CN114890810B - Mullite lightweight aggregate with rice hull genetic structure and preparation method thereof - Google Patents

Mullite lightweight aggregate with rice hull genetic structure and preparation method thereof Download PDF

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CN114890810B
CN114890810B CN202210405775.1A CN202210405775A CN114890810B CN 114890810 B CN114890810 B CN 114890810B CN 202210405775 A CN202210405775 A CN 202210405775A CN 114890810 B CN114890810 B CN 114890810B
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lightweight aggregate
mullite lightweight
rice hulls
mullite
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CN114890810A (en
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王珊
王艳
雷皓翔
刘静静
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Jiaozuo Nuoerman Stove Industry Co ltd
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Jiaozuo Nuoerman Stove Industry Co ltd
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Abstract

The invention provides a mullite lightweight aggregate with a rice hull genetic structure and a preparation method thereof, wherein the mullite lightweight aggregate comprises 50-90 parts of coal gangue, 5-20 parts of bauxite, 5-30 parts of clay, 5-30 parts of pore-forming agent, 8-20 parts of water and 0.05-5.0 parts of binding agent; the pore-forming agent comprises modified rice hulls; the preparation method comprises the steps of obtaining modified rice hulls by an impregnation method, and then obtaining mullite lightweight aggregate with a rice hull genetic structure by mixing and sintering, wherein the raw materials are cheap and easy to obtain, the method and the process are simple, the obtained product has good performance, low heat conductivity coefficient, high strength and small change of reburning time line, and the modified rice hulls can be directly used as the raw materials of mullite lightweight castable, so that the preparation method is beneficial to industrial production and application.

Description

Mullite lightweight aggregate with rice hull genetic structure and preparation method thereof
Technical Field
The invention belongs to the technical field of light refractory materials, and particularly relates to mullite lightweight aggregate with rice hull genetic structure and a preparation method thereof.
Background
Along with the improvement of national requirements for energy conservation and energy consumption reduction, the lightweight aggregate is increasingly widely applied to various industrial kilns, and mullite lightweight aggregate is also widely focused due to the excellent thermal shock resistance. However, the raw materials used for preparing the mullite lightweight aggregate are high in price and complex in production process so far, and the application of the mullite lightweight aggregate is limited. In recent years, in order to reduce the cost, the refractory industry field begins to adopt solid wastes such as coal gangue, fly ash, electroceramic waste materials and the like to prepare mullite light materials, and the effect of controlling the production cost is achieved. However, the materials have the defects of low strength, high heat conductivity, low micropore ratio and the like in the practical application process. Therefore, there is an urgent need to develop a mullite lightweight aggregate having low cost, low heat conductivity and high strength.
The plant genetic material refers to a material which can retain a biological fine structure in nature and endow the biological fine structure with new characteristics and functions by means of an intrinsic structure of a plant and through an artificial synthesis method. The material takes natural plants as templates, has strong designability of pore structures, and therefore has wide application in the aspects of kiln energy conservation, aerospace equipment and part thermal management, burner thermal efficiency improvement and the like. At present, the special structure and the pore structure of the plant genetic material can be used for designing characteristics, and meanwhile, the improvement and the optimization of the thermal and mechanical characteristics of the heat-insulating material are realized, and the plant genetic material is still in a vacant state.
CN101838148A discloses a porous alumina with a genetic structure and using scindapsus aureus leaves as a template and a preparation method thereof, and the technology uses scindapsus aureus leaves as a template, uses sodium hydroxide and hydrochloric acid as digestion agents, and uses aluminum hydroxide as a precursor solution to prepare the porous alumina ceramic with the genetic structure. Patent' eucalyptus morpha-genetic Fe 2 O 3 -Fe 3 O 4 The patent technology of the preparation method of the composite heavy metal adsorbent (CN 102258976A) discloses that eucalyptus is taken as a biological template, ammonia water is taken as a digestion agent, and ferric nitrate is taken as a precursor solution, so that the Fe in the tree genetic state is obtained 2 O 3 -Fe 3 O 4 And (3) compounding a heavy metal adsorbent. The main drawbacks of this approach are manifested in: (1) Carbonized natural plants as templates or singly utilizing their natural structures, underutilizing other chemical components such as SiO in the natural plants 2 Indirectly causes waste; (2) The production process is complex, and can be completed by a plurality of procedures; (3) The pores of the product are all the pores of the replicated plant structure, and have no variability.
CN101817688A discloses a high-purity high-strength light mullite refractory aggregate, which is prepared from 20-30% of natural silica and 70-80% of industrial alumina as raw materials, 25% of carbonaceous loss-on-ignition material, and through wet co-grinding, extrusion forming, calcining and crushing to obtain the mullite refractory aggregate with the volume density of 1.1-1.3 g/cm 3 Mullite lightweight aggregate. The defects of the method are mainly expressed in that: (1) the cost of the raw materials of the product is high; (2) the production process is complex and the energy consumption is high; (3) Breaking and destroying aggregateAnd the grain size of the product is not easy to control.
CN101265118A discloses a microporous mullite lightweight aggregate and a preparation method thereof, and the product takes 35 to 40 percent of bauxite raw material, 14 to 20 percent of coal gangue, 4 to 13 percent of saw dust and 27 to 45 percent of petroleum coke as raw materials, and the raw materials are subjected to wet grinding, blending, extrusion molding, calcination and crushing to obtain the product with the volume density of 1.0 to 1.2g/cm 3 Is a mullite aggregate. The method also has certain limitations, and is specifically expressed as follows: the utilization amount of the coal gangue is small; (2) The structure of the aggregate is broken by crushing, and the granularity of the product is not easy to control; (3) The sieve bottom material with 400-450 meshes is used for forming, no aggregate component with supporting function exists, and large line change exists in high-temperature calcination; and a small amount of carbon in the gangue particles can not be utilized to burn out pores in the calcining process, so that the heat conductivity coefficient of the product is higher.
In conclusion, the mullite lightweight aggregate with low cost, simple process and excellent performance and the preparation method thereof have important significance.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide the mullite lightweight aggregate with the rice hull genetic structure and the preparation method thereof, wherein the mullite lightweight aggregate utilizes a large amount of piled solid waste coal gangue and agricultural waste rice hulls, thereby changing waste into valuables, the modified rice hulls can reduce the pore size of the material, the obtained mullite lightweight aggregate has high performance, and the production cost is greatly reduced; the preparation method is simple in process and suitable for industrial production.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a mullite lightweight aggregate with a rice hull genetic structure, wherein the mullite lightweight aggregate comprises 50-90 parts of coal gangue, such as 50 parts, 60 parts, 70 parts, 80 parts or 90 parts; 5 to 20 parts of alumina, for example, 5 parts, 10 parts, 15 parts, 20 parts, or the like; 5 to 30 parts of clay, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, or the like; 5 to 30 parts of pore-forming agent, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, etc.; 8 to 20 parts of water, for example 8 parts, 10 parts, 15 parts or 20 parts, etc.; 0.05 to 5.0 parts of a binding agent, for example, 0.05 parts, 0.1 parts, 0.5 parts, 1.0 parts, 2.0 parts, 3.0 parts, 4.0 parts, 5.0 parts, etc., and the above-mentioned values are not limited to the enumerated values, and other non-enumerated values are equally applicable within the respective numerical ranges;
the pore-forming agent comprises modified rice hulls.
In the invention, the main raw materials are a great amount of solid waste coal gangue and agricultural waste rice hulls which are piled up at present, thereby changing waste into valuable and saving a great amount of coal gangue and rice hull treatment cost; in addition, the silicon skeleton left in the rice hull in the high-temperature sintering process can react with redundant components in the modified substance, and woven mullite whiskers are generated in air holes formed by the rice hull in a burning-loss manner, so that the air hole size is further reduced, and the porosity and the normal-temperature compressive strength of the material are improved.
In the invention, the modified rice hulls play an important role, so that the addition amount of the modified rice hulls needs to be controlled. If the addition amount of the modified rice hulls is too large, the aggregate porosity is higher, the pore diameter of the pores is larger, and the SiO after the rice hulls are burned out is formed 2 More aggregate, more low-melting matters in the aggregate and lower use temperature; if the addition amount of the modified rice hulls is too small, the porosity of the aggregate is low, the number of micropores formed by braiding the mullite whiskers is also reduced, and the heat conductivity coefficient of the material is increased.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, fe in the gangue 2 O 3 Content of 3.0wt%, for example, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt% or 3.0wt%, etc.; tiO (titanium dioxide) 2 The content is 5.0wt%, for example, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, or 5.0wt%, etc., and the above values are not limited to the values recited, but other values not recited in the respective ranges are equally applicable.
Preferably, the gangue particle size is less than or equal to 0.074mm, such as 0.060mm, 0.062mm, 0.064mm, 0.066mm, 0.068mm, 0.070mm, 0.072mm or 0.074mm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable embodiment of the present invention, al in the alumina 2 O 3 The content is not less than 45wt%, for example, 45wt%, 50wt%, 55wt%, 60wt%, 65wt% or 70wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the alumina has a particle size of 0.088mm or less, for example, 0.070mm, 0.072mm, 0.074mm, 0.076mm, 0.078mm, 0.080mm, 0.082mm, 0.086mm or 0.088mm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, al in the clay 2 O 3 The content is not less than 25wt%, for example, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the clay has a particle size of 0.045mm or less, for example, 0.030mm, 0.032mm, 0.034mm, 0.036mm, 0.038mm, 0.040mm, 0.042mm, or 0.045mm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred technical scheme of the invention, the modified rice hulls comprise aluminum sol modified rice hulls.
In the invention, the silicon framework remained in the rice hull in the high-temperature sintering process and redundant Al in the aluminum sol and the material 2 O 3 The components react to generate the woven mullite whisker in the air holes formed by burning off the rice hulls, so that the size of the air holes is further reduced.
Preferably, al in the aluminum sol modified rice hulls 2 O 3 The content is 5wt%, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the modified rice hulls have a particle size of less than or equal to 0.045mm, such as 0.030mm, 0.032mm, 0.034mm, 0.036mm, 0.038mm, 0.040mm, 0.042mm, or 0.045mm, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the binding agent comprises any one or a combination of at least two of water glass, aluminum dihydrogen phosphate, sodium lignin sulfonate, carboxymethyl cellulose or dextrin, and typical but non-limiting examples of such combinations are: a combination of water glass and aluminum dihydrogen phosphate, a combination of carboxymethyl cellulose and dextrin, a combination of water glass, aluminum dihydrogen phosphate and sodium lignin sulfonate, and the like.
In a second aspect, the present invention provides a method for preparing the mullite lightweight aggregate according to the first aspect, the method comprising the steps of:
mixing 50-90 parts of gangue, 5-20 parts of bauxite, 5-30 parts of clay, 5-30 parts of pore-forming agent, 8-20 parts of water and 0.05-5.0 parts of bonding agent, granulating and forming, and then sequentially carrying out first baking and sintering to obtain the mullite lightweight aggregate with the rice hull genetic structure;
the pore-forming agent comprises modified rice hulls.
The preparation method has the characteristics of low production cost, simple process, resource conservation and environmental protection, and the mullite lightweight aggregate with the rice hull genetic structure has low heat conductivity coefficient, high strength and small change of the re-firing time line, and can be directly used as the raw material of the mullite lightweight castable.
As a preferred technical scheme of the invention, the modified rice hulls comprise aluminum sol modified rice hulls.
Preferably, the preparation method of the aluminum sol modified rice hulls comprises the following steps: vacuum soaking rice hulls by using aluminum sol, and then performing second baking to obtain aluminum sol modified rice hulls.
Preferably, the solids content of the aluminum sol is 0.5 to 15.0wt%, for example, 0.5wt%, 1.0wt%, 5.0wt%, 10.0wt%, 15.0wt%, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the solid content of the aluminum sol is very important in the process of preparing the modified rice hulls. If the solid content is too high, the modified rice hulls become hard and difficult to disperse; the solid content is too low, so that the secondary mullite whisker cannot be woven after the rice husk is burned out, and the micropore proportion is reduced, so that the heat conductivity coefficient of the aggregate is increased.
Preferably, the pH of the aluminum sol is 2.4 to 3.8, for example, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, or 3.8, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the rice hull is added in an amount of 10 to 70wt%, for example 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, etc.; the amount of the alumina sol added is 30 to 90wt%, for example, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, or 90wt%, and the selection of the above values is not limited to the values listed, but other values not listed in the respective value ranges are equally applicable.
Preferably, the vacuum degree of the vacuum impregnation is 10 3 ～10 5 Pa, e.g. 10 3 Pa、2×10 3 Pa、4×10 3 Pa、6×10 3 Pa、8×10 3 Pa、10 4 Pa、5×10 3 Pa、8×10 4 Pa or 10 5 Pa, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time of the vacuum impregnation is 3 to 24 hours, for example, 3 hours, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours, or 24 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
According to the invention, the vacuum impregnation can enable the binding property of the aluminum sol and the rice hulls to be more firm, and the loading capacity of the active aluminum sol on the rice hulls is improved.
Preferably, the temperature of the second baking is 60 to 120 ℃, for example 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the second baking time is 24 to 48 hours, for example, 24 hours, 27 hours, 30 hours, 33 hours, 36 hours, 39 hours, 42 hours, 45 hours, 48 hours, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second baking is followed by crushing.
Preferably, the particle size of the alumina sol modified rice hulls after the crushing is less than or equal to 0.045mm, for example, 0.030mm, 0.032mm, 0.034mm, 0.036mm, 0.038mm, 0.040mm, 0.042mm or 0.045mm, etc., but is not limited to the recited values, and other non-recited values within the recited range are equally applicable.
As a preferable embodiment of the present invention, the drying is performed between the granulation molding and the first baking.
In the present invention, the drying means natural drying.
Preferably, the temperature of the first baking is 100 to 120 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the first baking time is 20-30 hours, such as 20 hours, 22 hours, 24 hours, 26 hours, 28 hours or 30 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, the sintering temperature is 1000 to 1450 ℃, for example, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1450 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are similarly applicable.
Preferably, the sintering time is 2 to 6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) The mullite lightweight aggregate with the rice hull genetic structure provided by the invention uses solid waste coal gangue and agricultural waste rice hulls as main raw materials, so that the production cost is greatly reduced; secondly, the modified rice husk is burnedThe mullite whisker formed by reaction in the process can reduce the size of air holes and improve the quality of the obtained mullite lightweight aggregate; the mullite lightweight aggregate Al 2 O 3 The content is 30-62 wt%, the pore diameter is mainly distributed below 100 μm, the pore diameter is intensively distributed around 80 μm, and the volume density is 0.5-1.3/cm 3 The apparent porosity is 60-90%, and the normal temperature compressive strength is 5-18 MPa;
(2) The preparation method has the characteristics of low production cost, simple process, resource conservation and environmental protection, and the mullite lightweight aggregate with the rice hull genetic structure has low heat conductivity coefficient, high strength and small change of the re-firing time line, and can be directly used as the raw material of the mullite lightweight castable.
Drawings
Fig. 1 is an SEM image of mullite lightweight aggregate with a rice hull genetic structure provided in example 1 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
In a specific embodiment, the invention provides a mullite lightweight aggregate with a rice hull genetic structure and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) 10 to 70 weight percent of rice husk is taken as a template, 30 to 90 weight percent of aluminum sol is taken as an impregnant, and the vacuum degree is 10 3 ～10 5 Soaking for 3-24 h under Pa, stirring, baking rice husk soaked with aluminum sol at 60-120deg.C for 24-48 h, and crushing to obtain Al 2 O 3 Aluminum sol modified rice hulls with the content of more than or equal to 5 weight percent and the grain diameter of less than or equal to 0.045 mm;
wherein the pH value of the aluminum sol is 2.4-3.8, and the solid content is 0.5-15.0 wt%;
(2) Uniformly mixing 50-90 parts of gangue, 5-20 parts of bauxite, 5-30 parts of clay, 5-30 parts of alumina sol modified rice husk, 8-20 parts of water and 0.05-5.0 parts of binding agent, granulating, forming, naturally drying, baking for 20-30 hours at 100-120 ℃, heating to 1000-1450 ℃, and sintering for 2-6 hours to obtain the mullite lightweight aggregate with the rice husk genetic structure;
wherein, fe in the gangue 2 O 3 The content is less than or equal to 3.0 weight percent, tiO 2 The content is less than or equal to 5.0 weight percent, and the particle size of the coal gangue is less than or equal to 0.074mm;
al in the alumina 2 O 3 The content is more than or equal to 45 weight percent, and the grain diameter of the alumina is less than or equal to 0.088mm;
al in the clay 2 O 3 The content is more than or equal to 25 weight percent, and the particle size of the clay is less than or equal to 0.045mm.
The binding agent comprises any one or a combination of at least two of sodium silicate, aluminum dihydrogen phosphate, sodium lignin sulfonate, carboxymethyl cellulose or dextrin.
The test method related by the invention comprises the following steps:
(1) Al in the obtained product 2 O 3 The content is determined according to GB/T6900-2006.
(2) The pore size of the product is determined according to YB/T118-1997.
(2) Product volume density: measured according to GB/T2999-2002.
(3) The apparent porosity of the product: measured according to YB/T5200-1993.
(4) Product normal temperature compressive strength: measured according to GB/T2824-81.
The following are exemplary but non-limiting examples of the invention:
based on the preparation method in the specific embodiment, the specific condition parameters and performance test results of examples 1-4 provided by the invention are shown in table 1.
Wherein, fe in the selected gangue 2 O 3 The content of TiO is 2.5wt% 2 The content is 4.0 weight percent, and the particle size of the coal gangue is 74 mu m;
al in alumina 2 O 3 48wt% of alumina and 88 mu m of alumina particle size;
al in clay 2 O 3 The content was 31wt%, and the clay particle size was 45. Mu.m.
TABLE 1
Figure GDA0003739901050000101
In addition to the above embodiments, the present invention also provides the following embodiments:
example 5:
the embodiment provides a mullite lightweight aggregate with a rice hull genetic structure and a preparation method thereof, wherein the preparation method is characterized in that: the solid content of the aluminum sol in the step (1) is 20.0 weight percent, so that the aluminum sol obtained is used for modifying Al in rice hulls 2 O 3 The content was 12wt%.
Due to the increase of the solid content of the aluminum sol, the aluminum sol cannot be impregnated on the surfaces and in the pores of the rice hulls, so that the amount of the active aluminum sol loaded on the surfaces of the rice hulls is reduced, the number of mullite woven whiskers formed in the pores is reduced, and finally Al in the obtained product is caused 2 O 3 The content is 60wt%, the pore diameter is 110 mu m, and the volume density is 0.85g/cm 3 The apparent porosity was 55%, and the normal temperature compressive strength was 16MPa.
The invention also provides the following comparative examples:
comparative example 1:
this comparative example provides a mullite lightweight aggregate and a method for preparing the same, which is different from the preparation method in example 1 only in that: and (3) replacing the pore-forming agent added in the step (2) with sawdust, so that the aluminum sol modified rice hulls do not need to be prepared in the step (1).
As the conventional pore-forming agent is selected, the mullite whisker which is woven secondarily cannot be formed in the aggregate, and micropores formed by weaving the whisker cannot be obtained, so that the pore diameter of the obtained mullite lightweight aggregate is 120 mu m, and the volume density is 1.2g/cm 3 The apparent porosity was 55%, and the normal temperature compressive strength was 14MPa.
Comparative example 2:
this comparative example provides a mullite lightweight aggregate and a method for preparing the same, which is different from the preparation method in example 1 only in that: the aluminum sol modified rice hulls are not added in the step (2), so that the aluminum sol modified rice hulls are not required to be prepared in the step (1).
Because the pore-forming agent is not added, the formed aggregate is compact aggregate, the porosity in the material is lower, the pore diameter of the obtained mullite lightweight aggregate is 20 mu m, and the volume density is 1.8g/cm 3 The apparent porosity was 30%, and the normal-temperature compressive strength was 45MPa.
Comparative example 3:
this comparative example provides a mullite lightweight aggregate and a method for preparing the same, which is different from the preparation method in example 1 only in that: the pore-forming agent added in the step (2) is unmodified rice husk, so that the aluminum sol modified rice husk is not required to be prepared in the step (1).
Because the rice hulls are not modified, the inside of the pores of the aggregate cannot form mullite whiskers woven secondarily, so that the pore diameter of the obtained mullite lightweight aggregate is 110 mu m, and the volume density is 1.2g/cm 3 The apparent porosity was 58%, and the normal-temperature compressive strength was 16MPa.
Comparative example 4:
this comparative example provides a mullite lightweight aggregate of rice hull genetic structure and a preparation method thereof, which is different from the preparation method in example 1 only in that: in the step (2), the addition amount of the aluminum sol modified rice hulls is 2 parts.
Because the addition amount of the aluminum sol modified rice hulls is too small, the porosity of the material is low, the volume density is larger, the pore diameter of the obtained mullite lightweight aggregate is 110 mu m, and the volume density is 1.5g/cm 3 The apparent porosity was 48%, and the normal temperature compressive strength was 35MPa.
Comparative example 5:
this comparative example provides a mullite lightweight aggregate of rice hull genetic structure and a preparation method thereof, which is different from the preparation method in example 4 only in that: in the step (2), the addition amount of the aluminum sol modified rice hulls is 35 parts.
Because the addition amount of the aluminum sol modified rice hulls is too much, the volume density of the aggregate is lower, the porosity is too high, the pore diameter of the obtained mullite lightweight aggregate is 50 mu m, the volume density is 0.4g/cm, the apparent porosity is 93%, and the normal-temperature compressive strength is 3MPa.
In addition, SEM characterization is carried out on the mullite lightweight aggregate with the rice hull genetic structure obtained in the example 1, and an SEM diagram is shown in figure 1. As can be seen from FIG. 1, the prepared aggregate has a particle size of 1-2 mm, micropores with a pore diameter of 80-100 μm are uniformly distributed on the surface of the aggregate, and the braided staggered mullite whiskers are formed in the micropores.
According to the embodiment and the comparative example, the mullite lightweight aggregate with the rice hull genetic structure provided by the invention uses solid waste coal gangue and agricultural waste rice hulls as main raw materials, so that the production cost is greatly reduced; secondly, the mullite whisker formed by the reaction of the modified rice hull in the firing process can reduce the pore size and improve the quality of the obtained mullite lightweight aggregate; the mullite lightweight aggregate Al 2 O 3 The content is 30-62 wt%, the pore diameter is mainly distributed below 100 μm, the pore diameter is intensively distributed around 80 μm, and the volume density is 0.5-1.3/cm 3 The apparent porosity is 60-90%, and the normal temperature compressive strength is 5-18 MPa; the preparation method has the characteristics of low production cost, simple process, resource conservation and environmental protection, and the prepared mullite lightweight aggregate with the rice hull genetic structure has low heat conductivity coefficient, high strength and small change of the re-firing time line, and can be directly used as the raw material of the mullite lightweight castable.
The applicant states that the invention is illustrated by the above examples as a product and a detailed method of the invention, but the invention is not limited to, i.e. it does not mean that the invention must be practiced in dependence on the product and the detailed method. It should be apparent to those skilled in the art that any modifications, equivalent substitutions for operation of the present invention, addition of auxiliary operations, selection of specific modes, etc., are intended to fall within the scope of the present invention and the scope of the disclosure.

Claims (24)

1. The mullite lightweight aggregate with the rice hull genetic structure is characterized by comprising 50-90 parts of coal gangue, 5-20 parts of bauxite, 5-30 parts of clay, 5-30 parts of pore-forming agent, 8-20 parts of water and 0.05-5.0 parts of binding agent;
the mullite lightweight aggregate with the rice hull genetic structure is prepared by the following method:
mixing 50-90 parts of coal gangue, 5-20 parts of bauxite, 5-30 parts of clay, 5-30 parts of pore-forming agent, 8-20 parts of water and 0.05-5.0 parts of binding agent, granulating and forming, and then sequentially performing first baking and sintering to obtain mullite lightweight aggregate with rice hull genetic structure;
wherein the pore-forming agent is modified rice husk; the modified rice hulls are aluminum sol modified rice hulls; the preparation method of the aluminum sol modified rice hulls comprises the following steps: vacuum soaking rice hulls by using aluminum sol, and then performing second baking to obtain aluminum sol modified rice hulls; the solid content of the aluminum sol is 5-15.0wt%;
the mullite lightweight aggregate Al 2 O 3 The content is 30-62 wt%, the pore diameter distribution is below 100 μm, and the volume density is 0.5-1.3 g/cm 3 The apparent porosity is 60-90%, and the normal-temperature compressive strength is 5-18 MPa.
2. The mullite lightweight aggregate of claim 1 wherein the gangue is Fe 2 O 3 The content is less than or equal to 3.0 weight percent, tiO 2 The content is less than or equal to 5.0wt%.
3. The mullite lightweight aggregate of claim 1 wherein the gangue particle size is less than or equal to 0.074mm.
4. The mullite lightweight aggregate of claim 1 wherein the alumina is Al 2 O 3 The content is more than or equal to 45 weight percent.
5. The mullite lightweight aggregate of claim 1 wherein the alumina has a particle size of 0.088mm or less.
6. The mullite lightweight aggregate of claim 1 wherein the clay is Al 2 O 3 The content is more than or equal to 25 weight percent.
7. The mullite lightweight aggregate of claim 1 wherein the clay has a particle size of 0.045mm or less.
8. The mullite lightweight aggregate of claim 1 wherein the aluminum sol modified rice hulls are Al 2 O 3 The content is more than or equal to 5 weight percent.
9. The mullite lightweight aggregate of claim 1 wherein the modified rice hulls have a particle size of 0.045mm or less.
10. The mullite lightweight aggregate of claim 1 wherein the binder comprises any one or a combination of at least two of water glass, aluminum dihydrogen phosphate, sodium lignin sulfonate, carboxymethyl cellulose, or dextrin.
11. A method for preparing mullite lightweight aggregate with rice hull genetic structure, wherein the mullite lightweight aggregate is the mullite lightweight aggregate as claimed in any one of claims 1 to 10, and the preparation method comprises the following steps:
mixing 50-90 parts of coal gangue, 5-20 parts of bauxite, 5-30 parts of clay, 5-30 parts of pore-forming agent, 8-20 parts of water and 0.05-5.0 parts of binding agent, granulating and forming, and then sequentially performing first baking and sintering to obtain mullite lightweight aggregate with rice hull genetic structure;
the pore-forming agent is modified rice husk; the modified rice hulls are aluminum sol modified rice hulls;
the preparation method of the aluminum sol modified rice hulls comprises the following steps: vacuum soaking rice hulls by using aluminum sol, and then performing second baking to obtain aluminum sol modified rice hulls; the solid content of the aluminum sol is 5-15.0wt%;
the mullite lightweight aggregate Al 2 O 3 The content is 30-62 wt%, the pore diameter distribution is below 100 μm, and the volume density is 0.5-1.3 g/cm 3 The apparent porosity is 60-90%, and the temperature is normalThe compressive strength is 5-18 MPa.
12. The method according to claim 11, wherein the aluminum sol has a pH of 2.4 to 3.8.
13. The preparation method of claim 11, wherein the rice hull is added in an amount of 10-70wt% and the aluminum sol is added in an amount of 30-90wt%.
14. The method according to claim 11, wherein the vacuum degree of the vacuum impregnation is 10 3 ~10 5 Pa。
15. The method according to claim 11, wherein the time for vacuum impregnation is 3 to 24 hours.
16. The method according to claim 11, wherein the second baking temperature is 60-120 ℃.
17. The method of claim 11, wherein the second baking time is 24-48 hours.
18. The method of claim 11, wherein the second baking is followed by crushing.
19. The method of claim 18, wherein the alumina sol modified rice hulls have a particle size of 0.045mm or less after the crushing.
20. The method of claim 11, wherein drying is performed between the granulation and the first baking.
21. The method according to claim 11, wherein the temperature of the first baking is 100-120 ℃.
22. The method according to claim 11, wherein the first baking time is 20 to 30 hours.
23. The method according to claim 11, wherein the sintering temperature is 1000-1450 ℃.
24. The method of claim 11, wherein the sintering time is 2-6 hours.
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