Fly ash-based adsorption material based on ore-drawing excitation modification and preparation method and application thereof

Abstract

The application relates to the technical field of adsorbing materials, in particular to a fly ash-based adsorbing material based on ore-drawing excitation modification as well as a preparation method and application thereof, wherein fly ash, alkaline substances and ore-drawing agents are uniformly mixed according to a mass ratio of 30-90:5-35:15-35 to obtain a solid mixture; the solid mixture is uniformly mixed with water, stirred and reacted, the reaction product is separated into solid and liquid, dried, and the product is obtained; the ore-drawing agent is composed of tetracalcium sulphoaluminate, dicalcium silicate, calcium sulphate dihydrate, aluminum oxide, silicon dioxide and calcium carbonate. The fly ash-based adsorbing material based on ore-drawing excitation modification has excellent CPM adsorption capacity, the inorganic component adsorption rate reaches more than 75%, the organic component adsorption rate can reach more than 60%, and the material has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of adsorption materials technology, and in particular to a fly ash-based adsorption material modified by ore extraction, its preparation method, and its application. Background Technology

[0002] Condensable particulate matter (CPM) exists in gaseous form in high-temperature flue gas. After being released into the atmosphere, it transforms into particulate matter through condensation or chemical reactions, posing a significant threat to the environment and human health. CPM has an extremely complex composition, with inorganic components including SO4. 2- Cl - NO3 - Other components and Na + K + It contains heavy metal elements, while the organic components include hundreds of macromolecular organic compounds such as alkanes, esters, and benzene series compounds.

[0003] Existing technology discloses a high-efficiency CPM removal system using low-temperature condensation coupled adsorption, which consists of a low-temperature condensation unit and a heat-carrying adsorption unit coupled together. Flue gas is first subjected to low-temperature condensation and spray humidification to reach a supersaturated state, causing gaseous precursors to condense and be initially removed. It then enters the adsorption unit, where residual pollutants are further captured by the adsorbent under temperature control, achieving synergistic removal of CPM. However, the coupled system has a complex structure, is highly dependent on temperature, humidity, and flow field conditions, and its overall removal efficiency is easily affected, resulting in high operating costs. Furthermore, the condensate generated during the low-temperature condensation process is rich in sulfates and organic pollutants, requiring further treatment and further increasing costs. Summary of the Invention

[0004] In view of this, the present invention provides a fly ash-based adsorbent material modified by ore extraction, its preparation method and application.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution: In a first aspect, the present invention provides a method for preparing a fly ash-based adsorbent material modified by ore extraction, comprising the following steps: Fly ash (CFA), alkaline substances and ore-initiating agents are mixed evenly at a mass ratio of 30-90:5-35:15-35 to obtain a solid mixture; Mix the solid mixture with water until homogeneous, stir, react, separate the solid and liquid products, and dry them to obtain the final product. The ore-attracting agent is composed of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate.

[0006] Furthermore, the alkaline substance is CaO.

[0007] Furthermore, the mass ratio of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate in the ore-initiating agent is 10-15:5-10:55-75:1-5:1-5:1-5.

[0008] Furthermore, the mass ratio of the solid mixture to water is 1:4-8.

[0009] Furthermore, the stirring is magnetic stirring, and the magnetic stirring speed is 500-600 r / min.

[0010] Furthermore, the reaction temperature is 40-60 ℃; the reaction time is 4-8 h.

[0011] Furthermore, the drying temperature is 40-50 ℃.

[0012] Furthermore, the method also includes a process of crushing and screening the dried product, and passing the crushed product through a 200-mesh sieve.

[0013] Secondly, the present invention provides a fly ash-based adsorbent material prepared by the preparation method described in the first aspect, based on ore-induced modification.

[0014] Thirdly, the present invention provides the application of the fly ash-based adsorbent material modified by ore introduction as described in the second aspect in CPM adsorption and removal.

[0015] Furthermore, the adsorption material is used in the adsorption and removal of CPM in coal-fired flue gas.

[0016] Furthermore, the adsorption and removal method is fixed-bed adsorption.

[0017] Compared with the prior art, the present invention has achieved the following beneficial effects: This invention improves the specific surface area of ​​fly ash through specific mineral-initiating modification, generating active minerals such as ettringite and hydrated calcium silicate. These minerals, combined with physical adsorption, enable efficient adsorption of carbon dioxide (CPM). The mineral-initiated modified fly ash exhibits excellent CPM adsorption capacity, with inorganic component adsorption rates exceeding 75% and organic component adsorption rates exceeding 60%. This invention provides an effective CPM adsorption and removal method with broad application prospects. Attached Figure Description

[0018] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0019] Figure 1This invention relates to a method for preparing fly ash-based adsorbent materials modified by ore extraction and a flowchart of the adsorption and removal of CPM. Figure 2 This is a SEM image of fly ash; Figure 3 This is a SEM image of the fly ash-based adsorbent material modified by ore extraction prepared in Example 1; Figure 4 This is a SEM image of the fly ash-based adsorbent material modified by ore introduction and adsorbed CPM after being prepared in Example 1. Detailed Implementation

[0020] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0021] Coal, as a major fossil fuel used in my country and globally, has increasingly highlighted the problem of flue gas pollution during its combustion. Particulate matter (PM) emissions are a significant factor affecting the atmospheric environment and human health. In recent years, driven by ultra-low emission policies, filterable particulate matter (FPM) emissions have achieved ultra-low levels; however, the problem of volatile particulate matter (CPM) is becoming increasingly prominent. CPM exists in gaseous form in high-temperature flue gas and, after being released into the atmosphere, transforms into particulate matter through condensation or chemical reactions, posing a significant threat to the environment and human health. Adsorption technology has the advantages of low investment, simple operation, and strong adaptability, making it particularly suitable for the treatment of CPM with complex compositions. Fly ash, as a major industrial solid waste, has the potential to be used for the adsorption and removal of CPM due to its wide availability, low cost, and certain porous structure and surface activity. To further improve the adsorption performance of fly ash, this invention modifies fly ash through a series of methods to generate active minerals such as CSH gel (calcium silicate hydrate) and AFt (ettringite) with high specific surface area. These active minerals can enhance the synergistic adsorption of inorganic ions and organic matter by fly ash through electrostatic and chemical bonding (covalent bonds, ion substitution, surface complexation, etc.).

[0022] This invention provides a method for preparing fly ash-based adsorbent materials modified by ore extraction, comprising the following steps: Fly ash, alkaline substances, and ore-initiating agents are mixed evenly at a mass ratio of 30-90:5-35:15-35 to obtain a solid mixture. Mix the solid mixture with water until homogeneous, stir, react, separate the solid and liquid products, and dry them to obtain the final product. The ore-attracting agent is composed of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate.

[0023] The adsorbent material prepared in this invention employs a specific mineral-initiating agent, introducing alumina, silica, and calcium carbonate based on previous research. The mineral-initiating agent used in this invention consists of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silica, and calcium carbonate. It can induce and enhance the dissolution of active aluminum and generate more AFt around AFt seeds. Simultaneously, the coupling of CaO and CaSO4 reactions dissolves more active silica and aluminum, resulting in a rapid activation reaction. A large amount of AFt and CSH gel minerals are generated early on, and these continue to be generated subsequently, significantly increasing the amount of active minerals produced.

[0024] Furthermore, the alkaline substance is CaO. Introducing CaO breaks the glassy phase on the CFA surface, disrupts the original dense structure, provides a Ca source, and can generate a small amount of CSH.

[0025] Furthermore, the mass ratio of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate in the ore-initiating agent is 10-15:5-10:55-75:1-5:1-5:1-5.

[0026] Among them, tetracalcium sulfoaluminate is one of the most important active minerals in the ore-attracting agent. It rapidly hydrates with calcium sulfate dihydrate to generate AFt seeds with a "nucleation effect", which can induce and enhance the dissolution of active aluminum and generate more AFt around the AFt seeds; dicalcium silicate can promote the formation of CSH; alumina can provide active Al and increase the amount of CSH generated; silica can provide active Si and increase the amount of AFt generated; calcium carbonate provides crystal nucleation sites and optimizes the mineral structure.

[0027] Preferably, in the ore-initiating agent, the mass ratio of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate is 12-15:6-10:65-75:1-3:1-3:1-3.

[0028] Furthermore, the mass ratio of the solid mixture to water is 1:4-8; the mass ratio of the solid mixture to water is any ratio between 1:4-8, for example, 1:5, 1:6, 1:7; preferably 1:6.

[0029] Furthermore, the stirring is magnetic stirring, and the magnetic stirring speed is 500-600 r / min. The stirring speed can be any value between 500-600 r / min, such as 510 r / min, 520 r / min, 530 r / min, 540 r / min, 550 r / min, 560 r / min, 570 r / min, 580 r / min, 590 r / min, etc.

[0030] Furthermore, the reaction temperature is 40-60 °C, and the reaction time is 4-8 h. A reaction temperature of 40-60 °C and a reaction time of 4-8 h can promote the dissolution of active components and the formation of mineral phases, as well as increase the degree of mineralization and the number of active sites. The reaction temperature can be any value between 40-60 °C, such as 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, etc.; the reaction time can be any value between 4-8 h, such as 5 h, 6 h, 7 h, 8 h, etc.

[0031] Furthermore, the drying temperature is 40-50 ℃. The drying temperature can be any value between 40-50 ℃, such as 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, etc.

[0032] Furthermore, the method also includes a process of crushing and screening the dried product, and passing the crushed product through a 200-mesh sieve.

[0033] This invention provides a fly ash-based adsorbent material modified by ore extraction, which is prepared by the above-described preparation method.

[0034] The fly ash-based adsorbent material based on mineral-induced modification provided by this invention not only utilizes the pore adsorption sites of the mineral-induced modified fly ash for physical adsorption during CPM adsorption and removal, but also adsorbs CPM through electrostatic attraction and chemical bonding between the generated active minerals and CPM.

[0035] This invention also provides the application of the above-mentioned fly ash-based adsorbent material modified by ore introduction in CPM adsorption and removal.

[0036] Furthermore, the adsorption material is used in the adsorption and removal of CPM in coal-fired flue gas.

[0037] Furthermore, the adsorption and removal method is fixed-bed adsorption.

[0038] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0039] Example 1 The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 7 g fly ash, 2 g ore-initiating agent (the ore-initiating agent, by mass percentage, consists of 13% tetracalcium sulfoaluminate, 8% dicalcium silicate, 70% calcium sulfate dihydrate, 3% alumina, 3% silicon dioxide, and 3% calcium carbonate), and 4 g calcium oxide. After being poured into a beaker and mixed evenly, 78 g of water was added at a water-ash ratio of 6:1. The beaker was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 40 ℃, the magnetic stirring speed at 500 r / min, and the reaction time at 4 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0040] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, phthalic acid esters (PAEs), and polycyclic aromatic hydrocarbons (PAHs)) was 5 mg / Nm³. 3 The temperature was 70 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components CPM in the adsorption tail liquid was determined by ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this embodiment, it is 5 mg / Nm) 3 ).

[0041] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0042] Example 2 The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 14 g fly ash, 4 g ore-initiating agent (the ore-initiating agent, by mass percentage, consists of 13% tetracalcium sulfoaluminate, 8% dicalcium silicate, 70% calcium sulfate dihydrate, 3% alumina, 3% silicon dioxide, and 3% calcium carbonate), and 4 g calcium oxide. After being mixed evenly, 132 g of water was added at a water-ash ratio of 6:1. The mixture was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 45 ℃, the magnetic stirring speed at 500 r / min, and the reaction time at 6 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0043] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 70 ℃ and the relative humidity was 30%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components (CPM) in the adsorption tail liquid was measured by IC50 and GC-MS, respectively. i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this embodiment, it is 5 mg / Nm) 3 ).

[0044] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0045] Example 3 The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 21 g fly ash, 6 g ore-initiating agent (the ore-initiating agent, by mass percentage, consisted of 13% tetracalcium sulfoaluminate, 8% dicalcium silicate, 70% calcium sulfate dihydrate, 3% alumina, 3% silicon dioxide, and 3% calcium carbonate), and 4 g calcium oxide. Then, 186 g of water was added at a water-ash ratio of 6:1. The mixture was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 50 ℃, the magnetic stirring speed at 550 r / min, and the reaction time at 4 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0046] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 50 ℃ and the relative humidity was 90%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components (CPM) in the adsorption tail liquid was measured by IC50 and GC-MS, respectively. i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this embodiment, it is 5 mg / Nm) 3 ).

[0047] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0048] Example 4 The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 28 g fly ash, 8 g ore-initiating agent (the ore-initiating agent, by mass percentage, consisted of 13% tetracalcium sulfoaluminate, 8% dicalcium silicate, 70% calcium sulfate dihydrate, 3% alumina, 3% silicon dioxide, and 3% calcium carbonate), and 4 g calcium oxide. Then, 240 g of water was added at a water-ash ratio of 6:1. The mixture was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 50 ℃, the magnetic stirring speed at 550 r / min, and the reaction time at 6 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0049] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 50 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components (CPM) in the adsorption tail liquid was measured by IC50 and GC-MS, respectively. i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this embodiment, it is 5 mg / Nm) 3 ).

[0050] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0051] Example 5 The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 35 g fly ash, 10 g ore-initiating agent (the ore-initiating agent, by mass percentage, consists of 13% tetracalcium sulfoaluminate, 8% dicalcium silicate, 70% calcium sulfate dihydrate, 3% alumina, 3% silicon dioxide, and 3% calcium carbonate), and 4 g calcium oxide. Then, 294 g of water was added at a water-ash ratio of 6:1. The mixture was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 60 ℃, the magnetic stirring speed at 600 r / min, and the reaction time at 6 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0052] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 30 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components (CPM) in the adsorption tail liquid was measured by IC50 and GC-MS, respectively. i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this embodiment, it is 5 mg / Nm) 3 ).

[0053] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0054] Comparative Example 1 The components for preparing the CPM high-efficiency adsorption and removal material were mixed evenly in the following mass ratios: 7 g fly ash, 2 g ore-initiating agent (the ore-initiating agent, by mass percentage, consists of 15% tetracalcium sulfoaluminate, 10% dicalcium silicate, and 75% calcium sulfate dihydrate), and 4 g calcium oxide. Then, 78 g of water was added at a water-ash ratio of 6:1. The mixture was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 40 ℃, the magnetic stirring speed at 500 r / min, and the reaction time at 4 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0055] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 70 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components CPM in the adsorption tail liquid was determined by ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this example, the concentration is 5 mg / Nm³) 3 ).

[0056] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0057] Comparative Example 2 The ore-attracting agent consists of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, and alumina, with the remainder being the same as in Example 1.

[0058] The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 7 g fly ash, 2 g ore-initiating agent (the ore-initiating agent, by mass percentage, consisted of 15% tetracalcium sulfoaluminate, 10% dicalcium silicate, 72% calcium sulfate dihydrate, and 3% alumina), and 4 g calcium oxide. After being poured into a beaker and mixed evenly, 78 g of water was added at a water-ash ratio of 6:1. The beaker was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 40 ℃, the magnetic stirring speed at 500 r / min, and the reaction time at 4 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0059] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 70 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components CPM in the adsorption tail liquid was determined by ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this example, the concentration is 5 mg / Nm³) 3 ).

[0060] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula.i Adsorption rate η of organic components o ; .

[0061] Comparative Example 3 The ore-attracting agent consists of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, and silicon dioxide. The rest is the same as in Example 1.

[0062] The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 7 g fly ash, 2 g ore-initiating agent (the ore-initiating agent, by mass percentage, consisted of 15% tetracalcium sulfoaluminate, 10% dicalcium silicate, 72% calcium sulfate dihydrate, and 3% silicon dioxide), and 4 g calcium oxide. After being poured into a beaker and mixed evenly, 78 g of water was added at a water-ash ratio of 6:1. The beaker was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 40 ℃, the magnetic stirring speed at 500 r / min, and the reaction time at 4 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0063] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 70 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components CPM in the adsorption tail liquid was determined by ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). i1 and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C.o0 (In this example, the concentration is 5 mg / Nm³) 3 ).

[0064] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0065] Comparative Example 4 The ore-initiating agent consists of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, and calcium carbonate. The rest is the same as in Example 1.

[0066] The components for preparing the CPM high-efficiency adsorption and removal material were mixed in the following mass ratios: 7 g fly ash, 2 g ore-initiating agent (the ore-initiating agent, by mass percentage, consisted of 15% tetracalcium sulfoaluminate, 10% dicalcium silicate, 72% calcium sulfate dihydrate, and 3% calcium carbonate), and 4 g calcium oxide. After being poured into a beaker and mixed evenly, 78 g of water was added at a water-ash ratio of 6:1. The beaker was then placed in a magnetically stirred oil bath for magnetic stirring. The reaction temperature was set at 40 ℃, the magnetic stirring speed at 500 r / min, and the reaction time at 4 h to ensure that the active components of the fly ash were fully activated and modified. After the reaction is complete, the resulting slurry is filtered and separated to obtain the ore-induced modified fly ash solid product. The solid product is then placed in a 40 ℃ oven for drying. The dried fly ash is ground and passed through a 200-mesh sieve to obtain uniformly sized ore-induced modified fly ash powder, which is the CPM high-efficiency removal material.

[0067] Take 10 g of fly ash-based CPM high-efficiency adsorbent material modified by ore extraction and place it in a fixed-bed adsorption device. The CPM concentration is determined according to the actual coal-fired flue gas conditions, and the inorganic component (SO4) is... 2- NO3 - Cl - Na + K + The concentration is 100 mg / Nm 3 The concentration of organic components (n-alkane, PAEs, PAHs) was 5 mg / Nm³. 3 The temperature was 70 ℃ and the relative humidity was 60%. The adsorption tail liquid consisted of n-hexane solution and deionized water. After 2 h of fixed-bed adsorption, the concentration of inorganic components CPM in the adsorption tail liquid was determined by ion chromatography (IC) and gas chromatography-mass spectrometry (GC-MS). i1and the concentration of organic components is C o1 The initial concentration of the inorganic component is C. i0 (In this example, it is 100 mg / Nm) 3 The initial concentration of organic components was C. o0 (In this example, the concentration is 5 mg / Nm³) 3 ).

[0068] The adsorption rate η of the inorganic component of the adsorbent material can be calculated using the following formula. i Adsorption rate η of organic components o ; .

[0069] Table 1 Adsorption test results

[0070] In a mineral-attracting agent system composed of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silica, and calcium carbonate, multiple mineral phases interact to induce enhanced dissolution of active silica and alumina, generating abundant hydration products such as AFt and CSH. Needle-like AFt and gel-like CSH intertwine to form a well-developed porous structure and abundant active sites, thereby improving the adsorption capacity for CPM. With the simplification of the mineral-attracting agent composition, the CPM adsorption efficiency gradually decreases, mainly due to a reduction in the amount of hydration products generated and a weakening of inter-mineral synergistic effects. When calcium carbonate, silica, and alumina are gradually removed, the system lacks calcium, silicon, and aluminum sources, resulting in a significant decrease in the generation of minerals such as AFt and CSH. This leads to insufficient specific surface area, inadequate pore development, and a reduction in surface active sites, weakening ion exchange and electrostatic adsorption capabilities. Simultaneously, the synergistic effect between multiple mineral phases decreases, causing a gradual decline in CPM adsorption performance.

[0071] When only tetracalcium sulfoaluminate, dicalcium silicate, and calcium sulfate dihydrate are retained, i.e., Comparative Example 1, the system lacks additional active aluminum and silicon sources. The formation of AFt and CSH is significantly limited, resulting in the fewest hydration products and insufficient development of pore structure and active sites. Therefore, it exhibits the lowest CPM adsorption efficiency.

[0072] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing fly ash-based adsorbent materials modified by ore extraction, characterized in that, Includes the following steps: Fly ash, alkaline substances, and ore-initiating agents are mixed evenly at a mass ratio of 30-90:5-35:15-35 to obtain a solid mixture. Mix the solid mixture with water until homogeneous, stir, react, separate the solid and liquid products, and dry them to obtain the final product. The ore-attracting agent is composed of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate.

2. The preparation method according to claim 1, characterized in that, The alkaline substance is CaO.

3. The preparation method according to claim 1, characterized in that, The mass ratio of tetracalcium sulfoaluminate, dicalcium silicate, calcium sulfate dihydrate, alumina, silicon dioxide, and calcium carbonate in the ore-initiating agent is 10-15:5-10:55-75:1-5:1-5:1-5.

4. The preparation method according to claim 1, characterized in that, The mass ratio of the solid mixture to water is 1:4-8.

5. The preparation method according to claim 1, characterized in that, The stirring is magnetic stirring, and the magnetic stirring speed is 500-600 r / min.

6. The preparation method according to claim 1, characterized in that, The reaction temperature is 40-60 ℃; the reaction time is 4-8 h.

7. The preparation method according to claim 1, characterized in that, The drying temperature is 40-50 ℃; or, the method further includes a process of crushing and screening the dried product, and passing the crushed product through a 200-mesh sieve.

8. The fly ash-based adsorbent material prepared by the preparation method according to any one of claims 1 to 7.

9. The application of the fly ash-based adsorbent material modified by ore introduction as described in claim 8 in CPM adsorption and removal.

10. The application as described in claim 9, characterized in that, The adsorption material is used in the adsorption and removal of CPM in coal-fired flue gas; or, the adsorption and removal method is fixed-bed adsorption.

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