CN115594493A - Solar heat storage composite ceramic material prepared from bauxite and Suzhou soil and method - Google Patents
Solar heat storage composite 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 by bauxite and Suzhou soil and a method thereof, wherein the raw materials comprise, by mass, 40-55% of calcined bauxite and 45-60% of Suzhou soil; the preparation method comprises the following steps: uniformly mixing the calcined bauxite and Suzhou soil according to the proportion to obtain mixed powder; the mixed powder is granulated, aged, pressed, molded and dried to obtain a green body, and the green body is sintered at 1600-1640 ℃ to obtain the solar heat storage composite ceramic material. The invention only adopts two raw materials with lower relative price, namely calcined bauxite and Suzhou soil, and the production process is also sintering in a non-pressure oxidation atmosphere, so the cost is lower; compared with silicon carbide heat storage ceramic, 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, the materials grow in a staggered mode to form a dense net structure, and the material is high in service temperature, high in density, high in strength and good in 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 complex-phase ceramic material prepared from bauxite and Suzhou soil and a method.
Background
The solar heat storage ceramic material is a key material for the next-generation efficient solar tower type high-temperature thermal power generation technology, and is required to have high service temperature (generally required to resist temperature of 1300-1500 ℃), high density, high heat storage density and good thermal shock resistance (suitable for high-temperature and low-temperature thermal shock generated by solar energy fluctuation in the daytime and at night). People use corundum, silicon carbide, mullite, zircon quartz and the like to manufacture high-temperature heat storage materials, but the materials are all 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, in the invention patent (CN 111269015A), silicon carbide is used as a main raw material, a small amount of bauxite and kaolin are added to prepare the heat storage ceramic material, and the heat storage density is 996 J.g -1 Bulk density of 2.30 g.cm -3 The strength is only 77.05MPa at most; 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 modifier is used to improve the above patent, and the performance is improved, and the heat storage density is 1202.18 J.g -1 The bulk density is only 2.55 g.cm -3 The strength is 121.88MPa; however, the main raw materials of the heat storage ceramic are silicon carbide, so that the production cost is high, and the silicon carbide is easily oxidized at high temperature, so that the heat storage material has short service life and high use cost, can only be used as a medium-temperature heat storage ceramic material, and has low service temperature (only 800-1000 ℃); in the invention patent (CN 101602605) preparation method of mullite corundum composite phase material, high bauxite and kaolin are used as raw materials, yttrium oxide, manganese oxide and carboxymethyl cellulose are also used for preparing the mullite corundum composite phase ceramic material, and the volume density of the mullite corundum composite phase ceramic material reaches 2.88g cm -3 But due toThe production cost is relatively high due to the use of additives such as yttrium oxide, manganese oxide and carboxymethyl cellulose, and meanwhile, the material has a porosity of 2.22% and does not reach the densification effect, so that the heat storage density is not high.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a solar heat storage complex phase ceramic material prepared from bauxite and Suzhou soil and a method.
In order to achieve the technical purpose, the invention provides a technical scheme for preparing a solar heat storage complex phase ceramic material by using bauxite and Suzhou soil, which comprises the following steps:
the raw materials comprise, by mass, 40-55% of calcined bauxite and 45-60% of Suzhou soil.
Further, the main components of the calcined bauxite comprise, by mass percent: 55-75% of alumina, 15-35% of silicon dioxide, 5-10% of ferric oxide and titanium oxide, and no more than 5% of other impurities.
Further, the Suzhou soil comprises the following main components in percentage by mass: 35 to 55 percent of silicon dioxide, 30 to 50 percent of aluminum oxide, 0.5 to 2 percent of ferric oxide and titanium oxide, and the content of other impurities is not more than 8 percent.
Furthermore, the particle sizes of the calcined bauxite and the Suzhou soil are both 250 to 325 meshes.
The invention also provides a technical scheme of a method for preparing the solar heat storage complex-phase 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 ratio to obtain mixed powder;
(2) Granulating and ageing 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 blank 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.
Further, 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 after granulation, the mixture is aged for more than 24 hours to prepare a blank.
Further, in the step (3), the pressure of the press molding is 30 to 40MPa.
Further, in the step (4), the drying is carried out for 24-48 h at the temperature of 85-100 ℃.
Further, in the step (5), in the firing process, the heating rate is 3-5 ℃/min, the temperature is kept for 30-60 min every 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 raw materials of calcined bauxite and Suzhou soil with lower relative price, does not add any other raw material with high price, and has low cost because the production process is sintering in a pressureless oxidizing atmosphere; compared with silicon carbide heat storage ceramic, the production cost is reduced by nearly 80%. The invention is beneficial to greatly reducing the power generation cost of the solar thermal power generation technology.
2. The high-temperature heat storage complex phase ceramic material has better comprehensive performance. The main crystal phase of the material obtained by the invention 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 grown in a staggered way to form a dense net structure, so that higher density, heat storage density and strength are obtained, and meanwhile, the structure ensures that the material has better 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 heat storage complex phase ceramic material in example 1 of the present invention.
Fig. 2 is an SEM image of the solar high-temperature heat storage composite ceramic material in example 1 of the present invention.
Fig. 3 is an XRD pattern of the solar high-temperature heat-storage complex-phase ceramic material in example 1 after 30 thermal shock resistance cycles.
Fig. 4 is an SEM image of the solar high-temperature heat storage composite ceramic material in example 1 after 30 thermal shock resistance cycles.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention provides a method for preparing a solar high-temperature heat-storage complex-phase ceramic material from bauxite and Suzhou soil, which has the advantages of high service temperature, high density, high strength, thermal shock resistance and the like, good comprehensive properties and low cost, and the preparation method comprises the following steps:
(1) Raw material treatment: ball milling and mixing the calcined bauxite and the Suzhou soil powder for 30min to prepare powder which is uniformly mixed for 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou soil powder is (40-55): (45-60). And the ball-milling ratio is 1. 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 meshes of calcined bauxite particle size; the main components of the suzhou soil are as follows: 35 to 55 percent of silicon dioxide, 30 to 50 percent of alumina, 0.5 to 2 percent of ferric oxide and titanium oxide, no more than 8 percent of other impurities and 250 to 325 meshes of Suzhou soil grain size.
(2) Granulation and staling: and adding 2-4% by mass of water into the mixed powder by adopting a spray drying method for granulation, and ageing for more than 24 hours after granulation to obtain a blank.
As more Suzhou soil is adopted in the invention, water can be adopted as a binder, and a traditional polyvinyl alcohol solution is not required to be added, so that a mixture with strong plasticity can be obtained, and granulation is facilitated.
(3) Semi-dry pressing and forming: and pressing and molding the aged blank by using a hydraulic press at the pressure of 30-40 MPa to obtain the high-temperature heat storage complex-phase ceramic material green blank.
(4) And (3) drying: and (3) placing the molded green body in a drying oven, and drying for 24-48 h at 85-100 ℃ to obtain the green body.
(5) And (3) firing: and (3) putting the dried blank into a sagger, and then putting the sagger into a resistance furnace to be fired at a certain temperature (the temperature is raised to 1600-1640 ℃ at the temperature rise rate of 3-5 ℃/min and is kept for 1.5-2.5 h), so as to prepare the densified solar high-temperature heat storage material.
The bauxite and the Suzhou clay adopted by the invention are clay minerals with higher aluminum content, the cost is low, the high-temperature resistance is good, the heat storage complex phase ceramic material with mullite as a main crystal phase and corundum as a secondary crystal phase is generated by controlling the mass percentage of the bauxite and the Suzhou clay, and combining a specific sintering process without adding other raw materials and additives, long rod-shaped mullite and short column-shaped corundum are grown in a staggered mode to form a dense net-shaped structure, the compactness, the heat storage density and the strength of the obtained material are favorably improved, and the high-temperature resistance and the thermal shock resistance are good, so the cost can be effectively reduced, and the comprehensive performance of the material is good.
The solar high-temperature heat storage material obtained by the invention does not contain silicon carbide, is a pure oxide system after high-temperature sintering, has actual use temperature higher than sintering temperature, and is conservative estimation.
The present invention is further illustrated by the following specific examples.
Example 1
(1) Raw material treatment: ball-milling and mixing the calcined bauxite and the Suzhou soil powder for 30min to prepare powder which is uniformly mixed for 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou soil powder is 50:50. and the ball ratio during ball milling is 1. The calcined bauxite comprises the following main components: 72.72 percent of alumina, 20.81 percent of silicon dioxide, 5.15 percent of total content of ferric oxide (1.56 percent) and titanium oxide (3.59 percent), 1.32 percent of other impurities, and 250-325 meshes of calcined bauxite particle size; the Suzhou soil mainly comprises 45.14 percent of silicon dioxide, 37.88 percent of aluminum oxide, 0.30 percent of ferric oxide, 0.27 percent of titanium oxide, 16 percent of ignition loss, no more than 0.41 percent of other impurities and 250-325 meshes of particle size.
(2) Granulation and staling: adding 4% of water by mass into the mixed powder by adopting a spray drying method, and ageing for 24 hours after granulation to prepare a blank.
(3) Semi-dry pressing and forming: and pressing and molding the aged blank by using a hydraulic press under the pressure of 30MPa to obtain the high-temperature heat-storage complex-phase ceramic material green blank.
(4) And (3) drying: and (3) placing the formed green body in a drying oven, and drying for 24 hours at the temperature of 95 ℃ to obtain a green body.
(5) And (3) firing: and (2) putting the dried blank into a sagger, then placing the sagger into a resistance furnace, and firing at a certain temperature (the heating rate of 5 ℃/min is increased to 1000 ℃, the temperature is preserved for 30min every 100 ℃ midway, after the temperature is increased to 1620 ℃ at the heating rate of 3 ℃/min after the temperature is 1000 ℃, the temperature is preserved for 60min every 100 ℃ midway, and the temperature is preserved for 2h at the highest temperature), so as to prepare the solar high-temperature heat-storage composite ceramic material.
Tests prove that the heat storage complex phase ceramic material disclosed by the invention is high temperature resistant and can be used in a high-temperature environment of 1300-1500 ℃; according to Archimedes principle and static weighing method, a TXT type digital display ceramic water absorption rate tester manufactured by Hunan Tan instrument limited and an AuY120 electronic analytical balance manufactured by Shimadzu Japan were used to measure that the water absorption rate of the material was 0.12%, the apparent porosity was 0.35%, and the bulk density was 2.83 g.cm -3 The compactness is higher; the flexural strength of the material is up to 155.44MPa (the test conditions are that the span is 28mm and the load loading rate is 0.5 mm/min) measured by adopting an RGM-4100 microcomputer control electronic universal tester manufactured by Shenzhen Ruiguer company; the heat storage capacity is strong, the specific heat capacity of the material is up to 1.423 kJ/kg.K (25-800 ℃) measured by a C80 micro calorimeter produced by Setariam France, and the heat storage density is up to 1102.3 J.g -1 (25-800 ℃); the thermal shock resistance is good, and an SX-2-5-12 type box type energy-saving resistance furnace manufactured by Jian Li electric furnace manufacturing Limited in Hubei Yingshan is adopted to carry out a thermal shock resistance experiment on a sample (the thermal shock experiment flow is that the fired sample is put into a thermal shock furnaceThe temperature is raised to 1000 ℃ at the speed of 5 ℃/min, the temperature is kept for 15min, then the material is taken out and cooled to the room temperature, which is the thermal shock process for 1 time, after 30 times of thermal shock cycle tests (1000 ℃ -room temperature, air cooling), the high-temperature heat storage material of the invention has no cracks, the apparent porosity and the volume density of the material are kept unchanged compared with those before the thermal shock, the breaking strength of the material is increased to 166.15MPa, and the material meets and exceeds the relevant requirements in the test method for thermal shock resistance of refractory materials (GB/T30873-2014).
As shown in fig. 1, XRD analysis shows that the high-temperature heat storage ceramic material prepared in example 1 is a mullite-corundum composite material, in which the primary crystal phase is mullite, the secondary crystal phase is corundum, the content of mullite is 90.5%, and the content of corundum 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 example 1 has a compact structure, the material contains a small amount of closed pores, the average pore size is about 12 μm, mullite and corundum in the material are interlaced and grow to form a network structure, and a small amount of glass phase is filled around the grains, so that the material has high flexural strength.
As shown in FIG. 3, after XRD analysis, the high-temperature heat-storage complex-phase ceramic material prepared in example 1 has a mullite content of 92.4% and a corundum content of 7.6% after 30 thermal shock cycle experiments (1000-room temperature), and is tested in the same manner as above, and has a water absorption of 0.11%, an apparent porosity of 0.31%, and a bulk density of 2.83 g-cm -3 Meanwhile, the flexural strength is further improved to 166.15MPa and is improved by 6.89%, and the performance requirements of a new generation of solar thermal power generation technology on a high-temperature heat storage material can be met.
As can be seen from fig. 4, the high-temperature heat storage complex phase ceramic material prepared in example 1 undergoes growth of mullite grains and grain boundary migration during the thermal shock process, the fracture mode of the material gradually changes from along-crystal fracture to transgranular fracture, and the liquid phase gradually fills pores, so that after 30 thermal shock cycle experiments (1000 ℃ -room temperature), the prepared high-temperature heat storage ceramic material has increased breaking strength and basically unchanged bulk density, thereby showing that the prepared high-temperature heat storage ceramic material has good thermal shock resistance.
Example 2 (examination of the influence of the raw Material proportions)
Adjusting the mass percentage of the calcined bauxite in the step (1) and the Suzhou soil powder to 40:60, adding 3 percent by mass of water into the step (2), and performing other steps and conditions as in the example 1.
Tests prove that the solar high-temperature heat storage complex-phase ceramic material disclosed by the invention is high-temperature resistant, can be used in a high-temperature environment of 1300-1500 ℃, and has the apparent porosity of 0.27% and the volume density of 2.80 g-cm -3 The rupture strength is 139.49MPa, after 30 times of thermal shock cycle tests (1000-room temperature, air cooling), the solar high-temperature heat storage complex phase ceramic material has no cracks, the apparent porosity and the volume density of the material are unchanged compared with those before thermal shock, the rupture strength is slightly reduced to reach 131.84MPa, and the material can meet the relevant requirements of high-temperature heat storage materials.
Comparative example 1 (examination of the influence of the raw Material proportions)
Adjusting the mass percentage of the calcined bauxite and the Suzhou soil powder in the step (1) to be 30:70, adding 2 percent by mass of water into the step (2), and performing other steps and conditions as in the example 1.
Tests prove that the heat storage ceramic material of the comparative example 1 is high temperature resistant, can be used in a high temperature environment of 1-1 ℃, and has 0.25 percent of apparent porosity and 2.75 g-cm of volume density -3 And the breaking strength is 108.61MPa, after 30 times of thermal shock cycle tests (1000-room temperature, air cooling), the high-temperature heat storage material of the comparative example 1 has no cracks, the apparent porosity and the volume density are kept unchanged compared with those before thermal shock, and the breaking strength is reduced to 98.69MPa.
Comparative example 2 (examination of the influence of the raw Material proportions)
Adjusting the mass percentage of the calcined bauxite in the step (1) and the Suzhou soil powder to be 60: and 40, adding 4 percent by mass of water into the step (2), and performing other steps and conditions as in the example 1.
Tests prove that the heat storage ceramic material of the comparative example 1 is high temperature resistant, can be used in a high temperature environment of 1300-1500 ℃, is not sintered at 1620 ℃, has the apparent porosity of 10.35 percent and the volume density of 2.69g cm -3 The breaking strength was 129.27MPa.
Comparative example 3 (examination of the influence of the raw Material proportions)
Adjusting the mass percentage of the calcined bauxite in the step (1) and the Suzhou soil powder to 70:30, adding 4.5 percent of water by mass into the step (2), and the other steps and conditions are the same as those of the example 1.
Tests prove that the heat storage ceramic material in the comparative example 3 is high temperature resistant, can be used in a high temperature environment of 1300-1500 ℃, is not sintered at 1620 ℃, has the apparent porosity of 14.31 percent and the volume density of 2.63g cm -3 The flexural strength was 122.23MPa.
The heat storage ceramic materials obtained in examples 1 to 2 and comparative examples 1 to 3 were subjected to the test, and the results are shown in table 1 below.
TABLE 1 raw material ratios and test results of examples 1-2 and comparative examples 1-3
Comparing example 1, example 2 and comparative example 1 (wherein the water addition amount in the granulation process is slightly different, the plasticity of the granulation is ensured due to the adaptability adjustment carried out by the difference of the raw material proportion, and free water is discharged in the drying process, so that the performance of the subsequent obtained material is not influenced, and therefore a single-factor variable test can be formed), the ratio of calcined bauxite to Suzhou soil in the material is sequentially reduced, and the apparent porosity, the volume density and the breaking strength of the heat storage material are all reduced. This is because w (Al) in the material decreases with the bauxite to Suzhou earth ratio 2 O 3 )/w(SiO 2 ) The value is reduced, so that the volume density of the sintered material is reduced, and meanwhile, 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.
Comparing example 1, comparative example 2 and comparative example 3, the ratio of calcined bauxite to suzhou clay in the material was sequentially increased, and the Al/Si ratio in the material was increased, which also resulted in a decrease in the liquid phase content at high temperatures during firing, resulting in a higher firing temperature of the material. Because the sintering temperature can not be increased due to the limitation of laboratory equipment, the materials of the comparative example 2 and the comparative example 3 can not reach the 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 can not be met.
Therefore, the preferred mass percentages of the calcined bauxite and the Suzhou soil in the invention are (40-55): (45-60).
Comparative example 4 (investigation of the effects of different firing temperatures)
(1) Raw material treatment: ball-milling and mixing the calcined bauxite and the Suzhou soil powder for 30min to prepare powder which is uniformly mixed for 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou soil powder is 50:50. and the ball ratio during ball milling is 1.
(2) Granulation and staling: adding 3% water by mass into the mixed powder by adopting a spray drying method, and ageing for 24 hours after granulation to prepare a blank.
(3) Semi-dry pressing and forming: and pressing and molding the aged blank by using a hydraulic press, wherein the pressure is 30MPa, and thus obtaining the high-temperature heat-storage complex-phase 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) And (3) firing: and putting the dried blank into a sagger, then placing the sagger into a resistance furnace, and firing at a certain temperature (the heating rate of 5 ℃/min is increased to 1000 ℃, the temperature is preserved for 30min every 100 ℃ midway, after the temperature is increased to 1580 ℃ at the heating rate of 3 ℃/min after the temperature is 1000 ℃, the temperature is preserved for 60min every 100 ℃ midway, and the temperature is preserved for 2h at the highest temperature), thus preparing the solar high-temperature heat storage material.
Tests prove that the heat storage material obtained in the comparative example 3 is high temperature resistant, can be used in a high-temperature environment of 1300-1500 ℃, and has the apparent porosity of 7.78 percent and the volume density of 2.68 g-cm -3 The breaking strength is 90.70MPa. Comparative example 4 the firing temperature of the material was lowered compared to example 1As a result, it was found that the apparent porosity was increased and the bulk density and the flexural strength were both decreased, and at this time, since 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 completely develop, the flexural strength was greatly decreased.
From these results, it is understood that the firing temperature in the present invention is preferably 1600 to 1640 ℃ and more preferably 1600 to 1620 ℃.
Comparative example 5 (examination of the influence of the type of raw Material)
Suzhou clay was replaced with the named Kaolin under the same conditions as in example 1.
(1) Treating raw materials: ball-milling and mixing the calcined bauxite and the Mount Kaolin powder for 30min to prepare powder which is uniformly mixed for 250-325 meshes, wherein the mass percentage of the calcined bauxite to the Suzhou Kaolin powder is 50:50. and the ball ratio during ball milling is 1. The calcined bauxite comprises the following main components: 72.72 percent of alumina, 20.81 percent of silicon dioxide, 5.15 percent of ferric oxide and titanium oxide, 1.32 percent of other impurities and 250-325 meshes of calcined bauxite; the main components of the kaolin are 50.68% of silicon dioxide, 34.93% of alumina, 1.02% of ferric oxide and titanium oxide, 12.34% of ignition loss and no more than 1.03% of other impurities, and the particle size of the kaolin is 250-325 meshes.
(2) Granulating and staling: adding 4% of water by mass into the mixed powder by adopting a spray drying method, and ageing for 24 hours after granulation to prepare a blank.
(3) Semi-dry pressing and forming: and pressing and molding the aged blank by using a hydraulic press under the pressure of 30MPa to obtain the high-temperature heat-storage complex-phase ceramic material green blank.
(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) And (3) firing: and (2) putting the dried green body into a sagger, then putting the sagger into a resistance furnace, and firing at a certain temperature (the heating rate of 5 ℃/min is increased to 1000 ℃, the temperature is preserved for 30min every 100 ℃ midway, after the temperature is increased to 1600 ℃ at the heating rate of 3 ℃/min, the temperature is preserved for 60 ℃ every 100 ℃ midway after the temperature is 1000 ℃, and the temperature is preserved for 2h at the highest temperature), so that the solar high-temperature heat storage material is prepared.
Tests prove that 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 the apparent porosity of 0.47 percent and the volume density of 2.76g cm -3 The breaking 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 cracks, the apparent porosity and the volume density of the material are kept unchanged compared with those before thermal shock, and the breaking strength of the material is slightly reduced to 118.46MPa.
In comparative example 5, the Suzhou clay in example 1 was replaced with the Carolina kaolin, and as a result, it was found that the bulk density and the flexural strength of the heat storage material were reduced. This is because of the SiO of the Brand Kaolin compared to Suzhou soil 2 Relatively high content of Al 2 O 3 Relatively less, therefore, w (Al) in the material 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 is reduced, the apparent porosity is reduced, and the heat storage density is not favorably improved.
In conclusion, the heat storage ceramic material provided by the invention is high temperature resistant, can be used in a high temperature environment of 1300-1500 ℃, and has the apparent porosity of 0.27-0.35% and the volume density of 2.8-2.83 g-cm -3 The compactness is higher, the breaking 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 can reach 1102.3 J.g -1 (25-800 ℃); the high-temperature heat storage material has good thermal shock resistance, after 30 thermal shock cycle tests (1000-room temperature and gas cooling), the high-temperature heat storage material has no cracks, the apparent porosity and the volume density of the high-temperature heat storage material are unchanged compared with those before thermal shock, the breaking strength of the high-temperature heat storage material can be increased to 166.15MPa, and the high-temperature heat storage material meets and exceeds the relevant requirements in the thermal shock resistance test method of refractory materials (GB/T30873-2014).
Compared with the prior art, the invention has the advantages that:
1. the high-temperature heat storage complex phase ceramic material has lower production cost. The invention only adopts two raw materials of calcined bauxite and Suzhou soil with lower relative price, does not add any other raw material with high price, has the raw material cost of only 1 to 1 yuan per ton, and has the production process of sintering in non-pressure oxidation atmosphere, thereby having lower cost. Compared with silicon carbide heat storage ceramic, 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 complex phase ceramic material has better 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 grow in a staggered mode to form a dense net-shaped structure, so that high density, high heat storage density and high strength are obtained, and meanwhile, the high-temperature resistance and thermal shock resistance of the material are good due to the structure. 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 should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The solar heat storage composite ceramic material is characterized in that the raw materials comprise, by mass, 40-55% of calcined bauxite and 45-60% of Suzhou soil.
2. The solar heat storage composite ceramic material prepared from bauxite and Suzhou soil according to claim 1, wherein the calcined bauxite comprises the following main components in percentage by mass: 55-75% of alumina, 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 from bauxite and Suzhou soil as claimed in claim 1, wherein the Suzhou soil comprises the following main components in percentage by mass: 35 to 55 percent of silicon dioxide, 30 to 50 percent of aluminum oxide, 0.5 to 2 percent of ferric oxide and titanium oxide, and the content of other impurities is not more than 8 percent.
4. The solar heat-storage composite ceramic material prepared from bauxite and suzhou soil according to claim 1, wherein the grain sizes of the calcined bauxite and the suzhou soil are 250-325 meshes.
5. The method for preparing the solar heat storage complex phase ceramic material by using bauxite and Suzhou soil as claimed in any one of claims 1 to 4, which comprises the following steps:
(1) Uniformly mixing the calcined bauxite and Suzhou soil according to the proportion to obtain mixed powder;
(2) Granulating and ageing 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 blank at 1600-1640 ℃ to obtain the solar heat storage complex phase ceramic material.
6. The method for preparing the solar heat storage composite ceramic material by using the bauxite and the Suzhou soil as claimed in claim 5, wherein in the step (1), the calcined bauxite and the Suzhou soil are uniformly mixed by a ball milling method.
7. The method for preparing the solar heat-storage composite ceramic material by using the bauxite and the Suzhou soil as claimed in claim 5, wherein in the step (2), the water with the mass fraction of 2-4% is added into the mixed powder by a spray drying method for granulation, and after the granulation, the blank is aged for more than 24 hours to prepare the blank.
8. The method for preparing the solar heat storage composite ceramic material by using the bauxite and the Suzhou soil as claimed in claim 5, wherein in the step (3), the pressure for the compression molding is 30-40 MPa.
9. The method for preparing the solar heat storage composite ceramic material by using the bauxite and the Suzhou soil as claimed in claim 5, wherein in the step (4), the drying is carried out for 24-48 hours at the temperature of 85-100 ℃.
10. The method for preparing the solar heat-storage composite ceramic material by using the bauxite and the Suzhou soil as claimed in claim 5, wherein in the step (5), in the firing process, the temperature rise rate is 3-5 ℃/min, the temperature is kept for 30-60 min 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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