CN1552959A - Preparing process for calcium carbonate crystal whisker - Google Patents
Preparing process for calcium carbonate crystal whisker Download PDFInfo
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- CN1552959A CN1552959A CNA031342876A CN03134287A CN1552959A CN 1552959 A CN1552959 A CN 1552959A CN A031342876 A CNA031342876 A CN A031342876A CN 03134287 A CN03134287 A CN 03134287A CN 1552959 A CN1552959 A CN 1552959A
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- calcium carbonate
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- carbonate whiskers
- unslaked lime
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Abstract
Whiskers of calcium carbonate are prepared by: slaking, reactive liquid preparing, carbonating, finishing and recovering. The process is of easy control and operation with short preparing period, low cost and quality products.
Description
Technical field
The present invention relates to a kind of Synthesis of Calcium Carbonate Whiskers technology.
Background technology
Whisker is that diameter is that several microns, length are tens microns single crystal filamentary material.The kind of whisker is a lot of at present, and calcium carbonate crystal whisker is exactly one of them.As a kind of novel crystal whisker materials, calcium carbonate crystal whisker has characteristics such as intensity height, modulus height, heat-resisting heat-proof quality be good, is widely used in the manufacturing of plastics, rubber, coating, papermaking, electric component, the fields such as manufacturing of best bright finish structure unit.
The Synthesis of Calcium Carbonate Whiskers method is a lot, can be divided into following four kinds on technology: soluble calcium salt and soluble carbon hydrochlorate preparation method; The hydrolysis of urea preparation method; The Calcium hydrogen carbonate preparation method; Calcium hydroxide-carbonic acid gas gas-liquid preparation method.Soluble calcium salt is to utilize soluble calcium salt to mix with the soluble carbon hydrochlorate with soluble carbon hydrochlorate preparation method, and temperature is controlled at 90 ° and reacts, and prepares calcium carbonate crystal whisker; The urea water solution is to utilize nitrocalcite-urea system and calcium chloride-urea system, and control certain reaction condition is made whisker; The Calcium hydrogen carbonate preparation method is to be that 97.5% limestone powder is scattered in 2 ℃ the water with purity, feeds CO
2Gas is made the Calcium hydrogen carbonate aqueous solution earlier, by the conditions such as Heating temperature, heat-up rate, stirring velocity of control calcium bicarbonate solution, prepares calcium carbonate crystal whisker then; Calcium hydroxide-carbonic acid gas gas-liquid prepared in reaction method is the phosphoric acid series compound that adds the needle-like calcium carbonate crystal seed of 1-2um in advance and help the growth of whisker length direction in calcium hydroxide slurry, and, prepare calcium carbonate crystal whisker by controlling the conditions such as feeding amount of gas liquid reaction condition and carbonic acid gas.The whisker that different preparation methods produces, it varies in size, the yield difference.Preceding two kinds of method deficiencies in economic performance, back two kinds of method economy and easy to operate, but be difficult for mixing when adding needle-like calcium carbonate whisker and phosphoric acid series compound.
Summary of the invention
The Synthesis of Calcium Carbonate Whiskers technology of the purpose of this invention is to provide that a kind of cost is low, easy and simple to handle, catalyzer can uniform mixing, quality is good, yield is high.
Purpose of the present invention can realize by following measure:
A kind of Synthesis of Calcium Carbonate Whiskers method comprises following processing step:
(1) digestion operation: unslaked lime, water are mixed, stir with certain proportion, make slip;
(2) reaction solution preparation section: prepare certain density magnesium chloride solution,, and, form reaction solution with the adding in certain proportion of above-mentioned digestion operation finish mix slurry as reaction environment and catalyzer;
(3) carbonation process: reaction solution is heated to certain temperature, feeds carbon dioxide and carry out carbonation reaction;
(4) postprocessing working procedures: resultant of reaction is carried out separating and filtering, washing, oven dry, obtain the calcium carbonate crystal whisker product.
The processing step of described calcium carbonate crystal whisker preparation also comprises recovery process: filtered mother liquor is recyclable to be reused to reaction solution.
The concentration of described magnesium chloride solution is 4-5%.
The add-on of described unslaked lime is the unslaked lime that adds the 2-3 kilogram in per 100 kilograms of reaction solutions.
The temperature of described carbonation reaction is 70-90 °.
The pressure 1.0-1.5Mpa of described carbonation reaction.
The time of described carbonation reaction is 2-3 hour.
The present invention compared with prior art has the following advantages:
1, the present invention is the calcium raw material with unslaked lime, with magnesium chloride as catalyzer, and these body matrixes join in the solution system can uniform mixing, make carbonation reaction abundant, the calcium carbonate crystal whisker quality of producing is good, yield is high.
2, technology of the present invention be easy to control, easy and simple to handle, cost is low, preparation cycle is short, be easy to accomplish scale production.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
A kind of Synthesis of Calcium Carbonate Whiskers method comprises following processing step: drop into 2.1 kilograms unslaked lime in 10 kilograms the water (1), stirs and make its thorough mixing, makes the unslaked lime slip, leaves standstill some minutes; (2) get 4.3 kilograms of magnesium chloride material dissolutions in 90 kilograms water, the magnesium chloride solution of making concentration and be 4-5% is as reaction environment and catalyzer, and stir in the adding bubbling stirring tank, the unslaked lime slip that above-mentioned operation is made is added in the bubbling stirring tank and forms reaction solution again; (3) reaction solution is heated to 70-90 ℃, dioxo gas was fed reaction solution 2-6 hour by the gas distributor below the stirring tank, make the abundant carbonization of reaction solution; (4) resultant of reaction is filtered, washs, dries through whizzer, obtain the calcium carbonate crystal whisker product; Mother liquor after the filtration is delivered in the reactor and is reused, and measures its concentration, as does not reach requirement, can replenish certain magnesium chloride reagent in reaction solution.
Product is accredited as pure phase through the X-ray diffraction heavily fortified point, and calcium carbonate content is 92.8% in the product, and mean diameter is 0.5-1um, and mean length is 5-20um, and yield is 80%.
The source of raw material: the more unslaked lime place of production is arranged near the Xining, as the unslaked lime of the county's product of helping each other, the content height of CaO, Mg
2+Content low, be more satisfactory unslaked lime raw material.
Selection of technological conditions
1, determining of density of magnesium chloride: the concentration of magnesium chloride in mother liquor is the primary influence factor of carbonation reaction, and the quality and the pattern of calcium carbonate crystal whisker had tangible influence.With G in the carbonation reaction terminal point mother liquor
2+Concentration is judged, G
2+The concentration height, then carburizing reagent is complete, calcium carbonate crystal whisker quality height (down together).Table 1 is the test situation of density of magnesium chloride to carbonation reaction and calcium carbonate crystal whisker quality influence:
The input amount of table 1:(unslaked lime is the input amount in per 100 kilograms of mother liquors)
| Sequence number | Magnesium chloride initial concentration (W t％) | Unslaked lime input amount (kg) | Production intensity (kg/hr) | Quality product | Whisker length (um) | |
| ????Ga 2+(Wt％) | ????Mg 2+(Wt％) | |||||
| ??1 | ????0.10 | ??2.4 | ??0.7 | ????36.38 | ????1.76 | ????5-10 |
| ??2 | ????1.88 | ??2.0 | ??1.0 | ????37.74 | ????1.15 | ????5-15 |
| ??3 | ????3.93 | ??2.2 | ??0.93 | ????37.46 | ????0.46 | ????5-15 |
| ??4 | ????4.82 | ??1.1 | ??1.2 | ????38.22 | ????1.66 | ????10-20 |
From several index comprehensives of last table more as can be seen: the carbonation reaction result is comparatively desirable when the initial concentration of magnesium chloride the mother liquor is 4-5%.
2, determining of unslaked lime input amount: the add-on of unslaked lime can influence Mg in the solution (OH)
2The quantity of gelatinous precipitate, and then influence the flow state of mother liquor, be unfavorable for carbonation reaction speed: on the other hand, the an amount of add-on that increases unslaked lime, can increase the solid-to-liquid ratio of solution, the production intensity of carbonization jar, whizzer is increased, reduce production costs, therefore suitable unslaked lime add-on also is a very important technical parameters.The add-on of unslaked lime sees Table 2 experimental result to the influence of carbonation reaction:
The add-on of table 2:(unslaked lime is the input amount in per 100 kilograms of mother liquors)
| Sequence number | Unslaked lime input amount (kg) | Production intensity (kg/hr) | Quality product | Whisker length (um) | |
| ????Ga 2+(Wt％) | ????Mg 2+(Wt％) | ||||
| ????1 | ??0.8 | ????0.25 | ????37.83 | ????0.56 | ????10-25 |
| ????2 | ??1.1 | ????0.72 | ????38.22 | ????1.66 | ????10-25 |
| ????3 | ??1.6 | ????0.67 | ????38.18 | ????0.91 | ????15-25 |
| ????4 | ??2.0 | ????0.83 | ????37.18 | ????0.92 | ????15-20 |
| ????5 | ??3.0 | ????1.26 | ????36.15 | ????2.77 | ????10-16 |
| ????6 | ??4.0 | ????1.14 | ????36.58 | ????2.08 | ????10-15 |
As can be seen from the above table, along with the increase of charging capacity, the length and the quality product of whisker increase to some extent, and production intensity increases to some extent, but charging capacity is excessive, because the viscosity of solution is too big, production intensity descends on the contrary.The feeding quantity of taking all factors into consideration aspect unslaked limes such as quality product, production cost, production intensity is with in per 100 kilograms of mother liquors, and the unslaked lime that adds the 2-3 kilogram is advisable.
3, determining of carbonation reaction pressure: along with the increase of carbonization pressure tank, solution top CO
2Dividing potential drop can increase, dissolved CO in the solution
2Concentration increases, and carbonic acid changes speed of response to be accelerated.On the other hand, pressure increases, and can increase the manufacturing cost of equipment, reduces the security of using, and therefore, suitable reaction pressure also is one of important processing condition.Pressure sees Table 3 experimental result to the influence of carburizing reagent.
Table 3 (add-on of unslaked lime is the input amount in per 100 kilograms of mother liquors)
| Sequence number | Pressure (Mpa) | Unslaked lime input amount (kg) | Production intensity (kg/hr) | Quality product | Whisker length (um) | |
| ????Ga 2+(Wt％) | ????Mg 2+(Wt％) | |||||
| ????1 | ????0.5 | ????2.0 | ????0.7 | ????33.71 | ????5.44 | ????7-14 |
| ????2 | ????1.0 | ????2.0 | ????0.83 | ????38.10 | ????0.61 | ????15-25 |
| ????3 | ????1.5 | ????2.0 | ????1.14 | ????37.55 | ????0.37 | ????15-25 |
| ????4 | ????2.0 | ????2.0 | ????0.93 | ????37.19 | ????1.06 | ????15-25 |
From the experiment of table 3 as can be seen, reaction pressure is during less than 1.0Mpa, and production intensity is low, and carbonation reaction is incomplete; Reaction pressure is during greater than 1.5Mpa, and production intensity and quality product do not have obvious raising, so reaction pressure is relatively more suitable reaction conditions between 1.0-1.5Mpa.
4, determining of the temperature of reaction solution: in general, the temperature of reaction solution is high more, and speed of response is fast more, and carbonation reaction is complete more, and the quality of product is good more.So the temperature of reaction solution generally is controlled at 70-90 ℃ and is advisable.
5, carbon dioxide feeds determining of time: CO
2The time that feeds is long more, and carburizing reagent is complete more, but is vented to the regular hour, and carbonation reaction is finished fully, if feed CO again
2Gas is just nonsensical.Below by measuring Ga in the solution
2+Concentration, can obtain the data that carbonation reaction carries out degree.Experimental result sees Table 4.
Table 4
| Time (min) | 0.0 | ?20 | ?40 | ?60 | ?80 | ?120 | ?150 | ?180 |
| Ga 2+(Wt％) | 1.56 | ?1.49 | ?1.22 | ?1.06 | ?0.85 | ?0.53 | ?0.23 | ?0.07 |
| Reaction completeness (%) | 0 | ?4.5 | ?21.8 | ?32.1 | ?45.5 | ?66.0 | ?85.3 | ?95.6 |
From the experiment of table 4 as can be seen, the reaction times was controlled at 2-3 hour, and carbonation reaction is finished substantially.Therefore, the feeding time of carbon dioxide should be determined at 2-3 hour.
Determining of equipment
1, carbonization jar material: stainless steel; Volume rotating speed of agitator: 85rpm/min; 0.3 it is withstand voltage: Mpa.
2, whizzer material: stainless steel; Effective filtration area: 0.25m
2Power of motor: 1.5kw.
Claims (7)
1, a kind of Synthesis of Calcium Carbonate Whiskers method comprises following processing step:
(1) digestion operation: unslaked lime, water are mixed, stir with certain proportion, make slip;
(2) reaction solution preparation section: prepare certain density magnesium chloride solution, as reaction environment and catalyzer, and with above-mentioned digestion operation finish mix slurry adding formation in certain proportion reaction solution;
(3) carbonation process: reaction solution is heated to certain temperature, feeds carbon dioxide and carry out carbonation reaction;
(4) postprocessing working procedures: resultant of reaction is carried out separating and filtering, washing, oven dry, obtain the calcium carbonate crystal whisker product.
2, Synthesis of Calcium Carbonate Whiskers technology as claimed in claim 1, it is characterized in that: its processing step also comprises recovery process: filtered mother liquor is recyclable to be reused to reaction solution.
3, Synthesis of Calcium Carbonate Whiskers technology as claimed in claim 1 or 2 is characterized in that: the concentration of described magnesium chloride solution is 4-5%.
4, Synthesis of Calcium Carbonate Whiskers technology as claimed in claim 1 or 2 is characterized in that: the add-on of described unslaked lime is the unslaked lime that adds the 2-3 kilogram in per 100 kilograms of reaction solutions.
5, Synthesis of Calcium Carbonate Whiskers technology as claimed in claim 1 or 2 is characterized in that: the temperature of described carbonation reaction is 70-90 °.
6, Synthesis of Calcium Carbonate Whiskers technology as claimed in claim 1 or 2 is characterized in that: the pressure of described carbonation reaction is 1.0-1.5Mpa.
7, Synthesis of Calcium Carbonate Whiskers technology as claimed in claim 1 or 2 is characterized in that: the time of described carbonation reaction is 2-3 hour.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400719C (en) * | 2005-11-03 | 2008-07-09 | 福建师范大学 | Crystal whisker calcium carbonate preparation method |
| CN101935061A (en) * | 2010-09-08 | 2011-01-05 | 中国科学院青海盐湖研究所 | Method for removing impurity of mother liquid in preparation process of calcium carbonate crystal whisker |
| CN101507931B (en) * | 2009-03-24 | 2011-04-27 | 南京工业大学 | Preparation method of whisker reinforced shaped catalyst carrier or catalyst |
| CN103303955A (en) * | 2013-07-08 | 2013-09-18 | 郑州大学 | Production method of calcium carbonate whisker |
| CN103628124A (en) * | 2013-11-12 | 2014-03-12 | 西安交通大学 | Low-voltage direct-current electrolysis preparation method of calcium carbonate whisker |
| CN105883880A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of sheet superfine calcium carbonate for paper coating |
| CN106048709A (en) * | 2016-02-16 | 2016-10-26 | 沈阳建筑大学 | Preparation method for calcium carbonate whiskers extracted from limestone |
| CN108893775A (en) * | 2018-07-16 | 2018-11-27 | 浙江大学 | A kind of preparation method of purity calcium carbonate whisker |
-
2003
- 2003-05-26 CN CNA031342876A patent/CN1552959A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400719C (en) * | 2005-11-03 | 2008-07-09 | 福建师范大学 | Crystal whisker calcium carbonate preparation method |
| CN101507931B (en) * | 2009-03-24 | 2011-04-27 | 南京工业大学 | Preparation method of whisker reinforced shaped catalyst carrier or catalyst |
| CN101935061A (en) * | 2010-09-08 | 2011-01-05 | 中国科学院青海盐湖研究所 | Method for removing impurity of mother liquid in preparation process of calcium carbonate crystal whisker |
| CN101935061B (en) * | 2010-09-08 | 2012-03-21 | 中国科学院青海盐湖研究所 | Method for removing impurity of mother liquid in preparation process of calcium carbonate crystal whisker |
| CN103303955A (en) * | 2013-07-08 | 2013-09-18 | 郑州大学 | Production method of calcium carbonate whisker |
| CN103303955B (en) * | 2013-07-08 | 2015-07-22 | 郑州大学 | Production method of calcium carbonate whisker |
| CN103628124A (en) * | 2013-11-12 | 2014-03-12 | 西安交通大学 | Low-voltage direct-current electrolysis preparation method of calcium carbonate whisker |
| CN106048709A (en) * | 2016-02-16 | 2016-10-26 | 沈阳建筑大学 | Preparation method for calcium carbonate whiskers extracted from limestone |
| CN106048709B (en) * | 2016-02-16 | 2018-11-13 | 沈阳建筑大学 | A kind of preparation method of the calcium carbonate crystal whisker extracted from lime stone |
| CN105883880A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of sheet superfine calcium carbonate for paper coating |
| CN108893775A (en) * | 2018-07-16 | 2018-11-27 | 浙江大学 | A kind of preparation method of purity calcium carbonate whisker |
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