CN105624772A - Control method for orientated growth of hemi-hydrate gypsum monocrystals - Google Patents
Control method for orientated growth of hemi-hydrate gypsum monocrystals Download PDFInfo
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- CN105624772A CN105624772A CN201610030658.6A CN201610030658A CN105624772A CN 105624772 A CN105624772 A CN 105624772A CN 201610030658 A CN201610030658 A CN 201610030658A CN 105624772 A CN105624772 A CN 105624772A
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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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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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
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a control method for orientated growth of hemi-hydrate gypsum monocrystals. The control method comprises the following steps: adding an acidity regulating agent into phosphogypsum, adding water, uniformly mixing, aging, then loading into a reactor with a condensation refluxing device, adding an impurity stabilizer and a crystal face selective absorbent, uniformly mixing, performing the heating reaction, adding an ion movement controller into the reaction system, after the reaction is ended, cooling, filtering, and drying solids to obtain morphology-controllable hemi-hydrate gypsum monocrystals. The method has the characteristics of simple process and low cost and is suitable for industrialized production.
Description
Technical field
The present invention relates to Gypsum Fibrosum, particularly to the preparation method of the semi-hydrated gypsum monocrystal of a kind of column pattern that can serve as in building, plastics, rubber, coating.
Background technology
Gypsum Fibrosum is sulfate mineral, and its chemical molecular formula is CaSO4 2H2O. Gypsum Fibrosum dehydration can form anhydrite, and in nature, they are a kind of metastable condition, can convert mutually under certain condition. Natural gypsum chief value is that it heats under condition of different temperatures, and its calcined product takes on a different character. As started dehydration when the natural gypsum is heated to 65��70 DEG C, become semi-hydrated gypsum; Dehydration gradually within being heated to 200 DEG C, semi-hydrated gypsum partially changes into anhydrous gypsum, but contacts quickly condensation with water and become dihydrate gypsum; It is heated to 200��300 DEG C, mainly becomes anhydrous gypsum, condense slack-off, but intensity increases; Product when being heated to 300��450 DEG C is anhydrous gypsum, and condensation accelerates, but intensity is relatively low; Being heated between 400��700 DEG C, chemical composition is constant, becomes a kind of new variant " burning to death " Gypsum Fibrosum, and it is extremely difficult is dissolved in water, also noncondensing after adding water; When continuing to be heated to 800 DEG C, anhydrous gypsum becomes to condense slowly and hardening; When being heated to 800��1000 DEG C, generate free lime, obtain normal extremely valuable conventional calcination Gypsum Fibrosum; The prefabrication of Gypsum Fibrosum mainly made by semi-hydrated gypsum, such as plasterboard, wall body construction, heat insulation semicircular tile, building decoration product etc. The features such as gypsum building products has fire prevention, heat insulation, sound-absorbing, shrinkage factor are little and can follow closely, can saw, can bond and body weight is light, anti-seismic performance is good [feature of Gypsum Fibrosum and purposes [J]. Shandong land resources, 2005,21B:46].
Ardealite is the industrial residue of discharge in Wet-process Phosphoric Acid Production process, can contain dihydrate gypsum (CaSO4 2H2O) and semi-hydrated gypsum (CaSO4 0.5H2O) due to the difference of production procedure with dihydrate gypsum for Main Ingredients and Appearance. Additionally contain the impurity such as a small amount of undecomposed ground phosphate rock, free phosphoric acid, iron phosphate, aluminum phosphate and fluosilicate; The annual emissions of whole world ardealite is close to 200,000,000 tons, and the annual emissions of China's ardealite is also above 10,000,000 tons. This does not only take up a large amount of soil, and seriously pollute environment [Xi Meiyun. the comprehensive utilization [J] of ardealite. Environmental science and technology, 2001, (3): 10��13].
What flower is when utilizing ardealite, it is carried out water-washing pre-treatment, to remove the impurity in slag, it is to avoid impurity on the impact of Gypsum Fibrosum pattern [what flower. ardealite base alcohol��hydro-thermal method prepares big L/D ratio wastewaters with modified calcium sulfate whiskers research [J]. Xinan Science and Technology Univ., 2014:17]. With water, ardealite being processed, the waste water of generation is by contaminated environment.
The phosphogypsum powder obtained is mixed by Sun Hongjuan et al. with diluted acid, obtain the acid mixed solution of calcic and sulfate ion and insoluble matter, filter, obtain acid filtrate, the acid filtrate crystallization crystallization that will obtain, obtain calcium sulfate crystal whiskers [Sun Hongjuan, Liang Yaqin, Peng Tongjiang, etc. a kind of method [P] of preparing calcium sulphate whiskers from ardealite, China, 201510007196.1]. Utility in ardealite is extracted by this technique acid (nitric acid or hydrochloric acid), and acid is by etching apparatus, it is easy to volatilization, to environment.
The calcium sulfate crystal whiskers of what flower and Sun Hongjuan et al. preparation, for needle-like, pattern is uncontrollable; Easily to environment in production process.
Summary of the invention
It is an object of the invention to the deficiency for prior art scheme, it is provided that a kind of low cost, high efficiency, morphology controllable the preparation method of semi-hydrated gypsum monocrystalline, to realize the Gypsum Fibrosum monocrystalline morphology controllable of preparation, the purpose of environmentally safe.
For reaching object above, the present invention adopts the following technical scheme that:
The control method of a kind of semi-hydrated gypsum monocrystalline oriented growth, it is characterised in that comprise the steps: successively
A, pretreatment of raw material: in ardealite, add acidity regulator, add water, mix homogeneously, ageing 24h; Wherein acidity regulator addition is the 1��10% of phosphogypsum quality; The addition of water is the 100��500% of phosphogypsum quality;
B, Gypsum Fibrosum monocrystalline preparation: step A obtain process ardealite pour into in the reactor of condensation reflux unit, add impurity stabilizer, crystal face selection adsorbent, after mix homogeneously, it is heated reaction, simultaneously plus ion motion controller in reaction system, react after terminating, cool down, filter, solid is dried, obtain semi-hydrated gypsum monocrystalline.
In the present invention: described impurity stabilizer addition is phosphogypsum quality 100��500%; Crystal face selection adsorbent addition is phosphogypsum quality 1��10% impurity stabilizer; Acidity regulator described in step A is the one in calcium oxide, calcium carbonate; Impurity stabilizer described in step B is the one in sorbitol, mannitol, glycerol; Crystal face selection adsorbent is the one in maleic acid, polycarboxylic acids, succinic acid; Ion motion controller described in step B, is a device that can produce alternating electric field or alternating magnetic field, its frequency-adjustable, and frequency is 0.1��50HZ; Reaction temperature described in step B is 90��120 DEG C, and the response time is 0.5��2 hour.
This method acidity regulator, adjusts the pH value of ardealite so that it is become neutrality from acidity, can avoid the acid solution corrosion to equipment. Impurity stabilizer, it is to avoid impurity element dissolves in the solution, it is to avoid the impurity impact on semi-hydrated gypsum crystal growth; The selectable particular crystal plane being adsorbed on monocrystalline of crystal face selection adsorbent, thus suppressing the growth of this crystallographic direction, makes crystal grow along other crystallographic direction, thus realizing oriented growth; Ion motion controller, is controlled the direction of motion and the speed of effects of ion, promotes ion ordered arrangement on monocrystalline, improve single crystal growth rate by electric field or magnetic field. This method phosphorous chemical industry produce waste residue be raw material, prepare Gypsum Fibrosum monocrystalline, this Gypsum Fibrosum has the advantages that crystal development is complete, intensity is high, as plastics, rubber, coating filler, its intensity can be improved; As gypsum sheet material, it is possible to obtain high strength gypsum sheet material. It is simple that this method has technique, the feature that cost is low, is suitable for industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
A, pretreatment of raw material:
Table 1 lists and is numbered in 13 embodiment pretreatments of raw material of 1��13 consumption of various raw materials: determine the addition of acidity regulator (calcium oxide, calcium carbonate) and water according to the embodiment that table 1 is different, and ageing 24h, ardealite raw material is carried out pretreatment.
Table 1 pretreatment of raw material (unit: g)
B: the preparation of Gypsum Fibrosum monocrystalline
Pour into in the reactor of condensation reflux unit in the step A ardealite that processes obtained, add impurity stabilizer, crystal face selection adsorbent, after mix homogeneously, it is heated reaction, simultaneously plus ion motion controller in reaction system, react after terminating, cool down, filter, solid is dried, obtain semi-hydrated gypsum monocrystalline.
The preparation (unit: g) of table 2 Gypsum Fibrosum monocrystalline
Note: alternating electric field 3000V/m, alternating magnetic field is 500 Gausses.
Embodiments of the invention all can be implemented and can reach goal of the invention, obtain the good semi-hydrated gypsum monocrystalline of crystallization, and pattern is short cylinder.
Claims (5)
1. the control method of a semi-hydrated gypsum monocrystalline oriented growth, it is characterised in that comprise the steps:
A, pretreatment of raw material: in ardealite, add acidity regulator, add water, mix homogeneously, ageing 24h; Wherein acidity regulator addition is the 1��10% of phosphogypsum quality; The addition of water is the 100��500% of phosphogypsum quality;
B, Gypsum Fibrosum monocrystalline preparation: step A obtain process ardealite pour into in the reactor of condensation reflux unit, add impurity stabilizer, crystal face selection adsorbent, after mix homogeneously, it is heated reaction, simultaneously plus ion motion controller in reaction system, react after terminating, cool down, filter, solid is dried, obtain semi-hydrated gypsum monocrystalline; Wherein impurity stabilizer addition is phosphogypsum quality 100��500%; Crystal face selection adsorbent addition is phosphogypsum quality 1��10%.
2. the control method of semi-hydrated gypsum monocrystalline oriented growth according to claim 1, it is characterised in that acidity regulator described in step A is the one in calcium oxide, calcium carbonate.
3. the control method of semi-hydrated gypsum monocrystalline oriented growth according to claim 1, it is characterised in that impurity stabilizer described in step B is the one in sorbitol, mannitol, glycerol; Crystal face selection adsorbent is the one in maleic acid, polycarboxylic acids, succinic acid.
4. the control method of semi-hydrated gypsum monocrystalline oriented growth according to claim 1, it is characterised in that ion motion controller described in step B, is a device that can produce alternating electric field or alternating magnetic field, and its frequency-adjustable, frequency is 0.1��50HZ.
5. the control method of semi-hydrated gypsum monocrystalline oriented growth according to claim 1, it is characterised in that reaction temperature described in step B is 90��120 DEG C, and the response time is 0.5��2 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442731A (en) * | 2020-11-06 | 2021-03-05 | 昆明理工大学 | Method for directionally regulating and controlling crystal transformation and growth by multiple physical fields |
| CN113046832A (en) * | 2021-03-10 | 2021-06-29 | 西安建筑科技大学 | Method for preparing calcium sulfate hemihydrate crystal whisker by short-period low-cost hydrothermal method |
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Cited By (3)
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| CN113046832A (en) * | 2021-03-10 | 2021-06-29 | 西安建筑科技大学 | Method for preparing calcium sulfate hemihydrate crystal whisker by short-period low-cost hydrothermal method |
| CN113046832B (en) * | 2021-03-10 | 2022-05-13 | 西安建筑科技大学 | Method for preparing calcium sulfate hemihydrate crystal whiskers through short-period low-cost hydrothermal method |
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