CN114438438A - Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy - Google Patents

Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy Download PDF

Info

Publication number
CN114438438A
CN114438438A CN202011107426.9A CN202011107426A CN114438438A CN 114438438 A CN114438438 A CN 114438438A CN 202011107426 A CN202011107426 A CN 202011107426A CN 114438438 A CN114438438 A CN 114438438A
Authority
CN
China
Prior art keywords
alloy
resistance
treatment
atmosphere
partial pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011107426.9A
Other languages
Chinese (zh)
Inventor
王申祥
郏景省
王红霞
王国清
张利军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202011107426.9A priority Critical patent/CN114438438A/en
Publication of CN114438438A publication Critical patent/CN114438438A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
    • C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated

Abstract

The invention discloses a method for improving oxidation resistance, coking resistance and carbonization resistance of an alloy. The method comprises the following steps: (1) carrying out extrusion grinding treatment on the surface of the alloy; (2) and (3) simultaneously carrying out high-temperature low-oxygen partial pressure treatment and vulcanization treatment on the extruded and ground alloy in a low-oxygen partial pressure atmosphere and a vulcanization atmosphere. The invention does not improve the oxidation resistance, coking resistance and anti-carburizing capability of the cracking furnace tube alloy in a coating mode, but finely adjusts the contents of Si and Mn elements in the components of the alloy, and basically does not influence the mechanical property and welding property of the alloy; the surface of the alloy is subjected to extrusion grinding treatment, and a brittle layer on the surface is removed; finally, the invention also carries out high-temperature low-oxygen partial pressure treatment and vulcanization treatment on the alloy under the low-oxygen partial pressure atmosphere and the vulcanization atmosphere at the same time to obtain a compact oxide-sulfide protective layer, and the oxidation resistance, the coking resistance and the carbonization resistance are very obvious.

Description

Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy
Technical Field
The invention relates to the technical field of materials, in particular to a method for improving oxidation resistance, coking resistance and carbonization resistance of an alloy.
Background
Ethylene yield, production scale and technology mark a state of the petrochemical industry. The current method for producing ethylene is mainly based on the tubular furnace cracking technology, and is widely applied worldwide.
After hydrocarbon steam cracking for a period of time, a layer of thick coke is deposited on the inner surface of a furnace tube of a cracking furnace radiation section, the thermal resistance of the furnace tube is increased by a coke layer, the heat transfer coefficient is reduced, when the coke layer reaches a certain thickness, the cracking furnace tube must stop producing, and air-steam combined coking is adopted. In order to further remove coke, pure air at 850 ℃ for 20 hours is often burnt in the later stage of burning, and the pure air without water vapor causes excessive oxidation of the cracking furnace tube at high temperature, so that the matrix of the furnace tube is peeled off or the matrix oxide is volatilized, for example, very thick Cr is generated on the inner surface2O3Oxide film, excessive thickness of Cr2O3The difference between the thermal expansion coefficients of the oxide film and the furnace tube substrateLarge in size, easily peeled off, and excessively oxidized Cr on the surface of the substrate2O3Will be transformed into CrO3The gas is volatilized. Matrix Cr2O3The areas left after the oxide film is peeled off or volatilized are areas rich in Fe and Ni elements which are the key factors causing catalytic coking, so that local severe coking and carburization can be caused by excessive oxidation, and the service life of the hydrocarbon cracking furnace tube can be greatly reduced.
The method for preventing the inner surface of the cracking furnace tube from being oxidized and coked generally adopts the method of coating a metallurgical coating on the inner surface of the furnace tube, mainly forming one or more layers of metallurgical coatings with good mechanical property and thermal stability on the inner surface of the furnace tube by the methods of plasma spraying, hot sputtering, high-temperature sintering and the like, such as Al2O3、Cr2O3、SiO2And the like.
U.S. Pat. No. 4, 5648178 discloses a method for producing HP-50 metal Cr coatings by chemical vapor deposition of CrCl2The powder is prepared into a coating with certain viscosity, and the coating is coated on the metal surface and then is subjected to pure H2Heat treating in atmosphere to form firm Cr coating, dry carbonizing the Cr coating with propane-containing hydrogen to form carbon-rich binding layer, and bonding with N2Treating to form CrN filled cracks, and treating with steam to form thin Cr2O3And the layer is covered on the surface of the chromium layer. Cr formed by the method2O3The coating easily peels off.
Chinese patent CN 1580316A embeds a furnace tube into a device filled with a co-permeation agent, then carries out temperature-changing heating, constant temperature and cooling heat treatment on the furnace tube, the whole process is protected by argon, finally a layer of metal inert material is formed on the inner surface of the furnace tube, and small test results show that the coke content is reduced by 50%. The method has the disadvantages that the preparation process of the coating is complex, and the coating and the substrate are easy to peel off because a transition layer is not arranged between the coating and the substrate. US 6585864 discloses a coat-alloy inhibiting ethylene furnace tube coking technique, which adopts magnetron sputtering method to deposit NiCrAlY coating material on the base alloy, then carries out heat treatment to the base alloy, and forms a coating layer which comprises a diffusion barrier layer, a enriching pool layer and alpha-Al2O3And (3) a composite coating of an anti-coking layer. The method has the disadvantages of complex coating preparation process, multiple steps and high cost.
In the US patent US 6537388, Cr and Si compounds are filled in a furnace tube, Cr and Si elements are diffused into the metal of a substrate furnace tube to form a Cr-Si bottom layer after passivation treatment, then Si and Al compounds are sprayed on the Cr-Si bottom layer by adopting a hot sputtering method, and an Si-Al outer layer is formed after heat treatment. The method has the defects of complex coating preparation process and certain damage effect on the furnace tube matrix.
U.S. Pat. No. 4, 6423415 discloses a mixture of K and K in a certain molar ratio2O、SiO2、Al2O3、ZnO、MgO、Co3O4、Na2O、ZrO2Spraying inorganic substances onto the furnace tube at high temperature2、N2And sintering in a water vapor atmosphere to form the glass coating. The method has the defects that the expansion coefficients of the inorganic coating and the furnace tube matrix are greatly different, and the service life of the coating is influenced after the temperature of production and decoking is repeatedly changed.
The coating in the patent covers Fe and Ni elements with catalytic coking activity on the inner wall of the furnace tube, and although oxygen elements and carbon elements in the atmosphere can be prevented from entering the substrate of the furnace tube, the coating process is complex, the cost is high, the service life of the coating is limited, and the coating process has great influence on the component distribution and the tissue structure of the whole furnace tube, so that the coating technology is not adopted by ethylene manufacturers in a large scale.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for improving the oxidation resistance, coking resistance and carbonization resistance of an alloy. The invention does not improve the oxidation resistance, coking resistance and anti-carburizing capability of the cracking furnace tube alloy in a coating mode, but finely adjusts the contents of Si and Mn elements in the components of the alloy, and basically does not influence the mechanical property and welding property of the alloy; the surface of the alloy is subjected to extrusion grinding treatment, and a brittle layer on the surface is removed; finally, the invention also carries out high-temperature low-oxygen partial pressure treatment and vulcanization treatment on the alloy under the low-oxygen partial pressure atmosphere and the vulcanization atmosphere at the same time to obtain a compact oxide-sulfide protective layer, and the oxidation resistance, the coking resistance and the carbonization resistance are very obvious.
The invention aims to provide a method for improving the oxidation resistance, coking resistance and carbonization resistance of an alloy.
The method comprises the following steps:
(1) carrying out extrusion grinding treatment on the surface of the alloy;
(2) and (3) simultaneously carrying out high-temperature low-oxygen partial pressure treatment and vulcanization treatment on the extruded and ground alloy in a low-oxygen partial pressure atmosphere and a vulcanization atmosphere.
In a preferred embodiment of the present invention,
step (1), the grinding material after extrusion grinding treatment is formed by mixing abrasive particles and a viscous liquid carrier;
the abrasive particles are selected from one or more of tungsten oxide, cerium oxide, chromium oxide, aluminum oxide, silicon carbide, boron carbide and diamond;
the viscous liquid carrier is selected from one or more of vaseline, paraffin, turpentine and oleic acid.
In a preferred embodiment of the present invention,
the granularity of the abrasive particles is 40-1000 meshes, and the abrasive particles account for 10-80 wt% of the total weight of the abrasive;
the viscous liquid carrier accounts for 20-90 wt% of the total weight of the abrasive.
In a preferred embodiment of the present invention,
the pressure of extrusion grinding is 0.5MPa-15 MPa; the extrusion grinding time is 5-3600 seconds.
In a preferred embodiment of the present invention,
step (2), the low-oxygen partial pressure atmosphere and the vulcanizing atmosphere are mixed gases comprising hydrogen, water vapor and sulfide steam;
the sulfide vapor is H2S、SO2、SF6、COS、CS2、CH3SH、CH3CH2SH、CH3SCH3、CH3CH2SCH2CH3、CH3S-SCH3、CH3CH2S-SCH2CH3At least one of (1).
In a preferred embodiment of the present invention,
the water vapor accounts for 0.1-2% of the total gas volume percentage;
the volume percentage of the sulfide vapor in the total gas is 0.01-0.2%.
In a preferred embodiment of the present invention,
a step (2) of carrying out a treatment,
the treatment temperature is 800-1100 ℃; the treatment time is 5 to 50 hours.
The second purpose of the invention is to provide an alloy treated by the method.
Based on the total weight of the alloy as 100 percent,
the alloy comprises:
1-50% of chromium; preferably 10-40%;
1-50% of nickel; preferably 10-50%;
0.2-3% of manganese; preferably 0.5-3%;
0-3% of silicon; preferably 0.5-3%;
carbon < 0.75%;
0-5% of trace elements and/or trace elements;
the balance being iron;
the trace elements are one or more of niobium, titanium, tungsten, aluminum and rare earth elements,
the trace elements are sulfur or/and phosphorus.
In a preferred embodiment of the present invention,
the mass percentage of Si and Mn in the alloy meets the following conditions:
Figure BDA0002727422550000041
[Mn]≥1.0
[Si]≥1.0
the invention also aims to provide the application of the alloy in the furnace tube.
The invention can adopt the following technical scheme:
specifically, the oxidation-resistant, coking-resistant and carbonization-resistant alloy comprises the following components:
(1) the alloy comprises the following components in percentage by weight: 1-50% of chromium, 1-50% of nickel, 0.2-3% of manganese, 0-3% of silicon, 0.75% of carbon, 0-5% of trace elements and/or trace elements and the balance of iron; the trace elements are one or more of niobium, titanium, tungsten, aluminum and rare earth elements, and the trace elements are sulfur or/and phosphorus.
(2) The mass percentage of Si and Mn in the alloy meets the following conditions:
Figure BDA0002727422550000051
[Mn]≥1.0
[Si]≥1.0
(3) the surface of the alloy is subjected to extrusion grinding treatment, and the grinding material is formed by mixing abrasive particles and a viscous liquid carrier according to a certain proportion. The abrasive particles are selected from one or more of tungsten oxide, cerium oxide, chromium oxide, aluminum oxide, silicon carbide, boron carbide and diamond. The grain size of the abrasive particles is 40-1000 meshes, and the weight percentage of the abrasive particles is 10-80%. The viscous liquid carrier is selected from one or more of vaseline, paraffin, oleum Terebinthinae, and oleic acid. The weight percentage of the viscous liquid carrier is 20-90%. The pressure of the extrusion grinding is 0.5MPa-15 MPa. The extrusion grinding time is 5-3600 seconds.
(4) And (3) simultaneously carrying out high-temperature low-oxygen partial pressure treatment and vulcanization treatment on the extruded and ground alloy in a low-oxygen partial pressure atmosphere and a vulcanization atmosphere. The low oxygen partial pressure atmosphere and the sulfuration atmosphere are a mixed gas comprising hydrogen, water vapor and H2S、SO2、SF6、COS、CS2、CH3SH、CH3CH2SH、CH3SCH3、CH3CH2SCH2CH3、CH3S-SCH3、CH3CH2S-SCH2CH3At least one of (1), water vapor in percent by volume of the total gasThe ratio is 0.1-2%, and the volume percentage of sulfide steam in the total gas is 0.01-0.2%. The temperature of the low-oxygen partial pressure treatment and the vulcanization treatment is 800-1100 ℃, and the time is 5-50 hours.
According to the invention, the step of extrusion grinding is added before vulcanization treatment, under the action of extrusion grinding, a large number of brittle layers and microscopic defects on the inner surface of the furnace tube are removed, the organization structure of the inner surface of the furnace tube is more compact, the crystal grains are refined, the surface roughness can be greatly improved, and finally a protective layer formed on the compact and refined alloy surface is not easy to peel off, so that the protective effect is better.
The cracking furnace tube alloy is oxidized by water vapor in the cracking atmosphere in the service process, and Cr is formed on the surface2O3Mainly an oxide film. The alloy of the invention increases the content of Si and Mn, and mainly aims at increasing the content of MnO in an alloy oxide layer and reducing Cr2O3Content because Si forms SiO during oxidation2A layer which, like a barrier, prevents part of the Cr element from migrating to the surface layer and thus does not form excessive Cr2O3，Cr2O3Is not very protective since it is converted to CrO above 950 ℃3The gas is volatilized. The MnO content in the alloy oxide film of the invention is increased and then is mixed with Cr2O3Form more stable MnCr2O4Or Mn1.5Cr1.5O4. The oxide film formed in the low oxygen partial pressure mainly comprises chromium manganese oxide and certain amounts of FeO and NiO, but sulfide in the atmosphere reacts with FeO/NiO in the oxide film to form FeS/NiS, and finally a mixed film with the oxide film and the sulfide film staggered is formed, and the mixed film has better protection than a pure oxide film.
The method can be used for laboratory-scale cracking furnace tubes or industrial cracking furnace tubes, and has excellent effect. The protective layer formed by the invention has lasting effect and can keep the effect of a plurality of cycles.
Drawings
FIG. 1 is a schematic view of an oxidation experimental apparatus according to the present invention;
FIG. 2 is an oxidation weight gain curve for comparative example 1, comparative example 2, comparative example 3, example 1;
FIG. 3 is a coke weight gain curve for comparative example 1, comparative example 2, comparative example 3, example 1;
FIG. 4 is a graph of the carbonization weight gain of comparative example 1, comparative example 2, comparative example 3, and example 1;
FIG. 5 is an oxidation weight gain curve for comparative example 4, comparative example 5, comparative example 6, example 2;
FIG. 6 is a coke weight gain curve for comparative example 4, comparative example 5, comparative example 6, example 2;
FIG. 7 is a graph of the carbonization weight gain of comparative example 4, comparative example 5, comparative example 6, and example 2;
FIG. 8 is an oxidation weight gain curve for comparative example 7, comparative example 8, comparative example 9, example 3;
FIG. 9 is a coke weight gain curve for comparative example 7, comparative example 8, comparative example 9, example 3;
fig. 10 is a carbonization weight gain curve of comparative example 7, comparative example 8, comparative example 9, and example 3.
Description of reference numerals:
(1) a gas mass flow meter; (2) a peristaltic pump; (3) a preheater; (4) an electric heating furnace; (5) a condenser; (6) a vacuum pump; (7) a wet gas flowmeter.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
The adjustment of the silicon-manganese content described in the examples and comparative examples means that: the contents of silicon and manganese are slightly increased in the smelting process, and other elements and smelting processes do not need to be changed.
Comparative examples 1, 4 and 7
The alloys used were the common 2520, 2535, 3545 alloys.
Comparative examples 2, 5 and 8
The used alloys are 2520, 2535 and 3545 alloys with adjusted contents of Si and Mn elements, and are numbered 2520-1, 2535-1 and 3545-1.
Comparative example 3
After the content of silicon and manganese is adjusted by adopting 2520 alloy, a square sample with the size of 5mm multiplied by 3mm is cut by a numerical control linear cutting machine, and the wire moving speed of wire cutting is controlled, so that the surface roughness of each sample is basically consistent. The sample was then treated as follows:
extruding and grinding: (1) abrasive formulation, 15% alumina (800 mesh) + 35% boron carbide (400 mesh) + 35% paraffin + 15% oleic acid; (2) extrusion grinding pressure, 5 MPa; (3) extrusion milling time, 60 seconds.
The alloy sample No. 2520-2 was analyzed for its surface composition by X-ray energy dispersive spectroscopy, and the results are shown in Table 1.
Comparative example 6
After the content of silicon and manganese is adjusted by adopting 2535 alloy, a square sample with the size of 5mm multiplied by 3mm is cut by a numerical control linear cutting machine, and the wire moving speed of wire cutting is controlled, so that the surface roughness of each sample is basically consistent. The sample was then treated as follows:
extruding and grinding: (1) abrasive formula, 76% boron carbide (1000 mesh), 12% paraffin, 10% oleic acid and 2% turpentine; (2) extrusion grinding pressure, 10 MPa; (3) extrusion milling time, 15 seconds.
The alloy sample No. 2535-2 was analyzed for surface composition using an X-ray energy dispersive spectrometer and the results are shown in Table 1.
Comparative example 9
After the content of silicon and manganese is adjusted by using 3545 alloy, a square sample with the size of 5mm multiplied by 3mm is cut by using a numerical control linear cutting machine, and the wire moving speed of wire cutting is controlled, so that the surface roughness of each sample is basically consistent. The sample was then treated as follows:
extruding and grinding: (1) abrasive formulation, 83% silicon carbide (400 mesh) + 17% petrolatum; (2) extrusion grinding pressure is 2 MPa; (3) extrusion milling time, 500 seconds.
Alloy specimen No. 3545-2 was analyzed for surface composition using an X-ray energy dispersive spectrometer and the results are shown in table 1.
Example 1
After the content of silicon and manganese is adjusted by adopting 2520 alloy, a square sample with the size of 5mm multiplied by 3mm is cut by a numerical control linear cutting machine, and the wire moving speed of wire cutting is controlled, so that the surface roughness of each sample is basically consistent. The sample was then treated as follows:
extruding and grinding: (1) abrasive formulation, 15% alumina (800 mesh) + 35% boron carbide (400 mesh) + 35% paraffin + 15% oleic acid; (2) extrusion grinding pressure, 5 MPa; (3) extrusion milling time, 60 seconds.
Low oxygen partial pressure-vulcanization treatment: at H2S, steam, Hydrogen gas atmosphere (H)2S volume concentration 0.1%, water vapor volume concentration 0.6%) at 900 deg.C for 20 hr.
The alloy sample No. 2520-3 was analyzed for its surface composition by X-ray energy dispersive spectroscopy, and the results are shown in Table 1.
Example 2
After the content of silicon and manganese is adjusted by adopting 2535 alloy, a square sample with the size of 5mm multiplied by 3mm is cut by a numerical control linear cutting machine, and the wire moving speed of wire cutting is controlled, so that the surface roughness of each sample is basically consistent. The sample was then treated as follows:
extruding and grinding: (1) abrasive formula, 76% boron carbide (1000 mesh), 12% paraffin, 10% oleic acid and 2% turpentine; (2) extrusion grinding pressure, 10 MPa; (3) extrusion milling time, 15 seconds.
Low oxygen partial pressure-vulcanization treatment: 2535 alloy in CH3SH, steam, hydrogen atmosphere (CH)3SH steam volume concentration of 0.05%, water vapor volume concentration of 1.2%) at 1000 deg.C for 30 hr.
The alloy sample No. 2535-3 was analyzed for surface composition using an X-ray energy dispersive spectrometer and the results are shown in Table 1.
Example 3
After the content of silicon and manganese is adjusted by using 3545 alloy, a square sample with the size of 5mm multiplied by 3mm is cut by using a numerical control linear cutting machine, and the wire moving speed of wire cutting is controlled, so that the surface roughness of each sample is basically consistent. The sample was then treated as follows:
extruding and grinding: (1) abrasive formulation, 83% silicon carbide (400 mesh) + 17% petrolatum; (2) extrusion grinding pressure is 2 MPa; (3) extrusion milling time, 500 seconds.
Low oxygen partial pressure-vulcanization treatment: 3545 alloy in CH3S-SCH3Atmosphere of water vapor and hydrogen (CH)3S-SCH3Steam concentration 0.15% by volume and water vapor concentration 2%) at 850 deg.C for 40 hr.
Alloy specimen No. 3545-3 was analyzed for surface composition using an X-ray energy dispersive spectrometer and the results are shown in Table 1.
TABLE 1 chemical composition of alloy (wt%)
Figure BDA0002727422550000101
Bal in the table indicates the balance.
Oxidation test of test piece
The oxidation experiment of the sample was carried out in the apparatus shown in FIG. 1, with the sample suspended in the constant temperature region of the electric heating furnace. The oxidizing gas was air and the flow rate was 200 ml/min. The temperature rising rate of the electric heating furnace is 10 ℃/min, the electric heating furnace is heated to 850 ℃, the temperature is kept for 4 hours, and finally the temperature is reduced, the temperature reduction rate is about-2 ℃/min, and air is introduced in the whole process. Each sample was oxidized 3 times for the first two 3h, the third 4h, and 10 h. And weighing the mass of the sample before and after each oxidation experiment by using an analytical balance to obtain the oxidation weight gain.
Coking experiment of samples
The coking experiment of the sample was carried out in the apparatus shown in FIG. 1, with the sample suspended in the constant temperature zone of an electric furnace. When a coking experiment is carried out, the coking gas is N2-2％C2H6The temperature is raised to 900 ℃ at the temperature raising rate of 10 ℃/min, the temperature is kept for 4 hours at the temperature lowering rate of-2 ℃/min, the coking gas is always introduced in the temperature raising and keeping process, and the gas flow is 200 ml/min. Each sample is coked for 3 times, the first two times are coked for 3 hours, the third time is coked for 4 hours, and the total time is 10 hours. And weighing the mass of the sample before and after each coking experiment to obtain the coking weight gain.
Carbonization test of test specimens
The sample was carbonized in the apparatus shown in FIG. 1, and the sample was suspended in the constant temperature region of the electric heating furnace. When the carbonization experiment is carried out, the carbonization gas is 98 percent H2-2％CH4The temperature is raised to 1000 ℃ at the heating rate of 10 ℃/min and then kept constant for 10h, the temperature reduction rate is about-2 ℃/min, and the carbonized gas is introduced in the heating and constant temperature processes, wherein the gas flow is 200 ml/min. Each sample was carbonized 4 times for 10h each time for 40 h. Before and after each carbonization experiment, the mass of the sample is weighed, and the surface composition of the sample is analyzed by an X-ray energy dispersion spectrometer after carbonization for 40 hours.
Analysis and characterization of samples
The samples were analyzed for surface element content using an Apollo XP type X-ray Energy Dispersive Spectrometer (EDS) from EDAX. The mass of the sample before and after each coking and carbonization test was weighed with an AA-200 electronic analytical balance of Denver corporation to an accuracy of 0.1 mg.
The oxidation weight gain curve, the coking weight gain curve and the carbonization weight gain curve of the comparative example 1, the comparative example 2, the comparative example 3 and the example 1 are shown in figures 2, 3 and 4; the surface elemental analysis after carbonization is shown in table 2.
TABLE 22520 carbonized surface elements in percent by mass
Figure BDA0002727422550000111
The oxidation weight gain curve, the coking weight gain curve and the carbonization weight gain curve of the comparative example 4, the comparative example 5, the comparative example 6 and the example 2 are shown in figures 5, 6 and 7; the surface elemental analysis after carbonization is shown in table 3.
Table 32535 carbonized surface element mass percent content
Figure BDA0002727422550000121
The oxidation weight gain curve, the coking weight gain curve and the carbonization weight gain curve of the comparative example 7, the comparative example 8, the comparative example 9 and the example 3 are shown in figures 8, 9 and 10; the surface elemental analysis after carbonization is shown in table 4.
Surface element mass percentage content of carbonized table 43545 alloy
Figure BDA0002727422550000122
By combining all the data, the oxidation resistance, the coking resistance and the carbonization resistance of the alloy provided by the invention are greatly improved compared with the conventional alloy.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A method for improving the oxidation resistance, coking resistance and carbonization resistance of an alloy is characterized by comprising the following steps:
(1) carrying out extrusion grinding treatment on the surface of the alloy;
(2) and (3) simultaneously carrying out high-temperature low-oxygen partial pressure treatment and vulcanization treatment on the extruded and ground alloy in a low-oxygen partial pressure atmosphere and a vulcanization atmosphere.
2. The method of claim 1, wherein:
step (1), the grinding material after extrusion grinding treatment is formed by mixing abrasive particles and a viscous liquid carrier;
the abrasive particles are selected from one or more of tungsten oxide, cerium oxide, chromium oxide, aluminum oxide, silicon carbide, boron carbide and diamond;
the viscous liquid carrier is selected from one or more of vaseline, paraffin, turpentine and oleic acid.
3. The processing method of claim 2, wherein:
the granularity of the abrasive particles is 40-1000 meshes, and the abrasive particles account for 10-80 wt% of the total weight of the abrasive;
the viscous liquid carrier accounts for 20-90 wt% of the total weight of the abrasive.
4. The process of claim 1, wherein:
the pressure of extrusion grinding is 0.5MPa-15 MPa; the extrusion grinding time is 5-3600 seconds.
5. The process of claim 1, wherein:
step (2), the low-oxygen partial pressure atmosphere and the vulcanizing atmosphere are mixed gases comprising hydrogen, water vapor and sulfide steam;
the sulfide vapor is H2S、SO2、SF6、COS、CS2、CH3SH、CH3CH2SH、CH3SCH3、CH3CH2SCH2CH3、CH3S-SCH3、CH3CH2S-SCH2CH3At least one of (1).
6. The processing method of claim 5, wherein:
the water vapor accounts for 0.1-2% of the total gas volume percentage;
the volume percentage of the sulfide vapor in the total gas is 0.01-0.2%.
7. The process of claim 1, wherein:
a step (2) of carrying out a treatment,
the treatment temperature is 800-1100 ℃; the treatment time is 5 to 50 hours.
8. An alloy treated according to the method of any one of claims 1 to 7, wherein:
based on the total weight of the alloy as 100 percent,
the alloy comprises:
Figure FDA0002727422540000021
0-5% of trace elements and/or trace elements;
the balance being iron;
the trace elements are one or more of niobium, titanium, tungsten, aluminum and rare earth elements,
the trace elements are sulfur or/and phosphorus.
9. The alloy of claim 8, wherein:
the mass percentage of Si and Mn in the alloy meets the following conditions:
Figure FDA0002727422540000022
[Mn]≥1.0
[Si]≥1.0。
10. use of an alloy according to any one of claims 8 to 9 in a furnace tube.
CN202011107426.9A 2020-10-16 2020-10-16 Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy Pending CN114438438A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011107426.9A CN114438438A (en) 2020-10-16 2020-10-16 Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011107426.9A CN114438438A (en) 2020-10-16 2020-10-16 Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy

Publications (1)

Publication Number Publication Date
CN114438438A true CN114438438A (en) 2022-05-06

Family

ID=81357913

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011107426.9A Pending CN114438438A (en) 2020-10-16 2020-10-16 Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy

Country Status (1)

Country Link
CN (1) CN114438438A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5164270A (en) * 1990-03-01 1992-11-17 The United States Of America As Represented By The Department Of Energy Iron-based alloys with corrosion resistance to oxygen-sulfur mixed gases
CN1140197A (en) * 1995-03-23 1997-01-15 菲利浦石油公司 Method for providing tube having coke formation and carbon monoxide inhibiting properties when used for thermal cracking of hydrocarbons
CN101379362A (en) * 2005-12-21 2009-03-04 埃克森美孚研究工程公司 Corrosion resistant material for reduced fouling, heat transfer component with improved corrosion and fouling resistance, and method for reducing fouling
CN103421531A (en) * 2013-07-19 2013-12-04 济南开发区星火科学技术研究院 Method for restraining cracking furnace pipe from coking
CN106590725A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Method for treating internal surface of pyrolysis furnace tube
CN107881392A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of anti-coking alloy material and preparation method thereof and a kind of anti-coking cracking furnace pipe
CN107881431A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of anti-coking alloy material and preparation method thereof and a kind of anti-coking cracking furnace pipe

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5164270A (en) * 1990-03-01 1992-11-17 The United States Of America As Represented By The Department Of Energy Iron-based alloys with corrosion resistance to oxygen-sulfur mixed gases
CN1140197A (en) * 1995-03-23 1997-01-15 菲利浦石油公司 Method for providing tube having coke formation and carbon monoxide inhibiting properties when used for thermal cracking of hydrocarbons
CN101379362A (en) * 2005-12-21 2009-03-04 埃克森美孚研究工程公司 Corrosion resistant material for reduced fouling, heat transfer component with improved corrosion and fouling resistance, and method for reducing fouling
CN103421531A (en) * 2013-07-19 2013-12-04 济南开发区星火科学技术研究院 Method for restraining cracking furnace pipe from coking
CN106590725A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Method for treating internal surface of pyrolysis furnace tube
CN107881392A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of anti-coking alloy material and preparation method thereof and a kind of anti-coking cracking furnace pipe
CN107881431A (en) * 2016-09-29 2018-04-06 中国石油化工股份有限公司 A kind of anti-coking alloy material and preparation method thereof and a kind of anti-coking cracking furnace pipe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李成凯等: "模具制造工艺学", 电子科技大学出版社 *

Similar Documents

Publication Publication Date Title
CN101565807B (en) Method for processing high-temperature alloy furnace tube
CA2474834C (en) Stainless steel and stainless steel pipe having resistance to carburization and coking
MX2011003923A (en) Nickel-chromium alloy.
EP0186800B1 (en) Process for coating carbon and graphite bodies
US7553517B1 (en) Method of applying a cerium diffusion coating to a metallic alloy
CN105154811B (en) A kind of anti-coking alloy material processing method
JP4372243B2 (en) Corrosion resistance of high temperature alloys
US8206658B2 (en) Tube and use of said tube
Staia et al. Chemical vapour deposition of TiN on stainless steel
Li et al. A glass based coating for enhancing anti-coking and anti-carburizing abilities of heat-resistant steel HP
JP5112596B2 (en) Stainless steel matrix surface
CN114438438A (en) Method for improving oxidation resistance, coking resistance and carbonization resistance of alloy
EP0090428A1 (en) A highly buildup-resistant hearth roll for conveying a steel strip through a continuous annealing furnace and a method therefor
CN114438437A (en) Method for heat treatment and vulcanization treatment of alloy, alloy and application
CN114427072A (en) Alloy on-line treatment method, alloy and application
CN114427071A (en) Alloy surface treatment method, alloy and application
CN114427063A (en) Oxidation-resistant coking-resistant carbonization-resistant alloy, and preparation method and application thereof
JP2015190005A (en) Cast product having alumina barrier layer
Mitsui et al. The sulfidation and oxidation behavior of sputter-deposited amorphous Al-Nb-Si alloys at high temperatures
CN112725008B (en) Method for treating inner surface of hydrocarbon cracking furnace tube
CN112725007B (en) Method for treating inner surface of hydrocarbon cracking furnace tube
Habazaki et al. New amorphous alloys resistant to high temperature corrosion
Put et al. Processing of hardmetal coatings on steel substrates
CN107881393B (en) Anti-coking alloy material, preparation method thereof and anti-coking cracking furnace tube
Mitsui et al. High temperature sulfidation and oxidation behavior of sputter-deposited Al-refractory metal alloys

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination