form of amorphous hydroxide) and other inorganic salts, which limits direct landfill or resource recycling and utilization. The water supply sludge has a certain hardness, a certain porosity and a large specific surface area after dewatering.

[0004] Porous materials loaded with magnetic catalysts have good catalytic performance, and magnetic separation is considered as an efficient technology because of its simplicity, easy separation and operation.

[0005] Based on the above problems, it is necessary to explore more technical methods for fully utilizing water supply sludge recycling, and it is a technology worth developing to prepare magnetic filler from the rich iron salt and aluminum salt. SUMMARY

[0006] The purpose of the present application is to use water supply sludge rich in iron salt and aluminum salt as raw material to modify it to prepare a material with magnetic properties and high catalytic performance.

[0007] To achieve the above purpose, the present application realizes the technical scheme as follows:

[0008] A method for preparing magnetic filler from water supply sludge, the method comprising the following steps:

[0009] A. Purification of water supply sludge carbon-based precursor material

[0010] The solid material after dewatering of the water supply sludge is dried and calcined at high temperature to obtain a water supply sludge carbon-based precursor material S;

[0011] An acid leaching agent is added to the carbon-based precursor material S for acid leaching, and after acid leaching, solid-liquid separation is performed to obtain an acid leaching carbon-based precursor material S1 and an acid leaching liquid W rich in iron and aluminum metal ions;

[0012] The pH of the acid leaching solution W is adjusted with alkali, when the pH is 5.5-6.5, solid precipitate S2 rich in Al(OH)3 is extracted, and after being dissolved in H2SO4, cooling and crystallization are carried out to obtain solid mixture rich in Al2(SO4)3 as magnetic material precursor S3; when the pH is 12.5-13.5, solid precipitate S4 rich in Fe(OH)2 / Fe(OH)3 is extracted, and after being dissolved in HCl, cooling and crystallization are carried out to obtain solid mixture rich in FeCl2 / FeCl3 as magnetic material precursor S5;

[0013] B. Preparation of magnetic material matrix

[0014] (1) The magnetic material precursor S5, the acid leaching carbon-based precursor material S1, NaAc and PEG are mixed in proportion, and then mixed and stirred with ethylene glycol to obtain a mixture S6;

[0015] (2) The mixture S6 is placed in a reaction kettle, and hydrothermal synthesis is completed through high-temperature and high-pressure reaction;

[0016] (3) After the reaction is completed, cooling, solid-liquid separation, washing of the solid phase S7, and drying are carried out to obtain the iron-loaded magnetic sludge carbon-based material S8;

[0017] (4) According to weight parts, 1 / 3-2 / 3 parts of the magnetic material precursor S3 is added to each part of the iron-loaded magnetic sludge carbon-based material S8, and then the mixture is placed in an environment with a temperature of 60-80℃ for 4-6 hours, followed by solid-liquid separation and drying to obtain the iron-aluminum-loaded acid leaching carbonized water treatment sludge magnetic material S9;

[0018] C. Preparation of magnetic plastic matrix

[0019] The magnetic material precursor S5, NaAc and ethylene glycol are uniformly mixed in proportion, and then mixed liquid is obtained through a high-temperature and high-pressure reaction kettle; the mixed liquid is mixed with a plastic matrix and a processing aid, plasticized, molded and magnetized to obtain the magnetic plastic matrix S 10 ;

[0020] D. Preparation of magnetic filler

[0021] The iron-aluminum-loaded acid leaching carbonized magnetic material S9 is filled into the magnetic plastic matrix S 10 to obtain the magnetic filler.

[0022] In an embodiment of the present application, in step A, after mechanical dewatering, the water treatment sludge has a water content of 50-80%, an aluminum element mass fraction of 10-20% and an iron element mass fraction of 7%-15%.

[0023] In an embodiment of the present application, in step A, the drying is preferably carried out at 25-80℃ until the water content is below 30%.

[0024] In one embodiment of the present application, in step A, after drying and grinding, the mixture is sieved, preferably through a 40-80 mesh sieve.

[0025] In one embodiment of the present application, in step A, the calcination is preferably carried out at 280-420°C for 2-4h.

[0026] In one embodiment of the present application, in step A, the acid leaching agent is 2-5 mol / L hydrochloric acid; wherein 5-10 mL of the acid leaching agent is added per gram of the carbon-based precursor material S.

[0027] In one embodiment of the present application, in step A, the mixture is subjected to sufficient acid leaching by ultrasonic treatment, preferably at a power of 60-100W for 1-2h.

[0028] In one embodiment of the present application, in step A, the base used to adjust the pH of the acid leaching solution W is preferably NaOH or ammonia.

[0029] In one embodiment of the present application, in step B(1), the mixing is preferably carried out at room temperature, preferably at 10-40°C, which can be 10°C, 20°C, 30°C or 40°C.

[0030] In one embodiment of the present application, in step B(1), the weight parts of S5, S1, NaAc and PEG are 5-10 parts of S5, 30-50 parts of S1, 20-50 parts of NaAc and 5-10 parts of PEG.

[0031] In one embodiment of the present application, in step B(1), the amount of ethylene glycol is 3-5 times the weight parts of S1.

[0032] In one embodiment of the present application, in step B(2), the mixture S6 is subjected to ultrasonic treatment in a reaction kettle, preferably for 10-20 minutes.

[0033] In one embodiment of the present application, in step B(2), the high-temperature and high-pressure reaction is carried out at a temperature of 160-260°C for 10-15 hours.

[0034] In one embodiment of the present application, in step B(3), the solid-liquid separation can be any method that can separate the solid phase, such as suction filtration or centrifugation; the washing is preferably carried out by alternating ethanol and water, preferably 5-10 times each.

[0035] In an embodiment of the present application, in step B(3), the drying is preferably performed at 45-60℃ for 6-10 hours to complete the drying process, preferably in a vacuum drying oven.

[0036] In an embodiment of the present application, in step B(4), after mixing, the mixture is ultrasonically treated for 10 minutes, and then the mixture is treated at 60-80℃ for 4-6 hours, preferably in a constant temperature shaker.

[0037] In an embodiment of the present application, in step B(4), the solid-liquid separation is preferably performed by magnetic separation, and the drying is preferably performed at 45-60℃ in a vacuum drying oven.

[0038] In an embodiment of the present application, in step B(4), the acid leaching and carbonization of the water treatment sludge magnetic material S9 comprises the following components in percentage by weight: activated components Fe3O4, Fe2O3, Al2O3 and Fe2Al2(SiO4)3, wherein: Fe3O4: 10-15%; Fe2O3: 9-11%; Al2O3: 7-9%; Fe2Al2(SiO4)3: 4-5%, and the balance is an acid leaching and carbonization water treatment sludge-based carrier.

[0039] In an embodiment of the present application, in step C, the mixing ratio of S5, NaAc and ethylene glycol is 1:2:(3-5), respectively.

[0040] In an embodiment of the present application, in step C, the high-temperature and high-pressure reaction is performed for 1-2 hours, and the temperature control range is 120-210℃.

[0041] In an embodiment of the present application, in step C, in order to comprehensively utilize waste, the plastic matrix can be selected from waste plastic matrices, wherein the waste plastic matrix is preferably one or any combination of waste plastics rich in polypropylene (PP), chlorinated polyethylene (CPE), polystyrene (PS), polyethylene glycol, and nylon (PA).

[0042] In an embodiment of the present application, in step C, the processing aid is an organic silane or an organic titanate.

[0043] In an embodiment of the present application, in step C, the mixed solution accounts for 10%-15% of the total mass of the plastic matrix and the processing aid.

[0044] In an embodiment of the present application, in step C, the molding is to make the shape of the acid leaching and carbonization magnetic material S9 that can be filled with iron and aluminum, which can be a cuboid, a cylinder or any other shape that can be filled with a substance.

[0045] In one embodiment of the present application, in step D, the iron-aluminum loaded acid leaching carbonized magnetic material S9 is filled into the magnetic plastic matrix S 10 In one embodiment of the present application, in step D, the iron-aluminum loaded acid leaching carbonized magnetic material S9 is filled into the magnetic plastic matrix S 10 In one embodiment of the present application, in step D, the iron-aluminum loaded acid leaching carbonized magnetic material S9 is filled into the magnetic plastic matrix S

[0046] In one embodiment of the present application, the method specifically comprises the following steps:

[0047] A. Purification of waterworks sludge carbon-based precursor material

[0048] After mechanical dewatering of the waterworks sludge, a solid material with a water content of 50-80%, an aluminum element mass fraction of 10-20%, and an iron element mass fraction of 7-15% is obtained; it is dried at 25-80°C to a water content of less than 30%, ground, sieved through a 40-80 mesh sieve, and calcined at 280-420°C for 2-4h to obtain a waterworks sludge carbon-based precursor material S;

[0049] 5-10mL of acid leaching agent (2-5mol / L hydrochloric acid) is added per gram of carbon-based precursor material S, and the mixture is fully acid leached by ultrasonic, with an ultrasonic power of 60-100W and a time of 1-2h, to obtain an acid leaching carbon-based precursor material S1 and an acid leaching liquid W rich in iron and aluminum metal ions through solid-liquid separation;

[0050] The pH of the acid leaching liquid is adjusted with NaOH or ammonia water, when the pH is 5.5-6.5, a solid precipitate S2 rich in Al(OH)3 is extracted, and after dissolving in H2SO4 and cooling crystallization, a solid mixture rich in Al2(SO4)3 is obtained as a magnetic material precursor S3; when the pH is 12.5-13.5, a solid precipitate S4 rich in Fe(OH)2 / Fe(OH)3 is extracted, and after dissolving in HCl and cooling crystallization, a solid mixture rich in FeCl2 / FeCl3 is obtained as a magnetic material precursor S5;

[0051] B. Preparation of magnetic material matrix

[0052] (1) The magnetic material precursor S5 and the acid leaching carbon-based precursor material S1, NaAc (anhydrous sodium acetate), and PEG (polyethylene glycol) are mixed in proportion and added to ethylene glycol to obtain a mixture S6 by stirring at room temperature;

[0053] 1) The weight parts of S5, S1, NaAc, and PEG are S5 5-10 parts, NaAc 20-50 parts, and PEG 5-10 parts;

[0054] 2) After ultrasonic treatment, the mixture S6 is placed in a reaction kettle made of polytetrafluoroethylene, and hydrothermal synthesis is completed through high-temperature and high-pressure reaction. The ultrasonic treatment time is 10-20 minutes, the high-temperature and high-pressure reaction time is 10-15 hours, and the temperature control range is 160-260℃;

[0055] 3) After cooling to room temperature, the solid-liquid separation is performed, and the solid S7 on the filter membrane is cross-rinsed with ethanol and distilled water for 5-10 times. The solid is placed in a vacuum drying box and dried at 45-60℃ for 6-10 hours to complete the drying process. Finally, the iron-loaded magnetic sludge carbon-based material S8 is obtained;

[0056] 4) According to the weight parts, 1 / 3-2 / 3 parts of the magnetic material precursor S3 is added to each part of the iron-loaded magnetic sludge carbon-based material S8, and the mixture is placed in a solution with a pH of 5.5-6.5 and ultrasonic treated for 10 minutes. The mixture is placed in a constant-temperature shaking table at 60-80℃ for 4-6 hours, separated from water by a magnet, and dried in a vacuum drying box at 45-60℃. The iron and aluminum-loaded acid-leached carbonized water treatment sludge magnetic material S9 is collected, which includes the following components in weight percentage: activated components Fe3O4, Fe2O3, Al2O3 and Fe2Al2(SiO4)3, wherein: Fe3O4: 10-15%; Fe2O3: 9-11%; Al2O3: 7-9%; Fe2Al2(SiO4)3: 4-5%, and the balance is an acid-leached carbonized water treatment sludge-based carrier;

[0057] C. Preparation of magnetic plastic matrix

[0058] The magnetic material precursor S5, NaAc (anhydrous sodium acetate) and ethylene glycol are mixed in proportion and ultrasonic treated to obtain a mixed solution. The mixed solution, waste plastic matrix and processing aids are mixed, plasticized, molded and magnetized to obtain the magnetic plastic matrix S 10 ;

[0059] 1) The mixing ratio of S5, NaAc and ethylene glycol is 1:2:(3-5);

[0060] 2) The high-temperature and high-pressure reaction is performed for 1-2 hours, and the temperature control range is 120-210℃;

[0061] 3) The waste plastic matrix is one or any combination of polypropylene (PP), chlorinated polyethylene (CPE), polystyrene (PS), polyethylene glycol and nylon (PA);

[0062] 4) The processing aid is an organic silane or an organic titanate;

[0063] D. Preparation of magnetic filler

[0064] The iron-aluminum loaded acid leaching carbonized magnetic material S9 is filled into the magnetic plastic matrix S 10 to obtain the magnetic filler.

[0065] The application further provides the magnetic filler prepared by the method.

[0066] The application further provides application of the magnetic filler in sewage treatment.

[0067] In an embodiment of the application, the sewage is preferably sewage or refractory wastewater containing antibiotics and / or resistance genes, including but not limited to livestock manure fermentation biogas.

[0068] In an embodiment of the application, in the application of the magnetic filler in sewage treatment, the filling rate of the filler is 20%-60% measured by volume.

[0069] In an embodiment of the application, the magnetic filler can be used in combination with other water treatment fillers.

[0070] In an embodiment of the application, the filling rate ratio of the magnetic filler to other water treatment fillers is 1-2:1-2.

[0071] The application further provides a sewage treatment device, which comprises the magnetic filler.

[0072] In an embodiment of the application, the sewage treatment device can be a suspended or suspended sewage treatment device.

[0073] Compared with the prior art, the application has the following advantages:

[0074] (1) The carbon-based material is prepared by calcination using water supply sludge as raw material, and Fe3O4, Fe2O3 and Al2O3 are highly dispersed on the carbon-based material by extracting iron and aluminum metal ions through acid leaching, adjusting pH and adding hydrochloric acid and sulfuric acid to obtain FeCl3 and Al2(SO4)3 as precursors, and then synthesizing the magnetic material rich in Fe3O4, Fe2O3, Al2O3 and Fe2Al2(SiO4)3 with catalytic activity by hydrothermal and wet impregnation. 3+ 3+ SiO2 in the water supply sludge forms stable compounds with Fe3O4, Fe2O3 and Al2O3, promoting the high dispersion of Fe3O4, Fe2O3 and Al2O3 on the carbon-based material.

[0075] ​(2) Water supply sludge such as direct land use may cause soil compaction, resulting in reduced soil fertility and certain toxicity to plant growth; and environmental problems may be caused after sanitary landfill and incineration, and a large amount of manpower and material resources are wasted, the entire technical process of the present application does not produce by-products that pollute the environment, and a new technical route for water supply sludge resource is found, and the engineering application value is improved. There is no application technology for preparing magnetic filler from water supply sludge on the market at present, and the removal of COD and color in refractory wastewater currently adopts advanced oxidation and other deep treatment methods, which is expensive and has certain safety hazards, and a sustainable treatment technology is urgently needed, and the magnetic filler prepared from water supply sludge realizes waste treatment with waste in combination with the conventional wastewater treatment process. It can also be used for effective removal of antibiotics and antibiotic resistance genes (ARGs) in livestock and poultry manure fermentation biogas. BRIEF DESCRIPTION OF DRAWINGS

[0076] Figure 1 Process flow chart for preparing magnetic filler from water supply sludge.

[0077] Figure 2 Hysteresis regression line of the magnetic filler prepared in Example 1.

[0078] Figure 3 Filling effect diagram of the magnetic filler prepared in Examples 1-3. DETAILED DESCRIPTION

[0079] The present application will be further illustrated in detail by specific examples, but is not limited to the present application, and is only illustrative.

[0080] Example 1

[0081] The present application provides a method for preparing magnetic filler from water supply sludge, and the specific implementation process is as follows:

[0082] A. Purification of water supply sludge carbon-based precursor material

[0083] After mechanical dewatering of the water supply sludge, a solid material with a water content of 55%, an aluminum element mass fraction of 20%, and an iron element mass fraction of 15% is obtained. It is dried at 70℃ to a water content of less than 30%, ground and sieved through a 50 mesh screen, and calcined at 380℃ for 3h to obtain a water supply sludge carbon-based precursor material S.

[0084] 10mL of acid leaching agent (5mol / L hydrochloric acid) is added to each gram of carbon-based precursor material S, and the mixture is fully acid leached by ultrasonic, the ultrasonic power is 80W, and the time is 2h, and the acid leaching carbon-based precursor material S1 and the iron and aluminum metal ion-rich acid leaching liquid W are obtained by solid-liquid separation;

[0085] The pH of the acid leaching solution is adjusted with NaOH or ammonia water. When the pH is 6, the solid precipitate S2 rich in Al(OH)3 is extracted, and after being dissolved in H2SO4, the solid mixture rich in Al2(SO4)3 is obtained by cooling and crystallization as the precursor of the magnetic material S3; when the pH is 13, the solid precipitate S4 rich in Fe(OH)2 / Fe(OH)3 is extracted, and after being dissolved in HCl, the solid mixture rich in FeCl2 / FeCl3 is obtained by cooling and crystallization as the precursor of the magnetic material S5;

[0086] B. Preparation of the magnetic material matrix

[0087] (1) The magnetic material precursor S5 and the acid leaching carbon-based precursor material S1, NaAc (anhydrous sodium acetate), and PEG (polyethylene glycol) are mixed in a weight ratio of S5:10 parts, NaAc 40 parts, and PEG 10 parts, and added to 30 parts of ethylene glycol for stirring at room temperature to obtain a mixture S6; after ultrasonic treatment of the mixture S6, it is placed in a polytetrafluoroethylene reaction kettle for hydrothermal synthesis through high-temperature and high-pressure reaction, the ultrasonic treatment time is 20 minutes, the high-temperature and high-pressure reaction is 15 hours, and the temperature control is 240°C;

[0088] (2) After cooling to room temperature, it is taken out, and after solid-liquid separation, the solid S7 on the filter membrane is cross-rinsed with ethanol and distilled water for 10 times. It is placed in a vacuum drying box for drying at 60°C for 10 hours to complete the drying process, and finally the iron-loaded magnetic sludge carbon-based material S8 is obtained;

[0089] (3) According to the weight parts, 1 / 3 part of the magnetic material precursor S3 is added to the solution with pH = 6 for each part of the iron-loaded magnetic sludge carbon-based material S8, and after being mixed thoroughly, it is ultrasonically treated for 10 minutes, placed in a constant-temperature shaking bed at 80°C for 4 hours, separated from water by a magnet, and dried in a vacuum drying box at 60°C, and the iron-aluminum-loaded acid leaching carbonized water treatment sludge magnetic material S9 is collected, which includes the following components in weight percentage: acid leaching carbonized water treatment sludge-based carrier 60%; activated components Fe3O4, Fe2O3, Al2O3, and Fe2Al2(SiO4)3, wherein: Fe3O4: 15%; Fe2O3: 11%; Al2O3: 9%; Fe2Al2(SiO4)3: 5%;

[0090] C. Preparation of the magnetic plastic matrix

[0091] The magnetic material precursor S5, NaAc (anhydrous sodium acetate), and ethylene glycol are mixed in a ratio of 1:2:5, ultrasonically treated uniformly, and reacted in a high-temperature and high-pressure reaction kettle for 2 hours to obtain a mixed solution, and the reaction temperature is 200°C; the mixed solution is mixed with a waste plastic matrix rich in polypropylene (PP) and a processing aid organic silane, and the mixed solution accounts for 14% of the total mass of the plastic matrix and the processing aid, and through plasticizing and extrusion molding (such as Figure 3As shown, a plurality of hollow cylinders are presented in communication, the hollow cylinders are arranged in a 4x4 array, the size of the hollow cylinders is: an inner diameter of 4mm, an outer diameter of 8mm, and a length of 2cm, and the magnetic plastic matrix S is obtained by magnetization 10 .

[0092] D. Preparation of the magnetic filler

[0093] The iron-aluminum-loaded acid-leached carbonized magnetic material S9 is filled into the magnetic plastic matrix S 10 to obtain a magnetic filler, and the filling rate is 100%.

[0094] The magnetic filler is used for a method for catalyzing ozone oxidation treatment of refractory wastewater or a method for treating livestock manure fermentation biogas slurry containing antibiotic resistance genes: the filler is made into a suspended filler, the filler layer should be higher than the aeration head by 200mm or more, the filling rate of the filler is 20%-60% measured by volume, and the filler is mixed with other suspended fillers or suspended fillers (see Table 1).

[0095] The magnetic filler is used for catalyzing ozone oxidation treatment of refractory wastewater with a COD concentration of 12000mg / L, and the COD removal rate can reach 98.2% 11 copies / L of livestock manure fermentation biogas slurry containing antibiotic resistance genes, the resistance genes can be reduced by 3.6 logarithmic units, and 200t / h of wastewater or biogas slurry can be treated.

[0096] Example 2

[0097] The method for preparing a magnetic filler from water supply sludge provided by the application is as follows:

[0098] A. Purification of the carbon-based precursor material of the water supply sludge

[0099] After mechanical dewatering of the water supply sludge, a solid material with a water content of 65%, an aluminum element mass fraction of 18%, and an iron element mass fraction of 12% is obtained. The solid material is dried at 50℃ until the water content is less than 30%, ground and sieved through a 60-mesh sieve, and calcined at 320℃ for 1.5h to obtain the carbon-based precursor material S of the water supply sludge.

[0100] 8mL of acid leaching agent (4mol / L hydrochloric acid) is added to each gram of the carbon-based precursor material S, and the mixture is fully acid-leached by ultrasonic, the ultrasonic power is 80W, and the time is 1.5h, and the acid-leached carbon-based precursor material S1 and the iron and aluminum-rich metal ion acid leaching liquid W are obtained by solid-liquid separation;

[0101] The pH of the acid leaching solution is adjusted with NaOH or ammonia water. When the pH is 6, solid precipitate S2 rich in Al(OH)3 is extracted, and after being dissolved in H2SO4, a solid mixture rich in Al2(SO4)3 is obtained by cooling and crystallization as a magnetic material precursor S3; when the pH is 13, solid precipitate S4 rich in Fe(OH)2 / Fe(OH)3 is extracted, and after being dissolved in HCl, a solid mixture rich in FeCl2 / FeCl3 is obtained by cooling and crystallization as a magnetic material precursor S5;

[0102] B. Preparation of magnetic material matrix

[0103] (1) The magnetic material precursor S5 and the acid leaching carbon-based precursor material S1, NaAc (anhydrous sodium acetate), and PEG (polyethylene glycol) are mixed in a weight ratio of S5:7 parts, NaAc 30 parts, and PEG 8 parts, and added to 28 parts of ethylene glycol for stirring at room temperature to obtain a mixture S6; after ultrasonic treatment of the mixture S6, it is placed in a polytetrafluoroethylene reaction kettle for hydrothermal synthesis by high-temperature and high-pressure reaction, the ultrasonic treatment time is 15 minutes, the high-temperature and high-pressure reaction is 12 hours, and the temperature control range is 200°C;

[0104] (2) After cooling to room temperature, it is taken out, and after solid-liquid separation, the solid S7 on the filter membrane is cross-rinsed with ethanol and distilled water for 8 times. It is placed in a vacuum drying box for drying at 50°C for 8 hours to complete the drying process, and finally the iron-loaded magnetic sludge carbon-based material S8 is obtained;

[0105] (3) According to the weight ratio, 2 / 3 parts of the magnetic material precursor S3 are added to the solution with pH = 6 for each part of the iron-loaded magnetic sludge carbon-based material S8, and after being mixed thoroughly, it is ultrasonically treated for 10 minutes, placed in a constant-temperature shaking bed at 70°C for 5 hours, separated from water by a magnet, and dried in a vacuum drying box at 50°C, and the iron-aluminum-loaded acid leaching carbonized water treatment sludge magnetic material S9 is collected, which includes the following components in weight percentage: acid leaching carbonized water treatment sludge-based carrier 65%; activated components Fe3O4, Fe2O3, Al2O3, and Fe2Al2(SiO4)3, wherein: Fe3O4: 12%; Fe2O3: 10.5%; Al2O3: 8%; Fe2Al2(SiO4)3: 4.5%;

[0106] C. Preparation of magnetic plastic matrix

[0107] The magnetic material precursor S5, NaAc (anhydrous sodium acetate) and ethylene glycol are mixed in a ratio of 1:2:4 and uniformly ultrasonicated, and a mixed solution is obtained by reacting in a high-temperature and high-pressure reaction kettle for 1.5 hours, and the reaction temperature is 150°C; the mixed solution is mixed with the waste plastic matrix rich in chlorinated polyethylene (CPE) and a processing aid organic titanate, and the mixed solution accounts for 12% of the total mass of the plastic matrix and the processing aid, and the magnetic plastic matrix S is obtained by plasticizing and extruding (same as in Example 1) and magnetizing 10 .

[0108] D. Preparation of the magnetic filler

[0109] The iron-aluminum-loaded acid-leached carbonized magnetic material S9 is filled into the magnetic plastic matrix S 10 to obtain a magnetic filler, and the filling rate is 100%.

[0110] The magnetic filler is used for catalytic ozone oxidation treatment of refractory wastewater with a COD concentration of 12000 mg / L, and the method is the same as in Example 1, and the COD removal rate can reach 97.3%, and the treatment of livestock and poultry manure fermentation biogas slurry containing antibiotic resistance genes at 10 11 copies / L can reduce the resistance genes by 3.1 logarithmic units, and the wastewater or biogas slurry can be treated at a rate of 180 t / h.

[0111] Example 3

[0112] The method for preparing a magnetic filler from water supply sludge provided by the application is as follows:

[0113] A. Purification of carbon-based precursor material of water supply sludge

[0114] After mechanical dewatering of the water supply sludge, a solid material with a water content of 80%, an aluminum element mass fraction of 13%, and an iron element mass fraction of 8% is obtained. The solid material is dried at 80°C until the water content is less than 30%, ground, sieved through an 80-mesh sieve, and calcined at 420°C for 1 hour to obtain a carbon-based precursor material S of water supply sludge.

[0115] 8 mL of an acid leaching agent (2 mol / L hydrochloric acid) is added to each gram of the carbon-based precursor material S, and the mixture is thoroughly acid-leached by ultrasonic, the ultrasonic power is 100 W, and the time is 1 hour, and an acid-leached carbon-based precursor material S1 and an acid leaching solution W rich in iron and aluminum metal ions are obtained by solid-liquid separation;

[0116] The pH of the acid leaching solution is adjusted with NaOH or ammonia water. When the pH is 6.5, solid precipitate S2 rich in Al(OH)3 is extracted, and after being dissolved in H2SO4, a solid mixture rich in Al2(SO4)3 is obtained by cooling and crystallization as a magnetic material precursor S3; when the pH is 12.5, solid precipitate S4 rich in Fe(OH)2 / Fe(OH)3 is extracted, and after being dissolved in HCl, a solid mixture rich in FeCl2 / FeCl3 is obtained by cooling and crystallization as a magnetic material precursor S5;

[0117] B. Preparation of magnetic material matrix

[0118] (1) The magnetic material precursor S5 and the acid leaching carbon-based precursor material S1, NaAc (anhydrous sodium acetate), and PEG (polyethylene glycol) are mixed in a weight ratio of S5:5 parts, NaAc 20 parts, and PEG 5 parts, and added to 15 parts of ethylene glycol for stirring at room temperature to obtain a mixture S6; after ultrasonic treatment of the mixture S6, it is placed in a polytetrafluoroethylene reaction kettle for hydrothermal synthesis by high-temperature and high-pressure reaction, with an ultrasonic treatment time of 15 minutes and a high-temperature and high-pressure reaction time of 10 hours, and the temperature control range is 180°C;

[0119] (2) After cooling to room temperature, it is taken out, and after solid-liquid separation, the solid S7 on the filter membrane is cross-rinsed with ethanol and distilled water for 8 times. It is placed in a vacuum drying box for drying at 50°C for 8 hours to complete the drying process, and finally the iron-loaded magnetic sludge carbon-based material S8 is obtained;

[0120] (3) According to the weight ratio, 2 / 3 parts of the magnetic material precursor S3 are added to each part of the iron-loaded magnetic sludge carbon-based material S8 into a solution with a pH of 6, mixed thoroughly, ultrasonically treated for 10 minutes, placed in a constant-temperature shaking bed at 70°C for 5 hours, separated from water by a magnet, and dried in a vacuum drying box at 50°C, and the iron-aluminum-loaded acid leaching carbonized water treatment sludge magnetic material S9 is collected, which includes the following components in weight percentage: acid leaching carbonized water treatment sludge-based carrier 70%; activated components Fe3O4, Fe2O3, Al2O3, and Fe2Al2(SiO4)3, wherein: Fe3O4: 10%; Fe2O3: 9%; Al2O3: 7%; Fe2Al2(SiO4)3: 4%;

[0121] C. Preparation of magnetic plastic matrix

[0122] The magnetic material precursor S5, NaAc (anhydrous sodium acetate) and ethylene glycol are mixed in a ratio of 1:2:3 and uniformly ultrasonicated, and a mixed solution is obtained by reacting in a high-temperature and high-pressure reaction kettle for 1.5 hours, with a reaction temperature of 180°C; the mixed solution is mixed with a waste plastic matrix rich in polystyrene (PS) and a processing aid organic titanate, and the mixed solution accounts for 10% of the total mass of the plastic matrix and the processing aid, and the magnetic plastic matrix S is obtained by plasticizing and extruding (as in Example 1) and magnetizing 10 .

[0123] D. Preparation of the magnetic filler

[0124] The iron-aluminum-loaded acid-leaching and carbonization magnetic material S9 is filled into the magnetic plastic matrix S 10 to obtain a magnetic filler, with a filling rate of 100%.

[0125] The magnetic filler is used for catalytic ozone oxidation treatment of refractory wastewater with a COD concentration of 12000 mg / L, and the method is the same as in Example 1, and the COD removal rate can reach 89.5%, and the treatment of livestock and poultry manure fermentation biogas slurry containing antibiotic resistance genes 10 11 copies / L can reduce the resistance genes by 1.8 logarithmic units, and the wastewater or biogas slurry can be treated at a rate of 150 t / h.

[0126] The treatment effects of refractory wastewater COD or ARGs in Examples 1-3 are shown in Table 1.

[0127] Table 1 Comparison of treatment effects of refractory wastewater or ARGs in Examples 1-3 (data after 30°C for 60 days of filler biofilm formation)

[0128]

[0129]

[0130] *MBBR05 filler of Anhui Juntaide Plastic Industry.

[0131] Although the content of the present application has been described in detail through the above preferred embodiments, it should be recognized that the above description should not be considered as a limitation of the present application. After reading the above content, various modifications and alternatives of the present application will be apparent to those skilled in the art. Therefore, the scope of protection of the present application should be defined by the appended claims.

Claims

1. A method for preparing magnetic filler using water treatment sludge, characterized by, The method comprises the following steps: A. Purification of water supply sludge carbon-based precursor material The solid material after dewatering of water supply sludge is dried and calcined at high temperature to obtain a water supply sludge carbon-based precursor material S; An acid leaching agent is added to the carbon-based precursor material S for acid leaching, and after acid leaching, solid-liquid separation is performed to obtain an acid leaching carbon-based precursor material S1 and an acid leaching liquid W rich in iron and aluminum metal ions; The pH of the acid leaching liquid W is adjusted with an alkali, when the pH is 5.5-6.5, solid precipitate S2 rich in Al(OH)3 is extracted, and after being dissolved in H2SO4, cooling and crystallization are performed to obtain a solid mixture rich in Al2(SO4)3 as a magnetic material precursor S3; when the pH is 12.5-13.5, solid precipitate S4 rich in Fe(OH)2 / Fe(OH)3 is extracted, and after being dissolved in HCl, cooling and crystallization are performed to obtain a solid mixture rich in FeCl2 / FeCl3 as a magnetic material precursor S5; B. Preparation of a magnetic material matrix (1) The magnetic material precursor S5, the acid leaching carbon-based precursor material S1, NaAc and PEG are mixed in a certain proportion, and then mixed and stirred with ethylene glycol to obtain a mixture S6; (2) The mixture S6 is placed in a reaction kettle, and hydrothermal synthesis is completed through high-temperature and high-pressure reaction; (3) After the reaction is completed, cooling, solid-liquid separation and washing of the solid phase S7 are performed, and after drying, a magnetic sludge carbon-based material loaded with iron S8 is obtained; (4) According to weight parts, 1 / 3-2 / 3 parts of the magnetic material precursor S3 is added to each part of the magnetic sludge carbon-based material loaded with iron S8 in an aqueous solution with a pH of 5.5-6.5, and after mixing, the mixture is treated in an environment with a temperature of 60-80℃ for 4-6 hours, and then solid-liquid separation and drying are performed to obtain a magnetic material S9 of acid leaching carbonized water supply sludge loaded with iron and aluminum; C. Preparation of a magnetic plastic matrix The magnetic material precursor S5, NaAc and ethylene glycol are uniformly mixed in a certain proportion, and then mixed liquid is obtained through a high-temperature and high-pressure reaction kettle; the mixed liquid, a plastic matrix and a processing aid are mixed, plasticized, shaped and magnetized to obtain a magnetic plastic matrix S10; D. Preparation of a magnetic filler The magnetic filler is obtained by filling the magnetic material S9 of acid leaching carbonized water supply sludge loaded with iron and aluminum into the magnetic plastic matrix S10. The processing aid is an organic silane or an organic titanate. In step A, the solid material obtained after mechanical dewatering of water supply sludge has a water content of 50-80%, an aluminum element mass fraction of 10-20% and an iron element mass fraction of 7-15%.

2. The method of claim 1, wherein, The drying is performed at 25-80℃ until the water content is below 30%; The calcination is performed at 280-420℃ for 2-4h.

3. The method of claim 1, wherein, In step B(1), the weight parts of S5, S1, NaAc and PEG are S5 5-10 parts, S1 30-50 parts, NaAc 20-50 parts and PEG 5-10 parts.

4. The method of claim 1, wherein, In step B(2), the high-temperature and high-pressure reaction is performed at a temperature of 160-260℃ for 10-15 hours.

5. The method according to any one of claims 1 to 4, characterized in that, In step C, the mixing ratio of S5, NaAc and ethylene glycol is 1:2:(3-5) respectively; the high-temperature and high-pressure reaction is performed for 1-2 hours, and the temperature control range is 120-210℃.

6. The method according to any one of claims 1 to 4, characterized in that, In step C, the plastic matrix is a waste plastic matrix, wherein the waste plastic matrix is one or any combination of waste plastics rich in polypropylene, chlorinated polyethylene, polystyrene, polyethylene glycol, and nylon.

7. The magnetic filler prepared by the method of any one of claims 1-6.

8. The use of the magnetic filler of claim 7 in sewage treatment.

9. A sewage treatment apparatus characterised by The device comprises the magnetic filler of claim 7.

Images