CN110877962A - Surface modified heavy calcium carbonate suitable for artificial stone filler - Google Patents
Surface modified heavy calcium carbonate suitable for artificial stone filler Download PDFInfo
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- CN110877962A CN110877962A CN201910926975.XA CN201910926975A CN110877962A CN 110877962 A CN110877962 A CN 110877962A CN 201910926975 A CN201910926975 A CN 201910926975A CN 110877962 A CN110877962 A CN 110877962A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- artificial stone
- heavy calcium
- modified heavy
- coupling agent
- 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.)
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Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 120
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 54
- 239000002969 artificial stone Substances 0.000 title claims abstract description 49
- 239000000945 filler Substances 0.000 title claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 229920002401 polyacrylamide Polymers 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001444 polymaleic acid Polymers 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000011049 filling Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000010438 granite Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses surface modified heavy calcium carbonate suitable for artificial stone filler, which comprises the following raw materials: the ore, the additive A and the additive B are obtained by adopting a vertical mill device and controlling specific production parameters. The invention adds the assistant A and the assistant B on the basis of the existing heavy calcium carbonate, adopts a vertical mill for grinding, and is controlled by specific production parameters, the obtained modified calcium carbonate has the characteristics of wide particle size distribution, large specific surface area, high activation degree, low oil absorption value and application performance greatly superior to that of common calcium carbonate, the obtained modified calcium carbonate has good dispersibility and compatibility in the production of artificial stones, the calcium carbonate filling amount accounts for more than 81 percent of the mass of artificial stones, the production cost is greatly reduced, and the invention is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of heavy calcium carbonate preparation, and particularly relates to surface modified heavy calcium carbonate suitable for artificial stone filler.
Background
The artificial stone as the latest artificial building material has the advantages of high strength, high hardness, high temperature resistance, corrosion resistance, ageing resistance, easy cleaning, wear resistance, pure material, no radiation and the like which are incomparable with natural stone. The artificial stone is the best substitute of natural stone as non-renewable resources, and meanwhile, the artificial stone can adopt leftover materials of marble materials and calcite materials as raw materials, so that the resource recycling is realized while the environment is protected, and the advantages enable the artificial stone to become a new and expensive building decoration industry and to be widely applied to the ground, wall decoration and home furnishing industries of cabinets, bathrooms, offices and large markets.
Calcium carbonate is a common inorganic filler, and is widely used in the fields of artificial stones, plastics, rubber, coatings and the like due to wide sources, low price and the like. However, the calcium carbonate has hydrophilic and oleophobic surfaces, large specific surface area, high surface energy and easy agglomeration among particles, and is difficult to disperse uniformly and weak in binding force with a matrix when being directly or greatly filled in an organic matrix material, so that the defects of two-phase interfaces and certain performances of the composite material are reduced. Therefore, in order to widen the application field, the surface of calcium carbonate must be modified to make the surface oleophilic and hydrophobic, to enhance the compatibility with the artificial stone, to enhance the dispersibility in organic matrix materials, and to improve and enhance the performance of the composite material.
Disclosure of Invention
The invention provides surface modified heavy calcium carbonate suitable for artificial stone filler, which aims to solve the practical problems of how to develop novel modified calcium carbonate, improve the filling amount of calcium carbonate in artificial stone, reduce the production cost of artificial stone and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a surface modified heavy calcium carbonate suitable for artificial stone filler comprises the following raw materials: ore, an additive A and an additive B.
Preferably, the assistant A comprises one or more of titanate coupling agent, silane coupling agent, aluminate coupling agent and zircoaluminate coupling agent.
Preferably, the auxiliary agent A is a titanate coupling agent.
Preferably, the addition amount of the titanate coupling agent is 0.8-1% of the mass of the ore.
Preferably, the auxiliary agent B comprises one or more of polyacrylic acid, polyethylene glycol, polymaleic acid and polyacrylamide.
Preferably, the auxiliary agent B is polyacrylamide.
Preferably, the amount of acrylamide added is 0.5-0.7% of the mass of the ore.
Preferably, the particle size distribution of the surface modified heavy calcium carbonate is 60-80 μm D97 and 4-6 μm D50.
Preferably, the particle size distribution of the surface modified heavy calcium carbonate is D97 ═ 100-.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds the assistant A and the assistant B on the basis of the existing heavy calcium carbonate, adopts a vertical mill for grinding, and is controlled by specific production parameters, the obtained modified calcium carbonate has the characteristics of wide particle size distribution, large specific surface area, low oil absorption value, high activation degree and application performance greatly superior to that of common calcium carbonate, the obtained modified calcium carbonate has good dispersibility and compatibility in the production of artificial stones, the filling amount of the calcium carbonate obtained by modifying the calcium carbonate by adopting the titanate coupling agent and the acrylamide accounts for more than 81 percent of the mass of the artificial stones, the production cost is greatly reduced, and the invention is more environment-friendly.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
A surface modified heavy calcium carbonate suitable for artificial stone filler comprises the following raw materials: ore, an additive A and an additive B;
the auxiliary agent A comprises one or more of titanate coupling agent, silane coupling agent, aluminate coupling agent and zircoaluminate coupling agent;
the auxiliary agent B comprises one or more of polyacrylic acid, polyethylene glycol, polymaleic acid and polyacrylamide;
the preparation method of the surface modified heavy calcium carbonate suitable for the artificial stone filler comprises the following steps: the ore is crushed after being cleaned, the auxiliary agent A and the auxiliary agent B are added into a screw conveyer to be mixed into paste, the paste enters grinding equipment to be ground, and after being classified by a rotating speed classifier, calcium carbonate with the particle size distribution suitable for being special for the artificial stone is obtained through collection.
In order to ensure that the special calcium carbonate for the artificial stone meets the production requirements, the invention screens the optimal auxiliary agent type and dosage and the control parameters of the vertical mill, and concretely comprises the following steps:
(1) screening research test for type and dosage of optimal auxiliary agent A
Researches find that the types and the adding amount of the auxiliary agent A (titanate coupling agent, silane coupling agent, aluminate coupling agent and zircoaluminate coupling agent) have small influence on the fineness of the product and mainly influence the modification effect, and the invention is tested by a small granite testing machine:
when the adding amount of the polyacrylamide is 0.7 percent and other parameters are not changed, the special calcium carbonate for the artificial stone is added with the coupling agent of the titanate and other testing auxiliary agents in the amount of 0.5 to 1.2 percent and is mixed with the resin to form blocks for comparison, and the results are shown in the following table:
| amount of addition | Silane coupling agent | Aluminate coupling agent | Zircoaluminate coupling agent | Coupling of titanatesAgent for treating cancer |
| 0.5％ | 71：29 | 73：27 | 66：34 | 79：21 |
| 0.6％ | 73：27 | 76：24 | 69：31 | 81：19 |
| 0.7％ | 75：25 | 78：22 | 71：29 | 83：17 |
| 0.8％ | 76：24 | 79：21 | 72：28 | 85：15 |
| 0.9％ | 76：24 | 80：20 | 73：27 | 86：14 |
| 1％ | 75：25 | 79：21 | 73：27 | 86：14 |
| 1.1％ | 75：25 | 78：22 | 72：28 | 85：15 |
| 1.2％ | 75：25 | 78：22 | 72：28 | 85：15 |
From the data in the table, the calcium carbonate powder added in the artificial stone industry with the modification dosage of the titanate coupling agent of 0.8-1.0% is superior to other modification additives, which indicates that the modification effect is the best, and also indicates that the modification effect is not increased basically by increasing the additive dosage, but the production cost is increased, so the type of the optimal additive A is the titanate coupling agent, and the optimal dosage of the titanate coupling agent is 0.8-1.0%.
(2) Screening research test for type and dosage of optimal auxiliary agent B
The types of the screened auxiliary agents B comprise polyacrylic acid, polyethylene glycol, polymaleic acid and polyacrylamide, and the types and the dosage of the optimum auxiliary agents B are screened through a small granite tester test.
When the addition amount of the titanate coupling agent is 0.9 percent, other parameters are unchanged, and the modified special calcium carbonate for the artificial stone is added with polyacrylamide and other auxiliary agents in an amount of 0.3 to 1.0 percent and is mixed with resin to form blocks, the results are as follows:
from the data, when the modification dosage of the titanate coupling agent is 0.9%, 0.5% -0.7% of polyacrylamide is added for adding calcium carbonate powder in the artificial stone industry better than other modification auxiliary agents, which indicates that the modification effect is the best, and also indicates that the modification effect is not increased basically by increasing the auxiliary amount of the polyacrylamide, but the production cost is increased, so that the type of the optimal auxiliary agent B is polyacrylamide, and the optimal dosage of the polyacrylamide is 0.5% -0.7%.
(3) Control parameter screening research of vertical mill
The parameters influenced by the vertical mill are several, namely host machine current, host machine material layer thickness, grinding roller oil pressure, classifier rotating speed, classifier current, fan rotating speed and fan current. The particle size (D97, D50) of the calcium carbonate special for the artificial stone can be obtained by the following parameter combinations through repeated tests.
The serial numbers 1 and 2 in the table are full powder plates for artificial stones, the process is relatively simple, and the cost is relatively low; the numbers 3 and 4 in the table are the powder sand plates for the artificial stone, and the mechanical properties are better.
The following is a more specific example.
Example 1
A surface modified heavy calcium carbonate suitable for artificial stone filler comprises the following raw materials: the preparation method of the mineral, the titanate coupling agent and the polyacrylamide comprises the following steps: after being cleaned, the ore is crushed to the particle size of less than 28mm, 1 percent of titanate coupling agent of the mass of the ore and 0.5 percent of polyacrylamide of the mass of the ore are added into a screw conveyer to be mixed into paste to be ground in a grinding device of a vertical mill, the oil pressure of a grinding roller is 5MPa during grinding, the paste is classified by a rotating speed classifier, the rotating speed of the rotating speed classifier is 380-400r/min, and the surface modified heavy calcium carbonate with the particle size distribution (D97 is 110 mu m when being 100-11 mu m and D50 is 11-12 mu m) suitable for the artificial stone filler is collected.
Example 2
A surface modified heavy calcium carbonate suitable for artificial stone filler comprises the following raw materials: the preparation method of the mineral, the titanate coupling agent and the polyacrylamide comprises the following steps: after being cleaned, the ore is crushed to the particle size of less than 30mm, a titanate coupling agent accounting for 0.8 percent of the mass of the ore and polyacrylamide accounting for 0.6 percent of the mass of the ore are added into a screw conveyer to be mixed into paste to be ground in a grinding device of a vertical mill, the oil pressure of a grinding roller during grinding is 6.5MPa, the paste is classified by a rotating speed classifier, the rotating speed of the rotating speed classifier is 420-430r/min, and the surface modified heavy calcium carbonate with the particle size distribution (D97 is 70-80 mu m, D50 is 5-6 mu m) suitable for the artificial stone filler is collected.
Example 3
A surface modified heavy calcium carbonate suitable for artificial stone filler comprises the following raw materials: the preparation method of the mineral, the titanate coupling agent and the polyacrylamide comprises the following steps: after being cleaned, the ore is crushed to the particle size of less than 29mm, a titanate coupling agent accounting for 0.9 percent of the mass of the ore and polyacrylamide accounting for 0.7 percent of the mass of the ore are added into a screw conveyer and are mixed into paste to be ground in a vertical mill grinding device, the oil pressure of a grinding roller is 7MPa during grinding, the paste is classified by a rotating speed classifier, the rotating speed of the rotating speed classifier is 420-430r/min, and the surface modified heavy calcium carbonate with the particle size distribution (D97 is 60-70 mu m, D50 is 4-5 mu m) suitable for the artificial stone filler is collected.
Comparative example 1
A surface modified heavy calcium carbonate suitable for artificial stone filler comprises the following raw materials: ore, polyacrylamide, a process for their preparation comprising the steps of: after cleaning, crushing the ore until the particle size is less than 29mm, adding polyacrylamide accounting for 0.7 percent of the mass of the ore into a screw conveyer, mixing the mixture into paste, grinding the paste by a ring roller mill grinding device, grading the paste by a rotary speed grader at the rotary speed of 600 plus materials of 650r/min, and collecting the modified heavy calcium carbonate.
Compared with the performances of the surface modified heavy calcium carbonate and the unmodified calcium carbonate of the artificial stone filler produced by the embodiments 1-3 of the invention, the oil absorption value of the obtained modified heavy calcium carbonate is reduced by at least 40.56 percent, the viscosity is reduced by at least 51.74 percent, and the activation rate is improved by at least 82.97 percent compared with the unmodified calcium carbonate; compared with the performance of the modified calcium carbonate of the comparative example 1, the modified heavy calcium carbonate of the artificial stone filler produced by the implementation 1-3 of the invention has the advantages that the performance of the modified calcium carbonate of the comparative example 1 is compared, the modified heavy calcium carbonate obtained by the common ring roller mill equipment has narrower particle size distribution, although the modification is carried out, the oil absorption value of the modified heavy calcium carbonate obtained by the implementation 1-3 of the invention is at least reduced by 16.39 percent compared with that of the modified calcium carbonate of the comparative example 1, the viscosity is at least reduced by 14.31 percent, the activation rate is at least improved by 12.08 percent, the modified calcium carbonate is oleophilic and hydrophobic, the compatibility with other raw materials of the artificial stone is good, the filling amount of the calcium carbonate accounts for more than 80 percent of the mass of the artificial stone, and the filling amount of the modified calcium carbonate of the comparative example.
The above description should not be taken as limiting the invention to the specific embodiments, but rather, as will be readily apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined in the claims appended hereto.
Claims (9)
1. The surface modified heavy calcium carbonate suitable for the artificial stone filler is characterized by comprising the following raw materials: ore, an additive A and an additive B.
2. A surface-modified heavy calcium carbonate suitable for artificial stone fillers according to claim 1, wherein said assistant a comprises one or more of titanate coupling agent, silane coupling agent, aluminate coupling agent, zircoaluminate coupling agent.
3. A surface-modified heavy calcium carbonate suitable for artificial stone fillers according to claim 2, characterized in that the aid a is a titanate coupling agent.
4. A surface-modified heavy calcium carbonate suitable for artificial stone fillers according to claim 3, wherein the titanate coupling agent is added in an amount of 0.8-1% by mass of the ore.
5. A surface-modified heavy calcium carbonate suitable for artificial stone filler according to claim 1, characterized in that said auxiliary agent B comprises one or more of polyacrylic acid, polyethylene glycol, polymaleic acid, polyacrylamide.
6. A surface-modified heavy calcium carbonate suitable for artificial stone filler according to claim 1, characterized in that the aid B is polyacrylamide.
7. A surface-modified heavy calcium carbonate suitable for artificial stone fillers according to claim 6, characterized in that said acrylamide is added in an amount of 0.5-0.7% of the ore mass.
8. A surface-modified heavy calcium carbonate suitable for artificial stone fillers according to claim 1, characterized in that the particle size distribution of the surface-modified heavy calcium carbonate is 60-80 μ ι η when D97 is 60-80 μ ι η and 4-6 μ ι η when D50 is 4-6 μ ι η.
9. A surface-modified heavy calcium carbonate suitable for artificial stone fillers according to claim 1, wherein the particle size distribution of the surface-modified heavy calcium carbonate is D97 ═ 100-.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910926975.XA CN110877962B (en) | 2019-09-27 | 2019-09-27 | Surface modified heavy calcium carbonate suitable for artificial stone filler |
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| Publication Number | Publication Date |
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| CN110877962A true CN110877962A (en) | 2020-03-13 |
| CN110877962B CN110877962B (en) | 2022-03-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116925573A (en) * | 2023-07-20 | 2023-10-24 | 浙江钦堂钙业有限公司 | Activated modified heavy calcium carbonate and preparation method thereof |
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| CN104497636A (en) * | 2014-11-28 | 2015-04-08 | 黄国新 | Preparation method of polyacrylamide modified heavy calcium carbonate powder |
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| CN107572901A (en) * | 2017-07-31 | 2018-01-12 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of application of modified calcium carbonate in quartzite slate |
| CN108948795A (en) * | 2018-08-03 | 2018-12-07 | 广西贺州市科隆粉体有限公司 | Surface modification method of special flame-retardant heavy calcium carbonate for wires and cables |
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2019
- 2019-09-27 CN CN201910926975.XA patent/CN110877962B/en active Active
Patent Citations (6)
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| CN102504608A (en) * | 2011-10-20 | 2012-06-20 | 张家界恒亮新材料科技有限公司 | Preparation method of micronano level surface-modified ground limestone and product thereof |
| CN104497636A (en) * | 2014-11-28 | 2015-04-08 | 黄国新 | Preparation method of polyacrylamide modified heavy calcium carbonate powder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116925573A (en) * | 2023-07-20 | 2023-10-24 | 浙江钦堂钙业有限公司 | Activated modified heavy calcium carbonate and preparation method thereof |
| CN116925573B (en) * | 2023-07-20 | 2024-04-05 | 浙江钦堂钙业有限公司 | Activated modified heavy calcium carbonate and preparation method thereof |
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