CN103304226A - Thermal storage ceramic material and preparation method thereof - Google Patents
Thermal storage ceramic material and preparation method thereof Download PDFInfo
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- CN103304226A CN103304226A CN2013101812948A CN201310181294A CN103304226A CN 103304226 A CN103304226 A CN 103304226A CN 2013101812948 A CN2013101812948 A CN 2013101812948A CN 201310181294 A CN201310181294 A CN 201310181294A CN 103304226 A CN103304226 A CN 103304226A
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Abstract
The invention provides a thermal storage ceramic material and a preparation method thereof. The thermal storage ceramic material comprises the following ingredients by weight percent: 42.0-55.0% of Al2O3, 32.5-46.7% of SiO2, 3.8 -8.0% of MgO and 0.8-4% of rare earth oxide, wherein the rare earth oxide comprises La2O3, Eu2O3 and Tb2O3. When being used as a thermal storage medium to perform thermal oxidation on a silicon-containing organic waste gas, the thermal storage ceramic material provided by the invention can effectively prevent silicon dioxide generated by organic silicon in the waste gas from crystallizing on the ceramic surface so as to prolong the service lives of ceramic fillers and ceramic bed equipment and solve the problem that organic silicon gases cannot be treated by a thermal storage type thermal oxidation method.
Description
Technical field
The present invention relates to stupalith, relate in particular to a kind of thermal storage ceramic material as accumulation of heat, heat-transfer medium.
Background technology
Stupalith is widely used as the accumulation of heat of environmental protection equipment, the development that heat-transfer medium is accompanied by environmental protection equipment.Accumulation of heat, the employed stupalith of heat-transfer medium mainly contain mullite (3Al
2O
32SiO
2) material, trichroite+mullite material, trichroite+aluminum oxide material, mullite+aluminum oxide material etc., these materials can satisfy the requirement of accumulation of heat, heat transfer, and cost is relatively cheap again simultaneously.
If contain organosilicon compound in the organic exhaust gas, when waste gas was oxidized, organosilicon can be oxidized to inorganic silicon-dioxide and form crystallization at the thermal storage ceramic filling surface.Because the main component silico-aluminate of pottery and the proximity of silicon-dioxide crystallization cause the silico-aluminate of silicon-dioxide and ceramic surface to combine securely with the form that is similar to chemical bond, macroscopic view then shows as the silicon-dioxide crystallization and grows at ceramic surface.Silica deposit can cause the bed of packings effective drift diameter to reduce, and increase falls in bed resistance, and the residence time reduction of processed gas waits impact, then causes device processes complete failure when developing into severity, and must change filler this moment.Owing to changing difficult realization and the diseconomy of pottery, common way is when adopting combustion method to process organic volatile material (VOC) waste gas, requires can not contain in the waste gas silicon composition of trace, just can avoid the generation of this problem.
Therefore, how to provide a kind of silicon-dioxide crystallization that can prevent that the organosilicon material oxidation among the VOC generates under operational condition to become the problem that this area needs to be resolved hurrily at the thermal storage ceramic material of ceramic material surfaces deposition.
Summary of the invention
For the problems referred to above, one object of the present invention is to provide a kind of thermal storage ceramic material, and this thermal storage ceramic material can prevent effectively that the silicon-dioxide crystallization that the organosilicon material oxidation among the VOC generates under operational condition from depositing in ceramic material surfaces.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
The invention provides a kind of thermal storage ceramic material, calculate by mass percentage, it comprises following component: 42.0～55.0%Al
2O
3, 32.5～46.7%SiO
2, 3.8～8.0%MgO and 0.8～4.0% rare earth oxide, wherein said rare earth oxide comprises: La
2O
3, Eu
2O
3And Tb
2O
3
Further, described thermal storage ceramic material comprises Na
2O, K
2O, CaO, Fe
2O
3, TiO
2And BaO, wherein Na
2O+K
2O+CaO≤3.5%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
Further, described thermal storage ceramic material comprises following component: 47～50.1%Al
2O
3, 34.4～43.5%SiO
2, 3.8～5.2%MgO and 1.2～2.9% rare earth oxides, Na
2O+K
2O+CaO≤3.5%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
Further, the raw material of described thermal storage ceramic material comprises: trichroite, Al
2O
3, talcum and rare earth oxide.
Further, the Al in the described trichroite
2O
3Content is greater than 32.8%, SiO
2Content greater than 48.3%, MgO content greater than 12.8%;
Preferably, the SiO in the described talcum
2Content greater than 58.4%, MgO content greater than 29.2%.
Further, the raw material of described thermal storage ceramic material comprises: 5380-7210 part trichroite, 2190-3570 part Al
2O
3, 810-1810 part talcum and 78-395 part rare earth oxide.
Further, described thermal storage ceramic material is the thermal storage ceramic filler, preferred loose heap ceramic packing, honeycomb ceramic packing or combination cellular structured ceramic packing;
Preferably, described loose heap ceramic packing comprises ceramic saddle ring, Raschig ring, cascade ring, cross diaphragm rings, Pall ring or Ceramic Balls;
Preferably, described honeycomb ceramic packing inside is by the hole of a plurality of up/down perforations, and preferred square opening forms.
The present invention further provides a kind of above-mentioned thermal storage ceramic material preparation method, may further comprise the steps:
Step a: ceramic raw material is mixed, pulverize, sieve, obtain compound;
Step b: remove the impurity in the compound;
Step c: in the compound that step b obtains, add rare earth oxide, compound is carried out the vacuum mud refining, old;
Steps d: the compound that step c is obtained carries out drying, sintering obtains the thermal storage ceramic material.
In the aforesaid method, among the described step a, ceramic raw material is mixed, pulverize, cross 300 mesh sieves, obtain compound;
Preferably, among the described step b, adopt the iron in the wet method sizing material iron removing technique removal compound;
Preferably, among the described step c, in the compound that step b obtains, add rare earth oxide, with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, then the old time adopted plasticity extrusion molding technology controlling and process to be shaped less than or equal to 72 hours;
Preferably, in the described steps d, the compound that step c is obtained carries out microwave drying under less than 45 ℃, and be 20-120min time of drying, carries out subsequently sintering under 950-1200 ℃, and sintering time is 30～40 hours, obtains the thermal storage ceramic material.
Thermal storage ceramic material of the present invention can be made into various forms of fillers, comprise that loose heap ceramic packing is (such as ceramic saddle ring (shown in Fig. 1 (A)), Raschig ring (shown in Fig. 1 (B)), cascade ring (shown in Fig. 1 (C)), cross diaphragm rings (shown in Fig. 1 (D)), Pall ring (shown in Fig. 1 (E)) and Ceramic Balls (shown in Fig. 1 (F)) etc.), (this ceramic packing inside is comprised of the hole of a plurality of up/down perforations honeycomb ceramic packing, see from cross section and to be similar to honeycomb arrangement, therefore be called honeycomb ceramic packing, as shown in Figure 2) and combination cellular structured ceramic packing (shown in Fig. 3 (A-B)) etc.
The present invention selects rare earth oxide (lanthanum trioxide/europium sesquioxide/terbium sesquioxide) to prepare the thermal storage ceramic material as ceramic modified component, when the amount of the rare earth oxide that wherein adds is less, do not reach and prevent that effectively silicon-dioxide is in the effect of ceramic surface crystallization, when content is too much, then can cause the price of stupalith to raise, increase production cost, the present invention considers performance and the cost of stupalith, and the content of preferred rare earth oxide is 0.8～4.0%.
The present invention selects trichroite, talcum and Al
2O
3As main raw material, add mixed rare-earth oxide and prepare the thermal storage ceramic material, the principal crystalline phase of the stupalith that finally prepares is trichroite and mullite, the density reachable of thermal storage ceramic material is to 2.35g/cm
3Above.
The present invention is at existing accumulation of heat, the employed mullite (3Al of heat-transfer medium
2O
32SiO
2) on the basis of material, trichroite+mullite material, trichroite+aluminum oxide material, mullite+stupaliths such as aluminum oxide material, use trichroite, talcum and Al
2O
3As main raw material, and in raw material, add ceramic modified component rare earth oxide (lanthanum trioxide/europium sesquioxide/terbium sesquioxide), make rare earth oxide in pottery generation and moulding process, be scattered in equably in the ceramic systems, changed the electronic migration changing pattern of ceramic surface electrical behavior and hot lower system inside, thereby make thermal storage ceramic material of the present invention can prevent effectively that the silicon-dioxide of the organosilicon material oxidation formation in the VOC waste gas under common operational condition and the atom of ceramic surface from forming chemical bond and making silicon-dioxide deposit or make silicon-dioxide to be taken out of system (namely very little being easy to of sticking power of ceramic surface deposition by waste gas power at ceramic surface, under operational condition, do not produce crystallization, perhaps crystallization velocity is very slow and be easy to be taken out of system by waste gas power), thereby prolonged the work-ing life of ceramic packing and ceramic bed equipment, solved the technical barrier that the heat accumulation type thermal oxidation method can not be processed organosilicon gas.Simultaneously, Na in the thermal storage ceramic material of the present invention
2O, K
2O, CaO, Fe
2O
3, TiO
2And the content of the composition such as BaO all meets corresponding composition requirement in the stupalith.
Description of drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 is the schematic diagram of the loose heap ceramic packing that adopts thermal storage ceramic material of the present invention and make;
Fig. 2 is the schematic diagram of the honeycomb ceramic packing that adopts thermal storage ceramic material of the present invention and make;
Fig. 3 is the schematic diagram of the combination cellular structured ceramic packing that adopts thermal storage ceramic material of the present invention and make;
To be thermal storage ceramic material of the present invention and existing thermal storage ceramic material use surface topography schematic diagram after 3 months as the thermal storage ceramic filler to Fig. 4;
Fig. 5 is that existing thermal storage ceramic material uses surface topography enlarged diagram after 3 months as the thermal storage ceramic filler among Fig. 4;
Fig. 6 is the schematic diagram of regenerative thermal oxidizer (Regenerative Thermal Oxidizer the is called for short RTO) testing apparatus of employing thermal storage ceramic filler of the present invention.
Embodiment
Referring to specific embodiment the present invention is described.It will be appreciated by those skilled in the art that these embodiment only are used for explanation the present invention, the scope that it does not limit the present invention in any way.
The molecular formula of the trichroite in the embodiment of the invention is (Mg, Fe)
2Al
3[AlSi
5O
18], originating from Shandong, content is greater than 94%, wherein Al
2O
3Content is greater than 32.8%, SiO
2Content greater than 48.3%, MgO content greater than 12.8%; The molecular formula of talcum is [Mg
3(Si
4O
10) (OH)
2], originating from Fujian, content is greater than 92%, wherein SiO
2Content greater than 58.4%, MgO content greater than 29.2%.
Preparation Example 1The thermal storage ceramic material preparation
Step a: with 6700g trichroite, 2190g Al
2O
3And the mixing of 1010g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in the wet method sizing material iron removing technique removal compound;
Step c: in the compound that step b obtains, add the 78g rare earth oxide and (comprise La
2O
3, Eu
2O
3And Tb
2O
3), with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, then the old time adopted plasticity extrusion molding technique to extrude shaping less than or equal to 72 hours;
Steps d: the compound that step c is obtained carries out drying under less than 45 ℃, be 20-60min time of drying, carries out subsequently sintering under 950-1000 ℃, and sintering time is 32-35 hour, obtains the thermal storage ceramic material.
The component concentration of the thermal storage ceramic material that obtains by aforesaid method is as follows:
Al
2O
342.0%, SiO
246.7%, MgO 5.2%, rare earth oxide (La
2O
3+ Eu
2O
3+ Tb
2O
3) 0.8%, Na
2O+K
2O+CaO≤3.5%, Fe
2O
3≤ 1.0%, TiO
2+ BaO≤0.80%.
Preparation Example 2The thermal storage ceramic material preparation
Step a: with 6810g trichroite, 2380g Al
2O
3And the mixing of 810g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in the wet method sizing material iron removing technique removal compound;
Step c: in the compound that step b obtains, add the 145g rare earth oxide and (comprise La
2O
3, Eu
2O
3And Tb
2O
3), with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, then the old time adopted plasticity extrusion molding technique to extrude shaping less than or equal to 72 hours;
Steps d: the compound that step c is obtained carries out drying under less than 45 ℃, be 60-100min time of drying, carries out subsequently sintering under 1000-1100 ℃, and sintering time is 30-33 hour, obtains the thermal storage ceramic material.
The component concentration of the thermal storage ceramic material that obtains by aforesaid method is as follows:
Al
2O
347.0%, SiO
243.5%, MgO 3.8%, rare earth oxide (La
2O
3+ Eu
2O
3+ Tb
2O
3) 1.5%, Na
2O+K
2O+CaO≤2.2%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
Preparation Example 3The thermal storage ceramic material preparation
Step a: with 7210g trichroite, 2210g Al
2O
3And the mixing of 970g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in the wet method sizing material iron removing technique removal compound;
Step c: in the compound that step b obtains, add the 214g rare earth oxide and (comprise La
2O
3, Eu
2O
3And Tb
2O
3), with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, then the old time adopted plasticity extrusion molding technique to extrude shaping less than or equal to 72 hours;
Steps d: the compound that step c is obtained carries out drying under less than 45 ℃, be 80-120min time of drying, carries out subsequently sintering under 1100-1200 ℃, and sintering time is 30-35 hour, obtains the thermal storage ceramic material.
The component concentration of the thermal storage ceramic material that obtains by aforesaid method is as follows:
Al
2O
347.3%, SiO
240.8%, MgO 5.2%, rare earth oxide (La
2O
3+ Eu
2O
3+ Tb
2O
3) 2.2%, Na
2O+K
2O+CaO≤2.5%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
Preparation Example 4The thermal storage ceramic material preparation
Step a: with 5380g trichroite, 3230g Al
2O
3And the mixing of 1810g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in the wet method sizing material iron removing technique removal compound;
Step c: in the compound that step b obtains, add the 286g rare earth oxide and (comprise La
2O
3, Eu
2O
3And Tb
2O
3), with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, then the old time adopted plasticity extrusion molding technique to extrude shaping less than or equal to 72 hours;
Steps d: the compound that step c is obtained carries out drying under less than 45 ℃, be 60-120min time of drying, carries out subsequently sintering under 950-1100 ℃, and sintering time is 35-40 hour, obtains the thermal storage ceramic material.
The component concentration of the thermal storage ceramic material that obtains by aforesaid method is as follows:
Al
2O
350.1%, SiO
234.4%, MgO 8.0%, rare earth oxide (La
2O
3+ Eu
2O
3+ Tb
2O
3) 2.9%, Na
2O+K
2O+CaO≤3.0%, Fe
2O
3≤ 0.8%, TiO
2+ BaO≤0.80%.
Preparation Example 5The thermal storage ceramic material preparation
Step a: with 5530g trichroite, 3570g Al
2O
3And the mixing of 915g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in the wet method sizing material iron removing technique removal compound;
Step c: in the compound that step b obtains, add the 395g rare earth oxide and (comprise La
2O
3, Eu
2O
3And Tb
2O
3), with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, then the old time adopted plasticity extrusion molding technique to extrude shaping less than or equal to 72 hours;
Steps d: the compound that step c is obtained carries out drying under less than 45 ℃, be 20-100min time of drying, carries out subsequently sintering under 1000-1200 ℃, and sintering time is 33-39 hour, obtains the thermal storage ceramic material.
The component concentration of the thermal storage ceramic material that obtains by aforesaid method is as follows:
Al
2O
355%, SiO
232.5%, MgO 3.8%, rare earth oxide (La
2O
3+ Eu
2O
3+ Tb
2O
3) 4.0%, Na
2O+K
2O+CaO≤2.7%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
Comparative example
Adopt the method identical with embodiment 1 to prepare the thermal storage ceramic material, wherein do not add rare earth oxide in the preparation process.
Test case 1Surface topography is observed
Under thermooxidizing organic volatile material (VOC) operating mode, adopt respectively the thermal storage ceramic material of preparation among comparative example and the embodiment 1 to process siliceous organic exhaust gas as filler, adopt (the Electricity Federation Rui Ma Energy Saving Technology Co self-control in the Jiangsu of RTO testing apparatus, model XYQ-R-1.2, test as shown in Figure 6), chamber temperature is 800-850 ℃, and VOC(replaces with kerosene) content is 450mg/m
3, wherein organosilicon (replacing with dimethyl silicone oil) content is 4.5mg/m
3, observe the surface topography of thermal storage ceramic materials'use after 3 months.
The thermal storage ceramic material that Fig. 4-5 shows respectively the embodiment of the invention 1 preparation and existing thermal storage ceramic material are as the surface topography schematic diagram of ceramic packing use after 3 months.As seen from Figure 4, thermal storage ceramic material of the present invention is brick-red after using as filler, and filling surface does not have silicon-dioxide crystallization deposition thing (shown in Fig. 4 (A)), and ceramic surface form and use properties do not change yet; And the thermal storage ceramic material that adopts existing method (comparative example) preparation is white in color after using as filler, filling surface deposits a large amount of silica crystals (such as Fig. 4 (B) and shown in Figure 5, wherein Fig. 5 is partial enlarged drawing, illustrate that the crystallization of existing thermal storage ceramic material surface silicon-dioxide is serious), the silica crystals deposition easily causes the bed of packings effective drift diameter to reduce, increase falls in bed resistance, and the residence time reduction of processed gas waits impact, thereby affects the use of stupalith.Thus explanation, with respect to existing thermal storage ceramic material, thermal storage ceramic material of the present invention can stop the silicon-dioxide crystallization of the generation of the organosilicon material oxidation among the VOC under operational condition at the ceramic packing surface deposition effectively.
Above specific description of embodiments of the present invention does not limit the present invention, and those skilled in the art can make according to the present invention various changes or distortion, only otherwise break away from spirit of the present invention, all should belong to the scope of claims of the present invention.
Claims (9)
1. a thermal storage ceramic material is calculated by mass percentage, and it comprises following component: 42.0～55.0%Al
2O
3, 32.5～46.7%SiO
2, 3.8～8.0%MgO and 0.8～4.0% rare earth oxide, wherein said rare earth oxide comprises: La
2O
3, Eu
2O
3And Tb
2O
3
2. thermal storage ceramic material according to claim 1 is characterized in that, described thermal storage ceramic material further comprises Na
2O, K
2O, CaO, Fe
2O
3, TiO
2And BaO, wherein Na
2O+K
2O+CaO≤3.5%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
3. thermal storage ceramic material according to claim 1 and 2 is characterized in that, described thermal storage ceramic material comprises following component: 47～50.1%Al
2O
3, 34.4～43.5%SiO
2, 3.8～5.2%MgO and 1.2～2.9% rare earth oxides, Na
2O+K
2O+CaO≤3.5%, Fe
2O
3≤ 1.2%, TiO
2+ BaO≤0.80%.
4. each described thermal storage ceramic material in 3 according to claim 1 is characterized in that, the raw material of described thermal storage ceramic material comprises: trichroite, Al
2O
3, talcum and rare earth oxide.
5. thermal storage ceramic material according to claim 4 is characterized in that, the Al in the described trichroite
2O
3Content is greater than 32.8%, SiO
2Content greater than 48.3%, MgO content greater than 12.8%;
Preferably, the SiO in the described talcum
2Content greater than 58.4%, MgO content greater than 29.2%.
6. according to claim 4 or 5 described thermal storage ceramic materials, it is characterized in that, the raw material of described thermal storage ceramic material comprises: 5380-7210 part trichroite, 2190-3570 part Al
2O
3, 810-1810 part talcum and 78-395 part rare earth oxide.
7. each described thermal storage ceramic material in 6 according to claim 1 is characterized in that, described thermal storage ceramic material is the thermal storage ceramic filler, preferred loose heap ceramic packing, honeycomb ceramic packing or combination cellular structured ceramic packing;
Preferably, described loose heap ceramic packing comprises ceramic saddle ring, Raschig ring, cascade ring, cross diaphragm rings, Pall ring or Ceramic Balls;
Preferably, described honeycomb ceramic packing inside is by the hole of a plurality of up/down perforations, and preferred square opening forms.
8. each described thermal storage ceramic material preparation method in 7 according to claim 1 may further comprise the steps:
Step a: ceramic raw material is mixed, pulverize, sieve, obtain compound;
Step b: remove the impurity in the compound;
Step c: in the compound that step b obtains, add rare earth oxide, compound is carried out the vacuum mud refining, old;
Steps d: the compound that step c is obtained carries out drying, sintering obtains the thermal storage ceramic material.
9. preparation method according to claim 8 is characterized in that, among the described step a, ceramic raw material is mixed, and pulverizes, and crosses 300 mesh sieves, obtains compound;
Preferably, among the described step b, adopt the iron in the wet method sizing material iron removing technique removal compound;
Preferably, among the described step c, in the compound that step b obtains, add rare earth oxide, with compound in vacuum tightness greater than carrying out the vacuum mud refining under the 720mmHg, old, the old time is less than or equal to 72 hours, then adopts plasticity extrusion molding technology controlling and process to be shaped;
Preferably, in the described steps d, the compound that step c is obtained carries out microwave drying under less than 45 ℃, and be 20-120min time of drying, carries out subsequently sintering under 950-1200 ℃, and sintering time is 30～40 hours, obtains the thermal storage ceramic material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712708A (en) * | 2016-01-12 | 2016-06-29 | 西南民族大学 | High-efficiency energy-saving ceramic material |
| CN105712711A (en) * | 2016-01-12 | 2016-06-29 | 西南民族大学 | High-performance microwave dielectric ceramic material and preparation method thereof |
| CN106085376A (en) * | 2016-06-22 | 2016-11-09 | 王斐芬 | A kind of high specific heat fused salt mixt heat transfer heat storage medium |
| CN106085375A (en) * | 2016-06-22 | 2016-11-09 | 王斐芬 | A kind of fused salt mixt heat transfer heat storage medium and preparation method thereof |
| CN106495673A (en) * | 2016-10-21 | 2017-03-15 | 过冬 | A kind of Thermal storage ceramic material and preparation method thereof |
| CN110818400A (en) * | 2019-10-26 | 2020-02-21 | 辽宁科技大学 | Preparation method of high-density mullite ceramic powder |
| WO2022120551A1 (en) * | 2020-12-08 | 2022-06-16 | 苏州惠林节能材料有限公司 | Heat energy recovery device for novel efficient total heat exchange fresh-air ventilation system |
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| CN1745042A (en) * | 2003-02-05 | 2006-03-08 | 3M创新有限公司 | Methods of making ceramic particles |
| CN101839643A (en) * | 2009-03-20 | 2010-09-22 | 通用电气公司 | Enhancement type fire-proof crucible for smelting titanium alloy |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1745042A (en) * | 2003-02-05 | 2006-03-08 | 3M创新有限公司 | Methods of making ceramic particles |
| CN101839643A (en) * | 2009-03-20 | 2010-09-22 | 通用电气公司 | Enhancement type fire-proof crucible for smelting titanium alloy |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712708A (en) * | 2016-01-12 | 2016-06-29 | 西南民族大学 | High-efficiency energy-saving ceramic material |
| CN105712711A (en) * | 2016-01-12 | 2016-06-29 | 西南民族大学 | High-performance microwave dielectric ceramic material and preparation method thereof |
| CN105712711B (en) * | 2016-01-12 | 2018-06-26 | 西南民族大学 | A kind of high performance microwave medium ceramic material and preparation method thereof |
| CN106085376A (en) * | 2016-06-22 | 2016-11-09 | 王斐芬 | A kind of high specific heat fused salt mixt heat transfer heat storage medium |
| CN106085375A (en) * | 2016-06-22 | 2016-11-09 | 王斐芬 | A kind of fused salt mixt heat transfer heat storage medium and preparation method thereof |
| CN106495673A (en) * | 2016-10-21 | 2017-03-15 | 过冬 | A kind of Thermal storage ceramic material and preparation method thereof |
| CN110818400A (en) * | 2019-10-26 | 2020-02-21 | 辽宁科技大学 | Preparation method of high-density mullite ceramic powder |
| WO2022120551A1 (en) * | 2020-12-08 | 2022-06-16 | 苏州惠林节能材料有限公司 | Heat energy recovery device for novel efficient total heat exchange fresh-air ventilation system |
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|---|---|
| CN103304226B (en) | 2015-07-08 |
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