CN1792803A - Process for preparing high thixotropic nano calcium carbonate - Google Patents
Process for preparing high thixotropic nano calcium carbonate Download PDFInfo
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- CN1792803A CN1792803A CN 200510112372 CN200510112372A CN1792803A CN 1792803 A CN1792803 A CN 1792803A CN 200510112372 CN200510112372 CN 200510112372 CN 200510112372 A CN200510112372 A CN 200510112372A CN 1792803 A CN1792803 A CN 1792803A
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Abstract
A process for preparing the high-thixotropy calcium carbonate nano-particles used for paint or adhesive includes such steps as digestion, carbonizing, coating and drying.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the lime carbonate in chemistry painting industry and adhesive technology field, relate in particular to a kind of preparation method of high thixotropic nano calcium carbonate.
Background technology
Thixotropy is one of important content of dispersion system Research on The Rheology, is meant some systems under stirring or other mechanical effect, the time dependent a kind of rheological phenomena of the viscosity of system or shear force.
Positive thixotropy (Positive thixotropy) is meant that the viscosity of system under the effect of shear force outside descends in time, recovers again after static, promptly has the rare phenomenon of cutting of time factor.
Negative thixotropy is just in time opposite with positive thixotropy, is a kind of thick phenomenon of cutting of time factor that has, and is promptly adding shear force or is cutting under the speed, and the viscosity of system rises, the phenomenon of recovering again after leaving standstill.
Nano-calcium carbonate thixotropy testing method
1. the preparation of sample: accurately take by weighing 175gDOP, 100g nano-calcium carbonate, 10g calcium oxide with 3000r/s high-speed stirring 5 minutes, leave standstill in iron flask;
2. will leave standstill the sample HAARKE VT550 rheometer test of 24h, the variation program of thixotropy test shearing rate is: Os
-1→ (1min rises to) 452s
-1(keeping 5min) → (1min reduces to) Os
-1
According to the long-pending thixotropy that can judge that nano-calcium carbonate DOP sticks with paste of the measured rheology anchor ring of rheometer, the rheology anchor ring is long-pending big more, shows that then the time dependent degree of yield value (or viscosity) of lime carbonate DOP paste is big, illustrates that thixotropy is good more.
Nanometer CaCO
3The thixotropic behavior mechanism of/DOP plastipaste system: from thixotropic property, along with the increase of shearing force, CaCO
3The equilibrium state of network structure is destroyed gradually between particle, and the microtexture form of system changes, and interparticle distance is drawn back, and intergranular reactive force changes attraction into by repulsion.After externally shearing force was eliminated, the intergranular magnetism of pedesis and the coacervate system that makes returned to the plan network structure of stationary state again, but recovery process needs certain hour, thereby made system embody thixotropic behavior.
Nano-calcium carbonate is widely used in coating and adhesive area, nano-calcium carbonate is applied to coating and adhesive industry, thereby the filler effect that plays traditional lime carbonate on the one hand reduces production costs, nano-calcium carbonate is as nano particle on the other hand, and the rheological property that it has has caused scientific research personnel's concern.In association areas such as coating and tackiness agent,, keep not sagging of coating for the workability that improves coating and tackiness agent has good surface appearance after making the construction of coating and tackiness agent simultaneously.In the prescription of coating or tackiness agent, the thixotropic agent of normal use is the white carbon black of gas phase, because the white carbon black of vapor phase process production has good thixotropy, so obtained using widely at coating and adhesive industry; Along with the technology of preparing of nano-calcium carbonate constantly develops, nano-calcium carbonate has had further development in the application of coating and adhesive industry, and nano-calcium carbonate has replaced the expensive white carbon black of part owing to have certain thixotropy in the prescription of coating and tackiness agent.At present, there is the crystal development imperfection in domestic nano-calcium carbonate calcium product, and the deficiency that particle size distribution range is wide causes prepared nano-calcium carbonate powder thixotropy relatively poor or do not have a thixotropy thus.
Because the nano-calcium carbonate good thixotropy and the extensive use that have, the exploitation of its preparation method and product innovation has been subjected to noticing that widely present industrial nano-calcium carbonate mainly is Ca (OH)
2-CO
2-H
2The O system, this reactive system is with Ca (OH)
2The water miscible liquid system is the calcium source, uses CO
2Carbonization obtains CaCO
3Ca (OH)
2Generally be sintered into lime, obtain through digestion then by natural whiting.The flue gas that obtains behind the calcination of calcium carbonate is after filtering as the CO that reacts
2Source of the gas by controlling different reaction conditionss, can obtain the nano-calcium carbonate powder of different crystal forms.Nano-calcium carbonate generally is the reaction of carrying out in stirred reactor, improves mass transfer, the heat-transfer effect of reaction system by stirring, importantly also must carry out strict control to reaction conditions, and main controlling factor has Ca (OH)
2Concentration, CO
2Flow, temperature of reaction, additive amount, additive joining day etc.By controlling different conditions, can access the nano-calcium carbonate of multiple crystalline structure such as sphere, cubes at present.
When but domestic nano-calcium carbonate powder is applied in coating and the tackiness agent at present, exist following problem:
1. prepared nano-calcium carbonate crystal development imperfection can not be prepared the cubes nano-calcium carbonate of complete crystallization;
2. prepared nano-calcium carbonate particle size range is wide;
3. do not find suitable surface-modifying agent, prepared nano-calcium carbonate thixotropy difference or do not have thixotropy.
Summary of the invention
Defective at the thixotropy difference of the nano-calcium carbonate that is applied to coating and adhesive industry at present, the object of the present invention is to provide a kind of preparation method of high thixotropic nano calcium carbonate, prepare that a kind of crystal development is good, particle size distribution range is narrow, have the nano-calcium carbonate of high thixotropic simultaneously.
The technical scheme that realizes objects of the present invention is as follows:
A kind of preparation method of high thixotropic nano calcium carbonate in turn includes the following steps:
(1), natural whiting after cleaning at first the temperature lower calcination at 900-1100 ℃ become CaO, add cold water then and be digested to Ca (OH)
2, be mixed with certain density milk of lime through control digestion water;
(2), milk of lime drops in the reactor, adds the nucleus inhibitor and stir before carburizing reagent, the add-on of nucleus inhibitor is the 0.002%-0.01% of weight of calcium carbonate, the stack gas of calcination of calcium carbonate after purifying as the CO of carbonization
2Source of the gas feeds CO
2React CO
2Volume content between 18%～20%, after form a certain amount of nucleus quantity, add the growth velocity that the crystalline form conditioning agent is controlled each crystal face in carbonization, crystalline form conditioning agent add-on is the 0.1%-0.8% of weight of calcium carbonate; Continue carbonization to terminal, add dispersion agent again and regulate the calcium carbonate slurry that the particle surface electric charge obtains good dispersity, the starting temperature of solution is controlled at 18-40 ℃ in the reaction process, when the PH of molten stream is neutrality, stopped reaction, the reaction times was about about 1.5-2.2 hour;
(3), adding coating after reaction finishes coats: coating is configured to the aqueous solution, is warmed up to 70～90 ℃, get covering liquid lime carbonate is coated; Described coating is compound coating: Ca (ST)
2: NaST=1: 2-1: 1 (weight percent), the amount of coating are 2.5～3.5% of nano-calcium carbonate weight, and the coating time is 15～30 minutes;
(4), the lime carbonate after coating is carried out press filtration, drying, high thixotropic nano calcium carbonate.
The lime milk concentration of wherein said step (1) is controlled at 110～115g/l.
Wherein the nucleus inhibitor described in the step (2) is citric acid, lactic acid.
Wherein crystalline form conditioning agent described in the step (2) is a kind of in lactic acid, the sulfuric acid or the mixture of the two.
Wherein dispersion agent described in the step (2) is dodecyl triethyl amine bromide (C
12S) and sodium lauryl sulphate (SDS), its thixotroping compositional range zone is C
12S: DS=1: 1-1: 2 ratio, and SDS is excessive; Or hydro-polyacrylamide (PHPA).
Coating in the wherein said step (3) is hard ester acid, NaOH, Ca (OH)
2Saponification forms.
The preparation feedback equation of nano-calcium carbonate is as follows:
Processing parameter of the present invention:
1. raw material: Wingdale, calcium carbonate content are greater than 98%, and whiteness is greater than 92%;
2. digest water: tap water;
3. the kiln gas of calcination of calcium carbonate: need to remove impurity and dust in the kiln gas, the CO after the purification through three sections purifications
2Gas participates in carburizing reagent after entering air compressor machine;
4. Ca (OH)
2Emulsion concentration is controlled at about 110～115g/l;
5. reacting initial temperature is controlled at 18--40 ℃;
6. CO in the kiln gas
2Content between 18%～20%; Surface charge and sterically hindered conditioning agent (dispersion agent): dodecyl triethyl amine bromide (C
12NE) and sodium lauryl sulphate (C
12S or SDS), its thixotroping compositional range zone is C
12S: SDS=1: 1-1: 2 ratio, and SDS is excessive; The mixing total concn of the two, i.e. C
Tot/ moldm
-3, be 0.05/moldm
-3, ratio is 1: 1.5; Hydro-polyacrylamide (PHPA), add-on 0.05%.
7. stirring velocity: 400-1000RPM
The final product quality that obtains is: crystalline form is a cubes, particle diameter 60-90nm, oil-absorption(number)＜35gDop/100gCaCO
3, the rheology anchor ring amasss＞70000Pa/s.
The present invention adopts special carbonization technique and additive to adopt special coating and technology, technological operation control intermittent type simple, that be easy to transform stirs carborization, prepare that a kind of crystal development is good, particle size distribution range is narrow, have the nano-calcium carbonate of high thixotropic simultaneously.This nano-calcium carbonate is applied to coating and adhesive industry, can replace the white carbon black of vapor phase process to use as thixotropic agent fully.
The present invention compares with the production technology of other nano-calcium carbonates, has following outstanding feature:
1. crystalline form is complete cubes crystalline form, and crystal development is perfect;
2. nano-calcium carbonate crystalline narrow diameter distribution is 60-90nm;
3. prepared nano-calcium carbonate powder is applied to have good thixotropy in the pvc plastisol, can replace expensive white carbon black to improve the thixotropic property of tackiness agent fully.
Description of drawings
The nano-calcium carbonate crystal TEM photo that Fig. 1 makes for the embodiment of the invention 1;
The Ma Erwen particle size distribution figure of the nano-calcium carbonate that Fig. 2 makes for inventive embodiments 1 of the present invention.
Embodiment
How further specify the present invention below in conjunction with specific embodiment realizes:
Embodiment 1
At 2m
3Reactor in add 0.8m
3Concentration is the calcium hydroxide slurry of 4% (weight concentration, being converted into calcium carbonate content concentration is 56g/l), and reacting initial temperature is controlled at 18 ℃, adds the 3.36g citric acid and stir before the reaction beginning, feeds CO then
2Content is that the kiln gas of 25% (volumetric concentration) carries out carbonization, and the kiln gas flow is 7.5m
3/ h adds 224g lactic acid behind the carbonization 0.5h, continuing carbonization to pH value again is 7, adds 0.016molC then
12S and 0.024molSDS stir 0.5h, obtain homodisperse nano-calcium carbonate slurry.
The saponification in 85 ℃ water with 1254g stearic acid and 164g dissolution of sodium hydroxide, wait pH value stable after, add 77g calcium hydroxide and continue saponification 1 hour, make covering liquid, add then in the carbonization slurry, the coating time is 30 minutes.Press filtration, drying obtain nano-powder.
Obtained powder test result sees Table one:
Table one
| Sample number into spectrum | Yield value (Pa) | Viscosity (Pas) | Rheology anchor ring long-pending (* 10 4pa/s) |
| 1 | 154 | 0.56 | 8.97 |
Crystal morphology as shown in Figure 1, the Ma Erwen size-grade distribution is as shown in Figure 2.
Embodiment 2
At 2m
3Reactor in add 0.8m
3Concentration is the calcium hydroxide slurry of 4% (weight concentration, being converted into calcium carbonate content concentration is 56g/l), and reacting initial temperature is controlled at 25 ℃, adds the 3.36g citric acid and stir before the reaction beginning, feeds CO then
2Content is that the kiln gas of 17% (volumetric concentration) carries out carbonization, and the kiln gas flow is 10m
3/ h adds 224g sulfuric acid behind the carbonization 0.5h, continuing carbonization to pH value again is 7, adds 0.016molC then
12S and 0.024molSDS stir 0.5h, obtain homodisperse nano-calcium carbonate slurry.
The saponification in 85 ℃ water with 1254g stearic acid and 164g dissolution of sodium hydroxide, wait pH value stable after, add 77g calcium hydroxide and continue saponification 1 hour, make covering liquid, add then in the carbonization slurry, the coating time is 30 minutes.Press filtration, drying obtain nano-powder.
Obtained powder B sample test result:
| Sample number into spectrum | Yield value (Pa) | Viscosity (Pas) | Rheology anchor ring long-pending (* 10 4Pa/s) |
| 2 | 198 | 0.55 | 9.08 |
Embodiment 3
At 2m
3Reactor in add 0.8m
3Concentration is the calcium hydroxide slurry of 4% (weight concentration, being converted into calcium carbonate content concentration is 56g/l), and reacting initial temperature is controlled at 40 ℃, adds the 3.36g citric acid and stir before the reaction beginning, feeds CO then
2Content is that the kiln gas of 17% (volumetric concentration) carries out carbonization, and the kiln gas flow is 7.5m
3/ h adds 224g sulfuric acid behind the carbonization 0.5h, continuing carbonization to pH value again is 7, adds 22.4g hydro-polyacrylamide (PHPA) then, stirs 0.5h, obtains homodisperse nano-calcium carbonate slurry.
The saponification in 85 ℃ water with 1254g stearic acid and 164g dissolution of sodium hydroxide, wait pH value stable after, add 77g calcium hydroxide and continue saponification 1 hour, make covering liquid, add then in the carbonization slurry, the coating time is 30 minutes.Press filtration, drying obtain nano-powder.
Obtained powder B sample test result:
| Sample number into spectrum | Yield value | Viscosity | The rheology anchor ring is long-pending |
| (Pa) | (Pa·s) | (×10 4Pa/s) | |
| 3 | 221 | 0.49 | 8.83 |
Claims (6)
1, a kind of preparation method of high thixotropic nano calcium carbonate in turn includes the following steps:
(1), the natural whiting high-temperature calcination becomes CaO, add cold water then and be digested to Ca (OH)
2, be mixed with certain density milk of lime through control digestion water;
(2), milk of lime drops in the reactor, adds the nucleus inhibitor and stir before carburizing reagent, the add-on of nucleus inhibitor is the 0.002%-0.01% of weight of calcium carbonate, feeds CO
2React, after form a certain amount of nucleus quantity, add the growth velocity that the crystalline form conditioning agent is controlled each crystal face in carbonization, crystalline form conditioning agent add-on is the 0.1%-0.8% of weight of calcium carbonate; Continue carbonization to terminal, add dispersion agent again and regulate the calcium carbonate slurry that the particle surface electric charge obtains good dispersity, the starting temperature of solution is controlled at 18-40 ℃ in the reaction process, when the PH of molten stream is neutrality, and stopped reaction, the reaction times is about 1.5-2.2 hour;
(3), adding coating after reaction finishes coats: coating is configured to the aqueous solution, is warmed up to 70～90 ℃, get covering liquid lime carbonate is coated; Described coating is compound coating: the two weight percent is: Ca (ST)
2: NaST=1: 2-1: 1, the amount of coating is 2.5～3.5% of a nano-calcium carbonate weight, the coating time is 15～30 minutes;
(4), the lime carbonate after coating is carried out press filtration, drying, high thixotropic nano calcium carbonate.2, the preparation method of a kind of high thixotropic nano calcium carbonate according to claim 1 is characterized in that: the CO of the stack gas of calcination of calcium carbonate conduct (2) step carbonization after purifying in described (1) step
2Source of the gas, CO
2Volume content between 18%～20%.
3, the preparation method of a kind of high thixotropic nano calcium carbonate according to claim 1 is characterized in that: the lime milk concentration of wherein said step (1) is controlled at 110～115g/l.
4, the preparation method of a kind of high thixotropic nano calcium carbonate according to claim 1 is characterized in that: the nucleus inhibitor described in the step (2) is a kind of in citric acid, the lactic acid or the mixture of the two.
5, the preparation method of a kind of high thixotropic nano calcium carbonate according to claim 1 is characterized in that: crystalline form conditioning agent described in the step (2) is a kind of in lactic acid, the sulfuric acid or the mixture of the two.
6, the preparation method of a kind of high thixotropic nano calcium carbonate according to claim 1, it is characterized in that: dispersion agent is dodecyl triethyl amine bromide and sodium lauryl sulphate described in the step (2), its thixotroping compositional range zone is a dodecyl triethyl amine bromide: sodium lauryl sulphate=1: 1-1: 2 ratio, and sodium lauryl sulphate is excessive.
7, the preparation method of a kind of high thixotropic nano calcium carbonate according to claim 1 is characterized in that: the coating in the described step (3) is hard ester acid, NaOH, Ca (OH)
2Saponification forms.
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| CN101967310A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing nano calcium carbonate with low viscosity and medium thixotropic property |
| CN102167915A (en) * | 2011-03-03 | 2011-08-31 | 淄博嘉泽纳米材料有限公司 | Preparation method of medium/low-viscosity high-thixotropy nano calcium carbonate for aqueous system |
| CN102732065A (en) * | 2011-04-15 | 2012-10-17 | 池州凯尔特纳米科技有限公司 | Preparation method of PVC special-purpose functional filler superfine active calcium carbonate with low oil absorption |
| CN104098928A (en) * | 2014-03-17 | 2014-10-15 | 福建省万旗非金属材料有限公司 | Preparation method and thixotropy test method of nano calcium carbonate with negative thixotropy |
| CN105217673A (en) * | 2015-10-21 | 2016-01-06 | 常山县南方碳酸钙有限公司 | A kind of preparation method of high thixotropic silicone adhesive special-purpose nanometer activated Calcium carbonate |
| CN105329928A (en) * | 2015-12-10 | 2016-02-17 | 湖南化工职业技术学院 | Activation method for nanometer calcium carbonate |
| CN106458624A (en) * | 2014-04-30 | 2017-02-22 | 欧米亚国际集团 | Production of precipitated calcium carbonate |
| CN109399683A (en) * | 2018-12-06 | 2019-03-01 | 东北大学 | A kind of preparation method of PVC automobile bottom gluing surrender enhancing nanometer calcium carbonate |
| CN110028093A (en) * | 2018-07-31 | 2019-07-19 | 荆门市东宝区凯龙矿业股份有限公司 | A kind of preparation and detection method of antithixotropy nanometer calcium carbonate |
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| CN1085188A (en) * | 1992-09-29 | 1994-04-13 | 李维家 | Industrial smoke is used to produce light calcium carbonate and calcium chloride technology |
| CN1375456A (en) * | 2002-02-07 | 2002-10-23 | 上海建筑材料集团新材料有限公司 | Nano level active calcium carbonate for special use |
| CN100455515C (en) * | 2003-12-24 | 2009-01-28 | 上海华明高技术（集团）有限公司 | Method for preparing nano calcium carbonate particle |
| CN1256280C (en) * | 2004-03-12 | 2006-05-17 | 浙江大学 | Process for water heat synthesis of nano grade cubic calcium carbonate |
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| CN101967310A (en) * | 2010-07-14 | 2011-02-09 | 山东海泽纳米材料有限公司 | Method for preparing nano calcium carbonate with low viscosity and medium thixotropic property |
| CN102167915A (en) * | 2011-03-03 | 2011-08-31 | 淄博嘉泽纳米材料有限公司 | Preparation method of medium/low-viscosity high-thixotropy nano calcium carbonate for aqueous system |
| CN102167915B (en) * | 2011-03-03 | 2013-04-17 | 淄博嘉泽纳米材料有限公司 | Preparation method of medium/low-viscosity high-thixotropy nano calcium carbonate for aqueous system |
| CN102732065A (en) * | 2011-04-15 | 2012-10-17 | 池州凯尔特纳米科技有限公司 | Preparation method of PVC special-purpose functional filler superfine active calcium carbonate with low oil absorption |
| CN104098928A (en) * | 2014-03-17 | 2014-10-15 | 福建省万旗非金属材料有限公司 | Preparation method and thixotropy test method of nano calcium carbonate with negative thixotropy |
| CN104098928B (en) * | 2014-03-17 | 2016-08-17 | 福建省万旗非金属材料有限公司 | The preparation method of a kind of nano-calcium carbonate with negative thixotroping and thixotropy method of testing thereof |
| CN106458624A (en) * | 2014-04-30 | 2017-02-22 | 欧米亚国际集团 | Production of precipitated calcium carbonate |
| CN105217673A (en) * | 2015-10-21 | 2016-01-06 | 常山县南方碳酸钙有限公司 | A kind of preparation method of high thixotropic silicone adhesive special-purpose nanometer activated Calcium carbonate |
| CN105329928A (en) * | 2015-12-10 | 2016-02-17 | 湖南化工职业技术学院 | Activation method for nanometer calcium carbonate |
| CN110028093A (en) * | 2018-07-31 | 2019-07-19 | 荆门市东宝区凯龙矿业股份有限公司 | A kind of preparation and detection method of antithixotropy nanometer calcium carbonate |
| CN110028093B (en) * | 2018-07-31 | 2021-07-20 | 荆门市东宝区凯龙矿业股份有限公司 | Preparation and detection method of inverse thixotropic nano calcium carbonate |
| CN109399683A (en) * | 2018-12-06 | 2019-03-01 | 东北大学 | A kind of preparation method of PVC automobile bottom gluing surrender enhancing nanometer calcium carbonate |
| CN109399683B (en) * | 2018-12-06 | 2020-12-01 | 东北大学 | Preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer |
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