CN115584148A - High-heat-conductivity high-strength composite material for flexibility transformation of circulating fluidized bed boiler and preparation method thereof - Google Patents
High-heat-conductivity high-strength composite material for flexibility transformation of circulating fluidized bed boiler and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 24
- 230000009466 transformation Effects 0.000 title description 3
- 239000000843 powder Substances 0.000 claims abstract description 106
- 239000010431 corundum Substances 0.000 claims abstract description 62
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 62
- 239000004927 clay Substances 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 38
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 33
- 229920000570 polyether Polymers 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000004568 cement Substances 0.000 claims abstract description 27
- 229920002545 silicone oil Polymers 0.000 claims abstract description 26
- 239000002798 polar solvent Substances 0.000 claims abstract description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 23
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 19
- 239000010453 quartz Substances 0.000 claims abstract description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
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- 239000000463 material Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 54
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
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- 238000001816 cooling Methods 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 5
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- -1 sorbic amide Chemical class 0.000 claims description 4
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 3
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075554 sorbate Drugs 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 description 20
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical class [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910003465 moissanite Inorganic materials 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
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- JPXCVMIARYLSGU-MQQKCMAXSA-N (2e,4e)-hexa-2,4-dienamide Chemical compound C\C=C\C=C\C(N)=O JPXCVMIARYLSGU-MQQKCMAXSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-heat-conductivity high-strength composite material for flexibility modification of a circulating fluidized bed boiler, which comprises the following components in parts by mass: 15 to 20 portions of corundum fine powder specification mixture, 3 to 7 portions of zirconium diboride with the grain diameter of 0.005 to 0.025mm, 5 to 8 portions of nano silicon dioxide, 8 to 10 portions of silicon carbide fine powder with the SiC content of more than 98 percent, 1 to 3 portions of quartz powder, 3 to 6 portions of graphene, 10 to 15 portions of alumina fine powder, 3 to 7 portions of barium metaborate, curing agent5 to 7 portions of organic adhesive, 3 to 5 portions of organic adhesive, 1 to 2 portions of composite stabilizer, 5 to 7 portions of silica sol, 2 to 5 portions of sodium nitrite and FeCl 2 1 to 3 parts of polar solvent, 5 to 8 parts of polyamine compound, 5 to 10 parts of polyether modified silicone oil, 0.2 to 0.5 part of explosion-proof fiber, 1 to 3 parts of modified white clay, 3 parts of pure water, 2 to 5 parts of calcium carbonate powder and 8 to 10 parts of pure calcium aluminate cement, thus solving the problem of poor adaptability of the inner wall raw material of the existing fluidized bed.
Description
Technical Field
The invention relates to the technical field of boiler materials of coal-fired power stations, in particular to a high-heat-conductivity high-strength composite material for flexibly reforming a circulating fluidized bed boiler and a preparation method thereof.
Background
The circulating fluidized bed is a novel coal-fired boiler, coal is crushed into particles with the particle size of less than 10mm and then is introduced into a hearth, the coal and inert high-temperature materials in the hearth are fully mixed through air distribution at the bottom of the hearth to form fluidized combustion, a gas-solid separation device is arranged in the subsequent process, and the incompletely combusted coal particles are collected and then continuously combusted. The circulating fluidized bed boiler has the advantages that fuel can be fully utilized, compared with a pulverized coal furnace, the aim of fully combusting and utilizing coal can be achieved without high-quality crushing of the coal fuel, the circulating fluidized bed boiler has low requirement on the quality of the fuel, and inferior fuel can be fully combusted in the boiler.
In recent years, the problem of wind abandoning (light and water) is increasingly serious, and the contradiction between heat supply and power supply is prominent. However, renewable energy sources (such as solar energy, wind energy and water energy) are greatly influenced by natural factors, and power generation is unstable, so that the power system cannot guarantee the safety of a power grid by only relying on the renewable energy sources for power generation. In order to fully and preferentially consume renewable energy power generation, solve the problems of light abandonment, wind abandonment and water abandonment and maintain the safety and stability of a power grid, the coal-fired boiler can utilize the flexible and stable characteristics to undertake deep peak regulation more.
The circulating fluidized bed combustion technology is a reliable technology which accords with the development of clean energy, and a circulating fluidized bed boiler relying on the technology is widely applied in China and is one of main thermal power for undertaking a deep peak regulation task. When the power generation amount of the renewable energy is high, the circulating fluidized bed unit reduces the power generation amount and keeps running under a lower load; when the power generation amount of the renewable energy source is low, the circulating fluidized bed unit improves the power generation amount and keeps running under a higher load. The current circulating fluidized bed unit becomes the operation normality by a wide margin with variable load, therefore the further requirement unit of degree of depth peak shaving not only will improve load response rate at the in-process that becomes the load by a wide margin, still guarantee that each operating parameter is in reasonable within range, ensure unit safe operation, based on this, this just requires to act as circulating fluidized bed's interior lining material and should possess stronger heat conductivility, can high-efficient and rapid heating up heat transfer at circulating fluidized bed unit high load operation in-process, in low-load operation in-process, then will realize quick heat dissipation, and traditional circulating fluidized bed interior lining material is difficult to satisfy this kind of requirement.
In addition, in the working process of the circulating fluidized bed, fuel can move at a high speed in the fluidized bed to impact the inner wall of the fluidized bed, so as to improve the working safety of the fluidized bed, a layer of wear-resistant refractory material can be poured on the inner wall of the fluidized bed to achieve the protection effect, in the actual production process, a high-heat-conduction material is required to be poured on a water wall and other parts of a boiler, so that the refractory material at the part needs to have good heat conduction effects besides the effects of fire resistance and high temperature resistance, and in order to solve the problem, a corresponding material scheme is provided in the prior art, for example, 201910963427.4 is a high-heat-conduction wear-resistant material for the circulating fluidized bed boiler, but because the fuel doped with biomass is adopted, the biomass is abundant in variety and different in physicochemical properties, the adaptability of the raw material of the inner wall of the existing boiler is poor, the heat conduction and strength requirements on the material are high, the prior art is still deficient in this respect, and simultaneously, a large amount of slag adhering to the inner wall can be generated in the fuel combustion process, the corrosion resistance and the oxidation resistance can not be guaranteed, and the service life of the boiler can be reduced.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention is provided in view of the problems of the existing fluidized bed inner wall pouring material.
Therefore, the technical problem solved by the invention is as follows: the problems that the adaptability of the raw materials on the inner wall of the existing fluidized bed is poor, the heat conductivity and the strength are not high, a large amount of slag is easy to be generated and adhered to the inner wall, the corrosion resistance and the oxidation resistance can not be guaranteed, and the service life of a boiler is shortened are solved.
In order to solve the technical problems, the invention provides the following technical scheme: a high-heat-conductivity high-strength composite material for flexibility transformation of a circulating fluidized bed boiler comprises the following components in parts by mass: 15 to 20 portions of corundum fine powder specification mixture, 3 to 7 portions of zirconium diboride with the grain diameter of 0.005 to 0.025mm, 5 to 8 portions of nano silicon dioxide and SiC content>8 to 10 portions of 98 percent silicon carbide fine powder, 1 to 3 portions of quartz powder, 3 to 6 portions of graphene, 10 to 15 portions of alumina fine powder, 3 to 7 portions of barium metaborate, 5 to 7 portions of curing agent, 3 to 5 portions of organic adhesive, 1 to 2 portions of composite stabilizer, 5 to 7 portions of silica sol, 2 to 5 portions of sodium nitrite, feCl 2 1 to 3 parts of polar solvent, 5 to 8 parts of polyamine compound, 1 to 5 parts of polyether modified silicone oil, 0.2 to 0.5 part of explosion-proof fiber, 1 to 3 parts of modified white clay, 3 parts of pure water, 2 to 5 parts of calcium carbonate powder and 8 to 10 parts of pure calcium aluminate cement.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the corundum fine powder specification mixture specifically comprises: 40 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 35 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 25 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm; or 20 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 45 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 35 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the curing agent is any one of sorbate, sorbamide, sodium silicate and zinc fluoborate.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the organic adhesive comprises 10-35 wt% of organic resin and 65-90 wt% of organic solvent.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the polar solvent is one or a mixture of more of DPG, PG and DPMA.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
As a preferred scheme of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, the invention comprises the following steps: the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
In order to solve the technical problems, the invention also provides the following technical scheme: a preparation method of a high-heat-conductivity and high-strength composite material for flexibility improvement of a circulating fluidized bed boiler comprises the following steps:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) The main material A, the binding agent B, the curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, and regulating the pH to be 12000-16000 r/min at normal temperatureReacting at a rotating speed for 30min, and adding an organic adhesive to obtain the adhesive.
The invention has the beneficial effects that:
1. the invention provides a high-heat-conductivity high-strength composite material for flexibility modification of a circulating fluidized bed boiler, which is characterized in that materials with high heat-conductivity effects, such as nano silicon dioxide, graphene, alumina fine powder, zirconium diboride, silicon carbide fine powder and the like, which are added into main materials have good heat-conductivity effects, and the thermal stability and corrosion resistance are improved, so that air holes are not easy to form after the materials are used, and the surface density and the smoothness can be improved; the corundum fine powder specification mixture, the quartz powder, the pure calcium aluminate cement and other materials with fire-resistant and wear-resistant effects are added, so that the high-temperature-resistant corundum cement has good high-temperature-resistant characteristics;
2. in the process of preparing the bonding agent, the barium metaborate is added into the silica sol and the polyether modified silicone oil, so that the barium metaborate has the characteristics of low apparent porosity and good self-lubricating property;
3. modified Bai Niantu and explosion-proof fiber are added, wherein the modified Bai Niantu is uniformly dispersed in pure calcium aluminate cement during subsequent mixing, the formation of a fibrous CSH gel mesh structure is accelerated, and the coagulation of the cement is accelerated by matching polyether modified silicone oil, so that the strength of the lining at the initial pouring stage is improved, and internal bubbles and surface cracks generated by initial dehydration are avoided;
4. by adding zirconium diboride, the material has stronger oxidation resistance at high temperature, higher thermal shock stability and abrasion resistance, has the effects of strengthening and toughening the whole material by matching with graphene, greatly improves the strength of the material, has stronger heat conductivity by taking the zirconium diboride as a ceramic-based material, also has higher heat conductivity by taking the graphene as the ceramic-based material, and can effectively improve the heat conductivity of the whole material by uniformly dispersing the zirconium diboride and the graphene in the material;
5. the polyamine compound is subjected to polycondensation at high temperature to obtain a poly-fused substance, so that the mixing property and the caking property are improved for the addition of a subsequent mixed matrix substance; the organic adhesive increases the viscosity of the coating; meanwhile, the electrode catalyzes the shearing liquid, partial polar solvent and amine ions to accelerate the decomposition of ions in the sodium nitrite, so that the ions in the sodium nitrite accelerate the divalent Fe 2+ The polarization is carried out, and the polarization is carried out,the high-strength slagging-resistant product is obtained, the oxidation resistance of the product is further improved by electrode catalysis, and the corrosion resistance and the oxidation resistance of the material are improved.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanying specific embodiments of the present invention are described in detail below, and it is apparent that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
The biomass-doped fuel is adopted, the biomass is very rich in variety, and the physical and chemical properties of the biomass are different, so that the adaptability of the raw material of the inner wall of the existing fluidized bed boiler is poor, the requirements on the heat conductivity and the strength of the material are high, the prior art is still deficient in the aspect, a large amount of slag can be generated in the combustion process of the fuel and adhered to the inner wall, the corrosion resistance and the oxidation resistance cannot be guaranteed, and the service life of the boiler is shortened.
Therefore, in order to solve the above problems, the present invention provides a high thermal conductivity and high strength composite material for flexibly modifying a circulating fluidized bed boiler and a preparation method thereof, please refer to the following embodiments:
example (b):
example 1
The invention provides a high-heat-conductivity high-strength composite material for flexibly reforming a circulating fluidized bed boiler, which comprises the following components in parts by mass: 15 portions of corundum fine powder specification mixture, 3 portions of zirconium diboride with grain diameter of 0.005-0.025 mm, 5 portions of nano silicon dioxide and SiC content>8 parts of 98 percent silicon carbide fine powder, 1 part of quartz powder, 3 parts of graphene, 10 parts of alumina fine powder, 3 parts of barium metaborate, 5 parts of curing agent, 3 parts of organic adhesive, 1 part of composite stabilizer, 5 parts of silica sol, 2 parts of sodium nitrite and FeCl 2 1.5 parts of polar solvent, 5 parts of polyamine compound, 1 part of polyether modified silicone oil, 0.2 part of explosion-proof fiber, 1 part of modified white clay, 3 parts of pure water, 2 parts of calcium carbonate powder and pure water8 parts of calcium aluminate cement.
Further, the corundum fine powder specification mixture specifically comprises: 40 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 35 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 25 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm.
Wherein the corundum fine powder is fused zirconia corundum; the curing agent is sorbate; the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/1; the polar solvent is DPG; the polyamine compound is N-aminoethylpiperazine.
Further, the organic binder includes 10 to 35wt% of an organic resin and 65 to 90wt% of an organic solvent.
Further, the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
The invention also provides a preparation method of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, which comprises the following steps:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) The main material A, the binding agent B, the curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, reacting at the normal temperature at the rotating speed of 12000-16000 r/min for 30min, and adding organic bondingThe preparation is successfully prepared.
Wherein the pH regulator is sodium bicarbonate with 3% purity.
Additionally, the alumina fines particle size is less than 0.044mm 2 O 3 The content is more than or equal to 99.5wt%; the grain diameter of the pure calcium aluminate cement is less than 200 meshes, and Al 2 O 3 The content is more than 75wt%.
The preparation method of the modified white clay comprises the following steps:
s1, preparing a saturated calcium nitrate aqueous solution, completely immersing white clay in the saturated calcium nitrate aqueous solution, carrying out ultrasonic treatment for 10-20min, and filtering to obtain wet white clay;
s2, adding sodium silicate and the white clay obtained by processing in the step S1 into a ball mill, wherein the weight ratio of the white clay to the sodium silicate is 20: 0.5-1, ball milling for 1-2 h by a ball mill at the rotating speed of 300-600 r/min to obtain a CSH gel polymer taking white clay as a carrier;
s3, preparing a saturated sodium silicate aqueous solution, adding the CSH gel polymer which is obtained in the previous step and takes the white clay as a carrier into the saturated sodium silicate aqueous solution, and stirring, mixing and reacting for 1.5-2 h;
and S4, filtering the mixture obtained in the previous step to obtain a filter cake, washing the filter cake with deionized water, filtering again, repeating for 3-7 times, drying the filter cake, and crushing to obtain the modified white clay.
Example 2
The invention provides a high-heat-conductivity high-strength composite material for flexibly reforming a circulating fluidized bed boiler, which is characterized by comprising the following components in parts by mass: 20 parts of corundum fine powder specification mixture, 7 parts of zirconium diboride with the grain diameter of 0.005-0.025 mm, 8 parts of nano silicon dioxide and SiC content>10 parts of 98% silicon carbide fine powder, 3 parts of quartz powder, 6 parts of graphene, 15 parts of alumina fine powder, 7 parts of barium metaborate, 7 parts of curing agent, 5 parts of organic adhesive, 2 parts of composite stabilizer, 7 parts of silica sol, 5 parts of sodium nitrite and FeCl 2 3 parts of polar solvent, 8 parts of polyamine compound, 5 parts of polyether modified silicone oil, 0.5 part of explosion-proof fiber, 3 parts of modified white clay, 3 parts of pure water, 5 parts of calcium carbonate powder and 10 parts of pure calcium aluminate cement。
Wherein, the corundum fine powder specification mixture specifically comprises: 20 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 45 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 35 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm.
Specifically, the corundum fine powder is fused plate-shaped corundum; the curing agent is sorbic amide; the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l; the polar solvent is PG; the polyamine compound is diethylenetriamine.
Further, the organic binder includes 10 to 35wt% of an organic resin and 65 to 90wt% of an organic solvent.
Furthermore, the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
The invention also provides a preparation method of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, which comprises the following steps:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) The main material A, the binding agent B, the curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, reacting at the normal temperature at the rotating speed of 12000-16000 r/min for 30min, and adding an organic adhesive to obtain the high-shear emulsion.
Wherein the pH regulator is sodium bicarbonate with 3% purity.
Additionally, the alumina fines particle size is less than 0.044mm 2 O 3 The content is more than or equal to 99.5wt%; the grain diameter of the pure calcium aluminate cement is less than 200 meshes, and Al 2 O 3 The content is more than 75wt%.
The preparation method of the modified white clay comprises the following steps:
s1, preparing a saturated calcium nitrate aqueous solution, completely immersing white clay in the saturated calcium nitrate aqueous solution, carrying out ultrasonic treatment for 10-20min, and filtering to obtain wet white clay;
s2, adding sodium silicate and the white clay obtained by processing in the step S1 into a ball mill, wherein the weight ratio of the white clay to the sodium silicate is 20: 0.5-1, ball milling for 1-2 h by a ball mill at the rotating speed of 300-600 r/min to obtain a CSH gel polymer taking white clay as a carrier;
s3, preparing a saturated sodium silicate aqueous solution, adding the CSH gel polymer which is obtained in the previous step and takes the white clay as a carrier into the saturated sodium silicate aqueous solution, and stirring, mixing and reacting for 1.5-2 h;
and S4, filtering the mixture obtained in the last step to obtain a filter cake, washing the filter cake with deionized water, filtering again, repeating for 3-7 times, drying the filter cake, and crushing to obtain the modified white clay.
Example 3
The invention provides a high-heat-conductivity high-strength composite material for flexibly reforming a circulating fluidized bed boiler, which comprises the following components in parts by mass: 18 parts of corundum fine powder specification mixture, 5 parts of zirconium diboride with the grain diameter of 0.005-0.025 mm, 6 parts of nano silicon dioxide and SiC content>9 parts of 98 percent silicon carbide fine powder, 2 parts of quartz powder, 4 parts of graphene, 13 parts of alumina fine powder, 5 parts of barium metaborate, 6 parts of curing agent, 4 parts of organic adhesive, 2 parts of composite stabilizer, 6 parts of silica sol, 3 parts of sodium nitrite and FeCl 2 2. The material comprises the following components of 7 parts of polar solvent, 8 parts of polyamine compound, 3 parts of polyether modified silicone oil, 0.3 part of explosion-proof fiber, 2 parts of modified white clay, 3 parts of pure water, 3 parts of calcium carbonate powder and 9 parts of pure calcium aluminate cement.
Wherein, the corundum fine powder specification mixture specifically comprises: 40 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 35 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 25 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm.
Specifically, the corundum fine powder is fused zirconia corundum; the curing agent is sodium silicate; the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l; the polar solvent is DPMA; the polyamine compound is triethylene tetramine.
Further, the organic binder comprises 10-35 wt% of organic resin and 65-90 wt% of organic solvent;
further, the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
The invention also provides a preparation method of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, which comprises the following steps:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) The main material A, the binding agent B, the curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, reacting at the normal temperature at the rotating speed of 12000-16000 r/min for 30min, and adding an organic adhesive to obtain the high-shear emulsion.
Wherein the pH regulator is sodium bicarbonate with 3% purity.
Additionally, the alumina fine powder has a particle size of less than 0.044mm 2 O 3 The content is more than or equal to 99.5wt%; the grain diameter of the pure calcium aluminate cement is less than 200 meshes, and Al 2 O 3 The content is more than 75wt%.
The preparation method of the modified white clay comprises the following steps:
s1, preparing a saturated calcium nitrate aqueous solution, completely immersing white clay in the saturated calcium nitrate aqueous solution, carrying out ultrasonic treatment for 10-20min, and filtering to obtain wet white clay;
s2, adding sodium silicate and the white clay obtained by processing in the step S1 into the ball mill, wherein the weight ratio of the white clay to the sodium silicate is 20: 0.5-1, ball milling for 1-2 h by a ball mill at the rotating speed of 300-600 r/min to obtain a CSH gel polymer taking white clay as a carrier;
s3, preparing a saturated sodium silicate aqueous solution, adding the CSH gel polymer which is obtained in the previous step and takes the white clay as a carrier into the saturated sodium silicate aqueous solution, and stirring, mixing and reacting for 1.5-2 h;
and S4, filtering the mixture obtained in the previous step to obtain a filter cake, washing the filter cake with deionized water, filtering again, repeating for 3-7 times, drying the filter cake, and crushing to obtain the modified white clay.
Example 4
The invention provides a high-heat-conductivity high-strength composite material for flexibly reforming a circulating fluidized bed boiler, which comprises the following components in parts by mass: 16 portions of corundum fine powder specification mixture, 4 portions of zirconium diboride with grain diameter of 0.005-0.025 mm, 7 portions of nano silicon dioxide and SiC content>8 parts of 98% silicon carbide fine powder, 3 parts of quartz powder, 5 parts of graphene, 14 parts of alumina fine powder, 6 parts of barium metaborate, 7 parts of curing agent, 5 parts of organic adhesive, 1 part of composite stabilizer, 5 parts of silica sol, 4 parts of sodium nitrite and FeCl 2 3. The material comprises, by weight, 6 parts of a polar solvent, 9 parts of a polyamine compound, 4 parts of polyether modified silicone oil, 0.4 part of an explosion-proof fiber, 3 parts of modified white clay, 3 parts of pure water, 4 parts of calcium carbonate powder and 8 parts of pure calcium aluminate cement.
Wherein, the corundum fine powder specification mixture specifically comprises: 20 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 45 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 35 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm.
Specifically, the corundum fine powder is fused zirconia corundum; the curing agent is zinc fluoborate; the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l; the polar solvent is DPG; the polyamine compound is tetraethylenepentamine.
Further, the organic binder comprises 10 to 35wt% of organic resin and 65 to 90wt% of organic solvent.
Further, the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
The invention also provides a preparation method of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, which comprises the following steps of:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) Main material A, binding agent B, curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, reacting at the normal temperature at the rotating speed of 12000-16000 r/min for 30min, and adding an organic adhesive to obtain the high-shear emulsion.
Wherein the pH regulator is sodium bicarbonate with 3% purity.
Additionally, the alumina fines particle size is less than 0.044mm 2 O 3 The content is more than or equal to 99.5wt%; the grain diameter of the pure calcium aluminate cement is less than 200 meshes, and Al 2 O 3 The content is more than 75wt%.
The preparation method of the modified white clay comprises the following steps:
s1, preparing a saturated calcium nitrate aqueous solution, completely immersing white clay in the saturated calcium nitrate aqueous solution, carrying out ultrasonic treatment for 10-20min, and filtering to obtain wet white clay;
s2, adding sodium silicate and the white clay obtained by processing in the step S1 into a ball mill, wherein the weight ratio of the white clay to the sodium silicate is 20: 0.5-1, ball milling for 1-2 h by a ball mill at the rotating speed of 300-600 r/min to obtain a CSH gel polymer taking white clay as a carrier;
s3, preparing a saturated sodium silicate aqueous solution, adding the CSH gel polymer which is obtained in the previous step and takes the white clay as a carrier into the saturated sodium silicate aqueous solution, and stirring, mixing and reacting for 1.5-2 h;
and S4, filtering the mixture obtained in the last step to obtain a filter cake, washing the filter cake with deionized water, filtering again, repeating for 3-7 times, drying the filter cake, and crushing to obtain the modified white clay.
Example 5
The invention provides a high-heat-conductivity high-strength composite material for flexibly reforming a circulating fluidized bed boiler, which is characterized by comprising the following components in parts by mass: 19 parts of corundum fine powder specification mixture, 5 parts of zirconium diboride with the grain diameter of 0.005-0.025 mm, 8 parts of nano silicon dioxide and SiC content>10 parts of 98% silicon carbide fine powder, 1 part of quartz powder, 5 parts of graphene, 13 parts of alumina fine powder, 6 parts of barium metaborate, 5 parts of curing agent, 3 parts of organic adhesive, 1 part of composite stabilizer, 7 parts of silica sol, 4 parts of sodium nitrite and FeCl 2 1 part, 7 parts of polar solvent, 9 parts of polyamine compound, 4 parts of polyether modified silicone oil, 0.3 part of explosion-proof fiber, 3 parts of modified white clay, 3 parts of pure water, 3 parts of calcium carbonate powder and 10 parts of pure calcium aluminate cement.
Wherein, the corundum fine powder specification mixture specifically comprises: 40% of corundum fine powder with a particle size of 0.075-0.1 mm, 35% of corundum fine powder with a particle size of 0.5-1.2 mm and 25% of corundum fine powder with a particle size of 1.5-2.6 mm
Specifically, the corundum fine powder is fused zirconia corundum; the curing agent is sodium silicate; the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l; the polar solvent is DPMA; the polyamine compound is diethylenetriamine.
Further, the organic binder comprises 10 to 35wt% of organic resin and 65 to 90wt% of organic solvent.
Furthermore, the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
The invention also provides a preparation method of the high-heat-conductivity high-strength composite material for flexibly reforming the circulating fluidized bed boiler, which comprises the following steps of:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and adding N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) The main material A, the binding agent B, the curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, reacting at the normal temperature at the rotating speed of 12000-16000 r/min for 30min, and adding an organic adhesive to obtain the high-shear emulsion.
Wherein the pH regulator is sodium bicarbonate with 3% purity.
Additionally, oxygenThe granularity of the fine aluminum powder is less than 0.044mm 2 O 3 The content is more than or equal to 99.5wt%; the grain diameter of the pure calcium aluminate cement is less than 200 meshes, and Al 2 O 3 The content is more than 75wt%.
The preparation method of the modified white clay comprises the following steps:
s1, preparing a saturated calcium nitrate aqueous solution, completely immersing white clay in the saturated calcium nitrate aqueous solution, carrying out ultrasonic treatment for 10-20min, and filtering to obtain wet white clay;
s2, adding sodium silicate and the white clay obtained by processing in the step S1 into a ball mill, wherein the weight ratio of the white clay to the sodium silicate is 20: 0.5-1, ball milling for 1-2 h by a ball mill at the rotating speed of 300-600 r/min to obtain a CSH gel polymer taking white clay as a carrier;
s3, preparing a saturated sodium silicate aqueous solution, adding the CSH gel polymer which is obtained in the previous step and takes the white clay as a carrier into the saturated sodium silicate aqueous solution, and stirring, mixing and reacting for 1.5-2 h;
and S4, filtering the mixture obtained in the last step to obtain a filter cake, washing the filter cake with deionized water, filtering again, repeating for 3-7 times, drying the filter cake, and crushing to obtain the modified white clay.
Comparative example
COMPARATIVE EXAMPLE 1
The basic physicochemical properties of the composite material obtained according to the invention were first evaluated by means of application tests:
during manufacturing, the prepared coating is subjected to fluidized bed boiler lining construction, a stable coating is formed after 3 days, and the performance parameters of the lining are shown in a table 1:
table 1: project parameters (physical and chemical properties of sintering lining)
COMPARATIVE EXAMPLE 2
The corrosion resistance of the composite material produced according to the invention is evaluated again below by means of an application test from another angle, loss rate:
the evaluation basis is as follows: the corrosion resistance of the composite material is detected according to GB/T17601-2008 test method for sulfuric acid corrosion resistance of refractory materials.
A sample prepared according to the specified method is put into sulfuric acid with the boiling mass fraction of 70% for corrosion for 6h, then the mass loss amount is measured, and the sulfuric acid corrosion resistance rate is expressed by the percentage of the mass loss amount of the sample to the initial mass.
The data are recorded as in table 3 below:
table 3: corrosion resistance related properties
| Sample (I) | Initial mass/g | Final mass/g | Loss amount per g | Erosion rate/%) |
| Example 1 | 20 | 19.95 | 0.05 | 0.25 |
| Example 2 | 20 | 19.93 | 0.07 | 0.35 |
| Example 3 | 20 | 19.88 | 0.12 | 0.60 |
| Example 4 | 20 | 19.83 | 0.17 | 0.85 |
| Example 5 | 20 | 19.44 | 0.56 | 2.80 |
| Existing products | 20 | 17.31 | 2.69 | 13.45 |
COMPARATIVE EXAMPLE III
Selecting the prior common antioxidant: zinc dialkyldithiophosphate (ZDDP), dialkyldithiocarbamate (ADTC), and dialkyldithiophosphate (ADDP) were added as comparative antioxidants to equal parts of the coating to verify a uniform synthetic environment.
1. Pressurized differential calorimetry (PDSC) test; the determination was made according to ASTM D6186-1998 using a standard test method for measuring the oxidation induction time of different coatings using pressure differential scanning calorimetry (PSDC).
2. Rotary pressurized vessel oxidation test: according to the determination of the national standard ASTM D2272-2009, the antioxidant characteristics of the paint synthesized by the invention and the paint added with the existing antioxidant are considered, and the longer the time is, the better the antioxidant effect is.
3. The detergency test: according to SH/T0269-1992, the results are classified into seven grades 0-6. No. 0 is cleanest, color is lightest, no. 6 is dirtiest, and the smaller the number, the better the detergency.
The comparative results are shown in Table 2:
table 2: conventional performance comparison table
As can be seen from Table 2 above, the antioxidant stability of the present invention is superior to that of the conventional inner wall coating.
The invention has the beneficial effects that:
1. the invention provides a high-heat-conductivity high-strength composite material for flexibility modification of a circulating fluidized bed boiler, which is characterized in that materials with high heat-conductivity effects, such as nano silicon dioxide, graphene, alumina fine powder, zirconium diboride, silicon carbide fine powder and the like, which are added into main materials have good heat-conductivity effects, and the thermal stability and corrosion resistance are improved, so that air holes are not easy to form after the materials are used, and the surface density and the smoothness can be improved; the corundum fine powder specification mixture, quartz powder, pure calcium aluminate cement and other materials with fireproof and wear-resistant effects are added, so that the material has good high-temperature resistance;
2. in the process of preparing the bonding agent, the barium metaborate is added into the silica sol and the polyether modified silicone oil, so that the barium metaborate has the characteristics of low apparent porosity and good self-lubricating property;
3. modified Bai Niantu and explosion-proof fiber are added, wherein the modified Bai Niantu is uniformly dispersed in pure calcium aluminate cement during subsequent mixing, the formation of a fibrous CSH gel mesh structure is accelerated, and the coagulation of the cement is accelerated by matching polyether modified silicone oil, so that the strength of the lining at the initial pouring stage is improved, and internal bubbles and surface cracks generated by initial dehydration are avoided;
4. by adding zirconium diboride, the material has stronger oxidation resistance at high temperature, higher thermal shock stability and abrasion resistance, has the effects of strengthening and toughening the whole material by matching with graphene, greatly improves the strength of the material, has stronger heat conductivity by taking the zirconium diboride as a ceramic-based material, also has higher heat conductivity by taking the graphene as the ceramic-based material, and can effectively improve the heat conductivity of the whole material by uniformly dispersing the zirconium diboride and the graphene in the material;
5. the polyamine compound is subjected to polycondensation at high temperature to obtain a poly-fused substance, so that the mixing property and the caking property are improved for the addition of a subsequent mixed matrix substance; the organic adhesive increases the viscosity of the coating; meanwhile, the electrode catalyzes the shearing liquid, partial polar solvent and amine ions to accelerate the decomposition of ions in the sodium nitrite, so that the ions in the sodium nitrite accelerate the divalent Fe 2+ And (3) polarizing to obtain a high-strength slagging-resistant product, and further increasing the oxidation resistance of the product by electrode catalysis, thereby improving the corrosion resistance and oxidation resistance of the material.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. The high-heat-conductivity high-strength composite material for flexibility reformation of the circulating fluidized bed boiler is characterized by comprising the following components in parts by mass: 15 to 20 portions of corundum fine powder specification mixture, 3 to 7 portions of zirconium diboride with the grain diameter of 0.005 to 0.025mm, 5 to 8 portions of nano-silica, 8 to 10 portions of silicon carbide fine powder with SiC content of more than 98 percent, 1 to 3 portions of quartz powder, 3 to 6 portions of graphene, 10 to 15 portions of alumina fine powder, 3 to 7 portions of barium metaborate, 5 to 7 portions of curing agent, 3 to 5 portions of organic adhesive, 1 to 2 portions of composite stabilizer, 5 to 7 portions of silica sol, 2 to 5 portions of sodium nitrite, feCl 2 1 to 3 portions of polar solvent, 5 to 8 portions of polar solvent, 5 to 10 portions of polyamine compound, 1 to 5 portions of polyether modified silicone oil and 0.2 to 0.5 portion of explosion-proof fiber1 to 3 portions of modified white clay, 3 portions of pure water, 2 to 5 portions of calcium carbonate powder and 8 to 10 portions of pure calcium aluminate cement.
2. The high thermal conductivity and high strength composite material for flexible modification of a circulating fluidized bed boiler according to claim 1, wherein the corundum fine powder specification mixture specifically comprises: 40 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 35 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 25 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm; or 20 percent of corundum fine powder with the grain diameter of 0.075-0.1 mm, 45 percent of corundum fine powder with the grain diameter of 0.5-1.2 mm and 35 percent of corundum fine powder with the grain diameter of 1.5-2.6 mm.
3. The high thermal conductivity high strength composite material for flexibility modification of a circulating fluidized bed boiler according to claim 2, wherein: the curing agent is any one of sorbate, sorbic amide, sodium silicate and zinc fluoborate.
4. The high thermal conductivity and high strength composite material for flexible modification of a circulating fluidized bed boiler according to claim 3, wherein: the organic adhesive comprises 10-35 wt% of organic resin and 65-90 wt% of organic solvent.
5. The high thermal conductivity high strength composite material for flexibility modification of a circulating fluidized bed boiler according to claim 4, wherein: the composite stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l.
6. The high thermal conductivity high strength composite material for flexibility modification of a circulating fluidized bed boiler according to claim 5, wherein: the polar solvent is one or a mixture of more of DPG, PG and DPMA.
7. The high thermal conductivity high strength composite material for flexibility modification of a circulating fluidized bed boiler according to claim 6, wherein: the polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
8. The high thermal conductivity high strength composite material for flexibility modification of a circulating fluidized bed boiler of claim 7, wherein: the chemical structural formula of the polyether modified silicone oil is as follows:
R(CH 3 ) 2 SiO[(CH 3 )RSiO] m SiR(CH 3 ) 2 wherein R is a polyether chain segment.
9. A preparation method of the high-heat-conductivity high-strength composite material for the flexible modification of the circulating fluidized bed boiler, which is described in the claims 1-8, is characterized by comprising the following steps:
(1) Preparation of main materials: starting stirring, mixing the corundum fine powder specification mixture, nano silicon dioxide, quartz powder, explosion-proof fiber, modified white clay, zirconium diboride, graphene, calcium carbonate powder, alumina fine powder, silicon carbide fine powder and pure calcium aluminate cement at normal temperature, and stirring for more than 1h to obtain a main material A;
(2) Preparing a binding agent: starting stirring, sequentially adding polyamine compound and polar solvent into the reaction kettle, starting stirring, and N 2 Heating to 120 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous phase mixed solution, adding a composite stabilizer, continuously stirring for 1h, cooling to 80 ℃, adding barium metaborate, silica sol, polyether modified silicone oil and pure water, and stirring for 30min at a temperature maintained to obtain a binding agent B;
(3) The main material A, the binding agent B, the curing agent and FeCl 2 Adding the mixture into a high shear emulsifying machine, adding a pH regulator to regulate the pH to be 5-7, externally connecting an electrode catalytic system with a 24V power supply, adding sodium nitrite, reacting at the normal temperature at the rotating speed of 12000-16000 r/min for 30min, and adding an organic adhesive to obtain the high-shear emulsion.
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