201042023 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。 【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 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。 Ο 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 ,〇〇〇度（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1，550F的範圍內。在沒有任何觸媒的協助 之下完成了熱裂解。 這種方法是在熱解爐（蒸汽裂解器）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 〇 一個對流區段（區域）和一個獨立的輻射區段（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原料的本質而定 ，爐子的排出物可含有非常多樣的氣態烴，例如每個分子 含一至三十五個碳原子。這些氣態烴可以是飽和、單一不 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）。 201042023 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產品流，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、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，極具價値的 產品。 ^ 熱裂解是在1913年開始使用，最初係應用於做爲裂解 Ο 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烴類氣態和/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1 0重量％的甲烷、約2 5重量％的乙烯和約1 7 重量％的丙烯，所有的重量％係以產物的總重量爲基準，其 〇 餘大部分是由每分子具有4至35個碳原子的烴類分子所構 成。 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 201042023 子。 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 Ο 。因此，其爲適合用於煉油廠之蒸餾或其它分餾之原油， 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。對於全原油而言 ，很難提供沸騰的範圍。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 〇 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 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20重量％。許多（並非全部）天然氣流在由陸地產出時可 含有較少數量（低於約50重量％)毎分子具有5至12個碳原 子的烴類（C5-C 12) ’其在地表一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 201042023 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 處，烴組成物於一般大氣環境的溫度和壓力之下通常會由 所製得的天然氣流中自然凝結出來。在相同的普徧狀況之 下，會有正常液態的烴類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類餾分一般 Ο 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 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 〇 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 徵化。冷凝油一般會在約100至約650F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。 201042023 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 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，一般係使用真空輔助熱蒸餾塔（真 〇 空塔）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餾分做爲裂 解爐之主要進料之外，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部分。201042023 VI. Description 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. [Prior Art] Thermal cracking (pyrolysis) of hydrocarbons is a petrochemical process which is widely used for the production of olefins such as ethylene, propylene, butylene, butadiene, and aromatics such as benzene, toluene and xylene.基本上 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 about 900 to about 1, F, (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 1,550F. Thermal cracking was completed without the aid of any catalyst. This process is carried out in a pyrolysis furnace (steam cracker) at a pressure in the reaction zone of from about 10 to about 30 psig. The interior of the pyrolysis furnace has 〇 a convection section (area) and a separate radiant section (area). The preheating function is mainly done in the convection section, while the severe cracking occurs almost in the radiation section. After thermal cracking, depending on the nature of the feed to the main feedstock of the pyrolysis furnace, 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, monounsaturated, and polyunsaturated, and may be aliphatic, alicyclic, and/or aromatic. The cracked gas may also contain significant amounts of molecular hydrogen (hydrogen). 201042023 The cleavage product is then further processed in an olefins manufacturing plant to produce a variety of high purity individual product streams, 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 commercial product of value. As a result, olefin manufacturing plants currently take a portion of the total crude oil stream or condensed oil and produce several different, highly valued products. ^ Thermal cracking was started in 1913 and was initially applied to gaseous ethane as the main feed to the cracking furnace for ethylene production. Since then, the industry has progressed to using heavier and more complex hydrocarbon 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 product-based. Based on the total weight, most of the remainder is composed of hydrocarbon molecules having 4 to 35 carbon atoms per molecule. Natural gas and whole crude oil are naturally formed in many subterranean geological layers with varying porosity. 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 points 201042023 are adsorbed by the crude oil. Natural gas and/or crude oil can be recovered to the surface via the well when the well is drilled through the ground and penetrates one or more of such hydrocarbon containing 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 Includes 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 of a refinery, but 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. For whole crude oil, it is difficult to provide a range of boiling. 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, when natural gas is produced from the surface, its composition can vary greatly, but it usually contains a large amount. The most common condition is that it contains a major quantity 'that is more than about 50 weight percent (wt. %). Methane. Natural gas typically also carries one or more minor amounts (less than about 50% by weight) of ethane 'propane, butane, nitrogen, carbon dioxide, hydrogen sulfide, and the like, typically less than about 20% by weight. Many (but not all) natural gas streams may contain a smaller amount (less than about 50% by weight) of a hydrocarbon having 5 to 12 carbon atoms (C5-C 12) when produced from land. The temperature and pressure of the environment are usually not gaseous. Once it is produced by the surface, it can be condensed from natural gas 201042023. All weight % is based on the total weight of the natural gas stream in question. When various natural gas streams are produced at the surface, at the surface where the natural gas is collected, the hydrocarbon composition is naturally condensed from the produced natural gas stream under the temperature and pressure of the general atmospheric environment. Under the same general conditions, normal liquid hydrocarbon 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 〇 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 will generally boil in the range of from about 100 to about 650F. 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.). 201042023 The atmospheric residue oil ("residual oil,") obtained from a conventional atmospheric distillation column can have a large boiling range, especially when using a mixture of residual oils 'but generally at about 600F to only residual The boiling range of the boiling point of the non-boiling solids. These residual oils are mainly composed of gas-forming oils boiling in the range of about 600 to about 1 〇〇〇F and boiling above about 1000F to only the remaining unboiling solids. The composition of the heavier fraction boiling in the temperature range of the end point is relative to the atmospheric distillation column. The vacuum-assisted thermal distillation column (true hollow tower) is generally used to separate the gas-to-liquid component from the above-mentioned heavier fraction. Out, thus allowing the gas-to-oil fraction to be separately recovered and used elsewhere. The olefins industry now has the advantage of using crude oil or condensed oil fractions as the primary feedstock for cracking furnaces, and has progressed to the availability of whole crude oil, crude oil residues and / or its condensed oil as 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 ‘ 96 1”）。此專利係關於藉由利用含有塡料之 〇 氣化/輕度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50-5 8行。 因此，該專利的第二區域9係做爲在製程所使用條件 201042023 下無法被裂解或汽化之原油進料成分（包括含烴材料）的捕 集器，請參閱該專利第8欄第60-64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/輕度裂解單元的所有功能，使其更朝向於氣 化（沒有預先輕度裂解）-輕度裂解（接在氣化之後進行）的輕 度裂解端移動。 核發給Donald H· Powers的美國專利7,404,889係針 ❸ 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烴類進料。 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烴類 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)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等人所教示的是在其 201042023 方法中不要使用殘油。Donald H. Powers recently obtained US Patent 6,743,961 (hereinafter referred to as "USP ‘ 96 1"). This patent relates to the cracking of whole crude oil by utilizing a gasification/light cracking zone containing hydrazine. 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 crucible. These residues will be burned off by conventional steam air decoking, ideally during the normal furnace decoking cycle, see column 5, lines 50-5 of the patent. Therefore, the second zone 9 of the patent is used as a trap for crude oil feed components (including hydrocarbonaceous materials) that cannot be cracked or vaporized under the conditions used in the process 201042023, see column 8 of the patent 60- 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 of the functions of the gasification/mild cracking unit to make it more vaporized ( There is no light cleavage in advance (light lysis) - mild cleavage end movement (after gasification). U.S. Patent No. 7,404,889 issued to Donald H. Powers is the method disclosed in USP '961, but uses atmospheric residue oil as the primary liquid hydrocarbon feed for the vaporization unit and the 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 feed 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, issued to Mar. The boiling tank of the cracking furnace. This patent publication states that the quenching bucket 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 drum is substantially the same as the composition of the liquid phase entering the quench drum. The preferred high TAN feed disclosed therein 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 its 201042023 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C0、C02和較低分 子量的酸，如甲酸、乙酸、丙酸和丁酸。 在烴類進料（如原油）中，有機酸（包括環烷酸）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400F以上處理總酸値（TAN)大 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。世界對於烴類生產力要求愈來愈高以符合需求 ，含有這些酸的原料（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 〇 換）原有的酸含量，同時也由那些原料形成額外的熱裂解進 料。 依照本發明，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熱裂解爐 ，藉由汽化單元來產生額外的裂解進料，同時藉由裂解操 作來降低原本存在於原料中的有機酸含量。 【發明內容】 本文中所使用的“烴”、“烴類”和“含烴材料”並 201042023 非完全或只是代表含氫原子和碳原子的材料》此類名詞包 括本質上爲含烴的材料，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，如製氣油、殘渣油等。也包括天然氣的冷凝液。 本發明中所用的“氣態”乙詞係指一或多種基本上處 於汽相狀態的氣體，例如只有蒸汽、蒸汽和烴類蒸氣的混 合物等。 Ο 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。 可用於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 裂解烴類進料。這種高裂解熱係藉由配置於裂解爐輻射區 〇 段（有時稱爲“照射區段”）的燃燒器。來自這些燃燒器的 廢氣被循環送至裂解爐的對流區段，以提供預熱進來烴料 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。 在一個典型的裂解爐中，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 子區域中加熱鍋爐進料水，在第三子區域中加熱混合的進 -10- 201042023 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次流，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遠 遠不如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 ^ 射管（線圈）入口處開始，而此在低溫下，故在該處的反應 速度常數低。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。在線圏的中間，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和局部濃度的乘積。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。 〇 烴類進料的蒸汽稀釋降低了烴類的分壓，增加嫌烴的 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，而在輻射防火牆之間 的中央設置了垂直豎立的管子。這些管子係由其頂部支撐 〇 輻射區段的引燃係以安裝了器壁或底板的燃燒器或者 是結合使用氣態或混合氣態_/液態兩種燃料來進行。燃燒 室一般是處於輕微負壓的狀態下，最常搭配著向上流動的 -11- 201042023 煙道氣。進入對流區段的煙道氣流係藉由至少一個自然通 風或抽氣通風的風扇來產生。 輻射線圈通常是掛在燃燒室中心下方的單一平面中。 它們可以套在一個單一平面中或者是以交錯雙排管排列方 式平行置放。由燃燒室到輻射管的熱傳主要係藉由輻射方 式，因此，烴類會在“輻射區段”中被加熱到約1，400F至 約1，5 5 0F，因而遭受到劇烈的裂解並且形成焦炭。 _ 因此，最初是空的輻射線圈爲火管式化學反應器。燃 ❸ 燒爐的烴類進料係在對流區段由約900F預熱至約l，〇〇〇F ，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， ，此進料已可用於進入輻射區段。 離開輻射區段的裂解氣態烴類將被快速的降低溫度， 以避免裂解型態的破壞。在烯烴製造工廠中的相同下游進 行進一步處理之前將裂解氣體冷卻，可回收高壓蒸汽的大 Q 量熱能，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 〇 在液態烴類原料下游處理方面，雖然在各個工廠間可 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，並且從其中去除酸性氣體和水。然後將各 -12- 201042023 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、熱解汽油和高純度 的氫流。 第1圖顯示的是一個汽化/裂解系統，其可針對以含 有機酸的全原油、冷凝油、含殘油之全原油的餾分（特別 是常壓殘油）以及其混合物做爲重要（主要）系統進料來進 行操作。 0 爲了簡單及簡潔起見，第1圖是非常槪略性的示意圖 ’但如同前面所述，真正的裂解爐是相當複雜的結構。 總酸値或TAN是含烴材料之有機酸含量的一種量測指 標。此類有機酸包括，但非侷限於，環烷酸。 TAN係以ASTM D-644方法來測量，並且其單位爲毫 克（mg)/被測試含烴材料的公斤數（kg)。爲了簡潔起見， 以下將不再重覆說明量測的方法和單位。 可適用於本發明之含有機酸進料流包括任何一種含烴 Ο 材料，如原油本身、一或多種含殘渣油的原油餾分（特別是 常壓殘油）、天然氣冷凝液，以及其兩種或以上所構成之混 合物。 羧酸是在前述酸性進料流中最具有腐蝕性的一類。在 竣酸類之中’又以環烷酸子群最具腐蝕性，且在有關操作 設備腐蝕最小化的方面，將對於裂解廠的整體操作造成問 題。 本發明所使用的常壓殘油進料可以來自單一或多重的 -13- 201042023 來源，因此，可能是單一的殘油或是兩種或以上的殘油所 形成的混合物，其可具有或不具有其它如原油和冷凝油之 類的材料。用於本發明之常壓殘油可具有相當廣的沸騰範 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l〇〇〇F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 〇 V 之較重餾分所組成。 真空輔助熱蒸餾塔（真空塔）通常可將這種氣製油成分 自上述相關的較重餾分中分離出來，因而產生不同組成的 殘油。 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2 0重 量％，但不需要嚴格限制在這個範圍內。 Q 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 石油腦’或者是其中兩種或以上之混合物。輕汽油可具有 的沸騰範圍是從戊院（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 0F。輕、中和重石油腦餾分的沸騰範圍分別爲從約 •14- 201042023The Buchanan et al. patent publication further discloses that the naphthenic acid present in the high TAN feed will be substantially converted to C0, CO 2 and lower molecular weight acids such as formic acid, acetic acid, propionic acid and butyric acid. In hydrocarbon feeds (such as crude oil), the content of organic acids (including naphthenic acids) has shown a growing trend, which 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 a total acid tantalum (TAN) greater than 1.0 above 400F because these acids are highly corrosive, especially naphthenic acids. The world's requirements for hydrocarbon productivity are increasing to meet demand, and the use of raw materials containing these acids (especially crude oil) must also meet the world's growing demand. 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) and an additional thermal cracking feed is formed from those materials. In accordance with the present invention, there is provided a unique process for treating organic acid containing feedstocks which utilizes a vaporization unit in combination with at least one thermal cracking furnace to produce additional cracking feed by a vaporization unit while being operated by a cracking operation. Reduce the organic acid content originally present in the raw material. SUMMARY OF THE INVENTION As used herein, "hydrocarbon", "hydrocarbon" and "hydrocarbon-containing material" and 201042023 are not exclusively or merely representative of materials containing hydrogen atoms and carbon atoms." Such terms include materials that are substantially hydrocarbon-containing. It is mainly 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 oils, residual oils, and the like. Also includes condensate for natural gas. As used herein, "gaseous" refers to one or more gases that are substantially in a vapor phase, such as only a mixture of steam, steam, and hydrocarbon vapors.焦 Coke as used herein refers to a high molecular weight carbonaceous solid and includes a compound formed by condensation of a polynuclear aromatic. An olefin production plant useful in the present invention 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 cracking hydrocarbons. Feeding. This high pyrolysis heat is provided by a burner disposed in the radiant section of the cracking furnace (sometimes referred to as the "irradiation section"). Exhaust gases from these burners are recycled to the convection section of the cracking furnace to provide the heat required to preheat the incoming hydrocarbon feed. The convection and radiant sections of the cracking furnace are at "crossing" connections 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, 'feeding can be preheated in the first upper layer. The area is heated in the second sub-area, and the mixed feed into the -10-201042023 and steam in the third sub-area. The superheated steam in the subzone, the final feed/steam mixture splits into a plurality of secondary streams, and is preheated in the lower (bottom) or fifth subregion. The number of sub-areas and their functions can vary greatly. Each sub-zone 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 far less severe than 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 radiation tube (coil), which is at a low temperature, so that the reaction rate constant there is low. Most of the heat transferred is simply to raise the hydrocarbons from the inlet temperature to the reaction temperature. In the middle of the line, 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 and the local concentration. At the end of the coil, the reactant concentration is low' and additional cracking can be achieved by increasing the gas temperature of the process. The steam dilution of the hydrazine feed reduces the partial pressure of the hydrocarbons, increases the formation of suspicion of hydrocarbons and reduces any tendency to form coke in the radiant tubes. Cracking furnaces typically have a rectangular combustion chamber with vertically erected tubes in the center between the radiant firewalls. These tubes are supported by a burner that supports the radiant section at the top to mount the burner of the wall or floor or a combination of gaseous or mixed gaseous _/liquid. The combustion chamber is generally under a slight negative pressure, most often with an upward flow of -11-201042023 flue gas. The flue gas flow entering the convection section is produced by at least one fan that is naturally ventilated or ventilated. The radiant coil is usually hung in a single plane below the center of the combustion chamber. They can be placed in a single plane or placed in parallel in a staggered double row arrangement. The heat transfer from the combustion chamber to the radiant tube is mainly by radiation, so that the hydrocarbons are heated in the "radiation section" to about 1,400F to about 1,550F, thus suffering severe cracking and Form coke. _ Therefore, the initially empty radiant coil is a fire tube chemical reactor. The hydrocarbon feed to the furnace is preheated from about 900F to about 1, 〇〇〇F in the convection section, which is diluted by the flue gas from the radiant section, steam fed from the convection section. .. wait for convection heating. This feed is already available for entry into the radiant section after preheating in a conventional commercial furnace. The cracked gaseous hydrocarbons leaving the radiant section will be rapidly reduced in temperature to avoid damage by the cleavage pattern. The cracked gas is cooled prior to further processing in the same downstream of the olefins manufacturing plant, and the high Q amount of heat of the high pressure steam can be recovered for reuse in the cracking furnace and/or olefins plant. This is usually done using a transfer line heat exchanger, which is known in the art as a downstream treatment of liquid hydrocarbon feedstocks, although it can vary from plant to plant, typically, for example, as described above. After heat exchange in the transfer line heat exchanger, the cracking furnace effluent is oil quenched. 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. Each of the desired products of -12-201042023 is then separated, such as ethylene, propylene, a mixture of hydrocarbons having four carbon atoms per molecule, fuel oil, pyrolysis gasoline, and a high purity hydrogen stream. Figure 1 shows a vaporization/cracking system that is important for fractions of whole crude oil, condensed oil, residual oil containing residual oil (especially atmospheric residual oil) and mixtures thereof (mainly The system is fed to operate. 0 For the sake of simplicity and brevity, Figure 1 is a very schematic diagram ‘but as mentioned earlier, a real cracking furnace is a fairly complex structure. Total acid strontium or TAN is a measure of the organic acid content of the hydrocarbonaceous material. Such organic acids include, but are not limited to, naphthenic acids. The TAN is measured by the ASTM D-644 method and is expressed in milligrams (mg) per kilogram (kg) of the hydrocarbon-containing material being tested. For the sake of brevity, the methods and units of measurement will not be repeated below. The organic acid-containing feed stream suitable for use in the present invention includes any hydrocarbon-containing hydrazine material such as crude oil itself, one or more crude oil fractions containing residual oil (particularly atmospheric residual oil), natural gas condensate, and two of them. Or a mixture of the above. Carboxylic acids are the most corrosive of the aforementioned acidic feed streams. Among the tannins, the naphthenic acid subgroup is the most corrosive, and in terms of minimizing the corrosion of the operating equipment, it will cause problems for the overall operation of the cracking plant. The atmospheric residual oil feed used in the present invention may be derived from a single or multiple source of-13-201042023, and thus may be a single residual oil or a mixture of two or more residual oils, which may or may not be There are other materials such as crude oil and condensed oil. The atmospheric residue used in the present invention can have a relatively broad boiling range, particularly when a residual oil mixture is used, but is generally in the boiling range of from about 600 F to only the boiling end of the unboiling solids. The atmospheric residue from the atmospheric distillation column is mainly composed of a gas-to-liquid component boiling in the range of about 600 to about 1 000 F and a boiling end point of from about 1 〇〇〇F to only the remaining unboiling solids. The heavier fraction of boiling 〇V in the temperature range of helium. Vacuum assisted thermal distillation columns (vacuum columns) typically separate such gas oil components from the above mentioned heavier fractions, thereby producing residual oils of different compositions. The amount of residual oil used in Feed 2 of the present invention can be an important component of the entire feed 2. The residual oil component may be at least about 20% by weight based on the total weight of Feed 2, but need not be strictly limited to this range. Q Other materials can be added to the feed, which are determined by the special physical and chemical properties of the residual oil added to Feed 2. Such additional materials may include light gasoline, petroleum brain, natural gasoline, and/or condensed oil. The form of the petroleum brain used may be a full range of petroleum brain, light petroleum brain, medium petroleum brain, heavy petroleum brain or a mixture of two or more thereof. Light gasoline can have a boiling range from the boiling point of the Wuyuan (C5) to about 158F. A full range of petroleum brains including light, medium and heavy petroleum brain fractions may have a boiling range of from about 158 to about 350F. The boiling ranges of light, medium and heavy petroleum brain fractions are from about 14 to 201042023
1 5 8到約2 1 2 F、從約2 1 2到約3 0 2 F、及從約3 0 2到約3 5 0 F ο 小心添加至進料2之殘油中的輕物質數量可以有很大 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1 〇和汽化單元Π中 之進料2的重要成分。 【實施方式】 _ 第1圖顯示的是一個液體裂解爐1，其中高TAN的含 〇 烴主要進料2被通入上半部的進料預熱子區域3，其係位 於裂解爐1對流區段較高、較冷的地區。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)，該單元被分成蒸氣氣化 上半區域12和氣化下半區域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 〇 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接收的汽態材料，以及可 在特殊條件下形成並接著散佈在區域12中的額外汽態材 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，並且可以運送 一些氣態的酸性物質。在區域12中所存在的液態餾出物（ -15- 201042023 可具有或不具有一些液態汽油和/或石油腦）將經由管線 15從該處移出，並且通入下半區域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16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，區域12和13可 以藉由修改內壁16而在其間有內部的流體連通管道，其可 _ 藉由使用一或多個塔盤使得至少有部分內壁可穿透液體’ 〇 其設計可使得液體向下流入區域1 3的內部且使蒸氣向上 流入區域12的內部。舉例而言，取代使用不透水的內壁 16,可以使用煙囪式塔盤，使得單元11內的液體由內部向 下流入區段1 3來取代經由管線1 5從外部進入單元1 1。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 體係向下移動進入區域1 3，因而可能遇到至少一個配液裝 〇 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的下半部22。在塡料19中， 來自管線21的液體和蒸汽彼此緊密的混合，因而使得部分 的液體15氣化。這種新形成的含烴蒸氣，隨著蒸汽21， 係經由管線1 7從區域1 3中移出，並且可以添加至管線1 4 -16- 201042023 的蒸氣中，以形成管線25中的綜合烴蒸氣產物。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、製氣油和蒸汽。 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26中來自進料2的烴液剩餘物。流25 中含有出現在初始原料2中的有機酸類。流25將通過一個 管集箱（圖中未顯示），在該處流25被分成多個子流，並且 ^ 經過多個導管（圖中未顯示）而進入裂解爐1的對流區段預 〇 熱子區域27。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至適合在輻射區域29中進行 裂解的溫度。 在區段27中實質加熱之後，包括有機酸類的流25藉 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2 8來代表。 〇 在爐1的輻射燃燒室29中，來自管線28且含有許多 種不同烴成分的進料，包括酸性物質，將遭受如前所述的 嚴苛熱裂解條件。這些裂解條件使相當數量，甚至大部分 內含的環烷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3 0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中所示。 -17- 201042023 當使用原油、冷凝油、殘油等做爲進料2的重要成分 時，含有機酸之餾出物的實質數量最後會在單位I1中被氣 化，特別是區域13，通入爐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 0 0F且壓力爲略高於 常壓至約l〇〇psig(以下簡稱爲”常壓至l〇〇psig”）的條件下 進入爐1。 進料2可經由管線10在溫度爲約室溫至約7 5 0F，例 〇 如約500至約75 0F，且壓力爲常壓至100 psig的條件下進 入區域1 2 » 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存在於進料2之中的某些酸類。 流15基本上可以是進料2所有的殘留液體再扣除在預 熱器3和區域12中被汽化者，並且溫度爲約室溫至約70 0F Q 且壓力爲略高於常壓至約1〇〇 psig(以下簡稱爲“常壓至 100 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，除此之外，可在適合 引起經由管線1 0進入區域1 2之液態烴額外汽化的條件下 操作。 區域13係在約700至約l，l〇〇F的溫度下操作，因而 使得其經由管線15所收集來自區域12的液體形成相當數 -18- 201042023 量的額外汽態烴類。 因此，除了將初始進料2中所含的有機酸予以汽化之 外，汽化單元11可使預熱進料流1〇中所含的液體形成相 當數量的額外氣態烴類。 因此，經由管線1 4和1 7離開單元1 1之汽相的化學組 成與經由管線1 〇進入單元11之汽相的化學組成有實質上 的差異。同樣的’經由管線2 6離開單元1 1之液相的化學 組成與經由管線1 〇進入單元1 1之液相的化學組成也有實 質上的差異。也就是說，單元I1除了使經由管線10進入 單元1 1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/烴類比率爲約0·1至約2 ，較佳爲約〇·1至約1’磅蒸汽/每磅烴類。 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 凝油的組成變動範圍相當大。一般而言’在區域13頂部的 熱氣（例如蒸汽）和烴類的含量比率爲蒸汽相對於烴類約 0.1 /1 至約 5/1。 蒸汽是適合經由管線21引入之熱氣的一個實例。流6 可以是一般在傳統裂解工廠中所使用的蒸汽類型。在所使 用的蒸汽中可以存在其它物質。所有此類氣體的較佳溫度 -19- 201042023 係足以使得有相當部分進入區域1 3的液態烴類1 5揮發。 一般而言，在常壓至100Psig的壓力下，由導管21進入區 域13之氣體的溫度至少爲約65 0F ’較佳爲約900至約 1，2 00F。爲了簡單起見，此類氣體在下文中將僅以蒸汽乙 詞來表示。 因此，流1 7可以是蒸汽、酸類物質和沸點低於約1，1 00 F之烴類蒸氣的混合物。流1 7的溫度可以是約6 0 0至約 800F且壓力爲常壓至l〇〇Psig。 來自管線21的蒸汽不只是在一般情況下於裂解操作 中做爲分壓的稀釋劑。反而是’來自管線21的蒸汽不只是 提供了稀釋的功能，同時也可將單元11中仍處於液態的烴 類提供進一步的汽化及溫和裂解能量。這只需要足夠的能 量來達成較重烴類成分（例如在全原油和殘油中所可發現 的成分）的氣化和/或溫和裂解即可完成。舉例而言’利用 管線2 1中的蒸汽，可以達到進料2液體的實質汽化/溫和 裂解。當液態烴的液滴漸漸朝向區域13較低的方向移動時 ，將非常高的蒸汽稀釋比和最高溫度的蒸汽提供於最需要 的地方。 依照本發明，在第1圖進料10中所殘留比約丨，10017 較輕（較低）沸騰之烴類和酸類物質（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或兩者 移出，並且如前文中所述，被送至爐1。除此之外’比本 段先前所述之較輕實體物爲重之含烴實體物可以（至少有 -20- .201042023 一部分）在單元11中被溫和的裂解或者是分解成如先前所 述之較輕含烴實體物，並且那些剛形成的較輕實體物將經 由管線17移出，成爲爐1的額外進料。如果有的話’進料 1 〇的液體殘餘物將經由管線2 6移出以移置到別處。 實施例 將TAN値爲4.5的Dob a常壓殘油以相同的重量份數 與輕汽油和石油腦混合，形成了 TAN値爲2.25的摻合物 。這種摻合物被進料至熱解爐1之對流區段的預熱區段3 ❹ 中。此進料混合物2的溫度爲260F，壓力爲80 psig。在此 對流區段中，進料2在約60 psig下被預熱至約690F，並 且接著通過管線1〇進入汽化單元11，其中溫度爲約690F 且壓力爲60 psig的汽油、石油腦和製氣油氣體之混合物係 在該單元的區域12中分離。 這些分離的氣體藉由管線25自區域12移出至相同爐 子的對流預熱子區域27中。 Q 在分離先前所提的烴類氣體，從進料2中持續提出的 烴類液體，由管線1 5被移轉到較低區域1 3，並且允許在 此區域由頂端掉落。 溫度約爲1，〇5 0F的預熱蒸汽被引入接近汽化區域13 的底部，而使得在區段13中的蒸汽相對於烴類之比率約爲 1。落下的液滴係與來自區域13底部而朝向其頂部上升的 蒸汽逆向流動，由區段19頂部到底部之蒸汽相對於液態烴 類的比率會增加。 -21- 201042023 溫度爲約75 OF之蒸汽和烴類蒸氣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/烴類蒸氣流25，其 中每磅的烴類中含有約0.5磅的蒸汽。這種複合流在子區1 5 8 to about 2 1 2 F, from about 2 1 2 to about 3 0 2 F, and from about 3 0 2 to about 3 5 0 F ο The amount of light matter that is carefully added to the residue of feed 2 can be There are large variations, depending on the operator's needs, but the residual oil in feed 2, if present, can still be an important component of feed 2 in line 1 and the vaporization unit. [Embodiment] _ Figure 1 shows a liquid cracking furnace 1 in which a high TAN containing hydrazine-containing main feed 2 is introduced into the upper preheating sub-zone 3, which is located in the cracking furnace 1 convection A section with a higher, cooler area. The steam 6 is also superheated at a higher position in the convection section of the cracker. The preheated crack feed is then passed through a line (line) 1 to a vaporization unit 11 (completely disclosed in USP '961) which is divided into a vapor gasification upper half zone 12 and a gasification lower half zone 13. In unit 11, at least a substantial portion of the material that remains liquid after the preheating step 3 (e.g., the petroleum brain and gasoline boiling range and lighter fraction) can be brought to a primary (majority) gasification. The vaporous material received by unit 11 with the preheated feed, and the additional vaporous material (hydrocarbon-containing and acidic) that can be formed under special conditions and then dispersed in zone 12 is from zone 12 by line 14. Move out. Thus, line 14 carries nearly all of the lighter hydrocarbon vapors present in zone 12, such as the petroleum brain and petroleum boiling range and lighter oil, and can carry some gaseous acidic species. The liquid distillate present in zone 12 (-15-201042023 may or may not have some liquid gasoline and/or petroleum brain) will be removed therefrom via line 15 and passed over the interior of lower half zone 13. In this particular embodiment, the ' regions 1 2 and 1 3 are separated from one another by a watertight inner wall 16 such that fluid cannot communicate. 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, regions 12 and 13 may have internal fluid communication conduits therebetween by modifying inner wall 16 which may be worn by at least a portion of the inner wall by using one or more trays The permeable liquid 'is designed to allow liquid to flow downward into the interior of zone 13 and to allow vapor to flow upward into the interior of zone 12. For example, instead of using a water-impermeable inner wall 16, a chimney tray can be used such that the liquid in unit 11 flows inwardly from section 13 into the section 13 instead of entering unit 1 1 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 down 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 half 22 of the region 13 below the crucible 19 via line 21. In the dip 19, the liquid and steam from the line 21 are intimately mixed with each other, thereby partially vaporizing the liquid 15. This newly formed hydrocarbon-containing vapor, with steam 21, is removed from zone 13 via line 17 and can be added to the vapor of line 14-16-201042023 to form a combined hydrocarbon vapor in line 25. product. Stream 25 primarily contains hydrocarbon vapors from feed 2, such as gasoline, petroleum brain, middle distillates, gas oils, 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. Stream 25 contains the organic acids present in the starting material 2. The stream 25 will pass through a header (not shown) where the stream 25 is divided into a plurality of substreams and the convection section of the cracking furnace 1 is preheated through a plurality of conduits (not shown). Sub-region 27. Section 27 is in the lower section of furnace 1 and is therefore at a higher temperature. Section 27 is used to preheat stream 25 to a temperature suitable for cracking in radiation zone 29. After substantial heating in section 27, stream 25 comprising organic acids is passed through line 28 into radiation section sub-region 29. Again, for the sake of brevity, these various flow lines, which typically flow from sub-region 27 to and into sub-region 29, are represented by a single stream 28. 〇 In the radiant combustor 29 of furnace 1, the feed from line 28 containing many different hydrocarbon components, including the acidic material, will be subjected to the severe thermal cracking conditions as previously described. These cleavage conditions convert a significant amount, and even a substantial portion of the naphthenic acid contained therein, 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. -17- 201042023 When crude oil, condensed oil, residual oil, etc. are used as an important component of feed 2, the substantial amount of distillate containing organic acid will eventually be gasified in unit I1, especially zone 13, through Into the furnace 1, and thus the distillate is cracked and converted into a lighter component. Feed 2 can be fed to furnace 1 at a temperature of from about room temperature to about 30,000 F and a pressure slightly above atmospheric pressure to about 10 psig (hereinafter referred to as "normal pressure to l psig"). Feed 2 can enter zone 1 via a line 10 at a temperature of from about room temperature to about 750F, such as from about 500 to about 75 Hz, and at a pressure from atmospheric to 100 psig. It is all hydrocarbon vapors 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 present in feed 2. Stream 15 can be substantially all of the residual liquid of feed 2 and then deducted from vaporizers in preheater 3 and zone 12, and the temperature is from about room temperature to about 70 °F and the pressure is slightly above normal pressure to about 1 〇〇psig (hereinafter referred to as "normal pressure to 100 psig"). Zone 12 can be used as a physically separate zone, as is the bubbling bucket proposed by Buchanan et al., as discussed above, and in addition to conditions suitable for causing additional vaporization of liquid hydrocarbons entering zone 12 via line 10 Under the operation. Zone 13 operates at a temperature of from about 700 to about 1, 〇〇F, such that it collects liquid from zone 12 via line 15 to form a comparable amount of additional vaporous hydrocarbons from -18 to 201042023. Thus, in addition to vaporizing the organic acid contained in the initial feed 2, the vaporization unit 11 allows the liquid contained in the preheated feed stream to form a relatively large amount of additional gaseous hydrocarbons. Thus, the chemical composition of the vapor phase exiting unit 1 1 via lines 14 and 17 is substantially different from the chemical composition of the vapor phase entering unit 11 via line 1 . There is also a substantial difference in the chemical composition of the liquid phase exiting unit 1 via line 26 and the chemical composition of the liquid phase entering unit 1 via line 1 . That is to say, the unit I1 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, bulk steam/hydrocarbons The ratio is from about 0.1 to about 2, preferably from about 1 to about 1 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. Generally, the ratio of hot gas (e.g., steam) to hydrocarbons at the top of zone 13 is from about 0.1 /1 to about 5/1 of steam relative to hydrocarbons. Steam is an example of a hot gas suitable for introduction via line 21. Stream 6 can be the type of steam typically used in conventional cracking plants. Other materials may be present in the steam used. The preferred temperature for all such gases, -19-201042023, is sufficient to volatilize a substantial portion of the liquid hydrocarbons 15 entering zone 13. In general, the temperature of the gas entering the zone 13 from the conduit 21 at a pressure from atmospheric pressure to 100 psig is at least about 65 F', preferably from about 900 to about 1,200 F. For the sake of simplicity, such gases will be referred to hereinafter only as steam words. Thus, stream 17 can be a mixture of steam, an acid species, and a hydrocarbon vapor having a boiling point of less than about 1,100 F. The temperature of stream 17 can be from about 600 to about 800F and the pressure is from atmospheric to l〇〇Psig. The steam from line 21 is not just a diluent that is typically divided as a partial pressure in the cracking operation. Rather, the steam from line 21 not only provides the function of dilution, but also provides further vaporization and mild cracking energy for hydrocarbons still in liquid state in unit 11. This requires only sufficient energy to achieve gasification and/or mild cracking of heavier hydrocarbon components, such as those found in whole crude oil and residual oil. For example, by using the steam in line 21, substantial vaporization/mild cracking of the feed 2 liquid can be achieved. When the liquid hydrocarbon droplets gradually move toward the lower direction of the region 13, a very high steam dilution ratio and the highest temperature steam are provided where they are most needed. According to the present invention, the hydrocarbons and acids which are lighter (lower) boiling in the feed 10 of Figure 1 will be vaporized in unit 11 by the lower (lower) boiling hydrocarbons and acids (and all as defined above). It is removed via line 14 or 17 or both and is sent to furnace 1 as previously described. In addition to this, a hydrocarbon-containing solid that is heavier than the lighter entity previously described in this paragraph may be (at least -20-. 201042023 part) be gently cracked in unit 11 or decomposed into as previously described The lighter hydrocarbon-containing entities, and those lighter bodies that have just formed, will be removed via line 17 to become an additional feed to furnace 1. If any, the liquid residue of the feed 1 将 will be removed via line 26 to be displaced elsewhere. EXAMPLES A Dob a atmospheric residual oil having a TAN 値 of 4.5 was mixed with light gasoline and petroleum brain in the same parts by weight to form a blend having a TAN 値 of 2.25. This blend is fed into the preheating section 3 ❹ of the convection section of the pyrolysis furnace 1. This feed mixture 2 had a temperature of 260 F and a pressure of 80 psig. In this convection section, Feed 2 is preheated to about 690 F at about 60 psig, and then enters vaporization unit 11 through line 1 , where gasoline, petroleum brain, and gas are at a temperature of about 690 F and a pressure of 60 psig. The mixture of oil gases is separated in zone 12 of the unit. These separated gases are removed from zone 12 by line 25 to the convective preheating subregion 27 of the same furnace. Q In the separation of the previously proposed hydrocarbon gas, the hydrocarbon liquid continuously raised from feed 2 is transferred from line 15 to lower zone 13 and allowed to fall from the top in this zone. At a temperature of about 1, 预50F of preheated steam is introduced near the bottom of the vaporization zone 13, such that the ratio of steam to hydrocarbons in zone 13 is about one. The falling droplets flow countercurrently to the vapor rising from the bottom of zone 13 towards the top thereof, and the ratio of steam from the top to the bottom of section 19 relative to the liquid hydrocarbons increases. -21- 201042023 A mixture of steam and hydrocarbon vapor 17 having a temperature of about 75 OF is taken from the top of zone 13 and mixed with gas removed from zone 12 earlier via line 14 to form a composite steam/hydrocarbon. Vapor stream 25, wherein each pound of hydrocarbon contains about 0.5 pounds of steam. This composite stream is in the sub-area
域27中被預熱，使其在低於約50psig的情況下達約l，0〇〇F ，並且接著通入輻射燃燒室子區域29,以在1，400F至1，550 F的溫度範圍內進行裂解。在裂解爐中的CO和C02產量將 _ 提高，這是因爲流25中所含的環烷酸被轉化。 〇 單元11的底部產物係在溫度約900F及壓力約60psig 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C02及較低分子量的酸 〇 在此同時，經由汽化單元U的操作，特別是汽化區域 〇 13,使得更多數量的液體進料被汽化，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 2 進料 -22- 201042023The zone 27 is preheated to a temperature of less than about 50 psig of about 1,0 〇〇F and then passed into the radiant combustion chamber subregion 29 to be in the temperature range of 1,400 F to 1,550 F. The lysis is carried out. The CO and CO 2 production in the cracking furnace will increase, because the naphthenic acid contained in stream 25 is converted. The bottom product of unit 11 is removed at a temperature of about 900F 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 CO 2 and lower molecular weight acid hydrazine in a cracking furnace while operating via vaporization unit U, especially The vaporization zone 〇13 causes a greater amount of liquid feed to be vaporized 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 2 Feed -22- 201042023
3 預 熱 子 區 域 6 蒸 汽 10 管 線 11 汽 化 單 元 12 葱 / ΐ、、 氣 汽 化 上 半 區 域 13 蒸 氣 汽 化 下 半 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 21 管 線 22 下 半 部 25 管 線 26 底 部 流 27 對 流 段 28 單 一 流 29 輻 射 域 30 管 線 -23-3 Preheating zone 6 Steam 10 Pipeline 11 Vaporization unit 12 Onion / ΐ, gas vaporization upper half 13 Vapor vaporization lower half 14 Pipe 15 Pipe 16 Inner wall 17 Pipeline 18 Dosing device 19 Tanning 20 Superheating zone 21 Line 22 Lower half 25 Line 26 Bottom flow 27 Convection section 28 Single prime 29 Radiation 30 Pipeline-23-