CN115805095A - High-specific-surface-area porous composite photocatalyst, preparation method, integrated treatment system and treatment method - Google Patents
High-specific-surface-area porous composite photocatalyst, preparation method, integrated treatment system and treatment method Download PDFInfo
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- CN115805095A CN115805095A CN202211588893.7A CN202211588893A CN115805095A CN 115805095 A CN115805095 A CN 115805095A CN 202211588893 A CN202211588893 A CN 202211588893A CN 115805095 A CN115805095 A CN 115805095A
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Abstract
The invention discloses a porous composite photocatalyst with high specific surface area, a preparation method, an integrated treatment system and a treatment method thereof, wherein the general formula of the composite photocatalyst is LaCu x Ti 1‑x O 3 /yP‑S‑g‑C 3 N 4 Wherein x is 0.1-0.5, y is 0.5-0.9, active material LaCu x Ti 1‑x O 3 Is Cu ion doped modified LaTiO 3 Prepared by preparing the active substance with multiple poresStripping of P-S-g-C 3 N 4 Is P, S codoped modified g-C 3 N 4 And (4) preparing. The perovskite material is compounded with the modified carbon nitride, so that the electronic structure of the perovskite material is changed to increase the photocatalysis effect, the recombination of photon-generated carriers is inhibited, more active sites of perovskite are exposed, the traditional Fenton method and the photocatalysis method are coupled, and the wastewater processed by the biological product preparation with ultrahigh COD is degraded through an integrated treatment system matched with the catalyst, and the degradation rate is over 60 percent.
Description
Technical Field
The invention relates to a high-specific-surface-area porous composite photocatalyst, a preparation method, an integrated treatment system and a treatment method, in particular to a high-specific-surface-area composite photocatalyst which is large in specific surface area, high in stability, high in photocatalytic activity and high in charge separation efficiency and is used for degrading ultra-high COD biological product preparation processing wastewater, a preparation method, a modular integrated treatment system and a wastewater treatment method, and belongs to the technical field of photocatalysis and wastewater treatment.
Background
Coenzyme Q10 (Coenzyme Q10, also called as decene quinone and ubiquinone) is a Coenzyme of oxidoreductase existing on the inner membrane of cell mitochondria, and a great deal of research on medical value, clinical application and other aspects of the Coenzyme Q10 is carried out successively at home and abroad in recent years, and the Coenzyme Q10 is widely applied to the aspects of heart protection, hypertension reduction, oxidation resistance and the like. The animal cell extraction method for extracting coenzyme Q10 is one of the first production processes adopted in the world, and mainly extracts target substances from animal organs such as pig hearts, cow hearts and the like. The content of coenzyme Q10 in the beef heart is as high as 85nmol/g, which is the best choice for extracting the coenzyme Q10, and the beef heart extract wastewater, which is used as the derivative wastewater of the method, can generate various inorganic salts, organic solvents and other pollution components in the extraction process, including organic alcohols, organic aldehydes, organic esters and organic amines, and meanwhile, the wastewater has the characteristics of large water quality fluctuation, complex components, high salt and high COD, and is animal viscera biological product processing wastewater which is difficult to treat. These waste waters, if left untreated to their standards, flow into the environment, are subject to constant harm to living organisms and, because of their chemical stability and difficulty in biodegradation, tend to accumulate and diffuse in the environment. Long-term exposure to such waste water can cause unpredictable damage to human target organs and biological communities, and in particular can cause pathogens to generate resistance genes, which seriously jeopardize human health and environmental safety.
At present, the commonly used method for treating wastewater of the bovine heart extract mainly comprises the following steps: biological treatment, ozone oxidation, wet oxidation and homogeneous Fenton oxidation. Considering that the ox heart extract wastewater has antibiotic property, and single biological degradation is difficult to be effective, the physicochemical and biological combined method is usually adopted for treatment. Although the ozone oxidation method has a high reaction rate, secondary pollution is generated, the preparation condition and leakage problem of ozone are difficult to solve, the cost is high, and the conditions are harsh. Although the homogeneous Fenton oxidation method has high degradation efficiency, controllable cost and easy operation of a device, the treatment cost of the subsequent iron mud is high, and the consumption of hydrogen peroxide is large. The Fenton method is coupled with the photocatalysis method, has the characteristics of low energy consumption, small pollution, low cost and the like, and is expected to replace the traditional degradation technology to treat the wastewater of the bovine heart extract with ultrahigh COD.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a high-specific-surface-area porous composite photocatalyst LaCu which can effectively degrade processing wastewater of an extra-high COD biological product preparation under the condition of visible light x Ti 1-x O 3 /yP-S-g-C 3 N 4 (ii) a The second purpose of the invention is to provide a preparation method of the porous composite photocatalyst with high specific surface area; the third purpose of the invention is to provide the application of the high specific surface area porous composite photocatalyst in treating the wastewater from the processing of biological products with ultra-high COD; the fourth purpose of the invention is to provide a modular integrated treatment system for treating the ultra-high COD biological product preparation processing wastewater by using the high-specific surface area porous composite photocatalyst; the fifth purpose of the invention is to provide a method for treating the processing wastewater of the biological product preparation with ultra-high COD by utilizing the special equipment and the porous composite photocatalyst with high specific surface area.
The technical scheme is as follows: the general formula of the high-specific surface area porous composite photocatalyst is LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4 Wherein x is 0.1-0.5, y is 0.5-0.9, active material LaCu x Ti 1-x O 3 Is prepared by doping Cu ions to modify LaTiO 3 Preparation of active substance P-S-g-C 3 N 4 Is co-doped modified g-C by P, S 3 N 4 And (4) preparing.
The preparation method of the porous composite photocatalyst with high specific surface area comprises the following steps:
(1) Preparation of LaCu by low-temperature sol-gel method x Ti 1-x O 3 : dissolving lanthanum nitrate hexahydrate and copper nitrate trihydrate in water, stirring to obtain solution A, dissolving tetrabutyl titanate in isopropanol to obtain solution B, slowly adding solution B into solution A in ice-water bath, adding complexing agent, stirring and mixing, adjusting pH, continuously stirring for reaction, heating for evaporation, drying, grinding to obtain precursor powder, calcining the precursor powder to obtain LaCu x Ti 1-x O 3 ；
(2) Preparation of porous stripped P-S-g-C with high specific surface area by adopting gas template method 3 N 4 : mixing and grinding a nitrogen-rich source, a sulfur source, a phosphorus source and a gas template agent, and calcining the ground powder to obtain porous P-S-g-C 3 N 4 Adding porous P-S-g-C 3 N 4 Placing in dispersant, ultrasonic stripping, centrifuging, drying to obtain porous stripped P-S-g-C 3 N 4 ；
(3) Stripping off the porous P-S-g-C 3 N 4 Dispersing in ethanol, adding LaCu x Ti 1-x O 3 Stirring and mixing evenly, and drying in vacuum to obtain a final product LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4 。
Wherein in the step (1), the molar ratio of the lanthanum nitrate hexahydrate, the copper nitrate trihydrate and the tetrabutyl titanate is 1.
Wherein, in the step (1), the volume ratio of the tetrabutyl titanate to the isopropanol is 1:2-3.
In the step (1), the complexing agent is one of citric acid, polymaleic anhydride, diglycolic acid and succinic acid.
In the step (1), the molar ratio of the total mole of lanthanum, copper and titanium to the complexing agent is 1:1-2.
Wherein, in the step (1), the pH is 2-3.
Wherein in the step (1), the heating evaporation is carried out at the temperature of 60-90 ℃ until a sol-gel product is formed.
Wherein in the step (1), the drying temperature is 100-110 ℃, and the drying time is 20-24h.
Wherein in the step (1), the calcining temperature is 700-750 ℃, and the calcining time is 5-6h.
Wherein in the step (2), the nitrogen-rich source is one of melamine, guanidine hydrochloride and urotropine.
In the step (2), the sulfur source is one of thiourea, 2-thiobarbituric acid and L-cysteine.
In the step (2), the phosphorus source is one of diammonium hydrogen phosphate, ammonium polyphosphate and hexachlorotriphosphazene.
Wherein, in the step (2), the mass ratio of the nitrogen-rich source, the sulfur source and the phosphorus source is 1.
Wherein in the step (2), the calcining temperature is 500-550 ℃, and the calcining time is 2-4h.
Wherein, in the step (2), the gas template agent is ammonium chloride, ammonium carbonate or ammonium bicarbonate.
Wherein in the step (2), the mass ratio of the nitrogen-rich source to the gas template is 1:5-10.
Wherein in the step (2), the dispersant is one of ethanol, isopropanol and acetone.
Wherein, in the step (2), the porous P-S-g-C 3 N 4 The solid-liquid ratio of the dispersant and the dispersant is 3-5mg/mL.
Wherein, in the step (3), the LaCu x Ti 1-x O 3 Stripping with porous P-S-g-C 3 N 4 The mass ratio is 1,
wherein, in the step (3), the temperature of the vacuum drying is 100-110 ℃, and the time of the vacuum drying is 20-24h.
LaCu prepared by the invention x Ti 1-x O 3 /yP-S-g-C 3 N 4 The porous composite photocatalyst with high specific surface area simultaneously has Fenton-like oxidation catalytic activity and photocatalytic activity. The Fenton-like oxidation catalytic activity is mainly composed of LaCu x Ti 1-x O 3 Provided that the photocatalytic activity is mainly P-S-g-C 3 N 4 Provided is a method. In the preparation of LaCu x Ti 1-x O 3 When in monomer, perovskite LaTiO is doped by copper ions 3 The B site cation of the catalyst introduces cation with Fenton-like reaction activity, so that metal ions and lattice oxygen become active sites for reaction, and meanwhile, the substituted perovskite can keep the crystal structure unchanged, has quite stable mechanical strength, and reduces loss caused by ion dissolution in the using process of the catalyst. And after copper ions are introduced, a symmetry-broken active center is constructed, the hydrogen peroxide molecules with high symmetry are polarized by a local polarization field formed by utilizing the charge density gradient of the active center and the spontaneous driving electron migration through thermodynamics, and the hydrogen peroxide molecules are finally activated under the action of local moment through an electron-rich area, so that the utilization rate of hydrogen peroxide is improved. Deprivation of water molecule H from electron-deficient center 2 The electrons of O oxidize water to OH, and the catalyst surface is like countless micro-primary batteries, and the synergistic system is rich in particles such as electrons, ions, metastable molecules, active free radicals and the like, and oxidizes organic functional groups such as hydroxyl, aldehyde carbonyl, ester carbonyl and the like in the wastewater from the processing of the biological product preparation with the ultrahigh COD. During the preparation process, the type and the proportion of the complexing agent are controlled at low temperature, so that the complexing agent can completely react with metal ions as far as possible, the formed colloid ions have good dispersibility and particle size, and a stable multidentate complex is obtained.
The invention prepares porous stripped P-S-g-C with photoactivity and high specific surface area 3 N 4 . Albeit g-C 3 N 4 The material is a photocatalytic hot door material, but the material has the defects of small specific surface area, high photon-generated carrier recombination rate, narrow visible light response range, low charge transfer speed and the like, and the wide application of the material is severely limited. Porous exfoliation of P-S-g-C 3 N 4 Co-doping of g-C with P, S 3 N 4 Break through g-C 3 N 4 Hydrogen bonding between building blocksThe molecular plane is distorted, causing the charge redistribution of the conjugated system, resulting in the differentiation of the charge distribution. The introduced P, S element has higher electronegativity, electrons can be quickly obtained in the reaction process, the visible light response range is expanded, and the separation speed of electron-hole pairs is accelerated. Meanwhile, a gas template agent is used in the preparation process, a proper amount of gas is generated in the calcining process, so that the catalyst structure tends to be porous and fluffy, the specific surface area of the catalyst structure is increased, ultrasonic stripping is carried out in a dispersing agent, and the Van der Waals force and intermolecular hydrogen bond action between layers of the original bulk phase carbon nitride are broken, so that the layer number of the nanosheets is gradually reduced, and the specific surface area is obviously increased. LaCu x Ti 1-x O 3 And P-S-g-C 3 N 4 After recombination, a special contact interface is constructed between the two catalysts, the energy band structures are staggered, the forbidden band width is reduced, the recombination of photo-generated charges is inhibited, photo-generated electron-hole pairs are effectively separated, the service life is prolonged, and the quantum yield is improved. Meanwhile, the composite photocatalyst has high mechanical strength and good stability after being calcined, can not easily fall off and be inactivated after being prepared into a photocatalytic film, and can be repeatedly used.
LaCu of the invention x Ti 1-x O 3 In the preparation process, the increase of the specific surface area of the catalyst is realized by regulating and controlling the type and the dosage of the complexing agent and controlling the calcining temperature, the agglomeration of nano-ions is reduced, and a series of B-site doped perovskite materials with different mass ratios are prepared; by the pair g-C 3 N 4 The doping modification of (2) adopts non-metal mixed elements to be introduced into a two-dimensional carbon nitride system, thereby changing the band gap structure of the material, increasing the specific surface area and accelerating the separation and transfer of the surface charges of the catalyst. In order to further increase the specific surface area of the carbon nitride material, a gas template agent is introduced when the mixed element doped carbon nitride is prepared, proper types and dosage are researched, and a large amount of gas is generated in the calcining process to enable the catalyst structure to tend to be fluffy and porous; bulk carbon nitride has a specific surface area of less than 10m and is overlapped with each other due to Van der Waals force and intermolecular hydrogen bonding between layers 2 G, in order to increase the specific surface area even furtherThe carbon nitride nanosheets are obtained by stripping with a proper dispersion solvent through an ultrasonic effect, so that hydrogen bonds and van der Waals force between carbon nitride layers are destroyed, the specific surface area is greatly increased, meanwhile, the nanosheets with the reduced particle sizes have enhanced light absorption capacity and light response capacity, the separation of photon-generated carriers is accelerated, and the defects of the traditional bulk-phase carbon nitride are effectively overcome. P-S-g-C 3 N 4 In the preparation process, the specific surface area of the catalyst is increased and the hydrogen bond action and the intermolecular action between carbon nitride layers are weakened by selecting a gas template agent, a sulfur source and a phosphorus source, selecting an ultrasonic dispersion solvent and controlling ultrasonic time. The perovskite material is compounded with the modified carbon nitride, the energy band positions of the two materials are changed, the electronic structures of the two materials are changed to increase the conductivity, the recombination of photon-generated carriers is inhibited, more active sites of the perovskite are exposed, the traditional Fenton method is coupled with the photocatalysis method, and the high-efficiency treatment of various waste water is further realized.
The invention discloses application of a high-specific surface area porous composite photocatalyst in degradation of wastewater from biological preparation processing with ultrahigh COD.
Wherein the processing waste of the biological product preparation with the ultrahigh COD comprises one or more of organic alcohols, organic aldehydes, organic esters and organic amines.
Wherein the COD value of the processing waste of the biological product preparation with the ultrahigh COD is 200000-240000mg/L, and the salt content is 6000-7000mg/L.
The invention also comprises an integrated treatment system for degrading the processing wastewater of the biological product preparation with ultrahigh COD by using the porous composite photocatalyst with high specific surface area, wherein the integrated treatment system comprises a pH adjusting module, a heat exchange module, a premixing module, a photocatalytic reaction module and a desalting module which are sequentially connected; the pH adjusting module comprises an acid liquid storage tank, an alkali liquid storage tank and a pH adjusting and mixing tank, wherein the acid liquid storage tank and the alkali liquid storage tank are respectively communicated with the pH adjusting and mixing tank, a first stirring paddle is arranged at the bottom of the pH adjusting and mixing tank, and a pH online detector is arranged at the top of the pH adjusting and mixing tank; the premixing module comprises an oxidant liquid storage tank and a premixing tank, the oxidant liquid storage tank is communicated with the top of the premixing tank, and a second stirring tank is arranged at the bottom of the premixing tankA paddle; the photocatalytic module is provided with a photocatalytic reaction tank, a light source and a plurality of layers of organic glass plates containing the porous composite photocatalyst with the high specific surface area are arranged in the photocatalytic reaction tank, and a first COD online detection system is arranged at the bottom of the photocatalytic reaction tank; the desalting module is provided with a cation exchange resin device and a CO removing device which are sequentially connected 2 The device comprises a device and an anion exchange resin device, wherein a water outlet of the anion exchange resin device is provided with an electric conduction on-line monitoring system.
The integrated treatment system further comprises an assembled modularized MBR membrane reaction module, the assembled modularized MBR membrane reaction module is communicated with the photocatalytic module and the desalting module respectively, the MBR membrane reaction module comprises an MBR membrane reactor and an air blower, an MBR membrane with a lining is arranged in the MBR membrane reactor, an aeration pipe is arranged at the bottom of the MBR membrane reactor, and the aeration pipe is communicated with the air blower.
Wherein, the MBR membrane reaction module can be assembled according to the requirement of the COD value of the effluent.
The method for degrading the processing wastewater of the biological product preparation with the ultrahigh COD by using the integrated treatment system comprises the following steps:
(1) The method comprises the following steps of putting high-COD biological product preparation processing wastewater into a pH adjusting and mixing tank, turning on a first stirring paddle for stirring, adjusting the pH of the wastewater in the pH adjusting and mixing tank by controlling an acid liquid storage tank or an alkali liquid storage tank, and when a pH on-line detector shows 5.5-8.0, sending the wastewater into a heat exchange module for heat exchange;
(2) The waste water enters the premixing tank after being subjected to heat exchange by the heat exchange module, the oxidant in the oxidant liquid storage tank is controlled to enter the premixing tank, and the second stirring paddle is started to stir and premix;
(3) Feeding the pre-mixed wastewater into a photocatalytic reaction tank, sequentially flowing through a high-transmittance organic glass plate provided with a photocatalytic film prepared by the high-specific-surface-area porous composite photocatalyst in claim 1 from top to bottom, simultaneously turning on a light source to perform photocatalytic degradation reaction, measuring the COD value of the reacted effluent by a first COD online monitor, and if the COD value is less than 100000mg/L, sequentially feeding the wastewater into a cation exchange resin device of a desalting module to remove CO 2 And anion exchange resin apparatus, via electrical conductionAnd discharging the salt from the system after the salt content is detected to be less than 1000mg/L by the online monitoring system.
(4) If the COD value required by the wastewater treatment is less than 10000mg/L, the wastewater after the photocatalytic degradation reaction enters an MBR membrane reactor, an air blower is started to blow air into an aeration pipe, the wastewater stays for 4-5h through the MBR membrane reactor, a second COD online monitor determines that the COD value is less than 10000mg/L, and the wastewater sequentially enters a cation exchange resin device of a desalting module and is subjected to CO removal 2 The device and the anion exchange resin device are discharged out of the system after the salt content is detected to be less than 1000mg/L by the electric conduction on-line monitoring system.
Wherein the solid-liquid ratio of the high-specific surface area porous composite photocatalyst to the ultra-high COD biological product preparation processing wastewater is 30.
Wherein, the acid liquid storage tank is selected from a 10% hydrochloric acid solution, and the alkali liquid storage tank is selected from a 20% sodium hydroxide solution.
The photocatalytic film prepared by the porous composite photocatalyst with the high specific surface area is loaded on the organic glass plate with high transparency in the photocatalytic reaction tank.
The loading mode of the high-transmittance organic glass photocatalyst film plate is as follows: the polysulfone substrate and polyvinylpyrrolidone additive were dissolved in N-methyl-2-pyrrolidone solvent with heating, under magnetic stirring until the solution became transparent. After cooling to room temperature, adding the porous composite photocatalyst with high specific surface area, dispersing the porous composite photocatalyst uniformly under the action of ultrasound, then blowing off by using inert gas to completely degas the solution, coating the solution on a dry and clean high-transparency organic glass plate by using a coating agent, and carefully placing the organic glass plate coated with the photocatalyst film in cold water until the solution is completely solidified to form the photocatalytic film loaded on the high-transparency organic glass plate.
Wherein the volume ratio of the oxidant to the wastewater from the processing of the biological product preparation with ultrahigh COD is 0.15-0.30.
Wherein, the light source is a microwave electrodeless lamp.
Wherein, the resin in the cation exchange resin device is weak acid cation resin, and the resin in the anion exchange resin device is weak base anion resin.
The special system for processing the processing wastewater of the biological product preparation with ultrahigh COD by the high-specific surface area porous composite photocatalyst is based on that the high-specific surface area porous composite photocatalyst of the invention makes full use of hydrogen peroxide to mainly generate OH and O 2 - 、e - And cavities, etc., catalytically oxidize organic pollutants, while the desalting module can remove inorganic salts in the wastewater by using ion exchange resin. The device is specially designed for the wastewater with high COD, the catalyst is coated on the high-transmittance organic glass plate in a film forming manner, the contact area between the catalyst and a reaction substrate is greatly increased, meanwhile, the high-transmittance organic glass can reduce the energy loss caused by light source reflection, and the reaction efficiency is improved. This high transparent organic glass photocatalysis membrane has solved the easy gathering of membrane separation field pollutant and has attached to the problem on surface or membrane pore, and the continuous degradation pollutant of photocatalyst combines together photocatalyst and membrane process, accomplishes the self-cleaning of membrane to realize long-term stable use, realize the high stability of catalyst. Meanwhile, the structure of the polymer membrane is more complex relative to pollutants, and the damage of generated active species to the membrane is selectively prevented, so that the service life of the photocatalytic membrane is prolonged. And this high transparent organic glass photocatalysis diaphragm can integral dismantlement and equipment, is convenient for adjust the load and the board quantity of the catalyst of diaphragm by oneself as required.
The invention relates to a photocatalysis membrane organic glass plate in a special system reaction tank for the matched treatment of extra-high COD biological product preparation processing wastewater, which aims at the characteristics that most of photocatalysts exist in a powder form, are easy to agglomerate in aqueous solution, and simultaneously, the specific surface area is small, so that pollutants cover the surface of the catalyst in the high-COD wastewater, an active center cannot be contacted with a substrate, and the like, the photocatalyst is fixed on a polysulfone membrane substrate, and the agglomeration phenomenon of a common powder catalyst cannot be generated during reaction; meanwhile, aiming at the characteristic of high COD of the wastewater processed by the biological product preparation with ultra-high COD, the designed photocatalyst with the characteristic of high specific surface area can not cause the problem that a substrate can not reach an active site because the substrate wraps a pore channel when the concentration of organic pollutants is high, and the membrane is effectively matched with the photocatalyst with porous high specific surface area, can quickly adsorb an oxidant and the substrate, generates a high-level oxidation reaction on the surface of the catalyst, and greatly and quickly degrades the components of the organic pollutants in the wastewater processed by the biological product preparation with ultra-high COD; meanwhile, the photocatalytic membrane has smaller diffusion resistance, has selective permeability on reactants and micromolecule products, can separate a reaction area from a separation area, selectively permeates micromolecules generated by degradation in a catalyst active area, and enables the concentration of local reactants to be higher, so that the reaction is promoted to be carried out forward in dynamics, the problem of chemical balance is broken through, and the catalytic effect and the reaction rate are greatly improved. The high-transmittance organic glass photocatalytic film solves the problem that pollutants are easy to gather and adhere to the surface or film pores in the field of film separation, the photocatalyst continuously degrades the pollutants, the photocatalyst is combined with the film process, the self-cleaning of the film is completed, the long-term stable use is realized, the high stability of the catalyst is realized, meanwhile, the polymer film is more complex in structure relative to the pollutants, the damage of generated active species to the film is selectively prevented, and the service life of the photocatalytic film is prolonged. And the high-transmittance organic glass photocatalytic membrane can be integrally disassembled and assembled, so that the loading capacity and the number of the plates of the catalyst of the membrane can be adjusted automatically according to requirements.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) The high specific surface area porous composite photocatalyst of the invention is doped with Cu ions and enters LaTiO 3 Introducing Fenton reaction active ions into the B site to enable the B site and lattice oxygen to become active centers, and then co-doping the active centers with P, S to remove the g-C 3 N 4 The combination effectively improves the capability of the photocatalyst in treating the wastewater of the bovine heart extract with extra high COD. After the wastewater passes through the special equipment, the COD removal rate reaches more than 60 percent, and the salt content of the wastewater after the desalination is below 1000 mg/L.
(2) The preparation method of the porous composite photocatalyst with the high specific surface area is simple to operate, the raw materials are easy to obtain, and the cost is low. The method has the advantages of simple required equipment and flexible process.
(3) The porous composite photocatalyst with high specific surface area is fixed on a polysulfone membrane substrate, and the agglomeration phenomenon of a common powder catalyst is avoided during reaction; the porous composite photocatalyst with the characteristic of high specific surface area does not cause the problem that a substrate cannot reach an active site because the substrate wraps a pore channel when the concentration of organic pollutants is high.
(4) The high-specific-surface porous composite photocatalyst is a special matched treatment system for treating the processing wastewater of the biological product preparation with ultrahigh COD, so that the utilization rate of hydrogen peroxide can be increased, and the quantum yield of the catalyst can be improved. The online detection system can effectively detect the treatment condition of waste water, and circulating treatment system can be up to standard to the difficult degradation pollutant multiple treatment simultaneously, and the photocatalysis membrane coating can improve mass transfer efficiency greatly on the high-transparent organic glass, improves the catalytic degradation effect, and the high-transparent organic glass can reduce the light loss simultaneously. The high-transmittance organic glass photocatalytic membrane can be integrally disassembled and assembled, so that the loading capacity and the number of the plates of the catalyst of the membrane can be automatically adjusted according to the requirement.
(5) The assembled modular MBR membrane reaction module can be flexibly assembled into a desalting module according to requirements, and ion exchange resin with high ion exchange capacity, high chemical stability and high wear resistance is adopted, so that the effective treatment of inorganic salt is realized; meanwhile, no gas is generated, secondary pollution caused by gas emission is avoided, and the environment is protected.
Drawings
FIG. 1 is a process flow diagram of a special system for treating wastewater from the processing of biological preparations with ultra-high COD by using the porous composite photocatalyst with high specific surface area;
FIG. 2 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 A photo picture of the composite photocatalyst;
FIG. 3 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 SEM picture of the compound photocatalyst;
FIG. 4 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 A TEM image of the composite photocatalyst;
FIG. 5 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 A BET specific surface area data graph of the composite photocatalyst;
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
As shown in figure 1, the integrated treatment system for degrading the wastewater of the bovine heart extract with the ultra-high COD by using the porous composite photocatalyst with the high specific surface area comprises a pH adjusting module, a heat exchange module, a premixing module, a photocatalytic reaction module, an assembled and modularized MBR membrane reaction module and a desalting module, wherein pipelines are connected among the modules.
Wherein, the pH adjusting module comprises a first one-way valve 1, an acid liquid storage tank 2, an alkali liquid storage tank 3, a first metering pump 5, a pH adjusting mixing tank 10 and a second one-way valve 55, the acid liquid storage tank 2 and the alkali liquid storage tank 3 are communicated with the first metering pump 5 through a first three-way valve 4, and the first metering pump 5 is communicated with the pH adjusting mixing tank 10. The acid liquid storage tank 2 is provided with a first liquid level meter 12, the alkali liquid storage tank 3 is provided with a second liquid level meter 11, the upper part of the pH adjusting and mixing tank 10 is provided with a pH on-line monitor 7, a first safety valve 8, a first pressure gauge 6 and a third liquid level meter 13, the bottom of the pH adjusting and mixing tank 10 is provided with a first stirring paddle 9, and a first one-way valve 1 is communicated with the pH adjusting and mixing tank 10. The communicating bottom of the pH adjusting mixing tank 10 is communicated with a second one-way valve 55.
The heat exchange module comprises a first heat insulation pipe 14, a heat exchanger 15 and a second heat insulation pipe 16 which are connected in sequence; the pH adjusting mixing tank 10 is communicated with the first heat insulating pipe 14 through a second one-way valve 55.
The premixing module comprises an oxidant liquid storage tank 26, a second metering pump 27 and a premixing tank 21 which are sequentially communicated, wherein the premixing tank 21 is provided with a fourth liquid level meter 20, the bottom of the premixing tank 21 is provided with a second stirring paddle 19, and the top of the premixing tank 21 is provided with a second safety valve 18 and a second pressure gauge 17; the oxidant storage tank 26 is provided with a fifth liquid level meter 25, the top of the oxidant storage tank 26 is provided with a third safety valve 23 and a third pressure gauge 24, the oxidant storage tank 26 is communicated with a second metering pump 27 through a third one-way valve 56, and a second heat-insulating pipe 16 is communicated with the premixing tank 21.
The photocatalytic reaction module comprises a first liquid inlet pump 22, a second three-way valve 28, a photocatalytic reaction tank 32, a first COD online monitor 34 and a third one-way valve 35, wherein the top of the photocatalytic reaction tank 32 is provided with two liquid inlets, a fourth safety valve 30 and a fourth pressure gauge 29, and the top of the photocatalytic reaction tank 32 extends inwards to form a light source 33. The photocatalytic reaction tank 32 is internally provided with a plurality of layers of organic glass plates 31 containing the high-specific-surface-area porous composite photocatalyst, the organic glass plates 31 are formed by coating the high-specific-surface-area porous composite photocatalyst film on high-transmittance organic glass, are fixed by support rings installed by bolts at an angle of 5 degrees and are distributed in the photocatalytic reaction tank 32 from top to bottom, a light source 33 is a microwave electrodeless lamp, and the outer side of the microwave electrodeless lamp is sleeved with a quartz sleeve; the first liquid inlet pump 22 is communicated with two liquid inlets at the top of the photocatalytic reaction tank 32 through a second three-way valve 28. The first COD online monitor 34 is arranged on the water outlet pipeline of the photocatalytic reaction tank 32, and the third one-way valve 35 is communicated with the first COD online monitor 34.
The desalination module comprises a fourth three-way valve 59, a third liquid inlet pump 43, a cation exchange resin column 45 and a CO removal device which are sequentially communicated 2 A device 48, a fourth liquid inlet pump 49, an anion exchange resin column 52, an electric conduction on-line monitoring system 53 and a fifth one-way valve 54, wherein the top of the cation exchange resin column 45 is provided with a first regenerant liquid inlet 44, the bottom of the cation exchange resin column 45 is provided with a first liquid outlet 57, the top of the anion exchange resin column 52 is provided with a second regenerant liquid inlet 50, the bottom of the anion exchange resin column 52 is provided with a second liquid outlet 51 for removing CO 2 An air inlet 46 is provided at the top of the device 48 for removing CO 2 CO is arranged at the bottom of the device 48 2 And an air outlet 47. The conductivity on-line monitoring system 53 is in communication with the fifth check valve 54, and the third check valve 35 is in communication with the third feed pump 43.
Wherein, the acid in the acid liquid storage tank 2 is a 10% hydrochloric acid solution, the alkali in the alkali liquid storage tank 3 is a 20% sodium hydroxide solution, and the oxidant in the oxidant liquid storage tank 26 is 30% hydrogen peroxide. The cation exchange resin column 45 is weakly acidic acrylic cation exchange resin, and the anion exchange resin column 52 is weakly basic styrene anion exchange resin
The integrated treatment system further comprises an assembled modularized MBR membrane reaction module, and the assembled modularized MBR membrane reaction module is respectively communicated with the photocatalytic reaction module and the desalting module. The assembled modular MBR membrane reaction module comprises a second liquid inlet pump 36, an MBR membrane reactor 37, a third three-way valve 38, a fourth one-way valve 41, a blower 40 and a second COD online monitor 42, wherein multiple groups of MBR membranes 38 with linings are arranged inside the MBR membrane reactor 37, an aeration pipe 39 is arranged at the bottom of the MBR membrane reactor 37, and the aeration pipe 39 is communicated with the blower 40. The second COD on-line monitor 42 communicates with the MBR membrane reactor 37 through a fourth check valve 41. The second COD on-line monitor 42 is in communication with the fourth three-way valve 59 of the desalination module. The third one-way valve 35 of the photocatalytic reaction module is respectively communicated with the second liquid inlet pump 36 and the fourth three-way valve 59 through a third three-way valve 58.
As shown in fig. 1, the method for degrading the ultra-high COD biological preparation processing wastewater by using the above system comprises the steps of opening a first check valve 1, feeding the ultra-high COD biological preparation processing wastewater into a pH adjusting mixing tank 10 with a pH online monitor 7, controlling a first three-way valve 4 and a first metering pump 5, controlling the flow rate of an acid liquid storage tank 2 or an alkali liquid storage tank 3 into the pH adjusting mixing tank 10, opening a stirring paddle 9 for stirring, and closing the first stirring paddle 9 and the first metering pump 5 when the pH is adjusted to 5.5-8.0, observing a first liquid level meter 12 on the acid liquid storage tank 2 or a second liquid level meter 11 on the alkali liquid storage tank 3 in the operation process, so as to avoid the excess or deficiency of the liquid storage, and simultaneously paying attention to control a first safety valve 8, a first pressure meter 6 and a third liquid level meter 20 on the top of the pH adjusting mixing tank 10, thereby ensuring the safe operation. And opening the second check valve 55, enabling the wastewater to flow through the first heat-insulating pipe 14 to enter the heat exchanger 15 for heat exchange, and enabling the wastewater to flow through the second heat-insulating pipe 16 to enter the premixing tank 21 after heat exchange. Meanwhile, the second metering pump 27 and the third one-way valve 56 are opened, 30% of hydrogen peroxide in the oxidant liquid storage tank 26 is controlled to enter the premixing tank 21, the second stirring paddle 19 is opened to stir and mix, the second safety valve 18, the second pressure gauge 17 and the fourth liquid level gauge 20 of the premixing tank 21 are observed in the operation process, the pressure is prevented from being overlarge, and the operation is ensured to be safely carried out. When the addition of hydrogen peroxide to the pre-mix tank 21 is completed, the second metering pump 27, the third check valve 56 anda second paddle 19. The first liquid inlet pump 22 is opened, so that the wastewater flows through the two liquid inlets at the top of the photocatalytic reaction tank 32 through the second three-way valve 28 from top to bottom in sequence through the photocatalytic film high-transmittance organic glass plate 31 prepared by the porous composite photocatalyst with the high specific surface area, and simultaneously the light source 33 of the microwave electrodeless lamp is opened for photocatalytic reaction. The operation process is careful to control the third safety valve 30 and the third pressure gauge 29 of the photocatalytic reaction tank 32, so that the pressure is prevented from being overlarge, and the operation is ensured to be safely carried out. The COD of the effluent after reaction is measured by the first COD on-line monitor 34, if the COD value is less than 100000mg/L, the third three-way valve 58 and the fourth three-way valve 59 are controlled to lead the wastewater to enter the third liquid inlet pump 43, the third liquid inlet pump 43 is opened, the wastewater sequentially enters the cation exchange resin column 45 (the column is filled with weakly acidic acrylic acid cation exchange resin) and the CO is removed 2 48 (air inlet 41, CO) 2 From CO 2 An air outlet 37) and an anion exchange resin column 52 (weak acid styrene anion exchange resin is filled in the column), after the effluent enters an electric conduction on-line monitor 53 to measure the salt content of the effluent to be below 1000mg/L, a fifth one-way valve 54 is opened, the effluent flows out, and the primary wastewater treatment is completed.
After the wastewater is subjected to photocatalytic reaction, the COD value of the wastewater is less than 100000mg/L, and the wastewater can enter a desalting system. If the COD value of the wastewater is less, the wastewater can enter the assembled modularized MBR membrane reaction module by controlling the third three-way valve 58, the fourth one-way valve 35 and the second liquid inlet pump 36 are opened, the wastewater enters the MBR membrane reactor 38, the air blower 40 is simultaneously opened, air is blown into the aeration pipe 39, the wastewater stays for 4 to 5 hours through the MBR membrane reactor, the fifth one-way valve 41 is opened, the reacted wastewater enters the second COD online monitor 42, and if the COD value is less than 10000mg/L, the fourth three-way valve 59 is controlled to enable the wastewater to enter the desalting module for continuous treatment.
If the cation exchange resin column 45 needs resin regeneration, the cation resin regenerant is added from the first regenerant inlet 44, and similarly, if the anion exchange resin column 52 needs resin regeneration, the anion resin regenerant is added from the second regenerant inlet 50 and then flows out from the first liquid outlet 57 and the second liquid outlet 51 respectively.
Example 1
(1)LaCu 0.1 Ti 0.9 O 3 Preparation of
2.165g of lanthanum nitrate hexahydrate and 8978 g of copper nitrate trihydrate were taken out in a molar ratio of 1.1, and dissolved in 250mL of distilled water, and the mixture was stirred uniformly in a constant temperature bath containing ice to obtain solution A. Weighing 1.53g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.9, weighing an isopropanol solvent with the volume ratio of the tetrabutyl titanate of 1:2, and uniformly mixing and stirring the isopropanol solvent with the tetrabutyl titanate to obtain a solution B. The solution B was slowly added dropwise to the solution a in an ice-water bath, and stirring was continued to obtain a mixed solution. 2.1g of citric acid monohydrate is weighed according to the molar ratio of the total metal ion molar amount of lanthanum, copper and titanium to the citric acid monohydrate of 1:1, dissolved in 50mL of distilled water and slowly added into the mixed solution to generate the corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 60 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.1 Ti 0.9 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of nitrogen-rich source melamine, 0.15g of sulfur source thiourea, 0.15g of phosphorus source ammonium dihydrogen phosphate and 7.5g of gas template agent ammonium chloride according to a mass ratio of 1 3 N 4 . Taking a proper amount of formed porous P-S-g-C 3 N 4 Dispersing in ethanol to form porous P-S-g-C 3 N 4 The volume ratio of the mass to the ethanol is 3mg/mL, and the sample is placed in an ultrasonic instrument to work for 10 hours. Obtaining a suspension, centrifuging, drying at 60 ℃ overnight to obtain porous stripped P-S-g-C 3 N 4 。
(3)LaCu 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 Preparation of
Weighing 1g of Lacu prepared in the above manner according to a mass ratio of 1 0.1 Ti 0.9 O 3 And 0.5g of porous exfoliated P-S-g-C 3 N 4 In 30mL ethanol, the mixture is magnetically stirred for 1h and then transferred to a vacuum drying oven for drying at 100 ℃ for 24h. Drying to obtain catalyst powder LaCu 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 。
(4) Adding LaCu 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
Dissolving polysulfone substrate and polyvinylpyrrolidone additive in N-methyl-2-pyrrolidone solvent at 70 deg.C, the mass fraction of polysulfone in the mixed solution is 17%, and the mass fraction of polyvinylpyrrolidone is 0.5%, and magnetically stirring until the solution becomes transparent. After cooling to room temperature, 300g of LaCu were added 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 The photocatalyst is dispersed uniformly under the action of ultrasound for 2 hours, then helium is used for blowing off for 15 hours to completely degas the solution, the solution is coated on a dry and clean high-transparency organic glass plate by using a film coating agent, and the organic glass plate coated with the photocatalyst film is carefully placed in cold water until the organic glass plate is completely solidified to form the photocatalytic film loaded on the high-transparency organic glass plate.
(5) The integrated treatment system and the ultra-high COD biological product preparation processing wastewater catalyst LaCu are utilized 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of processing the biological product preparation with extra high COD, wherein the wastewater of processing the biological product preparation with extra high COD is the wastewater of extracting solution of the beef heart with extra high COD
As shown in figure 1, a first check valve 1 is opened, 10L of high COD cow heart extract wastewater (COD is 240000mg/L, salt content is 7000 mg/L) enters a pH adjusting mixing tank 10 with a pH online monitor 7, a first three-way valve 4 and a first metering pump 5 are controlled, the flow of an alkali liquid storage tank 3 is controlled to enter the pH adjusting mixing tank 10, a first stirring paddle 9 is opened for stirring, when the pH is adjusted to be 5.5-8.0, the first stirring paddle 9 and the first metering pump 5 are closed, a first liquid level meter 12 on an acid liquid storage tank 2 or a first liquid level meter 12 on the alkali liquid storage tank 3 is observed in the operation processThe second level gauge 11 of (2) avoids stock solution excessive or not enough, and the first relief valve 8 at the top of the control pH regulation blending tank 10, the first manometer 6 and the third level gauge 20 are paid attention to simultaneously, guarantee that the operation is carried out safely. And opening the second check valve 55, enabling the wastewater to flow through the first heat-insulating pipe 14 to enter the heat exchanger 15 for heat exchange, and enabling the wastewater to flow through the second heat-insulating pipe 16 to enter the premixing tank 21 after heat exchange. Meanwhile, the second metering pump 27 and the third one-way valve 56 are opened, 30% hydrogen peroxide (1.5L in total) in the oxidant liquid storage tank 26 is controlled to enter the premixing tank 21, the second stirring paddle 19 is opened to stir and mix for 10min, the second safety valve 18, the second pressure gauge 17 and the fourth liquid level gauge 20 of the premixing tank 21 are observed in the operation process, the pressure is prevented from being overlarge, and the operation is ensured to be safely carried out. When the addition of hydrogen peroxide to the premix tank 21 is complete, the second metering pump 27, the third one-way valve 56 and the second paddle 19 are closed. The first liquid inlet pump 22 is opened to make the wastewater flow through the two liquid inlets on the top of the photocatalytic reaction tank 32 from top to bottom in sequence through the second three-way valve 28 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 The prepared photocatalytic film is high in transmittance of the organic glass plate 31, and meanwhile, a light source 33 microwave electrodeless lamp is turned on to perform photocatalytic reaction. The operation process is careful to control the third safety valve 30 and the third pressure gauge 29 of the photocatalytic reaction tank 32, so that the pressure is prevented from being overlarge, and the operation is ensured to be safely carried out. The COD of the effluent after reaction is measured by a first COD on-line monitor 34, if the COD value is less than 100000mg/L, a fourth one-way valve 35 and a third liquid inlet pump 43 are opened, and the wastewater sequentially enters a cation exchange resin column 45 (in which weak acid acrylic cation exchange resin is filled) and is subjected to CO removal by controlling a third three-way valve 58 and a fourth three-way valve 59 2 48 (air inlet 41, CO) 2 From CO 2 An air outlet 37), an anion exchange resin column 52 (weak acid styrene anion exchange resin is arranged in the column), after the effluent enters an electric conduction on-line monitor 53 to measure that the salt content is below 1000mg/L, a fifth one-way valve 54 is opened, the effluent flows out, and the primary wastewater treatment is finished. The results are shown in Table 1.
TABLE 1
Example 2
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of (2)
2.165g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and uniformly stirred in a constant temperature bath containing ice to obtain solution A. Weighing 1.19g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1. The solution B was slowly added dropwise to the solution a in an ice-water bath, and stirring was continued to obtain a mixed solution. 2.1g of citric acid monohydrate is weighed according to the molar ratio of the total metal ion molar amount of lanthanum, copper and titanium to the citric acid monohydrate of 1:1 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate the corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at 70 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at 110 ℃ for 20h, and grinding the product to obtain precursor powder. Heating the precursor powder to 750 ℃ at a speed of 5 ℃/min, preserving heat for 6 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
The same procedure as in step (2) of example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD cow heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 2.
TABLE 2
Example 3
(1)LaCu 0.5 Ti 0.5 O 3 Preparation of
2.165g of lanthanum nitrate hexahydrate and 8978 g of copper nitrate trihydrate were taken out in a molar ratio of 1.5, and dissolved in 250mL of distilled water, and the mixture was stirred uniformly in a constant temperature bath containing ice to obtain solution A. Weighing 0.85g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.5, weighing an isopropanol solvent with the volume ratio of the isopropanol solvent to the tetrabutyl titanate of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain a solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. 2.1g of citric acid monohydrate is weighed according to the molar ratio of the total metal ion molar amount of lanthanum, copper and titanium to the citric acid monohydrate of 1:1 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate the corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 730 ℃ at the speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.5 Ti 0. O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as step (2) in example 1.
(3)LaCu 0.5 Ti 0.5 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.5 Ti 0.5 O 3 /0.5P-S-g-C 3 N 4 Loaded at high permeabilityOn the machine glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.5 Ti 0.5 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 3.
TABLE 3
Example 4
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of the tetrabutyl titanate of 1:2, and uniformly mixing and stirring the isopropanol solvent with the tetrabutyl titanate to obtain solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. And weighing 6.0000g of polymaleic anhydride according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the polymaleic anhydride of 1:1, dissolving in 50mL of distilled water, and slowly adding the mixed solution to generate a corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 90 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
The same procedure as in step (2) of example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N is loaded on the high-transmittance organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L.
TABLE 4
Example 5
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of the isopropanol solvent to the tetrabutyl titanate of 1:2, and mixing and stirring the isopropanol solvent with the tetrabutyl titanate uniformly to obtain a solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. 1.3400g diglycolic acid is weighed according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the diglycolic acid of 1:1 and dissolved in 50mL distilled water, and the mixed solution is slowly added to generate the corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, and preserving heatNaturally cooling for 5h, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
The same procedure as in step (2) of example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 5.
TABLE 5
Example 6
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of the tetrabutyl titanate of 1:2, and uniformly mixing and stirring the isopropanol solvent with the tetrabutyl titanate to obtain solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. 1.1800g of succinic acid is weighed and dissolved in 50mL of distilled water according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the succinic acid being 1.5, and the mixed solution is slowly added to produce the corresponding metal complex. Blending with concentrated ammonia waterThe pH is adjusted to a final value of 2-3 and the suspension formed is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of (2)
The same procedure as in step (2) of example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
Same as step (4) in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 6.
TABLE 6
Example 7
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of the tetrabutyl titanate of 1:2, and uniformly mixing and stirring the isopropanol solvent with the tetrabutyl titanate to obtain solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. Polymaleic anhydride 9.0000g is weighed and dissolved in 50mL of distilled water according to the mole ratio of the total metal ions of lanthanum, copper and titanium to the polymaleic anhydride acid being 1.5, and the mixed solution is slowly added to generate the corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as step (2) in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 7.
TABLE 7
Example 8
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of the tetrabutyl titanate of 1:2, and uniformly mixing and stirring the isopropanol solvent with the tetrabutyl titanate to obtain solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. And weighing 12.0000g of polymaleic anhydride according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the polymaleic anhydride of 1:2, dissolving in 50mL of distilled water, and slowly adding the mixed solution to generate a corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
The same procedure as in step (2) of example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transmittance organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 8.
TABLE 8
Example 9
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of a nitrogen-rich source, 0.15g of a sulfur source, 0.15g of a phosphorus source and 7.5g of a gas template ammonium chloride according to a mass ratio of 1. And (3) dispersing a proper amount of the formed catalyst into ethanol, wherein the volume ratio of the mass of the catalyst to the volume of the solvent is 3mg/mL, and placing the catalyst into an ultrasonic instrument to work for 10 hours. Centrifuging the obtained suspension, and drying at 60 deg.C overnight to obtain desired monomer P-S-g-C 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
Same as step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L.
In order to investigate the influence of the selection of nitrogen-rich source, sulfur source and phosphorus source on the performance of the catalyst, an orthogonal experiment was designed by using SPSS software to studyThe effect and influence of multiple factors on the degradation rate of a dependent variable and the effect of the combined action of these factors. Nitrogen-rich source A 1 : melamine, A 2 : guanidine hydrochloride, A 3 : urotropin; a sulfur source: b is 1 : thiourea, B 2 2-Thiobabituric acid, B 3 : l-cysteine; c 1 : ammonium dihydrogen phosphate, C 2 : ammonium polyphosphate C 3 : the hexachlorotriphosphazene is prepared by generating 9 groups of orthogonal experiments through SPSS software to obtain the degradation rate of the 9 groups of experiments, obtaining the influence of three factors on the catalyst through multi-factor variance analysis, and screening the optimal raw material, wherein the orthogonal experiment results are shown in the following table 9.
TABLE 9
| Experimental group | Carbon source A | Sulfur source B | Phosphorus source C | Degradation Rate (%) |
| Experimental group 1 | A 3 | B 3 | C 1 | 64.94 |
| Experimental group 2 | A 1 | B 2 | C 3 | 72.95 |
| Experimental group 3 | A 3 | B 1 | C 3 | 68.83 |
| Experimental group 4 | A 1 | B 3 | C 2 | 63.38 |
| Experimental group 5 | A 2 | B 3 | C 3 | 67.08 |
| Experimental group 6 | A 3 | B 2 | C 2 | 69.83 |
| Experimental group 7 | A 2 | B 2 | C 1 | 70.38 |
| Experimental group 8 | A 2 | B 1 | C 2 | 65.28 |
| Experimental group 9 | A 1 | B 1 | C 1 | 66.03 |
The results are input into the SPSS software, and after selecting the "general linear model" option, the output multi-factor variance table is shown in table 10 below:
watch 10
According to the result analysis of the table 10, the significance level shows that the main effect of the sulfur source is significant for the factor B, and the P value is less than 0.05, which indicates that the reliability of the result reaches 99.5%; for the factor C, the main effect of the phosphorus source is obvious, and the P value is less than 0.05, which shows that the reliability of the result reaches 99.5%; while for element a, the main effect of the nitrogen-rich source is not significant. The results show that the nitrogen-rich source has no significant effect on the degradation rate, while the sulfur source and the phosphorus source have significant effect on the degradation rate.
The effect of three levels of three factors output by SPSS on degradation rate is shown in tables 11-13 below:
TABLE 11
As can be seen from the degradation rate, the three carbon sources had no significant effect on the degradation rate.
TABLE 12
As can be seen from the degradation rate, the sulfur source has a significant effect on the degradation rate, and the best effect is 2-thiobarbituric acid.
Watch 13
As can be seen from the degradation rate, the sulfur source has a significant influence on the degradation rate, and hexachlorotriphosphazene is the best effect.
In summary, the optimum nitrogen-rich source is selected: urotropin, sulfur source: 2-thiobarbituric acid, a phosphorus source: use of hexachlorotriphosphazene for the preparation of P-S-g-C 3 N 4 。
Example 10
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of urotropin as a nitrogen-rich source, 0.15g of 2-thiobarbituric acid as a sulfur source, 0.15g of hexachlorotriphosphazene and 7.5g of ammonium chloride as a gas template in a mass ratio of 1. And (3) dispersing a proper amount of the formed catalyst into ethanol, wherein the volume ratio of the mass of the catalyst to the volume of the solvent is 3mg/mL, and placing the catalyst into an ultrasonic instrument to work for 10 hours. Centrifuging the obtained suspension, and drying at 60 deg.C overnight to obtain desired monomer P-S-g-C 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of (2)
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transmittance organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 14.
TABLE 14
Example 11
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of nitrogen-rich urotropine, 0.30g of sulfur source 2-thiobarbituric acid, 0.30g of hexachlorotriphosphazene and 11.25g of gas template ammonium carbonate according to a mass ratio of 1. And (3) dispersing a proper amount of the formed catalyst into acetone, wherein the volume ratio of the mass of the catalyst to the volume of the solvent is 3mg/mL, and placing the mixture in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60 deg.C overnight to obtain desired monomer P-S-g-C 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same as in (3) in example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 15.
Example 12
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of urotropin as a nitrogen-rich source, 0.45g of 2-thiobarbituric acid as a sulfur source, 0.45g of hexachlorotriphosphazene and 15g of ammonium bicarbonate as a gas template agent according to a mass ratio of 1. And (3) dispersing a proper amount of the formed catalyst into acetone, wherein the volume ratio of the mass of the catalyst to the volume of the solvent is 3mg/mL, and placing the mixture in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60 deg.C overnight to obtain desired monomer P-S-g-C 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
Same as step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD cow heart extract
The procedure was as in (5) of example 11, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 16.
TABLE 16
Example 13
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of urotropine as a nitrogen-rich source, 0.15g of 2-thiobarbituric acid as a sulfur source, 0.15g of hexachlorotriphosphazene and 15g of ammonium bicarbonate as a gas template agent according to a mass ratio of 1. And (3) dispersing a proper amount of the formed catalyst into isopropanol, wherein the volume ratio of the mass of the catalyst to the volume of the solvent is 3mg/mL, and placing the catalyst in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60 deg.C overnight to obtain the desired monomer P-S-g-C 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
LaCu prepared by the invention 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 The photograph is shown in FIG. 2, which is in powder form.
For LaCu obtained in this example 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 The results of the SEM analysis are shown in FIG. 3. FIG. 3 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 SEM picture of the composite photocatalyst;from FIG. 3a, the morphology of the catalyst, P-S-g-C after stripping can be observed 3 N 4 Is of a nano flaky structure, and the surface of the nano flaky structure is loaded with uneven LaCu 0.3 Ti 0.7 O 3 Particles; as can be seen from FIG. 3b with higher resolution, the catalyst surface has a porous structure, which indicates that the porous nanosheet P-S-g-C growing on the surface is successfully prepared 3 N 4 LaCu of 0.3 Ti 0.7 O 3 A catalyst.
FIG. 5 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 A BET specific surface area data graph of the composite photocatalyst;
for the LaCu obtained in this example 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4. The transmission electron microscopy analysis results are shown in FIG. 4. FIG. 4 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 A TEM image of the composite photocatalyst; as can be seen from FIG. 4, the catalyst is two-dimensionally lamellar, a large amount of LaCu 0.3 Ti 0.7 O 3 Closely attached to P-S-g-C 3 N 4. The surface of the nanoplatelets.
For LaCu obtained in this example 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4. The BET specific surface area analysis was carried out, and the results are shown in FIG. 5. FIG. 5 shows powdery LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 A BET specific surface area data graph of the composite photocatalyst; as can be seen from FIG. 5, the specific surface area is 172.1684m 2 Is much higher than the block g-C 3 N 4 (10m 2 /L), which proves to be a porous catalyst with high specific surface area.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the extrahigh COD cow heart extractWaste water
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 17.
TABLE 17
Example 14
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as in example 13, step (2)
(3)LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 Preparation of
Weighing 1g of LaCu prepared in the mass ratio of 1 0.3 Ti 0.7 O 3 And 0.7g P-S-g-C 3 N 4 In 30mL ethanol, the mixture is magnetically stirred for 1h and then transferred to a vacuum drying oven for drying at 90 ℃ for 24h. Drying to obtain catalyst powder LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 。
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 18.
Watch 18
Example 15
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as in example 13, step (2)
(3)LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 Preparation of
Weighing 1g of Lacu prepared in the above manner according to a mass ratio of 1 0.3 Ti 0.7 O 3 And 0.9g P-S-g-C 3 N 4 In 30mL ethanol, the mixture is magnetically stirred for 1h and then transferred to a vacuum drying oven for drying at 90 ℃ for 24h. Drying to obtain catalyst powder LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 。
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 Loaded on a high-transmittance organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 19.
Watch 19
Example 16
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as in example 13, step (2)
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transmittance organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The treatment process is similar to the step (5) in the same embodiment 1, and the difference is that the dosage of hydrogen peroxide of the photocatalytic reaction module is increased to 3.0L, and the assembled modular MBR membrane reaction module is selectively started after the photocatalytic reaction module. The effluent after the photocatalytic reaction is used for measuring COD by a first COD online monitor 34, if the COD value is less than 100000mg/L, a fourth one-way valve 35 and a second liquid inlet pump 36 are opened, the wastewater enters an MBR membrane reactor 38 by controlling a third three-way valve 58, an air blower 40 is simultaneously opened, air is blown into an aeration pipe 39, the wastewater stays for 4-5 hours through the MBR membrane reactor, a fifth one-way valve 41 is opened, the reacted wastewater enters a second COD online monitor 42, and if the COD value is less than 10000mg/L, a fourth three-way valve 59 is controlled, a third liquid inlet pump 43 is opened, and the wastewater enters a desalting module for continuous treatment. Wherein the initial COD of the wastewater of the extra-high COD bovine heart extract liquid is 240000mg/L, and the salt content is 7000mg/L. The results are shown in Table 20.
Comparative example 1 not doped with Cu ions
(1)LaTiO 3 Preparation of
2.165g of lanthanum nitrate hexahydrate are taken and dissolved in 250mL of distilled water inStirring in a constant temperature tank containing ice to obtain solution A. Weighing 1.700g of tetrabutyl titanate according to the mole ratio 1:1 of lanthanum and titanium ions, weighing an isopropanol solvent with the volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent with tetrabutyl titanate to obtain liquid B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. And weighing 12.0000g of polymaleic anhydride according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the polymaleic anhydride of 1:2, dissolving in 50mL of distilled water, and slowly adding the mixed solution to generate a corresponding metal complex. The pH is adjusted to a final value of 2-3 with concentrated ammonia and the suspension formed is stirred vigorously for 2h in a thermostatic bath at 0 ℃. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the LaTiO monomer 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as in example 13, step (2)
(3)LaTiO 3 /0.5P-S-g-C 3 N 4 Preparation of
Weighing 1g of LaTiO prepared by the above method according to the mass ratio of 1 3 And 0.5g P-S-g-C 3 N 4 In 30mL ethanol, the mixture is magnetically stirred for 1h and then transferred to a vacuum drying oven for drying at 90 ℃ for 24h. Drying to obtain catalyst powder LaTiO 3 /0.5P-S-g-C 3 N 4 。
(4) Mixing LaTiO with water 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transmittance organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaTiO 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 21.
TABLE 21
Comparative example 2 Small amount of complexing agent
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of (2)
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent with tetrabutyl titanate to obtain a solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. 3.0000g of polymaleic anhydride is weighed and dissolved in 50mL of distilled water according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the polymaleic anhydride being 1, and the mixed solution is slowly added to generate the corresponding metal complex. The pH is adjusted to a final value of 2-3 with concentrated ammonia and the suspension formed is stirred vigorously for 2h in a thermostatic bath at 0 ℃. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
The same procedure as in step (2) of example 13.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Handle extra-high COD cow heartLiquid-taking waste water
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 22.
TABLE 22
Comparative example 3 complexing agent in high amount
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
2.1650g lanthanum nitrate hexahydrate and 0.3615g copper nitrate trihydrate are taken according to the mol ratio of 1.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the molar ratio of lanthanum to titanium ions of 1.7, weighing an isopropanol solvent with the volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent with tetrabutyl titanate to obtain a solution B. The solution B was slowly added dropwise to the solution a in an ice water bath, and stirring was continued to obtain a mixed solution. And weighing 18.0000g of polymaleic anhydride according to the molar ratio of the total metal ions of lanthanum, copper and titanium to the polymaleic anhydride of 1:3, dissolving in 50mL of distilled water, and slowly adding the mixed solution to generate a corresponding metal complex. The final pH value is adjusted to 2-3 with strong ammonia water, and the formed suspension is stirred vigorously in a thermostatic bath at 0 ℃ for 2h. Then stirring and evaporating the solvent at the temperature of 80 ℃ in a water bath until a sol-gel product is generated, transferring the sol-gel product to a watch glass, placing the watch glass in an air-blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and grinding the product to obtain precursor powder. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving the heat for 5 hours, naturally cooling, and grinding to obtain the monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
The same procedure as in step (2) of example 13.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
Same as step (4) in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 23.
TABLE 23
Comparative example 4 g-C using undoped P, S 3 N 4
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2)g-C 3 N 4 Preparation of
Weighing 10g of urea, placing the urea in an agate mortar for fully grinding, pouring the urea into a crucible, covering the crucible, transferring the crucible into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, preserving the heat for 4h, and naturally cooling to room temperature.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5g-C 3 N 4 Preparation of
Weighing 1g of Lacu prepared in the above manner according to a mass ratio of 1 0.3 Ti 0.7 O 3 And 0.5g g-C3N4 in 30mL ethanol, magnetically stirring for 1h, transferring to a vacuum drying oven, and drying at 90 ℃ for 24h. Drying to obtain catalyst powder LaCu 0.3 Ti 0.7 O 3 /0.5g-C 3 N 4 。
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 24.
Watch 24
Comparative example 5P-S-g-C having no porous structure without using gas template 3 N 4
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Stripping of P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of urotropin as a nitrogen-rich source, 0.15g of 2-thiobarbituric acid as a sulfur source and 0.15g of hexachlorotriphosphazene according to a mass ratio of 1. And (3) dispersing a proper amount of the formed catalyst into isopropanol, wherein the volume ratio of the mass of the catalyst to the volume of the solvent is 3mg/mL, and placing the catalyst in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60 deg.C overnight to obtain desired monomer P-S-g-C 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 25.
TABLE 25
Comparative example 6 non-ultrasonic-debonded P-S-g-C 3 N 4
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of (2)
Same as in example 8, step (1)
(2) Porous P-S-g-C 3 N 4 Preparation of
Weighing 1.5g of urotropine serving as a nitrogen-rich source, 0.15g of 2-thiobarbituric acid serving as a sulfur source, 0.15g of hexachlorotriphosphazene and 15g of ammonium bicarbonate serving as a gas template agent according to a mass ratio of 1 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same procedure as in step (4) of example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 26
Watch 26
Comparative example 7 the catalyst did not form a film, but the binder was coated on the plexiglass
(1)LaCu 0.3 Ti 0.7 O 3 Preparation of
Same as in example 8, step (1)
(2) Porous exfoliation of P-S-g-C 3 N 4 Preparation of
Same as in example 13, step (2)
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Preparation of (2)
The same procedure as in step (3) of example 1.
(4) Adding LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-transparency organic glass plate
The same as the step (4) in the example 1, wherein the catalyst coating mode of the high-transmittance organic glass photocatalytic plate 31 in the photocatalytic reaction tank 32 is changed: the catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 The sodium silicate inorganic adhesive is mixed according to the mass ratio of 1:1, then the mixed solution of 2:1 acetic acid and water is added to form catalyst silica sol, the catalyst silica sol is uniformly coated on a dry and clean high-transparency organic glass plate, and the organic glass plate coated with the photocatalyst film is carefully placed in cold water until the organic glass plate is completely solidified to form the photocatalytic plate loaded on the high-transparency organic glass plate.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treating the wastewater of the extrahigh COD bovine heart extract
The procedure was as in step (5) of example 1, wherein the initial COD of the wastewater of the extra-high COD bovine heart extract was 240000mg/L and the salt content was 7000mg/L. The results are shown in Table 27.
Watch 27
As can be seen by combining examples 1-16 and comparative examples 1-7, the undoped Cu in comparative example 1 is modifiedOf LaTiO 3 /0.5P-S-g-C 3 N 4 The COD degradation rate of the extra-high COD beef heart extract wastewater degraded by the catalyst is only 35.33 percent, which shows that the LaTiO which is not doped with Cu has no Cu 3 /0.5P-S-g-C 3 N 4 In the catalyst, cu ions do not enter LaTiO 3 The crystal lattice of (2) does not introduce cations with Fenton-like reaction activity, is not beneficial to the transfer of current carriers, and can not effectively utilize hydrogen peroxide to generate free radicals to degrade sewage; comparative examples 2 and 3 use the consumption of complexing agent polymaleic anhydride to exceed and fall short of the optimum application range, the degradation rate is not more than 55%, show that when the complexing agent is complexed, the metal ion can not be completely chelated with polydentate ligand, when the complexing agent is insufficient, the metal ion can not be completely complexed, part of metal ion can not form complex, free metal ion exists in the sol-gel stage, catalyst monomer with large specific surface area can not be formed during calcination; when the complexing agent is excessive, a large amount of impurity elements are introduced to destroy the stability of the system, so that the exposure of active sites of the catalyst is reduced, and the catalytic effect is reduced. Comparative example 4 uses undoped, non-exfoliated bulk g-C 3 N 4 The degradation rate is only 39.89%, which is due to the g-C of the bulk phase 3 N 4 The specific surface area is small, the recombination rate of photon-generated carriers is high, the visible light response range is narrow, the charge transfer speed is low, the adsorption capacity is reduced, and the performance of the catalyst is severely limited; comparative example 5 porous P-S-g-C prepared 3 N 4 The degradation rate is only 56.21% without ultrasonic action for 10h, because hydrogen bonding and Van der Waals force between layers of graphite phase carbon nitride in bulk phase, stronger covalent C-N bonds between sheets, and the overlapping layered structure causes serious agglomeration of the graphite phase carbon nitride and reduces the specific surface area. The ultrasonic action is used for stripping, so that the hydrogen bond action and van der Waals force between layers are destroyed, and the nano-film is stripped into a single-layer or multi-layer nano-film, so that the specific surface area is greatly increased, the dispersity is increased, and the photocatalyst effect is also obviously improved; in comparative example 6, P-S-g-C exfoliation without calcination with a gaseous template was used 3 N 4 The degradation rate is also significantly reduced compared to catalysts containing templating agent due to the loss of gas templating agent calcinationIn the process, the pore-forming effect of the gas is realized, the catalyst has no porous surface, the specific surface area is reduced, and the catalytic effect is also obviously reduced. In comparative example 7, the catalyst loading mode was changed, and the catalyst was coated on a high-permeability organic glass using a common sodium silicate binder, and compared with a photocatalytic film, it was found that the degradation rate was significantly decreased because the selectivity and the anti-agglomeration ability of the film were lost, the active sites of the catalyst could not be completely contacted with the substrate, and the local substrate concentration was kinetically lost too high, which prompted the forward progress of the reaction, resulting in a decrease in the degradation rate, further illustrating the specific suitability of the catalyst for a dedicated reactor.
Claims (10)
1. The porous composite photocatalyst with high specific surface area is characterized in that the general formula of the porous composite photocatalyst with high specific surface area is LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4 Wherein x is 0.1-0.5, y is 0.5-0.9, active material LaCu x Ti 1-x O 3 Is prepared by doping Cu ions to modify LaTiO 3 Preparation of active substance P-S-g-C 3 N 4 Is co-doped modified g-C by P, S 3 N 4 And (4) preparing.
2. The method for preparing the porous composite photocatalyst with high specific surface area as claimed in claim 1, which is characterized by comprising the following steps:
(1) Preparation of LaCu by low-temperature sol-gel method x Ti 1-x O 3 : dissolving lanthanum nitrate hexahydrate and copper nitrate trihydrate in water, stirring to obtain solution A, dissolving tetrabutyl titanate in isopropanol to obtain solution B, slowly adding solution B into solution A in ice-water bath, adding complexing agent, stirring and mixing, adjusting pH, continuously stirring for reaction, heating for evaporation, drying, grinding to obtain precursor powder, calcining the precursor powder to obtain LaCu x Ti 1-x O 3 ；
(2) Preparation of porous stripped P-S-g-C with high specific surface area by adopting gas template method 3 N 4 : nitrogen-rich source, sulfur source, phosphorus source and gas template agentMixing and grinding, calcining the ground powder to obtain porous P-S-g-C 3 N 4 Adding porous P-S-g-C 3 N 4 Placing in dispersant, ultrasonic stripping, centrifuging, drying to obtain porous stripped P-S-g-C 3 N 4 ；
(3) Stripping off the porous P-S-g-C 3 N 4 Dispersing in ethanol, adding LaCu x Ti 1-x O 3 Stirring and mixing evenly, and drying in vacuum to obtain a final product LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4 。
3. The method for preparing the porous composite photocatalyst with high specific surface area as claimed in claim 2, wherein in the step (1), the molar ratio of lanthanum nitrate hexahydrate, copper nitrate trihydrate and tetrabutyl titanate is 1:0.1-0.5, the volume ratio of tetrabutyl titanate to isopropanol is 1:2-3, the complexing agent is one of citric acid, polymaleic anhydride, diglycolic acid and succinic acid, the molar ratio of the total mole of lanthanum, copper and titanium to the complexing agent is 1:1-2, the pH is 2-3, the heating and evaporation is carried out at the temperature of 60-90 ℃ until a sol-gel product is formed, the drying temperature is 100-110 ℃, the drying time is 20-24h, the calcining temperature is 700-750 ℃, and the calcining time is 5-6h.
4. The method for preparing the porous composite photocatalyst with high specific surface area according to claim 2, wherein in the step (2), the nitrogen-rich source is one of melamine, guanidine hydrochloride and urotropine, the sulfur source is one of thiourea, 2-thiobarbituric acid and L-cysteine, the phosphorus source is one of diammonium hydrogen phosphate, ammonium polyphosphate and hexachlorotriphosphazene, the mass ratio of the nitrogen-rich source, the sulfur source and the phosphorus source is 1.1-0.3 3 N 4 The solid-liquid ratio of the dispersant and the dispersant is 3-5mg/mL.
5. The method for preparing the porous composite photocatalyst with high specific surface area as claimed in claim 2, wherein in the step (3), the LaCu is added x Ti 1-x O 3 Stripping with porous P-S-g-C 3 N 4 The mass ratio is 1.
6. The use of the high specific surface area porous composite photocatalyst of claim 1 in the degradation of wastewater from the processing of biological preparations with very high COD.
7. The use according to claim 6, wherein the ultra-high COD biological product preparation processing waste contains one or more of organic alcohols, organic aldehydes, organic esters and organic amines, the COD value is 200000-240000mg/L, and the salt content is 6000-7000mg/L.
8. The integrated treatment system for degrading the processing wastewater of the biological preparation with ultra-high COD by using the porous composite photocatalyst with high specific surface area of claim 1, which is characterized by comprising a pH regulation module, a heat exchange module, a premixing module, a photocatalytic reaction module and a desalting module which are sequentially connected; the pH adjusting module comprises an acid liquid storage tank (2), an alkali liquid storage tank (3) and a pH adjusting and mixing tank (10), the acid liquid storage tank (2) and the alkali liquid storage tank (3) are respectively communicated with the pH adjusting and mixing tank (10), a first stirring paddle (9) is arranged at the bottom of the pH adjusting and mixing tank (10), and a pH online detector (7) is arranged at the top of the pH adjusting and mixing tank (10); the premixing module comprises an oxidant liquid storage tank (26) and a premixing tank (21), the oxidant liquid storage tank (26) is communicated with the top of the premixing tank (21), and a second stirring paddle (19) is arranged at the bottom of the premixing tank (21); the photocatalysis module is provided with a photocatalysis reaction tank (32), a light source (33) and a high-transmittance organic glass plate (31) with a plurality of layers of photocatalysis films prepared by the high-specific-surface-area porous composite photocatalyst in claim 1 are arranged in the photocatalysis reaction tank (32), and the bottom of the photocatalysis reaction tank (32) is provided with a first COD (chemical oxygen demand) on-line detectionA system (34); the desalting module is provided with a cation exchange resin device (45) and a CO removing device which are connected in sequence 2 The device comprises a device (48) and an anion exchange resin device (52), wherein a water outlet of the anion exchange resin device (52) is provided with an electric conduction on-line monitoring system (53).
9. The integrated treatment system of claim 8, further comprising an assembled modular MBR membrane reaction module, wherein the assembled modular MBR membrane reaction module is respectively communicated with the photocatalytic module and the desalination module, the MBR membrane reaction module comprises an MBR membrane reactor (37) and a blower (40), the MBR membrane reactor (37) is internally provided with an MBR membrane (38) with a lining, the bottom of the MBR membrane reactor (37) is provided with an aeration pipe (39), and the aeration pipe (39) is communicated with the blower (40).
10. A method for degrading ultra high COD bioproduct agent process wastewater using the integrated processing system of claim 8 or 9, comprising the steps of:
(1) high COD biological product preparation processing wastewater enters a pH adjusting mixing tank (10), a stirring paddle (9) is started to stir, the pH of the wastewater in the pH adjusting mixing tank (10) is adjusted by controlling an acid liquid storage tank (2) or an alkali liquid storage tank (3), and when a pH on-line detector (7) displays 5.5-8.0, the wastewater is sent to a heat exchange module for heat exchange;
(2) The wastewater enters a premixing tank (21) after being subjected to heat exchange by a heat exchange module, an oxidant in an oxidant storage tank (26) is controlled to enter the premixing tank (21), and a stirring second stirring paddle (19) is opened to stir and premix;
(3) Sending the pre-mixed wastewater into a photocatalytic reaction tank (32), sequentially flowing through a high-transparency organic glass plate (31) provided with a photocatalytic film prepared by the high-specific-surface-area porous composite photocatalyst in claim 1 from top to bottom, simultaneously turning on a light source (33) to perform photocatalytic degradation reaction, measuring the COD value of the effluent after the reaction by a first COD online monitor (34), and if the COD value is less than 100000mg/L, sequentially entering a cation exchange resin device (45) of a desalting module and removing CO into a cation exchange resin device (45) of the desalting module 2 A device (48) and an anion exchange resin device (52), the salt content of which is less than that of the salt content detected by a conductivity on-line monitoring system (53)Discharging the product out of the system after 1000 mg/L;
(4) If the COD value required by the wastewater treatment is less than 10000mg/L, the wastewater after the photocatalytic degradation reaction enters an MBR membrane reactor (37), an air blower (40) is started, air is blown into an aeration pipe (39), the wastewater stays for 4-5 hours through the MBR membrane reactor (37), a second COD online monitor (42) determines that the COD value is less than 10000mg/L, and the wastewater sequentially enters a cation exchange resin device (45) of a desalting module and is subjected to CO removal 2 The device (48) and the anion exchange resin device (52) are discharged out of the system after the salt content is detected to be less than 1000mg/L by a conductance on-line monitoring system (53).
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