CN112441608B - Preparation method of nano calcium hydroxide whisker - Google Patents
Preparation method of nano calcium hydroxide whisker Download PDFInfo
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- CN112441608B CN112441608B CN201910799318.3A CN201910799318A CN112441608B CN 112441608 B CN112441608 B CN 112441608B CN 201910799318 A CN201910799318 A CN 201910799318A CN 112441608 B CN112441608 B CN 112441608B
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- 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
- C01F11/46—Sulfates
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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
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Composite Materials (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for preparing nano calcium hydroxide whisker by using a calcium sulfate raw material, which comprises the following steps: 1) Grinding the calcium sulfate raw material to obtain calcium sulfate powder; 2) Mixing the powder obtained in the step 1) according to an inorganic alkali solution with a liquid-solid ratio of 5-20 mL/g and a concentration of 0.5-5mol/L and a crystal form control agent, placing the mixture into a reaction container with stirring, and reacting for 30-120 min at a temperature of 30-150 ℃ to obtain a solid-liquid mixture; 3) And (3) carrying out solid-liquid separation on the solid-liquid mixture obtained in the step (2) to obtain filtrate and a filter cake, drying the filter cake at a low temperature to obtain the nano calcium hydroxide whisker, and recycling the filtrate as sulfate solution. The invention takes calcium sulfate powder as raw material, inorganic alkali as auxiliary agent, and crystal form control agent is added, and nano calcium hydroxide whisker is prepared at low temperature and normal pressure; the crystal form control agent can be recycled. The material can be used for carbon dioxide adsorption or sewage treatment, and can also be used as a raw material for flue gas desulfurization or light calcium preparation.
Description
Technical Field
The invention relates to a preparation method of nano calcium hydroxide whiskers, in particular to a method for preparing whisker-shaped nano calcium hydroxide from a calcium sulfate raw material, belonging to the fields of inorganic functional materials and chemical materials.
Background
Calcium hydroxide is a binary strong base rich in calcium ions, can be applied to carbon dioxide adsorption, environment-friendly neutralization, acid wastewater and sewage treatment, boiler flue gas desulfurization and the like, can also be used as a filler to be applied to a polymer, and has better reinforcing performance when fibrous nano calcium hydroxide is filled into the polymer. There is no disclosure report about the preparation method of nano calcium hydroxide whisker.
Disclosure of Invention
The invention aims to provide a preparation method of a calcium sulfate raw material, which is low in temperature, normal in pressure, easy to realize in industry and good in applicability.
The preparation process of nanometer calcium hydroxide whisker includes the following steps:
1) Grinding the calcium sulfate raw material to obtain calcium sulfate powder with the average granularity of 80-160 meshes;
2) Preparing the calcium sulfate powder raw material obtained in the step 1), an inorganic alkali solution and a crystal form control agent, placing the mixture in a reaction vessel with stirring, and reacting for 30-120 min at the temperature of 30-150 ℃ under normal pressure to obtain a solid-liquid mixture;
3) And (3) carrying out suction filtration, washing and drying on the solid-liquid mixture obtained in the step (2) to obtain solid powder with sulfate solution and nano calcium hydroxide whisker as main components.
The main chemical components in the calcium sulfate raw material in the step 1) are calcium sulfate, including natural gypsum, industrial byproduct gypsum and the like; the concentration of the inorganic alkali solution in the step 2) is 0.5-5mol/L; the addition amount of the inorganic alkali is 5-20 mL/g of liquid-solid ratio; the inorganic alkali is one or more of sodium hydroxide, potassium hydroxide or magnesium hydroxide.
The addition amount of the crystal form control agent in the step 2) is 0.1-5% of the mass fraction of the raw materials; the crystal form control agent is one or more of sodium salicylate, EDTA, magnesium chloride or potassium phosphate.
The crystal form of the nano calcium hydroxide whisker prepared by the preparation method is calcite, the morphology is fibrous, the diameter is 80-100 nm, and the length-diameter ratio is more than 20.
The method for preparing the nano calcium hydroxide whisker material has the following beneficial effects: 1) The raw materials used in the invention are natural gypsum or industrial byproduct gypsum, etc., and the raw materials are easy to obtain and the price is low; 2) The whole preparation process is carried out at low temperature and normal pressure, so that the preparation process is safer; 3) The crystal form control agent can be recycled, sulfate is a byproduct in the preparation process, and the preparation cost is low; 4) The purity of the prepared nano calcium hydroxide whisker can reach more than 90% and the length-diameter ratio of the whisker is more than 20 under the premise of reducing the dosage of chemical auxiliary agents and shortening the production period.
Detailed Description
The invention relates to a preparation method of nano calcium hydroxide whisker, which comprises the following steps.
1) Grinding the calcium sulfate raw material to obtain calcium sulfate powder with the average granularity of 80-160 meshes;
wherein, the main chemical components in the calcium sulfate raw material in the step 1) are calcium sulfate, mainly natural gypsum, industrial byproduct gypsum and the like.
2) Preparing the calcium sulfate powder raw material obtained in the step 1), an inorganic alkali solution and a crystal form control agent, placing the mixture in a reaction vessel with stirring, and reacting for 30-120 min at the temperature of 30-150 ℃ under normal pressure to obtain a solid-liquid mixture;
wherein, the concentration of the inorganic alkali solution in the step 2) is 0.5-5mol/L; the addition amount of the inorganic alkali is 5-20 mL/g of liquid-solid ratio; the inorganic alkali is one or more of sodium hydroxide, potassium hydroxide or magnesium hydroxide; the addition amount of the crystal form control agent is 0.1-5% of the mass fraction of the raw materials; the crystal form control agent is one or more of sodium salicylate, EDTA, magnesium chloride or potassium phosphate.
3) Filtering, washing and drying the solid-liquid mixture obtained in the step 2) to obtain solid powder with sulfate solution and nano calcium hydroxide whisker as main components;
wherein, the filtrate in the step 3) can be recycled, and the sulfate concentration in the solution is increased after the filtrate is recycled once, thereby realizing precipitation and recovery of sulfate through recycling; the crystal form control agent in the filtrate can be recycled.
The crystal form of the prepared nano calcium hydroxide whisker material is calcite, the morphology is fibrous, the diameter is 80-100 nm, the length-diameter ratio is more than 20, and the content is more than 90.
The technical scheme of the invention is further described in detail by specific examples.
Example 1:
the calcium sulfate raw material in the embodiment adopts phosphogypsum, and the main chemical components of the phosphogypsum are as follows in percentage by weight: SO (SO) 3 40%，CaO30%，SiO 2 5%, other 25%; the specific process comprises the following steps:
1) Taking 10g of phosphogypsum powder, preparing 1 mol/L sodium hydroxide solution 120 mL, pouring a phosphogypsum sample into the sodium hydroxide solution, adding 0.1 g of EDTA into the solution, stirring at 65 ℃ for reacting for 45 min, and carrying out suction filtration and washing after the reaction is completed to obtain a solid reactant;
2) Drying the solid reaction product at 60 ℃ for 12 h to obtain a nano calcium hydroxide whisker sample;
3) The calcium hydroxide whisker content in the obtained sample is 92.6%, the average diameter of the whisker is 87. 87 nm, and the length is 25-40 mu m.
Example 2:
the raw material of the calcium sulfate in the embodiment adopts the desulfurized gypsum, and the main chemical components of the desulfurized gypsum are as follows in percentage by weight: SO (SO) 3 26%，CaO48%，SiO 2 1%, other 25%; specifically process is performed byThe process is as follows:
1) Taking 10g of the desulfurized gypsum powder, preparing 80. 80 mL of magnesium hydroxide solution with the concentration of 1.5 mol/L, pouring a desulfurized gypsum sample into the magnesium hydroxide solution, adding 0.25 g of EDTA and 0.1 g of magnesium chloride into the solution, stirring and reacting for 83 min at 78 ℃, and carrying out suction filtration and washing after the reaction is completed to obtain a solid reactant;
2) Drying the solid reaction product at 60 ℃ for 12 h to obtain a nano calcium hydroxide whisker sample;
3) The sample obtained above had a content of 98.6% of nano calcium hydroxide whiskers, the average diameter of the whiskers being 67. 67 nm, and the length being 26-50. Mu.m.
Claims (4)
1. The preparation process of nanometer calcium hydroxide whisker includes the following steps:
1) Grinding the calcium sulfate raw material to obtain calcium sulfate powder with the average granularity of 80-160 meshes;
2) Preparing the calcium sulfate powder raw material obtained in the step 1), an inorganic alkali solution and a crystal form control agent, placing the mixture in a reaction vessel with stirring, and reacting for 30-120 min at the temperature of 30-150 ℃ under normal pressure to obtain a solid-liquid mixture;
3) Filtering, washing and drying the solid-liquid mixture obtained in the step 2) to obtain solid powder with sulfate solution and nano calcium hydroxide whisker as main components;
wherein, the concentration of the inorganic alkali solution in the step 2) is 0.5-5mol/L; the addition amount of the inorganic alkali solution is 5-20 mL/g of liquid-solid ratio; the inorganic base is one or two of sodium hydroxide and potassium hydroxide;
the addition amount of the crystal form control agent in the step 2) is 0.1-5% of the mass fraction of the raw materials; the crystal form control agent is one or more of sodium salicylate, magnesium chloride, EDTA or potassium phosphate.
2. The method of manufacturing according to claim 1, characterized in that: the main chemical component in the calcium sulfate raw material in the step 1) is calcium sulfate, which is natural gypsum or industrial byproduct gypsum.
3. The method of manufacturing according to claim 1, characterized in that: sulfate in the filtrate in the step 3) can be naturally separated out and recovered through repeated cyclic utilization of the filtrate; the crystal form control agent in the filtrate can be recycled.
4. A production method according to any one of claims 1 to 3, characterized in that: in the preparation process of the nano calcium hydroxide whisker, calcium sulfate is used as a main raw material, and the whole preparation process is completed at low temperature and normal pressure; in the preparation process, the selectivity control of the aspect ratio of the nano calcium hydroxide whisker can be realized by controlling the proportion of the crystal form control agent; the crystal form of the nano calcium hydroxide whisker is calcite, the morphology is fibrous, the diameter is 80-100 nm, and the length-diameter ratio is more than 20.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910799318.3A CN112441608B (en) | 2019-08-28 | 2019-08-28 | Preparation method of nano calcium hydroxide whisker |
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| CN201910799318.3A CN112441608B (en) | 2019-08-28 | 2019-08-28 | Preparation method of nano calcium hydroxide whisker |
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| CN112441608B true CN112441608B (en) | 2023-06-16 |
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| CN113856236B (en) * | 2021-10-14 | 2023-06-23 | 昆明理工大学 | Method for preparing nano material by regulating and controlling calcium-based solid waste dissolution crystallization by multiple physical fields |
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