CN108914041B - High-temperature-resistant and hydrochloric acid corrosion-resistant composite material for synthesis furnace and preparation method thereof - Google Patents

High-temperature-resistant and hydrochloric acid corrosion-resistant composite material for synthesis furnace and preparation method thereof Download PDF

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CN108914041B
CN108914041B CN201810683673.XA CN201810683673A CN108914041B CN 108914041 B CN108914041 B CN 108914041B CN 201810683673 A CN201810683673 A CN 201810683673A CN 108914041 B CN108914041 B CN 108914041B
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CN108914041A (en
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王泽�
仇建国
吴建珍
季新忠
李小平
叶霞
单文桃
黄亚男
卢雅琳
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/137—Spraying in vacuum or in an inert atmosphere
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment

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Abstract

The invention discloses a high-temperature-resistant hydrochloric acid corrosion-resistant composite material for a synthetic furnace and a preparation method thereof, wherein the composite material consists of two parts: a substrate and an anticorrosive coating. The matrix is carbon steel or special steel, and the anticorrosive coating is a mixture of high-entropy alloy coated graphite C. The mass ratio of the high-entropy alloy to the graphite C is 4-5: 5-6. The preparation method comprises the steps of passivating the surface of the substrate, spraying and depositing a coating, densifying the coating, and performing cold rolling treatment on the substrate with the coating to obtain the composite material.

Description

High-temperature-resistant and hydrochloric acid corrosion-resistant composite material for synthesis furnace and preparation method thereof
Technical Field
The invention belongs to the field of materials, and particularly relates to a high-temperature-resistant hydrochloric acid corrosion-resistant composite material for a synthesis furnace and a manufacturing method thereof.
Background
In the process of synthesizing hydrochloric acid, chlorine and hydrogen are combusted in a synthesis furnace to generate HCI (hydrogen chloride) which generates a large amount of heat, the central temperature of flame is as high as more than 2500 ℃, the temperature of generated hydrogen chloride gas is also more than 2000 ℃, and the synthesis furnace needs to resist high temperature and hydrochloric acid corrosion. At present, the domestic synthesis furnace mainly has two types: steel synthesis furnaces and graphite synthesis furnaces. The steel hydrochloric acid synthetic furnace is easy to corrode at the top and the bottom of the furnace, the application range of the hot water with short service life and by-product is limited, the graphite hydrochloric acid synthetic furnace is limited by the strength and the use temperature because the graphite is non-metal brittle material, a graphite furnace cylinder is taken as a pressure part for steam production when steam is by-produced, certain hidden danger exists in safety, accidents are easy to occur, the utilization of the heat energy of the hot water or the low-pressure steam by-product by adopting the method can only reach 40%, and the application range is also limited. Therefore, solving the corrosion resistance, high thermal conductivity and high strength of the synthesis furnace is an important issue of the hydrochloric acid synthesis equipment.
The prior high-temperature-resistant and hydrochloric acid corrosion-resistant composite material for the synthetic furnace and the preparation method mainly adopt graphite as an inner container and steel as an outer shell, so that the high-temperature corrosion resistance of the synthetic furnace is improved. The search of the prior art documents shows that the Chinese patent publication number is CN205590282U, and the publication date is: 2016.09.2, the invention is a hydrogen chloride synthetic furnace, which adopts graphite as the furnace pipe to generate larger steam pressure, and has strong corrosion resistance and long service life. The method has the defects of large brittleness, low tensile strength and bending strength and poor heat absorption effect of the graphite furnace pipe. The invention discloses an immersion type graphite synthesis furnace with the publication number of CN205878923U and the publication date of 2017.01.11, and the name of the invention is that the synthesis furnace comprises a synthesis part, a cooling part, a steam condensation part, a furnace shell and a graphite layer, wherein the graphite layer is positioned on the inner wall of the furnace shell, and the immersion type graphite synthesis furnace has the advantages of good corrosion resistance, long service life, high purity of hydrogen chloride gas, no iron ions, high production efficiency and the like. The method has the defects of large brittleness of the graphite furnace pipe and lower tensile strength and bending strength.
Disclosure of Invention
Aiming at the defects, the synthetic furnace is made of steel, and a high-temperature and hydrochloric acid corrosion resistant coating is deposited on the inner surface of the furnace wall and is made of Ni60Nb20Ti12.5Hf7.5The graphite C powder coated by the metal glass alloy has the advantages of ultrahigh corrosion resistance, good heat conductivity, good comprehensive mechanical property and good interface cohesiveness and compatibility with a matrix. The high-temperature-resistant hydrochloric acid corrosion-resistant composite material for the synthesis furnace and the preparation method thereof have important significance for prolonging the service life of the hydrochloric acid synthesis furnace and improving the purity of hydrochloric acid and the steam utilization rate.
The technical problem to be solved by the invention is to overcome the defects of the prior artThe high-temperature resistance and the corrosion resistance of the steel synthetic furnace are improved by depositing the coating on the inner wall of the steel synthetic furnace. The invention provides a high-temperature-resistant hydrochloric acid corrosion-resistant composite material for a synthetic furnace and a preparation method thereof, and the technical scheme adopted for realizing the technical problem of the invention is as follows: firstly, polishing and passivating the surface of a steel matrix; then spraying and depositing a coating to form Ni60Nb20Ti12.5Hf7.5Coating the graphite C coating, wherein the thickness of the coating is 3-5 mm; finally, the coating is densified, the substrate with the coating is cold-rolled in three working procedures, and finally the high-temperature resistant and hydrochloric acid corrosion resistant composite material for the synthesis furnace is obtained, wherein the specific technical scheme of the invention is as follows:
the invention provides a high-temperature-resistant hydrochloric acid corrosion-resistant composite material for a synthesis furnace, which consists of a substrate and an anticorrosive coating, wherein the substrate is carbon steel or special steel, and the anticorrosive coating is a mixture of high-entropy alloy coated graphite C.
The preferable component of the high-entropy alloy is Ni60Nb20Ti12.5Hf7.5Or TiCoCrFeNiAlSi.
The mixture of the high-entropy alloy and the graphite C preferably comprises the high-entropy alloy and the graphite C according to the mass ratio of 4-5: 5-6.
The thickness of the anticorrosive coating of the composite material is preferably 3-5 mm.
The preparation method of the composite material comprises the following steps:
1) polishing the surface of the matrix, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol, air-drying, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passivation film on the surface of the matrix;
2) preparing raw materials of high-entropy alloy metal according to an atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 8-12 mu m into a solid fluidized conveyor, and setting the deposition distance to be 200-450 mm, the deposition amount to be 6-9 Kg/min and the substrate rotation speed to be 150 r/min;
3) introducing 2-3 MPa of high-pressure helium gas into the metal liquid bag and the conveyor in the step 2), synchronously atomizing the high-entropy alloy metal liquid and the graphite powder to form liquid drops mixed with solid and liquid, rapidly solidifying the liquid drops under the action of a cooler at the lower end of an atomizing chamber, and depositing the liquid drops on the substrate obtained in the step 1) to obtain a coating of the high-entropy alloy coated graphite C, wherein the thickness of the coating is 3-5 mm, so that the substrate with the coating is obtained;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
The composite material is applied to the preparation of a synthetic furnace.
The invention has the beneficial effects that: the synthetic furnace adopts steel, and the high-temperature resistant and hydrochloric acid corrosion resistant coating is deposited on the inner surface of the furnace wall and is made of Ni60Nb20Ti12.5Hf7.5The metallic glass alloy coated graphite C coating has ultrahigh corrosion resistance or is formed by coating TiCoCrFeNiAlSi metallic glass alloy with graphite C powder, has ultrahigh corrosion resistance, good heat conduction performance and good comprehensive mechanical property, and has good interface cohesiveness and interface compatibility with a matrix. The high-temperature-resistant hydrochloric acid corrosion-resistant composite material for the synthesis furnace and the preparation method have important significance for prolonging the service life of the hydrochloric acid synthesis furnace and improving the purity and the heat utilization rate of the hydrochloric acid.
Drawings
FIG. 1: the invention relates to a process flow chart for preparing a high-temperature-resistant hydrochloric acid corrosion-resistant composite material of a synthetic furnace; FIG. 2: the working principle of the solid-liquid synchronous atomization device is shown schematically; 1-solid particles, 2-molten metal, 3-solid particle fluidized conveyor, 4-molten metal bag, 5-closing valve, 6-sealing plug, 7-atomizer and 8-cooler
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples.
Example 1: a high temperature resistant and hydrochloric acid corrosion resistant composite material for a synthetic furnace and a preparation method thereof, the preparation method comprises the following steps:
1) polishing the surface of a matrix by using sand paper, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol to remove surface stains, naturally drying the surface, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passive film on the surface of the matrix;
2) preparing raw materials of Ni, Nb, Ti and Hf metals according to the atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 12 mu m into a solid fluidized conveyor, and setting the deposition distance to be 300mm, the deposition amount to be 9Kg/min and the rotating speed of a matrix to be 150 r/min;
3) introducing 2-3 MPa of high-pressure helium gas into the metal liquid bag and the conveyor in the step 2) to allow Ni to pass60Nb20Ti12.5Hf7.5Synchronously atomizing a metal liquid and graphite powder to form liquid drops mixed with solid and liquid, wherein the Ni-based metal glass alloy and the graphite C are composed according to the mass ratio of 4:6, the liquid drops are rapidly solidified under the action of a cooler at the lower end of an atomizing chamber, and are deposited on the substrate obtained in the step 1) to obtain Ni60Nb20Ti12.5Hf7.5Coating the graphite C to obtain a substrate with a coating, wherein the thickness of the coating is 3 mm;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
Example 2: a high temperature resistant and hydrochloric acid corrosion resistant composite material for a synthetic furnace and a preparation method thereof, the preparation method comprises the following steps:
1) polishing the surface of a matrix by using sand paper, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol to remove surface stains, naturally drying the surface, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passive film on the surface of the matrix;
2) preparing raw materials of Ni, Nb, Ti and Hf metals according to the atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 8 mu m into a solid fluidized conveyor, and setting the deposition distance to be 450mm, the deposition amount to be 6Kg/min and the rotating speed of a matrix to be 150 r/min;
3) introducing 2-3 MPa of high-pressure helium gas into the metal liquid bag and the conveyor in the step 2) to allow Ni to pass60Nb20Ti12.5Hf7.5Synchronously atomizing a metal liquid and graphite powder to form liquid drops mixed with solid and liquid, wherein the Ni-based metal glass alloy and the graphite C are composed according to the mass ratio of 4:6, the liquid drops are rapidly solidified under the action of a cooler at the lower end of an atomizing chamber, and are deposited on the substrate obtained in the step 1) to obtain Ni60Nb20Ti12.5Hf7.5Coating the graphite C to obtain a substrate with a coating, wherein the thickness of the coating is 5 mm;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
Example 3: a high temperature resistant and hydrochloric acid corrosion resistant composite material for a synthetic furnace and a preparation method thereof, the preparation method comprises the following steps:
1) polishing the surface of a matrix by using sand paper, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol to remove surface stains, naturally drying the surface, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passive film on the surface of the matrix;
2) preparing raw materials of Ni, Nb, Ti and Hf metals according to the atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 12 mu m into a solid fluidized conveyor, and setting the deposition distance to be 400mm, the deposition amount to be 8Kg/min and the rotating speed of a matrix to be 150 r/min;
3) introducing 2-3 MPa of high-pressure helium gas into the metal liquid bag and the conveyor in the step 2) to allow Ni to pass60Nb20Ti12.5Hf7.5Synchronously atomizing a metal liquid and graphite powder to form liquid drops mixed with solid and liquid, wherein the Ni-based metal glass alloy and the graphite C are prepared according to the mass ratio of 4:6, and the liquid drops are obtained under the action of a cooler at the lower end of an atomizing chamberThe drops are rapidly solidified and deposited on the substrate obtained in step 1) to obtain Ni60Nb20Ti12.5Hf7.5Coating the graphite C to obtain a substrate with a coating, wherein the thickness of the coating is 4 mm;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
Example 4: a high temperature resistant and hydrochloric acid corrosion resistant composite material for a synthetic furnace and a preparation method thereof, the preparation method comprises the following steps:
1) polishing the surface of a matrix by using sand paper, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol to remove surface stains, naturally drying the surface, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passive film on the surface of the matrix;
2) preparing raw materials of Ti, Co, Cr, Fe, Ni, Al and Si according to the atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling the molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 12 mu m into a solid fluidized conveyor, setting the deposition distance to be 300mm, the deposition amount to be 9Kg/min and the substrate rotation speed to be 150 r/min;
3) introducing 2-3 MPa high-pressure helium gas into the metal liquid bag and the conveyor in the step 2) to synchronously atomize the TiCoCrFeNiAlSi metal liquid and the graphite powder to form liquid drops mixed with solid and liquid, wherein the TiCoCrFeNiAlSi and the graphite C consist of the TiCoCrFeNiAlSi and the graphite C according to the mass ratio of 5:5, the liquid drops are quickly solidified under the action of a cooler at the lower end of an atomizing chamber and are deposited on the substrate obtained in the step 1) to obtain a coating of the TiCoCrFeNiAlSi coated graphite C, and the thickness of the coating is 3mm to obtain the substrate with the coating;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
Example 5: a high temperature resistant and hydrochloric acid corrosion resistant composite material for a synthetic furnace and a preparation method thereof, the preparation method comprises the following steps:
1) polishing the surface of a matrix by using sand paper, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol to remove surface stains, naturally drying the surface, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passive film on the surface of the matrix;
2) preparing raw materials of Ti, Co, Cr, Fe, Ni, Al and Si according to the atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling the molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 8 mu m into a solid fluidized conveyor, setting the deposition distance to be 450mm, the deposition amount to be 6Kg/min and the substrate rotation speed to be 150 r/min;
3) introducing 2-3 MPa high-pressure helium gas into the metal liquid bag and the conveyor in the step 2) to synchronously atomize the TiCoCrFeNiAlSi metal liquid and the graphite powder to form liquid drops mixed with solid and liquid, wherein the TiCoCrFeNiAlSi and the graphite C consist of the TiCoCrFeNiAlSi and the graphite C according to the mass ratio of 5:5, the liquid drops are quickly solidified under the action of a cooler at the lower end of an atomizing chamber and are deposited on the substrate obtained in the step 1) to obtain a coating of the TiCoCrFeNiAlSi coated graphite C, and the thickness of the coating is 5mm to obtain the substrate with the coating;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
Example 6: a high temperature resistant and hydrochloric acid corrosion resistant composite material for a synthetic furnace and a preparation method thereof, the preparation method comprises the following steps:
1) polishing the surface of a matrix by using sand paper, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol to remove surface stains, naturally drying the surface, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passive film on the surface of the matrix;
2) preparing raw materials of Ti, Co, Cr, Fe, Ni, Al and Si according to the atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling the molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 12 mu m into a solid fluidized conveyor, setting the deposition distance to be 400mm, the deposition amount to be 8Kg/min and the substrate rotation speed to be 150 r/min;
3) introducing 2-3 MPa of high-pressure helium gas into the metal liquid bag and the conveyor in the step 2) to synchronously atomize the TiCoCrFeNiAlSi metal liquid and the graphite powder to form liquid drops mixed with solid and liquid, wherein the TiCoCrFeNiAlSi and the graphite C are mixed according to the mass ratio of 5:5, rapidly solidifying liquid drops under the action of a cooler at the lower end of the atomizing chamber, and depositing the liquid drops on the substrate obtained in the step 1) to obtain a coating of the TiCoCrFeNiAlSi-coated graphite C, wherein the thickness of the coating is 4mm, so that the substrate with the coating is obtained;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
Comparative example 1: only the composition of the Ni-based metallic glass alloy and graphite C in the step 3) was adjusted in a mass ratio of 7:6, and the remaining steps were the same as in example 3 to obtain a composite material of comparative example 1.
Comparative example 2: only the composition of the Ni-based metallic glass alloy and graphite C in the step 3) was adjusted in a mass ratio of 3:6, and the remaining steps were the same as in example 3 to obtain a composite material of comparative example 2.
Comparative example 3: only the thickness of the coating layer in step 3) was adjusted to 2mm, and the remaining steps were the same as in example 3 to obtain a composite material of comparative example 3.
Comparative example 4: only the thickness of the coating layer in step 3) was adjusted to 6mm, and the remaining steps were the same as in example 3 to obtain a composite material of comparative example 4.
Comparative example 5: the deposition distance was adjusted to 500mm only in the step 2), and the remaining steps were the same as in example 3 to obtain a composite material of comparative example 5.
Comparative example 6: only the deposition distance in step 2) was adjusted to 150mm, and the remaining steps were the same as in example 6, to obtain a composite material of comparative example 6.
Comparative example 7: only the composition of the TiCoCrFeNiAlSi alloy and the graphite C in the step 3) is adjusted according to the mass ratio of 7:6, and the rest steps are the same as the step 6 to prepare the composite material of the comparative example 7.
Comparative example 8: only the composition of the TiCoCrFeNiAlSi alloy and the graphite C in the step 3) is adjusted according to the mass ratio of 3:6, and the rest steps are the same as the step 6 to prepare the composite material of the comparative example 8.
Comparative example 9: only the thickness of the coating layer in step 3) was adjusted to 2mm, and the remaining steps were the same as in example 6 to obtain a composite material of comparative example 9.
Comparative example 10: only the thickness of the coating layer in step 3) was adjusted to 6mm, and the remaining steps were the same as in example 6, to obtain a composite material of comparative example 10.
In the synthesis furnace composite materials prepared in examples 1 to 3 and comparative examples 1 to 6 of the method of the present invention, a 5 × 5 × 5cm sample was taken from the composite material, and the sample was immersed in a hydrochloric acid container having a pH of 1 and a concentration of 0.lmol/L, and the container was taken out after the synthesis furnace was operated for a certain time, and the degree of corrosion was judged according to the color shade of hydrochloric acid. The color is dark, the corrosion is serious, and the color is marked as change; the color is not obviously changed when the color is close to clear water, the corrosion is very slight, and the color is recorded as unchanged, the acid resistance pH value of the workpiece is 1.0, and the test is passed, otherwise, the workpiece is not passed.
Results of acid resistance test on the composites prepared in examples 1 to 6 and comparative examples 1 to 10
Figure BDA0001711161600000091
Figure BDA0001711161600000101
The high-temperature-resistant hydrochloric acid corrosion-resistant composite material of the synthetic furnace prepared by the 3 embodiments and the experiments adopts steel, and a high-temperature-resistant hydrochloric acid corrosion-resistant coating is deposited on the inner surface of the furnace wall and is made of Ni60Nb20Ti12.5Hf7.5The graphite C powder coated by the metal glass alloy has the advantages of ultrahigh corrosion resistance, good heat conductivity, good comprehensive mechanical property, and good interface cohesiveness and interface compatibility with a matrix. The coating is formed by coating graphite C powder on the TiCoCrFeNiAlSi metal glass alloy through depositing a high-temperature-resistant and hydrochloric acid corrosion-resistant coating on the inner surface of the furnace wall, has ultrahigh corrosion resistance, thermal conductivity and comprehensive mechanical properties, and has good interface cohesiveness and compatibility with a matrix.
The high-temperature-resistant hydrochloric acid corrosion-resistant composite material for the synthesis furnace and the preparation method have important significance for prolonging the service life of the hydrochloric acid synthesis furnace and improving the purity of hydrochloric acid.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. The high-temperature-resistant and hydrochloric acid corrosion-resistant composite material for the synthesis furnace is characterized by consisting of a substrate and an anticorrosive coating, wherein the substrate is carbon steel or special steel, and the anticorrosive coating is a mixture of high-entropy alloy coated graphite C;
the preparation method of the high-temperature-resistant and hydrochloric acid corrosion-resistant composite material for the synthetic furnace comprises the following steps:
1) polishing the surface of the matrix, removing oxides and impurities on the surface, cleaning the surface by using absolute ethyl alcohol, air-drying, soaking the matrix in a sulfuric acid solution with the concentration of 70%, standing for 30min, and cleaning by using absolute ethyl alcohol to obtain an iron oxide passivation film on the surface of the matrix;
2) preparing raw materials of high-entropy alloy metal according to an atomic ratio, placing the raw materials in a crucible smelting furnace, heating the raw materials to be molten under the protection of argon, then filling molten liquid into a metal liquid bag in a jet deposition machine, simultaneously filling graphite powder with the particle size of 8-12 mu m into a solid fluidized conveyor, and setting the deposition distance to be 200-450 mm, the deposition amount to be 6-9 Kg/min and the substrate rotation speed to be 150 r/min;
3) introducing 2-3 MPa of high-pressure helium gas into the metal liquid bag and the conveyor in the step 2), synchronously atomizing the high-entropy alloy metal liquid and the graphite powder to form liquid drops mixed with solid and liquid, rapidly solidifying the liquid drops under the action of a cooler at the lower end of an atomizing chamber, and depositing the liquid drops on the substrate obtained in the step 1) to obtain a coating of the high-entropy alloy coated graphite C, wherein the thickness of the coating is 3-5 mm, so that the substrate with the coating is obtained;
4) and (3) carrying out cold rolling treatment on the substrate with the coating obtained in the step 3), and carrying out cold rolling in three working procedures, wherein the first reduction is 10%, the second reduction is 5%, and the third reduction is 5%.
2. The composite material as claimed in claim 1, wherein the composition of the high-entropy alloy is Ni60Nb20Ti12.5Hf7.5Or TiCoCrFeNiAlSi.
3. The composite material according to claim 1, wherein the high-entropy alloy graphite C-containing mixture is composed of a high-entropy alloy and graphite C in a mass ratio of 4-5: 5-6.
4. The composite material of claim 1, wherein the composite material has an anticorrosive coating thickness of 3-5 mm.
5. Use of a composite material according to any one of claims 1-4 in the preparation of a synthesis furnace.
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