CN116282020A - New application of copper selenide catalyst - Google Patents

New application of copper selenide catalyst Download PDF

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CN116282020A
CN116282020A CN202310167189.2A CN202310167189A CN116282020A CN 116282020 A CN116282020 A CN 116282020A CN 202310167189 A CN202310167189 A CN 202310167189A CN 116282020 A CN116282020 A CN 116282020A
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copper selenide
catalyst
carbon dioxide
copper
solid
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马懿星
石玮麟
张欣
陈怡�
宁平
王郎郎
王学谦
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Kunming University of Science and Technology
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Abstract

The invention discloses a copper selenide catalyst for decomposing CO in low-temperature dielectric barrier discharge plasma 2 In the invention, the dielectric barrier discharge plasma is cooperated with the copper selenide catalyst to directly decompose carbon dioxide, and when the specific energy input is 5-60kJ/L, the temperature is lowThe temperature is 35-100 ℃, and can catalyze and decompose CO 2 The CO is obtained, the carbon dioxide conversion rate is 9.88-28.05%, the carbon monoxide selectivity is more than or equal to 99%, the preparation process of the copper selenide catalyst is simple, and the copper selenide catalyst can efficiently decompose CO under the synergistic effect with plasma 2 The invention provides an effective catalytic conversion path for the technology of converting carbon dioxide by plasma.

Description

New application of copper selenide catalyst
Technical Field
The invention relates to a carbon dioxide decomposition catalyst, in particular to a preparation method of a copper selenide catalyst and a method for directly decomposing CO in low-temperature dielectric barrier discharge plasma 2 Is used in the field of applications.
Background
With the progress of technology and the development of society, the use amount of fossil fuels has been increased year by year, and serious climate change problems have been caused by the annual increase of the contents of carbon dioxide and carbon monoxide in the atmosphere. The problem of carbon dioxide emission is mainly solved by starting from carbon capture and utilization. Due to the stable molecular structure of carbon dioxide, the pressure is 1bar at 1673K, and the conversion is only 0.2%. Conventional thermodynamic reactions are not able to decompose them efficiently. At present, technologies of carbon dioxide conversion mainly include technologies of photocatalytic conversion, thermocatalytic conversion, electrocatalytic conversion, plasma catalysis and the like. The low-temperature plasma technology is widely applied in the field of carbon dioxide conversion, and the low-temperature plasma has the characteristics of low reaction temperature, high activity, high energy density and low energy consumption, can generate synergistic effect with a catalyst, and is a carbon dioxide conversion technology with great prospect. The low-temperature plasma technology is mainly divided into microwave discharge plasma, sliding arc discharge plasma and dielectric barrier discharge plasma. Among them, dielectric barrier discharge plasma is the most widely studied plasma technology at present, and carbon dioxide can be directly decomposed into carbon monoxide and oxygen by collision of high-energy electrons generated by plasma. Currently, dielectric barrier discharge plasma technology has been widely used in the field of carbon dioxide conversion.
The ultimate purpose of the carbon dioxide decomposition reaction is to convert carbon dioxide into carbon monoxide and oxygen, but the energetic electrons inside the plasma may further break down the carbon-oxygen bonds of the carbon monoxide so that the decomposition reaction produces carbon deposits or ozone, and thus, it is very challenging to control the selectivity of the product.
In CN108430914a, a method for decomposing carbon dioxide by using a hot blast stove is disclosed, which comprises separating carbon dioxide from exhaust gas discharged from a blast furnace, transporting the carbon dioxide into a regeneration chamber of the hot blast stove, and decomposing the carbon dioxide by using heat energy stored in the regeneration chamber of the hot blast stove and combustion heat of methane gas supplied from the outside, which requires heating to 1250 ℃ for carbon dioxide decomposition, and has a problem of high energy consumption.
CN103464134a discloses a method for preparing a catalyst for preparing carbon monoxide by decomposing carbon dioxide, which is characterized in that a composite metal oxide is obtained by doping a solid solution of cerium and zirconium with magnesium and calcium. The catalyst preparation in this scheme uses rare earth metal doping, and has the problem of high cost.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of a copper selenide catalyst and a method for directly decomposing CO in low-temperature dielectric barrier discharge plasma 2 The conversion rate of directly decomposing carbon dioxide by the single low-temperature dielectric barrier discharge plasma and the selectivity of products can be improved.
In order to achieve the reaction effect, the invention provides the following technical scheme:
1. the copper selenide catalyst is prepared by hydrothermal synthesis, and the loading amount of the copper selenide is 1-10% by mass;
the specific preparation process is as follows:
A. copper salt and 1.5-1.8g of ethylenediamine tetraacetic acid are added into 1-1.5mmol/L of sodium hydroxide solution at the same time, ultrasonic treatment is carried out after mixing, then 0.1-0.2g of hydrazine hydrate and 12-16mL of hydrazine hydrate are sequentially added into the mixture, after stirring and mixing evenly, the mixture is transferred into a high-pressure reaction kettle to react for 2-12h at 140-220 ℃, the mixture is naturally cooled to room temperature, hydrochloric acid solution with the concentration of 1-1.5mol/L is added into the reaction product for 20-30mL, after reacting for 10-20min, solid-liquid separation is carried out, the solid is sequentially washed by deionized water and absolute ethyl alcohol, each washing is carried out for 3 times, and the washed product is dried in vacuum, thus obtaining the copper selenide catalyst.
B. Fully dissolving copper salt in deionized water to obtain a mixed solution, and adding gamma-Al into the mixed solution 2 O 3 Fully stirring the carrier, and drying at 75-85 ℃ to obtain a dried product; 1.5-1.7g of dried materials and 1.5-1.8g of ethylenediamine tetraacetic acid are added into 1-1.5mmol/L of sodium hydroxide solution at the same time, ultrasonic treatment is carried out after mixing until the ethylenediamine tetraacetic acid is completely dissolved, 0.1-0.2g of sodium selenite and 12-16mL of hydrazine hydrate are sequentially added into the mixture, the mixture is stirred and mixed uniformly, then the mixture is transferred into a high-pressure reaction kettle with polytetrafluoroethylene lining, the reaction is carried out for 2-12h at 140-220 ℃, the reaction kettle is naturally cooled to room temperature, 1-1.5mol/L of hydrochloric acid solution is added into the reaction product for 20-30mL, after the reaction is carried out for 10-20min, solid-liquid separation is carried out, the solid is washed for 3 times by deionized water and absolute ethyl alcohol in sequence, and the washed product is dried in vacuum, thus obtaining the copper selenide nano catalyst.
2. The copper selenide catalyst prepared by the method is applied to low-temperature dielectric barrier discharge plasma to decompose CO 2 In the reaction, the specific energy input is 5-60kJ/L, and the experimental result shows that the catalyst prepared by the invention can decompose CO at the low temperature of 35-100 DEG C 2 And the carbon dioxide conversion rate is 9.88-28.05%.
Compared with the prior art, the invention has the following advantages:
compared with the traditional high-temperature high-pressure selenide synthesis method, the preparation method has the advantages that the copper selenide catalyst is prepared by a hydrothermal method, the preparation process is simpler, and the conditions are not harsh;
copper selenide nano catalyst and dielectric barrier discharge plasma technology are synergistic, the conversion rate is improved by more than 4 times compared with that of single plasma for decomposing carbon dioxide, and the carbon monoxide selectivity is more than or equal to 99 percent, so that the CO is converted by the plasma 2 The technology provides an effective catalytic conversion pathway.
Drawings
FIG. 1 is a graph of CO decomposition with the copper selenide nanocatalyst of example 1 2 Conversion and CO selectivity results of (2)；
FIG. 2 is a graph of CO decomposition with the copper selenide nanocatalyst of example 2 2 Conversion and CO selectivity results;
FIG. 3 is a graph of CO decomposition with the copper selenide nanocatalyst of example 3 2 Conversion and CO selectivity results;
FIG. 4 is a graph of CO decomposition with the copper selenide nanocatalyst of example 4 2 Conversion and CO selectivity results;
FIG. 5 is CO of comparative example 1 2 Conversion and CO selectivity results;
FIG. 6 is CO of comparative example 2 2 Conversion and CO selectivity results.
Detailed Description
The present invention will be described in further detail by way of examples, but the scope of the present invention is not limited to the above.
Example 1
1. 0.53mmol of copper nitrate was weighed and dissolved in deionized water, and 1.425g of gamma-Al was added to the copper nitrate solution 2 O 3 After the carrier is fully stirred for 12 hours, the carrier is placed in a drying oven for drying at 80 ℃ overnight; 1.5g of dried material and 1.754g of ethylenediamine tetraacetic acid are simultaneously added into 28mL of 1mmol/L sodium hydroxide solution, ultrasonic treatment is carried out until the ethylenediamine tetraacetic acid is completely dissolved, then 0.118g of sodium selenite and 14mL of hydrazine hydrate are sequentially added, magnetic stirring is carried out for 10min, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 100mL, the high-pressure reaction kettle is continuously heated for 6h at 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 220 ℃ respectively, natural cooling is carried out to room temperature, 25mL of 1mol/L hydrochloric acid solution is added into a hydrothermal product, after 15min of reaction, solid-liquid separation is carried out, the solid is respectively washed for 3 times by deionized water and absolute ethyl alcohol, and the washed product is put into a vacuum drying box, and is dried in vacuum for 3h at 60 ℃ to obtain the copper selenide nano catalyst;
2. placing a copper selenide nano catalyst in a plasma reaction device, selecting a quartz tube with the total length of 300mm, the inner diameter of 22mm and the outer diameter of 26mm as a plasma reactor, wherein a high-voltage electrode is a 304 stainless steel rod with the diameter of 16mm, the experimental gas is 99.99% carbon dioxide, and a stainless steel mesh is fixed at the central position outside the reactor by using an insulating adhesive tape as an external electrode, and the experimental discharge interval is 15mm; the specific energy input is set to be 9.24-59.54kJ/L, the temperature is 35-100 ℃, and the discharge is continuously carried out for 2 hours in the carbon dioxide atmosphere;
the experimental results are shown in FIG. 1, when the hydrothermal temperature in the preparation process is 180 ℃, the specific energy input is 58.07kJ/L, the carbon dioxide conversion rate is 28.05%, and the carbon monoxide selectivity is 100%; when the hydrothermal temperature during preparation is 140 ℃ and 160 ℃ and the specific energy input is 58.07kJ/L, the carbon dioxide conversion rate is about 15%, and the CO selectivity is 100%. When the hydrothermal temperature is higher than 180 ℃, the specific energy input is 58.07kJ/L, CO 2 The conversion rate is 22.4 percent and 23.21 percent, and the CO selectivity is 100 percent and 100 percent.
Example 2
0.53mmol of copper nitrate is weighed and fully dissolved in deionized water, and 1.425g of gamma-Al is added into the copper nitrate solution 2 O 3 The carrier is fully stirred for 12 hours and then is placed in a drying oven for drying overnight at 80 ℃; 1.5g of dried material and 1.754g of ethylenediamine tetraacetic acid are simultaneously added into 28mL of 1mmol/L sodium hydroxide solution, ultrasonic treatment is carried out until the ethylenediamine tetraacetic acid is completely dissolved, then 0.118g of sodium selenite and 14mL of hydrazine hydrate are sequentially added, magnetic stirring is carried out for 10min, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 100mL, heating is carried out for 2h, 6h and 12h at 180 ℃, natural cooling is carried out to room temperature, 1mol/L hydrochloric acid solution 25mL is added into a hydrothermal product, after reaction is carried out for 15min, solid-liquid separation is carried out, the solid is respectively washed for 3 times by deionized water and absolute ethyl alcohol, and the washed product is put into a vacuum drying box, and is dried in vacuum at 60 ℃ for 3h, thus obtaining the copper selenide nano catalyst;
2. putting the copper selenide nano catalyst into a plasma reaction device, wherein the plasma reaction device is the same as in the embodiment 1, the specific energy input is 9.24-58.07kJ/L, and the discharge is continuously carried out for 2 hours in the carbon dioxide atmosphere;
the experimental results are shown in FIG. 2, and when the hydrothermal duration is 6h and the specific energy input is 58.07kJ/L, the carbon dioxide conversion rate is 28.05% and the carbon monoxide selectivity is 100%; when the hydrothermal duration is 2h and the specific energy input is 58.07kJ/L, the carbon dioxide conversion rate is 19.88 percent, the carbon monoxide selectivity is 100 percent, and when the specific energy input is 12.18kJ/L, the carbon dioxide conversion rate is only 5 percent, and the carbon monoxide selectivity is 85 percent; when the hydrothermal time length is 12h and the specific energy input is 58.07kJ/L, the carbon dioxide conversion rate is 23.19%, and the carbon monoxide selectivity is 100%.
Example 3
1. 0.53mmol of copper nitrate is weighed and fully dissolved in deionized water, and 7.425g, 2.425g, 1.425g, 0.995g and 0.625g of gamma-Al are respectively added into the copper nitrate solution 2 O 3 The carrier is fully stirred for 12 hours and then is placed in a drying oven for drying overnight at 80 ℃; 1.5g of dried material and 1.754g of ethylenediamine tetraacetic acid are simultaneously added into 28mL of 1mmol/L sodium hydroxide solution, ultrasonic treatment is carried out until the ethylenediamine tetraacetic acid is completely dissolved, then 0.118g of sodium selenite and 14mL of hydrazine hydrate are sequentially added, magnetic stirring is carried out for 10min, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 100mL, heating is carried out for 2h, 6h and 12h at 180 ℃, natural cooling is carried out to room temperature, 25mL of 1mol/L hydrochloric acid solution is added into a hydrothermal product, after 15min of reaction, solid-liquid separation is carried out, the solid is respectively washed for 3 times by deionized water and absolute ethyl alcohol, and the washed product is put into a vacuum drying box, and is dried in vacuum at 60 ℃ for 3h, thus obtaining copper selenide nano catalyst with the capacity of 1%, 3%, 5%, 7% and 10%;
2. putting the copper selenide nano catalyst into a plasma reaction device, wherein the plasma reaction device is the same as in the embodiment 1, the specific energy input is 9.24-59.54kJ/L, and the discharge is continuously carried out for 2 hours in the carbon dioxide atmosphere;
the results are shown in FIG. 3, where carbon dioxide conversion was 28.05% and carbon monoxide selectivity was 100% at a copper selenide loading of 5% and a specific energy input of 58.07 kJ/L; when the copper selenide loading is 1% and 3%, the conversion rate of carbon dioxide increases along with the increase of specific energy input, and when the specific energy input is 58.07kJ/L, the conversion rate of carbon dioxide is 25.05% and 24.08% respectively, and the carbon monoxide selectivity is 94.26% and 89.66% respectively; when the copper selenide loading is 7% and 10% and the specific energy input is 58.07kJ/L, the carbon dioxide conversion rate is 19.13% and 18.21%, and the carbon monoxide selectivity is 100% and 100%, respectively.
Example 4
1. Performing ultrasonic treatment on 0.53mmol of copper nitrate and 1.754g of ethylenediamine tetraacetic acid in 28mL of 1mmol/L sodium hydroxide solution until the ethylenediamine tetraacetic acid is completely dissolved, then sequentially adding 0.118g of sodium selenite and 14mL of hydrazine hydrate, magnetically stirring for 10min, transferring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining with the capacity of 100mL, continuously heating at 180 ℃ for 6h, naturally cooling to room temperature, adding 25mL of 1mol/L hydrochloric acid solution into a hydrothermal product, reacting for 15min, performing solid-liquid separation, washing the solid with deionized water and absolute ethyl alcohol for 3 times respectively, and placing the washing product into a vacuum drying box, and vacuum drying at 60 ℃ for 3h to obtain a copper selenide catalyst;
2. putting the copper selenide nano catalyst into a plasma reaction device, wherein the plasma reaction device is the same as in the embodiment 1, the specific energy input is 9.24-59.54kJ/L, and the discharge is continuously carried out for 2 hours in the carbon dioxide atmosphere;
the results are shown in FIG. 4, the copper selenide catalyst of the embodiment, under the cooperation of plasmas, CO when the specific energy input is 58.07kJ/L 2 The conversion rate can reach 17.55%, and the CO selectivity can reach 100%.
Comparative example 1:
1. 0.53mmol of copper nitrate was weighed and dissolved in deionized water, and 1.425g of gamma-Al was added to the copper nitrate solution 2 O 3 After the carrier is fully stirred for 12 hours, the carrier is placed in a drying oven for drying at 80 ℃ overnight; 1.5g of dried material and 1.754g of ethylenediamine tetraacetic acid are simultaneously added into 28mL of 1mmol/L sodium hydroxide solution, ultrasonic treatment is carried out until the ethylenediamine tetraacetic acid is completely dissolved, then 0.118g of sodium selenite and 14mL of hydrazine hydrate are sequentially added, magnetic stirring is carried out for 10min, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 100mL, the high-pressure reaction kettle is continuously heated at 180 ℃ for 6h respectively, and then naturally cooled to room temperature, 25mL of 1mol/L hydrochloric acid solution is added into a hydrothermal product, after 15min of reaction, solid-liquid separation is carried out, the solid is respectively washed for 3 times by deionized water and absolute ethyl alcohol, and the washed product is put into a vacuum drying box and is dried in vacuum at 60 ℃ for 3h, thus obtaining the copper selenide nano catalyst;
2. placing copper selenide nano catalyst in a thermal catalytic reaction device, and adding 99.99% CO 2 Continuously heating for 4 hours at 150-600 ℃ in atmosphere;
as a result, as shown in FIG. 5, decomposition of carbon dioxide was not found throughout the thermocatalytic reaction.
Comparative example 2:
the plasma reactor of the same structure as that of the example 1 is adopted, and the specific energy input is 9.24-59.54kJ/L
A quartz tube with the total length of 300mm, the inner diameter of 22mm and the outer diameter of 26mm is selected as a plasma reactor, a high-voltage electrode is a 304 stainless steel rod with the diameter of 16mm, the experimental gas is 99.99% carbon dioxide, the stainless steel mesh is fixed at the central position outside the reactor by an insulating adhesive tape to be used as an external electrode, and the experimental discharge interval is 15mm.
The results are shown in FIG. 6, the carbon dioxide conversion is 1.75-6.83% and the carbon monoxide selectivity is 54% -94%.

Claims (4)

1. Copper selenide catalyst for decomposing CO in low-temperature dielectric barrier discharge plasma 2 Is used in the field of applications.
2. The method according to claim 1, wherein the copper selenide catalyst is prepared by adding copper salt and ethylenediamine tetraacetic acid into 1-1.5mmol/L sodium hydroxide solution simultaneously, mixing, performing ultrasonic treatment, sequentially adding sodium selenite and hydrazine hydrate into the mixture, stirring, mixing uniformly, transferring into a high-pressure reaction kettle, reacting for 2-12h at 140-220 ℃, naturally cooling to room temperature, adding hydrochloric acid solution with concentration of 1-1.5mol/L into the reaction product for 20-30mL, performing solid-liquid separation after reacting for 10-20min, sequentially washing the solid with deionized water and absolute ethyl alcohol for 3 times, and performing vacuum drying on the washed product to obtain the copper selenide catalyst.
3. Use according to claim 1, characterized in that the copper selenide catalyst is prepared as follows:
(1) Adding gamma-Al into copper salt solution 2 O 3 The carrier is fully stirred and evenly mixed, and then dried at 75-85 ℃ to obtain a dried product;
(2) And (3) adding the dried product obtained in the step (1) and ethylenediamine tetraacetic acid into 1-1.5mmol/L sodium hydroxide solution simultaneously, mixing, performing ultrasonic treatment, sequentially adding sodium selenite and hydrazine hydrate into the mixture, stirring, uniformly mixing, transferring into a high-pressure reaction kettle, reacting for 2-12h at 140-220 ℃, naturally cooling to room temperature, adding 20-30mL of hydrochloric acid solution with the concentration of 1-1.5mol/L into the reaction product, reacting for 10-20min, performing solid-liquid separation, sequentially washing the solid with deionized water and absolute ethyl alcohol for 3 times, and performing vacuum drying on the washed product to obtain the copper selenide nano catalyst.
4. The use according to claim 1, characterized in that: low temperature dielectric barrier discharge plasma decomposition of CO 2 The specific energy input is 5-60kJ/L.
CN202310167189.2A 2023-02-27 2023-02-27 New application of copper selenide catalyst Pending CN116282020A (en)

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