CN113860307A - Mineralization of CO by blast furnace slag2Method for co-production of X-type zeolite - Google Patents
Mineralization of CO by blast furnace slag2Method for co-production of X-type zeolite Download PDFInfo
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- CN113860307A CN113860307A CN202111248674.XA CN202111248674A CN113860307A CN 113860307 A CN113860307 A CN 113860307A CN 202111248674 A CN202111248674 A CN 202111248674A CN 113860307 A CN113860307 A CN 113860307A
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010457 zeolite Substances 0.000 title claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 30
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000002893 slag Substances 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002386 leaching Methods 0.000 claims abstract description 35
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 15
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- NEKPCAYWQWRBHN-UHFFFAOYSA-L magnesium;carbonate;trihydrate Chemical compound O.O.O.[Mg+2].[O-]C([O-])=O NEKPCAYWQWRBHN-UHFFFAOYSA-L 0.000 claims abstract description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 7
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 239000010440 gypsum Substances 0.000 claims description 14
- 229910052602 gypsum Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- -1 uniformly mixing Chemical compound 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
- C01B32/55—Solidifying
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- 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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/22—Type X
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种利用高炉渣矿化CO2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CO2分别生成碳酸钙和三水碳酸镁，实现CO2矿化。
The invention discloses a method for co-producing X-type zeolite by using blast furnace slag to mineralize CO 2 . The method includes: (1) mixing blast furnace slag and ammonium sulfate, leaching with sulfuric acid solution to obtain sulfate leaching solution, and leaching hemihydrate gypsum slag; (2) adding ammonia water to the leachate obtained in the first step, adjusting the pH, making silicon and aluminum precipitate to form a silica-alumina gel, and filtering to obtain a mother liquor rich in silica-alumina gel and magnesium sulfate; Aluminum, sodium hydroxide and sodium silicate are dissolved in water according to a certain proportion, and fully stirred to obtain a white sol (directing agent) for subsequent use; (4) adding an appropriate amount of directing agent to the silica-alumina gel obtained in the second step, And fully mix with sodium hydroxide and place in the reactor to carry out hydrothermal reaction for a period of time, wash the solid product with deionized water to obtain X-type zeolite; (5) to the hemihydrate gypsum leaching residue obtained in the first step and the second step Ammonia water is added with magnesium sulfate mother liquor and CO 2 is introduced to generate calcium carbonate and magnesium carbonate trihydrate, respectively, to realize CO 2 mineralization.
Description
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.
Claims (7)
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.
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