WO2021259233A1 - 抗结焦设备及其制备方法与应用 - Google Patents

抗结焦设备及其制备方法与应用 Download PDF

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Publication number
WO2021259233A1
WO2021259233A1 PCT/CN2021/101435 CN2021101435W WO2021259233A1 WO 2021259233 A1 WO2021259233 A1 WO 2021259233A1 CN 2021101435 W CN2021101435 W CN 2021101435W WO 2021259233 A1 WO2021259233 A1 WO 2021259233A1
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WIPO (PCT)
Prior art keywords
partial pressure
oxygen partial
low oxygen
furnace tube
oxide film
Prior art date
Application number
PCT/CN2021/101435
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English (en)
French (fr)
Inventor
王红霞
王国清
王申祥
郏景省
张利军
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority claimed from CN202010582151.8A external-priority patent/CN113831934B/zh
Priority claimed from CN202010582969.XA external-priority patent/CN113831931B/zh
Priority claimed from CN202010582144.8A external-priority patent/CN113831933B/zh
Priority claimed from CN202010582183.8A external-priority patent/CN113828250B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to US18/002,687 priority Critical patent/US20230313056A1/en
Priority to EP21829149.0A priority patent/EP4151768A4/en
Priority to KR1020237002168A priority patent/KR20230026465A/ko
Priority to JP2022580164A priority patent/JP7500784B2/ja
Publication of WO2021259233A1 publication Critical patent/WO2021259233A1/zh

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    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • 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
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/005—Inhibiting corrosion in hydrotreatment processes
    • 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
    • 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
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • C10G9/203—Tube furnaces chemical composition of the tubes
    • 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
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C23C8/14—Oxidising of ferrous surfaces
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the field of petroleum hydrocarbon cracking and light hydrocarbon aromatization equipment, in particular to an anti-coking equipment and a preparation method and application thereof.
  • Cracking furnaces, quenching boilers and aromatization reactors are commonly used equipment in the petrochemical industry, and are one of the important equipment in the production of ethylene or light hydrocarbon aromatization by hydrocarbon cracking.
  • the materials used in the cracking furnace, quenching boiler and aromatization reactor mainly contain elements such as Fe, Cr, Ni, etc., and the operation of the cracking furnace, quenching boiler and aromatization reactor Under conditions, the Fe and/or Ni elements in the equipment will cause catalytic coking, carburization and other phenomena on the inner wall of the equipment, and eventually lead to cracking furnace tubes, quenching boiler tubes, and light hydrocarbon aromatization reactors.
  • the carbon is serious, the bed pressure drop increases, and it cannot run for a long period of time.
  • the cracking process of heavier hydrocarbon feedstocks is accompanied by a large amount of free radical coking and condensation coking.
  • the researchers also used measures such as increasing the internal components of the reactor, reducing the pressure in the reactor, reducing the residence time, lowering the cracking temperature, and optimizing cracking raw materials to reduce free radical coking and condensation coking during the cracking process.
  • a protective layer on the inner surface of the reactor There are two different methods for forming a protective layer on the inner surface of the reactor: one is to form a protective layer on the inner surface of the reactor by means of thermal spraying, thermal sputtering, high-temperature sintering, chemical heat treatment, chemical vapor deposition, etc.
  • the disadvantage of this type of method is that the protective layer is not firmly bonded to the reactor matrix and is easy to peel off; the other is to form an oxide protective layer in situ on the inner surface of the reactor through a specific atmosphere treatment at a certain temperature.
  • the advantages of this method The protective layer has a strong bonding force with the furnace tube base, and it is not easy to peel off.
  • the coking is also based on catalytic coking
  • condensation coking accounts for more than 50% of the total coke, and condensation coking can completely cover the oxide film. Therefore, the oxide film in the liquid cracking furnace tube is only effective in the initial stage of service of the furnace tube, because at this time the oxide film has not been covered by condensation coking, and when the cracking furnace runs to the middle and late stages, the oxide film cannot exert its effect.
  • CN105506713A discloses a method for forming a chromium-based coating on a component, which includes: immersing the component and a counter electrode in an electrolyte containing trivalent chromium salt and nano-ceramic particles; applying on the component and the counter electrode Electric current; and electroplating a chromium-based coating including chromium and nano-ceramic particles on the component. It is electroplated to form a chromium coating to cover Fe and Ni elements.
  • CN103374705A discloses a magnetron sputtering device, which includes a reaction chamber, a chuck and a target.
  • the chuck is arranged at the bottom of the reaction chamber and is used to carry a workpiece to be processed.
  • the target is arranged at the bottom of the reaction chamber.
  • a side magnet is provided on the outside of the side wall of the reaction chamber, and the side magnet is located above the chuck, wherein an auxiliary magnet is included on the edge of the chuck, and the auxiliary magnet
  • the magnetic poles of the magnet are arranged in the same direction as the magnetic poles of the side magnets, the auxiliary magnet and the side magnets form a magnetic circuit, and the metal ions in the plasma are moved to the edge area of the reaction chamber by means of the magnetic circuit, In order to increase the deposition amount of target particles in the edge area of the processed workpiece.
  • the inert coating is formed by a magnetron sputtering device.
  • the purpose of the present invention is to overcome the problems of coking and carburization of the inner wall of the equipment in the prior art, and the difficulty in preparing the oxide film on the inner surface of the equipment, and to provide an anti-coking equipment and a preparation method and application thereof.
  • a dense and stable oxide film is formed on the inner surface of the equipment prepared by this method to inhibit or slow down the catalysis Coking phenomenon reduces the degree of equipment carburization and prolongs the service life of equipment.
  • the first aspect of the present invention provides a method for preparing an anti-coking device, characterized in that the method comprises: contacting and reacting a low oxygen partial pressure gas with the device to obtain an anti-coking device containing an oxide film on the inner surface equipment;
  • the dew point of the low oxygen partial pressure gas is -40°C to 40°C.
  • the second aspect of the present invention provides an anti-coking device prepared by the above preparation method.
  • the third aspect of the present invention provides an application of the above-mentioned anti-coking equipment in at least one of a cracking furnace, a quenching boiler and an aromatization reactor.
  • the anti-coking equipment provided by the present invention and the preparation method and application thereof obtain the following beneficial effects:
  • the present invention controls the dew point of the low oxygen partial pressure gas, in particular, by controlling the relationship between the dew point of the low oxygen partial pressure gas and the content of metal elements in the oxide film of the anti-coking equipment, it can ensure that the internal surface of the equipment is formed with a dense and compact structure.
  • the stable oxide film significantly inhibits or slows down the phenomenon of catalytic coking, reduces the degree of equipment carburization, and prolongs the service life of the equipment.
  • the inner surface of the anti-coking equipment provided by the present invention contains an oxide film generated by in-situ growth, and the obtained oxide film has a strong bonding force with the equipment substrate. While solving the equipment coking and carburization problems, the equipment can long-term use.
  • the first aspect of the present invention provides a method for preparing an anti-coking device, which is characterized in that the method includes: contacting and reacting a low oxygen partial pressure gas with the device to obtain an anti-coking device with an oxide film on the inner surface;
  • the dew point of the low oxygen partial pressure gas is -40°C to 40°C.
  • the low oxygen partial pressure atmosphere refers to a reducing atmosphere in which the oxygen partial pressure is low, so the oxidation process that occurs is very slow, which is beneficial to the formation of a dense oxide film on the surface of the material.
  • the oxygen partial pressure refers to the pressure occupied by the oxygen existing in the atmosphere.
  • the oxygen in the atmosphere mainly comes from the oxygen generated by the decomposition of oxygen- containing compounds (such as H 2 O).
  • a low oxygen partial pressure atmosphere is difficult to obtain, and it is very difficult and difficult to achieve a stable low oxygen partial pressure atmosphere through a flow control device.
  • the inventor surprisingly found that by controlling the dew point of the mixed gas, for example, controlling the dew point of the low oxygen partial pressure gas at -40°C to 40°C, it is possible to ensure a compact and stable structure on the inner surface of the device.
  • the oxide film significantly inhibits or slows down the phenomenon of catalytic coking, reduces the degree of equipment carburization, and prolongs the service life of the equipment.
  • the dew point refers to the temperature at which saturated water vapor in the air begins to condense and dew.
  • the temperature of the surrounding environment is the dew point temperature.
  • the method further includes the step of measuring the dew point of the low oxygen partial pressure gas.
  • the method further includes testing the dew point of the low oxygen partial pressure gas (using a commercially available dew point tester) before the low oxygen partial pressure gas contacts the equipment, so that the low oxygen partial pressure gas in contact with the equipment
  • the partial pressure gas has the dew point defined by the present invention.
  • the method further includes the step of using a commercially available dew point tester to monitor the dew point of the low oxygen partial pressure gas in the contact reaction system in real time during the contact reaction.
  • the constituent elements of the device include iron and/or nickel.
  • the oxide film includes chromium manganese oxide and metal elements, and the metal elements are iron and/or nickel.
  • the composition of the chromium manganese oxide is Mn x Cr 3-x O 4 , and the value of x is 0.5-2.
  • the content of metal elements in the equipment before the contact reaction and the content of metal elements in the oxide film of the anti-coking equipment after the contact reaction are measured by the X-ray energy spectrum analysis (EDS) method.
  • EDS X-ray energy spectrum analysis
  • the dew point of the low oxygen partial pressure gas and the content of metal elements in the oxide film of the anti-coking device satisfy the following relationship:
  • W1 is the content of metal elements in the equipment before the contact reaction, wt%
  • W2 is the content of metal elements in the oxide film of the equipment after the contact reaction, wt%
  • T is the dew point of the low oxygen partial pressure gas, °C.
  • the present invention by controlling the dew point of the low-oxygen partial pressure gas and the content of metal elements in the oxide film of the anti-coking device to meet the above relationship, it can further ensure the formation of a dense and stable oxide film on the inner surface of the device, significantly suppressing or Reduce the phenomenon of catalytic coking, reduce the degree of equipment carburization, and extend the service life of the equipment.
  • the equipment is selected from at least one of alloy furnace tubes, quench boilers and light hydrocarbon aromatization reactors.
  • the alloy furnace tube may be a nickel-chromium alloy furnace tube commonly used in the prior art.
  • the total content of metal elements in the alloy furnace tube before the contact reaction is 25-90 wt%.
  • the metal element contains 20-50wt% of nickel and 5-40wt% of iron. Further, in addition to the above-mentioned iron and nickel, the alloy furnace tube also contains Including 12-50wt% of chromium, 0.2-3wt% of manganese, 1-3wt% of silicon, 0.1-0.75wt% of carbon, 0-5wt% of trace elements and trace elements.
  • the total content of the metal element is 37-83wt%, specifically, the metal element contains 25-48wt% nickel and 12-35wt% iron.
  • the alloy furnace tube In addition to the iron and nickel elements mentioned above, it also includes 20-38wt% chromium, 1-2.5wt% manganese, 1-2wt% silicon, 0.1-0.6wt% carbon, 0-3wt% Trace elements and trace elements.
  • the trace element is selected from one or more of niobium, titanium, tungsten, aluminum and rare earth; the trace element is selected from sulfur and/or phosphorus.
  • the total content of metal elements in the tube side of the quenching boiler tube before the contact reaction is 76.4-98wt%.
  • the metal element in the tube side furnace tube of the quenching boiler is iron.
  • the tube side furnace tube alloy of the quenching boiler also includes 1.5-20wt% of chromium and 0.2-0.6wt% of molybdenum. , 0.3-0.8wt% of manganese, 0.4-2wt% of silicon, 0.1-0.2wt% of carbon, ⁇ 5wt% of oxygen, 0-1wt% of trace elements.
  • the trace element in the tube side furnace tube of the quenching boiler is at least one of Al, Nb, Ti, W and rare earth elements.
  • the quenching boiler can be a conventional boiler in the prior art, and can be manufactured by using a conventional manufacturing technology in the prior art.
  • the inner surface is bright, without oxide scale, and the oxygen content is less than 5wt%.
  • the total content of the metal element (iron element) in the tube side of the quenching boiler tube before the contact reaction is 80-97wt%, in addition to the above-mentioned metal element (iron element), it also includes 2- 15wt% chromium, 0.25-0.35wt% molybdenum, 0.55-0.65wt% manganese, 0.5-1.9wt% silicon, 0.14-0.17wt% carbon, ⁇ 3wt% oxygen, 0.15 -0.65wt% of trace elements.
  • the tube side furnace tube alloy of the quenching boiler may be a conventional alloy in the art, such as 15Mo3.
  • the alloy material of the aromatization reactor is selected from at least one of stainless steel 304, 316, and 321. More preferably, the alloy material of the aromatization reactor is stainless steel 304.
  • the content of metal elements in the structured reactor is 68-81 wt%.
  • the aromatization reactor may be a conventional aromatization reactor in the prior art or an aromatization reactor prepared by a conventional manufacturing technology in the prior art.
  • the dew point of the low oxygen partial pressure gas is -30°C to 30°C; in formula I, -0.0005 ⁇ a ⁇ -0.0003, 0.001 ⁇ b ⁇ 0.0092, 0.7355 ⁇ c ⁇ 0.8308, R 2 ⁇ 0.9539.
  • the dew point of the low oxygen partial pressure gas is -20°C to 20°C; in formula I, -0.0006 ⁇ a ⁇ -0.0003, 0.001 ⁇ b ⁇ 0.0092, 0.7269 ⁇ c ⁇ 0.8308, R 2 ⁇ 0.879.
  • the dew point of the low oxygen partial pressure gas is -15°C to 15°C; in formula I, -0.0006 ⁇ a ⁇ -0.0005, 0.0021 ⁇ b ⁇ 0.0049, 0.7419 ⁇ c ⁇ 0.8109, R 2 ⁇ 0.879.
  • the dew point of the low oxygen partial pressure gas is -15°C to 10°C; in formula I, -0.0005 ⁇ a ⁇ -0.0003, 0.0021 ⁇ b ⁇ 0.0053, 0.7419 ⁇ c ⁇ 0.8138, R 2 ⁇ 0.8943.
  • the low oxygen partial pressure gas is CO 2 and/or H 2 O and selected from CO, CH 4 , C 2 H 6 , C 3 H 8 , NH 3 , H 2 , N 2 , Ar, He A gas mixture of at least one of, air and cracked gas.
  • the low oxygen partial pressure gas is selected from the group consisting of a gas mixture of CH 4 and H 2 O, a gas mixture of CO 2 and CO, a gas mixture of H 2 O and CO, and a gas mixture of H 2 O and H 2 At least one.
  • the method further includes the step of determining the dew point of the low oxygen partial pressure gas.
  • the conditions of the contact reaction include: a reaction temperature of 400-1100°C, preferably 600-1100°C; and a reaction time of 5-100h, preferably 5-72h.
  • the conditions of the contact reaction include: a reaction temperature of 750-1000° C., and a reaction time of 20-50 h.
  • the conditions of the contact reaction include: a contact temperature of 700-950°C, and a reaction time of 10-80h.
  • the conditions of the contact reaction include: a contact temperature of 750-950° C., and a contact time of 20-60 h.
  • the conditions of the contact reaction include: a reaction temperature of 800-1050° C., and a reaction time of 30-60 h.
  • the flow rate of the low oxygen partial pressure gas is 100-500 mL/min, preferably 200-400 mL/min.
  • the contact reaction can be carried out in equipment that can maintain a certain atmosphere in the conventional art, for example, the contact can be carried out in at least one of a tube furnace, a pit furnace, and an atmosphere box furnace. reaction.
  • the equipment is an alloy furnace tube for a cracking furnace.
  • the alloy furnace tube includes a strengthened heat transfer member fixed in the furnace tube.
  • the inventors discovered that by installing an enhanced heat transfer member in the furnace tube, the enhanced heat transfer member changes the flow state of the low oxygen partial pressure gas during the contact reaction between the furnace tube and the low oxygen partial pressure gas.
  • the trace amount of O 2 in the low oxygen partial pressure gas can fully contact the tube wall, so that the tube wall is completely oxidized, and the content of metal elements in the formed oxide film is further reduced.
  • the gas contacts the tube wall in a laminar flow state, and the O 2 in the middle of the gas flow basically does not participate in the oxidation reaction of the tube wall. It cannot be completely oxidized, so the metal element content in the formed oxide film is relatively high.
  • the enhanced heat transfer member changes the flow state of the cracked gas near the tube wall from laminar flow to turbulent flow, and the condensation coking on the inner surface of the furnace tube is easily washed away by the cracking airflow.
  • Condensation coking is generally relatively loose coke, and its adhesion to the inner wall of the furnace tube is relatively weak. Therefore, the coke attached to the inner wall of the furnace tube containing the enhanced heat transfer component is still mainly catalytic coking, so that the oxide film formed by the low oxygen partial pressure can fully exert its effect, thereby significantly extending the operating cycle of the cracking furnace.
  • the enhanced heat transfer member may be a conventional component in the prior art that can change the fluid flow state and improve the thermal conductivity, for example, preferably at least one selected from the group consisting of twisted fins, internal fins and internal fins.
  • an alloy furnace tube for a cracking furnace provided with a heat transfer enhancement member can be obtained by a conventional method in the art.
  • alloy furnace tubes for cracking furnaces are usually cast by centrifugal casting, while furnace tubes with strengthened heat transfer components in the tubes have different processing forms, such as: furnace tubes with twisted fins or internal fin components in the tube Usually, it is obtained by static casting; the furnace tube with internal fin members is formed by welding the fins inside the furnace tube.
  • alloy furnace tubes for cracking furnaces equipped with enhanced heat transfer components are also commercially available, such as Kellogg’s plum tube (a tube with internal fins in the tube), and Kubota’s MERT tube (with internal ribs in the tube). Sheet tube) and Sinopec's twisted sheet tube (a tube with a twisted sheet inside the tube), etc.
  • the length of the strengthened heat transfer member tube is 20-80 cm, and the number is 1-200, which are distributed in different tube passes of the entire furnace tube.
  • the second aspect of the present invention provides an anti-coking device prepared by the above preparation method.
  • the inner surface of the anti-coking device contains an oxide film including chromium manganese oxide and metal elements.
  • the activity is higher than the Fe element and/or Ni element, so the chromium and manganese elements on the inner surface of the equipment will be reduced under the condition of very low oxygen partial pressure.
  • Slow oxidation occurs, but iron and/or nickel are basically not oxidized, and because the oxygen partial pressure of the atmosphere is very low, the oxidation process is very slow, and the internal surface of the equipment is formed in situ with strong and dense binding force to the equipment matrix.
  • Oxide film which can cover the iron and nickel elements that have a catalytic effect on equipment coking, so that the iron and/or nickel content on the inner wall of the equipment is reduced, thereby slowing or inhibiting the coking and carburization of the equipment, and extending the equipment Operation cycle.
  • the total content of iron and/or nickel in the oxide film on the inner surface of the equipment obtained by the above method is relatively low, which can inhibit the catalytic coking of the hydrocarbon cracking process or aromatization reaction process and extend the equipment
  • the operating cycle meets the requirements of long-term use of the equipment.
  • the third aspect of the present invention provides the application of the above-mentioned anti-coking equipment in at least one of a cracking furnace, a quenching boiler and an aromatization reactor.
  • the raw material for cracking may be gaseous hydrocarbons or liquid hydrocarbons.
  • the gaseous hydrocarbons are at least one of ethane, propane, butane and liquefied petroleum gas;
  • the liquid hydrocarbons are at least one of naphtha, condensate oil, hydrocracking tail oil and diesel oil. A sort of.
  • the cracking reaction can be carried out according to the conventional cracking process in the prior art.
  • the cracking temperature is 770-880°C, and the water-oil ratio is 0.3-0.8.
  • the cracking temperature of naphtha is 830-850°C, and the water-oil ratio is 0.5-0.55.
  • the light hydrocarbon aromatization reaction can be carried out according to the conventional aromatization reaction conditions in the prior art. Specifically, the reaction temperature is 280-530°C, and the reaction pressure is 0.3 MPa.
  • the element composition of the equipment is measured by the X-ray energy spectrum analysis (EDS) method;
  • the dew point of the low oxygen partial pressure gas is measured by a commercially available dew point tester
  • the coking amount of the equipment is calculated by using an infrared meter to measure the concentration of CO and CO 2 in the coking gas online and using a wet gas flowmeter to measure the volume of the coking gas online;
  • the raw material for cracking is naphtha, and its physical properties are: distillation range 32.8-173.8°C, specific gravity D 20 of 0.7058g/ml.
  • a small-scale cracking furnace tube or simulated quench boiler low-oxygen partial pressure atmosphere treatment and naphtha cracking production ethylene coking evaluation test were carried out on a self-made laboratory device with a 200g/h feed rate.
  • the aromatization reaction of light hydrocarbons is carried out in a small-scale reactor after treatment in a low oxygen partial pressure atmosphere.
  • the HZSM-5 catalyst is used.
  • the raw material is n-hexane.
  • the aromatization reaction conditions reaction volumetric space velocity 1h -1 , reaction temperature 500 °C, hydrogen oil volume ratio 400:1, reaction pressure 0.3MPa, reaction time 20 hours.
  • the furnace tube of the radiant section of the industrial cracking furnace whose tube material is 35Cr45Ni has been treated with a low oxygen partial pressure gas atmosphere.
  • the element composition of the furnace tube alloy is (wt%): Cr: 32.55, Ni: 42.60, Fe: 21.12, Mn: 0.98, Si: 1.41, Nb: 0.64, C: 0.53, and others: 0.17.
  • twisted sheet tubes integrally made with the furnace tube are arranged along the axial direction. The axial length of the twisted sheet twisted by 180° is a pitch.
  • the distance between them is 15 pitches, the length of the twisted sheet tube is 35cm, and the number is 100, which are distributed in different tube passes of the entire furnace tube.
  • the low oxygen partial pressure gas used is a gas mixture of CO and water vapor.
  • the dew point of the mixed gas is 5°C, the treatment temperature is 900°C, and the treatment time is 50 hours.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4 , and the total content of iron and nickel is 9.93 wt% relative to the total weight of the oxide film.
  • Hydrocarbon steam cracking reaction is carried out in an industrial cracking furnace treated with a low oxygen partial pressure gas atmosphere.
  • the cracking raw material is naphtha. Its physical properties are: distillation range 32.8-173.8°C, specific gravity D 20 of 0.7058g/ml; cracking conditions The temperature at the outlet of the furnace tube is 830°C, and the water-oil ratio is 0.55.
  • the operating cycle of the cracking furnace reaches 230 days.
  • the HP40 (Cr25Ni35) small test furnace tube containing a twisted sheet tube is pre-oxidized with low oxygen partial pressure.
  • the element composition of the furnace tube alloy is: Cr: 25.1, Ni: 35.2, Mn: 1.0, Si: 1.5, C : 0.4, p ⁇ 0.03, S ⁇ 0.03, the balance is Fe (wt%).
  • a gas mixture of CO and water vapor is used as the low oxygen partial pressure atmosphere treatment gas, where the dew point of the mixed gas is 5°C, the flow rate of the low oxygen partial pressure gas is 400ml/min, the treatment temperature is 950°C, and the treatment time is 30 hours.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 11.27 wt% relative to the total weight of the oxide film.
  • Hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated in a low oxygen partial pressure atmosphere.
  • the cracking raw material is naphtha. Its physical properties are: distillation range 32.8-173.8°C, specific gravity D 20 of 0.7058g/ml; cracking conditions It is: the cracking temperature is 845°C, and the water-oil ratio is 0.5.
  • the amount of coking of the furnace tube of the present invention is reduced by 95.21% compared with the amount of coking of the HP40 (Cr25Ni35) furnace tube that does not contain a heat transfer enhancement member and is not treated with a low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixture was 8°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 12.88 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the furnace tube of the present invention is reduced by 90.15% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain the heat transfer member in the prior art and is not treated with low oxygen partial pressure.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixture was 2°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 13.29 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the amount of coking of the furnace tube of the present invention is reduced by 86.38% compared with the amount of coking of the HP40 (Cr25Ni35) furnace tube that does not contain heat transfer enhancement members and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference is that the dew point of the mixed gas of CO and steam is 10°C.
  • the other treatment conditions are the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 14.80 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the furnace tube of the present invention is reduced by 81.46% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain the heat transfer member in the prior art and is not treated with low oxygen partial pressure.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixed gas was 0°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 15.89 wt% relative to the total weight of the oxide film.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the furnace tube of the present invention is reduced by 75.69% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain a heat transfer enhancement member and is not treated with a low oxygen partial pressure in the prior art.
  • the steam cracking reaction of hydrocarbons is carried out in the industrial cracking furnace, and the cracking raw materials and cracking conditions are the same as in Example 1.
  • the operating cycle of the cracking furnace is 100 days.
  • the operation period of the cracking furnace is 55 days.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixed gas was 20°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 17.62 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 33.90% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CO and steam was -10°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 19.01 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 24.55% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CO and steam was -30°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 42.39 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is reduced by 17.15% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixed gas was -40°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 51.72 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is reduced by 13.09% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CO and steam was -20°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 34.96 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 18.64% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixture was -15°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4 , and the total content of iron and nickel is 26.98 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 20.73% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixed gas was 15°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 15.4 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 65.88% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted flakes and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixed gas was 30°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 27.94 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 30.23% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO and steam mixture was 40°C. The other treatment conditions were the same as in Example 2.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel relative to the total weight of the oxide film is 37.41 wt%.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the small test furnace tube is 28.56% less than that of the HP40 (Cr25Ni35) furnace tube that does not contain twisted pieces and is not treated with low oxygen partial pressure in the prior art.
  • Example 2 The same small test furnace tube as in Example 2, except that it does not contain twisted pieces and is not treated with low oxygen partial pressure.
  • the hydrocarbon steam cracking reaction is carried out in the small test furnace tube.
  • the cracking raw materials and cracking conditions are the same as those in Example 2. same.
  • the coking amount of the small test furnace tube is 100%.
  • the HP40 (Cr25Ni35) small test furnace tube was pre-oxidized with low oxygen partial pressure, and the element composition of the furnace tube alloy was (wt%): Cr: 25.1, Ni: 35.2, Mn: 1, Si: 1.5, C: 0.4, P ⁇ 0.03, S ⁇ 0.03, and the balance is Fe.
  • a gas mixture of H 2 and H 2 O is used as the low oxygen partial pressure atmosphere treatment gas, where the dew point of the mixed gas is 10°C, the flow rate of the low oxygen partial pressure gas is 400ml/min, the treatment temperature is 950°C, and the treatment time is 30
  • an oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the furnace tube.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4
  • the contents of iron and nickel in the oxide film are 3.76 wt% and 4.58 wt%, respectively.
  • Hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated in a low oxygen partial pressure atmosphere.
  • the cracking raw material is naphtha. Its physical properties are: distillation range 32.8-173.8°C, specific gravity D 20 of 0.7058g/ml; cracking conditions It is: the cracking temperature is 845°C, and the water-oil ratio is 0.5.
  • the amount of coking of the furnace tube of the present invention is reduced by 91.85% compared with the amount of coking of the HP40 (Cr25Ni35) furnace tube that has not been treated with low oxygen partial pressure in the prior art.
  • Example 16 The same small test furnace tube as in Example 16 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the H 2 and H 2 O mixed gas was 20°C. The other treatment conditions were the same as in Example 16.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the wall surface.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4 , and the contents of iron and nickel in the oxide film are 5.23 wt% and 4.87 wt%, respectively.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 16.
  • the coking amount of the furnace tube of the present invention is reduced by 87.65% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube without low oxygen partial pressure treatment in the prior art.
  • Example 16 The same small test furnace tube as in Example 16 was subjected to low oxygen partial pressure pre-oxidation treatment, except that the dew point of the H 2 and H 2 O mixed gas was 0°C, and the other treatment conditions were the same as in Example 16.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the wall surface.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4 , and the contents of iron and nickel in the oxide film are 6.48 wt% and 5.69 wt%, respectively.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 16.
  • the coking amount of the furnace tube of the present invention is reduced by 80.65% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube without low oxygen partial pressure treatment in the prior art.
  • Example 16 The same small test furnace tube as in Example 16 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the H 2 and H 2 O mixed gas was 40°C. The other treatment conditions were the same as in Example 16.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the wall surface.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4 , and the contents of iron and nickel in the oxide film are 11.02wt% and 8.28wt%, respectively.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 16.
  • the coking amount of the furnace tube of the present invention is 51.87% less than that of the HP40 (Cr25Ni35) furnace tube that has not been treated with low oxygen partial pressure in the prior art.
  • Example 16 The same small test furnace tube as in Example 16 was subjected to low-oxygen partial pressure pre-oxidation treatment, except that the dew point of the H 2 and H 2 O mixed gas was -40°C, and the other treatment conditions were the same as in Example 16.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the tube.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4 , and the contents of iron and nickel in the oxide film are 15.89wt% and 13.95wt%, respectively.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 16.
  • the coking amount of the furnace tube of the present invention is reduced by 32.58% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube without low oxygen partial pressure treatment in the prior art.
  • Example 16 The same small test furnace tube as in Example 16 was subjected to low oxygen partial pressure pre-oxidation treatment, except that the dew point of the H 2 and H 2 O mixed gas was 50 °C, and the other treatment conditions were the same as in Example 16.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the wall surface.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4 , and the contents of iron and nickel in the oxide film are 20.13 wt% and 19.78 wt%, respectively.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 16.
  • the coking amount of the small test furnace tube is 19.69% less than that of the HP40 (Cr25Ni35) furnace tube without low oxygen partial pressure treatment in the prior art.
  • Example 16 The same small test furnace tube as in Example 16 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the H 2 and H 2 O mixed gas was -50°C. The other treatment conditions were the same as in Example 16.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the tube.
  • the chromium manganese oxide in the oxide film is MnCr 2 O 4
  • the contents of iron and nickel in the oxide film are 25.09wt% and 24.95wt%, respectively.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 16.
  • the coking amount of the small test furnace tube is reduced by 13.48% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that has not been treated with low oxygen partial pressure in the prior art.
  • Example 16 The same small test furnace tube as in Example 16, without low oxygen partial pressure pre-oxidation treatment, the hydrocarbon steam cracking reaction was carried out in the small test furnace tube, and the cracking raw materials and cracking conditions were the same as in Example 16.
  • the coking amount of the small test furnace tube is 100%.
  • the element composition of the furnace tube alloy is (wt%): Cr: 1.03, Mo: 0.47, Mn: 0.58, Si: 0.32, C: 0.16 , O: 2.13, Fe: 96.87, and other 0.24.
  • a gas mixture of CO 2 and CO is used as a low oxygen partial pressure atmosphere treatment gas, where the dew point of the mixed gas is 0°C, the flow rate of the low oxygen partial pressure gas is 400ml/min, the treatment temperature is 900°C, and the treatment time is 35 hours.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the surface of the inner wall of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4 , and the content of iron in the oxide film is 25 wt%.
  • the steam cracking reaction of hydrocarbons is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere.
  • the cracking conditions are: cracking temperature 845°C and water-oil ratio 0.5.
  • the experimental results show that the coking capacity of the quenching boiler of the present invention is reduced by 88% compared with the coking capacity of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO 2 and CO mixed gas was 10°C. The other treatment conditions were the same as in Example 21.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4
  • the content of iron in the oxide film is 28 wt%.
  • the steam cracking reaction of hydrocarbons was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 21.
  • the coking amount of the quenching boiler of the present invention is reduced by 82% compared with the coking amount of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO 2 and CO mixture was -10°C. The other treatment conditions were the same as in Example 21.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4 , and the content of iron in the oxide film is 32 wt%.
  • the steam cracking reaction of hydrocarbons was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 21.
  • the coking amount of the quenching boiler of the present invention is reduced by 78% compared with the coking amount of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO 2 and CO mixture was 20°C. The other treatment conditions were the same as in Example 21.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4
  • the content of iron in the oxide film is 35 wt%.
  • the steam cracking reaction of hydrocarbons was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 21.
  • the coking amount of the quenching boiler of the present invention is reduced by 51% compared with the coking amount of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO 2 and CO mixed gas was -20°C. The other treatment conditions were the same as in Example 21.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4 , and the content of iron in the oxide film is 38 wt%.
  • the steam cracking reaction of hydrocarbons was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 21.
  • the coking amount of the quenching boiler of the present invention is reduced by 40% compared with the coking amount of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO 2 and CO mixed gas was 30°C. The other treatment conditions were the same as in Example 21.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the inner wall surface of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4
  • the content of iron in the oxide film is 51 wt%.
  • the steam cracking reaction of hydrocarbons was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 21.
  • the coking capacity of the quenched boiler after treatment was reduced by 21% compared with the coking capacity of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the CO 2 and CO mixture was -30°C. The other treatment conditions were the same as in Example 21.
  • An oxide film mainly containing Cr, Mn, Fe, O, Si and other elements is formed on the surface.
  • the chromium manganese oxide in the oxide film is Mn 2 CrO 4 , and the content of iron in the oxide film is 57 wt%.
  • the steam cracking reaction of hydrocarbons was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 21.
  • the coking capacity of the quenched boiler after treatment is reduced by 15% compared with the coking capacity of the untreated quenching boiler.
  • Example 21 The same small test furnace tube as in Example 21, except that the low oxygen partial pressure treatment is not performed, and the hydrocarbon steam cracking reaction is carried out in the small test furnace tube.
  • the cracking raw materials and the cracking conditions are the same as in Example 21.
  • the coking capacity of the quench boiler is 100%.
  • the low-oxygen partial pressure atmosphere treatment of the aromatization reactor and the light hydrocarbon aromatization reaction evaluation test were carried out on the small-scale test device. After mechanical processing, the inner surface of the reactor is bright and has no scale.
  • the element composition of the reactor alloy is (wt%): Cr: 18.05, Ni: 7.71, Mn: 1.43, Si: 1.34, C: 1.91, O: 2.78, Al: 0.64, Fe: 66.14.
  • a gas mixture of CH 4 and H 2 O is used as a low oxygen partial pressure atmosphere treatment gas, where the dew point of the mixed gas is 3°C, the flow rate of the low oxygen partial pressure gas is 400ml/min, the treatment temperature is 900°C, and the treatment time is 30
  • an oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4
  • the sum of the content of iron and nickel in the oxide film is 14 wt%.
  • Example 28 The same small-scale reactor as in Example 28 was subjected to low oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CH 4 and H 2 O was 5°C. The other treatment conditions were the same as in Example 28.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4
  • the sum of the content of iron and nickel in the oxide film is 18 wt%.
  • the light hydrocarbon aromatization reaction was carried out in a small-scale reactor treated with a low oxygen partial pressure atmosphere, using the same catalyst, and the reaction raw materials and reaction conditions were the same as in Example 28.
  • the coking capacity of the aromatization reactor of the present invention is reduced by 80% compared with the coking capacity of the untreated aromatization reactor.
  • Example 28 The same small-scale reactor as in Example 28 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CH 4 and H 2 O was -5°C. The other treatment conditions were the same as in Example 28.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the vessel.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4
  • the sum of the content of iron and nickel in the oxide film is 21 wt%.
  • the light hydrocarbon aromatization reaction was carried out in a small-scale reactor treated with a low oxygen partial pressure atmosphere, using the same catalyst, and the reaction raw materials and reaction conditions were the same as in Example 28.
  • the coking capacity of the aromatization reactor of the present invention is reduced by 76% compared with the coking capacity of the untreated aromatization reactor.
  • Example 28 The same small-scale reactor as in Example 28 was subjected to low oxygen partial pressure pre-oxidation treatment, except that the dew point of the CH 4 and H 2 O mixed gas was 15° C.
  • the other treatment conditions were the same as in Example 28.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4
  • the sum of the content of iron and nickel in the oxide film is 24 wt%.
  • the light hydrocarbon aromatization reaction was carried out in a small-scale reactor treated with a low oxygen partial pressure atmosphere, using the same catalyst, and the reaction raw materials and reaction conditions were the same as in Example 28.
  • the coking capacity of the aromatization reactor of the present invention is reduced by 50% compared with the coking capacity of the untreated aromatization reactor.
  • Example 28 The same small-scale reactor as in Example 28 was subjected to low oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CH 4 and H 2 O was -15°C. Other treatment conditions were the same as those in Example 28.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the vessel.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4
  • the sum of the content of iron and nickel in the oxide film is 28 wt%.
  • the light hydrocarbon aromatization reaction was carried out in a small-scale reactor treated with a low oxygen partial pressure atmosphere, using the same catalyst, and the reaction raw materials and reaction conditions were the same as in Example 28.
  • the coking capacity of the aromatization reactor of the present invention is reduced by 39% compared with the coking capacity of the untreated aromatization reactor.
  • Example 28 The same small-scale reactor as in Example 28 was subjected to low oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CH 4 and H 2 O was 25° C. The other treatment conditions were the same as in Example 28.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4
  • the sum of the content of iron and nickel in the oxide film is 37 wt%.
  • the light hydrocarbon aromatization reaction was carried out in a small-scale reactor after treatment in a low oxygen partial pressure atmosphere, using the same catalyst, and the reaction raw materials and reaction conditions were the same as in Example 28.
  • the coking capacity of the treated aromatization reactor was reduced by 20% compared with the coking capacity of the untreated aromatization reactor.
  • Example 28 The same small-scale reactor as in Example 28 was subjected to low oxygen partial pressure pre-oxidation treatment. The difference was that the dew point of the mixed gas of CH 4 and H 2 O was -25°C. The other treatment conditions were the same as those in Example 28.
  • An oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the vessel.
  • the chromium manganese oxide in the oxide film is Mn 0.5 Cr 2.5 O 4 , and the sum of the content of iron and nickel in the oxide film is 45% by weight.
  • the light hydrocarbon aromatization reaction was carried out in a small-scale reactor treated with a low oxygen partial pressure atmosphere, using the same catalyst, and the reaction raw materials and reaction conditions were the same as in Example 28.
  • the coking capacity of the treated aromatization reactor was reduced by 14% compared with the coking capacity of the untreated aromatization reactor.
  • the coking capacity of the aromatization reactor is 100%.
  • Example 2 The same small test furnace tube as in Example 2 was subjected to low-oxygen partial pressure pre-oxidation treatment. The difference was that the volume percentage of water vapor in the low-oxygen partial pressure gas was 7.5% (corresponding to a dew point of 41°C), and other treatment conditions were the same as The same as in Example 2, an oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 52.85 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction is carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions are the same as in Example 2.
  • the coking amount of the furnace tube of the present invention is reduced by 12.32% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain a heat transfer enhancement member and is not treated with a low oxygen partial pressure in the prior art.
  • Example 14 The same small test furnace tube as in Example 14 was subjected to low-oxygen partial pressure pre-oxidation treatment, the difference is: control the volume percentage of water vapor in the low-oxygen partial pressure gas to 4.2% (corresponding to a dew point of 30 °C), other treatments
  • the conditions are the same as in Example 14, an oxide film mainly containing Cr, Mn, Ni, Fe, O, Si and other elements is formed on the surface of the inner wall of the furnace tube.
  • the chromium manganese oxide in the oxide film is Mn 1.5 Cr 1.5 O 4
  • the total content of iron and nickel is 38.08 wt% relative to the total weight of the oxide film.
  • the hydrocarbon steam cracking reaction was carried out in a small test furnace tube treated with a low oxygen partial pressure atmosphere, and the cracking raw materials and cracking conditions were the same as in Example 14.
  • the coking amount of the furnace tube of the present invention is reduced by 25.45% compared with the coking amount of the HP40 (Cr25Ni35) furnace tube that does not contain a heat transfer enhancement member and is not treated with a low oxygen partial pressure in the prior art.

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Abstract

一种抗结焦设备及其制备方法与应用。该制备方法包括：将低氧分压气体与设备进行接触反应，得到内表面含有氧化膜的抗结焦设备；所述低氧分压气体的露点为-40℃至40℃。由该方法制得的设备内表面形成致密、稳定的氧化膜，可抑制或减缓催化结焦现象，降低设备渗碳程度，延长设备使用寿命。

Description

抗结焦设备及其制备方法与应用
相关申请的交叉引用
本申请要求2020年06月23日
2020年06月23日
2020年06月23日
2020年06月23日提交的中国专利申请202010582151.8
202010582144.8
202010582969.X
202010582183.8的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及石油烃裂解领域和轻烃芳构化设备领域，具体地，涉及一种抗结焦设备及其制备方法与应用。
背景技术
裂解炉、急冷锅炉和芳构化反应器等是石油化工行业常用的设备，是烃类裂解生产乙烯或轻烃芳构化反应中的重要设备之一。为了保证上述设备在使用过程中的高温强度，裂解炉、急冷锅炉和芳构化反应器所用材质主要包含Fe、Cr、Ni等元素，而在裂解炉、急冷锅炉以及芳构化反应器的运行条件下，设备中的Fe和/或Ni元素会导致设备内壁发生催化结焦、产生渗碳等现象，最终导致裂解炉管、急冷锅炉管程炉管以及轻烃芳构化反应器等设备内壁积碳严重，床层压降增大，不能长周期运行。另外，较重的烃类原料在裂解过程中也伴随着大量的自由基结焦和缩聚结焦。
目前主要采取两种方法来减缓结焦和渗碳：在裂解原料中添加结焦抑制剂和在反应器内表面涂敷防焦涂层。采用添加结焦抑制剂钝化反应器内表面或使焦碳气化的方法，不仅会对下游产品带来污染，而且需要增加专用的注入设备，而且该方法对于低温结焦的效果较差。而采用在反应器内表面制备惰性涂层是目前研究的主要方向，该惰性涂层能够减少烃类与裂解炉管内表面Fe和/或Ni活性组分的接触，从而减少由Fe和/或Ni活性组分引起的催化结焦。另一方面，研究者还使用反应器内部增加构件、减小反应器中的压力、减少停留时间、降低裂解温度、优化裂解原料等措施减少裂解过程中的自由基结焦和缩聚结焦。
在反应器内表面形成保护层的方法，有两种不同的形式：一种是通过热喷涂、热溅射、高温烧结、化学热处理、化学气相沉积等手段，在反应器内表面形成保护层，此类方法的缺点是保护层与反应器基体的结合不够牢固，容易剥落；另一种是通过一定温度下特定的气氛处理，在反应器内表面原位生成氧化物保护层，此法的优点是保护层与炉管基体的结合力强，不易剥落。
加拿大NOVA化学公司公开了一系列在低氧分压气氛下处理裂解炉管内表面得到铬锰尖晶石氧化膜的专利，包括US5630887A、US6436202B1、US6824883B 1、US7156979B2、US7488392B2等。公开材料显示，该技术在以乙烷、丙烷等轻烃为原料的气体裂解炉展示了良好的抑制结焦效果，但是在液体原料裂解过程中抗结焦效果较差。因为气体裂解炉的结焦以催化结焦为主，氧化膜会将炉管中具有催化结焦活性的Fe、Ni元素与烃类结焦源隔离。而对于以石脑油、柴油等为原料的液体裂解炉而言，虽然其结焦也是以催化结焦为基础，但是 缩聚结焦占总结焦量的50％以上，其中缩聚结焦能完全将氧化膜覆盖。因此，氧化膜在液体裂解炉管中只在炉管服役初期有效，因为这时的氧化膜还没有被缩聚结焦覆盖，而当裂解炉运行到中后期，氧化膜则不能发挥它的功效。
CN105506713A公开了一种在构件上形成铬基涂层的方法，其包括：将所述构件及对电极浸入包括三价铬盐和纳米陶瓷微粒的电解液中；在所述构件和对电极上施加电流；以及在所述构件上电镀一层包括铬和纳米陶瓷微粒的铬基涂层。其通过电镀形成铬涂层来覆盖Fe、Ni元素。
CN103374705A公开了一种磁控溅射装置，包括反应腔室、卡盘以及靶材，所述卡盘设置在所述反应腔室底部，其用于承载被加工工件，所述靶材设置在所述反应腔室顶部，在所述反应腔室侧壁的外侧设有边磁体，而且所述边磁体位于所述卡盘的上方，其中，在所述卡盘的边缘包括辅助磁体，所述辅助磁体的磁极与所述边磁体的磁极同向设置，所述辅助磁体和所述边磁体形成磁回路，借助所述磁回路使等离子体中的金属离子向所述反应腔室的边缘区域移动，以增加靶材粒子在所述被加工工件边缘区域的沉积量。通过磁控溅射装置来形成惰性涂层。
但是，这些施加外来元素形成的惰性涂层在实际工业应用过程中，使用寿命较短，往往经过几个周期运行后涂层就会大量剥落，因此这些涂层并没有在工业上广泛使用。
发明内容
本发明的目的是为了克服现有技术存在的设备内壁的结焦以及渗碳，且设备内表面氧化膜制备困难的问题，提供一种抗结焦设备及其制备方法与应用。通过控制低氧分压气体的露点与处理前后设备中Fe和/或Ni金属元素的含量之间的关系，使得由该方法制得的设备内表面形成致密、稳定的氧化膜，抑制或减缓催化结焦现象，降低设备渗碳程度，延长设备使用寿命。
为了实现上述目的，本发明第一方面提供一种抗结焦设备的制备方法，其特征在于，所述方法包括：将低氧分压气体与设备进行接触反应，得到内表面含有氧化膜的抗结焦设备；
所述低氧分压气体的露点为-40℃至40℃。
本发明第二方面提供一种由上述制备方法制得的抗结焦设备。
本发明第三方面提供一种上述抗结焦设备在裂解炉、急冷锅炉和芳构化反应器中的至少一种中的应用。
通过上述技术方案，本发明所提供的抗结焦设备及其制备方法与应用获得以下有益的效果：
本发明通过控制低氧分压气体的露点，特别地，通过控制低氧分压气体的露点与抗结焦设备的氧化膜中金属元素的含量之间的关系，能够确保设备内表面形成结构致密、稳定的氧化膜，显著抑制或减缓催化结焦现象，降低设备渗碳程度，延长设备使用寿命。
进一步地，本发明提供的抗结焦设备内表面含有以原位生长方式生成的氧化膜，所获得的氧化膜与设备基体的结合力强，在解决设备结焦和渗碳问题的同时，使得设备能够长期使用。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围 的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种抗结焦设备的制备方法，其特征在于，所述方法包括：将低氧分压气体与设备进行接触反应，得到内表面含有氧化膜的抗结焦设备；
所述低氧分压气体的露点为-40℃至40℃。
本发明中，低氧分压气氛是指一种还原性气氛，其中的氧分压较低，所以发生的氧化过程非常缓慢，利于在材料表面生成致密的氧化膜。氧分压是指气氛中存在的氧气所占的压力，在低氧分压气氛下，气氛中的氧气主要来自含氧化合物(如H 2O)分解产生的氧。
无论是在工程上还是在实验室中，低氧分压气氛是很难获得的，通过流量控制装置获得稳定的低氧分压气氛非常困难且难以实现。本发明人通过理论分析及大量试验，惊奇地发现了通过控制混合气的露点，例如控制低氧分压气体的露点为-40℃至40℃时，能够确保设备内表面形成结构致密、稳定的氧化膜，显著抑制或减缓催化结焦现象，降低设备渗碳程度，延长设备使用寿命。
本发明中，露点，指空气中饱和水汽开始凝结结露的温度，在100％的相对湿度时，周围环境的温度就是露点温度。
本发明中，所述方法还包括测定低氧分压气体的露点的步骤。
本发明中，所述方法还包括在低氧分压气体与设备进行接触反应前，(采用市售的露点测定仪)对低氧分压气体的露点进行测试，以使得与设备接触的低氧分压气体具有本发明所限定的露点。
进一步地，所述方法还包括在接触反应期间，采用市售的露点测定仪实时地对接触反应体系中低氧分压气体的露点进行监控的步骤。
根据本发明，所述设备的组成元素包括铁元素和/或镍元素。
根据本发明，所述氧化膜包括铬锰氧化物和金属元素，所述金属元素为铁元素和/或镍元素。
本发明中，所述铬锰氧化物的组成为Mn xCr 3-xO 4，x数值为0.5-2。
本发明中，接触反应前设备中金属元素的含量以及接触反应后抗结焦设备的氧化膜中金属元素的含量采用X-射线能谱分析(EDS)方法测得。
根据本发明，所述低氧分压气体的露点与抗结焦设备的氧化膜中金属元素的含量满足以下关系：
(W1-W2)/W1＝aT 2+bT+c   式I；
式I中，-0.0039≤a≤-0.0001，0.001≤b≤0.0294，0.7269≤c≤0.8577，R 2≥0.879；
其中，W1为接触反应前设备中金属元素的含量，wt％；W2为接触反应后设备的氧化膜中金属元素的含量，wt％；T为低氧分压气体的露点，℃。
本发明中，通过控制低氧分压气体的露点与抗结焦设备的氧化膜中金属元素的含量之间满足上述关系时，能够进一步确保设备内表面形成结构致密、稳定的氧化膜，显著抑制或减少催化结焦现象，降低设备渗碳程度，延长设备使用寿命。
本发明的一个具体实施方式中，式I中，-0.0005≤a≤-0.0001，0.001≤b≤0.0035，0.7355≤c≤0.8577，R 2≥0.9463。
本发明的一个具体实施方式中，式I中，a＝-0.0003，b＝0.0035，c＝0.7882， R1＝0.9463。
本发明的一个具体实施方式中，式I中，a＝-0.0001，b＝0.002，c＝0.8577，R 2＝0.9785。
本发明的一个具体实施方式中，式I中，a＝-0.0003，b＝0.001，c＝0.7355，R 2＝0.9867。
本发明的一个具体实施方式中，式I中，a＝-0.0005，b＝0.0022，c＝0.7678，R 2＝0.98。
根据本发明，式I中，(W1-W2)/W1≥0.281，优选地，(W1-W2)/W1≥0.583。
本发明的一个具体实施方式中，(W1-W2)/W1≥0.791，优选地，(W1-W2)/W1≥0.861。
本发明的一个具体实施方式中，(W1-W2)/W1≥0.587，优选地，(W1-W2)/W1≥0.690。
本发明的一个具体实施方式中，(W1-W2)/W1≥0.594，优选地，(W1-W2)/W1≥0.797。
根据本发明，所述设备选自合金炉管、急冷锅炉和轻烃芳构化反应器中的至少一种。
本发明中，所述合金炉管可以是现有技术通常采用的镍铬合金炉管。
根据本发明，所述设备为合金炉管时，接触反应前合金炉管中金属元素的总含量为25-90wt％。
具体的，合金炉管中，所述金属元素中包含20-50wt％的镍元素和5-40wt％的铁元素，进一步地，所述合金炉管中，除了上述铁元素和镍元素外，还包括12-50wt％的铬元素、0.2-3wt％的锰元素，1-3wt％的硅元素，0.1-0.75wt％的碳元素，0-5wt％的微量元素和痕量元素。
进一步地，合金炉管中，所述金属元素的总含量为37-83wt％，具体地，金属元素中包含25-48wt％的镍元素和12-35wt％的铁元素，所述合金炉管中，除了上述铁元素和镍元素外，还包括20-38wt％的铬元素、1-2.5wt％的锰元素，1-2wt％的硅元素，0.1-0.6wt％的碳元素，0-3wt％的微量元素和痕量元素。
本发明中，所述微量元素选自铌、钛、钨、铝和稀土中的一种或几种；所述痕量元素选自硫和/或磷。
根据本发明，所述设备为急冷锅炉时，接触反应前急冷锅炉管程炉管中金属元素的总含量为76.4-98wt％。
本发明中，急冷锅炉管程炉管中的金属元素为铁元素，除了铁元素外，急冷锅炉的管程炉管合金中还包括1.5-20wt％的铬元素、0.2-0.6wt％的钼元素、0.3-0.8wt％的锰元素、0.4-2wt％的硅元素、0.1-0.2wt％的碳元素、＜5wt％的氧元素、0-1wt％的微量元素。
本发明中，所述急冷锅炉管程炉管中的微量元素为Al、Nb、Ti、w和稀土元素中的至少一种。
本发明中，所述急冷锅炉可以为现有技术中的常规锅炉，并可以采用现有技术中常规的制造技术制得。本发明中，所述急冷锅炉的管段经机械加工后，其内表面光亮，无氧化皮，氧含量＜5wt％。
进一步地，所述设备为急冷锅炉时，接触反应前急冷锅炉管程炉管中金属元素(铁元素)的总含量为80-97wt％，除了上述金属元素(铁元素)外，还包括2-15wt％的铬元素、0.25-0.35wt％的钼元素、0.55-0.65wt％的锰元素、0.5-1.9wt％的硅元素、0.14-0.17wt％的碳元素、＜3wt％的氧元素、0.15-0.65wt％的微量元素。
本发明中，所述急冷锅炉的管程炉管合金可以是本领域常规的合金，例如15Mo3。
根据本发明，所述芳构化反应器的合金材料选自不锈钢304、316和321中的至少一种，更优选地，所述芳构化反应器的合金材料为不锈钢304，接触反应前芳构化反应器中金属元素的含量为68-81wt％。
本发明中，所述芳构化反应器可以为现有技术中常规的芳构化反应器或采用现有技术中常规的制造技术制得的芳构化反应器。
本发明的一个具体实施方式中，所述低氧分压气体的露点为-30℃至30℃；式I中，-0.0005≤a≤-0.0003，0.001≤b≤0.0092，0.7355≤c≤0.8308，R 2≥0.9539。
本发明的一个具体实施方式中，所述低氧分压气体的露点为-20℃至20℃；式I中，-0.0006≤a≤-0.0003，0.001≤b≤0.0092，0.7269≤c≤0.8308，R 2≥0.879。
本发明的一个具体实施方式中，所述低氧分压气体的露点为-15℃至15℃；式I中，-0.0006≤a≤-0.0005，0.0021≤b≤0.0049，0.7419≤c≤0.8109，R 2≥0.879。
本发明的一个具体实施方式中，所述低氧分压气体的露点为-15℃至10℃；式I中，-0.0005≤a≤-0.0003，0.0021≤b≤0.0053，0.7419≤c≤0.8138，R 2≥0.8943。
本发明的一个具体实施方式中，所述低氧分压气体的露点为-10℃至10℃；式I中，a＝-0.0005，b＝0.0021，c＝0.7419，R 2＝1。
本发明的一个具体实施方式中，所述低氧分压气体的露点为-5℃至5℃；式I中，a＝-0.0039，b＝0.0041，c＝0.8333，R 2＝1。
本发明的一个具体实施方式中，所述低氧分压气体的露点为0℃至20℃，式I中，a＝-0.0004，b＝0.0092，c＝0.8308，R 2＝1。
本发明的一个具体实施方式中，所述低氧分压气体的露点为0℃至10℃；式I中，a＝-0.0022，b＝0.0238，c＝0.7787，R 2＝0.9887。
本发明的一个具体实施方式中，所述低氧分压气体的露点为2℃至8℃；式I中，a＝-0.0028，b＝0.0294，c＝0.7678，R 2＝0.9995。
根据本发明，所述低氧分压气体为CO 2和/或H 2O以及选自CO、CH 4、C 2H 6、C 3H 8、NH 3、H 2、N 2、Ar、He、空气和裂解气中的至少一种的气体混合物。
优选地，所述低氧分压气体选自CH 4和H 2O的气体混合物、CO 2和CO的气体混合物、H 2O和CO的气体混合物和H 2O和H 2的气体混合物中的至少一种。
优选地，所述方法还包括测定低氧分压气体的露点的步骤。
根据本发明，所述接触反应的条件包括：反应温度400-1100℃，优选为600-1100℃；反应时间5-100h，优选为5-72h。
本发明的一个具体实施方式中，所述接触反应的条件包括：反应温度为750-1000℃，反应时间为20-50h。
本发明的一个具体实施方式中，所述接触反应的条件包括：接触温度为700-950℃，反应时间为10-80h。
本发明的一个具体实施方式中，所述接触反应的条件包括：接触温度为750-950℃，接触时间为20-60h。
本发明的一个具体实施方式中，所述接触反应的条件包括：反应温度为800-1050℃，反应时间为30-60h。
本发明中，低氧分压气体的流速为100-500mL/min，优选为200-400mL/min。
本发明中，所述接触反应可以在本领域中常规的能够保持一定气氛的设备中进行，例如，可以为管式炉、井式炉和气氛箱式炉中的至少一种中进行所述接触反应。
根据本发明，所述设备为裂解炉用合金炉管。
进一步地，所述合金炉管包括固定于炉管内的强化传热构件。
本发明中，发明人研究发现，通过在炉管内设置强化传热构件，在炉管与低氧分压气体进行接触反应的过程中，强化传热构件改变了低氧分压气体的流动状态，低氧分压气体中痕量的O 2能够与管壁充分接触，使管壁被完整氧化，形成的氧化膜中金属元素的含量进一步降低。
相对于此，对不含强化传热构件的炉管进行低氧分压气体处理时，气体是以层流状态与管壁接触，气流中间的O 2基本没有参与管壁的氧化反应，管壁不能被完整氧化，所以形成的氧化膜中金属元素的含量较高。
另外，通过该强化传热构件，在裂解过程中，强化传热构件将靠近管壁裂解气的流动状态从层流变成湍流后，炉管内表面的缩聚结焦很容易被裂解气流冲刷掉，因为缩聚结焦一般是比较疏松的焦炭，在炉管内壁的附着力比较弱。因此，含有强化传热构件的炉管内壁附着的焦炭仍然以催化结焦为主，这样低氧分压形成的氧化膜就能充分发挥其功效，从而显著延长裂解炉运转周期。
本发明中，所述强化传热构件可以为现有技术中常规的能够改变流体流动状态，提高热传导系数的部件，例如优选选自扭曲片、内肋片和内翅片中的至少一种。
本发明中，设置有强化传热构件的裂解炉用合金炉管可以通过本领域常规的方法获得。例如，裂解炉用合金炉管通常采用离心浇铸方式铸造而成，而带有管内强化传热构件的炉管则有不同的加工形式，例如：管内带有扭曲片或内翅片构件的炉管通常采用静态浇铸方式整铸得到；而管内具有内肋片构件的炉管是通过在炉管内部焊接肋片形成的。
另外，设置有强化传热构件的裂解炉用合金炉管也可以商购获得，例如Kellogg公司的梅花管(为管内设置有内翅片的管)，Kubota的MERT管(为管内设置有内肋片的管)以及中国石化的扭曲片管(为管内设置有扭曲片的管)等。
根据本发明，所述强化传热构件管的长度为20-80cm，数量为1-200个，分布于整个炉管的不同管程。
本发明第二方面提供一种由上述制备方法制得的抗结焦设备。
本发明中，所述抗结焦设备的内表面含有包括铬锰氧化物和金属元素的氧化膜。
本发明中，发明人研究发现，本发明所述的抗结焦设备能够减缓或抑制设备在高温下的结焦和渗碳现象的原因是：将设备采用本发明所述技术方案与低氧分压气体接触反应后，由于设备中Cr元素、Mn元素与氧发生反应形成氧化物的活性高于Fe元素和/或Ni元素，所以设备内表面的铬、锰元素在很低的氧分压条件下将发生缓慢氧化，而铁元素和/或镍元素基本不被氧化，并且由于气氛的氧分压很低，因此氧化过程非常缓慢，进而在设备内表面原位生成与设备基体结合力强且致密的氧化膜，该氧化膜能将对设备结焦具有催化作用的铁、镍元素覆盖，使得设备内壁的铁元素和/或镍元素含量降低，进而减缓或抑制设备的结焦以及渗碳现象，延长设备的运行周期。
本发明中，由上述方法处理得到的设备内表面的氧化膜中，铁元素和/或镍元素的总含量较低，进而能够抑制烃类裂解过程或芳构化反应过程的催化结焦，延长设备的运转周期，满足设备长期使用的要求。
本发明第三方面提供上述抗结焦设备在裂解炉、急冷锅炉和芳构化反应器中的至少一种中的应用。
本发明中，裂解用原料可以为气体烃类或液体烃类。具体的，所述气体烃类为乙烷、丙烷、丁烷和液化石油气中的至少一种；所述液体烃类为石脑油、凝析油、加氢裂化尾油和柴油中的至少一种。
本发明中，可以按照现有技术中的常规裂解工艺进行裂解反应。例如，裂解温度为770-880℃，水油比为0.3-0.8。优选地，石脑油的裂解温度为830-850℃，水油比为0.5-0.55。
本发明中，可以按照现有技术中的常规芳构化反应条件进行轻烃芳构化反应。具体的，反应温度280-530℃，反应压力0.3MPa。
以下将通过实施例对本发明进行详细描述。以下实施例中，
设备的元素组成采用X-射线能谱分析(EDS)方法测得；
低氧分压气体的露点采用市售的露点测定仪检测方法测得；
设备的结焦量采用红外仪在线测量烧焦气体中的CO和CO 2浓度及采用湿式气体流量计在线测量烧焦气体的体积后计算得到；
裂解原料为石脑油，其物性为：馏程32.8-173.8℃，比重D 20为0.7058g/ml。
以下实施例以及对比例中：
在自制的200g/h进料量的试验室装置上进行小试裂解炉管或模拟急冷锅炉低氧分压气氛处理及石脑油裂解制乙烯结焦评价试验。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用HZSM-5催化剂，原料为正己烷，芳构化反应条件：反应体积空速1h -1，反应温度500℃，氢油体积比400∶1，反应压力0.3MPa，反应时间20小时。
实施例1
对炉管材质为35Cr45Ni的工业裂解炉辐射段炉管进行了低氧分压气体气氛处理。炉管合金的元素组成为(wt％)：Cr：32.55、Ni：42.60、Fe：21.12、Mn：0.98、Si：1.41、Nb：0.64、C：0.53、其他：0.17。在裂解炉辐射段炉管中以相互间隔的形式，沿轴向设置与炉管一体制成的扭曲片管，扭曲片扭曲180°的轴向长度为一节距，两个相邻扭曲片之间的距离为15个节距，扭曲片管长度为35cm，数量为100个，分布于整个炉管的不同管程。所采用的低氧分压气体为CO和水蒸汽的气体混合物，其中混合气的露点为5℃，处理温度为900℃，处理时间为50小时，在辐射段炉管内壁表面形成了包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为9.93wt％。
在低氧分压气体气氛处理后的工业裂解炉中进行烃类蒸汽裂解反应，裂解原料为石脑油，其物性为：馏程32.8-173.8℃，比重D 20为0.7058g/ml；裂解条件为：炉管出口温度830℃，水油比为0.55。裂解炉的运行周期达到230天。
实施例2
对含有1节扭曲片管的HP40(Cr25Ni35)小试炉管进行低氧分压预氧化处理，炉管合金的元素组成为：Cr：25.1、Ni：35.2、Mn：1.0、Si：1.5、C：0.4、p＜0.03、S＜0.03、余量为Fe(wt％)。
采用CO和水蒸汽的气体混合物作为低氧分压气氛处理气体，其中混合气的露点为5℃，低氧分压气体的流速为400ml/min，处理温度为950℃，处理时间为30小时，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素 的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为11.27wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料为石脑油，其物性为：馏程32.8-173.8℃，比重D 20为0.7058g/ml；裂解条件为：裂解温度845℃，水油比为0.5。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少95.21％。
实施例3
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为8℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为12.88wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少90.15％。
实施例4
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为2℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为13.29wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少86.38％。
实施例5
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为10℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为14.80wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少81.46％。
实施例6
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为0℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为15.89wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及 裂解条件与实施例2相同。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少75.69％。
对比例1
与实施例1相同炉型的工业裂解炉辐射段炉管，所不同的仅是未进行低氧分压气氛处理。在该工业裂解炉中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例1相同。裂解炉的运行周期为100天。
对比例2
与实施例1相同炉型的工业裂解炉辐射段炉管，不同的是，辐射段炉管中不含扭曲片，并且未进行低氧分压气体气氛处理，裂解炉的运行周期为55天。
实施例7
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为20℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为17.62wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少33.90％。
实施例8
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为-10℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为19.01wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少24.55％。
实施例9
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为-30℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为42.39wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少17.15％。
实施例10
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 和水蒸汽混合气的露点为-40℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为51.72wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少13.09％。
实施例11
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为-20℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为34.96wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少18.64％。
实施例12
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为-15℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为26.98wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少20.73％。
实施例13
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为15℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为15.4wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少65.88％。
实施例14
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为30℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为27.94wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少30.23％。
实施例15
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是CO和水蒸汽混合气的露点为40℃，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为37.41wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量比现有技术不含扭曲片且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少28.56％。
对比例3
与实施例2相同的小试炉管，所不同的是不含扭曲片且未进行低氧分压处理，在小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。小试炉管的结焦量为100％。
实施例16
对HP40(Cr25Ni35)小试炉管进行低氧分压预氧化处理，炉管合金的元素组成为(wt％)：Cr：25.1、Ni：35.2、Mn：1、Si：1.5、C：0.4、P＜0.03、S＜0.03、余量为Fe。
采用H 2和H 2O的气体混合物作为低氧分压气氛处理气体，其中混合气的露点为10℃，低氧分压气体的流速为400ml/min，处理温度为950℃，处理时间为30小时，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为3.76wt％和4.58wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料为石脑油，其物性为：馏程32.8-173.8℃，比重D 20为0.7058g/ml；裂解条件为：裂解温度845℃，水油比为0.5。本发明的炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少91.85％。
实施例17
对与实施例16相同的小试炉管进行低氧分压预氧化处理，所不同的是H 2和H 2O混合气的露点为20℃，其他处理条件与实施例16相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为5.23wt％和4.87wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。本发明的炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少87.65％。
实施例18
对与实施例16相同的小试炉管进行低氧分压预氧化处理，所不同的是H 2 和H 2O混合气的露点为0℃，其他处理条件与实施例16相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为6.48wt％和5.69wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。本发明的炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少80.65％。
实施例19
对与实施例16相同的小试炉管进行低氧分压预氧化处理，所不同的是H 2和H 2O混合气的露点为40℃，其他处理条件与实施例16相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为11.02wt％和8.28wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。本发明的炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少51.87％。
实施例20
对与实施例16相同的小试炉管进行低氧分压预氧化处理，所不同的是H 2和H 2O混合气的露点为-40℃，其他处理条件与实施例16相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为15.89wt％和13.95wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。本发明的炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少32.58％。
对比例4
对与实施例16相同的小试炉管进行低氧分压预氧化处理，所不同的是H 2和H 2O混合气的露点为50℃，其他处理条件与实施例16相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为20.13wt％和19.78wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。小试炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少19.69％。
对比例5
对与实施例16相同的小试炉管进行低氧分压预氧化处理，所不同的是H 2和H 2O混合气的露点为-50℃，其他处理条件与实施例16相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为MnCr 2O 4，氧化膜中，铁元素与镍元素的含量分别为25.09wt％和24.95wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。小试炉管的结焦量比现有技术未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少13.48％。
对比例6
与实施例16相同的小试炉管，未进行低氧分压预氧化处理，在小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例16相同。小试炉管的结焦量为100％。
实施例21
将15CrMoG管材的无缝钢管冷拔制成
Figure PCTCN2021101435-appb-000001
的小试炉管，经机械加工后炉管内表面光亮、无氧化皮，炉管合金的元素组成为(wt％)：Cr：1.03、Mo：0.47、Mn：0.58、Si：0.32、C：0.16、O：2.13、Fe：96.87、其他为0.24。
采用CO 2和CO的气体混合物作为低氧分压气氛处理气体，其中混合气的露点为0℃，低氧分压气体的流速为400ml/min，处理温度为900℃，处理时间为35小时，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为25wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解条件为：裂解温度845℃，水油比为0.5。实验结果表明，本发明的急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了88％。
实施例22
对与实施例21相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 2和CO混合气的露点为10℃，其他处理条件与实施例21相同，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为28wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。本发明的急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了82％。
实施例23
对与实施例21相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 2和CO混合气的露点为-10℃，其他处理条件与实施例21相同，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为32wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。本发明的急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了78％。
实施例24
对与实施例21相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 2和CO混合气的露点为20℃，其他处理条件与实施例21相同，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为35wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。本发明的急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了51％。
实施例25
对与实施例21相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 2和CO混合气的露点为-20℃，其他处理条件与实施例21相同，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为38wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。本发明的急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了40％。
实施例26
对与实施例21相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 2和CO混合气的露点为30℃，其他处理条件与实施例21相同，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为51wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。处理后急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了21％。
实施例27
对与实施例21相同的小试炉管进行低氧分压预氧化处理，所不同的是CO 2和CO混合气的露点为-30℃，其他处理条件与实施例21相同，在炉管内壁表面形成了主要包含Cr、Mn、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 2CrO 4，氧化膜中，铁元素的含量为57wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。处理后急冷锅炉的结焦量比未处理的急冷锅炉的结焦量减少了15％。
对比例7
与实施例21相同的小试炉管，所不同的是未进行低氧分压处理，在小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例21相同。急冷锅炉的结焦量为100％。
实施例28
在由304不锈钢制成的
Figure PCTCN2021101435-appb-000002
小试试验装置上进行芳构化反应器的低氧分压气氛处理及轻烃芳构化反应评价试验。经机械加工后反应器内表面光亮、无氧化皮，反应器合金的元素组成为(wt％)：Cr：18.05、Ni：7.71、Mn：1.43、Si：1.34、C：1.91、O：2.78、Al：0.64、Fe：66.14。
采用CH 4和H 2O的气体混合物作为低氧分压气氛处理气体，其中混合气的露点为3℃，低氧分压气体的流速为400ml/min，处理温度为900℃，处理时间为30小时，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为14wt％。
实验结果表明，本发明的芳构化反应器的结焦量比未处理的芳构化反应器 的结焦量减少了86％。
实施例29
对与实施例28相同的小试反应器进行低氧分压预氧化处理，所不同的是CH 4和H 2O混合气的露点为5℃，其他处理条件与实施例28相同，在反应器内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为18wt％。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用相同的催化剂，反应原料及反应条件与实施例28相同。本发明的芳构化反应器的结焦量比未处理的芳构化反应器的结焦量减少了80％。
实施例30
对与实施例28相同的小试反应器进行低氧分压预氧化处理，所不同的是CH 4和H 2O混合气的露点为-5℃，其他处理条件与实施例28相同，在反应器内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为21wt％。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用相同的催化剂，反应原料及反应条件与实施例28相同。本发明的芳构化反应器的结焦量比未处理的芳构化反应器的结焦量减少了76％。
实施例31
对与实施例28相同的小试反应器进行低氧分压预氧化处理，所不同的是CH 4和H 2O混合气的露点为15℃，其他处理条件与实施例28相同，在反应器内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为24wt％。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用相同的催化剂，反应原料及反应条件与实施例28相同。本发明的芳构化反应器的结焦量比未处理的芳构化反应器的结焦量减少了50％。
实施例32
对与实施例28相同的小试反应器进行低氧分压预氧化处理，所不同的是CH 4和H 2O混合气的露点为-15℃，其他处理条件与实施例28相同，在反应器内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为28wt％。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用相同的催化剂，反应原料及反应条件与实施例28相同。本发明的芳构化反应器的结焦量比未处理的芳构化反应器的结焦量减少了39％。
实施例33
对与实施例28相同的小试反应器进行低氧分压预氧化处理，所不同的是CH 4和H 2O混合气的露点为25℃，其他处理条件与实施例28相同，在反应器内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为37wt％。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用相同的 催化剂，反应原料及反应条件与实施例28相同。处理后的芳构化反应器的结焦量比未处理的芳构化反应器的结焦量减少了20％。
实施例34
对与实施例28相同的小试反应器进行低氧分压预氧化处理，所不同的是CH 4和H 2O混合气的露点为-25℃，其他处理条件与实施例28相同，在反应器内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 0.5Cr 2.5O 4，氧化膜中，铁元素与镍元素的含量之和为45wt％。
在低氧分压气氛处理后的小试反应器中进行轻烃芳构化反应，采用相同的催化剂，反应原料及反应条件与实施例28相同。处理后的芳构化反应器的结焦量比未处理的芳构化反应器的结焦量减少了14％。
对比例8
与实施例28相同的小试反应器，所不同的是未进行低氧分压处理，在小试反应器中进行轻烃芳构化反应，采用相同的催化剂，反应原料及反应条件与实施例28相同。芳构化反应器的结焦量为100％。
对比例9
对与实施例2相同的小试炉管进行低氧分压预氧化处理，所不同的是水蒸汽占低氧分压气体的体积百分数为7.5％(对应露点为41℃)，其他处理条件与实施例2相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为52.85wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例2相同。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少12.32％。
对比例10
对与实施例14相同的小试炉管进行低氧分压预氧化处理，所不同的是：控制水蒸汽占低氧分压气体的体积百分数为4.2％(对应露点为30℃)，其他处理条件与实施例14相同，在炉管内壁表面形成了主要包含Cr、Mn、Ni、Fe、O、Si等元素的氧化膜。氧化膜中的铬锰氧化物为Mn 1.5Cr 1.5O 4，相对于氧化膜的总重量，铁元素和镍元素的总含量为38.08wt％。
在低氧分压气氛处理后的小试炉管中进行烃类蒸汽裂解反应，裂解原料及裂解条件与实施例14相同。本发明的炉管的结焦量比现有技术不含强化传热构件且未进行低氧分压处理的HP40(Cr25Ni35)炉管的结焦量减少25.45％。

Claims (17)

  1. 一种抗结焦设备的制备方法，其特征在于，所述方法包括：将低氧分压气体与设备进行接触反应，得到内表面含有氧化膜的抗结焦设备；
    所述低氧分压气体的露点为-40℃至40℃。
  2. 根据权利要求1所述的制备方法，其中，所述设备的组成元素包括铁元素和/或镍元素；
    优选地，所述氧化膜包括铬锰氧化物和金属元素，所述金属元素为铁元素和/或镍元素。
  3. 根据权利要求2所述的制备方法，其中，所述低氧分压气体的露点与抗结焦设备的氧化膜中金属元素的含量满足以下关系：
    (W1-W2)/W1＝aT 2+bT+c  式I；
    式I中，-0.0039≤a≤-0.0001，0.001≤b≤0.0294，0.7269≤c≤0.8577，R 2≥0.879；
    其中，W1为接触反应前设备中金属元素的含量，wt％；W2为接触反应后设备的氧化膜中金属元素的含量，wt％；T为低氧分压气体的露点，℃。
  4. 根据权利要求1-3中任意一项所述的制备方法，其中，所述设备选自合金炉管、急冷锅炉和轻烃芳构化反应器中的至少一种；
    优选地，所述设备为合金炉管时，接触反应前合金炉管中金属元素的总含量为25-90wt％；
    优选地，所述设备为急冷锅炉时，接触反应前急冷锅炉管程炉管中金属元素的总含量为76.4-98wt％；
    优选地，所述芳构化反应器的合金材料选自不锈钢304、316和321中的至少一种，更优选地，所述芳构化反应器的合金材料为不锈钢304，接触反应前芳构化反应器中金属元素的含量为68-81wt％。
  5. 根据权利要求3或4所述的制备方法，其中，(W1-W2)/W1≥0.281，优选地，(W1-W2)/W1≥0.583。
  6. 根据权利要求3-5中任意一项所述的制备方法，其中，所述低氧分压气体的露点为-30℃至30℃；
    式I中，-0.0005≤a≤-0.0003，0.001≤b≤0.0092，0.7355≤c≤0.8308，R 2≥0.9539。
  7. 根据权利要求3-5中任意一项所述的制备方法，其中，所述低氧分压气体的露点为-20℃至20℃；
    式I中，-0.0006≤a≤-0.0003，0.001≤b≤0.0092，0.7269≤c≤0.8308，R 2≥0.879。
  8. 根据权利要求3-5中任意一项所述的制备方法，其中，所述 低氧分压气体的露点为-15℃至15℃；
    式I中，-0.0006≤a≤-0.0005，0.0021≤b≤0.0049，0.7419≤c≤0.8109，R 2≥0.879。
  9. 根据权利要求3-5中任意一项所述的制备方法，其中，所述低氧分压气体的露点为-15℃至10℃；
    式I中，-0.0005≤a≤-0.0003，0.0021≤b≤0.0053，0.7419≤c≤0.8138，R 2≥0.8943。
  10. 根据权利要求3-5中任意一项所述的制备方法，其中，所述低氧分压气体的露点为0℃至10℃；
    式I中，a＝-0.0022，b＝0.0238，c＝0.7787，R 2＝0.9887。
  11. 根据权利要求1-10中任意一项所述的制备方法，其中，所述低氧分压气体为CO 2和/或H 2O以及选自CO、CH 4、C 2H 6、C 3H 8、NH 3、H 2、N 2、Ar、He、空气和裂解气中的至少一种的气体混合物；
    优选地，所述低氧分压气体选自CH 4和H 2O的气体混合物、CO 2和CO的气体混合物、H 2O和CO的气体混合物和H 2O和H 2的气体混合物中的至少一种；
    优选地，所述方法还包括测定低氧分压气体的露点的步骤。
  12. 根据权利要求1-11中任意一项所述的制备方法，其中，所 述接触反应的条件包括：反应温度400-1100℃，优选为600-1100℃；反应时间5-100h，优选为5-72h。
  13. 根据权利要求1-12中任意一项所述的制备方法，其中，所述设备为合金炉管；
    优选地，所述合金炉管包括固定于炉管内的强化传热构件。
  14. 根据权利要求13所述的制备方法，其中，所述强化传热构件选自扭曲片、内肋片和内翅片中的至少一种。
  15. 根据权利要求13或14所述的制备方法，其中，所述强化传热构件管的长度为20-80cm，数量为1-200个，分布于整个炉管的不同管程。
  16. 一种由权利要求1-15中任意一项所述的制备方法制得的抗结焦设备。
  17. 权利要求16所述的抗结焦设备在裂解炉、急冷锅炉和芳构化反应器中的至少一种中的应用。
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