A catalyst prepared by using waste polyester spun fabric and nickel-containing solid waste, a preparation method and application thereof

Abstract

The application provides a catalyst prepared by using waste polyester spun fabric and nickel-containing solid waste, a preparation method and application. The catalyst is prepared by using a water solvent method to load BDC and metallurgical solid waste product nickel ferrite. The MOF catalyst has the advantages of large specific surface area, excellent catalytic effect, high activity of loaded compounds and CO2 cracking effect higher than that of a single catalyst. Compared with the prior art, the catalyst prepared by introducing waste polyester spun fabric and nickel-containing solid waste can make important progress in environmental governance and resource utilization, and can crack CO2 by using the obtained catalyst while comprehensively utilizing the waste, thereby reducing the CO2 concentration in the atmosphere, and providing a new idea and direction for promoting sustainable development.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of catalyst preparation, and particularly relates to a catalyst prepared from waste polyester spun fabric and nickel-containing solid waste, a preparation method and application. BACKGROUND

[0002] In recent years, the excessive emission of greenhouse gases has affected the global ecological environment, and the concentration of carbon dioxide in the atmosphere has exceeded 400 ppm, which will have a negative impact on the climate and the environment. To address this problem, more and more research is being conducted to reduce carbon dioxide emissions. There are many existing measures to reduce carbon emissions, such as reducing the use of fossil energy, improving energy use efficiency, promoting clean production technology, promoting forest regeneration, and developing carbon capture and storage technology (CCS). Carbon capture and storage technology (CCS) is an important way to reduce carbon, which can convert carbon dioxide into carbon-based materials, but it is difficult to industrialize and has poor economic benefits. These shortcomings make low-temperature plasma (LTP) cracking of carbon dioxide a more promising solution. Low-temperature plasma (LTP) cracking of carbon dioxide can operate at lower temperatures and pressures, can generate valuable CO and CH3OH, and can use solid waste as a catalyst to improve resource utilization efficiency. Therefore, low-temperature plasma (LTP) cracking of carbon dioxide is considered a good and effective solution.

[0003] On June 6, 2024, Cheng He, Lei Xiaoting, Zhang Wenchao, and Lu Xinpei published a paper entitled "Research on the conversion of CO2 by low-temperature plasma and the decomposition mechanism" [High Voltage Technology], which summarizes the research progress of different types of LTP in converting CO2. However, the catalysts used in existing technologies are relatively expensive, leading to increased use costs. Therefore, it is particularly necessary to develop a low-cost catalyst.

[0004] The treatment and utilization of waste polyester and metallurgical solid waste containing nickel is also a widely concerned problem. Polyester is one of the most widely used synthetic fibers in the world, and in 2021, China's polyester production reached 5363 tons, an increase of 8.94% year-on-year. However, due to its good stability in the environment, polyester is difficult to degrade in nature. Traditional waste polyester treatment methods, such as incineration and landfill, can solve the problem in the short term, but they will lead to resource waste and pollution, seriously endangering the environment and human health. Metallurgical solid waste containing nickel contains a large amount of harmful substances, and nickel and other metal elements are difficult to decompose in nature, and long-term accumulation may lead to soil deterioration. Therefore, improper treatment of metallurgical solid waste containing nickel will cause serious damage to the surrounding ecological environment.

[0005] Therefore, it is necessary to provide a technology that can simultaneously crack carbon dioxide and utilize waste materials, which has broad application prospects. SUMMARY

[0006] The application aims to provide a catalyst prepared from waste polyester spun yarn and nickel-containing solid waste, and a preparation method.

[0007] The application further aims to provide an application of the catalyst prepared from waste polyester spun yarn and nickel-containing solid waste, which is used for cracking carbon dioxide.

[0008] The application has the following specific technical solutions:

[0009] A preparation method of a catalyst prepared from waste polyester spun yarn and nickel-containing solid waste, comprising the following steps:

[0010] 1) drying, grinding and calcining the nickel-containing solid waste to obtain nickel ferrite;

[0011] 2) washing, drying and mixing the waste polyester spun yarn with alkali in water, and then heating and reacting to obtain BDC by centrifugation, adjusting the pH of the supernatant to acidity (0.5-1.5), and then centrifugation again;

[0012] 3) mixing the nickel ferrite prepared in step 1) and the BDC prepared in step 2) in an organic solvent, and then heating and reacting to obtain the catalyst.

[0013] In step 1), the nickel-containing solid waste has a nickel element mass percentage content of greater than 15%, and is derived from NiSO4, and has an iron element mass percentage content of greater than 20%.

[0014] In step 1), the drying refers to drying at 90℃ overnight for 10-12h.

[0015] In step 1), the grinding refers to grinding, sieving and collecting the obtained powder after the nickel-containing solid waste is dried, cooled, ground and sieved to 200 mesh.

[0016] In step 1), the calcining refers to heating at 5℃ / min to 1000℃, and then keeping the temperature at 1000℃ for 4h.

[0017] In step 1), after calcining, the product is obtained by grinding in a mortar and sieving to 200 mesh.

[0018] Preferably, step 1) is: the ground nickel-containing solid waste is evenly laid in a crucible and gently compacted with a wooden stick to ensure that the powder does not exceed the crucible; the crucible is placed in a muffle furnace and calcined at a temperature rising rate of 5 ℃ / min, the temperature is raised to 1000 ℃, and the temperature is kept at 1000 ℃ for 4 hours; after cooling to room temperature, the crucible is taken out, and the solid waste calcination product is put into a mortar and ground, and sieved to 200 meshes. The sieved product is the obtained nickel ferrite.

[0019] In step 1), the carbon-containing substances in the solid waste are burned to generate carbon-containing gas, and the iron oxide and nickel oxide react to generate nickel ferrite.

[0020] In step 2), the drying is performed at 80 ℃ in an oven for 2 hours.

[0021] Preferably, in step 2), the waste polyester fabric is cut into pieces with a size of 1.2 cm×1.5 cm using scissors, and then the pieces are washed with clean water and alcohol, and then dried.

[0022] In step 2), the waste polyester fabric is polyester or waste polyester fabric with a purity of polyester of more than 90%.

[0023] In step 2), the mass ratio of the waste polyester fabric to the alkali is 1:0.3-0.6.

[0024] The alkali is selected from sodium hydroxide NaOH.

[0025] In step 2), the mass ratio of the waste polyester fabric to water is 1:10.

[0026] In step 2), the heating reaction is performed at 160-220 ℃ for 6 h.

[0027] In step 2), after the heating reaction, an alkali solution is added to the reaction product to adjust the pH to 12-13, and then centrifuged at a centrifugal speed of 2500-8000 r / min for 6 min, and the supernatant is taken. The alkali solution used is a 2 mol / L NaOH solution.

[0028] In step 2), the adjustment of the pH of the supernatant to the acid washing refers to adjusting the pH value of the system to a pH value of 0.5-1.5 using an HCl solution; a 36%-38% mass concentration HCl solution is used.

[0029] In step 2), the re-centrifugation is performed at a centrifugal speed of 2500-8000 r / min for 5 min, and the supernatant is poured out after the centrifugation is completed, and the product is a white precipitate.

[0030] Further, the white precipitate and pure water are mixed and washed for 3 times, then washed with ethanol for 2 times, and finally the obtained precipitate is placed in a vacuum drying oven at 90 DEG C for 12h, and the obtained product is BDC. - The hydrolysis process of polyester under alkaline conditions in this step includes disordered breaking of molecular chains, reaction with carbonyl carbon, formation of intermediates (phthalate), and conversion into di-sodium terephthalate (BDC) and ethylene glycol.

[0031] In step 3), the mass ratio of the nickel ferrite prepared in step 1) and the BDC prepared in step 2) is 0.19-0.21:1;

[0032] In step 3), the amount of the nickel ferrite prepared in step 1) and the organic solvent is 0.70-0.75mg / mL;

[0033] In step 3), the organic solvent is selected from N,N-dimethylformamide and anhydrous ethanol; and the volume ratio of the N,N-dimethylformamide and the anhydrous ethanol is 16:1;

[0034] In step 3), the heating reaction refers to heating treatment at 180 DEG C for 48h.

[0035] In step 3), the nickel ferrite reacts with BDC to generate Ni-MOF, BDC provides phthalate to coordinate with the nickel ferrite to form a novel metal organic framework. The carboxyl group of BDC can coordinate with the nickel ion, thereby stabilizing the structure and promoting polymerization.

[0036] In step 3), after the heating reaction, after cooling, after centrifugal washing with water and ethanol, the obtained product is placed in an oven at 90 DEG C for 3h, and the catalyst is obtained.

[0037] The application provides a catalyst prepared from waste polyester spun fabric and nickel-containing solid waste.

[0038] The application of the catalyst prepared from waste polyester spun fabric and nickel-containing solid waste is used for cracking carbon dioxide.

[0039] The specific method is that the catalyst is mixed with the filler to be used for ionization cracking of CO2, the ionization voltage is 1kv, and the current needs to be controlled at 1A.

[0040] The mass ratio of the catalyst and the filler is 1:80-110;

[0041] The filler is SiO2 glass bead of 0.3-0.8mm; the filler includes but is not limited to SiO2 glass microbead, and Al2O3, ZrO2 and BaTiO3 microbead can also be used as the filling material, which can generate large electron energy density and electric field strength in the discharge process; at the same time, it has a large specific surface area, and can provide more surface for CO2 molecule adsorption after being added, thereby increasing the contact opportunity of reactants with the catalyst or active site and improving the reaction rate.

[0042] The inventors find that the application of the catalyst prepared from solid waste mainly uses metal elements and compounds in the solid waste as active components, but the active components are limited, and it is difficult to improve the performance of the catalyst. The present application uses water solvent method to load BDC and nickel ferrite prepared from metallurgical solid waste to prepare a catalyst, the MOF catalyst has a large specific surface area, excellent catalytic effect, high activity of the loaded compound, and the effect of cracking CO2 is better than that of a single catalyst. The catalytic effects of the catalysts prepared from different mass ratios of BDC and nickel ferrite are explored, and it is found that the catalyst prepared from 50mg of nickel ferrite and 249mg of BDC has the best catalytic effect.

[0043] Compared with the prior art, the catalyst prepared from waste polyester yarn and nickel-containing solid waste can make important progress in environmental governance and resource utilization, and can crack CO2 by using the obtained catalyst to reduce the concentration of CO2 in the atmosphere, thereby providing a new idea and direction for promoting sustainable development. BRIEF DESCRIPTION OF DRAWINGS

[0044] Figure 1 It is a flowchart of the preparation method of the present application;

[0045] Figure 2 It is a characterization graph of BDC, nickel ferrite and MOF catalyst;

[0046] Figure 3 It is an XRD graph of BDC. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0048] The test materials and reagents used in the following examples, unless otherwise specified, can be obtained commercially.

[0049] The specific techniques or conditions not specified in the examples can be carried out according to the techniques or conditions described in the literature in the art or according to the product instructions.

[0050] Example 1

[0051] A preparation method of a catalyst prepared from waste polyester yarn and nickel-containing solid waste, comprising the following steps:

[0052] 1) Use the metallurgical electroplating waste liquid filtration material generated during the cleaning of the electroplating process of a certain steel plant as the nickel-containing solid waste, wherein the mass percentage content of nickel element is 18% and exists in the form of NiSO4, the mass percentage content of iron element is 33% and is derived from leaching in steel production, 90°C overnight drying for 10h, after drying, cooling, grinding, and sieving to 200 mesh, the obtained powder is collected; the sieved nickel-containing solid waste is laid flat in a crucible and gently compacted with a wooden rod to ensure that the powder does not exceed the crucible. Put the crucible into a muffle furnace and calcine. The calcination conditions are 5°C / min heating, heating to 1000°C, and keeping at 1000°C for 4 hours. After cooling to room temperature, take out the crucible and put the solid waste calcination end product into a mortar and grind, sieve to 200 mesh, and the sieved product is the obtained nickel ferrite, the composition detection is shown in Table 1.

[0053] Table 1 Main compound composition and element composition of nickel ferrite (mass percentage)

[0054] Compound Mass percent Element Mass percent NiFe2O4 71.52 Fe 33.56 SiO2 15.04 Ni 18.5 Al2O3 3.74 Si 7.03 CaO 2.9 Al 1.98

[0055] The remaining impurities are not shown in Table 1.

[0056] As can be seen from Table 1, the main component of the material after calcination is NiFe2O4, the main elements are Fe and Ni, and SiO2 shows mildness in catalysis and has no effect on the catalytic process.

[0057] 2) Select waste polyester clothes (waste polyester yarn with a purity of more than 90%), cut the polyester clothes into pieces of about 1.2cm x 1.5cm with scissors, then wash the pieces with clean water and alcohol, and then place them in an oven at 80°C for 2 hours; take 3.0g of dried waste polyester pieces and 1.25g of NaOH solid and 30ml of water, add them to a 100ml tetrafluoroethylene high-pressure reaction kettle, tightly cover the reaction kettle, put it into an oven, and heat to 200°C for 70 minutes, and keep at 200°C for 6 hours. After cooling to room temperature, take out the reaction kettle solution and pour it into a beaker.

[0058] Then take 2 mol / l NaOH solution to adjust the pH of the solution in the beaker to 12.5. The solution with pH = 12.5 is loaded into a 15 ml capacity centrifuge tube with a pipette. The centrifuge tube is placed in the centrifuge, the centrifugal speed is 3000 r / min, and the centrifugation time is 6 minutes. After the centrifugation is finished, the supernatant is taken in a beaker. The pH value of the system is adjusted to 1.2 with a mass concentration of 36% HCl solution, and the obtained solution is a milky white solution. The solution is loaded into a centrifuge tube, and the white precipitate BDC is separated by centrifugation, the centrifugation condition is 5 minutes, 3000 r / min. The supernatant is poured out after the centrifugation is finished, and the product is left as a white precipitate. 5 ml of pure water is poured into a test tube, and the white precipitate is mixed with pure water for washing. Then it is washed with 5 ml of ethanol for 2 times respectively. Finally, the obtained precipitate is the product, which is placed in a vacuum drying oven at 90℃ for 12 hours. The obtained product is BDC, and its XRD characterization is shown in Figure 3

[0059] 3) Add 64.0 mL of DMF and 4.0 mL of C2H5OH to the beaker and stir until uniform; then, add 249 mg of BDC and 50 mg of nickel ferrite and stir thoroughly to dissolve and disperse. Finally, place it in a high-pressure reaction kettle and heat treat at 180℃ for 48 hours. After cooling, wash with water and ethanol for 5 times, then place it in an oven at 90℃ for 3 hours to dry, and the obtained product is the catalyst.

[0060] An application of a catalyst prepared from waste polyester yarn and nickel-containing solid waste for cracking carbon dioxide, specifically:

[0061] An application of the catalyst prepared from waste polyester yarn and nickel-containing solid waste in Example 1 for cracking carbon dioxide, the specific method is as follows: the catalyst prepared in Example 1 (60 mg) is mixed with fillers (0.5 mm SiO2 glass beads, 5 g) and used for ionization cracking of CO2, the ionization voltage is 1 kv, the current needs to be controlled at about 1 A, the reactor needs to be cooled by water to prevent the temperature from being too high, and the carbon dioxide flow rate is 24-30 ml / min.

[0062] Figure 2 The characterization graphs of BDC, nickel ferrite and MOF catalyst, BDC: presents obvious strip structure, regular crystal structure, and certain accumulation of each strip structure, showing good crystallinity, which helps to improve the performance of catalysis. Nickel ferrite: the surface is rough and the morphology is complex, which is conducive to the coupling of other substances to improve the surface activity of the catalyst. Catalyst: the catalyst shows flower-like flaky structure with obvious flaky characteristics, showing good porosity, so it has a large specific surface area, which is conducive to the adsorption of gas and is an excellent catalytic material.

[0063] ​Example 2 (as a comparison)

[0064] The difference between this example and Example 1 is that no catalyst is added during filling, only 5g of glass beads is added.

[0065] Example 3 (as a comparison)

[0066] The difference between the catalytic process of this example and Example 1 is that the catalyst preparation method is different, i.e. the mass ratio of BDC to nickel ferrite is different, 500mg of nickel ferrite and 249mg of BDC are put into a tetrafluoroethylene reaction kettle for water bath heating, and the obtained catalyst is the catalyst in Example 3.

[0067] Example 4 (as a comparison)

[0068] The difference between the catalytic process of this example and Example 1 is that the catalyst preparation method is different, i.e. 50mg of calcium ferrite and 249mg of BDC are selected for water bath heating, and the obtained catalyst is the catalyst in Example 4.

[0069] Example 5 (as a comparison)

[0070] The difference between the catalytic process of this example and Example 1 is that the catalyst preparation method is different, i.e. 500mg of calcium ferrite and 249mg of BDC are selected for water bath heating, and the obtained catalyst is the catalyst in Example 5.

[0071] Example 6 (as a comparison)

[0072] The difference between the catalytic process of this example and Example 1 is that the catalyst preparation method is different, i.e. 20ml of nickel-containing waste liquid (Ni ion concentration 2000ppm) and 249mg of BDC are selected for water bath heating, and the obtained catalyst is the catalyst in Example 4.

[0073] Example 7

[0074] The difference between the catalytic process of this example and Example 1 is that the catalyst preparation method is different, i.e. the heating time is different, the heating time is 24h, and the obtained catalyst is the catalyst in Example 7.

[0075] The amount of catalyst used in the above examples is 60mg.

[0076] The results of carbon dioxide cracking of each example are shown in Tables 2-8.

[0077] Table 2 CO2 cracking effect of Example 1

[0078] Time / min O2 / % CO / % CO2 / % 5 4.985357 14.86567 80.14627 10 5.010593 14.91905 80.06754 15 5.032176 14.99888 79.96621

[0079] Table 3 CO2 cracking effect of Example 2

[0080]

[0081]

[0082] Table 4 CO2 cracking effect of example 3

[0083] Time / min O2 / % CO / % CO2 / % 5 3.698518 12.53648 83.76115 10 3.698284 12.59838 83.69972 15 3.686881 12.5647 83.74453

[0084] Table 5 CO2 cracking effect of example 4

[0085] Time / min O2 / % CO / % CO2 / % 5 4.50 14.34 81.16 10 4.53 14.44 81.02 15 4.56 14.47 80.96

[0086] Table 6 CO2 cracking effect of example 5

[0087] Time / min O2 / % CO / % CO2 / % 5 3.87 12.06 84.06 10 3.90 12.08 84.02 15 3.93 12.11 83.96

[0088] Table 7 CO2 cracking effect of example 6

[0089] Time / min O2 / % CO / % CO2 / % 5 4.362667 13.40006 82.23336 10 4.352778 13.44165 82.20153 15 4.324208 13.52273 82.14911

[0090] Table 8 CO2 cracking effect of example 7

[0091] Time / min O2 / % CO / % CO2 / % 5 4.20025 14.15843 81.63925 10 4.192221 14.08411 81.72148 15 4.190051 14.13062 81.67711

[0092] According to the above embodiments, it can be obtained that appropriate preparation time can ensure sufficient reaction and uniform distribution of the catalyst, thereby improving its activity and stability. Different mass ratios of BDC and nickel ferrite can affect the electronic structure, acid-base property and surface property of the catalyst, and the optimal catalytic ratio is shown in example 1. The iron-nickel catalyst generally has good thermal stability and can maintain activity in high temperature and complex reaction environment. In addition, compared with iron-calcium elements, iron-nickel elements can enhance the electronic conductivity of the catalyst and improve the efficiency of the reaction. Therefore, in summary, the catalytic effect of example 1 is the best.

[0093] The present application is a kind of waste clothes terylene and metallurgical solid waste preparation catalyst and its application, the catalyst utilizes two kinds of waste, realizes the comprehensive utilization of waste and resource, reduces the harm of waste to environment at the same time also reduces the dependence of catalyst on existing valuable materials. The catalyst prepared by the present application is prepared from almost waste materials, and the process does not produce toxic substances, and the process cost is low. The catalyst prepared by the present application is a metal organic framework catalyst, which has a large specific surface area and more active sites, so that CO2 and catalyst can better contact, and the catalytic effect of the catalyst is improved. And the catalyst has high thermal stability and chemical stability, and can be reused multiple times.

[0094] The above description of the embodiments is made for the purpose of enabling a person of ordinary skill in the art to understand and use the application. It is obvious that those skilled in the art can easily make various modifications to the embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present application is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present application without departing from the scope of the present application should be within the scope of the present application.

Claims

1. A method for preparing a catalyst using waste polyester spun fabric and nickel-containing solid waste, characterized by, The preparation method comprises the following steps: 1) drying, grinding and calcining the nickel-containing solid waste to obtain nickel ferrite; 2) washing, drying and mixing the waste polyester yarn with alkali in water, and then adjusting the pH of the supernatant to acidity after centrifugation, and then adjusting the pH to 0.5-1.5 and centrifugation to obtain BDC; 3) mixing the nickel ferrite prepared in step 1) and the BDC prepared in step 2) in an organic solvent and heating to obtain a catalyst; In step 1), the nickel-containing solid waste has a nickel element mass percentage content of greater than 15%, and the source is NiSO4, and the iron element mass percentage content is greater than 20%; In step 3), the mass ratio of the nickel ferrite prepared in step 1) and the BDC prepared in step 2) is 0.19-0.21:1; the amount of the nickel ferrite prepared in step 1) and the organic solvent is 0.70-0.75 mg / mL; and the organic solvent is selected from N,N-dimethylformamide and anhydrous ethanol.

2. The production method according to claim 1, characterized by, In step 1), the calcination is performed at 1000 DEG C for 4 hours.

3. The preparation method according to claim 1, characterized in that, In step 2), the mass ratio of the waste polyester yarn and the alkali is 1:0.3-0.6; and the alkali is selected from sodium hydroxide.

4. The production method according to claim 1 or 3, characterized by, In step 2), the mass ratio of the waste polyester yarn and water is 1:

10.

5. The production method according to claim 1 or 3, characterized by, In step 2), the heating reaction is performed at 160-220 DEG C for 6 hours.

6. The production method according to claim 1 or 3, characterized by, In step 2), the supernatant is adjusted to acidity by adjusting the pH of the system to 0.5-1.5 with an HCl solution.

7. The preparation method according to claim 1, characterized in that, In step 3), the volume ratio of N,N-dimethylformamide and anhydrous ethanol is 16:

1.

8. The production method according to claim 1 or 7, characterized by, In step 3), the heating reaction refers to heating treatment at 180 DEG C for 48 hours.

9. A catalyst prepared by the preparation method of any one of claims 1-8.

10. Use of a catalyst as claimed in claim 9, characterized in that for cracking carbon dioxide.

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