CN107697940B - A kind of preparation method of nano combined superfine heavy calcium carbonate - Google Patents

A kind of preparation method of nano combined superfine heavy calcium carbonate Download PDF

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CN107697940B
CN107697940B CN201711025602.2A CN201711025602A CN107697940B CN 107697940 B CN107697940 B CN 107697940B CN 201711025602 A CN201711025602 A CN 201711025602A CN 107697940 B CN107697940 B CN 107697940B
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calcium carbonate
heavy calcium
nano combined
superfine heavy
slurry
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CN107697940A (en
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吕国章
杨芮平
李娟娟
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Shanxi Xintai Hengxin Nano Materials Technology Co Ltd
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The present invention is a kind of preparation method of nano combined superfine heavy calcium carbonate, solves nanometer calcium carbonate applied to other field oil absorption height, water imbibition height, the problems such as flowing and squeeze out difference.Present invention process, using series connection supergravity reactor advantage, prepares nano combined ultrafine heavy calcium using ultra-fine wet lapping coarse whiting as base core, while using supercritical CO2Fluid low temperature drying guarantees that the nanoparticle of superfine heavy calcium carbonate adsorption is not reunited coalescence.Nano combined ultrafine heavy calcium partial size made from the method for the present invention is small, BET is big, viscosity and thixotroping are good, reunites less, even particle size distribution, easily dispersion, and hydrophilic oil absorption is small in, flowing and extrudability good.

Description

A kind of preparation method of nano combined superfine heavy calcium carbonate
Technical field
The present invention relates to nanometer calcium carbonate preparation technical field, the system of specifically a kind of nano combined superfine heavy calcium carbonate Preparation Method.
Background technique
Nanometer calcium carbonate refers to particle size in the calcium carbonate superfine powder of 1-100nm, and nanometer calcium carbonate is since size is small, crystal Structure and Electronic Structure are changed, and are had small-size effect, quantum size effect, skin effect etc., are being applied In there is the advantages that viscosity is high, thixotroping is good, big with organic matter contact area, blending is good, the disadvantage is that size is small, specific surface area Greatly, difficult dispersion, oil absorption are big in, though existing various bonus point powder and Wet-dry method are modified, but still it is inevitable The secondary agglomeration that can not be reversed occurs in carbonization, drying process for ground, its application performance is made to have a greatly reduced quality.
Coarse whiting is usually made with mechanical lappings such as marble, lime stone, calcite, chalk, shells, there is dry method and wet Two kinds of method.Dry method product granularity is relatively thick, and dry method mainly produces the following product of 2500 mesh, generally have 400 mesh, 600 mesh, 800 mesh, 1250 mesh etc., broad particle distribution, Cheng Shuanfeng or multi-modal, how unsetting product is, and has obvious corner angle；Wet process Grinding production coarse whiting is superfine heavy calcium carbonate mostly more than 2500 mesh, and for D90 at 2 μm or more, granularity cloth degree is relatively narrow, in single Peak or bimodal morphology distribution, wet grinding coarse whiting are generally spherical or class ball due to grinding environment and force way difference, particle Shape.Coarse whiting product is since its is from a wealth of sources, production cost is low, cheap, with whiteness is high, oil absorption is low, dispersion in The advantages that good, the industries such as rubber, plastics, papermaking, coating, ink, daily use chemicals be widely applied, but due to its viscosity is low, without thixotroping Property, with organic substance binding force it is poor the disadvantages of, packing material can only be done, cannot function as functional material.
Summary of the invention
The purpose of the present invention is to solve above-mentioned problems of the prior art, and provide a kind of nano combined ultra-fine The preparation method of powdered whiting.
The present invention is achieved through the following technical solutions:
A kind of preparation method of nano combined superfine heavy calcium carbonate, includes the following steps:
(1) it is digested after taking calcium oxide decontamination, obtaining concentration is 15-30%, activity degree≤1min Ca (OH)2Suspension, Still aging 16-72h separates decontamination, finally obtains the Ca (OH) that concentration is 5-10%2It refining suspension and can not digest Lime lithophysa；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes D95≤2 μm Ultrafine heavy calcium slurry, crystalline form is spherical or spherical, and is 10-20% by obtained ultrafine heavy calcium pulp dilution to concentration；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) are simultaneously It is mixed in mass ratio for 5-10:1, is then pumped into hypergravity and answers in device I, and answered in device I to hypergravity and be passed through volumetric concentration For the CO of 50-80%2Gas controls CO2Gas flow is 100-150m3/ h, carbonation reaction temperature are 10-15 DEG C, react 5- Crystalline form promotor is added in 10min later, recycles at least 1min；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is led into supergravity reactor II Enter the CO that volumetric concentration is 40-50%2Gas controls CO2The flow of gas is 80-120m3/ h, carburizing temperature are 15-20 DEG C, after Continuous reaction 10-20min, anion and nonionic mixed dispersant are added later, recycles at least 1min；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is led into supergravity reactor III Enter the CO that volumetric concentration is 20-40%2Gas controls CO2Gas flow is 40-60m3/ h, carburizing temperature are 20-40 DEG C, are continued React to slurry pH=7-8 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 40%-50%, is put Enter supercritical CO2In fluid means, cyclic drying, so that material activating degree is up to 100%, water content≤0.5% unloads that be depressed into room temperature normal Pressure, then broken through Cyclone mill, is crushed classification in 25-35Hz, and temperature control is at 50-70 DEG C to get arriving nano combined fine heavy Calcium carbonate.
As a preferred technical solution, grinding distribution agent described in step (2) be polycarboxylate sodium's neutral dispersing agent and Polycarboxylate sodium's acidic dispersion agent is mixed in mass ratio with 1:1 ratio, and additional amount presses superfine heavy calcium carbonate butt quality 0.5-1.5% be added.
Crystalline form promotor described in step (3) is saccharin sodium as a preferred technical solution, and additional amount is Ca (OH)2 The 0.2%-0.5% of butt quality.
It is the poly- of 3000-5000 that anionic dispersing agents described in step (3), which are molecular weight, as a preferred technical solution, Sodium acrylate, the non-ionic dispersing agent are hydroxyethyl cellulose, and the two is mixed with arbitrary proportion, and additional amount is Ca (OH)2 The 1.0%-2.0% of butt quality.
As a preferred technical solution, in step (4), in supercritical CO2When dry in fluid means, when dry to moisture When for 5-10%, modifying agent is added, continues cycling through drying, so that material activating degree is 100%, water content≤0.5%.
As a preferred technical solution, in step (4), nano combined superfine heavy calcium carbonate slurry is in supercritical CO2Stream When dry in body device, using first low temperature, again heat up, the drying mode of rear constant temperature, the specially temperature of low temperature drying is 35-45 DEG C, operating pressure 12-20MPa, CO2Charge flow rate is 7-8L/h, when nano combined superfine heavy calcium carbonate slurry water content When being down to 5-10%, modifying agent is added；Heating drying is carried out later, and heating rate is 0.5-1 DEG C/min, operating pressure 10- 15MPa, CO2Charge flow rate is 5-6L/h；When temperature rises to 60-70 DEG C, progress freeze-day with constant temperature, operating pressure 8-12MPa, CO2Charge flow rate is 4-5L/h, so that material activating degree is up to 100%, water content≤0.5%.
The modifying agent is amphiphilic coupling agent, titanate coupling agent, white oil, octanoic acid, the last of the ten Heavenly stems as a preferred technical solution, Acid, palmitic acid, oleic acid, linoleic acid, the three kinds or more in stearic acid are arbitrarily matched and are used in mixed way, and additional amount is multiple for nanometer Close the 2%-5% of superfine heavy calcium carbonate butt quality.
In preparation method of the present invention, in supercritical CO2In fluid means drying process, modifying agent can be added, it can also be with It is added without modifying agent, wherein modifying agent, which is added, to be used in organic material, and it is in inorganic aqueous material that modifying agent, which is not added,.
The principle of the present invention are as follows: carbonization beforehand control low temperature big flow CO2, accelerate carbonization nucleation rate early period, and it is ultra-fine Barrier potential when nanometer calcium carbonate nucleation is effectively reduced in the addition of coarse whiting, and nanometer calcium carbonate is made to be deposited on the table of superfine heavy calcium carbonate Face forms nonhomogen-ous nucleation.Since ultra-fine wet grinding coarse whiting crystalline form is generally spherical or spherical, so finally obtained receive Rice composite superfine powdered whiting is spherical or spherical.Crystalline form promotor is added in the mid-term that is carbonized, and accelerates ultrafine heavy calcium surface and receives The fast reaction of rice corpuscles forms it into uniform physics and chemisorption.Anion and nonionic compounding dispersion are added simultaneously Agent, using Sodium Polyacrylate, dispersion effect is good within the scope of pH6-9, and hydroxyethyl cellulose can make dispersion colloid keep stable excellent Point, dispersion keeps unmodified nano combined superfine heavy calcium carbonate stability under its synergistic effect.It is modified, dry to be faced using super Boundary CO2Cryogenic technique avoids the disadvantage that material heating is modified, particle aggregation, thicker, specific surface area sharply decline in drying process End, maintains the original structure of material and state, prevents the reunion of nano surface particle, to obtain that a kind of partial size is small, granularity Regular, easy dispersion, the high spherical or spherical non-modified or modified Nano composite superfine powdered whiting product squeezed out.
In the step of the method for the present invention (3), carbonization technique is reacted using high-gravity carbonation thtee-stage shiplock, specifically using super Porous channel under gravity environment, it is fast with the gas that is entered by section by reaction liquid tearing at nanoscale film, silk and drop Speed reaction, forms new phase interface, to improve entire reaction process.The small product of partial size is generated, early period is largely quick Nucleation is necessary, so the characteristics of we utilize hypergravity, low temperature, big concentration C O are controlled in reactor I2Gas, fast fast-growing It is adsorbed on ultrafine heavy calcium surface at a large amount of small size nucleus, adds crystalline form promotor, cycle balance；In hypergravity II, control Make lower middle benefit gas concentration C O2Gas promotes particle to generate regular crystalline form, while dispersing agent is added, cycle balance；Into overweight In power III, the small concentration C O of room temperature is controlled2Gas, room temperature slowly release not anti-by the product for partially having package in reaction process The Ca (OH) answered 2Come, then reaction completely, since it joined anion and non-ionic dispersing agent, the nanometer calcium carbonate of regeneration The upper surface of existing particle will not be adsorbed on and formed and reunited, surpassed to obtain small partial size, complete crystal form, the nano combined of fully reacting Thin coarse whiting particle.
In the step of the method for the present invention (4), using the method for supercritical fluid drying, specifically first low temperature heats up, again again The drying means of constant temperature, its advantage is that: first low temperature drying utilizes medium CO2The low feature of supercritical temperature is kept for 35-45 DEG C Temperature range, dissolution takes away surface moisture in product, not will lead to product product when moisture reduces since its temperature is low Surface shrinkage, Microstructure Fracture maintain the characteristic of its nano surface particle；Heat up drying again, this stage, product residual moisture For the strong interior water of bond resultant force, certain dissolution carrying capacity is needed, heating can make the solvability of gas stronger, and at this time Heating not will cause the micro channel formed and collapse or reduce, and only can shorten the product cyclic drying time；Constant temperature again Dry, since the kernel of nano combined ultrafine heavy calcium is ultrafine heavy calcium, moisture easily goes out, and only need to keep constant temperature, gas is allowed to take away most Afterwards while a small amount of moisture, modifying agent is uniformly coated on to the surface of nano combined ultrafine heavy calcium.The product obtained in this way, is answered It is high in conjunction with jail, viscosity with middle first with the characteristic large specific surface area of nanometer calcium carbonate, and can be embodied in placement process ultra-fine heavy Characteristic oil absorption, the hydrophilic amount of calcium are small.
The present invention is the advantage and disadvantage based on nanometer calcium and coarse whiting, and a kind of nano combined superfine heavy calcium carbonate of preparation is got rid of The shortcomings that having abandoned nanometer calcium and coarse whiting, the oil factor with coarse whiting is low, easy dispersion, it is high squeeze out and nanometer calcium, viscosity is high, thixotroping Advantage that is good, mutually having melted with organic matter, becomes a kind of new function material.Coarse whiting used in the present invention is wet grinding coarse whiting, and D95≤2 μm, surface can it is higher, crystal form is more regular, more Lao is solid in conjunction with its nano surface calcium carbonate.Carbonizer in the present invention Skill is reacted using hypergravity thtee-stage shiplock, and it is 10-20nm that nanometer calcium carbonate is adsorbed outside ultrafine heavy calcium.The present invention mainly passes through following Approach is completed: one, nanometer calcium carbonate composite superfine wet lapping coarse whiting, using the spherical or spherical coarse whiting of ultra-fine wet lapping as core, The nanometer calcium carbonate of low temperature fast reaction is shell, forms the structure of nano combined superfine heavy calcium carbonate, since wet lapping is super Thin coarse whiting mesh number is thin, surface have certain surface can, and the not simple physical deposition of combination of nanometer calcium carbonate, There are certain chemisorption, in reaction process, control the growth of differential responses point ultrafine heavy calcium nano surface calcium carbonate with minute Dissipate, make nano combined superfine heavy calcium carbonate surface coating layer more evenly, compound particle is smaller, shape is regular, reunite few； Two, it using the overcritical modification of low temperature and drying, keeps that the nanostructure of product surface is complete, does not destroy, changes simultaneously its surface Property can be directly modified high-moisture or high hydroxyl content powder, be made with the cooperation of middle long chain fatty acids using amphiphilic coupling agent With certain space steric effect while cladding with, long-chain, middle chain covered effect is more preferable.The synergistic effect of above several respects Final nano combined superfine heavy calcium carbonate product cut size can be made small, brilliant diameter is regular, and specific surface area is high, and oil absorption is more in Low, mobility, extrudability, dispersed more preferable, application range is wider.
The method of the present invention solves nanometer calcium carbonate applied to other field oil absorption height, water imbibition height, flowing and extrusion The problems such as poor.Nano combined ultrafine heavy calcium partial size made from the method for the present invention is small, BET is big, viscosity and thixotroping are good, reunites less, grain Degree be evenly distributed, easily disperse, in hydrophilic oil absorption it is small, flowing and it is extrudability good.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, it should be noted that following embodiment It is only used for that the present invention is further described, is not intended to limit protection scope of the present invention.
Embodiment 1
A kind of preparation method of nano combined superfine heavy calcium carbonate, includes the following steps:
(1) it is digested after taking light-burned and middle burning calcium oxide decontamination, obtains the Ca (OH) that concentration is 30%, activity degree is 40s2 Suspension, still aging 72h separate decontamination, finally obtain the Ca (OH) that concentration is 5%2It refining suspension and can not digest Lime lithophysa；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes d95≤2 μm Ultrafine heavy calcium slurry, crystalline form is spherical or spherical, and is 10% by obtained ultrafine heavy calcium pulp dilution to concentration；It is described Grinding distribution agent be that polycarboxylate sodium's neutral dispersing agent and polycarboxylate sodium's acidic dispersion agent 1:1 in mass ratio are mixed, Additional amount is added by the 1.5% of superfine heavy calcium carbonate butt quality；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) are simultaneously It is mixed in mass ratio for 5:1, is then pumped into hypergravity and answers in device I, and answered to hypergravity and to be passed through volumetric concentration in device I and be 80% CO2Gas controls CO2Gas flow is 150m3/ h, carbonation reaction temperature are 10 DEG C, react 5min, crystalline form is added later Promotor recycles at least 1min；The crystalline form promotor is saccharin sodium, and additional amount is Ca (OH)2The 0.5% of butt quality；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is led into supergravity reactor II Enter the CO that volumetric concentration is 50%2Gas controls CO2The flow of gas is 120m3/ h, carburizing temperature are 15 DEG C, and the reaction was continued Anion and nonionic mixed dispersant is added in 10min later, recycles at least 1min；The anionic dispersing agents are molecule Amount is the Sodium Polyacrylate of 3000-5000, and the non-ionic dispersing agent is hydroxyethyl cellulose, and the two is mixed with arbitrary proportion It closes, additional amount is Ca (OH)2The 2.0% of butt quality；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is led into supergravity reactor III Enter the CO that volumetric concentration is 20%2Gas controls CO2Gas flow is 40m3/ h, carburizing temperature are 20 DEG C, and the reaction was continued to slurry PH=7 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 40%-50%, is put Enter supercritical CO2In fluid means, using first low temperature, again heat up, the drying mode of rear constant temperature, the specially temperature of low temperature drying It is 40 DEG C, operating pressure 18MPa, CO2Charge flow rate is 8L/h, when nano combined superfine heavy calcium carbonate slurry water content drops When to 8%, modifying agent is added, the modifying agent is that amphiphilic coupling agent, stearic acid and oleic acid mix in any proportion, is added Enter 5% that amount is nano combined superfine heavy calcium carbonate butt quality；Heating drying is carried out later, heating rate is 1 DEG C/min, Operating pressure is 15MPa, CO2Charge flow rate is 6L/h；When temperature rises to 65 DEG C, freeze-day with constant temperature is carried out, operating pressure is 8MPa, CO2Charge flow rate is 5L/h, so that material activating degree is up to 100%, water content≤0.42%；It unloads and is depressed into normal temperature and pressure, then pass through Cyclone mill is broken, is crushed classification in 35Hz, and temperature control is at 50 DEG C to get arriving nano combined superfine heavy calcium carbonate.
The nano combined superfine heavy calcium carbonate that embodiment 1 is prepared is suitable for adhesive class.
Embodiment 2
A kind of preparation method of nano combined superfine heavy calcium carbonate, includes the following steps:
(1) it is digested after taking calcium oxide decontamination, obtains the Ca (OH) that concentration is 20%, activity degree 50s2Suspension is stood old Change 46h, separate decontamination, finally obtains the Ca (OH) that concentration is 8%2Refining suspension and the lime lithophysa that can not be digested；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes d95≤2 μm Ultrafine heavy calcium slurry, crystalline form is spherical or spherical, and is 15% by obtained ultrafine heavy calcium pulp dilution to concentration；It is described Grinding distribution agent be that polycarboxylate sodium's neutral dispersing agent and polycarboxylate sodium's acidic dispersion agent 1:1 in mass ratio are mixed, Additional amount is added by the 1% of superfine heavy calcium carbonate butt quality；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) are simultaneously It is mixed in mass ratio for 8:1, is then pumped into hypergravity and answers in device I, and answered to hypergravity and to be passed through volumetric concentration in device I and be 60% CO2Gas controls CO2Gas flow is 140m3/ h, carbonation reaction temperature are 12 DEG C, react 10min, are added later brilliant Shape promotor recycles at least 1min；The crystalline form promotor is saccharin sodium, and additional amount is Ca (OH)2The 0.3% of butt quality；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is led into supergravity reactor II Enter the CO that volumetric concentration is 50%2Gas controls CO2The flow of gas is 100m3/ h, carburizing temperature are 18 DEG C, and the reaction was continued Anion and nonionic mixed dispersant is added in 15min later, recycles at least 1min；The anionic dispersing agents are molecule Amount is the Sodium Polyacrylate of 3000-5000, and the non-ionic dispersing agent is hydroxyethyl cellulose, and the two is mixed with arbitrary proportion It closes, additional amount is Ca (OH)2The 1.5% of butt quality；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is led into supergravity reactor III Enter the CO that volumetric concentration is 30%2Gas controls CO2Gas flow is 50m3/ h, carburizing temperature are 30 DEG C, and the reaction was continued to slurry PH=7.5 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 45%, is put into super Critical CO2In fluid means, using first low temperature, again heat up, the drying mode of rear constant temperature, specially the temperature of low temperature drying be 45 DEG C, operating pressure 20MPa, CO2Charge flow rate is 6L/h, when nano combined superfine heavy calcium carbonate slurry water content is down to When 10%, modifying agent is added, the modifying agent is that amphiphilic coupling agent, paraffin and palmitic acid mix in any proportion, is added Amount is the 4% of nano combined superfine heavy calcium carbonate butt quality；Heating drying is carried out later, heating rate is 0.8 DEG C/min, Operating pressure is 12MPa, CO2Charge flow rate is 5L/h；When temperature rises to 70 DEG C, freeze-day with constant temperature is carried out, operating pressure is 10MPa, CO2Charge flow rate is 4L/h, so that material activating degree is up to 100%, water content≤0.35%；It unloads and is depressed into normal temperature and pressure, then It is broken through Cyclone mill, it is crushed classification in 30Hz, temperature control is at 60 DEG C to get arriving nano combined superfine heavy calcium carbonate.
The nano combined superfine heavy calcium carbonate that embodiment 2 is prepared be suitable for PP PE Plastic.
Embodiment 3
A kind of preparation method of nano combined superfine heavy calcium carbonate, includes the following steps:
(1) it is digested after taking calcium oxide decontamination, obtains the Ca (OH) that concentration is 25%, activity degree 30s2Suspension is stood old Change 16h, separate decontamination, finally obtains the Ca (OH) that concentration is 6%2Refining suspension and the lime lithophysa that can not be digested；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes d95≤2 μm Ultrafine heavy calcium slurry, crystalline form is spherical or spherical, and is 13% by obtained ultrafine heavy calcium pulp dilution to concentration；It is described Grinding distribution agent be that polycarboxylate sodium's neutral dispersing agent and polycarboxylate sodium's acidic dispersion agent 1:1 in mass ratio are mixed, Additional amount is added by the 0.5% of superfine heavy calcium carbonate butt quality；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) are simultaneously It is mixed in mass ratio for 9:1, is then pumped into hypergravity and answers in device I, and answered to hypergravity and to be passed through volumetric concentration in device I and be 70% CO2Gas controls CO2Gas flow is 100m3/ h, carbonation reaction temperature are 14 DEG C, react 7min, crystalline form is added later Promotor recycles at least 1min；The crystalline form promotor is saccharin sodium, and additional amount is Ca (OH)2The 0.8% of butt quality；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is led into supergravity reactor II Enter the CO that volumetric concentration is 45%2Gas controls CO2The flow of gas is 90m3/ h, carburizing temperature are 19 DEG C, and the reaction was continued Anion and nonionic mixed dispersant is added in 20min later, recycles at least 1min；The anionic dispersing agents are molecule Amount is the Sodium Polyacrylate of 3000-5000, and the non-ionic dispersing agent is hydroxyethyl cellulose, and the two is mixed with arbitrary proportion It closes, additional amount is Ca (OH)2The 1.0% of butt quality；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is led into supergravity reactor III Enter the CO that volumetric concentration is 35%2Gas controls CO2Gas flow is 55m3/ h, carburizing temperature are 25 DEG C, and the reaction was continued to slurry PH=8 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 50%, is put into super Critical CO2In fluid means, cyclic drying, so that material activating degree unloads up to 100%, water content≤0.5% and is depressed into normal temperature and pressure, It is broken through Cyclone mill again, it is crushed classification in 30Hz, temperature control is at 65 DEG C to get arriving nano combined superfine heavy calcium carbonate.
The nano combined superfine heavy calcium carbonate that embodiment 3 is prepared is suitable for refractory material class.
Embodiment 4
A kind of preparation method of nano combined superfine heavy calcium carbonate, includes the following steps:
(1) it is digested after taking calcium oxide decontamination, obtains the Ca (OH) that concentration is 25%, activity degree 25s2Suspension is stood old Change 32h, separate decontamination, finally obtains the Ca (OH) that concentration is 9%2Refining suspension and the lime lithophysa that can not be digested；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes d95≤2 μm Ultrafine heavy calcium slurry, crystalline form is spherical or spherical, and is 18% by obtained ultrafine heavy calcium pulp dilution to concentration；It is described Grinding distribution agent be that polycarboxylate sodium's neutral dispersing agent and polycarboxylate sodium's acidic dispersion agent 1:1 in mass ratio are mixed, Additional amount is added by the 1.3% of superfine heavy calcium carbonate butt quality；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) are simultaneously It is mixed in mass ratio for 6:1, is then pumped into hypergravity and answers in device I, and answered to hypergravity and to be passed through volumetric concentration in device I and be 55% CO2Gas controls CO2Gas flow is 130m3/ h, carbonation reaction temperature are 11 DEG C, react 8min, crystalline form is added later Promotor recycles at least 1min；The crystalline form promotor is saccharin sodium, and additional amount is Ca (OH)2The 0.4% of butt quality；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is led into supergravity reactor II Enter the CO that volumetric concentration is 45%2Gas controls CO2The flow of gas is 110m3/ h, carburizing temperature are 16 DEG C, and the reaction was continued Anion and nonionic mixed dispersant is added in 13min later, recycles at least 1min；The anionic dispersing agents are molecule Amount is the Sodium Polyacrylate of 3000-5000, and the non-ionic dispersing agent is hydroxyethyl cellulose, and the two is mixed with arbitrary proportion It closes, additional amount is Ca (OH)2The 1.6% of butt quality；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is led into supergravity reactor III Enter the CO that volumetric concentration is 25%2Gas controls CO2Gas flow is 45m3/ h, carburizing temperature are 35 DEG C, and the reaction was continued to slurry PH=7 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 45%, is put into super Critical CO2In fluid means, cyclic drying is carried out, when drying to material moisture is 10-30%, modifying agent is added, described changes Property agent be titanate coupling agent, white oil, capric acid, palmitic acid, oleic acid and linoleic acid mix in any proportion, additional amount be receive The 3% of rice composite superfine powdered whiting butt quality；Drying is continued cycling through later, so that material activating degree is up to 100%, water content ≤0.5%；It unloads and is depressed into normal temperature and pressure, then is broken through Cyclone mill, be crushed classification in 25Hz, temperature control is at 55 DEG C to get arriving nanometer Composite superfine powdered whiting.
The nano combined superfine heavy calcium carbonate that embodiment 4 is prepared is suitable for organic material.
Embodiment 5
A kind of preparation method of nano combined superfine heavy calcium carbonate, includes the following steps:
(1) it is digested after taking calcium oxide decontamination, obtains the Ca (OH) that concentration is 15%, activity degree 1min2Suspension is stood Ageing for 24 hours, separates decontamination, finally obtains the Ca (OH) that concentration is 10%2Refining suspension and the lime lithophysa that can not be digested；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes d95≤2 μm Ultrafine heavy calcium slurry, crystalline form is spherical or spherical, and is 20% by obtained ultrafine heavy calcium pulp dilution to concentration；It is described Grinding distribution agent be that polycarboxylate sodium's neutral dispersing agent and polycarboxylate sodium's acidic dispersion agent 1:1 in mass ratio are mixed, Additional amount is added by the 0.5% of superfine heavy calcium carbonate butt quality；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) are simultaneously It is mixed in mass ratio for 10:1, is then pumped into hypergravity and answers in device I, and answered to hypergravity and to be passed through volumetric concentration in device I and be 50% CO2Gas controls CO2Gas flow is 110m3/ h, carbonation reaction temperature are 15 DEG C, react 10min, are added later brilliant Shape promotor recycles at least 1min；The crystalline form promotor is saccharin sodium, and additional amount is Ca (OH)2The 0.2% of butt quality；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is led into supergravity reactor II Enter the CO that volumetric concentration is 40%2Gas controls CO2The flow of gas is 80m3/ h, carburizing temperature are 20 DEG C, and the reaction was continued Anion and nonionic mixed dispersant is added in 15min later, recycles at least 1min；The anionic dispersing agents are molecule Amount is the Sodium Polyacrylate of 3000-5000, and the non-ionic dispersing agent is hydroxyethyl cellulose, and the two is mixed with arbitrary proportion It closes, additional amount is Ca (OH)2The 1.8% of butt quality；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is led into supergravity reactor III Enter the CO that volumetric concentration is 40%2Gas controls CO2Gas flow is 60m3/ h, carburizing temperature are 40 DEG C, and the reaction was continued to slurry PH=8 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 40%, is put into super Critical CO2In fluid means, using first low temperature, again heat up, the drying mode of rear constant temperature, specially the temperature of low temperature drying be 35 DEG C, operating pressure 12MPa, CO2Charge flow rate is 7L/h, when nano combined superfine heavy calcium carbonate slurry water content is down to 5% When, modifying agent is added, the modifying agent is that titanate coupling agent, octanoic acid, capric acid, oleic acid and linoleic acid mix in any proportion It forms, additional amount is the 2% of nano combined superfine heavy calcium carbonate butt quality；Heating drying is carried out later, and heating rate is 0.5 DEG C/min, operating pressure 10MPa, CO2Charge flow rate is 5L/h；When temperature rises to 60 DEG C, freeze-day with constant temperature, fortune are carried out Row pressure is 12MPa, CO2Charge flow rate is 5L/h, so that material activating degree is up to 100%, water content≤0.5%；It unloads and is depressed into room temperature Normal pressure, then broken through Cyclone mill, is crushed classification in 25Hz, and temperature control is at 70 DEG C to get arriving nano combined fine heavy carbonic acid Calcium.
It is obtained by the detection of profession and science, the nano combined superfine heavy calcium carbonate that the method for the present invention is prepared produces The performance indicator of product, Conventional nano calcium carbonate product and ultrafine heavy calcium product is as shown in table 1 below:
Table 1
Note: nanometer calcium carbonate, ultrafine heavy calcium, embodiment 1, embodiment 2 are indicated with the result after activating in table 1, are implemented Example 3 is unactivated processing result.Wherein nanometer calcium carbonate is to be added without in the method for the present invention obtained by ultrafine heavy calcium, and ultrafine heavy calcium is Obtained by lime lithophysa bonus point powder wet lapping.
Nano combined superfine heavy calcium carbonate obtained and nanometer by the method for the invention it can be seen from the result of table 1 Calcium carbonate is compared with ultrafine heavy calcium, and to be spherical or spherical, size distribution is narrower, and specific surface area is higher, and oil factor is lower, squeezes out It measures higher.It is used in plastic products, has the advantages that tensile strength is high, elongation is good；For adhesive industry, there is viscosity The advantages of raising spues and accelerates, and reinforcement improves；It is flowed applied to its additional amount can be improved in refractory material and keep better Property, lower apparent porosity.Nano combined superfine heavy calcium carbonate has both the advantages of the two, than exclusive use nanometer calcium carbonate or again Calcium performance is more preferable.

Claims (7)

1. a kind of preparation method of nano combined superfine heavy calcium carbonate, which comprises the steps of:
(1) it is digested after taking calcium oxide decontamination, obtaining concentration is 15-30%, activity degree≤1min Ca (OH)2Suspension is stood It is aged 16-72h, separates decontamination, finally obtains the Ca (OH) that concentration is 5-10%2Refining suspension and the lime that can not be digested Lithophysa；
(2) the advanced row of lime lithophysa is roughly ground, adds grinding distribution agent, wet grinding lime lithophysa becomes the super of D95≤2 μm Thin calcium carbonate slurry, crystalline form are spherical or spherical, and are 10-20% by obtained ultrafine heavy calcium pulp dilution to concentration；
(3) Ca obtained in step (1) (OH) is taken2Refining suspension and ultrafine heavy calcium slurry obtained in step (2) simultaneously press quality Than being then pumped into hypergravity and answering in device I for 5-10:1 mixing, and is answered to hypergravity and be passed through volumetric concentration in device I as 50- 80% CO2Gas controls CO2Gas flow is 100-150m3/ h, carbonation reaction temperature are 10-15 DEG C, react 5-10min, it Crystalline form promotor is added afterwards, recycles at least 1min；
Slurry in supergravity reactor I is pumped into again in supergravity reactor II, and is passed through body into supergravity reactor II The CO that product concentration is 40-50%2Gas controls CO2The flow of gas is 80-120m3/ h, carburizing temperature are 15-20 DEG C, are continued anti- 10-20min is answered, anion and nonionic mixed dispersant are added later, recycles at least 1min；
Slurry in supergravity reactor II is pumped into again in supergravity reactor III, and is passed through body into supergravity reactor III The CO that product concentration is 20-40%2Gas controls CO2Gas flow is 40-60m3/ h, carburizing temperature are 20-40 DEG C, and the reaction was continued To slurry pH=7-8 when, stop reaction, obtain nano combined superfine heavy calcium carbonate slurry；
(4) nano combined superfine heavy calcium carbonate slurry obtained in step (3) is taken, filters pressing to moisture is 40%-50%, is put into super Critical CO2In fluid means, cyclic drying, so that material activating degree is up to 100%, water content≤0.5% unloads and is depressed into normal temperature and pressure, It is broken through Cyclone mill again, it is crushed classification in 25-35Hz, temperature control is at 50-70 DEG C to get arriving nano combined fine heavy carbonic acid Calcium.
2. a kind of preparation method of nano combined superfine heavy calcium carbonate according to claim 1, it is characterised in that: step (2) the grinding distribution agent described in is polycarboxylate sodium's neutral dispersing agent and polycarboxylate sodium's acidic dispersion agent 1:1 in mass ratio It mixes, additional amount is added by the 0.5-1.5% of superfine heavy calcium carbonate butt quality.
3. a kind of preparation method of nano combined superfine heavy calcium carbonate according to claim 1, it is characterised in that: step (3) the crystalline form promotor described in is saccharin sodium, and additional amount is Ca (OH)2The 0.2%-0.5% of butt quality.
4. a kind of preparation method of nano combined superfine heavy calcium carbonate according to claim 1, it is characterised in that: step (3) anionic dispersing agents described in are the Sodium Polyacrylate that molecular weight is 3000-5000, and the non-ionic dispersing agent is hydroxyl Ethyl cellulose, the two are mixed with arbitrary proportion, and additional amount is Ca (OH)2The 1.0%-2.0% of butt quality.
5. a kind of preparation method of nano combined superfine heavy calcium carbonate according to claim 1, it is characterised in that: step (4) in, in supercritical CO2When dry in fluid means, when drying to moisture is 5-10%, modifying agent be added, continues cycling through dry It is dry, so that material activating degree is up to 100%, water content≤0.5%.
6. a kind of preparation method of nano combined superfine heavy calcium carbonate according to claim 5, it is characterised in that: step (4) in, nano combined superfine heavy calcium carbonate slurry is in supercritical CO2When dry in fluid means, using first low temperature, again rise The drying mode of warm, rear constant temperature, the specially temperature of low temperature drying are 35-45 DEG C, operating pressure 12-20MPa, CO2Air inlet Flow is 7-8L/h, and when nano combined superfine heavy calcium carbonate slurry water content is down to 5-10%, modifying agent is added；It is laggard Row heating drying, heating rate are 0.5-1 DEG C/min, operating pressure 10-15MPa, CO2Charge flow rate is 5-6L/h；Work as temperature When degree rises to 60-70 DEG C, freeze-day with constant temperature, operating pressure 8-12MPa, CO are carried out2Charge flow rate is 4-5L/h, so that material is living Change degree is up to 100%, water content≤0.5%.
7. a kind of preparation method of nano combined superfine heavy calcium carbonate according to claim 5 or 6, it is characterised in that: The modifying agent is amphiphilic coupling agent, titanate coupling agent, white oil, octanoic acid, capric acid, palmitic acid, oleic acid, linoleic acid, tristearin Three kinds or more in acid, which arbitrarily matches, to be used in mixed way, and additional amount is nano combined superfine heavy calcium carbonate butt quality 2%-5%。
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