CN102617179A - Porous ceramic carrier for high-temperature and high-pressure inorganic filtering membrane and preparation method for porous ceramic carrier - Google Patents
Porous ceramic carrier for high-temperature and high-pressure inorganic filtering membrane and preparation method for porous ceramic carrier Download PDFInfo
- Publication number
- CN102617179A CN102617179A CN2012101038399A CN201210103839A CN102617179A CN 102617179 A CN102617179 A CN 102617179A CN 2012101038399 A CN2012101038399 A CN 2012101038399A CN 201210103839 A CN201210103839 A CN 201210103839A CN 102617179 A CN102617179 A CN 102617179A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- ceramic carrier
- pore
- porous silicon
- carbide ceramic
- 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
Landscapes
- Ceramic Products (AREA)
- Filtering Materials (AREA)
Abstract
The invention discloses a porous ceramic carrier for a high-temperature and high-pressure inorganic filtering membrane and a preparation method for the porous ceramic carrier. The porous silicon carbide ceramic carrier is prepared by silicon carbide, a binding agent and a pore-forming agent, wherein the mass ratio of the silicon carbide to the binding agent is 80-90:10-20, and the utilization quantity of the pore-forming agent is 35-45% of the sum of the volumes of the silicon carbide, the binding agent and the pore-forming agent. The preparation method includes adding the binding agent and the pore-forming agent in silicon carbide powder; performing ball milling, drying and vacuum heat casting forming; and performing pressureless sintering for a formed blank. Sintering temperature ranges from 1250 DEG C to 1350 DEG C, and heat insulation time ranges from 2 hours to 4 hours. As raw materials form main materials by means of fine size grading, the binding agent and the pore-forming agent are added by a special process, technologies such as unique vacuum heat casting forming and the like are adopted, and mechanical strength and porosity of the porous carrier can be improved effectively. The prepared silicon carbide porous ceramic carrier has excellent performances of fine thermal shock resistance, low coefficient of thermal expansion, fine mechanical and chemical stability at high temperature and under high pressure, and the like.
Description
Technical field
The present invention relates to a kind of HTHP inorganic filter film with cellular ceramic substrate and preparation method thereof.
Background technology
Along with showing especially of energy problem, comprehensive effectively utilization of coal becomes more and more important.In the utilization of coal, a key issue that need to solve is the high temperature filtration dedusting technology, and the pyroceramic filtering membrane is considered to address this problem valid approach.On cellular ceramic substrate, cover one or more layers film, just formed so-called ceramic filter membrane pipe.Outstanding advantage such as ceramic membrane has high temperature resistantly, corrosion-resistant, anti-to be washed away, physical strength is big, Stability Analysis of Structures is indeformable, the life-span is long, thereby be to be widely accepted, and sung the praises of optimal selection into the hot particle filtering material.Mould material as one type of novel green science and technology; The pyroceramic filtering membrane tube has a series of characteristics compared with high-polymer membrane: Heat stability is good, and chemicalstability is good, and intensity is high; Mechanical Builds is stable, can carry out regenerative operations such as the cleaning of soda acid or hot steam, high pressure recoil.
Yet since inorganic ceramic filter membranous crisp, elasticity is little, frangible, therefore must they be gone up attached to the matrix with certain physical strength (carrier) and use.Thereby just must have good porosity, physical strength, unreactiveness, good binding property arranged, under HTHP and strong corrosive environment, be difficult for and teleblem takes off and splits with teleblem as carrier.So to some degree, the selection of carrier and preparation are the bases of pyroceramic filtering membrane research.Because carborundum porous ceramics has that the coefficient of expansion is low, characteristics such as favorable mechanical and chemicalstability under the good thermal shock, high temperature, its carrier as the inorganic filter film is widely used in the separating and filtering aspect of support of the catalyst and gas solid separation and molten metal.So carborundum porous ceramics just becomes the preferred material of pyroceramic filtering membrane tube carrier.
Preparation inorganic filter film is used the porous silicon carbide ceramic carrier, adopts the means of extrusion forming both at home and abroad at present usually.For the short carrier of size, such forming method a kind of ideal of can yet be regarded as is selected; But for the length carrier that has certain requirements, limitation has just appearred in this method.At first, extrude goods in sintering process, because length, often the phenomenon of appearance fracture causes yield rate very low; Secondly, owing to can not guarantee the consistence of entire body raw material, thus even burn till under the situation that fracture do not occur, also can't guarantee the consistence of overall mechanical strength at carrier, and can't satisfy the requirement of long period use.
Summary of the invention
The purpose of this invention is to provide a kind of under the HTHP environment for use, inorganic filter film with ideal chemicalstability, intensity and suitable pore size distribution, porosity is with cellular ceramic substrate and preparation method thereof.
Porous silicon carbide ceramic carrier provided by the present invention is processed by major ingredient silit, auxiliary material wedding agent and pore-forming material; Wherein, The mass ratio of said silit and wedding agent is 80~90: 10~20, and the volume(tric)fraction of said pore-forming material is 35~45% of said silit, wedding agent and a pore-forming material volume sum.
Wherein, said major ingredient silit is fine particle size fractionated silit, and its median size can be 250~300 μ m.
This fine particle size fractionated silit major ingredient specifically can prepare through following method: certain grain size (250~300 μ m) SiC powder is poured in the ceramic cylinder body, earlier through H
2SO
4The abundant alkali cleaning of NaOH is passed through in fully pickling again, at 100~200 ℃ of complete dryinies, is prepared into the silit major ingredient of required grain diameter grade through strict sieving and grading.
Said wedding agent specifically can be by thing phase composites such as clay, kaolin and feldspars, and wherein, clay, kaolin and felspathic mass ratio are followed successively by 4~8: 4~8: 2~4.
It is that 60~100 μ m, content are higher than 90% following substances: activated carbon, camwood knag or coke powder that said pore-forming material specifically can be median size.
The preparation method of porous silicon carbide ceramic carrier of the present invention comprises the steps:
1) in silicon carbide powder, adds wedding agent and pore-forming material, be made into mixed powder; In said mixed powder, add deionized water and be made into slurry;
2) after the slurry ball mill mixing with step 1), cross 60 mesh sieves behind spray-dried granulation or the pressure-filteration drying and obtain powder; Powder is adopted vacuum hot-cast moulding, process base substrate;
3) base substrate is carried out pressureless sintering, get said porous silicon carbide ceramic carrier after the cooling.
Wherein, sintering described in the step 3) carries out in air atmosphere, and said agglomerating temperature is 1250~1350 ℃, soaking time 2~4 hours.
The proportioning of mixed powder described in the step 1) and deionized water is 1: 1.5~2.0.
The time of ball milling step 2) is 12~24 hours.
Because the present invention forms major ingredient through the fine particle size classification of sic raw material, utilize special warfare to add wedding agent and pore-forming material, and adopt unique technology such as vacuum hot-cast moulding, can greatly improve the intensity and the porosity of porous support.Prepared carborundum porous ceramics have good thermal shock, the coefficient of expansion low, under HTHP, have excellent over-all propertieies such as favorable mechanical and chemicalstability.The inorganic filter film that on this porous silicon carbide propping material, prepares has the porosity height, hardness is high, wear-resisting and working process in characteristics such as chemical transformation do not take place; Thereby from material reduced that the inorganic filter film in use occurs owing to high temperature wear, decrease of hardness, fragility cause the probability that lost efficacy greatly, improved work-ing life and the result of use of inorganic filter film.Adopt the pressureless sintering method to improve the production efficiency of cellular ceramic substrate simultaneously in addition, reduced production cost.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further specified, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is ordinary method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
Fine particle size classification silit major ingredient used among the following embodiment prepares according to following method:
Certain grain size (250~300 μ m) SiC powder is poured in the ceramic cylinder body, earlier through H
2SO
4The abundant alkali cleaning of NaOH is passed through in fully pickling again, at 100~200 ℃ of complete dryinies, is prepared into the silit major ingredient that median size is 250~300 μ m variable grain grades through strict sieving and grading.
Embodiment one:
With 88 gram median sizes is 280 μ m silit major ingredients; The activated carbon (median size 90 μ m) of 12 gram wedding agents (clay 5g, kaolin 4g, feldspar 3g) and volume(tric)fraction 40% mixes; Pour into and carried out ball milling in the 200ml deionized water 24 hours, slurry is granulation in spray-drying tower.By the required powder that takes by weighing corresponding weight of reality, in steel die, the round tube type base substrate is processed in pressurization, cooling through the vacuum hot-cast.Base substrate is put into stove and is had the corundum crucible that buries powder, under air atmosphere, under the condition of 1300 ℃ of insulation 4h, burns till, and with the stove naturally cooling, obtains the porous silicon carbide ceramic carrier.
Test result: the porosity of the SiC cellular ceramic substrate of preparation is 43%, and mean pore size is 55 μ m, and ultimate compression strength reaches 28MPa.Can guarantee under the HTHP working conditions requirement fully to carrier.
Wherein, porosity is with reference to the testing method in the GB/T 1966-1996 standard; Ultimate compression strength is with reference to the testing method in the GB/T1964-1996 standard.
Embodiment two:
With 80 gram median sizes is 250 μ m silit major ingredients; 20 gram wedding agents (clay 8g, kaolin 8g, feldspar 4g) and volume(tric)fraction 35% camwood knag (median size 100 μ m) mix; Pour into and carried out ball milling in the 180ml deionized water 12 hours, slurry is granulation in spray-drying tower.By the required powder that takes by weighing corresponding weight of reality, in steel die, the round tube type base substrate is processed in pressurization, cooling through the vacuum hot-cast.Base substrate is put into stove and is had the corundum crucible that buries powder, under air atmosphere, under the condition of 1250 ℃ of insulation 3h, burns till, and with the stove naturally cooling, obtains the porous silicon carbide ceramic carrier.
Test result: the porosity of the SiC cellular ceramic substrate of preparation is 45%, and mean pore size is 57 μ m, and ultimate compression strength reaches 23MPa.Can guarantee under the HTHP working conditions requirement fully to carrier.
Embodiment three:
With 90 gram median sizes is 300 μ m silit major ingredients; 10 gram wedding agents (clay 4g, kaolin 3g, feldspar 3g) and volume(tric)fraction 42% coke powder (median size 60 μ m) mix; Pour into and carried out ball milling in the 220ml deionized water 16 hours, slurry is through crossing 60 mesh sieves behind the pressure-filteration drying.By the required powder that takes by weighing corresponding weight of reality, in steel die, the round tube type base substrate is processed in pressurization, cooling through the vacuum hot-cast.Base substrate is put into stove and is had the corundum crucible that buries powder, under air atmosphere, under the condition of 1350 ℃ of insulation 2h, burns till, and with the stove naturally cooling, obtains the porous silicon carbide ceramic carrier.
Test result: the porosity of the SiC cellular ceramic substrate of preparation is 38%, and mean pore size is 46 μ m, and ultimate compression strength reaches 35MPa.Can guarantee under the HTHP working conditions requirement fully to carrier.
Embodiment four:
With 83 gram median sizes is 270 μ m silit major ingredients; 17 gram wedding agents (clay 8g, kaolin 5g, feldspar 4g) and volume(tric)fraction 43% activated carbon (median size 75 μ m) mix; Pour into and carried out ball milling in the 235ml deionized water 20 hours, slurry is granulation in spray-drying tower.By the required powder that takes by weighing corresponding weight of reality, in steel die, the round tube type base substrate is processed in pressurization, cooling through the vacuum hot-cast.Base substrate is put into stove and is had the corundum crucible that buries powder, under air atmosphere, under the condition of 1320 ℃ of insulation 4h, burns till, and with the stove naturally cooling, obtains the porous silicon carbide ceramic carrier.
Test result: the porosity of the SiC cellular ceramic substrate of preparation is 46%, and mean pore size is 53 μ m, and intensity reaches 26.6MPa.Can guarantee under the HTHP working conditions requirement fully to carrier.
Claims (8)
1. porous silicon carbide ceramic carrier; Process by silit, wedding agent and pore-forming material; Wherein, the mass ratio of said silit and wedding agent is 80~90: 10~20, and the volume(tric)fraction of said pore-forming material is 35~45% of said silit, wedding agent and a pore-forming material volume sum.
2. porous silicon carbide ceramic carrier according to claim 1 is characterized in that: said silit is fine particle size fractionated silit, and its median size is 250~300 μ m.
3. porous silicon carbide ceramic carrier according to claim 1 and 2 is characterized in that: said wedding agent is made up of clay, kaolin and feldspar; Wherein, clay, kaolin and felspathic mass ratio are followed successively by 4~8: 4~8: 2~4.
4. according to each described porous silicon carbide ceramic carrier among the claim 1-3, it is characterized in that: said pore-forming material is that median size is that 60~100 μ m, content are higher than following any one material of 90%: activated carbon, camwood knag and coke powder.
5. according to each described porous silicon carbide ceramic carrier among the claim 1-4, it is characterized in that: said porous silicon carbide ceramic carrier is to prepare according to the method that comprises the steps:
1) in said silit, adds said wedding agent and pore-forming material, be made into mixed powder; In said mixed powder, add deionized water and be made into slurry;
2) after the slurry ball mill mixing with step 1), cross 60 mesh sieves behind spray-dried granulation or the pressure-filteration drying and obtain powder; Powder is adopted vacuum hot-cast moulding, process base substrate;
3) said base substrate is carried out pressureless sintering, get said porous silicon carbide ceramic carrier after the cooling.
6. porous silicon carbide ceramic carrier according to claim 5 is characterized in that: sintering described in the step 3) carries out in air atmosphere, and said agglomerating temperature is 1250~1350 ℃, soaking time 2~4 hours.
7. prepare the method for each described porous silicon carbide ceramic carrier among the claim 1-4, comprise the steps: 1) in said silit, add said wedding agent and pore-forming material, be made into mixed powder; In said mixed powder, add deionized water and be made into slurry;
2) after the slurry ball mill mixing with step 1), cross 60 mesh sieves behind spray-dried granulation or the pressure-filteration drying and obtain powder; Powder is adopted vacuum hot-cast moulding, process base substrate;
3) said base substrate is carried out pressureless sintering, get said porous silicon carbide ceramic carrier after the cooling.
8. method according to claim 7 is characterized in that: sintering described in the step 3) carries out in air atmosphere, and said agglomerating temperature is 1250~1350 ℃, soaking time 2~4 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201210103839 CN102617179B (en) | 2012-04-10 | 2012-04-10 | Preparation method of porous ceramic carrier for high-temperature and high-pressure inorganic filtering membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201210103839 CN102617179B (en) | 2012-04-10 | 2012-04-10 | Preparation method of porous ceramic carrier for high-temperature and high-pressure inorganic filtering membrane |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102617179A true CN102617179A (en) | 2012-08-01 |
CN102617179B CN102617179B (en) | 2013-06-05 |
Family
ID=46557454
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201210103839 Expired - Fee Related CN102617179B (en) | 2012-04-10 | 2012-04-10 | Preparation method of porous ceramic carrier for high-temperature and high-pressure inorganic filtering membrane |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102617179B (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103011786A (en) * | 2012-12-03 | 2013-04-03 | 郑州振东科技有限公司 | Method for producing expanded ceramic heat-insulating plate by using shale and clinker |
CN103539455A (en) * | 2013-10-09 | 2014-01-29 | 河南核净洁净技术有限公司 | High-temperature-resistant silicon carbide coated filter element for radioactive gas treatment and preparation method thereof |
CN103819219A (en) * | 2014-01-22 | 2014-05-28 | 湖南大学 | Acid and alkali corrosion-resistant silicon carbide porous support |
CN104261867A (en) * | 2014-09-23 | 2015-01-07 | 武汉工程大学 | Preparation method of pure silicon carbide porous ceramic membrane |
CN105254322A (en) * | 2015-11-04 | 2016-01-20 | 陕西科技大学 | Preparation method of oriented porous SiC ceramic with crystal boundary containing metal phases |
CN105330294A (en) * | 2015-12-01 | 2016-02-17 | 芜湖豫新世通汽车空调有限公司 | Filtering membrane used for automobile air conditioner and preparation method of filtering membrane |
CN105645986A (en) * | 2016-01-11 | 2016-06-08 | 梁小利 | High-bending-strength porous silicon carbide ceramic and preparation method thereof |
CN106631123A (en) * | 2017-01-10 | 2017-05-10 | 中国建筑材料科学研究总院 | Honeycomb-shaped silicon carbide ceramic carrier, and preparation method and application thereof |
CN106810290A (en) * | 2015-11-27 | 2017-06-09 | 衡阳凯新特种材料科技有限公司 | A kind of preparation method of carborundum porous ceramics |
CN108178655A (en) * | 2016-12-08 | 2018-06-19 | 辽宁法库陶瓷工程技术研究中心 | A kind of method added pore creating material technique and prepare silicon carbide ceramic filter |
CN108771912A (en) * | 2018-06-12 | 2018-11-09 | 山东华恩新材料科技有限公司 | A kind of board-like nanometer silicon carbide ceramic filter filter core and preparation method thereof |
CN109534817A (en) * | 2017-09-21 | 2019-03-29 | 中南大学 | A kind of orienting stephanoporate structure preparation method of polymer pyrolysis class ceramics |
CN109650938A (en) * | 2019-01-16 | 2019-04-19 | 赵志刚 | Ceramic filter and its preparation method and application |
CN110711494A (en) * | 2019-08-06 | 2020-01-21 | 北京中矿未来科技集团有限公司 | Tubular membrane assembly and system for purifying suspension liquid with high solid waste content |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1793040A (en) * | 2006-01-13 | 2006-06-28 | 清华大学 | Porous ceramic support for high strength inorganic separating film and preparation process thereof |
-
2012
- 2012-04-10 CN CN 201210103839 patent/CN102617179B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1793040A (en) * | 2006-01-13 | 2006-06-28 | 清华大学 | Porous ceramic support for high strength inorganic separating film and preparation process thereof |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103011786A (en) * | 2012-12-03 | 2013-04-03 | 郑州振东科技有限公司 | Method for producing expanded ceramic heat-insulating plate by using shale and clinker |
CN103011786B (en) * | 2012-12-03 | 2014-03-05 | 郑州振东科技有限公司 | Method for producing expanded ceramic heat-insulating plate by using shale and clinker |
CN103539455A (en) * | 2013-10-09 | 2014-01-29 | 河南核净洁净技术有限公司 | High-temperature-resistant silicon carbide coated filter element for radioactive gas treatment and preparation method thereof |
CN103539455B (en) * | 2013-10-09 | 2014-12-10 | 河南核净洁净技术有限公司 | High-temperature-resistant silicon carbide coated filter element for radioactive gas treatment and preparation method thereof |
CN103819219A (en) * | 2014-01-22 | 2014-05-28 | 湖南大学 | Acid and alkali corrosion-resistant silicon carbide porous support |
CN103819219B (en) * | 2014-01-22 | 2015-07-08 | 湖南大学 | Acid and alkali corrosion-resistant silicon carbide porous support |
CN104261867A (en) * | 2014-09-23 | 2015-01-07 | 武汉工程大学 | Preparation method of pure silicon carbide porous ceramic membrane |
CN104261867B (en) * | 2014-09-23 | 2016-01-20 | 武汉工程大学 | A kind of preparation method of pure carborundum porous ceramics film |
CN105254322A (en) * | 2015-11-04 | 2016-01-20 | 陕西科技大学 | Preparation method of oriented porous SiC ceramic with crystal boundary containing metal phases |
CN106810290A (en) * | 2015-11-27 | 2017-06-09 | 衡阳凯新特种材料科技有限公司 | A kind of preparation method of carborundum porous ceramics |
CN105330294A (en) * | 2015-12-01 | 2016-02-17 | 芜湖豫新世通汽车空调有限公司 | Filtering membrane used for automobile air conditioner and preparation method of filtering membrane |
CN105645986A (en) * | 2016-01-11 | 2016-06-08 | 梁小利 | High-bending-strength porous silicon carbide ceramic and preparation method thereof |
CN108178655A (en) * | 2016-12-08 | 2018-06-19 | 辽宁法库陶瓷工程技术研究中心 | A kind of method added pore creating material technique and prepare silicon carbide ceramic filter |
CN106631123A (en) * | 2017-01-10 | 2017-05-10 | 中国建筑材料科学研究总院 | Honeycomb-shaped silicon carbide ceramic carrier, and preparation method and application thereof |
CN106631123B (en) * | 2017-01-10 | 2019-09-10 | 中国建筑材料科学研究总院 | A kind of honeycomb silicon carbide ceramics carrier and its preparation method and application |
CN109534817A (en) * | 2017-09-21 | 2019-03-29 | 中南大学 | A kind of orienting stephanoporate structure preparation method of polymer pyrolysis class ceramics |
CN108771912A (en) * | 2018-06-12 | 2018-11-09 | 山东华恩新材料科技有限公司 | A kind of board-like nanometer silicon carbide ceramic filter filter core and preparation method thereof |
CN109650938A (en) * | 2019-01-16 | 2019-04-19 | 赵志刚 | Ceramic filter and its preparation method and application |
CN110711494A (en) * | 2019-08-06 | 2020-01-21 | 北京中矿未来科技集团有限公司 | Tubular membrane assembly and system for purifying suspension liquid with high solid waste content |
Also Published As
Publication number | Publication date |
---|---|
CN102617179B (en) | 2013-06-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102617179B (en) | Preparation method of porous ceramic carrier for high-temperature and high-pressure inorganic filtering membrane | |
Zong et al. | Preparation of anorthite-based porous ceramics using high-alumina fly ash microbeads and steel slag | |
CN101948316B (en) | Preparation method of ceramic filtration supporter | |
CN114105676A (en) | Corundum micro-nano-pore heat insulation refractory material and preparation method thereof | |
CN101555151B (en) | Corundum fireproof ball used for ball-type hot-blast stove and preparation method thereof | |
CN101781124A (en) | Method for preparing porzite porous honeycomb ceramic with needle-shaped crystal structure | |
CN101920142B (en) | Silicon carbide high-temperature ceramic filter pipe and preparation method thereof | |
CN103951394B (en) | A kind of high temperature anti-thermal shock aluminum oxide ceramic bearing burning plate and preparation technology thereof | |
CN102417368A (en) | Foam ceramic manufactured by high-silicon iron tailings and manufacture method thereof | |
CN1793040A (en) | Porous ceramic support for high strength inorganic separating film and preparation process thereof | |
CN108484149B (en) | Preparation method of NaA molecular sieve membrane support | |
CN106365669A (en) | Cordierite honeycomb ceramic carrier using complete oxides as raw materials and preparation method thereof | |
CN102249710B (en) | Method for making low-creepage and high-strength high temperature resisting ceramic roller | |
CN101671198A (en) | Method for synthesizing porous cordierite-mullite composite material by utilizing solid wastes | |
CN103833383A (en) | Corundum-magnesium aluminum spinelle-textured refractory aggregate with closed-hole structure and preparation method of refractory aggregate | |
CN102633532B (en) | High-temperature and high-pressure inorganic filter membrane and preparation method thereof | |
CN111153711A (en) | Foamed ceramic with high fire resistance limit and capable of being rapidly cooled and preparation method thereof | |
CN101265118A (en) | Micro-pore mullite lightweight aggregate and preparation method thereof | |
CN106431435A (en) | Porous periclase-forsterite multiphase material and preparation method thereof | |
CN112521177B (en) | Low-melting-point porous ceramic material and preparation method thereof | |
CN105036167A (en) | Calcium hexaluminate and preparation method thereof | |
CN110922164B (en) | Preparation method of forsterite type complex phase heat insulation material | |
CN111393156A (en) | Preparation method of cordierite porous ceramic | |
CN101550019A (en) | Composite fire resistant ball for ball type hot-air stove and method for preparing same | |
CN105837168A (en) | Preparation method of high-strength building blocks |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130605 Termination date: 20210410 |
|
CF01 | Termination of patent right due to non-payment of annual fee |