CN106747316B - A method of thermo store honeycomb ceramic is prepared using flyash and shale - Google Patents

A method of thermo store honeycomb ceramic is prepared using flyash and shale Download PDF

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CN106747316B
CN106747316B CN201611039616.5A CN201611039616A CN106747316B CN 106747316 B CN106747316 B CN 106747316B CN 201611039616 A CN201611039616 A CN 201611039616A CN 106747316 B CN106747316 B CN 106747316B
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shale
flyash
honeycomb
green body
aging
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CN106747316A (en
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邓腾飞
李江锋
徐晓虹
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Wuhan University of Technology WUT
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    • C04B33/00Clay-wares
    • C04B33/02Preparing or treating the raw materials individually or as batches
    • C04B33/13Compounding ingredients
    • C04B33/132Waste materials; Refuse; Residues
    • C04B33/135Combustion residues, e.g. fly ash, incineration waste
    • C04B33/1352Fuel ashes, e.g. fly ash
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    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006Honeycomb structures
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • C04B2235/3463Alumino-silicates other than clay, e.g. mullite
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606Drying
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/60Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The invention discloses a kind of methods for preparing thermo store honeycomb ceramic using flyash and shale, and shale, feldspar, quartzy three kinds of raw materials were crushed to 250 meshes respectively;Flyash crosses 250 meshes;Above-mentioned powder is mixed, gained mixture is middle again to be added binder, lubricant and water, and 20-30min is mixed in kneader and obtains plastic pug;Pugging is carried out to plastic pug with vacuum deairing machine, then obtains aging good pug through aging 36-48h;Aging good pug is squeezed out into honeycomb green body by vertical extruder;The honeycomb green body of extrusion is put into micro-wave oven and is formed, dry 1-2h is then placed in infrared drying oven;1140-1220 DEG C of heating is fired into ceramic honey comb thermal store.After tested, thermal diffusion coefficient is 0.88-1.01mm under room temperature of the present invention2/ s, thermal conductivity are 1.7-2.2W/ (mK), storage density 1180-1240J/cm3, room temperature to 600 DEG C of thermal shocks recycles 30 times and do not crack.

Description

A method of thermo store honeycomb ceramic is prepared using flyash and shale
Technical field
The invention belongs to environmental protection and energy saving and field of new materials, and in particular to a kind of to prepare heat accumulation bee using flyash and shale The method of nest ceramics.
Background technique
In Solar Energy Heat Utilization System, due to the discontinuity and unstability of solar energy, it usually needs setting heat accumulation system System is to ensure its continuous operation.According to the difference of heat accumulation mode, heat accumulating has sensible heat heat accumulation, latent heat of phase change storage thermally and chemically anti- Answer heat accumulation three classes.Sensible heat heat accumulation is the thermal capacity using heat accumulating, realizes storage by being raised and lowered for material temperature Heat, principle is simple, technology maturation, is the most widely used heat accumulation mode.Ceramics are good etc. because of its high temperature resistant, chemical stability Advantage is a kind of heat accumulating of great potential.
Heat accumulation ceramics common at present are mostly mullite, cordierite and aluminum oxide etc., and cost of material is higher, are burnt At temperature height, energy consumption is high.Chinese invention patent " Thermal storage ceramic material and preparation method thereof " (CN103304226A) discloses one The method that kind prepares dichroite-mullite matter ceramics as primary raw material using cordierite, talcum and aluminium oxide.Chinese invention patent " a kind of Cordierite-mullite honeycomb ceramic heat accumulator and preparation method " (CN104909732A) disclose it is a kind of with mullite, Suzhou soil and talcum etc. are the method that primary raw material prepares dichroite-mullite honeycomb ceramic heat storage.To further decrease Cost, a kind of Chinese patent " honeycomb ceramic heat accumulator and its manufacturing method using the preparation of rare earth tailings " of Bao Qifu is using dilute Native tailings and bauxite are primary raw material, have been burnt into honeycomb ceramic heat accumulator at 1370-1390 DEG C.The Chinese patent of Chen Ping " a method of environmental protection type honeycomb ceramic heat storage body is prepared using abandoned mine slag " use red shale waste material, abandoned mine slag, cullet etc. For primary raw material, repressed molding, laser sintered system honeycomb ceramic heat accumulator.Using waste residue or waste material can reduce raw material at This, but there are still firing temperatures it is low, thermal conductivity is lower the disadvantages of.
Flyash is the fine ash that catching is got off from the flue gas after coal combustion, is that the primary solids of coal-burning power plant's discharge are discarded Object, main component SiO2With Al2O3, and particle is more carefully without the levigate raw material that can be used as Production of Ceramics.Chinese invention is special Benefit " a kind of fly ash base accumulation of heat ceramic honey comb and preparation method thereof " (CN102875128A) discloses one kind with flyash and burning Knot auxiliary agent is primary raw material, the method that firing prepares ceramic honey comb at 1200-1450 DEG C, has that cost of material is low, intensity is high The advantages that, but its firing temperature is higher, and thermal conductivity is lower.
Summary of the invention
The object of the invention is providing a kind of method for preparing thermo store honeycomb ceramic using flyash and shale, this method preparation Heat accumulation ceramics storage density is big, good thermal shock, thermal conductivity are more excellent, and firing temperature is low, low production cost.
In order to achieve the above objectives, as follows using technical solution:
A method of thermo store honeycomb ceramic is prepared using flyash and shale, comprising the following steps:
1) shale, feldspar, quartzy three kinds of raw materials pretreatment of raw material: are crushed to 5mm respectively hereinafter, using ball mill grinding again 4h-10h simultaneously crosses 250 meshes;Flyash crosses 250 meshes;
2) ingredient and mixing: above-mentioned flyash, shale, feldspar and quartz powder materials are mixed, and gained mixture is middle again to be added Binder, lubricant and water mix 20-30min in kneader and obtain plastic pug;
3) pugging with it is aging: pugging is carried out to plastic pug with vacuum deairing machine, then obtain through aging 36-48h it is aging good Pug;
4) honeycomb body squeezes out: aging good pug is squeezed out honeycomb green body by vertical extruder;
5) body drying: being put into micro-wave oven the 10-20min that is formed for the honeycomb green body of extrusion, is then placed in infrared dry Dry 1-2h in dry case;
6) green body is burnt into: dried green body being put into high temperature furnace, 1140-1220 DEG C is warming up to and is fired into honeycomb pottery Porcelain thermal store.
According to the above scheme, each powder is by mass percentage in step 2 are as follows:
Flyash 30-45wt%, shale 5-35wt%, feldspar 15-20wt%, quartz 15-30wt%;Water is in mixture Additive amount be 15-20wt%.
According to the above scheme, binder described in step 2 is carboxymethyl cellulose (CMC);Binder adding in mixture Dosage is 3-5wt%.
According to the above scheme, lubricant described in step 2 is one of tung oil, soya-bean oil or any mixing;Lubricant is mixed Closing the additive amount in material is 3-5wt%.
According to the above scheme, the extrusion pressure of step 4 extruder is 2-4MPa.
According to the above scheme, microwave power described in step 5 is 5kW, and frequency is 2450MHz ± 50MHz;In infrared drying oven Drying temperature is at 100-110 DEG C.
According to the above scheme, 3~5 DEG C/min of step 6 high temperature furnace heating rate.
The beneficial effects of the present invention are:
It is low in cost, it economizes on resources.Flyash is a kind of solid waste, and the utilization rate for improving flyash may be implemented to give up Object effective use, reduces environmental pollution.For shale as a kind of low-grade clay, rich reserves are cheap.
Comprehensive performance is good.Ceramic honey comb thermal store prepared by the present invention uses flyash and shale for primary raw material, page Rock promotes the generation of liquid phase at high temperature, facilitates the disintegration of fly ash float structure, so that short cylinder is not using floating bead as template Carry out stone intersection and grow into shell-like structure, there is good thermal property, thermal conductivity is higher than a kind of Chinese invention patent " flyash Base accumulation of heat ceramic honey comb and preparation method thereof " thermal conductivity 1.32-1.48W/ (mK) ceramic in (CN102875128A).Simultaneously Since the mullite shell-like structure facilitates relaxed stress, improves thermal shock resistance, solar energy medium temperature heat utilization heat accumulation system can be met For the performance requirement of heat accumulating in system.In addition, feldspar can dissolve clay, stone as the liquid phase that flux is formed at high temperature The raw materials such as English, Al2O3And SiO2It interacts, promote the formation of mullite crystal and grows up in the liquid phase, while feldspar melts The liquid phase formed afterwards can fill green body gap, increase consistency, improve the mechanical strength of green body.Quartz is in ceramic firing process Volume expansion play the role of compensating green body and shrink, while skeleton of the quartz particles as green body plays a part of to enhance, subtract A possibility that having lacked blank deformation.In addition, carboxymethyl cellulose (CMC) is used to improve the plasticity of plastic pug as binder, Enhance the intensity of ceramic honey comb green compact, the wetability of powder can be improved as lubricant for tung oil, soya-bean oil, reduce between powder particles And the friction between powder and die wall, promote the density for squeezing out green body to increase and homogenize.
Energy-saving and emission-reduction.Ceramic honey comb thermal store firing temperature prepared by the present invention is 1140-1220 DEG C, compares existing skill The firing temperature of art is lower, energy saving.
Detailed description of the invention
Fig. 1: embodiment 1 prepares the electron-microscope scanning figure of heat accumulation ceramics.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but not as limiting the scope of the invention.
Embodiment 1
A method of medium temperature thermo store honeycomb ceramic being prepared using flyash and shale, it includes the following steps:
1. pretreatment of raw material: shale, feldspar, quartzy three kinds of raw materials are crushed to 5mm with crusher respectively hereinafter, using ball again Grinding machine grinds 4h and crosses 250 meshes, and direct 250 mesh of mistake of flyash is spare;
2. ingredient and mixing: by flyash, shale, feldspar and quartz according to flyash 30wt%, shale 35wt%, length Stone 20wt%, quartz 15wt% proportion mix 2h in batch mixer, mixture again in 3wt% binder, 4wt% lubrication is added Agent and 15wt% water mix 20min in kneader and obtain plastic pug.
The binder is carboxymethyl cellulose (CMC), and lubricant is tung oil;
3. pugging with it is aging: pugging is carried out to plastic pug with vacuum deairing machine, then obtains aging good mud through aging 40h Material;
4. honeycomb body squeezes out: aging good pug being squeezed out honeycomb green body by vertical extruder, extruder squeezes Pressure is 3MPa out;
5. body drying: the honeycomb green body of extrusion being put into micro-wave oven the 10min that is formed, is then placed in infrared drying oven In at 110 DEG C dry 1.5h;The microwave power is 5kW, frequency 2450MHz;
6. green body is burnt into: dried green body being put into high temperature furnace, through 1140 DEG C of firing (1000 DEG C or less heating rates For 5 DEG C/min, 1000 DEG C or more heating rates are 3 DEG C/min) obtain ceramic honey comb thermal store;
After tested, the storage density of thermo store honeycomb ceramic of the invention is 1180J/cm3, thermal conductivity is 1.702W/ (m K), do not crack after thermal shock 30 times from room temperature to 600 DEG C, high comprehensive performance.
As shown in Figure 1, the mullite that can be seen that short cylinder from microscopic appearance crosses one another and grows into shell-like structure, The mullite shell-like structure facilitates relaxed stress, improves thermal shock resistance.The liquid phase being distributed in around mullite simultaneously is filled with Ceramic internal porosity promotes densification, improves the heat accumulation and heating conduction of ceramics.
Comparative example 1
Shale is replaced all with into flyash, i.e. flyash proportion is 65%, repeats the design of embodiment 1.
After tested, the storage density of the thermo store honeycomb ceramic is 1103J/cm3, embodiment 1 is close compared with the heat accumulation in comparative example 1 Degree improves 6.98%;Thermal conductivity is 1.532W/ (mK), and comparative example 1 reduces 11% compared with the thermal conductivity of embodiment 1;From room Temperature does not crack after thermal shock 30 times to 600 DEG C, and thermal shock resistance is good.
Comparative example 2
Flyash is replaced all with into shale, i.e. shale proportion is 65%, repeats the design of embodiment 1.
After tested, the storage density of the thermo store honeycomb ceramic is 1055J/cm3, embodiment 1 is close compared with the heat accumulation in comparative example 2 Degree improves 11.85%;Thermal conductivity is 1.570W/ (mK), and comparative example 2 reduces 8% compared with the thermal conductivity of embodiment 1;From room Temperature has crackle appearance to 600 DEG C after thermal shock 30 times, and intensity decline 82.5%, thermal shock resistance is poor.
Embodiment 2
A method of medium temperature thermo store honeycomb ceramic being prepared using flyash and shale, it includes the following steps:
1. pretreatment of raw material: shale, feldspar, quartzy three kinds of raw materials are crushed to 5mm with crusher respectively hereinafter, using ball again Grinding machine grinds 6h and crosses 250 meshes, and direct 250 mesh of mistake of flyash is spare;
2. ingredient and mixing: by flyash, shale, feldspar and quartz according to flyash 40wt%, shale 15wt%, length Stone 20wt%, quartz 25wt% proportion mix 2.5h in batch mixer, mixture again in 5wt% binder, 5wt% profit is added Lubrication prescription and 18wt% water mix 25min in kneader and obtain plastic pug.
The binder is carboxymethyl cellulose (CMC), lubricant soya-bean oil;
3. pugging with it is aging: pugging is carried out to plastic pug with vacuum deairing machine, then obtains aging good mud through aging 48h Material;
4. honeycomb body squeezes out: aging good pug being squeezed out honeycomb green body by vertical extruder, extruder squeezes Pressure is 4MPa out;
5. body drying: the honeycomb green body of extrusion being put into micro-wave oven the 15min that is formed, is then placed in infrared drying oven In at 110 DEG C dry 2h;The microwave power is 5kW, frequency 2450MHz;
6. green body is burnt into: dried green body being put into high temperature furnace, through 1180 DEG C of firing (1000 DEG C or less heating rates 5 DEG C/min, 1000 DEG C or more heating rates, 3 DEG C/min) obtain ceramic honey comb thermal store;
After tested, the storage density of thermo store honeycomb ceramic of the invention is 1193J/cm3, thermal conductivity is 2.090W/ (m K), do not crack after thermal shock 30 times from room temperature to 600 DEG C, high comprehensive performance.
Embodiment 3
A method of medium temperature thermo store honeycomb ceramic being prepared using flyash and shale, it includes the following steps:
1. pretreatment of raw material: shale, feldspar, quartzy three kinds of raw materials are crushed to 5mm with crusher respectively hereinafter, using ball again Grinding machine grinds 10h and crosses 250 meshes, and direct 250 mesh of mistake of flyash is spare;
2. ingredient and mixing: by flyash, shale, feldspar and quartz according to flyash 45wt%, shale 5wt%, feldspar 20wt%, quartz 30wt% proportion mix 2h in batch mixer, mixture again in 4wt% binder, 4wt% lubricant is added With 20wt% water, 30min is mixed in kneader and obtains plastic pug.
The binder is carboxymethyl cellulose (CMC), and lubricant is tung oil, soya-bean oil is prepared according to the ratio of 1:1;
3. pugging with it is aging: pugging is carried out to plastic pug with vacuum deairing machine, then obtains aging good mud through aging 48h Material;
4. honeycomb body squeezes out: aging good pug being squeezed out honeycomb green body by vertical extruder, extruder squeezes Pressure is 4MPa out;
5. body drying: the honeycomb green body of extrusion being put into micro-wave oven the 10min that is formed, is then placed in infrared drying oven In at 110 DEG C dry 1.5h;The microwave power is 5kW, frequency 2450MHz;
6. green body is burnt into: dried green body being put into high temperature furnace, through 1220 DEG C of firing (1000 DEG C or less heating rates 5 DEG C/min, 1000 DEG C or more heating rates, 3 DEG C/min) obtain ceramic honey comb thermal store;
After tested, thermo store honeycomb ceramic of the invention is 1240J/cm3, thermal conductivity is 2.218W/ (mK), from room temperature It does not crack after thermal shock 30 times to 600 DEG C, high comprehensive performance.
After tested, the bulk density of medium temperature ceramic honey comb thermal store of the invention reaches 2.40-2.44g/cm3, under room temperature (25 DEG C) thermal diffusion coefficient is 0.88-1.01mm2/ s, thermal conductivity are 1.7-2.2W/ (mK), and room temperature (25 DEG C) is to 500 DEG C Storage density is 1180-1240J/cm3, room temperature to 600 DEG C of thermal shocks recycles 30 times and do not crack.Ceramic honey comb thermal store of the invention Heat reservoir suitable for solar thermal utilization middle-temperature section (100-500 DEG C).
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter are (such as Temperature, time etc.) bound, section value can realize the present invention, embodiment numerous to list herein.

Claims (4)

1. a kind of method for preparing thermo store honeycomb ceramic using flyash and shale, it is characterised in that the following steps are included:
1) shale, feldspar, quartzy three kinds of raw materials pretreatment of raw material: are crushed to 5mm respectively hereinafter, again with ball mill grinding 4h- 10h simultaneously crosses 250 meshes;Flyash crosses 250 meshes;
2) ingredient and mixing: flyash and above-mentioned shale, feldspar and quartz powder materials are mixed, and gained mixture is middle again to be added bonding Agent, lubricant and water mix 20-30min in kneader and obtain plastic pug;Each powder is by mass percentage are as follows: fine coal Grey 30-45wt%, shale 5-35wt%, feldspar 15-20wt%, quartz 15-30wt%;Additive amount of the water in mixture be 15-20wt%;The binder is carboxymethyl cellulose;Additive amount of the binder in mixture is 3-5wt%;The lubrication Agent is one of tung oil, soya-bean oil or any mixing;Additive amount of the lubricant in mixture is 3-5wt%;
3) pugging with it is aging: pugging is carried out to plastic pug with vacuum deairing machine, then obtains aging good mud through aging 36-48h Material;
4) honeycomb body squeezes out: aging good pug is squeezed out honeycomb green body by vertical extruder;
5) body drying: the honeycomb green body of extrusion is put into micro-wave oven the 10-20min that is formed, is then placed in infrared drying oven Middle dry 1-2h;
6) green body is burnt into: dried green body being put into high temperature furnace, 1140-1220 DEG C is warming up to and is fired into ceramic honey comb storage Hot body.
2. the method for preparing thermo store honeycomb ceramic using flyash and shale as described in claim 1, it is characterised in that step 4 is squeezed The extrusion pressure of machine is 2-4MPa out.
3. the method for preparing thermo store honeycomb ceramic using flyash and shale as described in claim 1, it is characterised in that step 5 institute Stating microwave power is 5kW, and frequency is 2450MHz ± 50MHz;Drying temperature is at 100-110 DEG C in infrared drying oven.
4. the method for preparing thermo store honeycomb ceramic using flyash and shale as described in claim 1, it is characterised in that step 6 is high Warm 3~5 DEG C/min of furnace heating rate.
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CN109233753A (en) * 2018-12-03 2019-01-18 安徽恒明工程技术有限公司 A kind of phase change heat storage material and preparation method thereof
CN109504353B (en) * 2018-12-24 2020-10-16 中国有色集团晋铝耐材有限公司 High specific heat capacity heat storage material and preparation method thereof
CN111018560B (en) * 2019-12-24 2021-01-05 北京大学 Multi-scale pore honeycomb ceramic and preparation method thereof
CN112552022B (en) * 2020-12-29 2023-05-02 武汉理工大学 Method for preparing solar heat storage ceramic by using ferrotitanium slag
CN113943555A (en) * 2021-11-18 2022-01-18 北京华能长江环保科技研究院有限公司 Power plant fly ash based high-value heat storage material synthesis system and synthesis method
CN114349476A (en) * 2021-12-27 2022-04-15 中国华能集团清洁能源技术研究院有限公司 Preparation method of solid heat storage material and solid heat storage material
CN116903386A (en) * 2023-06-08 2023-10-20 桐乡泰爱斯环保能源有限公司 Preparation method of fly ash-based honeycomb ceramic

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CN103992099A (en) * 2014-05-20 2014-08-20 陕西科技大学 Method for preparing environment-friendly honeycomb ceramic heat accumulator by use of waste slag

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CN103992099A (en) * 2014-05-20 2014-08-20 陕西科技大学 Method for preparing environment-friendly honeycomb ceramic heat accumulator by use of waste slag

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