Aluminum-based composite silicon removal agent and application thereof

Abstract

The invention relates to the technical field of water treatment, and discloses an aluminum-based composite silicon removal agent and application thereof. The aluminum-based composite silicon removal agent comprises a component A and a component B, the component A is sodium metaaluminate; the component B comprises one or more of crystalline aluminum chloride, polyaluminum chloride and polyaluminum sulfate. The two components in the aluminum-based composite silicon removal agent can form multi-stage aluminum form distribution of'multi-core-mononuclear-colloid 'in wastewater, so that a complete silicon removal path of'pH regulation and control, charge neutralization, adsorption complexing, bridging flocculation and chemical precipitation' is constructed, and efficient removal of silicate radicals can be realized. The composite silicon removal agent does not need to accurately adjust the pH value of the system, the requirement for operation precision is low, operation is easy, and the dosage of the agent is small.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment, in particular to an aluminum-based composite silicon remover and application thereof. Background Art

[0002] During coal mining, drilling and grouting are often required to reinforce and support the goaf, preventing safety accidents such as collapse, collapse, underground water inrush, and gas outbursts. Among the grouting materials used, water glass (primarily composed of sodium silicate), a low-cost material with good curing properties, is often used as an accelerating setting agent in the grouting material. This allows the slurry injected into the goaf to solidify quickly, forming a curtain and preventing slurry loss.

[0003] However, in this process, there is often an overdose of sodium silicate. Excessive sodium silicate enters the mine water, causing many problems for the surface mine water treatment system. Usually, the coal mine water treatment system uses aluminum salts or iron salts as coagulants to accelerate the coagulation and sedimentation of particles such as coal powder and rock powder, thereby achieving the purpose of purifying the mine water. However, when the mine water contains a large amount of sodium silicate, due to its hydrolysis, a large amount of OH is generated. - This raises the pH of the water, typically to 9-11. The optimal pH range for commonly used coagulants is typically between 5 and 8, rendering the coagulants ineffective. Furthermore, the silicate ions produced by the dissolution of sodium silicate in water react with the metal ions in the coagulant to form insoluble silicate precipitates. This not only fails to achieve water purification but also increases the amount of sludge, leading to poor effluent quality from the mine water treatment system and placing an increased burden on subsequent water treatment facilities. Currently, a common solution to this problem is to increase the coagulant dosage. Since sodium silicate dissolves in water, it increases the total negative charge density in the water. Therefore, increasing the dosage increases the positive charge density in the solution to neutralize the potential, which is an effective solution. However, this also imposes additional treatment costs on coal mining companies.

[0004] Traditional coagulation desiliconization methods all have certain limitations: the magnesium agent method requires a large amount of agent dosage, and will introduce a large amount of hardness, increasing the agent dosage in the subsequent hardness removal process; the lime method has a low desiliconization efficiency, and this method will produce a large amount of sludge (for example, CN202423030375.0); sodium aluminate agent has a good desiliconization effect, but the pH conditions required for its precipitation are relatively harsh; therefore, for coal mining enterprises, finding a desiliconization agent with good desiliconization effect, simple operation and few limitations has practical significance and application value. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the present invention provides an aluminum-based composite desiliconizer and its application. The two components in the aluminum-based composite desiliconizer of the present invention can form a multi-level aluminum morphology distribution of "multinuclear-mononuclear-colloidal" in wastewater, thereby constructing a complete desiliconization pathway of "pH regulation-charge neutralization-adsorption complexation-bridging flocculation-chemical precipitation", which can achieve efficient removal of silicate. The composite desiliconizer of the present invention does not require precise adjustment of the system pH, not only has low operating precision requirements, but also is simple to operate and requires less reagent.

[0006] The specific technical solutions of the present invention include: In a first aspect, the present invention provides an aluminum-based composite desiliconizer, comprising component A and component B. Component A is sodium metaaluminate; and component B comprises one or more of crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate.

[0007] The composite silicon remover of the present invention consists of two parts, component A and component B. Component A, after being added to mine water, can generate aluminum colloid through self-hydrolysis, and inhibit the hydrolysis and polymerization of silicate by adjusting the solution environment. After being added, component B can first generate a large amount of hydrogen ions through hydrolysis to adjust the pH value of the solution, and then cooperate with component A to form a multi-level aluminum form distribution of "multinuclear-mononuclear-colloid" in the wastewater. Among them, the monomeric form of aluminum can quickly neutralize the charge of silicate, the polymeric form of aluminum can enhance the flocculation and precipitation rate through bridging flocculation and net capture and sweeping, and the colloidal form of aluminum can provide a large number of adsorption sites, thereby efficiently and quickly adsorbing and removing silicate ions in the water.

[0008] In summary, component B and component A form a multi-stage aluminum morphology distribution in water, spanning "polynuclear-mononuclear-colloidal," creating a complete silicon removal pathway encompassing "pH regulation-charge neutralization-adsorption-complexation-bridging flocculation-chemical precipitation," enabling efficient silicate removal. The composite silicon remover of this invention allows for adjustment of addition levels based on the amount of soluble silicon in the water, eliminating the need for precise pH control. This reduces operational precision requirements, simplifies operation, and reduces reagent usage.

[0009] Preferably, the dosage of component A is 0.8 to 2.5 times the mass of soluble silicon in mine water.

[0010] Preferably, according to the different compositions of component B, the amounts thereof are as follows: (1) When the component B is crystalline aluminum chloride, the amount used is 1.2 to 3.75 times the mass of soluble silicon in the mine water.

[0011] Crystalline aluminum chloride dissolves in water and dissociates into Al 3+ , Al 3+ The hydrolysis process releases a large amount of H + , Al 3+Through hydrolysis, mononuclear hydroxyaluminum ions, polynuclear hydroxyaluminum complexes, and aluminum hydroxide colloids are formed. Silicate ions in water are removed through adsorption, complexation, flocculation bridging, and net capture and sweeping. At the same time, crystalline aluminum chloride can synergistically interact with component A to produce a large amount of fine and uniform aluminum hydroxide colloids, which have stronger bridging and complexation effects than aluminum hydroxide colloids produced by traditional processes.

[0012] (2) When the component B is polyaluminium chloride, the dosage is 1.4 to 3.95 times the mass of soluble silicon in the mine water.

[0013] When polyaluminium chloride is dissolved in water, its hydrolysis process releases a large amount of H + Its hydrolysis produces amorphous aluminum hydroxide colloid and polynuclear hydroxyaluminum complex, which removes silicate ions in water through adsorption, electrical neutralization and net capture and sweeping. However, due to the hydrolysis of polyaluminum chloride, H + The amount is less than that of crystalline aluminum chloride. Therefore, when component B is polyaluminum chloride, its usage should be higher than that of crystalline aluminum chloride.

[0014] (3) When the component B is polyaluminium sulfate, the dosage is 1.55 to 4.08 times the mass of soluble silicon in the mine water.

[0015] When polyaluminium sulfate is dissolved in water, its hydrolysis process releases a large amount of H + Its hydrolysis produces dense aluminum hydroxide colloid and polynuclear hydroxyaluminum complex containing sulfate radical, which removes silicate ions from water through adsorption, electrical neutralization, flocculation bridging and net capture and sweeping. + The amount is less than that of crystalline aluminum chloride and polyaluminum chloride. Therefore, when component B is polyaluminum sulfate, its usage should be higher than that of crystalline aluminum chloride and polyaluminum chloride.

[0016] (4) When the component B is crystalline aluminum chloride and polyaluminum chloride in a mass ratio of 0.6 to 1.4:1, the amount used is 1.33 to 3.85 times the mass of soluble silicon in mine water.

[0017] Crystalline aluminum chloride and polyaluminum chloride release a large amount of H through the hydrolysis process + The mononuclear hydroxyaluminum ions, polynuclear hydroxyaluminum complexes, and aluminum hydroxide colloids produced during the hydrolysis process remove silicate ions from the water through adsorption, complexation, flocculation bridging, electrical neutralization, and net capture and sweeping. Since polyaluminum chloride replaces part of crystalline aluminum chloride, its usage is higher than that of crystalline aluminum chloride, but lower than that of polyaluminum chloride.

[0018] (5) When the component B is crystalline aluminum chloride and polyaluminum sulfate in a mass ratio of 0.75 to 1.35:1, the amount used is 1.29 to 3.95 times the mass of soluble silicon in mine water.

[0019] Crystalline aluminum chloride and polyaluminum sulfate release a large amount of H through the hydrolysis process + The mononuclear hydroxyaluminum ions, polynuclear hydroxyaluminum complexes, polynuclear hydroxyaluminum complexes containing sulfate groups, and aluminum hydroxide colloids produced during the hydrolysis process remove silicate ions from the water through adsorption, complexation, flocculation bridging, electrical neutralization, and net capture and sweeping. Because polyaluminum sulfate replaces part of crystalline aluminum chloride, its usage is higher than that of crystalline aluminum chloride, but lower than that of polyaluminum sulfate.

[0020] (6) When the component B is polyaluminium chloride and polyaluminium sulfate in a mass ratio of 0.85 to 1.55:1, the amount used is 1.31 to 4.01 times the mass of soluble silicon in the mine water.

[0021] Crystalline aluminum chloride and polyaluminum sulfate release a large amount of H through the hydrolysis process + The polynuclear hydroxyaluminum complex, sulfate-containing polynuclear hydroxyaluminum complex, and aluminum hydroxide colloid produced during the hydrolysis process remove silicate ions from water through adsorption, complexation, flocculation bridging, electrical neutralization, and net capture and sweeping. Because polyaluminum sulfate replaces part of polyaluminum chloride, its usage is higher than polyaluminum chloride but lower than polyaluminum sulfate.

[0022] (7) When the component B comprises crystalline aluminum chloride, polyaluminum chloride and polyaluminum sulfate in a mass ratio of 1: (0.6-1.4): (0.75-1.2), the amount used is 1.26-3.88 times the mass of soluble silicon in the mine water.

[0023] The three release a large amount of H + At the same time, a multi-level aluminum form distribution of "single-core-multi-core-colloid" is constructed through the hydrolysis process, achieving the purpose of efficiently and quickly removing soluble silicon by integrating adsorption, complexation, flocculation bridging, electrical neutralization and net capture and sweeping.

[0024] From the above, it can be seen that the present invention can determine the addition amount of component A and component B by measuring the content of soluble silicon in the water body, and can achieve efficient and rapid removal of soluble silicon without the need to accurately adjust the pH value of the system, reducing the complexity of the operation and at the same time using less reagents.

[0025] In a second aspect, the present invention provides the use of the above-mentioned aluminum-based composite silicon remover in removing soluble silicon from coal mine water.

[0026] Preferably, the soluble silicon is sodium silicate.

[0027] In a third aspect, the present invention provides a method for removing soluble silicon from coal mine water using the aluminum-based composite desiliconizer, which comprises the following steps: S1. Add component A to the mine water to hydrolyze component A to form aluminum colloid. At the same time, adjust the pH value of the water to inhibit the hydrolysis and polymerization of silicate. The reaction equation of this step is as follows: NaAlO2→Na + +AlO2 - AlO2 - +2H2O→Al(OH)3+OH - S2. Add component B to the mine water to hydrolyze component B to produce hydrogen ions, forming a multi-level aluminum form distribution in the water. Among them, the monomer form of aluminum quickly neutralizes the charge of silicate, the polymer form of aluminum strengthens the growth of flocs, and the colloidal form of aluminum provides a large number of adsorption sites to efficiently and quickly remove silicate ions.

[0028] Whether it is crystalline aluminum chloride, polyaluminum chloride or polyaluminum sulfate, its essence is Al 3+ The hydrolysis reaction equation is as follows: (1)Al 3+ +H2O→Al(OH) 2+ +H + (2)Al(OH) 2+ +H2O→Al(OH)2 + +H + (3)Al(OH)2 + +H2O→Al(OH)3+H + Al 3+ Aluminum hydroxide colloid is finally generated through multi-step hydrolysis of reaction equations (1), (2) and (3). The hydrolysis steps to generate polynuclear hydroxyaluminum complex are more complicated, and the simplified reaction equation is as follows: (4)1 3Al 3+ +32H2O→[Al 13 O4(OH) 24 ] 7+ +32H + S3. Add polyacrylamide, stir and let stand to settle. The supernatant is the mine water with soluble silicon removed.

[0029] Preferably, in S1, the soluble silicon content in the mine water is measured before adding component A. The soluble silicon mass is measured using "SL 91.1-1994 Determination of Silicon Dioxide (Soluble) (Silicon Molybdenum Yellow Spectrophotometric Method)", and the result is the soluble silicon content in the mine water.

[0030] Preferably, in S1, component A is fully hydrolyzed by rapid stirring, with a stirring rate of 250 to 300 r / min and a stirring time of 0.5 to 2 min.

[0031] Preferably, in S2, component B is fully mixed by slow stirring and the colloidal aluminum is prevented from being broken by stirring. The stirring rate is 40 to 60 r / r / min and the stirring time is 3 to 5 min.

[0032] Preferably, in S3, the amount of polyacrylamide added is 0.5-2 mg / L; the stirring rate is 30-40 r / r / min, the stirring time is 1-2 min; and the standing time is 20-30 min.

[0033] In a fourth aspect, the present invention provides another method for removing soluble silicon from coal mine water using the above-mentioned aluminum-based composite desiliconizer, which comprises the following steps: S1. Add component A to the mine water to hydrolyze component A to form aluminum colloid, while inhibiting the hydrolysis and polymerization of silicate.

[0034] S2. First add 50-70% of component B and stir to hydrolyze component B to generate hydrogen ions, adjust the pH value and form a large amount of fine and uniform colloidal aluminum in the water, which removes part of the silicate ions by adsorption by providing adsorption sites; then add the remaining component B and stir to hydrolyze component B, further adjust the pH value and form a large amount of monomeric and polymeric aluminum; the monomeric aluminum neutralizes the silicate charge, reduces the repulsion between flocs and accelerates coagulation, and the polymeric aluminum further strengthens the flocculation and precipitation process through bridging flocculation and net capture and sweeping.

[0035] S3. Sedimentation: This method can achieve complete sedimentation of flocs in a short time without adding polyacrylamide during sedimentation.

[0036] The technical principle of the above method of the present invention is: according to the different pH values ​​of the solution, Al 3+ The ion hydrolysis products are also different: when the pH value is alkaline to weakly alkaline, Al 3+ The main hydrolysis product of ions is aluminum hydroxide colloid; when the pH value is neutral to weakly acidic, Al 3+ The ion hydrolysis product is mainly a polynuclear hydroxyaluminum complex. This method first adds 50-70% component B, adjusts the solution pH to alkaline or weakly alkaline, and makes Al 3+ The ions preferentially form aluminum hydroxide colloid, thereby increasing the adsorption and complexation reaction time of colloidal aluminum and soluble silicon; then the remaining component B is added and the pH value is further adjusted to make Al 3+Ion hydrolysis forms a polynuclear hydroxyaluminum complex, which further strengthens the coagulation and sedimentation process through flocculation bridging, net capture and sweeping, achieving the effect of aggregating colloidal particles and accelerating sedimentation. Compared with the previous method, this method controls the pH environment of the solution by adding component B step by step to control the Al content in the solution. 3+ The hydrolysis products of ions can enhance the removal of soluble silicon and the coagulation and sedimentation effect. The use of this method can effectively reduce or eliminate the use of flocculants such as polyacrylamide, shorten the sedimentation time and further improve the removal of soluble silicon.

[0037] Preferably, in S1, component A is fully hydrolyzed by rapid stirring, with a stirring rate of 250 to 300 r / r / min and a stirring time of 0.5 to 2 min.

[0038] Preferably, in S2, the conditions for the first stirring are: a stirring rate of 150 to 200 r / r / min, and a stirring time of 2 to 3 min; the conditions for the second stirring are: a stirring rate of 60 to 100 r / min, and a stirring time of 2 to 3 min.

[0039] Preferably, in S3, the standing time is 10 to 15 minutes.

[0040] Compared with the prior art, the present invention has the following beneficial effects: (1) When the composite desiliconizer of the present invention is added to silicon-containing wastewater, a multi-level aluminum morphology distribution of "multinuclear-mononuclear-colloidal" is formed, thereby constructing a complete desiliconization pathway of "pH regulation-charge neutralization-adsorption complexation-bridging flocculation-chemical precipitation", which can achieve efficient removal of silicate. Among them, the monomeric form of aluminum can quickly neutralize the charge of silicate, the polymeric form of aluminum can enhance the growth of flocs, and the colloidal form of aluminum can provide a large number of adsorption sites, thereby efficiently and quickly adsorbing and removing silicate ions in water.

[0041] (2) The composite desiliconizer of the present invention does not require precise adjustment of the pH of the system, which not only requires lower operating precision but also is simple to operate and requires less agent.

[0042] (3) The present invention further enhances the removal of soluble silicon and the coagulation and sedimentation effects by further optimizing the feeding method of components A and B. This method can effectively reduce or eliminate the use of flocculants such as polyacrylamide, shortening the sedimentation time while further improving the removal of soluble silicon. DETAILED DESCRIPTION

[0043] The present invention will be further described below with reference to the embodiments.

[0044] Overall embodiment In a first aspect, an aluminum-based composite desiliconizer comprises component A and component B. Component A is sodium metaaluminate; and component B comprises one or more of crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate.

[0045] Preferably, the dosage of component A is 0.8 to 2.5 times the mass of soluble silicon in mine water.

[0046] Preferably, according to the different compositions of component B, the amounts thereof are as follows: (1) When the component B is crystalline aluminum chloride, the amount used is 1.2 to 3.75 times the mass of soluble silicon in the mine water.

[0047] (2) When the component B is polyaluminium chloride, the dosage is 1.4 to 3.95 times the mass of soluble silicon in the mine water.

[0048] (3) When the component B is polyaluminium sulfate, the dosage is 1.55 to 4.08 times the mass of soluble silicon in the mine water.

[0049] (4) When the component B is crystalline aluminum chloride and polyaluminum chloride in a mass ratio of 0.6 to 1.4:1, the amount used is 1.33 to 3.85 times the mass of soluble silicon in mine water.

[0050] (5) When the component B is crystalline aluminum chloride and polyaluminum sulfate in a mass ratio of 0.75 to 1.35:1, the amount used is 1.29 to 3.95 times the mass of soluble silicon in mine water.

[0051] (6) When the component B is polyaluminium chloride and polyaluminium sulfate in a mass ratio of 0.85 to 1.55:1, the amount used is 1.31 to 4.01 times the mass of soluble silicon in the mine water.

[0052] (7) When the component B comprises crystalline aluminum chloride, polyaluminum chloride and polyaluminum sulfate in a mass ratio of 1: (0.6-1.4): (0.75-1.2), the amount used is 1.26-3.88 times the mass of soluble silicon in the mine water.

[0053] Secondly, the application of the above-mentioned aluminum-based composite desiliconizer in removing soluble silicon from coal mine water.

[0054] Preferably, the soluble silicon is sodium silicate.

[0055] In a third aspect, a method for removing soluble silicon from coal mine water using the aluminum-based composite desiliconizer comprises the following steps: S1. Add component A to the mine water to hydrolyze component A to form aluminum colloid, while inhibiting the hydrolysis and polymerization of silicate.

[0056] S2. Add component B to the mine water to hydrolyze component B to produce hydrogen ions, forming a multi-level aluminum form distribution in the water. Among them, the monomer form of aluminum quickly neutralizes the charge of silicate, the polymer form of aluminum strengthens the growth of flocs, and the colloidal form of aluminum provides a large number of adsorption sites to efficiently and quickly remove silicate ions.

[0057] S3. Add polyacrylamide, stir and let stand to settle. The supernatant is the mine water with soluble silicon removed.

[0058] Preferably, in S1, the soluble silicon content in the mine water is measured before adding component A. The soluble silicon mass is measured using "SL 91.1-1994 Determination of Silicon Dioxide (Soluble) (Silicon Molybdenum Yellow Spectrophotometric Method)", and the result is the soluble silicon content in the mine water.

[0059] Preferably, in S1, component A is fully hydrolyzed by rapid stirring, with a stirring rate of 250 to 300 r / min and a stirring time of 0.5 to 2 min.

[0060] Preferably, in S2, component B is fully mixed by slow stirring and the colloidal aluminum is prevented from being broken by stirring. The stirring rate is 40 to 60 r / r / min and the stirring time is 3 to 5 min.

[0061] Preferably, in S3, the amount of polyacrylamide added is 0.5-2 mg / L; the stirring rate is 30-40 r / r / min, the stirring time is 1-2 min; and the standing time is 20-30 min.

[0062] In a fourth aspect, another method for removing soluble silicon from coal mine water using the aluminum-based composite desiliconizer comprises the following steps: S1. Add component A to the mine water to hydrolyze component A to form aluminum colloid, while inhibiting the hydrolysis and polymerization of silicate.

[0063] S2. First add 50-70% of component B and stir to hydrolyze component B to generate hydrogen ions, adjust the pH value and form a large amount of fine and uniform colloidal aluminum in the water, which removes part of the silicate ions by adsorption by providing adsorption sites; then add the remaining component B and stir to hydrolyze component B, further adjust the pH value and form a large amount of monomeric and polymeric aluminum; the monomeric aluminum neutralizes the silicate charge, reduces the repulsion between flocs and accelerates coagulation, and the polymeric aluminum further strengthens the flocculation and precipitation process through bridging flocculation and net capture and sweeping.

[0064] S3. Precipitation.

[0065] This method can achieve complete sedimentation of flocs in a short time without adding polyacrylamide during precipitation.

[0066] Preferably, in S1, component A is fully hydrolyzed by rapid stirring, with a stirring rate of 250 to 300 r / r / min and a stirring time of 0.5 to 2 min.

[0067] Preferably, in S2, the conditions for the first stirring are: a stirring rate of 150 to 200 r / r / min, and a stirring time of 2 to 3 min; the conditions for the second stirring are: a stirring rate of 60 to 100 r / min, and a stirring time of 2 to 3 min.

[0068] Preferably, in S3, the standing time is 10 to 15 minutes.

[0069] Specific Examples and Comparative Examples Example 1 An aluminum-based composite silicon remover comprises component A and component B, wherein component A is sodium metaaluminate and component B is B-crystalline aluminum chloride.

[0070] Example 2 An aluminum-based composite silicon remover comprises component A and component B, wherein component A is sodium metaaluminate and component B is polyaluminum chloride.

[0071] Example 3 An aluminum-based composite silicon remover comprises component A and component B, wherein component A is sodium metaaluminate and component B is polyaluminum sulfate.

[0072] Example 4 An aluminum-based composite silicon remover comprises component A and component B. Component A is sodium metaaluminate, and component B is crystalline aluminum chloride and polyaluminum chloride.

[0073] Example 5 An aluminum-based composite silicon remover comprises component A and component B, wherein component A is sodium metaaluminate, and component B is crystalline aluminum chloride and polyaluminum sulfate.

[0074] Example 6 An aluminum-based composite silicon remover comprises component A and component B, wherein component A is sodium metaaluminate, and component B is polyaluminum chloride and polyaluminum sulfate.

[0075] Example 7 An aluminum-based composite silicon remover comprises component A and component B. Component A is sodium metaaluminate, and component B is crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate.

[0076] Application Examples 1-7 A method for removing soluble silicon from coal mine water comprises the following steps: 1) First, determine the soluble silicon content in the coal mine water sample. Soluble silicon mass is determined using "SL 91.1-1994 Determination of Silicon Dioxide (Soluble) (Silicon-Molybdenum Yellow Spectrophotometric Method)". The result is the soluble silicon content in the mine water.

[0077] 2) Component A from Examples 1-7 was added to each coal mine water sample and rapidly stirred at 280 rpm for 1 minute to fully hydrolyze Component A. After stirring, Component A hydrolyzed to form aluminum colloid, while simultaneously inhibiting the hydrolysis and polymerization of silicate.

[0078] 3) Component B from Examples 1-7 was added to each coal mine water sample, and the component B was thoroughly mixed by slow stirring at a rate of 50 r / min for 4 minutes to avoid breaking the alum flocs. During stirring, component B was hydrolyzed to produce hydrogen ions, forming a multi-stage aluminum distribution in the water. The monomeric aluminum rapidly neutralized the silicate charge, the polymeric aluminum enhanced floc growth, and the colloidal aluminum provided a large number of adsorption sites for efficient and rapid removal of silicate ions.

[0079] 4) Add 1 mg / L of polyacrylamide (PAM) to the mine water, slowly stir it at 40 rpm for 2 minutes, and let it settle. The supernatant is the mine water from which the soluble silicon has been removed.

[0080] In the above steps, the addition amounts of combination A and component B in application examples 1-7 are as follows: Application Example 1: Using the aluminum-based composite silicon remover of Example 1, the addition amount of component A is 1 times the mass of soluble silicon, and the addition amount of component B is crystalline aluminum chloride, which is 2.25 times the mass of soluble silicon. The final silicate removal rate is 91.93%; Application Example 2: Using the aluminum-based composite desiliconizer of Example 2, the addition amount of component A is 1.2 times the mass of soluble silicon, and the component B is polyaluminum chloride, and the addition amount is 1.9 times the mass of soluble silicon; the final silicate removal rate is 92.75%; Application Example 3: Using the aluminum-based composite desiliconizer of Example 3, the addition amount of component A is 1.5 times the mass of soluble silicon, and the component B is polyaluminum sulfate, and the addition amount is 2.8 times the mass of soluble silicon; the final silicate removal rate is 95.47%; Application Example 4: Using the aluminum-based composite desiliconizer of Example 4, the addition amount of component A is 2 times the mass of soluble silicon, and the component B is crystalline aluminum chloride and polyaluminum chloride, wherein the mass ratio of crystalline aluminum chloride to polyaluminum chloride is 0.8:1, and the addition amount of component B is 3.65 times the mass of soluble silicon; the final silicate removal rate is 99.18%; Application Example 5: Using the aluminum-based composite silicon remover of Example 5, the addition amount of component A is 1.8 times the mass of soluble silicon, and the components of component B are crystalline aluminum chloride and polyaluminum sulfate, wherein the mass ratio of crystalline aluminum chloride to polyaluminum sulfate is 1.15:1, and the addition amount of component B is 3.25 times the mass of soluble silicon. The final silicate removal rate is 98.27%; Application Example 6: Using the aluminum-based composite silicon remover of Example 6, the addition amount of component A is 1.65 times the mass of soluble silicon, and the components of component B are polyaluminum chloride and polyaluminum sulfate, wherein the mass ratio of polyaluminum chloride to polyaluminum sulfate is 1.3:1, and the addition amount of component B is 2.88 times the mass of soluble silicon; the final silicate removal rate is 96.58%; Application Example 7: The aluminum-based composite silicon remover of Example 7 is used, with component A added in an amount of 2.5 times the mass of soluble silicon, and component B composed of crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate, wherein the mass ratio of crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate is 1:1:1.15, and the amount of component B added is 4.27 times the mass of soluble silicon; the final silicate removal rate is 96.21%.

[0081] In each application example, the addition amount of component A and component B and the silicate removal rate are shown in the following table: Comparative Examples 1-8 As a control, sodium metaaluminate and other compound reagents were selected for comparison. The addition amount of each reagent and the silicate removal rate in the comparative example are shown in the following table: Comparison of the data between each application example and each comparative example shows that the silicate removal rate of each application example can reach over 90%. For comparative examples 1 to 5, when the amount of sodium metaaluminate added is the same, the pH value has a significant impact on the removal rate, with the removal rate fluctuating between 29.73% and 98.17%. While comparative examples 6 to 8 can also achieve a certain removal rate, the amount of reagent added is significantly higher than that of each application example. The above results all show that the silicate removal effect of each application example is significantly better than that of the comparative example, and the reagent consumption is significantly reduced, indicating that the composite desiliconizer used in the present invention can not only achieve efficient silicate removal, but also effectively reduce the reagent cost in the water treatment process.

[0082] Application Examples 8-14 A method for removing soluble silicon from coal mine water comprises the following steps: 1) First, determine the soluble silicon content in the coal mine water sample. Soluble silicon mass is determined using "SL 91.1-1994 Determination of Silicon Dioxide (Soluble) (Silicon-Molybdenum Yellow Spectrophotometric Method)". The result is the soluble silicon content in the mine water.

[0083] 2) Add component A to the mine water and stir rapidly at a rate of 280 r / min for 1 minute to fully hydrolyze component A. After stirring, component A hydrolyzes to form aluminum colloid, while simultaneously inhibiting the hydrolysis and polymerization of silicate.

[0084] 3) First, add 50-70% of Component B to the mine water and rapidly stir to hydrolyze Component B to produce hydrogen ions. This adjusts the pH and simultaneously forms a large amount of fine, uniform colloidal aluminum in the water, which removes some silicate ions by providing adsorption sites. The stirring rate is 180 rpm and the stirring time is 2 minutes. Then, add the remaining Component B to the mine water and stir at a constant speed to hydrolyze Component B. The pH is further adjusted and a large amount of monomeric and polymeric aluminum is formed. The monomeric aluminum neutralizes the silicate charge, reducing repulsion between flocs and accelerating coagulation. The polymeric aluminum further enhances the flocculation and precipitation process through bridging flocculation and net sweeping. The stirring rate for this step is 80 rpm and the stirring time is 2 minutes.

[0085] 4) Let the mixture settle for 10 minutes, and take the supernatant to determine the amount of soluble silicon. In the above steps, the amounts of component A and component B added in application examples 8-14 are as follows: Application Example 8: The aluminum-based composite silicon remover of Example 1 was used, with component A added in an amount of 1 times the mass of the soluble silicon, and component B, which was crystalline aluminum chloride, added in an amount of 2.25 times the mass of the soluble silicon; the final silicate removal rate was 93.27%; Application Example 9: Using the aluminum-based composite desiliconizer of Example 2, the addition amount of component A is 1.2 times the mass of soluble silicon, and the component B is polyaluminum chloride, and the addition amount is 1.9 times the mass of soluble silicon; the final silicate removal rate is 94.86%; Application Example 10: Using the aluminum-based composite desiliconizer of Example 3, the addition amount of component A is 1.5 times the mass of soluble silicon, and the component B is polyaluminum sulfate, and the addition amount is 2.8 times the mass of soluble silicon; the final silicate removal rate is 96.87%; Application Example 11: Using the aluminum-based composite desiliconizer of Example 4, the addition amount of component A is 2 times the mass of soluble silicon, and the component B is crystalline aluminum chloride and polyaluminum chloride, wherein the mass ratio of crystalline aluminum chloride to polyaluminum chloride is 0.8:1, and the addition amount of component B is 3.65 times the mass of soluble silicon; the final silicate removal rate is 99.47%; Application Example 12: The aluminum-based composite silicon remover of Example 5 was used, with component A added in an amount of 1.8 times the mass of the soluble silicon, component B comprising crystalline aluminum chloride and polyaluminum sulfate, wherein the mass ratio of crystalline aluminum chloride to polyaluminum sulfate was 1.15:1, and component B added in an amount of 3.25 times the mass of the soluble silicon; the final silicate removal rate was 99.23%; Application Example 13: The aluminum-based composite silicon remover of Example 6 was used, with component A added in an amount of 1.65 times the mass of the soluble silicon, component B comprising polyaluminum chloride and polyaluminum sulfate, wherein the mass ratio of polyaluminum chloride to polyaluminum sulfate was 1.3:1, and component B added in an amount of 2.88 times the mass of the soluble silicon; the final silicate removal rate was 98.21%; Application Example 14: The aluminum-based composite silicon remover of Example 7 is used, with component A added in an amount of 2.5 times the mass of soluble silicon, and component B consisting of crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate, wherein the mass ratio of crystalline aluminum chloride, polyaluminum chloride, and polyaluminum sulfate is 1:1:1.15, and the amount of component B added is 4.27 times the mass of soluble silicon; the final silicate removal rate is 97.92%.

[0086] The silicate removal rates for each application example are shown in the following table: As shown in the table above, under the same conditions, the removal rate in Examples 8-14 was significantly higher than that in Examples 1-7, indicating that, at the same dosage, the stepwise addition of Component B can improve the silicate removal rate. Furthermore, since Examples 8-14 did not add polyacrylamide (PAM) during the precipitation step, the stepwise addition of Component B can also reduce the amount of flocculant used, thereby lowering treatment costs.

[0087] Unless otherwise specified, the raw materials and equipment used in the present invention are commonly used in the art; the methods used in the present invention are conventional methods in the art unless otherwise specified.

[0088] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. An aluminum-based composite silicon remover, characterized in that: Comprising component A and component B; The component A is sodium metaaluminate; The component B includes one or more of crystalline aluminum chloride, polyaluminum chloride and polyaluminum sulfate.

2. The aluminum-based composite silicon remover according to claim 1, characterized in that: The amount of component A is 0.8 to 2.5 times the mass of soluble silicon in mine water; and The component B is crystalline aluminum chloride, and the amount used is 1.2 to 3.75 times the mass of soluble silicon in the mine water; or The component B is polyaluminium chloride, and the amount used is 1.4 to 3.95 times the mass of soluble silicon in the mine water; or The component B is polyaluminium sulfate, and the amount used is 1.55 to 4.08 times the mass of soluble silicon in the mine water; or The component B is crystalline aluminum chloride and polyaluminum chloride in a mass ratio of 0.6 to 1.4:1, and the amount used is 1.33 to 3.85 times the mass of soluble silicon in the mine water; or The component B is crystalline aluminum chloride and polyaluminum sulfate in a mass ratio of 0.75 to 1.35:1, and the amount used is 1.29 to 3.95 times the mass of soluble silicon in the mine water; or The component B is polyaluminium chloride and polyaluminium sulfate in a mass ratio of 0.85 to 1.55:1, and the amount used is 1.31 to 4.01 times the mass of soluble silicon in the mine water; or The component B comprises crystalline aluminum chloride, polyaluminum chloride and polyaluminum sulfate in a mass ratio of 1: (0.6-1.4): (0.75-1.2), and the amount used is 1.26-3.88 times the mass of soluble silicon in mine water.

3. Use of the aluminum-based composite silicon remover according to claim 1 or 2 in removing soluble silicon from coal mine water.

4. The use according to claim 3, characterized in that: The soluble silicon is sodium silicate.

5. A method for removing soluble silicon from coal mine water using the aluminum-based composite desiliconizer according to claim 1 or 2, characterized in that include: S1. Add component A to the mine water to hydrolyze component A to form aluminum colloid, while inhibiting the hydrolysis and polymerization of silicate; S2. Add component B to hydrolyze component B to generate hydrogen ions, forming multi-level aluminum forms in the water; wherein the monomeric aluminum neutralizes the charge of silicate, the polymeric aluminum strengthens the growth of flocs, and the colloidal aluminum provides adsorption sites to adsorb and remove silicate ions; S3. Add polyacrylamide, stir and let stand to settle.

6. The method according to claim 5, characterized in that: In S1, component A is fully hydrolyzed by rapid stirring at a rate of 250-300 r / min and a stirring time of 0.5-2 min; In S2, component B is fully mixed by slow stirring and the colloidal aluminum is prevented from being broken by stirring. The stirring rate is 40-60 r / min and the stirring time is 3-5 min.

7. The method according to claim 5, characterized in that: In S3, The amount of polyacrylamide added is 0.5~2 mg / L; The stirring rate is 30~40r / min and the stirring time is 1~2min; The standing time is 20~30min.

8. A method for removing soluble silicon from coal mine water using the aluminum-based composite desiliconizer according to claim 1 or 2, characterized in that include: S1. Add component A to the mine water to hydrolyze component A to form aluminum colloid, while inhibiting the hydrolysis and polymerization of silicate; S2. First, add 50-70% of component B and stir to hydrolyze component B to generate hydrogen ions, forming colloidal aluminum in the water, which removes some silicate ions by adsorption by providing adsorption sites; then add the remaining component B and stir to hydrolyze component B to form monomeric and polymeric aluminum; the monomeric aluminum neutralizes the silicate charge and reduces repulsion between flocs to accelerate coagulation, while the polymeric aluminum further enhances the flocculation and precipitation process through bridging flocculation and net capture and sweeping; S3. Precipitation.

9. The method according to claim 8, characterized in that: In S1, component A is fully hydrolyzed by rapid stirring at a stirring rate of 250-300 r / min and a stirring time of 0.5-2 min.

10. The method according to claim 8, characterized in that: In S2, The conditions for the first stirring are: stirring rate 150~200r / min, stirring time 2~3min; The conditions for the second stirring are: stirring rate 60~100r / min, stirring time 2~3min.

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