CN108083312A - A kind of carbonization reactor and preparation small particle, polymolecularity, the method for low oil factor nano-calcium carbonate - Google Patents
A kind of carbonization reactor and preparation small particle, polymolecularity, the method for low oil factor nano-calcium carbonate Download PDFInfo
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- 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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Abstract
The invention discloses a kind of carbonization reactor and prepare small particle, polymolecularity, low oil factor nano-calcium carbonate method, be related to nano-calcium carbonate technical field；The carbonization reactor includes liquid film nucleation device and crystal grower；Gas distributor is equipped in liquid film nucleation device, blender is equipped in crystal grower；Using the carbonization reactor prepare small particle, polymolecularity, low oil factor nano-calcium carbonate method, including being calcined, digesting, filtering, cooling down by lime, once the processes such as carbonization, ageing, secondary carbonization, surface treatment, filter-press dehydration, drying, crushing are to get to the product of the present invention；Nano-calcium carbonate produced by the present invention is cube, and primary particle size is 20~30nm, is tested through Malvern laser particle analyzer, and nano-calcium carbonate produced by the present invention is Unimodal Distribution, and average grain diameter 220nm, oil factor is less than 18mlDOP/100gCaCO3, have the advantages that small grain size, good dispersion, oil factor are low, production cost is low and stable quality.
Description
Technical field
The present invention relates to nano-calcium carbonate technical field more particularly to a kind of carbonization reactor and use the reactor system
Standby small particle, polymolecularity, the method for low oil factor nano-calcium carbonate.
Background technology
At present, on Nano-meter CaCO33Preparation method have very much, calcium carbonate preparation method is divided into liquid phase reactor method and carbonization
Method.Liquid phase reactor method is to prepare calcium carbonate, gained by reaction between two kinds of solution of calcium salt and polcarb or bicarbonate
The most of patterns of product are relatively regular and particle size is micron order, and the reaction volume used due to it is few and preparation process is difficult
With the limitation of control, it is difficult to application of being magnified.Carbonizatin method is the main method of current industrial production nano-calcium carbonate, should
Method raw material sources are extensive, and primary raw material is to pass through selected lime stone.Lime stone obtains CaO by calcining；By CaO digestion then
It is passed through CO2, chemical additives are added in, carbonization is to terminal；Final product was waited by surface treatment, dehydration, drying, crushing and classification
Journey obtains nano-calcium carbonate calcium product.According to CO2With Ca (OH)2Carbonizatin method can be divided into interval by the difference of the suspension way of contact
Carbonizatin method, multilevel spray carbonization and high-gravity carbonation method.
Existing interval bubbling type carbonizatin method synthesis nano-calcium carbonate is equipped with refined calcium hydroxide in carbonization kettle
Slurry, kiln gas enter from carbonization kettle bottom, and gas-liquid mixed is made to generate nano-calcium carbonate under mechanical stirring.This synthesis nano-sized carbon
The method of sour calcium is that the formation of calcium carbonate nucleus is carried out continuously with being grown in same system.Since the formation of nucleus does not have with growth
There is stringent differentiation, the calcium carbonate growth period that the calcium carbonate growth period length being first nucleated then is nucleated is short, causes granular size different, no
With size particles in same system, surface energy differential is not big between causing particle, be easy to cause agglomeration.
Also have carry out the nucleation of nano-calcium carbonate and growth substep in the prior art, such as Chinese patent
CN103011226B discloses a kind of preparation method for being nucleated and growing the nano-calcium carbonate that substep carries out, and this method is by kiln gas
After spraying and dedusting, foam dust-removing, it is compressed and is cooled to less than 30 DEG C, calcium hydroxide slurry is imported in mixing chamber, by leading
Tracheae sucks a large amount of kiln gas, and reaction forms calcium carbonate nucleus；The slurry for having formed calcium carbonate nucleus feeding gap bubbling is stirred again
It mixes in formula carbonization kettle, is passed through kiln gas under stiring and continues carburizing reagent, when the pH value of reaction solution is less than 7, be as carbonized terminal, kiln
The volumetric concentration of carbon dioxide is 25.0-35.0% in gas.Although the patent divides the nucleation of nano-calcium carbonate and growth
Step carries out, but relatively low into gas concentration lwevel in the kiln gas in nuclear reaction, and carbon dioxide contacts not with calcium hydroxide slurry
Fully, reaction is caused to be not thorough, therefore nano-calcium carbonate nucleus nucleation quantity is few and uneven.
In addition, carbonizatin method is used to prepare technology relative maturity of the grain size for the cubic calcium carbonate of 60~100nm, but it is right
In preparing calcium carbonate of the grain size in below 60nm, since calcium carbonate grain size is small, secondary agglomeration is serious, and dispersiveness is difficult control, is made
Higher into its oil factor, especially when preparing the nano-calcium carbonate that grain size is 30~40nm, dispersiveness is the pass of technology of preparing
Key.
The present inventor is found through experiments that, influences the granular size because being known as nano-calcium carbonate of nano-calcium carbonate oil factor
And dispersiveness, wherein dispersiveness is to influence the principal element of oil factor size.Nano-calcium carbonate grain size is bigger, and specific surface area is got over
Small, then oil factor is lower；Nano-calcium carbonate dispersiveness is better, and particle agglomeration is fewer, then oil factor is lower.The prior art
In, it is next often by the larger Nano particles of calcium carbonate of grain size is prepared in order to obtain the nano-calcium carbonate calcium product of low oil factor
It realizes, without solving the problems, such as that small particle nano-calcium carbonate oil factor is high, also disperses without solving small particle nano-calcium carbonate
The problem of property, so affecting the application range of small particle nano-calcium carbonate.
The content of the invention
The technical problems to be solved by the invention are the shortcomings that overcoming the more than prior art：A kind of carbonization reactor is provided
And small particle, polymolecularity, the method for low oil factor nano-calcium carbonate are prepared using the carbonization reactor, to solve small particle
The problem of nano-calcium carbonate bad dispersibility and high oil factor.
The technical solution of the present invention is as follows：
A kind of carbonization reactor is nucleated device and crystal grower including liquid film, the upper end of the liquid film nucleation device be equipped with into
Mouth one and grout outlet one are starched, lower end is equipped with gas access one, and stock inlet one and grout outlet one are located at the two of liquid film nucleation device respectively
End, liquid film are nucleated in device and are additionally provided with gas distributor；The upper end of crystal grower is equipped with stock inlet two, and lower end is equipped with gas access
Two and grout outlet two, blender is additionally provided in crystal grower, and crystal grower is externally provided with the motor being connected with blender, described
Grout outlet one and stock inlet two connected by pump.
Preferably, it is equipped with to control at the stock inlet one, stock inlet two, gas access one and gas access two
The flow control valve of slurry and gas intake.
Using above-mentioned carbonization reactor prepare small particle, polymolecularity, low oil factor nano-calcium carbonate method, including with
Lower step：
First, lime is calcined, keeps raw burn, the whiteness of the lime of firing is more than 95%；
2nd, lime particle of the whiteness more than 95% is selected by color selector, carrying out digestion reaction with water obtains hydroxide
Calcium is slightly starched, and hydrogen calcium hydroxide is slightly starched to the sieve for passing through 100 mesh, 200 mesh, 325 mesh, 500 mesh successively, obtains calcium hydroxide essence
Slurry；
3rd, water is added to be modulated into mass percent concentration calcium hydroxide refining to be 6~8%, be cooled to temperature as 7~10
℃；
4th, the calcium hydroxide refining that step 3 obtains is passed through from stock inlet one in liquid film nucleation device, from gas access one
It is passed through pure CO2Gas to liquid film is nucleated in device, and adds in crystal growth controlling agent, pure CO2Gas is nucleated device by being arranged on liquid film
Gas distributor and calcium hydroxide refining come into full contact with carry out carburizing reagent, be carbonized to slurry pH value be 9~11 when, Ran Houchen
When change 8~12 is small；
5th, the ripe slurry of the calcium carbonate after ageing is pumped into from stock inlet two in crystal grower, under stiring from gas access
Two are passed through the CO that volumetric concentration is 55~65%2Gas adds in crystal growth controlling agent into crystal grower, carries out secondary
Carburizing reagent, it is 7~9 to react to the pH value of the ripe slurry of calcium carbonate, and be as carbonized terminal；
6th, the ripe slurry of calcium carbonate obtained step 5 is added in wet method fine grinding or grinding machine for cutting charge into pieces, adds zirconium oxide
Ball, alumina balls after grinding 20~40min, add in surfactant, continue 20~40min of grinding as abrasive media；
7th, the calcium carbonate obtained step 6 carries out filter-press dehydration, drying, crushing, classification to get to small particle, high score
Dissipate property, the nano-calcium carbonate of low oil factor.
Preferably, in the step 3, calcium hydroxide refining is carried out by plate heat exchanger and less than 7 DEG C of cooling water
Heat exchange, makes the temperature of calcium hydroxide refining be reduced to 7~10 DEG C.
Preferably, in the step 4, the temperature reacted in liquid film nucleation device is 15~25 DEG C.
Preferably, in the step 4, crystal growth controlling agent is NaCO3。
Preferably, in the step 5, crystal growth controlling agent is sucrose, beet sugar, one kind in maltose or one
Kind or more mixture.
Preferably, in the step 5, volumetric concentration is 55~65% CO2The preparation method of gas is：By lime
The kiln gas that kiln generates carries out dust removal process by pulse dust collector and water dust scrubber, is then compressed to kiln gas through water ring compressor
In storage tank, the pure CO with being stored in pressurized reservoir2Gas carry out distribution to get to volumetric concentration be 55~65% CO2Gas.
Preferably, in the step 6, the zirconia ball and oxygen of a diameter of 0.5~1.5nm and a diameter of 1.5~2nm
The mass ratio for changing aluminium ball is 3:1~6.
Preferably, in the step 6, surfactant is complexed surfactant, by ionic surfactant,
Sodium Polyacrylate, odium stearate composition.
Preferably, the primary particle size of nano-calcium carbonate obtained is 20~30nm in the step 7.
The beneficial effects of the invention are as follows：
1st, the present invention carries out the nucleation of nano-calcium carbonate and growth substep, and nano-calcium carbonate is carried out in liquid film nucleation device
Nucleation, in crystal grower carry out nucleus growth.Gas distributor is set in liquid film nucleation device first, and makes dioxy
Change tower gas to contact in opposite directions with slurry, ensure that solution-air contact is good, so as to ensure that calcium hydroxide refining obtains in carbonators
To abundant reaction, in favor of the generation of nucleus, make to be formed that nano-calcium carbonate nucleus is uniform and stable, and Nano particles of calcium carbonate grain size exists
It is controllable between 20~30nm.Secondly, the nucleation of nano-calcium carbonate and growth are strictly distinguished and carried out under different conditions, kept away
It is different with growth period length to have exempted from nano-calcium carbonate nucleation, has caused particle diameter distribution wide, bad dispersibility, serious weakness of reuniting, from
And the nano-calcium carbonate of the cubic type of small particle is made, it ensure that the dispersiveness of nano-calcium carbonate.Finally, nucleation of the invention
Density of carbon dioxide gas in reaction is 100%, ensure that the concentration of reactant, so that fully being carried out into nuclear reaction, is protected
Demonstrate,prove crystal nucleation quantity；In addition in crystal growth phase, secondary carbonization is carried out using carbon dioxide mixed with kiln gas,
It not only ensure that the growth of nucleus, but also reused kiln gas this by-product, it is energy saving.
2nd, the present invention is aged after being once carbonized, and makes nano-calcium carbonate regular appearance, so as to which dispersiveness is better.Simultaneously
Nano-calcium carbonate surface is modified simultaneously using compound base amount method agent and grinding, is handled by using surface conditioning agent, it can
Nano particles of calcium carbonate surface charge is adjusted, ensures that grain size is appropriate, is allowed to homodisperse not conglomeration.Using wet method fine grinding or grind
Mill machine for cutting charge into pieces is ground, and plays the role of breaing up nano-calcium carbonate particles reunion, so as to further reduce nano-calcium carbonate
Calcium agglomeration.
3rd, compared with prior art, nano-calcium carbonate produced by the present invention is cube, and primary particle size is 20~30nm, is passed through
Malvern laser particle analyzer test, nano-calcium carbonate produced by the present invention be Unimodal Distribution, average grain diameter 220nm, oil factor
Less than 18mlDOP/100gCaCO3, have grain size is small, good dispersion, oil factor is low, production cost is low and stable quality it is excellent
Point.
Description of the drawings
Fig. 1 is the structure diagram of carbonization reactor of the present invention；
Shown in figure：1st, liquid film nucleation device；11st, stock inlet one；12nd, gas access one；13rd, gas distributor；14th, pulp
Mouth one；2nd, crystal grower；21st, stock inlet two；22nd, gas access two；23rd, grout outlet two；24th, blender；25th, motor；3、
Pump；
Fig. 2 is the scanning electron microscopic picture of nano-calcium carbonate particles made from embodiment one；
Fig. 3 (a) is the particle size distribution figure of nano-calcium carbonate particles made from embodiment one；
Fig. 3 (b) is the particle size distribution figure of nano-calcium carbonate particles made from embodiment two；
Fig. 4 is the multiple spot BET graphs of nano-calcium carbonate particles made from embodiment one.
Specific embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact
Apply example.
Embodiment one
The carbonization reactor of the present invention as shown in Figure 1, includes liquid film nucleation device 1 and crystal grower 2, the liquid film into
The upper end of core device 1 is equipped with stock inlet 1 and grout outlet 1, and lower end is equipped with gas access 1, stock inlet 1 and grout outlet
One 14 are located at the both sides of liquid film nucleation device 1 respectively, and gas distributor 13 is additionally provided in liquid film nucleation device 1；The crystal grower 2
Upper end be equipped with stock inlet 2 21, lower end is equipped with gas access 2 22 and grout outlet 2 23, is additionally provided with stirring in crystal grower 2
Device 24, crystal grower 2 are externally provided with the motor 25 being connected with blender 24, and the grout outlet 1 and stock inlet 2 21 pass through
Pump 3 connects, and is equipped with to control slurry gentle at the stock inlet one, stock inlet two, gas access one and gas access two
The flow control valve (not indicated in Fig. 1) of body intake, liquid film nucleation device 1 and crystal grower 2 by support column (in Fig. 1 not
Mark) it fixes on the ground.
Using the carbonization reactor prepare small particle, polymolecularity, low oil factor nano-calcium carbonate preparation method, including
Following steps：
First, lime is calcined, lime will wilfully be burnt in calcination process so that the whiteness of the lime of firing is 95%
More than；
2nd, select the lime particle that whiteness is more than 95% by color selector to add in digestion machine, water is added digest instead
Should, it obtains calcium hydroxide and slightly starches, hydrogen calcium hydroxide is slightly starched to the sieve for passing through 100 mesh, 200 mesh, 325 mesh, 500 mesh successively, is obtained
To calcium hydroxide refining；
3rd, it is 6% water to be added to be modulated into mass percent concentration calcium hydroxide refining, through plate heat exchanger and less than 7 DEG C
Cooling water exchange heat, the temperature that calcium hydroxide refines slurries is made to be reduced to 7 DEG C；
4th, the kiln gas that limekiln generates is subjected to dust removal process by pulse dust collector and water dust scrubber, then through water
Ring compressor compresses are into kiln gas storage tank, the pure CO with being stored in pressurized reservoir2Gas carries out distribution, and obtaining volumetric concentration is
55% CO2Gas；
5th, the calcium hydroxide refining that step 3 obtains is passed through from stock inlet one in liquid film nucleation device, from gas access one
It is passed through pure CO2Gas to liquid film is nucleated in device, and adds in crystal growth controlling agent, pure CO2Gas is nucleated device by being arranged on liquid film
Gas distributor and calcium hydroxide refining come into full contact with carry out carburizing reagent, the temperature of reaction is 15 DEG C, obtains CaCO3Nucleus
Liquid；
6th, treat carbonization to CaCO3When the pH of nucleus liquid is 9, by CaCO3Nucleus liquid be passed through in aging tank ageing 8 it is small when；
7th, by the CaCO after ageing3Nucleus liquid is pumped into from stock inlet two in crystal grower, under stiring from gas access
Two are passed through the CO that volumetric concentration is 55%2Gas adds in crystal growth controlling agent into crystal grower, carries out secondary carbonization
Reaction, it is 7 to react to the pH value of the ripe slurry of calcium carbonate, and be as carbonized terminal；
8th, by CaCO3Ripe slurry is added in wet method fine grinding, adds in zirconia ball, alumina balls as abrasive media, diameter
It is 3 for the zirconia ball of 0.5~1.5nm and a diameter of 1.5~2nm and the mass ratio of alumina balls:1, after grinding 20min, add
Enter polyacrylic acid natrium surfactant, continue to grind 20min；
9th, through filter-press dehydration, band drier is dry, the classification of grinding machine powder grader, packs to get to polymolecularity, low
The nano-calcium carbonate of oil factor.
By nano-calcium carbonate made from embodiment one carry out electron-microscope scanning, grain size analysis, specific surface area and oil factor into
Row test, test result are as follows：
1st, nano-calcium carbonate is scanned using electron microscope, obtains electron-microscope scanning figure, as shown in Figure 2.
2nd, the testing to nano-calcium carbonate particles using Malvern laser particle analyzer, obtains particle size distribution figure, such as attached
Shown in Fig. 3 (a), for Unimodal Distribution, average grain diameter 227.3nm.
3rd, the specific surface area of nano-calcium carbonate is tested using V-Sorb 2800P specific surface areas and Porosimetry,
BET absorption test charts are obtained, as shown in Figure 4, obtain its specific surface area as 42.230620m2/g。
4th, calculated according to the method for standard GB/T/T19590-2004, measure its oil factor as 17.2mlDOP/
100gCaCO3。
Embodiment two
Using the carbonization reactor prepare small particle, polymolecularity, low oil factor nano-calcium carbonate preparation method, including
Following steps：
First, lime is calcined, lime will wilfully be burnt in calcination process so that the whiteness of the lime of firing is 95%
More than；
2nd, select the lime particle that whiteness is more than 95% by color selector to add in digestion machine, water is added digest instead
Should, it obtains calcium hydroxide and slightly starches, hydrogen calcium hydroxide is slightly starched to the sieve for passing through 100 mesh, 200 mesh, 325 mesh, 500 mesh successively, is obtained
To calcium hydroxide refining；
3rd, it is 7% water to be added to be modulated into mass percent concentration calcium hydroxide refining, through plate heat exchanger and less than 7 DEG C
Cooling water exchange heat, the temperature that calcium hydroxide refines slurries is made to be reduced to 8 DEG C；
4th, the kiln gas that limekiln generates is subjected to dust removal process by pulse dust collector and water dust scrubber, then through water
Ring compressor compresses are into kiln gas storage tank, the pure CO with being stored in pressurized reservoir2Gas carries out distribution, and obtaining volumetric concentration is
60% CO2Gas；
5th, the calcium hydroxide refining that step 3 obtains is passed through from stock inlet one in liquid film nucleation device, from gas access one
It is passed through pure CO2Gas to liquid film is nucleated in device, and adds in crystal growth controlling agent, pure CO2Gas is nucleated device by being arranged on liquid film
Gas distributor and calcium hydroxide refining come into full contact with carry out carburizing reagent, the temperature of reaction is 20 DEG C, obtains CaCO3Nucleus
Liquid；
6th, treat carbonization to CaCO3When the pH of nucleus liquid is 10, by CaCO3Nucleus liquid be passed through in aging tank ageing 10 it is small when；
7th, by the CaCO after ageing3Nucleus liquid is pumped into from stock inlet two in crystal grower, under stiring from gas access
Two are passed through the CO that volumetric concentration is 60%2Gas adds in crystal growth controlling agent into crystal grower, carries out secondary carbonization
Reaction, it is 8 to react to the pH value of the ripe slurry of calcium carbonate, and be as carbonized terminal；
8th, by CaCO3Ripe slurry is added in wet method fine grinding, adds in zirconia ball, alumina balls as abrasive media, diameter
It is 1 for the zirconia ball of 0.5~1.5nm and a diameter of 1.5~2nm and the mass ratio of alumina balls:1, after grinding 30min, add
Enter odium stearate surfactant, continue to grind 30min；
9th, through filter-press dehydration, band drier is dry, the classification of grinding machine powder grader, packs to get to polymolecularity, low
The nano-calcium carbonate of oil factor.
Nano-calcium carbonate obtained is tested according to the method for embodiment one, test result is as follows：
1st, attached drawing 3 (b) is the particle size distribution figure of embodiment two, for Unimodal Distribution, average grain diameter 223.3nm.
2nd, the specific surface area of nano-calcium carbonate is 43.15320m2/g。
3rd, the oil factor of nano-calcium carbonate is 16.1mlDOP/100gCaCO3。
Embodiment three
Using the carbonization reactor prepare small particle, polymolecularity, low oil factor nano-calcium carbonate preparation method, including
Following steps：
First, lime is calcined, lime will wilfully be burnt in calcination process so that the whiteness of the lime of firing is 95%
More than；
2nd, select the lime particle that whiteness is more than 95% by color selector to add in digestion machine, water is added digest instead
Should, it obtains calcium hydroxide and slightly starches, hydrogen calcium hydroxide is slightly starched to the sieve for passing through 100 mesh, 200 mesh, 325 mesh, 500 mesh successively, is obtained
To calcium hydroxide refining；
3rd, it is 8% water to be added to be modulated into mass percent concentration calcium hydroxide refining, through plate heat exchanger and less than 7 DEG C
Cooling water exchange heat, the temperature that calcium hydroxide refines slurries is made to be reduced to 10 DEG C；
4th, the kiln gas that limekiln generates is subjected to dust removal process by pulse dust collector and water dust scrubber, then through water
Ring compressor compresses are into kiln gas storage tank, the pure CO with being stored in pressurized reservoir2Gas carries out distribution, and obtaining volumetric concentration is
65% CO2Gas；
5th, the calcium hydroxide refining that step 3 obtains is passed through from stock inlet one in liquid film nucleation device, from gas access one
It is passed through pure CO2Gas to liquid film is nucleated in device, and adds in crystal growth controlling agent, pure CO2Gas is nucleated device by being arranged on liquid film
Gas distributor and calcium hydroxide refining come into full contact with carry out carburizing reagent, the temperature of reaction is 25 DEG C, obtains CaCO3Nucleus
Liquid；
6th, treat carbonization to CaCO3When the pH of nucleus liquid is 11, by CaCO3Nucleus liquid be passed through in aging tank ageing 12 it is small when；
7th, by the CaCO after ageing3Nucleus liquid is pumped into from stock inlet two in crystal grower, under stiring from gas access
Two are passed through the CO that volumetric concentration is 65%2Gas adds in crystal growth controlling agent into crystal grower, carries out secondary carbonization
Reaction, it is 9 to react to the pH value of the ripe slurry of calcium carbonate, and be as carbonized terminal；
8th, by CaCO3Ripe slurry is added in wet method fine grinding, adds in zirconia ball, alumina balls as abrasive media, diameter
It is 1 for the zirconia ball of 0.5~1.5nm and a diameter of 1.5~2nm and the mass ratio of alumina balls:2, after grinding 40min, add
Enter polyacrylic acid natrium surfactant, continue to grind 40min；
9th, through filter-press dehydration, band drier is dry, the classification of grinding machine powder grader, packs to get to polymolecularity, low
The nano-calcium carbonate of oil factor.
Nano-calcium carbonate obtained is tested according to the method for embodiment one, test result is as follows：
1st, nano-calcium carbonate is in Unimodal Distribution, average grain diameter 228.4nm.
2nd, the specific surface area of nano-calcium carbonate is 42.52170m2/g。
3rd, the oil factor of nano-calcium carbonate is 16.7mlDOP/100gCaCO3。
It the above is only the feature implementation example of the present invention, the scope of the present invention be not limited in any way.It is all to use together
The technical solution formed Deng exchange or equivalence replacement, all falls within rights protection scope of the present invention.
Claims (10)
1. a kind of carbonization reactor, it is characterised in that：It includes liquid film nucleation device (1) and crystal grower (2), the liquid film into
The upper end of core device (1) is equipped with stock inlet one (11) and grout outlet one (14), and lower end is equipped with gas access one (12), stock inlet one
(11) and grout outlet one (14) is located at the both sides that liquid film is nucleated device (1) respectively, and gas distributor is additionally provided in liquid film nucleation device (1)
(13)；The upper end of the crystal grower (2) is equipped with stock inlet two (21), and lower end is equipped with gas access two (22) and grout outlet two
(23), blender (24) is additionally provided in crystal grower (2), crystal grower (2) is externally provided with the electricity being connected with blender (24)
Machine (25), the grout outlet one (14) and stock inlet two (21) are connected by pumping (3).
2. a kind of side that polymolecularity, low oil factor nano-calcium carbonate are prepared using carbonization reactor as described in claim 1
Method, it is characterised in that：Comprise the following steps：
Step 1: lime is calcined, raw burn is kept, the whiteness of the lime of firing is more than 95%；
Step 2: selecting lime particle of the whiteness more than 95% by color selector, carrying out digestion reaction with water obtains hydroxide
Calcium is slightly starched, and hydrogen calcium hydroxide is slightly starched to the sieve for passing through 100 mesh, 200 mesh, 325 mesh, 500 mesh successively, obtains calcium hydroxide essence
Slurry；
It is 6~8%, is cooled to temperature as 7~10 Step 3: water is added to be modulated into mass percent concentration calcium hydroxide refining
℃；
Step 4: the calcium hydroxide refining that step 3 obtains is passed through from stock inlet one in liquid film nucleation device, from gas access one
It is passed through pure CO2Gas to liquid film is nucleated in device, and adds in crystal growth controlling agent, pure CO2Gas is nucleated device by being arranged on liquid film
Gas distributor and calcium hydroxide refining come into full contact with carry out carburizing reagent, be carbonized to slurry pH value be 9~11 when, Ran Houchen
When change 8~12 is small；
Step 5: the ripe slurry of the calcium carbonate after ageing is pumped into from stock inlet two in crystal grower, under stiring from gas access
Two are passed through the CO that volumetric concentration is 55~65%2Gas adds in crystal growth controlling agent into crystal grower, carries out secondary
Carburizing reagent, it is 7~9 to react to the pH value of the ripe slurry of calcium carbonate, and be as carbonized terminal；
Step 6: the ripe slurry of the calcium carbonate that step 5 is obtained is added in wet method fine grinding or grinding machine for cutting charge into pieces, zirconium oxide is added
Ball, alumina balls after grinding 20~40min, add in surfactant, continue 20~40min of grinding as abrasive media；
Step 7: the calcium carbonate that step 6 is obtained carries out filter-press dehydration, drying, crushing, classification to get to small particle, high score
Dissipate property, the nano-calcium carbonate of low oil factor.
3. according to claim 2 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 3, calcium hydroxide refining is exchanged heat by plate heat exchanger with less than 7 DEG C of cooling water, makes calcium hydroxide refining
Temperature be reduced to 7~10 DEG C.
4. according to claim 2 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 4, the temperature reacted in liquid film nucleation device is 15~25 DEG C.
5. according to claim 2 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 4, crystal growth controlling agent is NaCO3。
6. according to claim 2 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 5, crystal growth controlling agent is sucrose, one or more kinds of mixtures in beet sugar, maltose.
7. according to claim 2 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 5, volumetric concentration is 55~65% CO2The preparation method of gas is：The kiln gas that limekiln is generated is through extra pulse
Deduster and water dust scrubber carry out dust removal process, are then compressed to through water ring compressor in kiln gas storage tank, with being stored in compression
The pure CO of storage tank2Gas carry out distribution to get to volumetric concentration be 55~65% CO2Gas.
8. according to claim 1 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 6, the zirconia ball of a diameter of 0.5~1.5nm and a diameter of 1.5~2nm and the mass ratio of alumina balls are 3:1
~6.
9. according to claim 1 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
It states in step 6, surfactant is complexed surfactant, by ionic surfactant, Sodium Polyacrylate, odium stearate
Composition.
10. according to claim 1 prepare polymolecularity, the method for low oil factor nano-calcium carbonate, it is characterised in that：Institute
The primary particle size for stating nano-calcium carbonate obtained in step 7 is 20~30nm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451469A (en) * | 2019-08-21 | 2019-11-15 | 武汉工程大学 | A kind of processing method of Sodium hypophosphite production residue |
| CN110484023A (en) * | 2019-09-30 | 2019-11-22 | 建德市华宇纳米科技有限公司 | A kind of high-dispersion nano calcium carbonate Preparation equipment and preparation method |
| CN111559752A (en) * | 2020-05-20 | 2020-08-21 | 建德市双超钙业有限公司 | Production method of nano calcium carbonate for PE direct film blowing |
| CN112811456A (en) * | 2021-01-26 | 2021-05-18 | 江西势通钙业有限公司 | Nano calcium carbonate with high specific surface area and preparation method thereof |
| CN113461042A (en) * | 2021-07-19 | 2021-10-01 | 合肥工业大学 | Optimization method of modification process of nano calcium carbonate |
| CN115744956A (en) * | 2022-11-19 | 2023-03-07 | 山西新泰恒信纳米材料有限公司 | Preparation method of high-dispersion transparent nano calcium carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117232A (en) * | 2007-07-10 | 2008-02-06 | 杨第伦 | Preparation of calcium carbonate nano particle material by air bubble liquid film process |
| CN103011226A (en) * | 2012-12-07 | 2013-04-03 | 池州凯尔特纳米科技有限公司 | Method for preparing nano calcium carbonate through nucleation and growth step by step |
-
2017
- 2017-12-01 CN CN201711249143.6A patent/CN108083312B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117232A (en) * | 2007-07-10 | 2008-02-06 | 杨第伦 | Preparation of calcium carbonate nano particle material by air bubble liquid film process |
| CN103011226A (en) * | 2012-12-07 | 2013-04-03 | 池州凯尔特纳米科技有限公司 | Method for preparing nano calcium carbonate through nucleation and growth step by step |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451469A (en) * | 2019-08-21 | 2019-11-15 | 武汉工程大学 | A kind of processing method of Sodium hypophosphite production residue |
| CN110484023A (en) * | 2019-09-30 | 2019-11-22 | 建德市华宇纳米科技有限公司 | A kind of high-dispersion nano calcium carbonate Preparation equipment and preparation method |
| CN110484023B (en) * | 2019-09-30 | 2021-05-14 | 建德市华宇纳米科技有限公司 | Preparation equipment and preparation method of high-dispersion nano calcium carbonate |
| CN111559752A (en) * | 2020-05-20 | 2020-08-21 | 建德市双超钙业有限公司 | Production method of nano calcium carbonate for PE direct film blowing |
| CN112811456A (en) * | 2021-01-26 | 2021-05-18 | 江西势通钙业有限公司 | Nano calcium carbonate with high specific surface area and preparation method thereof |
| CN113461042A (en) * | 2021-07-19 | 2021-10-01 | 合肥工业大学 | Optimization method of modification process of nano calcium carbonate |
| CN115744956A (en) * | 2022-11-19 | 2023-03-07 | 山西新泰恒信纳米材料有限公司 | Preparation method of high-dispersion transparent nano calcium carbonate |
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