CN112357933A - Mineralization of CO by steel slag2Method for co-producing CAN type zeolite - Google Patents
Mineralization of CO by steel slag2Method for co-producing CAN type zeolite Download PDFInfo
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention discloses a method for mineralizing CO by using steel slag2A method for co-producing CAN-type zeolite, the method comprising: 1, leaching the steel slag by using ammonium bisulfate to obtain calcium sulfate leaching slag and leachate containing silicon, aluminum and magnesium; 2, coprecipitation of silicon and aluminum is realized by adjusting the pH value of the leachate obtained in the first step to obtain silicon-aluminum gel; 3, further fully mixing the silicon-aluminum gel with NaOH, heating for reaction, and washing the solid product with water after the reaction to obtain CAN zeolite and alkaline washing liquor; 4, respectively regulating the pH value of the silicon-aluminum precipitation mother liquor and the calcium sulfate leaching residue by the washing liquid obtained in the third step, and introducing CO2Reaction to realize CO2Mineralization of (1).
Description
Technical Field
The invention belongs to CO2The field of emission reduction and solid waste resource utilization, and mainly relates to a method for mineralizing CO by using iron and steel slag2A method for co-producing CAN zeolite.
Background
Since the industrial revolution, human beings have largely used fossil fuels, resulting in CO2Rapid increase in emission of CO2Emission reduction has become a global hot topic. CO 22Trapping and sequestration (CCS) is the terminal carbon emission reduction technology of major research at home and abroad. CO 22The mineralization and sealing is to adopt alkaline natural minerals or industrial solid wastes to remove CO2Mineralized and fixed to obtain chemical with high added value, and CO2Is converted into solid carbonate which stably exists in the nature. The industrial solid waste with high content of calcium and magnesium is often used as CO2A mineralized feedstock.
The iron and steel industry is the largest industrial CO2One of the emission sources is also one of the largest industrial solid waste sources, and the main solid waste comprises blast furnace slag and steel slag. According to statistics, about 2 tons of CO are discharged per ton of crude steel produced2And simultaneously discharging 0.3 ton of blast furnace slag and 0.15 ton of steel slag. The global crude steel yield in 2019 is about 19 million tons, so about 8.6 million tons of steel iron slag are discharged. If the steel slag is used for carbon fixation, the CO can be theoretically fixed every year2About 2 to 6 hundred million tons. In addition, if the silicon and aluminum in the steel slag can be effectively recovered, 2.3 million tons of natural bauxite (in terms of Al) can be reduced theoretically every year in the world2O3Measured) and 3 tons of quartz ore in CO2The sustainable development of the aluminum industry is realized while the emission is reduced, and solid wastes generated in the steel industry can be treated.
Chinese patent CN106082322A discloses a method for co-producing TiO by mineralizing carbon dioxide with titanium-containing blast furnace slag2、Al2O3Firstly, mixing titanium-containing blast furnace slag and ammonium sulfate, roasting, leaching, precipitating titanium and aluminum from a leaching solution step by step to obtain a magnesium-rich solution, and mineralizing, wherein the main component of leaching slag is calcium sulfate, and mineralizing is carried out after size mixing by ammonia water. This patent realizes CO2Emission reduction and blast furnace slag resource utilization. Chinese patent CN1068300037A discloses a method for mineralizing CO by using blast furnace slag2The method for coproducing ammonium alum is similar to the above-mentioned patent, and said method adopts ammonium sulfate as adjuvant to extract valuable component from blast furnace slag, and further adopts the processes of leaching, crystallizing and mineralizing so as to recover ammonium alum, at the same time crystallizing mother liquor (mainly using MgSO)4) And leaching residue (mainly CaSO)4And SiO2) Adjusting pH with ammonia water, introducing CO2And carrying out mineralization reaction. This patent recovers the aluminum from the blast furnace slag in different ways and mineralizes the CO with calcium and magnesium2And double benefits of comprehensive utilization of industrial solid waste and carbon emission reduction are realized. However, it is noted that the above method does not utilize the silicon component in the slag, and if the silicon component can be recycled, the full utilization of the main component in the blast furnace slag can be realized. Zeolite is an aqueous alkali or alkaline earth metal alumino silicate mineral composed of silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra, wherein the tetrahedra are connected only by vertices, i.e., share an oxygen atom. The CAN-type zeolite has strong adsorptivity, ion exchange property, catalysis property, acid resistance and heat resistance, and is widely used as an adsorbent, an ion exchanger and a catalyst, and CAN also be used in the aspects of gas drying, purification, sewage treatment and the like. In order to fully utilize the calcium-magnesium-silicon-aluminum components in the blast furnace slag, firstly, ammonium bisulfate is adopted to leach the steel slag to obtain calcium sulfate leaching slag and leaching solution containing silicon, aluminum and magnesium; coprecipitation of silicon and aluminum is realized by adjusting the pH value of the leaching solution, and silicon-aluminum gel is obtained; further fully mixing the silicon-aluminum gel with NaOH and heating for reaction to synthesize the CAN zeolite under the solvent-free condition; respectively adjusting the pH of the silicon-aluminum precipitation mother liquor and the calcium sulfate leaching residue, and then mixing with CO2Reaction to realize CO2Mineralization of (1).
Disclosure of Invention
The present invention is directed to CO2The problem of solid waste treatment in the mineralization and iron and steel industry is to provide a method for mineralizing CO by using iron and steel slag2A method for co-producing CAN zeolite.
The invention relates to a method for mineralizing CO by using iron and steel slag2The method for coproducing CAN type zeolite takes blast furnace slag or steel slag as a raw material, and comprises the following process steps in sequence:
1. ammonium bisulfate leaching iron and steel slag
Grinding iron and steel slag with particle size below 150 μm and ammonium hydrogen sulfate (NH)4HSO4) Adding the solid into water and fully mixing, wherein the mass ratio of ammonium bisulfate to slag is controlled to be 2-4: 1, and the mass ratio of water to the solid material is controlled to be 0.5-1.5: 1; the mixture is at 25 toStirring for 5-60 min at 90 ℃, and filtering to obtain leaching residues and a leaching solution;
2. preparation of silica-alumina gel
Sending the leachate obtained in the step 1 to a sedimentation tank, adjusting the pH value of the solution by using ammonia water, controlling the concentration of the ammonia water to be 10-20 wt.%, controlling the sedimentation temperature to be 25-75 ℃ and the final pH value to be 5.5-8.5, and filtering to obtain a silicon-aluminum gel sediment and a sediment mother liquor;
3. preparation of zeolites
Fully washing the silicon-aluminum gel precipitate obtained in the step 2 with water, drying and finely grinding to be below 150 microns; further fully and uniformly mixing the finely ground silicon-aluminum gel with NaOH particles, placing the mixture in an oven for zeolite crystallization reaction, and controlling the mass ratio of NaOH to silicon-aluminum gel to be 0.2-1.5: 1, the reaction temperature to be 70-130 ℃, and the reaction time to be 0.5-48 h; after the reaction is finished, fully washing the solid product by using water, and filtering to obtain a zeolite product and alkaline washing liquor;
4. mineralization of leached residues
Adding the alkaline washing liquid obtained in the step 3 into the leaching residue obtained in the step 1, mixing into slurry, controlling the end point pH value to be 9-12, and introducing CO2Reacting the gas at 25-60 ℃ for 30-120 min, and filtering to obtain the calcium carbonate mineralized slag used as the raw material for producing cement;
5. mineralization of magnesium-rich solutions
Adding the alkaline washing liquid obtained in the step 3 into the precipitation mother liquid obtained in the step 2, controlling the end point pH value to be 10-12, and introducing CO2Reacting the gas at 25-60 ℃ for 30-120 min to obtain the magnesium carbonate mineralized slag.
The method comprises the steps of extracting calcium-magnesium-silicon-aluminum components in the steel slag by using ammonium bisulfate, further adopting precipitation and alkali treatment to obtain zeolite products, and using calcium sulfate and magnesium sulfate for mineralizing CO2。
Compared with the prior art, the invention has the following advantages: (1) compared with the traditional hydrothermal method, the method adopts a solvent-free method to prepare the CAN zeolite, thereby increasing the production capacity and reducing the corrosion of equipment; (2) the process has mild reaction conditions, and the obtained zeolite has high purity; (3) the raw materials of the process are waste residues in the steel industry, the sources are wide, the effective utilization of wastes is realized, the environmental pollution is reduced, and the production cost is saved; (4) the method has the advantages of simple process, convenient operation, no wastewater discharge, no secondary pollution, low production cost and industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of the resulting zeolite product of the present invention
Figure 2 is an SEM image of the resulting zeolite product of the present 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.
The blast furnace slag used in the following examples was ordinary blast furnace slag having a main chemical composition (mass%) of 41.84% CaO, 6.74% MgO, and 13.98% Al2O3、32.08%SiO2XRD analysis shows that the main phase of the blast furnace slag is Ca2Al2SiO7And Ca2MgSi2O7(ii) a The steel slag is converter slag, and the main chemical compositions (mass percentage) of the steel slag are 36.13 percent of CaO, 7.18 percent of MgO and 12.98 percent of Al2O3、22.8%SiO2,13.21Fe2O3XRD analysis shows that the main phase of the converter slag is Ca2SiO4、Ca2Fe2O3And Ca3Si2O7。
Example one
(1) Adding blast furnace slag which is finely ground to be less than 150 mu m and ammonium bisulfate solids into water and fully mixing, wherein the mass ratio of ammonium bisulfate to slag is controlled to be 3:1, and the mass ratio of water to solid materials is controlled to be 1: 1; stirring the mixture at 55 deg.C for 20min, and filtering to obtain leaching residue and leaching solution;
(2) sending the leachate obtained in the step 1 to a sedimentation tank, adjusting the pH value of the solution to 5.5 by adopting 10 wt.% ammonia water, controlling the sedimentation temperature to be 50 ℃, and filtering to obtain a silicon-aluminum gel sediment and a sediment mother liquor;
(3) fully washing the silicon-aluminum gel precipitate obtained in the step 2 with water, drying and finely grinding to be below 150 microns; further fully and uniformly mixing the finely ground silicon-aluminum gel with NaOH particles, placing the mixture in an oven for zeolite crystallization reaction, controlling the mass ratio of NaOH to silicon-aluminum gel to be 1:1, the reaction temperature to be 100 ℃, and the reaction time to be 4 hours; after the reaction is finished, fully washing the solid product by using water, and filtering to obtain a CAN type zeolite product and alkaline washing liquor;
(4) adding the alkaline washing liquid obtained in the step 3 into the leaching residue obtained in the step 1, mixing into slurry, controlling the end point pH value to be 12, and introducing CO2Reacting the gas at 40 ℃ for 30min, and filtering to obtain the raw material of the calcium carbonate mineralized slag for cement production;
(5) adding the alkaline washing solution obtained in the step 3 into the precipitation mother liquor obtained in the step 2, controlling the pH value of the end point to be 12, and introducing CO2Reacting the gas at 40 ℃ for 60min to obtain the magnesium carbonate mineralized slag.
Example two
(1) Adding blast furnace slag which is finely ground to be less than 150 mu m and ammonium bisulfate solids into water and fully mixing, wherein the mass ratio of ammonium bisulfate to slag is controlled to be 4:1, and the mass ratio of water to solid materials is controlled to be 0.5: 1; stirring the mixture at 90 deg.C for 5min, and filtering to obtain leaching residue and leaching solution;
(2) sending the leachate obtained in the step 1 to a sedimentation tank, adjusting the pH value of the solution to 8.5 by adopting 15 wt.% ammonia water, controlling the sedimentation temperature to be 75 ℃, and filtering to obtain a silicon-aluminum gel sediment and a sediment mother liquor;
(3) fully washing the silicon-aluminum gel precipitate obtained in the step 2 with water, drying and finely grinding to be below 150 microns; further fully and uniformly mixing the finely ground silicon-aluminum gel with NaOH particles, placing the mixture in an oven for zeolite crystallization reaction, and controlling the mass ratio of NaOH to silicon-aluminum gel to be 0.2:1, the reaction temperature to be 130 ℃, and the reaction time to be 0.5 h; after the reaction is finished, fully washing the solid product by using water, and filtering to obtain a CAN type zeolite product and alkaline washing liquor;
(4) adding the alkaline washing liquid obtained in the step 3 into the leaching residue obtained in the step 1, mixing into slurry, controlling the end point pH value to be 9, and introducing CO2Reacting the gas at 60 ℃ for 120min, and filtering to obtain the calcium carbonate mineralized slag used as the raw material for producing cement;
(5) adding the alkaline washing solution obtained in the step 3 into the precipitation mother liquor obtained in the step 2, controlling the pH value of the end point to be 11, and introducing CO2Reacting the gas at 60 ℃ for 120min to obtain the magnesium carbonate mineralized slag.
EXAMPLE III
(1) Adding steel slag which is finely ground to be less than 150 mu m and ammonium bisulfate solids into water and fully mixing, wherein the mass ratio of the ammonium bisulfate to the slag is controlled to be 2:1, and the mass ratio of the water to the solid materials is controlled to be 1.2: 1; stirring the mixture at 25 deg.C for 60min, and filtering to obtain leaching residue and leaching solution;
(2) sending the leachate obtained in the step 1 to a sedimentation tank, adjusting the pH value of the solution to 7 by adopting 20 wt.% ammonia water, controlling the sedimentation temperature to be 25 ℃, and filtering to obtain a silicon-aluminum gel sediment and a sediment mother liquor;
(3) fully washing the silicon-aluminum gel precipitate obtained in the step 2 with water, drying and finely grinding to be below 150 microns; further fully and uniformly mixing the finely ground silicon-aluminum gel with NaOH particles, placing the mixture in an oven for zeolite crystallization reaction, and controlling the mass ratio of NaOH to silicon-aluminum gel to be 1.5:1, the reaction temperature to be 120 ℃ and the reaction time to be 24 hours; after the reaction is finished, fully washing the solid product by using water, and filtering to obtain a CAN type zeolite product and alkaline washing liquor;
(4) adding the alkaline washing liquid obtained in the step 3 into the leaching residue obtained in the step 1, mixing into slurry, controlling the end point pH value to be 10, and introducing CO2Reacting the gas for 80min at 25 ℃, and filtering to obtain the calcium carbonate mineralized slag used as the raw material for producing cement;
(5) adding the alkaline washing solution obtained in the step 3 into the precipitation mother liquor obtained in the step 2, controlling the pH value of the end point to be 12, and introducing CO2Reacting the gas at 25 ℃ for 100min to obtain the magnesium carbonate mineralized slag.
Example four
(1) Adding steel slag which is finely ground to be less than 150 mu m and ammonium bisulfate solids into water and fully mixing, wherein the mass ratio of the ammonium bisulfate to the slag is controlled to be 4:1, and the mass ratio of the water to the solid materials is controlled to be 1.5: 1; stirring the mixture at 50 ℃ for 15min, and filtering to obtain leaching residues and a leaching solution;
(2) sending the leachate obtained in the step 1 to a sedimentation tank, adjusting the pH value of the solution to 6 by adopting 20 wt.% ammonia water, controlling the sedimentation temperature to be 70 ℃, and filtering to obtain a silicon-aluminum gel sediment and a sediment mother liquor;
(3) fully washing the silicon-aluminum gel precipitate obtained in the step 2 with water, drying and finely grinding to be below 150 microns; further fully and uniformly mixing the finely ground silicon-aluminum gel with NaOH particles, placing the mixture in an oven for zeolite crystallization reaction, and controlling the mass ratio of NaOH to silicon-aluminum gel to be 0.8:1, the reaction temperature to be 70 ℃ and the reaction time to be 48 hours; after the reaction is finished, fully washing the solid product by using water, and filtering to obtain a CAN type zeolite product and alkaline washing liquor;
(4) adding the alkaline washing liquid obtained in the step 3 into the leaching residue obtained in the step 1, mixing into slurry, controlling the end point pH value to be 10, and introducing CO2Reacting the gas at 30 ℃ for 60min, and filtering to obtain the raw material of the calcium carbonate mineralized slag for cement production;
(5) adding the alkaline washing solution obtained in the step 3 into the precipitation mother liquor obtained in the step 2, controlling the pH value of the end point to be 12, and introducing CO2Reacting the gas at 60 ℃ for 30min to obtain the magnesium carbonate mineralized slag.
Claims (4)
1. Mineralization of CO by steel slag2The method for co-producing the CAN zeolite is characterized by comprising the following steps:
step 1, leaching iron and steel slag by ammonium bisulfate: adding the iron and steel slag which is finely ground to be less than 150 mu m and the ammonium bisulfate solid into a certain amount of water according to a certain proportion, fully mixing, stirring and reacting at a certain temperature, and filtering to obtain leaching slag and leaching solution; the steel slag is blast furnace slag or converter slag; the mass ratio of the ammonium bisulfate to the slag is 2-4: 1, and the mass ratio of the water to the solid materials is 0.5-1.5: 1; the reaction temperature is 25-90 ℃, and the reaction time is 5-60 min;
step 2, preparation of silicon-aluminum gel: sending the leachate obtained in the step 1 to a sedimentation tank, adjusting the pH value of the solution at a certain temperature by adopting ammonia water with a certain concentration, and filtering to obtain a silicon-aluminum gel precipitate and a precipitation mother liquor; the concentration of the ammonia water is 10-20 wt.%, the precipitation temperature is 25-75 ℃, and the end point pH value is 5.5-8.5;
step 3, preparing zeolite: fully washing the silicon-aluminum gel precipitate obtained in the step 2 with water, drying and finely grinding to be below 150 microns; further fully mixing the finely ground silicon-aluminum gel with NaOH particles with certain mass, placing the mixture in an oven to perform zeolite crystallization reaction at a certain temperature, fully washing a solid product with water after the reaction is finished, and filtering to obtain a zeolite product and alkaline washing liquor;
step 4, mineralization of leached residues: adding the alkaline washing liquid obtained in the step 3 into the leaching residue obtained in the step 1, mixing into slurry, enabling the pH of the slurry to reach a certain value, controlling a certain temperature, and introducing CO2Reacting for a period of time, and filtering to obtain calcium carbonate mineralized slag;
step 5, mineralization of the magnesium-rich solution: adding the alkaline washing liquid obtained in the step 3 into the precipitation mother liquid obtained in the step 2 to ensure that the pH value of the mother liquid reaches a certain value, controlling a certain temperature and introducing CO2Reacting for a period of time, and filtering to obtain the magnesium carbonate mineralized slag.
2. The method of claim 1 for mineralizing CO using iron and steel slag2The method for co-producing the CAN zeolite is characterized in that the mass ratio of NaOH to silicon-aluminum gel in the step 3 is 0.2-1.5: 1, the reaction temperature is 70-130 ℃, and the reaction time is 0.5-48 h.
3. The method of claim 1 for mineralizing CO using iron and steel slag2The method for co-producing CAN zeolite is characterized in that in the step 4, the pH value of the slurry after adding the alkaline washing liquid is 9-12, the reaction temperature is 25-60 ℃, and the reaction time is 30-120 min.
4. The method of claim 1 for mineralizing CO using iron and steel slag2The method for co-producing CAN zeolite is characterized in that in the step 5, the pH value of the slurry after adding the alkaline washing liquid is 10-12, the reaction temperature is 25-60 ℃, and the reaction time is 30-120 min.
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