200940171 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於在固態觸媒上之吸熱氣相反應之 反應器及利用該反應器之方法。該反應器尤其適合用於催 化重整及碳氫化合物脫氫反應。 本發明係關於一種反應器，其可從受壓燃燒氣體中回收 熱量並將其用於反應。 該方法利用一受壓燃燒氣體藉由在該反應器内的間接熱 交換來加熱該反應器。 【先前技術】 建其活性來迫使其週期性再生。 劇。從而，於一低壓時產量較佳。 時’焦化程度較高。 重汽油餾份（80-180°C)主要包括C6至Cw碳氫化合物，其 衍生自石油的最初蒸餾產物’該重汽油餾份通常被加工以 使其辛烷值達至一較高值以用於一機動車輛引擎。該催化 重整方法可實行該操作。該方法由在氫存在時在包含貴金 屬之觸媒上於一高溫（接近5〇〇。(〕）使該汽油餾分通過所組 成。該催化重整反應主要由使存在於進料中的環烷與石蠟 脫氫以將其轉化為具有一高辛烷值的芳香族化合物及使該 等殘留石蠟異構化以額外增加該汽油之辛烷值所組成。一 第一有害反應為裂化，其產出輕質碳氫化合物如曱烷、 乙烷、丙烷與丁烷，且其降低該操作之產量。一第二有害 反應為觸媒焦化’其降低該觸媒活性並藉由燃燒焦炭以重 。裂化隨壓力的遞增而加 °然而’當氫之分壓較低 136573.doc 200940171 於高壓（約15至30巴）操作之老式單元具有一高氫回收 率，獲得中等產量，且在該觸媒必須被再生前可操作約11 個月。 連續觸媒再生單元能使所有觸媒在數天内再生以允許低 壓操作（約3至5巴），且從而提高產量。該觸媒在該等徑向 型的反應器内連續移動並被送至一再生段以在其該處再生 後送回至該第一反應器《脫氫反應為高度吸熱且當溫度過 低時該反應停止。當前的方法通常包括三或四個反應器及200940171 IX. Description of the Invention: [Technical Field] The present invention relates to a reactor for an endothermic gas phase reaction on a solid state catalyst and a method of using the same. The reactor is particularly suitable for use in catalytic reforming and hydrocarbon dehydrogenation reactions. The present invention relates to a reactor which recovers heat from a pressurized combustion gas and uses it for the reaction. The method utilizes a pressurized combustion gas to heat the reactor by indirect heat exchange within the reactor. [Prior Art] The activity was built to force it to periodically regenerate. drama. Thus, the yield is better at a low pressure. The degree of coking is higher. The heavy gasoline fraction (80-180 ° C) mainly comprises a C6 to Cw hydrocarbon derived from the initial distillation product of petroleum 'the heavy gasoline fraction is usually processed to bring its octane number to a higher value Used in a motor vehicle engine. This catalytic reforming method can perform this operation. The process consists of passing a gasoline fraction at a high temperature (close to 5 Torr.) on a catalyst comprising a noble metal in the presence of hydrogen. The catalytic reforming reaction is mainly carried out by a naphthenic acid present in the feed. Dehydrogenation with paraffin to convert it to an aromatic compound having a high octane number and isomerization of the residual paraffin to additionally increase the octane number of the gasoline. A first adverse reaction is cracking, which produces Light hydrocarbons such as decane, ethane, propane and butane are available and which reduce the yield of the operation. A second deleterious reaction is catalyst coking, which reduces the activity of the catalyst and is heavier by burning coke. Cracking increases with increasing pressure. However, 'when the hydrogen partial pressure is lower 136573.doc 200940171 The old unit operating at high pressure (about 15 to 30 bar) has a high hydrogen recovery rate, achieving medium yield, and in the catalyst It must be operated for about 11 months before being regenerated. The continuous catalyst regeneration unit enables all catalysts to be regenerated in a few days to allow low pressure operation (about 3 to 5 bar) and thus increase throughput. The catalyst is in these radial directions. Continuous reactor And sent to a regeneration section to be returned to the first reactor after regeneration there. "The dehydrogenation reaction is highly endothermic and the reaction stops when the temperature is too low. Current methods usually involve three or four reactions. And
相同量的串聯熔爐。每一熔爐接著一反應器。由於高溫， 該熔爐產量較低，且通常產生蒸汽以改進該熔爐之總產 量。通常利用該蒸汽開動一渦輪，其驅動該回收壓縮機與 該氫輸出壓縮機。近來，更普遍的係利用一變速電動馬達 用於該等壓縮機，及更少的蒸汽被用於現代化煉油廒，其 出於經濟原因更趨向利用電。由於該原因，產生蒸汽的大 號熔爐的利用及其相關操作與維護問題現今被視作該方法 之一缺點。 如長鏈石蠟脫氫作用之其他碳氫化合物脫氫方法係利用 一種與催化重整相同的方法且遭受到相同問題。 【發明内容】 本發明係關於一種用於催化重整或碳氫化合物脫氫作用 之反應器’其具有沿一垂直軸之一圓柱外形；一上端頂部 及下方底邛，其包括至少二個以該垂直轴為中心之環形 區域，该二個環形區域為一稱為催化區域之區域及一稱為 交換區域之區域。垂直密封板將該反應器分成數部分，該 136573.doc 200940171 等部分之每一個都包括至少一個交換段及至少一個催化 段’該等交換段之全體形成該交換區域，且該等催化段之 全體形成該催化區域。 本發明亦關於利用本發明之反應器之方法。 為了加熱該反應器’較佳為一重整反應器，本發明通常 利用受壓燃燒氣體，其意味著可產生電力供用於催化重整 單元且可能用於其他單元。通常運用一具有特定内部裝置 的單一反應器，其意味著藉由與該燃燒氣體交換以進行加 熱的该等段可被該等絕熱催化段代替，該觸媒可在重力作 用下於該反應器内移動。從而可降低該單元之總覆蓋區、 設備之數量及該反應段之成本。 如果該反應器尺寸過大，那麼在極大容量的情況下，此 類型的數個反應器可較佳地平行存在。然後，每一反應器 通常供應有一專用空氣壓縮機與一專用火爐。 【實施方式】 在本文中，1巴相當於0.1 MPa。 本發明係關於一種用於在氣相時實行一吸熱氣相反應之 反應器，其具有沿一垂直軸之一圓柱外形且包括： •至少二個以該垂直軸為中心之環形區域：一催化區域 及一交換區域； •位於沿該圓柱反應器之半徑之垂直密封板65，其將該 反應器分成數部分’該等部分之每一個都包括至少一 個交換段61及至少一個催化段62，該等交換段之全體 形成該交換區域204 ’且該等催化段之全體形成該催 136573.doc 200940171 化區域202。 在本發明之上下文中，該第一部分被定義為該反應器被 供應有反應混合物之部分。該等其他部分被稱為第二部 分、第二部分直至最後部分’其中該反應混合物在該反應 器内依照該順序移動’。作為一實例，在4個部分的情況 下，於該第一部分該反應混合物被供應至該反應器。然 後’在該反應混合物接著依序從該第一1部分移動到該第二 部分，然後到該第三部分然後到該最後部分之後，被排出 〇 於該反應器。 在一較佳執行中，該催化區域與該交換區域依序從該邊 緣朝向該反應器之中心。 在一較佳執行中’以該垂直轴為中心之至少四個環形區 域依序從該邊緣朝向該反應器之中心，亦即稱為該供應區 域之一第一區域201、稱為該催化區域之一第二區域2〇2、 稱為該收集區域之一第三區域203及稱為該交換區域之一 第四區域204。在此變化中’將該反應器分成數部分之該 ® 等垂直密封板65係沿一中央圓柱區域2〇5而固定。通常， 該等部分之每一個都包括一交換段61、一催化段62、一供 ' 應段161及一收集段162，該等交換段之全體形成該交換區 .域204，該等催化段之全體形成該催化區域2〇2，該等供應 段之全體形成該供應區域201，且該等收集段之全體形成 該收集區域203。通常’該反應器包括一上端頂部與一下 方底部。通常每段有至少一導管163經過該反應器之上端 頂部以將觸媒供應入該等催化段，且每段有至少一導管 136573.doc 200940171 263經過該反應器之下方底部以將觸媒排出該等催化段。 通常，一通過該反應器之該上端頂部之供應管道17可將反 應混合物供應入一部分（其被表示為該第一部分），一通過 該反應器之該上端頂部之排出管道18可將反應混合物排出 該反應器之最後部分。通常存在一管道67，其將該最後部 分之該收集區域連接至該管道18以便排出該反應混合物。 在此相同變化中’一通過該反應器之該下方底部之入口管 道6被連接至通向管狀腔室71之管道70。該等管狀腔室藉 由管狀板69經由該反應器之底部將燃燒氣體分配至每一交 換段中。管狀腔室72可從每一交換段之頂部收集燃燒氣 體，然後設有膨脹風箱74之管道73可向通過該反應器之上 端頂部的該出口管道7排出該燃燒氣體。 通常’每一交換段係由管式交換器或板式交換器組成。 每一父換段具有一相同的表面積，或該表面積從該第一交 換段向該最後交換段遞增。 通常，每一催化段係由二個同心金屬網形成，較佳為 「強生網（Johnson screen)」型。通常，所有催化段具有相 同的尺寸或該等催化段之尺寸從該第一部分向該最後部分 遞增。 該等垂直密封板65通常將該反應器分成3、4、6或8個部 分，較佳為4或6個部分。 在一高度較佳實施例中，一管道（64)將每一部分之該收 集段連接至下一部分之該交換段，但該最後部分除外。 本發明亦關於用於在一依照本發明之反應器内實行—催 136573.doc -10- 200940171 化重整反應或碳氫化合物脫氫反應之方法。 本發明亦關於一種用於在一反應器之固體觸媒上實行一 吸熱氣相催化重整或碳氫化合物脫氫反應之方法，其係依 照本發明之一高度較佳實施例，其中該反應混合物經由該 管道17進入該反應器然後在該第一交換段61中從頂部向底 部移動。該反應混合物接著通過於該觸媒下行導管236之 f 間之該第一催化段62之下，然後徑向通過該第_催化段 62，從該供應區域201通到該反應器之收集區域2〇3，經由 © 該管道64通到該第二部分之該交換段。最終，該反應混合 物在該下個交換段與該下個催化段中以依序且交替方式移 動。 通常，該觸媒在所有催化段内以相同的速率從頂部向底 部移動。該觸媒可以一速率從頂部向底部移動，該速率從 該第一催化段向該最後催化段遞增。 本發明亦關於藉由間接熱交換利用受壓燃燒氣體加熱該 反應混合物之方法。 在燃燒氣體生產之一第一變化例中，經由該管道6供應 6玄反應益60之燃燒氣體衍生自於·—大氣壓之熱空氣，其經 - 由線1向一空氣壓縮機2移動然後經由線3向一燃燒腔室4移 動，其中經由線5移動之可燃氣體之燃燒可將該燃燒氣體 加熱至600°C至800°C的範圍内之溫度，較佳在650°C至 750°C的範圍内。 在燃燒氣體生產之一第二變化例中，經由該管道6供應 該反應器60之燃燒氣體衍生自於一大氣壓之熱空氣，其經 136573.doc 200940171 由線1向一空氣壓縮機2移動然後經由線3向一燃燒腔室4移 動，其中經由線5移動之可燃氣體之燃燒可加熱該燃燒氣 體，其接著通過一膨脹渦輪12，該膨脹渦輪12在該空氣壓 縮機之相同軸上並提供必需的動力用於壓縮；離開該膨脹 渦輪12之該燃燒氣體壓力係於〇.2至〇 45 MPa範圍，及溫度 於600 C至800 C之範圍且較佳於650°C至750°C之範圍。 在各該二個燃燒氣體生產變化例中，經由該管道7離開 該反應器之該燃燒氣體可在其被送至一渦輪式膨脹機1〇以 生產電力前於一燃燒腔室8中被再加熱。 圖1描述對該反應器供熱之其中一種方式。大氣經由線1 被供應至一空氣壓縮機2。該空氣被壓縮至一接近絕對4巴 (0.4 MPa)之壓力且然後經由線3被送至一燃燒腔室4。經由 線5供應一可燃氣體用於在該燃燒腔室4内燃燒。藉由於一 接近700°C之溫度之燃燒而加熱之損耗空氣經由線6被送至 反應器60。 該反應混合物經由線1 7進入及經由線1 8離開。該燃燒氣 體藉由與經歷一吸熱催化重整反應之該反應混合物進行交 換而冷卻。 於該反應器出口，該冷卻氣體經由線7被送至一第二燃 燒腔室8’於此其藉由經由線9而被供應之可燃氣體之燃燒 而被再加熱。於該燃燒腔室之出口，該高溫氣體於接近 750°C之一溫度被送至一驅動交流發電機11以生產電力之 渦輪式膨脹機10。 圖2描述對該反應器60供熱之一另外方式。大氣經由線i 136573.doc -12- 200940171 被供應至一空氣壓縮機2。被壓縮至一接近20巴之壓力之 該空氣接著經由線3被送至燃燒腔室4。經由線5供應一可 燃氣體用於在該燃燒腔室4内燃燒。藉由燃燒至一接近 1300C之溫度而加熱之該彳貝耗空氣被送至一驅動該空氣壓 縮機2之渦輪式膨脹機12。於該渦輪出口之氣體約為3巴且 溫度接近70(TC。其經由線6被送至反應器60。 該反應混合物經由線1 7進入及經由線1 8離開。該燃燒氣 體藉由與經歷一吸熱催化重整反應之該反應混合物進行交 換而冷卻。 於該反應器出口 ’該冷卻氣體經由線7被送至一第二燃 燒腔室8，於此其藉由經由線9而被供應之可燃氣體之燃燒 而被再加熱。於該燃燒腔室之出口，該高溫氣體於接近 750 C之溫度被送至一驅動交流發電機丨丨以生產電力之渴 輪式膨服機10。 圖3描述圖1之一變化例，其中從於該渦輪1〇之出口之經 由線40移動之高溫氣體回收熱量。該交換器41可藉由以下 ❹回收熱量： •藉由生產可用於煉油廠或生產電力之蒸汽； •或藉由加熱一熱傳流體（熱油），其例如可用於使該 方法之塔再次沸騰。 Λ 從該父換器41流出的汽油經由線42移動。 明顯地，此變化例在圖2之情況下亦可為相同方式（未顯 示）。 圖4顯示依照本發明之一催化重整段之該反應段。 136573.doc -13- 200940171 該燃燒氣體經由線6進入該反應器60及經由線7離開。 該進料經由線14到達一進料泵15。該進料從該泵出口經 由線16被送至該熱交換器19，其較佳為？狀]<：丨11〇\型。 經由線26移動之該回收氣體也被送至該交換器19用於與 在該交換器内經由線16移動之該進料混合，且藉由與經由 線1 8離開該反應器60之反應混合物進行交換而被加熱至接 近440C之溫度。於該熱交換器19之出口，該反應混合物 經由線17被送至該反應器60。經由線18離開該反應器之該 反應混合物約為490°C並被送至該熱交換器19之頂部，此 處其被冷卻至約100°C。於該熱交換器19之出口，該流出 物經由線20被送至一熱交換器21，此處其藉由與空氣或冷 卻水進行熱交換而被冷卻。於該交換器21之出口，該冷卻 及部分濃縮之流出物經由線22被送至一分離槽23。來自該 槽之液體經由線28被排出至一穩定段。主要由氫組成的該 分離槽24之部分氣相被用於構成一氣體循環，其藉由壓縮 機25而被壓縮然後經由線26移動，該剩餘物經由線27被送 至一純化段。 圖5、6、7與8顯不該反應|§之一較佳變化例之不同段。 圖5圖示顯示該反應器60之橫截面側視圖。 以該垂直軸為中心之四個環形區域依序從該邊緣朝向該 反應器之中心’即稱為該供應區域之一第一區域（可見於 圖6’參考數字2〇1)、稱為該催化區域之一第二區域（可見 於圖ό，參考數字202)、稱為該收集區域之一第三區域（可 見於圖6，參考數字203)及稱為該交換區域之一第四區域 136573.doc -14- 200940171 (可見於圖6，參考數字204)。 垂直密封板（可見於圖6，參考數字65)被固定於該圓柱 中央區域（可見於圖6,參考數字205)上並將該反應器分成 數部分。 每一部分都包括一交換段61及一催化段62。該等交換段 之全體形成該交換區域204及該等催化段之全體形成該催 化區域202。每一部分都包括一供應段161及一收集段 162。該等供應段之全體形成該供應區域2〇ι，且該等收集 Φ 段之全體形成該收集區域203。 該燃燒氣體在該反應器内從底部移動到頂部。燃燒氣體 經由通過該入口管道6之該反應器之底部而被供應然後經 由管道70再經由管狀腔室71而被分配至每一交換段中，之 後經由管狀板69被分配到管99中。於該等管之出口，該燃 燒氣體從該反應器之頂部被收集至管狀腔室72中然後經由 設有膨脹風箱74之管道73而被送至該出口管道7。 該反應混合物依序通過所有部分。該反應混合物經由該 管道17進入且於該最後部分之該收集段其經由該管道 (可見於圖6，參考数字67)收集然後經由該管道_開該反 應器。 包括氫與碳氫化合物之該反應混合物之移動係以該等箭 頭表示。 該反應器入口之Μ力為約4巴。該反應混合物經由該入 口 66進入該第一部分之該交換區域（參見箭頭ι〇ι)。於此第 一部分，該反應混合物加熱同時隨一逆流（箭頭1〇2)下降至 136573.doc 15 200940171 該燃燒氣體及經由該出口 75離開該第一交換段。該氣體經 過於該觸媒下行導管263之間之該催化段62(箭頭103)下 方，沿該外殼上升並通過該催化段62(箭頭104)。由於存在 於該進料中的環烷快速反應並以一高度吸熱方式反應，所 以該反應混合物在該觸媒上快速反應及冷卻。 該第一觸媒段之出口溫度通常低於400°C。該反應混合 物然後從該反應器之頂部之該第一段被排出並經由一管道 (可見於圖6 ’數字64)被送至該第二段。該反應混合物在該 第二部分之該交換段中被再次加熱然後冷卻，其在該第二 部分之該催化段中發生反應。 隨著反應進程，越來越少的環烷殘留，該石蠟反應較慢 且放熱裂化部分補償其他反應之吸熱特性。於該等依序部 分之該反應混合物之出口與入口溫度曲線圖從而上升，其 被認為有利於產量。 與該最後部分之出口 ’該反應混合物藉由該管道（可見 於圖6’參考數字67)被收集然後被送至出口管道18。 圖ό顯示從該頂部觀察之該反應器並以分段顯示。 以該垂直軸為中心之四個環形區域依序從該邊緣朝向反 應器之中心為：該供應區域2〇1、該催化區域2〇2、該收集 區域203及該交換區域204。 垂直密封板65被固定於該中央圓柱區域2〇5上並將該反 應器分成8個部分。 該管道64允許存在從一部分至另一部分之通冑。該反應 混合物經由該入口 66進入該第一交換段。於該最後部分之 136573.doc •16· 200940171 出口 ’該反應混合物經由該管道67而被收集。 圖7代表從該反應器之中心觀察到的部分，其具有於前 面之二個相連交換段61、該管狀板69及於背後之該催化段 62 ’其具有觸媒下行導管163與263及該閉合板68。圖8顯 示從該外殼觀察到的相同部分，其具有於背後之該交換段 61、於前面之該催化段62、該交換段出口 75、從一部分至 另一部分之該通道64及一閉合板68。 實例 φ 本實例利用圖5至8所示之該反應器之構造。 考慮一催化重整單元每小時可處理60公噸含35公噸觸媒 之進料。 該進料為一 90-170°C餾份’其具有體積含量為60%之石 蠟、體積含量為25%之環烷及體積含量為15%之芳香族内 容物。 該純的氫/進料莫耳比率為2.5。 該目標辛烷值為102。 _ 該整個觸媒可在2·5天内被連續再生。 為向該反應供熱約 75.24xl06 kJ/h(18xl06 kcal/h)，將 • 3 3 0公》頓空氣壓縮至絕對4巴。該離心空氣壓縮機具有一 80。/。之多方效率及消耗16.7 MW。該壓縮機出口處之溫度 為192 C。於該第一燃燒腔室，於15°C4160 kg/h之天然氣 以46439.8 kJ/kg(l 111〇 kcal/kg)之低熱值加以燃燒。該燃 燒腔室出口處之溫度為700。〇。於約700°C時，該燃燒氣體 經由管道6到達。 136573.doc 17 200940171 各個部分中的該入口及催化重整侧出口之溫度如下： 反應混合物 於450 C時’該反應混合物從該packinox進料_流出物交 換器到達該反應器。其係藉由與來自該第一部分之熱煙進 行交換而被加熱及於486°C時到達該第一部分之觸媒及然 後被送至該第二部分’於此其經加熱隨後被供應入該第二 部分。本實例中存在8個部分： 催化段1 :於4 8 6 °C時進入觸媒，於3 9 6 °C時離開； 催化段2 :於441 °C時進入觸媒，於419°C時離開； 催化段3 :於460°C時進入，於43 7°C時離開； 催化段4 :於475°C時進入，於451°C時離開； 催化段5 :於487°C時進入，於463°C時離開； 催化段6 :於497°C時進入，於475°C時離開； 催化段7 :於507°C時進入，於487°C時離開； 催化段8:於517°(：時進入，於5〇1°0：時離開（於絕對4.8 巴）。 燃燒氣想 第一交換段： 第二交換段： 第三交換段： 第四交換段： 第五交換段： 第六交換段： 第七交換段： 於700°C時進入 於700°C時進入 於700°C時進入 於700。(：時進入 於700°C時進入 於700°C時進入 於70CTC時進入 於471°C時離開 於422°C時離開 於442°C時離開 於460°C時離開 於472°C時離開 於483°C時離開 於494°C時離開 136573.doc -18- 200940171 第八交換段：於70CTC時進入，於505 °c時離開。 該燃燒氣體於其放出88198xl〇6 KJ/h(21.1 MM Kcal/h)至 該反應混合物之後，於469°C時離開該反應器。 該流出的燃燒氣體被送至一第二燃燒腔室，於此2560 kg/h之可燃氣體被燃燒以在一絕對3.4巴壓力下於該膨脹渦 輪之入口達到760°C。此渦輪具有一 85%之多方效率及提 供約26 MW之電力’其可驅動該空氣壓縮機及供應足夠的 電力用於該等催化重整與預處理單元。The same amount of tandem furnace. Each furnace is followed by a reactor. Due to the high temperatures, the furnace yield is low and steam is typically produced to improve the overall throughput of the furnace. The steam is typically utilized to actuate a turbine that drives the recovery compressor and the hydrogen output compressor. More recently, it has become more common to utilize a variable speed electric motor for such compressors, and less steam is used in modern refinery crucibles, which tend to utilize electricity for economic reasons. For this reason, the use of large furnaces that generate steam and their associated operation and maintenance issues are now considered to be a disadvantage of this approach. Other hydrocarbon dehydrogenation processes such as the dehydrogenation of long chain paraffins utilize the same method as catalytic reforming and suffer from the same problems. SUMMARY OF THE INVENTION The present invention relates to a reactor for catalytic reforming or hydrocarbon dehydrogenation having a cylindrical profile along a vertical axis; an upper end top and a lower bottom cymbal comprising at least two The vertical axis is a central annular region, and the two annular regions are a region called a catalytic region and a region called an exchange region. The vertical sealing plate divides the reactor into a plurality of portions, each of the portions 136573.doc 200940171 and the like including at least one exchange section and at least one catalytic section 'the entire exchange section forms the exchange area, and the catalytic sections are The entire catalytic region is formed. The invention also relates to a method of using the reactor of the invention. In order to heat the reactor' preferably a reforming reactor, the present invention generally utilizes pressurized combustion gases, which means that electrical power can be generated for use in the catalytic reforming unit and possibly for other units. A single reactor having a particular internal device is generally employed, which means that the segments that are heated by exchange with the combustion gases can be replaced by the adiabatic catalytic segments, which can be gravity-treated in the reactor Move inside. Thereby the total coverage area of the unit, the number of equipment and the cost of the reaction section can be reduced. If the reactor is oversized, then several reactors of this type may preferably be present in parallel in the case of very large capacities. Each reactor is then typically supplied with a dedicated air compressor and a dedicated furnace. [Embodiment] Herein, 1 bar is equivalent to 0.1 MPa. The present invention relates to a reactor for performing an endothermic gas phase reaction in a gas phase, having a cylindrical shape along a vertical axis and comprising: • at least two annular regions centered on the vertical axis: a catalysis a region and an exchange region; • a vertical sealing plate 65 located along the radius of the cylindrical reactor, which divides the reactor into portions. Each of the portions includes at least one exchange segment 61 and at least one catalytic segment 62, The entire exchange segment forms the exchange region 204' and the entirety of the catalytic segments form the urging 136573.doc 200940171 region 202. In the context of the present invention, the first portion is defined as the portion of the reactor to which the reaction mixture is supplied. These other portions are referred to as the second portion, the second portion until the last portion 'where the reaction mixture moves in the sequence in the reactor'. As an example, in the case of 4 parts, the reaction mixture is supplied to the reactor in the first part. The reaction mixture is then discharged from the first portion to the second portion, then to the third portion and then to the final portion, and is discharged to the reactor. In a preferred implementation, the catalytic zone and the exchange zone are sequentially directed from the edge toward the center of the reactor. In a preferred implementation, at least four annular regions centered on the vertical axis are sequentially directed from the edge toward the center of the reactor, also referred to as one of the supply regions, a first region 201, referred to as the catalytic region. One of the second regions 2, 2 is referred to as one of the collection regions, a third region 203, and a fourth region 204, which is referred to as one of the exchange regions. In this variation, the reactor is divided into a plurality of sections, and the vertical sealing plates 65 are fixed along a central cylindrical region 2〇5. Typically, each of the sections includes an exchange section 61, a catalytic section 62, a supply section 161 and a collection section 162, the entirety of the exchange sections forming the exchange zone. Domain 204, the catalytic segments The entire formation of the catalytic region 2〇2, the entirety of the supply segments form the supply region 201, and the entirety of the collection segments form the collection region 203. Typically, the reactor includes an upper top and a lower bottom. Typically, at least one conduit 163 per section passes through the top of the upper end of the reactor to supply the catalyst to the catalytic sections, and each section has at least one conduit 136573.doc 200940171 263 passing through the lower bottom of the reactor to discharge the catalyst The catalytic segments. Typically, a supply conduit 17 through the top of the upper end of the reactor supplies a portion of the reaction mixture (which is referred to as the first portion), and a reaction mixture through the top of the upper end of the reactor discharges the reaction mixture. The last part of the reactor. There is typically a conduit 67 which connects the collection portion of the last portion to the conduit 18 for discharging the reaction mixture. In this same variation, the inlet conduit 6 through the lower bottom of the reactor is connected to the conduit 70 leading to the tubular chamber 71. The tubular chambers distribute combustion gases into each of the exchange sections via the tubular plate 69 via the bottom of the reactor. The tubular chamber 72 collects combustion gases from the top of each exchange section, and then a conduit 73 provided with an expansion bellows 74 discharges the combustion gases to the outlet conduit 7 through the top of the upper end of the reactor. Usually 'each exchange segment consists of a tubular exchanger or a plate exchanger. Each parent segment has an identical surface area, or the surface area is incremented from the first switching segment to the last segment. Typically, each catalytic section is formed from two concentric metal meshes, preferably a "Johnson screen" type. Typically, all of the catalytic segments have the same size or the size of the catalytic segments increases from the first portion to the last portion. The vertical sealing plates 65 typically divide the reactor into 3, 4, 6 or 8 sections, preferably 4 or 6 sections. In a highly preferred embodiment, a conduit (64) connects the collection section of each section to the exchange section of the next section, except for the last section. The invention also relates to a process for carrying out a reforming reaction or a hydrocarbon dehydrogenation reaction in a reactor according to the invention. The invention also relates to a method for performing an endothermic gas phase catalytic reforming or hydrocarbon dehydrogenation reaction on a solid catalyst of a reactor, in accordance with a highly preferred embodiment of the invention wherein the reaction The mixture enters the reactor via the conduit 17 and then moves from top to bottom in the first exchange section 61. The reaction mixture then passes under the first catalytic section 62 between the catalyst downcomers 236 and then radially through the first catalytic section 62 from the supply zone 201 to the collection zone 2 of the reactor. 〇3, via the pipe 64 to the exchange section of the second part. Finally, the reaction mixture moves in a sequential and alternating manner in the next exchange section and the next catalytic section. Typically, the catalyst moves from top to bottom at the same rate throughout all catalytic stages. The catalyst can be moved from top to bottom at a rate that increases from the first catalytic segment to the last catalytic segment. The invention also relates to a method of heating a reaction mixture by means of a pressurized combustion gas by indirect heat exchange. In a first variation of combustion gas production, the combustion gas supplied via the conduit 6 is derived from hot air of atmospheric pressure, which is moved by line 1 to an air compressor 2 and then via The line 3 moves toward a combustion chamber 4, wherein combustion of the combustible gas moving via the line 5 can heat the combustion gas to a temperature in the range of 600 ° C to 800 ° C, preferably 650 ° C to 750 ° C In the range. In a second variation of combustion gas production, the combustion gas supplied to the reactor 60 via the conduit 6 is derived from hot air at atmospheric pressure, which is moved from line 1 to an air compressor 2 via 136573.doc 200940171 and then Moving through a line 3 to a combustion chamber 4, wherein combustion of combustible gas moving via line 5 heats the combustion gas, which in turn passes through an expansion turbine 12 on the same axis of the air compressor and provides The necessary power is used for compression; the combustion gas pressure leaving the expansion turbine 12 is in the range of 〇.2 to 〇45 MPa, and the temperature is in the range of 600 C to 800 C and preferably 650 ° C to 750 ° C. range. In each of the two combustion gas production variations, the combustion gas exiting the reactor via the conduit 7 can be re-injected into a combustion chamber 8 before it is sent to a turboexpander 1 to produce electricity. heating. Figure 1 depicts one of the ways in which heat is supplied to the reactor. The atmosphere is supplied to an air compressor 2 via line 1. The air is compressed to a pressure of approximately 4 bar (0.4 MPa) and then sent via line 3 to a combustion chamber 4. A combustible gas is supplied via line 5 for combustion in the combustion chamber 4. The lost air heated by combustion at a temperature close to 700 °C is sent to the reactor 60 via line 6. The reaction mixture enters via line 17 and exits via line 18. The combustion gas is cooled by exchange with the reaction mixture undergoing an endothermic catalytic reforming reaction. At the outlet of the reactor, the cooling gas is sent via line 7 to a second combustion chamber 8' where it is reheated by combustion of the combustible gas supplied via line 9. At the outlet of the combustion chamber, the high temperature gas is sent to a turboexpander 10 that drives the alternator 11 to produce electricity at a temperature close to 750 °C. FIG. 2 depicts an additional manner of heating the reactor 60. The atmosphere is supplied to an air compressor 2 via line i 136573.doc -12- 200940171. The air, which is compressed to a pressure of approximately 20 bar, is then sent to the combustion chamber 4 via line 3. A combustible gas is supplied via line 5 for combustion in the combustion chamber 4. The mussel air consumed by being burned to a temperature close to 1300 C is sent to a turbo expander 12 that drives the air compressor 2. The gas at the turbine outlet is about 3 bar and the temperature is close to 70 (TC. It is sent via line 6 to reactor 60. The reaction mixture enters via line 17 and exits via line 18. The combustion gas is experienced and experienced. The reaction mixture of an endothermic catalytic reforming reaction is exchanged for cooling. At the outlet of the reactor, the cooling gas is sent via line 7 to a second combustion chamber 8, where it is supplied via line 9. The combustion of the combustible gas is reheated. At the outlet of the combustion chamber, the high temperature gas is sent to a thirsty wheel expander 10 that drives the alternator to produce electricity at a temperature of approximately 750 C. Figure 3 A variation of Figure 1 is described in which heat is recovered from the high temperature gas moving through the line 40 of the turbine 1 . The exchanger 41 can recover heat by: • can be used in a refinery or production by production Steam of electricity; or by heating a heat transfer fluid (hot oil) which can be used, for example, to boil the tower of the process again. 汽油 The gasoline flowing from the parent exchanger 41 moves via line 42. Obviously, this change Example in Figure 2 The same can be the case (not shown). Figure 4 shows the reaction zone of a catalytic reforming section according to one of the inventions. 136573.doc -13- 200940171 The combustion gas enters the reactor 60 via line 6 and via the line 7. The feed exits via line 14 to a feed pump 15. The feed is sent from the pump outlet via line 16 to the heat exchanger 19, which is preferably in the shape of <:丨11〇\ The recovered gas moved via line 26 is also sent to the exchanger 19 for mixing with the feed moving through the line 16 within the exchanger, and by reacting with the reactor 60 via line 18. The mixture is exchanged and heated to a temperature near 440 C. At the outlet of the heat exchanger 19, the reaction mixture is sent to the reactor 60 via line 17. The reaction mixture exiting the reactor via line 18 is about 490°. C is sent to the top of the heat exchanger 19 where it is cooled to about 100 ° C. At the outlet of the heat exchanger 19, the effluent is sent via line 20 to a heat exchanger 21, where It is cooled by heat exchange with air or cooling water. At the exit of the exchanger 21 The cooled and partially concentrated effluent is sent to a separation tank 23 via line 22. The liquid from the tank is discharged to a stabilizing section via line 28. A portion of the gas phase of the separation tank 24 consisting essentially of hydrogen is used. To form a gas cycle, which is compressed by compressor 25 and then moved via line 26, the remainder is sent via line 27 to a purification section. Figures 5, 6, 7 and 8 show no reaction | Different sections of a preferred variation. Figure 5 is a cross-sectional side view showing the reactor 60. The four annular regions centered on the vertical axis are sequentially directed from the edge toward the center of the reactor. a first region of the supply region (see Figure 6 'reference numeral 2〇1), a second region called the catalytic region (see Figure ό, reference numeral 202), called one of the collection regions The region (see Figure 6, reference numeral 203) and the fourth region 136573.doc -14- 200940171, which is referred to as one of the exchange regions (see Figure 6, reference numeral 204). A vertical sealing plate (see Figure 6, reference numeral 65) is attached to the central region of the cylinder (see Figure 6, reference numeral 205) and divides the reactor into portions. Each portion includes an exchange section 61 and a catalytic section 62. The entire exchange segment forms the exchange region 204 and the entirety of the catalytic segments to form the catalytic region 202. Each portion includes a supply section 161 and a collection section 162. The entire supply section forms the supply area 2〇, and the entire collection Φ section forms the collection area 203. The combustion gases move from the bottom to the top within the reactor. Combustion gases are supplied via the bottom of the reactor through the inlet conduit 6 and then distributed to each exchange section via conduit 70 and via tubular chamber 71, and thereafter distributed into tube 99 via tubular plate 69. At the outlet of the tubes, the combustion gases are collected from the top of the reactor into the tubular chamber 72 and then sent to the outlet conduit 7 via a conduit 73 provided with an expansion bellows 74. The reaction mixture passed through all the fractions in sequence. The reaction mixture enters via the conduit 17 and is collected at the last portion of the collection section via the conduit (see Figure 6, reference numeral 67) and then the reactor is opened via the conduit. The movement of the reaction mixture comprising hydrogen and hydrocarbons is indicated by the arrows. The reactor inlet has a force of about 4 bar. The reaction mixture enters the exchange zone of the first portion via the inlet 66 (see arrow ι〇ι). In this first part, the reaction mixture is heated while descending with a countercurrent (arrow 1〇2) to 136573.doc 15 200940171. The combustion gases exit the first exchange section via the outlet 75. The gas passes below the catalytic section 62 (arrow 103) between the catalyst downcomers 263, rises along the outer casing and passes through the catalytic section 62 (arrow 104). Since the naphthenic acid present in the feed reacts rapidly and reacts in a highly endothermic manner, the reaction mixture rapidly reacts and cools on the catalyst. The outlet temperature of the first catalyst section is typically below 400 °C. The reaction mixture is then discharged from the first section of the top of the reactor and sent to the second section via a conduit (visible in Figure 6 'number 64). The reaction mixture is again heated and then cooled in the exchange section of the second portion, which reacts in the catalytic section of the second portion. As the reaction progresses, less and less naphthenic remains, the paraffin wax reacts slowly and the exothermic cracking portion compensates for the endothermic properties of the other reactions. The exit and inlet temperature profiles of the reaction mixture in these sequential portions are thus increased, which is believed to be advantageous for yield. The reaction mixture with the last portion is collected by the conduit (see reference numeral 67 in Figure 6) and then sent to the outlet conduit 18. Figure ό shows the reactor as viewed from the top and is shown in segments. The four annular regions centered on the vertical axis are sequentially directed from the edge toward the center of the reactor: the supply region 2〇1, the catalytic region 2〇2, the collection region 203, and the exchange region 204. A vertical sealing plate 65 is fixed to the central cylindrical region 2〇5 and divides the reactor into eight portions. This conduit 64 allows for the presence of a pass from one portion to another. The reaction mixture enters the first exchange section via the inlet 66. In the last part, 136573.doc •16·200940171 exit 'The reaction mixture is collected via the conduit 67. Figure 7 represents a portion viewed from the center of the reactor having two front exchange sections 61, the tubular plate 69 and the catalytic section 62' behind it having catalyst downcomers 163 and 263 and The plate 68 is closed. Figure 8 shows the same portion as viewed from the outer casing with the exchange section 61 at the back, the catalytic section 62 at the front, the outlet 75 of the exchange section, the passage 64 from one portion to the other, and a closure plate 68. . EXAMPLE φ This example utilizes the configuration of the reactor shown in Figures 5-8. Consider a catalytic reforming unit that can process 60 metric tons of feed containing 35 metric tons of catalyst per hour. The feed was a 90-170 ° C fraction which had a 60% by volume paraffin, a 25% by volume naphthenes and a 15% by volume aromatic content. The pure hydrogen/feed molar ratio was 2.5. The target octane number is 102. _ The entire catalyst can be continuously regenerated in 2.5 days. To heat the reaction to approximately 75.24 x 106 kJ/h (18 x 106 kcal/h), the air pressure of • 3 3 0 is compressed to an absolute 4 bar. The centrifugal air compressor has an 80. /. The efficiency and consumption of 16.7 MW. The temperature at the exit of the compressor is 192 C. In the first combustion chamber, natural gas at 4160 kg/h at 15 ° C is burned at a low calorific value of 46439.8 kJ/kg (l 111 〇 kcal/kg). The temperature at the exit of the combustion chamber is 700. Hey. At about 700 ° C, the combustion gases arrive via conduit 6. 136573.doc 17 200940171 The temperature of the inlet and catalytic reforming side outlets in each section is as follows: The reaction mixture is at 450 C. The reaction mixture is passed from the packinox feed_effluent exchanger to the reactor. It is heated by the exchange with the hot smoke from the first portion and reaches the first portion of the catalyst at 486 ° C and then sent to the second portion 'where it is heated and then supplied to the the second part. There are 8 parts in this example: Catalytic section 1: Entering the catalyst at 4 8 6 °C, leaving at 3 9 ° °C; Catalytic section 2: Entering the catalyst at 441 °C, at 419 °C Leaving; Catalytic section 3: entering at 460 ° C, leaving at 43 7 ° C; Catalytic section 4: entering at 475 ° C, leaving at 451 ° C; Catalytic section 5: entering at 487 ° C, Leaving at 463 ° C; Catalytic section 6 : entering at 497 ° C, leaving at 475 ° C; Catalytic section 7 : entering at 507 ° C, leaving at 487 ° C; Catalytic section 8: at 517 ° (: Enter, leave at 5〇1°0: (absolute 4.8 bar). Combustion gas wants the first exchange segment: Second exchange segment: Third exchange segment: Fourth exchange segment: Fifth exchange segment: Six exchange segments: The seventh exchange segment: enters at 700 °C at 700 °C and enters 700 at 700 °C. (: enters at 700 °C and enters at 700 °C when entering 70CTC. Leave at 442 ° C when leaving at 422 ° C leaving at 442 ° C leaving at 460 ° C leaving at 472 ° C leaving at 483 ° C leaving at 494 ° C leaving 136573.doc -18- 200940171 Eight exchange segments: enter at 70CTC, Leaving at 505 ° C. The combustion gas leaves 88198 x 1 〇 6 KJ / h (21.1 MM Kcal / h) to the reaction mixture, leaving the reactor at 469 ° C. The effluent combustion gas is sent to A second combustion chamber where the 2560 kg/h combustible gas is combusted to reach 760 ° C at the inlet of the expansion turbine at an absolute pressure of 3.4 bar. The turbine has an efficiency of 85% and provides about 26 MW's power's can drive the air compressor and supply enough power for the catalytic reforming and pretreatment units.
於該渦輪出口，該氣態流出物在526。(：之溫度，其意味 著可藉由產生蒸汽來生產更多的電力，或一熱傳遞流體可 被再加熱’其可使該方法之塔（用於預處理及重整穩定之 氣提塔）再次沸騰。 在本實例中，於526°C與400。(：之間可得到48 〇7x1〇6 kJ/h(11.5 MM kcal/h)，其足夠用於該二個塔。 一交換表面係必需的’其約為4〇〇〇 m2，亦即，5〇〇 V 之8倍。這相當於350個30mm直徑及15瓜長之管的8倍。 本實例提供管式交換器以簡化計算，但本發明之範圍亦 包含利用其他類型的交換器，舉例而言，㈣峨型焊接 板式交換器，其可導致一更緊凑的構造。 5 B 一門々八诋文衮，其具有一間距P=38 mm。 於亡間距，需要-請125 m2(G.866xp2)之橫截面以覆蓋— 個官，及從而需約3.5 m2以覆蓋28〇〇個管。 藉由留下該中心之一 0.8 m古 值之通路並使該表面積辦 加I5%而將該分段列入考慮， 只θ 可應則對該整個交換區域，亦 136573.doc •19· 200940171 即，2.4 m直徑需要一 0.5 + 3 ·5χ1.15=4.5 m2之表面積。 該觸媒被安裝於一内徑為3.2 m及南接近14 m之環形區 域。存在35公噸觸媒，亦即，約50 m3，且從而存在3.6 m2 之催化區域（50/14)。該環形催化區域之外徑因此為3.85 m。 因此’自該外殼開始，每一部分包括： •—空白段（約60 cm); •在二個強生網或其等效物之間填充有觸媒之一段 (約 65 cm); •—自由段（約40 cm) ; ^ •—交換段（約80 cm) ’其填充有直徑為30 mm之垂直 管； •—中央自由段（半徑為約40 cm)。 如上之說明，為了安裝該等交換管與該觸媒，於係需要 一内徑為5·7瓜及高為約16.5 m之外殼。 於该第一部分產出的焦炭量很低且自一個部分至（下一） 部分而遞增，於該最後部分最高（若該觸媒在此部分内移 動2.5天，則焦炭為8%)。一個解決方法為使該觸媒在整個 ❹ 期間以相同速率進行循環，以於該反應器之出口混合該觸 媒以便將其送至再生器並將其再生為一混合物則該平均 焦炭含量僅約為4%，從而允許安全再生。 然而，這意味著於該第一部分之該觸媒在其為必需前被 再生=所以明顯較佳的係制定觸媒下行裝置之尺寸，使得 來自i等第。卩分之觸媒較慢下降，且來自該等最後部分 之觸媒較快下降。 136573.doc •20- 200940171 【圖式簡單說明】 圖1描述對該反應器供熱之其中一種方式。 圖2描述對該反應器60供熱之一另外方式。 圖3描述圖1之一變化例’其中從於該巧輪丨〇之出口之經 由線40移動之高溫氣體回收熱量。 圖4顯示依照本發明之一催化重整段之該反應段。 圖5圖示顯示該反應器6〇之橫截面側視圖。 圖6顯示從該頂部觀察之該反應器並以分段顯示。 圖7代表從該反應器之中心觀察到的部分。 圖8顯示從該外殼觀察到的相同部分。 【主要元件符號說明】 2 空氣壓縮機 4 燃燒腔室 6 入口管道 7 出口管道 8 燃燒腔室 10 渦輪式膨脹機 11 交流發電機 12 膨脹渦輪 15 進料泵 17 供應管道 18 排出管道 19 熱交換器 21 熱交換器 136573.doc <21 - 200940171 23 分離槽 24 分離槽 25 壓縮機 60 反應器 61 交換段 62 催化段 64 管道 65 垂直密封板 66 入口 67 管道 68 閉合板 69 管狀板 70 管道 71 管狀腔室 72 管狀腔室 73 管道 74 膨脹風箱 75 出口 99 管 101 箭頭 102 箭頭 103 箭頭 104 箭頭 161 供應段 136573.doc 200940171 162 163 201 202 203 204 205 263 ❿ 收集段 導管 供應區域 催化區域 收集區域 交換區域 中央圓柱區域 導管At the turbine outlet, the gaseous effluent is at 526. (: temperature, which means that more electricity can be produced by generating steam, or a heat transfer fluid can be reheated. 'It can make the tower of the method (for the pretreatment and reforming stable stripper) ) boil again. In this example, between 526 ° C and 400 ° (:: 48 〇 7 x 1 〇 6 kJ / h (11.5 MM kcal / h), which is sufficient for the two towers. It is required to be 'about 4 〇〇〇 m2, which is 8 times 5 〇〇 V. This is equivalent to 8 times that of 350 30 mm diameter and 15 melon length tubes. This example provides a tube exchanger to simplify Calculations, but the scope of the invention also encompasses the use of other types of exchangers, for example, (d) 峨-type welded plate exchangers, which can result in a more compact construction. 5 B A 々 々 诋 衮 衮 衮P = 38 mm. For the dead space, a cross-section of 125 m2 (G.866xp2) is required to cover - the official, and thus about 3.5 m2 to cover 28 cells. By leaving the center a 0.8 m ancient value path and the surface area is added to I5% to take this segment into consideration, only θ can be applied to the entire exchange area, 136573.doc •19· 200940171 That is, the 2.4 m diameter requires a surface area of 0.5 + 3 · 5 χ 1.15 = 4.5 m 2 . The catalyst is installed in an annular area with an inner diameter of 3.2 m and a south of approximately 14 m. The metric ton of catalyst, that is, about 50 m3, and thus the catalytic region (50/14) of 3.6 m2. The outer diameter of the annular catalytic region is therefore 3.85 m. Therefore, starting from the outer casing, each part includes: Blank section (approximately 60 cm); • Filled between one of the two Johnson Networks or its equivalents with a section of catalyst (approximately 65 cm); • Free section (approximately 40 cm); ^ •—Exchange section (approximately 80 cm) 'It is filled with a vertical tube with a diameter of 30 mm; • The central free section (with a radius of about 40 cm). As explained above, in order to install the exchange tube and the catalyst, an internal diameter is required for the system. 5. 7 melons and shells with a height of about 16.5 m. The amount of coke produced in this first part is very low and increases from one part to the next (the next part), the highest in the last part (if the catalyst is in this part) Within 2.5 days of internal movement, the coke is 8%. One solution is to make the catalyst enter the same rate throughout the entire period. The line is cycled so that the catalyst is mixed at the outlet of the reactor to send it to the regenerator and regenerated into a mixture. The average coke content is only about 4%, allowing safe regeneration. However, this means The first portion of the catalyst is regenerated before it is necessary = so it is significantly better to set the size of the catalyst down device so that the catalyst from i, etc. is slower and slower, and from the last part The catalyst has dropped rapidly. 136573.doc •20- 200940171 [Simplified Schematic] Figure 1 depicts one of the ways to provide heat to the reactor. FIG. 2 depicts an additional manner of heating the reactor 60. Fig. 3 depicts a variation of Fig. 1 in which heat is recovered from the high temperature gas moving through the line 40 from the exit of the rim. Figure 4 shows the reaction section of a catalytic reforming section in accordance with one of the present invention. Figure 5 is a schematic cross-sectional side view showing the reactor 6A. Figure 6 shows the reactor as viewed from the top and is shown in segments. Figure 7 represents the portion observed from the center of the reactor. Figure 8 shows the same portion as viewed from the outer casing. [Main component symbol description] 2 Air compressor 4 Combustion chamber 6 Inlet pipe 7 Outlet pipe 8 Combustion chamber 10 Turboexpander 11 Alternator 12 Expansion turbine 15 Feed pump 17 Supply pipe 18 Discharge pipe 19 Heat exchanger 21 Heat exchanger 136573.doc <21 - 200940171 23 Separation tank 24 Separation tank 25 Compressor 60 Reactor 61 Exchange section 62 Catalytic section 64 Piping 65 Vertical sealing plate 66 Inlet 67 Pipe 68 Closure plate 69 Tubular plate 70 Pipe 71 Tubular Chamber 72 Tubular Chamber 73 Pipe 74 Expansion Bellows 75 Outlet 99 Tube 101 Arrow 102 Arrow 103 Arrow 104 Arrow 161 Supply Section 136573.doc 200940171 162 163 201 202 203 204 205 263 收集 Collection Section Conduit Supply Area Catalytic Area Collection Area Exchange Regional central cylindrical area catheter
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