阅读说明：本技术 一种利用高炉渣矿化co2联产x型沸石的方法 (Mineralization of CO by blast furnace slag2Method for co-production of X-type zeolite ) 是由 杨臣 刘维燥 吴泓利 曹俊 刘清才 于 2021-10-26 设计创作，主要内容包括：本发明公开了一种利用高炉渣矿化CO-(2)联产X型沸石的方法,其方法包括：(1)采用高炉渣和硫酸铵混合,硫酸溶液浸出,获得硫酸盐浸出液,以及半水石膏浸出渣；(2)向第一步获得的浸出液中加入氨水,调节pH,使硅和铝沉淀形成硅铝凝胶,过滤以获得富含硅铝凝胶和硫酸镁母液；(3)将氢氧化铝,氢氧化钠,硅酸钠按照一定比例溶解于水中,并充分搅拌,得到白色溶胶(导向剂)备用；(4)将适量的导向剂加入至第二步获得的硅铝凝胶中,并与氢氧化钠充分混合置于反应釜内进行水热反应一段时间,用去离子水洗涤固体产物,得到X型沸石；(5)向第一步和第二步获得的半水石膏浸出渣与硫酸镁母液加入氨水并通入CO-(2)分别生成碳酸钙和三水碳酸镁,实现CO-(2)矿化。(The invention discloses a method for mineralizing CO by using blast furnace slag 2 A method for co-producing X-type zeolite, the method comprising: (1) mixing blast furnace slag and ammonium sulfate, and leaching with a sulfuric acid solution to obtain a sulfate leaching solution and semi-hydrated gypsum leaching slag; (2) adding ammonia water into the leachate obtained in the first step, adjusting the pH value to precipitate silicon and aluminum to form silicon-aluminum gel, and filtering to obtain mother liquor rich in silicon-aluminum gel and magnesium sulfate; (3) dissolving aluminum hydroxide, sodium hydroxide and sodium silicate in water according to a certain proportion, and fully stirring to obtain white sol (guiding agent) for later use; (4) guiding the right amountAdding the agent into the silicon-aluminum gel obtained in the second step, fully mixing the agent with sodium hydroxide, placing the mixture into a reaction kettle for hydrothermal reaction for a period of time, and washing a solid product by deionized water to obtain X-type zeolite; (5) adding ammonia water into the semi-hydrated gypsum leaching residues obtained in the first step and the second step and magnesium sulfate mother liquor, and introducing CO 2 Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO 2 And (4) mineralization.)

1. Mineralization of CO by blast furnace slag₂The method for co-producing the X-type zeolite is characterized by comprising the following steps:

step 1: uniformly mixing blast furnace slag finely ground to be less than 150 mu m with ammonium sulfate according to a certain proportion, adding a sulfuric acid solution, magnetically stirring at a certain temperature, and filtering to obtain a sulfate leaching solution and semi-hydrated gypsum leaching slag;

step 2: adding a proper amount of ammonia water into the leachate obtained in the step (1), adjusting the pH value to enable silicon and aluminum to precipitate to form silicon-aluminum gel, and filtering to obtain mother liquor rich in the silicon-aluminum gel and magnesium sulfate;

and step 3: dissolving aluminum hydroxide, sodium hydroxide and sodium silicate in a proper amount of aqueous solution according to a certain proportion, and fully stirring to obtain white sol (guiding agent);

and 4, step 4: adding a proper amount of the guiding agent obtained in the step 3 into the silicon-aluminum gel obtained in the step two, fully mixing the guiding agent with sodium hydroxide, placing the mixture into a reaction kettle, carrying out hydrothermal reaction for a certain time at a certain temperature, and washing a solid product with deionized water to obtain X-type zeolite;

and 5: adding ammonia water into the semi-hydrated gypsum leaching residue obtained in the step 1 and the step 2 and the magnesium sulfate mother liquor, and introducing CO₂Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO₂And (4) mineralization.

2. The mineralization of CO with blast furnace slag as set forth in claim 1₂The method for co-producing the X-type zeolite is characterized in that the mass ratio of the blast furnace slag to the ammonium sulfate in the step 1 is 1: 1-6.

3. The mineralization of CO with blast furnace slag as set forth in claim 1₂The method for co-producing X-type zeolite is characterized in that the concentration of the sulfuric acid solution in the step 1 is 10-40 wt%, the leaching temperature is 25-70 ℃, the leaching time is 15-80 min, and the liquid-solid mass ratio is 0.5-4: 1.

4. The mineralization of CO with blast furnace slag as set forth in claim 1₂The method for co-producing the X-type zeolite is characterized in that after ammonia water is added in the step 2, the pH value is 6-8, and the solution temperature is 25-80 ℃.

5. The mineralization of CO with blast furnace slag as set forth in claim 1₂The method for co-producing the X-type zeolite is characterized in that the molar ratio of silicon to aluminum in the step 3 is 1-4: 1.

6. the mineralization of CO with blast furnace slag as set forth in claim 1₂The method for co-producing the X-type zeolite is characterized in that the mass ratio of the guiding agent to the silicon-aluminum gel in the step 4 is 1-5: 1, the mass ratio of the sodium hydroxide to the silicon-aluminum gel is 0.6-1.4: 1.

7. The mineralization of CO with blast furnace slag as set forth in claim 1₂A process for the co-production of X-type zeolite,the method is characterized in that in the step 4, the hydrothermal temperature is 70-110 ℃, and the hydrothermal time is 4-24 hours.

Technical Field

The invention belongs to CO₂The field of emission reduction and solid waste resource utilization, and mainly relates to the mineralization of CO by using blast furnace slag₂A method for co-producing X-type zeolite.

Background

The increase in energy demand and the overuse of fossil fuels have led to large amounts of carbon dioxide (CO)₂) Emissions, global warming. According to the data of the United states Global monitoring laboratory, the CO in the current atmosphere₂The concentration (6 months at 2021) has reached 419ppm, with an annual growth rate of 2.3 ppm. At present, as the proportion of new energy in the current energy structure is low, carbon dioxide mineralization and sequestration are regarded as the most promising carbon dioxide emission reduction strategy. Wherein CO is introduced₂Reacting with Ca/Mg containing ore or solid waste to form stable carbonates (CaCO)₃/MgCO₃) Form and permanent sealing. Blast furnace slag is one of the solid wastes generated in the iron-making process. The blast furnace slag is considered to be CO due to the high content of CaO (30-50%) and magnesia (5-15%) in the blast furnace slag₂A mineralized suitable feedstock.

Aiming at the mineralization of CO by blast furnace slag₂Field of application, researchers have conducted a great deal of research. Patent CN106430264B mineralization of CO by utilizing ironmaking blast furnace slag₂And co-producing aluminum oxide, namely uniformly mixing, roasting and leaching the blast furnace slag ammonium sulfate, and carrying out aluminum precipitation on the leaching solution to obtain a magnesium-rich solution for mineralization. Similar to the above patent, patent CN106082322B mineralizes CO with titaniferous blast furnace slag₂Co-production of titanium dioxide and alumina, patent CN106830037B, using blast furnace slag to mineralize CO₂And ammonium alum is co-produced. It is noted that blast furnace slag also contains a large amount of Al₂O₃(7-18%) and SiO₂(30-41%). However, the above patent does not consider the simultaneous recovery of Al₂O₃And SiO₂. Zeolite is an aluminosilicate microporous material and is widely applied to the fields of catalysis, adsorption, dehumidification and the like. Thus, CO is converted₂Mineralization and zeolite synthesis are combined into one process flow. In this way, the main elements in the blast furnace slag are fully utilized (magnesium and calcium are used for CO)₂Mineral adsorption, aluminium and siliconFor zeolite synthesis), CO is realized₂The dual benefits of emission reduction and solid waste treatment.

Based on the above, the invention provides a method for preparing CO by using blast furnace slag as a raw material₂The mineralization and zeolite synthesis combined new process. Firstly, leaching blast furnace slag by using a mixed solution of ammonium sulfate and sulfuric acid to form leachate and semi-hydrated gypsum leaching slag; precipitating silicon-aluminum gel from the leachate through a hydrothermal reaction to synthesize X zeolite; simultaneously, mother liquor rich in magnesium sulfate and semi-hydrated gypsum leaching residue are used for mineral sequestration CO₂. The process makes full use of main components of blast furnace slag, realizes the recovery of high value-added X-type zeolite, and simultaneously realizes CO₂Emission reduction, which provides a new method for resource utilization of a large amount of industrial waste residues.

Disclosure of Invention

The present invention is directed to CO₂The problems of emission reduction and utilization of solid waste of blast furnace slag are solved, and the method for mineralizing CO by using the blast furnace slag is provided₂A method for co-producing X-type zeolite.

The invention relates to the mineralization of CO by using blast furnace slag₂The method for co-producing the X-type zeolite takes blast furnace slag as a raw material, and comprises the following process steps in sequence:

1. leaching blast furnace slag

Uniformly mixing blast furnace slag and ammonium sulfate which are finely ground to be less than 150 mu m, adding the mixture into a sulfuric acid solution, and controlling the mass ratio of the blast furnace slag to the ammonium sulfate to be 1: 1-6, the concentration of the sulfuric acid solution to be 10-40 wt%, and the mass ratio of sulfuric acid to solid materials to be 0.5-4: 1; magnetically stirring the mixed materials at 25-70 ℃ for 15-80 min, and filtering to obtain sulfate leaching liquid and semi-hydrated gypsum leaching residue;

2. preparation of silica-alumina gel

Slowly adding ammonia water into the sulfate leaching solution obtained in the step (1), adjusting the pH value to be 6-8, controlling the temperature to be 25-80 ℃, and filtering to obtain silicon-aluminum gel and magnesium sulfate mother liquor;

3. preparation of directing agent

Mixing and dissolving aluminum hydroxide and sodium hydroxide in water, adding a proper amount of sodium silicate, and controlling the molar ratio of silicon to aluminum to be 1-4: 1, obtaining a directing agent;

4. preparation of zeolites

Adding the guiding agent obtained in the step 3 into the silicon-aluminum gel obtained in the step two, fully mixing the guiding agent with sodium hydroxide, placing the mixture into a reaction kettle, performing hydrothermal reaction at a certain temperature, and controlling the mass ratio of the guiding agent to the silicon-aluminum gel to be 1-5: 1, the mass ratio of sodium hydroxide to silicon-aluminum gel is 0.6-1.4: 1, the hydrothermal temperature is 70-110 ℃, the hydrothermal time is 4-24 h, and the solid product is washed by deionized water to obtain the X-type zeolite.

5. Mineralising CO₂

Adding ammonia water into the semi-hydrated gypsum leaching residue obtained in the step 1 and the step 2 and the magnesium sulfate mother liquor, and introducing CO₂Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO₂And (4) mineralization.

Compared with the prior art, the invention has the following advantages: (1) the process adopts industrial solid waste blast furnace slag as a raw material, has wide sources, successfully prepares the X-type zeolite, realizes the resource utilization of waste, reduces the environmental pollution and saves the production cost; (2) the process has mild reaction conditions and high zeolite purity; (3) the method has the advantages of simple process, convenient operation, low production cost, no wastewater discharge and industrial application prospect.

Drawings

FIG. 1 is an abstract attached drawing and is a process flow chart of the invention

FIG. 2 is an XRD pattern of the zeolite product obtained in the present invention

FIG. 3 is an SEM image of the zeolite product obtained by the invention

Detailed Description

The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Table 1: chemical composition (wt.%) of blast furnace slag

Example one

(1) Uniformly mixing blast furnace slag which is finely ground to be less than 150 mu m and ammonium sulfate, adding the mixture into a sulfuric acid solution, controlling the mass ratio of the blast furnace slag to the ammonium sulfate to be 1:2, controlling the concentration of the sulfuric acid solution to be 10 wt%, and controlling the mass ratio of the sulfuric acid solution to the solid material to be 4: 1; magnetically stirring the mixed materials at 25 ℃ for 60min, and filtering to obtain sulfate leaching liquid and semi-hydrated gypsum leaching residue;

(2) slowly adding ammonia water into the sulfate leaching solution obtained in the step (1), adjusting the pH value to be 6, controlling the temperature to be 30 ℃, and filtering to obtain silicon-aluminum gel and magnesium sulfate mother liquor;

(3) mixing and dissolving aluminum hydroxide and sodium hydroxide in water, adding a proper amount of sodium silicate, and controlling the mole ratio of silicon to aluminum to be 1:1, obtaining a directing agent;

(4) adding the guiding agent obtained in the step 3 into the silicon-aluminum gel obtained in the step two, fully mixing the guiding agent with sodium hydroxide, placing the mixture into a reaction kettle, and carrying out hydrothermal reaction at a certain temperature, wherein the mass ratio of the guiding agent to the silicon-aluminum gel is controlled to be 1:1, the mass ratio of sodium hydroxide to silicon-aluminum gel is 0.6:1, the hydrothermal temperature is 70 ℃, the hydrothermal time is 24 hours, and the solid product is washed by deionized water to obtain the X-type zeolite.

(5) Adding ammonia water into the semi-hydrated gypsum leaching residue obtained in the step 1 and the step 2 and the magnesium sulfate mother liquor, and introducing CO₂Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO₂And (4) mineralization.

Example two

(1) Uniformly mixing blast furnace slag which is finely ground to be less than 150 mu m and ammonium sulfate, adding the mixture into a sulfuric acid solution, controlling the mass ratio of the blast furnace slag to the ammonium sulfate to be 1:3, controlling the concentration of the sulfuric acid solution to be 20 wt%, and controlling the mass ratio of the sulfuric acid to the solid material to be 3: 1; magnetically stirring the mixed materials at 40 ℃ for 50min, and filtering to obtain sulfate leaching liquid and semi-hydrated gypsum leaching residue;

(2) slowly adding ammonia water into the sulfate leaching solution obtained in the step (1), adjusting the pH value to 6.5, controlling the temperature to be 45 ℃, and filtering to obtain silicon-aluminum gel and magnesium sulfate mother liquor;

(3) mixing and dissolving aluminum hydroxide and sodium hydroxide in water, adding a proper amount of sodium silicate, and controlling the mole ratio of silicon to aluminum to be 2:1, obtaining a directing agent;

(4) adding the guiding agent obtained in the step 3 into the silicon-aluminum gel obtained in the step two, fully mixing the guiding agent with sodium hydroxide, placing the mixture into a reaction kettle, and carrying out hydrothermal reaction at a certain temperature, wherein the mass ratio of the guiding agent to the silicon-aluminum gel is controlled to be 2:1, the mass ratio of sodium hydroxide to silicon-aluminum gel is 0.8:1, the hydrothermal temperature is 80 ℃, the hydrothermal time is 18h, and the solid product is washed by deionized water to obtain the X-type zeolite.

(5) Adding ammonia water into the semi-hydrated gypsum leaching residue obtained in the step 1 and the step 2 and the magnesium sulfate mother liquor, and introducing CO₂Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO₂And (4) mineralization.

EXAMPLE III

(1) Uniformly mixing blast furnace slag which is finely ground to be less than 150 mu m and ammonium sulfate, adding the mixture into a sulfuric acid solution, controlling the mass ratio of the blast furnace slag to the ammonium sulfate to be 1:4, controlling the concentration of the sulfuric acid solution to be 30 wt%, and controlling the mass ratio of the sulfuric acid to the solid material to be 1: 1; magnetically stirring the mixed materials at 55 ℃ for 35min, and filtering to obtain sulfate leaching liquid and semi-hydrated gypsum leaching residue;

(2) slowly adding ammonia water into the sulfate leaching solution obtained in the step (1), adjusting the pH value to 7, controlling the temperature to be 65 ℃, and filtering to obtain silicon-aluminum gel and magnesium sulfate mother liquor;

(3) mixing and dissolving aluminum hydroxide and sodium hydroxide in water, adding a proper amount of sodium silicate, and controlling the molar ratio of silicon to aluminum to be 3:1 to obtain a guiding agent;

(4) adding the guiding agent obtained in the step 3 into the silicon-aluminum gel obtained in the step two, fully mixing the guiding agent with sodium hydroxide, placing the mixture into a reaction kettle, performing hydrothermal reaction at a certain temperature, and controlling the mass ratio of the guiding agent to the silicon-aluminum gel to be 3:1, the mass ratio of sodium hydroxide to silicon-aluminum gel is 1:1, the hydrothermal temperature is 100 ℃, the hydrothermal time is 12 hours, and the solid product is washed by deionized water to obtain the X-type zeolite.

(5) Adding ammonia water into the semi-hydrated gypsum leaching residue obtained in the step 1 and the step 2 and the magnesium sulfate mother liquor, and introducing CO₂Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO₂And (4) mineralization.

Example four

(1) Uniformly mixing blast furnace slag which is finely ground to be less than 150 mu m and ammonium sulfate, adding the mixture into a sulfuric acid solution, and controlling the mass ratio of the blast furnace slag to the ammonium sulfate to be 1:1, the concentration of the sulfuric acid solution to be 40 wt% and the mass ratio of the sulfuric acid to the solid material to be 0.5: 1; magnetically stirring the mixed materials at 70 ℃ for 20min, and filtering to obtain sulfate leaching liquid and semi-hydrated gypsum leaching residue;

(2) slowly adding ammonia water into the sulfate leaching solution obtained in the step (1), adjusting the pH value to 8, controlling the temperature to be 80 ℃, and filtering to obtain silicon-aluminum gel and magnesium sulfate mother liquor;

(3) mixing and dissolving aluminum hydroxide and sodium hydroxide in water, adding a proper amount of sodium silicate, and controlling the molar ratio of silicon to aluminum to be 4:1 to obtain a guiding agent;

(4) adding the guiding agent obtained in the step 3 into the silicon-aluminum gel obtained in the step two, fully mixing the guiding agent with sodium hydroxide, placing the mixture into a reaction kettle, and carrying out hydrothermal reaction at a certain temperature, wherein the mass ratio of the guiding agent to the silicon-aluminum gel is controlled to be 5:1, the mass ratio of sodium hydroxide to silicon-aluminum gel is 1.2:1, the hydrothermal temperature is 110 ℃, the hydrothermal time is 4h, and the solid product is washed by deionized water to obtain the X-type zeolite.

(5) Adding ammonia water into the semi-hydrated gypsum leaching residue obtained in the step 1 and the step 2 and the magnesium sulfate mother liquor, and introducing CO₂Respectively generate calcium carbonate and magnesium carbonate trihydrate to realize CO₂And (4) mineralization.