CN101565564B - SiO2 enveloped spherical nanometer calcium carbonate and preparation method thereof - Google Patents
SiO2 enveloped spherical nanometer calcium carbonate and preparation method thereof Download PDFInfo
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- CN101565564B CN101565564B CN2009100746374A CN200910074637A CN101565564B CN 101565564 B CN101565564 B CN 101565564B CN 2009100746374 A CN2009100746374 A CN 2009100746374A CN 200910074637 A CN200910074637 A CN 200910074637A CN 101565564 B CN101565564 B CN 101565564B
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- calcium carbonate
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- nanometer calcium
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Abstract
The invention provides a SiO2 enveloped spherical nanometer calcium carbonate which is enveloped with a SiO2 envelope with the weight of 0.34 percent to 11.7 percent of that of calcium carbonate. A preparation method comprises the following steps of: A. taking calcium oxide and adding 5 times of water for digestion at the temperature of 60 DEG C, allowing the calcium oxide solution to stand for 45 minutes and adding water to dilute the solution to an appropriate concentration for preparing Ca(OH)2 suspending liquid, and then removing the impurities by filtration with a 325-mesh sieve, and placing the suspending liquid into a carburizing reaction container; B. before carbonation, quantitatively adding sodium silicate or potassium silicate solution with 2.2 to 3.5 of modulus, the weight of which is 5 percent to 15 percent of that of calcium carbonate, into the Ca(OH)2 suspending liquid, adjusting the temperature to 18 DEG C to 30 DEG C and the concentration of the suspending liquid to 100 to 180 g/L, and mixing the suspending liquid for 10 minutes to 30 minutes on the stirring condition; and C. conducting carburizing reaction in a tower, and obtaining spherical nanometer calcium carbonate particles with the diameter of 60nm to 100nm when being carburized till the pH of calcium carbonate slurry is 7.5. The invention takes the calcium oxide as raw materials and takes cheap sodium silicate (Na2O.nSiO2) or potassium silicate (K2O.nSiO2) as crystal control agent and coating agent, adds the sodium silicate or the potassium silicate into the Ca(OH)2 suspending liquid for playing a role of crystal orientation, and reduces the cohesive force between the calcium carbonate molecules, thereby forming the modified SiO2 enveloped spherical nanometer calcium carbonate.
Description
Technical field
The present invention relates to a kind of SiO
2The spherical nanometer calcium carbonate of coating and preparation method belong to the inorganic nano material preparing technical field.
Background technology
Nano-calcium carbonate is as a kind of novel industrial chemicals, and the quality of its function depends primarily on the parameters such as chemical constitution, shape characteristic, particle distribution form and dispersing property of product, wherein the most important thing is the crystalline form and the size-grade distribution of particle.The Nano particles of calcium carbonate of different crystal forms, its Application Areas is different with function.At present, domestic nano-calcium carbonate calcium product is many is main with the cubes crystalline form.Working method generally adopts the carbonization at low temperature method; Promptly adopting refrigerator control carbonization starting temperature is 15 ℃-18 ℃; Simultaneously under the effect of crystal control agent; Be no more than 35 ℃ through the omnidistance temperature of cooling water circulation control carbonization, the carbonization terminal point can obtain the nano-calcium carbonate cubes crystallization of particle diameter less than 100 nanometers.
Spherical nanometer calcium carbonate then is different from this.Usually, spherical nanometer calcium carbonate is to adopt the metathesis process preparation and get, and promptly in concentrated alkali solution, keeps coldcondition, reacts and then obtains the spherical nanometer calcium carbonate crystalline particle with calcium salt and carbonate, and reaction formula is Ca (NO
3)
2+ (NH
4)
2CO
3→ CaCO
3+ 2NH
4NO
3, but this product processes requires harshness, and product is stable poor, realizes comparatively difficulty of industrialization degree.Chinese patent CN101074106A discloses a kind of preparation method of high-purity spherical nano-calcium carbonate; This method is to be the calcium source with calcium chloride; And be cleaner with the mixture of calcium hydroxide and SEPIGEL 305, directly react, and carry out bubbling carbonizing pure carbon dioxide and be prepared from sodium hydroxide.Chinese patent CN1462776A discloses a kind of micron nano combined lime carbonate of spheroplast and preparation method thereof; This method be with the styrene-propene acid copolymer that contains Nano particles of calcium carbonate under the latter's chemical action, Nano particles of calcium carbonate is flocked together forms the micron order macrobead.Chinese patent CN1429772A discloses the method that a kind of preparation has the lime carbonate of concrete form; This method is under the rotating bed super gravity field condition, and regulating carbonation reaction temperature is 30 ℃, rotating bed rotating speed 1440rpm; With calcium hydroxide and mol ratio with respect to calcium hydroxide is that 0.05 ammoniacal liquor mixes and adds stirring tank; When the pH value of reaction mixture is 8.5, stop carbonization, can obtain having the calcium carbonate particles of spherical morphology.Problems such as but above-mentioned these methods all exist complex manufacturing, and facility investment is big, and product cost is high, and production efficiency is low.Chinese patent 200810222650.5 discloses " a kind of preparation method of composite calcium carbonate particle ", adopts the water glass hydrolysis to form SiO on the lime carbonate surface
2Coating is in the hope of the preparation modified calcium carbonate.
Summary of the invention
The object of the present invention is to provide a kind of SiO
2The spherical nanometer calcium carbonate of coating and preparation method in the hope of the crystal habit of control Nano particles of calcium carbonate, avoid the reunion between the particle, improve its dispersiveness, rheological, introduce SiO simultaneously
2Coating lime carbonate is to improve the product over-all properties and to meet the need of market.
The objective of the invention is to realize like this: this SiO
2The spherical nanometer calcium carbonate of coating, its characteristic comprises: the outer SiO that coats with respect to weight of calcium carbonate 0.34%-11.7% of spherical nanometer calcium carbonate
2Coating.
Described SiO
2The preparation method of the spherical nanometer calcium carbonate of coating, its characteristic comprises the steps:
A, get quicklime and add 5 times of water 60 ℃ of down digestion, put 45 minutes only after, add water to convert degree Beaume to 6-15, be prepared into Ca (OH)
2Suspension-s through 325 mesh sieve filtering and impurity removings, places in the carburizing reagent container;
B, before carbonization begins, water glass or the potassium silicate solution of modulus 2.2-3.5 quantitatively joined Ca (OH) by relative weight of calcium carbonate 5%-15%
2In the suspension-s, 18 ℃-30 ℃ of adjustment temperature, suspension concentration 100-180 grams per liter, agitation condition mixed 10-30 minute down;
C, Shang Ta carry out carbonation reaction, and during carbonization to lime carbonate slip PH7.5, can obtain particle diameter is the spherical nanometer calcium carbonate particle of 60-100nm.
Described SiO
2The preparation method of the spherical nanometer calcium carbonate of coating, step C feed CO under agitation condition
2Mixed gas, CO
2Source of the gas adopts cylinder gas, with air as diluents, through the mixed CO of gas mixing chamber
2Concentration is 30-35%, with Ca (OH)
2Carbonation reaction is carried out in contact.
Described SiO
2The preparation method of the spherical nanometer calcium carbonate of coating; Step C is at carbonation reaction during near terminal point; The sodium silicate solution of getting again with respect to weight of calcium carbonate 1%-5% quantitatively adds, and continues carbonization 15-30 minute, can obtain the spherical nanometer calcium carbonate particle of 40-80nm.
The present invention is a raw material with the quicklime of cheapness, adopts preparation method---sodium silicate (water glass, the Na of innovation
2OnSiO
2, be commonly called as water glass or bubble flower alkali) or potash water glass (potassium silicate, K
2OnSiO
2) as crystal control agent double as filming agent, add Ca (OH) to
2In the suspension-s, play the crystalline form guide effect.SiO of the present invention
2The spherical nanometer calcium carbonate of coating has following characteristics:
1, in Any shape, spheroidal particle has minimum specific surface area, therefore in organic resin, can increase the loading level of nano-calcium carbonate, that is correspondingly reduce the consumption of organic resin, reduces the finished product production cost.
2, different with erose particle, the spheroidal particle good dispersivity makes spheroidal particle in infill system, demonstrate lower viscosity, good mobility.
3, the particle of globosity is easy to be filled in the space of resin or other packing material, makes plastics processing fluidity and any surface finish property improve greatly;
4, the accumulation form of spheroidal particle has air permeability and good, is filled in the products such as sanitary napkin, baby's diaper, can increase the ventilation property of product.
5, oil-absorption(number) is low---and spherical surface has lower oil number.
Description of drawings
Fig. 1, Fig. 2 are the SEM photos of gained sample, and SiO of the present invention is described
2The spherical calcium carbonate of coating is a nano level.
Embodiment
Embodiment 1:
Get quicklime 15g, after digesting under 60 ℃, putting 45 minutes only, add water to convert to suitable concentration with 5 times of water; Through 325 mesh sieve filtering and impurity removings, place in the carburizing reagent container, be cooled to 20 ℃; The adding modulus is 2.6 sodium silicate solution 2.5 grams, and agitation condition feeds CO down
2Mixed gas (CO
2Source of the gas adopts cylinder gas, with air as diluents, through the mixed CO of gas mixing chamber
2Concentration is 34%, with Ca (OH)
2Carbonation reaction is carried out in contact, and the pH value of carbonization to slurries is 7.5 o'clock, with this dope filtration, drying, obtains 21 gram nano-calcium carbonate dry powder.Detect through the SEM sem, the median size of calcium carbonate crystal body is 50nm, and crystalline form is spherical, as shown in Figure 1.
Embodiment 2:
Concrete grammar is with embodiment 1, and the crystal control agent that is added is a potash water glass, and the nano-calcium carbonate dry powder that obtains detects through the SEM sem, and median size is 50nm, and crystalline form is spherical.
Embodiment 3:
Get quicklime 1.2kg, after digesting under 60 ℃, putting 45 minutes only, add water to convert, be prepared into Ca (OH) to suitable concentration with 5 times of water
2Suspension-s through 325 mesh sieve filtering and impurity removings, places in the carburizing reagent container.This carburizing reagent container is-the stainless steel reaction device of jacketed, feed water coolant in the chuck, and initial carbonization temperature is reduced to 28 ℃, add modulus and be 2.8 sodium silicate solution 0.15kg, agitation condition feeds CO down
2Mixed gas and Ca (OH)
2Carbonation reaction is carried out in contact, and the pH value of carbonization to slurries is 7.5 o'clock, with this dope filtration, drying, obtains 1.44kg nano-calcium carbonate dry powder.Detect through the SEM scanning electron microscope, the median size of calcium carbonate crystal body is 60nm, and crystalline form is spherical.
Embodiment 4:
With 5 times of postdigestive CaO of water, assorted through filtering, adding water, to be mixed with 7 degree Beaume, temperature be 30 ℃ Ca (OH)
2Suspension-s 10m
3, squeeze into pump in the carbonation reaction container of jacketed of 5 meters of height, 2 meters of diameters, it is 3.4 sodium silicate solution 12kg that agitation condition adds modulus down, with air with the CO in the limestone kiln
2Mixed gas is compressed in the carburizing reagent container, CO in the mixed gas
2Concentration be 30%, the compressor wind flow is 24m
3/ min when carbonization closes on terminal point, adds water glass solution 3kg again, to the pH value of lime carbonate slip be 7.5 o'clock, omnidistance reaction finishes.Obtain nano-calcium carbonate dry powder 1240kg.Detect through the SEM scanning electron microscope, the median size of calcium carbonate crystal body is 80nm, and crystalline form is spherical, as shown in Figure 2.
Described in the foregoing description as water glass (the sodium silicate Na of crystal control agent
2OnSiO
2), potassium silicate (potash water glass K
2OnSiO
2) modulus---that is the mol ratio of silicon oxide and alkalimetal oxide.
Listed examples of the present invention is intended to further illustrate this SiO
2The preparation method of the spherical nanometer calcium carbonate of coating and application direction, and protection scope of the present invention is not constituted any restriction.
Claims (3)
1. SiO
2The preparation method of the spherical nanometer calcium carbonate of coating, its characteristic comprises: the outer SiO that coats with respect to weight of calcium carbonate 0.34%-11.7% of spherical nanometer calcium carbonate
2Coating, it is prepared by following steps:
A, get quicklime add 5 times of water 60 ℃ of down digestion, only put 45 minutes after, through 325 mesh sieve filtering and impurity removings, add water to convert degree Beaume to 6-15, place in the carbonation reaction container;
B, before carbonating begins, water glass or the potassium silicate solution of modulus 2.2-3.5 quantitatively joined Ca (OH) by relative weight of calcium carbonate 5%-15%
2In the suspension-s, 18 ℃-30 ℃ of adjustment temperature, suspension concentration 100-180 grams per liter, agitation condition mixed 10-30 minute down;
C, Shang Ta carry out carbonation reaction, and during carbonating to lime carbonate slip pH7.5, can obtain particle diameter is the spherical nanometer calcium carbonate particle of 60-100nm.
2. SiO according to claim 1
2The preparation method of the spherical nanometer calcium carbonate of coating, its characteristic comprises: step C feeds CO under agitation condition
2Mixed gas, CO
2Source of the gas adopts cylinder gas, with air as diluents, through the mixed CO of gas mixing chamber
2Concentration is 30-35%, with Ca (OH)
2Carbonation reaction is carried out in contact.
3. SiO according to claim 1
2The preparation method of the spherical nanometer calcium carbonate of coating; Its characteristic comprises: step C is at carbonation reaction during near terminal point; The sodium silicate solution of getting again with respect to weight of calcium carbonate 1%-5% quantitatively adds, and continues carbonating 15-30 minute, can obtain the spherical nanometer calcium carbonate particle of 40-80nm.
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|---|---|---|---|
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| CN101565564A CN101565564A (en) | 2009-10-28 |
| CN101565564B true CN101565564B (en) | 2012-04-11 |
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|---|---|---|---|---|
| CN106337322A (en) * | 2016-10-11 | 2017-01-18 | 常州市鼎升环保科技有限公司 | Preparation method of coated paper for high-speed inkjet printer |
| CN109232989B (en) * | 2018-10-11 | 2021-03-02 | 河北化工医药职业技术学院 | Preparation method of composite nano calcium carbonate for rubber |
| CN109294280A (en) * | 2018-11-05 | 2019-02-01 | 江苏师范大学 | A kind of low oil absorption calcium carbonate |
| CN114853049B (en) * | 2022-05-30 | 2023-11-03 | 广西华纳新材料股份有限公司 | Preparation method of high-stability nano calcium carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377921A (en) * | 2002-04-05 | 2002-11-06 | 中山大学 | Process for preparing nano CaCO3/SiO2 core-shell structure particle |
| CN101353486A (en) * | 2008-09-19 | 2009-01-28 | 华南师范大学 | Preparation of calcium carbonate complex particle |
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2009
- 2009-06-05 CN CN2009100746374A patent/CN101565564B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377921A (en) * | 2002-04-05 | 2002-11-06 | 中山大学 | Process for preparing nano CaCO3/SiO2 core-shell structure particle |
| CN101353486A (en) * | 2008-09-19 | 2009-01-28 | 华南师范大学 | Preparation of calcium carbonate complex particle |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平8－113727A 1996.05.07 |
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