CN108069451A - A kind of method that ultra tiny amorphous calcium carbonate is prepared in alcohol-water mixed system - Google Patents
A kind of method that ultra tiny amorphous calcium carbonate is prepared in alcohol-water mixed system Download PDFInfo
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Abstract
The present invention relates to a kind of new processes that ultra tiny amorphous calcium carbonate can on a large scale, simply, be economically produced in alcohol-water system.The present invention proposes, and using carbide slag, calcium hydroxide, calcium chloride as calcium source, in alcohol-water system, quickly prepares the general new process of amorphous calcium carbonate.This method has not only well solved amorphous super fine calcium carbonate commercial synthesis and has stablized the problem preserved, and the industrial wastes such as carbide slag, calcium chloride, flue gas is made to have obtained good utilization.Environment of the present invention, economic and social benefit are notable.
Description
Technical field
The present invention relates to raw material production technical fields.It specifically, can in alcohol-water system the present invention relates to one kind
The extensive simple, method of the ultra tiny amorphous calcium carbonate of economical production.
Background technology
Calcium carbonate is the inorganic particle being widely used in the industries such as papermaking, plastics, rubber, construction material, daily-use chemical industry
Material, dosage and application field are also gradually increasing.2011, the output of whole world calcium carbonate was 70,000,000 tons, Chinese
Yield is 7,000,000 tons, and by 2015, Chinese calcium carbonate total output has reached 12,000,000 tons.However, fast-developing I
State's calcium carbonate industry still remains problems with：
1st, production capacity is seriously superfluous, and mostly using lime-carbonated technique, dust pollution is serious, and CO2 emissions are high, kind
It is single.
2nd, the homogeneity of calcium carbonate low-quality is serious, lacks high-quality calcium carbonate production technology, and kind, specification are few, product whiteness,
Fineness is low, it is impossible to meet quality requirements.
3rd, the by-products resource such as China's tens million of tons annual carbide slag, calcium chloride is not applied very well.It develops and fills
Divide using the rich carbonated exhaust gas such as carbon dioxide in the industrial residues such as carbide slag or calcium chloride and flue gas, exploitation surpasses
Fine, high-quality calcium carbonate production new technique, for subtracting carbon, Implementation of Recycling Economy and promoting calcium carbonate and its application industry
Technological progress is significant.
The main production process of common industrial light calcium carbonate has that carbonizatin method, ammonium chloride method and causticizing process are several, chlorination
Calcium method is also one of method for producing nano-calcium carbonate.Wherein carbonizatin method is divided into as interval carbonizatin method, continuous spray-on process, hypergravity
Method.These existing production methods are difficult to control there are product quality, it is difficult to obtain ultra-fine and uniform particle sizes crystal, energy consumption it is big and
The problems such as product quality is difficult to improve.Concrete technology is as follows：
Carbonizatin method：
Ammonium chloride method：
Calcium Chloride Method
CaCl2+Na2CO3→CaCO3+2NaCl
Suhl ties up (Solvay) method --- the by-product of-sodium acid carbonate industry
Ratio of the nano-calcium carbonate in lightweight carbonate product of Japan is more than 70%, and China is less than 5%, and
Most of product quality is difficult to reach imported product standard.
Calcium carbonate has 6 kinds of crystalline forms：Amorphous calcium carbonate (ACC), calcite, aragonite, vaterite, single aqueous carbonate calcium, six water
Calcium carbonate.Amorphous calcium carbonate therein is the presoma for being changed into other calcium carbonate crystals.It such as can be according to amorphous carbonic acid
The isotropism of calcium and transformable feature develop can on a large scale, simple economy production technology and can not only stablize preservation, but also
The ultra tiny amorphous calcium carbonate product of energy favourable conversions will be very valuable.
Amorphous calcium carbonate can interact in vivo with the organic matter in biology, slowly grow into various patterns
Monocrystalline calcium carbonate.The biomimetic mineralization process of simulation organism is also rested on to the research of amorphous calcium carbonate at present, there is no can work
The method of industry metaplasia production is mainly prepared by following several laboratory approach：
1st, using calcium chloride and sodium carbonate as raw material, quickly mixed by low temperature, quick separating obtains amorphous calcium carbonate.This
Kind method requirement reaction and disengaging time are short, and the difficulty of large-scale production is big, and amorphous calcium carbonate can not be avoided to continue to convert
For other crystalline forms, single amorphous calcium carbonate can not be obtained, and is difficult to stablize preservation.
2nd, the macromoleculars such as poly-aspartate, organic polymer are added in during research is found in the solution system for preparing calcium carbonate
The inorganic ions such as template or sodium metasilicate, magnesium ion can inhibit amorphous calcium carbonate conversion, have stabilization.It is but this extremely slow
Slow biomimetic mineralization preparation method control is difficult, and the formation time is long, and efficiency is very low, is not suitable for industrial production.
3rd, the slow source of release using Organic Ingredients dimethyl carbonate as carbon dioxide utilizes its contact with calcium salt soln
Reaction slowly discharges carbon dioxide, and progressively precipitation generates amorphous calcium carbonate in ammonia atmosphere.Obviously, the environmental protection of the technique
Property, economy and production efficiency are all very poor, are not suitable as the production technology of amorphous calcium carbonate.
At present, it there is no people's research and development that can stablize the ultra tiny amorphous calcium carbonate production technology of preservation.
In this R＆D team on the basis of early-stage study, a kind of side for quickly preparing ultra tiny amorphous calcium carbonate has been invented
Method.
The content of the invention
The object of the present invention is to provide a kind of methods for quickly preparing ultra tiny amorphous calcium carbonate.
We have found under study for action, alcohol can not only regulation system dissolubility and polarity, additionally it is possible to inhibit very well amorphous
Calcium carbonate nucleus is changed into the growth course of crystal, can basis particularly in a certain proportion of alcohol-water mixed solvent system
The operability of device is settled out super fine calcium carbonate nucleus, and can stablize the amorphous stage that rests on, and need not deliberately prolong
The long or shortening time.The solubility calciums such as calcium chloride, calcium glycine and calcium hydroxide raw material or microsolubility calcium raw material, are mixed in alcohol-water
It closes in solution and can obtain amorphous calcium carbonate.Further study show that add in certain density Mg in the mixed solvent2+Afterwards, may be used
Almost 100% amorphous calcium carbonate is obtained, and preservation can be stablized.
Based on above-mentioned discovery, we have invented a kind of simple economy, quick side finally by groping repeatedly and process optimization
Just, can mass production have fine stability ultra tiny amorphous calcium carbonate new process.
Described method includes following steps：One is added in soluble Amino acid calcium salt or soluble calcium salt-ammonia spirit
Certainty ratio alcohol and magnesium salt solution, are mixed evenly；Carbon dioxide or purified flue gas are passed directly into mixed liquor, instead
It after terminal should being reached, is post-processed, you can obtain amorphous calcium carbonate.
Wherein, it is reaction end when pH value in reaction is reduced in the range of 7.5-9.Post processing includes filtering, washs, is dry
Step.
Wherein, soluble Amino acid calcium salt is preferably calcium glycine, Alanine calcium salt or its combination.The amino acid calcium can be with
By making amino acid and the calcium hydroxide reaction in carbide slag or white lime slurries and filtering, the amino acid of purification can conveniently be made
Calcium solution.For amino acid and carbide slag prepare amino acid calcium technique can be found in this research team before in the patent asked
200710098833.6 method, since the fine calcium carbonate that the method for the patent obtains is vaterite-type calcium carbonate, that is,
It says, amorphous calcium carbonate can not be prepared by the method for the patent.But the patented technology can be provided used in the present invention
Raw material amino acid calcium, here, the full content of the patent is herein incorporated by reference.
Wherein, the one kind or more of soluble calcium salt in calcium chloride, calcium sulfate, calcium nitrate or other soluble calcium salts
Kind, it is preferably calcium chloride.The molar ratio of soluble calcium salt and ammonia is preferably 1: 5~5: 1 in soluble calcium salt-ammonia spirit.
Wherein, magnesium salt solution can arbitrary can provide Mg2+Solution, such as magnesium chloride solution, magnesium nitrate solution, sulfuric acid
Magnesium.Calcium ion and magnesium ion molar concentration rate in mixed solution can obtain amorphous calcium carbonate when being 10: 1, and slurry can
To be stabilized, therefore calcium ion and magnesium ion ratio are preferably 10: 1-10 in mixed liquor.
Wherein, the carbon dioxide being passed through is selected from pure carbon dioxide gas, boiler cleaning of off-gas or other carbonateds
Mixed gas carbon source.
The alcohol that the present invention uses can be that monohydric alcohol can also be polyalcohol, can miscible with water or partial miscibility,
It can be the alcohol of C1-C10, be preferably the alcohol of C1-C5, more preferably methanol, ethyl alcohol, propyl alcohol, butanol or amylalcohol.For the use of alcohol
Amount, due to the volume ratio of calcium solution and alcoholic solution more than 2: 1 when, can obtain amorphous calcium carbonate as main product,
The volume ratio of calcium solution and alcohol is preferably 1: 0.5-10.
Wherein, the filtrate obtained by this method can directly apply mechanically or be used by post-processing rear enclosure.Wherein, obtained after processing
Contain amino acid, MgCl2Aqueous solution can continue on for next group carbide slag reaction purification.
Filtrate after separation amorphous calcium carbonate takes following processing mode：
When using calcium glycine solution or calcium chloride and ammonia water mixture as raw material, filtrate can be directly covered for calcium carbide
The dissolving of slag, quick lime or white lime carries calcium；In order to adjust alcohol water ratio, can also carry out after being distilled to recover ethyl alcohol and partial solvent water
The dissolving covered again for carbide slag, quick lime or white lime carries calcium.
About in 50-100nm, amorphous calcium carbonate holds the amorphous calcium carbonate aggregate diameter that new process is prepared very much
Easily disperse in aqueous solution, to suspend steadily in the long term.
The present invention can be further illustrated by embodiment in detail below：
1st, carbide slag raw material prepares amorphous calcium carbonate：
By carbide slag for exemplified by calcium source, specific embodiments of the present invention prepare amorphous calcium carbonate and include the following steps：
Using our 200710098833.6 method of patent, by the calcium hydroxide reaction in amino acid and carbide slag simultaneously
The amino acid calcium solution of purification can be conveniently made in filtering.Chemical equation carry out as follows (wherein, R for example can be H or
Methyl)：
Ca(OH)2+NH2CHRCOOH→(NH2CHRCOO)2Ca+H2O
The amino acid calcium solution for dissolving reaction can be by carbon slag, silicon, iron, the insoluble impurities such as aluminium in carbide slag by filtering
It removes, obtains the preferable amino acid calcium salting liquid of purity.
Soluble amino acid can be conveniently made by the calcium hydroxide reaction in amino acid and carbide slag or white lime slurries
Calcium solution, while purified raw material.At room temperature, amino acid calcium solution is mixed with ethanol solution according to certain volume ratio
Uniformly, then into mixed liquor a certain amount of magnesium chloride is added in, is stirred evenly.Pure carbon dioxide gas is passed directly into mixed solution
Body, purified flue gas gas control the pH value of terminal solution to 7.5 or so, stop carbon dioxide raw material and add in, filtering,
Washing, can obtain white lotion, and drying obtains the amorphous calcium carbonate product of white.Reaction equation is following, and (wherein R is
H)：
(NH2CHRCOO)2Ca+CO2+H2O=CaCO3+2NH2CHRCOOH
This technique is by glycine to carbide slag purifying technique and glycine -ol-carbonic acid of the magnesium ion in carbonisation
Calcium nucleus jointly controls effect, it can be achieved that the recycling of carbide slag and flue gas, while produces the ultra tiny nothing of high-quality
Shape calcium carbonate product.
The present invention is developed with the calcium salts raw material such as calcium chloride or/and calcium glycine or/and calcium hydroxide, and body is adjusted using alcohol
It is polarity and inhibits the characteristic that crystal is grown up, in the alcohol and water mixed solvent of optimization ratio, exists in certain density magnesium salts
Under, prepare ultra-fine grain diameter, the new process for the amorphous calcium carbonate that preservation can be stablized.What is particularly worth mentioning is that new process passes through
Glycine jointly controls work in carbonisation to carbide slag purifying technique and glycine -ol-magnesium ion to calcium carbonate nucleus
With realizing the recycling of carbide slag and flue gas, the ultra tiny amorphous calcium carbonate of high-quality, stabilization can be produced.
It is controllable in the range of 5-30min using the reaction time of the amorphous calcium carbonate prepared by the method for the present invention, profit
With X-ray diffractometer (XRD), field emission electron scanning electron microscope (SEM), Fourier infrared spectrograph (FT-IR), surface tension instrument
The product obtained after reaction is characterized.Characterization result shows：1st, the amorphous calcium carbonate prepared by this method is all without fixed
Shape calcium carbonate, no other impurities, and amorphous calcium carbonate slurries can be stablized a week, the aggregate of amorphous calcium carbonate
Grain size is in 50-100nm.
The method of the present invention has many advantages, such as that simple for process, condition controlled range is big, raw material is cheap and easy to get, easy to operate, fits
For industrial a wide range of production, pure calcium carbonate obtained is high, can be big with different crystal forms, pattern, grain size further to obtain
Small calcium carbonate provides presoma, meets the needs of calcium carbonate industry is to different calcium carbonate.
The method of the present invention can be cheap the three wastes such as calcium chloride, carbide slag and cleaned flue gas prepare with high price
The amorphous calcium carbonate of value.
Description of the drawings
Fig. 1 is the XRD diagram to 1 product of embodiment；
Fig. 2 is that the SEM of 1 product of embodiment is schemed；
Fig. 3 is the calcium carbonate XRD that is obtained under different volume ratio of alcohol to water (R=alcohol/water) to the XRD diagram of 2 product of embodiment
Figure, a, 0.42, b, 0.83, c, 1.7, d, 2.5, e, 5；
Fig. 4 is to the XRD diagram of 3 product of embodiment, volume ratio of alcohol to water 3: 1, the calcium carbonate XRD that different ageing obtains
Figure, a, 0h, b, 1h, c, 2h, d, 3h, e, 4h；
Fig. 5 is the calcium carbonate XRD diagram obtained at a temperature of differential responses to the XRD diagram of 4 product of embodiment, a, 30 DEG C, b, 40
DEG C, c, 50 DEG C, d, 60 DEG C, e, 70 DEG C；
Fig. 6 is the XRD diagram to 5 product of embodiment, the calcium carbonate XRD diagram that reaction end obtains under different pH, a, 8.3,
B, 7.8, c, 7.2, d, 6.8；
Fig. 7 is the XRD diagram of 7,8,9,10 product of embodiment.
Specific embodiment
With reference to specific embodiment, the technical solution that the present invention is further explained.These embodiments are merely to illustrate this
It invents rather than limits the scope of the invention.
Embodiment 1：Be 3: 1 using calcium glycine as raw material, ethyl alcohol and calcium solution volume ratio, calcium ion and magnesium ion mole
Than to prepare amorphous calcium carbonate under conditions of 5: 1
The absolute ethyl alcohol of 30mL is measured in three-necked flask, then the calcium glycine of the 1mol/L of addition 10mL is molten into flask
Liquid adds in the MgCl of the 1mol/L of 2mL into solution2Solution makes calcium ion in solution with magnesium ion molar ratio be 5: 1, stirs
After mixing uniformly, CO is passed through2, until stopping being passed through CO when the pH value of solution is 7.52.The calcium carbonate serosity of gained is taken out at once
Filter, is washed with absolute ethyl alcohol or alcohol-water mixture, and by obtained calcium carbonate, drying obtains for 24 hours in 60 DEG C of vacuum drying oven
Calcium carbonate product 0.96g.Products obtained therefrom purity is 97.9%, yield 96%.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample X-ray diffraction (XRD) of gained
As shown in Figure 1, the product arrived as we know from the figure should be amorphous calcium carbonate, the SEM of gained sample is as shown in Figure 1, its aggregate
Diameter is between 50-100nm.
Embodiment 2：Using calcium glycine as raw material, ethyl alcohol and calcium solution different volumes ratio, calcium ion and magnesium ion mole
Than to prepare amorphous calcium carbonate under conditions of 5: 1
Respectively measure 30mL absolute ethyl alcohol in 5 three-necked flasks, then into flask bonus point do not enter 5mL, 10mL,
The calcium glycine solution of the 1mol/L of 15mL, 30mL, 60mL, number are respectively 1,2,3,4,5.It is added in again into 5 solution
The MgCl of the 1mol/L of 1mL, 2mL, 3mL, 6mL, 12mL2Solution, it is 5: 1 to make the calcium ion in solution and magnesium ion molar ratio.
After stirring evenly, CO is passed through2, until stopping being passed through CO when the pH value of solution is 82.The calcium carbonate serosity of gained is taken out at once
Filter, is washed with absolute ethyl alcohol or alcohol-water mixture, and by obtained calcium carbonate, drying obtains for 24 hours in 60 DEG C of vacuum drying oven
Product.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample x-ray diffraction (XRD) of gained
As shown in Figure 3.As we know from the figure ethyl alcohol and calcium solution volume ratio respectively than for 1: 2,1: 1 when, obtained product should be carbonic acid
The mixture of calcium and calcium glycine；When ethyl alcohol and calcium solution volume ratio are 2: 1, obtained product is substantially amorphous carbonic acid
Calcium；When ethyl alcohol and calcium solution volume ratio are 3: 1, obtained calcium carbonate product is all amorphous calcium carbonate.Therefore, ethyl alcohol and calcium
Liquor capacity is than not preferably less than 1: 2.
Embodiment 3：Be 3: 1 using calcium glycine as raw material, ethyl alcohol and calcium solution volume ratio, calcium ion and ion molar ratio
To prepare amorphous calcium carbonate under the conditions of 5: 1, different ageing
The absolute ethyl alcohol of 30mL is measured in three-necked flask with the graduated cylinder of 50mL, then the 1mol/L of 10mL is added in into flask
Calcium glycine solution, then into solution add in 2mL 1mol/L MgCl2Solution makes calcium ion and magnesium ion in solution
Molar ratio is 5: 1.It stirs and is passed directly into CO2, until stopping being passed through CO when the pH value of solution is 82.It is respectively in digestion time
Be sampled when 0h, 1h, 2h, 3h, 4h, the calcium carbonate serosity of gained filtered, with absolute ethyl alcohol or alcohol-water mixture into
Row washing, the drying in 60 DEG C of vacuum drying oven of obtained calcium carbonate obtain product for 24 hours.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample x-ray diffraction (XRD) of gained
As shown in Figure 4.It can be seen that digestion time interior obtained calcium carbonate in 2h remains as amorphous calcium carbonate.Digestion time
Extending amorphous calcium carbonate can gradate as aragonite calcium carbonate.Therefore, the ageing of amorphous calcium carbonate slurries is no more than 2h.
Embodiment 4：Be 3: 1 using calcium glycine as raw material, ethyl alcohol and calcium solution volume ratio, calcium ion and magnesium ion mole
Than to prepare amorphous calcium carbonate under 5: 1, differential responses temperature conditionss
The absolute ethyl alcohol that 30mL is measured with the graduated cylinder of 50mL is poured into respectively in 5 three-necked flasks, and to number be respectively 1,2,
3rd, 4,5, then the calcium glycine solution of the 1mol/L of 10mL is added in into flask respectively, it is stirred with magneton by 600r/min of speed
5min adds in the MgCl of the 1mol/L of 2mL into each there-necked flask again afterwards2Solution makes calcium ion and magnesium ion in solution
Molar ratio is 5: 1.Stir 5min after, will number be 1,2,3,4,5 there-necked flask be respectively placed in 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C,
To constant temperature in 70 DEG C of water bath with thermostatic control, CO is passed directly into2, until stopping being passed through CO when the pH value of solution is 82.By the carbonic acid of gained
Calcium slurries are filtered, and are washed with absolute ethyl alcohol or alcohol-water mixture, and obtained calcium carbonate is in 60 DEG C of vacuum drying oven
Drying obtains product for 24 hours.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample x-ray diffraction (XRD) of gained
As shown in figure 5, the calcium carbonate obtained as we know from the figure when reaction temperature is 30 DEG C is amorphous calcium carbonate.With reaction temperature
Increase, amorphous calcium carbonate part is seldom partially converted into aragonite calcium carbonate.Until reaction temperature is 70 DEG C, calcium carbonate
Crystal form has calcite, aragonite, amorphous coexists.Therefore, amorphous calcium carbonate slurry reaction temperature is unsuitable higher, and reaction temperature can
Control is in the range of 30-60 DEG C, relatively low control.
Embodiment 5：Be 3: 1 using calcium glycine as raw material, ethyl alcohol and calcium solution volume ratio, calcium ion and magnesium ion mole
Than to prepare amorphous calcium carbonate under 5: 1, difference pH end-conditions
The absolute ethyl alcohol of 30mL is measured in three-necked flask with the graduated cylinder of 50mL, then the 1mol/L of 10mL is added in into flask
Calcium glycine solution again into solution add in 2mL 1mol/L MgCl2Solution makes the calcium ion in solution rub with magnesium ion
You are than being 5: 1.CO is passed directly into whipping process2, sample solution is extracted in different solutions difference pH value, by the carbonic acid of gained
Calcium slurries are filtered, and are washed with absolute ethyl alcohol or alcohol-water mixture, and obtained calcium carbonate is in 60 DEG C of vacuum drying oven
Drying obtains product for 24 hours.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample X-ray diffraction (XRD) of gained
As shown in fig. 6, it can be seen that when pH terminals are 8.3, obtained calcium carbonate is amorphous calcium carbonate；When pH terminals are 7.8,
The obtained calcium carbonate overwhelming majority is amorphous calcium carbonate, wherein, the glycine that the XRD peaks of appearance are remained on carbonic acid is adsorbed
In calcium carbonate surface；But when pH is down to 7.2, gained calcium carbonate is pure vaterite calcium carbonate.So prepare amorphous carbonic acid
The terminal pH of calcium is preferably controlled more than 7.5.
Embodiment 6：As raw material, ethyl alcohol from calcium solution volume ratio be 3: 1 using calcium glycine, calcium ion and magnesium ion it is different
Amorphous calcium carbonate is prepared under molar ratio
For the absolute ethyl alcohol for measuring 30mL with the graduated cylinder of 50mL in 5 three-necked flasks, it is respectively 1,2,3,4,5 to number, then
The calcium glycine solution of the 1mol/L of 10mL is added in into flask, and the MgCl of different amounts of 1mol/L is added in into solution2It is molten
Liquid makes the calcium ion in solution and magnesium ion molar ratio to be respectively 1: 0,1: 1,2: Isosorbide-5-Nitrae: 1,8: 1.After stirring 5min, directly
It is passed through CO2Until pH is 8, the sample solution of gained is filtered, is washed with absolute ethyl alcohol or alcohol-water mixture, is obtained
Calcium carbonate in 60 DEG C of vacuum drying oven drying obtain product for 24 hours.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The crystal form of the sample of gained such as 1 institute of table
Show.As seen from the table, when calcium ion and magnesium ion molar ratio are 8: 1, obtained calcium carbonate remains as amorphous calcium carbonate, and
Amorphous calcium carbonate slurries can be stablized 3 days；With calcium ion and magnesium ion than increase, what amorphous calcium carbonate slurries were stablized
Time is also longer.However, amorphous calcium carbonate cannot be accessed in the case where lacking magnesium ion, illustrate that magnesium ion plays surely
Determine the effect of amorphous calcium carbonate.
1. calcium ion of table stands calcium carbonate obtained by different time with the calcium carbonate serosity obtained under magnesium ion different mol ratio
Crystal form
Embodiment 7：Be 3: 1 using calcium chloride as raw material, n-butanol and calcium solution volume ratio, calcium ion and magnesium ion mole
Than to prepare amorphous calcium carbonate under conditions of 5: 1
The n-butanol of 30mL is measured in three-necked flask, the CaCl of the 1mol/L of 10mL is added in into flask2Solution, then add
Enter the MgCl of the 1mol/L of 2mL2Solution, it is 5: 1 to make the calcium ion in solution and magnesium ion molar ratio.In whipping process, to three
The mass fraction that 2mL is added in mouth flask is 27% ammonia spirit, is passed through CO2, until stopping when the pH value of solution is 8.5 logical
Enter CO2.The calcium carbonate serosity of gained is filtered, is washed with absolute ethyl alcohol or alcohol-water mixture, the carbonic acid that will be obtained
Calcium drying in 60 DEG C of vacuum drying oven for 24 hours, obtains calcium carbonate 0.952g, purity 97.3%, yield 95.2%.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample X-ray diffraction (XRD) of gained
As shown in Fig. 7-a, resulting product is amorphous calcium carbonate.
Embodiment 8：Be 3: 1 using calcium chloride as raw material, methanol and calcium solution volume ratio, calcium ion and magnesium ion molar ratio
To prepare amorphous calcium carbonate under conditions of 5: 1
The methanol of 30mL is measured in three-necked flask, bonus point does not enter the CaCl of the lmol/L of 10mL into flask2Solution.With
Magneton is stirred solution, mixing speed 600r/min.After stirring, the MgCl of the lmol/L of 2mL is added in into solution2
Solution, it is 5: 1 to make the calcium ion in solution and magnesium ion molar ratio.After stirring 5min, the quality of 2mL is added in into three-necked flask
Fraction is 27% ammonia spirit, is passed through CO2, until stopping being passed through CO when the pH value of solution is 8.52.At once by the carbonic acid of gained
Calcium slurries are filtered, and are washed with absolute ethyl alcohol or alcohol-water mixture, by vacuum drying oven of the obtained calcium carbonate at 60 DEG C
Middle drying for 24 hours, obtains calcium carbonate 0.873g, purity 98.5%, yield 87.3%.
The product obtained after reaction is characterized with X-ray diffractometer (XRD).The sample X-ray diffraction (XRD) of gained
As shown in Fig. 7-b, resulting product is amorphous calcium carbonate.
Embodiment 9：Be 3: 1 using calcium chloride as raw material, ethyl alcohol and calcium solution volume ratio, calcium ion and magnesium ion ratio is 5:
1st, digestion time prepares amorphous calcium carbonate under conditions of being 5min
The absolute ethyl alcohol for measuring 30mL with the graduated cylinder of 50mL adds in the 1mol/L's of 10mL into flask in three-necked flask
CaCl2Solution adds in the MgCl of the 1mol/L of 2mL in whipping process into solution2Solution makes calcium ion and magnesium in solution
Ion molar ratio is 5: 1.The mass fraction for adding in 2mL in whipping process into three-necked flask is 27% ammonia spirit, is stirred
CO is passed directly into after ageing 5min2, until stopping being passed through CO when the pH value of solution is 8.52.The calcium carbonate serosity of gained is carried out
It filters, is washed with absolute ethyl alcohol or alcohol-water mixture, obtained calcium carbonate dries for 24 hours at 60 DEG C in baking oven, obtains carbonic acid
Calcium product 0.968g, product purity reach 99.1%, yield 96.8%.
With X-ray diffractometer (XRD), the product obtained after reaction is characterized.The sample X-ray diffraction of gained
(XRD) as shown in Fig. 7-c, obtained calcium carbonate is amorphous calcium carbonate.
Embodiment 10：Be 3: 1 using calcium chloride as raw material, propyl alcohol and calcium solution volume ratio, calcium ion and magnesium ion ratio are
5th, digestion time prepares amorphous calcium carbonate under conditions of being 5min
The propyl alcohol of 30mL is measured in three-necked flask with the graduated cylinder of 50mL, then add in into flask the 1mol/L of 10mL
CaCl2Solution adds in the MgCl of the 1mol/L of 2mL in whipping process into solution2Solution, make calcium ion in solution and magnesium from
Son is than being 5: 1.The mass fraction for adding in 2mL in whipping process into three-necked flask is 27% ammonia spirit, and stirring is aged
CO is passed directly into after 5min2, until stopping being passed through CO when the pH value of solution is 8.52.The calcium carbonate serosity of gained is filtered,
It is washed with absolute ethyl alcohol or alcohol-water mixture, the drying in 60 DEG C of vacuum drying oven of obtained calcium carbonate obtains carbonic acid for 24 hours
Calcium product 0.971g, product purity reach 98.3%, yield 97.1%.
With X-ray diffractometer (XRD), the product obtained after reaction is characterized.The sample X-ray diffraction of gained
(XRD) as shown in Fig. 7-d, obtained calcium carbonate is amorphous calcium carbonate.
Claims (8)
1. a kind of method that amorphous calcium carbonate is prepared in alcohol-water mixed system, includes the following steps：
Certain proportion alcohol and magnesium salt solution are added in soluble Amino acid calcium salt or soluble calcium salt-ammonia spirit, stirring is mixed
It closes uniform；Carbon dioxide or purified flue gas are passed directly into mixed liquor, after reaction reaches terminal, is post-processed,
It can obtain amorphous calcium carbonate.
2. the method according to claim 1, wherein, it is reaction end when pH value in reaction is reduced in the range of 7.5-9, post-processes
Including filtering, washing, drying steps.
3. according to the method for claim 1 or 2, wherein, soluble Amino acid calcium salt is selected from calcium glycine or Alanine calcium salt；It is described
One or more of the soluble calcium salt in calcium chloride, calcium sulfate, calcium nitrate or other soluble calcium salts are preferably chlorination
Calcium.
4. according to the method for any one of claim 1-3, wherein, magnesium salt solution can arbitrary can provide Mg2+Solution, such as
Magnesium chloride solution, magnesium nitrate solution, Adlerika；Calcium ion and magnesium ion ratio are preferably 10: 1-10 in mixed solution.
5. according to the method for any one of claim 1-4, wherein, the carbon dioxide being passed through is selected from pure carbon dioxide gas, boiler
Cleaning of off-gas or other carbonated mixed gas carbon sources.
6. according to the method for any one of claim 1-5, wherein, alcohol is the alcohol of C1-C10, is preferably the alcohol of C1-C5, more preferably
For methanol, ethyl alcohol, propyl alcohol, butanol or amylalcohol；The volume ratio of calcium solution and alcohol is preferably 1: 0.5-10.
7. according to the method for any one of claim 1-6, wherein, it separates the filtrate after amorphous calcium carbonate and directly applies mechanically or pass through
Cross processing rear enclosure use.
8. method according to claim 7, wherein, it separates the filtrate after amorphous calcium carbonate and takes following processing mode：
When using calcium glycine solution or calcium chloride and ammonia water mixture as raw material, filtrate is directly covered for carbide slag, life
The dissolving of lime or white lime carries calcium；Alternatively, in order to adjust alcohol water ratio, applied mechanically again after ethyl alcohol and partial solvent water is distilled to recover
Calcium is carried in the dissolving of carbide slag, quick lime or white lime.
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