CN114853486A - Preparation method of thermal shock resistance composite nozzle brick - Google Patents
Preparation method of thermal shock resistance composite nozzle brick Download PDFInfo
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- CN114853486A CN114853486A CN202210438844.9A CN202210438844A CN114853486A CN 114853486 A CN114853486 A CN 114853486A CN 202210438844 A CN202210438844 A CN 202210438844A CN 114853486 A CN114853486 A CN 114853486A
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- 239000011449 brick Substances 0.000 title claims abstract description 70
- 230000035939 shock Effects 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000004927 clay Substances 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 40
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 40
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 40
- JBQATDIMBVLPRB-UHFFFAOYSA-N isoliquiritigenin Natural products OC1=CC(O)=CC=C1C1OC2=CC(O)=CC=C2C(=O)C1 JBQATDIMBVLPRB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000008718 isoliquiritigenin Nutrition 0.000 claims abstract description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 15
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims abstract description 6
- 238000007654 immersion Methods 0.000 claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 33
- DXDRHHKMWQZJHT-FPYGCLRLSA-N isoliquiritigenin Chemical compound C1=CC(O)=CC=C1\C=C\C(=O)C1=CC=C(O)C=C1O DXDRHHKMWQZJHT-FPYGCLRLSA-N 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims 1
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 abstract description 26
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 239000011819 refractory material Substances 0.000 abstract description 8
- -1 isoliquiritigenin modified phenolic resin Chemical class 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 17
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
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- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
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Abstract
The invention discloses a preparation method of a thermal shock resistant composite nozzle brick, and relates to the technical field of refractory materials. The method adopts isoliquiritigenin modified phenolic resin as a binder, uses (-) -epigallocatechin modified rosin resin as an antioxidant, adds bauxite chamotte, semi-soft clay, zirconium dioxide and clay chamotte for mixing, and performs pressurization molding, drying, firing, vacuum oil immersion, carbonization and polishing to prepare the thermal shock resistance composite nozzle brick which has the characteristics of low porosity, high volume density, good thermal shock resistance stability and good oxidation resistance.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a preparation method of a thermal shock resistant composite nozzle brick.
Background
From the 80 s in China, carbon-containing refractory materials are greatly developed, the variety of the carbon-containing refractory materials is more and more, the carbon-containing refractory materials comprise magnesium carbon, aluminum magnesium carbon, aluminum zirconium carbon and the like, and the aluminum carbon and aluminum zirconium carbon sliding nozzle bricks are widely applied to continuous casting ladles. The use of the sliding water bricks is a great innovation of the steelmaking ingot casting process, and only saddle steel can save refractory materials every year, improve the working environment and greatly reduce the labor intensity. In the steel making process, the nozzle brick is damaged not only by the chemical action of the liquid metal and the slag but also by physical actions such as cracking and flaking due to the rapid thermal shock of the molten metal and wear of the liquid metal, so that in order to allow a stable operation of the nozzle brick, refractory materials that are very resistant to thermal shock and erosion must be used for the manufacture of the nozzle brick. With the development of steel-making technology, the requirements on the sliding nozzle brick are increasingly improved, and especially higher requirements on thermal shock resistance, erosion resistance, high-temperature structural strength and high-temperature wear resistance are provided. However, production practices show that along with the rise of temperature, volatile components of the binding agent are dissipated, part of closed pores are communicated, the apparent porosity is multiplied, the structure is weakened, and the strength is reduced, so that the oxidation resistance, molten steel scouring resistance and corrosion resistance of the product are adversely affected.
The invention provides a preparation method of a thermal shock resistant composite nozzle brick, thermosetting resin is added into an aluminum zirconium carbon sliding nozzle brick, the defect that the existing nozzle brick material is easy to oxidize is overcome, and the nozzle brick prepared by the invention has low porosity, high volume density, good thermal shock resistance stability and good oxidation resistance.
Disclosure of Invention
The invention aims to provide a preparation method of a thermal shock resistant composite nozzle brick, and the composite nozzle brick prepared by the method has the characteristics of low porosity, high volume density, good thermal shock resistance stability and good oxidation resistance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a thermal shock resistant composite nozzle brick comprises the following steps:
s1: adding a binder and an antioxidant into the raw materials, and mixing;
s2: pressure forming and drying;
s3: firing by adopting a flame-proof protection process, vacuum oil-immersing, carbonizing and polishing to prepare the thermal shock resistant composite nozzle brick;
the raw materials comprise bauxite chamotte, semi-soft clay, zirconium dioxide and clay chamotte; the binder comprises a modified phenolic resin; the modified phenolic resin is obtained by modifying phenolic resin with isoliquiritigenin.
The invention provides a preparation method of a thermal shock resistance composite nozzle brick, which takes modified phenolic resin as a binder and rosin resin as an antioxidant, adds the modified phenolic resin and the rosin resin into bauxite clinker, semi-soft clay, zirconium dioxide and clay clinker, mixes the two, adopts a press machine to press, form and dry the mixture, does not contact with flame to carry out firing, then carries out vacuum oil immersion treatment, further improves the carbon content of a product, and after carbonization and polishing, the prepared thermal shock resistance composite nozzle brick has the characteristics of low porosity, high volume density, good thermal shock resistance stability and good oxidation resistance; in the preparation process of the composite nozzle brick, isoliquiritigenin is adopted to modify phenolic resin, so that the performance of the composite nozzle brick is further improved, probably because more isoliquiritigenin reacts with formaldehyde, the content of free aldehyde is reduced, and a three-dimensional network with better cross-linking property is formed.
Specifically, the preparation method of the thermal shock resistance composite nozzle brick comprises the following steps:
s1: adding a binder and an antioxidant into the clay clinker, mixing for 5-8min, and then adding bauxite clinker, semi-soft clay and zirconium dioxide, and mixing for 20-25 min;
s2: pressing and molding by adopting a press, naturally drying for 3-5h, and drying for 30-36h at the temperature of 190-;
s3: and (3) firing by adopting a flame-proof protection process, carbonizing at the temperature of 530-550 ℃ after vacuum oil immersion, and polishing to obtain the thermal shock resistant composite nozzle brick.
For the present invention, the bauxite clinker has a particle size of 0.088-1 mm; the grain size of the semi-soft clay is less than or equal to 0.088 mm; the grain diameter of the zirconium dioxide is less than or equal to 0.045 mm; the particle size of the clay clinker is 2-5 mm.
For the invention, the mass ratio of the bauxite clinker to the clay clinker is 1: 3-4; the mass ratio of the semi-soft clay to the clay clinker is 1: 8-10; the mass ratio of the zirconium dioxide to the clay clinker is 1: 30-35.
For the present invention, the mass ratio of the clay clinker to the binder is: 1: 0.08-0.12; the mass ratio of the clay clinker to the antioxidant is as follows: 1:0.08-0.12.
For the present invention, the antioxidant comprises a rosin resin.
For the present invention, the above-mentioned pressure forming process conditions are: the pressure is 25-30 kg/s; the time is 20-35 s.
For the present invention, the process conditions of the flame-proof protection are as follows: the temperature is 1200-1260 ℃; the time is 4-6 h.
In the present invention, the vacuum oil immersion conditions are: pressure of 5-8kgf/cm 2 And the time is 5-8 h.
The invention also provides a preparation method of the modified phenolic resin, which comprises the following steps: the modified phenolic resin is prepared by addition condensation reaction of isoliquiritigenin and formaldehyde.
Specifically, the preparation method of the modified phenolic resin comprises the following steps:
adding phenol into formaldehyde, adjusting the pH value of the solution to 9.5-10, and reacting at 85-90 ℃ for 1-1.5 h; cooling to 60-70 deg.C, adding 1/3-1/2 amount of isoliquiritigenin, reacting for 1-1.5 hr, adding the rest isoliquiritigenin, and reacting for 1.5-2 hr to obtain modified phenolic resin.
For the invention, the molar ratio of the isoliquiritigenin to the formaldehyde is as follows: 1: 4.5-5.5; the molar ratio of the isoliquiritigenin to the phenol is 1: 3-3.5.
More preferably, in the preparation process of the thermal shock resistant composite nozzle brick, the modified rosin resin is used for replacing the rosin resin.
The invention also discloses a preparation method of the modified rosin resin, and the modified rosin resin is prepared by carrying out esterification reaction on (-) -epigallocatechin and the rosin resin.
The invention also provides a modification method of the antioxidant, wherein (-) -epigallocatechin is adopted to carry out esterification modification on the rosin resin, and the prepared modified rosin resin is used for preparing the thermal shock resistance composite nozzle brick, so that the thermal shock resistance composite nozzle brick has the characteristics of better oxidation resistance, low porosity, high volume density and good thermal shock resistance stability.
Specifically, the preparation method of the modified rosin resin comprises the following steps:
adding the rosin resin into fumaric acid, mixing and stirring, then adding a small amount of distilled water, heating to 160-165 ℃ under the protection of nitrogen, and continuously stirring for reacting for 2.5-3.5 h; heating to 210 ℃ and 215 ℃, adding (-) -epigallocatechin and zinc oxide, and reacting for 1.5-2h to obtain the modified rosin resin.
For the invention, the mass ratio of the rosin resin to the fumaric acid is as follows: 1: 4.5-6.5; the mass ratio of the rosin resin to the (-) -epigallocatechin is as follows: 1: 0.5-0.8; the mass ratio of the rosin resin to the zinc oxide is as follows: 1:0.01-0.015.
The invention also discloses the application of the modified phenolic resin obtained by the preparation method in preparing a nozzle brick.
The beneficial effects of the invention include:
the invention has obtained the preparation method of a thermal shock resistance compound nozzle brick, add binder, antioxidant to bauxite chamotte, semi-soft clay, zirconium dioxide, chamotte of clay and mix, pressurize and shape, dry; sintering by adopting a flame-proof protection process, vacuum oil-immersing, carbonizing and polishing; the prepared thermal shock resistant composite nozzle brick has the characteristics of low porosity, high volume density, good thermal shock resistance stability and good oxidation resistance; the invention also adopts isoliquiritigenin modified phenolic resin in the preparation process, thereby further improving the performance of the composite nozzle brick; the invention also provides a preparation method of the modified antioxidant rosin resin, and (-) -epigallocatechin is adopted to esterify and modify the rosin resin, so that the prepared thermal shock resistance composite nozzle brick has better oxidation resistance, and has the characteristics of low porosity, high volume density and good thermal shock resistance stability.
Therefore, the invention provides a preparation method of the thermal shock resistant composite nozzle brick, and the composite nozzle brick prepared by the method has the characteristics of low porosity, high volume density, good thermal shock resistance stability and good oxidation resistance.
Drawings
FIG. 1 shows the results of IR spectrum measurements of modified phenolic resins prepared in examples 1 and 5;
FIG. 2 shows the results of IR spectrogram tests of modified rosin resin and rosin resin prepared in example 4;
FIG. 3 shows the results of the porosity and bulk density tests of the thermal shock resistant composite nozzle brick prepared in examples 1 to 6;
fig. 4 shows the results of the thermal shock resistance test of the thermal shock resistance composite nozzle brick prepared in examples 1 to 6.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the clay clinker used in the embodiment of the invention is purchased from Zhengzhou Kairegdi kiln refractory Co., Ltd;
bauxite chamotte used in the examples of the present invention was purchased from asahi building materials ltd, north Hei;
the semi-soft clay used in the examples of the present invention was purchased from Zhengzhou Zhengnai industries, Ltd;
the zirconium dioxide used in the examples of the present invention was obtained from Shandong national chemical Co., Ltd.
Example 1:
a preparation method of a thermal shock resistant composite nozzle brick comprises the following steps:
s1: adding phenolic resin as binder and rosin resin as antioxidant into the clay clinker, mixing for 5min, adding bauxite clinker, semi-soft clay and zirconium dioxide, and mixing for 20 min;
s2: adopting a press machine for pressing and forming, wherein the pressing conditions are as follows: pressure 25 kg/s; the time is 20 s; then naturally drying for 3h, and then drying for 30h at 190 ℃;
s3: firing by adopting a flame-proof protection process at 1200 ℃ for 4 h; vacuum oil immersion, pressure5kgf/cm 2 The time is 5 h; carbonizing at 530 ℃, and polishing to obtain the thermal shock resistant composite nozzle brick;
wherein the mass ratio of the bauxite clinker to the clay clinker is 1: 3; the mass ratio of the semi-soft clay to the clay clinker is 1: 8; the mass ratio of the zirconium dioxide to the clay clinker is 1: 30; the mass ratio of the clay clinker to the binder is as follows: 1: 0.08; the mass ratio of the clay clinker to the antioxidant is as follows: 1:0.08.
The preparation method of the modified phenolic resin comprises the following steps:
adding phenol into formaldehyde, adjusting the pH value of the solution to 9.5, and reacting for 1h at 85 ℃; cooling to 60 deg.C, adding 1/3 amount of isoliquiritigenin, reacting for 1 hr, adding the rest isoliquiritigenin, and reacting for 1.5 hr to obtain modified phenolic resin; wherein the molar ratio of the isoliquiritigenin to the formaldehyde is as follows: 1: 4.5; the molar ratio of the isoliquiritigenin to the phenol is 1:3.
Example 2:
the difference between the preparation method of the thermal shock resistant composite nozzle brick and the embodiment 1 is as follows: the mass ratio of the bauxite clinker to the clay clinker is 1: 4; the mass ratio of the semi-soft clay to the clay clinker is 1: 10; the mass ratio of the zirconium dioxide to the clay clinker is 1: 35; the mass ratio of the clay clinker to the binder is as follows: 1: 0.12; the mass ratio of the clay clinker to the antioxidant is as follows: 1:0.12.
The difference between the preparation method of the modified phenolic resin and the example 1 is that: the molar ratio of the isoliquiritigenin to the formaldehyde is as follows: 1: 5.5; the molar ratio of the isoliquiritigenin to the phenol is 1: 3.5.
Example 3:
the difference between the preparation method of the thermal shock resistance composite nozzle brick and the embodiment 1 is as follows: the mass ratio of the bauxite clinker to the clay clinker is 1: 3.5; the mass ratio of the semi-soft clay to the clay clinker is 1: 9; the mass ratio of the zirconium dioxide to the clay clinker is 1: 32; the mass ratio of the clay clinker to the binder is as follows: 1: 0.1; the mass ratio of the clay clinker to the antioxidant is as follows: 1:0.1.
The difference between the preparation method of the modified phenolic resin and the example 1 is that: the molar ratio of the isoliquiritigenin to the formaldehyde is as follows: 1: 5; the molar ratio of the isoliquiritigenin to the phenol is 1: 3.3.
Example 4:
the difference between the preparation method of the thermal shock resistance composite nozzle brick and the embodiment 1 is as follows: the modified rosin resin is adopted to replace the rosin resin.
The modified phenolic resin was prepared in the same manner as in example 1.
The preparation method of the modified rosin resin comprises the following steps:
adding rosin resin into fumaric acid, mixing and stirring, then adding a small amount of distilled water, heating to 160 ℃ under the protection of nitrogen, and continuously stirring for reacting for 2.5 hours; heating to 210 ℃, adding (-) -epigallocatechin and zinc oxide, and reacting for 1.5h to prepare modified rosin resin; wherein the mass ratio of the rosin resin to the fumaric acid is as follows: 1: 4.5; the mass ratio of the rosin resin to the (-) -epigallocatechin is as follows: 1: 0.5; the mass ratio of the rosin resin to the zinc oxide is as follows: 1:0.01.
Example 5:
the difference between the preparation method of the thermal shock resistance composite nozzle brick and the embodiment 4 is as follows: the modified phenolic resin was prepared in this example.
The difference between the preparation method of the modified phenolic resin and the example 4 is that: the preparation process does not add isoliquiritigenin.
The preparation method of the modified rosin resin was the same as in example 4.
Example 6:
the difference between the preparation method of the thermal shock resistance composite nozzle brick and the embodiment 1 is as follows: the modified phenolic resin was prepared in this example.
The difference between the preparation method of the modified phenolic resin and the example 1 is that: the preparation process does not add isoliquiritigenin.
Test example:
1. infrared Spectrum testing
Analyzing and testing the sample by adopting a Fourier infrared spectrometer, mixing the sample with KBr, tabletting, and scanning with the wavelength of 4000- -1 。
The modified phenolic resins prepared in examples 1 and 5 were subjected to the above tests, and the results are shown in fig. 1. As can be seen from FIG. 1, example 1 was prepared in comparison to example 5The modified phenolic resin is 1665cm -1 The existence of a characteristic absorption peak of C ═ C bond indicates that isoliquiritigenin participates in the generation reaction of the modified phenolic resin.
The modified rosin resin and the rosin resin prepared in example 4 were subjected to the above-described tests, and the results are shown in fig. 2. As can be seen from FIG. 2, the modified rosin resin is 1400-1600cm -1 The characteristic absorption peak of the benzene ring exists, which indicates that (-) -epigallocatechin participates in the generation reaction of the modified rosin resin.
2. Measurement of bulk Density and porosity
According to the national standard of GB2997-2015, the sample is cut into 40X 60mm, and the porosity and the volume density of the sample are tested and analyzed by an M360131 type apparent porosity and volume density tester.
The thermal shock resistant composite nozzle brick prepared in examples 1 to 6 was subjected to the above test, and the results are shown in fig. 3. As can be seen from fig. 3, the porosity of the composite nozzle brick prepared by example 4 is reduced compared with that of example 1 and that of example 5 is reduced compared with that of example 6, which indicates that the porosity of the composite nozzle brick prepared by (-) -epigallocatechin modified rosin resin is low; the porosity of example 1 is significantly reduced compared to example 6 and example 4 is significantly reduced compared to example 5, which indicates that the composite nozzle brick prepared from the modified phenolic resin prepared from isoliquiritigenin has lower porosity.
The thermal shock resistant composite nozzle brick prepared in examples 1 to 6 was subjected to the above test, and the results are shown in fig. 3. As can be seen from fig. 3, the bulk density of example 4 is increased compared to example 1, and the bulk density of example 5 is increased compared to example 6, which shows that the bulk density of the composite nozzle brick prepared by (-) -epigallocatechin modified rosin resin is also increased; the bulk density of example 1 is significantly higher than that of example 6 and that of example 4 is significantly higher than that of example 5, which shows that the modified phenolic resin prepared from isoliquiritigenin promotes the increase of the bulk density of the composite nozzle brick.
3. Test for Oxidation resistance
Cutting a composite nozzle brick sample, placing the cut composite nozzle brick sample into a high-temperature furnace, roasting for 2 hours at 1400 ℃ in an oxidizing atmosphere, naturally cooling the sample to room temperature, testing the oxidation weight loss rate of the sample, and judging the oxidation resistance of the sample according to the weight loss rate.
The thermal shock resistant composite nozzle brick prepared in examples 1 to 6 was subjected to the above test, and the results are shown in fig. 4. As can be seen from fig. 4, the oxidation weight loss rate of example 4 is reduced compared to example 1, and the oxidation weight loss rate of example 5 is reduced compared to example 6, which shows that the oxidation weight loss rate of the composite nozzle brick prepared after (-) -epigallocatechin modified rosin resin is also reduced; compared with the embodiment 6 and the embodiment 4 and the embodiment 5, the oxidation weight loss rate of the embodiment 1 is obviously reduced, which shows that the modified phenolic resin prepared from the isoliquiritigenin promotes the oxidation resistance of the composite nozzle brick and reduces the oxidation weight loss rate of the composite nozzle brick.
4. Thermal shock resistance test
Testing a sample by using a GB/T30873-2014 thermal shock resistance test method for the refractory material; cutting a sample into 230 multiplied by 114 multiplied by 65mm, drying at 110 ℃ to constant weight, then placing in a heating furnace at 1100 ℃, keeping for 20min, taking out, rapidly immersing a heated end into flowing water at 25 ℃, cooling for 3min, immediately taking out, staying in air for 5min, and repeating the rapid cooling and rapid heating process until the heated end face of the sample is half crushed or reaches the appointed number; the times of rapid cooling and rapid heating cycle are the times of thermal shock resistance.
Table 1 thermal shock resistance test results of composite nozzle brick samples
The thermal shock resistant composite nozzle brick prepared in examples 1 to 6 was subjected to the above test, and the results are shown in table 1. As can be seen from Table 1, the thermal shock resistance times of example 4 are obviously increased compared with those of example 1 and example 5 are obviously increased compared with those of example 6, which shows that the composite nozzle brick prepared by using (-) -epigallocatechin modified rosin resin has good thermal shock resistance; compared with the example 6 and the example 4 and the example 5, the thermal shock resistance times of the example 1 are increased, which shows that the thermal shock resistance of the composite nozzle brick is enhanced by the modified phenolic resin prepared from the isoliquiritigenin.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein. The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a thermal shock resistant composite nozzle brick comprises the following steps:
s1: adding a binder and an antioxidant into the raw materials, and mixing;
s2: pressure forming and drying;
s3: firing by adopting a flame-proof protection process, vacuum oil-immersing, carbonizing and polishing to prepare the thermal shock resistant composite nozzle brick;
the raw materials comprise bauxite chamotte, semi-soft clay, zirconium dioxide and clay chamotte; the binder comprises a modified phenolic resin; the modified phenolic resin is obtained by modifying phenolic resin with isoliquiritigenin.
2. The preparation method of the thermal shock resistant composite nozzle brick according to claim 1, characterized in that: the particle size of the bauxite clinker is 0.088-1 mm; the grain size of the semi-soft clay is less than or equal to 0.088 mm; the grain diameter of the zirconium dioxide is less than or equal to 0.045 mm; the particle size of the clay clinker is 2-5 mm.
3. The preparation method of the thermal shock resistant composite nozzle brick according to claim 1, characterized in that: the mass ratio of the bauxite clinker to the clay clinker is 1: 3-4; the mass ratio of the semi-soft clay to the clay clinker is 1: 8-10; the mass ratio of the zirconium dioxide to the clay clinker is 1: 30-35.
4. The preparation method of the thermal shock resistant composite nozzle brick according to claim 1, characterized in that: the antioxidant comprises a rosin resin.
5. The preparation method of the thermal shock resistant composite nozzle brick according to claim 1, characterized in that: the pressure forming process conditions are as follows: the pressure is 25-30 kg/s; the time is 20-35 s.
6. The preparation method of the thermal shock resistant composite nozzle brick according to claim 1, characterized in that: the process conditions of the flame-proof protection are as follows: the temperature is 1200-1260; the temperature is 4-6 h.
7. The preparation method of the thermal shock resistant composite nozzle brick according to claim 1, characterized in that: the vacuum oil immersion conditions are as follows: pressure of 5-8kgf/cm 2 And the time is 5-8 h.
8. A process for preparing a modified phenolic resin as claimed in claim 1, comprising: the modified phenolic resin is prepared by addition condensation reaction of isoliquiritigenin and formaldehyde.
9. The method for producing a modified phenol resin according to claim 8, characterized in that: the molar ratio of the isoliquiritigenin to the formaldehyde is as follows: 1:4.5-5.5.
10. Use of the modified phenolic resin obtained by the preparation method according to any one of claims 8 to 9 for the preparation of a nozzle brick.
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