CN100455515C - Method for preparing nano calcium carbonate particle - Google Patents
Method for preparing nano calcium carbonate particle Download PDFInfo
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- CN100455515C CN100455515C CNB200310122700XA CN200310122700A CN100455515C CN 100455515 C CN100455515 C CN 100455515C CN B200310122700X A CNB200310122700X A CN B200310122700XA CN 200310122700 A CN200310122700 A CN 200310122700A CN 100455515 C CN100455515 C CN 100455515C
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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 77
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 44
- 239000002245 particle Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- -1 alkali metal salt Chemical class 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- 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 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 2
- IAGCDJZAYOZMCS-UHFFFAOYSA-N 2-hydroxypropanoic acid;titanium Chemical compound [Ti].CC(O)C(O)=O IAGCDJZAYOZMCS-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 11
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 239000013538 functional additive Substances 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 239000004831 Hot glue Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000565 sealant Substances 0.000 abstract 1
- 238000005255 carburizing Methods 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 238000001994 activation Methods 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 235000011116 calcium hydroxide Nutrition 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention discloses a preparation method for nanometer level calcium carbonate particles, which comprises the following steps that a nucleation accelerator is added in the suspending liquid of calcium hydroxide, carbon dioxide gas is charged, a dispersing agent is added, and then the water solution of a covering agent is added; the covered calcium carbonate suspending liquid is filtered at the temperature, and then is dried so as to obtain the cubical nanometer level calcium carbonate product with controllable particle size and distribution of the present invention. In the obtained calcium carbonate particles, the particle diameter distribution is controllable in the particle diameter range of 12 nm to 100 nm, the shape is cubed, the specific surface area is regulated in the range of 18 m<2>/g to 60m<2>/g, and the oil absorption number is smaller than 40gDOP/100g; the obtained calcium carbonate particles have no agglomeration phenomenon, can be widely used as functional additives in industries such as high-grade coating material, PVC hot-melt adhesive for automobiles, rubber, plastics, fluid sealant, etc., and provide high performance and high added value for products.
Description
Technical field
The present invention relates to a kind of preparation method of calcium carbonate granule, be specifically related to preparing nanometic particle of calcium carbonate, especially its particle diameter has the controlled average particle size particle size and the preparing nanometic particle of calcium carbonate of distribution thereof in 15～100nm scope.
Technical background
Nano-calcium carbonate is meant the superfine powder of particle diameter less than 100nm, be widely used in fields such as rubber, plastics, high-grade paint, papermaking, high-grade printing ink, be the functional mineral filler of a kind of novel high-grade, thereby carry out at different application systems that surface modification treatment obtains high reactivity, dispersing property product good, that interface compatibility is good is the basic demand that nano-calcium carbonate is used.
Nano-calcium carbonate of the present invention can be widely used in industries such as plastics, rubber, coating, seal gum as functional additive after surface activation process, give product high-performance and high added value and with low cost.
The preparation method commonly used of nano-calcium carbonate comprises at present, and multistage spray carbonation method, hypergravity carborization stir carborization continuously.
Multistage spray carbonation method and hypergravity carborization all are to carry out the gas-liquid mass transfer reaction with liquid as disperse phase continuously, increase the gas-to-liquid contact area greatly, strengthened carbonization process microcosmic mix and the microcosmic mass transfer process, easily form a large amount of nucleus in initial reaction stage, can under comparatively high temps, produce nano-calcium carbonate; But continuously multistage spray carbonation method production efficiency is low, and energy consumption is big, and nozzle stops up easily, is difficult to guarantee the uniform distribution of droplet.The facility investment of hypergravity carborization is big, operation easier is bigger, and how this technology keeps in the lab scale process factor such as former strong field distribution to await further further investigation after amplifying.
The stirring tank carborization is the domestic and international at present extensively method of the production nano-calcium carbonate of employing, this method needs strict control carbonization temperature at 10～30 ℃ at whole carbonization process, and the generative process of lime carbonate is thermopositive reaction, therefore needs to adopt huge pressure cooling heat transferring system.The open CN1330039A of Chinese patent application has announced a kind of method that adopts mechanical stirring blended mode synthesis of nano lime carbonate at a lower temperature, then low temperature synthetic calcium carbonate suspension is heated to 45～95 ℃, add surface-modifying agent and handle, make the active nano-calcium carbonate of 20～90nm; The open CN1179401 of Chinese patent application has announced a kind of method for preparing nanometer grade calcium carbonate in 2～28 ℃ of carbonization temperature scopes; U.S. Pat 5750086 discloses a kind of under 14～30 ℃ carbonization condition, prepares a kind of method of chain lock shape nanometer grade calcium carbonate.
Because the nano-calcium carbonate that generates is easy to reunite, the calcium carbonate suspension that generally needs to generate is heated to 60～95 ℃, add corresponding surface treatment agent again and carry out activation treatment, just can make meet the need of market active good, good dispersity, with the good product of base-material consistency.This shows that prior art is containing the significant wastage to energy in the preparation process of active nano-calcium carbonate.
One of technical issues that need to address of the present invention provide a kind of preparing nanometic particle of calcium carbonate, to overcome economy inadequately and the bigger defective of energy expenditure that prior art exists.
Technical conceive of the present invention is such:
The contriver adds suitable nucleus according to different grain size product demands at the reaction initial period and forms promotor, with quantity, the controlled amount that reaches the initial reaction stage nucleus.According to nucleus free energy of formation in the crystallisation process greater than the thermodynamic principles of crystal growth free energy, simultaneously by controlling the flow of carbonic acid gas kiln gas, the concentration of initial calcium hydroxide milk of lime and temperature, regulate the growth velocity of crystalline nucleation and each crystal face easily, reach 80% at carbonation rate and add dispersion agent when above to regulate the calcium carbonate particles surface charge, prevent the reunion between the calcium carbonate granule, thereby the particle diameter and the pattern that reach the finished product are easy to control, can significantly improve the dispersing property of the finished product by suitable surface treatment.
In the calcium hydroxide initial action suspension of finite concentration and temperature, add nucleus and form promotor, feed carbon dioxide containing gas then and carry out carbonization, by concentration to calcium hydroxide suspension, temperature, the nucleation rate of initial lime carbonate nucleus is controlled in the adjusting of flow of carbon dioxide gas amount etc., quantity and size, and the growth velocity of regulating each crystal face of nucleus, controlled to reach grain morphology, when reaction reaches certain carbonation rate, add dispersion agent again this moment and regulate the particle surface electric charge, with carbonization environment and the particulate dispersiveness of improving lime carbonate, thereby reach controllable particle size distribution, pattern is regular, the cube nano-calcium carbonate of favorable dispersity.Stopped reaction when the pH of suspension value reduces to 6.5～7.0.In the above-mentioned suspension of pH=6.5～7.0, add corresponding surface treatment agent such as soap emulsion and carry out surface coating activation treatment, filter after drying, thereby constitute economy power-economizing method of the present invention, and the cube nano activated calcium carbonate product that obtains the said granular size of the present invention and distribute controlled.
Method of the present invention may further comprise the steps:
(1) nucleus being formed promotor, to add the calcium hydroxide weight concentration be that 6～15% suspension reacts, temperature of reaction is 20～45 ℃, lower starting temperature needs more cooling energy and uneconomical, too high starting temperature will make size distribution broaden, pattern is wayward simultaneously, be prone to other as assorted shapes such as spindle-likes, best starting temperature is 25～36 ℃;
Said nucleus forms one or more mixtures in the alkaline metal salt that promotor comprises EDTA and alkaline metal salt, carboxylic acid inner complex, inorganic phosphate, hydroxyethyl di 2 ethylhexyl phosphonic acid and an alkali metal salt, sulfuric acid and vitriol thereof, trolamine, disaccharides or polysaccharide, tartrate, oxalic acid, citric acid, oxysuccinic acid and above-mentioned acid, wherein preferably: glucose, one or more mixtures in sucrose, sodium sulfate, trolamine, the Trisodium Citrate, the add-on that nucleus forms promotor is 0.5%～5% of a gained lime carbonate quality.
(2) form in the calcium hydroxide suspension of promotor at the above-mentioned nucleus that added then, feed carbon dioxide, preferably feed the kiln gas of carbonated 15～40%, its composition is similar to actual lime burner furnace gas mixture, and gas flow is 2～30m
3/ (hm
3Suspension).
(3) when carbonation rate to 80% is above, add dispersion agent, said dispersion agent comprises polyvinyl alcohol, phosphoric acid salt, muriate, one or more mixtures in the alkali-metal carbonate, wherein preferred magnesium chloride, Sodium hexametaphosphate 99 and sodium bicarbonate, add-on is 0.5～3% of a gained lime carbonate quality.When the pH of suspension value reduces to 6.5～7.0, continue ventilation 15～30 minutes, stop ventilation then.Whole carbonization process thermal insulation warming is about 15～35 ℃, and the outlet temperature of reacting slurry reaches 45～70 ℃, and carburizing reagent finishes;
(4) finishing the back temperature in carburizing reagent is 45～70 ℃ calcium carbonate suspension, adds the aqueous solution of temperature between 70～95 ℃ of coating concentration 5～20%;
Said coating comprises one or both in lipid acid and an alkali metal salt or the water-soluble titanate coupling agent, and the consumption of coating counts 0.75～4% with lime carbonate, and coating the activation treatment time is 1～2 hour.Calcium carbonate suspension filtered while hot after will coating is then carried out drying again, the cube nano activated calcium carbonate product that promptly obtains the said granular size of the present invention and distribute controlled.
Preferred water-soluble coupling agent is a kind of in alkanolamine metatitanic acid or two (tetra-sodium dialkoxy ester) (2-hydroxyl) propionic acid titanium or the hydramine lipid acid titanic acid ester, described water-soluble coupling agent is all the commercially available prod, can adopt a kind of in CT-54 coupling agent that newly developed area, Changzhou sharp evolution worker limited-liability company produces or the CT-64 coupling agent.
By the synthetic also calcium carbonate particles of activated processing of aforesaid method carburizing reagent of the present invention, particle diameter is in 12～100nm scope and have controlled size distribution, is shaped as cube, and specific surface area is at 18～60m
2Can regulate between/the g, oil-absorption(number)＜40gDOP/100g product, and do not have agglomeration, and can be widely used as high-grade paint, automobile PVC hot melt adhesive, rubber, plastics, the functional additive of industries such as seal gum is given product high-performance and high added value.
Characteristics of the present invention are to adopt above-mentioned specific technology, pressure cooling heat transferring system that must be not traditional in carbonization process not only, the carburizing reagent heat release heats up naturally, carburizing reagent finishes back calcium carbonate suspension temperature and reaches 45～70 ℃, greatly reduce and reach the temperature required energy expenditure of activation, make equipment and process cost reduce greatly.And, obviously quickened carburizing reagent because the carburizing reagent heat release improves suspension temperature gradually, shorten the carburizing reagent time, thereby obviously improved the throughput of unit reactor volume.The further advantage of the inventive method is the generation of growing up of gained nano activated calcium carbonate crystal grain under higher temperature, compare with traditional low-temp reaction, the calcium carbonate crystal that high temperature is grown up is fine and close more, surface energy density is lower, thereby shows better gloss and be easy to dispersive product application characteristics in application facet.
The said carbonation rate of the present invention is meant that the calcium hydroxide of calcium hydroxide cubage in the lime cream soliquoid of measuring according to the phenolphthalein indicator method has been converted into the mass percent of lime carbonate.
Description of drawings
Fig. 1 is the nanometer level calcium carbonate particle transmission electron microscope photo of embodiment 1 preparation.
Fig. 2 is the nanometer level calcium carbonate particle transmission electron microscope photo of embodiment 2 preparations.
Fig. 3 is the nanometer level calcium carbonate particle transmission electron microscope photo of embodiment 3 preparations.
Fig. 4 is the nanometer level calcium carbonate particle transmission electron microscope photo of embodiment 4 preparations.
Embodiment
Below by example the specific embodiment of the present invention is narrated, but embodiment does not limit protection scope of the present invention.
Embodiment 1
The starting temperature that adds 5 liters of concentration 10% (mass concentration) in 7 liters stirred autoclave is 30 ℃ a refining lime slurry, add 20g sucrose and 13.75g trolamine simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 30% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 150L/h.When carbonation rate to 90%, add the 20.2g magnesium chloride, continuing to ventilate to slurry pH is that to obtain temperature at 6.8 o'clock be 63 ℃ nano-calcium carbonate suspension, adding in this slurry and containing sodium stearate 27g concentration is that the temperature of 7% (weight concentration) is 95 ℃ of saponification emulsions, continue to stir 1.5h and coat activation treatment, then with the slip filtered while hot, through 100 ℃ of dryings, pulverize and promptly get cube and the class spherical calcium carbonate.The main size distribution of this product is 10-25nm, and specific surface area is 60m
2/ g, oil-absorption(number) are 35gDOP/100gCaCO
3, and not having agglomeration, the transmission electron microscope photo is seen accompanying drawing 1.
Embodiment 2
The starting temperature that adds 5 liters of concentration 6% (mass concentration) in 7 liters stirred autoclave is 35 ℃ a refining lime slurry, add 8.1g sucrose simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 15% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 25L/h.When carbonation rate to 80%, add the 6.1g Sodium hexametaphosphate 99, continuing to ventilate to slurry pH is that to obtain temperature at 6.5 o'clock be 55 ℃ nano-calcium carbonate suspension, adding in this slurry and containing sodium stearate 12.5g concentration is that the temperature of 5% (weight concentration) is 90 ℃ of saponification emulsions, continue to stir 2h and coat activation treatment, slip filtered while hot, 100 ℃ are drying to obtain cube and class ball shaped nano treated carbonates.The main size distribution of this product is 20～40nm, and specific surface area is 52m
2/ g, oil-absorption(number) are 32gDOP/100gCaCO
3, and not having agglomeration, the transmission electron microscope photo is seen accompanying drawing 2.
Embodiment 3
The starting temperature that adds 5 liters of concentration 15% (mass concentration) in 7 liters stirred autoclave is 25 ℃ a refining lime slurry, add the 6g Trisodium Citrate simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 40% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 80L/h.When carbonation rate to 95%, add 6g zinc chloride and 6g sodium bicarbonate, continuing to ventilate to slurry pH is that to obtain temperature at 6.9 o'clock be 70 ℃ nano-calcium carbonate suspension, adding in this slurry and containing the water miscible alkanolamine metatitanic acid of 8.5g CT-54 titanate coupling agent concentration is that the temperature of 15% (weight concentration) is 70 ℃ of aqueous solution, continue to stir 1h and coat activation treatment, with the slip filtered while hot, promptly get the cube nm-class active calcium carbonate through 100 ℃ of dryings, pulverizing.The main size distribution of this product is 70～100nm, and specific surface area is 22m
2/ g, oil-absorption(number) are 23gDOP/100gCaCO
3, and not having agglomeration, the transmission electron microscope photo is seen accompanying drawing 3.
Embodiment 4
The starting temperature that adds 5 liters of concentration 13% (mass concentration) in 7 liters stirred autoclave is 30 ℃ a refining lime slurry, add the 8g Trisodium Citrate simultaneously, after stirring, the feeding carbon dioxide content is that the kiln gas of 25% (volumetric concentration) begins to carry out carburizing reagent, and the kiln gas flow is 100L/h.When carbonation rate to 95%, add 4g magnesium chloride and 3g Sodium hexametaphosphate 99, continuing to ventilate to slurry pH is that to obtain temperature at 6.7 o'clock be 68 ℃ nano-calcium carbonate slip, by the method for embodiment 3 this slurry is coated activation and filtration, washing, drying treatment, promptly get the cube nm-class active calcium carbonate.The main size distribution of this product is 50～80nm, and specific surface area is 30m
2/ g, oil-absorption(number) are 28gDOP/100gCaCO
3, and not having agglomeration, the transmission electron microscope photo is seen accompanying drawing 4.
Claims (6)
1. a preparing nanometic particle of calcium carbonate is characterized in that, may further comprise the steps:
(1) nucleus being formed promotor, to add the calcium hydroxide weight concentration be that 6～15% suspension reacts, and initial reaction temperature is 25～36 ℃;
Said nucleus forms one or more mixtures in the alkaline metal salt that promotor comprises EDTA and alkaline metal salt, carboxylic acid inner complex, inorganic phosphate, hydroxyethyl di 2 ethylhexyl phosphonic acid and an alkali metal salt, sulfuric acid and vitriol thereof, trolamine, disaccharides or polysaccharide, tartrate, oxalic acid, citric acid, oxysuccinic acid and above-mentioned acid;
(2) form in the calcium hydroxide suspension of promotor at the above-mentioned nucleus that added, feed the kiln gas of carbonated 15～40%, gas flow is 2～30m
3/ (hm
3Suspension);
(3) add dispersion agent, said dispersion agent comprises one or more mixtures in polyvinyl alcohol, phosphoric acid salt, muriate, the alkali-metal carbonate, add-on is 0.5～3% of a gained lime carbonate quality, when the pH of suspension value reduces to 6.5～7.0, continue ventilation 15～30 minutes, the outlet temperature of reacting slurry reaches 45～70 ℃;
(4) adding contains coating;
Said coating comprises one or both in lipid acid and an alkali metal salt or the titanate coupling agent, and coating the activation treatment time is 1～2 hour.
2. method according to claim 1, it is characterized in that, nucleus formation promotor is one or more mixtures in glucose, sucrose, sodium sulfate, trolamine, the Trisodium Citrate, and the add-on that nucleus forms promotor is 0.5%～5% of a gained lime carbonate quality.
3. method according to claim 1 is characterized in that, adds dispersion agent when carbonation rate to 80% is above, and said dispersion agent is magnesium chloride, Sodium hexametaphosphate 99 or sodium bicarbonate.
4. method according to claim 1 is characterized in that, adding and containing the coating weight concentration is 5～20% the aqueous solution of temperature between 70～95 ℃.
5. method according to claim 1 is characterized in that the consumption of coating counts 0.75～4% with lime carbonate.
6. method according to claim 1 is characterized in that coupling agent is water-soluble coupling agent, is a kind of in alkanolamine metatitanic acid or two (tetra-sodium dialkoxy ester) (2-hydroxyl) propionic acid titanium or the hydramine lipid acid titanic acid ester.
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