CN116789157A - Preparation method of nano calcium carbonate for automobile welding seam sealant - Google Patents
Preparation method of nano calcium carbonate for automobile welding seam sealant Download PDFInfo
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- CN116789157A CN116789157A CN202310566419.2A CN202310566419A CN116789157A CN 116789157 A CN116789157 A CN 116789157A CN 202310566419 A CN202310566419 A CN 202310566419A CN 116789157 A CN116789157 A CN 116789157A
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- calcium carbonate
- slurry
- nano calcium
- seed crystal
- reaction kettle
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 278
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- 238000003466 welding Methods 0.000 title claims abstract description 45
- 239000012215 seam sealant Substances 0.000 title claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 141
- 239000002002 slurry Substances 0.000 claims abstract description 131
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 230000009471 action Effects 0.000 claims abstract description 17
- 239000011268 mixed slurry Substances 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 29
- 239000003292 glue Substances 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 235000001014 amino acid Nutrition 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 6
- 235000003704 aspartic acid Nutrition 0.000 claims description 6
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 4
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000008101 lactose Substances 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000000565 sealant Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007599 discharging Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000009974 thixotropic effect Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229920001944 Plastisol Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09J127/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- Y02P20/141—Feedstock
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Nanotechnology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of nano calcium carbonate for automobile welding seam sealant, which comprises the following steps of 2 Injecting the slurry into a seed crystal preparation tank, and introducing CO 2 The mixed gas of the above is reacted under the action of a gas distributor and ultrasonic waves to prepare nano calcium carbonate seed crystals; step two, connecting the mixed liquid pipeline with the bottom of a seed crystal preparation tank, and receiving the seed crystalThe calcium carbonate seed crystal flows into the mixed liquid pipeline, ca (OH) is injected into the mixed pipeline 2 Mixing the slurry; step three, the lower end of the liquid mixing pipeline extends into the carbonation reaction kettle and extends to the bottom of the carbonation reaction kettle, the mixed slurry mixed by the liquid mixing pipeline is injected into the carbonation reaction kettle from the bottom, and CO is introduced into the carbonation reaction kettle 2 When the pH of the slurry=7.2, the reaction is stopped, and the nano calcium carbonate slurry is prepared. The nano calcium carbonate product for the automobile welding seam sealant prepared by the invention has better stability and dispersibility, and can meet the performance requirements of sealant production enterprises.
Description
Technical Field
The invention relates to the technical field of nano calcium carbonate preparation, in particular to a preparation method of nano calcium carbonate for an automobile welding seam sealant.
Background
The sealing glue for automobile weld seam is one kind of high solid content plastisol sealing glue comprising polyvinyl chloride resin as main component, composite plasticizer and stuffing. Because it has functions of corrosion prevention, sealing, shock absorption, etc., it is usually applied to the coating of car, play a role in esthetic, waterproof, rainproof, dustproof; besides the conventional three-proofing requirement, the automobile welding seam adhesive has strict performance requirements, on one hand, the hardness, the cohesive force, the elongation, the shearing strength and the tensile strength of the sprayed coating are required to be good, and on the other hand, the automobile welding seam adhesive is required to have good dispersibility and proper viscosity. Meanwhile, the product is stable and the cost is low. The nano calcium carbonate can be widely applied to the automobile welding seam glue because the crystal form, the grain diameter and the surface modifier of the nano calcium carbonate can be regulated and controlled according to the type of the sealing glue.
The development time of the calcium carbonate industry is short, the product is influenced by late development and starting, and corresponding production equipment and process are deficient, so that the quality of the calcium carbonate is uneven, and the stability and the dispersibility are poor; the application and popularization of the domestic nano calcium carbonate in the automobile welding seam glue are limited.
Chinese patent CN112723402a discloses a method for high-pressure saponification wet method activation of nano calcium carbonate, and the activation device applied in the method comprises a reaction kettle, a saponification stirring device, a saponification discharging pipe, an activation kettle, a spiral nozzle, an activation stirring device, an emulsifying machine, a circulating pipe, a steam heating device and the like, and can be used for surface modification of nano calcium carbonate, but cannot be used for preparation of nano calcium carbonate.
Chinese patent CN111013521a discloses a nano calcium carbonate pressurized carbonation and surface modification integrated reaction kettle and application, the reaction kettle can integrate calcium carbonate reaction and surface modification, slurry does not need to be pumped to other reaction kettles, unreacted calcium hydroxide suspension is effectively controlled to enter a surface modification system, and product quality is improved; the reaction kettle can be used for producing and surface modifying common nano calcium carbonate, and for special calcium carbonate, the reaction speed is high due to the adoption of a high-speed dispersing stirring mode, and the calcium carbonate crystallization process has defects and is not suitable for preparing the special nano calcium carbonate.
Chinese patent CN 107973328A discloses a self-priming nano calcium carbonate carbonization reactor, which increases the residence time of bubbles in liquid phase by the cooperation of a guide cylinder and stirring paddles in various forms, effectively increases the gas-liquid mass transfer area of carbonation reaction, shortens the carbonation reaction time, and thus improves the carbon dioxide utilization rate; the equipment adopts hollow (mixing) shaft and turbine agitator, needs the agitator to play corresponding effect to liquid shearing action under high-speed rotation, and high-speed shearing can lead to the (mixing) shaft moment of torsion too big, and long-term use hollow (mixing) shaft can lead to fracture or eccentric, is unfavorable for the industrialization popularization.
Chinese patent CN109370261A discloses a method for preparing nano calcium carbonate for enhancing viscosity of PVC welding seam sealing adhesive, which adopts a reactor of patent CN204434303U, the reactor is provided with a plurality of annular temperature control coils around a reaction kettle stirrer, the bottom is provided with an annular gas distributor, the distributor is provided with a gas spray gun, a crushing rotary vane, a flow guiding grating plate and the like, the reaction kettle is used for preparing the nano calcium carbonate, and the reaction kettle is difficult to clean due to complex internal structure, large quality difference of different batches of products, and meanwhile, the gas spray gun adopted at the bottom has complex structure, has risk of difficult detection of blockage and is unfavorable for large-scale industrial production.
Chinese patent CN107699162a discloses a method for manufacturing a weld bead sealant, which uses calcium carbonate to fill the sealant, so as to play a role in reinforcement, but the patent does not examine the performance of the sealant from the angle of calcium carbonate.
In summary, the existing nano calcium carbonate for the automobile welding seam sealant has various defects, and the stability, the dispersibility and the like of each batch of products have certain defects, so that the performance requirements of sealant production enterprises cannot be well met, and the popularization of domestic calcium carbonate in the application of the automobile welding seam sealant is limited.
Disclosure of Invention
Aiming at the technical problems, the invention provides the preparation method of the nano calcium carbonate for the automobile welding seam sealant, which can be used for preparing the nano calcium carbonate for the automobile welding seam sealant, and the prepared nano calcium carbonate product has better stability and dispersibility in each batch and can well meet the performance requirements of sealant production enterprises.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the nano calcium carbonate for the automobile welding seam sealant comprises the following steps:
step one, preparing nano calcium carbonate seed crystals by a seed crystal preparation tank: ca (OH) 2 Injecting the slurry into a seed crystal preparation tank, and introducing CO 2 Under the action of gas distributor I and ultrasonic wave, CO 2 With Ca (OH) 2 Reacting the slurry to prepare nano calcium carbonate seed crystal;
step two, adopting a mixed liquid pipeline to carry out Ca (OH) 2 Mixing the slurry and nano calcium carbonate seed crystals: the mixed liquid pipeline is connected with the bottom of the seed crystal preparation tank, a valve is opened, nano calcium carbonate seed crystal flows into the mixed liquid pipeline, and Ca (OH) is injected into the mixed pipeline 2 Slurry, ca (OH) 2 Mixing the slurry with nano calcium carbonate seed crystal under the action of tubular static mixerMixing, the nano calcium carbonate seed crystal is uniformly distributed in Ca (OH) 2 The slurry is added;
step three, adopting a carbonation reaction kettle to carry out carbonization reaction: the lower end of the liquid mixing pipeline extends into the carbonation reaction kettle and extends to the bottom of the carbonation reaction kettle, the mixed slurry mixed by the liquid mixing pipeline is injected into the carbonation reaction kettle from the bottom, and CO is introduced into the carbonation reaction kettle 2 Performing carbonization reaction under the action of a gas distributor II, and stopping the reaction when the pH value of the slurry is 7.2, thus preparing nano calcium carbonate slurry;
and step four, carrying out surface modification, drying, crushing and packaging on the nano calcium carbonate slurry obtained in the step three to obtain the nano calcium carbonate product for the automobile welding seam sealant.
The seed crystal preparation tank is internally provided with a reactor bracket, a seed crystal reactor and CO 2 Air inlet pipe I, gas distributor I, ca (OH) 2 A slurry feeding pipe I and an ultrasonic homogenizer; the reactor bracket is arranged at the bottom of the seed crystal preparation tank, and the seed crystal reactor is of an arc-shaped structure and is arranged on the reactor bracket; the CO 2 Air inlet pipe I, ca (OH) 2 Slurry feeding pipe I is arranged on the side wall of the seed crystal preparation tank from top to bottom at intervals, and the CO is formed by 2 The front end of the air inlet pipe I is provided with a gas distributor I, and the gas distributor I is positioned in the seed crystal reactor; said Ca (OH) 2 The front end of the slurry feeding pipe I is connected with the bottom of the seed crystal reactor; when the nano calcium carbonate seed crystal reaches the upper edge of the seed crystal reactor, overflows to the bottom of the seed crystal preparation tank body and enters the mixing pipeline through the discharge port; the ultrasonic homogenizer is arranged on the side wall of the seed crystal preparation tank, and the working part of the ultrasonic homogenizer stretches into the seed crystal reactor.
Preferably, the device also comprises a water inlet pipe I and a spiral nozzle I, wherein the water inlet pipe I is horizontally arranged at the upper part in the seed crystal preparation tank and is positioned above the seed crystal reactor, and a water inlet of the water inlet pipe I is positioned on the side wall of the seed crystal preparation tank; the spiral nozzles I are arranged on the water inlet pipe I at intervals.
Preferably, the top of the seed crystal preparation tank is provided with a tail gas discharge port I and an observation port.
Preferably, the liquid mixing pipeCa (OH) is arranged on the road 2 And a pipe type static mixer is arranged in the slurry feeding port.
Preferably, a honeycomb duct bracket, a honeycomb duct and CO are arranged in the carbonation reaction kettle 2 An air inlet pipe II and a gas distributor II; the honeycomb duct bracket is arranged on the inner wall of the carbonation reaction kettle, the honeycomb duct is vertically arranged in the middle part of the carbonation reaction kettle, and the outer wall of the honeycomb duct is fixedly connected with the honeycomb duct bracket; the CO 2 The air inlet pipe II passes through the guide pipe from top to bottom, the upper end of the air inlet pipe II passes through the top of the carbonation reaction kettle, and the lower end of the air inlet pipe II is provided with the gas distributor II; stopping feeding when the liquid level of the mixed slurry reaches the top of the flow guide pipe.
Preferably, the carbonation reaction kettle also comprises a water inlet pipe II and a spiral nozzle II, wherein the water inlet pipe II is horizontally arranged at the upper part in the carbonation reaction kettle and is positioned above the diversion pipe, and a water inlet of the water inlet pipe II is positioned on the side wall of the carbonation reaction kettle; the spiral nozzles II are arranged on the water inlet pipe II at intervals.
Preferably, an ultrasonic liquid level meter interface and a manhole are arranged at the top of the carbonation reaction kettle.
Preferably, a pH sensor interface and a temperature sensor interface are arranged on the side wall of the bottom of the carbonation reaction kettle.
Preferably, the carbonation reaction kettle further comprises a slurry discharging pipe, one end of the slurry discharging pipe is connected with the bottom of the carbonation reaction kettle, the other end of the slurry discharging pipe penetrates through the base, and a slurry discharging valve is arranged on the slurry discharging pipe.
Preferably, in step one, ca (OH) 2 Adding a crystal form control agent into the slurry, wherein the crystal form control agent is one of sucrose, glucose, maltose and lactose, and the adding amount is Ca (OH) 2 0.1 to 1 percent of dry basis mass.
Preferably, the Ca (OH) 2 The temperature of the slurry is 10-15 ℃.
Preferably, in step two, ca (OH) 2 Adding an acidic amino acid stabilizer into the slurry, wherein the acidic amino acid stabilizer is one of glutamic acid and aspartic acid, and the addition amount of the acidic amino acid stabilizer is Ca (OH) 2 0.5 to 5 percent of dry basis mass.
Preferably, the Ca (OH) 2 The temperature of the slurry is 75 DEG CAt about 90 ℃.
Preferably, in step two, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 5:1-10:1.
Preferably, the CO 2 CO in a mixed gas of (a) 2 The concentration is 25% -35%.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention reasonably designs the skid-mounted equipment, has simple structure and convenient installation, simultaneously well solves the problems of stability and dispersibility of the nano calcium carbonate for the automobile welding seam sealant, is particularly suitable for industrial automatic control production, and has good economic and social benefits.
2. The invention creatively combines the seed crystal preparation tank with the carbonation reaction kettle, solves the problems of high seed crystal preparation cost and complex equipment structure in single equipment reaction, and simultaneously, the calcium carbonate seed crystal can induce calcium hydroxide and carbon dioxide to crystallize by taking the seed crystal as crystal nucleus in the synthesis reaction process of nano calcium carbonate, thereby avoiding the problems of irregular crystal morphology and uneven particle size caused by independent nucleation in the synthesis process.
3. The invention reasonably designs an arc seed crystal reactor, and the microporous disc aerator arranged in the reactor can be used for introducing CO 2 The mixed gas is dispersed into small bubbles, and the small bubbles are combined with Ca (OH) containing a crystal form control agent at low temperature under the action of ultrasonic waves 2 The slurry is more uniformly mixed, and the prepared calcium carbonate crystal has regular crystal form and small particle size.
4. The mixed liquid pipeline adopts Ca (OH) containing a stabilizer at high temperature 2 The slurry is mixed with low-temperature crystal seed-containing slurry, the solubility of calcium carbonate and calcium hydroxide can be reduced by increasing the temperature, the stability of the crystal form of the calcium carbonate is not affected, and the high temperature is helpful for the irregular movement of nano calcium carbonate crystal seed particles in the liquid, so that the crystal seeds are uniformly distributed in the slurry.
5. The invention adopts a gas stripping type carbonation reaction kettle for synthesizing nano calcium carbonate, the reaction kettle adopts a mode of ventilating gas from top gas inlet to middle and lower part gas, and the gas inlet is separated from the slurry outletThe problem that calcium carbonate crystal seeds remain in the air inlet is solved, meanwhile, the air distribution disc adopts the umbrella-shaped sawtooth air distribution disc, so that air bubbles can be cut to be smaller, the air-liquid contact surface is improved, and the CO is further improved 2 Utilization rate; the stripping reactor reduces slurry disturbance to enable Ca (OH) at high temperature 2 Slurry and CO 2 Low speed reaction at lower solubility; crystallizing under the induction of nano calcium carbonate seed crystal to form large-particle nano calcium carbonate with regular and uniform particle size of 80-200 nm.
6. The calcium carbonate prepared by the equipment of the invention has large particles, and is filled into the automobile welding seam sealant, the better the fluidity is, the more uniform and regular the particles of the calcium carbonate are, and the better the dispersibility in the system is.
Drawings
FIG. 1 is a schematic diagram of the production facility of the present invention;
FIG. 2 is a SEM image of examples 1-50000;
FIG. 3 is a SEM image of examples 2-50000;
FIG. 4 is a SEM image of examples 3-50000;
FIG. 5 is a SEM image of examples 4-50000;
FIG. 6 is a SEM image of comparative examples 1-50000;
FIG. 7 is a SEM image of comparative examples 2-50000;
FIG. 8 is a SEM image of comparative examples 3-50000;
FIG. 9 is a SEM image of comparative examples 4-50000;
in the figure, each serial number and name are as follows:
1-a seed crystal preparation tank; 2-a liquid mixing pipeline; 3-carbonating the reaction kettle; 4-a base;
111-an ultrasonic homogenizer; 112-CO 2 An air inlet pipe I; 113-gas distributor I; 114-Ca (OH) 2 A slurry feeding pipe I; 115-reactor rack; 116-seed reactor;
121-an exhaust outlet I; 122-viewing port; 123-a water inlet pipe I; 124-spiral nozzle I;
21-Ca(OH) 2 a slurry feed port; 22-tube static mixer;
311-a flow guide pipe; 312-a draft tube holder; 313-CO 2 An air inlet pipe II; 314-gas distributor II;
321-an ultrasonic level gauge interface; 322-manhole; 323-a water inlet pipe II; 324-spiral nozzle II; 325-pH sensor interface; 326—a temperature sensor interface; 327-slurry discharge pipe.
Detailed Description
One embodiment of the present invention will be described in detail below with reference to the attached drawings, but it should be understood that the scope of the present invention is not limited by the embodiment. It should be understood that the directions "up", "down", "left" and "right" in the following embodiments of the present invention are all based on the position of fig. 1. These directional terms are used for convenience of description only and do not represent any limitation on the specific technical solution of the present invention. Unless otherwise indicated, like reference numerals in the figures refer to like structures.
Example 1
As shown in figure 1, the skid-mounted nano calcium carbonate production equipment comprises a seed crystal preparation tank 1, a mixed liquid pipeline 2, a carbonation reaction kettle 3 and a base 4; the carbonation reaction kettle 3 is a gas stripping carbonation reaction kettle and is arranged on the base 4; the seed crystal preparation tank 1 is arranged above the carbonation reaction kettle 3; the upper end of the liquid mixing pipeline 2 is connected with the bottom of the seed crystal preparation tank 1, and the lower end of the liquid mixing pipeline extends into the carbonation reaction kettle 3 and extends to the bottom of the carbonation reaction kettle 3;
the seed crystal preparation tank 1 is internally provided with a reactor bracket 115, a seed crystal reactor 116 and CO 2 Air inlet pipe I112, air distributor I113 and Ca (OH) 2 Slurry feed pipe I114, ultrasonic homogenizer 111; the reactor bracket 115 is arranged at the inner bottom of the seed crystal preparation tank 1, the seed crystal reactor 116 is of an arc-shaped structure and is arranged on the reactor bracket 115; the CO 2 Air inlet pipe I112, ca (OH) 2 Slurry feeding pipe I114 is arranged on the side wall of the seed crystal preparation tank 1 from top to bottom at intervals, and the CO is 2 The front end of the air inlet pipe I112 is provided with a gas distributor I113, and the gas distributor I113 is positioned in the seed crystal reactor 116; said Ca (OH) 2 The front end of the slurry feeding pipe I114 is connected with the bottom of the seed crystal reactor 116; the ultrasonic waves are allThe mass 111 is arranged on the side wall of the seed preparation tank 1, and the working part of the mass extends into the seed reactor 116.
The device also comprises a water inlet pipe I123 and a spiral nozzle I124, wherein the water inlet pipe I123 is horizontally arranged at the upper part in the seed crystal preparation tank 1 and is positioned above the seed crystal reactor 116, and a water inlet of the water inlet pipe I123 is positioned on the side wall of the seed crystal preparation tank 1; the spiral nozzle I124 is arranged on the water inlet pipe I123 at intervals.
The top of the seed crystal preparation tank 1 is provided with a tail gas discharge port I121 and an observation port 122.
Ca (OH) is arranged on the liquid mixing pipeline 2 2 The slurry feed port 21 is provided with a tubular static mixer 22 inside.
The carbonation reaction kettle 3 is internally provided with a honeycomb duct bracket 312, a honeycomb duct 311 and CO 2 An intake pipe II 313 and a gas distributor II 314; the draft tube bracket 312 is arranged on the inner wall of the carbonation reaction kettle 3, the draft tube 311 is vertically arranged in the middle part of the carbonation reaction kettle 3, and the outer wall of the draft tube bracket 312 is fixedly connected with the draft tube bracket 312; the CO 2 The air inlet pipe II 313 passes through the guide pipe 311 from top to bottom, the upper end of the air inlet pipe II passes through the top of the carbonation reaction kettle 3, and the lower end of the air inlet pipe II is provided with the air distributor II 314.
The device also comprises a water inlet pipe II 323 and a spiral nozzle II 324, wherein the water inlet pipe II 323 is horizontally arranged at the upper part in the carbonation reaction kettle 3 and is positioned above the guide pipe 311, and a water inlet of the water inlet pipe II 323 is positioned on the side wall of the carbonation reaction kettle 3; the spiral nozzles II 324 are arranged on the water inlet pipe II 323 at intervals.
An ultrasonic liquid level meter interface 321 and a manhole 322 are arranged at the top of the carbonation reaction kettle 3.
The side wall of the bottom of the carbonation reaction kettle 3 is provided with a pH sensor interface 325 and a temperature sensor interface 326.
The device also comprises a slurry discharging pipe 327, one end of the slurry discharging pipe 327 is connected with the bottom of the carbonation reaction kettle 3, the other end of the slurry discharging pipe 327 passes through the base 4, and a slurry discharging valve is arranged on the slurry discharging pipe 327.
The preparation method of the nano calcium carbonate for the automobile welding seam sealant, which is applied to the equipment, comprises the following steps of:
step one, adoptPreparing nano calcium carbonate seed crystal by a seed crystal preparation tank: ca (OH) at 15℃temperature 2 Slurry from Ca (OH) 2 Slurry feed inlet pipe I114 opens into seed reactor 116; said Ca (OH) 2 Adding crystal form control agent lactose into the slurry, wherein the adding amount is Ca (OH) 2 0.1% of dry basis mass; at the same time, the ultrasonic homogenizer 111 is turned on and the ultrasonic homogenizer is turned on from CO 2 Air inlet pipe I112 is filled with CO 2 The mixed gas with the concentration of 25 percent is CO under the action of a gas distributor I113 and ultrasonic waves 2 With Ca (OH) 2 Reacting the slurry to prepare nano calcium carbonate seed crystal; when the mixed slurry reaches the upper edge of the seed crystal reactor 116, overflows to the bottom of the seed crystal preparation tank 1 and enters the mixing pipeline 2 through a discharge port at the bottom of the seed crystal preparation tank 1;
step two, adopting a mixed liquid pipeline to carry out Ca (OH) 2 Mixing the slurry and nano calcium carbonate seed crystals: when the nano calcium carbonate seed crystal overflows to the mixed liquid pipeline 2, ca (OH) is started 2 The slurry inlet 21 is used for introducing Ca (OH) with the temperature of 75 ℃ into the mixing pipeline 2 2 Slurry, ca (OH) 2 Adding glutamic acid stabilizer into the slurry with the addition amount of Ca (OH) 2 0.5% of dry basis mass; ca (OH) 2 The slurry is mixed with nano calcium carbonate seed crystals under the action of a pipe mixer 22, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 10:1, so that the nano calcium carbonate seed crystal is uniformly distributed in Ca (OH) 2 The slurry enters the bottom of the gas stripping carbonation reaction kettle 3;
step three, adopting a carbonation reaction kettle to carry out carbonization reaction: the liquid level of the mixed slurry continuously rises, when the mixed slurry reaches the top of the middle guide pipe 311 of the gas stripping type carbonation reaction kettle 3, the feeding is stopped, and the CO is started 2 An air inlet valve of an air inlet pipe II 313 introduces CO into the carbonation reaction kettle 3 2 The mixed gas with the concentration of 25 percent reacts, and when the pH value of the slurry is=7.2, the reaction is stopped, thus preparing the nano calcium carbonate slurry;
and step four, carrying out surface modification, drying, crushing and packaging on the nano calcium carbonate slurry obtained in the step three to obtain the nano calcium carbonate product for the automobile welding seam glue.
Example 2
The apparatus structure is the same as in example 1.
The preparation method of the nano calcium carbonate for the automobile welding seam sealant, which is applied to the equipment, comprises the following steps of:
step one, preparing nano calcium carbonate seed crystals by a seed crystal preparation tank: ca (OH) at 15℃temperature 2 Slurry from Ca (OH) 2 Slurry feed inlet pipe I114 opens into seed reactor 116; said Ca (OH) 2 Adding crystal form control agent glucose into the slurry, wherein the adding amount is Ca (OH) 2 0.5% of dry basis mass; at the same time, the ultrasonic homogenizer 111 is turned on and the ultrasonic homogenizer is turned on from CO 2 Air inlet pipe I112 is filled with CO 2 The mixed gas with the concentration of 28 percent is CO under the action of a gas distributor I113 and ultrasonic waves 2 With Ca (OH) 2 Reacting the slurry to prepare nano calcium carbonate seed crystal; when the mixed slurry reaches the upper edge of the seed crystal reactor 116, overflows to the bottom of the seed crystal preparation tank 1 and enters the mixing pipeline 2 through a discharge port at the bottom of the seed crystal preparation tank 1;
step two, adopting a mixed liquid pipeline to carry out Ca (OH) 2 Mixing the slurry and nano calcium carbonate seed crystals: when the nano calcium carbonate seed crystal overflows to the mixed liquid pipeline 2, ca (OH) is started 2 The slurry inlet 21 is used for introducing Ca (OH) with the temperature of 80 ℃ into the mixing pipeline 2 2 Slurry, ca (OH) 2 Adding glutamic acid stabilizer into the slurry with the addition amount of Ca (OH) 2 1% of the dry basis mass; ca (OH) 2 The slurry is mixed with nano calcium carbonate seed crystals under the action of a pipe mixer 22, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 8:1, so that the nano calcium carbonate seed crystal is uniformly distributed in Ca (OH) 2 The slurry enters the bottom of the gas stripping carbonation reaction kettle 3;
step three, adopting a carbonation reaction kettle to carry out carbonization reaction: the liquid level of the mixed slurry continuously rises, when the mixed slurry reaches the top of the middle guide pipe 311 of the gas stripping type carbonation reaction kettle 3, the feeding is stopped, and the CO is started 2 An air inlet valve of an air inlet pipe II 313 introduces CO into the carbonation reaction kettle 3 2 The mixed gas with the concentration of 28 percent reacts, and when the pH value of the slurry is=7.2, the reaction is stopped, thus preparing the nanometerA calcium carbonate slurry;
and step four, carrying out surface modification, drying, crushing and packaging on the nano calcium carbonate slurry obtained in the step three to obtain the nano calcium carbonate product for the automobile welding seam glue.
Example 3
The apparatus structure is the same as in example 1.
The preparation method of the nano calcium carbonate for the automobile welding seam sealant, which is applied to the equipment, comprises the following steps of:
step one, preparing nano calcium carbonate seed crystals by a seed crystal preparation tank: ca (OH) at a temperature of 12 DEG C 2 Slurry from Ca (OH) 2 Slurry feed inlet pipe I114 opens into seed reactor 116; said Ca (OH) 2 Maltose as crystal form controlling agent is added into the slurry, and the adding amount is Ca (OH) 2 1% of the dry basis mass; at the same time, the ultrasonic homogenizer 111 is turned on and the ultrasonic homogenizer is turned on from CO 2 Air inlet pipe I112 is filled with CO 2 The mixed gas with the concentration of 30 percent is CO under the action of a gas distributor I113 and ultrasonic waves 2 With Ca (OH) 2 Reacting the slurry to prepare nano calcium carbonate seed crystal; when the mixed slurry reaches the upper edge of the seed crystal reactor 116, overflows to the bottom of the seed crystal preparation tank 1 and enters the mixing pipeline 2 through a discharge port at the bottom of the seed crystal preparation tank 1;
step two, adopting a mixed liquid pipeline to carry out Ca (OH) 2 Mixing the slurry and nano calcium carbonate seed crystals: when the nano calcium carbonate seed crystal overflows to the mixed liquid pipeline 2, ca (OH) is started 2 The slurry inlet 21 is used for introducing Ca (OH) with the temperature of 85 ℃ into the mixing pipeline 2 2 Slurry, ca (OH) 2 Adding aspartic acid stabilizer into the slurry with the addition amount of Ca (OH) 2 3% of the dry basis mass; ca (OH) 2 The slurry is mixed with nano calcium carbonate seed crystals under the action of a pipe mixer 22, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 8:1, so that the nano calcium carbonate seed crystal is uniformly distributed in Ca (OH) 2 The slurry enters the bottom of the gas stripping carbonation reaction kettle 3;
step three, adopting a carbonation reaction kettle to carry out carbonization reaction: the liquid level of the mixed slurry is continuously increased until the gas stripping carbonic acid is reachedWhen the top of the middle guide pipe 311 of the reaction kettle 3 is in use, the feeding is stopped, and the CO is started 2 An air inlet valve of an air inlet pipe II 313 introduces CO into the carbonation reaction kettle 3 2 The mixed gas with the concentration of 30 percent reacts, and when the pH value of the slurry is=7.2, the reaction is stopped, thus preparing the nano calcium carbonate slurry;
and step four, carrying out surface modification, drying, crushing and packaging on the nano calcium carbonate slurry obtained in the step three to obtain the nano calcium carbonate product for the automobile welding seam glue.
Example 4
The apparatus structure is the same as in example 1.
The preparation method of the nano calcium carbonate for the automobile welding seam sealant, which is applied to the equipment, comprises the following steps of:
step one, preparing nano calcium carbonate seed crystals by a seed crystal preparation tank: ca (OH) at a temperature of 10 DEG C 2 Slurry from Ca (OH) 2 Slurry feed inlet pipe I114 opens into seed reactor 116; said Ca (OH) 2 Adding crystal form control agent sucrose into the slurry, wherein the adding amount is Ca (OH) 2 1% of the dry basis mass; at the same time, the ultrasonic homogenizer 111 is turned on and the ultrasonic homogenizer is turned on from CO 2 Air inlet pipe I112 is filled with CO 2 The mixed gas with the concentration of 35 percent is CO under the action of a gas distributor I113 and ultrasonic waves 2 With Ca (OH) 2 Reacting the slurry to prepare nano calcium carbonate seed crystal; when the mixed slurry reaches the upper edge of the seed crystal reactor 116, overflows to the bottom of the seed crystal preparation tank 1 and enters the mixing pipeline 2 through a discharge port at the bottom of the seed crystal preparation tank 1;
step two, adopting a mixed liquid pipeline to carry out Ca (OH) 2 Mixing the slurry and nano calcium carbonate seed crystals: when the nano calcium carbonate seed crystal overflows to the mixed liquid pipeline 2, ca (OH) is started 2 The slurry inlet 21 is used for introducing Ca (OH) with the temperature of 90 ℃ into the mixing pipeline 2 2 Slurry, ca (OH) 2 Adding aspartic acid stabilizer into the slurry with the addition amount of Ca (OH) 2 5% of dry basis mass; ca (OH) 2 The slurry is mixed with nano calcium carbonate seed crystals under the action of a pipe mixer 22, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 5:1, so that the nano calcium carbonate seed crystal is preparedThe calcium carbonate seed crystal is uniformly distributed in Ca (OH) 2 The slurry enters the bottom of the gas stripping carbonation reaction kettle 3;
step three, adopting a carbonation reaction kettle to carry out carbonization reaction: the liquid level of the mixed slurry continuously rises, when the mixed slurry reaches the top of the middle guide pipe 311 of the gas stripping type carbonation reaction kettle 3, the feeding is stopped, and the CO is started 2 An air inlet valve of an air inlet pipe II 313 introduces CO into the carbonation reaction kettle 3 2 The mixed gas with the concentration of 35 percent reacts, and when the pH value of the slurry is=7.2, the reaction is stopped, thus preparing the nano calcium carbonate slurry;
and step four, carrying out surface modification, drying, crushing and packaging on the nano calcium carbonate slurry obtained in the step three to obtain the nano calcium carbonate product for the automobile welding seam glue.
Comparative example 1
Substantially the same as in example 4, except that:
in the first step, the added amount of sucrose is Ca (OH) 2 2% of dry basis mass, ca (OH) 2 The slurry temperature was 16 ℃;
in the second step, the addition amount of aspartic acid is Ca (OH) 2 6% of dry basis mass, ca (OH) 2 The slurry temperature was 95℃and Ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 4:1.
Comparative example 2
Substantially the same as in example 4, except that:
in the first step, the added amount of sucrose is Ca (OH) 2 0.05% by mass of dry basis, ca (OH) 2 The slurry temperature was 9 ℃;
in the second step, the addition amount of aspartic acid is Ca (OH) 2 0.4% of dry mass, ca (OH) 2 The slurry temperature was 70 ℃, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 11:1.
Comparative example 3
Substantially the same as in example 4, except that: preparation of Ca (OH) from seed tank 1 2 The slurry feed line I114 was fed with tap water.
Comparative example 4
And the actual onesExample 4 is essentially the same except that: ca (OH) from mixing tube 2 2 The slurry feed port 21 is filled with tap water.
Comparative experiments
SEM test is carried out on the nano calcium carbonate prepared in the examples 1-4 and the comparative examples 1-4 according to the test method of GB/T19590 (nano calcium carbonate), and the test results are shown in the attached drawings; and the corresponding products are filled in the automobile welding seam sealant, and the formula of the automobile welding seam sealant is shown in table 1.
The preparation method of the automobile welding seam glue comprises the following steps: and (3) weighing PVC paste resin and nano calcium carbonate according to the formula proportion, putting the PVC paste resin and the nano calcium carbonate into a mixing cup of a high-speed dispersing machine, regulating the rotating speed to be 500rpm/min, premixing for 10min, weighing DOP, calcium stearate, calcium oxide and zinc oxide into the premix according to the proportion, starting stirring at 2500rpm/min, and mixing for 1h to obtain a required sample.
Table 1 automobile weld sealant formulation
| Name of the name | Parts by weight |
| PVC paste resin | 35 |
| Nanometer calcium carbonate | 25 |
| DOP | 20 |
| Calcium stearate | 3 |
| Zinc oxide | 2 |
| Calcium oxide | 5 |
The automobile welding seam sealant prepared above was subjected to a Bowler fly rotation viscosity test, an extrusion rate test, a thixotropic ring area test, a yield value test and a Bingham viscosity test according to the following methods, and the test results are shown in Table 2.
Bohler fly rotational viscosity: the samples were tested using a Bowler-femto DV-3T viscometer with a test rotor of # 7 and a shear rate of 2 rpm.
Extrusion rate: the time in s/40g required for the sample to flow out of 40g was measured using a pressure flow viscometer under a pressure of 2bar with a nozzle of 1.5 mm.
Touch ring area: the touch ring area test uses an Anton Paar MCR102 rotation mode test, and the shear rate change program is from (0-300) S-1 within 5 min; maintaining the shear rate at 300S-1 for 3min; the shear rate was then set to (300-0) S-1 in 5 min.
The yield value and the Bingham viscosity are obtained by fitting thixotropic ring area test data.
Table 2 results of test for performance of automotive bead sealant
From the test results and SEM test results in Table 2, it is clear that the nano calcium carbonate products for the automobile welding seam sealant prepared by the methods in examples 1 to 4 of the invention form regular large-particle cubic nano calcium carbonate with uniform particle size, good micro-dispersion effect and about 100 nm; the nano calcium carbonate filled automobile welding seam sealant has the characteristics of high viscosity, good flow property, high thixotropic ring area, and higher yield value and Bingham viscosity.
As can be seen from comparative examples 1 and 2, the same equipment is adopted, the technological parameters are not in the required range of the invention, and compared with the viscosity of example 4, the prepared nano calcium carbonate filled automobile welding seam sealant has the advantages of reduced viscosity, poor flow performance, and reduced touch ring, yield value and Bingham viscosity.
From comparative example 3, it is known that the nano calcium carbonate filled automotive bead sealant without using the seed crystal preparation tank has low viscosity and better flow property, but has lower contact ring area, yield value and Bingham viscosity and basically no thixotropic property.
As can be seen from comparative example 4, the prepared nano calcium carbonate seed crystal is not added with raw slurry for slurry supplementing and carbonation, the prepared nano calcium carbonate has small particles, more agglomeration, irregular morphology and chain nano calcium carbonate, and compared with example 4, the product filled in the automobile welding seam sealant has the advantages of reduced viscosity, poor flow property, reduced contact ring, yield value and Bingham viscosity, and poor thixotropic property.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The preparation method of the nano calcium carbonate for the automobile welding seam sealant is characterized by comprising the following steps of:
step one, preparing nano calcium carbonate seed crystals by adopting a seed crystal preparation tank (1): ca (OH) 2 Injecting slurry into a seed crystal preparation tank (1), and introducing CO 2 Under the action of a gas distributor I (113) and ultrasonic waves, CO 2 With Ca (OH) 2 Reacting the slurry to prepare nano calcium carbonate seed crystal;
step two, adopting a mixed liquid pipeline (2) to carry out Ca (OH) 2 Mixing the slurry and nano calcium carbonate seed crystals: the liquid mixing pipeline (2) is connected with the bottom of the seed crystal preparation tank (1), and a valve is opened to nano carbonic acidThe calcium seed crystal flows into the mixed liquid pipeline (2), and Ca (OH) is injected into the mixed pipeline (2) 2 Slurry, ca (OH) 2 The slurry is mixed with nano calcium carbonate seed crystals under the action of a tubular static mixer (22) to ensure that the nano calcium carbonate seed crystals are uniformly distributed in Ca (OH) 2 The slurry is added;
step three, performing carbonization reaction by adopting a carbonation reaction kettle (3): the lower end of the liquid mixing pipeline (2) stretches into the carbonation reaction kettle (3) and extends to the bottom of the carbonation reaction kettle (3), the mixed slurry mixed by the liquid mixing pipeline (2) is injected into the carbonation reaction kettle (3) from the bottom, and CO is introduced 2 Performing carbonization reaction under the action of a gas distributor II (314), and stopping the reaction when the pH value of the slurry is 7.2, thus preparing nano calcium carbonate slurry;
and step four, carrying out surface modification, drying, crushing and packaging on the nano calcium carbonate slurry obtained in the step three to obtain the nano calcium carbonate product for the automobile welding seam sealant.
2. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 1, wherein the method comprises the following steps: a reactor bracket (115), a seed crystal reactor (116) and CO are arranged in the seed crystal preparation tank (1) 2 Air inlet pipe I (112), gas distributor I (113), ca (OH) 2 A slurry feed pipe I (114) and an ultrasonic homogenizer (111); the reactor bracket (115) is arranged at the inner bottom of the seed crystal preparation tank (1), the seed crystal reactor (116) is of an arc-shaped structure and is arranged on the reactor bracket (115); the CO 2 Inlet I (112), ca (OH) 2 Slurry feeding pipes I (114) are arranged on the side wall of the seed crystal preparation tank (1) from top to bottom at intervals, and the CO 2 The front end of the air inlet pipe I (112) is provided with a gas distributor I (113), and the gas distributor I (113) is positioned in the seed crystal reactor (116); said Ca (OH) 2 The front end of the slurry feeding pipe I (114) is connected with the bottom of the seed crystal reactor (116); when the nano calcium carbonate seed crystal reaches the upper edge of the seed crystal reactor (116), overflows to the bottom of the seed crystal preparation tank body (1) and enters the mixing pipeline (2) through the discharge port; the ultrasonic homogenizer (111) is arranged on the side wall of the seed crystal preparation tank (1), and the working part of the ultrasonic homogenizer stretches into the seed crystal reactor116 Is provided) is provided.
3. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 1, wherein the method comprises the following steps: ca (OH) is arranged on the liquid mixing pipeline (2) 2 And a slurry feed port (21) inside which a tubular static mixer (22) is arranged.
4. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 1, wherein the method comprises the following steps: a draft tube bracket (312), a draft tube (311) and CO are arranged in the carbonation reaction kettle (3) 2 An air inlet pipe II (313) and a gas distributor II (314); the draft tube support (312) is arranged on the inner wall of the carbonation reaction kettle (3), the draft tube (311) is vertically arranged in the middle part of the carbonation reaction kettle (3), and the outer wall of the draft tube is fixedly connected with the draft tube support (312); the CO 2 The air inlet pipe II (313) passes through the guide pipe (311) from top to bottom, the upper end of the air inlet pipe II passes through the top of the carbonation reaction kettle (3), and the lower end of the air inlet pipe II is provided with the air distributor II (314); stopping feeding when the liquid level of the mixed slurry reaches the top of the guide pipe (311).
5. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 1, wherein the method comprises the following steps: in step one, ca (OH) 2 Adding a crystal form control agent into the slurry, wherein the crystal form control agent is one of sucrose, glucose, maltose and lactose, and the adding amount is Ca (OH) 2 0.1 to 1 percent of dry basis mass.
6. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 5, wherein the method comprises the following steps: said Ca (OH) 2 The temperature of the slurry is 10-15 ℃.
7. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 1, wherein the method comprises the following steps: in the second step, ca (OH) 2 Adding an acidic amino acid stabilizer into the slurry, wherein the acidic amino acid stabilizer is one of glutamic acid and aspartic acid, and the addition amount of the acidic amino acid stabilizer is Ca (OH) 2 0.5 to 5 percent of dry basis mass.
8. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 7, wherein the method comprises the following steps: said Ca (OH) 2 The temperature of the slurry is 75-90 ℃.
9. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 7, wherein the method comprises the following steps: in the second step, ca (OH) 2 The volume ratio of the slurry to the nano calcium carbonate seed crystal is 5:1-10:1.
10. The method for preparing nano calcium carbonate for automobile welding seam sealing glue according to claim 1, wherein the method comprises the following steps: the CO 2 CO in a mixed gas of (a) 2 The concentration is 25% -35%.
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