Titanium-containing slag-based porous microspheres, and preparation method and application thereof

Abstract

The application discloses a kind of porous microspheres based on titanium slag and its preparation method and application, belong to absorbent and solid waste secondary utilization technical field.The application first dries titanium slag, is screened after mechanical ball milling, obtains titanium slag powder, titanium slag powder is added to oxalic acid dissolved in aqueous solution, is uniformly prepared slurry, under the condition of stirring, slurry is added dropwise to oil phase, under the action of mechanical stirring, then aging treatment is formed into ball, solid-liquid separation is carried out, and the obtained solid is calcined, and the porous microspheres based on titanium slag are obtained after screening.The application can prepare the more excellent applicability of porous microspheres by treating titanium slag, reduce the raw material cost problem of producing porous microspheres, and the prepared porous microspheres can be applied to CO2 capture, so as to achieve the effect of waste treatment and pollution control.

Description

Technical Field

[0001] This invention belongs to the field of absorbent and solid waste secondary utilization technology, and particularly relates to a titanium slag-based porous microsphere, its preparation method and application. Background Technology

[0002] While the titanium industry makes significant contributions to my country's economy, it also generates a large amount of solid waste. The stockpile of titanium-containing blast furnace slag alone has reached over 70 million tons, and is increasing at a rate of more than 3.8 million tons per year. This accumulated titanium-containing slag not only occupies vast amounts of land, but also wastes its valuable elements. Furthermore, the metallic elements within it can enter water sources and soil through rainwater runoff, polluting groundwater and soil. Therefore, many scholars have studied the resource utilization of titanium-containing slag. The comprehensive utilization of titanium-containing slag mainly includes titanium extraction, building materials, photocatalytic materials, and cementing materials, which partially achieves the resource utilization of titanium-containing slag, but cannot fully realize its value.

[0003] In recent years, CO2 emissions have continued to grow. Synergistically improving environmental pollution through the resource utilization of solid waste and carbon dioxide capture has become an effective way to simultaneously address the issues of titanium-containing blast furnace slag and the continuous increase in CO2 emissions. However, to date, no research has been reported on the preparation of porous microspheres from titanium-containing blast furnace slag and their application in carbon dioxide capture. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a porous microsphere based on titanium slag, its preparation method, and its application. This invention uses titanium slag from industrial solid waste as raw material, and porous microspheres with good sphericity and high strength can be prepared through a simple acid-activated suspension polymerization method. The microspheres have a certain ability to capture CO2 gas, thereby achieving the effect of treating waste with waste and generating resources from waste, and have good application prospects.

[0005] The objective of this invention is achieved through the following means:

[0006] This invention provides a method for preparing titanium slag-based porous microspheres, comprising the following steps:

[0007] (1) The titanium-containing slag is dried, mechanically ball-milled, and then sieved to obtain titanium-containing slag powder;

[0008] (2) Add the titanium-containing slag powder obtained in step (1) to an aqueous solution containing oxalic acid, mix well to obtain a slurry, add the slurry to the oil phase under stirring conditions, form balls under mechanical stirring, and then age.

[0009] (3) Solid-liquid separation: the obtained solid is roasted and sieved to obtain titanium slag-based porous microspheres.

[0010] Based on the above technical solution, the titanium-containing slag mentioned in step (1) is titanium-containing blast furnace slag tailings.

[0011] Based on the above technical solution, the specific drying process in step (1) is to dry the titanium-containing slag at 60-80℃ for 24-48 hours; ball mill for 1-3 hours; and pass it through a 120-180 mesh sieve to obtain titanium-containing slag powder.

[0012] Based on the above technical solution, further, the mass ratio of oxalic acid to titanium-containing slag in step (2) is 0.5 to 2:1, and the mass ratio of oxalic acid to water is 1 to 2:1.

[0013] Based on the above technical solution, further, in step (2), the stirring speed is 700-900 rpm and the stirring time is 4-6 min.

[0014] Based on the above technical solution, the oil phase mentioned in step (2) further includes silicone oil, dimethyl silicone oil, liquid paraffin and kerosene, and the oil phase temperature is 20-40℃.

[0015] Based on the above technical solution, further, the aging process in step (2) specifically involves placing the obtained mixture at 60-80°C for 12-18 hours.

[0016] Based on the above technical solution, the solid-liquid separation method in step (3) further includes filtration and centrifugation.

[0017] Based on the above technical solution, further, in step (3), the roasting temperature is 650-750℃, the roasting time is 1-3h, and the sieve mesh is 40-80 mesh.

[0018] In another aspect, the present invention provides titanium slag-based porous microspheres prepared by the above-described preparation method.

[0019] The present invention also provides the application of the above-mentioned titanium slag-based porous microspheres in CO2 capture.

[0020] The advantages of this invention over the prior art are as follows:

[0021] 1. This invention prepares porous microspheres with better applicability by treating titanium-containing slag, which reduces the raw material cost problem in the production of porous microspheres. At the same time, the prepared porous microspheres can be used for CO2 capture, thereby achieving the effect of treating waste with waste and treating pollution with pollution.

[0022] 2. The preparation method of the present invention is not only simple to operate and has low energy consumption, but also significantly reduces the manufacturing cost of porous microspheres. It achieves the effect of turning waste into resources while treating waste, and has a very good industrial application prospect. Attached Figure Description

[0023] To more clearly illustrate the embodiments of the present invention, the accompanying drawings involved in the embodiments will be briefly described below.

[0024] Figure 1 Microscopic image of the titanium slag-based porous microspheres prepared in Example 1. Detailed Implementation

[0025] The present invention will be described in detail below with reference to the embodiments. However, the implementation of the present invention is not limited thereto. Obviously, the embodiments described below are only some embodiments of the present invention. For those skilled in the art, other similar embodiments can be obtained without creative effort and all fall within the protection scope of the present invention.

[0026] Example 1

[0027] This embodiment provides a method for preparing titanium slag-based porous microspheres, including the following steps:

[0028] (1) Titanium-containing blast furnace slag was placed in an electric oven and dried at a constant temperature of 60°C for 48 hours. After ball milling for 2 hours, it was passed through a 180-mesh sieve to obtain titanium-containing slag powder.

[0029] (2) Weigh 4g of oxalic acid and add it to 2.6g of deionized water and stir evenly. Add 4g of titanium slag powder and react with it. Stir until a large amount of heat is released and a large number of bubbles are generated. Then quickly use a glass rod to drop the slurry into dimethyl silicone oil at room temperature. Use a disperser to stir into balls at 800rpm for 4 minutes. Then age in an oven at 60℃ for 18 hours.

[0030] (3) Solid-liquid separation: the obtained solid is placed in a muffle furnace and calcined at 700°C for 1 hour to obtain titanium slag-based porous microspheres. The microspheres are then passed through a 60-mesh sieve for later use.

[0031] The titanium-containing slag-based porous microspheres prepared in this embodiment have a particle size of 30–180 μm and a specific surface area of ​​111.72 m². 2 / g, total pore volume is 0.21cm³ 3 / g, with an average pore size of 7.651nm.

[0032] 10 mg of titanium slag-based porous microspheres were placed in an alumina crucible on a synchronous thermal analyzer. Under the condition of N2 flow rate of 60 mL / min, the temperature was raised to 700℃ and stabilized for 20 min at a heating rate of 10℃ / min. Then, a N2+CO2 mixed gas (with CO2 flow rate of 15 mL / min) was introduced at a rate of 75 mL / min. Under these conditions, the adsorption reached saturation, and the saturated adsorption capacity of the titanium slag-based porous microspheres for CO2 was 68.4 mg / g.

[0033] Example 2

[0034] This embodiment provides a method for preparing titanium slag-based porous microspheres, including the following steps:

[0035] (1) Titanium-containing blast furnace slag was placed in an electric oven and dried at a constant temperature of 70°C for 36 hours. After ball milling for 1.5 hours, it was passed through a 120-mesh sieve to obtain titanium-containing slag powder.

[0036] (2) Weigh 3g of oxalic acid and add 2g of deionized water and stir evenly. Add 4g of titanium slag powder and react with it. Stir until a large amount of heat is released and a large number of bubbles are generated. Then quickly use a glass rod to drop the slurry into dimethyl silicone oil at room temperature. Use a disperser to stir into balls at 700rpm for 5 minutes. Aging in a 70℃ oven for 15 hours.

[0037] (3) Solid-liquid separation: the obtained solid is placed in a muffle furnace and calcined at 650°C for 2 hours to obtain porous microspheres based on titanium slag. The microspheres are then passed through a 60-mesh sieve for later use.

[0038] The titanium-containing slag-based porous microspheres prepared in this embodiment have a particle size of 30–180 μm and a specific surface area of ​​71.53 m². 2 / g, total pore volume is 0.13cm³ 3 / g, with an average pore size of 1.092nm.

[0039] 10 mg of titanium slag-based porous microspheres were placed in an alumina crucible on a synchronous thermal analyzer. Under the condition of N2 flow rate of 60 mL / min, the temperature was raised to 700℃ and stabilized for 20 min at a heating rate of 10℃ / min. Then, a N2+CO2 mixed gas (with CO2 flow rate of 15 mL / min) was introduced. Under these conditions, the adsorption reached saturation, and the saturated adsorption capacity of the titanium slag-based porous microspheres for CO2 was 41.83 mg / g.

[0040] Example 3

[0041] This embodiment provides a method for preparing titanium slag-based porous microspheres, including the following steps:

[0042] (1) Titanium-containing blast furnace slag was placed in an electric oven and dried at a constant temperature of 80℃ for 24 hours. After ball milling for 2 hours, it was passed through a 180-mesh sieve to obtain titanium-containing slag powder.

[0043] (2) Weigh 4g of oxalic acid and add it to 3g of deionized water and stir evenly. Add 5g of titanium slag powder and react with it. Stir until a large amount of heat is released and a large number of bubbles are generated. Then quickly use a glass rod to drop the slurry into dimethyl silicone oil at room temperature. Use a disperser to stir into balls at 800rpm for 4 minutes. Then age in an oven at 60℃ for 18 hours.

[0044] (3) Solid-liquid separation: the obtained solid is placed in a muffle furnace and calcined at 750°C for 1 hour to obtain titanium slag-based porous microspheres. The microspheres are then passed through a 60-mesh sieve for later use.

[0045] The titanium-containing slag-based porous microspheres prepared in this embodiment have a particle size of 30–180 μm and a specific surface area of ​​76.49 m². 2 / g, total pore volume is 0.11cm³ 3 / g, with an average pore size of 5.682nm.

[0046] 10 mg of titanium slag-based porous microspheres were placed in an alumina crucible on a synchronous thermal analyzer. Under the condition of N2 flow rate of 60 mL / min, the temperature was raised to 700℃ at a heating rate of 10℃ / min and stabilized for 20 min. Then, a N2+CO2 mixed gas (with CO2 flow rate of 15 mL / min) was introduced. Under these conditions, the adsorption reached saturation, and the saturated adsorption capacity of the titanium slag-based porous microspheres for CO2 was 42.76 mg / g.

[0047] Example 4

[0048] This embodiment provides a method for preparing titanium slag-based porous microspheres, including the following steps:

[0049] (1) Titanium-containing blast furnace slag was placed in an electric oven and dried at a constant temperature of 60°C for 48 hours. After ball milling for 2 hours, it was passed through a 160-mesh sieve to obtain titanium-containing slag powder.

[0050] (2) Weigh 5g of oxalic acid and add it to 3g of deionized water and stir evenly. Add 3g of titanium slag powder and react with it. Stir until a large amount of heat is released and a large number of bubbles are generated. Then quickly use a glass rod to drop the slurry into dimethyl silicone oil at room temperature. Use a disperser to stir into balls at 700rpm for 6 minutes. Then age in an oven at 80℃ for 10 hours.

[0051] (3) Solid-liquid separation: the obtained solid is placed in a muffle furnace and calcined at 700°C for 1 hour to obtain titanium slag-based porous microspheres. The microspheres are then passed through a 60-mesh sieve for later use.

[0052] The titanium-containing slag-based porous microspheres prepared in this embodiment have a particle size of 30–180 μm and a specific surface area of ​​124.62 m². 2 / g, total pore volume is 0.26cm³ 3 / g, with an average pore size of 5.857nm.

[0053] 10 mg of titanium slag-based porous microspheres were placed in an alumina crucible on a synchronous thermal analyzer. Under the condition of N2 flow rate of 60 mL / min, the temperature was raised to 700℃ and stabilized for 20 min at a heating rate of 10℃ / min. Then, a N2+CO2 mixed gas (with CO2 flow rate of 15 mL / min) was introduced. Under these conditions, the adsorption reached saturation, and the saturated adsorption capacity of the titanium slag-based porous microspheres for CO2 was 70.15 mg / g.

[0054] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing titanium slag-based porous microspheres, characterized in that, Includes the following steps: (1) The titanium-containing slag is dried, mechanically ball-milled, and then sieved to obtain titanium-containing slag powder; (2) Add the titanium-containing slag powder obtained in step (1) to an aqueous solution containing oxalic acid, mix well to obtain a slurry, add the slurry dropwise to the oil phase under stirring conditions, form balls under mechanical stirring, and then age. (3) Solid-liquid separation: the obtained solid is calcined and sieved to obtain titanium slag-based porous microspheres; In step (1), the ball milling time is 1~3 hours; titanium-containing slag powder is obtained by passing it through a 120~180 mesh sieve; The mass ratio of oxalic acid to titanium-containing slag in step (2) is 0.5~2:1, and the mass ratio of oxalic acid to water is 1~2:1; The aging process described in step (2) specifically involves placing the resulting mixture at 60-80°C for 12-18 hours. In step (3), the roasting temperature is 650~750℃, the roasting time is 1-3h, and the sieve mesh is 40-80 mesh.

2. The preparation method according to claim 1, characterized in that, The specific drying process described in step (1) involves drying the titanium-containing slag at 60-80℃ for 24-48 hours.

3. The preparation method according to claim 1, characterized in that, In step (2), the stirring speed is 700-900 rpm and the stirring time is 4-6 min.

4. The preparation method according to claim 1, characterized in that, The oil phase mentioned in step (2) includes silicone oil, dimethyl silicone oil, liquid paraffin and kerosene, and the oil phase temperature is 20~40℃.

5. The preparation method according to claim 1, characterized in that, The solid-liquid separation method described in step (3) includes filtration and centrifugation.

6. The titanium-containing slag-based porous microspheres prepared by the preparation method according to any one of claims 1-5.

7. The application of the titanium slag-based porous microspheres according to claim 6 in CO2 capture.

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