CN117946723A - Rapid cooling boiler for slowing down coking and carburization and preparation method and application thereof - Google Patents
Rapid cooling boiler for slowing down coking and carburization and preparation method and application thereof Download PDFInfo
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- 238000004939 coking Methods 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001816 cooling Methods 0.000 title claims description 23
- 239000007789 gas Substances 0.000 claims abstract description 148
- 238000010438 heat treatment Methods 0.000 claims abstract description 81
- 238000010791 quenching Methods 0.000 claims abstract description 79
- 230000000171 quenching effect Effects 0.000 claims abstract description 60
- 230000001590 oxidative effect Effects 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000003208 petroleum Substances 0.000 claims abstract description 5
- 238000004227 thermal cracking Methods 0.000 claims abstract description 4
- 238000011282 treatment Methods 0.000 claims description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 55
- UXJMPWMAAZYCMP-UHFFFAOYSA-N chromium(3+) manganese(2+) oxygen(2-) Chemical compound [O-2].[Cr+3].[Mn+2] UXJMPWMAAZYCMP-UHFFFAOYSA-N 0.000 claims description 54
- 239000010410 layer Substances 0.000 claims description 47
- 229910052742 iron Inorganic materials 0.000 claims description 27
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 16
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011573 trace mineral Substances 0.000 claims description 4
- 235000013619 trace mineral Nutrition 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 230000000116 mitigating effect Effects 0.000 claims 1
- 238000005336 cracking Methods 0.000 description 30
- 238000012360 testing method Methods 0.000 description 22
- 238000004230 steam cracking Methods 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000005255 carburizing Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- XCNJCXWPYFLAGR-UHFFFAOYSA-N chromium manganese Chemical compound [Cr].[Mn].[Mn].[Mn] XCNJCXWPYFLAGR-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及石油烃热裂解领域，公开了一种减缓结焦和渗碳的急冷锅炉及其制备方法与应用。该方法包括：(1)将还原性气体与急冷锅炉的管程炉管接触进行第一热处理反应，得到预处理急冷锅炉；(2)将氧化性气体与所述预处理急冷锅炉接触进行第二热处理反应，得到管程炉管内表面含有双层氧化膜的急冷锅炉；(3)将还原性气体与管程炉管内表面含有双层氧化膜的急冷锅炉接触进行第三热处理反应，得到管程炉管内表面含有双层抗结焦氧化膜的急冷锅炉；其中，所述还原性气体中氧气的含量为0ppm；所述氧化性气体中氧气的体积分数为6‑22％。该急冷锅炉的制备工艺简单，且能够显著降低急冷锅炉的结焦与渗碳，延长运行周期。The present invention relates to the field of thermal cracking of petroleum hydrocarbons, and discloses a quenching boiler for slowing down coking and carburization, and a preparation method and application thereof. The method comprises: (1) contacting a reducing gas with a tube-side furnace tube of a quenching boiler to carry out a first heat treatment reaction, thereby obtaining a pre-treated quenching boiler; (2) contacting an oxidizing gas with the pre-treated quenching boiler to carry out a second heat treatment reaction, thereby obtaining a quenching boiler with a double-layer oxide film on the inner surface of the tube-side furnace tube; (3) contacting a reducing gas with a quenching boiler with a double-layer oxide film on the inner surface of the tube-side furnace tube to carry out a third heat treatment reaction, thereby obtaining a quenching boiler with a double-layer anti-coking oxide film on the inner surface of the tube-side furnace tube; wherein the content of oxygen in the reducing gas is 0 ppm; and the volume fraction of oxygen in the oxidizing gas is 6-22%. The preparation process of the quenching boiler is simple, and can significantly reduce the coking and carburization of the quenching boiler, thereby extending the operation cycle.
Description
技术领域Technical Field
本发明涉及石油烃热裂解领域，具体地，涉及一种减缓结焦和渗碳的急冷锅炉及其制备方法与应用。The invention relates to the field of thermal cracking of petroleum hydrocarbons, and in particular to a quenching boiler for slowing down coking and carburization, and a preparation method and application thereof.
背景技术Background technique
乙烯是石油化学工业的基础原料。乙烯的产量、生产规模和技术标志着一个国家石油化工的发展水平。目前生产乙烯的方法以管式炉石油烃蒸汽裂解技术为主，据统计，世界上大约99％的乙烯和50％以上的丙烯通过该方法生产。在管式炉石油烃蒸汽裂解制乙烯、丙烯过程中，高温裂解气在通过急冷锅炉回收热量过程中，会在急冷锅炉管程炉管内壁上结焦，长期在结焦的情况下运行则可能会造成急冷锅炉管程炉管内壁的渗碳，结焦和渗碳会降低急冷锅炉的传热效率并可能会影响急冷锅炉的在线时间。急冷锅炉过短的在线时间和频繁的水力或者机械清焦，增加较多的人工成本，消耗大量的能量，减少有效生产时间，缩短设备使用寿命。Ethylene is the basic raw material of the petrochemical industry. The output, production scale and technology of ethylene indicate the development level of a country's petrochemical industry. At present, the main method for producing ethylene is petroleum hydrocarbon steam cracking technology in a tubular furnace. According to statistics, about 99% of ethylene and more than 50% of propylene in the world are produced by this method. In the process of producing ethylene and propylene by petroleum hydrocarbon steam cracking in a tubular furnace, the high-temperature cracked gas will coke on the inner wall of the tube of the quench boiler tube when recovering heat through the quench boiler. Long-term operation under coking conditions may cause carburization of the inner wall of the tube of the quench boiler tube. Coking and carburization will reduce the heat transfer efficiency of the quench boiler and may affect the online time of the quench boiler. Too short online time of the quench boiler and frequent hydraulic or mechanical coking increase labor costs, consume a lot of energy, reduce effective production time, and shorten the service life of the equipment.
急冷锅炉的管程炉管主要采用15Mo3材质，这种材质主要由Fe、Cr等金属元素组成。在高温下，石油烃与急冷锅炉管程炉管金属中的铁相互作用而脱氢沉积碳，即铁元素对急冷锅炉管程炉管内表面的结焦具有显著催化作用。随着温度的降低(低于500℃)，以催化结焦为基础的低温缩合结焦开始占据优势。The tube-side furnace tubes of the quench boiler are mainly made of 15Mo3 material, which is mainly composed of metal elements such as Fe and Cr. At high temperatures, petroleum hydrocarbons interact with the iron in the tube-side furnace tube metal of the quench boiler to dehydrogenate and deposit carbon, that is, the iron element has a significant catalytic effect on the coking on the inner surface of the tube-side furnace tube of the quench boiler. As the temperature decreases (below 500℃), low-temperature condensation coking based on catalytic coking begins to take advantage.
目前主要采取两种方法来减缓急冷锅炉的结焦和渗碳：在裂解原料中添加结焦抑制剂和在急冷锅炉管程炉管内表面涂敷防焦涂层。采用添加结焦抑制剂钝化炉管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；采用在炉管内表面涂敷防焦涂层的方法，目的是在炉管内表面形成一层力学性能和热稳定性能俱佳的隔离涂层，隔离石油烃物料与炉管内表面金属元素的接触，从而降低炉管内表面金属元素的催化结焦活性，减缓急冷锅炉的整个结焦过程。具有防焦涂层的炉管，有两种不同的制备方式，一种是通过等离子喷涂、热溅射、高温烧结、化学气相沉积等手段，形成在内表面具有如氧化铬、氧化硅、氧化铝和氧化钛等金属或非金属氧化物保护层的炉管，缺点是保护层与炉管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，在炉管内表面原位生成的具有氧化物保护层的炉管，优点是保护层与炉管基体的结合力强，不易剥落。At present, there are two main methods to slow down the coking and carburization of quench boilers: adding coking inhibitors to the cracking raw materials and applying anti-coking coatings on the inner surface of the furnace tubes in the quench boiler tubes. The method of adding coking inhibitors to passivate the inner surface of the furnace tubes or gasify the coke will not only pollute the downstream products, but also require the addition of special injection equipment, and this method is less effective for low-temperature coking; the method of applying anti-coking coatings on the inner surface of the furnace tubes aims to form an isolation coating with excellent mechanical properties and thermal stability on the inner surface of the furnace tubes, isolating the contact between the petroleum hydrocarbon materials and the metal elements on the inner surface of the furnace tubes, thereby reducing the catalytic coking activity of the metal elements on the inner surface of the furnace tubes and slowing down the entire coking process of the quench boiler. There are two different ways to prepare furnace tubes with anti-scorch coatings. One is to form a furnace tube with a protective layer of metal or non-metal oxides such as chromium oxide, silicon oxide, aluminum oxide and titanium oxide on the inner surface by means of plasma spraying, thermal sputtering, high-temperature sintering, chemical vapor deposition, etc. The disadvantage is that the bonding between the protective layer and the furnace tube substrate is not strong enough and is easy to peel off. The other is to generate a furnace tube with an oxide protective layer in situ on the inner surface of the furnace tube by a specific atmosphere treatment at a certain temperature. The advantage is that the bonding between the protective layer and the furnace tube substrate is strong and is not easy to peel off.
加拿大NOVA化学公司提出了以氢气和水蒸汽混合气作为处理气氛，在低氧分压下处理裂解炉管内表面得到铬锰尖晶石氧化膜的技术方案，并以此申请了一批专利，包括US5630887A、US6436202B1、US6824883B1、US7156979B2、US7488392B2等。但采用上述技术方案无法有效解决目前急冷锅炉的结焦和渗碳问题。NOVA Chemicals of Canada proposed a technical solution to treat the inner surface of cracking furnace tubes with hydrogen and water vapor as the treatment atmosphere under low oxygen partial pressure to obtain chromium-manganese spinel oxide film, and applied for a number of patents, including US5630887A, US6436202B1, US6824883B1, US7156979B2, US7488392B2, etc. However, the above technical solution cannot effectively solve the coking and carburization problems of the current quenching boiler.
发明内容Summary of the invention
本发明的目的是为了解决现有技术存在的急冷锅炉结焦以及渗碳问题，提供一种减缓结焦和渗碳的急冷锅炉及其制备方法与应用，该急冷锅炉的制备工艺简单，且能够显著降低急冷锅炉的结焦与渗碳，延长运行周期。The purpose of the present invention is to solve the coking and carburizing problems of quenching boilers in the prior art, and to provide a quenching boiler that can slow down coking and carburizing, and a preparation method and application thereof. The preparation process of the quenching boiler is simple, and can significantly reduce coking and carburizing of the quenching boiler and extend the operating cycle.
为了实现上述目的，本发明第一方面提供一种制备减缓结焦和渗碳的急冷锅炉的方法，其特征在于，所述方法包括：In order to achieve the above object, the first aspect of the present invention provides a method for preparing a quenching boiler for reducing coking and carburization, characterized in that the method comprises:
(1)将还原性气体与急冷锅炉的管程炉管接触进行第一热处理反应，得到预处理急冷锅炉；(1) contacting the reducing gas with the tube-side furnace tube of the quenching boiler to perform a first heat treatment reaction to obtain a pre-treated quenching boiler;
(2)将氧化性气体与所述预处理急冷锅炉接触进行第二热处理反应，得到管程炉管内表面含有双层氧化膜的急冷锅炉；(2) contacting the oxidizing gas with the pre-treatment quench boiler to perform a second heat treatment reaction, thereby obtaining a quench boiler having a double-layer oxide film on the inner surface of the tube-side furnace tube;
(3)将还原性气体与管程炉管内表面含有双层氧化膜的急冷锅炉接触进行第三热处理反应，得到管程炉管内表面含有双层抗结焦氧化膜的急冷锅炉；(3) contacting the reducing gas with the quenching boiler having a double-layer oxide film on the inner surface of the tube-side furnace tube to perform a third heat treatment reaction, thereby obtaining a quenching boiler having a double-layer anti-coking oxide film on the inner surface of the tube-side furnace tube;
其中，所述还原性气体中氧气的含量为0ppm；所述氧化性气体中氧气的体积分数为6-22％。The content of oxygen in the reducing gas is 0 ppm; the volume fraction of oxygen in the oxidizing gas is 6-22%.
本发明第二方面提供一种由上述方法制得的减缓结焦和渗碳的急冷锅炉。The second aspect of the present invention provides a rapid cooling boiler for alleviating coking and carburization, which is prepared by the above method.
本发明第三方面提供上述减缓结焦和渗碳的急冷锅炉在石油烃裂解中的应用。The third aspect of the present invention provides the use of the above-mentioned rapid cooling boiler for alleviating coking and carburization in petroleum hydrocarbon cracking.
通过上述技术方案，本发明所提供的减缓结焦和渗碳的急冷锅炉及其制备方法与应用获得以下有益效果：Through the above technical scheme, the quenching boiler for slowing down coking and carburization provided by the present invention and its preparation method and application obtain the following beneficial effects:
本发明所提供的减缓结焦和渗碳的急冷锅炉的制备工艺简单，且易于实现。由本发明所述方法制得的急冷锅炉能够抑制急冷锅炉管程炉管内的催化结焦、缩合结焦及整个结焦过程，并有效提高了管程炉管的抗渗碳性能，从而延长急冷锅炉的在线时间和使用寿命。The preparation process of the quenching boiler for slowing down coking and carburization provided by the present invention is simple and easy to implement. The quenching boiler prepared by the method of the present invention can inhibit catalytic coking, condensation coking and the entire coking process in the tube-side furnace tube of the quenching boiler, and effectively improve the anti-carburization performance of the tube-side furnace tube, thereby extending the online time and service life of the quenching boiler.
具体实施方式Detailed ways
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。The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.
本发明第一方面提供一种制备减缓结焦和渗碳的急冷锅炉的方法，其特征在于，所述方法包括：A first aspect of the present invention provides a method for preparing a quenching boiler capable of reducing coking and carburization, characterized in that the method comprises:
(1)将还原性气体与急冷锅炉的管程炉管接触进行第一热处理反应，得到预处理急冷锅炉；(1) contacting the reducing gas with the tube-side furnace tube of the quenching boiler to perform a first heat treatment reaction to obtain a pre-treated quenching boiler;
(2)将氧化性气体与所述预处理急冷锅炉接触进行第二热处理反应，得到管程炉管内表面含有双层氧化膜的急冷锅炉；(2) contacting the oxidizing gas with the pre-treatment quench boiler to perform a second heat treatment reaction, thereby obtaining a quench boiler having a double-layer oxide film on the inner surface of the tube-side furnace tube;
(3)将还原性气体与管程炉管内表面含有双层氧化膜的急冷锅炉接触进行第三热处理反应，得到管程炉管内表面含有双层抗结焦氧化膜的急冷锅炉；(3) contacting the reducing gas with the quenching boiler having a double-layer oxide film on the inner surface of the tube-side furnace tube to perform a third heat treatment reaction, thereby obtaining a quenching boiler having a double-layer anti-coking oxide film on the inner surface of the tube-side furnace tube;
其中，所述还原性气体中氧气的含量为0ppm；所述氧化性气体中氧气的体积分数为6-22％。The content of oxygen in the reducing gas is 0 ppm; the volume fraction of oxygen in the oxidizing gas is 6-22%.
本发明通过在急冷锅炉管程炉管内表面形成氧化膜的方式来解决急冷锅炉的结焦和渗碳问题，即依次采用还原性气体、氧化性气体及还原性气体分步进行热处理的方法，在急冷锅炉管程炉管内表面以原位生长的方式生成双层抗结焦氧化膜，所获得的双层抗结焦氧化膜与急冷锅炉管程炉管基体的结合力强，适于长期使用。The present invention solves the coking and carburizing problems of the quenching boiler by forming an oxide film on the inner surface of the quenching boiler tube side furnace tube, that is, a method of sequentially using reducing gas, oxidizing gas and reducing gas for step-by-step heat treatment is used to generate a double-layer anti-coking oxide film on the inner surface of the quenching boiler tube side furnace tube in an in-situ growth manner. The obtained double-layer anti-coking oxide film has a strong bonding force with the quenching boiler tube side furnace tube substrate and is suitable for long-term use.
急冷锅炉管程炉管在加工制造过程中不可避免地会在炉管内表面有残留物存在，这些残留物不仅会影响炉管服役时的使用性能，而且会影响后续处理中炉管内表面抗结焦氧化膜的生成。采用本发明的还原性气体对急冷锅炉管程炉管进行高温预处理，一方面能够将炉管内表面的残留物彻底清除，另一方面改善了炉管内表面金属的分散性能，有利于下一步氧化性气体进行热处理形成双层氧化膜；而再次采用还原性气体将内表面含有双层氧化膜的合金炉管降温至室温，有利于双层氧化膜进一步成为致密稳定的下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。During the manufacturing process, the quenching boiler tube side furnace tube inevitably has residues on the inner surface of the furnace tube, which not only affects the performance of the furnace tube when in service, but also affects the formation of the anti-coking oxide film on the inner surface of the furnace tube in the subsequent treatment. The high-temperature pretreatment of the quenching boiler tube side furnace tube by the reducing gas of the present invention can, on the one hand, completely remove the residues on the inner surface of the furnace tube, and on the other hand, improve the dispersion performance of the metal on the inner surface of the furnace tube, which is conducive to the next step of heat treatment with oxidizing gas to form a double-layer oxide film; and the alloy furnace tube with the double-layer oxide film on the inner surface is cooled to room temperature by the reducing gas again, which is conducive to the double-layer oxide film further becoming a dense and stable double-layer anti-coking oxide film with chromium oxide as the lower layer and chromium-manganese oxide film as the surface layer.
进一步地，通过控制还原性气体中氧气的含量为0ppm，氧化性气体中氧气的体积分数为6-22％时，能够在炉管内表面形成致密稳定的抗结焦氧化膜。Furthermore, by controlling the oxygen content in the reducing gas to 0 ppm and the volume fraction of oxygen in the oxidizing gas to 6-22%, a dense and stable anti-coking oxide film can be formed on the inner surface of the furnace tube.
本发明中，所述还原性气体中氧气的含量为0ppm是指还原性气体中不含有氧气或是能够产生氧气的气体。In the present invention, the oxygen content in the reducing gas being 0 ppm means that the reducing gas does not contain oxygen or is a gas that can generate oxygen.
本发明中，所述还原性气体和氧化性气体中氧气的含量分别采用微量氧分析仪和常量氧分析仪测得。In the present invention, the contents of oxygen in the reducing gas and the oxidizing gas are measured by a trace oxygen analyzer and a constant oxygen analyzer, respectively.
进一步地，所述氧化性气体中氧气的体积分数为13-22％。Furthermore, the volume fraction of oxygen in the oxidizing gas is 13-22%.
根据本发明，所述氧化性气体包括空气和选自氮气、氦气和氩气中的至少一种的气体。According to the present invention, the oxidizing gas includes air and at least one gas selected from nitrogen, helium and argon.
根据本发明，所述还原性气体包括一氧化碳、氢气和选自氮气、氦气和氩气中的至少一种的气体。According to the present invention, the reducing gas includes carbon monoxide, hydrogen and at least one gas selected from nitrogen, helium and argon.
根据本发明，以所述还原性气体的总体积为基准，所述一氧化碳和氢气的含量小于等于80vol％，优选为60-80vol％。According to the present invention, based on the total volume of the reducing gas, the content of carbon monoxide and hydrogen is less than or equal to 80 vol%, preferably 60-80 vol%.
本发明中，所述一氧化碳和所述氢气的体积比为1:0.2-5。In the present invention, the volume ratio of the carbon monoxide to the hydrogen is 1:0.2-5.
本发明中，通过控制还原性气体中一氧化碳和氢气的含量满足上述范围时，能够获得彻底清除急冷锅炉管程炉管内表面残留物、改善炉管内表面金属的分散性能及利于后续氧化性气体和还原性气体依次再处理形成致密稳定抗结焦氧化膜的效果。In the present invention, by controlling the contents of carbon monoxide and hydrogen in the reducing gas to meet the above-mentioned range, it is possible to completely remove the residues on the inner surface of the furnace tube of the quenching boiler tube, improve the dispersion performance of the metal on the inner surface of the furnace tube, and facilitate the subsequent reprocessing of the oxidizing gas and the reducing gas to form a dense and stable anti-coking oxide film.
根据本发明，所述第一热处理反应的条件包括：以小于等于150℃/h的升温速率从室温升温至800-1000℃，保温处理10小时以上。According to the present invention, the conditions of the first heat treatment reaction include: heating from room temperature to 800-1000° C. at a heating rate of less than or equal to 150° C./h, and heat preservation treatment for more than 10 hours.
本发明中，控制第一热处理的条件满足上述范围时，能够获得彻底清除炉管内表面残留物、改善炉管内表面金属的分散性能及，并利于后续氧化性气体和还原性气体再次处理形成致密稳定氧化膜。In the present invention, when the conditions of the first heat treatment are controlled to meet the above range, the residues on the inner surface of the furnace tube can be completely removed, the dispersion performance of the metal on the inner surface of the furnace tube can be improved, and the subsequent oxidizing gas and reducing gas treatment can be used to form a dense and stable oxide film.
进一步地，所述第一热处理的条件包括：以小于等于100℃/h的升温速率从室温升温至850-950℃，处理10-40小时。Furthermore, the conditions of the first heat treatment include: heating from room temperature to 850-950° C. at a heating rate of less than or equal to 100° C./h, and treating for 10-40 hours.
本发明中，所述第一热处理反应中，还原性气体的流速为100-800mL/min，优选为200-600mL/min。In the present invention, in the first heat treatment reaction, the flow rate of the reducing gas is 100-800 mL/min, preferably 200-600 mL/min.
本发明中，通过控制还原性气体的流速满足上述范围时，能够获得彻底清除急冷锅炉管程炉管内表面残留物、改善炉管内表面金属的分散性能，利于后续氧化性气体和还原性气体依次再处理形成致密稳定氧化膜。In the present invention, by controlling the flow rate of the reducing gas to meet the above-mentioned range, it is possible to completely remove the residues on the inner surface of the furnace tube of the quenching boiler tube pass, improve the dispersion performance of the metal on the inner surface of the furnace tube, and facilitate the subsequent oxidizing gas and reducing gas to be processed in sequence to form a dense and stable oxide film.
根据本发明，所述第二热处理反应的条件包括：处理温度为800-1000℃，处理时间为10小时以上。According to the present invention, the conditions of the second heat treatment reaction include: a treatment temperature of 800-1000° C. and a treatment time of more than 10 hours.
本发明中，控制第二热处理反应的条件满足上述范围时，能够实现在炉管内表面形成下层为氧化铬、表层为铬锰氧化膜的双层氧化膜。In the present invention, when the conditions for controlling the second heat treatment reaction satisfy the above range, a double oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film can be formed on the inner surface of the furnace tube.
进一步地，所述第二热处理反应的条件包括：反应温度为850-950℃，反应时间为10-100h，优选为10-50h。Furthermore, the conditions of the second heat treatment reaction include: reaction temperature of 850-950° C., reaction time of 10-100 h, preferably 10-50 h.
本发明中，所述第二热处理反应中，氧化性气体的流速为100-800mL/min，优选为200-600mL/min。In the present invention, in the second heat treatment reaction, the flow rate of the oxidizing gas is 100-800 mL/min, preferably 200-600 mL/min.
本发明中，通过控制氧化性气体的流速满足上述范围时，能够使得氧化性气体充分与预处理合金炉管接触，进而在合金炉管内壁形成双层抗结焦氧化膜。In the present invention, by controlling the flow rate of the oxidizing gas to meet the above range, the oxidizing gas can be fully contacted with the pre-treated alloy furnace tube, thereby forming a double-layer anti-coking oxidation film on the inner wall of the alloy furnace tube.
根据本发明，所述第三热处理反应的条件包括：以小于等于100℃/h的降温速率从800-1000℃降温至室温。According to the present invention, the conditions of the third heat treatment reaction include: cooling from 800-1000° C. to room temperature at a cooling rate of less than or equal to 100° C./h.
本发明中，控制第三热处理反应满足上述范围时，能够使得最终合金炉管内表面形成的双层抗结焦氧化膜更加致密且稳定。In the present invention, when the third heat treatment reaction is controlled to meet the above range, the double-layer anti-coking oxide film formed on the inner surface of the alloy furnace tube can be made denser and more stable.
进一步地，所述第三热处理反应的条件包括：以小于等于50℃/h的降温速率从850-950℃降温至室温。Furthermore, the conditions of the third heat treatment reaction include: cooling from 850-950° C. to room temperature at a cooling rate of less than or equal to 50° C./h.
本发明中，所述第三降温热处理反应中，还原性气体的流速为20-200mL/min，优选为50-100mL/min。In the present invention, in the third temperature-lowering heat treatment reaction, the flow rate of the reducing gas is 20-200 mL/min, preferably 50-100 mL/min.
本发明中，通过控制还原性气体的流速满足上述范围时，能够获得还原性气体处理形成致密稳定的双层抗结焦氧化膜的效果。In the present invention, by controlling the flow rate of the reducing gas to meet the above range, the effect of forming a dense and stable double-layer anti-coking oxide film by the reducing gas treatment can be obtained.
根据本发明，所述双层抗结焦氧化膜包括位于下层的氧化铬和位于表层的铬锰氧化膜。According to the present invention, the double-layer anti-coking oxide film comprises chromium oxide located in the lower layer and a chromium-manganese oxide film located in the surface layer.
本发明中，所述下层是指靠近合金炉管内壁的部分，而表层是指远离合金炉管内壁的部分。In the present invention, the lower layer refers to the portion close to the inner wall of the alloy furnace tube, and the surface layer refers to the portion away from the inner wall of the alloy furnace tube.
根据本发明，所述铬锰氧化膜包括铬锰氧化物和金属元素。According to the present invention, the chromium manganese oxide film includes chromium manganese oxide and metal elements.
根据本发明，所述铬锰氧化物的组成为MnxCr3-xO4，x数值为0.5-2。According to the present invention, the composition of the chromium manganese oxide is Mn x Cr 3-x O 4 , and the value of x is 0.5-2.
本发明中，通过依次采用还原性气体、氧化性气体及还原性气体对急冷锅炉的管程炉管进行热处理，能够确保急冷锅炉的管程炉管内表面通过原位生长形成结构致密、稳定的双层抗结焦氧化膜，所获得的双层抗结焦氧化膜与炉管基体结合牢固，可以显著抑制或减少催化结焦现象，降低急冷锅炉渗碳程度，延长急冷锅炉使用寿命。In the present invention, by sequentially using reducing gas, oxidizing gas and reducing gas to perform heat treatment on the tube-side furnace tubes of the quenching boiler, it can be ensured that a dense and stable double-layer anti-coking oxide film is formed on the inner surface of the tube-side furnace tubes of the quenching boiler through in-situ growth. The obtained double-layer anti-coking oxide film is firmly bonded to the furnace tube matrix, which can significantly inhibit or reduce catalytic coking, reduce the carburization degree of the quenching boiler, and extend the service life of the quenching boiler.
进一步地，本发明中，由上述方法处理得到的急冷锅炉的管程炉管内表面的表层氧化膜中，铁元素的含量较低，进而能够抑制烃类裂解过程的催化结焦，延长急冷锅炉的运转周期，满足急冷锅炉长期使用的要求。Furthermore, in the present invention, the surface oxide film on the inner surface of the tube-side furnace tube of the quenching boiler obtained by the above method has a low content of iron, which can inhibit catalytic coking in the hydrocarbon cracking process, extend the operation cycle of the quenching boiler, and meet the requirements for long-term use of the quenching boiler.
具体地，相对于铬锰氧化膜的总重量，铁元素的含量为小于等于40wt％。Specifically, the content of the iron element is less than or equal to 40 wt % relative to the total weight of the chromium-manganese oxide film.
本发明中，处理前急冷锅炉的管程炉管内表面金属元素的含量以及处理后急冷锅炉的管程炉管内表面表层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。In the present invention, the content of metal elements on the inner surface of the tube-side furnace tube of the quenching boiler before treatment and the content of metal elements in the surface oxide film on the inner surface of the tube-side furnace tube of the quenching boiler after treatment are measured by X-ray energy dispersive spectroscopy (EDS) method.
根据本发明，所述急冷锅炉的管程炉管合金的组成包括：Cr：1.0-20wt％，Mo：0.2-0.6wt％，Mn：0.3-0.8wt％，Si：0.3-2wt％，C：0.1-0.2wt％，O：＜5wt％，Fe：76.4-98wt％，微量元素：0-1wt％。According to the present invention, the composition of the tube-side furnace tube alloy of the quenching boiler includes: Cr: 1.0-20wt%, Mo: 0.2-0.6wt%, Mn: 0.3-0.8wt%, Si: 0.3-2wt%, C: 0.1-0.2wt%, O: <5wt%, Fe: 76.4-98wt%, and trace elements: 0-1wt%.
根据本发明，所述微量元素为Al、Nb、Ti、W和稀土元素中的至少一种。According to the present invention, the trace element is at least one of Al, Nb, Ti, W and rare earth elements.
本发明中，所述第一热处理反应、所述第二热处理反应和所述第三热处理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反应。In the present invention, the first heat treatment reaction, the second heat treatment reaction and the third heat treatment reaction can be carried out in a conventional device in the art that can maintain a certain atmosphere, for example, the reaction can be carried out in at least one of a tubular furnace, a pit furnace and an atmosphere box furnace.
本发明第二方面提供一种由上述方法制得的减缓结焦和渗碳的急冷锅炉。The second aspect of the present invention provides a rapid cooling boiler for alleviating coking and carburization, which is prepared by the above method.
本发明中，所述急冷锅炉的管程炉管内表面含有双层抗结焦氧化膜。所述双层抗结焦氧化膜包括位于下层的氧化铬和位于表层的铬锰氧化膜。In the present invention, the inner surface of the tube-side furnace tube of the quenching boiler contains a double-layer anti-coking oxide film, which includes chromium oxide located at the lower layer and a chromium-manganese oxide film located at the surface layer.
本发明中，所述双层抗结焦氧化膜是通过原位生长形成的。In the present invention, the double-layer anti-coking oxidation film is formed by in-situ growth.
本发明中，发明人研究发现，本发明所述的急冷锅炉能够减缓结焦和渗碳的原因是：采用本发明所述技术方案对急冷锅炉的管程炉管首先进行还原性气体热处理，然后再进一步进行氧化性气体及还原性气体分步热处理后，在急冷锅炉的管程炉管内表面原位生成与炉管基体结合力强的双层抗结焦氧化膜，屏蔽了管段中的铁元素。当裂解气通过所述的急冷锅炉回收热量时，管程炉管内壁上的氧化膜可以隔离裂解气与其内表面铁元素的接触，从而抑制了管段内的催化结焦、缩合结焦及整个结焦过程，并有效提高了管段的抗渗碳性能，从而延长急冷锅炉的在线时间和使用寿命。In the present invention, the inventors have found that the reason why the quenching boiler described in the present invention can slow down coking and carburization is that: the tube-side furnace tube of the quenching boiler is first subjected to reducing gas heat treatment by the technical solution described in the present invention, and then further subjected to oxidizing gas and reducing gas step-by-step heat treatment, and a double-layer anti-coking oxide film with strong bonding force with the furnace tube matrix is generated in situ on the inner surface of the tube-side furnace tube of the quenching boiler, shielding the iron elements in the tube section. When the cracked gas recovers heat through the quenching boiler, the oxide film on the inner wall of the tube-side furnace tube can isolate the cracked gas from the contact with the iron elements on its inner surface, thereby inhibiting catalytic coking, condensation coking and the entire coking process in the tube section, and effectively improving the anti-carburization performance of the tube section, thereby extending the online time and service life of the quenching boiler.
本发明第三方面提供上述减缓结焦和渗碳的急冷锅炉在石油烃热裂解中的应用。The third aspect of the present invention provides the use of the above-mentioned rapid cooling boiler for alleviating coking and carburization in thermal cracking of petroleum hydrocarbons.
本发明中，可以按照现有技术中的常规石脑油裂解工艺进行裂解反应。具体的，裂解温度为830-850℃，水油比为0.5-0.55。In the present invention, the cracking reaction can be carried out according to the conventional naphtha cracking process in the prior art. Specifically, the cracking temperature is 830-850° C. and the water-oil ratio is 0.5-0.55.
本发明中，如无特别说明，室温是指25℃。In the present invention, unless otherwise specified, room temperature refers to 25°C.
以下将通过实施例对本发明进行详细描述。以下实施例中：The present invention will be described in detail below by way of examples. In the following examples:
15CrMoG管材为急冷锅炉管程炉管常用材质；15CrMoG pipe is a common material for quench boiler tubes;
炉管合金的元素组成以及处理后炉管内表面表层氧化膜中元素的含量采用X-射线能谱分析(EDS)方法测得；The element composition of the furnace tube alloy and the content of elements in the surface oxide film on the inner surface of the furnace tube after treatment were measured by X-ray energy dispersive spectroscopy (EDS) method;
还原性气体的氧气含量采用微量氧分析仪测得；The oxygen content of the reducing gas was measured using a trace oxygen analyzer;
氧化性气体中的氧气含量采用常量氧分析仪测得；The oxygen content in the oxidizing gas was measured using a constant oxygen analyzer;
炉管的结焦量采用红外仪在线测量烧焦气体中的CO和H2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；The coking amount of the furnace tube is calculated by measuring the concentration of CO and H2 in the coking gas online with an infrared instrument and the volume of the coking gas online with a wet gas flow meter;
裂解原料油为石脑油，其物性为：馏程33.4-162.8℃，比重D20：0.7358g/mL。The cracking raw oil is naphtha, and its physical properties are: distillation range 33.4-162.8°C, specific gravity D 20 : 0.7358 g/mL.
实施例1Example 1
将15CrMoG管材的无缝钢管冷拔制成的小试炉管，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：95.07、其他为0.24。对小试炉管进行分步热处理：The seamless steel pipe of 15CrMoG pipe is cold drawn into 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: 95.07, and the others are 0.24. The small test furnace tube is heat treated in steps:
(1)采用CO、H2和N2的气体混合物作为还原性气体，对炉管进行第一热处理，得到预处理小试炉管，还原性气体中氧气的含量为0ppm，其中，CO与H2的体积比为1：1，CO和H2的体积百分数为70vol％，其余为N2，还原性气体的流速为400mL/min，升温速率为80℃/h，处理温度为900℃，处理时间为15小时；(1) using a gas mixture of CO, H2 and N2 as a reducing gas, performing a first heat treatment on the furnace tube to obtain a pre-treated test furnace tube, wherein the oxygen content in the reducing gas is 0 ppm, wherein the volume ratio of CO to H2 is 1:1, the volume percentage of CO and H2 is 70 vol%, and the rest is N2 , the flow rate of the reducing gas is 400 mL/min, the heating rate is 80°C/h, the treatment temperature is 900°C, and the treatment time is 15 hours;
(2)采用空气和N2组成的氧化性气体对预处理小试炉管进行第二热处理，其中O2的体积分数为16％，氧化性气体的流速为400mL/min，第二热处理的条件为：处理温度为900℃，处理时间为15小时；(2) using an oxidizing gas composed of air and N2 to perform a second heat treatment on the pretreatment pilot furnace tube, wherein the volume fraction of O2 is 16%, the flow rate of the oxidizing gas is 400 mL/min, and the conditions of the second heat treatment are: a treatment temperature of 900°C and a treatment time of 15 hours;
(3)采用与步骤(1)相同的CO、H2和N2的气体混合物作为还原性气体，对炉管进行第三降温热处理至室温，所不同的是：还原性气体的流速为80mL/min，第三降温热处理的条件为：降温速率为40℃/h，从900℃降温至室温。(3) Using the same gas mixture of CO, H2 and N2 as in step (1) as the reducing gas, the furnace tube is subjected to a third cooling heat treatment to room temperature, except that the flow rate of the reducing gas is 80 mL/min, and the conditions of the third cooling heat treatment are: a cooling rate of 40°C/h, from 900°C to room temperature.
通过以上还原性气体、氧化性气体、还原性气体分步热处理，在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为20.68wt％。Through the above reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, a double-layer anti-coking oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film is formed on the inner wall surface of the pilot furnace tube. The surface chromium-manganese oxide film contains chromium-manganese oxide Mn 2 CrO 4 and iron. The content of iron in the chromium-manganese oxide film is 20.68wt% relative to the total weight of the chromium-manganese oxide film.
在分步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，本发明的小试炉管的结焦量比未处理的小试炉管的结焦量减少了92.12wt％。The hydrocarbon steam cracking reaction was carried out in the small test furnace tube after the step-by-step treatment, and the cracking conditions were: cracking temperature 845°C, water-oil ratio 0.5. The experimental results showed that the coking amount of the small test furnace tube of the present invention was reduced by 92.12wt% compared with the coking amount of the untreated small test furnace tube.
实施例2Example 2
对与实施例1相同的小试炉管进行还原性气体、氧化性气体、还原性气体分步热处理，所不同的是：还原性气体第一热处理的条件为：处理温度为800℃，处理时间为20小时；氧化性气体第二热处理的条件为：处理温度为800℃，处理时间为20小时，还原性气体第三降温热处理的条件为：处理温度为800℃至室温，其他处理条件与实施例1相同。The same small test furnace tube as in Example 1 was subjected to reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, except that the conditions for the first heat treatment with reducing gas were: a treatment temperature of 800°C and a treatment time of 20 hours; the conditions for the second heat treatment with oxidizing gas were: a treatment temperature of 800°C and a treatment time of 20 hours; the conditions for the third cooling heat treatment with reducing gas were: a treatment temperature of 800°C to room temperature, and the other treatment conditions were the same as in Example 1.
通过以上还原性气体、氧化性气体、还原性气体分步热处理，在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为36.38wt％。Through the above reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, a double-layer anti-coking oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film is formed on the inner wall surface of the pilot furnace tube. The surface chromium-manganese oxide film contains chromium-manganese oxide Mn 2 CrO 4 and iron. The content of iron in the chromium-manganese oxide film is 36.38wt% relative to the total weight of the chromium-manganese oxide film.
在分步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1相同。本发明的小试炉管的结焦量比未处理的小试炉管的结焦量减少了45.12wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the step-by-step treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube of the present invention was reduced by 45.12 wt % compared with the coking amount of the untreated pilot furnace tube.
实施例3Example 3
对与实施例1相同的小试炉管进行还原性气体、氧化性气体、还原性气体分步热处理，所不同的是：还原性气体第一热处理的条件为：处理温度为1000℃，处理时间为10小时，氧化性气体第二热处理的条件为：处理温度为1000℃，处理时间为10小时，还原性气体第三热处理的条件为：处理温度为1000℃至室温，其他处理条件与实施例1相同。The same small test furnace tube as in Example 1 was subjected to reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, except that the conditions for the first heat treatment with reducing gas were: a treatment temperature of 1000°C and a treatment time of 10 hours, the conditions for the second heat treatment with oxidizing gas were: a treatment temperature of 1000°C and a treatment time of 10 hours, and the conditions for the third heat treatment with reducing gas were: a treatment temperature of 1000°C to room temperature. Other treatment conditions were the same as in Example 1.
通过以上还原性气体、氧化性气体、还原性气体分步热处理，在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为28.89wt％。Through the above reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, a double-layer anti-coking oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film is formed on the inner wall surface of the pilot furnace tube. The surface chromium-manganese oxide film contains chromium-manganese oxide Mn 2 CrO 4 and iron. The content of iron in the chromium-manganese oxide film is 28.89wt% relative to the total weight of the chromium-manganese oxide film.
在分步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1相同。本发明的小试炉管的结焦量比未处理的小试炉管的结焦量减少了65.28wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the step-by-step treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube of the present invention was reduced by 65.28 wt % compared with the coking amount of the untreated pilot furnace tube.
实施例4Example 4
对与实施例1相同的小试炉管进行还原性气体、氧化性气体、还原性气体分步热处理，所不同的是：The same small test furnace tube as in Example 1 was subjected to reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, except that:
(1)采用CO、H2和N2的气体混合物作为还原性气体，对炉管进行第一热处理，得到预处理小试炉管，还原性气体中氧气的含量为0ppm，其中，CO与H2的体积比为1：0.3，CO和H2的体积百分数为50vol％，其余为N2，还原性气体的流速为150mL/min，升温速率为110℃/h，处理温度为800℃，处理时间为42小时；(1) using a gas mixture of CO, H2 and N2 as a reducing gas, performing a first heat treatment on the furnace tube to obtain a pre-treated test furnace tube, wherein the oxygen content in the reducing gas is 0 ppm, wherein the volume ratio of CO to H2 is 1:0.3, the volume percentage of CO and H2 is 50 vol%, and the rest is N2 , the flow rate of the reducing gas is 150 mL/min, the heating rate is 110°C/h, the treatment temperature is 800°C, and the treatment time is 42 hours;
(2)采用空气和N2组成的氧化性气体对预处理小试炉管进行第二热处理，其中O2的体积分数为10％，氧化性气体的流速为150mL/min，第二热处理的条件为：处理温度为800℃，处理时间为42小时；(2) using an oxidizing gas composed of air and N2 to perform a second heat treatment on the pretreatment pilot furnace tube, wherein the volume fraction of O2 is 10%, the flow rate of the oxidizing gas is 150 mL/min, and the conditions of the second heat treatment are: a treatment temperature of 800°C and a treatment time of 42 hours;
(3)采用与步骤(1)相同的CO、H2和N2的气体混合物作为还原性气体，对炉管进行第三降温热处理至室温，所不同的是：还原性气体的流速为40mL/min，第三降温热处理的条件为：降温速率为70℃/h，从800℃降温至室温；(3) using the same gas mixture of CO, H2 and N2 as the reducing gas in step (1), the furnace tube is subjected to a third cooling heat treatment to room temperature, except that the flow rate of the reducing gas is 40 mL/min, and the conditions of the third cooling heat treatment are: the cooling rate is 70°C/h, and the temperature is reduced from 800°C to room temperature;
通过以上还原性气体、氧化性气体、还原性气体分步热处理，在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为39.25wt％。Through the above reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, a double-layer anti-coking oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film is formed on the inner wall surface of the pilot furnace tube. The surface chromium-manganese oxide film contains chromium-manganese oxide Mn 2 CrO 4 and iron. The content of iron in the chromium-manganese oxide film is 39.25wt% relative to the total weight of the chromium-manganese oxide film.
在分步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1相同。本发明的小试炉管的结焦量比未处理的小试炉管的结焦量减少了40.84wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the step-by-step treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube of the present invention was reduced by 40.84 wt% compared with the coking amount of the untreated pilot furnace tube.
实施例5Example 5
对与实施例1相同的小试炉管进行还原性气体、氧化性气体、还原性气体分步热处理，所不同的是：The same small test furnace tube as in Example 1 was subjected to reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, except that:
(1)采用CO、H2和N2的气体混合物作为还原性气体，对炉管进行第一热处理，得到预处理小试炉管，还原性气体中氧气的含量为0ppm，其中，CO与H2的体积比为1：6，CO和H2的体积百分数为85vol％，其余为N2，还原性气体的流速为80mL/min，升温速率为160℃/h，处理温度为750℃，处理时间为8小时；(1) using a gas mixture of CO, H2 and N2 as a reducing gas, performing a first heat treatment on the furnace tube to obtain a pre-treated test furnace tube, wherein the oxygen content in the reducing gas is 0 ppm, wherein the volume ratio of CO to H2 is 1:6, the volume percentage of CO and H2 is 85 vol%, and the rest is N2 , the flow rate of the reducing gas is 80 mL/min, the heating rate is 160°C/h, the treatment temperature is 750°C, and the treatment time is 8 hours;
(2)采用空气和N2组成的氧化性气体对预处理小试炉管进行第二热处理，其中O2的体积分数为5％，氧化性气体的流速为80mL/min，第二热处理的条件为：处理温度为750℃，处理时间为8小时；(2) using an oxidizing gas composed of air and N2 to perform a second heat treatment on the pretreatment pilot furnace tube, wherein the volume fraction of O2 is 5%, the flow rate of the oxidizing gas is 80 mL/min, and the conditions of the second heat treatment are: a treatment temperature of 750°C and a treatment time of 8 hours;
(3)采用与步骤(1)相同的CO、H2和N2的气体混合物作为还原性气体，对炉管进行第三降温热处理至室温，所不同的是：还原性气体的流速为15mL/min，第三降温热处理的条件为：降温速率为110℃/h，从750℃降温至室温；(3) using the same gas mixture of CO, H2 and N2 as in step (1) as the reducing gas, the furnace tube is subjected to a third cooling heat treatment to room temperature, except that the flow rate of the reducing gas is 15 mL/min, and the conditions of the third cooling heat treatment are: the cooling rate is 110°C/h, and the temperature is reduced from 750°C to room temperature;
通过以上还原性气体、氧化性气体、还原性气体分步热处理，在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为45.88wt％。Through the above reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, a double-layer anti-coking oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film is formed on the inner wall surface of the pilot furnace tube. The surface chromium-manganese oxide film contains chromium-manganese oxide Mn 2 CrO 4 and iron. The content of iron in the chromium-manganese oxide film is 45.88wt% relative to the total weight of the chromium-manganese oxide film.
在分步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1相同。本发明的小试炉管的结焦量比未处理的小试炉管的结焦量减少了31.56wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the step-by-step treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube of the present invention was reduced by 31.56 wt % compared with the coking amount of the untreated pilot furnace tube.
实施例6Example 6
对与实施例1相同的小试炉管进行还原性气体、氧化性气体、还原性气体分步热处理，所不同的是：还原性气体第一热处理的条件为：处理温度为700℃，处理时间为25小时，第二热处理的条件为：处理温度为700℃，处理时间为25小时，第三热处理的条件为：处理温度为700℃至室温，其他处理条件与实施例1相同。The small test furnace tube identical with Example 1 was subjected to reducing gas, oxidizing gas and reducing gas step-by-step heat treatment, except that the conditions of the first heat treatment with reducing gas were: treatment temperature was 700°C and treatment time was 25 hours, the conditions of the second heat treatment were: treatment temperature was 700°C and treatment time was 25 hours, the conditions of the third heat treatment were: treatment temperature was from 700°C to room temperature, and other treatment conditions were the same as in Example 1.
通过以上还原性气体、氧化性气体、还原性气体分步热处理，在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为42.47wt％。Through the above reducing gas, oxidizing gas, and reducing gas step-by-step heat treatment, a double-layer anti-coking oxide film with a lower layer of chromium oxide and a surface layer of chromium-manganese oxide film is formed on the inner wall surface of the pilot furnace tube. The surface chromium-manganese oxide film contains chromium-manganese oxide Mn 2 CrO 4 and iron. The content of iron in the chromium-manganese oxide film is 42.47wt% relative to the total weight of the chromium-manganese oxide film.
在分步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1相同。小试炉管的结焦量比未处理的小试炉管的结焦量减少了36.39wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the step-by-step treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube was reduced by 36.39 wt % compared with the coking amount of the untreated pilot furnace tube.
对比例1Comparative Example 1
与实施例1相同的小试炉管，所不同的是：仅采用氧化性气体对小试炉管进行第二热处理，氧化性气体中O2的体积分数为16％，处理温度为900℃，处理时间为55小时，其他条件与实施例1相同。在小试炉管内壁表面形成了氧化膜，氧化膜包含氧化铬和铁元素。相对于氧化膜的总重量，炉管内表面氧化膜中铁元素的含量为50.45wt％。The same small test furnace tube as in Example 1, except that only an oxidizing gas was used to perform the second heat treatment on the small test furnace tube, the volume fraction of O2 in the oxidizing gas was 16%, the treatment temperature was 900°C, the treatment time was 55 hours, and the other conditions were the same as in Example 1. An oxide film was formed on the inner wall surface of the small test furnace tube, and the oxide film contained chromium oxide and iron. Relative to the total weight of the oxide film, the content of iron in the oxide film on the inner surface of the furnace tube was 50.45wt%.
在氧化性气体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1相同。处理后小试炉管的结焦量比未处理的小试炉管的结焦量减少了17.37wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the oxidizing gas treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube after the treatment was reduced by 17.37 wt % compared with the coking amount of the untreated pilot furnace tube.
对比例2Comparative Example 2
与实施例1相同的小试炉管，所不同的是：仅采用还原性气体对炉管进行第一热处理和第三热处理。其他条件与实施例1相同，还原性气体处理后炉管内壁表面没有氧化铬和铬锰氧化物生成。炉管内表面铁元素的含量为53.63wt％。The same small test furnace tube as in Example 1, except that only reducing gas was used to perform the first and third heat treatments on the furnace tube. Other conditions were the same as in Example 1, and no chromium oxide and chromium-manganese oxide were generated on the inner wall surface of the furnace tube after the reducing gas treatment. The content of iron on the inner surface of the furnace tube was 53.63wt%.
在还原性气体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1相同。处理后小试炉管的结焦量比未处理的小试炉管的结焦量减少了9.78wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube treated with reducing gas, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube after treatment was reduced by 9.78wt% compared with the coking amount of the untreated pilot furnace tube.
对比例3Comparative Example 3
与实施例1相同的小试炉管，所不同的是未进行任何处理，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1相同。小试炉管的结焦量为100wt％。The same pilot furnace tube as in Example 1, except that no treatment was performed, and hydrocarbon steam cracking reaction was carried out in the pilot furnace tube, and the cracking feed and cracking conditions were the same as in Example 1. The coking amount of the pilot furnace tube was 100 wt%.
对比例4Comparative Example 4
与实施例1相同的小试炉管，所不同的是：不进行步骤(3)，其他条件与实施例1相同。在炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为48.38wt％。The same test furnace tube as in Example 1 is used, except that step (3) is not performed, and other conditions are the same as in Example 1. A double-layer anti-coking oxide film is formed on the inner wall surface of the furnace tube, wherein the lower layer is chromium oxide and the surface layer is chromium-manganese oxide film. The surface chromium-manganese oxide film comprises chromium-manganese oxide Mn 2 CrO 4 and iron, and the content of iron in the chromium-manganese oxide film is 48.38 wt% relative to the total weight of the chromium-manganese oxide film.
在分步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，小试炉管的结焦量比未处理的小试炉管的结焦量减少了26.52wt％。The hydrocarbon steam cracking reaction was carried out in the small test furnace tube after the step-by-step treatment, and the cracking conditions were: cracking temperature 845°C, water-oil ratio 0.5. The experimental results showed that the coking amount of the small test furnace tube was reduced by 26.52wt% compared with the coking amount of the untreated small test furnace tube.
对比例5Comparative Example 5
与实施例1相同的小试炉管，所不同的是：控制还原性气体中氧气的含量为10ppm，其他条件与实施例1相同。在小试炉管内壁表面形成了下层为氧化铬、表层为铬锰氧化膜的双层抗结焦氧化膜。表层铬锰氧化膜包含铬锰氧化物Mn2CrO4和铁元素，相对于铬锰氧化膜的总重量，铬锰氧化膜中铁元素的含量为49.27wt％。The same test furnace tube as in Example 1 is different in that the oxygen content in the reducing gas is controlled to be 10 ppm, and the other conditions are the same as in Example 1. A double-layer anti-coking oxide film is formed on the inner wall surface of the test furnace tube, wherein the lower layer is chromium oxide and the surface layer is chromium-manganese oxide film. The surface chromium-manganese oxide film comprises chromium-manganese oxide Mn 2 CrO 4 and iron, and the content of iron in the chromium-manganese oxide film is 49.27 wt% relative to the total weight of the chromium-manganese oxide film.
在分步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1相同。本发明的小试炉管的结焦量比未处理的小试炉管的结焦量减少了20.18wt％。The hydrocarbon steam cracking reaction was carried out in the pilot furnace tube after the step-by-step treatment, and the cracking feedstock and cracking conditions were the same as those in Example 1. The coking amount of the pilot furnace tube of the present invention was reduced by 20.18 wt % compared with the coking amount of the untreated pilot furnace tube.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.
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