CN115805095B - 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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- CN115805095B CN115805095B CN202211588893.7A CN202211588893A CN115805095B CN 115805095 B CN115805095 B CN 115805095B CN 202211588893 A CN202211588893 A CN 202211588893A CN 115805095 B CN115805095 B CN 115805095B
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- NPCOQXAVBJJZBQ-UHFFFAOYSA-N reduced coenzyme Q9 Natural products COC1=C(O)C(C)=C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)C(O)=C1OC NPCOQXAVBJJZBQ-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229940035936 ubiquinone Drugs 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Catalysts (AREA)
Abstract
The invention discloses a porous composite photocatalyst with high specific surface area, a preparation method, an integrated treatment system and a treatment method, wherein the general formula of the composite catalyst 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, and active substance LaCu x Ti 1‑x O 3 Is modified LaTiO by doping Cu ions 3 Is prepared by porous stripping of active substance P-S-g-C 3 N 4 Is P, S co-doped modified g-C 3 N 4 Is prepared. The perovskite material and the modified carbon nitride are compounded, so that the electronic structure of the perovskite material is changed to increase the photocatalysis effect, the photo-generated carrier is inhibited from being compounded, more active sites of the perovskite are exposed, the traditional Fenton method and the photocatalysis method are coupled, and the processing wastewater of the ultra-high COD biological product preparation is degraded by an integrated processing system matched with a catalyst, and the degradation rate is more than 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, a preparation method, a modularized integrated treatment system and a method for treating wastewater, which are used for degrading ultra-high COD biological product preparation processing wastewater, and belong to the technical fields of photocatalysis and wastewater treatment.
Background
Coenzyme Q10 (Coenzyme Q10, also called decenquinone, ubiquinone) is a Coenzyme of oxidoreductase existing on the inner membrane of cell mitochondria, and has been studied in great numbers in recent years, and its medical value and clinical application, etc. are being conducted successively at home and abroad, and it has been widely used in protecting heart, reducing hypertension, antioxidation, etc. The animal cell extraction method for extracting coenzyme Q10 is one of the first production processes in the world, and mainly extracts target substances from animal organs such as pig heart, cow heart, etc. The content of coenzyme Q10 in the ox heart is as high as 85nmol/g, which is the best choice for extracting coenzyme Q10, and the ox heart extract waste water is used as derivative waste water of the method, various inorganic salts, organic solvents and other pollution components including organic alcohols, organic aldehydes, organic esters and organic amines can be produced in the extraction process, and meanwhile, the waste water has the characteristics of large water quality fluctuation, complex components and high salt and COD, and is difficult to treat. These wastewater flows into the environment without being treated to the standard, causes continuous damage to organisms, and is easily accumulated and diffused in the environment due to chemical stability and difficulty in biodegradation. Long-term exposure to such wastewater can produce unpredictable damage to human targeted organs and biological communities, especially can contribute to the production of resistance genes by pathogens, severely compromising human health and environmental safety.
At present, the method for treating the ox heart extract waste water generally comprises the following steps: biological treatment, ozone oxidation, wet oxidation, and homogeneous Fenton oxidation. Considering that the ox heart extract waste water has biochemical resistance, single biological degradation is difficult to be effective, and physical and chemical and biological combined methods are generally adopted for treatment. The ozone oxidation method has the advantages of high reaction rate, secondary pollution, difficult solution of ozone preparation conditions and leakage problems, high cost and harsh conditions. Although the homogeneous Fenton oxidation method has high degradation efficiency, controllable cost and easy operation of the device, the subsequent treatment cost of the iron mud is high, and the consumption of hydrogen peroxide is large. The Fenton method and the photocatalysis method are coupled, and the method has the characteristics of low energy consumption, small pollution, low cost and the like, and is expected to replace the traditional degradation technology for treating the ultrahigh COD (chemical oxygen demand) ox heart extract wastewater.
Disclosure of Invention
The invention aims to: the first aim of the invention is to provide a porous composite photocatalyst LaCu with high specific surface area which can effectively degrade ultra-high COD biological product preparation processing wastewater under the condition of visible light x Ti 1-x O 3 /yP-S-g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the The second object 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 an application of the porous composite photocatalyst with high specific surface area in treating the processing wastewater of the ultra-high COD biological product preparation; the fourth object of the invention is to provide a modularized integrated treatment system for treating ultra-high COD biological product preparation processing wastewater by using the porous composite photocatalyst with high specific surface area; the fifth object of the invention is to provide a method for treating the extra-high COD biological product preparation processing wastewater by using the special equipment and the high specific surface area porous composite photocatalyst.
The technical scheme is as follows: the invention relates to a high specific surface area porous composite photocatalyst, which has a general formula of 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, and active substance LaCu x Ti 1-x O 3 Is prepared by doping Cu ions to modify LaTiO 3 Is prepared into active substance P-S-g-C 3 N 4 Is prepared by modifying g-C through P, S co-doping 3 N 4 Is prepared.
The preparation method of the porous composite photocatalyst with high specific surface area comprises the following steps:
(1) LaCu preparation 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 titanateSlowly adding solution B into solution A in ice water bath, adding complexing agent, stirring, mixing, regulating pH, stirring, reacting, heating for evaporating, drying, grinding to obtain precursor powder, and calcining to obtain LaCu x Ti 1-x O 3 ；
(2) Preparation of porous exfoliated P-S-g-C with high specific surface area by gas template method 3 N 4 : mixing and grinding the nitrogen-rich source, the sulfur source, the phosphorus source and the gas template agent, and calcining the ground powder to obtain porous P-S-g-C 3 N 4 Porous P-S-g-C 3 N 4 Placing into dispersant, ultrasonic stripping, centrifuging, and drying to obtain porous stripping P-S-g-C 3 N 4 ；
(3) Stripping the porous P-S-g-C 3 N 4 Dispersing into ethanol, adding LaCu x Ti 1-x O 3 Stirring and mixing uniformly, and vacuum drying to obtain the final product LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4 。
In the step (1), the mol ratio of the lanthanum nitrate hexahydrate, the copper nitrate trihydrate and the tetrabutyl titanate is 1:0.1-0.5:0.5-0.9.
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 mole of 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 performed at the temperature of 60-90 ℃ until a sol gel product is formed.
In the step (1), the drying temperature is 100-110 ℃ and the drying time is 20-24 hours.
Wherein in the step (1), the calcining temperature is 700-750 ℃ and the calcining time is 5-6h.
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 to the sulfur source to the phosphorus source is 1:0.1-0.3:0.1-0.3.
Wherein in the step (2), the calcining temperature is 500-550 ℃ and the calcining time is 2-4h.
In the step (2), the gas template agent is ammonium chloride, ammonium carbonate or ammonium bicarbonate.
In the step (2), the mass ratio of the nitrogen-rich source to the gas template agent is 1:5-10.
In the step (2), the dispersing agent is one of ethanol, isopropanol and acetone.
Wherein in step (2), the porous P-S-g-C 3 N 4 The solid-liquid ratio of the dispersant is 3-5mg/mL.
Wherein in the step (3), the LaCu x Ti 1-x O 3 P-S-g-C is peeled off from the porous plate 3 N 4 The mass ratio is 1:0.5-0.9,
in the step (3), the temperature of the vacuum drying is 100-110 ℃, and the time of the vacuum drying is 20-24 hours.
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 has Fenton-like oxidation catalytic activity and photocatalytic activity. Fenton-like oxidation catalytic activity is mainly formed by LaCu x Ti 1-x O 3 Provides that the photocatalytic activity is mainly composed of P-S-g-C 3 N 4 Providing. In the preparation of LaCu x Ti 1-x O 3 When in monomer, the perovskite LaTiO is doped by copper ions 3 B-site cations of Fenton-like reactive cations are introduced to make metal ions and lattice oxygen become oppositeThe active site is used, and meanwhile, the crystal structure of the substituted perovskite is kept unchanged, so that the perovskite has quite stable mechanical strength, and the loss caused by ion elution in the use process of the catalyst is reduced. After copper ions are introduced, a symmetry breaking active center is constructed, charge density gradient exists in the active center, electrons are spontaneously driven to migrate through thermodynamics, a formed local polarization field polarizes hydrogen peroxide molecules with high symmetry, and the hydrogen peroxide molecules are finally activated under the action of local moment through an electron-rich region, so that the utilization rate of hydrogen peroxide is improved. Depriving water molecules H from electron-deficient centers 2 The electrons of O oxidize and convert water into OH, the surface of the catalyst is similar to that of innumerable micro primary batteries, and the synergistic system is rich in electrons, ions, metastable molecules, active free radicals and other particles, so that the oxidation is carried out on organic functional groups such as hydroxyl groups, aldehyde carbonyl groups, ester carbonyl groups and the like in the ultra-high COD biological product preparation processing wastewater. The complexing agent can react with metal ions as completely as possible by regulating the types and the proportion of the complexing agent at low temperature in the preparation process, the formed colloid ions have good dispersibility and particle size, the stable multi-tooth complex is obtained, and the agglomeration of nano particles is weakened to the greatest extent by the catalyst powder formed in the calcination process, so that active sites are fully exposed.
The invention prepares the porous stripping P-S-g-C with high specific surface area and photoactivity 3 N 4 . Although g-C 3 N 4 The photocatalyst is a photocatalytic hot material since discovery, but 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 severely limits the wide application of the photocatalyst. Porous stripping P-S-g-C 3 N 4 Co-doping g-C with P, S 3 N 4 Breaking g-C 3 N 4 The hydrogen bonding between the structural units distorts the molecular plane, causing redistribution of the conjugated system charges, resulting in a differentiation of the charge distribution. The P, S element has high electronegativity, electrons can be quickly obtained in the reaction process, and the visible light response range is enlarged, so that the separation speed of electron-hole pairs is increased. At the same time in the preparation processThe gas template agent is used, 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 performed in the dispersing agent, the Van der Waals force and intermolecular hydrogen bond action between the original bulk carbon nitride layers are broken, the number of layers of the nano-sheet 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 the 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, the 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 calcination, can not easily fall off and deactivate 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 specific surface area of the catalyst is increased by regulating and controlling the type and the dosage of the complexing agent and the calcination temperature, the agglomeration of nano ions is reduced, and the B-site doped perovskite materials with different mass ratios are prepared; by reacting g-C 3 N 4 The doping modification of the catalyst is realized by introducing nonmetallic hetero elements into a two-dimensional carbon nitride system, so that the band gap structure of the material is changed, the specific surface area is increased, and the separation and transfer of the surface charge of the catalyst are accelerated. In order to further increase the specific surface area of the carbon nitride material, a gas template agent is introduced when the carbon nitride doped with the hetero element is prepared, proper types and dosage are explored, and a large amount of gas is generated in the calcining process so that the catalyst structure tends to be fluffy and porous; bulk carbon nitride has a specific surface area of less than 10m due to Van der Waals force and intermolecular hydrogen bonding between layers, which are overlapped with each other 2 In order to further increase the specific surface area, the proper dispersion solvent is used for stripping to obtain the carbon nitride nano-sheet through ultrasonic action, so that hydrogen bonds and Van der Waals force between carbon nitride layers are destroyed, the specific surface area is greatly increased, and meanwhile, the nano-sheet with smaller particle size has enhanced light absorption capacity and light response capacity, separation of photo-generated carriers is accelerated, and effective diffusion is realizedThe defects of the traditional bulk phase carbon nitride are overcome. P-S-g-C 3 N 4 In the preparation process, through the selection of a gas template agent, a sulfur source and a phosphorus source, the selection of an ultrasonic dispersion solvent and the control of ultrasonic time, the increase of the specific surface area of the catalyst and the weakening of the hydrogen bonding effect and intermolecular effect between the carbon nitride layers are realized. The perovskite material and the modified carbon nitride are compounded, the energy band positions of the two materials are changed, the electronic structure of the perovskite material is changed to increase conductivity, the combination of photo-generated carriers is inhibited, more active sites of the perovskite are exposed, and the traditional Fenton method and the photocatalysis method are coupled, so that the efficient treatment of various waste water is realized.
The invention relates to an application of a porous composite photocatalyst with high specific surface area in degrading ultra-high COD biological product preparation processing wastewater.
Wherein the processing waste of the ultra-high COD biological product preparation contains one or more of organic alcohols, organic aldehydes, organic esters and organic amines.
Wherein the COD value of the processing waste of the ultra-high COD biological product preparation is 200000-240000mg/L, and the salt content is 6000-7000mg/L.
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 mixing tank, wherein the acid liquid storage tank and the alkali liquid storage tank are respectively communicated with the pH adjusting mixing tank, a first stirring paddle is arranged at the bottom of the pH adjusting mixing tank, and a pH online detector is arranged at the top of the pH adjusting 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 paddle is arranged at the bottom of the premixing tank; the photocatalysis module is provided with a photocatalysis reaction tank, a light source and a plurality of layers of organic glass plates containing the high specific surface area porous composite photocatalyst are arranged in the photocatalysis reaction tank, and a first COD on-line detection system is arranged at the bottom of the photocatalysis reaction tank; the desalting module is provided with a cation exchange resin device and a CO removing device which are connected in sequence 2 The device comprises 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 MBR membrane reaction module capable of being modularized in an assembling mode, the MBR membrane reaction module is communicated with the photocatalysis module and the desalination module respectively, the MBR membrane reaction module comprises an MBR membrane reactor and a 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 blower.
Wherein, MBR membrane reaction module can be according to the needs of play water COD value whether the selection is assembled.
The method for degrading the extra-high COD biological product preparation processing wastewater by using the integrated treatment system comprises the following steps:
(1) Feeding the high COD biological product preparation processing wastewater into a pH adjusting mixing tank, opening a first stirring paddle for stirring, adjusting the pH of the wastewater in the pH adjusting mixing tank by controlling an acid liquid storage tank or an alkali liquid storage tank, and feeding the wastewater into a heat exchange module for heat exchange when the pH on-line detector shows 5.5-8.0;
(2) The waste water enters a premixing tank after heat exchange by a heat exchange module, the oxidant in an oxidant liquid storage tank is controlled to enter the premixing tank, and a second stirring paddle is opened to stir and premix;
(3) The pre-mixed wastewater is sent into a photocatalysis reaction tank, and flows through a high-permeability organic glass plate provided with a photocatalysis membrane prepared by the high specific surface area porous composite photocatalyst in claim 1 from top to bottom in sequence, meanwhile, a light source is turned on to carry out photocatalysis degradation reaction, the COD value of the effluent after the reaction is measured by a first COD on-line monitor, and if the COD value is less than 100000mg/L, the wastewater sequentially enters a cation exchange resin device of a desalting module to remove CO 2 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 a conductivity on-line monitoring system.
(4) If the COD value is less than 10000mg/L in wastewater treatment, the wastewater after photocatalytic degradation reaction enters an MBR membrane reactor, a blower is started, air is blown into an aeration pipe, and the wastewater stays through the MBR membrane reactor4-5h, the COD value measured by the second COD on-line monitor is less than 10000mg/L, and the wastewater sequentially enters a cation exchange resin device of a desalting module for removing CO 2 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 a conductivity on-line monitoring system.
Wherein the solid-to-liquid ratio of the porous composite photocatalyst with high specific surface area to the ultra-high COD biological product preparation processing wastewater is 30:1g/L.
Wherein, 10% hydrochloric acid solution is selected for the acid liquid storage tank, and 20% sodium hydroxide solution is selected for the alkali liquid storage tank.
Wherein, the high-permeability organic glass plate in the photocatalytic reaction tank is loaded with a photocatalytic film prepared by the porous composite photocatalyst with high specific surface area.
The loading mode of the high-permeability organic glass photocatalyst membrane plate is as follows: the polysulfone matrix and polyvinylpyrrolidone additive were dissolved in N-methyl-2-pyrrolidone solvent with heating and magnetic stirring until the solution became clear. Cooling to room temperature, adding the porous composite photocatalyst with high specific surface area, dispersing uniformly under the action of ultrasound, blowing off the solution by using inert gas to completely degas the solution, coating the solution on a dry and clean high-permeability 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 organic glass plate is completely solidified to form the photocatalyst film loaded on the high-permeability organic glass plate.
Wherein the volume ratio of the oxidant to the extra-high COD biological product preparation processing wastewater is 0.15-0.30:1.
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 alkaline anion resin.
The special system for processing the ultra-high COD biological product preparation processing wastewater by the high specific surface area porous composite photocatalyst is based on the high specific surface area porous composite photocatalyst of the invention to fully utilize hydrogen peroxide, mainly generate OH and O simultaneously 2 - 、e - And holes, etc., and the desalting module can utilize ion exchange resin to remove inorganic salts in the wastewater. The device is specially designed for high COD waste water, and the catalyst is formed into a film and coated on the high-permeability organic glass plate, so that the contact area of the catalyst and a reaction substrate is greatly increased, and meanwhile, the high-permeability organic glass can reduce the energy loss caused by light source reflection and improve the reaction efficiency. The high-permeability organic glass photocatalytic film solves the problem that pollutants are easy to gather and adhere to the surface or film holes in the field of film separation, the photocatalyst continuously degrades the pollutants, and the photocatalyst is combined with the film process to complete self-cleaning of the film, so that long-term stable use is realized, and high stability of the catalyst is realized. Meanwhile, compared with pollutants, the high polymer film has a more complex structure, and the generated active species are selectively prevented from damaging the film, so that the service life of the photocatalytic film is prolonged. And the high-permeability organic glass photocatalytic membrane plate can be integrally disassembled and assembled, so that the loading capacity of the catalyst of the membrane plate and the number of the plates can be automatically adjusted according to the requirements.
According to the photocatalysis membrane organic glass plate in the special system reaction tank for processing the ultra-high COD biological product preparation wastewater, aiming at the characteristics that most of the photocatalysts exist in a powder form, are easy to agglomerate in an aqueous solution, and meanwhile, the specific surface area is small, so that in the high COD biological product preparation wastewater, pollutants cover the surface of the catalyst, the active center cannot contact with a substrate and the like, the photocatalysts are fixed on a polysulfone membrane substrate, and the agglomeration phenomenon of common powder catalysts is avoided during the reaction; meanwhile, aiming at the characteristic of high COD of the ultra-high COD biological product preparation processing wastewater, the photocatalyst with the characteristic of high specific surface area is designed to prevent the problem that the substrate cannot reach an active site because the substrate wraps the pore canal when the concentration of the organic pollutant is high, and the photocatalyst with the porous high specific surface can be effectively matched with the porous photocatalyst with the high specific surface, so that the oxidant and the substrate can be rapidly adsorbed, and a high-grade oxidation reaction can be carried out on the surface of the catalyst to rapidly degrade the organic pollutant components in the ultra-high COD biological product preparation processing wastewater in a large amount; meanwhile, the photocatalytic film has small diffusion resistance, has selective permeability to reactants and small molecular products, can separate a reaction zone from a separation zone, selectively permeates small molecules generated by degradation in a catalyst active zone, and ensures that the concentration of local reactants is high, thereby promoting the forward reaction in dynamics, breaking through the chemical balance problem and greatly improving the catalytic effect and the reaction rate. The high-permeability organic glass photocatalytic film solves the problem that pollutants are easy to gather and adhere to the surface or film holes in the field of film separation, the photocatalyst continuously degrades the pollutants, and the photocatalyst is combined with the film process to complete self-cleaning of the film, so that long-term stable use is realized, high stability of the catalyst is realized, meanwhile, the high-molecular film has a more complex structure relative to the pollutants, and the generated active species are selectively prevented from damaging the film, so that the service life of the photocatalytic film is prolonged. And the high-permeability organic glass photocatalytic membrane plate can be integrally disassembled and assembled, so that the loading capacity of the catalyst of the membrane plate and the number of the plates can be automatically adjusted according to the requirements.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The porous composite photocatalyst with high specific surface area of the invention adopts Cu ion doping to enter LaTiO 3 Introducing Fenton reaction active ion into B site of the catalyst to make it and lattice oxygen become active center, then co-doping with P, S to make porous stripping g-C 3 N 4 The capability of the photocatalyst for treating the ultra-high COD ox heart extract wastewater is effectively improved by compounding. The COD removal rate of the wastewater after passing through the special equipment reaches more than 60%, and the salt content of the wastewater after desalting is less than 1000 mg/L.
(2) The preparation method of the porous composite photocatalyst with high specific surface area is simple to operate, and has the advantages of easily available raw materials and low cost. The method has the advantages of simple equipment and flexible process.
(3) The porous composite photocatalyst with high specific surface area is fixed on the polysulfone membrane substrate, and the agglomeration phenomenon of the common powder catalyst can not be generated during the reaction; the porous composite photocatalyst with high specific surface area characteristics of the invention can not wrap the pore canal due to the substrate when the concentration of the organic pollutant is high, and can not cause the problem that the substrate can not reach the active site.
(4) The special system for processing the ultra-high COD biological product preparation processing wastewater by the porous composite photocatalyst with the high specific surface can increase the utilization rate of hydrogen peroxide and improve the quantum yield of the catalyst. The on-line detection system can effectively detect the treatment condition of wastewater, and meanwhile, the circulating treatment system can treat refractory pollutants for a plurality of times to reach the standard, and the photocatalytic film is coated on the high-permeability organic glass, so that the mass transfer efficiency can be greatly improved, the catalytic degradation effect is improved, and meanwhile, the light loss of the high-permeability organic glass can be reduced. The high-permeability organic glass photocatalysis membrane plate can be integrally disassembled and assembled, so that the loading capacity of the catalyst of the membrane plate and the number of the plates can be automatically adjusted according to the requirement.
(5) The modular MBR membrane reaction module can flexibly assemble the desalting module according to the requirements, adopts ion exchange resin with high ion exchange capacity, high chemical stability and high wear resistance, and realizes the effective treatment of inorganic salt; meanwhile, no gas is generated, secondary pollution caused by gas emission is avoided, and the method is environment-friendly.
Drawings
FIG. 1 is a process flow diagram of a special system for treating ultra-high COD biological product preparation processing wastewater by using a porous composite photocatalyst with high specific surface area;
FIG. 2 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Photograph of the composite photocatalyst;
FIG. 3 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 SEM image of composite photocatalyst;
FIG. 4 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 TEM image of composite photocatalyst;
FIG. 5 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 BET specific surface area data plot of the composite photocatalyst;
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
As shown in FIG. 1, the integrated treatment system for degrading ultra-high COD (chemical oxygen demand) bovine heart extract wastewater by utilizing the porous composite photocatalyst with high specific surface comprises a pH adjusting module, a heat exchange module and a premixing module, wherein the photocatalytic reaction module is an assembled modularized MBR (Membrane biological reactor) membrane reaction module and a desalting module, and each module is connected by a pipeline.
Wherein, the pH adjustment module includes first check valve 1, sour liquid storage pot 2, alkali liquid storage pot 3, first measuring pump 5 and pH adjustment mixing tank 10 and second check valve 55, and sour liquid storage pot 2 and alkali liquid storage pot 3 are through first three-way valve 4 and first measuring pump 5 intercommunication, and first measuring pump 5 and pH adjustment mixing tank 10 intercommunication. 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 adjustment 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 adjustment mixing tank 10 is provided with a first stirring paddle 9, and the first one-way valve 1 is communicated with the pH adjustment mixing tank 10. The pH adjusting mixing tank 10 communicates with the second check valve 55 at the bottom.
The heat exchange module comprises a first heat insulation pipe 14, a heat exchanger 15 and a second heat insulation pipe 16 which are sequentially connected; the pH adjusting mixing tank 10 is communicated with the first insulating pipe 14 after passing through the second check 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 meter 17; the oxidant liquid storage tank 26 is provided with a fifth liquid level meter 25, a third safety valve 23 and a third pressure gauge 24 are arranged at the top of the oxidant liquid storage tank 26, the oxidant liquid storage tank 26 is communicated with a second metering pump 27 through a third one-way valve 56, and the second heat insulation pipe 16 is communicated with the premixing tank 21.
The photocatalysis reaction module comprises a first liquid inlet pump 22, a second three-way valve 28, a photocatalysis reaction tank 32, a first COD on-line monitor 34 and a third one-way valve 35, wherein two liquid inlets, a fourth safety valve 30 and a fourth pressure gauge 29 are arranged at the top of the photocatalysis reaction tank 32, and a light source 33 is arranged at the top of the photocatalysis reaction tank 32 in an inward extending manner. 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 coated with the high-specific-surface-area porous composite photocatalyst film according to the invention by high-permeability organic glass, the organic glass plates are fixed by supporting rings installed by bolts at an angle of 5 DEG and distributed inside the photocatalytic reaction tank 32 from top to bottom, the light source 33 is a microwave electrodeless lamp, and the outer side of the organic glass plates 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 on-line 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 on-line monitor 34.
The desalting module comprises a fourth three-way valve 59, a third liquid inlet pump 43, a cation exchange resin column 45 and a CO removing module which are communicated in sequence 2 The device 48, the fourth liquid inlet pump 49, the anion exchange resin column 52, the electric conduction on-line monitoring system 53 and the fifth one-way valve 54, 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, and CO is removed 2 An air inlet 46 is arranged at the top of the device 48 for removing CO 2 The bottom of the device 48 is provided with CO 2 And an air outlet 47. The conductance on-line monitoring system 53 is in communication with a fifth one-way valve 54, and the third one-way valve 35 is in communication with the third liquid inlet pump 43.
Wherein, the acid in the acid liquid storage tank 2 is 10% hydrochloric acid solution, the alkali in the alkali liquid storage tank 3 is 20% sodium hydroxide solution, and the oxidant in the oxidant liquid storage tank 26 is 30% hydrogen peroxide. Cation exchange resin column 45 is a weakly acidic acrylic cation exchange resin, and anion exchange resin column 52 is a weakly basic styrene anion exchange resin
The integrated processing system further comprises an assembled modularized MBR membrane reaction module which is respectively communicated with the photocatalytic reaction module and the desalting module. The 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 on-line monitor 42, wherein a plurality of groups of MBR membranes 38 with inner liners 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 is communicated with the MBR membrane reactor 37 through a fourth one-way valve 41. The second COD on-line monitor 42 is in communication with a fourth three-way valve 59 of the desalination module. The third check 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 figure 1, the method for degrading the ultra-high COD biological product preparation processing wastewater by using the system comprises the steps of opening a first one-way valve 1, feeding the ultra-high COD biological product preparation processing wastewater into a pH adjusting mixing tank 10 with a pH on-line monitor 7, controlling a first three-way valve 4 and a first metering pump 5, controlling the flow 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 to stir, 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, avoiding excessive or insufficient liquid storage, and simultaneously paying attention to controlling a first safety valve 8, a first pressure meter 6 and a third liquid level meter 20 at the top of the pH adjusting mixing tank 10, so as to ensure safe operation. The second one-way valve 55 is opened, the wastewater flows through the first heat insulation pipe 14 and enters the heat exchanger 15 for heat exchange, and the wastewater enters the premixing tank 21 through the second heat insulation pipe 16 after heat exchange. Simultaneously, 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 for stirring and mixing, the second safety valve 18 of the premixing tank 21 is observed in the operation process, the second pressure gauge 17 and the fourth liquid level gauge 20 are used for preventing the pressure from being too high, and the safe operation is ensured. When the addition of hydrogen peroxide to the premix tank 21 is completed, the second metering pump 27, the third check valve 56 and the second agitator paddle 19 are closed. The first liquid inlet pump 22 is started to enable the wastewater to pass through the second three-way valve 28 from two liquid inlets at the top of the photocatalysis reaction tank 32, and sequentially flow through the photocatalysis membrane high-permeability organic glass plate 31 prepared by the porous composite photocatalyst with high specific surface area from top to bottom, and meanwhile, the light source 33 is started to carry out photocatalysis by the microwave electrodeless lamp And (5) carrying out chemical reaction. The operation process takes care of controlling the third safety valve 30 and the third pressure gauge 29 of the photocatalytic reaction tank 32 to prevent the excessive pressure and ensure safe operation. The COD of the effluent after the 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 enable 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 (weak acid acrylic cation exchange resin is filled in the column) and CO is removed 2 Device 48 (air is taken in from air inlet 41, CO 2 From CO 2 Outlet 37), anion exchange resin column 52 (weak acid styrene anion exchange resin is arranged in the column), the salt content of the effluent is measured to be below 1000mg/L by an on-line conductivity monitor 53, a fifth one-way valve 54 is opened, the effluent is discharged, and the primary wastewater treatment is completed.
The COD value of the wastewater after the photocatalytic reaction is less than 100000mg/L, and the wastewater can enter a desalting system. If there is a smaller demand for the COD value of the wastewater, the third three-way valve 58 can be controlled to enter the modular MBR membrane reaction module, the fourth one-way valve 35 and the second liquid inlet pump 36 are opened, the wastewater enters the MBR membrane reactor 38, the blower 40 is opened, air is blown into the aeration pipe 39, the wastewater stays for 4-5 hours through the MBR membrane reactor, the fifth one-way valve 41 is opened, the reacted wastewater enters the second COD on-line 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 requires resin regeneration, the cation resin regenerant is added from the first regenerant inlet 44, and if the anion exchange resin column 52 requires resin regeneration, the anion resin regenerant is added from the second regenerant inlet 50 and then flows out from the first and second liquid outlets 57 and 51, respectively.
Example 1
(1)LaCu 0.1 Ti 0.9 O 3 Is prepared from
2.165g of lanthanum nitrate hexahydrate and 0.1205g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.1, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, so as to obtain solution A. Pressing the button1.53g of tetrabutyl titanate is weighed according to the lanthanum-titanium ion molar ratio of 1:0.9, the isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2 is measured, and the isopropanol solvent and the tetrabutyl titanate are mixed and stirred uniformly to obtain the 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 lanthanum, copper and titanium total metal ions to citric acid monohydrate of 1:1 and dissolved in 50mL of distilled water, and the distilled water is slowly added into the mixed solution to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia, and the resulting suspension was stirred vigorously in a constant temperature bath at 0deg.C for 2h. Then the solvent is stirred and evaporated at the water bath of 60 ℃ until sol gel products are generated, the sol gel products are transferred to a surface dish and are placed in a blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.1 Ti 0.9 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
1.5g of nitrogen-rich melamine, 0.15g of thiosemicarbazide, 0.15g of phosphorus-source monoammonium phosphate and 7.5g of gas template agent ammonium chloride are weighed according to the mass ratio of 1:0.1:0.1:5, are placed in an agate mortar for full grinding, are poured into a crucible, are capped and are transferred into a muffle furnace, are heated to 500 ℃ at a speed of 5 ℃/min, are kept for 2 hours, are naturally cooled to room temperature, and are subjected to porous P-S-g-C 3 N 4 . Taking a proper amount of molded porous P-S-g-C 3 N 4 Dispersing into ethanol, porous P-S-g-C 3 N 4 The volume ratio of the mass to the ethanol is 3mg/mL, and the mixture is placed in an ultrasonic instrument for 10 hours. Obtaining suspension, centrifuging, and drying at 60deg.C overnight to obtain porous stripping P-S-g-C 3 N 4 。
(3)LaCu 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Weighing 1g of LaCu prepared by the method according to the mass ratio of 1:0.5 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 was magnetically stirred for 1 hour and then transferred to a vacuum oven for drying at 100deg.C for 24 hours. Drying to obtain catalyst powder LaCu 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 。
(4) LaCu is to 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
The polysulfone matrix and polyvinylpyrrolidone additive were dissolved in N-methyl-2-pyrrolidone solvent at 70 ℃ with a mass fraction of polysulfone of 17% and a mass fraction of polyvinylpyrrolidone of 0.5% in the mixed solution and magnetically stirred until the solution became clear. After cooling to room temperature, 300g of LaCu was added 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 The photocatalyst is uniformly dispersed 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-permeability 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, so that the photocatalyst film loaded on the high-permeability organic glass plate is formed.
(5) LaCu catalyst for processing wastewater by utilizing integrated treatment system and ultra-high COD biological product preparation 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 Treating the processing wastewater of the ultra-high COD biological product preparation to obtain the ultra-high COD beef heart extract wastewater
As shown in fig. 1, the first one-way valve 1 is opened, 10L of high-COD cow-heart extract waste water (COD is 240000mg/L, and the salt content is 7000 mg/L) is fed into the pH adjusting mixing tank 10 with the pH on-line monitor 7, the first three-way valve 4 and the first metering pump 5 are controlled, the flow of the alkali liquid storage tank 3 is controlled to enter the pH adjusting mixing tank 10, the first stirring paddle 9 is opened for stirring, when the pH is adjusted to 5.5-8.0, the first stirring paddle 9 and the first metering pump 5 are closed, the first liquid level gauge 12 on the acid liquid storage tank 2 or the second liquid level gauge 11 on the alkali liquid storage tank 3 is observed in the operation process, excessive or insufficient liquid storage is avoided, meanwhile, the first safety valve 8, the first pressure gauge 6 and the third liquid level gauge 20 at the top of the pH adjusting mixing tank 10 are controlled, and safe operation is ensured. The second one-way valve 55 is opened, the wastewater flows through the first heat insulation pipe 14 and enters the heat exchanger 15 for heat exchange, and after heat exchange, the wastewater flows through the second heat insulation pipe 16 Into a premix tank 21. Simultaneously, the second metering pump 27 and the third one-way valve 56 are opened, 30% hydrogen peroxide (total 1.5L) in the oxidant liquid storage tank 26 is controlled to enter the premixing tank 21, the second stirring paddle 19 is opened for stirring and mixing for 10min, the operation process observes the second safety valve 18 of the premixing tank 21, the second pressure gauge 17 and the fourth liquid level gauge 20, the excessive pressure is prevented, and the safe operation is ensured. When the addition of hydrogen peroxide to the premix tank 21 is completed, the second metering pump 27, the third check valve 56 and the second agitator paddle 19 are closed. The first liquid inlet pump 22 is opened to enable the wastewater to flow through the second three-way valve 28 from the two liquid inlets at the top of the photocatalysis reaction tank 32 from top to bottom in sequence and then to be filled with LaCu 0.1 Ti 0.9 O 3 /0.5P-S-g-C 3 N 4 The prepared photocatalysis film high-permeability organic glass plate 31 is simultaneously turned on a light source 33 microwave electrodeless lamp to perform photocatalysis reaction. The operation process takes care of controlling the third safety valve 30 and the third pressure gauge 29 of the photocatalytic reaction tank 32 to prevent the excessive pressure and ensure safe operation. The COD of the effluent after the reaction is measured by the first COD on-line monitor 34, if the COD value is less than 100000mg/L, the fourth one-way valve 35 and the third liquid inlet pump 43 are opened, and the third three-way valve 58 and the fourth three-way valve 59 are controlled to enable the wastewater to sequentially enter the cation exchange resin column 45 (weak acid acrylic cation exchange resin is filled in the column) for CO removal 2 Device 48 (air is taken in from air inlet 41, CO 2 From CO 2 Outlet 37), anion exchange resin column 52 (weak acid styrene anion exchange resin is arranged in the column), the salt content of the effluent is measured to be below 1000mg/L by an on-line conductivity monitor 53, a fifth one-way valve 54 is opened, the effluent is discharged, and the primary wastewater treatment is completed. The results are shown in Table 1.
TABLE 1
Example 2
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.165g lanthanum nitrate hexahydrate and 0.3615g nitric acid trihydrate are taken according to the mol ratio of 1:0.3Copper was dissolved in 250mL of distilled water and stirred well in a thermostatic bath containing ice to obtain solution a. Weighing 1.19g of tetrabutyl titanate according to the lanthanum-titanium ion mole ratio of 1:0.7, measuring an isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain the 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 lanthanum, copper and titanium total metal ions to citric acid monohydrate of 1:1 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia, and the resulting suspension was stirred vigorously in a constant temperature bath at 0deg.C for 2h. Then the solvent is stirred and evaporated in a water bath at 70 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a forced air drying oven at 110 ℃ for drying for 20 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 750 ℃ at a speed of 5 ℃/min, preserving heat for 6 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 2.
TABLE 2
Example 3
(1)LaCu 0.5 Ti 0.5 O 3 Is prepared from
2.165g of lanthanum nitrate hexahydrate and 0.6025g of copper nitrate trihydrate are taken according to a molar ratio of 1:0.5, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, so as to obtain solution A. 0.85g of tetrabutyl titanate is weighed according to the lanthanum-titanium ion mole ratio of 1:0.5, the isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2 is measured, and the isopropanol solvent and the tetrabutyl titanate are mixed and stirred uniformly to obtain the 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 lanthanum, copper and titanium total metal ions to citric acid monohydrate of 1:1 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 730 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.5 Ti 0. O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.5 Ti 0.5 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.5 Ti 0.5 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.5 Ti 0.5 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 3.
TABLE 3 Table 3
Example 4
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, thus obtaining solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain the 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. 6.0000g of polymaleic anhydride is weighed according to the molar ratio of lanthanum, copper and titanium to polymaleic anhydride of 1:1, dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated at the water bath of 90 ℃ until sol gel products are generated, the sol gel products are transferred to a surface dish and are placed in a blast drying oven for drying at the temperature of 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N is loaded onOn a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L.
TABLE 4 Table 4
Example 5
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, thus obtaining solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain the 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 of diglycolic acid is weighed according to the molar ratio of lanthanum, copper and titanium to diglycolic acid of 1:1 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 5.
TABLE 5
Example 6
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, thus obtaining solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain the 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 was weighed out in 50mL of distilled water in such a manner that the molar ratio of the total metal ions of lanthanum, copper and titanium to succinic acid was 1:1.5, and the above mixed solution was slowly added to produce the corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min Preserving heat for 5h, naturally cooling, and grinding to obtain monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 6.
TABLE 6
Example 7
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, thus obtaining solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain the 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. 9.0000g of polymaleic anhydride is weighed according to the molar ratio of lanthanum, copper and titanium to polymaleic anhydride acid of 1:1.5 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complexation And (3) an object. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 7.
TABLE 7
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Example 8
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water, and then mixed with the mixture to obtain a mixtureStirring uniformly in a constant temperature tank containing ice to obtain solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the tetrabutyl titanate volume ratio of 1:2, and uniformly mixing and stirring the isopropanol solvent and the tetrabutyl titanate to obtain the 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. 12.0000g of polymaleic anhydride is weighed according to the molar ratio of lanthanum, copper and titanium to polymaleic anhydride of 1:2, dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was performed as in example 1.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 8.
TABLE 8
Example 9
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
1.5g of nitrogen-rich source, 0.15g of sulfur source, 0.15g of phosphorus source and 7.5g of gas template agent ammonium chloride are weighed according to the mass ratio of 1:0.1:0.1:5, are placed in an agate mortar for full grinding, are poured into a crucible, are capped and are transferred into a muffle furnace, are heated to 500 ℃ at a speed of 5 ℃/min, are kept for 4 hours, and are naturally cooled to room temperature. Dispersing a proper amount of molded catalyst into ethanol, wherein the volume ratio of the catalyst mass to the solvent is 3mg/mL, and placing the catalyst in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60deg.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 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L.
To examine the effect of nitrogen-rich, sulfur-rich, and phosphorus-rich selections on catalyst performance, orthogonal experiments were designed using SPSS software to investigate the effect and impact of multiple factors on the degradation rate of dependent variables and the effect of these factors in combination. Nitrogen-rich source A 1 : melamine, A 2 : guanidine hydrochloride, A 3 : urotropin; sulfur source: b (B) 1 : thiourea, B 2 2-thiobarbituric acid, B 3 : l-cysteine；C 1 : monoammonium phosphate, C 2 : ammonium polyphosphate, C 3 : hexachlorotriphosphazene was subjected to SPSS software to generate 9 sets of orthogonal experiments, the degradation rates of the 9 sets of experiments were obtained, the effect of three factors on the catalyst was obtained by multi-factor analysis of variance, and the optimal raw materials were screened, and the results of the orthogonal experiments are shown in Table 9 below.
TABLE 9
| Experimental group | Carbon source A | Sulfur source B | Phosphorus source C | Degradation rate (%) |
| Experiment group 1 | A 3 | B 3 | C 1 | 64.94 |
| Experiment group 2 | A 1 | B 2 | C 3 | 72.95 |
| Experiment group 3 | A 3 | B 1 | C 3 | 68.83 |
| Experiment group 4 | A 1 | B 3 | C 2 | 63.38 |
| Experiment group 5 | A 2 | B 3 | C 3 | 67.08 |
| Experiment group 6 | A 3 | B 2 | C 2 | 69.83 |
| Experiment group 7 | A 2 | B 2 | C 1 | 70.38 |
| Experiment group 8 | A 2 | B 1 | C 2 | 65.28 |
| Experiment group 9 | A 1 | B 1 | C 1 | 66.03 |
The results were input into the SPSS software and after the "general linear model" option was selected, the output multi-factor variance table is shown in table 10 below:
Table 10
From the analysis of the results in table 10 above, it can be seen from the significance level that the sulfur source main effect is significant for factor B, P value <0.05, indicating that the reliability of this result reaches 99.5%; for the factor C, the main effect of the phosphorus source is obvious, the P value is less than 0.05, and the reliability of the result reaches 99.5%; while for the element A, the main effect of the nitrogen-rich source is not obvious. In conclusion, the nitrogen-rich source has no obvious influence on the degradation rate, and the sulfur source and the phosphorus source have obvious influence on the degradation rate.
The effect of three levels of three factors output by the SPSS on degradation rate is shown in tables 11-13 below:
TABLE 11
It can be seen from the degradation rate that the three carbon sources have no significant effect on the degradation rate.
Table 12
From the degradation rate, it can be seen that the sulfur source has a significant effect on the degradation rate, with 2-thiobarbituric acid being the most effective.
TABLE 13
From the degradation rate, it can be seen that the sulfur source has a significant effect on the degradation rate, and hexachlorotriphosphazene is the best effect.
In summary, the best nitrogen-rich source is selected: urotropine, sulfur source: 2-thiobarbituric acid, phosphorus source: hexachlorotriphosphazene for preparing P-S-g-C 3 N 4 。
Example 10
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
1.5g of urotropine rich in nitrogen source, 0.15g of 2-thiobarbituric acid rich in sulfur source, 0.15g of hexachloro-tripolyphosphazene and 7.5g of ammonium chloride as a gas template agent are weighed according to the mass ratio of 1:0.1:0.1:5, fully ground in an agate mortar, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4h, and naturally cooled to room temperature. Dispersing a proper amount of molded catalyst into ethanol, wherein the volume ratio of the catalyst mass to the solvent is 3mg/mL, and placing the catalyst in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60deg.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 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalytic actionChemical agent LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 14.
TABLE 14
Example 11
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
1.5g of nitrogen-rich urotropine, 0.30g of sulfur source 2-thiobarbituric acid, 0.30g of hexachloro-tripolyphosphazene and 11.25g of gas template agent ammonium carbonate are weighed according to the mass ratio of 1:0.2:0.2:7.5, fully ground in an agate mortar, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4h and naturally cooled to room temperature. Dispersing a proper amount of molded catalyst into acetone, wherein the volume ratio of the catalyst mass to the solvent is 3mg/mL, and placing the catalyst into an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60deg.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 Is prepared from
The same as in (3) of example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 15.
TABLE 15
Example 12
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
1.5g of urotropine rich in nitrogen source, 0.45g of 2-thiobarbituric acid rich in sulfur source, 0.45g of hexachloro-tripolyphosphazene and 15g of ammonium bicarbonate serving as a gas template agent are weighed according to the mass ratio of 1:0.3:0.3:10, fully ground in an agate mortar, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4h, and naturally cooled to room temperature. Dispersing a proper amount of molded catalyst into acetone, wherein the volume ratio of the catalyst mass to the solvent is 3mg/mL, and placing the catalyst into an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60deg.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 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 11, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 16.
Table 16
Example 13
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
1.5g of urotropine rich in nitrogen source, 0.15g of 2-thiobarbituric acid rich in sulfur source, 0.15g of hexachloro-tripolyphosphazene and 15g of ammonium bicarbonate serving as a gas template agent are weighed according to the mass ratio of 1:0.1:0.1:10, fully ground in an agate mortar, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4h, and naturally cooled to room temperature. Dispersing a proper amount of molded catalyst into isopropanol, wherein the volume ratio of the mass of the catalyst to the solvent is 3mg/mL, and placing the catalyst in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60deg.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 Is prepared from
Step (3) was performed as in 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 the form of powder.
For LaCu obtained in this example 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Scanning electron microscope analysis was performed and the results are shown in fig. 3. FIG. 3 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 SEM image of composite photocatalyst; from FIG. 3a, the morphology of the catalyst can be observed, P-S-g-C after stripping 3 N 4 Is of a nano sheet structure, and the surface is loaded with rugged LaCu 0.3 Ti 0.7 O 3 Particles; as can be seen from the higher resolution of fig. 3b, the catalyst surface has a pore-like structure, which indicates successful productionIs prepared to grow on porous nano-sheet P-S-g-C 3 N 4 LaCu on 0.3 Ti 0.7 O 3 A catalyst.
FIG. 5 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 BET specific surface area data plot of the composite photocatalyst;
for LaCu obtained in this embodiment 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4. The results of transmission electron microscopy analysis are shown in FIG. 4. FIG. 4 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 TEM image of composite photocatalyst; as can be seen from FIG. 4, the catalyst in two-dimensional lamellar form, 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. BET specific surface area analysis was performed, and the results are shown in FIG. 5. FIG. 5 shows the powdered LaCu obtained in example 13 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 BET specific surface area data plot of the composite photocatalyst; as can be seen from FIG. 5, the specific surface area is 172.1684m 2 Per gram, far above the bulk g-C 3 N 4 (10m 2 and/L), a porous catalyst with a high specific surface area was confirmed.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 17.
TABLE 17
Example 14
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) in the same manner as in example 13
(3)LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 Is prepared from
Weighing 1g of LaCu prepared by the method according to the mass ratio of 1:0.7 0.3 Ti 0.7 O 3 And 0.7. 0.7g P-S-g-C 3 N 4 In 30mL ethanol, the mixture was magnetically stirred for 1 hour and then transferred to a vacuum oven for drying at 90℃for 24 hours. Drying to obtain catalyst powder LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 。
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.7P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 18.
TABLE 18
Example 15
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) in the same manner as in example 13
(3)LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 Is prepared from
Weighing 1g of LaCu prepared by the method according to the mass ratio of 1:0.9 0.3 Ti 0.7 O 3 And 0.9. 0.9g P-S-g-C 3 N 4 In 30mL ethanol, the mixture was magnetically stirred for 1 hour and then transferred to a vacuum oven for drying at 90℃for 24 hours. Drying to obtain catalyst powder LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 。
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.9P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 19.
TABLE 19
Example 16
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) in the same manner as in example 13
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is made of (1)Preparation method
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is similar to the step (5) in example 1, except that the hydrogen peroxide consumption of the photocatalytic reaction module is increased to 3.0L, and the modular MBR membrane reaction module is selectively started after the photocatalytic reaction module. The effluent after the photocatalytic reaction is subjected to COD measurement by the first COD on-line monitor 34, if the COD value is less than 100000mg/L, the fourth one-way valve 35 and the second liquid inlet pump 36 are opened, the wastewater enters the MBR membrane reactor 38 by controlling the third three-way valve 58, meanwhile, the blower 40 is opened, air is blown into the aeration pipe 39, the wastewater stays for 4-5h through the MBR membrane reactor, the fifth one-way valve 41 is opened, the reacted wastewater enters the second COD on-line monitor 42, and if the COD value is less than 10000mg/L, the third liquid inlet pump 43 is opened by controlling the fourth three-way valve 59, so that the wastewater enters the desalting module for continuous treatment. Wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 20.
Table 20
Comparative example 1 undoped with Cu ions
(1)LaTiO 3 Is prepared from
2.165g of lanthanum nitrate hexahydrate was taken and dissolved in 250mL of distilled water, and the solution A was obtained by stirring uniformly in a constant temperature bath containing ice. 1.700g of tetrabutyl titanate is weighed according to the lanthanum-titanium ion mole ratio of 1:1, the isopropanol solvent with the volume ratio of 1:2 is measured, and the isopropanol solvent and the tetrabutyl titanate are mixed and stirred uniformly to obtain the 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. Pressing the button12.0000g of polymaleic anhydride is weighed according to the molar ratio of lanthanum, copper and titanium to polymaleic anhydride of 1:2 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaTiO 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) in the same manner as in example 13
(3)LaTiO 3 /0.5P-S-g-C 3 N 4 Is prepared from
Weighing 1g of LaTiO prepared by the method according to the mass ratio of 1:0.5 3 And 0.5. 0.5g P-S-g-C 3 N 4 In 30mL ethanol, the mixture was magnetically stirred for 1 hour and then transferred to a vacuum oven for drying at 90℃for 24 hours. Drying to obtain catalyst powder LaTiO 3 /0.5P-S-g-C 3 N 4 。
(4) LaTiO 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaTiO 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 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 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, thus obtaining solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the volume ratio of 1:2, mixing with tetrabutyl titanate, and stirring uniformly 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. 3.0000g of polymaleic anhydride is weighed according to the mole ratio of lanthanum, copper and titanium total metal ions to polymaleic anhydride of 1:0.5 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was carried out as in example 13.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 22.
Table 22
Comparative example 3 multiple complexing agents
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
2.1650g of lanthanum nitrate hexahydrate and 0.3615g of copper nitrate trihydrate are taken according to the mol ratio of 1:0.3, dissolved in 250mL of distilled water and stirred uniformly in a constant temperature tank containing ice, thus obtaining solution A. Weighing 1.1900g of tetrabutyl titanate according to the lanthanum-titanium ion molar ratio of 1:0.7, measuring an isopropanol solvent with the volume ratio of 1:2, mixing with tetrabutyl titanate, and stirring uniformly 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. 18.0000g of polymaleic anhydride is weighed according to the molar ratio of lanthanum, copper and titanium to polymaleic anhydride of 1:3 and dissolved in 50mL of distilled water, and the mixed solution is slowly added to generate corresponding metal complex. The final pH value was adjusted to 2-3 using concentrated ammonia and the resulting suspension was stirred vigorously in a thermostatted bath at 0℃for 2h. Then the solvent is stirred and evaporated in a water bath at 80 ℃ until a sol gel product is generated, the sol gel product is transferred to a surface dish and is placed in a blast drying oven for drying at 100 ℃ for 24 hours, and the precursor powder is obtained by grinding. Heating the precursor powder to 700 ℃ at a speed of 5 ℃/min, preserving heat for 5 hours, naturally cooling, and grinding to obtain a monomer LaCu 0.3 Ti 0.7 O 3 。
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) was carried out as in example 13.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 23.
Table 23
Comparative example 4 use g-C without doping P, S 3 N 4
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2)g-C 3 N 4 Is prepared from
10g of urea is weighed, placed in an agate mortar for full grinding, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4 hours, and naturally cooled to room temperature.
(3)LaCu 0.3 Ti 0.7 O 3 /0.5g-C 3 N 4 Is prepared from
Weighing 1g of LaCu prepared by the method according to the mass ratio of 1:0.5 0.3 Ti 0.7 O 3 And 0.5-g g-C3N4 in 30mL ethanol, magnetically stirred for 1h, and then transferred to a vacuum oven for 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) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 24.
Table 24
Comparative example 5P-S-g-C without porous Structure Using gas template 3 N 4
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Stripping P-S-g-C 3 N 4 Is prepared from
1.5g of urotropine rich in nitrogen source, 0.15g of 2-thiobarbituric acid rich in sulfur source and 0.15g of hexachloro-tripolyphosphazene are weighed according to the mass ratio of 1:0.1:0.1, fully ground in an agate mortar, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4 hours, and naturally cooled to room temperature. Dispersing a proper amount of molded catalyst into isopropanol, wherein the volume ratio of the mass of the catalyst to the solvent is 3mg/mL, and placing the catalyst in an ultrasonic instrument for 10 hours. Centrifuging the obtained suspension, and drying at 60deg.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 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 25.
Table 25
Comparative example 6 non-ultrasonically peeled P-S-g-C 3 N 4
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous P-S-g-C 3 N 4 Is prepared from
1.5g of urotropine rich in nitrogen source, 0.15g of 2-thiobarbituric acid rich in sulfur source, 0.15g of hexachloro-tripolyphosphazene and 15g of ammonium bicarbonate serving as a gas template agent are weighed according to the mass ratio of 1:0.1:0.1:10, fully ground in an agate mortar, poured into a crucible, capped, transferred into a muffle furnace, heated to 500 ℃ at 5 ℃/min, kept for 4 hours, naturally cooled to room temperature, and the required monomer P-S-g-C is obtained 3 N 4 。
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) was performed as in example 1.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 26
Table 26
Comparative example 7 catalyst was not film-forming, but adhesive coated on plexiglas
(1)LaCu 0.3 Ti 0.7 O 3 Is prepared from
Step (1) in example 8
(2) Porous stripping P-S-g-C 3 N 4 Is prepared from
Step (2) in the same manner as in example 13
(3)LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Is prepared from
Step (3) was performed as in example 1.
(4) LaCu is to 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Loaded on a high-permeability organic glass plate
Step (4) of example 1 was repeated, wherein the catalyst-carrying manner of the high-transmittance organic glass photocatalytic plate 31 in the photocatalytic reaction tank 32 was changed: catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Mixing sodium silicate inorganic adhesive according to a mass ratio of 1:1, adding acetic acid and water mixed solution with a volume ratio of 2:1 to form catalyst silica sol, uniformly coating the catalyst silica sol on a dry and clean high-permeability organic glass plate, carefully placing the organic glass plate coated with the photocatalyst film in cold water until the organic glass plate is completely solidified, and forming the photocatalyst plate loaded on the high-permeability organic glass plate.
(5) Catalyst LaCu 0.3 Ti 0.7 O 3 /0.5P-S-g-C 3 N 4 Treatment of ultra-high COD ox heart extract waste water
The treatment process is the same as in step (5) in example 1, wherein the initial COD of the ultra-high COD ox heart extract waste water is 240000mg/L and the salt content is 7000mg/L. The results are shown in Table 27.
Table 27
As can be seen from a combination of examples 1 to 16 and comparative examples 1 to 7, comparative example 1 was not doped with Cu-modified LaTiO 3 /0.5P-S-g-C 3 N 4 The ultra-high COD cow heart extract wastewater with high COD is degraded by the catalyst, and the COD degradation rate is only 35.33%, which shows that the LaTiO which is not doped with Cu 3 /0.5P-S-g-C 3 N 4 In the catalyst, cu ions do not enter LaTiO 3 Cations with Fenton-like reactivity are not introduced, carrier transfer is not facilitated, and free radicals generated by hydrogen peroxide cannot be effectively utilized to degrade sewage; when the using amount of the complexing agent polymaleic anhydride exceeds and is less than the optimal using range, the degradation rate is not more than 55%, which indicates that when the complexing agent is compounded, metal ions cannot be completely chelated with the polydentate ligand, when the complexing agent is insufficient, partial metal ions cannot form a complex, free metal ions exist in a sol-gel stage, and catalyst monomers with large specific surface areas are not formed during calcination; when the complexing agent is excessive, a large amount of impurity elements are introduced, the stability of the system is destroyed, the exposure of the active site 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 was only 39.89%, because of the g-C in the bulk phase 3 N 4 The specific surface area is small, the photo-generated carrier recombination rate 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; in comparative example 5, porous P-S-g-C was prepared 3 N 4 The degradation rate is only 56.21% without ultrasonic action for 10 hours because of the hydrogen bonding action and Van der Waals force between graphite phase carbon nitride layers of bulk phase, strong covalent C-N bond between the sheet layers, and serious agglomeration of graphite phase carbon nitride caused by overlapped lamellar structure, and reduced specific surface area. The ultrasonic stripping is used to break the hydrogen bonding action and Van der Waals force between layers, and the ultrasonic stripping is used to strip the layers into single-layer or multi-layer nano sheets, so that the specific surface area is greatly increased, the dispersibility is increased, and the photocatalyst effect is also obviously improved; in comparative example 6, exfoliated P-S-g-C without calcination with a gas template was used 3 N 4 The degradation rate is also obviously reduced compared with the catalyst containing the template agent, because the porous surface of the catalyst is not available in the process of calcining the gas template agent due to the loss of the pore-forming effect of the gas, the specific surface area is reduced, and the catalytic effect is also obviously reduced. In comparative example 7, the loading pattern of the catalyst was changed, and it was found that the catalyst was coated on a high-permeability organic glass using a general sodium silicate binder, and the photocatalytic film was compared The degradation rate is obviously reduced because the selectivity and anti-agglomeration capability of the membrane are lost, the active site of the catalyst cannot be completely contacted with the substrate, and meanwhile, the local substrate concentration is lost too high dynamically, so that the forward reaction power is promoted, the degradation rate is reduced, and the special suitability of the catalyst to a special reactor is further illustrated.
Claims (7)
1. A 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, and active substance LaCu x Ti 1-x O 3 Is prepared by doping Cu ions to modify LaTiO 3 Is prepared into active substance P-S-g-C 3 N 4 Is prepared by modifying g-C through P, S co-doping 3 N 4 The preparation method of the porous composite photocatalyst with high specific surface area comprises the following steps:
(1) LaCu preparation 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 the solution B into the solution A under ice water bath, adding a complexing agent, stirring and mixing, regulating pH, continuing stirring and reacting, heating and evaporating, drying, grinding to obtain precursor powder, and calcining the precursor powder to obtain LaCu x Ti 1-x O 3 The method comprises the steps of carrying out a first treatment on the surface of the The lanthanum nitrate hexahydrate, copper nitrate trihydrate and tetrabutyl titanate have the molar ratio of 1:0.1-0.5:0.5-0.9, wherein 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 evaporation is that the heating 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;
(2) By usingPreparation of porous stripping P-S-g-C with high specific surface area by gas template method 3 N 4 : mixing and grinding the nitrogen-rich source, the sulfur source, the phosphorus source and the gas template agent, and calcining the ground powder to obtain porous P-S-g-C 3 N 4 Porous P-S-g-C 3 N 4 Placing into dispersant, ultrasonic stripping, centrifuging, and drying to obtain porous stripping P-S-g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the 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 1:0.1-0.3:0.1-0.3, the calcining temperature is 500-550 ℃, the calcining time is 2-4 hours, the gas template agent is ammonium chloride, ammonium carbonate or ammonium bicarbonate, the mass ratio of the nitrogen-rich source to the gas template agent is 1:5-10, the dispersing agent is one of ethanol, isopropanol and acetone, and the porous P-S-g-C is prepared by the steps of 3 N 4 The solid-liquid ratio of the dispersant to the dispersant is 3-5 mg/mL; the ultrasonic stripping time is 10 hours;
(3) Stripping the porous P-S-g-C 3 N 4 Dispersing into ethanol, adding LaCu x Ti 1-x O 3 Stirring and mixing uniformly, and vacuum drying to obtain the final product LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4； The LaCu x Ti 1-x O 3 P-S-g-C is peeled off from the porous plate 3 N 4 The mass ratio is 1:0.5-0.9, the temperature of the vacuum drying is 100-110 ℃, and the time of the vacuum drying is 20-24 hours.
2. The method for preparing the porous composite photocatalyst with high specific surface area according to claim 1, which is characterized by comprising the following steps:
(1) LaCu preparation 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 under ice water bath, and adding complexationStirring and mixing the agents, regulating the pH value, continuing stirring and reacting, heating and evaporating, drying, grinding to obtain precursor powder, and calcining the precursor powder to obtain LaCu x Ti 1-x O 3 The method comprises the steps of carrying out a first treatment on the surface of the The lanthanum nitrate hexahydrate, copper nitrate trihydrate and tetrabutyl titanate have the molar ratio of 1:0.1-0.5:0.5-0.9, wherein 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 evaporation is that the heating 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;
(2) Preparation of porous exfoliated P-S-g-C with high specific surface area by gas template method 3 N 4 : mixing and grinding the nitrogen-rich source, the sulfur source, the phosphorus source and the gas template agent, and calcining the ground powder to obtain porous P-S-g-C 3 N 4 Porous P-S-g-C 3 N 4 Placing into dispersant, ultrasonic stripping, centrifuging, and drying to obtain porous stripping P-S-g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the 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 1:0.1-0.3:0.1-0.3, the calcining temperature is 500-550 ℃, the calcining time is 2-4 hours, the gas template agent is ammonium chloride, ammonium carbonate or ammonium bicarbonate, the mass ratio of the nitrogen-rich source to the gas template agent is 1:5-10, the dispersing agent is one of ethanol, isopropanol and acetone, and the porous P-S-g-C is prepared by the steps of 3 N 4 The solid-liquid ratio of the dispersant to the dispersant is 3-5 mg/mL; the ultrasonic stripping time is 10 hours;
(3) Stripping the porous P-S-g-C 3 N 4 Dispersing into ethanol, adding LaCu x Ti 1-x O 3 Stirring and mixing uniformly, and vacuum drying to obtain the final product LaCu x Ti 1-x O 3 /yP-S-g-C 3 N 4； The LaCu x Ti 1-x O 3 P-S-g-C is peeled off from the porous plate 3 N 4 The mass ratio is 1:0.5-0.9, the temperature of the vacuum drying is 100-110 ℃, and the time of the vacuum drying is 20-24 hours.
3. The use of the porous composite photocatalyst with high specific surface area of claim 1 in degrading ultra-high COD biological product preparation processing wastewater.
4. The use according to claim 3, wherein the ultra-high COD biological product preparation processing wastewater contains one or more of organic alcohols, organic aldehydes, organic esters and organic amines, the COD value is 200000-240000 mg/L, and the salt content is 6000-7000mg/L.
5. The integrated treatment system for degrading the ultra-high COD biological product preparation processing wastewater by using the high specific surface area porous composite photocatalyst according to claim 1 is characterized by comprising a pH adjusting module, a heat exchange module, a premixing module, a photocatalytic reaction module and a desalting module which are connected in sequence; the pH adjusting module comprises an acid liquid storage tank (2), an alkali liquid storage tank (3) and a pH adjusting mixing tank (10), wherein the acid liquid storage tank (2) and the alkali liquid storage tank (3) are respectively communicated with the pH adjusting mixing tank (10), a first stirring paddle (9) is arranged at the bottom of the pH adjusting mixing tank (10), and a pH online detector (7) is arranged at the top of the pH adjusting mixing tank; 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-permeability organic glass plate (31) of a photocatalysis film prepared by the high specific surface area porous composite photocatalyst according to claim 1 are arranged in the photocatalysis reaction tank (32), and a first COD on-line detection system (34) is arranged at the bottom of the photocatalysis reaction tank (32); 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 an anion exchange resin 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).
6. The integrated treatment system of claim 5, further comprising an assembly-type modular MBR membrane reaction module, wherein the assembly-type 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), an MBR membrane (38) with a lining is arranged in the MBR membrane reactor (37), an aerator pipe (39) is arranged at the bottom of the MBR membrane reactor (37), and the aerator pipe (39) is communicated with the blower (40).
7. A method for degrading ultra-high COD biological product formulation process wastewater using the integrated treatment system of claim 5 or 6, comprising the steps of:
the method comprises the steps of (1) feeding high COD biological product preparation processing wastewater into a pH adjustment mixing tank (10), opening a stirring paddle (9) for stirring, adjusting the pH of the wastewater in the pH adjustment mixing tank (10) by controlling an acid liquid storage tank (2) or an alkali liquid storage tank (3), and feeding the wastewater into a heat exchange module for heat exchange when a pH online detector (7) displays 5.5-8.0;
(2) The waste water enters a premixing tank (21) after heat exchange by a heat exchange module, the oxidant in an oxidant liquid storage tank (26) is controlled to enter the premixing tank (21), and a second stirring paddle (19) is opened to stir and premix;
(3) The pre-mixed wastewater is sent into a photocatalysis reaction tank (32), and flows through a high-permeability organic glass plate (31) provided with a photocatalysis film prepared by the high specific surface area porous composite photocatalyst in the claim 1 from top to bottom in sequence, meanwhile, a light source (33) is turned on to carry out photocatalysis degradation reaction, the COD value of the effluent after the reaction is measured by a first COD on-line monitoring system (34), and if the COD value is smaller than 100000mg/L, the wastewater sequentially enters a cation exchange resin device (45) of a desalting module to remove CO 2 An anion exchange resin (52) and a device (48) which are electrically connected in-lineThe monitoring system (53) detects that the salt content is less than 1000mg/L and then is discharged out of the system;
(4) If the COD value is less than 10000mg/L in wastewater treatment, the wastewater after photocatalytic degradation reaction enters an MBR (membrane reactor) (37), a blower (40) is turned on, air is blown into an aeration pipe (39), the wastewater stays for 4-5h through the MBR (37), the COD value is less than 10000mg/L as measured by a second COD on-line monitor (42), and the wastewater sequentially enters a cation exchange resin (45) of a desalting module to remove CO 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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