CN115594493B - Solar heat storage multiphase ceramic material prepared from bauxite and Suzhou soil and method - Google Patents
Solar heat storage multiphase ceramic material prepared from bauxite and Suzhou soil and method Download PDFInfo
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Abstract
The invention relates to a solar heat storage composite ceramic material prepared from bauxite and Suzhou soil and a method thereof, wherein the raw materials comprise 40-55% of calcined bauxite and 45-60% of Suzhou soil by mass percent; the preparation method comprises the following steps: uniformly mixing calcined bauxite and Suzhou soil according to a proportion to obtain mixed powder; granulating, ageing, press forming and drying the mixed powder to obtain a green body, and sintering the green body at 1600-1640 ℃ to obtain the solar heat storage composite ceramic material. The invention only adopts two relatively low-price raw materials of calcined bauxite and Suzhou soil, and the production process is also pressureless oxidation atmosphere sintering, so the cost is low; compared with silicon carbide heat storage ceramics, the production cost is reduced by nearly 80 percent; the main crystal phase of the obtained material is mullite, the secondary crystal phase is corundum, and the material grows in a staggered way to form a dense net structure, and the material has high service temperature, high density, high strength and good thermal shock resistance.
Description
Technical Field
The invention relates to the technical field of solar thermal power generation, in particular to a solar heat storage composite ceramic material prepared from bauxite and Suzhou soil and a method thereof.
Background
The solar heat storage ceramic material is a key material for the next-generation high-efficiency solar tower type high-temperature thermal power generation technology, and is required to have high service temperature (generally, 1300-1500 ℃ temperature resistance is required), high density, high heat storage density and good thermal shock resistance (suitable for high-temperature thermal shock generated by solar fluctuation at daytime and evening). Corundum, silicon carbide, mullite, zirconium quartz and the like are used for manufacturing high-temperature heat storage materials, but the materials are prepared from artificially synthesized raw materials, so that the cost is high (the heat storage materials account for about 40% of the total cost of the solar thermal power generation technology), and the development of the solar thermal power generation technology is restricted.
In addition, as in the invention patent 'a compact mullite-corundum-SiC complex phase heat storage ceramic material for solar thermal power generation and a preparation method thereof' (CN 111269015A), silicon carbide is taken as a main raw material, and a small amount of bauxite and kaolin are added to prepare the heat storage ceramic material, wherein the heat storage density is 996 J.g -1 The bulk density was 2.30 g.cm -3 The highest strength is only 77.05MPa; in the invention patent 'a modified SiC-based heat storage ceramic for solar thermal power generation and a preparation method thereof', fe is added 2 O 3 The modified heat accumulating density of 1202.18 J.g -1 The volume density is only 2.55 g.cm -3 The strength is 121.88MPa; however, as the main raw materials of the heat storage ceramic are silicon carbide, the production cost is high, and meanwhile, the silicon carbide is easy to oxidize at high temperature, so that the heat storage material has shorter service life and higher use cost, can only be used as a medium-temperature heat storage ceramic material, and has lower service temperature (only 800-1000 ℃); in the invention patent of a preparation method of mullite corundum composite phase material (CN 101602605), high bauxite and kaolin are used as raw materials, and yttrium oxide, manganese oxide and carboxymethyl cellulose are also used to prepare the mullite corundum composite phase ceramic material, the volume density of which reaches 2.88 g.cm -3 However, since the additives of yttrium oxide, manganese oxide and carboxymethyl cellulose are used, the production cost is relatively high, and meanwhile, the porosity of the material is 2.22%, the densification effect is not achieved, and the heat storage density is not high.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a solar heat storage composite ceramic material prepared from bauxite and Suzhou soil and a method thereof.
In order to achieve the technical aim, the invention provides a technical scheme of a solar heat storage composite ceramic material prepared by bauxite and Suzhou soil, which comprises the following steps:
the raw materials comprise 40-55% of calcined bauxite and 45-60% of Suzhou soil by mass percent.
Further, the main components of the calcined bauxite include, in mass percent: 55-75% of aluminum oxide, 15-35% of silicon dioxide, 5-10% of ferric oxide and titanium oxide, and the content of other impurities is not more than 5%.
Further, the main components of the Suzhou soil comprise, by mass: 35-55% of silicon dioxide, 30-50% of aluminum oxide, 0.5-2% of ferric oxide and titanium oxide, and the content of other impurities is not more than 8%.
Further, the particle sizes of the calcined bauxite and the Suzhou soil are 250-325 meshes.
The invention also provides a technical scheme of a method for preparing the solar heat storage composite ceramic material by using bauxite and Suzhou soil, which comprises the following steps: the method comprises the following steps:
(1) Uniformly mixing calcined bauxite and Suzhou soil according to a proportion to obtain mixed powder;
(2) Granulating and aging the mixed powder to obtain a blank;
(3) Pressing and forming the blank to obtain a green body;
(4) Drying the green body to obtain a green body;
(5) The green body is sintered at 1600-1640 ℃ to obtain the solar heat storage complex phase ceramic material.
Further, in the step (1), the calcined bauxite and the Suzhou soil are uniformly mixed by adopting a ball milling mode.
In the step (2), water with the mass fraction of 2-4% is added into the mixed powder by adopting a spray drying method for granulation, and the blank is prepared after granulation and aging for more than 24 hours.
Further, in the step (3), the pressure of the compression molding is 30-40 MPa.
Further, in the step (4), the drying is carried out at the temperature of 85-100 ℃ for 24-48 hours.
Further, in the step (5), in the sintering process, the heating rate is 3-5 ℃/min, the temperature is kept for 30-60 min at intervals of 100 ℃, and the temperature is kept for 1.5-2.5 h when the temperature is raised to 1600-1640 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention only adopts two relatively low-price raw materials of calcined bauxite and Suzhou soil, no other high-price raw materials are added, and the production process is pressureless oxidation atmosphere sintering, so the cost is low; compared with silicon carbide heat storage ceramics, the production cost is reduced by nearly 80 percent. The invention is beneficial to greatly reducing the power generation cost of the solar thermal power generation technology.
2. The high-temperature heat storage composite ceramic material has good comprehensive performance. The main crystal phase of the material is mullite (the content is 90-95%), the secondary crystal phase is corundum (the content is 5-10%), and long-rod-shaped mullite and short-column-shaped corundum are alternately grown to form a dense reticular structure, so that higher density, heat storage density and strength are obtained, and meanwhile, the structure is also better in high temperature resistance and thermal shock resistance. The invention greatly prolongs the service life of the heat storage ceramic material, thereby greatly reducing the solar thermal power generation cost.
Drawings
Fig. 1 is an XRD pattern of the solar high temperature thermal storage composite ceramic material in example 1 of the present invention.
Fig. 2 is an SEM image of the solar high-temperature thermal storage composite ceramic material in example 1 of the present invention.
Fig. 3 is an XRD pattern of the solar high temperature heat storage composite ceramic material according to example 1 of the present invention after 30 thermal shock cycles.
Fig. 4 is an SEM image of the solar high-temperature heat storage composite ceramic material according to example 1 of the present invention after 30 thermal shock resistance cycles.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a method for preparing a solar high-temperature heat storage composite ceramic material from bauxite and Suzhou soil, which has high service temperature, high compactness, high strength, good comprehensive properties such as thermal shock resistance and the like and low cost, and the preparation method comprises the following steps:
(1) And (3) raw material treatment: ball milling and mixing calcined bauxite and Suzhou soil powder for 30min to obtain powder with the particle size of 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou soil powder is (40-55): (45-60). Ball ratio is 1:2 during ball milling. Wherein, the main components of the calcined bauxite are as follows: 55-75% of alumina, 15-35% of silicon dioxide, 5-10% of ferric oxide and titanium oxide, no more than 5% of other impurities, and 250-325 mesh of calcined bauxite; the main components of the Suzhou soil are as follows: 35-55% of silicon dioxide, 30-50% of alumina, 0.5-2% of ferric oxide and titanium oxide, and not more than 8% of other impurities, wherein the grain size of Suzhou soil is 250-325 meshes.
(2) Granulating and aging: adding water with the mass fraction of 2-4% into the mixed powder by adopting a spray drying method for granulating, and ageing for more than 24 hours after granulating to obtain a blank.
Because more Suzhou soil is adopted in the invention, water can be used as a binder, and a mixture with strong plasticity can be obtained without adding a traditional polyvinyl alcohol solution, so that the granulation is convenient.
(3) Semi-dry press molding: and (3) pressing and forming the aged blank by using a hydraulic press, wherein the pressure is 30-40 MPa, and preparing the high-temperature heat storage multiphase ceramic material green body.
(4) And (3) drying: and (3) placing the formed green body in a drying box, and drying at 85-100 ℃ for 24-48 h to obtain a green body.
(5) Firing: and (3) placing the dried green body into a sagger, and then placing the sagger into a resistance furnace to be burned at a certain temperature (the heating rate of 3-5 ℃/min is increased to 1600-1640 ℃ and the temperature is kept for 1.5-2.5 h), so as to obtain the densified solar high-temperature heat storage material.
According to the invention, bauxite and Suzhou soil adopted by the invention are clay minerals with high aluminum content, the cost is low, the high temperature resistance is good, by controlling the mass percentage, the heat storage composite ceramic material which takes mullite as a main crystalline phase and corundum as a secondary crystalline phase is generated by combining a specific sintering process while other raw materials and additives are not added, and long-rod-shaped mullite and short-column-shaped corundum are alternately grown to form a dense reticular structure, so that the compactness, heat storage density and strength of the obtained material are improved, and the high temperature resistance and thermal shock resistance are good.
The solar high-temperature heat storage material does not contain silicon carbide, is a pure oxide system after high-temperature sintering, and has actual use temperature higher than sintering temperature, and is estimated in a conservation way, and the heat storage ceramic material is high-temperature resistant and can be used in a high-temperature environment of at least 1300-1500 ℃.
The invention is further illustrated by the following specific examples.
Example 1
(1) And (3) raw material treatment: ball milling and mixing calcined bauxite and Suzhou soil powder for 30min to obtain powder with the particle size of 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou soil powder is 50:50. ball ratio is 1:2 during ball milling. Wherein, the main components of the calcined bauxite are as follows: alumina content 72.72%, silica content 20.81%, total content of ferric oxide (1.56%), titanium oxide (3.59%), content of other impurities of 1.32%, particle size of calcined bauxite of 250-325 mesh; the main components of the Suzhou soil are silicon dioxide 45.14%, aluminum oxide 37.88%, ferric oxide (0.30%) and titanium oxide (0.27%) which are contained in total, the ignition loss is 16%, the content of other impurities is not more than 0.41%, and the particle size of the Suzhou soil is 250-325 meshes.
(2) Granulating and aging: adding water with the mass fraction of 4% into the mixed powder by adopting a spray drying method, granulating and aging for 24 hours to obtain a blank.
(3) Semi-dry press molding: and (3) pressing and forming the aged blank by using a hydraulic press, wherein the pressure is 30MPa, and preparing the high-temperature heat storage multiphase ceramic material green body.
(4) And (3) drying: and (3) placing the formed green body in a drying box, and drying for 24 hours at 95 ℃ to obtain a green body.
(5) Firing: and (3) placing the dried green body into a sagger, then placing the sagger into a resistance furnace, and firing the sagger at a certain temperature (the heating rate of 5 ℃/min is raised to 1000 ℃, the temperature is kept at 30min every 100 ℃ in the middle, the temperature is raised to 1620 ℃ every 100 ℃ in the middle after the temperature is raised to 1000 ℃ at the heating rate of 3 ℃/min, the temperature is kept at 60min every 100 ℃ in the middle, and the temperature is kept at the highest temperature for 2 h), so as to obtain the solar high-temperature heat storage composite ceramic material.
Through testing, the heat storage composite ceramic material is high-temperature resistant and can be used in a high-temperature environment of 1300-1500 ℃; according to Archimedes principle and static weighing method, using TXT digital display ceramic water absorption tester produced by Xiangtan Hunan instruments, inc. and AuY electronic analytical balance produced by Shimadzu, the water absorption of the material is 0.12%, the apparent porosity is 0.35%, and the volume density is 2.83 g.cm -3 The density is higher; RGM-4100 microcomputer control electronic universal tester manufactured by Shenzhen Ruiger company is adopted to measure the flexural strength up to 155.44MPa (the test condition is that the span is 28mm, and the load loading rate is 0.5 mm/min); the heat storage capacity is strong, the specific heat capacity of the material measured by using a C80 microcalorimeter produced by the French Setalambda company reaches 1.423 kJ/kg.K (25-800 ℃), and the heat storage density reaches 1102.3 J.g -1 (25-800 ℃); the thermal shock resistance is better, SX-2-5-12 type box-type energy-saving resistance furnace manufactured by Hubei Yingshan Jian electric furnace is adopted to carry out thermal shock resistance experiment (thermal shock experiment flow is that the burnt sample is put into the thermal shock furnace to be heated to 1000 ℃ at the speed of 5 ℃/min, and is taken out to be cooled to room temperature after being kept warm for 15min, which is 1 thermal shock process), after 30 thermal shock cycle experiments (1000-room temperature and air cooling), the high-temperature heat storage material has no crack, the apparent porosity and the volume density of the high-temperature heat storage material are kept unchanged compared with those before thermal shock, the flexural strength of the high-temperature heat storage material is increased to 166.15MPa, and the related requirements in the refractory material thermal shock resistance test method (GB/T30873-2014) are met and exceeded.
As shown in figure 1, according to XRD analysis, the high-temperature heat storage ceramic material prepared in the embodiment 1 is mullite and corundum composite phase material, wherein the main crystal phase of the material is mullite, the secondary crystal phase is corundum, the mullite content is 90.5%, and the corundum content is 9.5%.
As can be seen from the SEM image of the material in FIG. 2, the high-temperature heat storage composite ceramic material prepared in the embodiment 1 has a compact structure, a small amount of closed pores are contained in the material, the average pore diameter is about 12 mu m, mullite and corundum in the material are interwoven and grow to form a net structure, and a small amount of glass phase is filled around crystal grains, so that the material has higher flexural strength.
As shown in figure 3, after XRD analysis, the high-temperature heat storage composite ceramic material prepared in example 1 is subjected to 30 times of thermal shock cycle experiments (1000-room temperature), the mullite content of the material is 92.4%, the corundum content is 7.6%, the water absorption rate is 0.11%, the apparent porosity is 0.31%, and the volume density is 2.83 g.cm, and the material is tested in the same manner as described above -3 Meanwhile, the flexural strength is further improved to 166.15MPa, and is improved by 6.89%, so that the performance requirement of the new generation solar thermal power generation technology on the high-temperature heat storage material can be met.
As can be seen from FIG. 4, the high-temperature heat-storage composite ceramic material prepared in example 1 has mullite grain growth and grain boundary migration during thermal shock, the material fracture mode is gradually changed from crystal fracture to crystal-through fracture, and the liquid phase gradually fills pores, so that after 30 thermal shock cycle experiments (1000-room temperature), the flexural strength of the prepared high-temperature heat-storage ceramic material is increased, and the volume density is basically kept unchanged, thus indicating that the prepared high-temperature heat-storage ceramic material has good thermal shock resistance.
Example 2 (investigating the influence of the proportions of the raw materials)
And (3) adjusting the mass percentage of the calcined bauxite and the Suzhou soil powder in the step (1) to 40:60, adding 3% water in the step (2), and otherwise, the other steps and conditions are the same as in example 1.
Through tests, the solar high-temperature heat storage composite ceramic material has high temperature resistance, can be used in a high-temperature environment of 1300-1500 ℃, has a apparent porosity of 0.27% and a volume density of 2.80g cm -3 The flexural strength is 139.49MPa, warpAfter 30 times of thermal shock cycle tests (1000-room temperature, air cooling), the solar high-temperature heat storage composite ceramic material has no cracks, the apparent porosity and the volume density of the solar high-temperature heat storage composite ceramic material are unchanged compared with those before thermal shock, the flexural strength of the solar high-temperature heat storage composite ceramic material is slightly reduced, the solar high-temperature heat storage composite ceramic material reaches 131.84MPa, and the related requirements of the high-temperature heat storage material can be met.
Comparative example 1 (examination of the influence of the proportions of raw materials)
And (3) adjusting the mass percentage of the calcined bauxite and the Suzhou soil powder in the step (1) to be 30:70, adding 2% of water in the step (2), and otherwise, performing the same steps and conditions as in example 1.
Through testing, the heat storage ceramic material of the comparative example 1 is high temperature resistant, can be used in a high temperature environment of 1 300-1 ℃ and 500 ℃, has a apparent porosity of 0.25% and a volume density of 2.75g cm -3 The flexural strength is 108.61MPa, after 30 times of thermal shock cycle tests (1000-room temperature, air cooling), the high-temperature heat storage material of comparative example 1 has no cracks, the apparent porosity and the volume density are unchanged compared with those before thermal shock, and the flexural strength is reduced to 98.69MPa.
Comparative example 2 (examination of the influence of the proportions of raw materials)
The mass percentage of the calcined bauxite and the Suzhou soil powder in the step (1) is adjusted to be 60:40, water with a mass fraction of 4% was added in step (2), and the other steps and conditions were the same as in example 1.
The test shows that the heat storage ceramic material of comparative example 1 is high temperature resistant, and can be used in 1300-1500 ℃ high temperature environment, when the material is not sintered at 1620 ℃, the apparent porosity is 10.35%, and the volume density is 2.69g cm -3 The flexural strength is 129.27MPa.
Comparative example 3 (examination of the influence of the proportions of raw materials)
The mass percentage of the calcined bauxite and the Suzhou soil powder in the step (1) is adjusted to be 70:30, water with a mass fraction of 4.5% was added in step (2), and the other steps and conditions were the same as in example 1.
Through testing, the heat storage ceramic material of the comparative example 3 is resistant to high temperature, can be used in a high-temperature environment of 1300-1500 ℃, is not sintered at 1620 ℃, has a apparent porosity of 14.31% and has a bulk density of 2.63g cm -3 The flexural strength is 122.23MPa。
The heat storage ceramic materials obtained in examples 1-2 and comparative examples 1-3 were tested and the results are shown in table 1 below.
TABLE 1 raw material ratios and test results for examples 1-2 and comparative examples 1-3
In comparative example 1, example 2 and comparative example 1 (wherein the amount of water added in the granulating process is slightly different, due to the adaptability adjustment performed by the different proportions of the raw materials, the granulating plasticity is ensured, free water is discharged in the drying process, the performance of the subsequently obtained materials is not affected, and thus a single factor variable test can be formed), the ratio of calcined bauxite to Suzhou soil in the materials is sequentially reduced, and as a result, the apparent porosity, the volume density and the flexural strength of the heat storage material are reduced. This is because as the ratio of bauxite to Suzhou soil decreases, w (Al 2 O 3 )/w(SiO 2 ) The value is reduced, so that the volume density of the sintered material is reduced, the mullite content in the sintered sample is reduced, the glass phase is relatively increased, and the glass phase fills pores, so that the apparent porosity is reduced, but the relative content of the mullite and the grain development morphology are main factors influencing the flexural strength of the material, so that the flexural strength of the material is reduced.
The ratio of calcined bauxite to Suzhou soil in the material is increased in the order of comparative example 1, comparative example 2 and comparative example 3, and the Al/Si ratio in the material is increased at this time, and the liquid phase content at high temperature is reduced at the time of firing, resulting in a higher firing temperature of the material. Because of the limitation of laboratory equipment, the sintering temperature can not be raised any more, and therefore the materials of the comparative example 2 and the comparative example 3 do not reach a sintering state when being sintered at 1620 ℃, so that the apparent porosity is large, the volume density is small, and the related requirements of high-temperature heat storage are not met.
Therefore, the preferred mass percentages of calcined bauxite and Suzhou soil of the invention are (40-55): (45-60).
Comparative example 4 (examination of the influence of different firing temperatures)
(1) And (3) raw material treatment: ball milling and mixing calcined bauxite and Suzhou soil powder for 30min to obtain powder with the particle size of 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou soil powder is 50:50. ball ratio is 1:2 during ball milling.
(2) Granulating and aging: adding 3% water by mass percent into the mixed powder by adopting a spray drying method, granulating and aging for 24 hours to obtain a blank.
(3) Semi-dry press molding: and (3) pressing and forming the aged blank by using a hydraulic press, wherein the pressure is 30MPa, and preparing the high-temperature heat storage multiphase ceramic material green body.
(4) And (3) drying: and (3) placing the formed green body in a drying box, and drying for 24 hours at 95 ℃ to obtain a green body.
(5) Firing: and (3) placing the dried green body into a sagger, then placing the sagger into a resistance furnace, and sintering at a certain temperature (the heating rate of 5 ℃/min is raised to 1000 ℃, the temperature is kept at 30min every 100 ℃ in the middle, the temperature is raised to 1580 ℃ at the heating rate of 3 ℃/min, the temperature is kept at 60min every 100 ℃ in the middle, and the temperature is kept at the highest temperature for 2 h), so as to obtain the solar high-temperature heat storage material.
The heat storage material obtained in the comparative example 3 is tested to resist high temperature, can be used in a high temperature environment of 1300-1500 ℃, has a apparent porosity of 7.78% and a volume density of 2.68g cm -3 The flexural strength is 90.70MPa. Comparative example 4 compared with example 1, the firing temperature of the material was lowered, and as a result, it was found that the apparent porosity was increased, the bulk density and the flexural strength were all reduced, at which time the sample did not reach the sintered state at 1580 ℃, the material did not reach densification, and the mullite grains as the main crystal phase did not develop completely, thus causing a significant decrease in flexural strength.
As a result, the firing temperature of the present invention is preferably 1600 to 1640℃and more preferably 1600 to 1620 ℃.
Comparative example 5 (examination of influence of raw material types)
The su state soil was replaced with the name of the bushel, and the other conditions were the same as in example 1.
(1) And (3) raw material treatment: ball milling and mixing calcined bauxite and powder of the metallocene kaolin for 30 minutes to obtain powder with the particle size of between 250 and 325 meshes, wherein the mass percentage of the calcined bauxite to the powder of the Suzhou clay is 50:50. ball ratio is 1:2 during ball milling. Wherein, the main components of the calcined bauxite are as follows: 72.72 percent of aluminum oxide, 20.81 percent of silicon dioxide, 5.15 percent of ferric oxide and titanium oxide, 1.32 percent of other impurities and 250 to 325 meshes of calcined bauxite; the main components of the clay with the name of China are 50.68% of silicon dioxide, 34.93% of aluminum oxide, 1.02% of ferric oxide and titanium oxide, 12.34% of ignition loss, less than 1.03% of other impurities, and the particle size of the clay with the name of China is 250-325 meshes.
(2) Granulating and aging: adding water with the mass fraction of 4% into the mixed powder by adopting a spray drying method, granulating and aging for 24 hours to obtain a blank.
(3) Semi-dry press molding: and (3) pressing and forming the aged blank by using a hydraulic press, wherein the pressure is 30MPa, and preparing the high-temperature heat storage multiphase ceramic material green body.
(4) And (3) drying: and (3) placing the formed green body in a drying box, and drying for 24 hours at 95 ℃ to obtain a green body.
(5) Firing: and (3) placing the dried green body into a sagger, then placing the sagger into a resistance furnace, and sintering at a certain temperature (the heating rate of 5 ℃/min is raised to 1000 ℃, the temperature is kept at 30min every 100 ℃ in the middle, the temperature is raised to 1600 ℃ at the heating rate of 3 ℃/min, the temperature is kept at 60 ℃ every 100 ℃ in the middle, and the temperature is kept at the highest temperature for 2 h), so as to obtain the solar high-temperature heat storage material.
Through testing, the heat storage material of the comparative example 5 is high temperature resistant, can be used in a high temperature environment of 1300-1500 ℃, has a apparent porosity of 0.47% and a volume density of 2.76g cm -3 The flexural strength is 124.23MPa, after 30 times of thermal shock cycle tests (1000-room temperature, air cooling), the high-temperature heat storage material has no crack, the apparent porosity and the volume density of the material are unchanged compared with those of the material before thermal shock, and the flexural strength of the material is slightly reduced to 118.46MPa.
As a result of the replacement of the sozhou clay in example 1 with the kaolin clay of the name of the luxury in comparative example 5, it was found that the bulk density and flexural strength of the heat storage material were reduced. This is because of the SiO of the metallocene kaolin compared to the Suzhou clay 2 The content is relatively high, al 2 O 3 Relatively less, and thus w (Al) 2 O 3 )/w(SiO 2 ) The value is reduced, the sintering temperature is reduced, but the mullite content in the sintered sample is reduced, the glass phase is relatively increased, and the volume density of the sintered material is reduced, so that the flexural strength of the sintered material is reduced, the apparent porosity is reduced, and the heat storage density is not improved.
In conclusion, the heat storage ceramic material of the invention is high temperature resistant, can be used in a high temperature environment of 1300-1500 ℃, has a apparent porosity of 0.27-0.35% and a bulk density of 2.8-2.83 g.cm -3 The compactness is higher, and the flexural strength is as high as 139.49-155.44 MPa; the heat storage capacity is strong, the specific heat capacity can reach 1.423 kJ/kg.K (25-800 ℃), and the heat storage density is as high as 1102.3 J.g -1 (25-800 ℃); the thermal shock resistance is better, after 30 times of thermal shock cycle tests (1000-room temperature and air cooling), the high-temperature heat storage material has no crack, the apparent porosity and the volume density of the material are unchanged compared with those of the material before thermal shock, and the flexural strength of the material can be increased to 166.15MPa, so that the material meets and exceeds the related requirements in refractory material thermal shock resistance test method (GB/T30873-2014).
Compared with the prior art, the invention has the advantages that:
1. the high-temperature heat storage composite ceramic material has lower production cost. The invention only adopts two relatively low-price raw materials of calcined bauxite and Suzhou soil, no other high-price raw materials are added, the cost of the raw materials is only 1 to 1 yuan/ton, and the production process is pressureless oxidation atmosphere sintering, so the cost is lower. Compared with silicon carbide heat storage ceramics, the production cost is reduced by nearly 80 percent. The invention is beneficial to greatly reducing the power generation cost of the solar thermal power generation technology.
2. The high-temperature heat storage composite ceramic material has good comprehensive performance. The main crystal phase of the material is mullite (the content is 90-95%), the secondary crystal phase is corundum (the content is 5-10%), and long-rod-shaped mullite and short-column-shaped corundum are alternately grown to form a dense reticular structure, so that higher density, heat storage density and strength are obtained, and meanwhile, the structure is also better in high temperature resistance and thermal shock resistance. The invention greatly prolongs the service life of the heat storage ceramic material, thereby greatly reducing the solar thermal power generation cost.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (10)
1. The solar heat storage composite ceramic material prepared by bauxite and Suzhou soil is characterized in that the material consists of 40-55% of calcined bauxite and 45-60% of Suzhou soil by mass percent;
the main crystal phase of the obtained material is mullite, the content of the main crystal phase is 90-95%, the secondary crystal phase is corundum, the content of the main crystal phase is 5-10%, and long-rod mullite and short-column corundum alternately grow to form a dense reticular structure.
2. The solar heat storage composite ceramic material prepared by using bauxite and Suzhou earth according to claim 1, wherein the main components of the calcined bauxite comprise, in mass percent: 55-75% of aluminum oxide, 15-35% of silicon dioxide, 5-10% of ferric oxide and titanium oxide, and the content of other impurities is not more than 5%.
3. The solar heat storage composite ceramic material prepared by bauxite and Suzhou soil according to claim 1, wherein the Suzhou soil comprises the following main components in percentage by mass: 35-55% of silicon dioxide, 30-50% of aluminum oxide, 0.5-2% of ferric oxide and titanium oxide, and the content of other impurities is not more than 8%.
4. The solar heat storage composite ceramic material prepared from bauxite and Suzhou soil according to claim 1, wherein the particle sizes of the calcined bauxite and Suzhou soil are 250-325 meshes.
5. The method for preparing a solar thermal storage composite ceramic material using bauxite and sozhou soil according to any one of claims 1 to 4, comprising the steps of:
(1) Uniformly mixing calcined bauxite and Suzhou soil according to a proportion to obtain mixed powder;
(2) Granulating and aging the mixed powder to obtain a blank;
(3) Pressing and forming the blank to obtain a green body;
(4) Drying the green body to obtain a green body;
(5) And sintering the green body at 1600-1640 ℃ to obtain the solar heat storage composite ceramic material.
6. The method for preparing solar heat storage composite ceramic material by using bauxite and Suzhou soil according to claim 5, wherein in the step (1), the calcined bauxite and the Suzhou soil are uniformly mixed by adopting a ball milling method.
7. The method for preparing the solar heat storage composite ceramic material by using bauxite and Suzhou soil, which is characterized in that in the step (2), water with the mass fraction of 2-4% is added into the mixed powder material by adopting a spray drying method for granulation, and the blank is prepared after granulation and aging for more than 24 hours.
8. The method for preparing the solar heat storage composite ceramic material by using bauxite and Suzhou soil according to claim 5, wherein in the step (3), the pressure of compression molding is 30-40 MPa.
9. The method for preparing the solar heat storage composite ceramic material by using bauxite and Suzhou soil according to claim 5, wherein in the step (4), the drying is carried out at the temperature of 85-100 ℃ for 24-48 hours.
10. The method for preparing the solar heat storage composite ceramic material by using bauxite and Suzhou soil according to claim 5, wherein in the step (5), the heating rate is 3-5 ℃/min in the sintering process, the temperature is kept for 30-60 min at every 100 ℃, and the temperature is kept for 1.5-2.5 h when the temperature is raised to 1600-1640 ℃.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302524A (en) * | 1999-04-15 | 2000-10-31 | Agency Of Ind Science & Technol | Manufacture of ceramic substrate for poly crystalline silicon thin film type solar cell using kaolin clay |
| CN102759292A (en) * | 2012-08-02 | 2012-10-31 | 朱建良 | Lessing ring-shaped ceramic heat-accumulation body and manufacturing process thereof |
| CN105130388A (en) * | 2015-08-24 | 2015-12-09 | 天津城建大学 | Preparation method for mullite whisker reinforced ceramic material |
| CN110105059A (en) * | 2019-05-17 | 2019-08-09 | 山东工业职业学院 | A kind of highly heatproof and shockproof, low creep hot-blast stove brick and its manufacturing method |
| CN111377723A (en) * | 2020-03-24 | 2020-07-07 | 洛阳中超新材料股份有限公司 | Low-cost environment-friendly corundum-mullite honeycomb ceramic heat accumulator and preparation method thereof |
| CN111440003A (en) * | 2020-04-07 | 2020-07-24 | 山东淄博沈淄耐火材料有限公司 | Bottom brick special for high-temperature section of tin bath of novel float glass kiln and preparation method thereof |
| CN112142490A (en) * | 2020-09-27 | 2020-12-29 | 江西新科环保股份有限公司 | Metal honeycomb ceramic heat accumulator |
| CN113321494A (en) * | 2021-06-11 | 2021-08-31 | 武汉理工大学 | Oxidation-resistant long-life heat absorption and storage integrated corundum-mullite ceramic and preparation method thereof |
| WO2022144014A1 (en) * | 2020-12-31 | 2022-07-07 | 郑州轻工业大学 | Mullite-based micro-nano-porous heat insulating refractory material and preparation method therefor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10757963B2 (en) * | 2018-08-09 | 2020-09-01 | Chun-Shyong LEE | Heat-transforming ceramic roasting cylinder and coffee bean roaster using the same |
| CN111676406B (en) * | 2020-06-05 | 2021-09-14 | 武汉科技大学 | Phase-change heat storage ceramic and preparation method thereof |
-
2022
- 2022-10-26 CN CN202211319168.XA patent/CN115594493B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302524A (en) * | 1999-04-15 | 2000-10-31 | Agency Of Ind Science & Technol | Manufacture of ceramic substrate for poly crystalline silicon thin film type solar cell using kaolin clay |
| CN102759292A (en) * | 2012-08-02 | 2012-10-31 | 朱建良 | Lessing ring-shaped ceramic heat-accumulation body and manufacturing process thereof |
| CN105130388A (en) * | 2015-08-24 | 2015-12-09 | 天津城建大学 | Preparation method for mullite whisker reinforced ceramic material |
| CN110105059A (en) * | 2019-05-17 | 2019-08-09 | 山东工业职业学院 | A kind of highly heatproof and shockproof, low creep hot-blast stove brick and its manufacturing method |
| CN111377723A (en) * | 2020-03-24 | 2020-07-07 | 洛阳中超新材料股份有限公司 | Low-cost environment-friendly corundum-mullite honeycomb ceramic heat accumulator and preparation method thereof |
| CN111440003A (en) * | 2020-04-07 | 2020-07-24 | 山东淄博沈淄耐火材料有限公司 | Bottom brick special for high-temperature section of tin bath of novel float glass kiln and preparation method thereof |
| CN112142490A (en) * | 2020-09-27 | 2020-12-29 | 江西新科环保股份有限公司 | Metal honeycomb ceramic heat accumulator |
| WO2022144014A1 (en) * | 2020-12-31 | 2022-07-07 | 郑州轻工业大学 | Mullite-based micro-nano-porous heat insulating refractory material and preparation method therefor |
| CN113321494A (en) * | 2021-06-11 | 2021-08-31 | 武汉理工大学 | Oxidation-resistant long-life heat absorption and storage integrated corundum-mullite ceramic and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 同继锋.《现代建筑卫生陶瓷技术手册》.中国建材工业出版社,2010,第61页. * |
| 郭海珠.《实用耐火原料手册》.中国建材出版社,2000,第74-75、111-116、564页. * |
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