200528554 九、發明說明： 【發明所屬之技術領域】 本發明係針對一種經由將剛於費雪-托崔 C Fischer-Tropsch)法中獲得的鏈烷烴原料與另一來源的 含硫原料合併而自天然氣製造含硫蒸汽裂解器原料的方 法0 【先前技術】 在蒸、/气裂解器方法技術領域中具有通常知識者皆知， 要將硫添加到進料中以降低焦炭的生成。在蒸汽裂解器加 熱爐管中的焦炭生成原則上係經由二種機制形成，即熱解 反應和催化脫氫反應。熱解反應係經由使用低的操作壓 力、具有高的蒸汽對烴的比例、於3〇%至6〇%的程度及避免 過里官金屬溫度和使未蒸發進料進入高溫區的可能性而降 到取小。為了承受高的管金屬溫度，高達21 00 °F，係使用 含南鎳與鉻，例如35%鎳與25%鉻的合金。這些金屬會催化 脫氫反應，因此必須被鈍化。硫化是解決鈍化的典型方法。 對於瘵汽裂解器操作者的常見實行方式是在脫焦炭操作之 1馬上注入焦炭抑制劑。亦即當管壁金屬催化活性最高的 日=候。在烴原料被送入加熱爐之前，係將DMS或DMDS隨蒸 2起’主入旋官中來形成硫化物膜。就典型液體原料而 口六原料中的硫含量通常足以在實際蒸汽裂解程序期間維 2瓜化物水平。如果在進料中已經沒有足夠的硫，則可將 J加到進料中。在這種情況下，或許可添加20 ppm至1〇〇 卿的硫以使焦炭與⑶的產生減到最小。 200528554 使用剛在費雪-托崔法中獲得之輕油鏈烷烴產物作為 蒸Λ裂解為原料亦為眾所周知者。例如，'' τ h e M a r k e t s f 〇 r200528554 IX. Description of the invention: [Technical field to which the invention belongs] The present invention is directed to a method for combining a paraffinic raw material obtained in the Fischer-Tropsch method and a sulfur-containing raw material from another source. Method for producing raw materials of sulfur-containing steam cracker from natural gas 0 [Prior art] It is known to those having ordinary knowledge in the technical field of steam / gas cracker method that sulfur is added to the feed to reduce coke formation. The formation of coke in the steam cracker heating furnace tube is in principle formed via two mechanisms, namely a pyrolysis reaction and a catalytic dehydrogenation reaction. Pyrolysis reactions are achieved through the use of low operating pressures, high steam-to-hydrocarbon ratios, to the extent of 30% to 60%, and the avoidance of excessive metal temperatures and the possibility of allowing unevaporated feeds to enter high temperature zones Drop to take small. In order to withstand high tube metal temperatures, up to 21 00 ° F, alloys containing south nickel and chromium, such as 35% nickel and 25% chromium, are used. These metals catalyze dehydrogenation and must be passivated. Vulcanization is a typical method to solve passivation. A common practice for radon steam cracker operators is to inject coke inhibitors as soon as one of the decoking operations. That is, the day when the metal wall has the highest catalytic activity. Before the hydrocarbon feedstock is sent to the heating furnace, the DMS or DMDS is steamed 2 'into the spinner to form a sulfide film. For typical liquid feedstocks, the sulphur content in the raw feedstock is usually sufficient to maintain the cucumenide level during the actual steam cracking process. If there is not enough sulfur in the feed, J can be added to the feed. In this case, 20 ppm to 100 ppm of sulfur may be added to minimize coke and CD production. 200528554 It is also well known to use the light oil paraffin product just obtained in the Fisher-Tottri process as the steam Λ cracking as a raw material. For example, "τ h e M a r k e t s f 〇 r
Shell Middle Distillate Synthesis Products，、Shell Middle Distillate Synthesis Products,
Presentation of Peter J.A. Tijm, Shell International Gas Ltd. , Alternative EnergyPresentation of Peter J.A. Tijm, Shell International Gas Ltd., Alternative Energy
Vancouver’ Canada, May 2 -4, 1995 在第 5 頁提到： SMDS輕油’即Shel 1 MDS法中費雪—托崔衍生的輕油餾份， 係在例如新加坡用作蒸汽裂解器進料。 因為費雪-托崔衍生的產物含有幾乎檢測不到的硫含 里，因此將必須將硫添加到此原料中，然後它才可被用作 瘵π裂解器進料。這可藉由添加硫添加劑如二甲基二硫醚 (DMDS)或藉由將費雪—托崔進料與高硫含量物質摻合來進 行，如，Preliminary Survey 〇n GTL 汕“此“ Based ⑽⑽恥 teChn〇1〇gy^ June 2川1， Japan External Trade Organization (JETR0)，secti〇n 6·2·3 中更詳細說明者。 在蒸八裂解裔方法中將硫添加到費雪-托崔衍生的進 料亦敘述於最近的專利公開# us + 2〇〇3/〇i35〇77中。此 公開案敘述在遠距離位置製造低硫費雪—托崔衍生的輕 油，將此產物運送到蒸汽裂解器位置，以及在使用該輕油 作為洛汽裂解器進料之前將硫化合物添加到輕油中。 一…”36揭示一種方法，其中係將剛自粗天缺 氣=離:現場冷凝物（fieldcGndensate)加氫處理㈣ 料3 :根據此公開案’硫必須要除去以便使用它作為 '.、、枓’或用來與其他煙類混合而作為化學方法的原料。 200528554 根據WO-A-9937736之方法的一個缺點是需要額外的加 氫處理單元。 【發明内容】 本發明的目的是要更有效地利用剛自粗製天然氣分離 之含高硫現場冷凝物，而不需額外的加氫處理。 此目的係經由下述方法達成。經由進行下列步驟而從 粗製天然氣製造含硫蒸汽裂解器原料的方法： (a )將含硫液體現場冷凝物餾份自天然氣分離， (b) 將液體現場冷凝物分成高沸點餾份和低沸點餾 參 份， (c) 自步驟（a)中獲得的氣體製備一氧化碳與氫的混 合物， (d)使用得自步驟（C)的一氧化碳與氫進行費雪一托崔 反應來製備鏈烷烴產物，及 )將鏈烷烃產物或部分的該產物與步驟（b)中獲得 之低彿點顧份合併，以择溫衣曰 乂 3又付石瓜含Ϊ在5 0與1 〇 〇 〇 ρρτη之間 的含硫蒸汽裂解器原料。 申請人已經發現至，丨，1V 4日4士丄心 兄則 以根據本發明之方法，可在簡單 的分離步驟，如蒗餾舟 .+ “留^驟之後，使用部分的現場氣體冷凝 物來提高費雪-托崔產物 物的口口、，及’而形成符合直接使用規格 的極佳蒸汽裂解器原料。 k 4 1 十 ^疋有利的，因為它節省在費雪- 托崔法生產場所的裝罐 也从办 ’訂得^ ^，而且一種產物可運送到 海外客戶而非兩種分開的產物。 【貫施方式】 9 200528554 發明詳細說明 /驟(a)可根據為人所熟知的方法 是從地下井採得。】至5個碳原子的氣^ =天“ 到这矣而尨ώ η 礼11類通常是在氣體 J達表面後自C5+烴類分離出來 ^ m ^ ^ r 1 J女在所明的未蒸發燃料 成渴捕收裔（slug catchers) 稱為頊塥、人n A疋獲传的液體產物亦 :::::物且可能有非常高的硫含量，例如在l_ppm 护，，中、+ 1 900卿以上。典型的較低含量是lOOOppm 二二場冷凝物的天然氣將稱為預淨化天然氣。 最炊μ ^驟⑷中獲得的液體冷凝物可具有非常高的 丄w 在3〇代以上，同時大部分的產物在300〇c '弗騰。稭由例如經由一個閃蒸步驟或蒸餾步驟分離出 2㈣份’可得到含有硫化合物且符合用作蒸汽裂解器 原广的沸點範圍要求的低沸點館份。此顧份不需進一步脫 ^處理以便用摻合成分來製備步驟（e)中可用作蒸汽裂解 $原料的混合物。 較佳而言，剛自步驟（b)之現場冷凝物離析的低沸點镏 印:有在120與230°C之間，且更佳在140與215〇c之間的 π = ’弗點。起始沸點符合仍存在於液體現場冷凝物中的C5 =類j低沸點鶴份的最終沸點可依據現場冷凝物中的硫含 =、含硫低沸點餾份與步驟（幻之費雪—托崔產物的摻合比 及所得混合物的所欲硫含量而改變。最佳操作可使用一般 ^ 3决疋。剛在步驟（b)中獲得富含硫化合物與有機酸的較 "4 “伤，可在所謂的局部冷凝物精煉器中做進一步處 理。低沸點餾份較佳含有2〇〇與6〇〇〇 ppm之間的硫。 200528554 在進行步驟（c )之前，硫係藉由各種可能的技術從剛在 步驟（a)中獲得的預淨化天然氣中分離出來。較佳而言，硫 係藉由所謂的吸收型程序從天然氣除去。這些著名程序包 括一個天然氣與含有物理與化學吸收劑的液體混合物接觸 的步驟。在這種程序中，氣體混合物係在超計大氣壓下在 二個步驟中連續用含有物理吸收劑與化學吸收劑的二種不 同液體混合物處理。典型的化學吸收劑為三級胺類，特別 是含有至少一個羥烷基的三級胺類。三乙醇胺、二乙基乙 醇胺（DEMEA)及甲基二乙醇胺（MDEA )是非常適合的。典 型的物理吸收劑為碳酸丙二§旨N -曱基p比υ各烧酮、二曱基甲 、聚乙二醇的二甲醚、四伸乙基二醇二甲基鱗及環丁 硼是非常適合的。這類程序的實例係詳細敘述於 US-A-43 72925 及教科書如 Gas Purificati〇n, 5th ed./Arthur Kohl and Richard Nielsen, 1997,Vancouver 'Canada, May 2 -4, 1995 mentioned on page 5: SMDS Light Oil', which is a Fisher-Totrium-derived light oil fraction in the Shel 1 MDS process, is used as a steam cracker feed in Singapore, for example . Because the Fisher-Tottri-derived product contains almost undetectable sulfur content, sulfur will have to be added to this feed before it can be used as a 瘵 π cracker feed. This can be done by adding a sulphur additive such as dimethyl disulfide (DMDS) or by blending Fisher-Tropsch feed with a high sulphur content material, for example, the Preliminary Survey 〇n GTL Shan "This" Based It is described in more detail in teChn〇1〇gy ^ June 2, Japan External Trade Organization (JETR0), secti0n 6.2.3. The addition of sulfur to Fisher-Tropsch-derived feeds in the steamed cleavage method is also described in the recent patent publication # us + 2003 / 〇i35〇77. This publication describes the manufacture of low-sulfur Fisher-Totley-derived light oil at a remote location, transporting this product to a steam cracker location, and adding sulfur compounds to the light oil prior to using the light oil as a feed for the Luo cracker. Light oil. A ... "36 reveals a method in which fresh air from the rough days = out of the field: fieldcGndensate hydrotreating material 3: according to this publication 'sulfur must be removed in order to use it as.' ,,枓 'or used as a raw material for chemical methods by mixing with other tobaccos. 200528554 One disadvantage of the method according to WO-A-9937736 is the need for an additional hydrotreating unit. SUMMARY OF THE INVENTION The object of the present invention is to be more effective The use of high-sulfur on-site condensate just separated from crude natural gas without additional hydroprocessing. This objective is achieved by the following method. A method for manufacturing a sulfur-containing steam cracker raw material from crude natural gas by performing the following steps : (A) Separating the on-site condensate fraction of the sulfur-containing liquid from natural gas, (b) Separating the liquid on-site condensate into high-boiling fractions and low-boiling fractions, and (c) preparation from the gas obtained in step (a) A mixture of carbon monoxide and hydrogen, (d) using a carbon monoxide obtained from step (C) to perform a Fisher-Tropsch reaction with hydrogen to prepare a paraffin product, and) paraffin product or part of the product Combined with the low buddha servings obtained in step (b) to select the warm clothing, ie, 3, and pay for the raw material of the sulfur-containing steam cracker containing 50% and 100% ρρτη of stone melon. It was found that, according to the method of the present invention, 1V 4 days and 4 people can use simple separation steps, such as a retort boat. + "After leaving the step, use part of the on-site gas condensate to increase the cost The mouth and mouth of the Snow-Tropir product, and 'forms an excellent steam cracker raw material that meets the specifications for direct use. k 4 1 10 ^ 疋 is advantageous because it saves on canning at the Fisher-Tottri method production site ^ ^ and one product can be shipped to overseas customers instead of two separate products. [Performance Mode] 9 200528554 Detailed description of the invention / Step (a) can be obtained from underground wells according to a well-known method. 】 To 5 carbon atoms gas ^ = heaven "To this 矣 尨 尨 11 Li 11 types are usually separated from C5 + hydrocarbons after the gas J reaches the surface ^ m ^ ^ r 1 Fuel slug catchers are called 顼 塥, human n A 疋 liquid products also passed :::::, and may have very high sulfur content, such as at 1 ppm, medium, + 1 Above 900 ° C. The typical lower content is 1000ppm natural gas condensate will be referred to as pre-purified natural gas. The liquid condensate obtained in the cooking process can have a very high 丄 w above 30 generations, At the same time, most of the products are at 300 ° C. Forten. The straw can be separated into 2 parts by, for example, a flash distillation step or a distillation step. The portion does not need to be further treated in order to use the blended component to prepare the mixture that can be used as the raw material for steam cracking in step (e). Preferably, the condensate has just been isolated from the spot in step (b). Low boiling point seal: between 120 and 230 ° C, and more preferably between 140 and 215 ° c Π = 'Eph point. The initial boiling point corresponds to C5 which is still present in the liquid on-site condensate = the final boiling point of the low-boiling point-like crane fraction can be based on the sulfur content of the on-site condensate =, sulfur-containing low-boiling fractions and steps (The blending ratio of the Fischer-Tropsch product and the desired sulfur content of the resulting mixture may vary. The best practice can use general ^ 3 decision. Just obtained in step (b) sulfur-rich compounds and organic acids The "4" injury can be further processed in a so-called local condensate refiner. The low boiling point fraction preferably contains sulfur between 2000 and 6000 ppm. 200528554 In step (c) Previously, the sulfur system was separated from the pre-purified natural gas just obtained in step (a) by various possible techniques. Preferably, the sulfur system is removed from natural gas by so-called absorption processes. These well-known processes include a The step of contacting natural gas with a liquid mixture containing a physical and chemical absorbent. In this procedure, the gas mixture is used in two steps under superatmospheric pressure to continuously use two different types of physical absorbent and chemical absorbent. Treatment of mixtures of chemicals. Typical chemical absorbents are tertiary amines, especially tertiary amines containing at least one hydroxyalkyl group. Triethanolamine, diethylethanolamine (DEMEA) and methyldiethanolamine (MDEA) are very suitable Typical physical absorbents are propylene carbonate, N-fluorenyl p ratio, each of ketones, dimethyl methyl, dimethyl ether of polyethylene glycol, tetraethylene glycol dimethyl scale and ring. Boron is very suitable. Examples of such procedures are described in detail in US-A-43 72925 and textbooks such as Gas Purificatión, 5th ed./Arthur Kohl and Richard Nielsen, 1997,
Gulf Publishing Company, ISBN 0-88415-220-0 第1章中。 較佳而言’任何具有3或更多個碳原子之烴化合物， 疋在將氣體轉化成合成氣之前從天然氣分離得到。較佳而 分離係經由將氣體冷卻到這些烴類會液化的溫度與壓 力條件來進行。液體產物然後可容易地自氣體分離。冷卻 較佳可經由間接對液態氮熱交換來進行。液態氮較佳可為 在刀離空氣獲得純化氧供用於步驟（C)時剛獲得的過剩 氮更佳的方法係經由降低壓力、分離冷凝的+烴類及視 而要增加壓力水平，然後利用該氣體製備合成氣。較佳而 200528554 ' 4氣體係從超過50巴的壓力降低到低於40巴，較佳 係低方；30巴的壓力。在液體煙類的分離之後，冑氣體壓力 =加到5G巴以上的水平，較佳係在與㈣巴之間。如是 ^传之C3和類可與剛從步驟（d)所製得產物離析的lPG 產物払cr +烴類較佳係被送往步驟（e )而與步驟（幻所 提及之餾份合併，以獲得更多的蒸氣裂解器原料。 擬用於費雪—托崔反應的合成氣係在步驟⑷中自步驟 (a)、仔之軋體經由部分氧化及/或蒸汽，甲烷重整而製得。 、，為調整合成氣中的H2/⑶比，可將二氧化碳及/或蒸汽 送入部分氧化程庠Φ。人 斤中曰成氣的H2/C0比宜在1· 3與2· 3之 番棼較佳係在1 · 6肖2· 1之間。若需要，可經由蒸汽甲烷 ^ ’較佳係與水煤氣轉移反應合併，來製得（小量）額 里勺氫冑外的氫亦可用於其他程序如加氮裂解中。 在另一個具體實例φ J中在催化氧化步驟中所獲得合成 乳的H2/C0比可藉由從人 、 k σ成乳除去氫而降低。這可經由習知 技術如壓力擺動吸附或田 低/皿私序進行。較佳的選擇是以薄 艇技術為主的分離。卹八 …一 Μ的氫可用於尤其是費雪-托崔反應 取重烴餾伤的加氫裂解步驟中。 以上述方式獲得的人 于旳σ成虱通常具有在900與1400〇C之 間的h度，其係被冷卻 450°C ^ Μ , . U ” b00 C 之間，宜在 150 與 曰 1幸父佳在3 0 〇虚4 〇 f)0 Γ夕pq a 0± ^ ^ ^ ^ ” 400 c之間的溫度，較佳係在同 =生動力的情況下，例如以蒸汽形式進行。進一步冷卻 到40與13〇。(：之間，妒杜+ y 習知執交換哭中進0與100°C之間的溫度，係在 …進仃，尤其是管式熱交換器。為從合成氣 12 200528554 除去任何雜質，可使用防護床。特別為了要除去所有微量 的HCN及/或NHU，可使用特定的催化劑。可能仍存在於步 驟（C)所用氣體中的微量硫可藉由使用氧化鐵及/或鋅的吸 收程序除去。 純化的氣悲混合物，主要包含氫、一氧化碳及視情況 的氮，係在催化轉化階段中與適當的催化劑接觸，其中生 成一般為液體的烴類。 用於在步驟（d)中將包含氫與一氧化碳之混合物催化 轉化成烴類的催化劑為此技藝中為人所知者，且通常被稱 籲 為費雪-托崔催化劑。用於此程序的催化劑常包含元素週期 表第VI11族的金屬作為催化上有效的成分。特別的催化上 有效的金屬包括釕、鐵、鈷及鎳。就可製得的重質費雪一托 崔餾份而言，鈷為較佳的催化上有效的金屬。如先前所討 順者，較佳的煙類進料為天然氣或伴隨的氣體。因為這些 原料通吊產生H2/C0比約2的合成氣，故始為非常好的費雪 -托崔催化劑，因為這類型催化劑的使用者比值也是約2。 催化上有效的金屬較佳係承載於多孔載體上。多孔載 _ 體可選自於任何此技藝中已知的適當耐高溫金屬氧化物或 矽酸鹽或其組合。較佳多孔載體的特定例子包括二氧化 矽、氧化鋁、二氧化鈦、氧化錯、二氧化鈽、氧化鎵及其 混合物，尤其是二氧化矽、氧化鋁及二氧化鈦。 催化上有效的金屬在載體上的量較佳係在每〗〇〇 载體材料有3至300 pbw，較佳從1〇至80 pbw，尤其是從 20至60 pbw的範圍内。 13 200528554 若需要，催化劑亦可包含一或多種金 作為促進劑。適當全14 、，“金屬乳化物 第ΠΑ、ΙΙΙΒ、ΙνΒ= 進劑可選自於元素週期表 # π ΠΒ IVB、VB及爪族，或㈣和 W鋇、銳f鈦、錯、給、 用…、 物為非*適“勺促進劑。對於用以製備 的催化劑而言，特佳的金屬氧化劑促進劑 為乳化猛和氧化錯。適合 第VII…"τ適田的金屬促進劑可選自於週期表的 β或VIII族。銖和第VIII族責重金Gulf Publishing Company, ISBN 0-88415-220-0 Chapter 1. Preferably, 'any hydrocarbon compound having 3 or more carbon atoms is separated from natural gas before the gas is converted to syngas. Preferably, the separation is performed by cooling the gas to a temperature and pressure conditions at which these hydrocarbons will liquefy. The liquid product can then be easily separated from the gas. The cooling can preferably be performed by indirect heat exchange of liquid nitrogen. The liquid nitrogen is preferably the excess nitrogen obtained when the purified oxygen is obtained from the air for use in step (C). The better method is to reduce the pressure, separate the condensed + hydrocarbons, and increase the pressure level, and then use This gas produces syngas. Preferably, the 200528554'4 gas system is reduced from a pressure of more than 50 bar to less than 40 bar, and the lower one is preferred; a pressure of 30 bar. After the separation of liquid smoke, the pressure of krypton gas = added to a level above 5G bar, preferably between krypton and krypton. If it is passed, C3 and its species can be separated from the lPG product 払 cr + hydrocarbons which have just been separated from the product prepared in step (d). It is preferably sent to step (e) and combined with the fractions mentioned in step (e). In order to obtain more raw materials for the steam cracker, the synthesis gas to be used in the Fisher-Tropsch reaction is obtained in step (i) from the step (a), the rolling body of the product through partial oxidation and / or steam, and methane reforming. Obtained. In order to adjust the H2 / ⑶ ratio in the synthesis gas, carbon dioxide and / or steam can be sent into the partial oxidation process 庠 Φ. The H2 / C0 ratio of the gas in the human kilogram should preferably be 1 · 3 and 2 · Panzhihua 3 is preferably between 1 · 6 Xiao 2 · 1. If necessary, it can be combined with water gas transfer reaction through steam methane ^ 'preferably to make (small amount) of hydrogen hydrazone outside Hydrogen can also be used in other processes such as nitrogen cracking. In another specific example φ J, the H2 / C0 ratio of the synthetic milk obtained in the catalytic oxidation step can be reduced by removing hydrogen from human, k σ milk. This Can be performed by conventional techniques such as pressure swing adsorption or field low / dish private sequence. The better choice is based on thin boat technology. One megawatt of hydrogen can be used in the hydrocracking step, especially in the Fisher-Tropir reaction to take heavy hydrocarbon distillates. The human 旳 σ adult lice obtained in the manner described above usually has a degree of h between 900 and 14 00 ° C. It is cooled at 450 ° C ^ Μ,. U ”b00 C, preferably between 150 and 1 Xingfujia at 3 0 〇 virtual 4 〇 f) 0 Γxi pq a 0 ± ^ ^ ^ ^ 400 The temperature between c is preferably under the condition of the same driving force, for example, in the form of steam. Further cooled to 40 and 130. (: Between, je du + y, acquainted with the exchange of crying temperature between 0 and 100 ° C, is tied to, especially the tube heat exchanger. In order to remove any impurities from Syngas 12 200528554, Guard beds can be used. In particular, to remove all traces of HCN and / or NHU, specific catalysts can be used. Traces of sulfur that may still be present in the gas used in step (C) can be absorbed by the use of iron oxide and / or zinc Removal by procedure. The purified gas-tragic mixture, which mainly contains hydrogen, carbon monoxide, and optionally nitrogen, is contacted with an appropriate catalyst during the catalytic conversion stage, which generates generally liquid hydrocarbons. It is used in step (d) to Catalysts containing a catalytic conversion of a mixture of hydrogen and carbon monoxide into hydrocarbons are known in the art and are often referred to as Fisher-Tropsch catalysts. Catalysts used in this procedure often include Group VI11 of the Periodic Table of the Elements Metal as a catalytically effective component. Special catalytically effective metals include ruthenium, iron, cobalt, and nickel. In terms of the heavy Fisher-Tropsch fractions that can be made, cobalt is better catalytically effective. Metal. As previously discussed, the preferred smoke feed is natural gas or accompanying gas. Because these raw materials pass through to produce a synthesis gas with an H2 / C0 ratio of about 2, it is a very good Fisher-Tropsch Catalyst, because the user ratio of this type of catalyst is also about 2. The catalytically effective metal is preferably supported on a porous support. The porous support can be selected from any suitable high temperature resistant metal oxide known in the art or Silicate or a combination thereof. Specific examples of preferred porous supports include silicon dioxide, aluminum oxide, titanium dioxide, oxide, hafnium dioxide, gallium oxide and mixtures thereof, especially silicon dioxide, aluminum oxide and titanium dioxide. The amount of effective metal on the carrier is preferably 3 to 300 pbw per 100 of the carrier material, preferably 10 to 80 pbw, especially in the range of 20 to 60 pbw. 13 200528554 If necessary, The catalyst may also contain one or more golds as promoters. Appropriately, "Metal Emulsions IIA, IIIB, IvB = agents may be selected from the Periodic Table of Elements # π ΠB IVB, VB and Claw Group, or W barium, Titanium, titanium, aluminum, titanium, titanium, aluminum, etc. are non-suitable accelerators. For the catalysts used for preparation, the best metal oxidant accelerators are emulsification and oxidation oxidation. Suitable for Section VII… " τ Shida's metal accelerators can be selected from Group β or VIII of the periodic table. Baht and Group VIII
f中以鉑和鈀為尤佳者。促進劑存在於催化劑中的、量°宜在 :二PbW載體有°·。1至1—，較佳為〇.!至40pbw， 更…至20 pbw的範圍内。最佳的促進劑係選自於釩、 在孟、銖、錯和鉑。In f, platinum and palladium are particularly preferred. The amount of the promoter present in the catalyst should preferably be in the range of: 2 for the PbW support. 1 to 1-, preferably in the range of 0.1 to 40 pbw, and more ... to 20 pbw. The best accelerators are selected from vanadium, Bangladesh, Baht, Co, and platinum.
〆催化上有效的金屬和促進劑，如果存纟，可藉由任何 、、处里例如次潰、捏合及擠壓，而被沉積於載體材 料上在金屬以及（若適當）促進劑沉積在載體材料上之 'I书使、座凌載的載體接受煅燒。煅燒處理的作用是要 除去結晶水、分解揮發性分解產物及將有機和無機化合物 轉化成其個別的氧化物。在煅燒之後，所得催化劑可經由 使催化糾與氫或含氫氣體接觸而予以活化，通常在約2 〇 〇 至350。(：的溫度進行。其他製備費雪-托崔催化劑的方法包 括捏和/研糊，通常接著擠壓、乾燥/煅燒及活化。 催化轉化方法可在此技藝中已知的習知合成條件下進 仃。通常，催化轉化可在150至300°C，較佳從180至260°C 範圍内的溫度進行。催化轉化方法的典型總壓力係在1至 14 200528554 200絕對巴，更佳從1〇至7〇絕對巴的範圍内。在催化轉化 方法中，尤其有超過75重量％的C5+，較佳超過85重量％ CW烴類形成。視催化劑與轉化條件而定，重質蠟的 量可高達60重量％，有時高達70重量％，有時甚至高達 85重量％。最好是使用鈷催化劑，使用低的H2/c〇比（尤 其疋1· 7或甚至更低者），並使用低溫（19〇 —24〇〇C)，視 而要與咼壓結合。為避免任何焦炭生成，最好使用至少〇 · 3 的h/CO比。尤佳的是在下述條件下進行費雪—托崔反應： ASF-α值（Anderson-Schulz-Flory鏈生長因子），就所獲 籲 付具有至少2 0個碳原子的產物而言，為至少〇 . g 2 5，較佳 為至少0.935,更佳為至少〇·945,甚至更佳為至少〇955。 較佳的疋，費雪-托崔烴類物流包含至少重量％ ，較 佳為50重量％，更佳為55重量％，且重量比C6Q + /C^+為至 少0.35，較佳為〇·45，更佳為〇.55。 較佳而言，係使用費雪-托崔，其產生實質量的鏈烷 烴，更佳為貫質上無分支的鏈烷烴。最適合此目的的催化 劑為含鈷費雪-托崔催化劑。這類催化劑係敘述於文獻中，鲁 例如參見 AU 698392 and WO 99/34917。 費雪-托崔方法可為淤漿FT方法或固定床FT方法，尤 其是多管式固定床。 鍵烧煙產物可自剛在步驟（e)中獲得之產物直接藉由 蒸餾而離析得到。較佳的是，這種餾份係先經氫化，以便 除去任何會負面影響所得用作蒸汽裂解器原料之摻合物性 質的烤煙及氧化產物。鏈烷烴產物亦可自加氫裂解步驟的 15 200528554 流出物中離析出來，如對於剛在步驟（d)中所獲得產物的整 月豆或。卩分上所執行者。這種鏈烧烴產物將包含較大含量的 異鏈烷烴。較佳的是，鏈烷烴產物中的異對正比係小於 〇. 5，較佳為小於〇. 3。〆 Catalytically effective metals and promoters, if present, can be deposited on the support material by any, or any such as secondary collapse, kneading, and extrusion. The metal and (if appropriate) promoters are deposited on the support. The 'I book' on the material allows the carrier contained in the block to be calcined. The role of the calcination process is to remove crystal water, decompose volatile decomposition products, and convert organic and inorganic compounds into their individual oxides. After calcination, the resulting catalyst may be activated by contacting the catalytic converter with hydrogen or a hydrogen-containing gas, typically between about 2000 and 350. (: Temperature is carried out. Other methods for preparing Fisher-Tropsch catalysts include kneading / pulverizing, usually followed by extrusion, drying / calcination, and activation. Catalytic conversion methods can be performed under conventional synthetic conditions known in the art In general, the catalytic conversion can be carried out at a temperature in the range of 150 to 300 ° C, preferably from 180 to 260 ° C. The typical total pressure of the catalytic conversion method is 1 to 14 200528554 200 absolute bar, more preferably from 1 Within the range of 0 to 70 absolute bar. In the catalytic conversion process, more than 75% by weight of C5 +, preferably more than 85% by weight of CW hydrocarbons are formed. Depending on the catalyst and conversion conditions, the amount of heavy wax may be Up to 60% by weight, sometimes up to 70% by weight, sometimes even up to 85% by weight. It is best to use a cobalt catalyst, use a low H2 / c0 ratio (especially 疋 1.7 or even lower), and use Low temperature (190-200 ° C), depending on the combination of pressure and pressure. To avoid any coke formation, it is best to use an h / CO ratio of at least 0.3. It is particularly preferable to perform Fisher under the following conditions— TOCRY response: ASF-α value (Anderson-Schulz-Flory chain growth factor ), In the case of products which have been appealed to have at least 20 carbon atoms, it is at least 0. 25, preferably at least 0.935, more preferably at least 0.945, and even more preferably at least 0955. Preferably, the Fischer-Tropsch hydrocarbon stream contains at least wt%, preferably 50 wt%, more preferably 55 wt%, and a weight ratio C6Q + / C ^ + of at least 0.35, preferably 0.45. , More preferably 0.55. More preferably, it uses Fisher-Tropsch, which produces a real mass of paraffin, more preferably a paraffin without branch. The catalyst most suitable for this purpose is cobalt-containing Fischer-Tropsch catalysts. Such catalysts are described in the literature, see for example AU 698392 and WO 99/34917. The Fischer-Tropsch process can be a slurry FT process or a fixed bed FT process, especially a multi-tubular process Fixed bed. The key-burned tobacco product can be isolated from the product just obtained in step (e) by distillation directly. Preferably, this fraction is first hydrogenated in order to remove any negatively affected products. Flue-cured tobacco and oxidation products of blended nature of steam cracker raw materials. Paraffin products can also be self-hydrogenated 15 200528554 of the solution step is isolated, such as for the whole moon beans or the product obtained in step (d). The chain burned hydrocarbon product will contain a larger content of hetero chains 3。 Alkanes, preferably, the parity ratio in the paraffin product is less than 0.5, preferably less than 0.3.
鍵烧煙產物較佳係包含超過90重量％的C5至在370°C 沸騰的化合物。更佳的是，鏈烷烴產物在輕油範圍内沸騰， 較佳包含超過90重量％從Cs開始之化合物及高達於2〇4〇c 沸騰的化合物。 鏈烷烴產物係在步驟（e)中與剛在步驟（b)中獲得的液鲁 =冷凝餾份合併。步驟（d)產物對步驟（b)產物的重量比較 佳係在30: 1和5:丨之間。所得摻合物較佳具有下列性質： 比重在〇· 65與〇· 74之間， 賽波特色度（Col〇ur Saybol t )超過+ 20， 不飽和物< 1體積％， 鍵燒煙含量在65%與1〇〇體積％之間。 異一正鏈烷烴比小於0. 5， 硫含ϊ在50與650 ppm之間，較佳在1〇〇與65〇 ppm φ 之間， 最終沸點在150與204%之間，以及 • 8 C %的雷德（Re丨d)蒸氣壓不超過^ i。 本^明亦針對藉由根據本發明之方法獲得的摻合物作 ί蒸汽裂解器原料來製造低級稀煙，尤其是丙稀及/或乙稀 的用途。 圖1說明根據本發明的方法。從高硫天然氣U，在未 16 200528554 蒸發液滴捕收器1中分離出現場冷凝物1 2。該現場冷凝物 1 2係在分離器2中分離成低沸點餾份13和高沸點顧份j 4。 I留份14係供應到選用的冷凝物精煉器3中。硫係在薩非努 爾（Sul finol )單元4中自天然氣15中除去，其在冷凝物 中很少。Ce烴類1 7係在分離單元5中自少硫氣體j 6中分 離出來。烴類17係進一步藉由蒸餾單元6分成（^與Q物流 1 9和主要含C5 +烴類的物流18。 淨化的氣體20係用於合成氣製造單元7中以獲得人成 氣21。此合成氣21係用作費雪一托崔反應步驟8中的原料，籲 於該步驟中獲得鏈烷烴類產物22。此產物係在分離器9中 分離成各種不同餾份，其係在輕油餾份24以下沸騰（餾份 23)和以上沸騰（餾份25和26 )。此輕油餾份24係與餾 份1 3和18在混合單元1 〇中混合，以獲得根據本發明較佳 具體實例的蒸汽裂解器原料27。 【圖式簡單說明】 圖1說明根據本發明的方法。 【主要元件符號說明】 鲁 1 未蒸發燃料液滴捕收器 2 分離器 3 冷凝物精煉器 4 薩非努爾（Sul f inol )單元 5 分離單元 6 蒸館單元 7 合成器製造單元 17 200528554 8 費雪-托崔反應步驟 9 分離器 1〇混合單元 11 高硫天然氣 12 現場冷凝物 13 低沸點餾份 14 高沸點餾份 15 天然氣 16 氣體 17 C3 +烴類 18 主要含C5 +烴類的物流18 19 C3與C4物流 20 淨化的氣體 21 合成氣 2 2 鏈烷烴產物 23 在輕油餾份2 4以下沸騰的餾份 2 4 輕油餾份 25 在輕油餾份2 4以上沸騰的餾份 26 在輕油餾份2 4以上沸騰的餾份 27 蒸汽裂解器原料 18The bonded soot product preferably contains more than 90% by weight of C5 to a compound that boils at 370 ° C. More preferably, the paraffinic product boils in the light oil range, preferably containing more than 90% by weight of compounds starting from Cs and compounds boiling up to 2400c. The paraffin product is combined in step (e) with the liquid condensate fraction just obtained in step (b). The weight of the product of step (d) to the product of step (b) is preferably between 30: 1 and 5: 丨. The resulting blend preferably has the following properties: Specific gravity between 0.65 and 0.74, Colbo Saybolt over + 20, Unsaturates < 1% by volume, Bonded smoke content Between 65% and 100% by volume. Iso-n-paraffin ratio is less than 0.5, sulfur content is between 50 and 650 ppm, preferably between 100 and 65 ppm φ, final boiling point is between 150 and 204%, and • 8 C % Reid vapor pressure does not exceed ^ i. The present invention is also directed to the use of the blend obtained by the method of the present invention as a raw material for steam crackers to produce low-grade thin smoke, especially acrylic and / or ethylene. Figure 1 illustrates a method according to the invention. Field condensate 12 was separated from the high-sulfur natural gas U in the evaporative droplet trap 1 in 2005 200528554. The on-site condensate 1 2 is separated into a low-boiling fraction 13 and a high-boiling fraction j 4 in the separator 2. The I fraction 14 is supplied to the optional condensate refiner 3. The sulfur system is removed from the natural gas 15 in the Sul finol unit 4 and it is rarely present in the condensate. Ce hydrocarbons 17 are separated from the sulfur-free gas j 6 in the separation unit 5. The hydrocarbon 17 series is further divided by the distillation unit 6 (^ and Q stream 19, and the stream mainly containing C5 + hydrocarbons. The purified gas 20 is used in the synthesis gas production unit 7 to obtain human-made gas 21. This Syngas 21 is used as the raw material in the Fisher-Tropsch reaction step 8. In this step, paraffin products 22 are obtained. This product is separated into various fractions in a separator 9, which is contained in light oil. Boiling below fraction 24 (fraction 23) and above (fractions 25 and 26). This light oil fraction 24 is mixed with fractions 13 and 18 in a mixing unit 10 to obtain a better quality according to the present invention. Specific example of steam cracker raw material 27. [Simplified illustration of the figure] Figure 1 illustrates the method according to the present invention. [Description of the symbols of the main elements] Lu 1 Unevaporated fuel droplet collector 2 Separator 3 Condensate refiner 4 Sa Sul f inol unit 5 Separation unit 6 Steaming hall unit 7 Synthesizer manufacturing unit 17 200528554 8 Fisher-Tropsch reaction step 9 Separator 1 10 Mixing unit 11 High sulfur natural gas 12 On-site condensate 13 Low boiling point distillation Portions 14 High-boiling fractions 15 Natural gas 16 Gas 17 C3 + hydrocarbons 18 Streams containing mainly C5 + hydrocarbons 18 19 C3 and C4 streams 20 Purified gases 21 Syngas 2 2 Paraffin products 23 Distillates boiling below 2 4 Light oil fractions 25 Fractions boiling above 4 in light oil fractions 26 Fractions boiling above 4 in light oil fractions 2 Fractions boiling above 4 in light oil fraction 27 Steam cracker feedstock 18