Modified baking-free ceramic granule and its preparation method and application

Abstract

The application provides a modified baking-free ceramic grain and a preparation method and application thereof, and belongs to the technical field of baking-free ceramic grains. Waste glass is treated by triethanolamine, and then is added into a balling machine; while being stirred, fly ash, iron tailings and adhesive mixed powder are added; water and hydrogen peroxide are sprayed to form balls; and the balls are cured to obtain porous baking-free ceramic grains; after MoS2 quantum dots are doped into TiO2 on the surface of the porous baking-free ceramic grains, coupling sulfurized zero-valent iron is carried out; and the coupling sulfurized zero-valent iron is modified by a silane coupling agent with a double bond, and is copolymerized with acrylic acid, styrene and 1-vinyl-3-carboxymethyl imidazole chloride salt to obtain modified baking-free ceramic grains. The modified baking-free ceramic grains have the characteristics of light weight, high strength, easy separation and large specific surface area, can effectively purify organic matters and heavy metal ions in sewage, have good purification effect, can be reused, and have a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of non-fired ceramsite technology, specifically to a modified non-fired ceramsite, its preparation method, and its application. Background Technology

[0002] Expanded clay aggregate (ECA), an important coarse aggregate in lightweight aggregate concrete, is favored by the construction industry due to its light weight and good thermal and sound insulation properties. However, traditional sintered ECA requires high investment and consumes a lot of energy, which affects its application. With the advent of non-fired ECA, it can be used directly after molding and curing, eliminating the need for high-temperature firing. This effectively avoids the energy consumption and environmental problems associated with high-temperature sintering, resulting in higher economic benefits compared to traditional ECA preparation methods.

[0003] However, most existing non-fired ceramsite is made from solid wastes such as fly ash, red mud, and coal gangue, with cement added as a binder to bind the raw materials together. Compared with traditional sintered ceramsite, the surface of the non-fired ceramsite is not as hard, and its overall structural strength is difficult to reach the level of traditional sintered ceramsite. This makes it prone to powdering and cracking during use, which greatly affects the performance of the ceramsite and makes it difficult to guarantee the strength of the concrete after construction. Moreover, compared with sintered ceramsite, it still has the disadvantages of higher density, lower strength, and higher water absorption. The core-shell structure is significantly effective in reducing density and water absorption.

[0004] Chinese invention patent CN109020418B discloses a method for producing non-fired and non-steam-cured ceramsite using solid waste-based sulfoaluminate cementitious materials. The preparation method involves mixing fly ash and solid waste-based sulfoaluminate cement in a certain proportion to form a mixture; spraying a certain amount of foaming agent aqueous solution into the mixture and stirring and granulating to form ceramsite blanks; and subjecting the ceramsite blanks to standard curing to obtain non-fired ceramsite. The non-fired ceramsite prepared in this patent eliminates the need for cement addition and high-temperature firing. However, the self-made cementitious material added still needs to be calcined at 1250℃, resulting in relatively high costs and environmental pollution during the firing process.

[0005] Chinese invention patent CN110835247B discloses a type of non-fired ceramsite for solidifying silt using a composite cementitious material of emulsified asphalt and cement. This patent utilizes raw materials such as emulsified asphalt, cement, admixtures, and silt in a fixed mix ratio to prepare a type of non-fired ceramsite. This type of non-fired ceramsite produced from silt makes full use of the silt at the bottom of rivers and lakes, greatly reducing costs. Moreover, the non-fired ceramsite does not require a large amount of energy to be consumed during the production process. However, the non-fired ceramsite produced by this method usually has a high water absorption rate, low strength, and poor stability. It is also more prone to softening when exposed to water than sintered ceramsite. Therefore, it is necessary to modify the prepared non-fired ceramsite to reduce its water absorption rate and improve its softening coefficient and mechanical properties. Summary of the Invention

[0006] The purpose of this invention is to propose a modified non-fired ceramsite, its preparation method, and its application. It has the characteristics of being lightweight, high-strength, easy to separate, and having a large specific surface area. It can effectively purify organic matter and heavy metal ions in wastewater, with good purification effect and can be reused, thus having broad application prospects.

[0007] The technical solution of this invention is implemented as follows: This invention provides a method for preparing modified non-fired ceramsite. Waste glass is treated with triethanolamine and then added to a pelletizing machine. While stirring, fly ash, iron tailings, and binder powder are added. Water and hydrogen peroxide are sprayed to form pellets, which are then cured to obtain porous non-fired ceramsite. After loading MoS2 quantum dots onto the surface to dope TiO2, zero-valent iron is coupled and modified with a silane coupling agent containing double bonds. The pellets are then copolymerized with acrylic acid, styrene, and 1-vinyl-3-carboxymethyl imidazole chloride to obtain modified non-fired ceramsite.

[0008] As a further improvement of the present invention, the following steps are included: S1. Waste glass is crushed, triethanolamine is added and stirred to mix evenly to obtain roughened glass powder; S2. Fly ash, iron tailings and binder are mixed evenly to obtain powder; S3. The roughened glass powder is added to a pelletizing machine, the machine is turned on, the powder is added evenly, and water and hydrogen peroxide are sprayed at the same time to obtain ceramsite pellets. The pellets are sealed and moisturized, then sealed and naturally cured, and discharged to obtain porous non-fired ceramsite; S4. The porous non-fired ceramsite is added to ethanol, tetrabutyl titanate, sodium molybdate, glutathione and deionized water are added, the pH value of the solution is adjusted, hydrothermal reaction is carried out, filtration, washing, drying and calcination are performed to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite; S5. MoS2 quantum dot-doped TiO2 modified non-sintered ceramsite was added to ethanesulfonic acid biological buffer solution. Under inert gas protection, zero-valent iron and copper sulfide were added, the mixture was stirred, filtered, washed, and dried to obtain ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-sintered ceramsite. S6. The ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-sintered ceramsite was added to ethanol, and a silane coupling agent with double bonds was added. The mixture was heated and stirred, filtered, washed, and dried to obtain modified ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-sintered ceramsite. S7. The modified ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-sintered ceramsite was added to acetonitrile, and acrylic acid, styrene, and 1-vinyl-3-carboxymethylimidazolium chloride were added. Under inert gas protection, an initiator was added, the mixture was heated and stirred, filtered, washed, and dried to obtain modified non-sintered ceramsite.

[0009] As a further improvement of the present invention, the mass ratio of waste glass and triethanolamine in step S1 is 100:7-11; the mass ratio of fly ash, iron tailings and binder in step S2 is 60-70:30-40:17-23, and the binder includes cement, alkali, water glass, quicklime and hydrated lime, with a mass ratio of 10-15:1-2:3-5:2-4:1-2.

[0010] As a further improvement of the present invention, the mass ratio of roughened glass powder, powder, water and hydrogen peroxide in step S3 is 20-40:100-150:2-5:6-9, the tilt angle of the pelletizing machine is 45-50°, the peripheral tangential velocity of the pelletizing disc is 1.5-2.0 m / s, the average diameter of the porous non-fired ceramsite is 1-2 cm, the sealing and moisturizing curing time is 20-24 h, and the sealing and natural curing time is 26-30 d.

[0011] As a further improvement of the present invention, in step S4, the mass ratio of porous non-fired ceramsite, ethanol, tetrabutyl titanate, sodium molybdate, glutathione, and deionized water is 10:80-100:2-3:0.1-0.15:0.15-0.2:15-20, the pH value of the adjusted solution is 6.5-6.7, the temperature of the hydrothermal reaction is 180-220℃, the time is 10-12h, and the calcination temperature is 400-450℃, the time is 0.5-1.5h.

[0012] As a further improvement of the present invention, the pH value of the ethanesulfonic acid biological buffer in step S5 is 6.2-6.5, and the mass ratio of the MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles, zero-valent iron and copper sulfide is 10-15:3-4:1.5-2.

[0013] As a further improvement of the present invention, in step S6, the mass ratio of the sulfided zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-sintered ceramic particles and the silane coupling agent with double bonds is 10:1-2. The silane coupling agent with double bonds is selected from at least one of KH570, A151, and A171. The heating and stirring reaction temperature is 45-55℃ and the time is 2-4h.

[0014] As a further improvement of the present invention, in step S7, the mass ratio of modified sulfided zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite, acrylic acid, styrene, 1-vinyl-3-carboxymethylimidazolium chloride, and initiator is 10-15:2-3:1-2:1-2:0.05-0.1, the heating and stirring reaction temperature is 55-65℃, and the time is 4-6h, and the initiator is selected from at least one of sodium persulfate, potassium persulfate, and ammonium persulfate.

[0015] The present invention further protects a modified non-fired ceramsite prepared by the above-described preparation method.

[0016] This invention further protects the application of the above-mentioned modified non-fired ceramsite in wastewater treatment.

[0017] The present invention has the following beneficial effects: untreated waste glass powder cannot be coated with powder. Using triethanolamine to roughen its surface makes it easier for the powder to coat its surface, and can also improve the strength of the obtained non-fired ceramsite; using fly ash as raw material to prepare ceramsite can effectively realize the recycling of solid waste and obtain value-added products. The non-fired method for preparing fly ash ceramsite has the characteristics of low cost, low energy consumption, and simple production process, and is more environmentally friendly and energy-saving.

[0018] Fly ash is mainly composed of oxides such as SiO2 and Al2O3, and does not possess hydraulic cementitious properties. These oxides need to undergo a pozzolanic reaction with Ca(OH)2 generated after cement hydration to form hydrated calcium silicate and hydrated calcium aluminate, which have cementitious properties, and further form ceramsite with a certain strength. However, only a small amount of these oxides remain on the surface of fly ash, resulting in low reactivity. Class F fly ash has a low calcium content, requiring the addition of cement or lime as a binder to increase its pelletizing efficiency and improve its strength. Therefore, this invention adds an additional binder, including silicate cement, NaOH, water glass, quicklime, and hydrated lime, wherein NaOH and water glass can react with OH- generated by hydrolysis. - The disruption of Si-O-Si, Al-O-Al, and Al-O-Si covalent bonds generates active SiO2 and Al2O3, activating the fly ash. The NaOH obtained from the hydrolysis of water glass, as well as added NaOH, reacts with acidic substances in the fly ash to form a gel-like Na2O-Al2O3-SiO2 compound, which both binds the particles and improves the strength of the ceramsite product. Adding calcium, such as hydrated lime (Ca(OH)2) and quicklime (CaO), causes a hydration reaction between the fly ash and calcium, further activating the fly ash. Additionally, the use of Ca(OH)2 accelerates the pelletizing time of the ceramsite. Furthermore, the spraying of hydrogen peroxide during the ceramsite preparation process acts as a foaming agent, increasing the pore structure of the ceramsite and producing lightweight, porous ceramsite with low bulk density and large specific surface area.

[0019] The surface of the prepared porous non-fired ceramic particles was coated with MoS2 quantum dots doped with anatase TiO2 via sol-gel reaction and hydrothermal reaction. MoS2 quantum dots, with their narrow band gap, can act as photosensitizers and electron traps, significantly promoting the effective separation of photogenerated electron-hole pairs in TiO2 and improving quantum efficiency. Simultaneously, it overcomes the limitation of low visible light utilization in TiO2 photocatalysis; the introduction of MoS2 quantum dots extends the response range to the visible light and even the near-infrared region, effectively utilizing solar energy. Furthermore, the heterojunction structure formed by MoS2 / TiO2 has tight interfacial contact, promoting interfacial charge transfer and enhancing photocatalytic redox capabilities, thereby improving the efficiency and persistence of photocatalytic degradation of organic pollutants.

[0020] Further surface loading with zero-valent iron sulfide allows sulfur-containing free radicals to gain electrons under the activation of zero-valent iron, resulting in strong oxidizing properties that can degrade many organic pollutants in dye wastewater. At the same time, zero-valent iron can also act as a reducing agent, reducing high-valent pollutants to low-toxicity or easily precipitated forms, thereby efficiently removing heavy metal ions from wastewater. Since zero-valent iron is an elemental form of iron and has ferromagnetism, it can be magnetically adsorbed and separated, making it easier to separate even after the ceramsite is crushed, thus preventing further pollution.

[0021] The surface of the sulfide-containing zero-valent iron / MoS2 quantum dot-doped TiO2-modified non-fired ceramsite, after being modified with a silane coupling agent containing double bonds, can be copolymerized with acrylic acid, styrene, and 1-vinyl-3-carboxymethyl imidazolium chloride. This modification not only improves the mechanical strength of the ceramsite but also gives it abundant carboxyl groups on its surface, enabling it to fix heavy metal ions through chelation, thereby significantly purifying wastewater. Furthermore, the 1-vinyl-3-carboxymethyl imidazolium chloride fraction of the ionic liquid also improves the solubility of organic matter and enhances its adsorption capacity, further improving the ability to degrade organic matter and thus enhancing the wastewater treatment effect.

[0022] The modified non-fired ceramsite prepared by this invention has the characteristics of being lightweight, high-strength, easy to separate, and having a large specific surface area. It can effectively purify organic matter and heavy metal ions in wastewater, with good purification effect and can be reused, thus having broad application prospects. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1

[0025] This embodiment provides a method for preparing modified non-fired ceramsite, including the following steps: S1. 100g of waste glass is crushed, and 7g of triethanolamine is added and stirred for 30min to obtain roughened glass powder; S2. 60g of F-grade fly ash, 30g of iron tailings, and 17g of binder are stirred and mixed for 10min to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 10:1:3:2:1; S3. 20g of roughened glass powder is added to a pelletizer, the machine is turned on, the inclination angle of the pelletizer is 45°, the peripheral tangential velocity of the pelletizing disc is 1.5m / s, 100g of powder is added evenly, and 2g of water and 6g of hydrogen peroxide are sprayed evenly in atomized form to obtain ceramsite balls, which are sealed and moisturized for 20h, then sealed and naturally cured for 26d, and discharged to obtain porous non-fired ceramsite with an average diameter of 1cm; S4. 10g of porous, non-fired ceramsite was added to 80g of ethanol, along with 2g of tetrabutyl titanate, 0.1g of sodium molybdate, 0.15g of glutathione, and 15g of deionized water. The pH of the solution was adjusted to 6.5, and the mixture was hydrothermally reacted at 180℃ for 10h. After filtration, washing, and drying, the mixture was calcined at 400℃ for 0.5h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. 10g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.2. Under nitrogen protection, 3g of zero-valent iron and 1.5g of copper sulfide were added, and the mixture was stirred and reacted for 12h. After filtration, washing, and drying, zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was obtained. S6. Add 10g of sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of ethanol, add 1g of silane coupling agent A151, heat to 45℃, stir and react for 2h, filter, wash, and dry to obtain modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles; S7. Add 10g of modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of acetonitrile, add 2g of acrylic acid, 1g of styrene, 1g of 1-vinyl-3-carboxymethylimidazolium chloride, under nitrogen protection, add 0.05g of ammonium persulfate, heat to 55℃, stir and react for 4h, filter, wash, and dry to obtain modified non-fired ceramic particles.

[0026] Example 2

[0027] This embodiment provides a method for preparing modified non-fired ceramsite, including the following steps: S1. 100g of waste glass is crushed, and 11g of triethanolamine is added and stirred for 30min to obtain roughened glass powder; S2. 70g of F-grade fly ash, 40g of iron tailings, and 23g of binder are stirred and mixed for 10min to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 15:2:5:4:2; S3. 40g of roughened glass powder is added to a pelletizer, the machine is turned on, the inclination angle of the pelletizer is 50°, the peripheral tangential velocity of the pelletizing disc is 2.0m / s, 150g of powder is added evenly, and 5g of water and 9g of hydrogen peroxide are sprayed evenly in atomized form to obtain ceramsite balls, which are sealed and moisturized for 24h, then sealed and naturally cured for 30d, and discharged to obtain porous non-fired ceramsite with an average diameter of 1cm; S4. 10g of porous, non-fired ceramsite was added to 100g of ethanol, along with 3g of tetrabutyl titanate, 0.15g of sodium molybdate, 0.2g of glutathione, and 20g of deionized water. The pH of the solution was adjusted to 6.7, and the mixture was hydrothermally reacted at 220℃ for 12h. After filtration, washing, and drying, the mixture was calcined at 450℃ for 1.5h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. 15g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.5. Under nitrogen protection, 4g of zero-valent iron and 2g of copper sulfide were added, and the mixture was stirred and reacted for 12h. After filtration, washing, and drying, zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was obtained. S6. Add 10g of sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of ethanol, add 2g of silane coupling agent A171, heat to 55℃, stir and react for 4h, filter, wash, and dry to obtain modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles; S7. Add 15g of modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of acetonitrile, add 3g of acrylic acid, 2g of styrene, 2g of 1-vinyl-3-carboxymethylimidazolium chloride, under nitrogen protection, add 0.1g of potassium persulfate, heat to 65℃, stir and react for 6h, filter, wash, and dry to obtain modified non-fired ceramic particles.

[0028] Example 3

[0029] This embodiment provides a method for preparing modified non-fired ceramsite, comprising the following steps: S1. Crushing 100g of waste glass, adding 10g of triethanolamine and stirring for 30min to obtain roughened glass powder; S2. Stirring 65g of grade F fly ash, 35g of iron tailings, and 20g of binder for 10min to obtain powder; the binder comprises PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizing machine, turn on the machine, set the pelletizing machine to an inclination angle of 47°, and set the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in atomized form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain porous non-fired ceramsite with an average diameter of 1cm. S4. Add 10g of porous non-fired ceramsite to 90g of ethanol, add 2.5g of tetrabutyl titanate, 0.12g of sodium molybdate, 0.17g of glutathione, and 17g of deionized water. Adjust the pH of the solution to 6.6, and perform a hydrothermal reaction at 200℃ for 11 hours. Filter, wash, dry, and calcine at 450℃ for 1 hour to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. Add 12g of... MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles were added to 200 mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, 3.5 g of zero-valent iron and 1.7 g of copper sulfide were added, and the mixture was stirred for 12 h. After filtration, washing, and drying, ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles were obtained. S6. 10 g of ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles were added to 200 mL of ethanol, along with 1.5 g of silane coupling agent KH570. The mixture was heated to 50 °C and stirred for 3 h. After filtration, washing, and drying, modified ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles were obtained. S7. 12 g of modified ferrous sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles were added to 200 mL of acetonitrile, along with 2.5 g of acrylic acid, 1.5 g of styrene, and 1.5 g of copper sulfide. 1-Vinyl-3-carboxymethylimidazolium chloride was added to 0.07 g of potassium persulfate under nitrogen protection, heated to 60 °C, stirred for 5 h, filtered, washed, and dried to obtain modified non-fired ceramsite.

[0030] Comparative Example 1

[0031] The difference from Example 3 is that NaOH and water glass were not added in step S2.

[0032] Specifically, the steps are as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and mix for 30 minutes to obtain roughened glass powder; S2. Mix 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10 minutes to obtain powder; the binder includes PO 42.5 silicate cement, quicklime, and hydrated lime in a mass ratio of 17.5:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain porous, non-fired ceramsite with an average diameter of 1cm; S4. 10g of porous, non-fired ceramsite was added to 90g of ethanol, along with 2.5g of tetrabutyl titanate, 0.12g of sodium molybdate, 0.17g of glutathione, and 17g of deionized water. The pH of the solution was adjusted to 6.6, and the mixture was hydrothermally reacted at 200℃ for 11h. After filtration, washing, and drying, the mixture was calcined at 450℃ for 1h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. 12g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, 3.5g of zero-valent iron and 1.7g of copper sulfide were added, and the mixture was stirred and reacted for 12h. After filtration, washing, and drying, zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was obtained. S6. Add 10g of sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of ethanol, add 1.5g of silane coupling agent KH570, heat to 50℃, stir and react for 3h, filter, wash, and dry to obtain modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles; S7. Add 12g of modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of acetonitrile, add 2.5g of acrylic acid, 1.5g of styrene, and 1.5g of 1-vinyl-3-carboxymethylimidazolium chloride, under nitrogen protection, add 0.07g of potassium persulfate, heat to 60℃, stir and react for 5h, filter, wash, and dry to obtain modified non-fired ceramic particles.

[0033] Comparative Example 2

[0034] The difference from Example 3 is that hydrogen peroxide was not added in step S3.

[0035] Specifically, the steps are as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and mix for 30 minutes to obtain roughened glass powder; S2. Mix 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10 minutes to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 10g of water evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain non-fired ceramsite with an average diameter of 1cm; S4. Add 10g of non-fired ceramsite to 90g of ethanol, then add 2.5g of tetrabutyl titanate, 0.12g of sodium molybdate, 0.17g of glutathione and 17g of deionized water. Adjust the pH of the solution to 6.6, and perform a hydrothermal reaction at 200℃ for 11h. Filter, wash, dry, and calcine at 450℃ for 1h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite; S5. Add 12g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, add 3.5g of zero-valent iron and 1.7g of copper sulfide, stir and react for 12h, then filter, wash, and dry to obtain zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite; S6. Add 10g of sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of ethanol, add 1.5g of silane coupling agent KH570, heat to 50℃, stir and react for 3h, filter, wash, and dry to obtain modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles; S7. Add 12g of modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of acetonitrile, add 2.5g of acrylic acid, 1.5g of styrene, and 1.5g of 1-vinyl-3-carboxymethylimidazolium chloride, under nitrogen protection, add 0.07g of potassium persulfate, heat to 60℃, stir and react for 5h, filter, wash, and dry to obtain modified non-fired ceramic particles.

[0036] Comparative Example 3

[0037] The difference from Example 3 is that sodium molybdate was not added in step S4.

[0038] Specifically, the steps are as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and mix for 30 minutes to obtain roughened glass powder; S2. Mix 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10 minutes to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain porous, non-fired ceramsite with an average diameter of 1cm; S4. 10g of porous non-fired ceramsite was added to 90g of ethanol, along with 2.62g of tetrabutyl titanate and 17g of deionized water. The pH of the solution was adjusted to 6.6, and the mixture was stirred for 5h. After filtration, washing, and drying, the mixture was calcined at 450℃ for 1h to obtain TiO2-modified non-fired ceramsite. S5. 12g of TiO2-modified non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, 3.5g of zero-valent iron and 1.7g of copper sulfide were added, and the mixture was stirred for 12h. After filtration, washing, and drying, zero-valent iron sulfide / TiO2-modified non-fired ceramsite was obtained. S6. Add 10g of sulfided zero-valent iron / TiO2 modified non-fired ceramsite to 200mL of ethanol, add 1.5g of silane coupling agent KH570, heat to 50℃, stir and react for 3h, filter, wash, and dry to obtain modified sulfided zero-valent iron / TiO2 modified non-fired ceramsite; S7. Add 12g of modified sulfided zero-valent iron / TiO2 modified non-fired ceramsite to 200mL of acetonitrile, add 2.5g of acrylic acid, 1.5g of styrene, and 1.5g of 1-vinyl-3-carboxymethylimidazolium chloride, under nitrogen protection, add 0.07g of potassium persulfate, heat to 60℃, stir and react for 5h, filter, wash, and dry to obtain modified non-fired ceramsite.

[0039] Comparative Example 4

[0040] The difference from Example 3 is that step S4 was not performed.

[0041] Specifically, the steps are as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and mix for 30 minutes to obtain roughened glass powder; S2. Mix 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10 minutes to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain porous, non-fired ceramsite with an average diameter of 1cm; S4. 12g of porous non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, 3.5g of zero-valent iron and 1.7g of copper sulfide were added, and the mixture was stirred for 12h. After filtration, washing, and drying, ferrous sulfide-modified non-fired ceramsite was obtained. S5. 10g of ferrous sulfide-modified non-fired ceramsite was added to 200mL of ethanol, along with 1.5g of silane coupling agent KH570. The mixture was heated to 50℃ and stirred for 3h. After filtration, washing, and drying, ferrous sulfide-modified non-fired ceramsite was obtained. S6. 12g of ferrous sulfide-modified non-fired ceramsite was added to 200mL of acetonitrile, along with 2.5g of acrylic acid, 1.5g of styrene, and 1.5g of copper sulfide. 1-Vinyl-3-carboxymethylimidazolium chloride was added to 0.07 g of potassium persulfate under nitrogen protection, heated to 60 °C, stirred for 5 h, filtered, washed, and dried to obtain modified non-fired ceramsite.

[0042] Comparative Example 5

[0043] The difference from Example 3 is that step S5 was not performed.

[0044] Specifically, the steps are as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and mix for 30 minutes to obtain roughened glass powder; S2. Mix 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10 minutes to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain porous, non-fired ceramsite with an average diameter of 1cm; S4. Add 10g of porous, non-fired ceramsite to 90g of ethanol, along with 2.5g of tetrabutyl titanate, 0.12g of sodium molybdate, 0.17g of glutathione, and 17g of deionized water. Adjust the pH of the solution to 6.6. Perform a hydrothermal reaction at 200℃ for 11h. Filter, wash, dry, and calcine at 450℃ for 1h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. Add 10g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite to 200mL of ethanol, along with 1.5g of silane coupling agent KH570. Heat to 50℃, stir for 3h, filter, wash, and dry to obtain modified MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S6. Add 12g of modified MoS2 quantum dot-doped TiO2 modified non-fired ceramsite to 200mL of acetonitrile, along with 2.5g of acrylic acid, 1.5g of styrene, and 1.5g of... 1-Vinyl-3-carboxymethylimidazolium chloride was added to 0.07 g of potassium persulfate under nitrogen protection, heated to 60 °C, stirred for 5 h, filtered, washed, and dried to obtain modified non-fired ceramsite.

[0045] Comparative Example 6

[0046] The difference from Example 3 is that steps S6 and S7 were not performed.

[0047] Specifically as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and stir for 30min to obtain roughened glass powder; S2. Stir 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10min to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22h, then seal and naturally cure for 28d. Discharge to obtain porous, non-fired ceramsite with an average diameter of 1cm; S4. 10g of porous, non-fired ceramsite was added to 90g of ethanol, along with 2.5g of tetrabutyl titanate, 0.12g of sodium molybdate, 0.17g of glutathione, and 17g of deionized water. The pH of the solution was adjusted to 6.6, and the mixture was hydrothermally reacted at 200℃ for 11h. After filtration, washing, and drying, the mixture was calcined at 450℃ for 1h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. 12g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, 3.5g of zero-valent iron and 1.7g of copper sulfide were added, and the mixture was stirred and reacted for 12h. After filtration, washing, and drying, zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was obtained, which is the modified non-fired ceramsite.

[0048] Comparative Example 7

[0049] The difference from Example 3 is that 1-vinyl-3-carboxymethylimidazolium chloride was not added in step S7.

[0050] Specifically, the steps are as follows: S1. Crush 100g of waste glass, add 10g of triethanolamine and mix for 30 minutes to obtain roughened glass powder; S2. Mix 65g of F-grade fly ash, 35g of iron tailings, and 20g of binder for 10 minutes to obtain powder; the binder includes PO 42.5 silicate cement, NaOH, water glass, quicklime, and hydrated lime in a mass ratio of 12:1.5:4:3:1.5; S3. Add 30g of roughened glass powder to a pelletizer, turn on the machine, set the pelletizer's tilt angle to 47°, and the peripheral tangential velocity of the pelletizing disc to 1.7m / s. Add 125g of powder evenly, and simultaneously spray 3g of water and 7g of hydrogen peroxide evenly in a mist form to obtain ceramsite pellets. Seal and moisturize for 22 hours, then seal and allow to cure naturally for 28 days. Discharge the material to obtain porous, non-fired ceramsite with an average diameter of 1cm; S4. 10g of porous, non-fired ceramsite was added to 90g of ethanol, along with 2.5g of tetrabutyl titanate, 0.12g of sodium molybdate, 0.17g of glutathione, and 17g of deionized water. The pH of the solution was adjusted to 6.6, and the mixture was hydrothermally reacted at 200℃ for 11h. After filtration, washing, and drying, the mixture was calcined at 450℃ for 1h to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramsite. S5. 12g of MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was added to 200mL of ethanesulfonic acid biological buffer solution with a pH of 6.3. Under nitrogen protection, 3.5g of zero-valent iron and 1.7g of copper sulfide were added, and the mixture was stirred and reacted for 12h. After filtration, washing, and drying, zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite was obtained. S6. Add 10g of sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of ethanol, add 1.5g of silane coupling agent KH570, heat to 50℃, stir and react for 3h, filter, wash, and dry to obtain modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles; S7. Add 12g of modified sulfide-based zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles to 200mL of acetonitrile, add 4g of acrylic acid and 1.5g of styrene, under nitrogen protection, add 0.07g of potassium persulfate, heat to 60℃, stir and react for 5h, filter, wash, and dry to obtain modified non-fired ceramic particles.

[0051] Test Example 1

[0052] According to the requirements of GB 17431.1-2010 "Lightweight aggregates and their test methods - Part 1: Lightweight aggregates",

[0053] The performance of the modified non-fired ceramsite prepared in Examples 1-3 and Comparative Examples 1-7 was compared. Performance tests were conducted according to GB 17431.2-2010 "Lightweight aggregates and their test methods Part 2: Lightweight aggregates test methods". The results are shown in Table 1. .

[0054] As can be seen from the table above, the modified non-fired ceramsite prepared in Examples 1-3 of the present invention has the characteristics of being lightweight, high-strength, and having low water absorption.

[0055] Test Example 2

[0056] The selected ceramic filter is 320mm high and 32mm in diameter, made of glass, with a bottom-in, top-out water intake. A 22mm diameter iron screen is placed as a support layer. The iron screen is positioned at the inlet and 55mm from the outlet. Modified non-fired ceramic particles prepared in Examples 1-3 or Comparative Examples 1-7 are then added, with a ceramic particle layer height of 200mm. 10L of artificial lake water is continuously circulated into the filter for 9 hours at a flow rate of 0.5m / s. After the operation, the COD, NH3-N, SS, TP, and Mn content of the water sample are tested. 2+ Cu 2+ Content, and removal rate of various indicators were measured.

[0057] COD was determined using the dichromate method specified in GB11914-1989; NH3-N was determined using the Kjeldahl method; SS was determined using the gravimetric method specified in GB11901-1989; TP was determined using the molybdenum-antimony spectrophotometric method specified in GB11893-1989; Mn... 2+ Cu 2+ The content was determined by atomic absorption spectrophotometry.

[0058] The original water quality test results of the artificial lake are shown in Table 2. The test results of the purified water sample are shown in Table 3. As can be seen from the table above, the modified non-fired ceramsite prepared in Examples 1-3 of the present invention has a good sewage purification effect.

[0059] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing modified non-fired ceramsite, characterized in that, Includes the following steps: S1. Crush waste glass, add triethanolamine and stir to mix evenly to obtain roughened glass powder; S2. Mix fly ash, iron tailings and binder evenly to obtain powder; S3. Add roughened glass powder to pelletizing machine, turn on the machine, add powder evenly, and spray water and hydrogen peroxide at the same time to obtain ceramsite pellets, seal and moisturize for curing, then seal and store for natural curing, and discharge to obtain porous non-fired ceramsite. S4. Porous non-fired ceramic particles were added to ethanol, along with tetrabutyl titanate, sodium molybdate, glutathione, and deionized water. The pH of the solution was adjusted, and a hydrothermal reaction was carried out. The mixture was then filtered, washed, dried, and calcined to obtain MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles. S5. MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles were added to ethanesulfonic acid biological buffer solution. Under inert gas protection, zero-valent iron and copper sulfide were added, and the mixture was stirred and reacted. The mixture was then filtered, washed, and dried to obtain zero-valent iron sulfide / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles. S6. Add the sulfide zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-sintered ceramic particles to ethanol, add a silane coupling agent with double bonds, heat and stir to react, filter, wash, and dry to obtain the modified sulfide zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-sintered ceramic particles. S7. Modified sulfided zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles are added to acetonitrile, along with acrylic acid, styrene, and 1-vinyl-3-carboxymethylimidazolium chloride. Under inert gas protection, an initiator is added, and the mixture is heated and stirred to react. The mixture is then filtered, washed, and dried to obtain modified non-fired ceramic particles.

2. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of waste glass to triethanolamine is 100:7-11; in step S2, the mass ratio of fly ash, iron tailings, and binder is 60-70:30-40:17-23. The binder includes cement, alkali, water glass, quicklime, and hydrated lime, with a mass ratio of 10-15:1-2:3-5:2-4:1-2.

3. The preparation method according to claim 1, characterized in that, In step S3, the mass ratio of roughened glass powder, powder, water, and hydrogen peroxide is 20-40:100-150:2-5:6-9. The tilt angle of the pelletizing machine is 45-50°, the peripheral tangential velocity of the pelletizing disc is 1.5-2.0 m / s, the average diameter of the porous non-fired ceramsite is 1-2 cm, the sealing and moisturizing curing time is 20-24 h, and the sealing and natural curing time is 26-30 d.

4. The preparation method according to claim 1, characterized in that, In step S4, the mass ratio of porous non-fired ceramsite, ethanol, tetrabutyl titanate, sodium molybdate, glutathione, and deionized water is 10:80-100:2-3:0.1-0.15:0.15-0.2:15-20. The pH of the solution is adjusted to 6.5-6.

7. The hydrothermal reaction temperature is 180-220℃ and the time is 10-12h. The calcination temperature is 400-450℃ and the time is 0.5-1.5h.

5. The preparation method according to claim 1, characterized in that, The pH value of the ethanesulfonic acid biological buffer solution in step S5 is 6.2-6.5, and the mass ratio of the MoS2 quantum dot-doped TiO2 modified non-fired ceramic particles, zero-valent iron and copper sulfide is 10-15:3-4:1.5-2.

6. The preparation method according to claim 1, characterized in that, In step S6, the mass ratio of the sulfided zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-sintered ceramic particles to the silane coupling agent with double bonds is 10:1-2. The silane coupling agent with double bonds is selected from at least one of KH570, A151, and A171. The heating and stirring reaction temperature is 45-55℃, and the time is 2-4h.

7. The preparation method according to claim 1, characterized in that, In step S7, the mass ratio of modified sulfided zero-valent iron / MoS2 quantum dot-doped TiO2 modified non-fired ceramsite, acrylic acid, styrene, 1-vinyl-3-carboxymethylimidazolium chloride, and initiator is 10-15:2-3:1-2:1-2:0.05-0.

1. The heating and stirring reaction temperature is 55-65℃, and the time is 4-6 hours. The initiator is selected from at least one of sodium persulfate, potassium persulfate, and ammonium persulfate.

8. A modified non-fired ceramsite prepared by the preparation method according to any one of claims 1-7.

9. The application of the modified non-fired ceramsite as described in claim 8 in wastewater treatment.

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