CN112777605B - Method for improving specific surface area of calcined coal-series kaolin - Google Patents
Method for improving specific surface area of calcined coal-series kaolin Download PDFInfo
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- CN112777605B CN112777605B CN202110106018.XA CN202110106018A CN112777605B CN 112777605 B CN112777605 B CN 112777605B CN 202110106018 A CN202110106018 A CN 202110106018A CN 112777605 B CN112777605 B CN 112777605B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
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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
- C01P2006/12—Surface area
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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
- C01P2006/14—Pore volume
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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
- C01P2006/16—Pore diameter
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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
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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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
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Abstract
The invention relates to a method for improving the specific surface area of calcined coal-series kaolin, which adopts the technical scheme that microwaves are introduced to irradiate in the process of dehydroxylation of the coal-series kaolin, and fiber filaments with large dielectric constants are added into raw coal-series kaolin in the process of microwave treatment to promote the absorption of materials to microwaves, so that the coal-series kaolin is rapidly heated and dehydroxylated in the dehydroxylation stage, the rapid reaction of carbon-containing components is promoted, the in-situ increase Kong Penghua of the calcined kaolin is realized, the specific surface area and the pore size of the calcined coal-series kaolin are increased, and the adsorption capacity, particularly the oil absorption performance of the calcined coal-series kaolin are improved. The specific surface area of the coal-series kaolin obtained by the method disclosed by the invention is 2-3 times that of the conventional calcined coal-series kaolin, and the oil absorption is improved by 35-45% compared with that of the common coal-series kaolin clinker.
Description
Technical Field
The invention belongs to the technical field of nonmetal mineral functional material processing, and particularly relates to a method for improving the specific surface area of calcined coal-series kaolin.
Background
Coal-based kaolin is an important inorganic nonmetallic clay mineral material, has different purposes after being calcined at different temperatures, and is widely applied to dozens of industries such as papermaking, paint, ceramics, rubber, chemical industry, medicine, national defense and the like after being calcined, and is mainly applied to the papermaking industry. Because of its stable properties, kaolin can be used as a filler and coating in the paper industry. The kaolin can endow paper with good coverage performance and excellent glossiness when being coated when being used in the paper industry, and can also increase the whiteness and smoothness of the paper and greatly improve the quality of the paper.
With the development of the paper industry in China, the expansion of the yield and the introduction of a high-speed knife coater, the dosage of calcined kaolin is gradually expanded, so that higher requirements are put on the calcined kaolin. In the fields of papermaking and environment, the oil absorption value and whiteness of kaolin are two of the most important indexes. The whiteness of the kaolin can be solved by surface coating and controlling the calcination conditions, but the oil absorption value is difficult to increase. At present, domestic researches on oil absorption values are few, the domestic kaolin oil absorption value is generally low, the oil absorption value of the domestic kaolin is only about 45g/100g, the calcined kaolin oil absorption value is only 60g/100g, and the index of the oil absorption value becomes one of important factors restricting the export of the calcined kaolin in China compared with 90g/100g of the American kaolin.
In conventional heating methods, heat is transferred in the material by conduction, radiation and convection mechanisms. In this case, the surface of the material is first heated, after which a temperature gradient is established between the surface of the material and the body, so that the temperature is gradually transferred from the surface to the body portion. In contrast, microwaves are used as a novel heating means, electromagnetic energy is absorbed by materials according to volume and converted into heat energy in the heating process, and the energy conversion is utilized to replace temperature transmission in the heating process, so that no temperature difference exists between the surface and the main body, and the distribution of temperature fields in the materials is more uniform. The microwaves can penetrate through the material and transfer energy, so that the reaction rate is greatly increased, the energy consumption in the material processing process is reduced, and the microwave can not pollute the environment and is applied to the material processing process. However, in the process of treating the kaolin, as the absorption rate of the kaolin to the microwaves is low in the low-temperature process, and the heating rate is greatly influenced, the invention uses the fiber yarn with large dielectric constant to promote the heating rate of the kaolin in the low-temperature stage, and the fiber yarn conducts heat to the kaolin material in the low-temperature stage, so that the heating of the material in the microwave irradiation process is accelerated, and the utilization rate of the microwaves is maximized.
Chinese patent CN109748286a discloses a calcined kaolin with high whiteness and high oil absorption and a preparation method thereof, wherein the method comprises adding water glass and strong acid into kaolin slurry, controlling pH value of a reaction system, drying, and calcining to obtain calcined kaolin with high whiteness and high oil absorption. The method obviously improves the whiteness and oil absorption value of the calcined kaolin, but the treatment with strong acid can cause certain pollution to the environment. In addition, chinese patent CN108483458A also discloses a method for improving the specific surface area of kaolin by wet method, but concentrated sulfuric acid is required to be added in the process, and the process is also complicated and has environmental pollution to some extent.
Chinese patent CN101857740a discloses a method for increasing the oil absorption value of calcined kaolin. The method is simple, low in cost and pollution-free, but has higher requirement on the purity granularity of anhydrous magnesium chloride, otherwise, the screen residues are easy to exceed standard and have certain corrosion on equipment, corrosive gas is generated in the calcining process, and the method has higher requirement on the equipment and is not beneficial to industrialized production.
Chinese patent CN108275688A discloses a method for preparing kaolin with high oil absorption, which improves the oil absorption of the product to a certain extent, but requires adding organic dispersant and intercalator in the production process, the quality of the product is not high, the impurity is more and the cost is higher.
Disclosure of Invention
In order to solve the technical problems that in the prior art, the production process for improving the specific surface area of the kaolin has certain corrosiveness to equipment due to raw materials, environmental pollution or excessive screen residues and higher requirements on the equipment are caused, the industrial production is not facilitated, the quality of the product is not high after adding additive components such as an organic dispersing agent, an intercalating agent and the like in the production process, and the like, the invention aims to provide a method for increasing the specific surface area of the kaolin by microwave-assisted treatment of coal-based kaolin, and simultaneously improving the adsorption capacity, particularly the oil absorption value of the kaolin. The method can overcome the technical problems in the prior art, relieves the demand of the paper industry on the calcined kaolin with high oil absorption value to a certain extent, and has simple working procedure and high oil absorption value of the product. It is another object of the present invention to obtain a calcined coal-based kaolin clay with high oil absorption.
The technical scheme of the invention is as follows:
a method for increasing the specific surface area of calcined coal-based kaolin, comprising the steps of:
1) Placing the coal-series kaolin raw soil and a certain amount of microwave absorption accelerator in a container, and uniformly mixing to obtain a mixed material;
2) Placing the container filled with the mixed materials into a microwave oven, setting the microwave power to be 1500-3000W, and carrying out microwave treatment for 3-8min;
3) Transferring the mixture subjected to microwave treatment into a conventional heating furnace preheated to the same temperature at constant temperature, continuously heating to 1000-1200 ℃, keeping the temperature at a heating rate of 5-8 ℃/min, keeping the temperature for a period of time, and cooling to 100 ℃;
4) Placing the calcined kaolin sample cooled to 100 ℃ into a dryer for continuous cooling to room temperature, and obtaining calcined coal-series kaolin with high specific surface area;
SiO in the raw soil of the coal-based kaolin 2 The content of Al is 40-53% 2 O 3 The content is 33-45%, tiO 2 The content of Fe is below 1% 2 O 3 The content is below 0.90%.
Further, the microwave absorption accelerator is a fiber filament with a dielectric constant not less than 3.6.
Further, the fiber yarn is made of one or more materials selected from silicon carbide, ferric oxide and graphite.
Further, the heat preservation time in the step 3) is 20min-60min.
The high oil absorption calcined coal-series kaolin prepared by the method is characterized in that the specific surface area of the high oil absorption calcined coal-series kaolin is 30-40m 2 Per gram, the total pore volume of single point adsorption is 0.10-0.15cm 3 And/g, adsorption average pore diameter of 10-15nm.
Further, the oil absorption value of the calcined coal-based kaolin with high oil absorption is not less than 80g/100g.
The method adopts a rapid heating method in the coal-series kaolin dehydroxylation stage, so that the coal-series kaolin is rapidly dehydroxylated in the dehydroxylation process, and the rapid reaction of carbon-containing components is promoted, thereby realizing the in-situ increase Kong Penghua of the calcined coal-series kaolin and increasing the specific surface area and the pore size of the calcined coal-series kaolin.
The method plays an auxiliary calcination role of microwaves, and the calcined coal-series kaolin sample with high specific surface area is obtained through the combined action of the microwaves and a conventional heating furnace.
The invention adds a fiber yarn in the microwave treatment process to promote the absorption efficiency of kaolin original soil to microwaves, the fiber yarn can be any metal material or inorganic nonmetallic material with dielectric constant more than 3.6, and the invention adopts fiber yarn made of silicon carbide, ferric oxide and graphite for experiment, and is convenient to separate from kaolin samples after microwave irradiation is finished.
Detailed Description
The coal-based kaolin used in the embodiments of the present invention comprises the following chemical components: siO (SiO) 2 The content is 42.684 percent, al 2 O 3 The content is 36.717 percent, tiO 2 The content is 0.934%, fe 2 O 3 The content is 0.429%.
Example 1:
(1) Mixing 3g of coal-series kaolin raw material with 1.5g of fiber yarn made of silicon carbide, and placing the mixture into a container;
(2) Placing the container filled with the kaolin raw soil into a microwave oven to be treated for 7min under 1800W microwave;
(3) Placing the coal-series kaolin subjected to the microwave pretreatment in the step (2) into a heating furnace preheated to the same temperature at a constant temperature, continuously heating to 1000 ℃, keeping the temperature at a heating rate of 5 ℃/min, keeping the temperature for 20min, and cooling to 100 ℃;
(4) And (3) placing the calcined kaolin sample cooled to 100 ℃ into a dryer for continuous cooling to room temperature, and obtaining the calcined coal-series kaolin product with high specific surface area.
Example 2:
(1) Mixing 5g of coal-series kaolin raw material with 2.5g of fiber yarn made of graphite, and placing the mixture into a container;
(2) Placing the container filled with the kaolin raw soil into a microwave oven for treatment under 2500W of microwave for 5min;
(3) Placing the coal-series kaolin subjected to the microwave pretreatment in the step (2) into a heating furnace which is preheated to the same temperature at a constant temperature, placing the coal-series kaolin into the heating furnace which is preheated to the same temperature at a constant temperature, continuing to heat the coal-series kaolin to 1100 ℃, keeping the temperature at a heating rate of 6 ℃/min, keeping the temperature for 60min, and then cooling the coal-series kaolin to 100 ℃;
(4) And (3) placing the calcined kaolin sample cooled to 100 ℃ into a dryer for continuous cooling to room temperature, and obtaining the calcined coal-series kaolin product with high specific surface area.
Example 3:
(1) Mixing 4g of coal-series kaolin raw soil with 2g of fiber yarn made of ferric oxide, and placing the mixture into a container;
(2) Placing the container filled with kaolin raw soil into a microwave oven, and treating for 3min under 2000W microwave;
(3) And (3) putting the coal-series kaolin subjected to the microwave pretreatment in the step (2) into a heating furnace preheated to the same temperature at a constant temperature, continuously heating to 1050 ℃, keeping the temperature at a heating rate of 5 ℃/min, keeping the temperature for 30min, and cooling to 100 ℃.
(4) And (3) placing the calcined kaolin sample cooled to 100 ℃ into a dryer for continuous cooling to room temperature, and obtaining the calcined coal-series kaolin product with high specific surface area.
Example 4:
(1) Mixing 6g of coal-series kaolin raw soil with 3g of fiber yarn made of silicon carbide, and placing the mixture into a container;
(2) Placing the container filled with the kaolin raw soil into a microwave oven and treating for 6min under 2800W of microwaves;
(3) Placing the coal-series kaolin subjected to the microwave pretreatment in the step (2) into a heating furnace preheated to the same temperature at a constant temperature, continuously heating to 1200 ℃, keeping the temperature at a heating rate of 6 ℃/min, keeping the temperature for 40min, and cooling to 100 ℃;
(4) And (3) placing the calcined kaolin sample cooled to 100 ℃ into a dryer for continuous cooling to room temperature, and obtaining the calcined coal-series kaolin product with high specific surface area.
The main BET parameters and oil absorption data of the calcined coal-based kaolin products with high specific surface areas obtained in examples 1 to 4 of the present invention are shown in Table 1.
Comparative example 1:
BET parameters and oil absorption data of the normal coal series kaolin clinker samples are shown in Table 1.
Comparative example 2:
comparative example 2 is a calcined coal-based kaolin product obtained by directly treating a normal coal-based kaolin clinker sample in a heating furnace, and the specific method comprises the following steps:
(1) Mixing 3g of coal-series kaolin raw material with 1.5g of fiber yarn made of silicon carbide, and placing the mixture into a container;
(2) Immediately placing the container with the materials into a heating furnace, heating the container to 1000 ℃ from room temperature, keeping the temperature for 20min at a heating rate of 5 ℃/min, and cooling to 100 ℃;
(3) And (3) placing the sample obtained in the step (2) into a dryer for continuous cooling to room temperature, and obtaining the calcined coal-based kaolin product.
TABLE 1
As can be seen from Table 1, the specific surface area of the sample after microwave irradiation is far greater than that of the sample directly processed by a common heating furnace, because the microwave treatment stage enables the coal-based kaolin to be rapidly heated in the dehydroxylation stage, the rapid reaction of carbon-containing components in the coal-based kaolin is promoted, and the swelling effect in the coal-based kaolin is generated, so that the specific surface area and the size of the adsorption average pore diameter of the calcined coal-based kaolin are increased. The calculation result shows that the specific surface area of the treated calcined coal-series kaolin reaches 2-3 times that of the conventional calcined coal-series kaolin, and the oil absorption value is improved by 35-45% compared with that of a sample treated by a common heating furnace.
Claims (6)
1. A method for increasing the specific surface area of calcined coal-based kaolin, comprising the steps of: 1) Placing the coal-series kaolin raw soil and a certain amount of microwave absorption accelerator in a container, and uniformly mixing to obtain a mixed material; 2) Placing the container filled with the mixed materials into a microwave oven, setting the microwave power to be 1500-3000W, and carrying out microwave treatment for 3-8min; 3) Transferring the mixture subjected to microwave treatment into a conventional heating furnace preheated to the same temperature at constant temperature, continuously heating to 1000-1200 ℃, keeping the temperature at a heating rate of 5-8 ℃/min, keeping the temperature for a period of time, and cooling to 100 ℃; 4) Placing the calcined kaolin sample cooled to 100 ℃ into a dryer for continuous cooling to room temperature, and obtaining calcined coal-series kaolin with high specific surface area; siO in the raw soil of the coal-based kaolin 2 The content of Al is 40-53% 2 O 3 The content is 33-45%, tiO 2 The content of Fe is below 1% 2 O 3 The content is below 0.90%.
2. A method for increasing the specific surface area of calcined coal-based kaolin according to claim 1, characterized by: the microwave absorption accelerator is a fiber filament with a dielectric constant not less than 3.6.
3. A method for increasing the specific surface area of calcined coal-based kaolin according to claim 2, characterized by: the fiber yarn is made of one or more materials of silicon carbide, ferric oxide and graphite.
4. A method for increasing the specific surface area of calcined coal-based kaolin according to claim 1, characterized by: the heat preservation time in the step 3) is 20min-60min.
5. A calcined coal-based kaolin having a high oil absorption as prepared by the method of claim 1, wherein the calcined coal-based kaolin having a specific surface area of 30 to 40m 2 Per gram, the total pore volume of single point adsorption is 0.10-0.15cm 3 And/g, adsorption average pore diameter of 10-15nm.
6. The high oil absorption calcined coal-based kaolin prepared by the method of claim 1, wherein the high oil absorption calcined coal-based kaolin has an oil absorption value of not less than 80g/100g.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131785A2 (en) * | 1983-07-14 | 1985-01-23 | Georgia Kaolin Company, Inc. | Processing of kaolinitic clays at high solids under acidic conditions |
| CN1915814A (en) * | 2006-09-12 | 2007-02-21 | 内蒙古蒙西高岭粉体股份有限公司 | Technique of fluidized instant calcinations of kaolin in coal series |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102491356B (en) * | 2011-11-30 | 2013-04-10 | 唐山麦迪逊高岭土有限公司 | Preparation method of calcined kaolin with high oil absorption |
| WO2019246082A1 (en) * | 2018-06-18 | 2019-12-26 | Basf Corporation | Methods of preparation and utilization of bauxitic kaolins |
| CN108905957A (en) * | 2018-06-22 | 2018-11-30 | 成都新柯力化工科技有限公司 | A method of building decoration specific surface area of diatomite is improved using microwave |
| CN110577225B (en) * | 2019-09-23 | 2022-07-08 | 山西金宇科林科技有限公司 | Preparation method of high-whiteness calcined kaolin with ultrahigh oil absorption |
| CN110844914A (en) * | 2019-12-08 | 2020-02-28 | 太原理工大学 | Method for improving specific surface area of coal-series kaolin under synergistic effect of ultrasonic microwaves |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131785A2 (en) * | 1983-07-14 | 1985-01-23 | Georgia Kaolin Company, Inc. | Processing of kaolinitic clays at high solids under acidic conditions |
| CN1915814A (en) * | 2006-09-12 | 2007-02-21 | 内蒙古蒙西高岭粉体股份有限公司 | Technique of fluidized instant calcinations of kaolin in coal series |
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