CN117105652B - Method for preparing mullite material by utilizing FCC spent catalyst and fly ash through low-temperature sintering and prepared mullite material - Google Patents

Method for preparing mullite material by utilizing FCC spent catalyst and fly ash through low-temperature sintering and prepared mullite material Download PDF

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CN117105652B
CN117105652B CN202311380652.8A CN202311380652A CN117105652B CN 117105652 B CN117105652 B CN 117105652B CN 202311380652 A CN202311380652 A CN 202311380652A CN 117105652 B CN117105652 B CN 117105652B
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sintering
fly ash
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朱成麟
方澎
李军远
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Shandong Shengri Aopeng Environmental Protection New Material Group Co ltd
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Abstract

The invention discloses a method for preparing a mullite material by utilizing FCC spent catalyst and fly ash through low-temperature sintering and the prepared mullite material, and belongs to the technical fields of high-value utilization of industrial wastes and preparation of mullite materials. The invention takes FCC dead catalyst as main material, fly ash waste as auxiliary material, bauxite tailings, kyanite tailings and Al are added 2 O 3 The mullite material is prepared from the powder and the sintering aid through the processes of proportioning, grinding, forming and low-temperature sintering. The mullite material is prepared by sintering the FCC dead catalyst and the fly ash at low temperature, the addition amount of the FCC dead catalyst and the fly ash is high, the preparation process is simple, and the cost is low; the sintering aid can reduce sintering temperature, greatly shorten sintering time, reduce energy consumption, and improve mechanical strength, high temperature resistance and compactness of the product.

Description

Method for preparing mullite material by utilizing FCC spent catalyst and fly ash through low-temperature sintering and prepared mullite material
Technical Field
The invention relates to the field of recycling of FCC spent catalyst and fly ash, in particular to a method for preparing mullite material by utilizing FCC spent catalyst and fly ash through low-temperature sintering and the prepared mullite material.
Background
Mullite is an aluminosilicate mineral at high temperature, is an orthorhombic crystal system, and is Al 2 O 3 -SiO 2 The binary system has only stable crystal phase under normal temperature and high temperature, and has important application value in aluminum-silicon refractory materials and ceramics, and the original mullite crystal is long and narrow needle-shaped and clustered in radial. Mullite ceramics are often used as filters, catalyst supports, high temperature binders, industrial kiln liners in the metallurgical and chemical industries, etc. because of their high service temperature, high specific heat capacity, low thermal conductivity, low coefficient of thermal expansion, etc.
At present, the cost for synthesizing mullite by utilizing industrial raw materials is high. The mullite synthesizing process includes sintering, electric smelting, chemical deposition, etc. The synthesis method of mullite widely used in the industrial field is mainly a sintering method. The raw materials for synthesizing mullite by a sintering method are wide in sources, and can be chemical raw materials or natural minerals, but the cost is high. How to utilize inexpensive resources to reduce the cost of synthesizing mullite is one of the main research directions.
FCC (catalytic cracking) catalysts are the largest catalyst species used in the oil refining industry at present, and the spent catalyst produced after use is about 15 ten thousand tons per year, which has become one of the main solid wastes in the oil refining industry. The main component of the FCC dead catalyst is silicon-aluminum composite oxide, and also contains a certain amount of rare earth elements and inorganic elements such as Na, K, ti and the like, and simultaneously contains a small amount (1-2%) of coke. Since the FCC spent catalyst is mainly inorganic and contains considerable amounts of heavy metals and rare earth elements, it cannot be treated by composting, pyrolysis, incineration and other techniques. At present, the FCC spent catalyst is mainly treated in a buried mode, and harmful heavy metals therein migrate and are converted under the soaking of rainwater and enter the environment to pollute soil and rivers. Therefore, the resource utilization of the waste FCC catalyst and the production of high added value products are necessarily a development trend.
Fly ash, like FCC, is also an industrial waste, and mainly consists of inorganic matters and organic matters. Part of the organic matters mainly comprise carbon, hydrogen, oxygen, nitrogen, sulfur and the like. In the existing utilization way, the utilization rate of the fly ash is not high, and the added value of the fly ash cannot be fully obtained. Therefore, the method has important significance for reinforcing the resource utilization of the fly ash and changing the fly ash into valuables.
The prior art has been directed to addressing the above problems. CN102320616a takes waste catalytic cracking balancing agent from oil refinery and industrial alumina as raw materials, and adopts a high-temperature calcination method to prepare mullite material. CN110002855A is prepared from FCC dead catalyst and Al 2 O 3 Powder and SiO 2 The powder is a ceramic base material, the proportion is optimized, and the obtained high-temperature-resistant foamed ceramic has higher use temperature and lower heat conductivity coefficient, so that the FCC spent catalyst is recycled. The research of synthesizing mullite material with catalytic cracking catalyst waste adopts solid phase synthesis to initially explore waste FCC catalyst, and systematically researches Al 2 O 3 A process for synthesizing mullite material by using waste FCC catalyst. CN103964866A, CN113277794A, CN107954742A, CN108083789A and the like also discloseThe technological process of synthesizing mullite material with flyash as material is disclosed. The researchers mostly adopt industrial raw materials and chemical raw materials to prepare mullite materials, so that the cost of the raw materials is high and the performance is poor. There are also related technologies that researchers use industrial solid waste to add high bauxite with different proportions and industrial grade aluminum hydroxide or industrial grade oxide to obtain mullite materials through high-temperature sintering, and although the FCC spent catalyst and alumina and silica useful components in fly ash are used, the mullite materials synthesized by the technology are added with a large amount of industrial grade aluminum hydroxide or industrial grade oxide, the cost is still higher, and the prepared mullite materials are low in density, high in apparent porosity, poor in mechanical property and high temperature resistance, especially high in sintering temperature, long in high-temperature time and high in energy consumption, and further application is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing mullite materials by using FCC spent catalyst and fly ash through low-temperature sintering, which has the advantages of wide raw material sources, low energy consumption and low production cost, and can directly produce mullite material products from industrial wastes and minerals, realize 100 percent utilization of the FCC spent catalyst and the fly ash, generate no secondary solid waste, be suitable for industrial production and generate higher economic and environmental benefits. The preparation process is simple and the cost is low; on the basis of reducing the sintering temperature and the sintering time, the mechanical property and the high temperature resistance of the mullite material are further improved.
The aim of the invention is achieved by the following technical scheme.
A method for preparing mullite material by using FCC dead catalyst and fly ash low-temperature sintering is characterized in that: the method comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
40-60 parts of FCC spent catalyst, 25-30 parts of fly ash, 25-35 parts of bauxite tailings, 15-30 parts of kyanite tailings and Al 2 O 3 15-30 parts of powder and 3-10 parts of sintering aid; wherein the sintering aid consists of 1-2 parts of MgF 2 1-4 parts of Y 2 O 3 1-4 partsMnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material;
(3) Pressurizing the mixed material to prepare a blank;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 850-1000 ℃ at a heating rate of 1-4 ℃/min, the temperature is kept for 0.5-2h, the sintering section is continuously heated to 1200-1400 ℃ at a heating rate of 7-10 ℃/min and kept at the constant temperature for 2-10h, and the cooling section is cooled to room temperature at a cooling rate of 2-8 ℃/min, so that the mullite material is obtained.
The invention takes FCC dead catalyst and fly ash as main raw materials and adds bauxite tailings, kyanite tailings and Al 2 O 3 Mineral components such as powder, on the one hand, most of the components form mullite phases at high temperature; on the other hand, small amounts of low-melting-point phases exist in the FCC spent catalyst, fly ash, bauxite tailings and kyanite tailings, and impurities existing in minerals are added, and the impurities are converted into liquid phases at high temperature. The existence of the liquid phase can promote the formation of columnar mullite in the product material, and the strength of the product is further improved while the load softening temperature of the product is improved. And the liquid phase among the grains is increased, so that the elimination of air holes in the sample is promoted, the densification degree of the sample is improved, the porosity is reduced, and the mechanical strength is increased.
In order to reduce the sintering temperature, shorten the sintering time and improve the mechanical property, high temperature resistance and compactness of the mullite material, mgF is added in the invention 2 、Y 2 O 3 、MnO 2 Ternary composite sintering aid. By addition of MgF 2 The liquid phase formed during calcination can promote the generation of the mullite material, but the addition amount of the mullite material should be controlled, because the existence of excessive liquid phase can possibly lead to abnormal growth of grains of the mullite material and influence the performance of the mullite material. Adding Y 2 O 3 The method is beneficial to the generation of glass phase at the grain boundary, promotes the dissolution of alumina, controls the growth of mullite material particles, reduces the apparent porosity of the mullite material, and is beneficial to the improvement of the thermal shock stability, the volume density, the bending strength and the like of the mullite material; also, an excessive amount of Y 2 O 3 The diffusion of ions and the transmission of substances are hindered, and the transformation of mullite phase is not facilitated. MnO (MnO) 2 Can be combined with Al 2 O 3 、SiO 2 Formation of Al 2 O 3 -SiO 2 -MnO 2 The ternary eutectic system has low eutectic point, can form a liquid phase region locally, has small diffusion resistance in the liquid phase, reduces the sintering temperature, simultaneously can promote sample densification, reduces apparent porosity, and improves the density and flexural strength of the mullite material.
The sintering process adopts a three-stage process, and the preheating stage adopts a low-speed heating mode. Since the FCC spent catalyst and the fly ash are industrial wastes, a large amount of organic matters inevitably exist on the surface and inside. Along with the rise of temperature, organic matters volatilize, and in order to prevent the mullite material sample from deforming or even cracking caused by gas, the temperature is slowly raised so as to be beneficial to exhaust. The sintering section is continuously heated to 1200-1400 ℃ at the heating rate of 7-10 ℃/min and kept at the constant temperature for 2-10h. The amorphous silicon dioxide and the crystalline silicon dioxide can be effectively promoted to generate mullite material reaction together with alumina in the sintering section, so that mullite material crystals grow rapidly, and columnar mullite material crystals are obviously increased.
In one embodiment, the FCC spent catalyst in step (1) comprises essentially, by weight: al (Al) 2 O 3 45-50％、SiO 2 40-43％、Na 2 O 0.1-1％、K 2 O 0.2-0.6％、CeO 2 0.05-0.3％、La 2 O 3 0.1-2％、TiO 2 0.1-0.5%, and loss on ignition 2-8%;
in one embodiment, the fly ash in step (1) comprises essentially, by weight: al (Al) 2 O 3 35-43% of SiO 2 36-45% of Fe 2 O 3 1-3%、TiO 2 0.5-2%, caO 1-5%, and loss on ignition 3-8%;
in one embodiment, the bauxite tailings in step (1) comprise essentially, in weight percent: al (Al) 2 O 3 50-60%、SiO 2 20-30％、Fe 2 O 3 1.2-3%、K 2 O 1-2%、TiO 2 0.5-1%, and 3-15% loss on ignition;
in one embodiment, the blue stone tailings in the step (1) mainly comprise the following components in percentage by weight: siO (SiO) 2 33-40％、Al 2 O 3 50-55％、ZrO 2 1.5-2.2％、Fe 2 O 3 0.6-1.2%, caO 0.5-1% and loss on ignition 2-7%.
In one embodiment, the raw material components in the step (1) are 45-55 parts of FCC dead catalyst, 26-30 parts of fly ash, 27-33 parts of bauxite tailings, 22-28 parts of blue crystal stone tailings and Al 2 O 3 20-30 parts of powder and 4-6 parts of sintering aid.
In one embodiment, the sintering aid in step (1) consists of 1-2 parts of MgF 2 2-3 parts of Y 2 O 3 2-3 parts of MnO 2 Composition is prepared.
In one embodiment, the Al in step (1) 2 O 3 The powder is selected from industrial alumina, alpha-Al 2 O 3 And gamma-Al 2 O 3 One or a combination of several of them.
In one embodiment, in the step (2), the grinding speed is 200-400r/min and the grinding time is 10-40min when the mixed concentrate is prepared.
In one embodiment, in the step (2), the particle size of the mixed material is less than or equal to 300 meshes.
In one embodiment, in step (3), the pressing into a green body has a pressure of 20-100MPa.
In one embodiment, in the step (4), the preheating section is heated to 900-1000 ℃ at a heating rate of 2-3 ℃/min, the temperature is kept for 1-2h, the sintering section is continuously heated to 1250-1350 ℃ at a heating rate of 7-9 ℃/min and kept at a constant temperature for 3-7h, and the cooling section is cooled to room temperature at a cooling rate of 3-7 ℃/min to obtain the mullite material.
Compared with the prior art, the method for preparing the mullite material by using the FCC dead catalyst and the fly ash through low-temperature sintering has the following technical effects:
the process method adopts a three-step method to prepare the mullite material by sintering, has short production period and can meet the requirement of large-scale industrial production. The main raw materials for production are industrial waste FCC dead catalyst and fly ash, and a small amount of bauxite tailings and kyanite tailings are also mixed, so that the production source is wide, no dangerous byproducts are produced in the preparation process, the preparation cost is low, the prepared mullite material has high densification degree, high strength and good high temperature resistance, and meanwhile, the thermal expansion coefficient of the mullite material is reduced by a complex phase structure introduced by various minerals. Not only solves the serious pollution problem that the FCC dead catalyst and the fly ash are difficult to repair to the environment, but also realizes the efficient recycling utilization of the FCC dead catalyst and the fly ash, and opens up a new path for the large-scale industrial utilization of the solid waste FCC dead catalyst and the fly ash. By adding the composite sintering aid, the mechanical property and the high-temperature property of the prepared mullite material are greatly improved while the sintering temperature is reduced.
In the technical proposal, the compressive strength of the mullite material is 150-200MPa, and the volume density is 2.5-3g/cm 3 The flexural strength is 90-150MPa, the rapid cooling and rapid heating resistance is good, the expansion coefficient is low, and the high temperature of 1700 ℃ can be resisted.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Wherein the raw materials used in the following examples and comparative examples are all commercially available products. Specific:
the FCC spent catalyst comprises the following main components in percentage by weight: al (Al) 2 O 3 48％、SiO 2 41％、Na 2 O 0.5％、K 2 O 0.4％、CeO 2 0.1％，La 2 O 3 1％、TiO 2 0.3% and loss on ignition of 7%;
the fly ash mainly comprises the following components in percentage by weight: al (Al) 2 O 3 42% of SiO 2 44% of Fe 2 O 3 2.5%、TiO 2 1 percent of CaO, 3 percent of CaO and 6.5 percent of loss on ignition;
the bauxite tailings mainly comprise the following components in percentage by weight: al (Al) 2 O 3 55%、SiO 2 27％、Fe 2 O 3 2%、K 2 O 1.5%、TiO 2 0.8% and loss on ignition 12%;
the kyanite tailings mainly comprise the following components in percentage by weight: siO (SiO) 2 36％、Al 2 O 3 54％、ZrO 2 1.7％、Fe 2 O 3 0.9%, caO 0.8% and loss on ignition 4%.
Example 1
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
45 parts of FCC spent catalyst, 28 parts of fly ash, 30 parts of bauxite tailings, 20 parts of kyanite tailings and industrial Al 2 O 3 20 parts of powder and 3 parts of sintering aid; wherein the sintering aid consists of 1 part of MgF 2 1 part Y 2 O 3 1 part MnO 2 Composition;
(2) The FCC dead catalyst, the fly ash, the bauxite tailings and the kyanite tailings Al in the step (1) are treated 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate, wherein the grinding speed is 300r/min, and the grinding time is 30min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 200 meshes;
(3) Pressurizing the mixed material to prepare a blank, wherein the molding pressure is 50MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 900 ℃ at a heating rate of 1 ℃/min, the temperature is kept for 1h, the sintering section is continuously heated to 1400 ℃ at a heating rate of 7 ℃/min and kept at the constant temperature for 6h, and the cooling section is cooled to room temperature at a cooling rate of 6 ℃/min to obtain the mullite material.
Example 2
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
50 parts of FCC spent catalyst, 25 parts of fly ash, 33 parts of bauxite tailings, 25 parts of blue crystal stone tailings and industrial Al 2 O 3 22 parts of powder and 10 parts of sintering aid; wherein the sintering aid consists of 2 parts of MgF 2 4 parts of Y 2 O 3 4 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate, wherein the grinding speed is 350r/min, and the grinding time is 40min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 250 meshes;
(3) Pressurizing the mixed material to prepare a green body, wherein the molding pressure is 80MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 950 ℃ at a heating rate of 3 ℃/min, the temperature is kept for 2 hours, the sintering section is continuously heated to 1300 ℃ at a heating rate of 8 ℃/min and kept at the constant temperature for 8 hours, and the cooling section is cooled to room temperature at a cooling rate of 8 ℃/min, so that the mullite material is obtained.
Example 3
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
58 parts of FCC spent catalyst, 26 parts of fly ash, 31 parts of bauxite tailings, 26 parts of blue crystal stone tailings and alpha-Al 2 O 3 25 parts of powder and 8 parts of sintering aid; wherein the sintering aid consists of 2 parts of MgF 2 3 parts of Y 2 O 3 3 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate, wherein the grinding speed is 330r/min, and the grinding time is 25min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 280 meshes;
(3) Pressurizing the mixed material to prepare a green body, wherein the molding pressure is 60MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 1000 ℃ at a heating rate of 4 ℃/min, the temperature is kept for 1.5h, the sintering section is continuously heated to 1200 ℃ at a heating rate of 10 ℃/min and kept at the constant temperature for 7h, and the cooling section is cooled to room temperature at a cooling rate of 3 ℃/min to obtain the mullite material.
Example 4
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
52 parts of FCC spent catalyst, 29 parts of fly ash, 33 parts of bauxite tailings, 18 parts of blue crystal stone tailings and gamma-Al 2 O 3 20 parts of powder and 6 parts of sintering aid; wherein the sintering aid consists of 1 part of MgF 2 3 parts of Y 2 O 3 2 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate, wherein the grinding speed is 400r/min, and the grinding time is 40min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 240 meshes;
(3) Pressurizing the mixed material to prepare a blank, wherein the molding pressure is 90MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 880 ℃ at a heating rate of 3 ℃/min, the temperature is kept for 1.2h, the sintering section is continuously heated to 1350 ℃ at a heating rate of 8 ℃/min and kept at the constant temperature for 6h, and the cooling section is cooled to room temperature at a cooling rate of 5 ℃/min to obtain the mullite material.
Example 5
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
55 parts of FCC spent catalyst, 30 parts of fly ash, 27 parts of bauxite tailings, 25 parts of kyanite tailings and gamma-Al 2 O 3 25 parts of powder and 5 parts of sintering aid; wherein the sintering aid consists of 1 part of MgF 2 2 parts of Y 2 O 3 2 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate, wherein the grinding speed is 350r/min, and the grinding time is 35min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 220 meshes;
(3) Pressurizing the mixed material to prepare a blank, wherein the molding pressure is 100MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 980 ℃ at a heating rate of 3 ℃/min, the temperature is kept for 1.3 hours, the sintering section is continuously heated to 1325 ℃ at a heating rate of 8 ℃/min and kept at the constant temperature for 5 hours, and the cooling section is cooled to room temperature at a cooling rate of 6 ℃/min to obtain the mullite material.
Example 6
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
40 parts of FCC spent catalyst, 25 parts of fly ash, 25 parts of bauxite tailings, 25 parts of blue crystal stone tailings and industrial Al 2 O 3 20 parts of powder and 9 parts of sintering aid; wherein the sintering aid consists of 2 parts of MgF 2 3 parts of Y 2 O 3 4 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Uniformly mixing the powder, and grinding to obtain a mixed concentrate, wherein the grinding speed is 370r/min, and the grinding time is 32min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 190 meshes;
(3) Pressurizing the mixed material to prepare a green body, wherein the molding pressure is 70MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 1000 ℃ at a heating rate of 4 ℃/min, the temperature is kept for 2 hours, the sintering section is continuously heated to 1400 ℃ at a heating rate of 10 ℃/min and kept at the constant temperature for 10 hours, and the cooling section is cooled to room temperature at a cooling rate of 8 ℃/min to obtain the mullite material.
Example 7
A method for preparing mullite material by using FCC spent catalyst and fly ash low-temperature sintering comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
60 parts of FCC spent catalyst, 30 parts of fly ash, 35 parts of bauxite tailings, 28 parts of kyanite tailings and alpha-Al 2 O 3 30 parts of powder and 7 parts of sintering aid; wherein the sintering aid consists of 2 parts of MgF 2 3 parts of Y 2 O 3 2 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate, wherein the grinding speed is 370r/min, and the grinding time is 20min; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material with the particle size less than or equal to 200 meshes;
(3) Pressurizing the mixed material to prepare a blank, wherein the molding pressure is 40MPa;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 900 ℃ at a heating rate of 3 ℃/min, the temperature is kept for 2 hours, the sintering section is continuously heated to 1400 ℃ at a heating rate of 8 ℃/min and kept at the constant temperature for 6 hours, and the cooling section is cooled to room temperature at a cooling rate of 7 ℃/min, so that the mullite material is obtained.
Comparative example 1
The composition and the proportion of the method for preparing the mullite material by using the FCC spent catalyst and the fly ash through low-temperature sintering are basically the same as those of the embodiment 4, except that 29 parts of the fly ash is replaced by 29 parts of the FCC spent catalyst, and the preparation method is the same as that of the embodiment 4.
Comparative example 2
The method for preparing the mullite material by utilizing the FCC dead catalyst and the fly ash through low-temperature sintering provided by the comparative example has the components and the proportion the same as those of the embodiment 4, and is different in that the preheating section is heated to 880 ℃ at the heating rate of 7 ℃/min, and the temperature is kept for 1.2 hours, and other steps of the preparation method are the same as those of the embodiment 4.
Comparative example 3
The composition and proportion of the method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash are basically the same as those of example 4, except that 6 parts of sintering aid consists of 3.6 parts of Y 2 O 3 2.4 parts of MnO 2 Composition, its preparation methodThe procedure was as in example 4.
Comparative example 4
The composition and proportion of the method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash are basically the same as those of the embodiment 4, except that 6 parts of sintering aid consists of 2 parts of MgF 2 4 parts of MnO 2 Composition, preparation method is the same as in example 4.
Comparative example 5
The composition and proportion of the method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash are basically the same as those of example 4, except that 6 parts of sintering aid consists of 1.5 parts of MgF 2 4.5 parts of Y 2 O 3 Composition, preparation method is the same as in example 4.
Comparative example 6
The composition and proportion of the method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash are basically the same as those of example 4, except that 6 parts of sintering aid consists of 4 parts of MgF 2 1 part Y 2 O 3 1 part MnO 2 Composition, preparation method is the same as in example 4.
Comparative example 7
The composition and proportion of the method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash are basically the same as those of the embodiment 4, except that 9 parts of sintering aid consists of 1 part of MgF 2 6 parts of Y 2 O 3 2 parts of MnO 2 Composition, preparation method is the same as in example 4.
Comparative example 8
The method for preparing the mullite material by using the FCC spent catalyst and the fly ash through low-temperature sintering provided by the comparative example has the same components and proportions as in the example 4, and is different in that the sintering section is continuously heated to 1450 ℃ at a heating rate of 8 ℃/min and is kept at the constant temperature for 6 hours, and other steps of the preparation method are the same as in the example 4.
The materials prepared in examples and comparative examples were subjected to the test of the relevant index, and the test results are shown in the following tables 1 to 2:
from comparative examples 1 to 8 and examples 1 to 7, it can be seen that: the mechanical property and the density of the mullite material are improved by adding the fly ash. And the heating rate of the preheating section of the comparative example 2 is too high, which is not beneficial to the discharge of volatile gases, resulting in poor mechanical properties of mullite materials.
Comparative examples 3 to 5 differ from example 4 in that: the sintering aid of comparative examples 3-5 was MgF 2 、Y 2 O 3 、MnO 2 The combination of two of them, the total amount of the sintering aid and the mixture ratio of two to one are the same as in example 4, namely Y in comparative example 3 2 O 3 With MnO 2 The ratio was 3:2, mgF in comparative example 4 2 With MnO 2 The ratio of MgF in comparative example 5 was 1:2 2 And Y is equal to 2 O 3 The ratio was 1:3, as can be seen from the data in tables 1-2: comparative example 4, comparative examples 3 to 5, which have poor mechanical properties and density and reduced heat resistance, shows that the sintering aid MgF 2 、Y 2 O 3 、MnO 2 The synergy between the two components promotes the mullite crystal to develop better.
From comparative examples 6 to 7 and examples 1 to 7, it can be seen that: excess MgF 2 Or Y 2 O 3 The mechanical property and the compactness of the mullite material are reduced. This may be due to abnormal growth of grains.
As can be seen from comparative example 8 and examples 1 to 7: the density of the mullite material does not rise even when the sintering temperature is increased. Compared with the prior art, the sintering temperature is higher than 1400 ℃, the addition of the sintering aid reduces the mullite sintering temperature, and the production cost is reduced.
In conclusion, the mullite material is prepared by sintering the FCC spent catalyst, the fly ash, the bauxite tailings and the kyanite tailings at low temperature, the FCC spent catalyst and the fly ash are added in high amounts, the preparation process is simple, and the cost is low; the sintering temperature can be reduced by adding the sintering aid, the sintering time is greatly shortened, the energy consumption is reduced, and the compressive strength, the high temperature resistance and the compactness of the product can be improved.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (10)

1. A method for preparing mullite material by using FCC dead catalyst and fly ash low-temperature sintering is characterized in that: the method comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
40-60 parts of FCC spent catalyst, 25-30 parts of fly ash, 25-35 parts of bauxite tailings, 15-30 parts of kyanite tailings and Al 2 O 3 15-30 parts of powder and 3-10 parts of sintering aid; wherein the sintering aid consists of 1-2 parts of MgF 2 1-4 parts of Y 2 O 3 1-4 parts of MnO 2 Composition;
(2) The FCC dead catalyst, fly ash, bauxite tailings, kyanite tailings and Al in the step (1) 2 O 3 Mixing the powder uniformly, and grinding to obtain a mixed concentrate; adding the sintering aid into the mixed concentrate, and grinding again to obtain a mixed material;
(3) Pressurizing the mixed material to prepare a blank;
(4) Sintering;
wherein, the sintering in the step (4) is divided into 3 stages, namely a preheating stage, a sintering stage and a cooling stage: the preheating section is heated to 850-1000 ℃ at a heating rate of 1-4 ℃/min, the temperature is kept for 0.5-2h, the sintering section is continuously heated to 1200-1400 ℃ at a heating rate of 7-10 ℃/min and kept at the constant temperature for 2-10h, and the cooling section is cooled to room temperature at a cooling rate of 2-8 ℃/min, so that the mullite material is obtained.
2. Root of Chinese characterThe method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as set forth in claim 1, wherein: the FCC spent catalyst in step (1) comprises, in weight percent: al (Al) 2 O 3 45-50％、SiO 2 40-43％、Na 2 O 0.1-1％、K 2 O 0.2-0.6％、CeO 2 0.05-0.3％、La 2 O 3 0.1-2％、TiO 2 0.1-0.5%, and loss on ignition 2-8%;
and/or
The fly ash in the step (1) comprises the following components in percentage by weight: al (Al) 2 O 3 35-43% of SiO 2 36-45% of Fe 2 O 3 1-3%、TiO 2 0.5-2%, caO 1-5%, and loss on ignition 3-8%;
and/or
The bauxite tailings in the step (1) comprise the following components in percentage by weight: al (Al) 2 O 3 50-60%、SiO 2 20-30％、Fe 2 O 3 1.2-3%、K 2 O 1-2%、TiO 2 0.5-1%, and 3-15% loss on ignition;
and/or
The blue stone tailings in the step (1) comprise the following components in percentage by weight: siO (SiO) 2 33-40％、Al 2 O 3 50-55％、ZrO 2 1.5-2.2％、Fe 2 O 3 0.6-1.2%, caO 0.5-1% and loss on ignition 2-7%.
3. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as set forth in claim 1, wherein: the raw material components in the step (1) are 45-55 parts of FCC spent catalyst, 26-30 parts of fly ash, 27-33 parts of bauxite tailings, 22-28 parts of blue crystal stone tailings and Al 2 O 3 20-30 parts of powder and 4-6 parts of sintering aid.
4. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as set forth in claim 1, wherein: the sintering aid in the step (1) consists of 1-2 parts of MgF 2 2-3 parts of Y 2 O 3 2-3 parts of MnO 2 Composition is prepared.
5. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as set forth in claim 1, wherein: the Al in step (1) 2 O 3 The powder is selected from industrial alumina, alpha-Al 2 O 3 And gamma-Al 2 O 3 One or a combination of several of them.
6. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as set forth in claim 1, wherein in the step (2), the grinding speed is 200-400r/min and the grinding time is 10-40min when preparing the mixed concentrate.
7. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as set forth in claim 1, wherein in the step (2), the particle size of the mixture is 300 mesh or less.
8. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash as claimed in claim 1, wherein the pressing into green body in step (3) has a pressure of 20-100MPa.
9. The method for preparing mullite material by low-temperature sintering of FCC spent catalyst and fly ash according to claim 1, wherein in the step (4), the preheating section is heated to 900-1000 ℃ at a heating rate of 2-3 ℃/min, the temperature is kept for 1-2h, the sintering section is continuously heated to 1250-1350 ℃ at a heating rate of 7-9 ℃/min and kept at a constant temperature for 3-7h, and the cooling section is cooled to room temperature at a cooling rate of 3-7 ℃/min to obtain mullite material.
10. A mullite material characterized by: a process according to any one of claims 1 to 9.
CN202311380652.8A 2023-10-24 2023-10-24 Method for preparing mullite material by utilizing FCC spent catalyst and fly ash through low-temperature sintering and prepared mullite material Active CN117105652B (en)

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Publication number Priority date Publication date Assignee Title
CN101643359A (en) * 2009-08-04 2010-02-10 陕西科技大学 Method for preparing porzite powder by fly ash
CN102351522A (en) * 2011-07-15 2012-02-15 郑州大学 Method for preparing homogeneous mullite material from kyanite
CN104496520A (en) * 2014-11-28 2015-04-08 中国科学技术大学先进技术研究院 Low-cost light mullite-based heat preservation material and preparation method thereof
CN107459339A (en) * 2017-09-14 2017-12-12 黄河三角洲京博化工研究院有限公司 A kind of FCC dead catalyst lytag and its production method
CN107640966A (en) * 2016-12-01 2018-01-30 中国石油化工股份有限公司 The method that mullite is prepared by FCC dead catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643359A (en) * 2009-08-04 2010-02-10 陕西科技大学 Method for preparing porzite powder by fly ash
CN102351522A (en) * 2011-07-15 2012-02-15 郑州大学 Method for preparing homogeneous mullite material from kyanite
CN104496520A (en) * 2014-11-28 2015-04-08 中国科学技术大学先进技术研究院 Low-cost light mullite-based heat preservation material and preparation method thereof
CN107640966A (en) * 2016-12-01 2018-01-30 中国石油化工股份有限公司 The method that mullite is prepared by FCC dead catalyst
CN107459339A (en) * 2017-09-14 2017-12-12 黄河三角洲京博化工研究院有限公司 A kind of FCC dead catalyst lytag and its production method

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