CN108033476A - A kind of preparation method of nano-calcium carbonate - Google Patents
A kind of preparation method of nano-calcium carbonate Download PDFInfo
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- CN108033476A CN108033476A CN201810121235.4A CN201810121235A CN108033476A CN 108033476 A CN108033476 A CN 108033476A CN 201810121235 A CN201810121235 A CN 201810121235A CN 108033476 A CN108033476 A CN 108033476A
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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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
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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
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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Abstract
The present invention provides a kind of preparation method of the nano-calcium carbonate using the self-priming agitating paddle in sweep short blade surface.This method prepares nano-calcium carbonate using the self-priming agitating paddle in sweep short blade surface, in the presence of dispersant, by calcium hydroxide slurry and carbon dioxide gas precursor reactant.Using the pH value of pH measuring probes (8) the measurement reaction solution of installation in stirred autoclave (1), when pH value is less than 8, stirring motor (4) and CO are closed2Intake valve (6), stops reaction.Slurries after the completion of reaction are discharged by blow-off valve (9), reaction solution obtains nano-calcium carbonate powder-product by centrifuging, wash, after drying.Nano-calcium carbonate prepared by the method according to the invention is relative to the nano-calcium carbonate obtained in the prior art, and evenly, particle disperses more preferably for particle diameter smaller, particle diameter distribution, in addition, carbonization time greatly shortens.
Description
Technical field
The present invention relates to one kind to use the self-priming agitating paddle in sweep short blade surface, anti-by carrying out being carbonized in stirred tank
The method that nano-calcium carbonate should be prepared.
Background technology
The increase of Carbon Dioxide in Air gas content causes Global Temperature to raise, and environment is continuous worsening.However, research table
Dependence of person of good sense's class to fuel such as kerosene will cause continuing to increase for carbon dioxide gas content in air.Reduce two in air
Carbon oxide gas content has become the much-talked-about topic of global concern.Reduce the method master of the content of Carbon Dioxide in Air gas
To include chemical absorption method, Physical Absorption method, membrane filter method and absorption method etc..Pass through gas-liquid preparation of nanometer calcium carbonate by carbonization
Method is then that a kind of method of Carbon Dioxide in Air gas is utilized by chemical absorption method.
Nano-calcium carbonate is to grow up the 1980s, and particle diameter is less than a kind of Novel super-thin solid of 100nm
Powder particle.Since nano-calcium carbonate compared with other nano-particles has the properties of many uniquenesses such as thermal conductivity, lubricity, anti-oxidant
Property, dissolving and decomposition temperature is higher and heat endurance is high, so nano-calcium carbonate is in rubber, plastics, papermaking, coating, ink
It is all very extensive Deng field application.
Chinese invention patent CN 1442363A disclose the side that a kind of supergravity reactor prepares microwhisker like calcium carbonate
Method.This method is in the presence of chemical additives, using calcium hydroxide and carbon dioxide as raw material, utilizes supergravity reactor height
Speed rotates the much bigger gravity environment of the ratio terrestrial gravitation produced, and carburizing reagent is effectively controlled on molecular scale and was crystallized
Journey, is made the crystal whisker-shaped calcium carbonate that particle diameter is small, is evenly distributed.But reaction unit design is complicated, equipment investment is big, energy consumption
Height, hardly possible cleaning is unfavorable to follow-up continuous production, and production cost will be improved for industrial production.
Chinese invention patent CN 101967310A disclose one kind in membrane reactor prepare with low viscosity and it is medium touch
Become the method for performance nano-calcium carbonate.This method calcined lime stone, digest after obtained calcium hydroxide slurry be put into film
In scattered carbonization reactor, under the conditions of existing for chemical additives, it is passed through carbon dioxide and carries out reaction preparation with low
Viscosity and medium thixotropic property nano-calcium carbonate.The nano-calcium carbonate particle diameter that this method is prepared is small and particle diameter distribution is uniform.But
It is to prepare nano-calcium carbonate using the reactor there is the problem of of high cost, equipment easily blocks, and industrialized production is difficult.
Chinese invention patent CN 104556184A disclose a kind of production method of industrial sedimentation type nano-calcium carbonate.Should
The calcium hydroxide suspension of preparation is added in autoclave by method, then passes to carbon dioxide, controls titanium dioxide
Carbon flow is certain value, prepares that particle diameter distribution is relatively narrow and stable quality by way of high pressure self-priming, the higher nanometer of purity
Calcium carbonate granule.But since this method self-priming speed is slower, longer the time required to reaction, production efficiency is relatively low, thus it is uncomfortable
Preferably it is applied to industrial production.
The purpose of the present invention is utilize the self-priming stirring in sweep short blade surface in Chinese patent (CN 103768980A)
Paddle is stirred to increase mass transfer rate, under the action of dispersant, is made calcium hydroxide slurry and carbon dioxide gas precursor reactant, is obtained
It is small to obtain particle diameter, the relatively narrow and well dispersed nano-calcium carbonate of particle diameter distribution.
The content of the invention
Technical problem:The object of the present invention is to provide a kind of preparation method of nano-calcium carbonate.It is mainly used for solving existing
Nano-calcium carbonate preparation process present in reaction speed is slow, energy consumption is big, particle diameter is big, particle diameter distribution is uneven, particle coagulation
The problems such as serious.Compared with prior art, it is stirred using the self-priming agitating paddle in sweep short blade surface and adds mass transfer speed
Rate, the nano-calcium carbonate particle diameter prepared is small, and particle diameter distribution is relatively narrow and well dispersed, and in addition, the reaction time is shorter.
Technical solution:A kind of preparation method of nano-calcium carbonate of the present invention utilizes the self-priming stirring in sweep short blade surface
Paddle prepares nano-calcium carbonate, in the presence of dispersant, by calcium hydroxide slurry and carbon dioxide gas precursor reactant, its specific steps
For:
1) calcium hydroxide slurry configured is added in stirred autoclave, in stirred tank equipped with sweep short blade surface certainly
Reacting slurry, by the constant temperature circulating medium in chuck, is heated or cooled to the temperature of setting by suction agitating paddle, then will be disperseed
Agent adds stirred autoclave, opens stirring motor, after the dispersant in reacting slurry is uniformly dispersed, closes stirring motor;
2) inert gas breather valve is opened, it is P that inert gas to pressure is passed through into stirred autoclave1Afterwards, inertia is closed
Gas ventilation valve, while open CO2Intake valve, adjusts constant pressure regulating valve, gas reactor stagnation pressure P is maintained at steady state value;
3) stirring motor is opened, and by the rotating speed of the rotational speed regulation of the self-priming agitating paddle in sweep short blade surface to agitating paddle
N, at this time in kettle ullage inert gas and CO2Mixed gas is automatically drawn under liquid level, forms substantial amounts of minute bubbles distribution
In reaction paste, the pH value of reaction solution is measured using the pH measuring probes installed in stirred autoclave, when pH value is less than 8,
Close stirring motor and CO2Intake valve, stops reaction;
4) slurries after the completion of reaction are discharged by blow-off valve, reaction solution obtains nanometer by centrifuging, wash, after drying
Calcium carbonate powder product.
Wherein:
The used self-priming agitating paddle in sweep short blade surface includes fixed disk, sweep, terminal pad and short blade, fixed
Disk, sweep, terminal pad and short blade, wherein, the top of connection sweep below fixed disk, the lower part connection terminal pad of sweep,
Short blade is connected below terminal pad.
The temperature control set in the step 1) is 0 DEG C to 60 DEG C.
The temperature of the setting is preferably 15 DEG C to 45 DEG C.
Calcium hydroxide slurry mass concentration described in the step 1) is 0.01wt% to 20wt%.
The calcium hydroxide slurry mass concentration is preferably 2wt% to 10wt%.
The dispersant of addition is sucrose, sulfuric acid, nitric acid, phosphoric acid or their mixture in the step 1), its addition
For the 0.01wt% to 5wt% of reactant gross mass.Preferably 1wt% to 2wt%.
Inert gas in the step 2) is and CO2And Ca (OH)2The nonreactive gas of slurry.Preferably air
Or nitrogen.
Inert gas to the pressure that is passed through is P1With gas reactor stagnation pressure P, the CO of expression2Gaseous phase volume divide rate (1-
P1/ P) scope be not less than 0.1%.Preferred scope is 5%-40%.
The condition that the rotating speed N of agitating paddle described in the step 3) should meet is:N × D is more than 10, and wherein D is sweep
(11) the corresponding diameter of a circle of inswept 1 circle of extension.Preferably N × D is more than 20.
Beneficial effect:Due to the use of the self-priming agitating paddle in sweep short blade surface in the present invention, pass through the agitating paddle
Stirring action mass transfer enhancement process, shortens the carburizing reagent time, and production efficiency improves, the grain diameter smaller produced,
It is more evenly distributed, disperses more preferable
Brief description of the drawings
Fig. 1 is the carbonizing plant schematic diagram that the present invention prepares nano-calcium carbonate;
Fig. 2 is the structure diagram of the self-priming agitating paddle in sweep short blade surface of the present invention;
Fig. 3 is the grain size distribution of nano-calcium carbonate prepared by embodiment 1;
Fig. 4 is the grain size distribution of nano-calcium carbonate prepared by embodiment 2.
Have in figure:Stirred autoclave 1, self-priming agitating paddle 2, chuck 3, stirring motor 4, inert gas breather valve 5, CO2
Intake valve 6, constant pressure regulating valve 7, pH measuring probes 8, blow-off valve 9, fixed disk 10, sweep 11, terminal pad 12, short blade 13.
Embodiment
The present invention is a kind of method for preparing nano-calcium carbonate using the self-priming agitating paddle in sweep short blade surface, will be configured
Good calcium hydroxide slurry is added in stirred autoclave 1, and the self-priming agitating paddle 2 in sweep short blade surface is housed in stirred tank, is led to
The constant temperature circulating medium in chuck 3 is crossed, reacting slurry is heated or cooled, then dispersant is added in stirred autoclave,
Stirring motor 4 is opened, after reacting slurry dispersant is uniformly dispersed, closes stirring motor 4.Inert gas breather valve 5 is opened, to
Inert gas is passed through in stirred autoclave 1 to P1Afterwards, inert gas breather valve 5 is closed, while opens CO2Intake valve 6, is adjusted permanent
Regulating valve 7 is pressed, gas reactor stagnation pressure is maintained at certain pressure P.Stirring motor 4 is opened, and by sweep short blade surface self-priming
The rotational speed regulation of formula agitating paddle 2 to certain rotating speed, at this time in kettle ullage inert gas and CO2Mixed gas is automatically drawn into
Under liquid level, form substantial amounts of minute bubbles and be distributed in reaction paste.Surveyed using the pH measuring probes 8 of installation in stirred autoclave 1
The pH value of quantitative response liquid, when pH value is less than 8, closes stirring motor 4 and CO2Intake valve 6, stops reaction.After the completion of reacting
Slurries discharged by blow-off valve 9, reaction solution by centrifuging, wash, it is dry after obtain nano-calcium carbonate powder-product.According to this
Nano-calcium carbonate prepared by the method for invention is relative to the nano-calcium carbonate obtained in the prior art, particle diameter smaller, particle diameter point
Evenly, particle disperses more preferably cloth, in addition, carbonization time greatly shortens.
Embodiment 1:
The calcium hydroxide slurry 8L that the concentration configured is 6wt% is added into a high 300mm, the stirring of diameter 200mm
In reaction kettle 1, the self-priming agitating paddle 2 in sweep short blade surface is housed in stirred tank.The sweep horizontal cross-section of the agitating paddle for 4 ×
The rectangle of 2mm, is highly 200mm;The length of short blade and high respectively 20mm and 15mm, thickness 1mm.By in chuck 3
Constant temperature circulating medium, reacting slurry is heated to 40 DEG C, then the dispersant of 0.2wt% is added into stirred autoclave, unlatching is stirred
Motor 4 is mixed, after reacting slurry dispersant is uniformly dispersed, closes stirring motor 4.Inert gas breather valve 5 is opened, it is anti-to stirring
Answer and inert gas is passed through in kettle 1 to after 0.2MPa, close inert gas breather valve 5, while open CO2Intake valve 6, adjusts constant pressure
Regulating valve 7, makes gas reactor stagnation pressure be maintained at 0.5MPa.Stirring motor 4 is opened, and by the self-priming stirring in sweep short blade surface
The rotational speed regulation of paddle 2 to 240rpm, at this time in kettle ullage inert gas and CO2Mixed gas is automatically drawn under liquid level,
Substantial amounts of minute bubbles are formed to be distributed in reaction paste.Reaction solution is measured using the pH measuring probes 8 of installation in stirred autoclave 1
PH value, when pH value is less than 8, close stirring motor 4 and CO2Intake valve 6, stops reaction.Slurries after the completion of reaction are led to
Cross blow-off valve 9 to discharge, reaction solution obtains nano-calcium carbonate powder-product by centrifugation, freeze-drying.Transmission electricity is carried out to product
Mirror is tested and counts grain diameter, and the statistical result of particle diameter distribution is shown in Fig. 3.
Embodiment 2:
The calcium hydroxide slurry 30L that the concentration configured is 7wt% is added into a high 1200mm, diameter 800mm's stirs
Mix in reaction kettle 1, the self-priming agitating paddle 2 in sweep short blade surface is housed in stirred tank.The sweep horizontal cross-section of the agitating paddle is
The rectangle of 16 × 8mm, is highly 850mm;The length of short blade and high respectively 80mm and 60mm, thickness 3mm.Pass through chuck
Constant temperature circulating medium in 3,10 DEG C are cooled to by reacting slurry, then the dispersant of 1wt% is added stirred autoclave, and unlatching is stirred
Motor 4 is mixed, after reacting slurry dispersant is uniformly dispersed, closes stirring motor 4.Inert gas breather valve 5 is opened, it is anti-to stirring
Answer and inert gas is passed through in kettle 1 to after 0.2MPa, close inert gas breather valve 5, while open CO2Intake valve 6, adjusts constant pressure
Regulating valve 7, makes gas reactor stagnation pressure be maintained at 0.3MPa.Stirring motor 4 is opened, and by the self-priming stirring in sweep short blade surface
The rotational speed regulation of paddle 2 to 100rpm, at this time in kettle ullage inert gas and CO2Mixed gas is automatically drawn under liquid level,
Substantial amounts of minute bubbles are formed to be distributed in reaction paste.Reaction solution is measured using the pH measuring probes 8 of installation in stirred autoclave 1
PH value, when pH value is less than 8, close stirring motor 4 and CO2Intake valve 6, stops reaction.Slurries after the completion of reaction are led to
Cross blow-off valve 9 to discharge, reaction solution is by centrifugation, the nano-calcium carbonate powder-product being dried to obtain.Transmission electron microscope is carried out to product
Test and count grain diameter, the statistical result of particle diameter distribution is shown in Fig. 4.
Claims (10)
1. a kind of preparation method of nano-calcium carbonate, it is characterised in that this method utilizes the self-priming agitating paddle in sweep short blade surface
Nano-calcium carbonate is prepared, in the presence of dispersant, by calcium hydroxide slurry and carbon dioxide gas precursor reactant, its specific steps
For:
1) calcium hydroxide slurry configured is added in stirred autoclave (1), in stirred tank equipped with sweep short blade surface certainly
Reacting slurry, by the constant temperature circulating medium in chuck (3), is heated or cooled to the temperature of setting by suction agitating paddle (2), then
Dispersant is added into stirred autoclave, opens stirring motor (4), after the dispersant in reacting slurry is uniformly dispersed, closing is stirred
Mix motor (4);
2) inert gas breather valve (5) is opened, is P to inert gas to pressure is passed through in stirred autoclave (1)1Afterwards, inertia is closed
Gas ventilation valve (5), while open CO2Intake valve (6), adjusts constant pressure regulating valve (7), gas reactor stagnation pressure P is maintained at permanent
Definite value;
3) stirring motor (4) is opened, and the rotational speed regulation of the self-priming agitating paddle in sweep short blade surface (2) to agitating paddle is turned
Fast N, at this time in kettle ullage inert gas and CO2Mixed gas is automatically drawn under liquid level, forms substantial amounts of minute bubbles point
It is distributed in reaction paste, using the pH value of pH measuring probes (8) the measurement reaction solution of installation in stirred autoclave (1), works as pH value
During less than 8, stirring motor (4) and CO are closed2Intake valve (6), stops reaction;
4) slurries after the completion of reaction are discharged by blow-off valve (9), reaction solution obtains nanometer by centrifuging, wash, after drying
Calcium carbonate powder product.
A kind of 2. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:The used short leaf of sweep
The self-priming agitating paddle in piece surface (2) includes fixed disk (10), sweep (11), terminal pad (12) and short blade (13), fixed disk
(10), sweep (11), terminal pad (12) and short blade (13), wherein, the top of connection sweep (11) below fixed disk (10),
The lower part of sweep (11) connects terminal pad (12), and short blade (13) is connected below terminal pad (12).
A kind of 3. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:Setting in the step 1)
Fixed temperature control is 0 DEG C to 60 DEG C.
A kind of 4. preparation method of nano-calcium carbonate according to claim 3, it is characterised in that:The temperature of the setting
Preferably 15 DEG C to 45 DEG C.
A kind of 5. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:Described in the step 1)
Calcium hydroxide slurry mass concentration be 0.01wt% to 20wt%.
A kind of 6. preparation method of nano-calcium carbonate according to claim 5, it is characterised in that:The calcium hydroxide slurry
Liquid mass concentration is preferably 2wt% to 10wt%.
A kind of 7. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:Addition in the step 1)
Dispersant be sucrose, sulfuric acid, nitric acid, phosphoric acid or their mixture, its addition is the 0.01wt% of reactant gross mass
To 5wt%.
A kind of 8. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:It is lazy in the step 2)
Property gas is and CO2And Ca (OH)2The nonreactive gas of slurry.
A kind of 9. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:Described is passed through indifferent gas
Body to pressure is P1With gas reactor stagnation pressure P, the CO of expression2Gaseous phase volume divide rate (1-P1/ P) scope be not less than 0.1%.
A kind of 10. preparation method of nano-calcium carbonate according to claim 1, it is characterised in that:Institute in the step 3)
The condition that stating the rotating speed N of agitating paddle should meet is:N × D is more than 10, and wherein D is the corresponding circle of inswept 1 circle of sweep (11) extension
Diameter.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110183126A (en) * | 2019-06-06 | 2019-08-30 | 长沙紫宸科技开发有限公司 | A method of carbonate cementitious material is prepared by raw material of lime stone |
CN111606344A (en) * | 2020-04-28 | 2020-09-01 | 广西夏阳环保科技有限公司 | Method for preparing nano calcium carbonate with high specific surface area |
CN112023871A (en) * | 2020-08-28 | 2020-12-04 | 安徽同益净化科技有限公司 | CO (carbon monoxide)2Method for preparing nano calcite VOCs adsorbent by diffusion method |
CN113877500A (en) * | 2021-10-09 | 2022-01-04 | 江西华明纳米碳酸钙有限公司 | Stirring formula nanometer calcium carbonate preparation equipment |
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CN1453216A (en) * | 2002-04-26 | 2003-11-05 | 北京化工大学 | Eddy flow process of preparing ultramicro calcium carbonate precipitate |
CN102897815A (en) * | 2012-11-08 | 2013-01-30 | 广西华纳新材料科技有限公司 | Nano-calcium carbonate carbonization reaction kettle |
CN102963918A (en) * | 2012-11-08 | 2013-03-13 | 广西华纳新材料科技有限公司 | Carbonation reaction method of nano calcium carbonate |
CN103768980A (en) * | 2014-01-20 | 2014-05-07 | 东南大学 | Long-paddle short-blade composite stirrer |
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2018
- 2018-02-07 CN CN201810121235.4A patent/CN108033476A/en active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1453216A (en) * | 2002-04-26 | 2003-11-05 | 北京化工大学 | Eddy flow process of preparing ultramicro calcium carbonate precipitate |
CN102897815A (en) * | 2012-11-08 | 2013-01-30 | 广西华纳新材料科技有限公司 | Nano-calcium carbonate carbonization reaction kettle |
CN102963918A (en) * | 2012-11-08 | 2013-03-13 | 广西华纳新材料科技有限公司 | Carbonation reaction method of nano calcium carbonate |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110183126A (en) * | 2019-06-06 | 2019-08-30 | 长沙紫宸科技开发有限公司 | A method of carbonate cementitious material is prepared by raw material of lime stone |
CN110183126B (en) * | 2019-06-06 | 2022-02-18 | 长沙紫宸科技开发有限公司 | Method for preparing carbonate cementing material by taking limestone as raw material |
CN111606344A (en) * | 2020-04-28 | 2020-09-01 | 广西夏阳环保科技有限公司 | Method for preparing nano calcium carbonate with high specific surface area |
CN112023871A (en) * | 2020-08-28 | 2020-12-04 | 安徽同益净化科技有限公司 | CO (carbon monoxide)2Method for preparing nano calcite VOCs adsorbent by diffusion method |
CN113877500A (en) * | 2021-10-09 | 2022-01-04 | 江西华明纳米碳酸钙有限公司 | Stirring formula nanometer calcium carbonate preparation equipment |
CN113877500B (en) * | 2021-10-09 | 2023-02-07 | 江西华明纳米碳酸钙有限公司 | Stirring formula nanometer calcium carbonate preparation equipment |
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Application publication date: 20180515 |