CN113035574A

CN113035574A - Preparation method and application of waste SCR denitration catalyst for dye-sensitized solar cell

Info

Publication number: CN113035574A
Application number: CN202110245011.6A
Authority: CN
Inventors: 许友; 赵羽; 王光应; 陈志�
Original assignee: Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
Current assignee: Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
Priority date: 2021-03-05
Filing date: 2021-03-05
Publication date: 2021-06-25

Abstract

The invention discloses a preparation method of a waste SCR denitration catalyst for a dye-sensitized solar cell, which comprises the steps of washing, drying, crushing and ball-milling the waste SCR denitration catalyst, then carrying out alkali liquor treatment, carrying out suction filtration, washing and drying on the treated waste SCR denitration catalyst, adding a nitric acid solution, an aqueous solution, an ethanol solution, a glacial acetic acid solution, glycerol and ethyl cellulose, and stirring the mixture to obtain TiO₂The slurry is reserved; printing by screen printing to obtain semi-finished product, calcining, and TiCl₄Soaking in the diluent at constant temperature, calcining for the second time, soaking and dyeing in N719 dye solution at constant temperature, washing, packaging, dropping electrolyte and the like to obtain the dye-sensitized solar cell. The invention also discloses the application of the preparation method. By adopting the technical scheme, the titanium dioxide is applied to the dye-sensitized solar cell in the SCR denitration catalyst recovery process, and the economic added value is improved.

Description

Preparation method and application of waste SCR denitration catalyst for dye-sensitized solar cell

Technical Field

The invention relates to the field of preparation of fuel-sensitized solar cells, in particular to a preparation method and application of a waste SCR denitration catalyst for a dye-sensitized solar cell.

Background

China is a large country with large coal energy consumption, and national coal consumption tends to increase year by year. From the main coal consumption industry, the coal consumption of the electric power industry is greatly increased. In the process of coal combustion and use in the power industry, pollutants in combustion products are mainly nitrogen oxides, and acid rain, ozone layer damage and haze formation can be caused by a large amount of emission of the nitrogen oxides, so that great harm is further caused to the ecological environment of the earth and the body health of human beings. With the development of national ecological civilization construction and environmental protection targets, the treatment of nitrogen oxides is receiving attention from various countries.

Selective Catalytic Reduction (SCR) is the most important technology for controlling nitrogen oxides, is widely used in the power plant industry, and has a service life of about three years. However, with the large amount of use thereof, disposal of the spent catalyst has been a problem of concern in the industry.

TiO in SCR denitration catalyst₂The content of the active ingredients reaches 80-90 percent, and the active ingredients have potential utilization value. As is well known, TiO₂The semiconductor belongs to a wide-forbidden band semiconductor, has a good energy level matching relation with dye (N719), and is widely applied to dye-sensitized or perovskite solar cell dye adsorption materials. Dye-sensitized solar cells and perovskite solar cells are used as one type of solar cells, have the characteristics of low cost, simple preparation, commercialization and the like, and are continuously and intensively researched by colleges and universities and enterprises.

Although disclosed in the prior art with respect to TiO in spent SCR catalysts₂But the method is not applied to the field of dye-sensitized solar energy and is used as a production material of new energy dye-sensitized solar energy.

For example, Chinese patent numbers are: CN107628642A discloses "TiO in waste SCR catalyst₂The separation and recovery method of (1). The patent discloses the technical scheme of using NaOH and Na₂CO₃The complexing agent is utilized and the pH of the hydrochloric acid is regulated and controlled, the process is too complex, the requirement on acid and alkali resistance of equipment is higher, and the industrialization is not facilitated

The Chinese patent numbers are: CN10705599A discloses a method for separating and recovering anatase titanium dioxide from a waste SCR denitration catalyst, wherein the process is simple, but two alkali soakings are involved, the time for each time of soaking is 3-5 h, the time is too long, and important related patents cannot well show the integrated treatment process of recovering and recycling the anatase titanium dioxide.

TiO₂As a dye sensitizer adsorption material, the material is required to have higher specific surface area, and the content of TiO in the SCR catalyst is TiO₂The catalyst is high, and is generally reused in the SCR denitration catalyst after being recovered, so that the economic added value is low. The substantial reasons for the technical defect of low economic added value are as follows: in the prior art, TiO obtained by recovering SCR catalyst cannot be obtained₂The method is applied to dye-sensitized solar cells, and the economic added value is improved.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: solves the problem that TiO in SCR catalyst in the prior art₂The content is high, and the dye-sensitized solar cell can not be applied to the dye-sensitized solar cell after being recycled, so that the economic added value is improved. Based on the method, the invention provides a preparation method of a waste SCR denitration catalyst for a dye-sensitized solar cell.

The invention solves the technical problems through the following technical scheme:

a preparation method of a waste SCR denitration catalyst for a dye-sensitized solar cell comprises the following steps:

(1) washing the used waste SCR denitration catalyst with hot water, and drying after washing;

after drying, crushing and ball milling are carried out to obtain catalyst powder passing through a 600-mesh screen;

(2) adding NaOH solution into the catalyst powder obtained in the step (1), transferring the material into a dispersion stirrer for dispersion stirring, after stirring and dispersion, performing suction filtration on the mixed material obtained by stirring, and washing and drying a filter cake to obtain dry powder;

(3) putting the dry powder obtained in the step (2) into grinding and stirring equipment, adding a nitric acid solution and an aqueous solution, grinding and mixing, adding an absolute ethyl alcohol solution, a glacial acetic acid solution, glycerol and ethyl cellulose, mixing and stirring, and grinding to obtain a mixed solution;

(4) distilling the mixed solution obtained in the step (3) in an atmospheric and vacuum distillation device to obtain TiO₂The slurry is reserved;

(5) TiO prepared in the step (4)₂Printing the slurry by adopting a screen printing mode to obtain a photo-anode semi-finished product, calcining the photo-anode semi-finished product obtained by printing in a muffle furnace, naturally cooling to room temperature after the first calcination, and placing the photo-anode semi-finished product in TiCl after cooling₄Soaking the photo-anode semi-finished product in the diluent at constant temperature, and then carrying out secondary calcination in a muffle furnace on the photo-anode semi-finished product, wherein a compact layer is formed on the surface of the photo-anode semi-finished product in the secondary calcination process;

and after secondary calcination, taking out the photo-anode semi-finished product, naturally cooling to 80 ℃, putting the photo-anode semi-finished product into an N719 dye solution for dip dyeing at constant temperature, taking out the photo-anode semi-finished product, washing to obtain a photo-anode for later use, packaging the cell by taking an electrode deposited with a Pt layer as a Pt electrode, and dripping electrolyte to obtain the fuel sensitized solar cell.

Here, the advantage corresponding to claim 1 is written, and it can be checked whether or not claim 1 is inventive.

Preferably, the step (1) is flushed by excess hot water in a manner that: according to the following, from the inside to the outside of the catalyst;

the temperature of hot water for washing is 80 ℃, and drying is carried out after washing;

and after drying, crushing by using a crusher, and adding the powder crushed by the crusher into a ball mill for grinding.

Preferably, after taking 500g of the catalyst powder obtained in the step (1), adding 1L of 5-10% NaOH solution by mass, transferring the material into a dispersion mixer, controlling the shearing and stirring speed of the dispersion mixer to be 80r/min and the dispersion speed of the dispersion mixer to be 3000r/min, and after stirring and dispersing, carrying out suction filtration on the mixed material obtained by stirring;

repeatedly washing the filter cake obtained by suction filtration with hot water at 80 ℃ for three times, wherein the volume consumption of the hot water is the same as that of the solution of NaOH;

after washing, the filter cake was dried in an oven at 120 ℃ for 1 h.

Preferably, 100g of the dried powder obtained in step (2) in step (3) is added with 20-40mL of nitric acid solution and 2L of aqueous solution, grinding and mixing are carried out, 2L of absolute ethyl alcohol solution is added,

wherein, the volume of the glacial acetic acid solution is the same as that of the nitric acid solution, and then 170g of glycerol and 100g of ethyl cellulose are added for mixing, stirring and grinding for 30min to obtain a mixed solution.

Preferably, the molar concentration of the nitric acid solution is 2 mol/L.

Preferably, in the step (4), water bath heating distillation is adopted, the water bath temperature is controlled to be 70 ℃, and the distillation time is 10-30 min.

Preferably, the primary calcination and the secondary calcination in the step (5) are both carried out in a muffle furnace;

the primary calcination temperature and the secondary calcination temperature are both controlled to be 500 ℃.

Preferably, after the first calcination in step (5), the photo-anode semi-finished product is placed in TiCl with a concentration of 0.5M₄Soaking in the diluent, placing in an oven for constant-temperature soaking in the soaking process, and controlling the temperature of the oven to be 70 ℃;

and after secondary calcination, taking out the photo-anode semi-finished product, and naturally cooling to 80 ℃, wherein the time of the secondary calcination is 30min, and the time of the secondary calcination is 30 min.

Preferably, in the step (5), the photo-anode semi-finished product is placed in N719 dye with the concentration of 0.3M for dip dyeing, the semi-finished product is placed in an oven for dip dyeing for 12 hours in the dip dyeing process, and the temperature of the oven is controlled to be 70 ℃; and (4) washing the surface of the photo-anode semi-finished product by using an absolute ethyl alcohol solution after the dip dyeing.

The invention also discloses application of the preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell in preparation of the fuel-sensitized solar cell.

Compared with the prior art, the invention has the following advantages:

the invention provides a method for using a waste SCR denitration catalyst for a dye-sensitized solar cell, which has the following advantages by the technical scheme disclosed by the invention:

1. the waste SCR denitration catalyst has the problem of low recycling added value, is applied to the field of dye-sensitized solar cells, expands the application field and obtains the highest photoelectric conversion efficiency of 6.8%;

2. the preparation method disclosed by the invention is simple and is easy for industrial scale-up production;

3. the technical blank that titanium dioxide obtained by recycling waste SCR denitration catalysts cannot be combined and applied to the dye-sensitized solar cell is made up.

Drawings

FIG. 1 is a graph comparing J-V performance of fuel-sensitized solar cells obtained in example 7 of the present invention for examples 1 to 4;

FIG. 2 is a graph showing comparative J-V characteristics of fuel-sensitized solar cells obtained in example 1, example 5 and example 6 of example 7 of the present invention.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

(1) Taking 1 waste catalyst, washing the catalyst with excessive 80 ℃ hot water, drying the catalyst at 120 ℃ for 10min from inside to outside, crushing the catalyst by using a crusher, putting the crushed catalyst into a ball mill for grinding, and screening the ground catalyst by using a 600-mesh screen to obtain catalyst powder;

(2) 500g of the catalyst powder passing through the screen is taken, 3L of 10% NaOH solution is added into the catalyst powder, the catalyst powder is transferred into a dispersion stirrer, the shearing stirring speed is 80r/min, the dispersion speed is 3000r/min, and the catalyst powder is stirred and dispersed for 90 min. After solid-liquid separation after suction filtration, adding hot water (the amount of the hot water is the same as the volume of the alkali liquor) into the filtrate, wherein the water temperature is 80 ℃, repeatedly washing for 3 times, and drying for 1 hour at 120 ℃ to obtain dry powder;

(3) putting 100g of dried powder into grinding and stirring equipment, adding 20mL of nitric acid (2M) and 2L of water, grinding and mixing, adding 2L of absolute ethyl alcohol, wherein the volume of glacial acetic acid is the same as that of the nitric acid, 170g of glycerol and 100g of ethyl cellulose, mixing, stirring and grinding for 30min to obtain a mixed solution;

(4) and putting the mixed solution into an atmospheric and vacuum distillation device for distillation, wherein the water temperature is 70 ℃, and the distillation time is 10 min. To obtain TiO₂And (5) filling the slurry into bottles, sealing and keeping out of the light for later use.

(5) Printing a photo-anode by adopting a screen printing mode, placing the photo-anode in a muffle furnace for primary calcination at 500 ℃ for 30min, naturally cooling to room temperature, and placing the photo-anode in TiCl₄The diluted solution of (A) was immersed in the solution, and the solution was immersed in an oven at 70 ℃ for 30 min. Taking out, and placing in a muffle furnace for 30min at 500 ℃ to form a dense layer (secondary calcination).

Naturally cooling to 80 ℃, placing the mixture into 0.3M N719 dye, soaking the mixture in an oven at 70 ℃ for more than 12h, taking out the mixture, washing the surface with absolute ethyl alcohol, using the washed mixture as a photo-anode for standby, using an electrode deposited with a Pt layer as a Pt electrode, packaging the battery, and dropping electrolyte. Thus obtaining the fuel sensitized solar cell.

Example 2

(2) taking 500g of the catalyst powder passing through the screen, adding 3L of 5% NaOH solution, transferring to a dispersion mixer, shearing and stirring at 80r/min and 3000r/min, and stirring and dispersing for 30-90 min. After solid-liquid separation after suction filtration, adding hot water (the amount of the hot water is the same as the volume of the alkali liquor) into the filtrate, wherein the water temperature is 80 ℃, repeatedly washing for 3 times, and drying for 1 hour at 120 ℃ to obtain dry powder;

Example 3

(1) Taking 1 waste catalyst, washing the catalyst with excessive 80 ℃ hot water, drying the catalyst at 120 ℃ for 10min from inside to outside, crushing the catalyst by using a crusher, putting the crushed catalyst into a ball mill for grinding, and sieving the crushed catalyst by using a 200-mesh sieve to obtain catalyst powder;

(3) putting 100g of dried powder into grinding and stirring equipment, adding 30mL of nitric acid (2M) and 2L of water, grinding and mixing, adding 2L of absolute ethyl alcohol, wherein the volume of glacial acetic acid is the same as that of the nitric acid, 170g of glycerol and 100g of ethyl cellulose, mixing, stirring and grinding for 30min to obtain a mixed solution;

(5) Printing sunlight by screen printingCalcining at 500 deg.C for 30min, naturally cooling to room temperature, and placing into TiCl₄The diluted solution of (A) was immersed in the solution, and the solution was immersed in an oven at 70 ℃ for 30 min. Taking out, and placing in a muffle furnace for 30min at 500 ℃ to form a dense layer (secondary calcination).

Example 4

(2) 500g of the catalyst powder passing through the screen is taken, 3L of 5% NaOH solution is added into the catalyst powder, the catalyst powder is transferred into a dispersion stirrer, the shearing stirring speed is 80r/min, the dispersion speed is 3000r/min, and the catalyst powder is stirred and dispersed for 90 min. After solid-liquid separation after suction filtration, adding hot water (the amount of the hot water is the same as the volume of the alkali liquor) into the filtrate, wherein the water temperature is 80 ℃, repeatedly washing for 3 times, and drying for 1 hour at 120 ℃ to obtain dry powder;

Example 5

(3) putting 100g of dried powder into grinding and stirring equipment, adding 20-40mL of nitric acid (2M) and 2L of water, grinding and mixing, adding 2L of absolute ethyl alcohol, wherein the volume of glacial acetic acid is the same as that of the nitric acid, 170g of glycerol and 100g of ethyl cellulose, mixing, stirring and grinding for 30min to obtain a mixed solution;

(4) and putting the mixed solution into an atmospheric and vacuum distillation device for distillation, wherein the water temperature is 70 ℃, and the distillation time is 20 min. To obtain TiO₂And (5) filling the slurry into bottles, sealing and keeping out of the light for later use.

Example 6

(3) putting 100g of dried powder into grinding and stirring equipment, adding 40mL of nitric acid (2M) and 2L of water, grinding and mixing, adding 2L of absolute ethyl alcohol, wherein the volume of glacial acetic acid is the same as that of the nitric acid, 170g of glycerol and 100g of ethyl cellulose, mixing, stirring and grinding for 30min to obtain a mixed solution;

(4) and putting the mixed solution into an atmospheric and vacuum distillation device for distillation, wherein the water temperature is 70 ℃, and the distillation time is 30 min. To obtain TiO₂And (5) filling the slurry into bottles, sealing and keeping out of the light for later use.

Example 7 Process parameter screening

In this example, the process parameters of the dye-sensitized solar cell manufacturing process obtained in the above example are screened and optimized.

First, the fuel-sensitized solar cells obtained in the above examples 1 to 4 were subjected to J-V performance test:

the test structure shows that: on the premise of the same dye-sensitized solar cell preparation process, process screening is performed on whether grinding and alkali liquor concentration/dosage/treatment time are performed in the preparation process, and the screening result is shown in fig. 1.

As can be seen from the data disclosed in fig. 1: the higher the alkali liquor concentration, the larger the dosage and the longer the treatment time, the better the photoelectric conversion performance of the obtained electrode, and the main reason is that the electrode is more beneficial to removing impurities such as metal ions in the waste SCR denitration catalyst. In addition, the grinding can significantly improve TiO₂Photoelectric conversion efficiency of (2) due to TiO₂The smaller the particle, the larger its specific surface area, and the more dye can be adsorbed.

Secondly, the fuel-sensitized solar cells obtained in the above examples 1, 5 and 6 were subjected to J-V performance test:

the test structure shows that: the preparation process of the dye-sensitized solar cell is optimized, and the optimization result is shown in fig. 2. As can be seen from fig. 2: the higher the nitric acid concentration, the longer the distillation time, and the higher the photoelectric conversion efficiency, since TiO is present with higher nitric acid concentration and longer distillation time₂The higher the viscosity of (A), the more advantageous the TiO is₂Printing is performed on the electrodes, and the dye adsorption capacity is achieved.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

1. A preparation method of a waste SCR denitration catalyst for a dye-sensitized solar cell is characterized by comprising the following steps:

after drying, crushing and ball milling are carried out to obtain catalyst powder passing through a 200-mesh and 600-mesh screen;

and after secondary calcination, taking out the photo-anode semi-finished product, naturally cooling, putting the photo-anode semi-finished product into an N719 dye solution, dip-dyeing at a constant temperature, taking out the photo-anode semi-finished product, washing to obtain a photo-anode for later use, packaging the cell by taking an electrode deposited with a Pt layer as a Pt electrode, and dripping electrolyte to obtain the fuel sensitized solar cell.

2. The preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 1 is characterized in that excess hot water washing is adopted in the step (1), and the washing mode is as follows: according to the following, from the inside to the outside of the catalyst;

3. The preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 1, wherein the step (2) comprises the steps of taking 500g of the catalyst powder obtained in the step (1), adding 1L of NaOH solution with the mass fraction of 5-10%, transferring the mixture into a dispersion mixer, controlling the shearing and stirring speed of the dispersion mixer to be 80r/min and the dispersion speed of the dispersion mixer to be 3000r/min, and performing suction filtration on the mixed material obtained by stirring and dispersing;

after washing, the filter cake was dried in an oven at 120 ℃ for 1 h.

4. The method for preparing the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 1, wherein 100g of the dried powder obtained in the step (2) in the step (3) is added with 20-40mL of nitric acid solution and 2L of aqueous solution, the mixture is ground and mixed, 2L of absolute ethyl alcohol solution is added into the mixture,

5. The preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 4, wherein the molar concentration of the nitric acid solution is 2 mol/L.

6. The preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 1, wherein in the step (4), water bath heating distillation is adopted, the temperature of the water bath is controlled to be 70 ℃, and the distillation time is 10-30 min.

7. The preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 1, wherein in the step (5), the primary calcination and the secondary calcination are both carried out in a muffle furnace;

8. The method for preparing the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 7, wherein after the primary calcination in the step (5), the photo-anode semi-finished product is placed in TiCl with a concentration of 0.5M₄Soaking in the diluent, placing in an oven for constant-temperature soaking in the soaking process, and controlling the temperature of the oven to be 70 ℃; and after secondary calcination, taking out the photo-anode semi-finished product, and naturally cooling to 80 ℃, wherein the time of the secondary calcination is 30 min.

9. The preparation method of the waste SCR denitration catalyst for the dye-sensitized solar cell according to claim 8, wherein in the step (5), the photo-anode semi-finished product is placed in N719 dye with the concentration of 0.3M for dip-dyeing, the semi-finished product is placed in an oven for dip-dyeing for 12 hours in the dip-dyeing process, and the temperature of the oven is controlled to be 70 ℃; and (4) washing the surface of the photo-anode semi-finished product by using an absolute ethyl alcohol solution after the dip dyeing.

10. The application of the waste SCR denitration catalyst as described in any one of claims 1 to 9 in the preparation of a dye-sensitized solar cell.