CN103628124A - Low-voltage direct-current electrolysis preparation method of calcium carbonate whisker - Google Patents
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Abstract
The invention discloses a low-voltage direct-current electrolysis preparation method of a calcium carbonate whisker, which comprises the steps of preparing a calcium salt solution by taking inorganic calcium salt as a solute; preparing alkaline liquid by taking carbonate as a solute; preparing a crystal form control agent solution by taking inorganic magnesium salt as a solute; adding the calcium salt solution, alkaline liquid and crystal form control agent solution into an electrolytic tank, and stirring and mixing uniformly to obtain reaction liquid; putting a cathode electrode and an anode electrode into the electrolytic tank, and applying a direct-current voltage between the cathode electrode and the anode electrode; performing a direct-current electrolysis reaction while stirring at 0-40 DEG C until a white solid is generated in the cathode area; collecting the white solid and naturally drying to obtain the calcium carbonate whisker. In the method disclosed by the invention, the reaction conditions are mild, and the energy is saved; by controlling the addition of the crystal form control agent and the electrochemical parameters such as the direct-current electric field of the voltage, the parameters such as short-axis diameter, length-diameter ratio, crystal form, components and the like of the calcium carbonate whisker can be adjusted and controlled, so that the generated calcium carbonate has obvious whisker characteristics.
Description
Technical field
The present invention relates to a kind of preparation method of calcium carbonate crystal whisker, be specifically related to the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker.
Background introduction
Whisker refers to the very thin single crystal being formed by cultivation under certain condition, there is no ubiquitous defect in common material (as crystal boundary, dislocation, hole etc.), its atomic arrangement high-sequential, physical strength are similar in abutting connection with valence f., close to the theoretical value of perfect crystal.
Calcium carbonate crystal whisker is the new type whisker material of developing in recent years, has good high temperature resistant, insulation, the function such as fire-retardant, and the advantage such as good physical strength, high elastic coefficient, high rigidity.At present, calcium carbonate crystal whisker be mainly used in strengthen organic or polymer composite, as paper making additive and friction materials filler etc.
Itself belongs to one of soil constituent calcium carbonate, even if therefore go out of use in environment after its main part is used to complete, can not produce the problem of environmental pollution that other material may bring difficult for biological degradation yet, be a kind of to human body and ecotope the material without injury.
The calcium carbonate crystal whisker synthetic method of documents and materials report comprises at present: carbonation method, double decomposition, urea water solution, Ca (HCO
3)
2heating water solution, high-gravity reactive precipitation etc.
1) carbonation method:
Carbonation method is by limestone calcination, obtains calcium oxide and kiln gas, makes calcium oxide digestion, and the suspension calcium hydroxide of generation is pulverized under high shear, makes certain density refining calcium hydroxide suspension, then passes through CO
2gas, adds suitable chemical additives, and carbonization to terminal, obtains calcium carbonate crystal whisker slurries; Dewater again, be dried, surface treatment, obtain calcium carbonate crystal whisker product.
Carbonation method is the method that current industrial production light calcium carbonate generally adopts, and simple to operation, raw material is Wingdale, and production cost is low.At Ca (OH)
2-CO
2in reaction system, carbonate synthesis calcium pyroborate need to add and promote that solubility magnesium salts or the phosphoric acid based compound of major axis growth are chemical additives in reaction process.Take magnesium salts during as chemical additives, have the shortcomings such as addition is large, product whiteness is low, diameter of whiskers is thick, and intensity is low, and can sneak into Mg (OH)
2impurity.In adding the document of phosphoric acid based compound, be generally first to synthesize the small needle-like calcium carbonate crystal of size, using that this adds in reaction system as crystal seed, and add chemical additives, a few footwork carbonate synthesis calcium pyroborates, complex process, production cycle is long, and phosphoric acid based compound consumption is large.
2) double decomposition:
Double decomposition is to utilize solubility calcium salts solution, as Ca (CH
3cOO)
2, CaCl
2, Ca (NO
3)
2solution and soluble carbonate salt solution, as Na
2cO
3, (NH
4)
2cO
3, K
2cO
3deng solution reaction, coordinating under the condition of other additive reagent, make calcium carbonate crystal whisker.Solution between common water-soluble calcium salt and carbonate is synthetic always produces calcite, and the synthetic needs of preparation of aragonite whisker are strictly controlled synthesis condition.In this method, reactant concn is generally very low, and digestion time is long, and the unhomogeneity of strength of solution, temperature can affect purity and the homogeneity of calcium carbonate crystal whisker.
3) urea water solution:
Urea water solution is to make urea and solubility calcium reactant salt, the CO that utilizes hydrolysis of urea to produce
2with Ca
2+calcium carbonate crystal whisker is prepared in reaction.Although in reaction process without adding crystal seed heterogeneous nucleation, also need not add chemical additives, can avoid well the introducing of impurity, but need under constant high temperature (>100 ℃) condition of high voltage, react, energy consumption is larger, because being confined reaction system, danger is higher, is not suitable for suitability for industrialized production again.
4) Ca (HCO
3)
2heating water solution:
Ca (HCO
3)
2preparation method is first to make Ca (HCO
3)
2solution, then prepares calcium carbonate crystal whisker by controlling the conditions such as Heating temperature, temperature rise rate, stirring intensity of solution.This method complex process, not easy to operate, production efficiency is low.
5) high-gravity reactive precipitation:
High-gravity reactive precipitation refers to Ca (OH)
2emulsion can obtain compared with the centrifugal speed of large 2～3 orders of magnitude of universal gravity constant when by rotating packed-bed reactor, in the case, emulsion is broken into minimum drop, brin and liquid film as thin as a wafer by filler, has greatly increased gas-to-liquid contact area, has strengthened carbonization speed.Meanwhile, because emulsion obtains high dispersing in rotating bed, limited growing up of crystal grain, even if do not add crystal control agent, also can prepare nanometer grade calcium carbonate, and reaction process controlling factor has been few, is easy to repetition, product granularity is adjustable.In addition the large flow circulating reaction of this process using, the advantage such as material carries out the cooling measure of Denging outward at reactor, has the reaction times short, and production efficiency is high, and single device throughput is large.But the method need to be carried out in specific hypergravity reaction unit, and energy consumption is larger, and length-to-diameter ratio is still not ideal enough.
Hence one can see that, and current developed calcium carbonate crystal whisker synthetic method, when having himself advantage, also has larger defect.The most outstanding feature be these technology all need to be in the solution of comparatively high temps carbonate synthesis calcium pyroborate, from application point, say, this will bring great energy consumption.If can find a kind of can carbonate synthesis calcium pyroborate under normal pressure and temperature condition, operating process is simultaneously relatively easy method also, will be to bringing great advantage with its industry preparation and application.
Summary of the invention
The low dc voltage electrolysis preparation method who the object of the present invention is to provide a kind of calcium carbonate crystal whisker, the method can realize at normal temperatures and pressures, and simple to operate, and energy consumption is low.
In order to achieve the above object, the technical solution used in the present invention comprises the following steps:
1) take inorganic calcium salt as solute, water and/or organic solvent are solvent, are mixed with calcium salt soln; Take carbonate as solute, and water and/or organic solvent are solvent, are mixed with alkali lye; Take inorganic magnesium salt as solute, and water is solvent, is mixed with chemical additives solution;
2) calcium salt soln, alkali lye and chemical additives solution are joined in electrolyzer, be uniformly mixed, form reaction solution; Wherein, inorganic calcium salt in the calcium salt soln adding and the mol ratio of the carbonate in alkali lye are (1～2): (1～4), and the chemical additives in chemical additives solution accounts for 0～5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in electrolyzer, pack cathode electrode and anode electrode into, and apply volts DS between cathode electrode and anode electrode, make cathode current density at 0.001mAcm
-2～2mAcm
-2, then under the agitation condition of 0～40 ℃, stir and carry out DC electrolysis reaction, until cathodic area generates white solid, seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Inorganic calcium salt in described step 1) is calcium chloride, calcium hydroxide, Calcium hydrogen carbonate or nitrocalcite.
Carbonate in described step 1) is sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood or volatile salt.
Inorganic magnesium salt in described step 1) is magnesium chloride or magnesium nitrate.
In described step 1), the concentration of calcium salt soln is 10
-4mg/L is to the saturation concentration of inorganic calcium salt, and the concentration of alkali lye is 10
-4mg/L is to the saturation concentration of carbonate, and the concentration of chemical additives solution is 0 saturation concentration to inorganic magnesium salt.
Organic solvent in described step 1) is methyl alcohol, ethanol, ethylene glycol or glycerol.
Described step 2) chemical additives in the chemical additives solution in accounts for 1～5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add.
Described step 3) Anodic electrode is metal oxide electrode, Graphite Electrodes or boron-doped diamond electrode, and cathode electrode is copper electrode, the ferroelectric utmost point or Graphite Electrodes.
Described metal oxide electrode is titanium matrix lead dioxide electrode or antimony Doped with Titanium matrix stannic oxide electrode.
The volts DS applying between cathode electrode and anode electrode in described step 3) is 0.001V～30V.
Further improvement of the present invention is: in step 1), water and organic solvent mix while using as solvent according to arbitrary volume than formulated.
The present invention adopts low dc voltage electrolytic process to synthesize the good calcium carbonate crystal whisker of pattern, its principle is: in being full of the electrolyzer of Ca ionogen (being reaction solution), between cathode electrode and anode electrode, apply a low dc voltage electric field, can cause following electrode reaction at Yu Shui interface, cathodic area:
O
2+2H
2O+4e→4OH
－
2H
2O+2e→2OH
－+H
2↑
Because reaction produces a large amount of OH
-, make the pH value of cathode electrode surface near zone increase, CO
3 2-increase.And Ca
2+because the effect meeting of the composite factors such as electrostatic attraction and diffusion is moved to cathodic area, and near finally enrichment cathodic area, cause partial concn much larger than bulk solution concentration; Ca now
2+with CO
3 2-reaction generates precipitation, is deposited on the negative electrode of electrochemical reactor, and concrete reaction is as follows:
HCO
3 －+OH
－→H
2O+CO
3 2－
Ca
2++CO
3 2－→CaCO
3↓
Compared with prior art, beneficial effect of the present invention is: reaction process of the present invention is carried out at normal temperatures and pressures, and meanwhile, DC electrolysis temperature of reaction is at 0～40 ℃, therefore, and reaction conditions gentleness of the present invention and save energy; In addition, the present invention by the add-on of chemical additives and electrochemical parameter as controlled voltage dc field, minor axis diameter that can regulation and control calcium carbonate crystal whisker, length-to-diameter ratio, crystal formation and group gradation parameter, make the calcium carbonate generating for having obvious whisker speciality.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the calcium carbonate crystal whisker prepared of the present invention;
Fig. 2 is the stereoscan photograph of the calcium carbonate crystal whisker prepared of the present invention.
Embodiment
Embodiment 1:
1) take analytical pure nitrocalcite as solute, water is solvent, and being mixed with concentration is 300mgL
-1calcium salt soln; Take analytical pure sodium bicarbonate as solute, and water is solvent, and being mixed with concentration is 600mgL
-1alkali lye;
2) calcium salt soln and alkali lye are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the nitrocalcite in the calcium salt soln adding and the mol ratio of the sodium bicarbonate in alkali lye are 1:2,
3) in aseptate electrolyzer, pack into as the antimony Doped with Titanium matrix stannic oxide electrode of anode electrode and as the copper electrode of cathode electrode, and the volts DS that applies 30V between cathode electrode and anode electrode to make cathode current density be 1.5mAcm
-2, then under room temperature condition, to stir and carry out DC electrolysis reaction, the DC electrolysis reaction times is 6h, now on the copper electrode in cathodic area, generates white solid, seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Gained calcium carbonate crystal whisker is identified (see figure 1) through X-ray diffraction, and wherein the massfraction of aragonite calcium carbonate surpasses 90%; By scanning electron microscope, identify (see figure 2), minor axis diameter is in 100-300nm rank, and length-to-diameter ratio is within the scope of 20-50.Product has obvious calcium carbonate crystal whisker speciality.
Embodiment 2:
1) take analytical pure calcium chloride as solute, water is solvent, and being mixed with concentration is 300mgL
-1calcium salt soln; Take analytical pure sodium bicarbonate as solute, and water is solvent, and being mixed with concentration is 600mgL
-1alkali lye; Take magnesium chloride as solute, and water is solvent, is mixed with magnesium chloride saturated solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the calcium chloride in the calcium salt soln adding, the mol ratio of the sodium bicarbonate in alkali lye are 1:2, and the magnesium chloride in chemical additives solution accounts for 5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the titanium matrix lead dioxide electrode of anode electrode and as the copper electrode of cathode electrode, and the volts DS that applies 15V between cathode electrode and anode electrode to make cathode current density be 1.5mAcm
-2, then under room temperature condition, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the copper electrode in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Gained calcium carbonate crystal whisker is through X-ray diffraction evaluation, and its aragonitic content surpasses 90%; By scanning electron microscope, identify, minor axis diameter is in 100-200nm rank, and length-to-diameter ratio is within the scope of 20-50.Product has obvious calcium carbonate crystal whisker speciality.
Embodiment 3:
1) with analytical pure calcium chloride, water is solvent, and being mixed with concentration is 300mgL
-1calcium salt soln; Take saleratus as solute, and water is solvent, and being mixed with concentration is 600mgL
-1alkali lye; Take magnesium chloride as solute, and water is solvent, is mixed with magnesium chloride saturated solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the calcium chloride in the calcium salt soln adding, the mol ratio of the saleratus in alkali lye are 1:2, and the magnesium chloride in chemical additives solution accounts for 5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the titanium matrix lead dioxide electrode of anode electrode and as the cast iron electrode of cathode electrode, and the volts DS that applies 0.001V between cathode electrode and anode electrode to make cathode current density be 1.5mAcm
-2, then under room temperature condition, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the cast iron electrode in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Gained calcium carbonate crystal whisker is through X-ray diffraction evaluation, and its aragonitic content surpasses 95%; By scanning electron microscope, identify, minor axis diameter is in 100-200nm rank, and length-to-diameter ratio is within the scope of 20-30.Product has obvious calcium carbonate crystal whisker speciality.
Embodiment 4:
1) take analytical pure calcium chloride as solute, water is solvent, and being mixed with concentration is 500mgL
-1calcium salt soln; Take saleratus as solute, and water is solvent, and being mixed with concentration is 1000mgL
-1alkali lye; Take magnesium chloride as solute, and water is solvent, is mixed with magnesium chloride saturated solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the calcium chloride in the calcium salt soln adding, the mol ratio of the saleratus in alkali lye are 1:2, and the magnesium chloride in chemical additives solution accounts for 5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the titanium matrix lead dioxide electrode of anode electrode and as the Graphite Electrodes of cathode electrode, and the volts DS that applies 8V between cathode electrode and anode electrode to make cathode current density be 1.5mAcm
-2, then under room temperature condition, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the Graphite Electrodes in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Gained calcium carbonate crystal whisker is through X-ray diffraction evaluation, and its aragonitic content surpasses 90%; By scanning electron microscope, identify, minor axis diameter is in 100-200nm rank, and length-to-diameter ratio is within the scope of 20-50.Product has obvious calcium carbonate crystal whisker speciality.
Embodiment 5:
1) take analytical pure calcium hydroxide as solute, water is solvent, and being mixed with concentration is 10
-4mgL
-1calcium salt soln; Take sodium carbonate as solute, and water is solvent, and being mixed with concentration is 100mgL
-1alkali lye; Take magnesium nitrate as solute, and water is solvent, is mixed with 200mgL
-1magnesium nitrate solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the calcium hydroxide in the calcium salt soln adding, the mol ratio of the sodium carbonate in alkali lye are 1:4, and the magnesium nitrate in chemical additives solution accounts for 2% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the boron-doped diamond electrode of anode electrode and as the Graphite Electrodes of cathode electrode, and the volts DS that applies 0.001V between cathode electrode and anode electrode to make cathode current density be 0.001mAcm
-2, then under the condition of 35 ℃, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the Graphite Electrodes in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Embodiment 6:
1) take analytical pure Calcium hydrogen carbonate as solute, methyl alcohol is solvent, is mixed with the saturated solution (being calcium salt soln) of Calcium hydrogen carbonate; Take salt of wormwood as solute, and methyl alcohol is solvent, and being mixed with concentration is 10
-4mgL
-1alkali lye; Take magnesium chloride as solute, and water is solvent, and being mixed with concentration is 500mgL
-1magnesium chloride solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the Calcium hydrogen carbonate in the calcium salt soln adding, the mol ratio of the salt of wormwood in alkali lye are 2:1, and the magnesium chloride in chemical additives solution accounts for 1% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the Graphite Electrodes of anode electrode and as the Graphite Electrodes of cathode electrode, and the volts DS that applies 8V between cathode electrode and anode electrode to make cathode current density be 2mAcm
-2, then under the condition of 40 ℃, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the Graphite Electrodes in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Embodiment 7:
1) take analytical pure Calcium hydrogen carbonate as solute, glycerol is solvent, is mixed with the saturated solution (being calcium salt soln) of Calcium hydrogen carbonate; Take salt of wormwood as solute, and glycerol is solvent, and being mixed with concentration is 10
-4mgL
-1alkali lye; Take magnesium chloride as solute, and water is solvent, and being mixed with concentration is 100mgL
-1magnesium chloride solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the Calcium hydrogen carbonate in the calcium salt soln adding, the mol ratio of the salt of wormwood in alkali lye are 2:1, and the magnesium chloride in chemical additives solution accounts for 4% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the Graphite Electrodes of anode electrode and as the Graphite Electrodes of cathode electrode, and the volts DS that applies 8V between cathode electrode and anode electrode to make cathode current density be 2mAcm
-2, then under the condition of 35 ℃, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the Graphite Electrodes in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Embodiment 8:
1) take analytical pure Calcium hydrogen carbonate as solute, ethylene glycol is solvent, is mixed with the saturated solution (being calcium salt soln) of Calcium hydrogen carbonate; Take salt of wormwood as solute, and ethylene glycol is solvent, and being mixed with concentration is 10
-4mgL
-1alkali lye; Take magnesium chloride as solute, and water is solvent, and being mixed with concentration is 50mgL
-1magnesium chloride solution (being chemical additives solution);
2) calcium salt soln, alkali lye and chemical additives solution are joined in septate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the Calcium hydrogen carbonate in the calcium salt soln adding, the mol ratio of the salt of wormwood in alkali lye are 2:1, and the magnesium chloride in chemical additives solution accounts for 4% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in septate electrolyzer, pack into as the Graphite Electrodes of anode electrode and as the Graphite Electrodes of cathode electrode, and the volts DS that applies 8V between cathode electrode and anode electrode to make cathode current density be 2mAcm
-2, then under the condition of 35 ℃, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the Graphite Electrodes in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
Embodiment 9:
1) take analytical pure calcium chloride as solute, the mixing solutions of water and ethanol is solvent, and being mixed with concentration is 500mgL
-1calcium salt soln; Take volatile salt as solute, and the mixing solutions of water and ethanol is solvent, is mixed with the saturated solution (being alkali lye) of volatile salt; Take magnesium chloride as solute, and water is solvent, is mixed with magnesium chloride saturated solution (being chemical additives solution); Wherein, in the mixing solutions of the water in step 1) and ethanol, the volume ratio of water and ethanol is 3:2;
2) calcium salt soln, alkali lye and chemical additives solution are joined in aseptate electrolyzer, be uniformly mixed, form reaction solution; Wherein, the calcium chloride in the calcium salt soln adding, the mol ratio of the volatile salt in alkali lye are 1:1, and the magnesium chloride in chemical additives solution accounts for 5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in aseptate electrolyzer, pack into as the titanium matrix lead dioxide electrode of anode electrode and as the Graphite Electrodes of cathode electrode, and the volts DS that applies 10V between cathode electrode and anode electrode to make cathode current density be 0.5mAcm
-2, then under 0 ℃ of condition, stirring and carry out DC electrolysis reaction, electrolytic reaction time 6h, now generates white solid on the Graphite Electrodes in cathodic area, and seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
In the electrolyzer that the present invention uses when electrolytic reaction, have or not middle spacer film all can.
Claims (10)
1. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker, is characterized in that, comprises the following steps:
1) take inorganic calcium salt as solute, water and/or organic solvent are solvent, are mixed with calcium salt soln; Take carbonate as solute, and water and/or organic solvent are solvent, are mixed with alkali lye; Take inorganic magnesium salt as solute, and water is solvent, is mixed with chemical additives solution;
2) calcium salt soln, alkali lye and chemical additives solution are joined in electrolyzer, be uniformly mixed, form reaction solution; Wherein, inorganic calcium salt in the calcium salt soln adding and the mol ratio of the carbonate in alkali lye are (1～2): (1～4), and the chemical additives in chemical additives solution accounts for 0～5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add;
3) in electrolyzer, pack cathode electrode and anode electrode into, and apply volts DS between cathode electrode and anode electrode, make cathode current density at 0.001mAcm
-2～2mAcm
-2, then under the agitation condition of 0～40 ℃, stir and carry out DC electrolysis reaction, until cathodic area generates white solid, seasoning after white solid is collected, obtains calcium carbonate crystal whisker.
2. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 1, is characterized in that: the inorganic calcium salt in described step 1) is calcium chloride, calcium hydroxide, Calcium hydrogen carbonate or nitrocalcite.
3. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 1, its feature is being: the carbonate in described step 1) is sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood or volatile salt.
4. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 1, is characterized in that: the inorganic magnesium salt in described step 1) is magnesium chloride or magnesium nitrate.
5. according to the low dc voltage electrolysis preparation method of the calcium carbonate crystal whisker described in any one claim in claim 1～4, it is characterized in that: in described step 1), the concentration of calcium salt soln is 10
-4mg/L is to the saturation concentration of inorganic calcium salt, and the concentration of alkali lye is 10
-4mg/L is to the saturation concentration of carbonate, and the concentration of chemical additives solution is 0 saturation concentration to inorganic magnesium salt.
6. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 1, is characterized in that: the organic solvent in described step 1) is methyl alcohol, ethanol, ethylene glycol or glycerol.
7. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 1, is characterized in that: the chemical additives in the chemical additives solution described step 2) accounts for 1～5% of the calcium salt soln, alkali lye and the chemical additives solution total mass that add.
8. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 1, it is characterized in that: described step 3) Anodic electrode is metal oxide electrode, Graphite Electrodes or boron-doped diamond electrode, cathode electrode is copper electrode, the ferroelectric utmost point or Graphite Electrodes.
9. the low dc voltage electrolysis preparation method of calcium carbonate crystal whisker according to claim 8, is characterized in that: described metal oxide electrode is titanium matrix lead dioxide electrode or antimony Doped with Titanium matrix stannic oxide electrode.
10. according to the low dc voltage electrolysis preparation method of the calcium carbonate crystal whisker described in claim 1 or 8, it is characterized in that: the volts DS applying between cathode electrode and anode electrode in described step 3) is 0.001V～30V.
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| CN104651943A (en) * | 2015-01-23 | 2015-05-27 | 成都新柯力化工科技有限公司 | Barium sulfate whisker and preparation method thereof |
| CN105660485A (en) * | 2016-03-11 | 2016-06-15 | 中国科学院南海海洋研究所 | Novel coral growing matrix with aragonite enrichment function and preparation method and application thereof |
| 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 |
| 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 |
| CN114959895A (en) * | 2022-06-14 | 2022-08-30 | 湖南大学 | Ultra-long calcium carbonate whisker and preparation method thereof |
| CN114988737A (en) * | 2022-06-02 | 2022-09-02 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Composite material for improving crack resistance of concrete and preparation method and application thereof |
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| CN105660485B (en) * | 2016-03-11 | 2019-06-21 | 中国科学院南海海洋研究所 | A kind of coral growth substrate and its preparation method and application having aragonite enrichment function |
| 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 |
| 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 |
| CN114988737A (en) * | 2022-06-02 | 2022-09-02 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Composite material for improving crack resistance of concrete and preparation method and application thereof |
| CN114959895A (en) * | 2022-06-14 | 2022-08-30 | 湖南大学 | Ultra-long calcium carbonate whisker and preparation method thereof |
| CN114959895B (en) * | 2022-06-14 | 2022-12-27 | 湖南大学 | Ultra-long calcium carbonate whisker and preparation method thereof |
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