CN112850725A - Preparation method of tobermorite - Google Patents
Preparation method of tobermorite Download PDFInfo
- Publication number
- CN112850725A CN112850725A CN202110374177.8A CN202110374177A CN112850725A CN 112850725 A CN112850725 A CN 112850725A CN 202110374177 A CN202110374177 A CN 202110374177A CN 112850725 A CN112850725 A CN 112850725A
- Authority
- CN
- China
- Prior art keywords
- red mud
- tobermorite
- carbide slag
- percent
- ultrasonic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The preparation method of tobermorite takes carbide slag and red mud as raw materials and prepares the tobermorite through the steps of drying, ball milling, mixing, ultrasonic combined alkaline leaching, hydrothermal synthesis and the like. The secondary particles formed by winding the tobermorite whiskers prepared by the method have the characteristics of small volume weight, large specific surface area, high porosity, high heat-resisting temperature and the like, and the method not only improves the utilization rate of industrial wastes, but also saves energy in production and reduces the production cost.
Description
Technical Field
The invention belongs to the field of mullite ceramic manufacturing, and particularly relates to a preparation method of low-cost tobermorite.
Background
Tobermorite is an important class of silicate minerals. In addition to being used as a main phase of an autoclaved silicate product, tobermorite has good performance in the adsorption of organic acid and heavy metal ions such as cobalt, copper, cadmium, chromium and lead due to high specific surface area and strong ion exchange performance, has strong selectivity on strontium and cesium, and has good application prospect in the field of heterogeneous catalysis. With the development of biotechnology, tobermorite nanowhiskers have related applications in the biological fields of bone tissue regeneration and the like, and a small amount of tobermorite is added into silicate products such as concrete and the like as a crystallization inducer, so that the strength of the products can be effectively improved.
The red mud is waste residue in alumina industrial production, and generally, 1.0 t-1.6 t of red mud is produced per ton of alumina. A large amount of red mud has direct or indirect influence on human production and life. Therefore, the utilization of red mud in multiple ways is urgent. CaO, SiO2And A12O3Accounts for more than 80 percent of the total amount of the red mud and is similar to the ceramic components. The production of ceramic products by utilizing red mud has become the mainstream direction of the recovery production of high value-added products from red mud. The carbide slag is used as industrial solid waste generated in the acetylene production process, and about 1.2t of carbide slag can be generated per 1t of calcium carbide, so that the problem of carbide slag treatment is generated. The common carbide slag treatment mode is landfill treatment, and the common carbide slag treatment mode can cause the problems of land pollution, underground water pollution and the like.
At present, the tobermorite is prepared by taking quartz powder, diatomite, zeolite, bentonite, zirconium silicon slag and the like as siliceous raw materials and lime and the like as calcareous raw materials, the raw materials are various but have limited sources and are mostly primary resources, and if the tobermorite can be prepared by utilizing solid wastes in industrial production, the solid wastes can be recycled, and the preparation cost of the tobermorite can be reduced.
Disclosure of Invention
The invention aims to provide a preparation method of tobermorite, which takes red mud and carbide slag as main raw materials, improves the reaction activity by high-energy ball milling and ultrasonic treatment and is used for preparing the tobermorite.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of tobermorite comprises the following steps:
step one, respectively drying the carbide slag and the red mud;
step two, respectively putting the carbide slag and the red mud dried in the step one into a ball mill for ball milling, and then sieving the carbide slag and the red mud by a 200-mesh sieve;
step three, respectively taking 20-25% of the carbide slag and 75-80% of the red mud in percentage by weight from the carbide slag and the red mud treated in the step two, and uniformly mixing for later use, wherein the molar ratio of Ca/(Si + Al) in the obtained mixed raw material is 0.95-1.05;
step four, carrying out ultrasonic combined alkaline leaching treatment on the raw materials mixed in the step three, wherein the conditions of the ultrasonic combined alkaline leaching treatment are as follows: the mass concentration of NaOH solution is 6%, the solid-to-liquid ratio is 1:1.5, the ultrasonic power is 35 kHz, the heating time of ultrasonic water bath is 3 hours, and the temperature of the ultrasonic water bath is 100 ℃;
and fifthly, filtering the melt obtained by ultrasonic and alkaline leaching treatment, and then putting a filter cake into a high-pressure reaction kettle to prepare tobermorite by a hydrothermal synthesis method.
In the first step, the carbide slag and the red mud are dried at the temperature of 150 ℃ for 6 hours.
And in the second step, the grinding time of the carbide slag and the red mud in the ball mill is 8-12 hours.
The red mud is sintered red mud, and mainly comprises the following components in percentage by weight: 6 to 8 percent of Al2O335 to 40 percent of CaO and 25 to 30 percent of SiO28% -12% of Fe2O33 to 8 percent of Na2O, 1 to 3 percent of K2O and 3% -5% of MgO.
The carbide slag mainly comprises the following components in percentage by weight: 85% -90% of Ca (OH)25% -8% of SiO21% -3% of Fe2O31 to 3 percent of Al2O3And 1% -2% of MgO.
In the fifth step, the hydrothermal synthesis conditions are that the solid-liquid ratio is 1:25, the reaction temperature is 220 ℃, and the reaction time is 8 hours.
The principle of the invention is as follows: when the molar ratio of Ca/(Si + Al) in the raw material is 0.95-1.05, firstly, the active SiO on the red mud surface2And Ca (OH) in the carbide slag2Reacting to form C-S-H gel particles and alkaline microenvironment, thus leading the inactive silicon mullite to be continuously activated, and reacting the activated mullite with Ca (OH) in the solution2Reacting to generate C-S-H gel, and continuously converting the C-S-H gel into tobermorite. Water (W)Reaction under thermal conditions:
5CaO+6SiO2+5H2O= 5CaO·6SiO2·5H2O
in the process of generating tobermorite, A13+Can substitute part of Si4+Entering the Tolbecco mullite structure to form a component of Tolbecco mullite, and obtaining a product of Tolbecco mullite Ca containing aluminum5Si5Al(OH)O17·5H2O。
In the ultrasonic combined alkaline leaching treatment, the alkaline leaching treatment can dissolve amphoteric oxide and improve reaction activity; the crystallization mechanism is improved through ultrasonic cavitation, the secondary nucleation rate and mass transmission are increased, and the crystal growth rate is correspondingly improved. Therefore, the product quantity is increased after the ultrasonic and alkaline leaching treatment, double-layer or even multi-layer tobermorite can be formed at low temperature, the heat-resistant temperature of the product can be correspondingly increased, and the heat-resistant temperature of the tobermorite prepared by the method is 820 ℃. Compared with the common tobermorite, the heat-resistant temperature is improved by nearly 80 ℃, and the tobermorite has good chemical stability at the temperature.
The invention has the beneficial effects that: (1) after ball milling and ultrasonic treatment of the red mud in the sintering method, the crystal structure of the red mud is destroyed, the degree of freedom of molecules is increased, the surface area of the red mud is increased, the degree of crystallization of crystals in the red mud is reduced, and amorphous substances are increased. Meanwhile, the reaction activity of the red mud is improved, the hydrothermal synthesis reaction is facilitated, and the reaction temperature can be reduced by about 25 ℃.
(2) The utilization rate of the solid waste of the carbide slag and the red mud of the sintering method can reach 60 percent to the maximum extent by utilizing the method, thereby not only improving the utilization rate of industrial waste, but also saving energy in production and reducing the production cost.
(3) The heat-resistant temperature of the tobermorite prepared by the invention is 820 ℃. Compared with the common tobermorite, the heat-resistant temperature is improved by nearly 80 ℃, and the tobermorite has good chemical stability at the temperature.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
Example 1: the preparation method of tobermorite comprises the following steps of taking carbide slag and sintering red mud as raw materials, wherein the carbide slag mainly comprises the following components in percentage by weight: ca (OH)2 85%、SiO28%、Fe2O33%、Al2O33 percent and 1 percent of MgO, and the sintering red mud comprises the following main components: al (Al)2O38%、CaO35%、SiO230%、Fe2O312%、Na2O8%、K2O2% and MgO 5%; the method comprises the following steps:
step one, respectively drying the carbide slag and the sintering-process red mud at 150 ℃ for 24 hours for later use;
step two, respectively putting the dried carbide slag and the sintering red mud into a ball mill for ball milling for 8-12 h, and then sieving with a 200-mesh sieve;
step three, respectively taking the carbide slag and the sintering-process red mud which are sieved in the step two for standby, wherein the usage amount of the carbide slag and the sintering-process red mud is respectively 20% of the carbide slag and 80% of the sintering-process red mud in percentage by weight;
step four, uniformly mixing the raw materials obtained in the step three for later use;
step five, carrying out ultrasonic combined alkaline leaching treatment on the uniformly mixed raw materials in the last step, wherein the conditions of the ultrasonic combined alkaline leaching treatment are as follows: the mass concentration of NaOH solution is 6%, the solid-to-liquid ratio is 1:1.5, the ultrasonic power is 35 kHz, the heating time of ultrasonic water bath is 3 hours, and the temperature of the ultrasonic water bath is 100 ℃;
and step six, filtering the solution after the ultrasonic and alkaline leaching treatment, and putting the filter cake into a high-pressure reaction kettle under the hydrothermal synthesis condition to prepare tobermorite, wherein the hydrothermal synthesis condition is that the solid-liquid ratio is 1:25, the reaction temperature is 220 ℃, and the reaction time is 8 hours.
The heat resistance temperature of the tobermorite product prepared by the method is 824 ℃ measured by Differential Thermal Analysis (DTA).
Example 2: the preparation method of tobermorite comprises the following steps of taking carbide slag and sintering red mud as raw materials, wherein the carbide slag mainly comprises the following components in percentage by weight: ca (OH)2 90%、SiO25%、Fe2O33%、Al2O31 percent and 1 percent of MgO, and the sintering red mud comprises the following main components: al (Al)2O38%、CaO40%、SiO225%、Fe2O312%、Na2O7%、K2O3% and MgO 5%; the method comprises the following steps:
step one, respectively drying the carbide slag and the sintering-process red mud at 150 ℃ for 24 hours for later use;
step two, respectively putting the dried carbide slag and the sintering red mud into a ball mill for ball milling for 8-12 h, and then sieving with a 200-mesh sieve;
step three, respectively taking the carbide slag and the sintering-process red mud which are sieved in the step two for standby, wherein the usage amount of the carbide slag and the sintering-process red mud is respectively 25% of the carbide slag and 75% of the sintering-process red mud by weight percentage;
step four, uniformly mixing the raw materials obtained in the step three for later use;
step five, carrying out ultrasonic combined alkaline leaching treatment on the uniformly mixed raw materials in the last step, wherein the conditions of the ultrasonic combined alkaline leaching treatment are as follows: the mass concentration of NaOH solution is 6%, the solid-to-liquid ratio is 1:1.5, the ultrasonic power is 35 kHz, the heating time of ultrasonic water bath is 3 hours, and the temperature of the ultrasonic water bath is 100 ℃;
and step six, filtering the solution after the ultrasonic and alkaline leaching treatment, and putting the filter cake into a high-pressure reaction kettle under the hydrothermal synthesis condition to prepare tobermorite, wherein the hydrothermal synthesis condition is that the solid-liquid ratio is 1:25, the reaction temperature is 220 ℃, and the reaction time is 8 hours.
The temperature resistance of the tobermorite product obtained by the above method was 826 ℃ by Differential Thermal Analysis (DTA).
Example 3: the preparation method of tobermorite comprises the following steps of taking carbide slag and sintering red mud as raw materials, wherein the carbide slag mainly comprises the following components in percentage by weight: ca (OH)2 87%、SiO27%、Fe2O31%、Al2O33 percent and MgO 2 percent, and the sintering red mud comprises the following main components: al (Al)2O36%、CaO40%、SiO230%、Fe2O310%、Na2O8%、K2O1% and MgO 5%; the method bagThe method comprises the following steps:
step one, respectively drying the carbide slag and the sintering-process red mud at 150 ℃ for 24 hours for later use;
step two, respectively putting the dried carbide slag and the sintering red mud into a ball mill for ball milling for 8-12 h, and then sieving with a 200-mesh sieve;
step three, respectively taking the carbide slag and the sintering-process red mud which are sieved in the step two for standby, wherein the usage amount of the carbide slag and the sintering-process red mud is respectively 20% of the carbide slag and 80% of the sintering-process red mud in percentage by weight;
step four, uniformly mixing the raw materials obtained in the step three for later use;
step five, carrying out ultrasonic combined alkaline leaching treatment on the uniformly mixed raw materials in the last step, wherein the conditions of the ultrasonic combined alkaline leaching treatment are as follows: the mass concentration of NaOH solution is 6%, the solid-to-liquid ratio is 1:1.5, the ultrasonic power is 35 kHz, the heating time of ultrasonic water bath is 3 hours, and the temperature of the ultrasonic water bath is 100 ℃;
and step six, filtering the solution after the ultrasonic and alkaline leaching treatment, and putting the filter cake into a high-pressure reaction kettle under the hydrothermal synthesis condition to prepare tobermorite, wherein the hydrothermal synthesis condition is that the solid-liquid ratio is 1:25, the reaction temperature is 220 ℃, and the reaction time is 8 hours.
The tobermorite product obtained by the above method was found to have a heat resistance temperature of 825 deg.c by Differential Thermal Analysis (DTA).
Example 4: the preparation method of tobermorite comprises the following steps of taking carbide slag and sintering red mud as raw materials, wherein the carbide slag mainly comprises the following components in percentage by weight: ca (OH)2 85%、SiO28%、Fe2O33%、Al2O33 percent and 1 percent of MgO, and the sintering red mud comprises the following main components: al (Al)2O38%、CaO40%、SiO230%、Fe2O312%、Na2O3%、K2O3% and MgO 4%; the method comprises the following steps:
step one, respectively drying the carbide slag and the sintering-process red mud at 150 ℃ for 24 hours for later use;
step two, respectively putting the dried carbide slag and the sintering red mud into a ball mill for ball milling for 8-12 h, and then sieving with a 200-mesh sieve;
step three, respectively taking the carbide slag and the sintering-process red mud which are sieved in the step two for standby, wherein the carbide slag and the sintering-process red mud are respectively 28% of the carbide slag and 72% of the sintering-process red mud in weight percentage;
step four, uniformly mixing the raw materials obtained in the step three for later use;
step five, carrying out ultrasonic combined alkaline leaching treatment on the uniformly mixed raw materials in the last step, wherein the conditions of the ultrasonic combined alkaline leaching treatment are as follows: the mass concentration of NaOH solution is 6%, the solid-to-liquid ratio is 1:1.5, the ultrasonic power is 35 kHz, the heating time of ultrasonic water bath is 3 hours, and the temperature of the ultrasonic water bath is 100 ℃;
and step six, filtering the solution after the ultrasonic and alkaline leaching treatment, and putting the filter cake into a high-pressure reaction kettle under the hydrothermal synthesis condition to prepare tobermorite, wherein the hydrothermal synthesis condition is that the solid-liquid ratio is 1:25, the reaction temperature is 220 ℃, and the reaction time is 8 hours.
The tobermorite product obtained by the above method was determined to have a heat resistance temperature of 828 ℃ by Differential Thermal Analysis (DTA).
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and it should be understood by those of ordinary skill in the art that the specific embodiments of the present invention can be modified or substituted with equivalents with reference to the above embodiments, and any modifications or equivalents without departing from the spirit and scope of the present invention are within the scope of the claims to be appended.
Claims (6)
1. The preparation method of tobermorite is characterized by comprising the following steps of:
step one, respectively drying the carbide slag and the red mud;
step two, respectively putting the carbide slag and the red mud dried in the step one into a ball mill for ball milling, and then sieving the carbide slag and the red mud by a 200-mesh sieve;
step three, respectively taking 20-25% of the carbide slag and 75-80% of the red mud in percentage by weight from the carbide slag and the red mud treated in the step two, and uniformly mixing for later use, wherein the molar ratio of Ca/(Si + Al) in the obtained mixed raw material is 0.95-1.05;
step four, carrying out ultrasonic combined alkaline leaching treatment on the raw materials mixed in the step three, wherein the conditions of the ultrasonic combined alkaline leaching treatment are as follows: the mass concentration of NaOH solution is 6%, the solid-to-liquid ratio is 1:1.5, the ultrasonic power is 35 kHz, the heating time of ultrasonic water bath is 3 hours, and the temperature of the ultrasonic water bath is 100 ℃;
and fifthly, filtering the melt obtained by ultrasonic and alkaline leaching treatment, and then putting a filter cake into a high-pressure reaction kettle to prepare tobermorite by a hydrothermal synthesis method.
2. The method for preparing tobermorite according to claim 1, wherein the drying temperature of the carbide slag and the red mud in the first step is 150 ℃ and the drying time is 6 hours.
3. The preparation method of tobermorite according to claim 1, wherein in the second step, the grinding time of the carbide slag and the red mud in the ball mill is 8-12 hours.
4. The preparation method of tobermorite according to claim 1, wherein the red mud is sintered red mud, and the red mud mainly comprises the following components in percentage by weight: 6 to 8 percent of Al2O335 to 40 percent of CaO and 25 to 30 percent of SiO28% -12% of Fe2O33 to 8 percent of Na2O, 1 to 3 percent of K2O and 3% -5% of MgO.
5. The preparation method of tobermorite according to claim 1, wherein the carbide slag mainly comprises the following components in percentage by weight: 85% -90% of Ca (OH)25% -8% of SiO21% -3% of Fe2O31 to 3 percent of Al2O3And 1% -2% of MgO.
6. The method for preparing tobermorite according to claim 1, wherein in the fifth step, the hydrothermal synthesis conditions are that the solid-to-liquid ratio is 1:25, the reaction temperature is 220 ℃, and the reaction time is 8 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110374177.8A CN112850725B (en) | 2021-04-07 | 2021-04-07 | Preparation method of tobermorite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110374177.8A CN112850725B (en) | 2021-04-07 | 2021-04-07 | Preparation method of tobermorite |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112850725A true CN112850725A (en) | 2021-05-28 |
CN112850725B CN112850725B (en) | 2023-08-15 |
Family
ID=75992285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110374177.8A Active CN112850725B (en) | 2021-04-07 | 2021-04-07 | Preparation method of tobermorite |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112850725B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010222190A (en) * | 2009-03-24 | 2010-10-07 | A & A Material Corp | Method for producing calcium silicate board |
CN104828834A (en) * | 2014-02-12 | 2015-08-12 | 中国科学院过程工程研究所 | Method of preparing tobermorite from fly ash and application thereof |
CN104988304A (en) * | 2015-08-04 | 2015-10-21 | 江苏省冶金设计院有限公司 | Comprehensive processing method of red mud and acetylene sludge |
CN105780121A (en) * | 2016-04-18 | 2016-07-20 | 中南大学 | Method for synthesizing tobermorite whiskers with fly ash as raw material |
CN107892307A (en) * | 2017-11-29 | 2018-04-10 | 东北大学 | Utilize the method for soda lime sintering process red mud alkaline process synthetic calcium silicate |
CN111807858A (en) * | 2020-05-08 | 2020-10-23 | 张延年 | Industrial solid waste autoclaved aerated concrete block and preparation method thereof |
-
2021
- 2021-04-07 CN CN202110374177.8A patent/CN112850725B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010222190A (en) * | 2009-03-24 | 2010-10-07 | A & A Material Corp | Method for producing calcium silicate board |
CN104828834A (en) * | 2014-02-12 | 2015-08-12 | 中国科学院过程工程研究所 | Method of preparing tobermorite from fly ash and application thereof |
CN104988304A (en) * | 2015-08-04 | 2015-10-21 | 江苏省冶金设计院有限公司 | Comprehensive processing method of red mud and acetylene sludge |
CN105780121A (en) * | 2016-04-18 | 2016-07-20 | 中南大学 | Method for synthesizing tobermorite whiskers with fly ash as raw material |
CN107892307A (en) * | 2017-11-29 | 2018-04-10 | 东北大学 | Utilize the method for soda lime sintering process red mud alkaline process synthetic calcium silicate |
CN111807858A (en) * | 2020-05-08 | 2020-10-23 | 张延年 | Industrial solid waste autoclaved aerated concrete block and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN112850725B (en) | 2023-08-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Cong et al. | Advances in geopolymer materials: A comprehensive review | |
AU2020100373A4 (en) | Method for preparing ssz-13 molecular sieve by using fly ash | |
CN109569545B (en) | Method for preparing aluminum-silicon porous material from fly ash | |
CN101367529B (en) | Method for synthesis of 4A molecular sieve with coal ash alkali melting method | |
CN104402019A (en) | Solid-phase preparation method of fly ash zeolite molecular sieve | |
CN109205638B (en) | Method for preparing analcite by utilizing electrolytic manganese slag | |
CN111777426B (en) | Method for preparing ceramsite raw material by using household garbage incineration fly ash, product and application thereof | |
CN109354029B (en) | Method for preparing mesoporous silicon oxide from fly ash | |
CN113072313B (en) | Method for preparing ecological concrete by cooperatively utilizing waste residues and wastewater in coal chemical industry | |
CN1669632A (en) | Method for preparing active fly ash phosphorus adsorbent | |
CN106984266A (en) | A kind of method that VOC molecular sieve adsorption materials are prepared by raw material of flyash | |
CN101591032B (en) | Method for preparing modified polyaluminium chloride flocculating agent by waste molecular sieve | |
CN103769045B (en) | A kind of preparation method of fly ash base high-performance adsorbing material | |
CN105439169B (en) | A kind of method for synthesizing na-pretreated zeolite using flyash and activated carbon | |
CN114212799B (en) | Fly ash pretreatment method for molecular sieve preparation | |
CN105130221A (en) | Method for comprehensively utilizing waste concrete and sludge to produce ecologic clinker | |
CN110302773B (en) | Catalyst for catalytic combustion of chlorine-containing volatile organic compounds and preparation method and application thereof | |
CN108585005A (en) | A kind of dealkalization method of Bayer process red mud | |
CN113548673B (en) | Method for preparing molecular sieve by using lithium slag | |
CN105621435A (en) | Method for treating high-concentration ammonia-nitrogen wastewater with molecular sieve prepared from flyash | |
CN101830553B (en) | Dephosphorizing crystal seed for sewage treatment and preparation method thereof | |
CN105498683A (en) | Preparation method of modified clay mineral material for purification of fluorine-containing sewage | |
CN115432713B (en) | Method for preparing fly ash-based molecular sieve | |
CN112850725A (en) | Preparation method of tobermorite | |
CN104107676B (en) | A kind of cinder of burned coal discarded object that utilizes prepares the method for aluminium for tobermorite sorbing material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |