CN102336426A - Preparation method of hydrophobic nanoscale calcium carbonate - Google Patents
Preparation method of hydrophobic nanoscale calcium carbonate Download PDFInfo
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- CN102336426A CN102336426A CN2010102320415A CN201010232041A CN102336426A CN 102336426 A CN102336426 A CN 102336426A CN 2010102320415 A CN2010102320415 A CN 2010102320415A CN 201010232041 A CN201010232041 A CN 201010232041A CN 102336426 A CN102336426 A CN 102336426A
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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 45
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 239000000292 calcium oxide Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000011065 in-situ storage Methods 0.000 claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 235000012255 calcium oxide Nutrition 0.000 claims description 39
- 230000032683 aging Effects 0.000 claims description 30
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 29
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 29
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 11
- 229960001763 zinc sulfate Drugs 0.000 claims description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- -1 zirconium ester Chemical class 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 5
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 5
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 5
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 5
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 13
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract 4
- 239000003607 modifier Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明公开了一种疏水性纳米碳酸钙的制备方法。它先将原位改性剂投入到50～80℃的水中搅拌5～30min，再将氧化钙加入其中搅拌0.5～2h，其中，氧化钙、水和原位改性剂间的重量比为1∶5～25∶0.005～0.1，得到浆液，将浆液静置陈化2～24h后，先向压力为0.1～2MPa下的陈化后的浆液中通入二氧化碳气体，并控制其反应温度为5～25℃，其中，每克氧化钙的二氧化碳气体流量为0.5～4mL/min，得到碳酸钙浆料，再向温度为60～85℃、剪切搅拌状态下的碳酸钙浆料中加入改性剂，其中，改性剂与氧化钙间的重量比为0.005～0.1∶1，制得疏水性纳米碳酸钙。它可用于改善纳米碳酸钙表面的润湿性，增加其与聚合物的界面相容性和实现纳米尺度分散，有效发挥纳米粒子对聚合物的改性作用。
The invention discloses a method for preparing hydrophobic nanometer calcium carbonate. It first puts the in-situ modifier into water at 50-80°C and stirs for 5-30 minutes, then adds calcium oxide into it and stirs for 0.5-2 hours, wherein the weight ratio between calcium oxide, water and in-situ modifier is 1 : 5 ~ 25: 0.005 ~ 0.1, to obtain the slurry, after the slurry was left to age for 2 ~ 24h, first to the pressure of 0.1 ~ 2MPa in the aged slurry, carbon dioxide gas was passed into, and the reaction temperature was controlled to be 5 ~25°C, wherein the flow rate of carbon dioxide gas per gram of calcium oxide is 0.5~4mL/min to obtain calcium carbonate slurry, and then add modified agent, wherein the weight ratio between the modifying agent and calcium oxide is 0.005-0.1:1 to obtain hydrophobic nano-calcium carbonate. It can be used to improve the wettability of the surface of nano-calcium carbonate, increase its interfacial compatibility with polymers and realize nano-scale dispersion, and effectively exert the modification effect of nanoparticles on polymers.
Description
Technical field
The present invention relates to a kind of preparation method of lime carbonate, especially a kind of preparation method of hydrophobic nano lime carbonate.
Background technology
Nano-calcium carbonate is a kind of polarity inorganics; Its surface hydrophilic oleophobic, particularly with the polymkeric substance compound tense, the dispersiveness and the interfacial bonding property of nano-calcium carbonate are poor; Be difficult to bring into play effectively the modifying function of nanoparticle, even can cause polymer properties to descend polymkeric substance.People are in order to improve the wettability of nano powder surface; Increase the interface compatibility of nano-powder and medium; The nanoscale that is implemented in the matrices of composite material disperses; Some trials and effort have been done, like " a kind of preparation method of surface modified nano calcium carbonate " who discloses among the disclosed Chinese invention patent ublic specification of application CN 1400167A on March 5th, 2003.This method is utilized quicklime and water reaction, feeds carbonic acid gas synthesis of nano lime carbonate then, carries out two step activation treatment after the carburizing reagent, and the first step adds a kind of saturated fatty acid sodium-salt, and second step added a kind of water-soluble divalent metal salt.Yet this preparation method exists weak point, and at first, the size distribution of the nano-calcium carbonate of acquisition is wide; Secondly, the effect of surface modification treatment is not good enough, nano-calcium carbonate active undesirable; Once more, the temperature drift during owing to carbonization needs 30～80 ℃, causes the size distribution of nano-calcium carbonate and activity all to be difficult to change.
Summary of the invention
The technical problem that the present invention will solve provides a kind of narrow diameter distribution for overcoming weak point of the prior art, and active effect is obvious, the preparation method of the hydrophobic nano lime carbonate that carbonization temperature is low.
For solving technical problem of the present invention, the technical scheme that is adopted is: the preparation method of hydrophobic nano lime carbonate adopts carborization, and particularly completing steps is following:
Step 1 is put in 50～80 ℃ the water in-situ modified dose earlier and is stirred 5～30min, quicklime is added wherein stir 0.5～2h again; Wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 5～25: 0.005～0.1, obtains slurries; Afterwards, with the still aging 2～24h of slurries;
Step 2 earlier feeds dioxide gas in the slurries after pressure is the ageing under 0.1～2MPa, and to control its temperature of reaction be 5～25 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 0.5～4mL/min, obtains calcium carbonate slurry; Be to add properties-correcting agent in the calcium carbonate slurry under 60～85 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.005～0.1: 1, makes hydrophobic nano lime carbonate.
As the preparing method's of hydrophobic nano lime carbonate further improvement, described in-situ modified dose is water-soluble stearate, or water-soluble dodecyl sulfate, or water-soluble dodecylbenzene sulfonate; Described water is deionized water, or zero(ppm) water; Described before feeding dioxide gas in the slurries after ageing or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time, to wherein adding the crystal formation control agent, wherein; Weight ratio between crystal formation control agent and quicklime is 0.005～0.05: 1; The crystal formation control agent is a zinc sulfate, or Hydrocerol A or its salt, or silicate; Or phosphoric acid salt, or borate; The purity of described dioxide gas is 30～100%; Described properties-correcting agent is Triple Pressed Stearic Acid or its salt, or titanate coupling agent, or aluminate coupling agent, or zirconium ester coupling agent; Described the hydrophobic nano lime carbonate that makes is filtered and drying treatment; Described drying treatment is spraying drying or vacuum-drying, and the temperature when dry is 100～150 ℃.
Beneficial effect with respect to prior art is; One of which; Use ESEM to characterize to the product that makes, can know by its result, product for dispersed well, size distribution is merely ± 5% granular substance; The pattern of granular substance is the spindle shape, and its maximum cross section diameter is that 180～200nm, length are 600nm～1 μ m.Its two, use the sedimentation experiment identical to test its modified effect to the product that makes with prior art, through a large amount of contrast tests, the activity index of product is significantly improved.They are three years old; The preparation method is employed in and adds the technical scheme of once more lime carbonate being carried out modification after properties-correcting agent and the carbonization in the reaction process of quicklime and water; Both made the size distribution of the product that obtains narrower, and made the activity of product reach maximization again, the activation rate of modification is up to 99.9%; Therefore also reduce carbonization temperature to 5～25 ℃ of product, and be more conducive to regulate and control effectively the size distribution and the activity of product.
Further embodiment as beneficial effect; The one, in-situ modified dose is preferably water-soluble stearate; Or water-soluble dodecyl sulfate; Or water-soluble dodecylbenzene sulfonate, except that making in-situ modified dose of leeway that has than choice, also make preparation technology more be prone to enforcement and flexible.The 2nd, before feeding dioxide gas in the slurries after ageing or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time, preferably to wherein adding the crystal formation control agent, wherein; Weight ratio between crystal formation control agent and quicklime is 0.005～0.05: 1; The crystal formation control agent is a zinc sulfate, or Hydrocerol A or its salt, or silicate; Or phosphoric acid salt; Or borate, not only make the pattern of product abundanter, also make the particle diameter of product littler, size distribution is narrower, activation effect is more obvious; Through test, when the crystal formation control agent was zinc sulfate, the pattern of product was cubic, and its particle diameter is about 50nm; Particle size distribution range is very narrow, and the activity index sedimentation unit diameter of product is 1.6 μ m, when the crystal formation control agent is Hydrocerol A or its salt; The pattern of product is a chain, and the catenate particle diameter is about 20nm, length-to-diameter ratio is>=6, and the activity index sedimentation unit diameter of product is 12 μ m; The crystal formation control agent is a silicate, or phosphoric acid salt, or during borate; The pattern of product is spherical, and its particle diameter is that particle size distribution range is very little about 50nm; The activity index sedimentation unit diameter of product is 1.5 μ m, more than the parameter of product of various patterns all be superior to the surface modified nano calcium carbonate that prior art makes, promptly its particle diameter is littler, size distribution is narrower, active effect is more obvious.The 3rd, properties-correcting agent is preferably Triple Pressed Stearic Acid or its salt, or titanate coupling agent, or aluminate coupling agent, or zirconium ester coupling agent, makes the source of properties-correcting agent abundant, is beneficial to its industrialized enforcement; The 4th, the hydrophobic nano lime carbonate that makes is preferably filtered and drying treatment, promoted degree of purity of production and quality; The 5th, drying treatment is preferably spraying drying or vacuum-drying, and the temperature when dry is preferably 100～150 ℃, has guaranteed the stable of product quality.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that ESEM (SEM) characterizes to the product that makes.Visible by this SEM photo, product is the cubic thing that dispersiveness is fine, size distribution is very narrow.
Fig. 2 uses one of result that ESEM (SEM) characterizes to the product that makes.Visible by this SEM photo, product be that dispersiveness is fine, particle diameter and all very narrow chain thing of length distribution.
Embodiment
At first buy or make with ordinary method from market:
Quicklime; As water-soluble stearate of in-situ modified dose, water-soluble dodecyl sulfate and water-soluble dodecylbenzene sulfonate; Deionized water and zero(ppm) water as water; Zinc sulfate, Hydrocerol A or its salt, silicate, phosphoric acid salt and borate as the crystal formation control agent; Triple Pressed Stearic Acid or its salt, titanate coupling agent, aluminate coupling agent and zirconium ester coupling agent as properties-correcting agent.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1 is put in 50 ℃ the water in-situ modified dose earlier and is stirred 30min; Wherein, in-situ modified dose is water-soluble stearate, and water is deionized water.Quicklime is added again and wherein stir 0.5h, wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 5: 0.005, obtains slurries.Afterwards, with the still aging 2h of slurries.
Step 2, before feeding dioxide gas in the slurries after ageing (or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time), to wherein adding the crystal formation control agent; Wherein, the weight ratio between crystal formation control agent and quicklime is 0.005: 1, and the crystal formation control agent is a zinc sulfate.Then, earlier feed dioxide gas in the slurries after pressure is the ageing under the 0.1MPa, and to control its temperature of reaction be 25 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 0.5mL/min, and the purity of dioxide gas is 100%, obtains calcium carbonate slurry.Be to add properties-correcting agent in the calcium carbonate slurry under 60 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.005: 1, and properties-correcting agent is Triple Pressed Stearic Acid or its salt.Make and be similar to hydrophobic nano lime carbonate shown in Figure 1.
Embodiment 2
The concrete steps of preparation are:
Step 1 is put in 58 ℃ the water in-situ modified dose earlier and is stirred 23min; Wherein, in-situ modified dose is water-soluble stearate, and water is deionized water.Quicklime is added again and wherein stir 0.9h, wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 10: 0.028, obtains slurries.Afterwards, with the still aging 8h of slurries.
Step 2, before feeding dioxide gas in the slurries after ageing (or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time), to wherein adding the crystal formation control agent; Wherein, the weight ratio between crystal formation control agent and quicklime is 0.016: 1, and the crystal formation control agent is a zinc sulfate.Then, earlier feed dioxide gas in the slurries after pressure is the ageing under the 0.6MPa, and to control its temperature of reaction be 20 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 1.4mL/min, and the purity of dioxide gas is 83%, obtains calcium carbonate slurry.Be to add properties-correcting agent in the calcium carbonate slurry under 66 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.028: 1, and properties-correcting agent is Triple Pressed Stearic Acid or its salt.Make and be similar to hydrophobic nano lime carbonate shown in Figure 1.
Embodiment 3
The concrete steps of preparation are:
Step 1 is put in 65 ℃ the water in-situ modified dose earlier and is stirred 17min; Wherein, in-situ modified dose is water-soluble stearate, and water is deionized water.Quicklime is added again and wherein stir 1.2h, wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 15: 0.05, obtains slurries.Afterwards, with the still aging 13h of slurries.
Step 2, before feeding dioxide gas in the slurries after ageing (or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time), to wherein adding the crystal formation control agent; Wherein, the weight ratio between crystal formation control agent and quicklime is 0.028: 1, and the crystal formation control agent is a zinc sulfate.Then, earlier feed dioxide gas in the slurries after pressure is the ageing under the 1MPa, and to control its temperature of reaction be 15 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 2.3mL/min, and the purity of dioxide gas is 65%, obtains calcium carbonate slurry.Be to add properties-correcting agent in the calcium carbonate slurry under 73 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.05: 1, and properties-correcting agent is Triple Pressed Stearic Acid or its salt.Make hydrophobic nano lime carbonate as shown in Figure 1.
Embodiment 4
The concrete steps of preparation are:
Step 1 is put in 73 ℃ the water in-situ modified dose earlier and is stirred 11min; Wherein, in-situ modified dose is water-soluble stearate, and water is deionized water.Quicklime is added again and wherein stir 1.6h, wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 20: 0.075～0.1, obtains slurries.Afterwards, with the still aging 19h of slurries.
Step 2, before feeding dioxide gas in the slurries after ageing (or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time), to wherein adding the crystal formation control agent; Wherein, the weight ratio between crystal formation control agent and quicklime is 0.039: 1, and the crystal formation control agent is a zinc sulfate.Then, earlier feed dioxide gas in the slurries after pressure is the ageing under the 1.5MPa, and to control its temperature of reaction be 10 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 3.2mL/min, and the purity of dioxide gas is 48%, obtains calcium carbonate slurry.Be to add properties-correcting agent in the calcium carbonate slurry under 79 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.075: 1, and properties-correcting agent is Triple Pressed Stearic Acid or its salt.Make and be similar to hydrophobic nano lime carbonate shown in Figure 1.
Embodiment 5
The concrete steps of preparation are:
Step 1 is put in 80 ℃ the water in-situ modified dose earlier and is stirred 5min; Wherein, in-situ modified dose is water-soluble stearate, and water is deionized water.Quicklime is added again and wherein stir 2h, wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 25: 0.1, obtains slurries.Afterwards, with the still aging 24h of slurries.
Step 2, before feeding dioxide gas in the slurries after ageing (or in the slurries after ageing, feed dioxide gas time≤1/6 o'clock of its total time), to wherein adding the crystal formation control agent; Wherein, the weight ratio between crystal formation control agent and quicklime is 0.05: 1, and the crystal formation control agent is a zinc sulfate.Then, earlier feed dioxide gas in the slurries after pressure is the ageing under the 2MPa, and to control its temperature of reaction be 5 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 4mL/min, and the purity of dioxide gas is 30%, obtains calcium carbonate slurry.Be to add properties-correcting agent in the calcium carbonate slurry under 85 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.1: 1, and properties-correcting agent is Triple Pressed Stearic Acid or its salt.Make and be similar to hydrophobic nano lime carbonate shown in Figure 1.
If obtain the powdered product of higher degree and quality, can filter and drying treatment the hydrophobic nano lime carbonate that makes again; Wherein, drying treatment is spraying drying or vacuum-drying, and the temperature when dry is 100～150 ℃.
Select water-soluble stearate more respectively for use as in-situ modified dose, or water-soluble dodecyl sulfate, or water-soluble dodecylbenzene sulfonate; As the deionized water of water, or zero(ppm) water; As the zinc sulfate of crystal formation control agent, or Hydrocerol A or its salt, or silicate, or phosphoric acid salt, or borate; As Triple Pressed Stearic Acid or its salt of properties-correcting agent, or titanate coupling agent, or aluminate coupling agent, or zirconium ester coupling agent, repeat the foregoing description 1～5, made equally as or be similar to Fig. 1 or hydrophobic nano lime carbonate shown in Figure 2.
Obviously, those skilled in the art can carry out various changes and modification to the preparation method of hydrophobic nano lime carbonate of the present invention and not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (8)
1. the preparation method of a hydrophobic nano lime carbonate adopts carborization, it is characterized in that completing steps is following:
Step 1 is put in 50～80 ℃ the water in-situ modified dose earlier and is stirred 5～30min, quicklime is added wherein stir 0.5～2h again; Wherein, the weight ratio between quicklime, water and in-situ modified dose is 1: 5～25: 0.005～0.1, obtains slurries; Afterwards, with the still aging 2～24h of slurries;
Step 2 earlier feeds dioxide gas in the slurries after pressure is the ageing under 0.1～2MPa, and to control its temperature of reaction be 5～25 ℃; Wherein, the flow of carbon dioxide gas amount of every gram quicklime is 0.5～4mL/min, obtains calcium carbonate slurry; Be to add properties-correcting agent in the calcium carbonate slurry under 60～85 ℃, shear agitation state to temperature again; Wherein, the weight ratio between properties-correcting agent and quicklime is 0.005～0.1: 1, makes hydrophobic nano lime carbonate.
2. the preparation method of hydrophobic nano lime carbonate according to claim 1 is characterized in that in-situ modified dose is water-soluble stearate, or water-soluble dodecyl sulfate, or water-soluble dodecylbenzene sulfonate.
3. the preparation method of hydrophobic nano lime carbonate according to claim 1 is characterized in that water is deionized water, or zero(ppm) water.
4. the preparation method of hydrophobic nano lime carbonate according to claim 1, it is characterized in that before feeding dioxide gas in the slurries after ageing or in the slurries after ageing, feeding dioxide gas time≤1/6 o'clock of its total time, to wherein adding the crystal formation control agent; Wherein, the weight ratio between crystal formation control agent and quicklime is 0.005～0.05: 1, and the crystal formation control agent is a zinc sulfate; Or Hydrocerol A or its salt; Or silicate, or phosphoric acid salt, or borate.
5. the preparation method of hydrophobic nano lime carbonate according to claim 1, the purity that it is characterized in that dioxide gas is 30～100%.
6. the preparation method of hydrophobic nano lime carbonate according to claim 1 is characterized in that properties-correcting agent is Triple Pressed Stearic Acid or its salt, or titanate coupling agent, or aluminate coupling agent, or zirconium ester coupling agent.
7. the preparation method of hydrophobic nano lime carbonate according to claim 1 is characterized in that the hydrophobic nano lime carbonate that makes is filtered and drying treatment.
8. the preparation method of hydrophobic nano lime carbonate according to claim 7 is characterized in that drying treatment is spraying drying or vacuum-drying, and the temperature when dry is 100～150 ℃.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693669A (en) * | 2013-12-03 | 2014-04-02 | 恩平市嘉维化工实业有限公司 | Method for preparing nano calcium carbonate special for rolling film |
| CN105483363A (en) * | 2015-12-10 | 2016-04-13 | 中南大学 | Method for co-production of activated calcium silicate by adopting copper tailings to produce iron ore concentrate |
| CN106032287A (en) * | 2016-02-16 | 2016-10-19 | 沈阳建筑大学 | A kind of preparation method of oil-dispersible calcium carbonate superfine powder |
| CN106048709A (en) * | 2016-02-16 | 2016-10-26 | 沈阳建筑大学 | Preparation method for calcium carbonate whiskers extracted from limestone |
| CN106189266A (en) * | 2016-08-05 | 2016-12-07 | 中玺新材料（安徽）有限公司 | A kind of hydrophobic type composite calcium carbonate and preparation method thereof |
| CN106431043A (en) * | 2016-09-13 | 2017-02-22 | 广西大学 | Method for strengthening limestone modified by utilizing double-functional-group modifying agent under microwave field |
| TWI625304B (en) * | 2014-05-26 | 2018-06-01 | 歐米亞國際公司 | Process for preparing a surface-modified material |
| CN112374520A (en) * | 2020-11-27 | 2021-02-19 | 广西华纳新材料科技有限公司 | Preparation method of active calcium carbonate for moisture-curing polyurethane sealant |
| CN113247936A (en) * | 2021-06-25 | 2021-08-13 | 安徽前江超细粉末科技有限公司 | Method for reducing energy consumption in production of nano calcium carbonate |
| CN116084203A (en) * | 2023-03-08 | 2023-05-09 | 东莞市协泰纸品有限公司 | Pit paper production process |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693669A (en) * | 2013-12-03 | 2014-04-02 | 恩平市嘉维化工实业有限公司 | Method for preparing nano calcium carbonate special for rolling film |
| TWI625304B (en) * | 2014-05-26 | 2018-06-01 | 歐米亞國際公司 | Process for preparing a surface-modified material |
| CN105483363A (en) * | 2015-12-10 | 2016-04-13 | 中南大学 | Method for co-production of activated calcium silicate by adopting copper tailings to produce iron ore concentrate |
| CN106032287A (en) * | 2016-02-16 | 2016-10-19 | 沈阳建筑大学 | A kind of preparation method of oil-dispersible calcium carbonate superfine powder |
| CN106048709A (en) * | 2016-02-16 | 2016-10-26 | 沈阳建筑大学 | Preparation method for calcium carbonate whiskers extracted from limestone |
| CN106048709B (en) * | 2016-02-16 | 2018-11-13 | 沈阳建筑大学 | A kind of preparation method of the calcium carbonate crystal whisker extracted from lime stone |
| CN106189266A (en) * | 2016-08-05 | 2016-12-07 | 中玺新材料（安徽）有限公司 | A kind of hydrophobic type composite calcium carbonate and preparation method thereof |
| CN106431043A (en) * | 2016-09-13 | 2017-02-22 | 广西大学 | Method for strengthening limestone modified by utilizing double-functional-group modifying agent under microwave field |
| CN106431043B (en) * | 2016-09-13 | 2018-11-02 | 广西大学 | Strengthen the method using dual-functional group modifier modification lime stone under a kind of microwave field |
| CN112374520A (en) * | 2020-11-27 | 2021-02-19 | 广西华纳新材料科技有限公司 | Preparation method of active calcium carbonate for moisture-curing polyurethane sealant |
| CN113247936A (en) * | 2021-06-25 | 2021-08-13 | 安徽前江超细粉末科技有限公司 | Method for reducing energy consumption in production of nano calcium carbonate |
| CN116084203A (en) * | 2023-03-08 | 2023-05-09 | 东莞市协泰纸品有限公司 | Pit paper production process |
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