TW201042025A - Processing of acid containing hydrocarbons - Google Patents

Processing of acid containing hydrocarbons Download PDF

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TW201042025A
TW201042025A TW99109372A TW99109372A TW201042025A TW 201042025 A TW201042025 A TW 201042025A TW 99109372 A TW99109372 A TW 99109372A TW 99109372 A TW99109372 A TW 99109372A TW 201042025 A TW201042025 A TW 201042025A
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Taiwan
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vaporization
hydrocarbon
zone
initial
feed
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TW99109372A
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Chinese (zh)
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Donald H Powers
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Equistar Chem Lp
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Priority claimed from US12/383,990 external-priority patent/US8721872B2/en
Priority claimed from US12/383,967 external-priority patent/US20100243523A1/en
Priority claimed from US12/383,989 external-priority patent/US20100243524A1/en
Application filed by Equistar Chem Lp filed Critical Equistar Chem Lp
Publication of TW201042025A publication Critical patent/TW201042025A/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14Thermal 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/40Thermal non-catalytic treatment
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14Thermal 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
    • C10G9/18Apparatus
    • C10G9/20Tube furnaces
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1033Oil well production fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/107Atmospheric residues having a boiling point of at least about 538 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1077Vacuum residues
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203Naphthenic acids, TAN
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for thermally cracking an organic acid containing hydrocarbonaceous feed wherein the feed is first processed in a vaporization step operated under conditions designed to disassociate acid species in the feed prior to passing the feed to a thermal cracking furnace.

Description

201042025 六、發明說明: 【發明所屬之技術領域】 本發明係關於含酸烴原料之熱裂解,其係使用結合至 少一個熱裂解爐的汽化單元(vaporization unit)。說的更明 確一點,本發明係關於操作此汽化單元,以使得初始原料 中所含之酸類在汽化單元中解離。 ‘ 【先前技術】 烴的熱裂解(熱解)是一種石化方法,其被廣泛用於製 0 造烯烴,如乙烯、丙烯、丁烯、丁二烯,以及芳香族,如 苯、甲苯和二甲苯。 基本上,含烴原料係與做爲稀釋劑的蒸汽混合,以使 得烴分子維持分離。這種蒸汽/烴混合物在爐子的對流區中 預熱至約華氏900到約1,000華氏溫度(F),並且接著進入 反應(輻射)區,在該處被非常快速的加熱到相當高的烴熱 解溫度,約在1,400至1,55 0F的範圍內。在沒有任何觸媒 的協助之下完成了熱裂解。 q 這種方法是在熱解爐(蒸汽裂解器)(steam cracker)中 於反應區壓力介於約10至約30 psig的條件下進行。熱解 爐的內部具有一個對流區段(convection zone)(區域)和一 個獨立的輻射區段(radiation section)(區域)。預熱功能主 要是在對流區段中完成,而嚴酷的裂解則幾乎是在輻射區 段發生。 在熱裂解之後’視進料至熱解爐主要進料的本質而定 ,爐子的排出物可含有非常多樣的氣態烴類,例如每個分 子含一至三十五個碳原子。這些氣態烴類可以是飽和、單 201042025 一不飽和和多重不飽和,並且可以是脂肪族、脂環族和/ 或芳香族。被裂解氣體也可含有明顯數量的分子氫(氫)。 被裂解產物接著會在烯烴製造工廠中進一步處理,以 產生各種不同高純度的各別流,成爲工廠的產物,如氫、 乙烯、丙烯、每個分子具有四個碳原子之混合烴類、燃料 油和熱解汽油。前述的每一種各別的產品流本身即爲有價 値的商業產品。因此,烯烴製造工廠目前會取出一部分全 原油流或冷凝油,並且由其生成數種不同的有價値產品。 〇 熱裂解是在1913年開始使用,最初係應用於做爲裂解 爐主要進料的氣態乙烷,以用來製造乙烯。自從那時開始 ,此產業已進展至使用更重和更複雜的含烴氣態和/或液 態進料做爲裂解爐的主要進料。此類進料現在已可使用一 部分的全原油或冷凝油,當其被熱裂解時,基本上會完全 被氣化。裂解產物可以含有,例如,約1重量百分比(重量 %)的氫、約10重量%的甲烷、約25重量%的乙烯和約17 重量%的丙烯,所有的重量%係以產物的總重量爲基準,其 Q 餘大部分是由每分子具有4至35個碳原子的烴分子所構成 〇 天然氣和全原油係在許多種多變化孔隙性的地下地質 層中自然形成。許多這樣的岩層是被岩石的不透水層所覆 蓋。天然氣和全原油(原油)也累積於地表以下的各種不同 地層封閉中。因此,有大量的天然氣和/或原油於地表以 下的不同深處形成了含烴的岩層。這樣的天然氣許多係與 原油緊密的實質接觸,因此,由原油吸附了 一些較輕的分 子。 201042025 當筒井鑽穿陸地並且穿入一或多個此類的含烴岩層時 ’可經由該筒井將天然氣和/或原油回收至地表。 本文中所使用的“全原油”和”原油”等詞彙係指當其與 任何可能存在的天然氣分離而由井口流出之液態(在地表 一般普徧的溫度和壓力條件之下)原油,並且不包括爲使此 類原油能夠運送至煉油廠進行原油精煉和/或傳統蒸餾而 可能接受的任何處理。這種處理可包括如脫鹽之類的步驟 。因此’其爲適合用於煉油廠之蒸餾或其它分餾之原油, 〇 但是尙未進行任何蒸餾或分餾之處理。它可包括,但不需 永遠包括,未沸騰物質,如瀝青質或塔。這樣很難提供全 原油的沸騰範圍。因此,全原油可以是直接來自油田管線 和/或傳統原油儲存設施的一或多種原油,如同可用性所 支配,沒有任何先前的分餾操作。 如同原油一樣,天然氣在由地表產出時,其組成可以 有很大的變化,但一般會含有大量,最常見的狀況是含有 主要數量,也就是高於約50重量百分比(wt. %)的甲烷。天 Q 然氣通常也帶有一或多種較少數量(低於約50重量%)的乙 烷、丙烷、丁烷、氮、二氧化碳、硫化氫等,通常是少於 約2 0重量%。許多(但非全部)天然氣流在由陸地產出時可 含有較少數量(低於約50重量%)每分子具有5至12個碳原 子的烴類(C5-C12)’通常是少於約20重量%,其在地表― 般大氣環境的溫度和壓力之下通常並非氣態,一旦其由地 表產出時’可以從天然氣中凝結出來。所有的重量%皆是 以所討論之天然氣流的總重量爲基準。 當各種天然氣流在地表產出時,在收集天然氣的地表 201042025 處,烴組成物於一般大氣環境的溫度和壓力之下通常會由 所產生的天然氣流中自然凝結出來。在相同的普徧狀況之 下,會有正常液態的含烴冷凝液由正常氣態的天然氣中分 離出來。正常氣態的天然氣可包含甲烷、乙烷、丙烷和丁 烷。由所產生天然氣流中冷凝之正常液態的烴餾分一般被 稱爲”冷凝油”,並且一般係含有重於丁烷的分子(C5至 約C20或稍微再高一些)。在與產生之天然氣分離之後, 這種液態冷凝油餾分與一般稱爲天然氣的殘留氣體餾分將 〇 分開予以處理。 因此,由首次從地表產生之天然氣流中回收的冷凝油 在材料和組成方面並非與天然氣(主要爲甲烷)完全相同。 它與原油在材料、組成方面也不相同。冷凝油在正常氣態 的天然氣和正常液態的全原油之間佔有一項利基。冷凝油 含有比正常氣態之天然氣爲重的烴類,以及在全原油最輕 端的一系列烴類。 冷凝油,不同於原油,可以藉由其沸點範圍而加以特 Q 徵化。冷凝油一般會在約1〇〇至約6 5 0F的範圍內沸騰。在 這樣的沸騰範圍內,冷凝油含有許多種含烴材料。這些材 料可包括組成一般稱爲石油腦、煤油、柴油燃料和製氣油( 燃料油、熔爐用油、取暖用油等)等餾分之化合物。 由傳統的常壓熱蒸餾塔所獲得之常壓殘渣油(“殘油,,) 可具有很大的沸騰範圍,特別是在使用殘渣油的混合物時 ,但一般是在約600F至只殘留未沸騰實體物之沸騰終點値 的沸騰範圍內。這些殘油主要是由在約600至約l〇〇〇F範 圍內沸騰之氣製油成分和在約1000F以上至只殘留未沸騰 201042025 實體物之沸騰終點値的溫度範圍內沸騰之較重餾分所組成 〇 相對於常壓蒸餾塔,真空輔助熱蒸餾塔(真空塔)一般 係將這種氣製油成分自上述相關的較重餾分中分離出來, 因而使得氣製油餾分在別處得以單獨回收和使用。 烯烴產業現在除了可以利用原油或冷凝油(氣態和/ 或液態)餾分做爲裂解爐的主要進料之外,也已進展到可 利用全原油、原油殘渣油和/或其冷凝油做爲進料的重要 Ο 部分。201042025 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to thermal cracking of acid-containing hydrocarbon feedstocks using a vaporization unit incorporating at least one thermal cracking furnace. More specifically, the present invention relates to the operation of the vaporization unit such that the acid contained in the starting material is dissociated in the vaporization unit. [Prior Art] Thermal cracking (pyrolysis) of hydrocarbons is a petrochemical process widely used in the manufacture of olefins such as ethylene, propylene, butylene, butadiene, and aromatics such as benzene, toluene and Toluene. Basically, the hydrocarbon-containing feedstock is mixed with steam as a diluent to maintain separation of the hydrocarbon molecules. This vapor/hydrocarbon mixture is preheated in the convection zone of the furnace to a temperature of about 900 to about 1,000 degrees Fahrenheit (F) and then into the reaction (radiation) zone where it is heated very quickly to a relatively high temperature. The hydrocarbon pyrolysis temperature is in the range of about 1,400 to 1,55 0F. Thermal cracking was completed without the aid of any catalyst. q This method is carried out in a pyrolysis furnace (steam cracker) at a reaction zone pressure of from about 10 to about 30 psig. The interior of the pyrolysis furnace has a convection zone (area) and a separate radiation section (area). The preheating function is mainly done in the convection section, while the severe cracking occurs almost in the radiant section. Depending on the nature of the main feed to the pyrolysis furnace after thermal cracking, the effluent of the furnace may contain a very wide variety of gaseous hydrocarbons, for example from one to thirty-five carbon atoms per molecule. These gaseous hydrocarbons may be saturated, single 201042025 monounsaturated and polyunsaturated, and may be aliphatic, cycloaliphatic and/or aromatic. The cracked gas may also contain significant amounts of molecular hydrogen (hydrogen). The cleavage product is then further processed in an olefins manufacturing plant to produce individual streams of various high purity, which are products of the plant, such as hydrogen, ethylene, propylene, mixed hydrocarbons with four carbon atoms per molecule, fuel Oil and pyrolysis gasoline. Each of the aforementioned individual product streams is itself a valuable commercial product. As a result, olefin manufacturing plants currently take a portion of the total crude oil stream or condensed oil and produce several different valuable strontium products. 〇 Thermal cracking was started in 1913 and was originally applied to the gaseous ethane used as the main feed to the cracker to produce ethylene. Since then, the industry has progressed to using heavier and more complex hydrocarbon-containing gaseous and/or liquid feeds as the primary feed to the cracking furnace. Such feeds are now ready for use with a portion of whole crude oil or condensed oil, which is substantially completely vaporized when it is thermally cracked. The cleavage product may contain, for example, about 1 weight percent (wt%) hydrogen, about 10 wt% methane, about 25 wt% ethylene, and about 17 wt% propylene, all of which are based on the total weight of the product. Benchmark, most of its Q is composed of hydrocarbon molecules with 4 to 35 carbon atoms per molecule. Natural gas and whole crude oil are naturally formed in many kinds of multi-variable porous subterranean geological layers. Many of these rock formations are covered by an impervious layer of rock. Natural gas and whole crude oil (crude oil) are also accumulated in various formation closures below the surface. Therefore, a large amount of natural gas and/or crude oil forms a hydrocarbon-bearing rock formation at different depths below the surface. Many of these natural gas systems are in close physical contact with the crude oil, so some lighter molecules are adsorbed by the crude oil. 201042025 Natural gas and/or crude oil may be recovered to the surface via the well when the well is drilled through the ground and penetrates one or more of such hydrocarbon-bearing formations. As used herein, the terms "total crude oil" and "crude oil" refer to liquids that are separated from any natural gas that may be present and that are discharged from the wellhead (under conditions of temperature and pressure generally prevailing on the surface) and are not Any treatment that may be accepted to enable such crude oil to be transported to a refinery for crude oil refining and/or conventional distillation. This treatment may include steps such as desalting. Therefore, it is a crude oil suitable for distillation or other fractionation in a refinery, but 尙 is not subjected to any distillation or fractionation treatment. It can include, but does not need to always include, non-boiling substances such as asphaltenes or towers. This makes it difficult to provide a boiling range for all crude oil. Thus, the whole crude oil can be one or more crude oils directly from the oil field pipeline and/or the conventional crude oil storage facility, as dictated by availability, without any prior fractionation operations. Like crude oil, the composition of natural gas can vary greatly when it is produced from the surface, but it usually contains a large amount. The most common condition is that it contains a major amount, that is, more than about 50% by weight (wt.%). Methane. The day Q gas typically also carries one or more minor amounts (less than about 50% by weight) of ethane, propane, butane, nitrogen, carbon dioxide, hydrogen sulfide, etc., typically less than about 20% by weight. Many, but not all, natural gas streams may contain less (less than about 50% by weight) of hydrocarbons having from 5 to 12 carbon atoms per molecule (C5-C12) when produced from land, typically less than about 20% by weight, which is usually not gaseous under the temperature and pressure of the surface atmosphere, and can be condensed from natural gas once it is produced from the surface. All weight % is based on the total weight of the natural gas stream in question. When various natural gas streams are produced on the surface, at the surface of the natural gas collection 201042025, the hydrocarbon composition will naturally condense out of the natural gas stream produced under the temperature and pressure of the general atmospheric environment. Under the same general conditions, normal liquid hydrocarbon-containing condensate is separated from normal gaseous natural gas. Normal gaseous natural gas may comprise methane, ethane, propane and butane. The normally liquid hydrocarbon fraction condensed from the produced natural gas stream is generally referred to as "condensed oil" and typically contains molecules that are heavier than butane (C5 to about C20 or slightly higher). After separation from the produced natural gas, this liquid condensed oil fraction is treated separately from the residual gas fraction, commonly referred to as natural gas. Therefore, the condensed oil recovered from the natural gas stream first produced from the surface is not identical in material and composition to natural gas (mainly methane). It is different from crude oil in terms of materials and composition. Condensate oil has a niche between normal gaseous natural gas and normal liquid crude oil. Condensate contains hydrocarbons that are heavier than normal gaseous natural gas and a series of hydrocarbons that are the lightest at all crude oils. Condensed oil, unlike crude oil, can be characterized by its boiling point range. The condensed oil generally boils in the range of from about 1 Torr to about 650 °F. In this boiling range, the condensed oil contains a variety of hydrocarbonaceous materials. These materials may include compounds which constitute a fraction generally referred to as petroleum brain, kerosene, diesel fuel, and gas oil (fuel oil, furnace oil, heating oil, etc.). The atmospheric residue oil ("residual oil") obtained from a conventional atmospheric distillation column can have a large boiling range, especially when a mixture of residual oils is used, but generally it is about 600F to only remain. The boiling point of the boiling body of the boiling body is within the boiling range of the boiling point. These residual oils are mainly composed of a gas-making oil component boiling in the range of about 600 to about 1 〇〇〇F and a boiling of about 1000F or more to only the unexpanded 201042025 physical substance. The composition of the heavier fraction boiling in the temperature range of the end point is relative to the atmospheric distillation column, and the vacuum-assisted thermal distillation column (vacuum column) generally separates the gas-to-liquid component from the above-mentioned heavier fraction, thus The gas-to-oil fraction can be separately recovered and used elsewhere. The olefins industry now has the advantage of using crude oil or condensed oil (gaseous and/or liquid) fractions as the main feed to the cracking furnace, and has progressed to the availability of all crude oil, Crude oil residue oil and/or its condensed oil is an important part of the feed.

Donald H. Powers最近取得了美國專利6,743,961(以 下稱爲”USP ‘961”)。此專利係關於藉由利用含有塡料之氣 化/溫和裂解區來裂解全原油。此區域的操作方式須使得 尙未氣化之全原油的液相停留在該區域,直到較黏的烴類 液體成分之裂解/汽化極大化爲止。這樣可形成最少量的 固態殘渣,該殘渣會成爲塡料上的沈積物而遺留下來。這 些殘渣將藉由傳統的蒸汽空氣除焦法將塡料燒掉,理想上 〇 是在正常熔爐除焦循環的期間進行,請參閱該專利第7欄 第5 0-5 8行。因此,該專利的第二區域9係做爲在製程所 使用條件下無法被裂解或氣化之原油進料成分(包括含烴 材料)的捕集器,請參閱該專利第8攔第6 0-64行。 核發給Donald H. Powers的美國專利7,019,187係針 對USP ‘961所揭露之方法,但使用了略微酸性的裂解觸媒 來驅動氣化/溫和裂解單元的所有功能,使其更朝向於汽 化(沒有預先溫和裂解)-溫和裂解(接在汽化之後進行)系列 (spectrum)的輕度裂解端移動。 201042025 核發給Donald H. Powers的美國專利7,404,8 8 9係針 對USP ‘961所揭露之方法,但使用了常壓殘渣油做爲汽化 單元和裂解爐的主要液態含烴進料。 前述專利的完整揭露內容皆倂入本文參照。 2006年3月1日遞件之美國11/365,212號專利申請案 係針對使用冷凝油做爲汽化單元和裂解爐的主要液態含烴 進料,其與USP ‘961具有共同的發明人和專利權人。 在2007年3月22日公告John S. Buchanan等人所提 〇 出之美國專利申請公告號2007/0066860中,揭露了具有高 總酸値(TAN)之原油的熱裂解,其係使用結合了熱裂解爐的 驟沸桶。此專利公告指出,驟沸桶只能將進入該桶的兩相( 氣相和液相)予以物理分離。也就是說,離開驟沸桶的氣相 組成實質上與進入驟沸桶的氣相組成相同。同樣的,離開 該驟沸桶的液相組成實質上與進入驟沸桶的液相組成相同 。其所揭露的較佳高TAN進料爲預先施以煉製處理以去除 殘油之原油或進料流。因此,Buchanan等人所教示的是在 Q 其方法中不要使用殘油。Donald H. Powers recently obtained US Patent 6,743,961 (hereinafter referred to as "USP ‘961"). This patent relates to the cracking of whole crude oil by utilizing a gasification/mild cracking zone containing a feedstock. This zone is operated in such a way that the liquid phase of the unvaporized whole crude oil stays in this zone until the cracking/vaporization of the more viscous hydrocarbon liquid component is maximized. This results in the formation of a minimum amount of solid residue which can be left as a deposit on the dip. These residues will be burned off by conventional steam air decoking, ideally during the normal furnace decoking cycle, see column 7 of the patent, lines 5 0-5. Therefore, the second zone 9 of the patent is used as a trap for crude oil feed components (including hydrocarbon-containing materials) that cannot be cracked or gasified under the conditions used in the process, see the eighth block of the patent. -64 lines. US Patent 7,019,187 issued to Donald H. Powers is directed to the method disclosed in USP '961, but uses a slightly acidic cracking catalyst to drive all functions of the gasification/mild cracking unit to make it more vaporized (no prior Mild cleavage) - Mild cleavage of the spectrum by mild cleavage (followed by vaporization). 201042025 U.S. Patent 7,404,8 8 9 issued to Donald H. Powers is directed to the method disclosed in USP '961, but uses atmospheric residue oil as the primary liquid hydrocarbon feed to the vaporization unit and cracking furnace. The complete disclosure of the aforementioned patents is incorporated herein by reference. US Patent Application No. 11/365,212, filed on March 1, 2006, is directed to the use of condensed oil as the primary liquid hydrocarbon feedstock for the vaporization unit and cracking furnace, which shares the inventor and patent rights with USP '961. people. U.S. Patent Application Publication No. 2007/0066860, filed on Mar. 22, 2007, to the disclosure of the disclosure of the entire disclosure of the disclosure of The boiling tank of the thermal cracking furnace. This patent publication states that the quenching tank can only physically separate the two phases (gas phase and liquid phase) entering the barrel. That is, the gas phase composition leaving the quench drum is substantially the same as the gas phase composition entering the quench drum. Similarly, the composition of the liquid phase leaving the quench tank is substantially the same as the composition of the liquid phase entering the quench drum. The preferred high TAN feed disclosed is a crude oil or feed stream that has been previously subjected to a refining process to remove residual oil. Therefore, what Buchanan et al. teach is not to use residual oil in the Q method.

Buchanan等人的專利公告還進一步揭露,在高TAN進 料中所存在的環烷酸將實質上被轉化成CO、C02和較低分 子量的酸,如甲酸、乙酸、丙酸和丁酸。 在如原油之類的含烴進料中,包括羧酸、環烷酸和酚 酸之有機酸(但非侷限於此)的含量呈現成長趨勢,已成爲 原油煉製加工業者的一個問題。環烷酸經常被挑出來考量 ,因爲它們特別具有腐蝕性。 大多數的煉油廠無法在4 0 0F以上處理總酸値(TAN)大 201042025 於1.0的原油,這是因爲這些酸具有高度的腐蝕性,特別 是環烷酸。爲符合需求,世界對於烴類的生產力要求愈來 愈高,這些含酸原料(特別是原油)的利用也要能符合世界 性的需求成長。 在本發明中,含有機酸的原料(如全原油和冷凝油), 以及含有機酸的原油餾分(例如殘渣油)係藉由汽化單元和 至少一個熱裂解爐的組合來進行處理,不只是降低(轉化或 轉換)原有的酸含量,同時也將汽化單元中的酸類予以解離 〇 ,並且在相同的汽化單元中,由那些原料形成額外的熱裂 解進料。 依據本發明,令人驚訝的發現,上述汽化單元可以被 謹慎操作而使得至少一部分初始裂解原料中所含的酸類被 解離或者是改變。因此,藉由本發明,可在它們被送入熱 裂解爐之前,使得至少一部分初始原料中所含的酸類被化 學和/或物理改變。 沒有本發明,許多在汽化單元中被解離或者是改變的 Q 酸類將會在未改變的條件下以其進料的形式傳送至裂解爐 中。因此,本發明可確使最多初始原料中所含酸類得以在 熱解爐中被破壞,因而避免下游單元與這些酸類接觸。 【發明內容】 本發明提供了一種用於處理含有機酸原料的獨特方法 ,其使用了一個汽化單元並結合至少一個裂解爐,其中該 汽化單元的操作方式可在將汽化單元所形成之氣態材料( 含烴且爲酸性)傳送到熱裂爐之前將至少一部分原本存在 於原料中的酸類解離。 201042025 本文中所使用的”烴”、”烴類”和”含烴材料”並 非完全或只是代表含氫原子和碳原子的材料。此類名詞包 括本質上含烴的材料,其主要或基本上係由氫和碳原子所 構成’但是也可以包含其它元素,如氧、硫、氮、金屬、 無機鹽等,甚至於有明顯的含量。這些名詞包括原油本身 或其餾分,如氣製油、殘渣油等。也包括天然氣的冷凝液 0 本發明中所用的”氣態”乙詞係指一或多種基本上爲 〇 氣相狀態的氣體,例如只有蒸汽、蒸汽和烴類蒸氣的混合 物等。 本文中所用的焦炭係指高分子量的含碳固體,並且包 括由多核芳香族縮合所形成之化合物。 可使用本發明之烯烴生產工廠將包括初始用於接收及 熱裂解進料的熱解(熱裂解)爐。蒸汽裂解烴類所用的熱解 爐係藉由對流和輻射的方式加熱,並且包括一系列的預熱 、循環及裂解管(通常是此類的管束),用來預熱、傳輸及 Q 裂解烴類進料。這種高裂解熱係藉由配置於輻射區段 (radient section)(有時稱爲”放射區段 ”(radiation section) )的燃燒器來供應。來自這些燃燒器的廢氣被循環通過裂 解爐的對流區段,以提供預熱進入烴類進料所需的熱量。 裂解爐的對流和輻射區段係在”跨越處”連接,並且前文中 所指的管子將烴類進料由一個區段的內部運送到下一個區 段的內部。 在典型的裂解爐中,對流區段可包含複數個子區域。 例如,進料可以先在第一上層子區域中預熱,在第二子區 -10- 201042025 域中加熱鍋爐進料水,在第三子區域中加熱混合的進料和 蒸汽,在第四子區域中過熱蒸汽,最終的進料/蒸汽混合 物分裂成複數個子流,並且在較低(底部)或第五子區域中 預熱。子區域的數目和它們的功能可以有很大的變化。每 一個子區域可以承載多個導管,其可運送裂解爐進料,而 許多導管的形狀爲正弦曲線。對流區段的操作條件沒有像 輻射區段的操作條件那麼嚴苛。 裂解爐被設計成可在輻射區段中快速加熱,其係從輻 0 射管(線圈)入口處開始,而在該處的反應速度常數低,這 是因爲低溫的關係。大部分轉移的熱量只是使烴類由入口 溫度升高至反應溫度。在線圈的中間,溫度上升速率較低 ,但是裂解的速率相當可觀。在線圈的出口處,溫度上升 速率有些許提高,但沒有像在入口處增加的那麼快。反應 物的消失速率爲反應速度常數乘上局部濃度的乘積。在線 圈的末端,反應物濃度低,並且可以藉由提高製程的氣體 溫度而得到額外的裂解。 Q 進料烴類的蒸汽稀釋降低了烴類的分壓,促進烯烴形 成,並且降低在輻射管中形成焦炭的任何傾向。 裂解爐通常具有矩形的燃燒室,而在輻射防火牆之_ 的中央設置了垂直豎立的管子。這些管子係由其頂部支胃 0 輻射區段的引燃係使用氣態或混合氣態/液態的燃g 以安裝了器壁或底板或者是兩者組合之燃燒器來進行。g 燒室一般是處於輕微負壓的狀態下,最常搭配著向上流 的煙道氣。進入對流區段的煙道氣流係藉由至少一個天$ -11- 201042025 通風(natural draft)或抽氣通風(induced draft)的風扇來產 生。 輻射線圈通常是懸掛在燃燒室中心朝下的單一平面。 它們可以套在一個單一平面中或者是以交錯雙排管 (staggered, double-row tube)排列方式平行置放。由燃燒室 到輻射管的熱傳主要是以輻射造成,因此,烴類會在”輻射 區段”中被加熱到約1,4 0 0 F至約1 , 5 5 0 F,因而遭受到劇烈 的裂解並且形成焦炭。 〇 因此,最初是空的輻射線圈是一種火管式化學反應器 。燃燒爐的烴類進料係在對流區段中被預熱到約90 0F至約 1,0 00F,其係藉由來自輻射區段的煙道氣、對流區段中進 料的蒸汽稀釋等來進行對流加熱。在傳統的商用爐中預熱 之後,此進料已可進入輻射區段。 離開輻射區段的裂解氣態烴類被快速的降低溫度,以 避免破壞裂解型態。在烯烴製造工廠相同下游進行進一步 處理之前將裂解氣體冷卻,可回收高壓蒸汽的大量熱能, Q 以在裂解爐和/或烯烴工廠中重複使用。通常係使用輸送 管線換熱器來完成,這在本領域中是已知的技術。 在液態烴類原料下游處理方面,雖然在各個裂解工廠 間可以有所差異,一般係在(例如)與前述相同輸送管線換 熱器中熱交換之後,使裂解爐流出物進行油淬火。之後, 將裂解的烴流施以基本的分餾,以去除重液,接著將未凝 結的烴類予以壓縮,並且從中去除酸性氣體和水。然後將 各種想要的產物各別予以分離,例如乙烯、丙烯、每分子 具有四個碳原子的烴類混合物、燃料油、熱解汽油和高純 -12- 201042025 度的氫流。 第1圖顯示的是一個汽化/裂解系統,其可針 有機酸的全原油、冷凝油、含殘油之全原油的餾分 是常壓殘渣油)以及其混合物做爲重要(主要)系統 進行操作。 爲了簡單及簡潔起見,第1圖是非常槪略性的 ’但如同前面所述,真正的裂解爐是相當複雜的結 總酸値或TAN是含烴材料之有機酸含量的—種 〇 標。此類有機酸包括,但非侷限於,至少一種羧酸 少一種環烷酸類和/或至少一種酚酸類。其它如本 所述之低分子量的酸類也可以較少的數量存在。 TAN係以ASTM D-644方法來測量,並且其單位 毫克數/被測試含烴材料公斤數。爲了簡潔起見, 不再重覆說明量測的方法和單位。 如前文中所定義且可適用於本發明之含有機酸 包括任何一種含烴材料,如原油本身、一或多種含 Q 的原油餾分(特別是常壓殘油)、天然氣冷凝液,以 種或以上所構成之混合物。 羧酸是在前述進料流中所含有機酸中最具有腐 一類。在羧酸類之中,又以環烷酸子群最具腐鈾性 於下游操作設備腐蝕的最小化會造成問題。 本發明所使用的常壓殘油進料可以來自單一或 來源,因此,可能是單一的殘油或是兩種或以上的 形成的混合物,其可具有或不具有其它如原油和冷 類的材料。用於本發明之常壓殘油可具有相當廣的 對以含 (特別 進料來 不意圖 構。 量測指 類、至 文前面 爲KOH 以下將 進料流 殘渣油 及其兩 蝕性的 ,且對 多重的 殘油所 凝油之 沸騰範 -13- 201042025 圍,特別是當使用殘油混合物時,但一般是在約600F至只 殘留未沸騰實體物之沸騰終點値的沸騰範圍內。 來自常壓熱蒸餾塔的常壓殘油底餾物主要是由在約 600至約1 000F範圍內沸騰之氣製油成分和在約1 000F以 上至只殘留未沸騰實體物之沸騰終點値的溫度範圍內沸騰 之較重餾分所組成。 真空輔助熱蒸餾塔(真空塔)通常可將氣製油成分自上 述相關的較重餾分中分離出來,因而產生不同組成的殘油 〇 在本發明進料2中所使用的殘油量可以是整個進料2 的重要組成。殘油成分可以爲進料2總重量的至少約20重 量%,但不需要嚴格限制在這個範圍內。 可以在進料中添加其它材料,其係由進料2中所添加 殘油的特殊物理及化學特性來決定。此類額外的材料可包 括輕汽油、石油腦、天然汽油和/或冷凝油。所使用石油 腦的形態可以是全範圍石油腦、輕石油腦、中石油腦、重 Q 石油腦,或者是其中兩種或以上之混合物。輕汽油可具有 的沸騰範圍是從戊烷(C5)沸點到約158F。包括輕、中和重 石油腦餾分之全範圍石油腦可具有的沸騰範圍是從約158 到約3 5 0 F。輕、中和重石油腦餾分的沸騰範圍分別爲從約The Buchanan et al. patent publication further discloses that the naphthenic acid present in the high TAN feed will be substantially converted to CO, CO 2 and lower molecular weight acids such as formic acid, acetic acid, propionic acid and butyric acid. In hydrocarbon-containing feeds such as crude oil, the content of organic acids including, but not limited to, carboxylic acids, naphthenic acids and phenolic acids is on the rise, and has become a problem for the crude oil refining and processing industry. Naphthenic acids are often picked up because they are particularly corrosive. Most refineries are unable to process crude oils with total strontium (TAN) and 201042025 at 1.0 above 400°F because these acids are highly corrosive, especially naphthenic acids. In order to meet the demand, the world's productivity requirements for hydrocarbons are getting higher and higher, and the use of these acid-containing raw materials (especially crude oil) can also meet the needs of world growth. In the present invention, the organic acid-containing raw materials (such as whole crude oil and condensed oil) and the organic acid-containing crude oil fraction (for example, residual oil) are treated by a combination of a vaporization unit and at least one thermal cracking furnace, not only The original acid content is reduced (converted or converted) while the acids in the vaporization unit are also dissociated, and additional thermal cracking feeds are formed from those feedstocks in the same vaporization unit. In accordance with the present invention, it has been surprisingly discovered that the vaporization unit described above can be handled with care such that at least a portion of the acid contained in the initial cracking feedstock is dissociated or altered. Thus, by the present invention, at least a portion of the acid contained in the starting material can be chemically and/or physically altered before they are fed to the thermal cracking furnace. Without the present invention, many of the Q acids that are dissociated or altered in the vaporization unit will be delivered to the cracking furnace in the form of their feed under unaltered conditions. Therefore, the present invention makes it possible to destroy the acid contained in most of the starting materials in the pyrolysis furnace, thereby preventing the downstream unit from coming into contact with these acids. SUMMARY OF THE INVENTION The present invention provides a unique process for treating organic acid-containing feedstocks that utilizes a vaporization unit in combination with at least one cracking furnace, wherein the vaporization unit operates in a gaseous material formed by the vaporization unit. (Carbonous and acidic) Dissociates at least a portion of the acid originally present in the feedstock prior to delivery to the thermal cracking furnace. 201042025 As used herein, "hydrocarbon", "hydrocarbon" and "hydrocarbon-containing material" are not exclusively or exclusively representative of materials containing hydrogen atoms and carbon atoms. Such terms include essentially hydrocarbon-containing materials that are primarily or substantially composed of hydrogen and carbon atoms 'but may also contain other elements such as oxygen, sulfur, nitrogen, metals, inorganic salts, etc., even with significant content. These terms include crude oil itself or its fractions, such as gas oil, residual oil, and the like. Also included is condensate for natural gas. The term "gaseous" as used in the present invention refers to one or more gases which are substantially in the gaseous state of hydrazine, such as only a mixture of steam, steam and hydrocarbon vapors, and the like. As used herein, coke refers to high molecular weight carbonaceous solids and includes compounds formed by polynuclear aromatic condensation. The olefin production plant in which the present invention can be used will include a pyrolysis (thermal cracking) furnace initially used for receiving and thermally cracking the feed. The pyrolysis furnace used for steam cracking hydrocarbons is heated by convection and radiation and includes a series of preheating, circulating and cracking tubes (usually such bundles) for preheating, transporting and Q cracking hydrocarbons. Class feed. This high heat of cracking is supplied by a burner disposed in a radial section (sometimes referred to as a "radiation section"). Exhaust gases from these burners are circulated through the convection section of the cracker to provide the heat required to preheat the hydrocarbon feed. The convection and radiant sections of the cracking furnace are connected at "crossovers" and the tubes referred to above transport the hydrocarbon feed from the interior of one section to the interior of the next section. In a typical cracking furnace, the convection section can include a plurality of sub-areas. For example, the feed may be preheated in the first upper subzone, the boiler feed water is heated in the second subzone-10-201042025, and the mixed feed and steam are heated in the third subzone, in the fourth The superheated steam in the subregion, the final feed/steam mixture splits into a plurality of substreams and is preheated in the lower (bottom) or fifth subregion. The number of sub-areas and their functions can vary greatly. Each sub-area can carry multiple conduits that can carry the cracker feed, while many conduits are sinusoidal in shape. The operating conditions of the convection section are not as severe as the operating conditions of the radiant section. The cracking furnace is designed to be rapidly heated in the radiation section starting from the entrance of the spoke (coil) where the reaction rate constant is low due to the low temperature relationship. Most of the heat transferred is simply to raise the hydrocarbons from the inlet temperature to the reaction temperature. In the middle of the coil, the rate of temperature rise is low, but the rate of cracking is considerable. At the exit of the coil, the rate of temperature rise is slightly increased, but not as fast as it is added at the inlet. The rate of disappearance of the reactant is the product of the reaction rate constant multiplied by the local concentration. At the end of the coil, the reactant concentration is low and additional cracking can be obtained by increasing the gas temperature of the process. Steam dilution of the Q feed hydrocarbon reduces the partial pressure of the hydrocarbon, promotes olefin formation, and reduces any tendency to form coke in the radiant tube. The cracking furnace usually has a rectangular combustion chamber, and a vertically erected tube is placed in the center of the radiation firewall. These tubes are made from a pilot system of the top abdomen 0 radiation section using a gaseous or mixed gaseous/liquid fuel to install a wall or a bottom plate or a combination of burners. g The burning chamber is generally in a state of slight negative pressure, most often with an upward flow of flue gas. The flue gas flow entering the convection section is produced by a fan of at least one day -11-201042025 natural draft or induced draft. The radiant coil is typically suspended in a single plane with the center of the combustion chamber facing down. They can be placed in a single plane or placed in parallel in a staggered, double-row tube arrangement. The heat transfer from the combustion chamber to the radiant tube is mainly caused by radiation, so the hydrocarbons are heated in the "radiation section" to about 1,400 F to about 1,500 F, thus suffering severely Cracking and forming coke. 〇 Therefore, the initially empty radiant coil is a fire tube chemical reactor. The hydrocarbon feed to the furnace is preheated in the convection section to between about 90 F to about 1,00 F, which is diluted by flue gas from the radiant section, steam fed to the convection section, etc. For convection heating. This feed has access to the radiant section after preheating in a conventional commercial furnace. The cracked gaseous hydrocarbons leaving the radiant section are rapidly reduced in temperature to avoid damaging the cleavage pattern. The cracking gas is cooled prior to further processing downstream of the olefin manufacturing plant to recover a significant amount of thermal energy from the high pressure steam, Q being reused in the cracking furnace and/or olefins plant. This is typically done using a transfer line heat exchanger, which is a technique known in the art. In the downstream processing of liquid hydrocarbon feedstocks, although there may be differences between the various cracking plants, the cracker effluent is typically oil quenched after, for example, heat exchange in the same transfer line heat exchanger as previously described. Thereafter, the cracked hydrocarbon stream is subjected to basic fractionation to remove the heavy liquid, followed by compression of the uncondensed hydrocarbons, and removal of the acid gas and water therefrom. The desired products are then separated separately, such as ethylene, propylene, a mixture of hydrocarbons having four carbon atoms per molecule, fuel oil, pyrolysis gasoline, and a high purity -12-201042025 degree hydrogen stream. Figure 1 shows a vaporization/cracking system in which all of the crude oil, condensate, and residual oil-containing crude oils of the organic acid are atmospheric residue oils and mixtures thereof are used as important (primary) systems for operation. . For the sake of simplicity and brevity, Figure 1 is very illustrative 'but as mentioned above, the real cracking furnace is quite complex. The total acid enthalpy or TAN is the organic acid content of the hydrocarbon-containing material. . Such organic acids include, but are not limited to, at least one carboxylic acid less than one naphthenic acid and/or at least one phenolic acid. Other low molecular weight acids as described herein may also be present in minor amounts. TAN is measured by the ASTM D-644 method and is expressed in milligrams per kilogram of hydrocarbon-containing material tested. For the sake of brevity, the methods and units of measurement will not be repeated. The organic acid as defined in the foregoing and applicable to the present invention includes any hydrocarbon-containing material such as crude oil itself, one or more crude oil fractions containing Q (especially atmospheric residual oil), natural gas condensate, or A mixture of the above. The carboxylic acid is the most rotted of the organic acids contained in the aforementioned feed stream. Among the carboxylic acids, the minimization of the most uranium in the naphthenic acid subgroup to the corrosion of downstream operating equipment poses a problem. The atmospheric residual oil feed used in the present invention may be from a single source or a source, and thus may be a single residual oil or a mixture of two or more, which may or may not have other materials such as crude oil and cold. . The atmospheric residue used in the present invention may have a relatively wide pair of inclusions (specially fed, not intended to be constructed. The measurement is referred to as KOH below the feed stream residue oil and its two etchants, and The boiling of the multiple residual oils is in the range of -13,420,420, especially when using a residual oil mixture, but generally in the boiling range of about 600F to the boiling end of only the unboiling solids. The atmospheric residue of the autoclave is mainly composed of a gas-to-liquid component boiled in the range of about 600 to about 1 000 F and a boiling temperature range of from about 1 000 F or more to only the boiling end of the unboiling entity. a boiled heavier fraction consisting of a vacuum-assisted thermal distillation column (vacuum column) which typically separates the gas-to-liquid component from the above-mentioned associated heavier fraction, thereby producing a residual oil of different composition, in the feed 2 of the present invention. The amount of residual oil used may be an important component of the entire feed 2. The residual oil component may be at least about 20% by weight of the total weight of feed 2, but need not be strictly limited to this range. It may be added to the feed. The material, which is determined by the special physical and chemical properties of the residual oil added to Feed 2. These additional materials may include light gasoline, petroleum brain, natural gasoline and/or condensed oil. It is a full range of petroleum brain, light petroleum brain, medium petroleum brain, heavy Q petroleum brain, or a mixture of two or more. Light gasoline can have a boiling range from pentane (C5) boiling point to about 158F. The full range of petroleum brains that neutralize heavy petroleum brain fractions can have a boiling range of from about 158 to about 350 F. The boiling ranges of the light, medium, and heavy petroleum brain fractions are from about

158到約212F、從約212到約302F、及從約3 02到約35〇F 〇 謹慎添加至進料2之殘油中的輕質材料數量可以有很 大的變動,端視操作者的需求而定,但是在進料2中的殘 油’如有存在的話,可以仍然是在管線10中之進料2的重 -14 - 201042025 要成分,並且進料至汽化單元11。 【實施方式】 第1圓顯示的是一個液體熱裂解爐1,其中含有,例如, 至少一種羧酸類之含烴主要進料2係被通入位於裂解爐1 對流區段較高、較冷區域的上半部進料預熱子區域3。蒸 汽6也在裂解爐對流區段的較高位置處過熱。 接著藉由管路(管線)1〇將預熱的裂解進料流通入汽化 單元11 (完全揭露於USP‘961),該單元被分成較高的蒸 〇 氣汽化區域12和較低的汽化區域13。在單元11中,可使 得預熱步驟3之後仍維持液態之材料(例如石油腦和汽油 沸騰範圍和較輕餾分)至少有一大部分達到主要(佔大多數 )氣化。 伴隨著預熱進料而被單元11接收的氣態材料(含烴且 爲酸性),以及可在特殊條件下形成並接著散佈在區域12 中的額外氣態材料(含烴且爲酸性)係藉由管線14自區域12 中移出。因此,管線14運送著幾乎所有存在於區域12中 Q 的較輕烴蒸氣,例如石油腦和石油沸騰範圍和較輕石油, 並且可以帶走一些汽態的酸性物質,經解離和/或未經解 離。在區域12中所存在的液態餾出物(可具有或不具有一 些液態汽油和/或石油腦)係經由管線1 5從該處移出,並 且隨著仍爲液態的酸類通入較低區域13的內部上方。 在這個特別的實施實例中,區域1 2和1 3彼此之間被 不透水的內壁1 6隔開,使得流體無法連通,該內壁可以是 實心的塔盤。管線1 5代表區域1 2和1 3之間向下的外部流 體連通管道。取而代之,或是除此之外,可以藉由修改內 -15- 201042025 壁16使得至少有部分內壁可穿透液體的方式,使得區域 12和13之間能有內部的流體連通,其可藉由使用一或多 個塔盤,其設計可讓液體向下流入區域13的內部且使蒸氣 向上進入區域12的內部。舉例而言’取代使用不透水的內 壁16,可以使用煙函式塔盤,使得單元11內的液體由內 部向下流入區段13而非經由管線15從外部進入單元U。 在由內部向下流動的情況下,配液裝置18就變成選用的。 無論液體是由那一種方式從區域12移至區域13,液 〇 體係向下移動進入區域13,因而可能遇到至少一個配液裝 置18。裝置18可均勻分配橫越單元11之截面的液體,使 得液體能夠均勻的流過蒸餾塔的寬度範圍,而與塡料19接 觸。 蒸汽6通過過熱的子區域20,並且接著經由管線21 進入塡料19下方之區域13的較低部分22。在塡料19中 ,來自管線15的液體和來自管線21的蒸汽彼此緊密的混 合,因而使得部分的液體15汽化,並且解離一些酸類,特 〇 別是羧酸類,因而協助這些酸的汽化,使其經由管線17自 區域13移出。這種新形成的酸性含烴蒸氣,隨著蒸汽21 ,經由管線1 7從區域1 3中移出,並且可以添加至管線i 4 的蒸氣中’以形成管線2 5中的綜合酸性烴蒸氣產物。流 25主要係含有來自進料2的烴蒸氣,例如汽油、石油腦、 中間餾分、氣製油、源自進料2之大量酸性物質和蒸汽。 因此’流17代表了進料流2的一部分再加上蒸汽21 減去存在於底部流2 6中來自進料2的烴液剩餘物。依照本 發明來操作汽化單元1 1 ’流25含有明顯數量(大多數)存在 -16- 201042025 於初始原料2中的羧酸類(包括經解離和未經解離的形態) ,然而,這些原本存在於進料2中之酸類的總量和本質(例 如分子量)已經被改變,使得所有通入管線1 4和1 7(特別是 管線17)的酸類,無論是在數量和本質方面’會與初始進料 2中所含有物理和化學上的差異。 令人驚訝的發現,藉由謹慎操作汽化單元’可將不少 數量的羧酸,特別是環烷酸,予以解離。 流25被通過一個管集箱(圖中未顯示),在該處流25 0 被分成多個子流,並且經過多個導管(圖中未顯示)而進入 熱裂解爐1的對流區段預熱子區域27中。區段27是在爐 1的下方區段,因而溫度較高。區段27被用來預熱流25 至前述適合在輻射區域29中進行熱裂解的溫度。 在區段27中大量加熱之後,包括其中所含初始有機酸 類和經解離酸類的流25經由管線28通入輻射區段子區域 29。再次地,爲了簡潔起見,這些通常由子區域27流至並 流入子區域29的許多各別流係以單一流28來代表。 q 在爐1的輻射燃燒室29中,來自管線28且含有許多 種不同烴類成分的進料,包括初始和經解離的酸類,將遭 受如前所述的嚴苛熱裂解條件。這些裂解條件使明顯數量 ,甚至於是大多數(基本上是全部)殘留的羧酸轉化成或者 是轉換成一氧化碳(CO)、二氧化碳(co2)和較低分子量的酸 (甲酸、乙酸、丙酸和丁酸)。 已裂解之產物經由管線30離開輻射燃燒室29,以在 爐1的烯烴工廠下游的其餘設施中進一步的處理,如同前 面所述並詳如USP ‘961和/或煉油廠中所示。 -17- 201042025 當使用原油、冷凝油、殘油等做爲進料2的重要成分 時,有大量的餾出物(有些含有機酸)最後會在單元11中被 汽化,特別是區域13,通入熱裂解爐1,並且因而將此類 餾出物裂解轉化成較輕的成分。 進料2可以在溫度爲約室溫至約3 00F且壓力爲略高於 常壓至約l〇〇psig(以下簡稱爲”常壓至lOOpsig”)的條件下 進入熱裂解爐1。 進料2可經由管線10在溫度爲約室溫至約750F,例 0 如約500至約750F,且壓力爲常壓至l〇〇psig的條件下進 入區域12。 流14基本上可以是所有由進料2形成的烴蒸氣,並且 溫度爲約室溫至約700F且壓力爲常壓至100 psig。流14 可以含有或不含原先在於進料2之中的某些酸類,包括經 解離和未經解離的形態,其係由進料2的本質和單元1 1的 操作條件而定。 流15基本上可以是進料2所有的殘留液體再扣除在預 q 熱器3和區域12中被汽化者,並且溫度爲約室溫至約700F 且壓力爲略高於常壓至約l〇〇psig(以下簡稱爲”常壓至1〇0 psig”)。 區域12可以做爲物理分離區域,如同在上文中所討論 Buchanan等人著作所提出之驟沸桶,在該情況下基本上並 沒有發生酸類解離。然而,依照本發明所教示,如有需要 ,單元11可在適合引起已經由管線10進入區域12中之液 態烴額外汽化及酸類解離的溫度下操作。 區域1 3是在謹慎計算的條件下操作,不只是要能夠將 -18- 201042025 明顯額外數量的液態烴類汽化,同時也要解離明顯數量( 較佳爲大多數)的羧酸類,其原本是在進料2中並且以液 態形式殘留在流15中。這可驅使最大數量的酸類進入管線 17以傳送至熱裂解爐1。 因此,依照本發明,汽化單元Π (特別是該單元的區 域13 )係在約700至約1,100F的溫度下謹慎操作,因而使 得經由管線15所收集來自區域12的液體形成相當數量的 額外汽態烴類和解離酸類。 〇 因此,整體而言,汽化單元11可由預熱進料流1〇中 所含的液體來形成相當數量的額外氣態烴類和酸,同時包 括經解離和未解離。 因此,經由管線1 4、1 7和25離開汽化單元1 1之汽相 化學組成(含烴且爲酸性)與經由管線1 〇進入單元1 1之氣 相化學組成有實質上的差異。同樣的,經由管線26離開單 元1 1之液相化學組成與經由管線1 〇進入單元1 1之液相化 學組成也有實質上的差異。也就是說,單元11除了使經由 ◎ 管線1 0進入單元11的兩相(液相和汽相)進行物理分離之 外,還產生了更多的影響。 流1 4和1 7的結合,如同流2 5所代表,可以在溫度爲 約600F至約800F且壓力爲常壓至lOOpsig的條件下進行 ,並且其所含之(例如)整體蒸汽/烴的比率爲每磅的烴約 有0_1至約2.0’較佳爲約0.1至約1.0磅的蒸汽。 在汽化區域13中,稀釋比率(熱氣/液滴)將會有相當 大幅度的變異,因爲原油、原油的餾分(特別是殘油)和冷 凝油的組成變動相當大。一般而言,在區域1 3頂部和管線 -19- 201042025 1 7中的熱氣(例如蒸汽)、烴和酸類的含量比 於烴/酸類爲約0 . 1 / 1至約5 / 1。 蒸汽是適合經由管線21引入之熱氣的一 可以是一般在傳統裂解工廠中所使用的蒸汽 用的蒸汽中可以存在其它物質。所有此類氣 係足以使得有相當部分進入區域1 3的液態焰 般而言’由導管21進入區域13之氣體溫度; ’較佳爲約900至約1,100F且壓力爲常壓至 0 了簡單起見,此類氣體在下文中將僅以蒸汽 因此,流1 7可以是蒸汽和沸點低於約1 酸類的混合物。流1 7的溫度可以是約600 3 力爲常壓至lOOpsig。 在裂解操作的一般情況下,來自管線2 1 做爲分壓的稀釋劑。反而是,來自管線21的 供了稀釋的功能,同時也可將單元11中仍處 提供進一步汽化及溫和裂解的能量。這只需 Q 來達到1 )使較重烴類成分(例如在全原油和 現的成分)汽化和/或溫和裂解以及2)使至 明顯數量)內含的羧酸類解離即可完成。舉例 線21中的蒸汽就可達成進料2液態烴類的實 裂解,同時可將原本存在於進料2中的酸類 的液態烴類液滴漸漸朝向區域1 3較低的方向 常高的蒸汽稀釋比和最高溫度的蒸汽提供於 〇 依照本發明,在第1圖之汽化單元11& 率爲蒸汽相對 •個實例。流6 類型。在所使 體的較佳溫度 ! 15揮發。一 g少爲約6 5 0 F 1 0 0 p s i g。爲 乙詞來表不。 ,1〇〇 F之烴/ h約8 0 0 F且壓 的蒸汽不只是 蒸汽不只是提 於液態的烴類 要足夠的能量 殘油中所可發 > 一些(較佳爲 而言,利用管 質氣化/溫和 解離。當酸性 丨移動時,將非 最需要的地方 5進料1 0中所 -20- 201042025 殘留比約1,100F較輕(較低)沸騰之烴類和酸類(所有皆如 同前面所定義)將會在單元11中被汽化,並且經由管線14 或17或同時經由兩者移出,並且如前文中所述,被送至裂 解爐1。除此之外’比本段短文先前所述之較輕實體物爲 重之含烴實體物可以(至少有一部分)在單元11 (特別是區 域13)中被溫和裂解或者是分解成如先前所述之較輕含煙 實體物’並且那些剛形成的較輕實體物將經由管線17移出 ’成爲裂解爐1的額外進料。同樣的,至少有一些原本存 〇 在於進料2中的酸類將會在單元11 (特別是區域13)中被解 離或者是化學改變,並且那些剛形成的物質將經由流1 7移 出以送入爐1。 因此,依照本發明,原本存在於酸性進料2中的腐触 性羧酸類,包括腐蝕性更高的環烷酸類,可以藉由本發明 單元11的操作,在被送入裂解爐1之前大部分轉化成實質 上不太有腐蝕性的物質。 進料1 0的液體殘餘物將經由管線2 6移出以移置到別 〇 處。 依照本發明前面所述的方式來操作汽化單元1 1 (特別 是區域13),可將相當數量原本存在於進料2中的酸類予以 氣化和/或解離,並且傳送至裂解爐1。依照本發明,大 多數原本存在於進料2中的高腐蝕性環烷酸類將會在被送 至裂解爐1之前,藉由汽化單元11的操作而被解離。在該 爐中,酸類至少會被完全破壞或者是轉化(轉換)成較低分 子量、較不具腐蝕性的酸類。 依照本發明,會有大量(幾乎全部)源自於進料2的酸 -21- 201042025 類以某種形式被送至裂解爐1,汽化單元11的底部產 將會含有極少(幾乎沒有)原存於進料2中的酸類。如 產物26中含有酸類’通常都是腐蝕性較低的酸。 ’ 因此’依照本發明,就底部產物26的酸含量而言 基本上是非腐鈾性的,並且可以在工廠的其它系統中 易且更迅速的處理’例如淬火油和/或燃料油系統, 需或幾乎不需要考量流26和其所形成之子流有任何 蝕的傾向。 〇 實施例 將TAN値爲4· 5的Doba常壓殘渣油以相同的重 數與輕汽油和石油腦混合,形成了 TAN値爲2.2 5的 物。這種摻合物被進料至熱解爐1之對流區段的預熱 3中。此進料混合物2爲260F及80psig。在此對流區 ’進料2在約60 psig下被預熱至約690F,並且接著 管線10進入汽化單兀11,其中約690F及60 psig的 、石油腦和氣製油氣體之混合物係在該單元的區域12 ^ 分離。 這些分離的氣體藉由管線25自區域12移出至相 子的對流預熱子區域27中。 由進料2之殘油所留下的烴類液體,在從前述所 的烴類氣體中分離出來之後,經由管線15傳送至較低 13’並且在該區段中朝下流向其底部。 溫度約爲1,050F的預熱蒸汽21被引入接近汽化 1 3的底部,而使得在區段1 3中的蒸汽相對於烴之比 爲1。落下的液滴(含烴且爲酸性)與來自區域13底部 訾 物26 果在 .,它 更容 而無 酸腐 量份 摻合 區段 段中 通過 汽油 中被 同爐 伴隨 區段 區域 率約 而朝 -22- 201042025 向其頂部上升的蒸汽爲逆向流動。至少有一些羧酸類在此 步驟中被解離。對於在區域13中向下滴落的液體而言,從 區段1 9頂部到底部,蒸汽相對於液態烴的比率會增加。 ' 溫度爲約750F之蒸汽和烴蒸氣17的混合物係由靠近 區域13的頂部取出,並且與稍早經由管線14自區域12移 出的氣體混合,以形成複合的蒸汽/烴蒸氣流2 5,其中每 磅的烴中含有約0.5磅的蒸汽。這種複合流在子區域27中 被預熱,使其在低於約50 psig的情況下達約1,000F,並 Q 且接著通入輻射燃燒室子區域29,以在1,400F至1,550F 的溫度範圍內進行裂解。在裂解爐中的CO和co2產量將 提高,這是因爲流25中所含的環烷酸被轉化的緣故。 單元11的底部產物26係在溫度約900F及壓力約60 psig的條件下被移出,並且通入下游的加工設備,以視需 要做進一步的處理。 有顯著數量的有機酸(包括環烷酸)消失在流25中,並 且之後在裂解爐中被轉化成CO和co2及較低分子量的酸 ❹ 在此同時,經由汽化單元1 1的操作,特別是汽化區域 1 3,使得更多數量的液態進料汽化而形成用於裂解爐之額 外汽態進料。 【圖式簡單說明】 第1圖所顯示的是可用於本發明方法的一個氣化/裂 解系統。 【主要元件符號說明】 1 液體裂解爐 -23- 201042025158 to about 212F, from about 212 to about 302F, and from about 3 02 to about 35 〇F 数量 The amount of lightweight material that is carefully added to the residue of feed 2 can vary widely, depending on the operator's Depending on the requirements, but the residual oil in feed 2, if present, may still be the heavy component of feedstock 2 in line 10 and is fed to vaporization unit 11. [Embodiment] The first circle shows a liquid thermal cracking furnace 1 in which, for example, at least one hydrocarbon-containing main hydrocarbon feed 2 is introduced into a higher, colder region of the convection section of the cracking furnace 1 The upper half feeds the preheating subzone 3. The steam 6 is also superheated at a higher position in the convection section of the cracking furnace. The preheated crack feed is then passed through a line (line) 1 to the vaporization unit 11 (completely disclosed in USP '961), which is divided into a higher vapor vaporization zone 12 and a lower vaporization zone. 13. In unit 11, at least a substantial portion of the material (e.g., petroleum brain and gasoline boiling range and lighter fraction) that remains liquid after the preheating step 3 is allowed to reach a major (mostly) gasification. The gaseous material (hydrocarbon-containing and acidic) received by unit 11 with the preheating feed, and the additional gaseous material (hydrocarbon-containing and acidic) that can be formed under special conditions and then dispersed in zone 12 is Line 14 is removed from zone 12. Thus, line 14 carries nearly all of the lighter hydrocarbon vapors present in zone 12, such as the petroleum brain and oil boiling range and lighter oil, and can carry away some of the vaporous acidic species, dissociated and/or not Dissociation. The liquid distillate present in zone 12 (with or without some liquid gasoline and/or petroleum brain) is removed therefrom via line 15 and passes into the lower zone as the still liquid acid is passed 13 Above the interior. In this particular embodiment, zones 1 2 and 1 3 are separated from each other by a watertight inner wall 16 such that fluid cannot communicate, and the inner wall can be a solid tray. Line 15 represents the downward external fluid communication conduit between zones 1 2 and 13. Alternatively, or in addition, internal fissures may be provided between regions 12 and 13 by modifying inner -15-201042025 wall 16 such that at least a portion of the inner wall is permeable to liquids. By using one or more trays, it is designed to allow liquid to flow downward into the interior of zone 13 and to allow vapor to enter the interior of zone 12. For example, instead of using the watertight inner wall 16, a smoky tray can be used such that the liquid within the unit 11 flows from the inside down into the section 13 rather than entering the unit U from the outside via line 15. In the case of downward flow from the inside, the dosing device 18 becomes optional. Regardless of the manner in which the liquid moves from zone 12 to zone 13, the liquid system moves downward into zone 13, and thus at least one dosing device 18 may be encountered. The device 18 can evenly distribute the liquid across the section of the unit 11 so that the liquid can flow uniformly through the width of the distillation column to contact the material 19. The steam 6 passes through the superheated subregion 20 and then enters the lower portion 22 of the region 13 below the crucible 19 via line 21. In the feedstock 19, the liquid from line 15 and the steam from line 21 are intimately mixed with each other, thereby causing a portion of the liquid 15 to vaporize and dissociating some of the acids, particularly carboxylic acids, thereby assisting in the vaporization of these acids. It is removed from zone 13 via line 17. This newly formed acidic hydrocarbon-containing vapor, with steam 21, is removed from zone 13 via line 17 and can be added to the vapor of line i4 to form a comprehensive acidic hydrocarbon vapor product in line 25. Stream 25 is primarily comprised of hydrocarbon vapors from feed 2, such as gasoline, petroleum brain, middle distillates, gas oil, a significant amount of acid species derived from feed 2, and steam. Thus, stream 17 represents a portion of feed stream 2 plus steam 21 minus the hydrocarbon liquid residue from feed 2 present in bottom stream 26. The vaporization unit 1 1 'flow 25 is operated in accordance with the present invention to contain a significant amount (mostly) of the carboxylic acids (including dissociated and undissociated forms) present in the starting material 2 from -16 to 201042025, however, these originally existed in The total amount and nature (e.g., molecular weight) of the acid in feed 2 has been altered so that all acids that pass into lines 14 and 17 (especially line 17), both in quantity and in nature, will Material 2 contains physical and chemical differences. Surprisingly, it has been found that a significant amount of carboxylic acid, particularly naphthenic acid, can be dissociated by careful manipulation of the vaporization unit. Stream 25 is passed through a header (not shown) where stream 25 is divided into a plurality of substreams and preheated into a convection section of thermal cracker 1 via a plurality of conduits (not shown) In sub-region 27. Section 27 is in the lower section of furnace 1 and thus the temperature is higher. Section 27 is used to preheat stream 25 to the aforementioned temperature suitable for thermal cracking in radiation zone 29. After extensive heating in section 27, stream 25 comprising the initial organic acids and dissociated acids contained therein is passed via line 28 to radiation section sub-region 29. Again, for the sake of brevity, these various individual flow systems, which typically flow from sub-region 27 to and into sub-region 29, are represented by a single stream 28. q In the radiant combustor 29 of furnace 1, the feed from line 28 containing many different hydrocarbon components, including the initial and dissociated acids, will be subjected to the severe thermal cracking conditions as previously described. These cleavage conditions convert a significant amount, even most (essentially all) residual carboxylic acid, into or converted to carbon monoxide (CO), carbon dioxide (co2) and lower molecular weight acids (formic acid, acetic acid, propionic acid and Butyric acid). The cracked product exits the radiant combustor 29 via line 30 for further processing in the remaining facilities downstream of the olefins plant of Furnace 1, as previously described and as detailed in USP '961 and/or Refinery. -17- 201042025 When crude oil, condensed oil, residual oil, etc. are used as an important component of feed 2, a large amount of distillate (some containing organic acid) will eventually be vaporized in unit 11, especially zone 13, It is passed to the thermal cracking furnace 1, and thus such distillate is cracked and converted into lighter components. Feed 2 can be fed to the thermal cracking furnace 1 at a temperature of from about room temperature to about 300 F and a pressure slightly above atmospheric pressure to about 10 psig (hereinafter referred to as "normal pressure to 100 psig"). Feed 2 can be fed to zone 12 via line 10 at a temperature of from about room temperature to about 750 F, such as from about 500 to about 750 F, and at a pressure from atmospheric to l psig. Stream 14 can be substantially all of the hydrocarbon vapor formed from feed 2 and has a temperature of from about room temperature to about 700F and a pressure from atmospheric to 100 psig. Stream 14 may or may not contain certain acids originally contained in feed 2, including dissociated and undissociated forms, depending on the nature of feed 2 and the operating conditions of unit 11. Stream 15 can be substantially all of the residual liquid of feed 2 and then deducted from the preheater 3 and zone 12, and the temperature is from about room temperature to about 700F and the pressure is slightly above normal pressure to about 1 Torr. 〇psig (hereinafter referred to as "normal pressure to 1〇0 psig"). Zone 12 can be used as a physically separate zone, as is the boiling bucket proposed by Buchanan et al., discussed above, in which case substantially no acid dissociation occurs. However, in accordance with the teachings of the present invention, unit 11 can be operated at temperatures suitable to cause additional vaporization and acid dissociation of liquid hydrocarbons that have entered the zone 12 from line 10, if desired. Zone 13 is operated under carefully calculated conditions, not only to be able to vaporize a significant additional amount of liquid hydrocarbons from -18 to 201042025, but also to dissociate a significant amount (preferably most) of carboxylic acids, which were originally It is in feed 2 and remains in stream 15 in liquid form. This can drive the maximum amount of acid into line 17 for delivery to thermal cracking furnace 1. Thus, in accordance with the present invention, the vaporization unit Π (particularly the region 13 of the unit) operates cautiously at temperatures of from about 700 to about 1,100 F, thereby allowing the liquid collected from the zone 12 via line 15 to form a substantial amount of additional Vapor hydrocarbons and dissociated acids. 〇 Thus, in general, the vaporization unit 11 can be formed by preheating the liquid contained in the feed stream 1 to form a significant amount of additional gaseous hydrocarbons and acids, including both dissociated and undissociated. Therefore, the vapor phase chemical composition (hydrocarbon-containing and acidic) leaving the vaporization unit 1 1 via lines 14, 4 and 25 is substantially different from the gas phase chemical composition entering the unit 11 via line 1 . Similarly, there is also a substantial difference in the chemical composition of the liquid phase leaving unit 1 via line 26 and the chemical composition of the liquid phase entering unit 1 1 via line 1 . That is to say, the unit 11 produces more influence than the physical separation of the two phases (liquid phase and vapor phase) entering the unit 11 via the ◎ line 10 . The combination of streams 14 and 17, as represented by stream 25, can be carried out at a temperature of from about 600F to about 800F and at a pressure from atmospheric to 100 psig, and which contains, for example, an overall vapor/hydrocarbon The ratio is from about 0 to about 2.0', preferably from about 0.1 to about 1.0, pounds of steam per pound of hydrocarbon. In the vaporization zone 13, the dilution ratio (hot gas/droplet) will vary considerably, as the composition of the crude oil, crude oil fraction (especially residual oil) and condensate varies considerably. In general, the content of hot gases (e.g., steam), hydrocarbons, and acids in the top of zone 13 and in line -19-201042025 17 is from about 0.1 to about 5 / 1 compared to the hydrocarbon/acid. Steam is one of the hot gases suitable for introduction via line 21. Other materials may be present in the steam used in conventional cracking plants. All such gas lines are sufficient to cause a substantial portion of the liquid flame entering zone 13 to be 'the gas temperature entering zone 13 from conduit 21; ' preferably from about 900 to about 1,100F and the pressure is from atmospheric to zero. For simplicity, such gases will hereinafter be only steam. Thus, stream 17 can be a mixture of steam and a boiling point of less than about 1 acid. The temperature of stream 17 can be about 600 3 and the force is from atmospheric to 100 psig. In the general case of the cracking operation, the line 2 1 is used as a diluent for partial pressure. Instead, the function of dilution from line 21 provides for further vaporization and gentle cracking of energy in unit 11. This requires only Q to achieve 1) dissociation of the heavier hydrocarbon components (e.g., in the whole crude oil and the present components) by vaporization and/or mild cleavage and 2) dissociation of the carboxylic acid contained in a significant amount. The steam in the line 21 can be used to achieve the solid cracking of the liquid hydrocarbons of the feed 2, while the liquid hydrocarbon droplets of the acid originally present in the feed 2 can be gradually directed toward the steam of the lower direction of the region 13 The dilution ratio and the maximum temperature of the steam are provided in accordance with the present invention, and the vaporization unit 11 & ratio in Fig. 1 is a relative example of steam. Stream 6 type. Volatilize at the preferred temperature of the body. A g is less than about 6 50 F 1 0 0 p s i g. For the word B to show. , 1〇〇F of hydrocarbon / h about 800 ° F and the pressure of steam is not only steam is not only available in liquid hydrocarbons, enough energy in the residual oil can be produced > Some (preferably, use Tube gasification / mild dissociation. When the acid enthalpy moves, the non-most needed place 5 feeds 10 -20- 201042025 Residue ratio is about 1,100F lighter (lower) boiling hydrocarbons and acids ( All, as defined above, will be vaporized in unit 11 and removed via line 14 or 17 or both, and sent to cracking furnace 1 as described above. The lighter physical entity previously described as a heavy hydrocarbon-containing solid may (at least in part) be gently cracked in unit 11 (particularly zone 13) or decomposed into lighter smoked entities as previously described. The 'and the lighter solids that have just formed will be removed via line 17' as an additional feed to the cracking furnace 1. Similarly, at least some of the acids originally stored in feed 2 will be in unit 11 (especially Dissociated or chemically altered in region 13), and those The newly formed material will be removed via stream 17 for feeding to furnace 1. Thus, in accordance with the present invention, the rotatory carboxylic acids originally present in acidic feed 2, including the more corrosive naphthenic acids, can be used by this The operation of the inventive unit 11 is mostly converted to a substantially less corrosive material prior to being sent to the cracking furnace 1. The liquid residue of the feed 10 will be removed via line 26 to be displaced to the other side. The vaporization unit 1 1 (particularly zone 13) is operated in the manner previously described in the present invention, and a substantial amount of the acid originally present in the feed 2 can be gasified and/or dissociated and transferred to the cracking furnace 1. In the present invention, most of the highly corrosive naphthenic acids originally present in the feed 2 will be dissociated by the operation of the vaporization unit 11 before being sent to the cracking furnace 1. In the furnace, the acid will be at least Completely destroyed or converted (converted) to lower molecular weight, less corrosive acids. According to the present invention, there will be a large (almost all) acid-derived from feed 2 - 201042025 class sent in some form To the cracking furnace 1, vaporization The bottom portion of element 11 will contain very little (nearly) the acid originally present in feed 2. For example, product 26 contains an acid 'usually a less corrosive acid. 'So 'in accordance with the present invention, the bottom product The acid content of 26 is substantially non-corrosive and can be easily and more quickly processed in other systems of the plant, such as quenching oil and/or fuel oil systems, with or without consideration of stream 26 and its The substream formed has any tendency to erect. 〇Example The Doba atmospheric residue oil with a TAN値 of 4.5 was mixed with light gasoline and petroleum brain at the same weight to form a TAN値 of 2.25. The blend is fed into the preheating 3 of the convection section of the pyrolysis furnace 1. This feed mixture 2 was 260F and 80 psig. Here the convection zone 'feed 2 is preheated to about 690F at about 60 psig, and then line 10 enters the vaporization unit 11, wherein a mixture of about 690F and 60 psig of naphtha and gas-to-oil gas is in the unit. Area 12 ^ separated. These separated gases are removed from zone 12 by line 25 to the convective preheating subregion 27 of the phase. The hydrocarbon liquid remaining from the residual oil of feed 2, after being separated from the aforementioned hydrocarbon gas, is conveyed via line 15 to the lower 13' and flows downward in this section to the bottom thereof. The preheated steam 21 having a temperature of about 1,050 F is introduced near the bottom of the vaporization 13, so that the ratio of steam to hydrocarbon in the section 13 is 1. The falling droplets (hydrocarbon-containing and acidic) and the material from the bottom of the region 13 are in the same region, and it is more compatible with the acid-free amount of the blending section. The steam rising toward the top of the -22-201042025 is a reverse flow. At least some of the carboxylic acids are dissociated in this step. For liquids that fall down in zone 13, the ratio of steam to liquid hydrocarbons increases from the top to the bottom of section 19. The mixture of steam and hydrocarbon vapor 17 having a temperature of about 750 F is taken near the top of zone 13 and mixed with the gas removed from zone 12 earlier via line 14 to form a composite vapor/hydrocarbon vapor stream 25, wherein Each pound of hydrocarbon contains about 0.5 pounds of steam. This composite stream is preheated in sub-region 27 to a temperature of less than about 50 psig up to about 1,000 F, and Q and then passed into the radiant combustion chamber sub-region 29 to be at 1,400 F to 1, Cracking is carried out in the temperature range of 550F. The CO and co2 production in the cracking furnace will increase because the naphthenic acid contained in stream 25 is converted. The bottom product 26 of unit 11 is removed at a temperature of about 900 F and a pressure of about 60 psig and passed to downstream processing equipment for further processing as needed. A significant amount of organic acid (including naphthenic acid) disappears in stream 25 and is subsequently converted to CO and co2 and lower molecular weight acid hydrazine in a cracking furnace. At the same time, via the operation of vaporization unit 1 1 It is the vaporization zone 13 that vaporizes a greater amount of liquid feed to form additional vapor feed for the cracking furnace. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a gasification/lysis system that can be used in the method of the present invention. [Main component symbol description] 1 Liquid cracking furnace -23- 201042025

2 進 料 3 預 熱 子 區 域 6 蒸 汽 10 管 線 11 汽 化 單 元 12 較 高 的 蒸 氣 汽 化 is 域 13 較 低 的 蒸 氣 汽 化 區 域 14 管 線 15 管 線 16 內 壁 17 管 線 18 配 液 裝 置 19 塡 料 20 過 熱 子 區 域 2 1 管 線 22 較 低 部 分 25 管 線 26 底 部 流 27 預 熱 子 區 域 28 管 線 29 射 區 域 30 管 線 -24-2 Feed 3 Preheating zone 6 Steam 10 Line 11 Vaporization unit 12 Higher vapor vaporization is domain 13 Lower vapor vaporization zone 14 Pipeline 15 Pipeline 16 Inner wall 17 Pipeline 18 Dosing device 19 Dip 20 Superheated subzone 2 1 Line 22 Lower part 25 Line 26 Bottom stream 27 Preheating sub-area 28 Line 29 Shot area 30 Line-24-

Claims (1)

201042025 七、申請專利範圍: l一種在至少一個熱裂解爐中用於熱裂解由至少一種含烴 材料所構成之含烴原料的方法,至少有一種該類含烴材 ' 料含有至少一種有機酸,該方法包括預熱該原料以形成 包含具有初始化學組成之初始汽相(vaporous phase)和具 有初始化學組成之初始液相的預熱流;將該預熱流通入 汽化步驟(vaporization step),在該步驟中有一部分該初 始液相被汽化,使得離開該汽化步驟之蒸氣的總化學組 〇 成不同於該初始汽相之初始化學組成,並且離開該汽化 步驟之殘留液體的化學組成不同於該初始液相之初始化 學組成;進行該汽化步驟,使得至少有一些該至少一種 有機酸在其中被解離;以及將至少部分離開該汽相步驟 的蒸氣通入該至少一個熱裂解爐中,做爲至少部分的進 料。 2·如申請專利範圍第1項之方法,其中該含烴原料具有的 TAN至少爲約1.0毫克K0H/克原料。 Q 3·如申請專利範圍第1項之方法’其中該含烴原料具有的 TAN至少爲約0.5毫克K0H/克原料。 4·如申請專利範圍第1項之方法,其中該含烴原料爲全原 油、冷凝油、殘渣油和兩種或以上之混合物其中的至少 一種。 5·如申請專利範圍第1項之方法,其中該含烴原料爲至少 一種常壓殘渣油。 6 .如申請專利範圍第1項之方法,其中該至少—種有機酸 類包括至少一種羧酸類’並且至少有一些該至少一種羧 -25- 201042025 酸在該汽化步驟中被解離。 7. 如申請專利範圍第6項之方法,其中該至少一種 括至少一種環烷酸類。 8. 如申請專利範圍第1項之方法,其中該汽化步驟 少第一和第二汽化區域,該第一汽化區域接收含 始氣相和該初始液相之該預熱原料並且至少使該 相與該初始液相分離,該分離之初始氣相材料由 汽化區域通入該至少一個熱裂解爐中做爲進料; 〇 汽化區域接收來自該第一汽化區域之預熱初始液 ,其在該第一汽化區域中並非以蒸氣形式存在, 此種材料在該第二汽化區域中遭受加熱和溫和裂 至少一種處理,直到此類材料在該第二汽化區域 顯數量被氣化而形成額外的氣態材料並且留下液 物爲止’並且在該第二汽化區域中形成之該額外 料自該處移出並且通入該至少一個熱裂解爐中做 :因而在該第二汽化區域中形成之該額外氣態材 Q 學組成與該初始氣相的化學組成不同,並且離開 氣相區域之該液體殘留物的化學組成不同於該初 的化學組成。 9. 如申請專利範圍第8項之方法,其中在該第二氣 中該初始液相材料所遭受的溫度係在約700至約 的範圍內。 10·如申請專利範圍第8項之方法,其中在該第一汽 中未以蒸氣形式存在在之初始液相材料在該第二 域中所遭受的溫度係在約700至約i,i〇〇f的範虐 羧酸包 使用至 有該初 初始氣 該第一 該第二 相材料 並且使 解之中 中的明 體殘留 氣態材 爲進料 料的化 該第二 始液相 相區域 1,1 00F 化區域 氣相區 丨內,並 -26- 201042025 且整體蒸汽相對於烴/酸類的比率爲約Λ W 0.1/1 至約 5/1 〇 Π·如申請專利範圍第8項之方法,其中 τ冰自該第一汽化區 ' 域的該分離之初始氣相材料含有至 . 些有機酸類,來 自該第二氣相區域的該移除之額外氣相材料含有明顯數 量經解離和未經解離之有機酸類,來自該第一汽化區域 的該分離之初始氣相材料和來自該第二氣相區域的該移 除之額外氣相材料被綜合在一起,並且此綜合流通入該 〇 至少一個熱裂解爐中。 1 2 .如申請專利範圍第1 1項之方法,其中源自該含烴原料 之該至少一種有機酸類的明顯數量在傳送至該至少一個 熱裂解爐之前於該汽化步驟中被解離或者是被改變。 Ο -27-201042025 VII. Patent application scope: l A method for thermally cracking a hydrocarbon-containing raw material composed of at least one hydrocarbon-containing material in at least one thermal cracking furnace, at least one of the hydrocarbon-containing materials containing at least one organic acid The method includes preheating the feedstock to form a preheat flow comprising an initial vaporous phase having an initialization composition and an initial liquid phase having an initialization composition; flowing the preheat into a vaporization step, A portion of the initial liquid phase is vaporized in the step such that the total chemical group exiting the vapor of the vaporization step is different from the initial composition of the initial vapor phase, and the chemical composition of the residual liquid leaving the vaporization step is different from An initializing composition of the initial liquid phase; performing the vaporization step such that at least some of the at least one organic acid is dissociated therein; and passing a vapor at least partially exiting the vapor phase step into the at least one thermal cracking furnace, For at least part of the feed. 2. The method of claim 1, wherein the hydrocarbon-containing feedstock has a TAN of at least about 1.0 mg K0H per gram of feedstock. Q. The method of claim 1, wherein the hydrocarbon-containing feedstock has a TAN of at least about 0.5 mg K0H per gram of starting material. 4. The method of claim 1, wherein the hydrocarbon-containing feedstock is at least one of a whole crude oil, a condensed oil, a residual oil, and a mixture of two or more. 5. The method of claim 1, wherein the hydrocarbon-containing feedstock is at least one atmospheric residue. 6. The method of claim 1, wherein the at least one organic acid comprises at least one carboxylic acid' and at least some of the at least one carboxy-25-201042025 acid is dissociated in the vaporization step. 7. The method of claim 6, wherein the at least one of the at least one naphthenic acid. 8. The method of claim 1, wherein the vaporization step has fewer first and second vaporization zones, the first vaporization zone receiving the preheated feedstock comprising the initial gas phase and the initial liquid phase and at least Separating from the initial liquid phase, the separated initial gas phase material is passed from the vaporization zone into the at least one thermal cracking furnace as a feed; the helium vaporization zone receives a preheated initial liquid from the first vaporization zone, Not present in the first vaporization zone as a vapor, such material undergoing at least one treatment of heating and mild cracking in the second vaporization zone until such material is vaporized in a significant amount in the second vaporization zone The additional gaseous material leaves the liquid material and the additional material formed in the second vaporization zone is removed therefrom and passed into the at least one thermal cracking furnace: thus formed in the second vaporization zone The additional gaseous material Q composition is different from the chemical composition of the initial gas phase, and the chemical composition of the liquid residue leaving the gas phase region is different from the initial chemical composition. 9. The method of claim 8, wherein the initial liquid phase material is subjected to a temperature in the second gas in the range of from about 700 to about. 10. The method of claim 8, wherein the first liquid phase is not present in vapor form in the first vapor, and the temperature of the initial liquid phase material in the second domain is between about 700 and about i, i〇 The first phasic carboxylic acid package of the 〇f is used to have the first initial phase of the second phase material and the morphological residual gaseous material in the solution is the feed material. , 1 00F zone gas phase zone 并, and -26- 201042025 and the ratio of the overall steam to the hydrocarbon / acid is about 0.1 W 0.1 / 1 to about 5 / 1 〇Π · The method of claim 8 Wherein the separated initial gas phase material of the τ ice from the first vaporization zone' domain contains to some organic acids, and the removed additional gas phase material from the second gas phase zone contains a significant amount of dissociation and The undissociated organic acid, the separated initial gas phase material from the first vaporization zone and the removed additional gas phase material from the second gas phase zone are combined and integrated into the 〇 At least one thermal cracking furnace. The method of claim 11, wherein the apparent amount of the at least one organic acid derived from the hydrocarbon-containing feedstock is dissociated or is removed in the vaporization step prior to delivery to the at least one thermal cracking furnace. change. Ο -27-
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