CN115845862A - Composite catalyst of modified sepiolite loaded reduced graphene oxide and Cu-Eu and preparation method thereof - Google Patents
Composite catalyst of modified sepiolite loaded reduced graphene oxide and Cu-Eu and preparation method thereof Download PDFInfo
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Abstract
The invention provides a composite catalyst of modified sepiolite loaded with reduced graphene oxide and Cu-Eu and a preparation method thereof, wherein the composite catalyst comprises the modified sepiolite and rGO, cu and Eu loaded on the modified sepiolite; wherein the modified sepiolite is prepared from Na 2 CO 3 The sepiolite is prepared after sodium modification. The composite catalyst prepared by the invention can effectively eliminate high-concentration formaldehyde (500-3000 ppm) at a lower temperature (30-90 ℃), has a good catalytic elimination effect, and has a higher stability; in addition, the composite catalyst has the advantages of simple preparation process, easy operation and low cost.
Description
Technical Field
The invention belongs to the technical field of preparation of formaldehyde catalysts, and particularly relates to a composite catalyst of modified sepiolite loaded reduced graphene oxide and Cu-Eu and a preparation method thereof.
Background
Formaldehyde (HCHO) is a colorless, toxic gas with a strong pungent odor, and is easily soluble in water, alcohol ethers, and the like. Formaldehyde, which is gaseous at normal temperature, is very volatile at room temperature, and its rate of volatilization increases with increasing temperature, is usually present as an aqueous solution, 37% of which is called formalin, the boiling point of which is 19 ℃.
The formaldehyde is widely available, and the formaldehyde generated by newly developed building materials, plastic cement and paint is a main source of indoor environment. In addition, formaldehyde can also be from cosmetics, detergents, insecticides, disinfectants, preservatives, printing ink, paper, textile fibers and other various chemical light industry products.
Formaldehyde, a highly toxic class of substances, is second-ranked on the chinese list of priority control of toxic chemicals, and has been identified by the world health organization as a carcinogenic and teratogenic substance, a recognized source of allergic reactions, and one of the potentially strong mutagens. The research shows that: formaldehyde has strong carcinogenic and carcinogenic effects. It is well documented that formaldehyde affects human health primarily in olfactory abnormalities, irritations, allergies, lung dysfunction, liver dysfunction, and immune dysfunction. When the concentration of formaldehyde in the air reaches 0.06-0.07 mg/m 3 When it is used, children can suffer slight asthma; the formaldehyde content reaches 0.1mg/m 3 In time, peculiar smell and uncomfortable feeling are generated; up to 0.5mg/m 3 It can stimulate eyes and cause lacrimation; up to 0.6mg/m 3 It can cause discomfort or pain in the throat. At higher concentrations, nausea, vomiting, cough, chest distress, asthma and even pulmonary edema can occur, reaching 30mg/m 3 And then immediately cause death. In 2004, formaldehyde was characterized by the international organization for cancer (IARC) as a primary carcinogen. The limit value of the indoor formaldehyde concentration of the non-working occasion specified in the standard implemented in China in 2002 is not higher than 0.1mg/m 3 This criterion may become more stringent with further assessment of chemical priority and exposure.
In consideration of the toxicity of formaldehyde and its harm to human body, the common treatment methods mainly include physical adsorption and catalysis. Wherein, the catalysis technology can completely oxidize the formaldehyde into carbon dioxide and water at room temperature, and is a real formaldehyde harmless treatment. At present, noble metal catalysts exhibit better performance for low-temperature catalytic oxidation, but have been limited to some extent in practical applications due to their high price, their relative ease of sintering at high temperatures, and the like. Therefore, the search for new catalytic materials to partially or completely replace noble metal catalysts has been a trend in the field of catalysis.
Disclosure of Invention
In view of the above, the present invention is directed to solving, at least to some extent, one of the problems in the related art. Therefore, the embodiment of the invention provides a composite catalyst of modified sepiolite loaded reduced graphene oxide and Cu-Eu and a preparation method thereof.
The embodiment of the invention provides a composite catalyst on one hand, which comprises modified sepiolite and rGO, cu and Eu which are loaded on the modified sepiolite;
wherein the modified sepiolite is prepared from Na 2 CO 3 The sepiolite is prepared after sodium modification.
In the composite catalyst of the embodiment of the invention, the sepiolite has low price, and the sepiolite has larger specific surface area, higher ion exchange capacity and better adsorption performance to formaldehyde due to the larger internal channel structure; meanwhile, the Cu and Eu are loaded, so that the electron transfer efficiency of the catalyst can be enhanced, the conversion of formaldehyde is further enhanced, the composite catalyst has a good catalytic elimination effect on formaldehyde, high-concentration formaldehyde can be efficiently eliminated at low temperature, and the composite catalyst has good stability.
In some embodiments of the invention, the Cu loading in the composite catalyst is ≦ 10wt%, preferably 3 to 10wt%; the Eu loading amount is less than or equal to 5wt%, preferably 2-5 wt%; the loading of the rGO is less than or equal to 2wt percent, and preferably ranges from 0.5 to 2wt percent.
In some embodiments of the invention, the BET specific surface area of the composite catalyst is 90 to 118m 2 /g。
The embodiment of the invention also provides a preparation method of the composite catalyst, which comprises the following steps:
(1) Preparation of modified sepiolite
Adding Na into purified sepiolite 2 CO 3 Obtaining a mixture; stirring the mixture for 4-8 h at the temperature of 60-80 ℃; then aging for 30-50 h at room temperature, cleaning, filtering, and drying for 24h at 80-120 ℃ to obtain modified sepiolite;
(2) Preparation of Cu-Eu/rGO suspensions
Dispersing single-layer graphene oxide powder in deionized water, and carrying out ultrasonic treatment for 6-10 h to obtain a single-layer graphene oxide suspension solution; adding copper nitrate and europium nitrate into deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; under the condition of ice-water bath at the temperature of between 10 ℃ below zero and 0 ℃, adding the single-layer graphene oxide suspension solution and polyvinyl alcohol into the mixed solution of copper nitrate and europium nitrate, stirring for 1 to 2 hours, and then injecting NaBH 4 The solution forms a dark brown suspension, and the solution is continuously stirred for 1 to 2 hours to obtain a Cu-Eu/rGO suspension;
(3) Preparation of the composite catalyst
Adding the modified sepiolite into the Cu-Eu/rGO suspension, stirring for 6-10 h, and then cleaning, drying and calcining to obtain the composite catalyst.
In the preparation method of the composite catalyst of the embodiment of the invention, firstly, the composite catalyst is prepared by adoptingNa 2 CO 3 The preparation method is simple in process and easy to operate, and the adopted raw materials are low in price and low in production cost.
In some embodiments of the invention, in step (1), in the mixture, na + The mass ratio of the sepiolite to the sepiolite is (2-6) to (100-120).
In some embodiments of the invention, in the step (2), the single-layer graphene oxide powder is 0.005 to 0.1 part by weight; 0.058-1.45 parts of copper nitrate; 0.022-0.55 part of europium nitrate; the polyvinyl alcohol accounts for 0.012 to 0.045 part.
In some embodiments of the invention, in step (2), the NaBH 4 The concentration of the solution is 1.5-3.0 g/L.
In some embodiments of the present invention, in the step (3), the drying temperature is 100 to 120 ℃ and the drying time is 12 to 24 hours.
In some embodiments of the invention, in the step (3), the calcination temperature is 400-500 ℃, the calcination time is 2-4 h, and the heating rate is 3-5 ℃/min.
The embodiment of the invention also provides application of the composite catalyst in catalytic elimination of formaldehyde, wherein the concentration of the formaldehyde is 500-3000 ppm.
The invention has the advantages and beneficial effects that:
in the embodiment of the invention, the reduced graphene oxide, cu and Eu are loaded on the sepiolite subjected to sodium modification to prepare the Cu-Eu/rGO/modified sepiolite composite catalyst, the composite catalyst has a good formaldehyde catalysis effect, high-concentration formaldehyde (500-3000 ppm) can be efficiently eliminated at a low temperature (30-90 ℃), and the composite catalyst has good stability; in addition, the composite catalyst has the advantages of simple preparation process, easy operation and low cost.
Drawings
FIG. 1 is an XRD pattern of catalysts prepared in examples 1 to 3 of the present invention and comparative example 1.
FIG. 2 is a graph showing N values of catalysts obtained in examples 1 to 3 of the present invention and comparative example 1 2 Adsorption/desorption scheme.
FIG. 3 is a graph showing the activity of catalysts prepared in examples 1 to 3 of the present invention and comparative example 1 for catalyzing the oxidation of formaldehyde.
FIG. 4 is a graph showing stability tests of catalysts prepared in examples 1 to 3 of the present invention and comparative example 1 reacted at 70 ℃ for 120 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The embodiment of the invention provides a composite catalyst on one hand, which comprises modified sepiolite, rGO (reduced graphene oxide), cu and Eu, wherein the rGO (reduced graphene oxide) is loaded on the modified sepiolite;
wherein the modified sepiolite is prepared from Na 2 CO 3 The sepiolite is prepared after sodium modification.
In the composite catalyst of the embodiment of the invention, the sepiolite has low price and contains rich hydroxyl, and can well adsorb aldehyde group of formaldehyde; meanwhile, the electronic migration efficiency of the catalyst can be enhanced by loading a certain amount of Cu and Eu, so that the conversion of formaldehyde is enhanced, and the Cu and Eu are cheaper than noble metals, so that the composite catalyst in the embodiment of the invention has lower cost, has a good catalytic elimination effect on formaldehyde, can effectively eliminate high-concentration formaldehyde at low temperature, and has good stability.
In some embodiments of the invention, the Cu loading is ≦ 10wt% (non-limiting examples are 1wt%, 3wt%, 5wt%, 8wt%, 10wt%, etc.), preferably 3 to 10wt% (non-limiting examples are 3wt%, 5wt%, 8wt%, 10wt%, etc.) in the composite catalyst; eu loading amount of 5 wt.% (non-limiting examples are 1 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, etc.), preferably 2 to 5 wt.% (non-limiting examples are 2 wt.%, 4 wt.%, 5 wt.%, etc.); rGO loading ≦ 2wt% (non-limiting examples are 0.2wt%, 0.5wt%, 1wt%, 1.2wt%, 1.5wt%, 2wt%, etc.), preferably 0.5 to 2wt% (non-limiting examples are 0.5wt%, 1wt%, 1.2wt%, 2wt%, etc.).
In some embodiments of the invention, the BET specific surface area of the composite catalyst is from 90 to 118m 2 (non-limiting examples are 90 m) 2 /g、95m 2 /g、100m 2 /g、110m 2 /g、118m 2 In terms of/g, etc.).
The embodiment of the invention also provides a preparation method of the composite catalyst, which comprises the following steps:
(1) Preparation of modified sepiolite
Adding Na into purified sepiolite 2 CO 3 Obtaining a mixture; stirring the mixture for 4-8 h at the temperature of 60-80 ℃; then aging for 30-50 h at room temperature, cleaning, filtering, and drying for 24h at 80-120 ℃ to obtain modified sepiolite;
(2) Preparation of Cu-Eu/rGO suspensions
Dispersing single-layer graphene oxide powder in deionized water, and carrying out ultrasonic treatment for 6-10 h to obtain a single-layer graphene oxide suspension solution; adding copper nitrate and europium nitrate into deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; under the condition of ice-water bath at the temperature of between 10 ℃ below zero and 0 ℃, adding the single-layer graphene oxide suspension solution and polyvinyl alcohol into the mixed solution of copper nitrate and europium nitrate, stirring for 1 to 2 hours, and then injecting NaBH 4 The solution forms dark brown suspension liquid, and the mixture is continuously stirred for 1 to 2 hours to obtain Cu-Eu/rGO suspension liquid;
(3) Preparation of the composite catalyst
Adding the modified sepiolite into the Cu-Eu/rGO suspension, stirring for 6-10 h, and then cleaning, drying and calcining to obtain the composite catalyst.
In the preparation method of the composite catalyst of the embodiment of the invention, na is adopted firstly 2 CO 3 The preparation method is simple in process and easy to operate, and the adopted raw materials are cheap, and the production cost is low.
In some embodiments of the invention, in step (1), in the mixture, na + The weight ratio of the sepiolite to the sepiolite is (2-6) to (100-120), and the non-limiting examples are as follows: 2. By carrying out sodium modification on the sepiolite, the sepiolite improves the thermal stability and the cation exchange capacity on the premise of not changing the structure of the sepiolite, is beneficial to the loading of subsequent active components, and improves the adsorption capacity of the sepiolite on formaldehyde.
In some embodiments of the present invention, in step (1), the specific process for purifying sepiolite is: adding sepiolite into deionized water according to the mass ratio of (0.5-3) to (100-300), and stirring for 12-24 h to ensure that the sepiolite fully absorbs water and expands; and stirring and standing for 1-2 h, mixing the suspension with a small amount of ammonium carbonate and standing for 0.5-2 h, pouring out supernatant, washing the obtained slurry with deionized water, performing suction filtration, and drying in an oven at 80-110 ℃ for 12-18 h to obtain the purified sepiolite.
In some embodiments of the present invention, in step (2), the monolayer graphene oxide powder is 0.005 to 0.1 parts by weight (for example, but not limited to, 0.005, 0.01, 0.02, 0.1, etc.); 0.058 to 1.45 parts of copper nitrate (for example, but not limited to, 0.058, 0.145, 0.29, 1.45 and the like); 0.022 to 0.55 parts of europium nitrate (for example, but not limited to, 0.022, 0.055, 0.11, 0.55, etc.); polyvinyl alcohol is 0.012 to 0.045 parts (for example, but not limited to, 0.012, 0.03, 0.045, etc.).
In some embodiments of the invention, in step (2), the NaBH 4 The concentration of the solution is 1.5-3.0 g/L (non-limiting examples are 1.5g/L, 1.8g/L, 2.0g/L, 2.5g/L, 3.0g/L, etc.).
In some embodiments of the invention, in step (3), the temperature of drying is between 100 and 120 ℃ (non-limiting examples: 100 ℃, 110 ℃, 115 ℃, 120 ℃, etc.); the drying time is 12-24 h (such as 12h, 15h, 18h, 20h, 24h and the like without limitation).
In some embodiments of the invention, in step (3), the temperature of calcination is 400-500 ℃ (such as, without limitation, 400 ℃, 420 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, etc.); the calcination time is 2 to 4 hours (such as 2 hours, 2.5 hours, 3 hours, 4 hours and the like without limitation); the heating rate is 3-5 deg.C/min (such as 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, etc., without limitation).
The embodiment of the invention also provides application of the composite catalyst in catalytic elimination of formaldehyde, wherein the concentration of the formaldehyde is 500-3000 ppm.
The following are non-limiting examples of the invention and comparative examples, which are to be construed as follows: the solution of the comparative example is not prior art, is provided only for comparison with the solution of the example, and is not intended as a limitation on the invention; the experimental methods in which specific conditions are not noted in examples and comparative examples are conventional methods and conventional conditions well known in the art.
Example 1
A preparation method of the composite catalyst comprises the following steps:
(1) Preparation of modified sepiolite
Adding Na into purified sepiolite 2 CO 3 To obtain a mixture (in the mixture, na) + The mass ratio of the sepiolite to the raw material is 2); the mixture was stirred at 70 ℃ for 4h; then aging for 48h at room temperature, washing with deionized water, filtering, and drying at 100 ℃ for 24h to obtain modified sepiolite;
(2) Preparation of Cu-Eu/rGO suspensions
Dispersing 0.005g of single-layer graphene oxide powder in 200mL of deionized water, and carrying out ultrasonic treatment for 10 hours to obtain a single-layer graphene oxide suspension solution; will be 0.22Adding copper nitrate and europium nitrate 0.083g into 200mL of deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; under the condition of ice-water bath at 0 ℃, adding the obtained single-layer graphene oxide suspension solution and 0.04g of polyvinyl alcohol into a mixed solution of copper nitrate and europium nitrate, stirring for 1h, and then injecting 2.0g/L NaBH 4 The solution forms a dark brown suspension, and the Cu-Eu/rGO suspension is obtained after the solution is continuously stirred for 2 hours;
(3) Preparation of the composite catalyst
Adding 1.0g of modified sepiolite into the Cu-Eu/rGO suspension, stirring for 10 hours, washing a product twice by using deionized water and absolute ethyl alcohol, and drying in an oven at 110 ℃ for 24 hours; and finally, placing the dried product in a muffle furnace, heating to 430 ℃ at the heating rate of 3 ℃/min, and calcining for 3h to obtain the composite catalyst, wherein the obtained composite catalyst is marked as Cu-Eu/rGO/NaSep-I.
N-Cu-Eu/rGO/NaSep-I from example 1 2 The results of the adsorption/desorption tests are shown in FIG. 2, from FIG. 2 it can be seen that the isotherms of Cu-Eu/rGO/NaSep-I correspond to type I in the lower range of relative pressures, due to the presence of the microporous structure; when the relative pressure is in the range of 0.8-1.0, the catalyst is an IV-type isotherm and an H3-type hysteresis loop, which indicates that the catalyst has a mesoporous structure; and has a BET specific surface area of 95m 2 /g。
The activity test of catalytic oxidation of formaldehyde was performed on the Cu-Eu/rGO/NaSep-I prepared in example 1 under the following test conditions: the reaction pressure is normal pressure 1atm, the space velocity is 200,000h -1 、20vol.％O 2 Formaldehyde concentration 1000ppm, equilibrium gas N 2 . As shown in FIG. 3, it can be seen from FIG. 3 that Cu-Eu/rGO/NaSep-I has high catalytic activity (formaldehyde conversion rate of 10-100%) in the temperature range of 30-90 deg.C, and it completely converts formaldehyde at 90 deg.C.
The stability test was performed on the Cu-Eu/rGO/NaSep-I prepared in example 1 under the following test conditions: the test temperature is 75 ℃, the reaction pressure is normal pressure and 1atm, the space velocity is 200,000h -1 、20vol.％O 2 Formaldehyde concentration 1000ppm and balance gas N 2 . The results are shown in FIG. 4, and it can be seen from FIG. 4 that the present invention is applicableThe composite catalyst Cu-Eu/rGO/NaSep-I prepared in the embodiment 1 still keeps good stability within 120 hours, and the conversion rate of formaldehyde is maintained at about 70%.
Example 2
A preparation method of the composite catalyst comprises the following steps:
(1) Preparation of modified sepiolite
Adding Na into purified sepiolite 2 CO 3 To obtain a mixture (in the mixture, na) + The mass ratio of the sepiolite to the raw material is 3); the mixture was stirred at 70 ℃ for 4h; then aging for 48h at room temperature, washing with deionized water, filtering, and drying at 100 ℃ for 24h to obtain modified sepiolite;
(2) Preparation of Cu-Eu/rGO suspensions
Dispersing 0.01g of single-layer graphene oxide powder in 200mL of deionized water, and carrying out ultrasonic treatment for 10 hours to obtain a single-layer graphene oxide suspension solution; adding 0.145g of copper nitrate and 0.055g of europium nitrate into 200mL of deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; adding the obtained single-layer graphene oxide suspension solution and 0.03g of polyvinyl alcohol into a mixed solution of copper nitrate and europium nitrate under the condition of an ice-water bath at the temperature of-5 ℃, stirring for 1h, and then injecting 2.0g/L of NaBH 4 The solution forms dark brown suspension liquid, and Cu-Eu/rGO suspension liquid is obtained after the solution is continuously stirred for 2 hours;
(3) Preparation of the composite catalyst
Adding 1.0g of modified sepiolite into the Cu-Eu/rGO suspension, stirring for 10 hours, washing a product twice by using deionized water and absolute ethyl alcohol, and drying in an oven at 100 ℃ for 24 hours; and finally, placing the dried product in a muffle furnace, heating to 400 ℃ at the heating rate of 5 ℃/min, and calcining for 3 hours to obtain the composite catalyst, namely Cu-Eu/rGO/NaSep-II.
N-treatment of Cu-Eu/rGO/NaSep-II prepared in example 2 2 The results of the adsorption/desorption tests are shown in FIG. 2, and it can be seen from FIG. 2 that the composite catalyst Cu-Eu/rGO/NaSep-II prepared in the example 2 has the same micropore and mesopore structures; and has a BET specific surface area of 100m 2 /g。
The activity test of catalytic oxidation of formaldehyde was performed on the Cu-Eu/rGO/NaSep-ii prepared in this example 2 under the following test conditions: the reaction pressure is normal pressure 1atm, the space velocity is 240,000h -1 、20vol.％O 2 The concentration of formaldehyde is 1500ppm, the balance gas is N 2 . As shown in FIG. 3, it can be seen from FIG. 3 that Cu-Eu/rGO/NaSep-II has high catalytic activity (formaldehyde conversion rate is 10-100%) in the temperature range of 30-80 deg.C, and it can completely convert formaldehyde at 80 deg.C.
The stability test of Cu-Eu/rGO/NaSep-II prepared in the embodiment 2 is carried out under the following test conditions: the test temperature is 75 ℃, the reaction pressure is normal pressure and 1atm, the space velocity is 240,000h -1 、20vol.％O 2 Formaldehyde concentration 1000ppm and balance gas N 2 . As shown in FIG. 4, it can be seen from FIG. 4 that the composite catalyst Cu-Eu/rGO/NaSep-II prepared in this example 2 still maintains good stability for 120 hours, and the conversion rate of formaldehyde is maintained at about 90%.
Example 3
A preparation method of the composite catalyst comprises the following steps:
(1) Preparation of modified sepiolite
Adding Na into purified sepiolite 2 CO 3 To obtain a mixture (in the mixture, na) + The mass ratio of the sepiolite to the raw material is 6); the mixture was stirred at 70 ℃ for 4h; then aging for 48h at room temperature, washing with deionized water, filtering, and drying at 100 ℃ for 24h to obtain modified sepiolite;
(2) Preparation of Cu-Eu/rGO suspensions
Dispersing 0.02g of single-layer graphene oxide powder in 200mL of deionized water, and carrying out ultrasonic treatment for 10 hours to obtain a single-layer graphene oxide suspension solution; adding 0.29g of copper nitrate and 0.11g of europium nitrate into 200mL of deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; under the condition of ice-water bath at 0 ℃, adding the obtained single-layer graphene oxide suspension solution and 0.045g of polyvinyl alcohol into a mixed solution of copper nitrate and europium nitrate, stirring for 1h, and then injecting 2.0g/L NaBH 4 The solution formed a dark brown suspensionContinuously stirring for 2 hours to obtain a Cu-Eu/rGO suspension liquid;
(3) Preparation of the composite catalyst
Adding 1.0g of modified sepiolite into the Cu-Eu/rGO suspension, stirring for 10 hours, washing a product twice by using deionized water and absolute ethyl alcohol, and drying in an oven at 120 ℃ for 24 hours; and finally, placing the dried product in a muffle furnace, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 3h to obtain the composite catalyst, wherein the composite catalyst is marked as Cu-Eu/rGO/NaSep-III.
The Cu-Eu/rGO/NaSep-III prepared in the example 3 is subjected to N 2 The results of the adsorption/desorption test are shown in fig. 2, and it can be seen from fig. 2 that the composite catalyst Cu-Eu/rGO/NaSep-iii prepared in the example 3 has the same microporous and mesoporous structure; and has a BET specific surface area of 118m 2 /g。
The activity test of catalytic oxidation of formaldehyde was performed on the Cu-Eu/rGO/NaSep-iii prepared in this example 3 under the following test conditions: the reaction pressure is normal pressure 1atm, the space velocity is 360,000h -1 、20vol.％O 2 The concentration of formaldehyde is 1500ppm, the balance gas is N 2 . As shown in FIG. 3, it can be seen from FIG. 3 that Cu-Eu/rGO/NaSep-III has high catalytic activity (formaldehyde conversion rate is 10-100%) in the temperature range of 30-75 ℃, and complete conversion of formaldehyde can be realized at 75 ℃.
The stability test of Cu-Eu/rGO/NaSep-III prepared in the embodiment 3 is carried out under the following test conditions: the test temperature is 75 ℃, the reaction pressure is 1atm under normal pressure, the space velocity is 360,000h -1 、20vol.％O 2 Formaldehyde concentration 1000ppm and balance gas N 2 . As shown in fig. 4, it can be seen from fig. 4 that the composite catalyst Cu-Eu/rGO/NaSep-iii prepared in this example 3 still maintains good stability for 120 hours, maintains the conversion rate of formaldehyde at about 100%, and shows excellent catalytic elimination effect for high concentration formaldehyde.
Comparative example 1
A method of preparing a catalyst comprising the steps of:
(1) Preparation of modified sepiolite
Purified sea foamAdding Na into stone 2 CO 3 To obtain a mixture (in the mixture, na) + The mass ratio of the sepiolite to the raw material is 2); the mixture was stirred at 70 ℃ for 4h; then aging for 48h at room temperature, washing with deionized water, filtering, and drying at 100 ℃ for 24h to obtain modified sepiolite;
(2) Preparation of a Cu-Eu suspension
Adding 0.145g of copper nitrate and 0.055g of europium nitrate into 200mL of deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; under the condition of ice-water bath at the temperature of minus 10 ℃, 0.03g of polyvinyl alcohol is added into a mixed solution of copper nitrate and europium nitrate, and after stirring for 1h, a Cu-Eu suspension is obtained;
(3) Preparation of the catalyst
Adding 1.0g of sodium sepiolite into the Cu-Eu suspension, stirring for 10h, washing a product by deionized water, and drying in an oven at 100 ℃ for 12h; and then placing the dried product in a muffle furnace, heating to 400 ℃ at the heating rate of 5 ℃/min, and calcining for 3h to obtain the catalyst, which is recorded as Cu-Eu/NaSep.
N treatment of Cu-Eu/NaSep prepared in comparative example 1 2 The adsorption/desorption test showed that the BET specific surface area of the composite catalyst Cu-Eu/NaSep prepared in comparative example 1 was 72m, as shown in FIG. 2, and it can be seen from FIG. 2 2 /g。
The activity test of catalytic oxidation formaldehyde is carried out on the Cu-Eu/NaSep prepared in the comparative example 1, and the test conditions are as follows: the reaction pressure is normal pressure 1atm, the space velocity is 150,000h -1 、20vol.％O 2 Formaldehyde concentration 1000ppm, equilibrium gas N 2 . As shown in FIG. 3, it can be seen from FIG. 3 that the Cu-Eu/NaSep catalyst prepared in comparative example 1 can completely convert formaldehyde at 100 ℃; and the conversion rate of the catalyst to formaldehyde is lower than that of the composite catalyst prepared in the embodiment 1-3 of the invention.
The stability test was performed on the Cu-Eu/NaSep prepared in comparative example 1 under the following test conditions: the test temperature is 75 ℃, the reaction pressure is normal pressure and 1atm, the space velocity is 150,000h -1 、20vol.％O 2 Formaldehyde concentration 1000ppm and balance gas N 2 . The results are shown in FIG. 4, which is a graph of FIG. 4It can be seen that the catalyst Cu-Eu/NaSep prepared in comparative example 1 has good stability, but the formaldehyde conversion rate is low, and is only maintained at about 60%, which is lower than that of the composite catalysts prepared in examples 1-3 of the invention.
XRD tests were performed on the catalysts prepared in examples 1 to 3 according to the present invention and comparative example 1, respectively, and as a result, as shown in fig. 1, it can be seen from fig. 1 that characteristic diffraction peaks of sepiolite generally appear at 20 °, 26 °, 28 °, 35 °, 40 ° and 50 °, and no diffraction peaks of Cu and Eu are observed in XRD diffraction patterns after loading rGO, cu and Eu, indicating that the loaded Cu and Eu are uniformly dispersed on the surface of sepiolite.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The composite catalyst is characterized by comprising modified sepiolite and rGO, cu and Eu which are loaded on the modified sepiolite;
wherein the modified sepiolite is prepared from Na 2 CO 3 The sepiolite is prepared after sodium modification.
2. The composite catalyst of claim 1, wherein the composite catalyst has a Cu loading of 10wt% or less, a Eu loading of 5wt% or less, and a rGO loading of 2wt% or less.
3. The composite catalyst according to claim 1, wherein the BET specific surface area of the composite catalyst is 90 to 118m 2 /g。
4. A method for preparing the composite catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) Preparation of modified sepiolite
Adding Na into purified sepiolite 2 CO 3 Obtaining a mixture; stirring the mixture at 60-80 ℃ for 4-8 h; then aging for 30-50 h at room temperature, cleaning, filtering, and drying for 24h at 80-120 ℃ to obtain modified sepiolite;
(2) Preparation of Cu-Eu/rGO suspensions
Dispersing single-layer graphene oxide powder in deionized water, and carrying out ultrasonic treatment for 6-10 h to obtain a single-layer graphene oxide suspension solution; adding copper nitrate and europium nitrate into deionized water, and uniformly mixing to obtain a mixed solution of the copper nitrate and the europium nitrate; under the condition of ice-water bath at the temperature of between 10 ℃ below zero and 0 ℃, adding the single-layer graphene oxide suspension solution and polyvinyl alcohol into the mixed solution of copper nitrate and europium nitrate, stirring for 1 to 2 hours, and then injecting NaBH 4 The solution forms a dark brown suspension, and the solution is continuously stirred for 1 to 2 hours to obtain a Cu-Eu/rGO suspension;
(3) Preparation of the composite catalyst
Adding the modified sepiolite into the Cu-Eu/rGO suspension, stirring for 6-10 h, and then cleaning, drying and calcining to obtain the composite catalyst.
5. The method for preparing a composite catalyst according to claim 4, wherein in the step (1), in the mixture, na is contained + The mass ratio of the sepiolite to the sepiolite is (2-6) to (100-120).
6. The preparation method of the composite catalyst according to claim 4, wherein in the step (2), the single-layer graphene oxide powder is 0.005-0.1 parts by weight; 0.058 to 1.45 parts of copper nitrate; 0.022-0.55 part of europium nitrate; the polyvinyl alcohol accounts for 0.012 to 0.045 part.
7. The method for preparing the composite catalyst according to claim 4, wherein in the step (2), the NaBH is added 4 The concentration of the solution is 1.5-3.0 g/L.
8. The method for preparing the composite catalyst according to claim 4, wherein the drying temperature in the step (3) is 100 to 120 ℃ and the drying time is 12 to 24 hours.
9. The method for preparing the composite catalyst according to claim 4, wherein in the step (3), the calcination temperature is 400 to 500 ℃ and the calcination time is 2 to 4 hours.
10. The application of the composite catalyst in catalytic elimination of formaldehyde is characterized in that: the composite catalyst is the composite catalyst according to any one of claims 1 to 3, or the composite catalyst prepared by the preparation method according to any one of claims 4 to 9; further, the concentration of the formaldehyde is 500-3000 ppm.
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