CN111874934A - Process for preparing regular cubic crystal form nano calcium carbonate - Google Patents
Process for preparing regular cubic crystal form nano calcium carbonate Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 215
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 106
- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 109
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 65
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 59
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 38
- 238000003763 carbonization Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 26
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 26
- 238000001723 curing Methods 0.000 claims description 26
- 239000004571 lime Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 238000003825 pressing Methods 0.000 claims description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 14
- 239000005642 Oleic acid Substances 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 230000029087 digestion Effects 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000007127 saponification reaction Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 239000010797 grey water Substances 0.000 claims 1
- 235000009165 saligot Nutrition 0.000 abstract description 4
- 230000001788 irregular Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 1
- 244000017160 saligot Species 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 15
- 235000021355 Stearic acid Nutrition 0.000 description 12
- 235000019864 coconut oil Nutrition 0.000 description 12
- 239000003240 coconut oil Substances 0.000 description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 12
- 239000008117 stearic acid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000010000 carbonizing Methods 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 235000021313 oleic acid Nutrition 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 240000001085 Trapa natans Species 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a process for preparing regular cubic crystal form nano calcium carbonate, belonging to the technical field of preparation of nano calcium carbonate powder of inorganic non-metallic materials. The preparation process of the regular cubic crystal form nano calcium carbonate comprises the steps of adding alkali metal ions before carbonation reaction, fully mixing the alkali metal ions with calcium hydroxide slurry, adjusting the initial carbonation temperature, introducing carbon dioxide mixed gas with a certain concentration to carry out rapid carbonation reaction to obtain calcium carbonate slurry, and curing, surface treating, dehydrating, drying and crushing the calcium carbonate slurry to obtain the regular cubic crystal form nano calcium carbonate. The invention solves the problems of long carbonation reaction time of the nano calcium carbonate, irregular product particle appearance, no water caltrop in cubic crystal particles, uneven particle size and unstable quality in the prior art.
Description
Technical Field
The invention belongs to the technical field of preparation of calcium carbonate powder in inorganic nonmetallic materials, and particularly relates to a preparation process of regular cubic crystal form nano calcium carbonate.
Background
The precipitated calcium carbonate for domestic industry is divided into two types according to the appearance: one is conventional spindle light calcium carbonate, which is called light calcium for short in China, and mainly divides the product quality and grade by the settlement volume; the other is cubic nano calcium carbonate which is called nano calcium for short in China, and the classification of the nano calcium carbonate is mainly distinguished by the difference of specific surface area and modification process. The foreign refining production process is mainly used for improving and perfecting the appearance of calcium carbonate crystals and dividing calcium carbonate products by regular crystal appearances in different degrees. The light calcium product has spindle crystal form, rice grain crystal form, rod crystal form or crystal whisker; the nano calcium carbonate can be in an orthorhombic crystal particle shape with clear water caltrops at 100-150nm, and the high-specific-surface-area nano calcium carbonate is in a cubic shape without water caltrops or with unobvious water caltrops but good dispersibility. The foreign advanced nano calcium carbonate technology is worthy of learning, and the refinement of the production technology and the fine division of the product types of domestic calcium carbonate production enterprises are yet to be enhanced.
The refinement of the production process technology needs to be improved in two aspects, namely the refinement of production equipment on one hand and the refinement of the production process on the other hand. The main process influencing the crystal morphology and the crystal grain size of the product is the carbonation reaction of calcium hydroxide, and the precise regulation and control of the carbonation process are the premise of ensuring the crystal morphology of calcium carbonate. The carbonation reaction process is somewhat dependent on the carbonation reactor. At present, the carbonation reactors for preparing the nano calcium carbonate in China are various and comprise a traditional bubbling carbonation reactor, an intermittent bubbling stirring carbonation reactor, a novel spraying carbonation reactor, a hypergravity carbonation reactor, a Venturi tube spraying carbonation reactor and the like. The production process comprises pure process regulation and control and crystal form control agent regulation and control. The domestic production technology is mainly based on pure process regulation, and a small number of enterprises regulate and control the crystal morphology by combining process regulation and control with a crystal form control agent. In view of various data such as comprehensive production process and product performance, the regulation and control production process of the domestic crystal form control agent needs further research and breakthrough to support production.
Disclosure of Invention
The invention provides a preparation process of regular cubic crystal form nano calcium carbonate, which aims to solve the problems of long carbonation reaction time, irregular product particle appearance, uneven particle size and unstable quality in the existing nano calcium carbonate preparation technology.
In order to solve the technical problems, the invention adopts the following technical scheme:
a process for preparing the regular cubic crystal nano calcium carbonate includes such steps as refining calcium hydroxide slurry, adding alkali metal ions, mixing them together, regulating initial carbonizing temp, introducing the mixture of carbon dioxide gas with a certain concentration, quick carbonating reaction to obtain calcium carbonate slurry, ageing, surface treating, dewatering, baking and pulverizing.
Further, the calcium hydroxide slurry is obtained by adding normal temperature water or hot water into light-burned or medium-burned lime for digestion, and the ratio of lime slaking ash water is 1: 5-9; sieving the lime slurry with a 80-220 mesh sieve for multiple times to remove large-particle impurities and insoluble substances, and further refining the obtained calcium hydroxide slurry by a suspension separator; the solid content of the calcium hydroxide obtained by refining is regulated and controlled to be 8-15%, and appropriate aging treatment is carried out.
Furthermore, the carbonation reaction has no special requirements on the reactor, and the requirements of the carbonation reaction can be met by an intermittent bubbling carbonation reactor, an intermittent bubbling stirring carbonation reactor, a super-gravity carbonation reactor and a venturi tube jet reaction kettle.
Further, the alkali metal ions can be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the dosage of the alkali metal ions is 0.5-6mol/L, and the carbonation reaction time is shorter when the dosage is larger.
Furthermore, the concentration of the carbon dioxide mixed gas is 25-100%, the initial carbonation temperature of the calcium hydroxide slurry is 15-35 ℃, the rapid carbonation reaction is started after the carbon dioxide is introduced, and the reaction is judged to be finished when the pH value of the slurry is lower than 10.
Further, in the carbonation reaction process, the initial carbonation temperature of the calcium hydroxide slurry is lower than that of the calcium hydroxide slurry, and the temperature of the calcium hydroxide slurry is rapidly increased after the carbonation reaction starts.
Furthermore, the carbonation reaction time is obviously reduced, the reaction time is reduced by more than 5 percent compared with the reaction process without adding alkali metal ions, and the production efficiency can be effectively improved.
Furthermore, the calcium carbonate slurry curing process has various processes, and can be slow curing or accelerated curing; the slow curing of the calcium carbonate slurry is to introduce gas with the carbon dioxide content lower than 15 percent under stirring, control the pH value to be 8.5-10 and perform curing, wherein the curing time is 4-48h according to actual needs; the accelerated curing is carried out by adding one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate into calcium carbonate slurry, mixing, adjusting pH to be more than 10, heating the slurry to 60-100 ℃, and aging for 0.5-8h under stirring.
Further, after the calcium carbonate slurry is slowly cured, introducing carbon dioxide to carbonate until the pH value is lower than 8, and then carrying out surface modification treatment; after the calcium carbonate slurry accelerated curing technology, surfactants such as fatty acid, oleic acid and the like which are well dissolved by hot water can be added at a higher temperature to carry out saponification reaction on metal ions in the slurry to neutralize alkali metal ions, and meanwhile, the surface of calcium carbonate particles can adsorb the alkali metal ions due to the negative ion effect, so that the saponified surfactant can better coat the nano calcium carbonate particles.
Further, the surface modified calcium carbonate slurry is subjected to pressure filtration to obtain a calcium carbonate filter cake, and the calcium carbonate filter cake is dried, crushed and screened to obtain regular cubic crystal form nano calcium carbonate; the filtrate obtained by filter pressing can be used for lime digestion to realize recycling after the purification treatment of the working procedures such as sedimentation, filtration and the like.
Furthermore, the regular cubic crystal form nano calcium carbonate has good dispersibility, regular appearance, uniform particle size and 70-180nm particle size range.
The invention has the following beneficial effects:
(1) the invention can effectively increase the utilization rate of carbon dioxide in the mixed gas, effectively reduce the production cost and simultaneously reduce the emission of carbon dioxide, and is beneficial to green production of products.
(2) The method can effectively reduce the carbonation reaction time of the calcium carbonate, improve the production efficiency and reduce the time cost.
(3) The regular cubic crystal form nano calcium carbonate has the grain diameter of 70-180 nanometers, is controllable in grain diameter, relatively weaker in cohesion of nano calcium carbonate grains, and has better dispersibility after surface treatment.
(4) The regular cubic crystal form nano calcium carbonate has larger grain diameter and good dispersibility, and has better fluidity and good processing performance when being filled and applied to downstream products.
(5) The method has the characteristics of simple process, low energy consumption, short reaction time and easy operation and control, and the regular cubic crystal form nano calcium carbonate produced by the method has uniform and stable quality.
Drawings
FIG. 1 is a scanning electron microscope analysis chart of the regular cubic crystal form nano calcium carbonate product prepared in example 1;
FIG. 2 is the scanning electron microscope analysis chart of the regular cubic crystal form nano calcium carbonate product prepared in example 2.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
Example 1
A process for preparing regular cubic crystal form nano calcium carbonate belongs to a calcium hydroxide solution carbonization method for preparing regular cubic crystal form nano calcium carbonate, and the preparation method comprises the following steps:
(1) lime slaking and calcium hydroxide slurry preparation: sufficiently stirring and digesting lime and hot water at 70 ℃ in a mass ratio of 1:5, aging and cooling properly, sieving the obtained lime slurry to remove large particles of insoluble matters and impurities to obtain calcium hydroxide slurry, further refining the calcium hydroxide slurry by a suspension separator, adjusting the calcium hydroxide slurry to be cooled to room temperature, and adjusting the solid content of the calcium hydroxide to be 10%;
(2) alkali metal ion addition: pumping the debugged calcium hydroxide slurry into an intermittent bubble carbonization tower with a stirring device by using a pump, adding sodium hydroxide serving as alkali metal ions, adjusting the concentration of sodium ions in the slurry to be 2.8mol/L, and uniformly stirring;
(3) carbonizing: adjusting the initial carbonization temperature of the calcium hydroxide slurry to 25 ℃, opening a gas valve, introducing mixed gas with the carbon dioxide concentration of 32% to carry out carbonization reaction, closing the gas valve when the pH of the reaction liquid is 10.0 after carbonization, stopping the reaction, and stopping stirring;
(4) curing: and introducing gas with the carbon dioxide content of less than 15% into the calcium carbonate slurry obtained by carbonization under stirring, controlling the pH value to be 8.5-10, and curing for 12 hours.
(5) Surface modification: stearic acid, oleic acid and coconut oil are mixed according to the proportion of 3:1:1, the total amount of the treating agent is 3 percent of the solid content of calcium carbonate, the stearic acid is heated and dissolved by hot water, then the oleic acid and the coconut oil are added and heated to 90 ℃, and the dissolved treating agent is added into the cured calcium carbonate slurry and stirred vigorously for 30 minutes.
(6) Filter pressing, drying and crushing: and (3) carrying out filter pressing dehydration, drying, crushing, screening and other processes on the calcium carbonate slurry subjected to surface modification treatment to obtain regular cubic crystal form nano calcium carbonate with the average particle size of 110 nanometers.
Example 2
A process for preparing regular cubic crystal form nano calcium carbonate belongs to a calcium hydroxide solution carbonization method for preparing regular cubic crystal form nano calcium carbonate, and the preparation method comprises the following steps:
(1) lime slaking and calcium hydroxide slurry preparation: sufficiently stirring and digesting lime and water at the mass ratio of 1:8 at room temperature, aging and cooling properly, sieving the obtained lime slurry to remove large particles of insoluble matters and impurities to obtain calcium hydroxide slurry, refining the calcium hydroxide slurry by a suspension separator, adjusting the calcium hydroxide slurry to be cooled to room temperature, and adjusting the solid content of the calcium hydroxide to be 12%;
(2) alkali metal ion addition: pumping the debugged calcium hydroxide slurry into an intermittent bubble carbonization tower with a stirring device by using a pump, adding sodium bicarbonate serving as alkali metal ions, adjusting the concentration of sodium ions in the slurry to be 2.2mol/L, and uniformly stirring;
(3) carbonizing: adjusting the initial carbonization temperature of the calcium hydroxide slurry to 24 ℃, opening a gas valve, introducing mixed gas with the carbon dioxide concentration of 39% to carry out carbonization reaction, closing the gas valve when the pH of the reaction liquid is 10.0 after carbonization, stopping the reaction, and stopping stirring;
(4) curing: and introducing gas with the carbon dioxide content of less than 15% into the calcium carbonate slurry obtained by carbonization under stirring, controlling the pH value to be 8.5-9.6, and curing for 17 hours.
(5) Surface modification: stearic acid, oleic acid and coconut oil are mixed according to the proportion of 1:3:1, the total amount of the treating agent is 3.1 percent of the solid content of calcium carbonate, the stearic acid is heated and dissolved by hot water, then the oleic acid and the coconut oil are added and heated to 90 ℃, and the dissolved treating agent is added into the cured calcium carbonate slurry and stirred vigorously for 30 minutes.
(6) Filter pressing, drying and crushing: and carrying out filter pressing dehydration, drying, crushing, screening and other processes on the calcium carbonate slurry subjected to surface modification treatment to obtain the regular cubic crystal form nano calcium carbonate with the average particle size of 150 nanometers.
Example 3
A process for preparing regular cubic crystal form nano calcium carbonate belongs to a calcium hydroxide solution carbonization method for preparing regular cubic crystal form nano calcium carbonate, and the preparation method comprises the following steps:
(1) lime slaking and calcium hydroxide slurry preparation: sufficiently stirring and digesting lime and water at the mass ratio of 1:9 at room temperature, aging and cooling properly, sieving the obtained lime slurry to remove large particles of insoluble matters and impurities to obtain calcium hydroxide slurry, refining the calcium hydroxide slurry by a suspension separator, adjusting the solid content of the calcium hydroxide to 11% after the calcium hydroxide slurry is cooled to room temperature;
(2) alkali metal ion addition: pumping the debugged calcium hydroxide slurry into an intermittent bubble carbonization tower with a stirring device by using a pump, adding sodium bicarbonate serving as alkali metal ions, adjusting the concentration of sodium ions in the slurry to be 2.0mol/L, and uniformly stirring;
(3) carbonizing: adjusting the initial carbonization temperature of the calcium hydroxide slurry to 23 ℃, opening a gas valve, introducing mixed gas with the carbon dioxide concentration of 35% to carry out carbonization reaction, closing the gas valve when the pH of the reaction liquid is 10.0 after carbonization, stopping the reaction, and stopping stirring;
(4) curing: and introducing gas with the carbon dioxide content of less than 8% into the calcium carbonate slurry obtained by carbonization under stirring, controlling the pH value to be 8.8-9.8, and curing for 20 hours.
(5) Surface modification: stearic acid, oleic acid and coconut oil are mixed according to the proportion of 3:1:1, the total amount of the treating agent is 3.5 percent of the solid content of calcium carbonate, the stearic acid is heated and dissolved by hot water, then the oleic acid and the coconut oil are added and heated to 90 ℃, and the dissolved treating agent is added into the cured calcium carbonate slurry and stirred vigorously for 30 minutes.
(6) Filter pressing, drying and crushing: the calcium carbonate slurry after the surface modification treatment is subjected to the processes of filter pressing dehydration, drying, crushing, sieving and the like to obtain the regular cubic crystal form nano calcium carbonate with the average grain diameter of 100 nanometers.
(7) Example 3 was repeated by changing the amount of sodium bicarbonate added to adjust the molar concentration to 0mlol/L, 2.5mol/L, 3mol/L, 3.5mol/L, and the carbonation times obtained were as follows:
| alkali concentration (mol/L) | 0 | 2 | 2.5 | 3.0 | 3.5 |
| Carbonization time (min) | 42 | 36 | 32 | 28 | 25 |
(8) Example 3 illustrates that an increased amount of alkali metal ions can effectively reduce the carbonation reaction time and effectively reduce the production cost.
Example 4
A process for preparing regular cubic crystal form nano calcium carbonate belongs to a calcium hydroxide solution carbonization method for preparing regular cubic crystal form nano calcium carbonate, and the preparation method comprises the following steps:
(1) lime slaking and calcium hydroxide slurry preparation: sufficiently stirring and digesting lime and water at the mass ratio of 1:7 at room temperature, aging and cooling properly, sieving the obtained lime slurry to remove large particles of insoluble matters and impurities to obtain calcium hydroxide slurry, refining the calcium hydroxide slurry by a suspension separator, adjusting the solid content of the calcium hydroxide to 9% after the calcium hydroxide slurry is cooled to room temperature;
(2) alkali metal ion addition: pumping the debugged calcium hydroxide slurry into an intermittent bubble carbonization tower with a stirring device by using a pump, adding potassium hydroxide serving as alkali metal ions, adjusting the concentration of potassium ions in the slurry to be 2.2mol/L, and uniformly stirring;
(3) carbonizing: adjusting the initial carbonization temperature of the calcium hydroxide slurry to 28 ℃, opening a gas valve, introducing mixed gas with the carbon dioxide concentration of 37% to carry out carbonization reaction, closing the gas valve when the pH of the reaction liquid is 10.0 after carbonization, stopping the reaction, and stopping stirring;
(4) curing: carbonizing to obtain calcium carbonate slurry, adjusting pH to 12 with potassium hydroxide under stirring, heating the slurry to 90 deg.C, and aging under stirring for 2.5 h. .
(5) Surface modification: stearic acid, oleic acid and coconut oil are mixed according to the proportion of 2:1:2, the total amount of the treating agent is 2.8 percent of the solid content of calcium carbonate, the stearic acid is heated and dissolved by hot water, then the oleic acid and the coconut oil are added and heated to 90 ℃, and the dissolved treating agent is added into the cured calcium carbonate slurry and stirred vigorously for 30 minutes.
(6) Filter pressing, drying and crushing: the calcium carbonate slurry after the surface modification treatment is subjected to the processes of filter pressing dehydration, drying, crushing, sieving and the like to obtain the regular cubic crystal form nano calcium carbonate with the average particle size of 120 nanometers.
Example 5
A process for preparing regular cubic crystal form nano calcium carbonate belongs to a calcium hydroxide solution carbonization method for preparing regular cubic crystal form nano calcium carbonate, and the preparation method comprises the following steps:
(1) lime slaking and calcium hydroxide slurry preparation: sufficiently stirring and digesting lime and hot water at 80 ℃ in a mass ratio of 1:6, aging and cooling properly, sieving the obtained lime slurry to remove large particles of insoluble matters and impurities to obtain calcium hydroxide slurry, refining the calcium hydroxide slurry by a suspension separator, and adjusting the solid content of the calcium hydroxide to 9% after the calcium hydroxide slurry is cooled to room temperature;
(2) alkali metal ion addition: pumping the adjusted calcium hydroxide slurry into an intermittent bubbling carbonization tower with a stirring device by using a pump, and adding sodium hydroxide and potassium bicarbonate with the molar ratio of 2:1 as alkali metal ions, adjusting the total concentration of the alkali metal ions in the slurry to be 3.2mol/L, and uniformly stirring;
(3) carbonizing: adjusting the initial carbonization temperature of the calcium hydroxide slurry to 22 ℃, opening a gas valve, introducing mixed gas with the carbon dioxide concentration of 38% to carry out carbonization reaction, closing the gas valve when the pH of the reaction liquid is 10.0 after carbonization, stopping the reaction, and stopping stirring;
(4) curing: carbonizing to obtain calcium carbonate slurry, introducing gas with carbon dioxide content less than 10% under stirring, controlling pH at 9-10, and aging for 18 h.
(5) Surface modification: stearic acid, oleic acid and coconut oil are mixed according to the proportion of 2:2:1, the total amount of the treating agent is 3.2 percent of the solid content of calcium carbonate, the stearic acid is heated and dissolved by hot water, then the oleic acid and the coconut oil are added and heated to 90 ℃, and the dissolved treating agent is added into the cured calcium carbonate slurry and stirred vigorously for 30 minutes.
(6) Filter pressing, drying and crushing: the calcium carbonate slurry after the surface modification treatment is subjected to the processes of filter pressing dehydration, drying, crushing, sieving and the like to obtain the regular cubic crystal form nano calcium carbonate with the average grain diameter of 90 nanometers.
Example 6
A process for preparing regular cubic crystal form nano calcium carbonate belongs to a calcium hydroxide solution carbonization method for preparing regular cubic crystal form nano calcium carbonate, and the preparation method comprises the following steps:
(1) lime slaking and calcium hydroxide slurry preparation: sufficiently stirring and digesting lime and water at the mass ratio of 1:9 at room temperature, aging and cooling properly, sieving the obtained lime slurry to remove large particles of insoluble matters and impurities to obtain calcium hydroxide slurry, refining the calcium hydroxide slurry by a suspension separator, adjusting the calcium hydroxide slurry to be cooled to room temperature, and adjusting the solid content of the calcium hydroxide to be 12%;
(2) alkali metal ion addition: pumping the adjusted calcium hydroxide slurry into an intermittent bubbling carbonization tower with a stirring device by using a pump, and adding sodium carbonate and sodium hydroxide according to the molar ratio of 1:1 is taken as alkali metal ions, the concentration of sodium ions in the slurry is adjusted to be 3.0mol/L, and the slurry is stirred uniformly;
(3) carbonizing: adjusting the initial carbonization temperature of the calcium hydroxide slurry to 26 ℃, opening a gas valve, introducing mixed gas with the carbon dioxide concentration of 36% to carry out carbonization reaction, closing the gas valve when the pH of the reaction liquid is 10.0 after carbonization, stopping the reaction, and stopping stirring;
(4) curing: carbonizing to obtain calcium carbonate slurry, adjusting pH to 12 with sodium hydroxide under stirring, heating the slurry to 80 deg.C, and aging under stirring for 3 hr.
(5) Surface modification: stearic acid, oleic acid and coconut oil are mixed according to the proportion of 8:1:1, the total amount of the treating agent is 2.8 percent of the solid content of calcium carbonate, the stearic acid is heated and dissolved by hot water, then the oleic acid and the coconut oil are added and heated to 90 ℃, and the dissolved treating agent is added into the cured calcium carbonate slurry and stirred vigorously for 30 minutes.
(6) Filter pressing, drying and crushing: and (3) carrying out filter pressing dehydration, drying, crushing, screening and other processes on the calcium carbonate slurry subjected to surface modification treatment to obtain regular cubic crystal form nano calcium carbonate with the average particle size of 110 nanometers.
Claims (10)
1. The preparation process of regular cubic crystal form nanometer calcium carbonate is characterized in that alkali metal ions are added into refined calcium hydroxide slurry, the alkali metal ions and the calcium hydroxide slurry are fully mixed, the initial carbonization temperature is adjusted, carbon dioxide mixed gas with certain concentration is introduced for rapid carbonation reaction to obtain calcium carbonate slurry, and the regular cubic crystal form nanometer calcium carbonate is obtained by curing, surface treatment, dehydration, drying and crushing the calcium carbonate slurry.
2. The process for preparing regular cubic crystal form nano calcium carbonate according to claim 1, wherein the calcium hydroxide slurry is obtained by adding normal temperature water or hot water into light burned or calcined lime for digestion, and the lime digestion gray-water ratio is 1: 5-9; sieving the lime slurry with a 80-220 mesh sieve for multiple times to remove large-particle impurities and insoluble substances, and further refining the obtained calcium hydroxide slurry by a suspension separator; the solid content of the calcium hydroxide obtained by refining is regulated and controlled to be 8-15%, and appropriate aging treatment is carried out.
3. The process for preparing the regular cubic crystal form nano calcium carbonate according to claim 1, wherein the carbonation reaction has no special requirements on a reactor, and comprises a batch bubbling carbonation reactor, a batch bubbling stirring carbonation reactor, a super-gravity carbonation reactor and a venturi tube jet reaction kettle which can meet the carbonation reaction requirements.
4. The process for preparing regular cubic crystal form nano calcium carbonate according to claim 1, wherein the alkali metal ions can be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; the dosage of the alkali metal ions is 0.5-6mol/L, and the carbonation reaction time is shorter when the dosage is larger.
5. The process for preparing the regular cubic crystal form nano calcium carbonate according to claim 1, wherein the concentration of the carbon dioxide mixed gas is 25-100%, the initial carbonation temperature of the calcium hydroxide slurry is 15-35 ℃, the rapid carbonation reaction is started after the carbon dioxide is introduced, and the reaction is judged to be finished when the pH value of the slurry is lower than 10.
6. The process for preparing regular cubic crystal form nanocalcium carbonate according to claim 1, wherein during the carbonation reaction, the initial carbonation temperature of the calcium hydroxide slurry is lower than the temperature of the slurry after the carbonation reaction is started.
7. The process for preparing the regular cubic crystal form nanocalcium carbonate according to claim 1, wherein the carbonation reaction time is significantly reduced, and the reaction time is reduced by more than 5% compared with the reaction process without adding alkali metal ions, which can effectively improve the production efficiency.
8. The process for preparing the regular cubic crystal form nano calcium carbonate according to claim 1, wherein the calcium carbonate slurry curing process is various, and can be slow curing or accelerated curing; the slow curing of the calcium carbonate slurry is to introduce gas with the carbon dioxide content lower than 15 percent under stirring, control the pH value to be 8.5-10 and perform curing, wherein the curing time is 4-48h according to actual needs; the accelerated curing is carried out by adding one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate into calcium carbonate slurry, mixing, adjusting pH to be more than 10, heating the slurry to 60-100 ℃, and aging for 0.5-8h under stirring.
9. The process for preparing the regular cubic crystal form nano calcium carbonate according to claim 1, wherein the surface modification treatment can be carried out by introducing carbon dioxide for carbonation until the pH is lower than 8 after the calcium carbonate slurry is slowly cured; after the calcium carbonate slurry accelerated curing technology is adopted, surfactants such as fatty acid and oleic acid which are well dissolved by hot water are added at a high temperature to carry out saponification reaction on metal ions in the slurry to neutralize alkali metal ions, and meanwhile, the surface of calcium carbonate particles can adsorb the alkali metal ions due to the negative ion effect, so that the saponified surfactant can better coat the nano calcium carbonate particles.
10. The process for preparing the regular cubic crystal form nano calcium carbonate according to claim 1, wherein the regular cubic crystal form nano calcium carbonate is obtained by drying, crushing and screening calcium carbonate filter cakes obtained by filter pressing the surface modified calcium carbonate slurry; the filtrate obtained by filter pressing can be used for lime digestion to realize recycling after the purification treatment of the working procedures such as sedimentation, filtration and the like.
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