CN114427071A - Alloy surface treatment method, alloy and application - Google Patents

Alloy surface treatment method, alloy and application Download PDF

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Publication number
CN114427071A
CN114427071A CN202011100634.6A CN202011100634A CN114427071A CN 114427071 A CN114427071 A CN 114427071A CN 202011100634 A CN202011100634 A CN 202011100634A CN 114427071 A CN114427071 A CN 114427071A
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alloy
gas
treatment
partial pressure
oxygen partial
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王申祥
郏景省
王红霞
王国清
张利军
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • 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
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • 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
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • C23C8/18—Oxidising of ferrous surfaces

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Abstract

The invention discloses an alloy surface treatment method, an alloy and application. The method comprises the following steps: (1) carrying out extrusion grinding treatment on the surface of the alloy; (2) in pure H2In the atmosphere, the alloy after extrusion grinding is subjected to heat treatment of temperature rise, temperature reduction and temperature rise; (3) and carrying out oxidation treatment on the alloy after heat treatment in the atmosphere of low oxygen partial pressure gas. The method of the invention carries out extrusion grinding treatment on the surface of the alloy, and removes the brittle layer on the surface; the alloy is also subjected to high-temperature low-oxygen partial pressure treatment, so that a very compact oxide layer is formed on the surface of the alloy, the oxidation resistance and carbon deposition resistance are improved, and the method has a good application prospect.

Description

Alloy surface treatment method, alloy and application
Technical Field
The invention relates to the technical field of materials, in particular to an alloy surface treatment method, an alloy and application.
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 oxide film is liable to peel off due to a large difference in thermal expansion coefficient between the oxide film and the furnace tube base, and excessive oxidation causes Cr on the base surface2O3Will 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.
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, 6585864 discloses a coke-inhibiting technique for a coat-alloy furnace tube, which adopts magnetron sputteringThe NiCrAlY coating material is deposited on the base alloy by injection method, then heat treatment is carried out on the base alloy to form a coating material which comprises a diffusion barrier layer, a enrichment 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.
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.
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.
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.
The coating in the patent covers Fe and Ni elements with catalytic coking activity on the inner wall of the furnace tube, and can prevent oxygen elements and carbon elements in the atmosphere from entering a furnace tube substrate, but the coating process is complex, high in cost and limited in service life, 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.
Therefore, the development of a new treatment method for treating the surface of the alloy and improving the carbon deposition resistance of the alloy is a problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an alloy surface treatment method, an alloy and application. 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 on the alloy to form a very compact oxide layer on the surface of the alloy.
The invention aims to provide an alloy surface treatment method.
The method comprises the following steps:
(1) carrying out extrusion grinding treatment on the surface of the alloy;
(2) in pure H2In the atmosphere, the alloy after extrusion grinding is subjected to heat treatment of temperature rise, temperature reduction and temperature rise;
(3) and carrying out oxidation treatment on the alloy after heat treatment in the atmosphere of low oxygen partial pressure gas.
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 heat treatment is carried out in pure H2Heating the alloy to 1100-1200 ℃ in an atmosphere of normal pressure, and then cooling to 300-500 ℃; then the alloy is heated to 800-1100 ℃.
In a preferred embodiment of the present invention,
the temperature rise rate of the step (2) is 20-150 ℃/h; the cooling rate is 20-150 ℃/h.
In a preferred embodiment of the present invention,
and (3) combining one or more of nitrogen, argon and helium with hydrogen and water vapor in the low oxygen partial pressure gas.
In a preferred embodiment of the present invention,
the molar ratio of hydrogen to water vapor in the low-oxygen partial pressure gas is 9-32; preferably 15 to 30;
one or more of nitrogen, argon and helium are used as diluent gas, and can be added or not added according to specific conditions, wherein one or more of nitrogen, argon and helium accounts for 0-80% of the total volume of the low-oxygen partial pressure gas, and more preferably 20-80%.
In a preferred embodiment of the present invention,
the low oxygen partial pressure oxidation temperature is 800-1100 ℃; the low oxygen partial pressure oxidation time is 5-50 hours.
It is another object of the invention 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 BDA0002725205890000051
[Mn]≥1.0
[Si]≥1.0
the invention also aims to provide the application of the alloy in a cracking device.
The invention can adopt the following technical scheme:
the oxidation-resistant, coking-resistant and carbonization-resistant alloy comprises the following contents.
(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 BDA0002725205890000052
[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) Extrusion-milled alloy in pure H2Heating the alloy to 1100-1200 ℃ at a heating rate of 20-150 ℃/h in an atmosphere of normal pressure, and then cooling the alloy to 300-500 ℃ at a cooling rate of 20-150 ℃/h; and then heating the alloy to the low oxygen partial pressure oxidation temperature at the heating rate of 20-150 ℃/h.
(5) Finally, the alloy is processed with low oxygen partial pressure, the low oxygen partial pressure gas comprises hydrogen, water vapor, one or more of nitrogen, argon and helium, wherein H2The molar ratio of the carbon dioxide to the water vapor is 9-32, the low oxygen partial pressure oxidation temperature is 800-1100 ℃, and the oxidation time is 5-50 hours.
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 contents of Si and Mn, and mainly aims at increasing MnO and SiO in an alloy oxide layer2The content of Cr is reduced2O3Content 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。
According to the invention, the step of extrusion grinding is added before low-oxygen partial pressure oxidation, 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, crystal grains are refined, the surface roughness can be greatly improved, and finally a protective layer formed on the surface of the compact and refined alloy is not easy to peel off, so that the anti-coking effect is better; the heating and cooling heat treatment step enables Cr and Mn elements in the furnace tube alloy to absorb oxygen atoms more easily, and the formed spinel protective layer is more uniform and compact.
The alloy matrix of the invention mainly comprises elements Fe, Ni, Cr and Mn, and the sequence of the affinity of the elements to oxygen is Mn>Cr>Fe>And (3) Ni. When the oxygen partial pressure is low2When the molar ratio of the metal oxide to the steam is in the range of 9-32, the formed oxygen partial pressure is very low, only Cr and Mn are oxidized under the oxygen partial pressure, Fe and Ni are not oxidized, and finally Cr is formed on the surface2O3And MnO, which is chemically reacted with MnO + Cr2O3＝MnCr2O4And MnCr2O4The spinel is a new stable spinel, and can prevent Fe and Ni elements from contacting with hydrocarbon gas, thereby inhibiting catalytic coking and prolonging the operation period of a cracking device.
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 numerical control linear cutting machine is used for cutting square samples with the size of 5mm multiplied by 3mm, 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 numerical control linear cutting machine is used for cutting square samples with the size of 5mm multiplied by 3mm, 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 numerical control linear cutting machine is used for cutting square samples with the size of 5mm multiplied by 3mm, 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 numerical control linear cutting machine is used for cutting square samples with the size of 5mm multiplied by 3mm, 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.
Heating and cooling heat treatment: in pure H2In the atmosphere, the temperature is increased to 1150 ℃ at the temperature increasing rate of 40 ℃/h, and then the temperature is decreased to 450 ℃ at the temperature decreasing rate of 40 ℃/h; then heating to 1000 ℃ at the heating rate of 60 ℃/h;
low oxygen partial pressure oxidation treatment: at H2H with a molar ratio to steam of 192-H2O, keeping the temperature at 1000 ℃ for 20 hours under the atmosphere of low oxygen partial pressure.
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 numerical control linear cutting machine is used for cutting square samples with the size of 5mm multiplied by 3mm, 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.
Heating and cooling heat treatment: in pure H2In the atmosphere, the temperature is increased to 1120 ℃ at the heating rate of 60 ℃/h, and then is reduced to 400 ℃ at the cooling rate of 60 ℃/h; then the temperature is increased to 900 ℃ at the heating rate of 50 ℃/h,
low oxygen partial pressure oxidation treatment: at H2H with a molar ratio to steam of 302-H2O oxygen partial pressure atmosphere (wherein nitrogen is 80% of the total gas volume), and maintaining the temperature at 900 ℃ for 40 hours.
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 numerical control linear cutting machine is used for cutting square samples with the size of 5mm multiplied by 3mm, 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.
Heating and cooling heat treatment: in pure H2In the atmosphere, the temperature is increased to 1160 ℃ at the heating rate of 80 ℃/h, and then the temperature is decreased to 480 ℃ at the cooling rate of 100 ℃/h; then heating to 1050 ℃ at the heating rate of 120 ℃/h;
low oxygen partial pressure oxidation treatment: at H2H with a molar ratio to steam of 252-H2O oxygen partial pressure atmosphere (wherein argon gas is 70% of the total gas volume), 1050 ℃ temperature preservation for 45 hours.
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 BDA0002725205890000101
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 temperature is kept constant for 3 hours after the temperature rises to 850 ℃, 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％C2H6Heating to 900 deg.C at a rate of 10 deg.C/min, maintaining at constant temperature for 4 hr at a rate of-2 deg.C/min, heating and maintaining constant temperatureCoking gas is introduced all the time in the temperature 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 BDA0002725205890000121
The oxidation weight gain curve, coking weight gain curve and carbonization weight gain curve of comparative example 4, comparative example 5, comparative example 6 and example 2 are shown in fig. 5, fig. 6 and fig. 7, and the surface element analysis after carbonization is shown in table 3.
Table 32535 carbonized surface element mass percent content
Figure BDA0002725205890000122
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 BDA0002725205890000131
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 (12)

1. A method for treating the surface of an alloy, the method comprising:
(1) carrying out extrusion grinding treatment on the surface of the alloy;
(2) in pure H2In the atmosphere, the alloy after extrusion grinding is subjected to heat treatment of temperature rise, temperature reduction and temperature rise;
(3) and carrying out oxidation treatment on the alloy after heat treatment in the atmosphere of low oxygen partial pressure gas.
2. The process 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; and/or the presence of a gas in the gas,
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; and/or the presence of a gas in the gas,
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 heat treatment is carried out in pure H2Heating the alloy to 1100-1200 ℃ in an atmosphere of normal pressure, and then cooling to 300-500 ℃; then the alloy is heated to 800-1100 ℃.
6. The processing method of claim 5, wherein:
the temperature rise rate of the step (2) is 20-150 ℃/h; the cooling rate is 20-150 ℃/h.
7. The process of claim 1, wherein:
and (3) combining one or more of nitrogen, argon and helium with hydrogen and water vapor in the low oxygen partial pressure gas.
8. The process of claim 7, wherein:
the molar ratio of hydrogen to water vapor in the low-oxygen partial pressure gas is 9-32, preferably 15-30; and/or the presence of a gas in the gas,
one or more of nitrogen, argon and helium accounts for 0-80%, preferably 20-80% of the total volume of the low-oxygen partial pressure gas.
9. The process of claim 7, wherein:
the oxidation treatment temperature is 800-1100 ℃; the oxidation treatment time is 5 to 50 hours.
10. An alloy treated by the method of any one of claims 1 to 9, wherein:
based on the total weight of the alloy as 100 percent,
the alloy comprises:
Figure FDA0002725205880000021
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.
11. The alloy of claim 10, wherein:
the mass percentage of Si and Mn in the alloy meets the following conditions:
Figure FDA0002725205880000022
[Mn]≥1.0
[Si]≥1.0。
12. use of an alloy according to any one of claims 10 to 11 in a cracking apparatus.
CN202011100634.6A 2020-10-15 2020-10-15 Alloy surface treatment method, alloy and application Pending CN114427071A (en)

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