CN106542557B - A kind of preparation technology of nano-calcium carbonate - Google Patents
A kind of preparation technology of nano-calcium carbonate Download PDFInfo
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- CN106542557B CN106542557B CN201610904393.8A CN201610904393A CN106542557B CN 106542557 B CN106542557 B CN 106542557B CN 201610904393 A CN201610904393 A CN 201610904393A CN 106542557 B CN106542557 B CN 106542557B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of preparation technology of nano-calcium carbonate, using high activity quick lime and high-pureness carbon dioxide as raw material, using three-level formula carbonators as consersion unit, carries out reaction preparation；The activity degree of high activity quick lime is 360 380；The purity of high-pureness carbon dioxide is more than or equal to 99%；Three-level formula carbonators is to be sequentially connected in series to form by the carbonators of three one-level carbonators, two level carbonators and three-level carbonators different capabilities, and the effecting reaction volumetric ratio of one-level carbonators, two level carbonators and three-level carbonators is 1:4:16, the intake per hour of high-pureness carbon dioxide and the effecting reaction volumetric ratio of the carbonators are 23 in each carbonators:0.08.Nano-calcium carbonate prepared by method provided by the invention has Particle dispersity good, uniform in size, it is distributed between 20 30nm, the advantage such as regular appearance, purity height, and the preparation technology carburizing reagent time provided by the invention is shortened significantly, production efficiency is high, the utilization rate of consersion unit is also improved simultaneously, suitable for popularization and application in the industrial production.
Description
Technical field
The present invention relates to the preparation field of calcium carbonate, specifically a kind of preparation technology of nano-calcium carbonate.
Background technology
Nano-calcium carbonate is a kind of Novel super-thin solid powder material to grow up the 1980s, is widely used in
The industries such as rubber, plastics, papermaking, chemical building material, ink, coating, fluid sealant and adhesive, its granularity between 10nm-100nm it
Between.At present, the preparation method of nano-calcium carbonate mainly has continuous multilevel spray carbonization, high-gravity carbonation method, interval bubbling carbonation method
Deng.Wherein, continuously the production efficiency of spraying multistage carbonizatin method is of a relatively high, also of a relatively high to the availability of carbon dioxide, but
The operability of its steady production is relatively poor, and the product cut size distribution finally prepared is wider, the application characteristic one of product
As it is relatively low.The product average grain diameter of high-gravity reactive precipitation is small, has that particle diameter distribution is narrow, product quality it is relatively stable and
Advantages such as carbonization time is relatively short, but its investment of production is larger, and the power consumption in producing is high, so as to cause production cost
It is higher, method large-scale application is there is no at present.And interval bubbling carbonation method invests relatively fewer and easy to operate, its technological parameter control
Make workable, but the raw material generally used in industry at present is purity for 28-35% carbon dioxide and 280 or so activity
The quick lime of degree is raw material, and its production efficiency is low, and the people in industry attempts high using high-purity carbon dioxide or/and activity degree
Quick lime is that raw material carries out carbonization preparation, but high-purity carbon dioxide and the quick lime of high activity prepare calcium carbonate, reaction be present
Speed is exceedingly fast, and the problem of unmanageable crystalline form be present；Even if forming crystalline form, the particle diameter of its product is present：Particle diameter distribution is wide, particle diameter
The defects of not of uniform size and lack of homogeneity, this greatly affected the stability of nano-calcium carbonate later stage application.Therefore, in Gao Sheng
Produce under efficiency, preparing the nano-calcium carbonate that particle diameter is small, particle diameter distribution is narrow, uniformity is good just turns into the class actively studied in industry
Topic.
The content of the invention
It is an object of the invention to provide a kind of preparation technology of nano-calcium carbonate, to solve the brewed standby nano-sized carbon of interval drum
The problem of low production efficiency, particle diameter are big, particle diameter distribution is wide, lack of homogeneity be present in sour calcium.
The purpose of the present invention is achieved through the following technical solutions：A kind of preparation technology of nano-calcium carbonate is living with height
Property quick lime and high-pureness carbon dioxide are raw material, using three-level formula carbonators as consersion unit, carry out reaction preparation；It is described high living
The activity degree of property quick lime is 360-380；The purity of described high-pureness carbon dioxide is more than or equal to 99%；The three-level formula carbon
It is to be sequentially connected in series to form by the carbonators of three one-level carbonators, two level carbonators and three-level carbonators different capabilities to change tower, institute
The effecting reaction volumetric ratio for stating one-level carbonators, two level carbonators and three-level carbonators is 1:4:16, it is high-purity in each carbonators
It is 2-3 to spend the intake per hour of carbon dioxide with the effecting reaction volumetric ratio of the carbonators:0.08；
Its preparation technology comprises the following steps：
（a）Quick lime and digestion water are pressed 1:5 mixture slakings, sieving, obtain milk of lime；
（b）Maintain at 20-25 DEG C, adjust the concentration of the milk of lime to 10 Baume degrees, add crystal control agent, obtain just
Beginning slurry；The addition of the crystal control agent is Ca in milk of lime (OH)2The 0.8-1.2% of butt quality；
（c）The initial slurry is pumped into one-level carbonators, is passed through the high-pureness carbon dioxide, keeps Ta Neiwen
Spend for the 7min that is carbonized at 20-24 DEG C, blowing；Initial slurry, carburizing reagent are repeatedly pumped into using same technique, put
Slurry, is stored in one-level slurry can, obtains one-level carbonized stock；
（d）The one-level carbonized stock is pumped into two level carbonators, is passed through the high-pureness carbon dioxide, is kept in tower
Temperature carries out carburizing reagent at 20-24 DEG C, when the pH value of slurry is to 9, blowing, is repeatedly pumped into using same technique
One-level carbonized stock, carburizing reagent, blowing, it is stored in two level slurry can, obtains two level carbonized stock；
（e）By the still aging 72h of two level carbonized stock, the two level carbonized stock after ageing is pumped into three-level carbonators,
It is passed through the high-pureness carbon dioxide, keeps temperature in tower to carry out carburizing reagent at 20-24 DEG C, treats the pH value of slurry to 6.8-
When 7.0, carbonization is terminated, the end reaction slurries filtration that will be obtained, is washed, dries, produces nano-calcium carbonate.
Step（b）Described crystal control agent is industrial white sugar.
Step（a）Quick lime and digestion water are pressed 1:The concrete technology of 5 mixture slakings is：Quick lime is placed in digestion machine
At charging scffold；Feedwater is heated to temperature as 45-55 DEG C；Open digestion machine；Warm water is added to the 2/ of digestion machine dischargeable capacity
3, while adding quick lime, Bian Jiashui, digested, you can.
Step（a）The equipment that the sieving uses is the circular vibrating screen of 80 mesh.
The present invention uses the CO of high-purity2With high activity CaO, by the three-level formula carbonators series devices of specific volume with
And specific low temperature three-level carbonization technique, it is prepared for nano-calcium carbonate particles.The nanometer prepared using method provided by the invention
Calcium carbonate has that Particle dispersity is good, uniform in size, the advantage such as particle diameter distribution is between 20-30nm, regular appearance, purity height,
And the preparation technology carburizing reagent time provided by the invention is shortened significantly, production efficiency is high, while also improves reaction and set
Standby utilization rate, suitable for the popularization and application in the production of high-performance nano calcium carbonate industry is prepared.
Brief description of the drawings
Fig. 1 is that embodiment 1 prepares electron-microscope scanning figure of the nano-calcium carbonate under 100nm precision.
Fig. 2 is electron-microscope scanning figure of the material of the preparation of comparative example 1 under 500nm precision.
Fig. 3 is electron-microscope scanning figure of the material of the preparation of comparative example 1 under 200nm precision.
Embodiment
Example below is used to the present invention be further described, but the invention is not limited in any way.
Embodiment 1
（1）The quick lime that the 100kg activity degrees weighed up are 380 is placed at digestion machine charging scffold；By 500kg water
50 DEG C are warming up to as digestion water；Open digestion machine；Digestion water is added into digestion machine effectively to digest at the 2/3 of volume, will be surplus
Remaining waterside Jia Shui, while adding quick lime, it is added step-wise in digestion machine, digests 45min, stop digestion, crosses 80 mesh circular vibrating screens, obtain
Milk of lime；
（2）Maintain at 20-25 DEG C, adjust the concentration of milk of lime to 10 Baume degrees, add Ca (OH) in milk of lime2Butt
The industrial white sugar crystal control agent of quality 1.0%, obtains initial slurry；
（3）By 0.08m3Initial slurry to be pumped into effecting reaction volume be 0.08m3One-level carbonators in, be passed through purity
For 99.5% carbon dioxide, the flow velocity for controlling high-pureness carbon dioxide is 2.5m3/ h, kept in carbonation reaction in tower
Temperature is the 7min that is carbonized at 20-24 DEG C, blowing, is stored in one-level slurry can；Same technique repeatedly pump is used again
Enter initial slurry, carbonization, blowing, be also stored in one-level slurry can, obtain one-level carbonized stock；
（4）By 0.32m3One-level carbonized stock to be pumped into effecting reaction volume be 0.32m3Two level carbonators in, be passed through pure
The carbon dioxide for 99.5% is spent, the flow velocity for controlling high-pureness carbon dioxide is 9m3/ h, kept in carbonation reaction in tower
Temperature carries out carburizing reagent at 20-24 DEG C, when the pH value of slurry reaches 9, blowing, is stored in two level slurry can；Using
Same technique is repeatedly pumped into one-level carbonized stock, carbonization, blowing, is stored in two level slurry can, obtains two level carbonized stock；
（5）Two level carbonized stock is placed in ageing tank and is aged 72h, by 1.28m3Two level carbonized stock after ageing has been pumped into
Validity response volume is 1.28m3Three-level carbonators in, be passed through purity be 99.5% carbon dioxide, control high-pureness carbon dioxide
Flow velocity be 35m3/ h, keep temperature in tower to carry out carburizing reagent at 20-24 DEG C in carbonation reaction, treat the pH of slurry
When being worth 7.0, carbonization is terminated, is filtered by plate and frame filter press after obtained end reaction slurry is activated, is washed with clear water, is dried
It is less than 0.35% to moisture, produces nano-calcium carbonate.
Embodiment 2
（1）The quick lime that the 100kg activity degrees weighed up are 360 is placed at digestion machine charging scffold；By 500kg water
50 DEG C are warming up to as digestion water；Open digestion machine；Digestion water is added into digestion machine effectively to digest at the 2/3 of volume, will be surplus
Remaining waterside Jia Shui, while adding quick lime, it is added step-wise in digestion machine, digests 40min, stops digestion, using 80 mesh circular vibrating screens
Sieving, obtains milk of lime；
（2）Maintain at 20-25 DEG C, adjust the concentration of milk of lime to 10 Baume degrees, add Ca (OH) in milk of lime2Butt
The industrial white sugar crystal control agent of quality 0.8%, obtains initial slurry；
（3）By 0.08m3Initial slurry to be pumped into effecting reaction volume be 0.08m3One-level carbonators in, be passed through purity
For 99 % carbon dioxide, the flow velocity for controlling high-pureness carbon dioxide is 2m3/ h, temperature in tower is kept in carbonation reaction
For the 7min that is carbonized at 20-24 DEG C, blowing, it is stored in one-level slurry can；Repeatedly it is pumped into just using same technique again
Beginning slurry, carbonization, blowing, also it is stored in one-level slurry can, obtains one-level carbonized stock；
（4）By 0.32m3One-level carbonized stock to be pumped into effecting reaction volume be 0.32m3Two level carbonators in, be passed through pure
The carbon dioxide for 99% is spent, the flow velocity for controlling high-pureness carbon dioxide is 10m3/ h, keeps Ta Neiwen in carbonation reaction
Degree carries out carburizing reagent at 20-24 DEG C, when the pH value of slurry reaches 9, blowing, is stored in two level slurry can；Using same
The technique of sample is repeatedly pumped into one-level carbonized stock, carbonization, blowing, is stored in two level slurry can, obtains two level carbonized stock；
（5）Two level carbonized stock is placed in ageing tank and is aged 72h, by 1.28m3Two level carbonized stock after ageing has been pumped into
Validity response volume is 1.28m3Three-level carbonators in, be passed through purity be 99% carbon dioxide, control high-pureness carbon dioxide
Flow velocity is 40m3/ h, keep temperature in tower to carry out carburizing reagent at 20-24 DEG C in carbonation reaction, treat the pH value of slurry
During to 6.8, carbonization is terminated, plate and frame filter press filtering will be crossed after the logical activation of obtained end reaction slurry, washed, dried extremely with clear water
Moisture is less than how many 0.35%, produces nano-calcium carbonate.
Embodiment 3
（1）The quick lime that the 100kg activity degrees weighed up are 370 is placed at digestion machine charging scffold；By 500kg water
50 DEG C are warming up to as digestion water；Open digestion machine；Digestion water is added into digestion machine effectively to digest at the 2/3 of volume, will be surplus
Remaining waterside Jia Shui, while adding quick lime, it is added step-wise in digestion machine, digests 45min, stops digestion, using 80 mesh circular vibrating screens
Sieving, obtains milk of lime；
（2）Maintain at 20-25 DEG C, adjust the concentration of milk of lime to 10 Baume degrees, add Ca (OH) in milk of lime2Butt
The industrial white sugar crystal control agent of quality 1.2%, obtains initial slurry；
（3）By 0.08m3Initial slurry to be pumped into effecting reaction volume be 0.08m3One-level carbonators in, be passed through purity
For 99.7% carbon dioxide, the flow velocity for controlling high-pureness carbon dioxide is 3m3/ h, keeps Ta Neiwen in carbonation reaction
Spend for the 7min that is carbonized at 20-24 DEG C, blowing, be stored in one-level slurry can；Repeatedly it is pumped into using same technique again
Initial slurry, carbonization, blowing, also it is stored in one-level slurry can, obtains one-level carbonized stock；
（4）By 0.32m3One-level carbonized stock to be pumped into effecting reaction volume be 0.32m3Two level carbonators in, be passed through pure
The carbon dioxide for 99.7% is spent, the flow velocity for controlling high-pureness carbon dioxide is 8m3/ h, kept in carbonation reaction in tower
Temperature carries out carburizing reagent at 20-24 DEG C, when the pH value of slurry reaches 9, blowing, is stored in two level slurry can；Using
Same technique is repeatedly pumped into one-level carbonized stock, carbonization, blowing, is stored in two level slurry can, obtains two level carbonized stock；
（5）Two level carbonized stock is placed in ageing tank and is aged 72h, by 1.28m3Two level carbonized stock after ageing has been pumped into
Validity response volume is 1.28m3Three-level carbonators in, be passed through purity be 99.7% carbon dioxide, control high-pureness carbon dioxide
Flow velocity be 32m3/ h, keep temperature in tower to carry out carburizing reagent at 20-24 DEG C in carbonation reaction, treat the pH of slurry
When being worth 6.8, carbonization is terminated, is filtered by half frame filter press after obtained end reaction slurry is activated, is washed with clear water, is dried
It is less than 0.35% to moisture, produces nano-calcium carbonate.
Comparative example 1
（1）The quick lime that the 100kg activity degrees weighed up are 370 is placed at digestion machine charging scffold；By 500kg water
50 DEG C are warming up to as digestion water；Open digestion machine；Digestion water is added into digestion machine effectively to digest at the 2/3 of volume, will be surplus
Remaining waterside Jia Shui, while adding quick lime, it is added step-wise in digestion machine, digests 45min, stop digestion, crosses 80 mesh circular vibrating screen mistakes
Sieve, obtains milk of lime；
（2）Maintain at 20-25 DEG C, adjust the concentration of milk of lime to 10 Baume degrees, add Ca (OH) in milk of lime2Butt
The industrial white sugar crystal control agent of quality 1.2%, obtains initial slurry；
（3）By 0.08m3Initial slurry to be pumped into effecting reaction volume be 0.08m3One-level carbonators in, be passed through purity
For 30% carbon dioxide, the flow velocity for controlling high-pureness carbon dioxide is 10m3/ h, temperature in tower is kept in carbonation reaction
For the 7min that is carbonized at 20-24 DEG C, blowing, it is stored in one-level slurry can；Repeatedly it is pumped into just using same technique again
Beginning slurry, carbonization, blowing, also it is stored in one-level slurry can, obtains one-level carbonized stock；
（4）By 0.32m3One-level carbonized stock to be pumped into effecting reaction volume be 0.32m3Two level carbonators in, be passed through pure
The carbon dioxide for 99.7% is spent, the flow velocity for controlling high-pureness carbon dioxide is 30m3/ h, kept in carbonation reaction in tower
Temperature carries out carburizing reagent at 20-24 DEG C, when the pH value of slurry reaches 9, blowing, is stored in two level slurry can；Using
Same technique is repeatedly pumped into one-level carbonized stock, carbonization, blowing, is stored in two level slurry can, obtains two level carbonized stock；
（5）Two level carbonized stock is placed in ageing tank and is aged 72h, by 1.28m3Two level carbonized stock after ageing has been pumped into
Validity response volume is 1.28m3Three-level carbonators in, be passed through purity be 99.7% carbon dioxide, control high-pureness carbon dioxide
Flow velocity be 120m3/ h, keep temperature in tower to carry out carburizing reagent at 20-24 DEG C in carbonation reaction, treat slurry
When pH value is to 6.8, carbonization is terminated, is filtered by half frame filter press after obtained end reaction slurry is activated, is washed with clear water, is done
It is dry to be less than 0.35% to moisture, produce nano-calcium carbonate.
The equipment that three-level formula carbonators in the present invention belongs to routine in the prior art, is by one-level carbonators, two level
The carbonators of three different capabilities of carbonators and three-level carbonators, which is sequentially connected in series, to be formed, and it is unlike the prior art according to anti-
Answer raw material particularity devise one-level carbonators, two level carbonators and three-level carbonators effecting reaction volumetric ratio be 1:4:
16, and have studied the intake per hour of specific reaction process and corresponding high-pureness carbon dioxide in each carbonators
Effecting reaction volumetric ratio with the carbonators is 2-3:The special process parameter of 0.08 grade.
The sign of the morphology microstructure of product prepared by the present invention of embodiment 4 and comparative example
Detection method：Perspective electron microscope.
By taking nano-calcium carbonate prepared by embodiment 1 as an example, its testing result is as shown in Figure 1.It can be seen that pass through
Nano-calcium carbonate prepared by method provided by the invention has particle size distribution range small, and crystal shape is uniform, is cube shaped.
Material prepared by comparative example 1 carries out electron-microscope scanning, and its surface sweeping figure as shown in Figures 2 and 3, can be with table from Fig. 2 and Fig. 3
The bright concentration for changing carbon dioxide under the same conditions, obtained product cut size is uneven, and it is serious to reunite.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of preparation technology of nano-calcium carbonate, it is characterised in that using high activity quick lime and high-pureness carbon dioxide as original
Material, using three-level formula carbonators as consersion unit, carries out reaction preparation；The activity degree of the high activity quick lime is 360-380；Institute
The purity for the high-pureness carbon dioxide stated is more than or equal to 99%；The three-level formula carbonators is by one-level carbonators, two level carbonators
It is sequentially connected in series and forms with the carbonators of three different capabilities of three-level carbonators, the one-level carbonators, two level carbonators and three-level
The effecting reaction volumetric ratio of carbonators is 1:4:16, the intake per hour of high-pureness carbon dioxide and the carbon in each carbonators
The effecting reaction volumetric ratio for changing tower is 2-3:0.08；
Its preparation technology comprises the following steps：
（a）It is 1 in mass ratio by quick lime and digestion water:5 mixture slakings, sieving, obtain milk of lime；
（b）Maintain at 20-25 DEG C, adjust the concentration of the milk of lime to 10 Baume degrees, add crystal control agent, obtain and initially starch
Material；The addition of the crystal control agent is Ca in milk of lime (OH)2The 0.8-1.2% of butt quality；
（c）The initial slurry is pumped into one-level carbonators, is passed through the high-pureness carbon dioxide, temperature is in holding tower
Be carbonized 7min at 20-24 DEG C, blowing；Initial slurry, carburizing reagent, blowing are repeatedly pumped into using same technique,
It is stored in one-level slurry can, obtains one-level carbonized stock；
（d）The one-level carbonized stock is pumped into two level carbonators, is passed through the high-pureness carbon dioxide, keeps temperature in tower
Carburizing reagent is carried out at 20-24 DEG C, when the pH value of slurry is to 9, blowing, one-level is repeatedly pumped into using same technique
Carbonized stock, carburizing reagent, blowing, it is stored in two level slurry can, obtains two level carbonized stock；
（e）By the still aging 72h of two level carbonized stock, the two level carbonized stock after ageing is pumped into three-level carbonators, is passed through
The high-pureness carbon dioxide, keep temperature in tower to carry out carburizing reagent at 20-24 DEG C, treat the pH value of slurry to 6.8-7.0
When, carbonization is terminated, the end reaction slurries filtration that will be obtained, is washed, dries, produces nano-calcium carbonate.
2. the preparation technology of nano-calcium carbonate according to claim 1, it is characterised in that step（b）Described crystalline form control
Preparation is industrial white sugar.
3. the preparation technology of nano-calcium carbonate according to claim 1 or 2, it is characterised in that step（a）By quick lime and
It is 1 in mass ratio to digest water:The concrete technology of 5 mixture slakings is：Quick lime is placed at the charging scffold of digestion machine；Feedwater adds
Heat to temperature is 45-55 DEG C；Open digestion machine；Warm water is added to the 2/3 of digestion machine dischargeable capacity, while add quick lime, Bian Jia
Water, digested, you can.
4. the preparation technology of nano-calcium carbonate according to claim 3, it is characterised in that step（a）The sieving uses
Equipment be 80 mesh circular vibrating screen.
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| CN107827136B (en) * | 2017-10-20 | 2019-07-30 | 石家庄祥博瑞环保有限公司 | A kind of preparation process of spherical nanometer calcium carbonate |
| CN107792872B (en) * | 2017-10-20 | 2019-07-30 | 石家庄祥博瑞环保有限公司 | A kind of preparation process of spindle nanometer calcium carbonate |
| CN108017079A (en) * | 2017-12-26 | 2018-05-11 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of method of lime foam production calcite |
| CN110589862B (en) * | 2019-09-09 | 2022-04-22 | 建德华明科技有限公司 | Multistage series method for producing nano-grade calcium carbonate by carbonization method with liquid phase as continuous phase |
| CN110540226B (en) * | 2019-10-07 | 2022-05-27 | 浙江省建德市正发药业有限公司 | Preparation method of high-density calcium carbonate powder |
| CN111453754A (en) * | 2020-04-28 | 2020-07-28 | 广西夏阳环保科技有限公司 | Preparation method of high-purity and high-activity nano calcium carbonate |
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