CN112675881A - Composite photocatalyst for degrading morpholine wastewater, preparation method and special equipment - Google Patents
Composite photocatalyst for degrading morpholine wastewater, preparation method and special equipment Download PDFInfo
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Abstract
The invention discloses a composite photocatalyst for degrading morpholine wastewater, a preparation method and special equipment, wherein the composite photocatalyst is a Zn-doped perovskite LaCo1‑xZnxO3And MoS2Compounding to obtain the product; the preparation method is to use MoCl with a certain molar ratio5And thiourea, and preparing and screening MoS with different shapes and high specific surface area2And LaCo1‑xZnxO3The visible light utilization rate is increased through recombination, the separation and migration of photoproduction electrons and holes are effectively promoted, and the photocatalyst which has good catalytic effect, large specific surface area, high stability and can be repeatedly used is obtained; the special equipment uses the composite catalyst of the invention to fully utilize visible light to induce and generate strong oxidizing free radicalsDegrading pollutants, efficiently and conveniently treating morpholine wastewater such as N-methylmorpholine, N-formylmorpholine, N-methylmorpholine oxide or N-acryloyl morpholine and the like, realizing efficient mineralization and being green and environment-friendly.
Description
Technical Field
The invention relates to a composite photocatalyst, a preparation method and special equipment, in particular to a composite photocatalyst which has high catalytic efficiency and large specific surface area, can be repeatedly used and is used for degrading morpholine wastewater, a preparation method and special equipment.
Background
Morpholine, N-methylmorpholine oxide and the like are very important fine chemical products and are widely applied to the fields of viscose, rubber, medicines, coatings, pesticides, dyes and the like. With the increasing demand of the market for morpholine substances, the large production and use of morpholine cause great pollution to the environment. Morpholine, N-methylmorpholine oxide, and the like, are irreversibly harmful to the human body and have a very high potential for conversion to carcinogenic, mutagenic nitramine and nitrosamine species. Therefore, the pollution of high-concentration morpholine wastewater such as morpholine, N-methylmorpholine oxide and the like has attracted wide attention of domestic and foreign scholars and the public.
The method for treating the high-concentration morpholine wastewater mainly comprises four steps: physical treatment, chemical treatment, biological treatment and advanced oxidation. For the treatment process of morpholine wastewater, the conventional treatment generally has insufficient oxidation capacity, and can not realize the complete mineralization of the morpholine wastewater, particularly for N-methyl morpholine oxide, the substance is prepared from N-methyl morpholine and an oxidant, can stably exist under low oxidation capacity, and for the substance, a degradation technology with stronger oxidation capacity is required for treatment. Among advanced oxidation technologies, the photocatalytic technology is preferably used due to its low energy consumption and low pollution. Commonly used photocatalysts such as TiO2The perovskite catalyst has the defects of wide forbidden band width, incapability of fully utilizing visible light, low quantum efficiency and the like, and the perovskite catalyst has the defects of narrow forbidden band width and small band gap and is a better photocatalyst, but the single perovskite photocatalyst has the problems of easy recombination of electron and hole and narrow visible light response range.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a reusable composite photocatalyst LaCo with high catalytic efficiency and large specific surface area1-xZnxO3/MoS2(ii) a The second purpose of the invention is to provide a preparation method of the composite photocatalyst; the third purpose of the invention is to provide special equipment for the composite catalyst.
The technical scheme is as follows: the photocatalyst of the invention isZn doped modified LaCo1-xZnxO3And MoS2Combined to form a composite photocatalyst LaCo1-xZnxO3/MoS2Wherein x is 0.1-0.5, and a carrier MoS2Perovskite nano particles and active material LaCo are dispersed on the surface1-xZnxO3Is in LaCoO3Is obtained by doping Zn in the mixture for modification.
Further, the morpholine wastewater is N-methylmorpholine, N-formylmorpholine, N-methylmorpholine oxide or N-acryloyl morpholine.
Further, the shape of the composite photocatalyst is a sheet shape, an eggshell shape, a honeycomb shape or a petal shape.
The preparation method of the composite photocatalyst comprises the following steps:
(1) adding MoCl5Adding a mixed solvent of water and N, N-dimethylformamide into thiourea, adding a surfactant, adjusting the pH value of the solution, carrying out thermal reaction, cooling, washing and drying to obtain MoS with different shapes2；
(2) Mixing MoS2Dispersing in glycol solution, ultrasonic treating to obtain suspension, adding lanthanum nitrate, cobalt nitrate and zinc nitrate, adding mineralizer, stirring, reacting, cooling, washing and drying to obtain LaCo1-xZnxO3/MoS2。
Preferably, in step (1), the MoCl is5And the molar ratio of the thiourea to the thiourea is 1: 2-10. The volume ratio of the water to the N, N-dimethylformamide is 1: 0.25-15.
Preferably, in the step (1), the surfactant is any one of dioctadecyl dimethyl ammonium bromide, sodium dodecyl benzene sulfonate, polyoxyethylene lauryl ether and polyvinylpyrrolidone.
Further, the amount of the surfactant added is 0.5 to 3.0 g.
Preferably, in step (1), the pH of the solution to be adjusted is 1 to 5. The thermal reaction is carried out in a polytetrafluoroethylene reaction kettle.
Further, the reaction temperature is 150-220 ℃, and the reaction time is 18-30 h.
Preferably, in step (2), the mineralizer is (NH)4)2CO3Ethanolamine and hexamethylenetetramine.
Furthermore, the concentration of the mineralizing agent is 5-20mol/L, and the addition amount is 10-40 mL.
Preferably, in the step (2), the molar ratio of the cobalt nitrate to the zinc nitrate is 1: 0.25-4. Mixture of cobalt nitrate and zinc nitrate, lanthanum nitrate and MoS2The molar ratio of (A) to (B) is 1:1: 6-30.
Preferably, in the step (2), the stirring time is 45-60 min. The reaction is carried out in a reaction kettle.
Further, the reaction temperature is 160-200 ℃, and the reaction time is 24-36 h.
The special equipment for the composite photocatalyst comprises an acid-base regulation small circulation module and a photocatalytic reaction large circulation module:
the acid-base regulation small circulation module is composed of an acid/base liquid tank, an acid-base liquid inlet pump, an acid-base regulation tank, a mixer, a material circulation pump, a first regulation valve, a second regulation valve and a third regulation valve, wherein the output end of the acid/base liquid tank is connected with the acid-base liquid inlet pump, the output end of the acid-base liquid inlet pump is connected with the mixer, and the output end and the input end of the acid-base regulation tank are respectively connected with the material circulation pump and the mixer through the first regulation valve, the second regulation valve and the third regulation valve to form a small circulation loop.
The wastewater sequentially enters an acid-base adjusting tank and a mixer, if the pH electrode on the mixer is monitored to be qualified, the wastewater enters a reaction tank, if the mixer is monitored to be unqualified, the wastewater returns to the acid-base adjusting tank through the mixer, a material circulating pump, a second adjusting valve and a third adjusting valve to form a backflow passage, an acid-base liquid inlet pump is started, and the pH value of the wastewater in the mixer is adjusted through acid/base liquid in an acid/base liquid tank until the monitoring is qualified.
The photocatalytic reaction large circulation module consists of a reaction tank, a mixer, a material circulating pump, a first regulating valve, a second regulating valve and a third regulating valve, wherein an inlet and a second outlet of the reaction tank are respectively connected with the material circulating pump and the mixer through the first regulating valve, the second regulating valve and the third regulating valve to form a large circulation loop.
And the wastewater with qualified pH value enters the reaction tank from the mixer through a second regulating valve and a third regulating valve of the material circulating pump. The first outlet of the reaction tank is communicated with the outside, and the wastewater qualified for degradation is discharged from the first outlet. The reaction tank is provided with a light source, a stirring paddle and a liquid level indicator.
Preferably, the adding amount of the composite photocatalyst is 5.0-20.0g per liter of morpholine wastewater.
Preferably, the pH electrode is qualified as pH 5-9.
Preferably, the light source is one of a 500W xenon lamp, a 300W high-pressure mercury lamp and a modified LED lamp.
Preferably, the stirring paddle is an electric stirring paddle.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
1. zn-doped modified LaCoO of the composite photocatalyst3And MoS2The composite photocatalyst is formed by combination, the energy level structure of the catalyst is reasonably adjusted and matched, the separation of photoproduction electrons and holes is effectively promoted, the strong oxidation-reduction capability can be kept, and the catalytic degradation efficiency of morpholine wastewater is greatly improved.
2. The preparation method of the composite photocatalyst is in MoS2The mixed solvent and the surfactant added in the preparation process can effectively regulate and control MoS2To obtain MoS with different shapes and high specific surface area2(ii) a In LaCo1- xZnxO3/MoS2The mineralizer added in the preparation process can effectively control LaCo1-xZnxO3In MoS2The deposition on the surface avoids the agglomeration of perovskite crystal grains, and the catalyst with high photocatalytic activity is obtained. The prepared photocatalyst has high catalytic efficiency, large specific surface area, high stability and reusability.
3. The special equipment for the composite photocatalyst uses LaCo1-xZnxO3/MoS2Reacting at normal temperature and normal pressure, and fully utilizing visible light to induce and generate strong oxidizing freeThe method has the advantages that pollutants are degraded, efficient mineralization is realized, sludge and secondary pollution are not generated, and the method is green and environment-friendly; and various oxidants are not used, so that the cost is greatly saved, and morpholine wastewater such as N-methylmorpholine, N-formylmorpholine, N-methylmorpholine oxide or N-acryloyl morpholine and the like can be efficiently and conveniently treated. The photocatalytic reaction large circulation module and the acid-base regulation small circulation module are self-circulation systems, so that the mass transfer process can be enhanced, and the degradation efficiency can be effectively improved; acid or alkali liquor in the acid-alkali regulation small circulation module does not directly contact with a catalytic bed, so that the activity of the composite photocatalyst is not damaged, and the photocatalytic degradation process is in a fully closed state and has no pollution to the environment.
Drawings
FIG. 1 is a process flow diagram of the treatment of morpholine wastewater by the photocatalyst in a photocatalytic reaction device;
Detailed Description
The technical solution of the present invention is further explained below:
example 1
(1) Honeycomb-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:451.522g of thiourea, 1.50g of Polyoxyethylene Lauryl Ether (PLE), 30mL of a mixed solvent (V) of water and N, N-dimethylformamideH2O:VDMF1:5), adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the mixture for a plurality of times by water and absolute ethyl alcohol, centrifugally separating the mixture, placing the mixture in an oven, and drying the mixture for 12 hours at the temperature of 80 ℃ to obtain the honeycomb MoS2。
(2)LaCo0.8Zn0.2O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the cobalt nitrate to the lanthanum nitrate is 0.8:0.2:1:20, 0.0727g of cobalt nitrate, 0.0186g of zinc nitrate and 0.1352g of lanthanum nitrate are added in sequence and are continuously stirred and dissolved; then 5mol/L (NH) is added4)2CO3The solution was 20mL and stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.8Zn0.2O3And MoS2LaCo with a theoretical molar ratio of 1:200.8Zn0.2O3/MoS2。
In a photocatalytic reaction device, 250g (2) of composite photocatalyst LaCo is added into a reaction tank 10.8Zn0.2O3/MoS2Adding 5L of N-methylmorpholine oxide waste liquid with COD value of 6200mg/L into the acid-base regulating pool 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to 7; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 300W high-pressure mercury lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 79.2%. The perovskite nano particles are uniformly deposited on the honeycomb-shaped MoS2In addition, the whole flow of the special photocatalysis equipment is self-circulation, so that the mass transfer is enhanced, the photocatalysis efficiency is improved, and the actual production and application are facilitated.
Example 2
(1) Sheet MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:250.761g of thiourea, 0.5g of dioctadecyldimethylammonium bromide (DMAB), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMFDissolving the mixture in a ratio of 4:1) by stirring, and adding hydrochloric acid to adjust the pH of the solution to 3. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the reaction product by water and absolute ethyl alcohol for a plurality of times, centrifugally separating the reaction product, placing the reaction product in an oven, and drying the reaction product at 80 ℃ for 12 hours to obtain sheet MoS2。
(2)LaCo0.8Zn0.2O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the raw materials is 0.8:0.2:1:10, 0.1455g of cobalt nitrate, 0.0372g of zinc nitrate and 0.2705g of lanthanum nitrate are sequentially added and continuously stirred for dissolution; then 20mL of 10mol/L hexamethylenetetramine solution is added, and the stirring is continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.8Zn0.2O3And MoS2LaCo with a theoretical molar ratio of 1:100.8Zn0.2O3/MoS2。
In a photocatalytic reaction device, 350g of (2) composite photocatalyst LaCo is added into a reaction tank 10.8Zn0.2O3/MoS2Adding 5L of N-formyl morpholine waste liquid with COD value of 3050mg/L into the acid-base adjusting tank 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 8, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the waste water passes through a mixer 6, a material circulating pump 5 and a secondThe regulating valve 12 and the third regulating valve 13 flow back to the acid-base regulating tank 2 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is regulated to about 8; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under the modified LED light source; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 75.0%. Sheet-like MoS2The photocatalyst obtained by compounding with the zinc-doped perovskite not only effectively promotes the separation of photoproduction electrons and holes, but also can keep strong oxidation-reduction capability, greatly improves the catalytic degradation efficiency of the N-formyl morpholine waste water, and the acid-alkali regulation small circulation module in the special photocatalysis equipment does not directly contact with a catalytic bed by acid or alkali liquor, thereby not damaging the activity of the photocatalyst.
Example 3
(1) Eggshell MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:351.142g of thiourea, 1.0g of Sodium Dodecylbenzenesulfonate (SDBS), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMFDissolving the mixture in a ratio of 1:1) by stirring, and adding hydrochloric acid to adjust the pH of the solution to 3. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning with water and absolute ethyl alcohol for a plurality of times, centrifugally separating, placing in an oven, and drying at 80 ℃ for 12h to obtain eggshell-shaped MoS2。
(2)LaCo0.7Zn0.3O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the raw materials is 0.7:0.3:1:20, 0.0636g of cobalt nitrate, 0.0279g of zinc nitrate and 0.1352g of lanthanum nitrate are sequentially added and continuously stirred for dissolution; then 5mol/L (NH) is added4)2CO3The solution was 20mL and stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.7Zn0.3O3And MoS2LaCo with a theoretical molar ratio of 1:200.7Zn0.3O3/MoS2。
In a photocatalytic reaction device, 350g of (2) composite photocatalyst LaCo is added into a reaction tank 10.7Zn0.3O3/MoS2Adding 5L of N-methylmorpholine waste liquid with the COD value of 4200mg/L into the acid-base adjusting tank 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 6, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 6; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 77.5%. The obtained eggshell-shaped composite photocatalyst has perovskite nano particles uniformly dispersed in MoS2The surface is coated, and the energy level structure of the catalyst is reasonably adjusted and matched through 30 percent of Zn doping and semiconductor compounding, so that the catalyst can be used at normal temperatureThe reaction is carried out at normal temperature and pressure, the visible light is fully utilized to induce and generate strong oxidizing free radicals to degrade pollutants, the efficient mineralization is realized, and the sludge and the secondary pollution are not generated, so that the method is green and environment-friendly.
Example 4
(1) Petal-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:551.903g of thiourea, 2.0g of polyvinylpyrrolidone (PVP), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMF1:9) and adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the reaction product by water and absolute ethyl alcohol for a plurality of times, centrifugally separating the reaction product, placing the reaction product in an oven, and drying the reaction product at 80 ℃ for 12 hours to obtain petal-shaped MoS2。
(2)LaCo0.8Zn0.2O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the cobalt nitrate to the lanthanum nitrate is 0.8:0.2:1:20, 0.0727g of cobalt nitrate, 0.0186g of zinc nitrate and 0.1352g of lanthanum nitrate are added in sequence and are continuously stirred and dissolved; then 5mol/L (NH) is added4)2CO3The solution was 20mL and stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.8Zn0.2O3And MoS2LaCo with a theoretical molar ratio of 1:200.8Zn0.2O3/MoS2。
In a photocatalytic reaction device, 250g (2) of composite photocatalyst LaCo is added into a reaction tank 10.8Zn0.2O3/MoS2Adding 5L of N-acryloyl morpholine waste liquid with a COD value of 4500mg/L into the acid-base adjusting tank 2; starting the material circulating pump 5, the first regulating valve 11, the second regulating valve 12 and the third regulating valve 13, and passing the liquid in the acid-base regulating tank 2 through the third regulating valveA regulating valve 11 enters the mixer 6, and the pH electrode 10 is used for detecting the pH of the liquid; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 7; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 300W high-pressure mercury lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 78.5%. Petal-shaped MoS2Shows larger specific surface area, and forms the composite photocatalyst with high chemical stability and high catalytic activity with a proper amount of perovskite nano particles. The catalyst is combined with high-automation special photocatalysis equipment, the mass transfer efficiency and the degradation efficiency are greatly improved, the full flow is totally closed when the morpholine wastewater is degraded by photocatalysis, no secondary pollution is caused to the environment, and the catalyst is green, safe, efficient and environment-friendly.
Example 5
(1) Honeycomb-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:451.522g of thiourea, 1.50g of Polyoxyethylene Lauryl Ether (PLE), 30mL of a mixed solvent (V) of water and N, N-dimethylformamideH2O:VDMF1:5), adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the mixture for a plurality of times by water and absolute ethyl alcohol, centrifugally separating the mixture, placing the mixture in an oven, and drying the mixture for 12 hours at the temperature of 80 ℃ to obtain the honeycomb MoS2。
(2)LaCo0.7Zn0.3O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the raw materials is 0.7:0.3:1:10, 0.1273g of cobalt nitrate, 0.0558g of zinc nitrate and 0.2705g of lanthanum nitrate are sequentially added and continuously stirred for dissolution; then, 20mL of 5mol/L ethanolamine solution was added, and the stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.7Zn0.3O3And MoS2LaCo with a theoretical molar ratio of 1:100.7Zn0.3O3/MoS2。
In a photocatalytic reaction device, 350g of (2) composite photocatalyst LaCo is added into a reaction tank 10.7Zn0.3O3/MoS2Adding 5L of N-methylmorpholine waste liquid with the COD value of 4200mg/L into the acid-base adjusting tank 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 6, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 6; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 80.4%. Suitable Zn dopingThe method has the advantages that the impurity ratio, the proper perovskite load capacity and the optimal process conditions of special catalytic equipment are adopted, the N-methylmorpholine waste water is efficiently degraded and has a higher mineralization rate, the sludge and secondary pollution are not generated in the whole process, the method is green and environment-friendly, and the actual production and application are convenient.
Example 6
(1) Petal-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:551.903g of thiourea, 2.0g of polyvinylpyrrolidone (PVP), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMF1:9) and adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the reaction product by water and absolute ethyl alcohol for a plurality of times, centrifugally separating the reaction product, placing the reaction product in an oven, and drying the reaction product at 80 ℃ for 12 hours to obtain petal-shaped MoS2。
(2)LaCo0.7Zn0.3O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the raw materials is 0.7:0.3:1:10, 0.1273g of cobalt nitrate, 0.0558g of zinc nitrate and 0.2705g of lanthanum nitrate are sequentially added and continuously stirred for dissolution; then, 20mL of 5mol/L ethanolamine solution was added, and the stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.7Zn0.3O3And MoS2LaCo with a theoretical molar ratio of 1:100.7Zn0.3O3/MoS2。
In a photocatalytic reaction device, 350g of (2) composite photocatalyst LaCo is added into a reaction tank 10.7Zn0.3O3/MoS2Adding 5L of N-methylmorpholine oxide waste liquid with COD value of 6200mg/L into the acid-base regulating pool 2; starting the material circulating pump 5, the first regulating valve 11, the second regulating valve 12 and the third regulating valveThe liquid in the acid-base adjusting tank 2 enters the mixer 6 through the first adjusting valve 11, and the pH electrode 10 is used for detecting the pH of the liquid; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 7; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 82.2%. Selection of petal-shaped MoS with high specific surface area2Effective control of LaCo by mineralizer0.7Zn0.3O3In MoS2The deposition on the surface avoids the agglomeration of perovskite crystal grains, thereby obtaining the photocatalyst with high stability and high photocatalytic activity. The obtained catalyst is matched with special photocatalysis equipment to ensure that the catalyst reacts at normal temperature and normal pressure, and strong oxidizing free radicals are generated by sufficiently utilizing visible light induction to degrade pollutants, so that efficient mineralization is realized, sludge and secondary pollution are not generated, the method is green and environment-friendly, various oxidants are not used, and the cost is greatly saved.
Example 7
(1) Petal-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:551.903g of thiourea, 2.0g of polyvinylpyrrolidone (PVP), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMF1:9) and adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. After the reaction is finished, naturally cooling to room temperature, and then coolingWashing with water and anhydrous ethanol alternately for several times, centrifuging, drying in oven at 80 deg.C for 12 hr to obtain petal-shaped MoS2。
(2)LaCo0.7Zn0.3O3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, zinc nitrate, lanthanum nitrate and MoS2The molar ratio of the raw materials is 0.7:0.3:1:10, 0.1273g of cobalt nitrate, 0.0558g of zinc nitrate and 0.2705g of lanthanum nitrate are sequentially added and continuously stirred for dissolution; then, 20mL of 5mol/L ethanolamine solution was added, and the stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.7Zn0.3O3And MoS2LaCo with a theoretical molar ratio of 1:100.7Zn0.3O3/MoS2。
In a photocatalytic reaction device, 350g of (2) composite photocatalyst LaCo is added into a reaction tank 10.7Zn0.3O3/MoS2Adding 5L of N-methylmorpholine oxide waste liquid with a COD value of 1080mg/L into the acid-base adjusting tank 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 7; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve is switched11 and a second regulating valve 12 for discharging liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 93.1%. Has high stability, large specific surface area and high photocatalytic activity0.7Zn0.3O3/MoS2The method not only effectively promotes the separation of photogenerated electrons and holes, but also maintains strong oxidation-reduction capability, and shows higher degradation rate when treating the low-concentration N-methylmorpholine oxide waste liquid.
Comparative example 1
(1)LaCo0.7Zn0.3O3Preparation of
0.1273g of cobalt nitrate, 0.0558g of zinc nitrate and 0.2705g of lanthanum nitrate are sequentially added into 50mL of glycol solution according to the molar ratio of the cobalt nitrate to the zinc nitrate to the lanthanum nitrate of 0.7:0.3:1, and are continuously stirred and dissolved; then, 20mL of 5mol/L ethanolamine solution was added, and the stirring was continued for 60 min. The resulting solution was transferred to a reaction kettle and reacted at 200 ℃ for 36 h. After the reaction is finished, the LaCo is obtained by natural cooling, water and absolute ethyl alcohol are alternately washed and dried0.7Zn0.3O3。
In a photocatalytic reaction device, 350g of photocatalyst LaCo in (2) is added into a reaction tank 10.7Zn0.3O3Adding 5L of N-methylmorpholine oxide waste liquid with COD value of 6200mg/L into the acid-base regulating pool 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 7; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; the stirring paddles 7 are started up and,turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 35.6%. Single perovskite photocatalyst LaCo0.7Zn0.3O3Although the wastewater is degraded to a certain degree, photo-generated electrons and holes are easy to recombine in the photocatalysis process, so that the visible light photocatalysis activity is low, and the large-scale production and application of the wastewater are greatly limited.
Comparative example 2
(1) Petal-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:551.903g of thiourea, 2.0g of polyvinylpyrrolidone (PVP), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMF1:9) and adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the reaction product by water and absolute ethyl alcohol for a plurality of times, centrifugally separating the reaction product, placing the reaction product in an oven, and drying the reaction product at 80 ℃ for 12 hours to obtain petal-shaped MoS2。
In a photocatalytic reaction device, 350g of photocatalyst MoS in (2) is added into a reaction tank 12Adding 5L of N-methylmorpholine oxide waste liquid with COD value of 6200mg/L into the acid-base regulating pool 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 7; the direction of the third regulating valve 13 is switched, and the fourth regulating valve 14, opening, adding the liquid in the acid-base adjusting tank 2 to the reaction tank 1 by using a material circulating pump 5, and closing a fourth adjusting valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 40.8%. Similar to a single perovskite photocatalyst, the single molybdenum sulfide photocatalyst also has the problem that photoproduction electrons and holes are easy to compound in the photocatalysis process, and has low visible light catalytic activity and poor photocatalytic degradation effect.
Comparative example 3
(1) Petal-shaped MoS2Preparation of
1.366g of MoCl was weighed out in a molar ratio of 1:551.903g of thiourea, 2.0g of polyvinylpyrrolidone (PVP), 30mL of a mixed solvent of water and N, N-dimethylformamide (V)H2O:VDMF1:9) and adding hydrochloric acid to adjust the pH of the solution to 2. The resulting homogeneous solution was transferred to a reaction vessel with polytetrafluoroethylene and subjected to solvothermal reaction at 220 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, alternately cleaning the reaction product by water and absolute ethyl alcohol for a plurality of times, centrifugally separating the reaction product, placing the reaction product in an oven, and drying the reaction product at 80 ℃ for 12 hours to obtain petal-shaped MoS2。
(2)LaCoO3/MoS2Preparation of
Weighing 1g of MoS in (1)2Dispersing into 50mL of glycol solution, and carrying out ultrasonic treatment for 30min to form a suspension; according to cobalt nitrate, lanthanum nitrate and MoS2The molar ratio of the cobalt nitrate to the lanthanum nitrate is 1:1:10, 0.1818g of cobalt nitrate and 0.2705g of lanthanum nitrate are sequentially added and are continuously stirred and dissolved; then, 20mL of 5mol/L ethanolamine solution was added, and the stirring was continued for 60 min. The resulting mixture was transferred to a reaction vessel and reacted at 200 ℃ for 36 hours. After the reaction is finished, the LaCoO is obtained after natural cooling, water and absolute ethyl alcohol are alternately washed and dried3And MoS2LaCoO with a theoretical molar ratio of 1:103/MoS2。
In a photocatalytic reaction device, 350g of (2) composite photocatalyst LaCoZnO is added into a reaction tank 13/MoS2Adding 5L of N-methylmorpholine oxide waste liquid with COD value of 6200mg/L into the acid-base regulating pool 2; starting a material circulating pump 5, a first regulating valve 11, a second regulating valve 12 and a third regulating valve 13, enabling liquid in an acid-base regulating tank 2 to enter a mixer 6 through the first regulating valve 11, and detecting the pH value of the liquid by using a pH electrode 10; if the pH is not about 7, starting an acid-base liquid inlet pump 4 to add acid or alkali liquid flow in an acid/alkali liquid tank 3 to a mixer 6 to adjust the pH; the wastewater flows back to the acid-base adjusting tank 2 through the mixer 6, the material circulating pump 5, the second adjusting valve 12 and the third adjusting valve 13 to form a passage, and the acid-base liquid inlet pump 4 is stopped until the pH value is adjusted to about 7; switching the direction of the third regulating valve 13, opening the fourth regulating valve 14, adding the liquid in the acid-base regulating tank 2 to the reaction tank 1 by the material circulating pump 5, and closing the fourth regulating valve 14 when the liquid level reaches a certain height; starting the stirring paddle 7, turning on a light source on the reaction tank after a period of time, and carrying out photocatalytic degradation on the reaction under a 500W xenon lamp; after the photocatalytic reaction is finished, the stirring paddle 7 and the light source 8 are closed, and the first regulating valve 11 and the second regulating valve 12 are switched to discharge liquid; when the liquid level of the reaction tank 1 is lower than a set value, the system automatically finishes working. The COD concentration in the system is measured after 5 hours of reaction, and the result shows that the removal rate of COD is 59.4%. Petal-shaped MoS2Compounding with proper amount of lanthanum cobaltate nano particles to obtain composite photocatalyst LaCoO3/MoS2The degradation effect of the catalyst on morpholine wastewater is better than that of a single semiconductor catalyst, but the visible light utilization rate is still not high, and the photocatalytic degradation effect is not ideal.
Examples 1-7 Synthesis of MoS of different morphologies using DMAB, SDBS, PLE and PVP as surfactants, with different DMF to water ratios2And with (NH)4)2CO3One of ethanolamine and hexamethylenetetramine is used as a mineralizer to disperse and grow the perovskite on MoS2On the surface, the composite photocatalyst LaCo with different shapes is finally and successfully prepared1-xZnxO3/MoS2. In the visibleUnder a light source, any one of morpholine derivatives N-methylmorpholine, N-formyl morpholine, N-methylmorpholine oxide or N-acryloyl morpholine is catalytically degraded by using special photocatalysis equipment, and the COD degradation rate of a reaction system is over 75 percent. The catalyst with high stability and high photocatalytic activity is matched with special catalytic equipment for treating four kinds of morpholine wastewater, the catalytic process realizes a fully closed state, the unique photocatalytic reaction large circulation module and the acid-base regulation small circulation module are self-circulation systems, the mass transfer process is enhanced, the degradation efficiency is greatly improved, and the acid/alkali liquor in the acid-base regulation small circulation module does not directly contact a catalytic bed, so that the service life of the photocatalyst is effectively prolonged.
By comparing comparative example 1 with examples 1 to 7, perovskite LaCo alone was used1-xZnxO3As a photocatalyst, the single catalyst can easily recombine photogenerated electrons and holes in the photocatalysis process, and the photocatalytic activity of the single catalyst is lower than that of a composite photocatalyst LaCo1-xZnxO3/MoS2Photocatalytic activity of (a);
by comparison of comparative example 2 and examples 1 to 7, used alone as MoS2As a photocatalyst, the single catalyst has lower photocatalytic activity than that of a composite photocatalyst LaCo1-xZnxO3/MoS2And single MoS2The catalyst has poor light stability and short service life;
by comparing comparative example 3 with examples 1 to 7, a Zn-undoped composite photocatalyst LaCoO3/MoS2The photocatalytic activity of the photocatalyst is lower than that of a composite photocatalyst LaCo1-xZnxO3/MoS2The photocatalytic activity and proper zinc doping can reasonably adjust and match the energy level structure of the catalyst, so that the separation and migration of photoproduction electrons and holes are promoted, the strong redox capability can be kept, and the photocatalytic degradation effect is effectively improved.
Claims (8)
1. A composite photocatalyst for degrading morpholine wastewater is characterized in that: the general formula of the composite photocatalyst is LaCo1-xZnxO3/MoS2Wherein x is 0.1-0.5, and a carrier MoS2Perovskite nano particles and active material LaCo are dispersed on the surface1-xZnxO3Is in LaCoO3Is obtained by doping Zn in the mixture for modification.
2. The composite photocatalyst of claim 1, wherein the MoS is2The appearance of the material is sheet, eggshell, honeycomb or petal.
3. The composite photocatalyst of claim 1, wherein the morpholine-based wastewater is N-methylmorpholine, N-formylmorpholine, N-methylmorpholine oxide or N-acryloylmorpholine.
4. A preparation method of a composite photocatalyst for degrading morpholine wastewater is characterized by comprising the following steps:
(a) adding MoCl5Adding thiourea into a mixed solvent of water and N, N dimethylformamide, adding a surfactant, adjusting pH, carrying out thermal reaction, cooling, washing and drying to obtain MoS2；
(b) In MoS2Adding lanthanum nitrate, cobalt nitrate, zinc nitrate and mineralizer, stirring, cooling, washing and drying to obtain LaCo1-xZnxO3/MoS2。
5. The method of claim 4, wherein: in step (a), the MoCl5The mol ratio of the N-dimethyl formamide to thiourea is 1:2-10, the volume ratio of water to N, N-dimethyl formamide is 1:0.25-15, the surfactant is any one of dioctadecyl dimethyl ammonium bromide, sodium dodecyl benzene sulfonate, lauryl alcohol polyoxyethylene ether and polyvinylpyrrolidone, and MoCl5The mass ratio of the surfactant to the surfactant is 1: 0.2-3.0.
6. The method of claim 4, wherein: in step (b), the mineralizer is (NH)4)2CO3One of ethanolamine and hexamethylenetetramine, wherein the molar ratio of lanthanum nitrate to a mineralizer is 1: 0.05-0.8, the molar ratio of the cobalt nitrate to the zinc nitrate is 1:0.25-4, the mixture of the cobalt nitrate and the zinc nitrate, and the lanthanum nitrate and MoS2The molar ratio of (A) to (B) is 1:1: 6-30.
7. A special device for applying the composite photocatalyst of claim 1, which is characterized in that: comprises a reaction tank (1) for filling the composite photocatalyst of claim 1, a mixer (6) connected with an inlet of the reaction tank (1) for monitoring the pH value of wastewater, wherein the mixer (6) is connected with an acid/alkali liquid tank (3) and an acid-alkali regulation tank (2); the wastewater sequentially enters an acid-base adjusting tank (2) and a mixer (6), if the monitoring of the mixer (6) is qualified, the wastewater enters a reaction tank (1), if the monitoring of the mixer (6) is unqualified, the wastewater returns to the acid-base adjusting tank (2), and the pH value of the wastewater in the mixer (6) is adjusted in an acid/alkali liquid tank (3) until the monitoring is qualified.
8. The dedicated apparatus according to claim 7, characterized in that: a first outlet of the reaction tank (1) is communicated with the outside, a second outlet of the reaction tank is connected with the mixer (6), and a light source (8), a stirring paddle (7) and a liquid level indicator (9) are arranged on the reaction tank (1).
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