CN104790024A - Preparation method for aragonite calcium carbonate whisker with high length-diameter ratio - Google Patents
Preparation method for aragonite calcium carbonate whisker with high length-diameter ratio Download PDFInfo
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Abstract
The invention relates to a preparation method for an aragonite calcium carbonate whisker with a high length-diameter ratio. The preparation method comprises the following specific implementation steps: adding a 1.0-8.2 wt% prepared Ca(OH)2 suspension liquid into a carbonation reactor, adding MgCl2 in the aqueous solution form into the reactor, controlling the magnesium-calcium ratio R to be 0.6-2.0 and the carbonization temperature to be 30-85 DEG C, under the action of stirring, mixing CO2 with the flow rate of (5-120)m<3>/(h.m<3> suspension liquid)and N2, introducing the mixture of the CO2 and N2 to a gas distributor at the bottom of the carbonation reactor, and tracking the whole process of carbonation reactor by adopting a digital display pH meter; performing suction filtration and washing on the slurry generated after the carbonization is completed, drying for 5 hours at the temperature of 80 DEG C, and crushing, so as to obtain a calcium carbonate whisker sample. Compared with the existing method for preparing the aragonite calcium carbonate whisker through a carbonation method, the preparation method provided by the invention has the advantages that the calcium carbonate whisker with the high length-diameter ratio is synthesized by adopting the one-step method, the multistage growth is avoided, and the operation is simpler; the co-heating reaction balance phase of magnesium chloride and calcium hydroxide is avoided, the magnesium-calcium ratio in the reaction slurry is low, and the synthesis efficiency is higher.
Description
Technical field
The invention belongs to inorganic salt materials technical field, relate to a kind of preparation method of Aragonite Style Calcium Carbonate Whiskers of high length-diameter ratio.
Background technology
Inorganic crystal whisker is as a kind of with the material of single crystal form growth, and pattern generally shows as the needle-like or threadiness that have compared with high length-diameter ratio.Its atomic arrangement high-sequential, whisker structure is more complete, and inner contained defect is less, therefore its strength and modulus is all close to the theoretical value of complete crystal whisker materials, is a kind of activeness and quietness agent of high performance advanced composite material.
At present, SiC, SiN, Al
2o
3, ZnO, potassium titanate, mullite, the minority whisker such as aluminum borate successfully realized suitability for industrialized production; but hinder its mass-producing application and development because its production cost is higher, find the higher whisker of a kind of cost performance and carry out one of alternative existing high price whisker important research target becoming material circle.
The preparation exciting the research enthusiasm calcium carbonate crystal whisker of numerous investigator along with the low and type material that performance is higher and the calcium carbonate crystal whisker appearance of a kind of abundant raw material source of development price of research has in recent years become the focus of research both at home and abroad.At present, Chinese scholars has done large quantifier elimination to the synthesis of aragonite calcium carbonate whisker, and its synthesis main points reduce degree of supersaturation at a certain temperature to suppress the generation of calcite, sums up and get up to have following 6 class methods: (1) double decomposition; (2) Ca (HCO
3)
2thermal decomposition method; (3) ureal antigen; (4) sol-gel method; (5) carbonation method.
Replacement(metathesis)reaction general theory of law is by the Ca of solubility
2+salt is (as CaCl
2, Ca (NO
3)
2deng) with the salt of solubility (as Na
2cO
3, (NH
4)
2cO
3deng) under the condition of 30 ~ 100 DEG C, there is replacement(metathesis)reaction thus the method for acquisition calcium carbonate crystal whisker.The required reactant solubility of this method reaction is lower comparatively speaking, and whisker resultant velocity is slow, so generally it also only carries out the production of calcium carbonate crystal whisker in a small amount for laboratory, as improved its reactant solubility, then needs to add admixture wherein.In addition because of the temperature of reaction of method and the uneven of solubility for this reason, length-to-diameter ratio and the quality of the calcium carbonate crystal whisker of synthesis is easily had influence on.
Ca (HCO
3)
2the ultimate principle of thermal decomposition method is scattered in the water of 2 DEG C by limestone powder higher for purity then to pass into CO wherein
2gas, the solution made by the temperature and the flow velocity of carbon dioxide controlling reaction, then controls the temperature of reacting, the speed of intensification, the calcium carbonate crystal whisker that the intensity of stirring is made.The reactant solubility of this method and temperature all control than being easier to compared with other method, do not need to add any crystal seed or control agent, operate also fairly simple, but make the length-to-diameter ratio of calcium carbonate crystal whisker prepared in this way be not so desirable, and energy consumption is also relatively high.
The ultimate principle of ureal antigen is the method being obtained calcium carbonate crystal whisker by urea and solubility calcium salt system generation chemical reaction.This method preparation method is simple, and condition is easy to control, and need not add crystal seed or crystal control agent, but reactant made by a large amount of urea of reaction needed, and production cost is too high.In addition, reaction carries out when High Temperature High Pressure, and energy consumption is high, danger is large, so be difficult to form suitability for industrialized production.
Sol-gel method is a kind of wet chemical preparation method can prepared from zero dimension to three-dimensional material.Its ultimate principle is through a series of step, calcium carbonate is converted into the intermediate of calcic, then carries out calcination processing to this intermediate, obtains calcium carbonate crystal whisker.The feature that this method reaction process is easy to control, the product of preparation has good uniformity, length-to-diameter ratio is large, but compared with the preparation method that other are traditional, sol-gel method needs to react under the condition of 700 DEG C, and this just requires the requirement of equipment higher, is also unfavorable for suitability for industrialized production.
Carborization is that most study is also a kind of comparatively ripe method both at home and abroad at present.Its ultimate principle passes into carbonic acid gas in calcium hydroxide suspension liquid, aragonite calcium carbonate whisker is prepared under the effect of crystal control agent (magnesium chloride, phosphoric acid etc.) or crystal seed, be similar to the gas-liquid system of industrial synthesis light calcium carbonate, therefore also have this method of person to be gas-liquid system.Carborization controls comparatively strict to temperature of reaction, but because it has, production cost is low, raw material can derive from the limestone resource that nature extensively exists substantially, the simple easy handling of its technique simultaneously, close with the method for traditional mode of production light calcium carbonate, and the calcium carbonate crystal whisker prepared has purity is high, length-to-diameter ratio is large advantage, be the most possible technology forming large-scale industrial production at present.
Chinese patent (patent No. ZL201010280862.6) discloses a kind of preparation method of high length-diameter ratio calcium carbonate crystal whisker, the method utilizes bischofite as chemical additives, recycle mother liquor, prepares by many and growth the calcium carbonate crystal whisker that diameter is 1.5 ~ 3.0 μm, length is 30 ~ 50 μm.This method recycle mother liquor, reduces production cost, but preparation process needs to be divided into three different stepss, utilization whisker is on last stage as crystal seed, rely on multistage growth to obtain, and every one-phase all needs the mass concentration adjusting lime slip and magnesium chloride solution, operation is comparatively complicated; And the mass concentration of magnesium chloride is more than 5 times of calcium hydroxide mass concentration in reaction soln.Chinese patent (patent No. ZL200410022834.9) discloses a kind of manufacture method of high purity Aragonite Style Calcium Carbonate Whiskers.The method magnesium salts is as chemical additives, and in calcium carbonate crystal whisker preparation process, magnesium salt solution is reused, evenly slaked lime slurry is added in carbonation reaction, preparing aragonite phase Whisker Content is 95%, and whisker length is 20 ~ 60 μm, and length-to-diameter ratio reaches the calcium carbonate whisker of 15 ~ 40.But after this method needs magnesium salts and calcium hydroxide slurry to react at room temperature ~ 80 DEG C and makes it to reach molecular balance in 0.5 ~ 2 hour, pass into carbonic acid gas again and carry out carburizing reagent, reaction time is longer, and this kind of method magnesium calcium is larger, calcium magnesium is about 4.0 than R, and raw materials cost is higher.Document (Chinese Journal of Inorganic Chemistry, 2008,24 (5): 737-742) in traditional gravity field, take soluble phosphate as chemical additives, one step carbonization synthesis is adopted to obtain the calcium carbonate crystal whisker product that length is 23 μm, length-to-diameter ratio is 15.3 first, whisker aragonite phase content is 88.3%, and crystallization degree is high, good stability.This method achieves one-step synthesis calcium carbonate crystal whisker, and technological operation is simple, but the whisker aragonite phase content obtained is lower slightly, and length-to-diameter ratio is also slightly little.
Generally speaking, make crystal seed control agent with magnesium chloride and be better than other auxiliary agents.And the price of magnesium salts is much lower relative to other chemical additives.Therefore selective chlorination magnesium is as chemical additives, and the production technique that simplification carbonation method prepares calcium carbonate whisker is significant to realizing calcium carbonate crystal whisker industrialization.
Summary of the invention
The object of this invention is to provide that a kind of cost is low, the preparation method of the simple aragonite calcium carbonate of technique, it is characterized in that utilizing carbonation method, is under the condition of chemical additives at magnesium chloride, the Aragonite Style Calcium Carbonate Whiskers of one-step synthesis method high length-diameter ratio.Be implemented as follows:
1, put in 60 ~ 90 DEG C of distilled water by unslaked lime by certain cement-water ratio, digestion 1 ~ 4 hour is stirred in sealing, by the Ca (OH) of gained
2suspension crosses 200 mesh standard sieves, adds water and is modulated to finite concentration, for subsequent use.
2, be 1.0 ~ 8.2wt%Ca (OH) by the mass concentration prepared
2suspension joins in carbonization reactor, by MgCl
2join reactor in form of an aqueous solutions, controlling magnesium calcium is 0.6 ~ 2.0 than R (magnesium chloride and calcium hydroxide mass ratio), carbonization temperature is 30 ~ 85 DEG C, under stirring, is (5 ~ 120) m by flow rate
3/ (hm
3suspension) CO
2and N
2pass into the gas distributor bottom carburizing reagent still after mixing, adopt digital display pH meter to follow the tracks of carburizing reagent whole process.When reacting slurry pH=6.5 ~ 7.0, stop ventilation, carburizing reagent terminates.Carbonization rear slurry carried out suction filtration, with deionized water wash, repeat twice, outwell supernatant liquor, 80 DEG C of dryings 5 hours, obtain sample.
Compared with the present invention prepares aragonite calcium carbonate technology with existing carbonation method, its outstanding substantive distinguishing features and significant progress are:
1, do not rely on multistage growth, single stage method can synthesize high length-diameter ratio calcium carbonate crystal whisker, operates simpler.
2, without the need to carrying out the common thermal response equilibrium stage of magnesium chloride and calcium hydroxide, magnesium calcium is than low, and combined coefficient is higher.
Accompanying drawing explanation
Fig. 1 is calcium carbonate whisker electron scanning micrograph
Fig. 2 is calcium carbonate whisker length, diameter statistical Butut
Fig. 3 is that calcium carbonate whisker EDS can spectrogram
Embodiment
(1) in an embodiment, the calculating of calcium carbonate whisker aragonite phase massfraction.The XRD figure spectrum of control sample, calculates the massfraction of aragonite phase in calcium carbonate product by formula (1):
In formula, y is the massfraction of aragonite phase in calcium carbonate product; Ia is the integrated intensity value of the strongest characteristic peak of aragonite phase in XRD figure spectrum, and Ic is the integrated intensity value of the strongest characteristic peak of calcite phase in XRD figure spectrum.
(2) in an embodiment, the calculating of calcium carbonate whisker length-to-diameter ratio.Select the SEM photo of different zones, measure length and the mid-diameter of 100 whiskers, and calculate its length-to-diameter ratio.
Embodiment 1
Be (1) 2.0wt% by compound concentration; (2) 2.9wt%; (3) 3.8wt% or (4) 4.7wt%Ca (OH)
2suspension joins in carbonization reactor, and be 1.0 add magnesium chloride brine by magnesium calcium than R, controlling carbonization temperature is 75 DEG C, applies to stir, then by flow rate 20m
3/ (hm
3suspension) CO
2and flow rate is 40m
3/ (hm
3suspension) N
2pass into the gas distributor bottom carburizing reagent still after mixing, adopt digital display pH meter to follow the tracks of carburizing reagent whole process.As reacting slurry pH=7, stop ventilation, carburizing reagent terminates.Slurries after carbonization being completed carry out suction filtration, washing, drying.Calculate calcium carbonate whisker aragonite phase content and length-to-diameter ratio, the results are shown in Table 1.
Embodiment 2
Be 2.0wt%Ca (OH) by compound concentration
2suspension joins in carbonization reactor, and be 1.0 add magnesium chloride brine by magnesium calcium than R, controlling carbonization temperature is (1) 55 DEG C; (2) 65 DEG C; (3) 75 DEG C or (4) 85 DEG C, apply to stir, then by flow rate 20m
3/ (hm
3suspension) CO
2and flow rate is 40m
3/ (hm
3suspension) N
2pass into the gas distributor bottom carburizing reagent still after mixing, adopt digital display pH meter to follow the tracks of carburizing reagent whole process.As reacting slurry pH=7, stop ventilation, carburizing reagent terminates.Slurries after carbonization being completed carry out suction filtration, washing, drying.Calculate calcium carbonate whisker aragonite phase content and length-to-diameter ratio, the results are shown in Table 1.
Embodiment 3
Be 2.0wt%Ca (OH) by compound concentration
2suspension joins in carbonization reactor, by magnesium calcium ratio (1) R=0.8; (2) R=1.0; (3) R=1.2 or (4) R=1.4 adds magnesium chloride brine, and controlling carbonization temperature is 75 DEG C, applies to stir, then by 20m
3/ (hm
3suspension) CO
2and flow rate is 40m
3/ (hm
3suspension) N
2pass into the gas distributor bottom carburizing reagent still after mixing, adopt digital display pH meter to follow the tracks of carburizing reagent whole process.As reacting slurry pH=7, stop ventilation, carburizing reagent terminates.Slurries after carbonization being completed carry out suction filtration, washing, drying.Calculate calcium carbonate whisker aragonite phase content and length-to-diameter ratio, the results are shown in Table 1.
Table 1
Claims (7)
1. the preparation method of a high length-diameter ratio Aragonite Style Calcium Carbonate Whiskers.Its concrete steps are:
(1) by unslaked lime by 1: 4 ~ 5 cement-water ratio put in hot water and digest, cross 200 mesh standard sieves, adding water be modulated to finite concentration, for subsequent use.
(2) Ca (OH) will prepared
2suspension joins in carbonization reactor, adds chemical additives, by CO
2and N
2pass into the gas distributor bottom carbonization reactor after mixing, carry out carburizing reagent.Adopt digital display pH meter to follow the tracks of carburizing reagent whole process, when reacting slurry pH=6.5 ~ 7.0, stop ventilation, carburizing reagent terminates.
(3) carbonization is completed rear slurry and carry out suction filtration, washing, repeat twice, at 80 DEG C, drying 5 hours, pulverizes, namely obtains required calcium carbonate whisker sample.
2. method according to claim 1, is characterized in that: the temperature of described step (1) digestion hot water is 60 ~ 90 DEG C, and digestion time is 4 hours.
3. method according to claim 2, is characterized in that: described step (1) Ca (OH)
2the concentration of suspension is 1.0 ~ 8.2wt%.
4. method according to claim 3, is characterized in that: the chemical additives added in described step (2) is magnesium chloride, and magnesium calcium is 0.6 ~ 2.0 than R.
5. method according to claim 4, is characterized in that: magnesium chloride joins in calcium hydroxide suspension in (2) by described step, namely carries out carburizing reagent without common thermal response balance.
6. method according to claim 5, is characterized in that: in described step (2), carbonation reaction needs circulator bath to control carbonization temperature, and applies to stir.Wherein carbonization temperature is 30 ~ 85 DEG C.
7. method according to claim 6, is characterized in that: in described step (2), carbonation reaction passes into the CO of gas distributor
2flow rate be (5 ~ 120) m
3/ (hm
3suspension), N
2flow rate be (5 ~ 120) m
3/ (hm
3suspension).
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Cited By (13)
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|---|---|---|---|---|
| CN105347362A (en) * | 2015-12-07 | 2016-02-24 | 上海弗鲁克科技发展有限公司 | System and method for producing cyanamide and aragonite type nano calcium carbonate through lime nitrogen |
| CN106398448A (en) * | 2016-06-14 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Preparation method for environment-friendly waterborne paint |
| CN106430272A (en) * | 2016-11-21 | 2017-02-22 | 广西华纳新材料科技有限公司 | Rodlike aragonite calcium carbonate preparation method |
| CN107475769A (en) * | 2017-08-10 | 2017-12-15 | 青阳县永诚钙业有限责任公司 | A kind of preparation method for extracting calcium carbonate crystal whisker |
| CN107916452A (en) * | 2017-11-14 | 2018-04-17 | 浙江大学 | A kind of preparation method of the continuous controllable calcium carbonate crystal whisker of pattern |
| CN108588842A (en) * | 2018-05-02 | 2018-09-28 | 四川大学 | CO2Mineralising prepares calcium carbonate crystal whisker device and preparation method thereof |
| CN108728899A (en) * | 2018-07-16 | 2018-11-02 | 浙江大学 | A method of purity calcium carbonate whisker is mixed with using circulating mother liquor pressurization spray |
| CN108893775A (en) * | 2018-07-16 | 2018-11-27 | 浙江大学 | A kind of preparation method of purity calcium carbonate whisker |
| CN111484060A (en) * | 2020-04-30 | 2020-08-04 | 广西夏阳环保科技有限公司 | Preparation method of high-purity calcium carbonate |
| CN111497353A (en) * | 2020-04-27 | 2020-08-07 | 福建和盛塑业有限公司 | Core layer microcellular foaming PVC/CPVC cable protection pipe and preparation method thereof |
| CN111778547A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Preparation method of aragonite type calcium carbonate whisker |
| CN111926386A (en) * | 2020-07-07 | 2020-11-13 | 广西夏阳环保科技有限公司 | Preparation method of calcium carbonate whisker |
| CN113151891A (en) * | 2021-04-21 | 2021-07-23 | 华东理工大学 | Method for softening water body and synchronously preparing calcium carbonate whiskers by adopting electrochemistry |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347362A (en) * | 2015-12-07 | 2016-02-24 | 上海弗鲁克科技发展有限公司 | System and method for producing cyanamide and aragonite type nano calcium carbonate through lime nitrogen |
| CN106398448A (en) * | 2016-06-14 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Preparation method for environment-friendly waterborne paint |
| CN106430272A (en) * | 2016-11-21 | 2017-02-22 | 广西华纳新材料科技有限公司 | Rodlike aragonite calcium carbonate preparation method |
| CN107475769A (en) * | 2017-08-10 | 2017-12-15 | 青阳县永诚钙业有限责任公司 | A kind of preparation method for extracting calcium carbonate crystal whisker |
| CN107916452B (en) * | 2017-11-14 | 2020-03-03 | 浙江大学 | Preparation method of calcium carbonate whiskers with continuously controllable morphology |
| CN107916452A (en) * | 2017-11-14 | 2018-04-17 | 浙江大学 | A kind of preparation method of the continuous controllable calcium carbonate crystal whisker of pattern |
| CN108588842A (en) * | 2018-05-02 | 2018-09-28 | 四川大学 | CO2Mineralising prepares calcium carbonate crystal whisker device and preparation method thereof |
| CN108728899A (en) * | 2018-07-16 | 2018-11-02 | 浙江大学 | A method of purity calcium carbonate whisker is mixed with using circulating mother liquor pressurization spray |
| CN108893775A (en) * | 2018-07-16 | 2018-11-27 | 浙江大学 | A kind of preparation method of purity calcium carbonate whisker |
| CN111778547A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Preparation method of aragonite type calcium carbonate whisker |
| CN111497353A (en) * | 2020-04-27 | 2020-08-07 | 福建和盛塑业有限公司 | Core layer microcellular foaming PVC/CPVC cable protection pipe and preparation method thereof |
| CN111497353B (en) * | 2020-04-27 | 2022-04-05 | 福建和盛塑业有限公司 | Core layer microcellular foaming PVC/CPVC cable protection pipe and preparation method thereof |
| CN111484060A (en) * | 2020-04-30 | 2020-08-04 | 广西夏阳环保科技有限公司 | Preparation method of high-purity calcium carbonate |
| CN111926386A (en) * | 2020-07-07 | 2020-11-13 | 广西夏阳环保科技有限公司 | Preparation method of calcium carbonate whisker |
| CN111926386B (en) * | 2020-07-07 | 2022-07-22 | 都安春旭新材料科技有限责任公司 | Preparation method of calcium carbonate whisker |
| CN113151891A (en) * | 2021-04-21 | 2021-07-23 | 华东理工大学 | Method for softening water body and synchronously preparing calcium carbonate whiskers by adopting electrochemistry |
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