CN110577232B - Preparation method of nano calcium carbonate - Google Patents
Preparation method of nano calcium carbonate Download PDFInfo
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- CN110577232B CN110577232B CN201911019741.3A CN201911019741A CN110577232B CN 110577232 B CN110577232 B CN 110577232B CN 201911019741 A CN201911019741 A CN 201911019741A CN 110577232 B CN110577232 B CN 110577232B
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 158
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 15
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 14
- 239000010959 steel Substances 0.000 claims abstract description 14
- 229930006000 Sucrose Natural products 0.000 claims abstract description 13
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 48
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- 239000005720 sucrose Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 229960004793 sucrose Drugs 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 238000007873 sieving Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- -1 hydrogen ions Chemical class 0.000 description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- ZRBROGSAUIUIJE-UHFFFAOYSA-N azanium;azane;chloride Chemical compound N.[NH4+].[Cl-] ZRBROGSAUIUIJE-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- YMIFCOGYMQTQBP-UHFFFAOYSA-L calcium;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Ca+2] YMIFCOGYMQTQBP-UHFFFAOYSA-L 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a preparation method of nano calcium carbonate, which obtains CaCl based on steel slag2‑NH4Cl‑NH3‑H2And adding cane sugar into the leachate of the O system, introducing carbon dioxide into the leachate, simultaneously starting ultrasonic waves with the power of 1500-1800W, and sieving to obtain the nano calcium carbonate. The method has the advantages of simple process, resource saving, environmental friendliness, low cost, easy industrial production, good application prospect and good economic benefit.
Description
Technical Field
The invention relates to the technical field of preparation of calcium carbonate, in particular to a preparation method of nano calcium carbonate.
Background
The nano calcium carbonate is generally calcium carbonate particles with characteristic dimension size of nano magnitude (1-100 nm), and comprises ultrafine calcium carbonate (particle size of 0.02-0.1 mu m) and ultrafine calcium carbonate (particle size of less than or equal to 0.02 mu m) which are generally called in light calcium carbonate industry, and due to the ultrafine property of the nano calcium carbonate, the particle crystal structure and the surface electronic structure of the nano calcium carbonate are changed, so that the quantum size effect, small size effect, surface effect and macroscopic quantum effect which are not possessed by common calcium carbonate are generated, and the nano calcium carbonate has superior performance compared with the conventional materials in the aspects of magnetism, catalyst, photo-thermal resistance, melting point and the like. The product filled in rubber and plastic has bright surface, good elongation, high tensile strength, strong tearing resistance, good bending resistance and good anti-cracking performance, and is an excellent white reinforcing material. The product has good gloss, transparency, stability, quick drying and other characteristics in high-grade printing ink and coating.
The preparation method of calcium carbonate materials mainly comprises three main categories: solid phase method, liquid phase method, gas phase method, the nano calcium carbonate mainly adopts the liquid phase method. According to the difference of the synthesis mechanism, the method can be divided into three reaction systems: ca (OH)2-H2O-CO2The reaction system, namely the traditional carbonization method, mainly comprises production methods such as an intermittent carbonization method, a continuous spray carbonization method, a supergravity carbonization method and the like, the reaction systems of the methods are simple, the reaction process is usually controlled by utilizing the conductivity and the pH value, but the preparation process of the system usually needs processes such as mining, transporting, calcining, digesting and the like on limestone, so that the environmental pollution is large, the preparation method is complicated and the cost is high; ca2+-H2O-CO3 2-Reaction system, i.e. containing Ca2+With a solution containing CO3 2-The solution is mixed and reacted under certain conditions to prepare the nano calcium carbonate; ca2+-R-CO3 2-Reaction systems (R is an organic medium), namely a microemulsion method and a gel method. The latter two methods have not been used in actual production for a while. For example, patent CN201811350972.8 discloses a spherical nano calcium carbonate and a preparation method thereof, which comprises the following steps: dissolving sodium carbonate, potassium carbonate or ammonium bicarbonate in water to obtain CO3 2-Solution A with the concentration of 0.25-1 mol/L; dissolving calcium acetate monohydrate or calcium chloride monohydrate in water to form Ca2+Solution B with the concentration of 0.25-1 mol/L; respectively adding a certain amount of glycerol into different containers, and then respectively adding deionized water according to the volume ratio of 4:5-8:1 to prepare a solution C; respectively adding the solution A into the solution C, stirring for 3-5 minutes, then adding the solution B while stirring, and continuing stirring for 4-5 hours after the solution becomes turbid; the resulting white precipitate was centrifuged, washed repeatedly with deionized water, and dried in an oven at 60 ℃ under vacuum overnight. The invention patent CN201910012324.X discloses a preparation method of nano calcium carbonate for MS glue, which is prepared by mixing calcium oxide (CaO) and water (H)2O) digestion of the resulting calcium hydroxide (Ca (OH)2) Removing impurities from the slurry, and aging under heat preservationAdding a crystal form control agent and carbon dioxide (CO) after washing2) The kiln gas is subjected to a primary carbonization synthesis reaction, and then an after-treatment agent is added, aged for a certain time and then mixed with the washed carbon dioxide (CO)2) The kiln gas is subjected to secondary carbonization synthesis reaction to obtain calcium carbonate (CaCO)3) And (3) curing the slurry, namely adding a modifier into the cured slurry, and performing filter pressing, dehydration, drying, crushing and classification after the reaction is finished to obtain the nano calcium carbonate for the MS glue. However, the method has complex process and high cost. In CaCl2-NH4Cl-NH3-H2The research of preparing the nano calcium carbonate under the O system has not been reported so far.
With the continuous mass production of steel enterprises in China for decades, the accumulation of steelmaking slag is gradually increased year by year, and at present, no ideal steel slag treatment technology is developed in China, and the utilization rate is only about 10%. A large amount of steel slag is stacked, which not only occupies land, but also easily causes salinization of the land, and causes a large amount of resource waste and serious environmental pollution. Meanwhile, the steel-making process is accompanied by the generation of a large amount of carbon dioxide, and the greenhouse effect brought by the carbon dioxide has obvious influence on the global climate: so that glaciers melt, natural ecological degeneration and natural disasters frequently occur, and the survival and development of human beings in partial regions are directly threatened. Therefore, how to realize the resource utilization of the steelmaking slag and the carbon dioxide becomes a problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of nano calcium carbonate, which solves the problems of complex process, high cost, great environmental pollution and the like of the existing preparation method and improves the resource utilization of steel slag.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of nano calcium carbonate comprises the following steps:
1) adding ammonium chloride solution into the steel slag for reaction to obtain CaCl2-NH4Cl-NH3-H2Standing the leaching solution of the O system overnight for later use;
2) adding cane sugar into the leachate obtained in the step 1), introducing carbon dioxide into the leachate, starting ultrasonic waves with the power of 1500-1800W, stopping the reaction when the pH value of the leachate is 7.1, immediately screening by using a 250-mesh screen, rinsing the screened product by using absolute ethyl alcohol, and drying in a vacuum drying oven to obtain the nano calcium carbonate.
Preferably, CaCl is contained in the leachate2Is 0.4mol/L, NH4Cl concentration of 1mol/L, NH4The concentration of HO was 0.8 mol/L.
Preferably, the temperature in the leaching reaction in the step 1) is 40-60 ℃.
Preferably, the temperature of the leachate obtained in the step 2) is 15-25 ℃ in the reaction process.
Preferably, the adding amount of the sucrose is 2% of the mass of the calcium chloride in the leaching solution.
Preferably, the flow rate of the carbon dioxide is 45 ml/min.
Preferably, the drying temperature is 80-125 ℃, and the drying time is 1-18 h.
The action mechanism of the invention is as follows: in CaCl2-NH4Cl-NH3-H2In the O solution system, the sucrose and the ultrasonic wave prolong the induction period in the early stage of the preparation of the calcium carbonate, which is beneficial to quickly and uniformly forming calcium carbonate crystal nuclei, thereby reducing the particle size of calcium carbonate particles. Meanwhile, the ultrasonic cavitation generates local high temperature and high pressure, which provides the required energy for the formation of crystal nucleus, so that the formation speed of the crystal nucleus can be increased by several orders of magnitude, when the ultrasonic power is larger (1500-1800W), the local high temperature caused by the ultrasonic cavitation is dominant, along with the preparation of calcium carbonate, a large amount of tiny cavitation bubbles generated in the reaction by ultrasonic waves can form a flushing effect on the surface of calcium carbonate particles, and instantaneous cavities are generated on the surface of the generated calcium carbonate particles, so that an erosion effect is generated, the surface area of mass transfer contact is increased, the specific surface free energy of tiny crystal grains is reduced, the coalescence and the growth of the crystal nucleus are inhibited, calcium carbonate crystals can grow rapidly and uniformly, and the crystal density is reduced. Then the carbon can be further increased by compounding cane sugarThe particle size of the calcium carbonate crystals is reduced, which is favorable for the rapid and uniform formation of calcium carbonate crystal nuclei. Because the surface energy of the nano calcium carbonate is high and the nano calcium carbonate is easy to agglomerate, the nano calcium carbonate is immediately filtered and dried after the reaction reaches 7.1, the agglomeration probability caused by mutual collision of the nano calcium carbonate during dissolution and recrystallization in an aging stage can be reduced, and meanwhile, a part of nano calcium carbonate aggregates generated can be screened out by sieving with a 250-mesh sieve, which is beneficial to ensuring the granularity and quality of products. Thus in CaCl2-NH4Cl-NH3-H2Under the system of O, the preparation of the nano calcium carbonate product is promoted under the synergistic action and the flow of the preparation process.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention realizes the comprehensive utilization of the steel slag in CaCl2-NH4Cl-NH3-H2The O system can fix a large amount of carbon dioxide which is generated along with the steelmaking process, the ammonium chloride solution can be regenerated and recycled, and the prepared nano calcium carbonate has good shape, narrow particle size distribution, uniform appearance and good repeatability, and is easy for large-scale production.
2. The method has the characteristics of simple process, low cost, green and environment-friendly preparation process, short production period, simple process, resource saving, environmental friendliness and low cost, is simple and controllable in experimental operation process, is easy for industrial production, and has good application prospect.
3. The invention improves the resource utilization of the industrial steel slag to realize high added value, avoids environmental pollution and resource waste, and realizes a process approach of treating wastes with processes of wastes against one another and changing wastes into valuables. And put forward for the first time based on CaCl2-NH4Cl-NH3-H2The O system is used for preparing the nano calcium carbonate, and provides a new idea and a new choice for preparing the nano calcium carbonate.
Drawings
FIG. 1 shows CaCl2-NH4Cl-NH3-H2The change curves of calcium content, pH value and conductivity in the reaction liquid along with the reaction time under the O system;
FIG. 2 is an SEM image of a crude product prepared by aging reaction in comparative examples 1-4; (a) comparative example 1; (b) comparative example 2; (c) comparative examples 3 and (d) comparative example 4;
FIG. 3 is a TEM image of nano calcium carbonate in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. The calcium ion content in the solution in the following examples was determined by the EDTA titration method, which is a chinese national standard. The particle size of the calcium carbonate is detected by a laser particle size analyzer (German flying, Analyzte 22MicroTec plus) and a national standard particle size analysis-laser diffraction method, and the appearance of the prepared calcium carbonate is detected by a field emission electron microscope (FEI, Nova 400Nano, USA) and a shooting electron microscope (JEOL, JEOL-JEM-1005, USA). The steel slag used in the following examples was calcium silicate as a main component.
Preparation method of nano calcium carbonate
In order to judge the end point of the carbonation reaction of the system, firstly, the CaCl leached based on the steel slag ammonium chloride under the action of ultrasonic waves is researched2-NH4Cl-NH3-H2The conductivity and pH value of the O system during the reaction change with the reaction time and the content of calcium ions, and the result is shown in FIG. 1.
As can be seen from FIG. 1, the conductivity of the reaction solution is basically unchanged during the whole reaction process, while the pH value is slowly decreased, and the pH value begins to rapidly decrease when the pH value is about 7.5, until the pH value reaches the equilibrium when the pH value is about 6.3, and the pH value of the system is decreased in an inverse S shape during the whole process. With conventional Ca (OH)2-H2Compared with the bubbling method under the O system, the pH value and the conductivity of the system are obviously different along with the change of the reaction time. This is probably because when carbon dioxide is introduced into the solution, the dissolution reaction of formula (1) occurs, that is, carbon dioxide is dissolved in the aqueous solution, and the dissolved carbon dioxide reacts with water to release hydrogen ions, bicarbonate ions, and carbonate ions (formulas (2) and (3)), and the amount of calcium carbonate precipitates due to the reaction of carbonate ions with calcium ions decreases (formula (4)), resulting in the movement of formulas (2) and (3) to the right of the equation, thereby increasing the hydrogen ion content in the system and lowering the pH. At the same time, due to the presence of chlorine in the systemThe ammonium-ammonia buffer balance is changed, and the continuously increased hydrogen ions enable the reaction (5) to move towards the right continuously, so that the pH value in the system is slowly reduced at the beginning, and after all the amino groups in the system are converted into ammonium ions, the continuously increased hydrogen ions enable the pH value of the system to be rapidly reduced. The final reaction equation for producing calcium carbonate by precipitation is shown in formula (6), and one divalent calcium ion is consumed while two monovalent hydrogen ions are produced. In addition, the hydrogen radical ion can react with ammonia (5) to form an ammonium radical ion, and the divalent calcium ion can also form a complex with ammonia, so that the electrical conductivity does not change much in the carbonation reaction that occurs in the system. Since the crystallization rate of calcium is already very high when the reaction is carried out to a pH of about 7 and the reaction system is maintained for a while if bubbling is stopped, the present invention fixes the reaction end point to a pH of about 7.1.
It can be seen that carbon dioxide is dissolved in an aqueous solution, and the dissolved carbon dioxide reacts with water to release hydrogen ions and hydrogen carbonateRoot ion and carbonate ion in CaCl2-NH4Cl-NH3-H2In the O system, the hydrogen radical ions and ammonia and ammonium radical ions exist in balance, so that the solution system can rapidly absorb and contain more carbon dioxide to form high-concentration carbonate ions, and the conductivity and pH value of the system are equal to those of the conventional Ca (OH) due to the existence of ammonium chloride-ammonia buffer balance in the system2-H2Compared with calcium carbonate prepared by a bubbling method under an O system, the calcium carbonate prepared by the bubbling method has great difference, and the reaction mechanisms of the two preparation processes are completely different.
Example 1
1) Adding an ammonium chloride solution into the steel slag, and carrying out leaching reaction at 40-60 ℃ to obtain CaCl2-NH4Cl-NH3-H2Leachate of O system, wherein, CaCl2Is 0.4mol/L, NH4Cl concentration of 1mol/L, NH4HO concentration of 0.8mol/L, standing overnight, standby.
2) Controlling the temperature of the leachate obtained in the step 1) to be 20 ℃, adding sucrose, wherein the adding amount of the sucrose is 2% of the mass of calcium chloride, introducing 45ml/min of carbon dioxide into the leachate, starting ultrasonic treatment with the power of 1620W, stopping the reaction when the pH value of the leachate is 7.1, immediately screening by using a 250-mesh screen, subsequently rinsing the filtered calcium carbonate by using absolute ethyl alcohol, and drying in a vacuum drying oven at 100 ℃ for 15 hours to obtain the product, namely the nano-scale calcium carbonate.
Example 2
1) Adding an ammonium chloride solution into the steel slag, and carrying out leaching reaction at 40-60 ℃ to obtain CaCl2-NH4Cl-NH3-H2And (4) leaching solution of an O system. Wherein, CaCl2Is 0.4mol/L, NH4The concentration of Cl is 1mol/L, NH4The concentration of HO was 0.8mol/L and left overnight for further use.
2) Controlling the temperature of the leachate obtained in the step 1) to be 20 ℃, adding sucrose, wherein the adding amount of the sucrose is 2% of the mass of the calcium chloride, introducing carbon dioxide of 45ml/min into the leachate, simultaneously starting ultrasonic treatment with the power of 1500W, stopping the reaction when the pH value of the leachate is 7.1, immediately screening by using a 250-mesh screen, subsequently rinsing the filtered calcium carbonate by using absolute ethyl alcohol, and placing the washed calcium carbonate in a vacuum drying oven at 100 ℃ for drying for 15h to obtain the product, namely the nano-scale calcium carbonate.
Example 3
1) Adding an ammonium chloride solution into the steel slag, and carrying out leaching reaction at 40-60 ℃ to obtain CaCl2-NH4Cl-NH3-H2Leachate of O system, wherein CaCl2Is 0.4mol/L, NH4Cl concentration of 1mol/L, NH4HO concentration of 0.8mol/L, standing overnight, standby.
2) Controlling the temperature of the leachate obtained in the step 1) to be 20 ℃, adding sucrose, wherein the adding amount of the sucrose is 2% of the mass of the calcium chloride, introducing carbon dioxide of 45ml/min into the leachate, simultaneously starting ultrasonic treatment with the power of 1800W, stopping the reaction when the pH value of the leachate is 7.1, immediately screening by using a 250-mesh screen, subsequently rinsing the filtered calcium carbonate by using absolute ethyl alcohol, and placing the washed calcium carbonate in a vacuum drying oven at 100 ℃ for drying for 15h to obtain the product, namely the nano-scale calcium carbonate.
Comparative example 1
And (3) carrying out ageing reaction for 3 hours after the reaction is stopped without ultrasonic waves, then carrying out vacuum filtration, subsequently rinsing the filtered calcium carbonate with absolute ethyl alcohol, and drying, wherein other steps and parameters are the same as those in example 1.
Comparative example 2
The ultrasonic power is 540W, the aging reaction is carried out for 3h after the reaction is stopped, then the vacuum filtration is carried out, then the calcium carbonate after the filtration is rinsed by absolute ethyl alcohol and dried, and other steps and parameters are the same as those of the example 1.
Comparative example 3
The ultrasonic power is 1080W, the aging reaction is carried out for 3h after the reaction is stopped, then the vacuum filtration is carried out, then the calcium carbonate after the filtration is rinsed by absolute ethyl alcohol and dried, and other steps and parameters are the same as those of the example 1.
Comparative example 4
After the reaction was stopped, an aging reaction was carried out for 3 hours, followed by vacuum filtration, followed by rinsing the filtered calcium carbonate with anhydrous ethanol, and drying, and the other steps and parameters were the same as in example 1.
Secondly, product detection
1. Scanning electron microscope observation is carried out on the crude products prepared in comparative examples 1-4, and the result is shown in figure 2.
As can be seen from the figure, no matter whether ultrasonic treatment exists in the reaction process or not, after the aging reaction is carried out after the reaction is finished, the crystal grains of the product calcium carbonate are mutually agglomerated to form an aggregate, so that the particle is coarse. The particle size of the calcium carbonate particles is further reduced with the increase of the ultrasonic power, which is mainly due to the fact that a large number of nucleation sites are generated by high-power ultrasonic, and the interaction with the sucrose can delay the induction period of the reaction, so that the outline of the calcium carbonate particles is obvious, the agglomeration degree is further reduced, but the particle size of the calcium carbonate is still micron or submicron. In addition, because sound microflow and shock waves generated by ultrasonic waves have double effects of breaking crystal grains and increasing the collision probability among particles, when the ultrasonic power is too high (more than 1800W), the calcium carbonate particles have the tendency of not only not having the effect of refining the crystal grains but also becoming aggregates.
2. The product prepared in example 1 was observed under a transmission electron microscope, and the result is shown in fig. 3.
As can be seen from FIG. 3, the nano calcium carbonate obtained by the invention has uniform particle size distribution, regular appearance and spherical shape. Because the surface energy of the nano calcium carbonate is high and the nano calcium carbonate is easy to agglomerate, the nano calcium carbonate is immediately filtered and dried after the reaction reaches 7.1, the agglomeration probability caused by mutual collision of the nano calcium carbonate during dissolution and recrystallization in an aging stage can be reduced, and meanwhile, a part of nano calcium carbonate aggregates generated can be screened out by sieving with a 250-mesh sieve, which is beneficial to ensuring the granularity and quality of products. Thus in CaCl2-NH4Cl-NH3-H2Under the system of O, the preparation process of the invention is beneficial to the preparation of the nano calcium carbonate product under the synergistic effect and the flow.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The preparation method of the nano calcium carbonate is characterized by comprising the following steps:
1) adding an ammonium chloride solution into the steel slag, and carrying out leaching reaction at 40-60 ℃ to obtain CaCl2-NH4Cl-NH3-H2Leachate of O system, wherein CaCl2Is 0.4mol/L, NH4Cl concentration of 1mol/L, NH4The concentration of HO is 0.8mol/L, and the mixture is kept stand overnight for standby;
2) controlling the temperature of the leachate obtained in the step 1) to be 20 ℃, adding sucrose, wherein the adding amount of the sucrose is 2% of the mass of calcium chloride, introducing 45ml/min of carbon dioxide into the leachate, starting ultrasonic treatment with the power of 1620W, stopping the reaction when the pH value of the leachate is 7.1, immediately screening by using a 250-mesh screen, subsequently rinsing the filtered calcium carbonate by using absolute ethyl alcohol, and drying in a vacuum drying oven at 100 ℃ for 15 hours to obtain the product, namely the nano-scale calcium carbonate.
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| CN103911197A (en) * | 2014-04-17 | 2014-07-09 | 南京工业大学 | Method for purifying biogas and co-producing nano calcium carbonate |
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| CN103911197A (en) * | 2014-04-17 | 2014-07-09 | 南京工业大学 | Method for purifying biogas and co-producing nano calcium carbonate |
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