CN106830042A - The method that a kind of utilization Weihe north Ordovician limestone prepares the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape - Google Patents
The method that a kind of utilization Weihe north Ordovician limestone prepares the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape Download PDFInfo
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- CN106830042A CN106830042A CN201710119863.4A CN201710119863A CN106830042A CN 106830042 A CN106830042 A CN 106830042A CN 201710119863 A CN201710119863 A CN 201710119863A CN 106830042 A CN106830042 A CN 106830042A
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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 174
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 86
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010419 fine particle Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000006028 limestone Substances 0.000 title claims abstract description 44
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 41
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 31
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 31
- 239000004571 lime Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 230000010355 oscillation Effects 0.000 claims abstract description 15
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229940082004 sodium laurate Drugs 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 60
- 238000003763 carbonization Methods 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract 1
- 101100399296 Mus musculus Lime1 gene Proteins 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 14
- 229910021532 Calcite Inorganic materials 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000021321 essential mineral Nutrition 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005255 carburizing Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005464 sample preparation method Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101000685982 Homo sapiens NAD(+) hydrolase SARM1 Proteins 0.000 description 1
- 241000134253 Lanka Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 102100023356 NAD(+) hydrolase SARM1 Human genes 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012812 sealant material Substances 0.000 description 1
- 239000000849 selective androgen receptor modulator Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention discloses the method that a kind of utilization Weihe north Ordovician limestone prepares ultra-fine carbonic acid fine particle calcium carbonate, including：Weihe north Ordovician limestone is crushed, clean, dry, sieved, obtain the particle of 1.6mm 2.0mm；Above-mentioned particle is calcined into 60min in 1000 DEG C, active lime is obtained；Above-mentioned active lime and 90 DEG C of water are mixed and made into 5.6wt% lime slurries；Above-mentioned lime slurry is placed in container, is put into ultrasonic oscillation device, to sodium laurate is added in container, be passed through CO2Gas, stirring, 20 DEG C of reaction temperature；When pH is down to 7, stopping is passed through CO2And ultrasonic oscillation device is closed, continue to stir 20min；Filtering, washing, ultra-fine carbonic acid fine particle calcium carbonate is obtained final product to solute drying, grinding.The present invention is advantageous in that：With Weihe north Ordovician limestone as raw material, using carbonizatin method, and crystal control agent sodium laurate was added before charing, gas distributor and ultrasonic technique are increased in carbonization process, prepared that function admirable, added value be high, ultra-fine carbonic acid fine particle calcium carbonate product in rhombohedron shape.
Description
Technical field
The present invention relates to a kind of method for preparing ultra-fine carbonic acid fine particle calcium carbonate, and in particular to one kind is using Weihe north Ordovician limestone
The method for preparing the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape, belongs to chemical technology field.
Background technology
The grain size that ultra-fine carbonic acid fine particle calcium carbonate refers to being prepared using chemical method is in molecular cluster body with macroscopic view
The powder granule that particle is mixed.The particle diameter of ultra-fine carbonic acid fine particle calcium carbonate is between 0.02 μm -0.1 μm；Nontoxic, tasteless, hygroscopicity is small,
It is normally stored in dry environment；Settling volume is 2.4mL/g-2.8mL/g, molecular weight is 100, specific surface area >=18m2/
G, fusing point are 1339 DEG C, relative density is 2.45-2.50；Under normal temperature (25 DEG C), the solubility in water is very small, and pH value is
Between 8.0-10.2；Under normal pressure, the stable chemical nature when temperature≤550 DEG C easily divides when temperature is between 800 DEG C -900 DEG C
Solution；Exothermic reaction can occur with each strong acid, and produce a certain amount of CO2。
Ultra-fine carbonic acid fine particle calcium carbonate possesses the special effectses such as macroscopic quantum, small size, these characteristics of ultra-fine carbonic acid fine particle calcium carbonate
So that its magnetic, catalytic, dispersiveness, thixotropy and levelability, etc. aspect show obvious advantage, therefore, will be super
Thin carbonic acid fine particle calcium carbonate is used in the production processes such as rubber, paper products, sealant material, cement, medicinal material, food, can play aobvious
Write the effect such as increase-volume, reinforcement, reduces cost.
Currently, the method for domestic synthesizing superfine carbonic acid fine particle calcium carbonate has：Carbonizatin method, the precipitation method, double decomposition, emulsion method, hydrolysis
Synthetic method, biomimetic method etc..Sri Lanka pendant rad Ni Ya university Mantilaka in 2013 etc. uses bubbling carbonizing method, respectively with
Dolomite be raw material, with sucrose as calcium ion extractant, with polyacrylic acid solution as stabilizer, successfully synthesize amorphous carbonic acid
Calcium.Nihon University Kojima uses ultrasonic atomizatio hybrid reaction method (SARM) within 2012, by reaction solution under the conditions of ultrasonic wave added
It is atomized, is prepared for new amorphous calcium carbonate.
The ultra-fine carbonic acid fine particle calcium carbonate yield of China occupies the whole world second, but product quality lags far behind developed country, there is grain
Footpath is big, size distribution is wide, whiteness is low, the defect such as industrial mass manufacture difficulty, the irregular, bad dispersibility of crystal morphology, causes me
State is still needed to from a large amount of high-grade ultra-fine carbonic acid fine particle calcium carbonate products of external import to meet industry requirement.
In Wei and Lo river Ordovician limestone, CaO content is high, and the content of harmful components (iron, manganese etc.) is low, is prepared with it super
Thin carbonic acid fine particle calcium carbonate, with inherent advantage, on the one hand, this area's limestone reserves are big, and cheap, low production cost can be solved
Certainly the devalued Utilizing question of limestone resources, improves the economic value added of limestone, has given full play to limestone resources advantage,
Widen the application field of limestone；On the other hand, limestone is used to prepare ultra-fine carbonic acid fine particle calcium carbonate, limestone can be reduced in building
Brought environmental pollution is applied in field, environmental protection is strengthened.
At present, the ultra-fine carbonic acid fine particle calcium carbonate pattern of China's production includes：Spherical, needle-like, bar-shaped, sheet, chain lock shape, cube
Shape and amorphous etc., and rare report is synthesized to the calcium carbonate superfine powder of other special appearances, especially with Weihe north Ordovician period stone
The method that limestone prepares the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape has no report.
The content of the invention
It is an object of the invention to provide one kind using Weihe north Ordovician limestone prepare purity it is high, whiteness is good, fine size,
Good dispersion, in rhombohedron shape ultra-fine carbonic acid fine particle calcium carbonate method.
In order to realize above-mentioned target, the present invention is adopted the following technical scheme that：
The method that a kind of utilization Weihe north Ordovician limestone prepares the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape, it is characterised in that tool
Body is comprised the following steps：
Step one：Weihe north Ordovician limestone is crushed, washing removal of impurities, drying, screening is then carried out, particle diameter is obtained
The feed particles of 1.6mm-2.0mm；
Step 2：Above-mentioned raw materials particle is placed in chamber type electric resistance furnace, 60min is calcined at 1000 DEG C, obtain high activity stone
Ash；
Step 3：Above-mentioned active lime and 90 DEG C of hot water are pressed 1:10 mass ratioes mix, and stir 4h, cross 400 mesh sieves,
It is refined into mass concentration and is 5.6% lime slurry, and lime slurry is stood into 30h；
Step 4：The above-mentioned lime slurry for modulating is placed in container, and is put into ultrasonic oscillation device, to above-mentioned appearance
Crystal control agent sodium laurate is added in device, the addition of sodium laurate is 1.5g/L, then passes to CO2Gas and by CO2Flow
Control starts agitator and by mixing speed control in 1000r/min in 200mL/min, and controlling reaction temperature is 20 DEG C, uses pH
Meter and conductivity meter are tracked and record reaction process；
Step 5：When pH is down to 7, stopping is passed through CO2Gas simultaneously closes ultrasonic oscillation device, continues stirring reaction
20min；
Step 6：Filtering, washing, are vacuum dried to gained solute, are ground, and obtain final product ultra-fine carbonic acid fine particle calcium carbonate.
Foregoing method, it is characterised in that in step one, carries out broken using Hubei Province to Weihe north Ordovician limestone
Formula breaking machine.
Foregoing method, it is characterised in that in step 2,10 are set to by the heating rate of foregoing chamber type electric resistance furnace
℃/min。
Foregoing method, it is characterised in that in step 4, is passed through CO2During gas, gas distributor is used.
Foregoing method, it is characterised in that the opening diameter of These gases distributor is 0.8mm.
The present invention is advantageous in that：With Weihe north Ordovician limestone as raw material, crystal control agent sodium laurate is added,
Using the improvement carbonization technique of increase gas distributor and ultrasonic technique in carbonisation, function admirable has been prepared (pure
The higher, whiteness of degree preferably, granularity it is thinner), added value is high, ultra-fine carbonic acid fine particle calcium carbonate product in rhombohedron shape.
Brief description of the drawings
Fig. 1 is that traditional carbonization method prepares the product scanning electron microscope analysis figure for obtaining；
Fig. 2 is the product scanning electron microscope analysis figure that embodiment 1 is prepared；
Fig. 3 is the X-ray diffraction analysis figure of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 1 is prepared；
Fig. 4 is the ultra-fine carbonic acid fine particle calcium carbonate Granularity Distribution figure of rhombohedron shape that embodiment 1 is prepared；
Fig. 5 is the ultra-fine carbonic acid fine particle calcium carbonate product infrared spectrum analysis figure of rhombohedron shape that embodiment 1 is prepared；
Fig. 6 is the product scanning electron microscope analysis figure that embodiment 2 is prepared；
Fig. 7 is the ultra-fine carbonic acid fine particle calcium carbonate product X-ray diffraction analysis figure of rhombohedron shape that embodiment 2 is prepared；
Fig. 8 is that the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape that embodiment 2 is prepared produces particle size distribution figure；
Fig. 9 is the ultra-fine carbonic acid fine particle calcium carbonate product infrared spectrum analysis figure of rhombohedron shape that embodiment 2 is prepared；
Figure 10 is the product scanning electron microscope analysis figure that embodiment 3 is prepared；
Figure 11 is the ultra-fine carbonic acid fine particle calcium carbonate product X-ray diffraction analysis figure of rhombohedron shape that embodiment 3 is prepared；
Figure 12 is the ultra-fine carbonic acid fine particle calcium carbonate Granularity Distribution figure of rhombohedron shape that embodiment 3 is prepared；
Figure 13 is the ultra-fine carbonic acid fine particle calcium carbonate product infrared spectrum analysis figure of rhombohedron shape that embodiment 3 is prepared.
Specific embodiment
Make specific introduction to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1
In the present embodiment, limestone used is (thick-layer shape, shallow Tongchuan Ordovician period horse man ditch group No. 1 limestone sample
Grey, bulk), according to the operation requirement in standard GB/T/T3286-2012, to CaO, MgO, SiO in limestone2、
Al2O3And Fe2O3Content be measured, by analyze determine, main chemical compositions content such as table 1 in the limestone for drawing
It is shown.
The content of main chemical compositions in the limestone of table 1
Method using Tongchuan Ordovician period horse man ditch group ultra-fine carbonic acid fine particle calcium carbonate of No. 1 limestone sample preparation includes following step
Suddenly：
Step one：Tongchuan Ordovician period horse man ditch No. 1 limestone sample Hubei Province formula breaking machine of group is crushed, is then cleaned
Removal of impurities, drying, screening, obtain the feed particles that particle diameter is 1.6mm-2.0mm.
Step 2：Above-mentioned raw materials particle is placed in chamber type electric resistance furnace and is calcined, heating rate is set to 10 DEG C/min, 1000
DEG C calcining 60min, obtains active lime, measures active lime activity degree for 365mL.
Step 3：Active lime and 90 DEG C of hot water are pressed 1:10 mass ratioes mix, and stir 4h, cross 400 mesh sieves, are refined into
Mass concentration is 5.6% lime slurry, and lime slurry is stood into 30h.
Step 4：Good lime slurry is placed in the four-necked bottle that capacity is 500mL to take the above-mentioned mediations of 200mL, by four-necked bottle
It is placed in ultrasonic oscillation device, gas distributor, conductivity meter, pH meter and the agitator that will be connected with airway are inserted respectively
In four-necked bottle, and it is put into ultrasonic oscillation device, adds to crystal control agent sodium laurate, sodium laurate is added in said vesse
Dosage is 1.5g/L, then passes to CO2Gas, is the gas distributor of 0.8mm using opening diameter, by CO2Flow control exists
200mL/min, starts agitator, and by mixing speed control in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and electricity
Electrical conductivity instrument is tracked and records reaction process.
Step 5：When pH is down to 7 or so, stopping is passed through CO2Gas simultaneously closes ultrasonic oscillation device, continues stirring reaction
About 20min.
Step 6：Filtering, washing, are vacuum dried to gained solute, are ground, and obtain final product ultra-fine carbonic acid fine particle calcium carbonate.
Properties of product that embodiment 1 is prepared prepared with traditional carbonization method the properties of product that obtain to the such as institute of table 2
Show.
2 two kinds of performance comparisons of carbonizatin method products obtained therefrom of table
As shown in Table 2, the product cut size that embodiment 1 is prepared is substantially reduced, pH value reduction, and the whiteness of product and biography
The whiteness of the product that system carbonizatin method is prepared is compared and not changed.
Traditional carbonization method prepares the pattern of the product that the pattern of the product for obtaining and embodiment 1 are prepared respectively such as Fig. 1
With shown in Fig. 2.
From Fig. 1 and Fig. 2, traditional carbonization method prepares that the product pattern for obtaining is various and irregular, granularity is uneven, grain
Footpath is larger, about 0.5 μm, and use improved carbonizatin method of the invention after, the product pattern for preparing in rhombohedron shape and
Even, epigranular, particle diameter are smaller, about 0.06 μm.
It can be seen that, improved carbonizatin method of the invention can promote the carrying out of carburizing reagent, be conducive to improving crystal nucleation rate, make
The properties of product for preparing are excellent.
X-ray diffraction analysis result such as Fig. 3 institutes of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 1 is prepared
Show.
From the figure 3, it may be seen that value of all principal character diffraction maximums at 2 θ is respectively：23.06°、29.4°、36.0°、
39.42 °, 43.14 °, 47.56 °, 48.54 °, 57.36 °, 60.72 °, 64.62 °, 77.58 °, principal character diffraction maximum is at 2 θ
Corresponding crystal face can be with standard calcite (JCPDS：Crystal face 05-0586) is corresponded, respectively (012), (104),
(110), (113), (202), (018), (116), (122), (124), (300), (134) etc..
It follows that the essential mineral of ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 1 is prepared is calcite.
The size distribution of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 1 is prepared is as shown in Figure 4.
As shown in Figure 4,90% grain diameter concentrates on 0.03 μm -0.1 μm in the ultra-fine carbonic acid fine particle calcium carbonate for preparing
In the range of, wherein d10=0.03 μm, d50=0.06 μm, d90=0.09 μm, product average grain diameter is 0.06 μm, has reached industry
The granularity requirements of ultra-fine carbonic acid fine particle calcium carbonate Grade A.
The infrared spectrum analysis of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 1 is prepared is as shown in Figure 5.
As shown in Figure 5, the major absorbance peak in infrared spectrum analysis figure is in 3451.75cm-1、1440.40cm-1、
1792.24cm-1、875.93cm-1And 713.69cm-1Characteristic absorption peak with calcite crystal form calcium carbonate is corresponding.
It follows that the essential mineral composition of the ultra-fine carbonic acid fine particle calcium carbonate product for preparing of embodiment 1 is calcite, with
XRD testing results match.Wherein, in 3451.75cm-1The absworption peak wide at place is the presence institute of absorption water in ultra-fine carbonic acid fine particle calcium carbonate
Cause；In 1440.40cm-1The strong absworption peak at place is the asymmetric stretching vibration peak of C-O keys in ultra-fine carbonic acid fine particle calcium carbonate；
1796.24cm-1The absworption peak at place is CO in ultra-fine carbonic acid fine particle calcium carbonate3 2-C=O vibration peaks；In 875.93cm-1And 713.69cm-1
The absworption peak at place is the flexural vibrations peak of C-O keys in ultra-fine carbonic acid fine particle calcium carbonate.
Advised in the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 1 is prepared and Commercial ultrafine carbonic acid fine particle calcium carbonate standard
Fixed index is contrasted.
The ultra-fine carbonic acid fine particle calcium carbonate quality index contrast of rhombohedron shape that the embodiment 1 of table 3 is prepared
As shown in Table 3, the ultra-fine carbonic acid fine particle calcium carbonate product whiteness that embodiment 1 is prepared is 95%, and pH value is that 9.0, iron contains
Measure as 0.06%, density is 2.57g/cm3, average grain diameter is 0.06 μm, is complied fully with one in Commercial ultrafine carbonic acid fine particle calcium carbonate index
Deng the regulation of product.
Embodiment 2
In the present embodiment, limestone used is (thick-layer shape, shallow Tongchuan Ordovician period horse man ditch group No. 2 limestone samples
Grey, bulk), according to the operation requirement in standard GB/T/T3286-2012, to CaO, MgO, SiO in limestone2、
Al2O3And Fe2O3Content be measured, by analyze determine, the content of main chemical compositions such as table in the limestone for drawing
Shown in 4.
The content of main chemical compositions in the limestone of table 4
Method using Tongchuan Ordovician period horse man ditch group ultra-fine carbonic acid fine particle calcium carbonate of No. 2 limestone sample preparations includes following step
Suddenly：
Step one：Tongchuan Ordovician period horse man ditch No. 2 limestone sample Hubei Province formula breaking machines of group are crushed, is then cleaned
Removal of impurities, drying, screening, obtain the feed particles that particle diameter is 1.6mm-2.0mm.
Step 2：Above-mentioned raw materials particle is placed in chamber type electric resistance furnace and is calcined, heating rate is set to 10 DEG C/min, 1000
DEG C calcining 60min, obtains active lime, measures active lime activity degree for 368mL.
Step 3：Active lime and 90 DEG C of hot water are pressed 1:10 mass ratioes mix, and stir 4h, cross 400 mesh sieves, refine
It is 5.6% lime slurry into mass concentration, and lime slurry is stood into 30h.
Step 4：Good lime slurry is placed in the four-necked bottle that capacity is 500mL to take the above-mentioned mediations of 200mL, by four-necked bottle
It is placed in ultrasonic oscillation device, gas distributor, conductivity meter, pH meter and the agitator that will be connected with airway are inserted respectively
In four-necked bottle, and it is put into ultrasonic oscillation device, adds to crystal control agent sodium laurate, sodium laurate is added in said vesse
Dosage is 1.5g/L, then passes to CO2Gas, is the gas distributor of 0.8mm using opening diameter, by CO2Flow control exists
200mL/min, starts agitator, and by mixing speed control in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and electricity
Electrical conductivity instrument is tracked and records reaction process.
Step 5：When pH is down to 7 or so, stopping is passed through CO2Gas simultaneously closes ultrasonic oscillation device, continues stirring reaction
About 20min.
Step 6：Filtering, washing, are vacuum dried to gained solute, are ground, and obtain final product ultra-fine carbonic acid fine particle calcium carbonate.
The pattern of the product that embodiment 2 is prepared is as shown in Figure 6.
It will be appreciated from fig. 6 that after using improved carbonizatin method of the invention, the product pattern for preparing is in rhombohedron shape and
Even, epigranular, particle diameter are smaller, about 0.05 μm.
It can be seen that, improved carbonizatin method of the invention can promote the carrying out of carburizing reagent, improve crystal nucleation rate, make to be prepared into
The properties of product for arriving are excellent.
X-ray diffraction analysis result such as Fig. 7 institutes of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 2 is prepared
Show.
As shown in Figure 7, value of the principal character diffraction maximum of sample at 2 θ be respectively 23.06 °, 29.4 °, 36.0 °,
39.42 °, 43.14 °, 44.04 °, 47.56 °, 48.54 °, 57.36 °, 60.72 °, 64.62 °, 77.58 °, principal character diffraction maximum
In 2 θ places, corresponding diffraction crystal face can be with standard calcite (JCPDS：Crystal face 05-0586) is corresponded, respectively
(012)、(104)、(110)、(113)、(202)、(024)、(018)、(116)、(122)、(124)、(300)、(134)。
It follows that the essential mineral of ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 2 is prepared is calcite.
The size distribution of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 2 is prepared is as shown in Figure 8.
As shown in Figure 8, the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape for preparing, 90% product cut size concentrate on 0.04 μm-
In the range of 0.09 μm, wherein d10=0.04 μm, d50=0.05 μm, d90=0.08 μm, products obtained therefrom particle diameter is more uniform, particle diameter
Smaller, average grain diameter is about 0.05 μm.
The infrared spectrum analysis of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 2 is prepared is as shown in Figure 9.
As shown in Figure 9, the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 2 is prepared is in 1440.40cm-1、
1792.14cm-1、875.93cm-1And 713.69cm-1There is stronger characteristic absorption peak in place, with standard calcite spectrogram
(Sadtler) characteristic peak in is corresponding.
Described above to show, the sample essential mineral composition that embodiment 2 is prepared is calcite, with X-ray diffraction
Analysis result matches.
Advised in the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 2 is prepared and Commercial ultrafine carbonic acid fine particle calcium carbonate standard
Fixed index is contrasted.
The ultra-fine carbonic acid fine particle calcium carbonate quality index contrast of rhombohedron shape that the embodiment 2 of table 5 is prepared
As shown in Table 5, particle diameter, specific surface area, whiteness, the pH value of the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 2 is prepared
Deng the basic demand for all meeting Commercial ultrafine carbonic acid fine particle calcium carbonate Grade A.
Embodiment 3
In the present embodiment, limestone used is (thick-layer shape, shallow Tongchuan Ordovician period horse man ditch group No. 3 limestone samples
Grey, bulk), according to the operation requirement in GB GB/T3286-2012, to CaO, MgO, SiO in limestone2、Al2O3With
And Fe2O3Content be measured, by analyze determine, the content of main chemical compositions is as shown in table 6 in the limestone for drawing.
The content of main chemical compositions in the limestone of table 6
Method using Tongchuan Ordovician period horse man ditch group ultra-fine carbonic acid fine particle calcium carbonate of No. 3 limestone sample preparations includes following step
Suddenly：
Step one：Tongchuan Ordovician period horse man ditch No. 3 limestone sample Hubei Province formula breaking machines of group are crushed, is then cleaned
Removal of impurities, drying, screening, obtain the feed particles that particle diameter is 1.6mm-2.0mm.
Step 2：Above-mentioned raw materials particle is placed in chamber type electric resistance furnace and is calcined, heating rate is set to 10 DEG C/min,
60min is calcined in the environment of 1000 DEG C, active lime is obtained, active lime activity degree is measured for 365mL.
Step 3：Active lime and 90 DEG C of hot water are pressed 1:10 mass ratioes mix, and stir 4h, cross 400 mesh sieves, are refined into
Mass concentration is 5.6% lime slurry, and lime slurry is stood into 30h.
Step 4：Good lime slurry is placed in the four-necked bottle that capacity is 500mL to take the above-mentioned mediations of 200mL, by four-necked bottle
It is placed in ultrasonic oscillation device, gas distributor, conductivity meter, pH meter and the agitator that will be connected with airway are inserted respectively
In four-necked bottle, and it is put into ultrasonic oscillation device, adds to crystal control agent sodium laurate, sodium laurate is added in said vesse
Dosage is 1.5g/L, then passes to CO2Gas, is the gas distributor of 0.8mm using opening diameter, by CO2Flow control exists
200mL/min, starts agitator, and by mixing speed control in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and electricity
Electrical conductivity instrument is tracked and records reaction process.
Step 5：When pH is down to 7 or so, stopping is passed through CO2Gas simultaneously closes ultrasonic oscillation device, continues stirring reaction
About 20min.
Step 6：Filtering, washing, are vacuum dried to gained solute, are ground, and obtain final product ultra-fine carbonic acid fine particle calcium carbonate.
The pattern of the product that embodiment 3 is prepared is as shown in Figure 10.
As shown in Figure 10, after using improved carbonizatin method of the invention, the product pattern for preparing is in rhombohedron shape, granularity
Uniformly, particle diameter is smaller, about 0.05 μm.
The X-ray diffraction spectrogram of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared is as shown in figure 11.
As shown in Figure 11, value of the principal character diffraction maximum of sample at 2 θ is respectively：23.06°、29.4°、36.0°、
39.42 °, 43.14 °, 44.04 °, 47.56 °, 48.54 °, 57.36 °, 60.72 °, 64.62 °, 77.58 °, principal character diffraction maximum
In 2 θ places, corresponding diffraction crystal face can be with standard calcite (JCPDS：Crystal face 05-0586) is corresponded, respectively
(012)、(104)、(110)、(113)、(202)、(024)、(018)、(116)、(122)、(124)、(300)、(134)。
It follows that the essential mineral composition of the ultra-fine carbonic acid fine particle calcium carbonate product for preparing of embodiment 3 is calcite.
The size distribution of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared is as shown in figure 12.
As shown in Figure 12, the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared, 90% grain diameter collection
In in the range of 0.04 μm -0.09 μm, wherein d10=0.04 μm, d50=0.05 μm, d90=0.08 μm, product cut size is more equal
Even, particle diameter is smaller, and average grain diameter is 0.05 μm, has reached the granularity requirements of Commercial ultrafine carbonic acid fine particle calcium carbonate Grade A.
The infrared spectrum analysis figure of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared is as shown in figure 13.
As shown in Figure 13, the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared is in 1440.40cm-1、
1792.14cm-1、875.93cm-1And 713.69cm-1There is stronger characteristic absorption peak in place, with standard calcite spectrogram
(Sadtler) characteristic peak in is corresponding.
It is described above to show, the essential mineral composition of the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared
Calcite is, is matched with X-ray diffraction analysis result.
Advised in the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared and Commercial ultrafine carbonic acid fine particle calcium carbonate standard
Fixed index is contrasted.
The ultra-fine carbonic acid fine particle calcium carbonate quality index contrast of rhombohedron shape that the embodiment 3 of table 7 is prepared
As shown in Table 7, particle diameter, specific surface area, whiteness, the pH value of the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 3 is prepared
Deng the basic demand for all meeting Commercial ultrafine carbonic acid fine particle calcium carbonate Grade A.
In sum, the present invention prepares ultra-fine carbonic acid fine particle calcium carbonate using carbonizatin method, and crystalline form is with the addition of before carburizing reagent
Controlling agent sodium laurate (addition is 1.5g/L), ultrasonic technique is increased in carbonation reaction and (improves ultra-fine carbonic acid
Fine particle calcium carbonate particle dispersion, reduce grain diameter) and gas distributor (accelerate course of reaction mass transfer, heat transfer, shorten carbon
The change time), the ultra-fine carbonic acid fine particle calcium carbonate properties of product that prepare it is excellent (purity is higher, whiteness is preferable, particle dispersion is higher,
Granularity is thinner), in rhombohedron shape, comply fully with the regulation of Grade A in Commercial ultrafine carbonic acid fine particle calcium carbonate index, development potentiality is huge.
It should be noted that above-described embodiment the invention is not limited in any way, all use equivalents or equivalent change
The technical scheme that the mode changed is obtained, all falls within protection scope of the present invention.
Claims (5)
1. the method that a kind of utilization Weihe north Ordovician limestone prepares the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape, it is characterised in that specific
Comprise the following steps：
Step one：Weihe north Ordovician limestone is crushed, cleaning removal of impurities, drying, screening is then carried out, particle diameter is obtained for 1.6mm-
The feed particles of 2.0mm；
Step 2：Above-mentioned raw materials particle is placed in chamber type electric resistance furnace, 60min is calcined at 1000 DEG C, obtain active lime；
Step 3：Above-mentioned active lime and 90 DEG C of hot water are pressed 1:10 mass ratioes mix, and stir 4h, cross 400 mesh sieves, refine
It is 5.6% lime slurry into mass concentration, and lime slurry is stood into 30h；
Step 4：The above-mentioned lime slurry for modulating is placed in container, and is put into ultrasonic oscillation device, in the container
Crystal control agent sodium laurate is added, the addition of sodium laurate is 1.5g/L, then passes to CO2Gas and by CO2Flow is controlled
In 200mL/min, start agitator and by mixing speed control in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and
Conductivity meter is tracked and records reaction process；
Step 5：When pH is down to 7, stopping is passed through CO2Gas simultaneously closes ultrasonic oscillation device, continues stirring reaction 20min；
Step 6：Filtering, washing, are vacuum dried to gained solute, are ground, and obtain final product ultra-fine carbonic acid fine particle calcium carbonate.
2. method according to claim 1, it is characterised in that in step one, breaks to Weihe north Ordovician limestone
It is broken to use Hubei Province formula breaking machine.
3. method according to claim 1, it is characterised in that in step 2, by the intensification speed of the chamber type electric resistance furnace
Rate is set to 10 DEG C/min.
4. method according to claim 1, it is characterised in that in step 4, be passed through CO2During gas, it is distributed using gas
Device.
5. method according to claim 4, it is characterised in that the opening diameter of the gas distributor is 0.8mm.
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Cited By (2)
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| CN110589866A (en) * | 2019-10-24 | 2019-12-20 | 长江师范学院 | Method for preparing ultrafine powder vaterite by using steel slag |
| CN110589865A (en) * | 2019-10-24 | 2019-12-20 | 长江师范学院 | Method for preparing loose porous calcite by using steel slag |
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| GB1074099A (en) * | 1963-12-07 | 1967-06-28 | Licencia Talalmanyokat | Improvements in or relating to the production of calcium and magnesium carbonates |
| CN1392101A (en) * | 2002-07-29 | 2003-01-22 | 上海天福机电化工技术研究所 | Process for producing nano calcium carbonate by ultrasonic cavitation technology |
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2017
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| GB1074099A (en) * | 1963-12-07 | 1967-06-28 | Licencia Talalmanyokat | Improvements in or relating to the production of calcium and magnesium carbonates |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589866A (en) * | 2019-10-24 | 2019-12-20 | 长江师范学院 | Method for preparing ultrafine powder vaterite by using steel slag |
| CN110589865A (en) * | 2019-10-24 | 2019-12-20 | 长江师范学院 | Method for preparing loose porous calcite by using steel slag |
| CN110589865B (en) * | 2019-10-24 | 2022-03-25 | 长江师范学院 | Method for preparing loose porous calcite by using steel slag |
| CN110589866B (en) * | 2019-10-24 | 2022-03-25 | 长江师范学院 | Method for preparing ultrafine powder vaterite by using steel slag |
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