CN113943498A - Modification method of calcium carbonate for tableware - Google Patents
Modification method of calcium carbonate for tableware Download PDFInfo
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- CN113943498A CN113943498A CN202010694330.0A CN202010694330A CN113943498A CN 113943498 A CN113943498 A CN 113943498A CN 202010694330 A CN202010694330 A CN 202010694330A CN 113943498 A CN113943498 A CN 113943498A
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- 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
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- 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
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- 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
- C09C3/06—Treatment with inorganic compounds
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- 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
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- 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
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/21—Attrition-index or crushing strength of granulates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/37—Stability against thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Abstract
The invention relates to a modification method of calcium carbonate for tableware, which comprises the following steps: 1) crushing and grinding light calcium carbonate to obtain calcium carbonate powder with the particle size of 600-1000 meshes, mixing the calcium carbonate powder with water according to the weight ratio of 1: mixing the first suspension liquid with the ratio of 10-20, and concentrating the suspension liquid into a second suspension liquid with the solid content of 40-60%; 2) adding the second suspension into a stirring reaction kettle, adding a first modifier while stirring, and dehydrating and drying after the reaction to obtain primary modified calcium carbonate; 3) continuously adding the primary modified calcium carbonate into a stirring reaction kettle, adding a second modifier while stirring, adding the second modifier in an atomized form, uniformly stirring, drying, and sieving with a 400-700-mesh sieve; the first modifier consists of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, and the second modifier consists of chitosan, 2, 6-di-tert-butyl cresol and castor oil maleate. The overall strength, antibacterial property and oxidation resistance of the modified light calcium carbonate are greatly improved.
Description
Technical Field
The invention relates to the technical field of calcium carbonate processing, in particular to a modification method of calcium carbonate for tableware.
Background
Light calcium carbonate is usedChemically processed, heavy calcium carbonate is called light calcium carbonate because it has a larger sediment volume than mechanically produced heavy calcium carbonate. It has the chemical formula of CaCO3It reacts with all strong acids to form the corresponding calcium salt with evolution of carbon dioxide. At normal temperature, the concentration product of the light calcium carbonate in water is 8.7/1029, and the solubility is 0.0014; the pH value of the light calcium carbonate aqueous solution is 9.5-10.2; the pH value of the air saturated light calcium carbonate aqueous solution is 8.0-8.6; the light calcium carbonate is non-toxic, odorless and nonirritating, is generally white, and has a relative density of 2.7-2.9; the sedimentation volume is more than 2.5ml/g, and the specific surface area is about 5m 2/g.
The existing tableware is mostly prepared from plastics, and calcium carbonate powder is filled in the preparation process, so that the cost is greatly reduced. However, the existing light calcium carbonate has the following problems: the surface of unmodified calcium carbonate powder is hydrophilic and oleophobic, better chemical crosslinking can not be generated between the calcium carbonate powder and resin, and the calcium carbonate powder is difficult to uniformly disperse in an organic medium, and a product obtained by applying the ordinary modified calcium carbonate powder to tableware processing in the prior art has poor heat resistance, low structural strength, easy aging and yellowing, poor antibacterial property and easy aging, yellowing and blackening after long-term use, even generates mould and the like, so the improvement is urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for modifying calcium carbonate for tableware, which solves the problems in the background art.
The technical problem solved by the invention is realized by adopting the following technical scheme:
a modification method of calcium carbonate for tableware comprises the following steps:
1) crushing and grinding light calcium carbonate to obtain calcium carbonate powder with the particle size of 600-1000 meshes, mixing the calcium carbonate powder with water according to the weight ratio of 1: mixing the first suspension liquid with the ratio of 10-20, and concentrating the suspension liquid into a second suspension liquid with the solid content of 40-60%;
2) adding the second suspension into a stirring reaction kettle, adding a first modifier while stirring, and dehydrating and drying after the reaction to obtain primary modified calcium carbonate;
3) continuously adding the primary modified calcium carbonate into a stirring reaction kettle, adding a second modifier while stirring, adding the second modifier in an atomized form, uniformly stirring, drying, and sieving with a 400-700-mesh sieve;
the first modifier consists of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, and the second modifier consists of chitosan, 2, 6-di-tert-butyl cresol and castor oil maleate.
Further, in the step 2), the adding amount of the first modifier is 1-2% of the weight of the calcium carbonate powder.
Further, in the step 2), in the first modifier, the mass ratio of pentaerythritol stearate to the silver antibacterial agent to the nano silicon dioxide is 1-1.5: 0.5-1: 1 to 2.
Further, in the step 2), the stirring speed of the stirring kettle is 300-500 r/min, and the stirring reaction is carried out for 40-60 min.
Further, in the step 3), the addition amount of the second modifier is 5-6% of the weight of the primarily modified calcium carbonate powder.
Further, in the step 3), the mass ratio of chitosan, 2, 6-di-tert-butylcresol and castor oil maleate in the second modifier is 2-4: 1-2: 3 to 5.
Further, in the step 3), the second modifier is atomized by ultrasonic atomization, the chitosan is dissolved in the citric acid, and the 2, 6-di-tert-butyl cresol is dissolved in the ricinoleic maleate and then atomized respectively.
Further, in the step 3), the speed of the stirring kettle is 1200-1400 r/min, and the stirring reaction is carried out for 20-30 min.
Further, the chitosan is low molecular weight chitosan with the molecular weight of less than 3000 and the polymerization degree of 2-20.
Has the advantages that: the invention relates to a modification method of calcium carbonate for tableware, which carries out primary surface modification on calcium carbonate by a first modifier consisting of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, improves the thermal stability, the overall strength and the antibacterial property of the calcium carbonate after the primary modification, ensures the dispersibility of the calcium carbonate, further carries out secondary modification by a second modifier consisting of chitosan, 2, 6-ditert-butylcresol and ricinoleic maleate, is used for coating the silver antibacterial agent which is easy to discolor, further improves the antibacterial performance, reduces the generation of oxidation blackening of the silver antibacterial agent and oxidation yellowing of plastics, has hydrophilic and oleophilic dual-polarity functions on the surface of the calcium carbonate, leads the surface of a filler to be excessive from inorganic to organic, improves the crosslinking degree of the surface of the calcium carbonate and resin by the synergistic action among various components, and compatibility, so that the structure is firmer.
According to the invention, the antibacterial property, the discoloration resistance and the overall strength of the modified calcium carbonate product are greatly improved through the first wet modification and the second atomization modification, and the modified calcium carbonate product has an excellent effect after being applied to tableware.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
The method for modifying calcium carbonate for tableware described in this example includes the following steps:
1) crushing and grinding light calcium carbonate to obtain calcium carbonate powder with the particle size of 1000 meshes, mixing the calcium carbonate powder with water according to the weight ratio of 1: 10, concentrating the suspension to a second suspension with a solid content of 40%;
2) adding the second suspension into a stirring reaction kettle, adding a first modifier while stirring, and dehydrating and drying after the reaction to obtain primary modified calcium carbonate; the first modifier consists of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, the adding amount of the first modifier is 2% of the weight of the calcium carbonate powder, and in the first modifier, the mass ratio of the pentaerythritol stearate to the silver antibacterial agent to the nano silicon dioxide is 1: 0.5: 1. the stirring speed of the stirring kettle is 300r/min, and the stirring reaction is carried out for 40 min.
3) Continuously adding the primary modified calcium carbonate into a stirring reaction kettle, adding a second modifier while stirring, adding the second modifier in an atomized form, uniformly stirring, drying, and sieving with a 700-mesh sieve; the second modifier is composed of chitosan, 2, 6-di-tert-butyl cresol and castor oil maleate, the adding amount of the second modifier is 6% of the weight of the primary modified calcium carbonate powder, and the mass ratio of the chitosan, the 2, 6-di-tert-butyl cresol and the castor oil maleate in the second modifier is 4: 2: and 5, atomizing the second modifier in an ultrasonic atomization mode, dissolving the chitosan in the citric acid, dissolving the 2, 6-di-tert-butyl cresol in the ricinoleic maleate, respectively atomizing, wherein the speed of a stirring kettle is 1400r/min, and stirring and reacting for 30 min.
In the embodiment, the chitosan is low molecular weight chitosan with the molecular weight of less than 3000 and the polymerization degree of 2-20.
Example 2
The method for modifying calcium carbonate for tableware described in this example includes the following steps:
1) crushing and grinding light calcium carbonate to obtain calcium carbonate powder with the particle size of 800 meshes, mixing the calcium carbonate powder with water according to the weight ratio of 1: 15, concentrating the suspension to a second suspension with a solids content of 50%;
2) adding the second suspension into a stirring reaction kettle, adding a first modifier while stirring, and dehydrating and drying after the reaction to obtain primary modified calcium carbonate; the first modifier consists of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, the adding amount of the first modifier is 1.8 percent of the weight of the calcium carbonate powder, and in the first modifier, the mass ratio of the pentaerythritol stearate to the silver antibacterial agent to the nano silicon dioxide is 1.2: 0.6: 1.5. the stirring speed of the stirring kettle is 400r/min, and the stirring reaction is carried out for 50 min.
3) Continuously adding the primary modified calcium carbonate into a stirring reaction kettle, adding a second modifier while stirring, adding the second modifier in an atomized form, uniformly stirring, drying, and sieving by a 600-mesh sieve; the second modifier is composed of chitosan, 2, 6-di-tert-butyl cresol and castor oil maleate, the adding amount of the second modifier is 5.5% of the weight of the primary modified calcium carbonate powder, and the mass ratio of the chitosan to the 2, 6-di-tert-butyl cresol to the castor oil maleate in the second modifier is 3: 1.5: and 4, atomizing the second modifier in an ultrasonic atomization mode, dissolving the chitosan in the citric acid, dissolving the 2, 6-di-tert-butyl cresol in the ricinoleic maleate, respectively atomizing, wherein the speed of the stirring kettle is 1250r/min, and stirring and reacting for 25 min.
In the embodiment, the chitosan is low molecular weight chitosan with the molecular weight of less than 3000 and the polymerization degree of 2-20.
Example 3
The method for modifying calcium carbonate for tableware described in this example includes the following steps:
1) crushing and grinding light calcium carbonate to obtain calcium carbonate powder with the particle size of 600 meshes, mixing the calcium carbonate powder with water according to the weight ratio of 1: 20, concentrating the suspension to a second suspension with a solids content of 60%;
2) adding the second suspension into a stirring reaction kettle, adding a first modifier while stirring, and dehydrating and drying after the reaction to obtain primary modified calcium carbonate; the first modifier consists of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, the adding amount of the first modifier is 1% of the weight of the calcium carbonate powder, and in the first modifier, the mass ratio of the pentaerythritol stearate to the silver antibacterial agent to the nano silicon dioxide is 1.5: 1: 2. the stirring speed of the stirring kettle is 500r/min, and the stirring reaction lasts for 60 min.
3) Continuously adding the primary modified calcium carbonate into a stirring reaction kettle, adding a second modifier while stirring, adding the second modifier in an atomized form, uniformly stirring, drying, and sieving by using a 500-mesh sieve; the second modifier is composed of chitosan, 2, 6-di-tert-butyl cresol and castor oil maleate, the adding amount of the second modifier is 5-6% of the weight of the primary modified calcium carbonate powder, and the mass ratio of the chitosan to the 2, 6-di-tert-butyl cresol to the castor oil maleate in the second modifier is 2-4: 1-2: and 3-5, atomizing a second modifier in an ultrasonic atomization mode, dissolving the chitosan in citric acid, dissolving the 2, 6-di-tert-butyl cresol in the ricinoleic maleate, and then respectively atomizing, wherein the speed of a stirring kettle is 1200-1400 r/min, and stirring and reacting for 20-30 min.
In the embodiment, the chitosan is low molecular weight chitosan with the molecular weight of less than 3000 and the polymerization degree of 2-20.
Comparative example 1
Compared with the example 2, the chitosan is the high molecular weight chitosan with the molecular weight of more than 5000, and the rest of the operation steps are the same.
Comparative example 2
Commercially available ordinary modified light calcium carbonate.
And (5) testing the performance.
The modified precipitated calcium carbonates of examples 1 to 3 and comparative examples 1 and 2 were added to a sample by a conventional method, and the antibacterial property, oxidation resistance and strength were measured by a conventional method. As shown in the table below.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A modification method of calcium carbonate for tableware is characterized by comprising the following steps:
1) crushing and grinding light calcium carbonate to obtain calcium carbonate powder with the particle size of 600-1000 meshes, mixing the calcium carbonate powder with water according to the weight ratio of 1: mixing the first suspension liquid with the ratio of 10-20, and concentrating the suspension liquid into a second suspension liquid with the solid content of 40-60%;
2) adding the second suspension into a stirring reaction kettle, adding a first modifier while stirring, and dehydrating and drying after the reaction to obtain primary modified calcium carbonate;
3) continuously adding the primary modified calcium carbonate into a stirring reaction kettle, adding a second modifier while stirring, adding the second modifier in an atomized form, uniformly stirring, drying, and sieving with a 400-700-mesh sieve;
the first modifier consists of pentaerythritol stearate, a silver antibacterial agent and nano silicon dioxide, and the second modifier consists of chitosan, 2, 6-di-tert-butyl cresol and castor oil maleate.
2. The method for modifying calcium carbonate for tableware according to claim 1, wherein in the step 2), the first modifying agent is added in an amount of 1-2% by weight based on the calcium carbonate powder.
3. The method for modifying calcium carbonate for tableware according to claim 2, wherein in the step 2), the mass ratio of pentaerythritol stearate, the silver antibacterial agent and the nano silica in the first modifying agent is 1-1.5: 0.5-1: 1 to 2.
4. The method for modifying calcium carbonate for tableware according to claim 3, wherein in the step 2), the stirring speed of the stirring kettle is 300 to 500r/min, and the stirring reaction is carried out for 40 to 60 min.
5. The method for modifying calcium carbonate for tableware according to claim 4, wherein in the step 3), the second modifier is added in an amount of 5 to 6% by weight based on the weight of the initially modified calcium carbonate powder.
6. The method for modifying calcium carbonate for tableware according to claim 5, wherein in the step 3), the mass ratio of chitosan, 2, 6-di-tert-butylcresol and castor oil maleate in the second modifier is 2-4: 1-2: 3 to 5.
7. The method for modifying calcium carbonate for tableware according to claim 6, wherein in step 3), the second modifier is atomized by ultrasonic atomization, the chitosan is dissolved in citric acid, and 2, 6-di-tert-butylcresol is dissolved in the ricinoleic maleate and then atomized respectively.
8. The method for modifying calcium carbonate for tableware according to claim 7, wherein in the step 3), the stirring speed of the stirring kettle is 1200-1400 r/min, and the stirring reaction is 20-30 min.
9. The method for modifying calcium carbonate for tableware according to any one of claims 1 to 8, wherein the chitosan is a low molecular weight chitosan having a molecular weight of less than 3000 and a degree of polymerization of 2 to 20.
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| CN202010694330.0A CN113943498A (en) | 2020-07-17 | 2020-07-17 | Modification method of calcium carbonate for tableware |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558316A (en) * | 2022-08-11 | 2023-01-03 | 秦志强 | Low-alkalinity calcium carbonate and preparation process thereof |
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| CN103554704A (en) * | 2013-07-02 | 2014-02-05 | 安徽金阳电器科技发展有限责任公司 | Modified calcium carbonate for anti-ultraviolet electric cable material, and preparation method thereof |
| CN104087024A (en) * | 2014-06-06 | 2014-10-08 | 凤台县精华助剂有限公司 | Modified calcium carbonate with antibacterial and antioxidation effects and preparing method thereof |
| CN104945704A (en) * | 2015-04-29 | 2015-09-30 | 安徽顺彤包装材料有限公司 | Packaging material with antistatic and antibacterial properties and preparation method of packaging material |
| CN106700655A (en) * | 2016-10-20 | 2017-05-24 | 青阳县金山粉业有限公司 | Nano calcium carbonate powder coated and modified with thiosemicarbazide-dialdehyde starch cross-linked polymer and preparation method of powder |
| CN108892995A (en) * | 2018-05-24 | 2018-11-27 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of method of modifying of car paint color inhibition calcium carbonate |
| CN109694590A (en) * | 2018-12-27 | 2019-04-30 | 李绿叶 | A kind of method of organic matter surface modified calcium carbonate |
-
2020
- 2020-07-17 CN CN202010694330.0A patent/CN113943498A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554704A (en) * | 2013-07-02 | 2014-02-05 | 安徽金阳电器科技发展有限责任公司 | Modified calcium carbonate for anti-ultraviolet electric cable material, and preparation method thereof |
| CN104087024A (en) * | 2014-06-06 | 2014-10-08 | 凤台县精华助剂有限公司 | Modified calcium carbonate with antibacterial and antioxidation effects and preparing method thereof |
| CN104945704A (en) * | 2015-04-29 | 2015-09-30 | 安徽顺彤包装材料有限公司 | Packaging material with antistatic and antibacterial properties and preparation method of packaging material |
| CN106700655A (en) * | 2016-10-20 | 2017-05-24 | 青阳县金山粉业有限公司 | Nano calcium carbonate powder coated and modified with thiosemicarbazide-dialdehyde starch cross-linked polymer and preparation method of powder |
| CN108892995A (en) * | 2018-05-24 | 2018-11-27 | 贺州钟山县双文碳酸钙新材料有限公司 | A kind of method of modifying of car paint color inhibition calcium carbonate |
| CN109694590A (en) * | 2018-12-27 | 2019-04-30 | 李绿叶 | A kind of method of organic matter surface modified calcium carbonate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115558316A (en) * | 2022-08-11 | 2023-01-03 | 秦志强 | Low-alkalinity calcium carbonate and preparation process thereof |
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Application publication date: 20220118 |