CN103304226B - Thermal storage ceramic material and preparation method thereof - Google Patents
Thermal storage ceramic material and preparation method thereof Download PDFInfo
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- CN103304226B CN103304226B CN201310181294.8A CN201310181294A CN103304226B CN 103304226 B CN103304226 B CN 103304226B CN 201310181294 A CN201310181294 A CN 201310181294A CN 103304226 B CN103304226 B CN 103304226B
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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, particularly relate to a kind of Thermal storage ceramic material as accumulation of heat, heat-transfer medium.
Background technology
Stupalith is widely used along with the development of environmental protection equipment as the accumulation of heat of environmental protection equipment, heat-transfer medium.The stupalith that accumulation of heat, heat-transfer medium use mainly contains mullite (3Al
2o
32SiO
2) material, trichroite+mullite material, trichroite+aluminum oxide material, mullite+aluminum oxide material etc., these materials can meet the requirement of accumulation of heat, heat transfer, simultaneously cost relative moderate again.
If containing organosilicon compound in organic exhaust gas, while waste gas is oxidized, organosilicon can be oxidized to inorganic silicon-dioxide and form crystallization at thermal storage ceramic filling surface.Due to the main component silico-aluminate of pottery and the proximity of silica crystalline, cause the silico-aluminate of silicon-dioxide and ceramic surface to combine securely with the form being similar to chemical bond, macroscopic view then shows as silica crystalline and grows at ceramic surface.Silica deposit can cause 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, now must change filler when developing into severity.Owing to changing not easily realization and the diseconomy of pottery, common way is when adopting combustion method process organic volatile material (VOC) waste gas, requires containing the silicon composition of trace, just can not to avoid the generation of this problem in waste gas.
Therefore, a kind of silica crystalline that can prevent the oxidation of the organosilicon material in VOC in the operating condition from generating how is provided to become this area problem urgently to be resolved hurrily in the Thermal storage ceramic material that ceramic material surfaces deposits.
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 the silica crystalline that this Thermal storage ceramic material can prevent the oxidation of the organosilicon material in VOC in the operating condition from generating effectively deposits 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 described trichroite
2o
3content is greater than 32.8%, SiO
2content is greater than 48.3%, and content of MgO is greater than 12.8%;
Preferably, the SiO in described talcum
2content is greater than 58.4%, and content of MgO is 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 thermal storage ceramic filler, preferably 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 multiple up/down perforation, and preferred square opening forms.
The present invention further provides a kind of preparation method of above-mentioned Thermal storage ceramic material, comprise the following steps:
Step a: mixed by ceramic raw material, pulverizes, sieves, obtain compound;
Step b: remove the impurity in compound;
Step c: add rare earth oxide in the compound that step b obtains, compound is carried out vacuum mud refining is old;
Steps d: the compound obtained by step c carries out drying, sintering obtains Thermal storage ceramic material.
In aforesaid method, in described step a, ceramic raw material is mixed, pulverize, cross 300 mesh sieves, obtain compound;
Preferably, in described step b, adopt the iron in wet process furnish deferrization process removal compound;
Preferably, in described step c, in the compound that step b obtains, add rare earth oxide, compound is carried out vacuum mud refining under vacuum tightness is greater than 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 described steps d, the compound obtained by step c carries out microwave drying being less than at 45 DEG C, and time of drying is 20-120min, sinters subsequently at 950-1200 DEG C, and sintering time is 30 ~ 40 hours, obtains Thermal storage ceramic material.
Thermal storage ceramic material of the present invention can be made into various forms of filler, comprise loose heap ceramic packing (as ceramic saddle ring (as Suo Shi Fig. 1 (A)), Raschig ring (as Suo Shi Fig. 1 (B)), cascade ring (as Suo Shi Fig. 1 (C)), cross diaphragm rings (as Suo Shi Fig. 1 (D)), Pall ring (as Suo Shi Fig. 1 (E)) and Ceramic Balls (as Suo Shi Fig. 1 (F)) etc.), (this ceramic packing inside is made up of the hole of multiple up/down perforation honeycomb ceramic packing, honeycomb arrangement is similar to viewed from cross section, therefore honeycomb ceramic packing is called, as shown in Figure 2) and combination cellular structured ceramic packing (as Suo Shi Fig. 3 (A-B)) etc.
The present invention selects rare earth oxide (lanthanum trioxide/europium sesquioxide/terbium sesquioxide) to prepare Thermal storage ceramic material as ceramic modified component, when the amount of the rare earth oxide wherein added is less, do not reach the effect effectively preventing silicon-dioxide in ceramic surface crystallization, when content is too much, the price of stupalith then can be caused 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, additional mixed rare-earth oxide prepares Thermal storage ceramic material, and the principal crystalline phase of the stupalith finally prepared is trichroite and mullite, and the density of Thermal storage ceramic material can reach 2.35g/cm
3above.
Mullite (the 3Al that the present invention uses at existing accumulation of heat, heat-transfer medium
2o
32SiO
2) stupalith such as material, trichroite+mullite material, trichroite+aluminum oxide material, mullite+aluminum oxide material basis on, use trichroite, talcum and Al
2o
3as main raw material, and add ceramic modified component rare earth oxide (lanthanum trioxide/europium sesquioxide/terbium sesquioxide) in the feed, make rare earth oxide in pottery generation and moulding process, be scattered in equably in ceramic systems, change the surface electrical behavior of pottery and the electronic migration changing pattern of hot lower system inside, thus (namely very little being easy to of sticking power that the atom of the silicon-dioxide enabling Thermal storage ceramic material of the present invention effectively prevent the oxidation of the organosilicon material in VOC waste gas under normal operating conditions from being formed and ceramic surface forms chemical bond and makes silicon-dioxide deposit or make silicon-dioxide to deposit at ceramic surface at ceramic surface taken out of system by exhaust dynamics, do not produce crystallization in the operating condition, or crystallization velocity is very slow and be easy to be taken out of system by exhaust dynamics), thus extend the work-ing life of ceramic packing and ceramic bed equipment, solve the technical barrier that heat accumulation type thermal oxidation method can not process organo-silicon gases.Meanwhile, Na in 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 component requirements in stupalith.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is the schematic diagram of the loose heap ceramic packing adopting Thermal storage ceramic material of the present invention to make;
Fig. 2 is the schematic diagram of the honeycomb ceramic packing adopting Thermal storage ceramic material of the present invention to make;
Fig. 3 is the schematic diagram of the combination cellular structured ceramic packing adopting Thermal storage ceramic material of the present invention to make;
Fig. 4 is that Thermal storage ceramic material of the present invention and existing Thermal storage ceramic material use the surface topography schematic diagram after 3 months as thermal storage ceramic filler;
Fig. 5 is that in Fig. 4, existing Thermal storage ceramic material uses the surface topography enlarged diagram after 3 months as thermal storage ceramic filler;
Fig. 6 is the schematic diagram of regenerative thermal oxidizer (Regenerative Thermal Oxidizer the is called for short RTO) testing apparatus adopting 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 embodiments are only for illustration of the present invention, its scope do not limited the present invention in any way.
The molecular formula of the trichroite in the embodiment of the present invention is (Mg, Fe)
2al
3[AlSi
5o
18], originate from Shandong, content is greater than 94%, wherein Al
2o
3content is greater than 32.8%, SiO
2content is greater than 48.3%, and content of MgO is greater than 12.8%; The molecular formula of talcum is [Mg
3(Si
4o
10) (OH)
2], originate from Fujian, content is greater than 92%, wherein SiO
2content is greater than 58.4%, and content of MgO is greater than 29.2%.
preparation embodiment 1the preparation of Thermal storage ceramic material
Step a: by 6700g trichroite, 2190g Al
2o
3and the mixing of 1010g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in wet process furnish deferrization process removal compound;
Step c: add 78g rare earth oxide and (comprise La in the compound that step b obtains
2o
3, Eu
2o
3and Tb
2o
3), compound is carried out vacuum mud refining under vacuum tightness is greater than 720mmHg, and old, the old time is less than or equal to 72 hours, then adopts plasticity extrusion molding technique to extrude shaping;
Steps d: the compound obtained by step c carries out drying being less than at 45 DEG C, and time of drying is 20-60min, sinters subsequently at 950-1000 DEG C, and sintering time is 32-35 hour, obtains Thermal storage ceramic material.
The component concentration of the Thermal storage ceramic material obtained 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 embodiment 2the preparation of Thermal storage ceramic material
Step a: by 6810g trichroite, 2380g Al
2o
3and the mixing of 810g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in wet process furnish deferrization process removal compound;
Step c: add 145g rare earth oxide and (comprise La in the compound that step b obtains
2o
3, Eu
2o
3and Tb
2o
3), compound is carried out vacuum mud refining under vacuum tightness is greater than 720mmHg, and old, the old time is less than or equal to 72 hours, then adopts plasticity extrusion molding technique to extrude shaping;
Steps d: the compound obtained by step c carries out drying being less than at 45 DEG C, and time of drying is 60-100min, sinters subsequently at 1000-1100 DEG C, and sintering time is 30-33 hour, obtains Thermal storage ceramic material.
The component concentration of the Thermal storage ceramic material obtained 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 embodiment 3the preparation of Thermal storage ceramic material
Step a: by 7210g trichroite, 2210g Al
2o
3and the mixing of 970g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in wet process furnish deferrization process removal compound;
Step c: add 214g rare earth oxide and (comprise La in the compound that step b obtains
2o
3, Eu
2o
3and Tb
2o
3), compound is carried out vacuum mud refining under vacuum tightness is greater than 720mmHg, and old, the old time is less than or equal to 72 hours, then adopts plasticity extrusion molding technique to extrude shaping;
Steps d: the compound obtained by step c carries out drying being less than at 45 DEG C, and time of drying is 80-120min, sinters subsequently at 1100-1200 DEG C, and sintering time is 30-35 hour, obtains Thermal storage ceramic material.
The component concentration of the Thermal storage ceramic material obtained 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 embodiment 4the preparation of Thermal storage ceramic material
Step a: by 5380g trichroite, 3230g Al
2o
3and the mixing of 1810g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in wet process furnish deferrization process removal compound;
Step c: add 286g rare earth oxide and (comprise La in the compound that step b obtains
2o
3, Eu
2o
3and Tb
2o
3), compound is carried out vacuum mud refining under vacuum tightness is greater than 720mmHg, and old, the old time is less than or equal to 72 hours, then adopts plasticity extrusion molding technique to extrude shaping;
Steps d: the compound obtained by step c carries out drying being less than at 45 DEG C, and time of drying is 60-120min, sinters subsequently at 950-1100 DEG C, and sintering time is 35-40 hour, obtains Thermal storage ceramic material.
The component concentration of the Thermal storage ceramic material obtained 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 embodiment 5the preparation of Thermal storage ceramic material
Step a: by 5530g trichroite, 3570g Al
2o
3and the mixing of 915g talcum, pulverize, cross 300 mesh sieves, obtain compound;
Step b: adopt the iron in wet process furnish deferrization process removal compound;
Step c: add 395g rare earth oxide and (comprise La in the compound that step b obtains
2o
3, Eu
2o
3and Tb
2o
3), compound is carried out vacuum mud refining under vacuum tightness is greater than 720mmHg, and old, the old time is less than or equal to 72 hours, then adopts plasticity extrusion molding technique to extrude shaping;
Steps d: the compound obtained by step c carries out drying being less than at 45 DEG C, and time of drying is 20-100min, sinters subsequently at 1000-1200 DEG C, and sintering time is 33-39 hour, obtains Thermal storage ceramic material.
The component concentration of the Thermal storage ceramic material obtained 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 Thermal storage ceramic material, wherein do not add rare earth oxide in preparation process.
test case 1surface topography is observed
Under thermooxidizing organic volatile material (VOC) operating mode, adopt the Thermal storage ceramic material of preparation in comparative example and embodiment 1 as the siliceous organic exhaust gas of filler process respectively, adopt (the Electricity Federation Rui Ma Energy Saving Technology Co self-control in Jiangsu of RTO testing apparatus, model XYQ-R-1.2, test as shown in Figure 6), chamber temperature is that 800-850 DEG C, VOC(kerosene replaces) content is 450mg/m
3, wherein organosilicon (replacing with dimethyl silicone oil) content is 4.5mg/m
3, observe Thermal storage ceramic material and use the surface topography after 3 months.
Fig. 4-5 respectively illustrate the embodiment of the present invention 1 prepare Thermal storage ceramic material and existing Thermal storage ceramic material use the surface topography schematic diagram after 3 months as ceramic packing.As seen from Figure 4, in brick-red after Thermal storage ceramic material of the present invention uses as filler, filling surface does not have silica crystalline settling (as shown in Figure 4 (A)), and ceramic surface form and use properties also do not change; And the Thermal storage ceramic material adopting existing method (comparative example) to prepare is white after using as filler, filling surface deposits a large amount of silica crystals (as shown in Fig. 4 (B) and Fig. 5, wherein Fig. 5 is partial enlarged drawing, illustrate that the crystallization of existing Thermal storage ceramic material surface silica dioxide is serious), silica crystals deposition easily causes bed of packings effective drift diameter to reduce, increase falls in bed resistance, and the residence time reduction of processed gas waits impact, thus affects the use of stupalith.Illustrate thus, relative to existing Thermal storage ceramic material, the silica crystalline that Thermal storage ceramic material of the present invention can stop the organosilicon material oxidation in VOC in the operating condition to generate effectively is at ceramic packing surface deposition.
Specific description of embodiments of the present invention does not above limit the present invention, and those skilled in the art can make various change or distortion according to the present invention, only otherwise depart from spirit of the present invention, all should belong to the scope of claims of the present invention.
Claims (16)
1. a Thermal storage ceramic material, calculates 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 is: La
2o
3, Eu
2o
3and Tb
2o
3; Wherein, described Thermal storage ceramic material comprises Na further
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%.
2. Thermal storage ceramic material according to claim 1, 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%.
3. Thermal storage ceramic material according to claim 1 and 2, is characterized in that, the raw material of described Thermal storage ceramic material comprises: trichroite, Al
2o
3, talcum and rare earth oxide.
4. Thermal storage ceramic material according to claim 3, is characterized in that, the Al in described trichroite
2o
3content is greater than 32.8%, SiO
2content is greater than 48.3%, and content of MgO is greater than 12.8%.
5. Thermal storage ceramic material according to claim 3, is characterized in that, the SiO in described talcum
2content is greater than 58.4%, and content of MgO is greater than 29.2%.
6. Thermal storage ceramic material according to claim 3, 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. Thermal storage ceramic material according to claim 1 and 2, is characterized in that, described Thermal storage ceramic material is thermal storage ceramic filler.
8. Thermal storage ceramic material according to claim 7, is characterized in that, described thermal storage ceramic filler is loose heap ceramic packing, honeycomb ceramic packing or combination cellular structured ceramic packing.
9. Thermal storage ceramic material according to claim 8, is characterized in that, described loose heap ceramic packing comprises ceramic saddle ring, Raschig ring, cascade ring, cross diaphragm rings, Pall ring or Ceramic Balls.
10. Thermal storage ceramic material according to claim 8, is characterized in that, described honeycomb ceramic packing inside is made up of the hole of multiple up/down perforation.
11. Thermal storage ceramic material according to claim 10, is characterized in that, the hole of multiple up/down perforations of described honeycomb ceramic packing inside is square opening.
The preparation method of 12. 1 kinds of Thermal storage ceramic material according to any one of claim 1 to 11, comprises the following steps:
Step a: mixed by ceramic raw material, pulverizes, sieves, obtain compound;
Step b: remove the impurity in compound;
Step c: add rare earth oxide in the compound that step b obtains, compound is carried out vacuum mud refining is old;
Steps d: the compound obtained by step c carries out drying, sintering obtains Thermal storage ceramic material.
13. preparation methods according to claim 12, is characterized in that, in described step a, are mixed by ceramic raw material, pulverize, cross 300 mesh sieves, obtain compound.
14. preparation methods according to claim 12, is characterized in that, in described step b, adopt the iron in wet process furnish deferrization process removal compound.
15. preparation methods according to claim 12, it is characterized in that, in described step c, rare earth oxide is added in the compound that step b obtains, compound is carried out vacuum mud refining under vacuum tightness is greater than 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.
16. preparation methods according to claim 12, it is characterized in that, in described steps d, the compound obtained by step c carries out microwave drying being less than at 45 DEG C, time of drying is 20-120min, sinter at 950-1200 DEG C subsequently, sintering time is 30 ~ 40 hours, obtains Thermal storage ceramic material.
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| CN105712708B (en) * | 2016-01-12 | 2018-02-13 | 西南民族大学 | A kind of energy-efficient ceramic material |
| 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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| 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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| 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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