CN115261728B - Corrosion-resistant steel pipe material for high-pressure boiler and preparation method thereof - Google Patents
Corrosion-resistant steel pipe material for high-pressure boiler and preparation method thereof Download PDFInfo
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- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/14—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
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Abstract
The invention provides a corrosion-resistant steel tube material for a high-pressure boiler and a preparation method thereof, wherein the corrosion-resistant steel tube material comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.03-0.08% of C, 0.3-0.6% of Si, 10-17% of Cr, 0.3-1% of Mn, 0.1-0.4% of Co, 0.01-0.05% of Ta, 0.001-0.003% of Ga, 0.001-0.005% of Ba, 0.01-0.03% of Zr, 0.03-0.06% of Sn, 0.001-0.003% of Te, 0.1-0.2% of Cu, 0.002-0.006% of N, 0.001-0.003% of rare earth elements, 0.001-0.003% of nano additive, and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 2-4 parts of aluminum silicate fiber, 3-6 parts of expanded vermiculite, 15-25 parts of mullite powder, 3-5 parts of nano zirconium silicide, 1-3 parts of nano molybdenum nitride, 10-20 parts of corundum, 5-8 parts of binder and 5-10 parts of water. The corrosion-resistant steel pipe material for the high-pressure boiler disclosed by the invention is good in corrosion resistance, good in mechanical property, steam oxidation resistance, high temperature resistance and durability and long in service life.
Description
Technical Field
The invention relates to the technical field of metallurgical materials, in particular to a corrosion-resistant steel pipe material for a high-pressure boiler and a preparation method thereof.
Background
A high pressure boiler is an energy conversion apparatus which discharges chemical energy by using fuel such as coal, oil, natural gas, etc., transfers the energy to water or other heat transfer media through a heat transfer process, and directly supplies various forms of energy required in industrial production in the form of high pressure steam or heat transfer media. The steel pipe is one of the important parts of the high-pressure boiler, and the performance of the steel pipe directly influences the operation safety and the economical efficiency of the high-pressure boiler. Therefore, it is imperative to develop steel tube materials for high-pressure boilers, which are excellent in comprehensive properties and performance stability.
At present, the common steel tube material for the high-pressure boiler has low grain size grade, poor corrosion resistance and steam oxidation resistance in a high-temperature environment and limited high-temperature creep stress, so that the steel tube material is easy to creep when working under high temperature and high pressure, and is likely to be subjected to permanent fracture, so that the high-pressure boiler fails, production safety accidents are caused, and great economic loss is caused.
In order to solve the above problems, patent CN103741075B discloses a corrosion-resistant steel tube material for high-pressure boilers and a preparation method thereof, wherein the corrosion-resistant steel tube material comprises the following chemical components by mass percent: 0.015-0.035 wt% of C, 0.4-0.6 wt% of Si, 8.0-12.0 wt% of Cr, 3.6-5.2 wt% of Ni, 0.5-1.5 wt% of Mn, 0.3-0.6 wt% of Sn, 0.2-0.4 wt% of Sb, 0.15-0.25 wt% of Mo, 0.1-0.2 wt% of W, 0.05-0.15 wt% of V, 0.003-0.006 wt% of N, less than or equal to 0.02 wt% of P, less than or equal to 0.01 wt% of S and the balance of Fe. The steel pipe material prepared by the invention has excellent corrosion resistance, steam oxidation resistance and stress creep resistance in a high-temperature environment, has high-temperature strength and good impact toughness, is durable in use, and completely meets the performance requirements of the steel pipe material for the high-pressure boiler. The production process is simple and easy to operate, low in cost, good in economic benefit and suitable for large-scale industrial production. However, the high-temperature and high-pressure resistance and corrosion resistance of the alloy are still to be further improved, and the mechanical properties and performance stability of the alloy are still to be further improved.
Therefore, the corrosion-resistant steel tube material for the high-pressure boiler and the preparation method thereof are still needed in the field, wherein the corrosion-resistant steel tube material has good corrosion resistance, mechanical property, steam oxidation resistance, high-temperature resistance, durability and long service life.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a corrosion-resistant steel pipe material for high-pressure boilers, which has excellent corrosion resistance, mechanical properties, steam oxidation resistance, high-temperature resistance, and durability, and a long service life, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the corrosion-resistant steel pipe material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.03-0.08% of C, 0.3-0.6% of Si, 10-17% of Cr, 0.3-1% of Mn, 0.1-0.4% of Co, 0.01-0.05% of Ta, 0.001-0.003% of Ga, 0.001-0.005% of Ba, 0.01-0.03% of Zr, 0.03-0.06% of Sn, 0.001-0.003% of Te, 0.1-0.2% of Cu, 0.002-0.006% of N, 0.001-0.003% of rare earth elements, 0.001-0.003% of nano additive, and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 2-4 parts of aluminum silicate fiber, 3-6 parts of expanded vermiculite, 15-25 parts of mullite powder, 3-5 parts of nano zirconium silicide, 1-3 parts of nano molybdenum nitride, 10-20 parts of corundum, 5-8 parts of binder and 5-10 parts of water.
Preferably, the binder is a mixture formed by mixing PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate and 2,4, 6-trivinyl boroxine according to the mass ratio of (3-5) to 1 (1-2) to (0.1-0.3).
Preferably, the corundum is brown corundum, and the grain size composition of the corundum is as follows: 25 to 45 weight percent of 5 to 3mm, 15 to 25 weight percent of 3 to 1mm, 20 weight percent of 0 to 1mm and the balance of 320 meshes.
Preferably, the particle size of the nano zirconium silicide is 300-500nm, and the particle size of the nano molybdenum nitride is 300-500nm.
Preferably, the particle size composition of the mullite powder is as follows: 25 to 45 weight percent of 5 to 3mm, 15 to 25 weight percent of 3 to 1mm, 20 weight percent of 0 to 1mm and the balance of 320 meshes.
Preferably, the particle size of the expanded vermiculite is 0.05-1 mm; the average diameter of the aluminum silicate fiber is 3-9 μm, and the length-diameter ratio is (10-15): 1.
Preferably, the nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 100-300nm.
Preferably, the rare earth element is a mixture formed by mixing Pr, dy and La according to the mass ratio of 1 (0.8-1.2) to (0.3-0.5).
Another object of the present invention is to provide a method for preparing the corrosion-resistant steel pipe material for a high-pressure boiler, comprising the steps of:
s1, preparing steel pipe blanks by using scrap steel, intermediate alloy, nano zirconium silicide and nano molybdenum nitride as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all the components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
Preferably, the heat treatment in step S1 includes a normalizing treatment, a tempering treatment, and a quenching treatment.
Preferably, the normalizing treatment temperature is 750-830 ℃, and the heat preservation time is 30-40min.
Preferably, the tempering temperature is 480-600 ℃, and the heat preservation time is 1-2 hours.
Preferably, the quenching treatment is graded quenching, the temperature is kept for 25-35min after the quenching treatment is carried out to 900-960 ℃, then oil quenching is carried out, the quenching treatment is carried out after the quenching treatment is carried out to room temperature, then the quenching treatment is carried out, the temperature is increased to 420-500 ℃ again, the temperature is kept for 30-40min, and the quenching treatment is carried out after the temperature is kept.
Preferably, the high-temperature curing in step S2 specifically includes: heating to 240-280 deg.C at a rate of 3-5 deg.C/min, maintaining for 1-2 hr, heating to 680-720 deg.C at a rate of 5-8 deg.C/min, and maintaining for 3-5 hr.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the corrosion-resistant steel pipe material for the high-pressure boiler, disclosed by the invention, has the advantages of small dependence on equipment, simple process, convenience in operation, high preparation efficiency and high qualification rate of finished products, and is suitable for large-scale production.
(2) The corrosion-resistant steel tube material for the high-pressure boiler disclosed by the invention has the advantages that through the formula design of the components of the alloy base material, the components can better exert interaction, so that the high-temperature oxidation resistance and corrosion resistance of the material are improved, meanwhile, the steel tube material product can also be endowed with excellent mechanical properties, and the service life is longer. The addition of the nano additive can play a role in strengthening and simultaneously improve the mechanical property, heat resistance and wear resistance.
(3) The corrosion-resistant steel pipe material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material, and through the structural design, the alloy base material can be well protected, and the service life of the steel pipe material is effectively prolonged; through the formula design, the thermal expansion matching characteristic of the surface functional coating and the alloy base material is good, so that the thermal shock resistance of the steel pipe material is obviously improved.
(4) The invention discloses a corrosion-resistant steel pipe material for a high-pressure boiler, which is characterized in that a functional coating is prepared from the following components in parts by weight: 2-4 parts of aluminum silicate fiber, 3-6 parts of expanded vermiculite, 15-25 parts of mullite powder, 3-5 parts of nano zirconium silicide, 1-3 parts of nano molybdenum nitride, 10-20 parts of corundum, 5-8 parts of binder and 5-10 parts of water; the adhesive is a mixture formed by mixing PA-80 high-temperature adhesive, sodium tripolyphosphate, sodium silicate and 2,4, 6-trivinyl boroxine according to the mass ratio of (3-5) to (1-2) to (0.1-0.3). Through the cooperation of all the components, the coating has high density and hardness, good combination with an alloy base material, excellent corrosion resistance, high temperature resistance and strong friction resistance.
(5) The corrosion-resistant steel tube material for the high-pressure boiler disclosed by the invention has better corrosion resistance and mechanical properties, higher hardness and longer service life through reasonable selection of heat treatment and high-temperature curing processes.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following provides a detailed description of the product of the present invention with reference to the examples.
Example 1
The corrosion-resistant steel pipe material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.03% of C, 0.3% of Si, 10% of Cr, 0.3% of Mn, 0.1% of Co, 0.01% of Ta, 0.001% of Ga, 0.001% of Ba, 0.01% of Zr, 0.03% of Sn, 0.001% of Te, 0.1% of Cu, 0.002% of N, 0.001% of rare earth elements, 0.001% of nano-additives, and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 2 parts of aluminum silicate fiber, 3 parts of expanded vermiculite, 15 parts of mullite powder, 3 parts of nano zirconium silicide, 1 part of nano molybdenum nitride, 10 parts of corundum, 5 parts of binder and 5 parts of water.
The binder is a mixture formed by mixing PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate, 2,4, 6-trivinyl boroxine according to the mass ratio of 3.
The corundum is brown corundum, and the grain size of the corundum is as follows: 25wt% for 5-3 mm, 15wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the granularity of the nanometer zirconium silicide is 300nm, and the granularity of the nanometer molybdenum nitride is 300nm.
The particle size of the mullite powder is as follows: 25wt% for 5-3 mm, 15wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the particle size of the expanded vermiculite is 0.05mm; the average diameter of the aluminum silicate fibers is 3 mu m, and the length-diameter ratio is 10; the nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 100nm; the rare earth element is a mixture formed by mixing Pr, dy and La according to the mass ratio of 1.
The preparation method of the corrosion-resistant steel tube material for the high-pressure boiler comprises the following steps:
s1, preparing a steel pipe blank by using scrap steel, a master alloy, nano zirconium silicide and nano molybdenum nitride as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at a high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
The heat treatment in the step S1 comprises normalizing treatment, tempering treatment and quenching treatment; the normalizing temperature is 750 ℃, and the heat preservation time is 30min; the tempering temperature is 480 ℃, and the heat preservation time is 1 hour; the quenching treatment is graded quenching, heating to 900 ℃, then preserving heat for 25min, then performing oil quenching, cooling to room temperature, then adding to 420 ℃ again, preserving heat for 30min, taking out after heat preservation is finished, and performing air cooling.
The high-temperature curing in the step S2 specifically comprises the following steps: heating to 240 ℃ at the heating rate of 3 ℃/min, preserving heat for 1 hour, heating to 680 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 hours.
Example 2
The corrosion-resistant steel tube material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.04% of C, 0.4% of Si, 12% of Cr, 0.5% of Mn, 0.2% of Co, 0.02% of Ta, 0.0015% of Ga, 0.002% of Ba, 0.015% of Zr, 0.04% of Sn, 0.0015% of Te, 0.12% of Cu, 0.003% of N, 0.0015% of rare earth elements, 0.0015% of nano additives and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 2.5 parts of aluminum silicate fiber, 4 parts of expanded vermiculite, 17 parts of mullite powder, 3.5 parts of nano zirconium silicide, 1.5 parts of nano molybdenum nitride, 13 parts of corundum, 6 parts of binder and 6 parts of water.
The binder is a mixture formed by mixing PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate, 2,4, 6-trivinyl boroxine according to the mass ratio of 3.5.
The corundum is brown corundum, and the grain size of the corundum is as follows: 30wt% for 5-3 mm, 19wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the granularity of the nano zirconium silicide is 350nm, and the granularity of the nano molybdenum nitride is 350nm.
The particle size of the mullite powder consists of the following components: 30wt% for 5-3 mm, 17wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the particle size of the expanded vermiculite is 0.25mm; the average diameter of the aluminum silicate fibers is 5 mu m, and the length-diameter ratio is 11.
The nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 150nm; the rare earth elements are a mixture formed by mixing Pr, dy and La according to the mass ratio of 1.
The preparation method of the corrosion-resistant steel tube material for the high-pressure boiler comprises the following steps:
s1, preparing steel pipe blanks by using scrap steel, intermediate alloy, nano zirconium silicide and nano molybdenum nitride as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at a high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
The heat treatment in the step S1 comprises normalizing treatment, tempering treatment and quenching treatment; the normalizing temperature is 780 ℃ and the heat preservation time is 33min; the tempering temperature is 510 ℃, and the heat preservation time is 1.2 hours; the quenching treatment is step quenching, heating to 920 ℃, then preserving heat for 28min, then performing oil quenching, cooling to room temperature, then adding to 450 ℃ again, preserving heat for 33min, taking out after heat preservation is finished, and performing air cooling.
The high-temperature curing in the step S2 specifically comprises the following steps: heating to 250 ℃ at the heating rate of 3.5 ℃/min, preserving heat for 1.2 hours, heating to 690 ℃ at the heating rate of 6 ℃/min, and preserving heat for 3.5 hours.
Example 3
The corrosion-resistant steel tube material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.06% of C, 0.45% of Si, 14% of Cr, 0.7% of Mn, 0.25% of Co, 0.035% of Ta, 0.002% of Ga, 0.0035% of Ba, 0.02% of Zr, 0.045% of Sn, 0.002% of Te, 0.15% of Cu, 0.004% of N, 0.002% of rare earth element, 0.002% of nano additive, and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 3 parts of aluminum silicate fiber, 4.5 parts of expanded vermiculite, 20 parts of mullite powder, 4 parts of nano zirconium silicide, 2 parts of nano molybdenum nitride, 15 parts of corundum, 6.5 parts of binder and 8 parts of water.
The binder is a mixture formed by mixing PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate, 2,4, 6-trivinyl boroxine according to the mass ratio of 4.
The corundum is brown corundum, and the grain size of the corundum is as follows: 35wt% for 5-3 mm, 20wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the granularity of the nanometer zirconium silicide is 400nm, and the granularity of the nanometer molybdenum nitride is 400nm.
The particle size of the mullite powder consists of the following components: 35wt% for 5-3 mm, 20wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the particle size of the expanded vermiculite is 0.65mm; the average diameter of the aluminum silicate fibers is 6 mu m, and the length-diameter ratio is 13.
The nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 200nm; the rare earth elements are a mixture formed by mixing Pr, dy and La according to the mass ratio of 1.
The preparation method of the corrosion-resistant steel tube material for the high-pressure boiler comprises the following steps:
s1, preparing steel pipe blanks by using scrap steel, intermediate alloy, nano zirconium silicide and nano molybdenum nitride as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all the components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
The heat treatment in the step S1 comprises normalizing treatment, tempering treatment and quenching treatment; the normalizing temperature is 800 ℃, and the heat preservation time is 35min; the tempering temperature is 530 ℃, and the heat preservation time is 1.5 hours; the quenching treatment is graded quenching, heating to 930 ℃, preserving heat for 30min, then oil quenching, cooling to room temperature, adding to 470 ℃ again, preserving heat for 35min, taking out after heat preservation is finished, and air cooling.
The high-temperature curing in the step S2 specifically comprises the following steps: heating to 260 ℃ at the heating rate of 4 ℃/min, preserving heat for 1.5 hours, heating to 700 ℃ at the heating rate of 6.5 ℃/min, and preserving heat for 4 hours.
Example 4
The corrosion-resistant steel pipe material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.07% of C, 0.55% of Si, 16% of Cr, 0.8% of Mn, 0.35% of Co, 0.04% of Ta, 0.0025% of Ga, 0.004% of Ba, 0.025% of Zr, 0.055% of Sn, 0.0025% of Te, 0.18% of Cu, 0.005% of N, 0.0025% of rare earth elements, 0.0025% of nano-additives and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 3.5 parts of aluminum silicate fiber, 5.5 parts of expanded vermiculite, 23 parts of mullite powder, 4.5 parts of nano zirconium silicide, 2.5 parts of nano molybdenum nitride, 18 parts of corundum, 7.5 parts of binder and 9 parts of water.
The binder is a mixture formed by mixing PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate, 2,4, 6-trivinyl boroxine according to the mass ratio of 4.5.
The corundum is brown corundum, and the grain size of the corundum is as follows: 40wt% for 5-3 mm, 23wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the granularity of the nanometer zirconium silicide is 450nm, and the granularity of the nanometer molybdenum nitride is 450nm; the particle size of the mullite powder consists of the following components: 43wt% for 5-3 mm, 23wt% for 3-1 mm, 20wt% for 0-1 mm, and the rest is 320 mesh.
The particle size of the expanded vermiculite is 0.85mm; the average diameter of the aluminum silicate fibers is 8 mu m, and the length-diameter ratio is 14; the nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 280nm; the rare earth elements are a mixture formed by mixing Pr, dy and La according to the mass ratio of 1.1.
The preparation method of the corrosion-resistant steel tube material for the high-pressure boiler comprises the following steps:
s1, preparing a steel pipe blank by using scrap steel, a master alloy, nano zirconium silicide and nano molybdenum nitride as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all the components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
The heat treatment in the step S1 comprises normalizing treatment, tempering treatment and quenching treatment; the normalizing temperature is 820 ℃, and the heat preservation time is 38min; the tempering temperature is 590 ℃, and the heat preservation time is 1.8 hours; the quenching treatment is graded quenching, heating to 950 ℃, then preserving heat for 33min, then performing oil quenching, cooling to room temperature, then adding to 490 ℃, preserving heat for 38min, taking out after heat preservation is finished, and performing air cooling.
The high-temperature curing in the step S2 specifically comprises the following steps: heating to 275 deg.C at a rate of 4.5 deg.C/min, holding for 1.8 hr, heating to 710 deg.C at a rate of 7.5 deg.C/min, and holding for 4.5 hr.
Example 5
The corrosion-resistant steel pipe material for the high-pressure boiler comprises an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.08% of C, 0.6% of Si, 17% of Cr, 1% of Mn, 0.4% of Co, 0.05% of Ta, 0.003% of Ga, 0.005% of Ba, 0.03% of Zr, 0.06% of Sn, 0.003% of Te, 0.2% of Cu, 0.006% of N, 0.003% of rare earth element, 0.003% of nano additive, and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 4 parts of aluminum silicate fiber, 6 parts of expanded vermiculite, 25 parts of mullite powder, 5 parts of nano zirconium silicide, 3 parts of nano molybdenum nitride, 20 parts of corundum, 8 parts of binder and 10 parts of water.
The binder is a mixture formed by mixing PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate, 2,4, 6-trivinyl boroxine according to the mass ratio of 5; the corundum is brown corundum, and the grain size of the corundum is as follows: 45wt% for 5-3 mm, 25wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the granularity of the nanometer zirconium silicide is 500nm, and the granularity of the nanometer molybdenum nitride is 500nm.
The particle size of the mullite powder is as follows: 45wt% for 5-3 mm, 25wt% for 3-1 mm, 20wt% for 0-1 mm, and the balance 320 mesh; the particle size of the expanded vermiculite is 1mm; the average diameter of the aluminum silicate fibers is 9 mu m, and the length-diameter ratio is 15; the nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 300nm; the rare earth elements are a mixture formed by mixing Pr, dy and La according to the mass ratio of 1.2.
The preparation method of the corrosion-resistant steel tube material for the high-pressure boiler comprises the following steps:
s1, preparing steel pipe blanks by using scrap steel, intermediate alloy, nano zirconium silicide and nano molybdenum nitride as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all the components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
The heat treatment in the step S1 comprises normalizing treatment, tempering treatment and quenching treatment; the normalizing temperature is 830 ℃, and the heat preservation time is 40min; the tempering temperature is 600 ℃, and the heat preservation time is 2 hours; the quenching treatment is graded quenching, heating to 960 deg.C, maintaining the temperature for 35min, oil quenching, cooling to room temperature, adding to 500 deg.C again, maintaining the temperature for 40min, taking out, and air cooling.
The high-temperature curing in the step S2 specifically comprises the following steps: heating to 280 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, heating to 720 ℃ at the heating rate of 8 ℃/min, and preserving heat for 5 hours.
Comparative example 1
A corrosion-resistant steel pipe material for a high-pressure boiler, which is substantially the same as in example 1, except that Ta, te, nano silicon boride, sodium tripolyphosphate and nano zirconium silicide were not added.
Comparative example 2
A corrosion-resistant steel pipe material for a high-pressure boiler, which is substantially the same as example 1, except that Sn, ba, nano molybdenum nitride, 2,4, 6-trivinyl boroxine and nano zirconia were not added.
In order to further illustrate the unexpected positive technical effects of the products of the embodiments of the invention, the corrosion-resistant steel pipe materials for high-pressure boilers manufactured in the embodiments are subjected to relevant performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) Salt spray corrosion resistance: the test temperature is 35 ℃, a 5% sodium chloride aqueous solution with mass concentration is sprayed in a test box to simulate the accelerated corrosion of the environment, and the endurance time (namely the time for keeping the steel tube material not rusted) of the corrosion-resistant steel tube material for the high-pressure boiler determines the quality of the salt fog corrosion resistance.
(2) High temperature chlorine corrosion resistance: the method is carried out on a high-temperature gas phase corrosion test bed. The temperature of the corrosion test is 550 ℃, and the corrosion atmosphere simulates the actual atmosphere (O) in the boiler 2 6.67Vol.％、N 2 75.00Vol.％、CO 2 13.33Vol.％、H 2 O4.95 Vol.%, HCl 0.05 Vol.%), the experiment was performed for a total of 168 hours. The high-temperature chlorine corrosion rate characterization adopts a weight gain method, and the high-temperature chlorine corrosion weight gain rate is adopted to characterize the corrosion condition of the sample, and is defined as: high temperature chlorine corrosion weight gain rate = (mass after corrosion-mass before corrosion)/(sample exposed area x corrosion time).
(3) Measurement of tensile strength: the test was carried out according to the national standard GB/T228-2002.
TABLE 1
| Item | Corrosion resistance to salt spray | High temperature chlorine corrosion weight gain rate | Tensile strength |
| Unit of | h | mg·cm -2 ·h -1 | MPa |
| Example 1 | 1128 | 0.0020 | 625 |
| Example 2 | 1135 | 0.0016 | 630 |
| Example 3 | 1140 | 0.0014 | 640 |
| Example 4 | 1143 | 0.0013 | 648 |
| Example 5 | 1149 | 0.0010 | 654 |
| Comparative example 1 | 1086 | 0.0042 | 572 |
| Comparative example 2 | 1072 | 0.0036 | 585 |
As can be seen from table 1, the corrosion-resistant steel pipe material for a high-pressure boiler disclosed in the examples of the present invention has more excellent mechanical properties and corrosion resistance than the comparative example.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; one of ordinary skill in the art can readily practice the present invention as described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. The corrosion-resistant steel pipe material for the high-pressure boiler is characterized by comprising an alloy base material and a functional coating coated on the surface of the alloy base material; the alloy base material comprises the following chemical components in percentage by weight: 0.03-0.08% of C, 0.3-0.6% of Si, 10-17% of Cr, 0.3-1% of Mn, 0.1-0.4% of Co, 0.01-0.05% of Ta, 0.001-0.003% of Ga, 0.001-0.005% of Ba, 0.01-0.03% of Zr, 0.03-0.06% of Sn, 0.001-0.003% of Te, 0.1-0.2% of Cu, 0.002-0.006% of N, 0.001-0.003% of rare earth elements, 0.001-0.003% of nano additive, and the balance of Fe and other inevitable impurities; the functional coating is prepared from the following components in parts by weight: 2-4 parts of aluminum silicate fiber, 3-6 parts of expanded vermiculite, 15-25 parts of mullite powder, 3-5 parts of nano zirconium silicide, 1-3 parts of nano molybdenum nitride, 10-20 parts of corundum, 5-8 parts of binder and 5-10 parts of water.
2. The corrosion-resistant steel pipe material for a high-pressure boiler according to claim 1, wherein the binder is a mixture of PA-80 high-temperature binder, sodium tripolyphosphate, sodium silicate, and 2,4, 6-trivinylboroxine mixed in a mass ratio of (3-5) to 1 (1-2) to (0.1-0.3).
3. The corrosion-resistant steel pipe material for a high-pressure boiler according to claim 1, wherein the nano zirconium silicide has a particle size of 300 to 500nm, and the nano molybdenum nitride has a particle size of 300 to 500nm.
4. The corrosion-resistant steel pipe material for a high-pressure boiler according to claim 1, wherein the particle size of the expanded vermiculite is 0.05-1 mm; the average diameter of the aluminum silicate fibers is 3-9 mu m, and the length-diameter ratio is (10-15): 1; the nano additive is a mixture formed by mixing nano silicon boride and nano zirconia according to a mass ratio of 3; the particle size of the nano additive is 100-300nm.
5. The corrosion-resistant steel tube material for a high-pressure boiler as claimed in claim 1, wherein said rare earth element is a mixture of Pr, dy and La in a mass ratio of 1 (0.8-1.2) to (0.3-0.5).
6. The method for preparing the corrosion-resistant steel pipe material for the high-pressure boiler according to claim 4, which comprises the following steps:
s1, preparing a steel pipe blank by taking scrap steel, intermediate alloy, nano silicon boride and nano zirconia as raw materials according to chemical components of an alloy base material and adopting continuous casting and rolling; then, preparing an alloy base material after heat treatment;
and S2, uniformly mixing all the components of the functional coating, coating the mixture on the surface of an alloy base material, and curing at high temperature to prepare the corrosion-resistant steel pipe material for the high-pressure boiler.
7. The method of manufacturing a corrosion-resistant steel pipe material for a high-pressure boiler according to claim 6, wherein the heat treatment in step S1 includes a normalizing treatment, a tempering treatment and a quenching treatment.
8. The method for preparing the corrosion-resistant steel pipe material for the high-pressure boiler according to claim 7, wherein the normalizing temperature is 750-830 ℃, and the holding time is 30-40min; the tempering temperature is 480-600 ℃, and the heat preservation time is 1-2 hours; the quenching treatment is graded quenching, heating to 900-960 deg.C, maintaining the temperature for 25-35min, oil quenching, cooling to room temperature, heating to 420-500 deg.C, maintaining the temperature for 30-40min, taking out, and air cooling.
9. The method for preparing the corrosion-resistant steel pipe material for the high-pressure boiler according to claim 6, wherein the high-temperature curing in the step S2 is specifically as follows: heating to 240-280 deg.C at a rate of 3-5 deg.C/min, maintaining for 1-2 hr, heating to 680-720 deg.C at a rate of 5-8 deg.C/min, and maintaining for 3-5 hr.
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