201042024 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 、 少一個熱裂解爐的氣化單元。說的更明確一點，本發明係 . 關於使用一種氣化單元來驅動明顯數量的酸類由原料進入 至少一個熱裂爐中。 【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 〇 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1，550F的範圍內。在沒有任何觸媒 的協助之下完成了熱裂解。 〇 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 201042024 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 k 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201042024 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to thermal cracking of acid-containing hydrocarbon feedstocks using a gasification unit incorporated into one less thermal cracking furnace. More specifically, the present invention relates to the use of a gasification unit to drive a significant amount of acid from a feedstock into at least one thermal cracking furnace. [Prior Art] Thermal cracking (pyrolysis) of hydrocarbons is a petrochemical process widely used in the manufacture of olefins such as ethylene, propylene 'butene, butadiene, and aromatics such as benzene, toluene and xylene. . 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 1,550F. Thermal cracking was completed without the aid of any catalyst. 〇 This method 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 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 radiant section. - After thermal cracking, depending on the nature of the feed to the main feed 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, single 201042024 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 a variety of high purity individual streams that become 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. This type of feed is now available in one k-part whole crude oil or condensed oil, which is essentially 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
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 201042024 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/或傳統蒸飽而 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。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 〇 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 院、丙院、丁院、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，可以從天然氣中凝結出來。所有的重量％皆是 201042024 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 a 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 〇 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 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 〇 w 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。 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 201042024 ，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i〇〇〇F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 - 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。 Ο 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 部分。 * 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 〇 v 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欄第6 0-64行。 核發給Donald H· Powers的美國專利7,0 19,187係針 201042024 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，使其更朝向於氣 化（沒有預先溫和裂解）-溫和裂解（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 對USP‘961所揭露之方法，但使用了常壓殘渣油做爲氣化 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。 〇 2006年3月1日遞件之美國11/3 65,212號專利申請案 係針對使用冷凝油做爲氣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 * 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Most of Q is composed of hydrocarbon molecules with 4 to 35 carbon atoms per molecule. 天然气 Natural gas and whole crude oil are naturally formed in many kinds of multi-variable porous underground 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 points 201042024 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-bearing formations. As used herein, the terms "whole crude oil" and "crude oil" refer to liquids that are separated from the * any possible natural gas and are discharged from the wellhead (under conditions of temperature and pressure generally prevailing on the surface). It does not include any treatment that may be accepted to enable such crude oil to be transported to a refinery for crude oil refining and/or conventional steaming. 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. 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 oil field pipelines and/or conventional crude oil storage facilities, as available, 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 of niobium, 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 B, DM, Ding, 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) hydrocarbons (C5-C12) having from 5 to 12 carbon atoms per molecule when produced from land, usually less than about 20% by weight, which is usually not gaseous under the temperature and pressure of the general atmospheric environment of the earth's surface, can be condensed from natural gas once it is produced from the surface. All weight % is 201042024 based on the total weight of the natural gas stream in question. When various natural gas streams are produced at the surface, the hydrocarbon composition at the surface where the natural gas is collected will naturally condense out of the natural gas stream produced by a under the temperature and pressure of the general atmospheric environment. Under the same general condition, there will be a normal liquid hydrocarbon-containing condensate 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 Cabout C20 or slightly higher). After separation from the produced natural gas, this liquid condensed oil fraction is separated from the residual gas fraction, commonly referred to as natural gas. Therefore, the condensed oil* recovered from the natural gas stream produced from the surface for the first time is not identical in material and composition to natural gas (mainly methane). It is not the same in terms of material and composition as crude oil. 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, as well as a range of hydrocarbons at the lightest end of the whole crude oil. 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.). 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 201042024, but generally at about 600F to only remain. Boiling the boiling point of the boiling point of the physical body. These residual oils are mainly composed of a gas-to-liquid component boiled in the range of about 600 to about i〇〇〇F and a heavier fraction boiling in a temperature range of from about 1 000 F to only the boiling end of the unboiling 'solids. Composition - 〇 Relative to an atmospheric distillation column, a vacuum-assisted thermal distillation column (vacuum column) generally separates the gas-to-liquid component from the above-mentioned heavier fraction, thereby allowing the gas-to-liquid fraction to be separately recovered elsewhere. use.烯烃 The olefins industry now has the advantage of using crude oil or condensed oil (gaseous and/or liquid) fractions as the primary feed to the cracking furnace, and has progressed to use all crude oil, crude oil residue oil and/or its condensed oil as An important part of the feed. * 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 should be 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 hydrocarbons 液体 v 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 a trap for crude oil feed components (including hydrocarbonaceous materials) that cannot be cracked or gasified under the conditions used in the process, see column 8 of the patent. -64 lines. U.S. Patent 7,0 19,187, issued to Donald H. Powers, 201042024, to the method disclosed in USP '961, but using a slightly acidic cracking catalyst to drive all functions of the gasification/mild cracking unit to make it more oriented At the light-degree crack end movement of gasification (without prior mild cracking) - mild cracking (following gasification). • U.S. Patent 7,404,889 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 gasification unit and cracking furnace. The complete disclosure of the aforementioned patents is incorporated herein by reference.美国 US Patent Application No. 11/3, 65,212, filed on March 1, 2006, is directed to the use of condensed oil as the main liquid hydrocarbon feedstock for gasification units and cracking furnaces, which has the same inventor as USP '961. And the patentee. In U.S. Patent Application Publication No. 2007/0066860, the entire disclosure of which is incorporated by reference to the entire disclosure of the entire 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, leaving the gas phase of the boiling tank
D w 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 其方法中不要使用殘油。The D w composition 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 its method.
Buchanan等人的專利公告還進—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、co2和較低分 子量的酸’如甲酸、乙酸、丙酸和丁酸。 201042024 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。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 〇 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）係藉由氣化單元和 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，同時也由那些原料形成額外的熱裂解 . 進料。 除此之外，依據本發明，上述氣化單元將被謹慎操作 以驅動明顯數量的酸類由含酸裂解原料進入熱裂爐中。藉 〇 由本發明而被驅動至裂解爐的許多酸類將會被氣化單元的 液態底餾產物留置，並且在後續處理底餾產物的工廠內造 成酸性腐蝕問題。 發明總結 本發明提供了一種用於處理含有機酸原料的獨特方法 ’其使用了一個氣化單元並結合至少一個裂解爐，其中該 氣化單元被謹慎地操作，從傳送至熱解爐的原料中移除明 顯數量的酸類，而這些酸類是原本就存在於原料中，若未 201042024 移除就會停留在氣化單元的液態底餾產物中。 【發明内容】 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 Ο 。 本發明中所用的”氣態”乙詞係指一或多種基本上爲 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 0 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輻射區段（有 時稱爲”放射區段，，）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。 -10- 201042024 .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 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 Ο 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（線圏）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 〇 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。 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 輻射區段的引燃係使用氣態或混合氣態/液態的燃料 -11- 201042024 以安裝了器壁或底板或者是兩者組合之燃燒器來進行。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 的煙道氣。進入對流區段的煙道氣流係藉由至少一個天然 通風或抽氣通風的風扇來產生。 • 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1，400F至約 O 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900F至約 U000F，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 避免破壞了裂解型態。在烯烴製造工廠相同下游進行進一 〇 步處理之前將裂解氣體冷卻，可回收高壓蒸汽的大量熱能 ，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。 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，並且從中去除酸性氣體和水。然後將各種 -12- 201042024 想要的產物各別予以分離，例如乙烯、丙烯、每分 四個碳原子的烴類混合物、燃料油、熱解汽油和高 氫流。 ’ 第1圖顯示的是一個氣化/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 〇 ，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 標。此類有機酸包括，但非侷限於，至少一種竣酸 少一種環院酸類和/或至少一種粉酸類。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。 〇 ^^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 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最具有腐触性的一類。 類之中，又以環院酸子群最具腐触性，且對於下游 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 子具有 純度的 對以含 (特別 進料來 示意圖 構。 量測指 類、至 文前面 爲KOH 以下將 進料流 殘渣油 及其兩 在羧酸 操作設 多重的 -13- 201042024 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1000F範圍內沸騰之氣製油成分和在約i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 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。The Buchanan et al. patent publication further discloses that the naphthenic acid present in the high TAN feed will be substantially converted to CO, co2 and lower molecular weight acids such as formic acid, acetic acid, propionic acid and butyric acid. . 201042024 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 out for consideration* 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. 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) must also meet the world's demand for growth. In the present invention, the raw material containing organic acid (such as whole crude oil and condensed oil), and the crude oil fraction containing organic acid (for example, residual oil) are treated by a combination of a gasification unit and at least one thermal cracking furnace, It simply reduces (converts or 'converts) the original acid content and also forms additional thermal cracking feeds from those materials. In addition to this, in accordance with the present invention, the gasification unit described above will be carefully operated to drive a significant amount of acid from the acid containing cracking feedstock into the thermal cracking furnace. Many of the acids that are driven to the cracking furnace by the present invention will be retained by the liquid bottoms product of the gasification unit and cause acid corrosion problems in the subsequent processing of the bottoms product. SUMMARY OF THE INVENTION The present invention provides a unique method for treating organic acid containing feedstocks which utilizes a gasification unit in combination with at least one cracking furnace, wherein the gasification unit is operated with care, from the feedstock to the pyrolysis furnace. A significant amount of acid is removed, and these acids are originally present in the feedstock and will remain in the liquid bottoms of the gasification unit if not removed in 201042024. SUMMARY OF THE INVENTION As used herein, "hydrocarbon", "hydrocarbon" and "hydrocarbon-containing material" and * are not exclusively or merely represent materials containing hydrogen atoms and carbon atoms. Such nouns include materials that are essentially hydrocarbon-containing, which are primarily or essentially composed of hydrogen and carbon atoms 'but may also contain other elements such as oxygen, sulfur, nitrogen, metals, inorganic salts, etc., even Obvious content. These terms include crude oil itself or its fractions, such as gas oil, residual oil, and the like. Also includes natural gas condensate Ο . As used herein, the term "gaseous" refers to one or more gases that are substantially in a gaseous state, such as only a mixture of steam, steam, and hydrocarbon vapors. * Coke as used herein refers to a high molecular weight carbonaceous solid and encompasses compounds formed by the condensation of polynuclear aromatics. 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 0 furnace used in steam cracking of 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. Class feed. This high pyrolysis heat is supplied by burners disposed in a radiant section (sometimes referred to as a "radiation section,"). Exhaust gases from these burners are circulated through the convection section of the cracking furnace to provide a pre-treatment The heat required to enter the hydrocarbon feed. The convection and radiation sections of the cracking furnace are connected at the "crossover" and the pipe referred to above transports the hydrocarbon feed from the interior of one section to the next. The interior of the segment. -10- 201042024. In a typical cracking furnace, the convection section may comprise 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, the mixed feed and steam are heated in the third subzone, and the superheated steam is in the fourth subzone. The final feed/steam mix • splits into a plurality of substreams and is preheated in the lower (bottom) or fifth subzone. 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 辐射 radiation section. The cracking furnace is designed to be rapidly heated in the radiant section starting from the entrance of the radiant tube, where the reaction rate constant is low due to the low temperature relationship. Most of the heat transferred is simply to bring the hydrocarbons from the inlet. The temperature rises 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 loop, the reactant concentration is low and additional cracking can be achieved by increasing the gas temperature of the process. Steam dilution of the feed hydrocarbons reduces the partial pressure of the hydrocarbons, promotes olefin formation, and reduces any tendency to form coke in the radiant tubes. The cracking furnace usually has a rectangular combustion chamber, and a vertically erected tube is placed in the center of the radiant firewall. These pipes are supported by a pilot system that supports the 辐射 radiating section at the top thereof using a gaseous or mixed gaseous/liquid fuel -11- 201042024 to install a wall or a bottom plate or a combination of burners. The combustion chamber is generally in a state of slight negative pressure, most often with an upward flowing 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 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 arrangement. The heat transfer from the combustion chamber to the radiant tube is primarily caused by radiation, so that the hydrocarbons are heated in the "radiation section" to about 1,400 F to about O 1,5 5 0F, 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 in the convection section to a temperature of from about 900F to about U000F, which is convected by flue gas from the radiant section, steam dilution of the feed in the convection section, and the like. heating. After preheating in a conventional commercial furnace * this feed has access to the radiant section. The cracked gaseous hydrocarbons leaving the radiant section are rapidly lowered in temperature to avoid damaging the cleavage pattern. The cracking gas is cooled prior to further downstream processing in the same downstream of the olefins manufacturing plant, and a large amount of thermal energy of the high pressure steam can be recovered for reuse in the cracking furnace and/or olefins plant. This is typically done using a transport 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 plants, the cracker effluent is typically oil quenched after, for example, heat exchange with 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 various desired products of -12-201042024 are then separated, such as ethylene, propylene, a mixture of hydrocarbons of four carbon atoms, fuel oil, pyrolysis gasoline, and high hydrogen flow. ' Figure 1 shows a gasification / cracking system, which can be used as a major (main) for needle-organic acid crude oil, condensed oil, residual crude oil-containing fractions of atmospheric crude oil, and mixtures thereof. The system operates. For the sake of simplicity and brevity, Figure 1 is a very sturdy enthalpy, but as mentioned earlier, a real cracking furnace is a fairly complex sulphate or TAN is a hydrocarbon-containing material. Standard. Such organic acids include, but are not limited to, at least one tannic acid and one or at least one powder 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 measured 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-containing material 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 (especially atmospheric residual oil), natural gas condensate, a mixture of one or more of the above. Carboxylic acids are one of the most corrosive in the aforementioned feed streams. Among the classes, the acid group of the ring is the most corrosive, and the minimization of downstream corrosion can cause problems. The atmospheric residual oil feed used in the present invention may be derived from a single or sub-purity pair (specially fed to the schematic structure. The measurement refers to the KOH below the feed stream residue oil and the two The carboxylic acid is operated from multiple sources from -13 to 201042024 and, therefore, may be a single residual oil or a mixture of two or more residual oils, with or without other materials such as crude oil and condensed oil. The atmospheric residual oil used in the present invention can have a relatively wide boiling range, especially when using a residual oil mixture, but generally in the boiling range of about 600F to only - the boiling end of the remaining unboiling solids. The atmospheric residue from the atmospheric distillation column is mainly composed of a gas-making component boiling in the range of about 600 to about 1000 F and boiling above about i〇〇〇F to only the remaining unboiling solids. The composition of the heavier fraction of boiling enthalpy in the temperature range of the end point" Vacuum-assisted thermal distillation column (vacuum tower) usually separates the gas-to-liquid component from the above-mentioned heavier fraction, thus producing a difference Residual oil 〇 - The amount of residual oil used in Feed 2 of the present invention 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 does not require strict Limit to this range.
可以在進料中添加其它材料，其係由進料2中所添加 〇 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 0F。輕、中和重石油腦餾分的沸騰範圍分別爲從約 158到約212F、從約212到約302F、及從約302到約350F -14 - 201042024 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1〇中之進料2的重 ' 要成分，並且進料至氣化單元11° 【實施方式】 第1圖顯示的是一個液體裂解爐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 Ο 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）10將預熱的裂解進料流通入氣化 單元11 (完全掲露於USP ‘961)，該單元被分成較高的蒸 • 氣氣化區域12和較低的氣化區域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。 〇 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1 4自區域1 2 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， 並且可以帶走~些氣態的酸性物質。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 -15- 201042024 入較低區域13的內部上方。 在這個特別的實施實例中，區域12和13彼 不透水的內壁1 6隔開，使得流體無法連通’該內 ' 實心的塔盤。管線1 5代表區域1 2和1 3之間向下 體連通管道。取而代之，或是除此之外’可以藉 壁16使得至少有部分內壁可穿透液體的方式， 12和13之間能有內部的流體連通，其可藉由使 個塔盤，其設計可讓液體向下流入區域13的內部 〇 向上進入區域12的內部。舉例而言，取代使用不 壁16，可以使用煙囪式塔盤，使得單元11內的 部向下流入區段13而非經由管線15從外部進入〗 在由內部向下流動的情況下，配液裝置18就變成 • 無論液體是由那一種方式從區域12移至區类 . 體係向下移動進入區域13，因而可能遇到至少一 置18。裝置18可均句分配橫越單元11之截面的 得液體能夠均勻的流過蒸餾塔的寬度範圍，而與每 〇 讎 觸。 蒸汽6通過過熱的子區域20，並且接著經E 進入塡料19下方之區域13的較低部分22。在壤 ’來自流15的液體和來自管線21的蒸汽彼此緊 ’因而使得部分的液體1 5氣化。這種新形成的酸 氣，隨著蒸汽21，經由管線17從區域1 3中移出 以添加至管線14的蒸氣中，以形成管線25中的 烴蒸氣產物。流25主要係含有來自進料2的烴蒸 此之間被 壁可以是 的外部流 由修改內 使得區域 用一或多 且使蒸氣 透水的內 液體由內 單元11。 選用的。 矣13，液 個配液裝 液體，使 I料19接 &管線21 I料19中 密的混合 性含烴蒸 ，並且可 綜合酸性 丨氣，例如 -16- 201042024 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26中來自進料2的烴液剩餘物。依照本 • 發明來操作氣化單元1 1，流25含有明顯數量（許多，例如 大多數）之存在於初始原料2中的有機酸，特別是羧酸和環 烷酸。 流25被通過一個管集箱（圖中未顯示），在該處流25 〇 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中進行裂解的溫度。 在區段27中實質加熱之後，包括其中所含有機酸類的 ‘ 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 0 許多各別流係以單一流28來代表。 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’包括羧酸類，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）’的羧酸轉化成或者是轉換成一氧化 碳（CO)、二氧化碳（C〇2)和較低分子量的酸（甲酸、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 -17- 201042024 面所述並詳如USP ‘961中所示。 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 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 進入爐卜 〇 進料2可經由管線10在溫度爲約室溫至約750F，例 如約5 00至約75 0F，且壓力爲常壓至1〇〇 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存在於進料2之中的某些酸類。Other materials may be added to the feed as determined by the particular physical and chemical properties of the 〇 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, a light petroleum brain, a petroleum brain, a heavy petroleum brain, or a mixture of two or more thereof. Light gasoline can have a boiling range from pentane (C5) boiling point 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 the light, medium and heavy petroleum brain fractions are from about 158 to about 212 F, from about 212 to about 302 F, and from about 302 to about 350 F -14 - 201042024, respectively, lightly added to the residue of feed 2 The amount of material can vary widely, depending on the operator's needs 'but the residual 'oil in feed 2, if any, can still be the weight of feed 2 in line 1' The composition is, and is fed to the gasification unit 11°. [Embodiment] FIG. 1 shows a liquid cracking furnace 1 containing, for example, at least one carboxylic acid-containing hydrocarbon main feed 2 is passed into the cracking chamber. Furnace 1 进 The upper half of the convective section is fed to the upper half of the cooler zone. 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) 10 to the gasification unit 11 (completely exposed to USP '961), which is divided into a higher vapor gasification zone 12 and lower Gasification 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) is capable of achieving a predominant (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 It is removed from zone 1 2 by line 14. Thus, line 14 carries almost 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 gaseous acids. The liquid distillate present in zone 12 (with or without some liquid gasoline and/or petroleum brain) is removed therefrom via line 15 and, with the still liquid acid, -15-201042024 Above the interior of the lower zone 13. In this particular embodiment, zones 12 and 13 are separated by a watertight inner wall 16 such that fluid cannot communicate with the 'inner' solid tray. Line 15 represents the downward communication conduit between zones 1 2 and 13. Instead, or in addition, 'the wall 16 can be borrowed such that at least a portion of the inner wall can penetrate the liquid, and there can be internal fluid communication between 12 and 13, which can be designed by means of a tray. Let the liquid flow downward into the interior of the region 13 and into the interior of the region 12. For example, instead of using the non-wall 16, a chimney tray can be used such that the portion within the unit 11 flows downwardly into the section 13 rather than entering it from the outside via the line 15. In the case of downward flow from the inside, dosing The device 18 becomes • whether the liquid is moved from the zone 12 to the zone by that way. The system moves down into the zone 13 and thus may encounter at least one set 18. The device 18 can uniformly distribute the liquid across the cross section of the unit 11 to uniformly flow through the width of the distillation column, and is in contact with each of the crucibles. 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 E. The liquid from the stream 15 and the steam from the line 21 are in close proximity to each other thus causing a portion of the liquid 15 to vaporize. This newly formed acid, with steam 21, is removed from zone 13 via line 17 for addition to the vapor of line 14 to form a hydrocarbon vapor product in line 25. Stream 25 is primarily comprised of a hydrocarbon stream from feed 2 which may be externally flowed by the inner unit 11 which is modified to allow the zone to be permeable to one or more vapors. Selected.矣13, the liquid is filled with liquid, so that the I material 19 is connected to the line 21 I material 19 in the dense mixed hydrocarbon-containing steam, and can be integrated with acidic helium gas, for example,-16-201042024 gasoline, petroleum brain, middle distillate , gas oil, a large amount of acidic substances and steam derived from feed 2. 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 gasification unit 1 is operated in accordance with the present invention. The stream 25 contains a significant amount (many, for example most) of the organic acids present in the starting material 2, particularly the carboxylic acid and the naphthenic acid. The stream 25 is passed through a header (not shown) where it is divided into a plurality of substreams ' and is convected through a plurality of conduits (not shown) into the convection section of the thermal cracking furnace 1 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 cracking in radiation zone 29. After substantial heating in section 27, the 'stream 25 containing the organic acids contained therein is passed via line 28 into the radiation section sub-region 29. Again, for the sake of brevity, these typically flow from sub-region 27 to and into sub-region 29 are represented by a single stream 28 of individual streams. In the radiant combustion chamber 29 of the furnace 1, the feed 'from the line 28 containing a plurality of different hydrocarbon components', including the carboxylic acids, will be subjected to severe thermal cracking conditions as previously described. These cleavage conditions result in significant amounts, even the majority (essentially all) of the carboxylic acid being converted or converted to carbon monoxide (CO), carbon dioxide (C〇2) and lower molecular weight acids (formic 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 described in the aforementioned -17-201042024 and as detailed in USP '961. 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) is finally vaporized in unit 11, especially the zone 13' is fed into the furnace. 1, and thus the cleavage of such distillate* is converted to a lighter component. Feed 2 can be fed into the furnace 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 12 via line 10 at a temperature of from about room temperature to about 750 F, such as from about 500 to about 75 F, and at a pressure from atmospheric to 1 psig. Stream 14 can be substantially all of the hydrocarbon vapor formed from feed 2, and • the temperature is from about room temperature to about 700F and the pressure is from atmospheric to 100 psig. Stream 14. may or may not contain certain acids originally present in Feed 2.
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中被氣化者，並且溫度爲約室溫至約70 0F D 且壓力爲略高於常壓至約100 psig (以下簡稱爲”常壓至1〇〇 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 〇進入區域1 2之液態烴和酸類額外氣化的 條件下操作。 區域1 3是在謹慎計算的條件下操作’不只是要能夠將 明顯額外數量的液態烴類氣化，同時也要氣化明顯數量（ -18- 201042024 較佳爲大多數，基本上是全部）的有機酸，特別是翔酸和 環烷酸’其原本是在進料2中並且殘留在流15中。這可驅 使最大數量的酸類進入管線17以傳送至爐1。 因此，依照本發明，氣化單元11 (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 額外氣態烴類和氣態酸。 因此’依照本發明來操作的氣化單元11，可由預熱進 ® 料流1 0中所含的液體來形成相當數量的額外氣態烴類和 未解離（未改變其化學組成）之氣態酸。 因此’經由管線1 4、1 7和2 5離開氣化單元1 1之氣相 化學組成（含烴且爲酸性）與經由管線10進入單元11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11之液相化學組成與經由管線1 〇進入單元11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10進入單元11的兩相（液相和氣相）進行物理分離之Stream 15 can be substantially all of the residual liquid of feed 2 and then degassed 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 100 psig (hereinafter referred to as "normal pressure to 1 psig"). Zone 12 can be used as a physically separate zone, as is the bubbling bucket proposed by Buchanan et al., as discussed above, in addition to liquid hydrocarbons and acid extra gases suitable for causing zone 1 to enter zone 1 via line 1 Under the conditions of operation. Zone 1 3 is operated under carefully calculated conditions 'not only to be able to gasify a significant additional amount of liquid hydrocarbons, but also to vaporize a significant amount (-18- 201042024 is preferably the majority, essentially all) The organic acids, especially citric acid and naphthenic acid, were originally in feed 2 and remained in stream 15. This can drive the maximum amount of acid into line 17 for delivery to furnace 1. Thus, in accordance with the present invention, the gasification unit 11 (particularly the zone 'domain 13 of the unit) operates cautiously at a temperature of from about 700 to about 1,100 F, thereby allowing the liquid collected from the zone 12 to be formed via line 15 to form a comparable The amount of additional gaseous hydrocarbons and gaseous acids. Thus, the gasification unit 11 operated in accordance with the present invention can be preheated into the liquid contained in the stream 10 to form a substantial amount of additional gaseous hydrocarbons and gaseous acids which are undissociated (without changing their chemical composition). Thus, the gas phase chemical composition (hydrocarbon containing and acidic) leaving the gasification unit 1 1 via lines 14 , 17 and 25 is substantially different from the gas phase chemical composition entering the unit 11 via line 10 . Similarly, the liquid phase chemical composition leaving unit 1 via line 26 and the liquid phase chemical composition entering unit 11 via line 1 are also substantially different. That is, unit 11 physically separates the two phases (liquid phase and gas phase) entering unit 11 via line 10.
Q 外，還產生了更多的影饗。 流1 4和1 7的結合，如同流25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，較佳爲約0.1至約1磅的蒸汽。 在氣化區域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13頂部和管線 -19- 201042024 • 1 7中的熱氣（例如蒸汽）、烴和酸類的含量比率爲蒸汽相對 於烴爲約〇 . 1 /1至約5 /1。 蒸汽是適合經由管線2 1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 係足以使得有相當部分進入區域1 3的液態烴1 5揮發。一 般而言，由導管21進入區域13之氣體溫度至少爲約65 0F ，較佳爲約900至約1，200F且壓力爲常壓至lOOpsig。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可以是蒸汽和沸點低於約1，1 00 F之烴/ 酸類的混合物。流17的溫度可以是約600至約800F且壓 力爲常壓至lOOpsig。 ' 在裂解操作的一般情況下，來自管線21的蒸汽不只是 - 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 提供進一步氣化及溫和裂解的能量。這只需要足夠的能量 〇 來達到1)使較重烴類成分（例如在全原油和殘油中所可發 現的成分）氣化和/或溫和裂解以及2)使明顯數量（幾乎全 部）內含的羧酸類氣化即可完成。舉例而言，利用管線21 中的蒸汽來達成進料2液態烴類的實質氣化/溫和裂解。 當酸性的液態烴類液滴漸漸朝向區域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圖之氣化單元11的進料10中所 -20- 201042024 殘留比約l，l〇〇F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中被氣化’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u(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烴實體物， 並且那些剛形成的較輕實體物將經由管線1 7移出，成爲爐 1的額外進料。所含之酸類將會以其原有的形式被氣化， 〇 並且經由管線17移出至爐1，以在該爐中進行解離或其它 化學改變。 進料10的液體殘餘物將經由管線26移出以移置到別 處。依照本發明前面所述的方式來操作氣化單元1 1 (特別是 ' 區域13)，可將最大（佔優勢）數量原本存在於進料2中的酸 • 類（特別是羧酸和環烷酸）予以氣化，並且傳送至爐1，以便 在其中進行化學破壞。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藉由氣化單元11的操作而 〇 被送至爐1。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 類被送至爐1 ’氣化單元11的底部產物26將會含有極少（ 幾乎沒有）原存於進料2中的羧酸類。如果在產物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，它 基本上是非腐蝕性的’並且可以在工廠的其它系統中更容 -21 - 201042024 易且更迅速的處理，例如淬火油和/或燃料油系統，而無 需考量流26和其所形成之子流有任何酸腐鈾的傾向。 實施例 將TAN値爲4.5的Doba常壓殘渣油以相同的重量份 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 中。此進料混合物2爲260F及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10進入氣化單元11，其中約690F及60 psig的汽油 、石油腦和氣製油氣體之混合物係在該單元的區域12中被 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。 由進料2之殘油所留下的烴類液體，在從前述所伴隨 的烴類氣體中分離出來之後，經由管線15傳送至較低區段 13，並且在該區段中朝下流向其底部。 溫度約爲l，〇50F的預熱蒸汽21被引入接近氣化區域 13的底部，而使得在區段13中的蒸汽相對於烴之比率約 爲1。落下的液滴（含烴且爲酸性）與來自區域13底部而朝 向其頂部上升的蒸汽爲逆向流動。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75 0F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 -22- 201042024In addition to Q, it has produced more impact. 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 includes, for example, the overall vapor/hydrocarbon ratio It is from about 0.1 to about 2, preferably from about 0.1 to about 1 pound, of steam per pound of hydrocarbon. In the gasification 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 ratio of hot gas (e.g., steam), hydrocarbons, and acids in the top of zone 13 and in line -19-201042024 • 17 is about 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 substances may be present in the steam used. The preferred temperature of all such gases is sufficient to cause a substantial portion of the liquid hydrocarbons entering zone 13 to volatilize. In general, the temperature of the gas entering the zone 13 from the conduit 21 is at least about 65 F, preferably from about 900 to about 1,200 F and the pressure is from atmospheric to 100 psig. For the sake of simplicity, such gases will be referred to below only in terms of steam. Thus, stream 17 can be a mixture of steam and a hydrocarbon/acid having a boiling point below about 1,100 F. Stream 17 may have a temperature of from about 600 to about 800 F and a pressure of from atmospheric to 100 psig. 'In the general case of the cracking operation, the steam from line 21 is not just a diluent for partial pressure. Instead, the steam from line 21 not only provides the function of dilution, but also the unit 11 is still in Liquid hydrocarbons provide energy for further gasification and mild cracking. This requires only enough energy to achieve 1) gasification and/or mild cracking of heavier hydrocarbon components (eg, components found in whole crude oil and residual oil) and 2) significant (almost all) The gasification of the contained carboxylic acid can be completed. For example, steam in line 21 is utilized to achieve substantial gasification/mild cracking of feed 2 liquid hydrocarbons. When the acidic liquid hydrocarbon droplets gradually move toward the lower direction of the region 13, the very high steam dilution ratio and the highest temperature steam are provided where it is most needed. According to the present invention, in the feed 10 of the gasification unit 11 of Fig. 1, the residue of -20-201042024 is lower than that of l, l〇〇F, which is lighter (lower) boiling hydrocarbons and acids (all as before) Defined) will be gasified in unit 11 and removed via line 14 or 17 or both, and sent to furnace '1 as described above. In addition, the lighter physical objects previously described in this essay are heavy • Hydrocarbon entities may (at least in part) be gently cracked or decomposed into units u (particularly region 13) as before The lighter hydrocarbon-containing entities are described, and those lighter bodies that have just formed will be removed via line 17 to become an additional feed to furnace 1. The acid contained will be vaporized in its original form, and removed via line 17 to furnace 1 for dissociation or other chemical changes in the furnace. The liquid residue of feed 10 will be removed via line 26 for displacement elsewhere. Operating the gasification unit 1 1 (especially 'region 13) in the manner previously described in the present invention, the largest (predominant) amount of acid species (especially carboxylic acids and naphthenes) originally present in the feed 2 can be The acid is vaporized and transferred to the furnace 1 for chemical destruction therein. According to the present invention, most of the highly corrosive naphthenic acids originally present in the feed 2 will be sent to the furnace 1 by the operation of the gasification unit 11. In this furnace, the acid is at least completely destroyed or converted (converted) into lower molecular weight, less corrosive acids. According to the present invention, a large amount (almost all) of the acid derived from feed 2 is sent to the furnace 1 'the bottom product 26 of the gasification unit 11 will contain very little (nearly) carboxylic acid originally present in the feed 2 Acids. If the product 26 contains an acid, it is usually a less corrosive acid. Thus, 'in accordance with the present invention, 'in terms of the acid content of the bottom product 26, it is substantially non-corrosive' and can be more easily processed in other systems of the factory - 201042024, such as quenching oil and/or Or a fuel oil system, without having to consider the tendency of stream 26 and the substream it forms to have any acid uranium. EXAMPLES A Doba atmospheric residue 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 of the convection section of the pyrolysis furnace 1. This feed mixture 2 was 260F and 80 psig. In this convection section, Feed 2 is preheated to about 690F at about 60 psig and then enters gasification unit 11 via line 10, wherein about 690F and 60 psig of gasoline, naphtha and gas-to-oil gas mixtures are It is separated in the area 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. 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 section 13, and flows downward in this section to the bottom thereof. The preheated steam 21 having a temperature of about 1, 〇50F is introduced near the bottom of the gasification zone 13, so that the ratio of steam to hydrocarbon in the zone 13 is about 1. The falling droplets (hydrocarbon-containing and acidic) flow in a reverse direction with the vapor rising from the bottom of the zone 13 towards the top. 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 75 °F is taken from the top of the zone 13 and moved from zone 12 via line 14 earlier -22- 201042024
出的氣體混合，以形成複合的蒸汽/烴蒸氣流25，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l，〇〇〇F’並 ' 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C02產量將 提高，這是因爲流25中所含的羧酸被轉化的緣故。 單元1 1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 〇 要做進一步的處理。 有顯著數量的有機酸（包括羧酸）消失在流25中’並且 之後在裂解爐中被轉化成CO和C〇2及較低分子量的酸。 在此同時，經由氣化單元1 1的操作’特別是氣化區域 • 13,使得更多數量的液態進料氣化而形成用於裂解爐之額 . 外氣態進料。 【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 〇 解系統。 【主要元件符號說明】 1 液體裂解爐 2 進料 3 預熱子區域 6 蒸汽 10 管線 11 氣化單元 -23- 201042024The resulting gases are combined to form a composite vapor/hydrocarbon vapor stream 25 containing about 0.5 pounds of steam per pound of hydrocarbon. This composite stream is preheated in sub-region 27 to a temperature of less than about 50 psig, 〇〇〇F' and' and then to the radiant combustion chamber sub-region 29 to be at 1,400F. Cracking is carried out up to a temperature range of 1,550F •. The CO and CO 2 production in the cracking furnace will increase because the carboxylic acid contained in stream 25 is converted. The bottom product 26 of unit 1 1 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 carboxylic acid) disappears in stream 25' and is subsequently converted to CO and C?2 and lower molecular weight acids in a cracking furnace. At the same time, the operation of the gasification unit 11, in particular the gasification zone, 13, causes a greater amount of liquid feed to be vaporized to form an amount for the cracking furnace. External gaseous feed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a gasification/cracking system that can be used in the method of the present invention. [Main component symbol description] 1 Liquid cracking furnace 2 Feed 3 Preheating sub-zone 6 Steam 10 Pipeline 11 Gasification unit -23- 201042024
12 較 高 的 蒸 氣 氣 化 區 域 13 較 低 的 蒸 氣 氣 化 區 域 14 管 線 15 管 線 16 內 壁 17 管 線 18 配 液 裝 置 19 塡 料 20 cm m 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 輻 射 區 域 3 0 管 線 -24-12 Higher vapor gasification zone 13 Lower vapor gasification zone 14 Pipeline 15 Pipeline 16 Inner wall 17 Pipeline 18 Dosing device 19 Tanning 20 cm m Thermal subzone 2 1 Pipeline 22 Lower section 25 Pipeline 26 Bottom flow 27 Preheater zone 28 Line 29 Radiation zone 3 0 Line-24-