CN101264920A - Method for preparing micro-fine and ultra-fine calcium carbonate of different crystal forms from carbide slag - Google Patents
Method for preparing micro-fine and ultra-fine calcium carbonate of different crystal forms from carbide slag Download PDFInfo
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- CN101264920A CN101264920A CNA2008100687155A CN200810068715A CN101264920A CN 101264920 A CN101264920 A CN 101264920A CN A2008100687155 A CNA2008100687155 A CN A2008100687155A CN 200810068715 A CN200810068715 A CN 200810068715A CN 101264920 A CN101264920 A CN 101264920A
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Abstract
The invention discloses a preparation method of using carbide slag to produce different micro-and ultra-fine calcium carbonate of various crystal forms, belonging to the calcium carbonate. The method comprises four steps: the first step is the pretreatment of the carbide slag; the second step is the preparation of the calcium chloride solution; the third step is the metathesis reaction for the preparation of micro-and ultra-fine calcium carbonate; the fourth step is to filter and dry. The preparation method has the advantages that (1) the problem of environmental pollution brought by the emission of the carbide slag is solved; (2) since NH<SUB>4</SUB>C is not used for the preparation of calcium carbonate, the problem of environmental pollution caused by the NH<SUB>3</SUB> is solved; (3) using HCI to react with carbide slag makes Ca(OH)<SUB>2</SUB> in the carbide slag and CaCO<SUB>3</SUB> generated after the carbonation of carbide slag by air both transfer into CaCl<SUB>2</SUB>, improving the recovery rate of the carbide slag; (4) adopting the method of mixing directly the carbide slag and water and preparing the mixture into slurry, instead of traditional drying or high-temperature calcinations pretreatment, reduces the energy consumption in the pretreatment of the carbide slag. The preparation method is suitable for the enterprises using large amount of calcium carbide, in particular to the chloral-alkali enterprises with the PVC production line.
Description
Technical field
The present invention is relevant with the carbonate of calcium, specifically, is to be raw material with the carbide slag, adopts double decomposition to prepare the method for the fine and calcium carbonate superfine powder of different crystal forms.
Background technology
Carbide slag is that the alkaline scrap material that acetylene produces is produced in calcium carbide and water reaction, and its main component is a calcium hydroxide.Annual about 1,500 ten thousand tons of the calcium carbide that consumes of China produces 1.2 tons of calculating of waste residue by 1 ton of calcium carbide of every consumption at present, and the annual carbide slag that produces just reaches 1,800 ten thousand tons, and its utilization ratio less than 30%.The carbide slag bulk deposition, this is land occupation but also can cause secondary pollution not only.Therefore, the recycling of carbide slag is extremely urgent.
Developed at present carbide slag prepare highly active calcium oxide (CN88100820.6), as the desulfurization absorbent (CN99121910.4) of boiler smoke, be used to prepare high calcium carbide and produce calcium carbide (CN03135103.4), be used to make high pressure no-baking carbide residue brick (CN200510020443.8), as the raw material (CN200510021024.6) of cement clinker etc.Carbide slag contains a large amount of calcium hydroxide compositions, can also with its as feedstock production fine and calcium carbonate superfine powder, existing patent of invention mainly contains: with the method (CN1058005) of preparing high-purity technical calcium carbonate from calcium carbide dregs, production technique for ultramicrofine light calcium carbonate (CN1172073), a kind of preparation method of nm-class active calcium carbonate (CN1438178), method (CN1796284) with carbide slag manufacturing nm-class active calcium carbonate coproduction carbon dust prepares the method (CN1854069) of calcium carbonate superfine powder etc. with carbide slag.But, more than all have only the method utilize carbide slag to prepare the fine or calcium carbonate superfine powder of single crystalline form of introducing.And the preparation method adopts carbide slag washing, oven dry or incinerating pretreatment mode, thereby increases the cost of preparation lime carbonate.
Summary of the invention
The object of the present invention is to provide a kind of carbide slag to prepare the method for the fine and calcium carbonate superfine powder of different crystal forms, utilize the calcium hydroxide composition in the carbide slag, fine and the calcium carbonate superfine powder product of the different crystal forms that the production added value is high, to overcome the shortcoming of prior art, for a new road is opened up in the utilization of carbide slag.
Method of the present invention realizes by following 4 processing steps:
The pre-treatment of the first step carbide slag
Carbide slag is mixed with the water of certain mass, make carbide slag slurries.
The preparation of the second one-step chlorination calcium solution
The carbide slag slurries that makes by previous step constantly drips HCl under the effect of stirring, reach about 8 until the pH value of water solution of carbide slag, filters, and the filtrate that obtains is calcium chloride solution, and the principal reaction formula is as follows:
Ca(OH)
2+2HCl=CaCl
2+2H
2O
The 3rd step replacement(metathesis)reaction prepares fine and calcium carbonate superfine powder
Add activator in calcium chloride solution, again solution is placed thermostatic bath, drip sodium carbonate solution then in solution, the temperature of controlling thermostatic bath simultaneously arrives preset value, produces the precipitation of calcium carbonate of white, and the principal reaction formula is as follows:
CaCl
2+Na
2CO
3=CaCO
3+2NaCl
The 4th step filtration drying
To make precipitation of calcium carbonate by previous step, and filter, oven dry, grinding can make the fine and calcium carbonate superfine powder of different crystal forms respectively.
In the first step of above-mentioned technology, carbide slag: water (mass ratio)=1: 10~20.
In second step of above-mentioned technology, the HCl concentration of described dropping is 3~5mol/L;
In the 3rd step of above-mentioned technology, described activator is a Sodium dodecylbenzene sulfonate, and the add-on of activator is 1%~3% of a lime carbonate growing amount; Described thermostatic bath temperature is banded in 2~100 ℃, the temperature that wherein prepares crystalline form and be calcite type calcium carbonate is controlled at 2 ℃~10 ℃, the preparation crystalline form is that the temperature of vaterite-type calcium carbonate is controlled at 6 ℃~15 ℃, and the preparation crystalline form is that the temperature of aragonite calcium carbonate is controlled at 70 ℃~90 ℃; The concentration of sodium carbonate of described dropping is 0.05~0.1mol/L, and the rate of addition of yellow soda ash is 10~20mL/min.
The activator Sodium dodecylbenzene sulfonate can use separately, also can be shared with dehydrated alcohol.
In the 4th step of above-mentioned technology, the temperature of described oven dry precipitation of calcium carbonate is 105 ℃.
The present invention has the following advantages:
(1) solved the problem of environmental pollution that the carbide slag discharging brings;
(2) because without NH
4Cl prepares lime carbonate, has solved generation NH
3The destruction problem that ecotope is caused;
(3) with HCl and carbide slag reaction, can make the Ca (OH) in the carbide slag
2And after the carbide slag ageing by the CaCO that generates after the air carbonization
3All be converted into CaCl
2, and then can improve the rate of recovery of carbide slag.
(4) adopt carbide slag directly to be mixed with into slip, replace traditional drying or high-temperature calcination pre-treatment with water, thus the energy expenditure when having reduced the carbide slag pre-treatment.
The technological line that method of the present invention adopts can realize that the carbide slag pretreatment process is simple, simultaneously, can also prepare the lime carbonate of different crystal forms.Fine and the calcium carbonate superfine powder product of different crystal forms of preparation can be widely used in numerous aspects such as filler of high-grade paper product and high-grade daily chemical products, and this opens up a new road for the utilization ratio that improves carbide slag.The present invention is applicable to the enterprise of a large amount of use calcium carbides, is particularly useful for having the chlor-alkali enterprise of Production of PVC line.
Description of drawings
Fig. 1 is the lime carbonate of calcite type for crystalline form, and Fig. 2 is the lime carbonate of vaterite-type for crystalline form, and Fig. 3 is the lime carbonate of aragonitic for crystalline form.
Embodiment
Embodiment 1: in carbide slag: water (mass ratio)=ratio prepared slip in 1: 20, under the effect of magnetic agitation, the HCl of Dropwise 5 mol/L, the pH value of solution is reached about 8, leave standstill, filter the back and add Sodium dodecylbenzene sulfonate in filtrate, the add-on of control Sodium dodecylbenzene sulfonate is for generating 1% of lime carbonate quality, the sodium carbonate solution that drips 0.08mol/L with the speed of 19mL/min is reached home until reaction in filtrate then.Controlled temperature is at 5 ℃ in the reaction process simultaneously, and filtration, drying are after scanning electron microscope is analyzed product, and obtaining crystalline form is the lime carbonate of calcite type.
Embodiment 2: in carbide slag: water (mass ratio)=ratio prepared slip in 1: 20, under the effect of magnetic agitation, the HCl of Dropwise 5 mol/L, the pH value of solution is reached about 8, leave standstill, filter the back and add Sodium dodecylbenzene sulfonate in filtrate, the add-on of control Sodium dodecylbenzene sulfonate is for generating 1% of back lime carbonate quality, the sodium carbonate solution that drips 0.08mol/L with the speed of 19mL/min is reached home until reaction in filtrate then.Controlled temperature is at 12 ℃ in the reaction process simultaneously, and filtration, drying are after scanning electron microscope is analyzed product, and obtaining crystalline form is the lime carbonate of vaterite-type.
Embodiment 3: in carbide slag: water (mass ratio)=ratio prepared slip in 1: 20, under the effect of magnetic agitation, the HCl of Dropwise 5 mol/L, the pH value of solution is reached about 8, leave standstill, filter the back and add Sodium dodecylbenzene sulfonate in filtrate, the add-on of control Sodium dodecylbenzene sulfonate is for generating 1% of lime carbonate quality, the sodium carbonate solution that drips 0.08mol/L with the speed of 19mL/min is reached home until reaction in filtrate then.Controlled temperature is at 80 ℃ in the reaction process simultaneously, and filtration, drying are after scanning electron microscope is analyzed product, and obtaining crystalline form is the lime carbonate of aragonitic.
Claims (7)
1 one kinds of carbide slags prepare the method for the fine and calcium carbonate superfine powder of different crystal forms, it is characterized in that this method realizes by following 4 processing steps:
The pre-treatment of the first step carbide slag
Carbide slag is mixed with clear water, make carbide slag slurries;
The preparation of the second one-step chlorination calcium solution
The carbide slag slurries that makes by previous step constantly drips HCl under the effect of stirring, reach about 8 until the pH value of water solution of carbide slag, filters, and the filtrate that obtains is calcium chloride solution;
The 3rd step replacement(metathesis)reaction prepares fine and calcium carbonate superfine powder
Add activator in calcium chloride solution, again solution is placed thermostatic bath, drip sodium carbonate solution then in solution, the temperature of controlling thermostatic bath simultaneously arrives preset value, produces the precipitation of calcium carbonate of white;
The 4th step filtration drying
To make precipitation of calcium carbonate by previous step, and filter, oven dry, grinding can make the fine and calcium carbonate superfine powder of different crystal forms respectively.
2 in accordance with the method for claim 1, it is characterized in that in the first step of described technology, and the mass ratio of described carbide slag and water is 1: 10~20.
3 in accordance with the method for claim 1, it is characterized in that the HCl concentration of described dropping is 3~5mol/L in second step of described technology;
4 in accordance with the method for claim 1, it is characterized in that described activator is a Sodium dodecylbenzene sulfonate in the 3rd step of described technology, and the activator add-on is 1%~3% of a lime carbonate growing amount; Described thermostatic bath temperature is banded in 2 ℃~100 ℃; The concentration of sodium carbonate of described dropping is 0.05~0.1mol/L, and the rate of addition of yellow soda ash is 10~20mL/min.
5 according to claim 1 or 4 described methods, the temperature that it is characterized in that preparing crystalline form and be calcite type calcium carbonate is controlled at 2 ℃~10 ℃, the preparation crystalline form is that the temperature of vaterite-type calcium carbonate is controlled at 6 ℃~15 ℃, and the preparation crystalline form is that the temperature of aragonite calcium carbonate is controlled at 70 ℃~90 ℃.
6 according to claim 1 and 4 described methods, it is characterized in that the activator Sodium dodecylbenzene sulfonate uses separately, or shared with dehydrated alcohol.
7 in accordance with the method for claim 1, it is characterized in that the temperature of described oven dry precipitation of calcium carbonate is 105 ℃ in the 4th step of described technology.
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Cited By (11)
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CN101792156A (en) * | 2009-07-17 | 2010-08-04 | 王嘉兴 | Method for producing granular sodium hydroxide and coproducing calcium carbonate by using carbide slag |
CN102249281A (en) * | 2011-06-16 | 2011-11-23 | 山东大学 | Lensing spherical vaterite calcium carbonate crystal with high purity and preparation method thereof |
CN103172100A (en) * | 2011-12-23 | 2013-06-26 | 杨晓林 | Method for preparing calcium carbonate in different grain sizes |
CN103663530A (en) * | 2013-12-04 | 2014-03-26 | 中国中材国际工程股份有限公司 | Method for preparing calcium carbonate powder |
CN104386729A (en) * | 2014-11-18 | 2015-03-04 | 辽宁石化职业技术学院 | Method for quickly preparing superfine calcium carbonate with co-product of ammonium chloride |
CN106219586A (en) * | 2016-08-02 | 2016-12-14 | 王延军 | A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method |
CN108084495A (en) * | 2017-12-08 | 2018-05-29 | 安徽新涛新材料科技股份有限公司 | The method that calcium carbonate superfine powder is prepared using carbide slag |
CN108483478A (en) * | 2018-05-21 | 2018-09-04 | 山西大学 | A method of preparing three kinds of crystal configuration calcium carbonate granules |
CN109354051A (en) * | 2018-12-03 | 2019-02-19 | 衡阳师范学院 | A method of calcium carbonate is prepared in Galuber's salt type brine cleaning procedure using carbide slag substitution lime |
CN110304845A (en) * | 2019-08-22 | 2019-10-08 | 新疆德安环保科技股份有限公司 | The method for preparing quick lime with the dry slag of calcium carbide and producing nanometer calcium carbonate using it |
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CN101792156A (en) * | 2009-07-17 | 2010-08-04 | 王嘉兴 | Method for producing granular sodium hydroxide and coproducing calcium carbonate by using carbide slag |
CN101792156B (en) * | 2009-07-17 | 2011-06-22 | 王嘉兴 | Method for producing granular sodium hydroxide and coproducing calcium carbonate by using carbide slag |
CN102249281A (en) * | 2011-06-16 | 2011-11-23 | 山东大学 | Lensing spherical vaterite calcium carbonate crystal with high purity and preparation method thereof |
CN103172100A (en) * | 2011-12-23 | 2013-06-26 | 杨晓林 | Method for preparing calcium carbonate in different grain sizes |
CN103663530B (en) * | 2013-12-04 | 2016-03-02 | 中国中材国际工程股份有限公司 | A kind of preparation method of calcium carbonate powder |
CN103663530A (en) * | 2013-12-04 | 2014-03-26 | 中国中材国际工程股份有限公司 | Method for preparing calcium carbonate powder |
CN104386729A (en) * | 2014-11-18 | 2015-03-04 | 辽宁石化职业技术学院 | Method for quickly preparing superfine calcium carbonate with co-product of ammonium chloride |
CN104386729B (en) * | 2014-11-18 | 2016-03-23 | 辽宁石化职业技术学院 | A kind of method preparing calcium carbonate superfine powder combined producting ammonium chloride fast |
CN106219586A (en) * | 2016-08-02 | 2016-12-14 | 王延军 | A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method |
CN108084495A (en) * | 2017-12-08 | 2018-05-29 | 安徽新涛新材料科技股份有限公司 | The method that calcium carbonate superfine powder is prepared using carbide slag |
CN108483478A (en) * | 2018-05-21 | 2018-09-04 | 山西大学 | A method of preparing three kinds of crystal configuration calcium carbonate granules |
CN109354051A (en) * | 2018-12-03 | 2019-02-19 | 衡阳师范学院 | A method of calcium carbonate is prepared in Galuber's salt type brine cleaning procedure using carbide slag substitution lime |
CN110304845A (en) * | 2019-08-22 | 2019-10-08 | 新疆德安环保科技股份有限公司 | The method for preparing quick lime with the dry slag of calcium carbide and producing nanometer calcium carbonate using it |
CN111717928A (en) * | 2020-04-24 | 2020-09-29 | 广西科学院 | Method for preparing nano calcium carbonate by in-situ electrochemical precipitation technology |
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