CN101519221B - Method for synthesizing hydrated calcium chloroaluminate - Google Patents
Method for synthesizing hydrated calcium chloroaluminate Download PDFInfo
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- CN101519221B CN101519221B CN2009100465099A CN200910046509A CN101519221B CN 101519221 B CN101519221 B CN 101519221B CN 2009100465099 A CN2009100465099 A CN 2009100465099A CN 200910046509 A CN200910046509 A CN 200910046509A CN 101519221 B CN101519221 B CN 101519221B
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- hydrated calcium
- calcium chloroaluminate
- aluminate cement
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Abstract
The invention relates to a method for synthesizing hydrated calcium chloroaluminate, which belongs to the technical field of water treatment adsorbents. The method comprises the following steps: under a stirring condition with ultrasonic waves, mixing CaCl2, Ca(OH)2 and aluminate cement in deionized water evenly according to a mass ratio of 24:31:45, and then putting the mixture into a constant-temperature water bath oscillator for oscillating for 24 to 72 hours; and drying the mixture after pumping filtration, and finally synthesizing the hydrated calcium chloroaluminate, a similar LDH substance with Cl ions among layers, through the hydration reaction process of the aluminate cement together with the CaCl2 and the Ca(OH)2. A new way for synthesizing the hydrated calcium chloroaluminate is provided, and a mass-production method of pollutant adsorbents is obtained simultaneously.
Description
Technical field
The present invention is a kind of synthetic method of hydrated calcium chloroaluminate, belongs to the water treatment absorbent technical field.
Background technology
Clay is a modal inorganic macromolecule material on the earth.Annual in the world have several hundred million ten thousand tons clay or clay mineral to be applied in aspects such as pottery, material of construction, field drilling liquid slurry, casting mould, medicine according to different characteristics, as functional materialss such as catalyzer (or support of the catalyst), sorbent material, ion-exchanger and fire retardants.Clay material divides usually makes cationic clay and anionic clay (stratiform complex hydroxide LDHs) two big classes, and the former extensively is present in nature, and the natural reserves of the latter are low but relatively easily synthetic and cost suitability for industrialized production is low.Cationic clay is obtained by natural mineral processing usually, and the anionic clay material is then mainly prepared by chemical synthesis.For to pollution problem and the optimized consideration of commercial run, need to substitute liquid acids, alkaline catalysts and traditional high pollution chemical with environmentally friendly solid catalyst and preparation.Anionic clay is because the advantage such as cheap of the wide in range property of the Modulatory character of the height universality of using, structure and synthetic factors vary and preparation cost, often is counted as the novel environmental friendly materials of tool application prospect.People carried out number of research projects to the LDHs various uses, and were expected to obtain important breakthrough in more novel field in the near future.
But present, the synthetic method of LDHs has
1. direct synthesis technique
Many kinds of hydrotalcites can directly synthesize.For example, the magnesium aluminum-hydrotalcite that contains can at room temperature add alkali lye with the nitrate wiring solution-forming of magnesium, aluminium, regulator solution pH value, and crystallization, washing is drying to obtain product.
2. ion exchange method
Utilize the anionic interchangeability of hydrotalcite, the negatively charged ion of required insertion and the negatively charged ion of hydrotalcite layers are exchanged under certain condition.This method is with unstable in alkaline medium, or employing when negatively charged ion does not have soluble salt when.PH value in the swelling of the degree that ion exchange reaction is carried out and ionic exchange capacity, layer and swelling agent, the exchange process and once accompanied factor such as electric density relevant.
3. roasting restoring method
Roast reduction process is that the hydrotalcite-like material with roasting under the certain temperature joins and contains in certain anionic aqueous solution, and the layer pole structure of this class material is rebuild, and the negatively charged ion in the solution can enter layer and ask, forms new columnar water talc materials.When adopting roast reduction process, must note the maturing temperature of fertile material.Generally speaking, maturing temperature does not surpass 500 ℃, and temperature is too high can to form spinel, and structure can not be rebuild.This method is generally used for the bigger hydrotalcite-based compound of synthetic anionic volume, is particularly suitable for negatively charged ion such as various oxysalts, organic acid salt.Utilize this legal system to be equipped with the influence that hydrotalcite compound is subjected to factors such as Mg-Al ratio, drying conditions, maturing temperature, roasting time, pH value, especially calcining temperature has considerable influence to catalyzer alkalescence and specific surface area.At 500～800 ℃, along with the rising of calcining temperature, catalyzer basic center quantity reduces, and specific surface area reduces, and catalytic activity descends.
4. hydrothermal method
The method of Hydrothermal Preparation oxyhydroxide is exactly to adopt to contain the divalent that can form hydrotalcite and the oxide compound or the oxyhydroxide of 3 valency metallic cations, and is mixed with alkaline solution, carries out hydrothermal treatment consists under high temperature, high pressure.Because at high temperature, the atom of metal oxide or oxyhydroxide rearranges, thereby forms hydrotalcite-based compound.Oxide compound or oxyhydroxide commonly used are Al2O3, MgO, Mg (OH) 2 etc.
Above method exists power consumption big, and efficient is low, and the raw material costliness waits some problems.
Hydrated calcium chloroaluminate (also being the Friedel compound) is a stranger compound, chemical formula is 3CaOAl2O3CaCl210H2O, also be the thermodynamically stable phase of concrete material in briny environment simultaneously, the formation of inducing it is the material design basis that suppresses the maritime concrete steel bar corrosion.Hydrated calcium chloroaluminate is to heavy metal, and pollutents such as phosphorus all have removes ability preferably.
Common anionic layer stability is followed successively by
CO32-＞OH-＞SO42-＞HPO42-＞F-＞Cl-＞B-＞NO3-＞I-; The LDH that contains NO3-and Cl-is considered to the optimal presoma of ion exchange reaction usually.This patent synthetic hydrated calcium chloroaluminate is exactly the Cl-LDHs of extensive applying value.
Since the interlayer structure of LDHs, anionic interchangeability with and memory effect, extensively apply to absorption, catalysis, field such as fire-retardant.But generally its synthetic method more complicated has coprecipitation method, the sol-gel method ion exchange method, and the pillared method of roasting etc., but the general condition control ratio is strict or consume energy higherly, and scale operation inconvenience or cost are too high.The cheapness of development of new of the present invention, convenient feasible hydrated calcium chloroaluminate synthetic method.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of cheapness, energy consumption is low and technology is easy hydrated calcium chloroaluminate.
The objective of the invention is to be achieved through the following technical solutions.
A kind of synthetic method of hydrated calcium chloroaluminate is characterized in that this method has following technological process and step:
A. with CaCl
2, Ca (OH)
2With CA50 type aluminate cement be to take by weighing powder, Ca (OH) at 24: 31: 45 by mass ratio
2Grind and cross 80 mesh sieves respectively with aluminate cement; With CaCl
2Add Erlenmeyer flask and add the proper amount of deionized water dissolving, again with Ca (OH)
2Drop in the Erlenmeyer flask, carry out ultrasonic vibration and mechanical stirring, when treating that turbid solution is uniformly dispersed, at the uniform velocity slowly drop into aluminate cement in about 20min;
B. Erlenmeyer flask is taken out, put into the water bath with thermostatic control vibrator after sealing at 30～50 ℃ of 24～72h that vibrate down; With getting solid-like behind the sample suction filtration in the Erlenmeyer flask 65 ℃ of oven dry, promptly obtaining the synthetic hydrated calcium chloroaluminate is main microparticle.
Described CA50 type aluminate cement refers to meet GB GB 201-2000, in aluminate cement the Al element with CA that can aquation, C2A, patterns such as C3A exist.Described ultrasonic vibration and mechanical stirring can be made ultrasonic wave microcell oscillator field in corresponding container, and make small particles in liquid thorough mixing uniform contact under mechanical stirring oar or the stirring of the magnetic stirring apparatus overall situation.CaCl
2, Ca (OH)
2Participate in the hydration reaction process of aluminate cement, making its last synthetic product main component is hydrated calcium chloroaluminate, has the Ca/Al laminate structure, and its chemical formula is 3CaOAl
2O
3CaCl
210H
2O.
The invention effect: the method for industrial large quantities of synthesizing hydrated calcium chloroaluminates is not arranged at present, and the existing laboratory synthesizing hydrated calcium chloroaluminate method that can find has coprecipitation method, high-temperature firing C3A phase synthesi.Wherein high-temperature firing C3A synthesis method is the method for using often, and it is with CaO and Al (OH)
3Repeatedly 1350 ℃ add the pure C3A of thermosetting again with the CaCl2 synthesizing hydrated calcium chloroaluminate.This method power consumption is high, is difficult for large quantities of synthetic.Present method directly adopts aluminate cement, has saved synthetic C3A process required a large amount of energy consumptions and technological process, the synthetic easily hydrated calcium chloroaluminate that has the environmental improvement potentiality.
The present invention utilizes CaCl
2, Ca (OH)
2With the CA in the aluminate cement, the common aquation of materials such as C2A forms the principle of hydrated calcium chloroaluminate, reaches the synthetic effect.The collection of illustrative plates of analyzing according to XRD (X-ray diffraction) can prove material composition, and XRD three strongest ones line is very obvious, and clearly laminate structure is arranged, and with the PDF2-2004 database of ICCD (diffraction data International Centre) in card number be that the collection of illustrative plates of 31-0245 is corresponding.The synthetics chemical formula is 3CaOAl
2O
3CaCl
210H2O shows and synthesizes successfully.
Present method is by the mixing hydration reaction between the solid phase under the water effect, and synthetic have pollutent constraint special construction ability, LDHs and characteristic and compounds such as negatively charged ion interchangeability, memory effect.Synthetic LDHs provides new way for cheapness, also obtains a kind of mass production method of pollutant absorbent simultaneously.
Characteristics of the present invention: the ingenious CaCl that utilizes of the present invention
2, Ca (OH)
2With the characteristic of aluminate cement, CaCl
2Provide calcium source and chlorine source, Ca (OH)
2The calcium source is provided and keeps pH, easy synthesizing hydrated calcium chloroaluminate dexterously.And the present invention adopts cheap raw material aluminate cement, CaCl
2, Ca (OH)
2, operation is easy, makes extensive synthesizing hydrated calcium chloroaluminate become possibility, and very big environmental potential is arranged.Hydrated calcium chloroaluminate is to various heavy, and pollutents such as phosphorus all have removes ability preferably, is a kind of novel and efficient environment-friendly materials.Can be widely used in the adsorption treatment of waste water.
Description of drawings
Fig. 1 synthesizer figure
Fig. 2 synthesis process flow diagram
The XRD analysis figure of Fig. 3 synthesizing hydrated calcium chloroaluminate
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Concrete synthetic route as shown in Figure 2.With CaCl
2, Ca (OH)
2, the powder of CA50 type aluminate cement is respectively 24g with quality, 31g, and 45g weighs up, Ca (OH)
2Grind and cross 80 mesh sieves respectively with aluminate cement.Earlier with CaCl
2Add Erlenmeyer flask and add the 400g deionized water dissolving, again with the Ca (OH) that weighs up
2Drop in the Erlenmeyer flask, the beginning ultrasonic vibration adds mechanical stirring.When treating that turbid solution is uniformly dispersed, from ultrasonic vibration and mechanical stirring, take out after at the uniform velocity slowly dropping into aluminate cement in about 20min, seal and put into the 72h that vibrates under 40 ℃ of temperature of water bath with thermostatic control vibrator.Concussion is main microparticle with getting 65 ℃ of oven dry of solid-like behind the sample suction filtration in the Erlenmeyer flask, promptly obtaining the synthetic hydrated calcium chloroaluminate later, and it generates the product chemical formula is 3CaOAl
2O
3CaCl
210H
2O.
Claims (1)
1. the synthetic method of a hydrated calcium chloroaluminate is characterized in that this method has following technological process and step:
A. with CaCl
2, Ca (OH)
2With CA50 type aluminate cement be to take by weighing powder, Ca (OH) at 24: 31: 45 by mass ratio
2Grind and cross 80 mesh sieves respectively with aluminate cement; With CaCl
2Add Erlenmeyer flask and add the proper amount of deionized water dissolving, again with Ca (OH)
2Drop in the Erlenmeyer flask, carry out ultrasonic vibration and mechanical stirring, when treating that turbid solution is uniformly dispersed, in 20min, at the uniform velocity slowly drop into aluminate cement;
B. Erlenmeyer flask is taken out, put into the water bath with thermostatic control vibrator after sealing at 30～50 ℃ of 24～72h that vibrate down; With getting solid-like behind the sample suction filtration in the Erlenmeyer flask 65 ℃ of oven dry, promptly obtaining the synthetic hydrated calcium chloroaluminate is main microparticle.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102294218B (en) * | 2011-03-01 | 2013-04-17 | 章兴华 | Method for producing Fred salts |
| CN103435066B (en) * | 2013-08-15 | 2015-11-04 | 江苏隆昌化工有限公司 | A kind of Resource comprehensive utilization method for ammonium chloride |
| CN104509531A (en) * | 2014-11-17 | 2015-04-15 | 江苏隆昌化工有限公司 | One-step assembly synthesis method of pesticide calcium chloroaluminate sustained release agent |
| CN104355387A (en) * | 2014-11-17 | 2015-02-18 | 江苏隆昌化工有限公司 | Phosphorus wastewater treatment method |
| CN104984725A (en) * | 2015-07-10 | 2015-10-21 | 常州市宏硕电子有限公司 | Hydrated calcium aluminate and preparation method thereof |
| CN108236937B (en) * | 2017-01-23 | 2020-10-23 | 常州清流环保科技有限公司 | Preparation method of hydrated calcium chloroaluminate |
| CN107312543A (en) * | 2017-07-06 | 2017-11-03 | 江苏隆昌化工有限公司 | A kind of heavy metal polluted soil of farmland repairs the preparation method of mineralizer |
| CN107936974A (en) * | 2017-11-14 | 2018-04-20 | 江苏隆昌化工有限公司 | A kind of method for reducing pollution of chromium farmland crops chromium content |
| CN108217775B (en) * | 2018-02-05 | 2022-04-29 | 合肥市联任科技有限公司 | Chlorine-containing wastewater treatment agent and preparation method thereof |
| CN108840356A (en) * | 2018-08-01 | 2018-11-20 | 江苏隆昌化工有限公司 | A kind of hydrated calcium chloroaluminate raw powder's production technology |
| CN110339807B (en) * | 2019-06-04 | 2022-07-08 | 南京工业大学 | Method for preparing hydrated calcium chloroaluminate |
| CN110314644A (en) * | 2019-07-24 | 2019-10-11 | 西安建筑科技大学 | A kind of sulphate aluminium cement-bentonite composite material and its preparation method and application for adsorbing heavy metal ion |
| CN113683249B (en) * | 2021-09-08 | 2022-07-12 | 山东国舜建设集团有限公司 | Method for removing chloride ions in desulfurization wastewater |
| CN114804174A (en) * | 2022-02-25 | 2022-07-29 | 茂名市和亿化工有限公司 | Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure |
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Non-Patent Citations (5)
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| JP特开平11-268937A 1999.10.05 |
| 朱建平 等.Alinite及C11A7 CaCl2矿物的合成.《济南大学学报（自然科学版）》.2002,第16卷(第1期),28-29，68. |
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Inventor after: Ren Zhong Inventor after: He Ying Inventor after: Yi Weifeng Inventor after: Yang Tao Inventor after: Xia Yaojun Inventor after: Zhao Wei Inventor after: Qian Guangren Inventor before: Ren Zhong Inventor before: Yi Weifeng Inventor before: Yang Tao Inventor before: Xia Yaojun Inventor before: Zhao Wei Inventor before: Qian Guangren |
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Effective date of registration: 20100906 Address after: 200444 Baoshan District Road, Shanghai, No. 99 Applicant after: Shanghai University Co-applicant after: Shanghai Solid Waste Management Center Address before: 200444 Baoshan District Road, Shanghai, No. 99 Applicant before: Shanghai University |
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