CN101117232A - Preparation of calcium carbonate nano particle material by air bubble liquid film process - Google Patents
Preparation of calcium carbonate nano particle material by air bubble liquid film process Download PDFInfo
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Abstract
The invention relates to a bubble liquid membrane method which prepares the material of calcium carbonate nanoparticle, belonging to the chemical nanometer material manufacture. The invention is processed in the bubble liquid membrane reactor. The process is as follows: calcium hydroxide aqueous suspension and carbon dioxide gas are used as the raw material; carboxylate aqueous solution is used as the coating agent; by using the gas strong dispersion function of the stirrer with bubble cap dish type, the adequate amount carbon dioxide bubble is obtained All calcium hydroxide aqueous suspension and carboxylate aqueous solution are separated into the liquid membrane which is thin enough by the bubble; the bubble is dispersed phase, the liquid membrane is continuous phase, the nanometer reaction environment is obtained, the interface between carbon dioxide and calcium hydroxide is significantly increased, and the mass and heat transfer is strengthened. Between the liquid membrane and the bubble or in the liquid membrane, the reactant carbonation reacts, nucleates and grows to obtain calcium carbonate nanoparticle, and then after the in-situ coating, calcium carbonate capsule nanoparticle is obtained. The surface of calcium carbonate capsule nanoparticle absorbs the massive gas to form the atmosphere interface which restrains conglobation, the mineralized vacuolar membrane is formed, after the mineralized vacuolar membrane is filtered and dried, calcium carbonate capsule nanoparticle powder material is formed.
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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| CN112591780B (en) * | 2020-12-02 | 2023-07-14 | 成都理工大学 | Preparation method of braided calcium carbonate |
| CN113896224A (en) * | 2021-09-24 | 2022-01-07 | 兰州兰石中科纳米科技有限公司 | Preparation method of nano zinc sulfide and nano barium sulfate |
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| CN115286028A (en) * | 2022-05-12 | 2022-11-04 | 四川大学 | Preparation method and device for synthesizing high-dispersion nano calcium carbonate without using additive |
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