CN101117232A - Preparation of calcium carbonate nano particle material by bubble liquid film method - Google Patents
Preparation of calcium carbonate nano particle material by bubble liquid film method Download PDFInfo
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- CN101117232A CN101117232A CNA2007100291789A CN200710029178A CN101117232A CN 101117232 A CN101117232 A CN 101117232A CN A2007100291789 A CNA2007100291789 A CN A2007100291789A CN 200710029178 A CN200710029178 A CN 200710029178A CN 101117232 A CN101117232 A CN 101117232A
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- carbon dioxide
- calcium carbonate
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- 239000007788 liquid Substances 0.000 title claims abstract description 116
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 94
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 78
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 30
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002775 capsule Substances 0.000 claims abstract description 11
- 230000005501 phase interface Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 229940113243 calci-mix Drugs 0.000 claims description 46
- 238000005255 carburizing Methods 0.000 claims description 38
- 239000003153 chemical reaction reagent Substances 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 238000003483 aging Methods 0.000 claims description 14
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
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- -1 titanic acid ester Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 235000011089 carbon dioxide Nutrition 0.000 claims description 8
- 230000003134 recirculating effect Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
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- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 240000005373 Panax quinquefolius Species 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
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- 150000007942 carboxylates Chemical class 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
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- 239000011575 calcium Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
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- 239000011858 nanopowder Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000219000 Populus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 244000100068 Triphasia aurantiola Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a bubble liquid film method for preparing calcium carbonate nano particle materials, belonging to the chemical nano material manufacturing industry. The invention is carried out in a bubble liquid film reactor, calcium hydroxide aqueous suspension and carbon dioxide gas are used as raw materials, carboxylate aqueous solution is used as a coating agent, and the function of a bubble disk type stirrer for strongly dispersing gas is utilized to generate enough carbon dioxide bubbles. The whole calcium hydroxide water suspension and the carboxylate water solution are divided into liquid films which are thin enough by the bubbles, the bubbles are dispersed phases, and the liquid films are continuous phases, so that a nano reaction environment is formed, the contact surface between carbon dioxide and calcium hydroxide is greatly increased, and the mass and heat transfer is enhanced. The reactants are carbonized between the liquid film and the air bubble or in the liquid film, nucleated and grow to generate calcium carbonate nano particles, and the calcium carbonate capsule nano particles are generated by in-situ coating. The surface of the calcium carbonate capsule nano particle adsorbs a large amount of gas to form a gas phase interface, agglomeration is inhibited, a mineralized bubble film is formed, and the calcium carbonate capsule nano particle powder material is obtained after filtration and drying.
Description
[technical field]
The present invention is a preparation of calcium carbonate nano particle material by air bubble liquid film process, belongs to chemical industry nano material production.
[background technology]
Lime carbonate is a kind of important inorganic chemical product, has characteristics such as abundant raw material, production technique are simple, stable performance, is widely used in industrial sectors such as plastics, rubber, coating, papermaking, printing ink, medicine, food, feed.It is about 80% that wherein plastics, rubber, paper industry consume calcium carbonate quantity, and coating is about 10%, other industry about 10%.Under the exhausted day by day situation of present petroleum resources,, has the meaning of particularly important with the compatibilization filler of lime carbonate as plastics, rubber etc.China needs about 4,000,000 tons of calcium carbonate product total amount every year, and is annual from external import nano-calcium carbonate 7～100,000 tons, and the demand of lime carbonate is also with annual 6～10% speed increment.Some international major companies also have an optimistic view of Chinese lime carbonate industry at present.
Because the particle diameter of ordinary calcium carbonate only plays compatibilization as weighting agent at 1 μ m～3 μ m or bigger in industries such as rubber, plastics, cause the mechanical property of product sharply to descend simultaneously.Particle diameter not only has the filling solublization at the calcium carbonate nano particle of 1nm～100nm, and has nanometer reinforcement, toughening effect, also can replace white carbon black in certain fields, so be subjected to extensive concern.
At present, there are more than 140 families of Production of Light Calcium Carbonate enterprise in China, and overall throughput reaches more than 300 ten thousand tons, but kind is single, and technology falls behind, and adopts easy intermittent type bubbling carbonizing technology basically, product mostly is the cheap particle diameter of price greatly at 2 μ m～5 μ m, even bigger fusiform product.And the market requirement increases comparatively fast, and added value is higher, particle diameter is very few less than the output of the calcium carbonate nano particle material of 100nm, accounts for 2～3% of light calcium carbonate ultimate production.China every year need be from about 100,000 tons of national import nano-calcium carbonates (3000～6000 yuan/ton of prices) such as Japan, Britain.In recent years, also there is the report that utilizes domestic and international technology to carry out nano-calcium carbonate production in China, but production cost is higher, and needs huge investment mostly, and medium-sized and small enterprises are difficult to adapt to.
The method of producing calcium carbonate nano particle is a lot, has wherein implemented industrially, mainly contains bubbling carbonizing method, multistage spray carbonation method and overweight force method etc.These methods all obtain certain success, but have difficult control product granularity and homogeneity, reunite, or are difficult for implementing original position and coat, or unsatisfactory part such as occluding device takes place.
Because the surface aggregation of nanoparticle bigger excess free energy, at room temperature just can reunite by discharging excess free energy, therefore, nanoparticle generally is difficult to single existence.Coacervate can not fully show nano functional.Usually the nano-powder of saying all is the tight type fine particle that is become by several nanoparticle agglomeration, is difficult to be separated into one nanoparticle.This causes very burden in Application for Field such as macromolecular materials for nano material.Solve nano-powder and in carrier, be separated into single nanoparticle problem, be still one of important research project in the nano science science and technology so far.Therefore, be necessary to develop the novel method of nanometer particle material of being produced on a large scale.
Inventor herein poplar human relations etc. have been developed to have the powerful bubble cap dish type agitator that disperses gas and liquid functional, patent No. ZL:200420044185.8, the applying date: on March 31st, 2004.The bubble cap dish type agitator is made up of rotating-disk, fixed cover and revolving power mechanism three parts.Disk is provided with several open blister, the bottom opening of each bubble-cap.When disk rotated, the reactant aqueous solution of participating in reaction was subjected to bubble-cap control by the bubble-cap on the rotating-disk, was ejected into the another side of rotating-disk from the bubble-cap base apertures, formed the injection direction bubble jet opposite with the disk sense of rotation.Total overall reaction liquid is divided into enough thin liquid film by bubble, and bubble is a disperse phase, and liquid film is an external phase, constitutes the nanometer reaction environment.The bubble cap dish type agitator unit in various reaction vessels, is just constituted bubble liquid film reactor, Chinese patent publication number: CN1833769A, open day: on September 20th, 2006.On the basis of the above, proposed to make the air bubble liquid-membrane method of nanometer particle material, Chinese patent publication number: CN1803272A, open day: on July 19th, 2006.Therefore bubble liquid film reactor and bubble liquid-film method are specially adapted to the chemical liquid phase precipitator method and produce nanometer particle material.The present invention succeeds in developing on this basis.
[summary of the invention]
The purpose of this invention is to provide a kind of preparation of calcium carbonate nano particle material by air bubble liquid film process, it is to adopt bubble liquid film reactor, calcium hydroxide aqeous suspension and carbon dioxide are raw material, carboxylic acid salt solution or emulsion are coating (also being tensio-active agent), utilize the brute force dispersion gas of bubble cap dish type agitator and the function of liquid, moment is with calcium hydroxide, coating and carbon dioxide mix, reach the slurries that microcosmic mixes, in reaction system, produce the carbonic acid gas bubble of q.s, all. slurries are separated into enough thin liquid film by the carbonic acid gas bubble, bubble is a disperse phase, and liquid film is an external phase, and the non-polar end of carboxylate radical stretches to bubble inside, polar end stretches to liquid film, form the nanometer reaction environment, greatly increased the contact surface between carbon dioxide and the calcium hydroxide, enhancing mass and heat transfer.Reactant carries out carburizing reagent between liquid film and bubble or in the liquid film, the lime carbonate nucleation, and growth generates the crystal nanoparticle, coats through original position, generates the Calci-Mix nanoparticle.The Calci-Mix nanoparticle surface is adsorbed a large amount of gases, constitutes gas phase interface, restrains and reunites, and form the mineralising vacuolar membrane, through ageing, filters, and drying obtains Calci-Mix nanoparticle powder.
One, processing step of the present invention, apparatus characteristic are as follows:
1, the present invention adopts the bubble liquid film reactor of device bubble cap dish type agitator, with calcium hydroxide aqeous suspension and carbon dioxide gas precursor reactant, produces loose type powder of Calci-Mix nanoparticle or block.The steps include:
(1) in the bubble liquid film reactor that the bubble cap dish type agitator is housed, add calcium hydroxide aqeous suspension and coating (also being tensio-active agent) aqueous solution or emulsion, import carbon dioxide, utilize the brute force dispersion gas of bubble cap dish type agitator and the function of liquid, in reaction system, produce the carbonic acid gas bubble of q.s, all the calcium hydroxide aqeous suspension and the coating aqueous solution or emulsion are separated into enough thin liquid film by the carbonic acid gas bubble, bubble is a disperse phase, liquid film is an external phase, the non-polar end of carboxylate radical stretches to bubble inside, and polar end stretches to liquid film, forms the nanometer reaction environment, greatly increased the contact surface between calcium hydroxide and the carbon dioxide, between liquid film and bubble or in liquid film, carry out carburizing reagent, generate lime carbonate, its crystal nucleation, growth generates calcium carbonate nano particle;
(2) in reaction system, be added in carboxylic acid, sulphonate, sulfuric ester, phosphoric acid ester, titanic acid ester or the silicon ester that has a hydroxyl (OH) on C, S, P, Ti or the Si central atom at least a kind of, two or more is as coating; Or they are converted into corresponding salt and make coating in reaction system; Be the surface modification coating perhaps with these carboxylate salts or inorganic acid ester salt, the non-polar end of these coatings stretches to bubble inside, polar end stretches to liquid film, bubble and liquid film at the interface with newly-generated calcium carbonate nano particle surface bonding, nanoparticle stops growth, form coating layer, promptly original position coats, and generates the Calci-Mix nanoparticle;
(3) gas of q.s is adsorbed on the surface of the Calci-Mix nanoparticle of Sheng Chenging from bubble, form gas phase interface, restrain and reunite, hinder water molecules simultaneously and form the hydrogen bond bridge between nanoparticle, restrain interparticle hydrogen bonded, the Calci-Mix nanoparticle has adsorbed q.s gas, generate Calci-Mix nanoparticle mineralized froth product, through ageing, after separation and the drying, make the loose type powder or the block of Calci-Mix nanoparticle;
2, technology characteristics is, used carbon dioxide is pure or with the mixed gas of various ratios and oxygen, nitrogen or other gas, or the aqueous solution of carbonic acid gas and water resultant of reaction.
3, product appearance consists of in three-dimensional space for loose powder or block, has the one dimension size at least in the 1nm-100nm scope, through the Calci-Mix nanoparticle of surface modification coating;
4, its technology characteristics is, circulating single stepping is arranged, in the calcium hydroxide aqeous suspension and the coating aqueous solution or emulsion adding bubble liquid film reactor with requirement, starting bubble cap dish type agitator feeds carbon dioxide, forms air bubble liquid-membrane, carry out carburizing reagent, reacting slurry enters recirculating still, and by recycle pump reacting slurry is returned bubble liquid film reactor, and carburizing reagent is carried out in circulation, during the whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor continuously, is 7 up to the pH of reacting slurry value, stops to feed carbon dioxide, till the pH value of reacting slurry does not rise, make Calci-Mix nanoparticle mineralized froth, through ageing, after separation and the drying, make the loose type powder or the block of Calci-Mix nanoparticle, as required, carrying out secondary coats, repeatedly coat, or add other auxiliary agent.
5, its technology characteristics is, circulating two steps operation is arranged, the calcium hydroxide aqeous suspension of requirement is added in the bubble liquid film reactor, starting bubble cap dish type agitator feeds carbon dioxide, forms air bubble liquid-membrane, carry out carburizing reagent, reacting slurry enters recirculating still, and by recycle pump reacting slurry is returned bubble liquid film reactor, and carburizing reagent is carried out in circulation, during the whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor continuously, after certain hour is carried out in carburizing reagent, or after the pH value reaches desired value, promptly prepare calcium carbonate nano particle earlier, the coating aqueous solution or emulsion with requirement adds bubble liquid film reactor again, continues reaction, carries out original position and coats, generate Calci-Mix nanoparticle mineralized froth, through ageing, separate drying, make loose type powder of Calci-Mix nanoparticle or block, as required, carrying out secondary coats, repeatedly coat, or add other auxiliary agent.
6, its technology characteristics is, the continous way operation is arranged, several bubble liquid film reactors are together in series, with the calcium hydroxide aqeous suspension, the coating aqueous solution or emulsion and carbon dioxide and stream add in first bubble liquid film reactor, starting bubble cap dish type agitator, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry and carbon dioxide also flow to into second bubble liquid film reactor, carry out carburizing reagent, go on according to this, reach desired value up to the pH of reacting slurry value, stop to feed carbon dioxide, till the pH value does not rise, make Calci-Mix nanoparticle mineralized froth continuously, through ageing, separate, dry, make loose type powder of Calci-Mix nanoparticle or block: the coating aqueous solution or emulsion do not add from first bubble liquid film reactor, but from second bubble liquid film reactor, or later any one or several bubble liquid film reactor, add with carbon dioxide and stream, perhaps the coating aqueous solution or emulsion and carbon dioxide and stream add in each bubble liquid film reactor that is together in series, loose type powder of preparation Calci-Mix nanoparticle or block: as required, carrying out secondary coats, repeatedly coat, or add other auxiliary agent.
7, its technology characteristics is, changes rotating speed, material concentration and the reaction conditions etc. of the rotating-disk of bubble cap dish type agitator, makes the loose type powder or the block of lime carbonate submicron particle or capsule submicron particle, lime carbonate micron particle or capsule micron particle.
8, its apparatus characteristic is, bubble liquid film reactor is by bubble cap dish type mixing component, reaction vessel assembly, metering pump assembly, flow meter assembly, pH meter assembly, support and casing, and the electrical accessorie that needs is formed, several bubble liquid film reactors can be together in series, constitute the tandem bubble liquid film reactor.
Here, said " loose type " has two implications: the first, the surface adsorption of the calcium carbonate nano particle of generation or capsule nanoparticle q.s gas, forming gas phase interface between nanoparticle or between the capsule nanoparticle, restrain interparticle reunion.Simultaneously, gas phase interface hinders water molecules forming the hydrogen bond bridge between calcium carbonate nano particle or between the capsule nanoparticle, restrains interparticle hydrogen bonded.The second, the initial product of Calci-Mix nanoparticle is the mineralized froth form, swims in the upper strata of reaction system, through ageing, has q.s gas in separation and the dried aggregate, and what make is the loose type powder or the block of Calci-Mix nanoparticle.
Two, raw material of the present invention
1, calcium hydroxide
General molecular formula: Ca (OH)
2
The place of production: Guangdong
2, carbon dioxide
General formula: CO
2
The place of production: Guangdong
3, coating:
Carboxylate salt
General formula: C
nH
(2n+2-m-k)(COOM)
m
N=1,2,3...; M=1,2,3...; One of them even number of k=0,2,4,6...;
M is H, NH
4, Li, Na, K or Ca one of them;
The place of production: Zhongshan city's applied chemistry institute, Zhongshan Weina New Industrial Material Co., Ltd
Three, chemical equation
Ca(OH)
2(s)+CO
2(g)＝CaCO
3(S)↓+H
2O+ΔH
Four, key equipment
Bubble liquid film reactor
The place of production: Zhongshan city's applied chemistry institute, Zhongshan Weina New Industrial Material Co., Ltd
Five, operation steps
1, preparation of raw material:
(1) calcium hydroxide is distributed in the water, filters, make the aqeous suspension that needs concentration.
(2) carboxylate salt is mixed with the aqueous solution that needs concentration.
(3) carbon dioxide.
2 operations:
(1) circulating single stepping: as shown in Figure 1, the calcium hydroxide aqeous suspension of requirement and the coating aqueous solution or emulsion are added in the bubble liquid film reactors 5 by conduit 1,2, starting bubble cap dish type agitator 6, feed carbon dioxide from conduit 3, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry enters recirculating still 7 from the outlet 12 of reactor 5, and by recycle pump 8 reacting slurry is returned in the bubble liquid film reactor 5, carburizing reagent is carried out in circulation.During whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor continuously, after the pH of reacting slurry value is 7, stops to feed carbon dioxide, till the pH value of reacting slurry does not rise, make Calci-Mix nanoparticle mineralized froth, after separating, make the loose type powder or the block of Calci-Mix nanoparticle, as required, carry out secondary and coat, repeatedly coat, or add other auxiliary agent.
2, circulating two steps operation: as shown in Figure 1, the calcium hydroxide aqeous suspension of requirement is added in the bubble liquid film reactor 5 by conduit 1, starting bubble cap dish type agitator 6, feed carbon dioxide from conduit 3, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry enters recirculating still 7 from the outlet 12 of reactor 5, and by recycle pump 8 reacting slurry is returned in the bubble liquid film reactor 5, carburizing reagent is carried out in circulation.During whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor continuously, after certain hour is carried out in carburizing reagent, or works as the end point values that the pH value reaches to be needed, and promptly the first step prepares calcium carbonate nano particle earlier; Second step added the coating aqueous solution or the emulsion of requirement the bubble liquid film reactor 5 from conduit 2 again, continued to stir, and carried out original position and coated, generate Calci-Mix nanoparticle mineralized froth, through ageing, separation, drying make loose type powder of Calci-Mix nanoparticle or block.As required, carry out secondary and coat, repeatedly coat, or add other auxiliary agent.
3, continous way operation: several bubble liquid film reactors are together in series, with the calcium hydroxide aqeous suspension, the coating aqueous solution or emulsion and carbon dioxide and stream add in first bubble liquid film reactor, starting bubble cap dish type agitator, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry and two is from a last carbon oxide gas and flow to into second bubble liquid film reactor, carry out carburizing reagent again, go on according to this, reach desired value up to the pH of reacting slurry value, stop to feed carbon dioxide, till the pH value does not rise, make Calci-Mix nanoparticle mineralized froth continuously, through separating, drying makes loose type powder of Calci-Mix nanoparticle or block.The coating aqueous solution or emulsion do not add from first bubble liquid film reactor, but from second bubble liquid film reactor, or later any one or several bubble liquid film reactor, add with carbon dioxide and stream, perhaps the coating aqueous solution or emulsion and carbon dioxide and stream add in each bubble liquid film reactor that is together in series.As required, carry out secondary and coat, repeatedly coat, or add other auxiliary agent.
Six, advantage of the present invention:
The advantage of preparation of calcium carbonate nano particle material by air bubble liquid film process is:
1, adopt the bubble liquid film reactor of device bubble cap dish type agitator, equipment is simply exquisite, and energy consumption is low, and easily starting is easily closed down, easily maintenance, and cost is low.
2, the brute force of bubble cap dish type agitator is disperseed the carbon dioxide function; solution-air phase, liquid-liquid phase moment is reached microcosmic to mix; form air bubble liquid-membrane; greatly increased the contact surface of carbon dioxide gas and calcium hydroxide; highly enriched mass transfer and heat transfer; the terse smoothness of technology is produced on a large scale.
3, carbon dioxide and calcium hydroxide is between bubble and liquid film or the liquid film internal reaction, the crystal nucleation of lime carbonate, and growth generates nanoparticle, original position coats, and generates the capsule nanoparticle, forms mineralized froth.Under certain reactant concn and other reaction conditions, the particle diameter of product lime carbonate and distribution are by the rotating speed control of bubble cap dish type agitator rotating-disk.This other method with the preparation nano-calcium carbonate is far different.
4, the surface adsorption of Calci-Mix nanoparticle the gas of q.s, form gas phase interface, restrain interparticle reunion.Calci-Mix nanoparticle powder or block easily are separated into single nanoparticle in carriers such as macromolecular material, hydro carbons, ester class, show tangible nano functional.
[description of drawings]
Further specify the technology of preparation of calcium carbonate nano particle material by air bubble liquid film process below by description of drawings and embodiment.
Accompanying drawing 1 prepares lime carbonate technology, equipment flowsheet for the present invention.
[embodiment]
Several embodiment of the present invention is provided below:
1, circulating single stepping example:
With 6000ml concentration is the calcium hydroxide aqeous suspension of 1.5mol/L, the carboxylic acid sodium aqueous solution that 6000ml concentration is 0.015mol/L, respectively by conduit 1 and 2 and circulation go into NA-LS-1L type bubble liquid film reactor 5, starting bubble cap dish type agitator 6, from conduit 3, with the flow velocity is that 2-4L/min feeds carbon dioxide, form air bubble liquid-membrane, carry out carburizing reagent.Reacting slurry flows into recirculating still 7 by the outlet 12 of reactor 6, and by recycle pump 8 reacting slurry is returned in the bubble liquid film reactor 5, and carburizing reagent is carried out in circulation.During whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor 5 continuously, is 7 up to the pH of reacting slurry value, after stopping to feed carbon dioxide, till the pH value of reacting slurry does not rise, make Calci-Mix nanoparticle mineralized froth, through ageing, separate, after the drying, obtain the loose type white of Calci-Mix nanoparticle powder, as required, carry out secondary and coat, repeatedly coat, or add other auxiliary agent.。
2, circulating two step operational instances:
The calcium hydroxide aqeous suspension that with 10L concentration is 1mol/L feeds NA-LS-1L type bubble liquid film reactor 5 by conduit 1, starting bubble cap dish type agitator 6 from conduit 3, is that 2-4L/min feeds carbon dioxide with the flow velocity, form air bubble liquid-membrane, carry out carburizing reagent.Reacting slurry flows into recirculating still 7 by the outlet 12 of reactor 6, and by recycle pump 8 reacting slurry is returned in the membrane reactor 5, and carburizing reagent is carried out in circulation.During whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor 5 continuously, after the pH of reacting slurry value is 7, stops to feed carbon dioxide, till the pH value of reacting slurry does not rise, needs 15min, makes calcium carbonate nano particle; 2L concentration is the carboxylic acid sodium aqueous solution of 0.015mol/L, add reactor 5 from conduit 2, continue to stir 10min, make Calci-Mix nanoparticle mineralized froth, through ageing, separate, after the drying, obtain the loose type white of Calci-Mix nanoparticle powder, as required, carry out secondary and coat, repeatedly coat, or add other auxiliary agent.
3, continous way operation scheme: several bubble liquid film reactors are together in series, in calcium hydroxide aqeous suspension, the coating aqueous solution or emulsion and carbon dioxide and first bubble liquid film reactor of stream adding, starting bubble cap dish type agitator forms air bubble liquid-membrane, carries out carburizing reagent.Reacting slurry is from first bubble liquid film reactor and carbon dioxide and flow to into second bubble liquid film reactor, carry out carburizing reagent again, go on according to this, reach desired value up to the pH of reacting slurry value, stop to feed carbon dioxide, till the pH value does not rise, make Calci-Mix nanoparticle mineralized froth continuously, through ageing, separate and drying, make loose type powder of Calci-Mix nanoparticle or block.The coating aqueous solution or emulsion do not add from first bubble liquid film reactor, but from second bubble liquid film reactor, or later any one or several bubble liquid film reactor, add with carbon dioxide and stream, perhaps the coating aqueous solution or emulsion and carbon dioxide and stream add in each bubble liquid film reactor that is together in series.As required, carry out secondary and coat, repeatedly coat, or add other auxiliary agent.
Claims (8)
1. preparation of calcium carbonate nano particle material by air bubble liquid film process is to carry out in bubble liquid film reactor, calcium hydroxide aqeous suspension and carbon dioxide gas precursor reactant, and the Calci-Mix nanometer particle material of the loose type of production the steps include:
(1) in the bubble liquid film reactor that the bubble cap dish type agitator is housed, add calcium hydroxide aqeous suspension (often being called slurries or mortar) and have the coating aqueous solution or the emulsion of surfactant properties, import carbon dioxide, utilize the brute force dispersion gas of bubble cap dish type agitator and the function of liquid, in reaction system, produce the carbonic acid gas bubble of q.s, all the calcium hydroxide aqeous suspension and the coating aqueous solution or emulsion are separated into enough thin liquid film by the carbonic acid gas bubble, bubble is a disperse phase, liquid film is an external phase, form the nanometer reaction environment, greatly increased the contact surface between calcium hydroxide and the carbon dioxide, between liquid film and bubble or in liquid film, carry out carburizing reagent, generate lime carbonate, nucleation, growth generates calcium carbonate nano particle;
(2) in reaction system, be added in carboxylic acid, sulphonate, sulfuric ester, phosphoric acid ester, titanic acid ester or the silicon ester that has a hydroxyl (OH) on C, S, P, Ti or the Si central atom at least a kind of, two or more is as coating; Or they are converted into corresponding salt and make coating in reaction system; Be the surface modification coating perhaps with these carboxylate salts or inorganic acid ester salt, the non-polar end of these coatings stretches to bubble inside, polar end stretches to liquid film, in the interface of bubble and liquid film and newly-generated calcium carbonate nano particle surface bonding, nanoparticle stops growth, form coating layer, promptly original position coats, and generates the Calci-Mix nanoparticle;
(3) gas of q.s is adsorbed on the surface of the Calci-Mix nanoparticle of Sheng Chenging from bubble, form gas phase interface, restrain and reunite, hinder water molecules simultaneously and form the hydrogen bond bridge between nanoparticle, restrain interparticle hydrogen bonded, the Calci-Mix nanoparticle has adsorbed q.s gas, generate Calci-Mix nanoparticle mineralized froth product, through ageing, after separation and the drying, make the loose type powder or the block of Calci-Mix nanoparticle.
2. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that used carbon dioxide is pure or with the mixed gas of various ratios and oxygen, nitrogen or other gas, or the aqueous solution of carbonic acid gas and water resultant of reaction.
3. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that product appearance is loose powder or block, consist of in three-dimensional space, have the one dimension size at least in the 1nm-100nm scope, through the Calci-Mix nanoparticle of surface modification coating.
4. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that by circulating single stepping, in the calcium hydroxide aqeous suspension and the coating aqueous solution or emulsion adding bubble liquid film reactor with requirement, starting bubble cap dish type agitator, feed carbon dioxide, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry enters recirculating still, and by recycle pump reacting slurry is returned bubble liquid film reactor, carburizing reagent is carried out in circulation, during the whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor continuously, is 7 up to the pH of reacting slurry value, stop to feed carbon dioxide, till the pH value of reacting slurry does not rise, make Calci-Mix nanoparticle mineralized froth, through ageing, separate, after the drying, make the loose type powder or the block of Calci-Mix nanoparticle, as required, carrying out secondary before separation or after separating coats, repeatedly coat, or add other auxiliary agent.
5. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that by circulating two steps operation, the calcium hydroxide aqeous suspension of requirement is added in the bubble liquid film reactor, starting bubble cap dish type agitator, feed carbon dioxide, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry enters recirculating still, and reacting slurry is returned bubble liquid film reactor by recycle pump, carburizing reagent is carried out in circulation, during the whole carburizing reagent, carbon dioxide feeds bubble liquid film reactor continuously, after certain hour is carried out in carburizing reagent, or after the pH value reaches desired value, promptly prepare calcium carbonate nano particle earlier, the coating aqueous solution or emulsion with requirement adds bubble liquid film reactor again, continue to stir, carry out original position and coat, generate Calci-Mix nanoparticle mineralized froth, through ageing, after separation and the drying, make loose type powder of Calci-Mix nanoparticle or block, as required, carrying out secondary before separation or after separating coats, repeatedly coat, or add other auxiliary agent.
6. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that, by the continous way operation, several bubble liquid film reactors are together in series, with the calcium hydroxide aqeous suspension, the coating aqueous solution or emulsion and carbon dioxide and stream add in first bubble liquid film reactor, starting bubble cap dish type agitator, form air bubble liquid-membrane, carry out carburizing reagent, reacting slurry and carbon dioxide also flow to into second bubble liquid film reactor, carry out carburizing reagent, go on according to this, reach desired value up to the pH of reacting slurry value, stop to feed carbon dioxide, till the pH value does not rise, make Calci-Mix nanoparticle mineralized froth continuously, through ageing, after separation and the drying, make loose type powder of Calci-Mix nanoparticle or block; The coating aqueous solution or emulsion do not add from first bubble liquid film reactor, but from second bubble liquid film reactor, or later any one or several bubble liquid film reactor, add with carbon dioxide and stream, perhaps the coating aqueous solution or emulsion and carbon dioxide and stream add in each bubble liquid film reactor that is together in series: as required, carry out secondary before separation or after separating and coat, repeatedly coat, or add other auxiliary agent.
7. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that changing rotating speed, material concentration and the reaction conditions etc. of the rotating-disk of bubble cap dish type agitator, make the loose type powder or the block of lime carbonate submicron particle or capsule submicron particle, lime carbonate micron particle or capsule micron particle.
8. preparation of calcium carbonate nano particle material by air bubble liquid film process according to claim 1, it is characterized in that bubble liquid film reactor is by bubble cap dish type mixing component, reaction vessel assembly, metering pump assembly, flow meter assembly, pH meter assembly, support and casing, and the electrical accessorie that needs is formed, several bubble liquid film reactors can be together in series, constitute the tandem bubble liquid film reactor.
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