CN109574057A - A kind of preparation method of calcium carbonate - Google Patents
A kind of preparation method of calcium carbonate Download PDFInfo
- Publication number
- CN109574057A CN109574057A CN201910030937.6A CN201910030937A CN109574057A CN 109574057 A CN109574057 A CN 109574057A CN 201910030937 A CN201910030937 A CN 201910030937A CN 109574057 A CN109574057 A CN 109574057A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- parts
- added
- temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of preparation methods of calcium carbonate, comprising: calcined product is added to lime stone high-temperature calcination in the mixed liquor of acetone and water, and is added in supercritical device and impregnates, obtains milk of lime；It is passed through carbonated limekiln flue gas in milk of lime to be carbonized, obtains thick calcium carbonate slurry；Thick calcium carbonate slurry is added in supercritical reaction apparatus, chemical additives and ethyl alcohol is then added, is passed through carbon dioxide reaction after device sealing, then release is cooled to room temperature, into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering crushes after being dried, and obtains calcium carbonate.Purity is high, dispersibility using the calcium carbonate of method preparation of the invention is high.
Description
Technical field
The present invention relates to a kind of preparation methods of inorganic raw material, and in particular to a kind of preparation method of calcium carbonate.
Background technique
Calcium carbonate is a kind of important functional inorganic filling, has cheap, rich reserves, performance stabilization, Yi Jia
Work, it is nontoxic the advantages that, can significantly improve processing performance of material, physical property and reduce production cost etc., extensively
Applied to fields such as plastics, rubber, coating, papermaking, currently, domestic current calcium carbonate industry the preparation method is as follows:
To the Ca (OH) of a certain concentration certain temperature2Be passed through in suspension washed carbonated limekiln flue gas into
Row carbonization, makes Ca (OH)2The pH value of suspension constantly declines, and after pH value reaches 7.0, carbonization reaches terminal, and calcium carbonate is made
Then slurry is dehydrated and is dried to calcium carbonate slurry obtained, then again to the agglomerated calcium carbonate body obtained after drying into
Row depolymerization screens out coarse granule to get finished product calcium carbonate powder.Saponification rouge can also be added into calcium carbonate slurry obtained
Fat acid carries out liquid phase surface cladding to calcium carbonate granule, and then calcium carbonate slurry is dehydrated and is dried again, the process is added
The performance of calcium carbonate product tool hydrophobic oleophilic oil obtained, referred to as activated Calcium carbonate.If at Ca (OH)2Carbonisation in,
Carbonization control is carried out in a certain temperature conditions, and certain morphology regulation additives are added, the partial size of calcium carbonate granule can be made
Within 100 nanometers, we term it nanometer calcium carbonates, later, are aged to nanometer calcium carbonate slurry obtained, Xiang Chenhua
Saponified fat acid is added in nanometer calcium carbonate slurry afterwards, liquid phase surface is carried out to the cube nano-calcium carbonate particles of Monodispersed
Then cladding is dehydrated and is dried to nanometer calcium carbonate slurry again, carried out to the nanometer calcium carbonate aggregate obtained after drying
Depolymerization, sieving, i.e. acquisition nm-class active calcium carbonate.The calcium carbonate that this method obtains generally existing powder in application process it is thin
Degree not enough, bad dispersibility and product the problems such as voluntarily degradation property is poor.
Further, since calcium carbonate is hydrophilic compounds, cause to exist in practical applications compatible with organic polymer
Property it is insufficient, the defects of bad dispersibility, satisfied filler reinforcement effect cannot be reached, it is therefore desirable to which place is modified to calcium carbonate
Reason, to improve its dispersibility and compatibility in various types of materials, to reach the effect of improving properties of product.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, a kind of preparation method of calcium carbonate is provided, is wrapped
Include following steps:
Step 1: the temperature lower calcination by lime stone at 1000 DEG C~1280 DEG C, by weight, by calcined product 50
~80 parts are added in the mixed liquor of 200~300 parts of acetone and water, and are added in supercritical device, are 360 DEG C~400 in temperature
DEG C and pressure be 15MPa~25MPa supercritical acetone-water system in impregnate 30~90min, obtain milk of lime；Described is super
The volume ratio of acetone and water is 3:1 in critical acetone-water system；
Step 2: being passed through flow in milk of lime is 0.5~1.5m3/ min, washed 30~50% carbon dioxide of containing
Limekiln flue gas carries out carbonization 6~12 hours, obtains thick calcium carbonate slurry；During carbonization, at the same into milk of lime with
The speed of 200~300mL/min is passed through 70~80 DEG C of nitrogen；
Step 3: by weight, by 50~100 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, being then added
3~10 parts and 5~8 parts of ethyl alcohol of chemical additives, carbon dioxide is passed through to 12~25MPa, temperature 60~80 after device sealing
It is reacted 5~8 hours under conditions of DEG C, then release is cooled to room temperature, and into vertical type blotter press pressure filtration, is obtained after filtering
Calcium carbonate crushed after being dried, obtain calcium carbonate.
Preferably, the chemical additives include that the raw material of following parts by weight is mixed to form: 3~5 parts of polyacrylic acid,
1.5~2.5 parts of triethanolamines, 0.1~0.2 part of Potassium Hydrogen Phthalate, 0.3~0.5 part of glycolic, 0.1~0.3 part of 1- second
Base -3- methylimidazole lactic acid, 0.3~0.5 part of sodium salicylate, 0.1~0.2 part of polydimethyl diallyl ammonium chloride.
Preferably, the chemical additives include that the raw material of following parts by weight is mixed to form: 4 parts of polyacrylic acid, 2
Part triethanolamine, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic, 0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of water
Poplar acid sodium, 0.2 part of polydimethyl diallyl ammonium chloride.
Preferably, in the step 3, obtained calcium carbonate carries out the following processing process: calcium carbonate is placed in low temperature etc.
10~15min is handled in gas ions processing instrument, is then added in blender, and eight aminophenyl cage types times are added in blender
Half siloxanes and Imarcaptoacetate dioctyltin, stir evenly, and are subsequently placed in60It is radiated in Co gamma radiation field,
Placement location selects 130~150Gy.min-1Absorbed dose rate, absorbed dose be 100~200kGy.
Preferably, the atmosphere of the Low Temperature Plasma Treating instrument is argon gas or nitrogen；At the low temperature plasma
The frequency for managing instrument is 40~70KHz, and power is 35~80W, and pressure is 30~80Pa.
Preferably, the weight ratio of the eight aminophenyls cagelike silsesquioxane and calcium carbonate is 1~3:100；It is described
The mass ratio of Imarcaptoacetate dioctyltin and calcium carbonate is 0.5~1.5:100.
Preferably, further include that will irradiate the calcium carbonate after post-processing to carry out following modifying process: by weight, facing super
15~30 parts of calcium carbonate, 20~25 parts of butyl acrylate, 3~5 parts of allylthiourea, two after irradiation is added in boundary's reaction unit
5~10 parts of allyl dimethyl ammonium chloride, 0.03~0.12 part of persalt ammonium, 150~200 parts of water, stir evenly, then by body
System's sealing, is passed through under conditions of carbon dioxide to 25~35MPa, 60~75 DEG C of temperature and reacts 1~3 hour, then second is used in release
Alcohol precipitating, it is dry, the homopolymer of dereaction generation is removed with butanone elution, obtains modified calcium carbonate.
Preferably, in the step 1, the temperature-rise period of use is calcined are as follows: be warming up to the speed of 5~10 DEG C/min
600~800 DEG C, 30min is kept the temperature, continues to be warming up to 800~1000 DEG C with the speed of 5~10 DEG C/min, keeps the temperature 1~2h, then
1100~1280 DEG C are warming up to the speed of 1~2 DEG C/min, keeps the temperature 1~3h.
The present invention is include at least the following beneficial effects:
(1) present invention improves the milk of lime of generation using calcined product is handled in supercritical water
Disperse the product purity of homogeneity, and by way of being carbonized in supercritical reaction apparatus, makes the calcium carbonate of preparation
Purity is high, dispersibility are high.
(2) by the way that calcium carbonate is carried out Low Temperature Plasma Treating, and by further modification, the modification that makes
The compatibility of calcium carbonate and organic polymer afterwards is high, and dispersibility is high, improves the performance of organic polymer.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment:
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 80 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1100 DEG C
It in the mixed liquor of 300 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 22MPa
60min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1m3/ min, the washed limekiln flue gas for containing 40% carbon dioxide into
Row carbonization 12 hours, obtains thick calcium carbonate slurry；During carbonization, while into milk of lime with the speed of 300mL/min
It is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 100 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form is then added
10 parts of controlling agent and 8 parts of ethyl alcohol, reaction 8 is small under conditions of carbon dioxide is passed through after device sealing to 25MPa, 80 DEG C of temperature
When, then release is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering is after being dried
It crushes, obtains calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 10 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 10 DEG C/min, keeps the temperature 2h, be then warming up to 1100 with the speed of 2 DEG C/min,
Keep the temperature 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 4 parts of polyacrylic acid, 2 part of three ethyl alcohol
Amine, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic, 0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of sodium salicylate,
0.2 part of polydimethyl diallyl ammonium chloride.
The purity 99.94% for the calcium carbonate that the embodiment obtains, whiteness 96%, 0.5~5um of size distribution.
Embodiment 2:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 60 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1200 DEG C
It in the mixed liquor of 250 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 25MPa
90min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1.2m3/ min, the washed limekiln flue gas for containing 35% carbon dioxide
Carbonization 12 hours is carried out, thick calcium carbonate slurry is obtained；During carbonization, while into milk of lime with the speed of 250mL/min
Degree is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 80 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form control is then added
8 parts of preparation and 8 parts of ethyl alcohol, react 8 hours under conditions of carbon dioxide is passed through after device sealing to 20MPa, temperature 70 C, so
Release afterwards is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering crushes after being dried,
Obtain calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 5 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 5 DEG C/min, keeps the temperature 2h, be then warming up to 1200 with the speed of 1 DEG C/min, protected
Warm 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 5 parts of polyacrylic acid, 2.5 part of three second
Hydramine, 0.1 part of Potassium Hydrogen Phthalate, 0.5 part of glycolic, 0.3 part of 1- ethyl-3-methylimidazole lactic acid, 0.5 part of salicylic acid
Sodium, 0.1 part of polydimethyl diallyl ammonium chloride.
The purity 99.95% for the calcium carbonate that the embodiment obtains, whiteness 97%, 0.5~5.5um of size distribution.
Embodiment 3:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 80 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1100 DEG C
It in the mixed liquor of 300 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 22MPa
60min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1m3/ min, the washed limekiln flue gas for containing 40% carbon dioxide into
Row carbonization 12 hours, obtains thick calcium carbonate slurry；During carbonization, while into milk of lime with the speed of 300mL/min
It is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 100 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form is then added
10 parts of controlling agent and 8 parts of ethyl alcohol, reaction 8 is small under conditions of carbon dioxide is passed through after device sealing to 25MPa, 80 DEG C of temperature
When, then release is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering is after being dried
It crushes, obtains calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 10 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 10 DEG C/min, keeps the temperature 2h, be then warming up to 1100 with the speed of 2 DEG C/min,
Keep the temperature 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 4 parts of polyacrylic acid, 2 part of three ethyl alcohol
Amine, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic, 0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of sodium salicylate,
0.2 part of polydimethyl diallyl ammonium chloride；
In the step 3, obtained calcium carbonate carries out the following processing process: calcium carbonate is placed at low temperature plasma
15min is handled in reason instrument, is then added in blender, and eight aminophenyl cagelike silsesquioxanes and double are added in blender
Isooctyl thioglycolate dioctyltin, stirs evenly, and is subsequently placed in60It is radiated in Co gamma radiation field, placement location is selected
150Gy.min-1Absorbed dose rate, absorbed dose 200kGy；The atmosphere of the Low Temperature Plasma Treating instrument is argon gas；Institute
The frequency for stating Low Temperature Plasma Treating instrument is 60KHz, power 40W, pressure 60Pa；The eight aminophenyls cage type sesquialter
The weight ratio of siloxanes and calcium carbonate is 2:100；The mass ratio of the Imarcaptoacetate dioctyltin and calcium carbonate
For 1.5:100, calcium carbonate is handled using low temperature plasma, improves the reactivity of calcium carbonate, enhance its with
The reaction bonded of eight aminophenyl cagelike silsesquioxanes and Imarcaptoacetate dioctyltin.
Embodiment 4:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 60 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1200 DEG C
It in the mixed liquor of 250 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 25MPa
90min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1.2m3/ min, the washed limekiln flue gas for containing 35% carbon dioxide
Carbonization 12 hours is carried out, thick calcium carbonate slurry is obtained；During carbonization, while into milk of lime with the speed of 250mL/min
Degree is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 80 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form control is then added
8 parts of preparation and 8 parts of ethyl alcohol, react 8 hours under conditions of carbon dioxide is passed through after device sealing to 20MPa, temperature 70 C, so
Release afterwards is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering crushes after being dried,
Obtain calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 5 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 5 DEG C/min, keeps the temperature 2h, be then warming up to 1200 with the speed of 1 DEG C/min, protected
Warm 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 5 parts of polyacrylic acid, 2.5 part of three second
Hydramine, 0.1 part of Potassium Hydrogen Phthalate, 0.5 part of glycolic, 0.3 part of 1- ethyl-3-methylimidazole lactic acid, 0.5 part of salicylic acid
Sodium, 0.1 part of polydimethyl diallyl ammonium chloride；
In the step 3, obtained calcium carbonate carries out the following processing process: calcium carbonate is placed at low temperature plasma
10min is handled in reason instrument, is then added in blender, and eight aminophenyl cagelike silsesquioxanes and double are added in blender
Isooctyl thioglycolate dioctyltin, stirs evenly, and is subsequently placed in60It is radiated in Co gamma radiation field, placement location is selected
130Gy.min-1Absorbed dose rate, absorbed dose 150kGy；The atmosphere of the Low Temperature Plasma Treating instrument is argon gas；Institute
The frequency for stating Low Temperature Plasma Treating instrument is 50KHz, power 50W, pressure 50Pa；The eight aminophenyls cage type sesquialter
The weight ratio of siloxanes and calcium carbonate is 1:100；The mass ratio of the Imarcaptoacetate dioctyltin and calcium carbonate
For 1:100.
Embodiment 5:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 80 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1100 DEG C
It in the mixed liquor of 300 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 22MPa
60min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1m3/ min, the washed limekiln flue gas for containing 40% carbon dioxide into
Row carbonization 12 hours, obtains thick calcium carbonate slurry；During carbonization, while into milk of lime with the speed of 300mL/min
It is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 100 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form is then added
10 parts of controlling agent and 8 parts of ethyl alcohol, reaction 8 is small under conditions of carbon dioxide is passed through after device sealing to 25MPa, 80 DEG C of temperature
When, then release is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering is after being dried
It crushes, obtains calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 10 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 10 DEG C/min, keeps the temperature 2h, be then warming up to 1100 with the speed of 2 DEG C/min,
Keep the temperature 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 4 parts of polyacrylic acid, 2 part of three ethyl alcohol
Amine, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic, 0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of sodium salicylate,
0.2 part of polydimethyl diallyl ammonium chloride；
In the step 3, obtained calcium carbonate carries out the following processing process: calcium carbonate is placed at low temperature plasma
15min is handled in reason instrument, is then added in blender, and eight aminophenyl cagelike silsesquioxanes and double are added in blender
Isooctyl thioglycolate dioctyltin, stirs evenly, and is subsequently placed in60It is radiated in Co gamma radiation field, placement location is selected
150Gy.min-1Absorbed dose rate, absorbed dose 200kGy；By weight, after irradiation being added in supercritical reaction apparatus
30 parts of calcium carbonate, 25 parts of butyl acrylate, 5 parts of allylthiourea, 10 parts of diallyldimethylammonium chloride, persalt ammonium
0.1 part, 200 parts of water, stir evenly, then seal system, are passed through under conditions of carbon dioxide to 35MPa, 75 DEG C of temperature instead
It answers 3 hours, release, then uses ethanol precipitation, it is dry, the homopolymer of dereaction generation is removed with butanone elution, obtains modified carbonic acid
Calcium；Calcium carbonate is modified using in supercritical reaction apparatus, its reactivity having with organic compound is improved, makes
The performance of obtained calcium carbonate is more excellent.
The atmosphere of the Low Temperature Plasma Treating instrument is argon gas；The frequency of the Low Temperature Plasma Treating instrument is
60KHz, power 40W, pressure 60Pa；The weight ratio of the eight aminophenyls cagelike silsesquioxane and calcium carbonate is 2:
100；The mass ratio of the Imarcaptoacetate dioctyltin and calcium carbonate is 1.5:100；
Embodiment 6:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 60 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1200 DEG C
It in the mixed liquor of 250 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 25MPa
90min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1.2m3/ min, the washed limekiln flue gas for containing 35% carbon dioxide
Carbonization 12 hours is carried out, thick calcium carbonate slurry is obtained；During carbonization, while into milk of lime with the speed of 250mL/min
Degree is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 80 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form control is then added
8 parts of preparation and 8 parts of ethyl alcohol, react 8 hours under conditions of carbon dioxide is passed through after device sealing to 20MPa, temperature 70 C, so
Release afterwards is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering crushes after being dried,
Obtain calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 5 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 5 DEG C/min, keeps the temperature 2h, be then warming up to 1200 with the speed of 1 DEG C/min, protected
Warm 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 5 parts of polyacrylic acid, 2.5 part of three second
Hydramine, 0.1 part of Potassium Hydrogen Phthalate, 0.5 part of glycolic, 0.3 part of 1- ethyl-3-methylimidazole lactic acid, 0.5 part of salicylic acid
Sodium, 0.1 part of polydimethyl diallyl ammonium chloride；
In the step 3, obtained calcium carbonate carries out the following processing process: calcium carbonate is placed at low temperature plasma
10min is handled in reason instrument, is then added in blender, and eight aminophenyl cagelike silsesquioxanes and double are added in blender
Isooctyl thioglycolate dioctyltin, stirs evenly, and is subsequently placed in60It is radiated in Co gamma radiation field, placement location is selected
130Gy.min-1Absorbed dose rate, absorbed dose 150kGy；The calcium carbonate after irradiation is added in supercritical reaction apparatus
20 parts, 20 parts of butyl acrylate, 5 parts of allylthiourea, 8 parts of diallyldimethylammonium chloride, 0.08 part of persalt ammonium, water
It 200 parts, stirs evenly, then seals system, be passed through under conditions of carbon dioxide to 30MPa, 75 DEG C of temperature and react 2 hours,
Then ethanol precipitation is used in release, dry, and the homopolymer of dereaction generation is removed with butanone elution, obtains modified calcium carbonate；
The atmosphere of the Low Temperature Plasma Treating instrument is argon gas；The frequency of the Low Temperature Plasma Treating instrument is
50KHz, power 50W, pressure 50Pa；The weight ratio of the eight aminophenyls cagelike silsesquioxane and calcium carbonate is 1:
100；The mass ratio of the Imarcaptoacetate dioctyltin and calcium carbonate is 1:100.
Comparative example 1:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 80 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1100 DEG C
60min is impregnated in the mixed liquor of 300 parts of acetone and water, obtains milk of lime
Step 2: being passed through flow in milk of lime is 1m3/ min, the washed limekiln flue gas for containing 40% carbon dioxide into
Row carbonization 12 hours, obtains thick calcium carbonate slurry；During carbonization, while into milk of lime with the speed of 300mL/min
It is passed through 80 DEG C of nitrogen；
Step 3: by weight, by 100 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form is then added
10 parts of controlling agent and 8 parts of ethyl alcohol, reaction 8 is small under conditions of carbon dioxide is passed through after device sealing to 25MPa, 80 DEG C of temperature
When, then release is cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering is after being dried
It crushes, obtains calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 10 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 10 DEG C/min, keeps the temperature 2h, be then warming up to 1100 with the speed of 2 DEG C/min,
Keep the temperature 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 4 parts of polyacrylic acid, 2 part of three ethyl alcohol
Amine, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic, 0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of sodium salicylate,
0.2 part of polydimethyl diallyl ammonium chloride.
Comparative example 2:
A kind of preparation method of calcium carbonate, comprising the following steps:
Step 1: 80 parts of calcined product are added by weight for the temperature lower calcination by lime stone at 1100 DEG C
It in the mixed liquor of 300 parts of acetone and water, and is added in supercritical device, in temperature be 380 DEG C and pressure is the overcritical of 22MPa
60min is impregnated in acetone-water system, obtains milk of lime；The volume ratio of acetone and water is in the supercritical acetone-water system
3:1；
Step 2: being passed through flow in milk of lime is 1m3/ min, the washed limekiln flue gas for containing 40% carbon dioxide into
Row carbonization 12 hours, obtains thick calcium carbonate slurry；During carbonization, while into milk of lime with the speed of 300mL/min
It is passed through 80 DEG C of nitrogen；
Step 3: by weight, 10 parts and 8 parts of ethyl alcohol of chemical additives will be added in 100 parts of thick calcium carbonate slurry, stirring
8 hours, then release was cooled to room temperature, and into vertical type blotter press pressure filtration, the calcium carbonate obtained after filtering is through being dried
After crush, obtain calcium carbonate.
In the step 1, the temperature-rise period of use is calcined are as follows: be warming up to 800 DEG C with the speed of 10 DEG C/min, heat preservation
30min is continued to be warming up to 1000 DEG C with the speed of 10 DEG C/min, keeps the temperature 2h, be then warming up to 1100 with the speed of 2 DEG C/min,
Keep the temperature 2h；
The chemical additives include that the raw material of following parts by weight is mixed to form: 4 parts of polyacrylic acid, 2 part of three ethyl alcohol
Amine, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic, 0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of sodium salicylate,
0.2 part of polydimethyl diallyl ammonium chloride.
Each 400g of calcium carbonate is prepared according to the preparation method of Examples 1 to 6 and comparative example 1~2, by Examples 1 to 5 and right
Calcium carbonate prepared by ratio 1~2 is separately added into 600g nitrile rubber, rubber product is obtained using identical technique, to each group
Rubber product be tested for the property, test result is as shown in table 1.
Table 1
| Elongation at break/% | Tensile strength/MPa | Hardness/A | |
| Embodiment 1 | 425 | 4.5 | 75.8 |
| Embodiment 2 | 426 | 4.6 | 76.1 |
| Embodiment 3 | 465 | 5.4 | 83.2 |
| Embodiment 4 | 467 | 5.5 | 83.4 |
| Embodiment 5 | 476 | 5.8 | 86.5 |
| Embodiment 6 | 477 | 5.9 | 86.7 |
| Comparative example 1 | 354 | 3.2 | 63.2 |
| Comparative example 2 | 336 | 2.8 | 50.5 |
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and example shown and described herein.
Claims (8)
1. a kind of preparation method of calcium carbonate, which comprises the following steps:
Step 1: the temperature lower calcination by lime stone at 1000 DEG C~1280 DEG C, by weight, by calcined product 50~80
Part be added in the mixed liquor of 200~300 parts of acetone and water, and be added in supercritical device, temperature be 360 DEG C~400 DEG C and
Pressure is that 30~90min is impregnated in the supercritical acetone-water system of 15MPa~25MPa, obtains milk of lime；Described is overcritical
The volume ratio of acetone and water is 3:1 in acetone-water system；
Step 2: being passed through flow in milk of lime is 0.5~1.5m3/ min, the washed limekiln for containing 30~50% carbon dioxide
Flue gas carries out carbonization 6~12 hours, obtains thick calcium carbonate slurry；During carbonization, at the same into milk of lime with 200~
The speed of 300mL/min is passed through 70~80 DEG C of nitrogen；
Step 3: by weight, by 50~100 parts of addition supercritical reaction apparatus of thick calcium carbonate slurry, crystal form is then added
3~10 parts of controlling agent and 5~8 parts of ethyl alcohol are passed through carbon dioxide to 12~25MPa, 60~80 DEG C of temperature after device sealing
Under the conditions of react 5~8 hours, then release is cooled to room temperature, into vertical type blotter press pressure filtration, the carbon that is obtained after filtering
Sour calcium crushes after being dried, and obtains calcium carbonate.
2. the preparation method of calcium carbonate as described in claim 1, which is characterized in that the chemical additives include following weight
Part raw material be mixed to form: 3~5 parts of polyacrylic acid, 1.5~2.5 parts of triethanolamines, 0.1~0.2 part of Potassium Hydrogen Phthalate,
0.3~0.5 part of glycolic, 0.1~0.3 part of 1- ethyl-3-methylimidazole lactic acid, 0.3~0.5 part of sodium salicylate, 0.1~0.2
Part polydimethyl diallyl ammonium chloride.
3. the preparation method of calcium carbonate as described in claim 1, which is characterized in that the chemical additives include following
The raw material of parts by weight is mixed to form: 4 parts of polyacrylic acid, 2 parts of triethanolamines, 0.2 part of Potassium Hydrogen Phthalate, 0.4 part of glycolic,
0.2 part of 1- ethyl-3-methylimidazole lactic acid, 0.4 part of sodium salicylate, 0.2 part of polydimethyl diallyl ammonium chloride.
4. the preparation method of calcium carbonate as described in claim 1, which is characterized in that in the step 3, obtained calcium carbonate
It carries out the following processing process: calcium carbonate being placed in 10~15min of processing in Low Temperature Plasma Treating instrument, blender is then added
In, and eight aminophenyl cagelike silsesquioxanes and Imarcaptoacetate dioctyltin are added in blender, it stirs
Uniformly, it is subsequently placed in60It is radiated in Co gamma radiation field, placement location selects 130~150Gy.min-1Absorbed dose rate,
Absorbed dose is 100~200kGy.
5. the preparation method of calcium carbonate as claimed in claim 4, which is characterized in that the gas of the Low Temperature Plasma Treating instrument
Atmosphere is argon gas or nitrogen；The frequency of the Low Temperature Plasma Treating instrument is 40~70KHz, and power is 35~80W, pressure 30
~80Pa.
6. the preparation method of calcium carbonate as claimed in claim 4, which is characterized in that the eight aminophenyls cage type silsesquioxane
The weight ratio of alkane and calcium carbonate is 1~3:100；The mass ratio of the Imarcaptoacetate dioctyltin and calcium carbonate is
0.5~1.5:100.
7. the preparation method of calcium carbonate as claimed in claim 4, which is characterized in that further include the carbonic acid that will be irradiated after post-processing
Calcium carries out following modifying process: by weight, 15~30 parts of calcium carbonate, propylene after irradiation is added in supercritical reaction apparatus
20~25 parts of acid butyl ester, 3~5 parts of allylthiourea, 5~10 parts of diallyldimethylammonium chloride, persalt ammonium 0.03~
0.12 part, 150~200 parts of water, stir evenly, then seal system, be passed through carbon dioxide to 25~35MPa, temperature 60~
It is reacted 1~3 hour under conditions of 75 DEG C, release, then uses ethanol precipitation, it is dry, the equal of dereaction generation is removed with butanone elution
Polymers obtains modified calcium carbonate.
8. the preparation method of calcium carbonate as described in claim 1, which is characterized in that in the step 1, calcine the liter of use
Warm process are as follows: be warming up to 600~800 DEG C with the speed of 5~10 DEG C/min, keep the temperature 30min, continue with the speed of 5~10 DEG C/min
Degree is warming up to 800~1000 DEG C, keeps the temperature 1~2h, is then warming up to 1100~1280 DEG C with the speed of 1~2 DEG C/min, heat preservation 1
~3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910030937.6A CN109574057B (en) | 2019-01-14 | 2019-01-14 | Preparation method of calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910030937.6A CN109574057B (en) | 2019-01-14 | 2019-01-14 | Preparation method of calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109574057A true CN109574057A (en) | 2019-04-05 |
| CN109574057B CN109574057B (en) | 2020-12-25 |
Family
ID=65916302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910030937.6A Active CN109574057B (en) | 2019-01-14 | 2019-01-14 | Preparation method of calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109574057B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112777618A (en) * | 2021-02-26 | 2021-05-11 | 绵阳远达电子材料有限公司 | Production process of magnesium carbonate |
| CN115196662A (en) * | 2022-07-20 | 2022-10-18 | 中国科学院兰州化学物理研究所 | Preparation method of cubic nano calcium carbonate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007254220A (en) * | 2006-03-24 | 2007-10-04 | Chugoku Electric Power Co Inc:The | Carbon dioxide fixation system and method for manufacturing carbonate |
| KR20120109683A (en) * | 2011-03-25 | 2012-10-09 | 박경원 | Manufacturing method of precipitated calcium carbonate using supercritical fluid |
| WO2014118281A1 (en) * | 2013-01-30 | 2014-08-07 | S.A. Lhoist Recherche Et Développement | Method for producing calcium carbonate gel and product obtained thereby |
| CN107445189A (en) * | 2017-09-30 | 2017-12-08 | 广西华洋矿源材料有限公司 | A kind of preparation method of needle-like nano calcium carbonate |
| CN108178177A (en) * | 2018-03-08 | 2018-06-19 | 蒋央芳 | A kind of preparation method of low agglomeration nano calcium carbonate |
| CN108975372A (en) * | 2018-07-12 | 2018-12-11 | 广西华纳新材料科技有限公司 | A kind of preparation method of spindle winnofil |
| CN109160531A (en) * | 2018-11-14 | 2019-01-08 | 绍兴文理学院 | A kind of environment-friendly preparation method thereof of nanometer calcium carbonate |
-
2019
- 2019-01-14 CN CN201910030937.6A patent/CN109574057B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007254220A (en) * | 2006-03-24 | 2007-10-04 | Chugoku Electric Power Co Inc:The | Carbon dioxide fixation system and method for manufacturing carbonate |
| KR20120109683A (en) * | 2011-03-25 | 2012-10-09 | 박경원 | Manufacturing method of precipitated calcium carbonate using supercritical fluid |
| WO2014118281A1 (en) * | 2013-01-30 | 2014-08-07 | S.A. Lhoist Recherche Et Développement | Method for producing calcium carbonate gel and product obtained thereby |
| CN107445189A (en) * | 2017-09-30 | 2017-12-08 | 广西华洋矿源材料有限公司 | A kind of preparation method of needle-like nano calcium carbonate |
| CN108178177A (en) * | 2018-03-08 | 2018-06-19 | 蒋央芳 | A kind of preparation method of low agglomeration nano calcium carbonate |
| CN108975372A (en) * | 2018-07-12 | 2018-12-11 | 广西华纳新材料科技有限公司 | A kind of preparation method of spindle winnofil |
| CN109160531A (en) * | 2018-11-14 | 2019-01-08 | 绍兴文理学院 | A kind of environment-friendly preparation method thereof of nanometer calcium carbonate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112777618A (en) * | 2021-02-26 | 2021-05-11 | 绵阳远达电子材料有限公司 | Production process of magnesium carbonate |
| CN115196662A (en) * | 2022-07-20 | 2022-10-18 | 中国科学院兰州化学物理研究所 | Preparation method of cubic nano calcium carbonate |
| CN115196662B (en) * | 2022-07-20 | 2023-12-19 | 中国科学院兰州化学物理研究所 | Preparation method of cubic nano calcium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109574057B (en) | 2020-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105400237B (en) | A kind of surface treatment method for the nano-calcium carbonate for being applied to filling silicone sealant | |
| CN106430890A (en) | Sludge dewatering method for reduction | |
| CN106881059A (en) | A kind of preparation method of iron/carbon composite | |
| CN109574057A (en) | A kind of preparation method of calcium carbonate | |
| CN105906725B (en) | A kind of preparation method of tartaric acid modified carboxyl nano-crystal cellulose | |
| CN105482500B (en) | The surface modifying method of silicone sealant antioxidant nano-calcium carbonate | |
| CN111994901B (en) | Preparation method and application of hydrophobic graphene aerogel | |
| CN109650431A (en) | A kind of preparation method of MS glue nanometer calcium carbonate | |
| CN105906723B (en) | A kind of preparation method of citric acid-modified carboxylated nano-crystal cellulose | |
| CN106752102A (en) | A kind of preparation method of the high-dispersion nano calcium carbonate for being applied to nylon engineering plastic | |
| CN111847492B (en) | Preparation method of nano ettringite particles and modified nano ettringite particles and application of nano ettringite particles and modified nano ettringite particles in polyurethane film | |
| CN106928753A (en) | A kind of preparation method for PVC automobile chassis stone-impact-proof paint modified calcium carbonates | |
| CN108862289A (en) | A kind of mesoporous silicon dioxide nano particle of small particle large aperture and preparation method thereof | |
| CN105347700A (en) | Preparing method of modified calcium hydroxide | |
| CN113247936A (en) | Method for reducing energy consumption in production of nano calcium carbonate | |
| CN112979198B (en) | Modified montmorillonite self-repairing agent and preparation method and application thereof | |
| CN109721330A (en) | GO-SiO2Preparation method of composite ultrahigh molecular weight polyethylene fiber gas distribution gel | |
| CN106752100A (en) | Modified morphology controllable nano-calcium carbonate powder of a kind of compound alkali lignin APEO activating agent and preparation method thereof | |
| CN107244667B (en) | A kind of amphipathic aeroge and preparation method | |
| CN109399683B (en) | Preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer | |
| CN106590052A (en) | Polydopamine polyethenoxy ether active agent modified shape-controllable nano calcium carbonate powder and preparation method thereof | |
| CN111171213A (en) | Preparation method of PAA hydrogel loaded with double-bonded dopamine | |
| CN109422287A (en) | A kind of preparation method of calcium carbonate-silica composite powder | |
| CN112408449B (en) | Preparation method of monodisperse precipitated calcium carbonate | |
| CN109985602A (en) | CaC2And CO2Or the method and its absorption demercuration application of carbonate ball milling preparation carbon material containing oxycetylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |