CN106830042B - A kind of method that the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape is prepared using Weihe north Ordovician limestone - Google Patents
A kind of method that the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape is prepared using Weihe north Ordovician limestone 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 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
- 239000006028 limestone Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 43
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 59
- 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
- 238000004519 manufacturing process Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 230000008859 change Effects 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
- 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
- 238000002360 preparation method Methods 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
- 230000005389 magnetism 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
- 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
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of method that ultra-fine carbonic acid fine particle calcium carbonate is prepared using Weihe north Ordovician limestone, including：Weihe north Ordovician limestone is crushed, clean, dry, is sieved, obtains the particle of 1.6mm 2.0mm；Above-mentioned particle is calcined into 60min in 1000 DEG C, obtains active lime；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, sodium laurate is added into container, is 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, to solute drying, grind up to ultra-fine carbonic acid fine particle calcium carbonate.The invention has the beneficial effects that：Using Weihe north Ordovician limestone as raw material, using carbonizatin method, and crystal control agent sodium laurate is added before charing, increases gas distributor and ultrasonic technique in carbonization process, has prepared function admirable, added value height, in the ultra-fine carbonic acid fine particle calcium carbonate product of 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 utilizes 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 and macroscopic view
The powder granule that particle mixes.The particle diameter of ultra-fine carbonic acid fine particle calcium carbonate is between 0.02 μm -0.1 μm；It is nontoxic, tasteless, hygroscopicity is small,
It is normally stored in dry environment；Settling volume is 2.4mL/g-2.8mL/g, molecular weight 100, specific surface area >=18m2/
G, fusing point be 1339 DEG C, relative density 2.45-2.50；Under room temperature (25 DEG C), solubility in water is very small, and pH value is
Between 8.0-10.2；Under normal pressure, when temperature≤550 DEG C, chemical property is stablized, when temperature is easily divided when 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 magnetism, catalytic, dispersiveness, thixotropy and levelability, etc. 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 increase-volume, reinforcement, reduce the effect such as 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 ladd Ni Ya university Mantilaka in 2013 etc. use bubbling carbonizing method, respectively with
Dolomite is raw material, take sucrose as calcium ion extractant, using polyacrylic acid solution as stabilizer, successfully synthesizes 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 in China occupies the whole world second, but product quality lags far behind developed country, and there are grain
The defects of footpath is big, size distribution is wide, whiteness is low, and industrial mass manufacture is difficult, crystal morphology is irregular, bad dispersibility, 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, super with its preparation
Thin carbonic acid fine particle calcium carbonate, has inherent advantage, on the one hand, this area's limestone large storage capacity, cheap, production cost is low, can solve
The certainly 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 and built
Caused environmental pollution is applied in field, strengthens environmental protection.
At present, the ultra-fine carbonic acid fine particle calcium carbonate pattern of China's production includes：Spherical, needle-shaped, 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 the northern Ordovician period stone in Weihe
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 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 adopts the following technical scheme that：
A kind of method that the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape is prepared using Weihe north Ordovician limestone, it is characterised in that tool
Body comprises the following steps：
Step 1：Weihe north Ordovician limestone is crushed, washing removal of impurities, drying, screening is then carried out, obtains particle diameter
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, obtains 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 modulated 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 additive amount of sodium laurate is 1.5g/L, then passes to CO2Gas and by CO2Flow
Control is 20 DEG C in 1000r/min, controlling reaction temperature in 200mL/min, startup blender and by mixing speed control, uses pH
Meter and conductivity meter track 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 dried in vacuo gained solute, are ground, up to ultra-fine carbonic acid fine particle calcium carbonate.
Foregoing method, it is characterised in that in step 1, crushed Weihe north Ordovician limestone using Hubei Province
Formula breaking machine.
Foregoing method, it is characterised in that in step 2, the heating rate of foregoing chamber type electric resistance furnace is arranged to 10
℃/min。
Foregoing method, it is characterised in that in step 4, be 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 invention has the beneficial effects that：Using Weihe north Ordovician limestone as raw material, crystal control agent sodium laurate is added,
Using gas distributor and the improvement carbonization technique of ultrasonic technique is increased in carbonisation, it is (pure that function admirable has been prepared
The higher, whiteness of degree preferably, granularity it is thinner), added value it is high, in the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape.
Brief description of the drawings
Fig. 1 is product scanning electron microscope analysis figure prepared by traditional carbonization method；
Fig. 2 is the product scanning electron microscope analysis figure that embodiment 1 is prepared；
Fig. 3 is the X-ray diffraction analysis figure for 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 the ultra-fine carbonic acid fine particle calcium carbonate production particle size distribution figure of rhombohedron shape that embodiment 2 is prepared；
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.
Embodiment
Make specific introduce 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 for 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, measured by analyzing, main chemical compositions content such as table 1 in the limestone drawn
It is shown.
The content of main chemical compositions in 1 limestone of table
Method using Tongchuan Ordovician period horse man ultra-fine carbonic acid fine particle calcium carbonate of No. 1 limestone sample preparation of ditch group includes following step
Suddenly：
Step 1：Tongchuan Ordovician period horse man ditch No. 1 limestone sample of group is crushed with Hubei Province formula breaking machine, is then cleaned
Removal of impurities, dry, 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 arranged to 10 DEG C/min, and 1000
DEG C calcining 60min, obtain active lime, it is 365mL to measure active lime activity degree.
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 30h.
Step 4：The lime slurry for taking the above-mentioned reconciliations of 200mL good is placed in the four-necked bottle that capacity is 500mL, by four-necked bottle
It is placed in ultrasonic oscillation device, the gas distributor for being connected with airway, conductivity meter, pH meter and blender is inserted into respectively
In four-necked bottle, and it is put into ultrasonic oscillation device, crystal control agent sodium laurate is added into said vesse, sodium laurate adds
Dosage is 1.5g/L, then passes to CO2Gas, using the gas distributor that opening diameter is 0.8mm, by CO2Flow control exists
200mL/min, starts blender, mixing speed is controlled in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and electricity
Electrical conductivity instrument tracks 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 dried in vacuo gained solute, are ground, up to ultra-fine carbonic acid fine particle calcium carbonate.
The properties of product that properties of product that embodiment 1 is prepared are prepared with traditional carbonization method to the such as institute of table 2
Show.
The performance comparison of 2 two kinds of carbonizatin method products obtained therefroms of table
As shown in Table 2, the product cut size that embodiment 1 is prepared is substantially reduced, pH value reduces, and the whiteness of product and biography
The whiteness for the product that system carbonizatin method is prepared, which is compared, not to change.
The pattern for the product that the pattern of product prepared by traditional carbonization method is prepared with embodiment 1 is respectively such as Fig. 1
Shown in Fig. 2.
From Fig. 1 and Fig. 2, product pattern prepared by traditional carbonization method is various and irregular, granularity is uneven, grain
Footpath is larger, about 0.5 μm, and after using the improved carbonizatin method of the present invention, and the product pattern being prepared is in rhombohedron shape and
Even, epigranular, particle diameter are smaller, about 0.06 μm.
As it can be seen that the improved carbonizatin method of the present invention can promote the progress of carburizing reagent, be conducive to improve crystal nucleation rate, make
The properties of product being prepared are excellent.
The X-ray diffraction analysis result such as Fig. 3 institutes for 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 main feature 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 °, main feature diffraction maximum is at 2 θ
Corresponding crystal face can be with standard calcite (JCPDS：Crystal face 05-0586) corresponds, be respectively (012), (104),
(110), (113), (202), (018), (116), (122), (124), (300), (134) etc..
It follows that the essential mineral for the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 1 is prepared is calcite.
The size distribution for 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 being prepared
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 for 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-1It is corresponding with the characteristic absorption peak of calcite crystal form calcium carbonate.
It follows that the essential mineral composition for the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 1 is prepared is calcite, with
XRD testing results match.Wherein, in 3451.75cm-1The wide absworption peak at place be in ultra-fine carbonic acid fine particle calcium carbonate adsorb water there are institute
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.
By the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 1 is prepared with being advised in 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 3 embodiment 1 of table 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 9.0, iron contain
Measure as 0.06%, density 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 for 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, measured by analyzing, the content such as table of main chemical compositions in the limestone drawn
Shown in 4.
The content of main chemical compositions in 4 limestone of table
Method using Tongchuan Ordovician period horse man ultra-fine carbonic acid fine particle calcium carbonate of No. 2 limestone sample preparations of ditch group includes following step
Suddenly：
Step 1：Tongchuan Ordovician period horse man ditch No. 2 limestone samples of group are crushed with Hubei Province formula breaking machine, are then cleaned
Removal of impurities, dry, 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 arranged to 10 DEG C/min, and 1000
DEG C calcining 60min, obtain active lime, it is 368mL to measure active lime activity degree.
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：The lime slurry for taking the above-mentioned reconciliations of 200mL good is placed in the four-necked bottle that capacity is 500mL, by four-necked bottle
It is placed in ultrasonic oscillation device, the gas distributor for being connected with airway, conductivity meter, pH meter and blender is inserted into respectively
In four-necked bottle, and it is put into ultrasonic oscillation device, crystal control agent sodium laurate is added into said vesse, sodium laurate adds
Dosage is 1.5g/L, then passes to CO2Gas, using the gas distributor that opening diameter is 0.8mm, by CO2Flow control exists
200mL/min, starts blender, mixing speed is controlled in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and electricity
Electrical conductivity instrument tracks 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 dried in vacuo gained solute, are ground, up to ultra-fine carbonic acid fine particle calcium carbonate.
The pattern for the product that embodiment 2 is prepared is as shown in Figure 6.
It will be appreciated from fig. 6 that after using the improved carbonizatin method of the present invention, the product pattern that is prepared is in rhombohedron shape and
Even, epigranular, particle diameter are smaller, about 0.05 μm.
As it can be seen that the improved carbonizatin method of the present invention can promote the progress of carburizing reagent, crystal nucleation rate is improved, makes to be prepared into
The properties of product arrived are excellent.
The X-ray diffraction analysis result such as Fig. 7 institutes for 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 main feature 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 °, main feature diffraction maximum
In 2 θ places, corresponding diffraction crystal face can be with standard calcite (JCPDS：Crystal face 05-0586) corresponds, and is respectively
(012)、(104)、(110)、(113)、(202)、(024)、(018)、(116)、(122)、(124)、(300)、(134)。
It follows that the essential mineral for the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 2 is prepared is calcite.
The size distribution for 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 being prepared, 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 for 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.
By the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 2 is prepared with being advised in 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 5 embodiment 2 of table is prepared
As shown in Table 5, the particle diameter for the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 2 is prepared, specific surface area, whiteness, pH value
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 for Tongchuan Ordovician period horse man ditch group No. 3 limestone samples
Grey, bulk), according to the operation requirement in national standard GB/T3286-2012, to CaO, MgO, SiO in limestone2、Al2O3With
And Fe2O3Content be measured, measured by analyzing, the content of main chemical compositions is as shown in table 6 in the limestone drawn.
The content of main chemical compositions in 6 limestone of table
Method using Tongchuan Ordovician period horse man ultra-fine carbonic acid fine particle calcium carbonate of No. 3 limestone sample preparations of ditch group includes following step
Suddenly：
Step 1：Tongchuan Ordovician period horse man ditch No. 3 limestone samples of group are crushed with Hubei Province formula breaking machine, are then cleaned
Removal of impurities, dry, 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 arranged to 10 DEG C/min,
60min is calcined in the environment of 1000 DEG C, obtains active lime, it is 365mL to measure active lime activity degree.
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 30h.
Step 4：The lime slurry for taking the above-mentioned reconciliations of 200mL good is placed in the four-necked bottle that capacity is 500mL, by four-necked bottle
It is placed in ultrasonic oscillation device, the gas distributor for being connected with airway, conductivity meter, pH meter and blender is inserted into respectively
In four-necked bottle, and it is put into ultrasonic oscillation device, crystal control agent sodium laurate is added into said vesse, sodium laurate adds
Dosage is 1.5g/L, then passes to CO2Gas, using the gas distributor that opening diameter is 0.8mm, by CO2Flow control exists
200mL/min, starts blender, mixing speed is controlled in 1000r/min, controlling reaction temperature is 20 DEG C, with pH meter and electricity
Electrical conductivity instrument tracks 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 dried in vacuo gained solute, are ground, up to ultra-fine carbonic acid fine particle calcium carbonate.
The pattern for the product that embodiment 3 is prepared is as shown in Figure 10.
As shown in Figure 10, after using the improved carbonizatin method of the present invention, the product pattern that is prepared is in rhombohedron shape, granularity
Uniformly, particle diameter is smaller, about 0.05 μm.
The X-ray diffraction spectrogram for 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 main feature 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 °, main feature diffraction maximum
In 2 θ places, corresponding diffraction crystal face can be with standard calcite (JCPDS：Crystal face 05-0586) corresponds, and is respectively
(012)、(104)、(110)、(113)、(202)、(024)、(018)、(116)、(122)、(124)、(300)、(134)。
It follows that the essential mineral composition for the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 3 is prepared is calcite.
The size distribution for 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 for 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 for the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared
It is calcite, matches with X-ray diffraction analysis result.
By the ultra-fine carbonic acid fine particle calcium carbonate product of rhombohedron shape that embodiment 3 is prepared with being advised in 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 7 embodiment 3 of table is prepared
As shown in Table 7, the particle diameter for the ultra-fine carbonic acid fine particle calcium carbonate product that embodiment 3 is prepared, specific surface area, whiteness, pH value
Deng the basic demand for all meeting Commercial ultrafine carbonic acid fine particle calcium carbonate Grade A.
In conclusion the present invention prepares ultra-fine carbonic acid fine particle calcium carbonate using carbonizatin method, and it with the addition of crystalline form before carburizing reagent
Controlling agent sodium laurate (additive amount 1.5g/L), ultrasonic technique is added in carbonation reaction and (improves ultra-fine carbonic acid
Fine particle calcium carbonate particle dispersion, reduce grain diameter) and gas distributor (accelerate reaction process mass transfer, heat transfer, shorten carbon
Change the time), the ultra-fine carbonic acid fine particle calcium carbonate properties of product that are prepared 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 the invention is not limited in any way for above-described embodiment, it is all to use equivalent substitution or equivalent change
The technical solution that the mode changed is obtained, all falls within protection scope of the present invention.
Claims (3)
- A kind of 1. method that the ultra-fine carbonic acid fine particle calcium carbonate of rhombohedron shape is prepared using Weihe north Ordovician limestone, it is characterised in that specific Comprise the following steps：Step 1：Weihe north Ordovician limestone is crushed, then carries out cleaning removal of impurities, drying, screening, it is 1.6mm- to obtain particle diameter 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, obtains 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 modulated is placed in container, and is put into ultrasonic oscillation device, into the container Crystal control agent sodium laurate is added, the additive amount of sodium laurate is 1.5g/L, is then passed through CO using gas distributor2Gas And by CO2In 200mL/min, the opening diameter of gas distributor is 0.8mm for flow control, starts blender and by mixing speed Control is 20 DEG C in 1000r/min, controlling reaction temperature, is tracked with pH meter and conductivity meter 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 dried in vacuo gained solute, are ground, up to ultra-fine carbonic acid fine particle calcium carbonate.
- 2. according to the method described in claim 1, it is characterized in that, in step 1, Weihe north Ordovician limestone is broken It is broken using Hubei Province formula breaking machine.
- 3. according to the method described in claim 1, it is characterized in that, in step 2, by the heating speed of the chamber type electric resistance furnace Rate is arranged to 10 DEG C/min.
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Citations (2)
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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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
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| "不同形貌纳米碳酸钙的制备、改性及应用研究";李强等;《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》;20150615(第06期);第12页第1-2段、第15页表3.1 * |
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