487695 Β7 五、發明說明（1 ) 揭示背景 發明領域 本發明關於一種環境友善的氣體轉化方法，其在製程中 製造和處置氨。更詳而言之，本發明關於一種氣體轉化方 法’其包括（i)合成氣發生，（ii)烴合成，及（ i i i)觸媒再生而產生含氨的氣體，用水由其移除氨， 及將烴氣送至合成氣發生器以由水脫除它及送入發生器（ 它在該處被消耗）內以處置氨。 發明背景 烴合成（HCS)方法係眾所周知的且包括固定床、流 體床、淤漿型方法，其中使一包含H2和C 0之混合物的合 成氣（合成氣體）於適當的費雪一缺卜夕型烴合成觸媒的 存在下於能有效形成烴類的條件反應，且較佳形成爲 C 5 +烴類，其在溫度和壓力的標準條件下係固態的。經由 熟知的方法，包括部分氧化（有或無觸媒），催化蒸汽重 組其組合，使用固定或流體觸媒床，使低分子量烴氣與氧 和蒸汽反應以製造合成氣。由烴氣所製成的合成氣含有氮 (即天然氣）或含氮的化合物（即衍生自殘渣、煤炭、頁 岩、焦炭、焦油砂等等），係一成不變地含有氮物（例如 H C N和N Η 3，其使1103觸媒鈍化）。此鈍化係可逆的 ，且藉使鈍化的觸媒接觸11一|氫的氣體（再生用氣體 )來恢復觸媒的活性，例如揭示於美國專利第 5，260，239號中。此再生過程產生氨，必須由氣 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------ 裝· 11 (請先閱讀背面之注意事項再填寫本頁) 訂--- 經濟部智慧財產局員工消費合作社印製 487695 κτ Β7__ · 五、發明說明（2 )487695 B7 V. Description of the invention (1) Disclosure background Field of the invention The present invention relates to an environmentally friendly gas conversion method, which manufactures and disposes ammonia in the process. More specifically, the present invention relates to a gas conversion method 'which includes (i) synthesis gas generation, (ii) hydrocarbon synthesis, and (iii) catalyst regeneration to generate ammonia-containing gas, which is used to remove ammonia, And send the hydrocarbon gas to the syngas generator to remove it from the water and into the generator where it is consumed to dispose of ammonia. BACKGROUND OF THE INVENTION Hydrocarbon synthesis (HCS) processes are well known and include fixed bed, fluid bed, slurry type processes in which a synthesis gas (syngas) containing a mixture of H2 and C0 is applied to a suitable Fisher-Equipment. The presence of a type-type hydrocarbon synthesis catalyst is a conditional reaction that can effectively form hydrocarbons, and is preferably formed as a C 5 + hydrocarbon, which is solid under standard conditions of temperature and pressure. Through well-known methods, including partial oxidation (with or without catalyst), catalytic steam recombination, and their combination, a fixed or fluid catalyst bed is used to react low molecular weight hydrocarbon gas with oxygen and steam to produce syngas. Syngas made from hydrocarbon gas contains nitrogen (that is, natural gas) or nitrogen-containing compounds (that is, derived from residues, coal, shale, coke, tar sands, etc.), and they always contain nitrogen (such as HCN and N Η 3, which inactivates the 1103 catalyst). This passivation is reversible, and the catalyst's activity is restored by contacting the passivated catalyst with 11- | hydrogen gas (regeneration gas), for example, disclosed in US Patent No. 5,260,239. Ammonia generated during this regeneration process must be made from air-coated paper in accordance with China National Standard (CNS) A4 specifications (210 X 297 mm). ------------ Packing · 11 (Please read the note on the back first (Please fill in this page again for matters) Order --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 487695 κτ Β7__ V. Description of the Invention (2)
體中移除氨及作處置。美國專利4，189，307、4 ，769，224及5，068，254及歐洲專利公開 EP 〇 661 3 7 2 A 和 EP 0 661 3 7 5 A 揭示由合成氣移除氨和氰化物之方法，包括使含有氨的氣 體和水循環回到合成氣發生器內，但是沒有提到氣體轉化 _，一— 良法，該氣體轉化方法包括後ϋ處置來自Η C S觸媒再 生廢氣的氣。 發明槪述 本發明關於一種氣體轉化方法，其包括（i )合成氣（ 合成氣體）發生，（i i )烴合成（H C S )，及（ i i i)HCS觸媒再生而產生含氨的氣體，用水由其移 除氨，及利用製造合成氣的烴氣進料來由水脫除它，及送 入合成氣發生器（它在該處被消耗）內。即使有非常少量 的鈍化可逆性H C S觸媒之氮物，如氨和氰化氫，將導致 烴製造用的H C S觸媒隨時間的經過而掼失活性，因此需 要使觸媒接觸一種包含氫的氣體以便恢復觸媒的活性（以 下稱作”再生”）。此再生過程需要氫且產生一種再生產 品氣體（以下稱作”廢氣”），其含有氨。用水由氣體中 移除氨以形成氨水溶液，其與氨還原的廢氣分離及與送入 合成氣發生器內的烴氣作接觸。烴氣將水中的氮脫除及將 其帶入氣體轉化作業中及用於各種不同之用途，如洗滌合 成氣或廢棄。將H C S反應（以下稱作”尾氣”）所產生 的氣體冷卻以獲得用於由廢氣中移除氨的水，該尾氣含有 本紙張尺莩適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 — II 訂 ----—Α) 一 經濟部智慧財產局員工消費合作社印製 487695 B7 五、發明說明（3 ) 大量由H C S反應所產生的水。 更詳而言之，本發明關於一種氣體轉化方法，包括合成 氣製造、催化烴合成及烴合成觸媒之再生，其中該方法包 括：（a )在合成器發生器中由烴氣製造一種合成氣，包 括H2和C 0的混合物，其亦含有氨和氰化氫中至少一者； (b )使合成氣接觸烴合成觸媒及使H2和C〇於觸媒之存 在下於有效形成烴類的反應條件下反應及可逆地鈍化觸媒 ;(c)使一含有氫的氣體接觸可逆的觸媒以再生它及製 造一種含有氨的再生廢氣；（d)使廢氣接觸水以溶解氨 及形成氨水溶液，及使溶液與廢氣分開，及（e )將烴氣 送至合成氣發生器及使它通入發生器內以由溶液脫除氨。 當氰化氫或氨可逆地鈍化H C S觸媒畤，氨於再生期間產 生。如已知的，HC S觸媒係在現場於HC S反應器內再 生或在現場外於外部容器內再生，藉使它與一包含氫的氣 體反應。再者，廢氣可能或可不與H C S反應尾氣作合倂 。再生用的廢氣典型上含有足夠的水以便由氣體中溶解出 大部分的氨，氨JS JLl務身1_係』5 _決於水溫_。與氨之形成 及氰化氫觸媒鈍化物有關地，控制合成氣發生器的平衡。 因此，將氨送入合成氣發生器內會使發生器內的平衡狀態 移向氮的形成且此有效地移除氨，藉限制它在發生器內的 平衡量及因此在合成氣內的量。在實施本發明時，較佳爲 在將氨由水中脫除且進入合成氣發生器之前，由氣體進料 移除大部分的硫，以減少送至合成氣發生器的烴氣之硫含 量。氣體的硫含量較佳爲少於1 v p pm的硫，更佳爲少 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注咅？事項再填寫本頁) 裝--------訂---------βν 經濟部智慧財產局員工消費合作往印製 487695 A7 --- B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4 ) 於〇·lvppm，且尤更佳爲少於50vppb。在合 成氣接觸H C S觸媒之前，較佳爲將合成氣中所存在的氰 化氫和氨之合倂總量的濃度降低至少於〇 . i ν p p m , 更佳少於50vppb，尤更佳少於20vppb。 圖式之簡單說明 圖係本發明方法之一實施例的示意方塊流程圖。 主要元件對照表 10 管線 12 塔 14 管線 16 管線 17 熱交換器 18 管線 19 管線 20 合成氣發生器 22 管線 24 管線 26 熱交換器 28 管線 30 汾丘里滌氣器 32 導管 34 分離器-除霧器 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Remove ammonia and dispose of it in the body. U.S. Patents 4,189,307, 4,769,224 and 5,068,254 and European Patent Publications EP 0661 3 7 2 A and EP 0 661 3 7 5 A disclose methods for removing ammonia and cyanide from syngas This includes recycling ammonia-containing gas and water back to the syngas generator, but there is no mention of gas conversion. This is a good method. The gas conversion method includes the subsequent treatment of the gas from the ΗCS catalyst regeneration exhaust gas. SUMMARY OF THE INVENTION The present invention relates to a gas conversion method, which includes (i) synthesis gas (synthetic gas) generation, (ii) hydrocarbon synthesis (HCS), and (iii) HCS catalyst regeneration to generate ammonia-containing gas. It removes ammonia and removes it from the water using a hydrocarbon gas feed for the synthesis gas, and sends it to a synthesis gas generator where it is consumed. Even a very small amount of passivated reversible HCS catalyst nitrogen, such as ammonia and hydrogen cyanide, will cause the HCS catalyst for hydrocarbon production to become inactive over time, so it is necessary to contact the catalyst with a hydrogen-containing catalyst. Gas in order to restore catalyst activity (hereinafter referred to as "regeneration"). This regeneration process requires hydrogen and produces a reproductive gas (hereinafter referred to as "exhaust gas") that contains ammonia. The ammonia is removed from the gas with water to form an aqueous ammonia solution, which is separated from the ammonia-reduced exhaust gas and brought into contact with the hydrocarbon gas sent into the syngas generator. Hydrocarbon gas removes nitrogen from water and carries it to gas conversion operations and is used for a variety of purposes, such as washing synthesis gas or discarding it. The gas produced by the HCS reaction (hereinafter referred to as "exhaust gas") is cooled to obtain water for removing ammonia from the exhaust gas. The exhaust gas contains this paper. Applicable to China National Standard (CNS) A4 (210 x 297 cm) Li) (Please read the notes on the back before filling out this page) Packing — Order II — —A) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 487695 B7 V. Invention Description (3) A large number of reactions by HCS The water produced. More specifically, the present invention relates to a gas conversion method, including synthesis gas production, catalytic hydrocarbon synthesis, and regeneration of hydrocarbon synthesis catalysts, wherein the method includes: (a) producing a synthesis from hydrocarbon gas in a synthesizer generator; Gas, including a mixture of H2 and CO, which also contains at least one of ammonia and hydrogen cyanide; (b) contacting the synthesis gas with a hydrocarbon synthesis catalyst and allowing H2 and C0 to effectively form a hydrocarbon in the presence of the catalyst React and reversibly passivate the catalyst under similar reaction conditions; (c) contact a gas containing hydrogen with the reversible catalyst to regenerate it and produce a regenerating exhaust gas containing ammonia; (d) contact the exhaust gas with water to dissolve ammonia and An aqueous ammonia solution is formed, and the solution is separated from the exhaust gas, and (e) a hydrocarbon gas is sent to the synthesis gas generator and passed into the generator to remove ammonia from the solution. When hydrogen cyanide or ammonia reversibly deactivates the H C S catalyst, ammonia is generated during regeneration. As is known, the HCS catalyst is regenerated in the HCS reactor on-site or in an external container off-site, so that it reacts with a gas containing hydrogen. Furthermore, the exhaust gas may or may not be combined with the H C S reaction exhaust gas. The waste gas for regeneration typically contains enough water to dissolve most of the ammonia from the gas. The ammonia JS JLl service 1_ system "5" depends on the water temperature. Related to the formation of ammonia and hydrogen cyanide catalyst passivation, control the balance of the syngas generator. Therefore, sending ammonia into the syngas generator will move the equilibrium state in the generator towards the formation of nitrogen and this effectively removes ammonia, by limiting its equilibrium amount in the generator and therefore the amount in the syngas . In the practice of the present invention, it is preferred to remove most of the sulfur from the gas feed before removing ammonia from the water and entering the syngas generator to reduce the sulfur content of the hydrocarbon gas sent to the syngas generator. The sulfur content of the gas is preferably less than 1 vp pm, more preferably the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back? Matters before filling in (This page) -------- Order --------- βν Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation to print 487695 A7 --- B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of Ministry of Economic Affairs Fifth, the invention description (4) is in the range of 0 · lvppm, and more preferably less than 50vppb. Before the syngas is contacted with the HCS catalyst, it is preferred to reduce the total concentration of the combined hydrogen cyanide and ammonia present in the syngas to less than 0.1 μv ppm, more preferably less than 50 vppb, and even more preferably less At 20vppb. Brief Description of the Drawings The drawing is a schematic block flow diagram of one embodiment of the method of the present invention. Comparison table of main components 10 Pipeline 12 Tower 14 Pipeline 16 Pipeline 17 Heat exchanger 18 Pipeline 19 Pipeline 20 Syngas generator 22 Pipeline 24 Pipeline 26 Heat exchanger 28 Pipeline 30 Fenchuri scrubber 32 Duct 34 Separator-demister The paper size of the device applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
養 « ί ϋ I 1 n ϋ ϋ · ϋ n ϋ i-i I mam— -ϋ I 487695 A7 -B7 五、發明說明（5 ) 36 管線 38 管線 40 熱交換器 42 管線 44 管線 46 .管線 48 水解反應器 50 管線 52 熱交換器 54 管線 56 分離器 58 管線 60 滌氣器 61 管線 62 管線 63 容器 64 管線 65 硫吸收器 66 管線 68 烴合成反應器 70 頂部 72 氣體空間 74 管線 76 液體過濾器 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度1¾用中國國家標準（CNS)A4規格（210 X 297公釐） -8-^ 487695 A7 B7 五、發明說明（6 ) 經濟部智慧財產局員工消費合作社印製 78 管線 80 HCS觸媒再生裝置 82 管線 84 箭頭 86 間接熱交換器 88 管線 90 分離容器 92 管線 94 管線 98 管線 100 第二階段反應器 102 再生導管或裝置 104 液體過濾器 106 氣體管線 108 濾液管 112 氣體空間 114 管線 116 熱交換器 118 管線 120 氣-液分離器 122 管線 124 管線 126 管線 ---I-------- 裝--------訂------I--々一 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 487695 A7 _ _______________ B7 五、發明說明（7) 詳細說明 在費雪一缺卜夕（Fischer-Tropsch)烴合成（H C S ) 期間，由於與存在於合成氣中的ΝΗ 3和H C Ν鈍化物接 觸且其來自合成反應，而使HC S觸媒損失活性（鈍化） 。即使這兩物或之一係少5 0 ν p p b的非常少量，仍導 致觸媒的鈍化且伴隨著烴生產力的減少。鈍化之發生與 H C S反應是否在固定床或流體床觸媒的存在下或其是否 在淤漿中進行無關。此鈍化係可逆的，且如已知的，藉使 鈍化的觸媒接觸氫或一包含氫的氣體來恢復觸媒的活性（ 觸媒的再生）。間歇地或連續地再生觸媒的活性，於現場 在H C S反應器內或於外部再生容器內，例如揭示於美國 專利5，260，239、5，268，344及 5，283，216中。觸媒的再生將發生在與以下所給 的H C S反應之相同溫度和壓力的條件下。’ 2 3 9專利 顯示再生過程的典型氫分壓、處理速率等等。再生用的氣 體可含有稀釋劑和甚少量的C 0，只要氫濃度足以消耗任 何在再生過程中可能出現的C 0及確保再生過程所產生的 廢氣含有未反應的氫。茲相信再生後的觸媒仍與氫接觸以 防止鈍化。喪失與氫的接觸所導致的鈍化係未完全可逆的 。再生過程產生一種廢氣，其含有氨，此氨必須被處置。 本發明提供一種方便且容易的方式，將氨通入平衡控制的 合成氣發生器內以處置氨。 在本發明方法中，由氫碳質氣體進料來形成一包含Η2 和C 0之混合物的合成氣。雖然合成氣發生器的烴氣進料 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) n an n n ϋ ·_1 ϋ 一：0, ϋ n ϋ ϋ ϋ ϋ t · 經濟部智慧財產局員工消費合作社印製 487695 A7 , B7 五、發明說明（8 ) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 方便上係得自天然氣（其含有大部分的甲烷），但是可藉 由任何可用的且方便的方式由任何適當的氫碳質材料獲得 它。典型上，HC S工廠將爲該氫碳質材料的最近來源， 且合成氣的發生作業將爲H C S工廠的一完整部分。進料 包括低分子量（例如Ci—Ca)烴氣，較佳爲烷類且更佳 爲甲烷，如天然氣中。天然氣係特佳的，因爲其主要包括 甲烷，係方便的、乾淨的且不留下需要處理或處置之大量 的灰、頁岩、硫化物等等。不論合成氣之製造或製法所用 的烴氣源爲何，該烴氣進料係一成不變地含有元素氮或含 氮的化合物，其在合成氣反應器內反應而形成含氮之物， 如HCN和NH3，其在HC S反應期間使HC S觸媒鈍化 。在移除硫且，若須要，移除C〇2後，將天然氣送入合成 氣發生器內，其中氣體的烴成分與氧或空氣及視情況與蒸 汽反應，以形成一包含H2和C 0以所欲莫耳比之混合物的 合成氣。如已知的，可由非催化及催化部分氧化、蒸汽重 組及部分氧化與蒸汽重組的組合來形成合成氣。在催化部 分氧化中，使烴氣、氧及視需要的蒸汽和水蒸氣的預混合 進料於貴金屬觸媒且較佳爲一受支撐的貴金屬觸媒之存在 下於合成氣發生器中反應以形成合成氣，如已知的。該合 倂部分氧化與蒸汽重組的方法可具有蒸汽重組觸媒在固定 或流體床中，流體床具有優秀的混合和熱傳遞特性。在流 體床合成氣發生（FB SG)方法中，部分氧化和蒸汽重 組皆發生流體化蒸汽重組觸媒的存在下。F B S G例如揭 示於美國專利第4，888，131號和5，160， -IV- 本紙張尺度.適用中國國家標準（CNS)A4規格（210 X 297公釐） 487695 κτ Β7 ____ 五、發明說明（9 ) (請先閱讀背面之注意事項再填寫本頁) 4 5 6號中。在自熱重組中，部分氧化發生在無觸媒的存 在下且在絕熱蒸汽重組（其發生在觸媒的固定床中）之前 發生。離開反應器的合成氣係包含Η 2和C 0之混合物， 伴隨著水蒸氣或蒸汽、C 0 2、少量的未反應之甲烷、 ΝΗ3及HCN。合成氣之進料中所存在的C〇2量將影響 反應平衡，且可與單元中的條件一起用於調整合成氣中 H2對C 0的比例。在進入HC S反應器之前，由合成氣移 除大部分的水。與發生器或反應器內所存在的H C N和 ΝΗ3量有關地，控制合成氣發生器反應器的平衡，其可由 以下反應來說明： N2-f3H2〇2NH3 N2+2CH402HCN+3H2 NH3+CO»HCN+C〇2 因此，HCN和NH3觸媒鈍化物的處置係發生在當這 些化合物送入平衡限制的合成氣發生器內時，藉使反應移 動回向氮。 經濟部智慧財產局員工消費合作社印製 在HC S方法中，使一含H2和C0之混合物的合成氣 接觸費雪-缺卜夕型H C S觸媒，於移動或不移動的條件 下且較佳於不移動的條件下，其中微少或沒有水的氣體移 動反應發生，尤質是當催化金屬包括C 〇、R u或其混合 物時。適合的費雪-缺卜夕型H C S觸媒例如包括一或多 種族VI I I催化金屬，如Fe、Ni、Co、Ru和 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 一 487695 Α7 Β7 五、發明說明（10) (請先閱讀背面之注意事項再填寫本頁) R e。在一實施例中，觸媒包括催化有效量的C 〇及一或 多種尺6、1111、？6、1^1、丁11、21：、；^1士、11、 Mg和L a在適當的無機載體材料上，該無機載體材料較 佳一種包括一或多種耐火性金屬氧化物。含C 〇的觸媒之 較佳載體係包括二氧化鈦，尤其是當採用淤漿H C S方法 時，其中想要較高分子量的主要爲烷屬液烴之產品。可用 的觸媒及它們的製法係已知的，且其之非用以限制的例子 例如可發現於美國專利4，568，663、4，663 ，305、4，542，122、4，621，072 和 5，545，674 中。 經濟部智慧財產局員工消費合作社印製 就烴合成而言，用於由一包含Η 2和^ 0之混合物的合 成氣來形成烴的固定床、流體床和淤漿烴合成（HC S ) 方法係眾所周知的且記載於文獻中。在所有的這些方法中 ，合成氣中的Η2和C 0係於適當的費雪-缺卜夕型烴合成 觸媒之存在下反應，於反應條件能有效地形成烴類時。在 2 5 °C和一大氣壓的標準溫度和壓力條件下，這些烴類中 有些是液體，有些是固體（例如蠟），且有些是氣體，特 別是若使用一種具有催化鈷成分的觸媒。淤漿H C S方法 常常是較佳的，因爲它們對於強放熱合成反應之優秀的熱 (及質量）傳遞特性及因爲當使用鈷觸媒時它們能產生相 當高分子量的烷屬烴。在淤漿HC S方法中，使一包含 Η2和C〇之混合物的合成氣向上冒泡，當作第三相經過反 應器內的淤漿，其含有分散和懸浮於淤漿液體中的粒狀費 雪-缺卜夕型烴合成觸媒，該淤漿液體含有在反應條件下 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 487695 A7 _— —___B7 五、發明說明（11 ) 爲液態的合成反應之烴產品。氫對一氧化碳的莫耳比可在 約0 · 5至4的寬廣範圍內，但是更典型地在約0 · 7至 2 · 75的範圍內，且較佳約0 · 7至2 · 5。費雪一缺 卜夕HCS反應的計算莫耳比係2 . 0，但是在實施本發 明時可增加它以由合成氣獲得所欲的氫量，用於H C S反 應以外者。在淤漿HCS方法中，Η2對C0的莫耳比典 型上係約2 · 1 / 1。淤漿H C S方法條件係取決於觸媒 和所欲的產品而有些不同。在一採用包含受支撐的鈷成分 之觸媒的H C S方法中，有效於形成烴類，包括大部分的 C5 +烷屬烴（例如C5 + - C2Qq)，及較佳C1Q +烷屬烴 ，的典型條件例如包括溫度、壓力及每小時氣體空間速度 分別在約 320 - 600°F、80 - 600ps i 及 100 — 40，000V/hr/V的範圍內，該空間速 度係以每小時每觸媒體積的氣態C 0和Η 2混合物之標準體 積表示（0°C，1大氣壓）。 參閱圖式，使一經胺處理和吸收以移除硫和C 0 2的實 質上無硫（例如<0 · lvppm)且含有約4%氮的預 熱天然氣經由管線1 0進入容器1 2所示的氣一液接觸塔 之底部內，其中它與經由管線1 4進入靠近塔頂的水作接 觸。塔1 2內裝有惰性塡充材料如拉西環、伯爾鞍、結構 性塡充物等等，或含有複數個盤，以確保充分的接觸，使 得合成氣發生器的下游之氣體含有足夠的水蒸氣。進入塔 內的水係H C S反應水，由H C S反應器6 8和1 0 0的 尾氣回收得，其含有觸媒再生時所產生的氨以及H C S反 I紙張尺度.適用中國國家標準（CNS)A4規格（210 X 297公釐） -14 - n ϋ ϋ ϋ I ϋ n ϋ ί · ϋ ammt ϋ ·ϋ n n 1 一 n n ·1 n >ϋ I emMmw I (請先閱讀背面之注意事項再填寫本頁) 487695«Ί 1 I 1 n ϋ ϋ · ϋ n ii ii I mam— -ϋ I 487695 A7 -B7 V. Description of the invention (5) 36 Line 38 Line 40 Heat exchanger 42 Line 44 Line 46 .Line 48 Hydrolysis reactor 50 line 52 heat exchanger 54 line 56 separator 58 line 60 scrubber 61 line 62 line 63 container 64 line 65 sulfur absorber 66 line 68 hydrocarbon synthesis reactor 70 top 72 gas space 74 line 76 liquid filter (please first Read the notes on the back and fill in this page) The paper size 1¾ uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8- ^ 487695 A7 B7 V. Description of the invention (6) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives 78 Line 80 HCS Catalyst Regeneration Device 82 Line 84 Arrow 86 Indirect Heat Exchanger 88 Line 90 Separation Vessel 92 Line 94 Line 98 Line 100 Second Stage Reactor 102 Regeneration Duct or Device 104 Liquid Filter 106 Gas Line 108 Filtrate tube 112 Gas space 114 Line 116 Heat exchanger 118 Line 120 Gas-liquid separator 122 Line 124 Line 126 Pipeline --- I -------- Install -------- Order ------ I--々 一 (Please read the precautions on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 487695 A7 _ _______________ B7 V. Invention description (7) Detailed description During Fischer-Tropsch hydrocarbon synthesis (HCS), due to Contact with the NH 3 and HC N passivation present in the synthesis gas and it comes from the synthesis reaction, so that the HC S catalyst loses its activity (passivation). Even a very small amount of these two or one of them is less than 50 ν p p b, which still leads to the passivation of the catalyst and is accompanied by a reduction in hydrocarbon productivity. The occurrence of passivation has nothing to do with whether the H C S reaction is in the presence of a fixed-bed or fluid-bed catalyst or whether it is carried out in a slurry. This passivation is reversible and, as is known, the catalyst is reactivated by contacting the passivated catalyst with hydrogen or a gas containing hydrogen (catalyst regeneration). The activity of the catalyst is intermittently or continuously regenerated, either on site in the HCs reactor or in an external regeneration vessel, as disclosed, for example, in U.S. Patents 5,260,239, 5,268,344, and 5,283,216. The regeneration of the catalyst will occur under the same temperature and pressure conditions as the H C S reaction given below. The '2 3 9 patent shows typical hydrogen partial pressures, processing rates, and the like during the regeneration process. The regeneration gas may contain a diluent and a very small amount of CO, as long as the hydrogen concentration is sufficient to consume any CO that may occur during the regeneration process and to ensure that the exhaust gas generated during the regeneration process contains unreacted hydrogen. It is believed that the regenerated catalyst is still in contact with hydrogen to prevent passivation. The passivation caused by the loss of contact with hydrogen is not completely reversible. The regeneration process produces an exhaust gas that contains ammonia, which must be disposed of. The present invention provides a convenient and easy way to pass ammonia into a balance-controlled syngas generator to dispose of ammonia. In the method of the present invention, a hydrogen carbonaceous gas feed is used to form a synthesis gas containing a mixture of rhenium 2 and C 0. Although the hydrocarbon gas feed of the syngas generator is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the precautions on the back before filling this page) n an nn ϋ · _1 ϋ 1 : 0, ϋ n ϋ ϋ ϋ · t · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 487695 A7, B7 V. Description of Invention (8) (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Employee consumer collaboration DuPont is conveniently derived from natural gas (which contains most of the methane), but it can be obtained from any suitable hydrogen carbonaceous material in any available and convenient way. Typically, the HCS plant will be the closest source of this hydrogen carbonaceous material, and syngas generation operations will be an integral part of the HCS plant. The feed comprises a low molecular weight (e.g. Ci-Ca) hydrocarbon gas, preferably alkanes and more preferably methane, such as in natural gas. Natural gas is particularly good because it mainly includes methane, which is convenient, clean, and does not leave a large amount of ash, shale, sulfide, etc. that needs to be treated or disposed of. Regardless of the hydrocarbon gas source used in the synthesis gas manufacturing process, the hydrocarbon gas feed system contains elemental nitrogen or nitrogen-containing compounds invariably, which react in the synthesis gas reactor to form nitrogen-containing substances, such as HCN and NH3. , Which deactivates the HCS catalyst during the HCS reaction. After the sulfur is removed and, if necessary, the CO2 is removed, the natural gas is sent to a synthesis gas generator, where the hydrocarbon component of the gas reacts with oxygen or air and optionally with steam to form a mixture containing H2 and C0 Syngas in a mixture of the desired mole ratio. As is known, synthesis gas can be formed from non-catalytic and catalytic partial oxidation, steam reforming, and a combination of partial oxidation and steam reforming. In catalytic partial oxidation, a premixed feed of hydrocarbon gas, oxygen, and optionally steam and water vapor is reacted in a synthesis gas generator in the presence of a noble metal catalyst and preferably a supported noble metal catalyst to Syngas is formed, as is known. The combined partial oxidation and steam reforming method can have steam reforming catalyst in a fixed or fluid bed, and the fluid bed has excellent mixing and heat transfer characteristics. In the fluid bed synthesis gas generation (FB SG) method, both partial oxidation and steam recombination occur in the presence of a fluidized steam reforming catalyst. FBSG is disclosed, for example, in US Patent Nos. 4,888,131 and 5,160, -IV- this paper size. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 487695 κτ B7 ____ 5. Description of the invention ( 9) (Please read the notes on the back before filling in this page) 4 5 6 In autothermal recombination, partial oxidation occurs in the absence of catalyst and before adiabatic steam recombination, which occurs in a fixed bed of catalyst. The synthesis gas leaving the reactor contains a mixture of Η 2 and C 0, accompanied by water vapor or steam, C 0 2, a small amount of unreacted methane, Ν 3 and HCN. The amount of CO2 present in the feed of the synthesis gas will affect the reaction equilibrium, and can be used together with the conditions in the unit to adjust the ratio of H2 to CO in the synthesis gas. Before entering the HCS reactor, most of the water is removed from the syngas. The balance of the synthesis gas generator reactor is controlled by the amount of HCN and ΝΗ3 present in the generator or reactor, which can be illustrated by the following reaction: N2-f3H2〇2NH3 N2 + 2CH402HCN + 3H2 NH3 + CO »HCN + Co. Therefore, the disposal of HCN and NH3 catalyst passivation occurs when these compounds are sent to the equilibrium-limited syngas generator, by which the reaction moves back to nitrogen. Printed in the HCS method by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, a synthesis gas containing a mixture of H2 and C0 is contacted with a Fisher-Jackson type HCS catalyst, which is better under moving or non-moving conditions Under immobile conditions, a gas shift reaction with little or no water occurs, especially when the catalytic metal includes Co, Ru or a mixture thereof. Suitable Fischer-Bausch-type HCS catalysts include, for example, one or more race VI II catalytic metals such as Fe, Ni, Co, Ru, and this paper. Applicable to China National Standard (CNS) A4 (210 x 297 mm) ) 487695 Α7 Β7 V. Description of the invention (10) (Please read the precautions on the back before filling this page) R e. In one embodiment, the catalyst includes a catalytically effective amount of C0 and one or more types of feet 6, 1111? 6, 1 ^ 1, D11, 21:,; ^ 1, 11, Mg, and La on a suitable inorganic support material, preferably one of the inorganic support materials including one or more refractory metal oxides. A preferred carrier for a catalyst containing C0 includes titanium dioxide, especially when a slurry H C S method is used, in which a product with a higher molecular weight is mainly a paraffinic liquid hydrocarbon. Available catalysts and their manufacturing methods are known and non-limiting examples can be found in, for example, U.S. Patents 4,568,663, 4,663,305, 4,542,122, 4,621, 072 and 5,545,674. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in terms of hydrocarbon synthesis, a fixed bed, fluid bed, and slurry hydrocarbon synthesis (HCS) method for forming hydrocarbons from a synthesis gas containing a mixture of Η 2 and ^ 0 They are well known and documented. In all of these methods, the plutonium 2 and C 0 in the syngas are reacted in the presence of an appropriate Fisher-Dessert-type hydrocarbon synthesis catalyst, when the reaction conditions can effectively form hydrocarbons. Under standard temperature and pressure conditions of 25 ° C and one atmosphere, some of these hydrocarbons are liquid, some are solid (such as wax), and some are gases, especially if a catalyst with a catalytic cobalt component is used. Slurry H C S methods are often preferred because of their excellent heat (and mass) transfer characteristics for strongly exothermic synthesis reactions and because they can produce relatively high molecular weight paraffins when cobalt catalysts are used. In the slurry HC S method, a synthesis gas containing a mixture of krypton 2 and CO is bubbled upwards as a slurry passing through the reactor as a third phase, which contains granular particles dispersed and suspended in the slurry liquid. Fisher-Oxford type hydrocarbon synthesis catalyst, the slurry liquid contains under reaction conditions -13- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Consumption by employees of Intellectual Property Bureau Printed by the cooperative 487695 A7 _ — — ___B7 V. Description of the invention (11) It is a liquid synthetic hydrocarbon product. The molar ratio of hydrogen to carbon monoxide may be in a broad range of about 0.5 to 4 but more typically in the range of about 0.7 to 2 75, and preferably about 0.7 to 2.5. Fisher's lack of Moore's calculation of the HCS reaction is 2.0, but it can be increased during the implementation of the present invention to obtain the desired amount of hydrogen from synthesis gas for use other than the H C S reaction. In the slurry HCS method, the mole ratio of Η2 to CO is typically about 2 · 1/1. The slurry H C S method conditions are somewhat different depending on the catalyst and desired product. In a HCS process using a catalyst containing a supported cobalt component, it is effective at forming hydrocarbons, including most C5 + paraffinic hydrocarbons (eg, C5 +-C2Qq), and preferably C1Q + paraffinic hydrocarbons. Typical conditions include, for example, temperature, pressure, and hourly space velocity of gas in the range of approximately 320-600 ° F, 80-600 psi, and 100-40,000 V / hr / V, respectively. Standard volume representation of the gaseous mixture of gaseous C 0 and Η 2 (0 ° C, 1 atmosphere). Referring to the diagram, a preheated natural gas that is substantially sulfur-free (e.g. < 0 · lvppm) and treated with amine to remove sulfur and C 0 2 and contains about 4% nitrogen enters the container 12 via line 10 The gas-liquid shown is in contact with the bottom of the tower, where it comes into contact with water entering near the top of the tower via line 14. Tower 12 is filled with inert filling materials such as Raschig ring, Burr saddle, structural filling materials, etc., or contains several disks to ensure sufficient contact so that the gas downstream of the syngas generator contains enough Water vapor. The HCS reaction water entering the tower is recovered from the tail gas of HCS reactor 68 and 100, which contains ammonia generated during catalyst regeneration and HCS anti-I paper size. Applicable to China National Standard (CNS) A4 Specifications (210 X 297 mm) -14-n ϋ ϋ ϋ I ϋ n ϋ ί · ϋ ammt ϋ · ϋ nn 1 nn · 1 n > ϋ I emMmw I (Please read the precautions on the back before filling in this Page) 487695
A7 B7 五、發明説明（12 ) (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產苟g(工消費合作社印製 應所產生的其它水溶性化合物（例如，充氧物如酸類、醇 類、醛類等等）。在所示的實施例中，觸媒係在現場再生 ’其產生含有氨的廢氣，而反應器正在製造烴類。如所示 ，在此實施例中，再生過程的廢氣係與H C S反應器尾氣 合倂，及冷卻合倂的束流以凝結出至少一部分的水，它與 氨和其它水溶性化合物形成氨溶液，其通入F B S G內。 用向上流的天然氣流由向下流的水中汽提出這些水溶性化 合物及與氣體通入合成氣發生器內，其中它們被加熱破壞 及被發生器內的平衡控制條件所破壞，而因此有效地處置 它們。由這些水溶性化合物之汽提所獲得的水（其已於以 上定義爲乾淨的水）係由容器底部經由管線1 6流出及經 過熱交換器1 7 ，其中它被冷卻然後經由管線1 9進入滌 氣器6 0內，其中它與水解的合成氣接觸，由其而已經移 除大部分的H C Ν和Ν Η 3，當作洗鍊或精整步驟以移除任 何殘留在氣體內的H C Ν和Ν Η 3，到少於5 Ο ν p p b的 程度，且較佳少於lOvppb。由水中汽提出至少95 %，較佳至少9 8 %，且更佳至少9 9 %的氨及任何殘留 的氰化氫，以產生乾淨的水。此水典型上將含有少於 1〇0毫克/升的氨及少於1毫克/升（例如〇 - < 1毫 克/升）的氰化氫。視情況地，一再沸器（未於圖示）可 設於塔1 2之底部或外部，如熟悉技藝者已知的，該再沸 器可用於加熱一部分的乾淨水以製造蒸汽，若需要確保烴 進料汽提氣體在所欲的濕度時。此蒸汽將與烴進料氣體向 上通過塔。使水飽和的天然氣經由管線i 8從增濕器-滌 -15- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公餐） 經濟部智慧財產局員工消費合作社印製 487695 κτ Β7___ 五、發明說明（13) 氣器1 2進入合成氣發生器2 0內。合成氣發生器可更包 括超過一個的容器，如熟悉技藝者所知的。其例如可爲流 體床合成氣發生器（FBSG)、自熱發生器、部分氧化 單元可一接在流體化觸媒床之後的觸媒固定床，如揭示於 美國專利5，42 1 ，850中。與這些單元之優點有關 的討論例如美國專利3，4 4 1，3 7 0和 5，244，641中所討論的。在FBSG中，部分氧 化係發生在蒸汽重組觸媒粒子之流體化床的存在下。典型 的蒸汽重組觸媒係包括一載於α氧化鋁上的催化鎳成分， 如美國專利5，395，406中所揭示的。FBSG具 有優秀的熱傳遞特性，而流體化觸媒床亦可含有高溫耐熱 材料，如α氧化鋁，如已知的。爲了說明之目的，合成氣 發生單元20將被視爲一種FBSG單元。FBSG中的 典型條件係包括約1 0 - 5 0大氣壓的壓力範圍，較佳 1 0 — 4 0大氣壓，且更佳2 0 — 4 0大氣壓，而溫度範 圍將在本質上非催化的帶熱粒子之軟化點的約5 0°F內， 較佳約1 6 50 °F至約2000 °F，且更佳約1 700 T 至約1 8 Ο 0T。若須要’可將額外的水蒸氣或蒸汽經由 管線2 2送入F B S G內，及將氧或含氧的氣體（例如空 氣、經N2或蒸汽稀釋的氧等等），較佳爲氧，經由管線 24送入FBSG內。在FBSG中，天然氣中的烴類， 其包括大部分的甲烷和典型上伴隨著少量的C 2 - C 8烴類 ，係部分地被氧化且經催化蒸汽重組，以產生一種包含 H2和C〇之混合物的合成氣。由水中所汽提出的氨係進入 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐) - (請先閱讀背面之注意事項再填寫本頁) 一 裝--— — — — — — 訂---！ιι·/:ν、 487695 Β7 五、發明說明（14) . — — 1 — — — — — — — — » · I - (請先閱讀背面之注意事項再填寫本頁) F B S G內，其中它的濃度被平衡狀態所調整，藉以有效 地處置氨。由1 2中之增濕水所汽提出的有機物係亦在發 生器內被破壞。因爲合成氣發生器內的高溫，所以經由管 線2 4離開單元的合成氣在通過第一旋風器和第二旋風器 (未於圖示）後係視需要地通過熱交換器2 6 (或經過一 經濟部智慧財產局員X-消費釜阼达印製 發電用的渦輪機），其可能爲一種蒸汽發生器，其將它冷 卻至低於10 0 0 °F的溫度，然後經由管線2 8進入高能 量氣體一水接觸裝置內，該裝置在此說明中係汾丘里滌氣 器3 0。若不使用熱交換器，則於滌氣器內與水接觸以冷 卻氣體。汾丘里（Venturi )滌氣器係眾所周知的且不需要 說明。其它形態的高能量接觸裝置包括旋風滌氣器、撞擊 板滌氣器、機械滌氣器如Roto-Clone (美國空氣過濾器公司 )等等。合成氣含有小量的來自於F B S G之粒狀物質（ 例如觸媒及熱傳遞固體細粒），當其向下通過汾丘里滌氣 器時，其與經由管線3 6進入汾丘里的水作接觸，它將氣 體冷卻至約3 0 0 — 4 0 0 °F及亦移除氣體中的粒狀物質 。洗滌後的氣體和含有粒狀物質的水係經由導管3 2進入 分離器-除霧器3 4內，其中含有水的細粒係與氣體分開 。在裝置上部（未於圖示）內的捲縮金屬線、金屬線網， 鬆的塡充物等等可脫除汾丘里滌氣器內所形成的含粒子之 霧氣，其聚結在含粒子的水內，此水與由滌氣器進入裝置 內的大量含粒子之水作合倂。由分離器5 6經由管線5 8 所取出的氨水係進入3 4的頂部及向下流動經過除霧裝置 ，其中它接觸聚結的霧氣及上流的氣體以確保氣體在離開 本紙張尺度.適用中國國家標準（CNS)A4規格（210 X 297公釐) ΓΤΤ- 487695 Α7 Β7 五、發明說明（15) 分離器-除霧器之前係不含有粒子。視情況況地，進入 3 4之頂部的水之全部或一部分可能來自滌氣器6 0的管 線6 1且其含有非常少量的溶解HCN和NH3。由分離器 -除霧器經由管線3 8移出不含粒子且除霧過的合成氣， 及使其通入另一熱交換器4 0內，其中它被冷卻至約 4 0 0°F以便用於後續的催化水解步驟。經由管線4 2由 容器3 4取出水相，及經由管線4 4將一部分循環回到汾 丘里滌氣器內，其餘經由管線4 4送出作處置。視情況地 ，通常入汾丘里滌氣器內的一部分水可包括5 6中所分離 的氨水或來自滌氣器6 0的水。離開熱交換器的冷氣體係 經由管線4 6通入水解反應器4 8內。此反應器含有一水 解區，其包括觸媒之固定床以用於將HCN水解成NH3。 H C N水解區內的觸媒較佳包括至少一種金屬之氧化物， 該金屬選自於本質上由族V I金屬、族I VB金屬及其混 合物所構成的族群，且尤其是A 1以及Mo和T i中至少 一者之氧化物，如揭示於歐洲專利公開E P 〇 7 5 7 969 A中。觸媒將包括約>〇至3〇重量％Mo之複合 氧化物當作氧化物，較佳1 0至2 0重量％，二氧化鈦的 存在量約> 0至3 0重量％，較佳4至2 0重量％，更佳 8 — 16重量％ (例如8重量％)，其餘爲氧化鋁。使適 當的鉬和鈦源沈積在氧化鋁載體上，在例如用浸漬或初期 潤濕技術作沈積後，然後在約2 5 0 - 5 0 0 °C的溫度茚 燒，且較佳在3 50 — 450 °C，以產生氧化物形式。較 喜愛在約200 - 600 °C的溫度，較佳230 — 550 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -裝·！ 1111 訂· II---1ΙΛ 經濟部智慧財產局員X消費合阼达印製 487695 ΚΓ B7 五、發明說明（16) °C，用氫處理觸媒1 - 24小時。氧化鋁可爲任何可用當 作觸媒載體的氧化鋁且典型上爲一種具有約1 〇 〇 一 4 0 0平方公尺/克之表面面積者。欲水解且欲由合成氣 中移除的HCN量典型上係非常少的（例如< 5 〇 〇 〇 vppb)。水典型上的存在量係約合成發生的約5-2 5體積％，但是水的實際存在量可能較大或較少，且此 水量係超過足以水解合成氣中所存在的相當少量之H C N 。在水解反應的期間，H C Ν與水反應及轉化成Ν Η 3和 C〇。至少約9 5%，典型上至少9 8%，且甚至超過 9 9%的HCN係轉化成NH3。天然氣包括約9 6%甲院 及4%氮，其在約1800卞和400ps i a操作的 F B S G中被催化部分氧化及蒸汽重組，而產生一種合成 氣，具有平衡限制量的約5 p pm之HCN及約3 0 0 p pm之NH3。在汾丘里滌氣器中用水可移除氣體中的一 些NH3和少部分的HCN。HCN水解區48中的溫度 、壓力和空間速度可在約100 — 400 °C、1 一 1〇〇 a tm和2000 — 50000GHSV的寬廣範圍內。 選擇水解溫度以便在水解反應器中所達成的水解速率係足 以使至少9 5%，較佳至少9 8%，且猶較佳至少9 9% 的HCN轉化成NH3，視氣體中的HCN含量及反應器內 的水解溫度而定，同時避免不宜的副反應，如合成氣中所 存在的C 0之甲烷化。水解後的合成氣經由管線5 0離開 反應器4 8，然後經過熱交換器5 2，其中它被冷卻至約 1 2 0°F，將氣體中大部分的水蒸氣冷凝出，其含有 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) · I ϋ n n n i_Bi ϋ < ( 經濟部智慧財產局員工消費合泎汪印製 -iy - 487695 A7 , B7 五、發明說明（17) N Η 3。此冷凝所產生的液態水係含大部分（例如〜9 0 % )的ΝΗ3，氣體中留下非常少的ΝΗ3。在一實驗中，使 一含有（以體積％基準計）43%Η2、21 · 2%C〇、 7%C〇2、8 · 6%N2、5 · 4%CH4、15%H2〇 、34〇vppm NH3和 6.4vppm HCN 的合成 氣以1 2 0 0 0小時-1的空間速度通過2 0 5 °C和 26 · 4a tm的HCN水解區，其中它接觸HCN水解 觸媒，此觸媒包括氧化鋁和二氧化鈦載體材料，其經七鉬 酸銨所浸漬且如上述煅燒。離開反應器的合成氣之H C N 濃度係少於20vppb，其代表移除超過99%的 H CN。重複此實驗，使用更敏感的分析程序，透露其係 少於1 Ο ν p p b。操作水解反應器1 2 7天，沒有測出 有減少的H C N移除活性。在另一實驗中，與上述實驗一 樣，但是水解反應器的溫度爲1 6 5°C，離開的合成氣之 HCN濃度係269vppb，表示反應器內有95 · 8 %的11 C N轉化。在水解及水洗滌後，可使合成氣通過一 或多個含H C N和NH3吸附劑如氧化鋁或活性碳的床，監 視HC S反應器之下游，防止合成氣中HCN和NH3濃度 的突破。雖然此較佳實施例中顯示將H C N催化水解成 ΝΗ3，但是亦可採用的爲將HCN催化氫化成ΝΗ3，例 如揭示於歐洲專利公開Ε Ρ 〇 7 6 7 1 3 7 Α及英國 專利申請案GB 2 267 048 A中。 然後使熱交換器內所形成的氣體和氨水經由管線5 4通 入氣-液分離器5 6內，其可能是一種簡單的分離桶，其 本紙張尺度通用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -· 1 I I I II I 訂·！ 11!· 經齊spfe»曰慧財產苟員11肖費釜乍i氏 -ZU - 487695 ΚΓ Β7 五、發明說明（18) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員X消費合泎法印製 中氨水溶液與氣體分開及經由管線5 5回到容器3 4內當 作洗水。將H C N轉化成N Η 3的優點爲N Η 3係極度水溶 性的，但是不能將H C Ν充分地溶於水中以便由氣體中移 除H C Ν使下降至所欲的程度。將天然氣送入合成氣發生 器內及用上述的水解觸媒和條件，則水解後合成氣中所殘 留的HCN量係<20vppb。離開分離器56的合成 氣係經由管線5 8進入滌氣器6 0內，該滌氣器是一種帽 和盤塔、一成有高表面面積塡充料如拉西環的塡充塔等等 。洗水是一種由容器1 2所回收的乾淨水，藉直接通過熱 交換器1 7而被冷卻至約5 0°C的溫度，經由管線1 9進 入滌氣器的頂部，及向下流以接觸向上流的合成氣，及實 質溶解氣體中全部的氨以產生一種經洗滌的合成氣，此合 成氣之NH3含量係少於20vppb，且較佳少於1〇 vppb的NH3，及約lOvppb的HCN。雖然此實 例中滌氣器係在5 0 °C操作，但是其可能在約2 5 -1 2 0°C的溫度操作。經由管線3 3由滌氣器移出含有被 移除的Ν Η 3之流出水，及以任何方便的方式作處置，包括 循環回到合成氣發生步驟、分離器-除霧器、高能量接觸 裝置，用氮或燃料氣來汽提出ΝΗ3，及將它倂入燃料束流 內，或作生物處理。洗滌後的合成氣經由管線6 2離開滌 氣器及通入容器6 3所示的吸附區內，其中它接一或多種 固態吸附劑，該吸附劑係選擇用於吸附H C Ν和Ν Η 3，於 C〇、C〇2、Η 2和Η 2 0的存在下，其之非用以限制的 說明性例子包括沸石分子篩、活性碳、Ζ η 0、氧化鋁等 -ΖΊ · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 487695 κτ _Β7_____ 五、發明說明（19 ) (請先閱讀背面之注意事項再填寫本頁) 等，其中較佳爲活性氧化鋁和活性碳。在2 5至1 2 0°C 的溫度、1至100a tm的壓力及約2000至 2〇〇〇〇 s c f/hr的空間速度，執行對殘餘HCN 和NH3的吸附。此吸附步驟所產生的合成氣將含有少於 5〇，較佳少於20，且更佳少於lOvppb的HCN 和NH3之合倂總量，且係適用於費雪一缺卜夕烴和甲醇的 合成。然而，在此實施例中，於經由管線6 3離開6 4後 ’氣體通經硫吸收器6 5，此吸收器含有適當的硫吸收劑 如氧化鋅，其移除氣體內的硫化合物至少於5 0 v p p b 的含量，且更佳少於lOvppb。此產生一種合成氣， 其本質上不含HCN、NH3和硫，其然後可用於費雪一缺 卜夕合成以降低對觸媒的鈍化。 經濟邨智慧財產局員X.消費合阼fi印製 在圖式的實施例中，此合成氣然後經由管線6 6進入第 一階段烴合成反應器6 8的底部，經過淤漿（未於圖示） 底部的氣體分配裝置（未於圖示），該淤漿之頂部以70 表示。在反應器中，合成氣以氣泡上升進入淤漿內，H2與 C 0於固體粒子的存在下反應，即粒狀費/雪一缺卜夕觸媒 懸浮或分散於淤漿中，而產生烴類，其在反應條件下至少 一部分係液態的。H C S反應亦產生水蒸氣（蒸汽）‘、 C 0 2及一些烴類，其在反應條件下係氣態的。合成的烴類 (其在反應條件下係液態的）包括淤漿液體，藉由適當的 裝置使其與觸媒粒子分開及由反應器取出，如藉由一或多 個以箱7 6所簡單表示的液體過濾器，烴類經由管線7 8 離開反應器以便升級。合成氣中僅有微少的觸媒鈍化物， 本紙張尺度適用中關家標準（CNS)A4規格（210 X 297公餐)h · " ----- 經齊卽智慧財產笱員11省費^乍:£肀製 487695 __Β7_ 五、發明說明（2G) 因此產生非常純的烴液體，其可容易地被分餾且可藉一或 多個加氫轉化作業來升級，不需要有處理該化合物之存在 所需要的加工。此係因爲氮化合物會毒化加氫處理觸媒， 其意味若硫存在著，則加氫處理必須在高溫和高壓進行， 此係對氣體較有選擇性的而對所欲的液體產品較沒選擇性 的（與低溫和低壓比較而言）。氣態反應產品，包括大量 的水蒸氣或蒸汽，倂隨著未反應的氣體，係向上經過淤漿 ，進入淤漿上方的氣體空間7 2內，然後當作尾氣經由管 線74離開反應器。HCS觸媒再生裝置80，如先前技 藝中所揭示的具有兩端開口的一導管，係浸入淤漿內且頂 部向上延伸進入氣體空間7 2內。氣體管線8 2將一包含 氫的HC S觸媒再生氣體向上噴入裝置8 0內部。上升中 的再生氣體充當一種上舉氣體，使淤漿循環上升，然後離 開裝置，同時再生隨淤漿循環上升而上升的鈍化觸媒粒子 ，離開頂部，然後回到反應器的主淤漿體內。觸媒之再生 產生一種含氨的廢氣，其上升及離開裝置，進入箭頭8 4 所示的氣體空間7 2內及經由管線7 4離開，伴隨氣以 H C S反應產品當作反應器尾氣的部分。此尾氣經由管線 7 4通過一間接熱交換器8 6，其將氣體冷卻，藉以將部 分的氣態烴類凝結成烴液體且將H C S反應所產生的水蒸 氣之大部分凝結成液態水，其含有觸媒鈍化物及充氧物。 剩餘的尾氣混合物、烴液體及反應水，在約1 0 0 — 30 0 °F的溫度範圍，經由管線8 8由熱交換器通往一分 離桶或分離容器9 0。在容器9 0中，液體與氣體分開及 本紙張尺度.適用中國國家標準（CNS)A4規格（210x297公釐） ' •-'--', H *^1 ϋ n ϋ n «^1 a— I k _1 ϋ i_i n ϋ ϋ』0, · I ma— I I —fli ϋ I . (請先閱讀背面之注意事項再填寫本頁) 487695 A7 一 B7 五、發明說明（21) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員X消費合作狂印製 形成兩層，一層爲凝結的H C S反應水，其現含有氨和其 它水溶性化合物，而另一層爲凝結的烴液體。經由管線 9 2由分離容器取出烴液體，然後送至更進一步的處理和 升級作業。經由管線9 4和1 4使含氨和充氧物的水溶液 通入容器1 2內，其中它與天然氣流接觸，該天然氣流由 水中汽提出氨和充氧物以形成乾淨的水及將它們帶入合成 氣發生器2 0內，於其內它們被消耗。然後使汽提所產生 的乾淨水經由管線1 6等通入氣一液接觸容器6 0內，其 中它溶解合成氣中實質上全部的殘餘觸媒鈍化物（例如氨 )。若於一與HCS反應器分開的容器中進行再生時，再 生過程的廢氣係合倂H C S反應器尾氣且送經過熱交換器 和進入氣-液分離器容器內。在氣一液分離之後採用至少 一個階段的熱交換冷卻來處理如所示的各H C S反應器階 段之尾氣。然後，可使用二或多個冷卻階段。例如，若採 用兩個階段，則第二階段中的冷卻後液體和氣體之溫度將 低於第一階段者，由合倂的各階段回收水溶液及送入容器 1 2內。第一階段HC S反應器係在少於1 0 0%CO轉 化率（例如〜8 0 % )下操作，俾經由管線9 8使含有未 反應的Η 2和C 0、減少的水、烴液體、氨和其它水溶性化 合物之第一階段尾氣通往第二HC S反應器1 0 0。因此 ，純化後的第一階段尾氣係爲第二階段H C S反應器的進 料，且藉相同於第一階段反應器6 8所用的方式和裝置向 上通入第二階段反應器1 0 0中的淤漿內。視情況地，一 壓縮機和C〇2移除裝置（未於圖示）可設於分離器9 0與 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 487695 A7 B7 五、發明說明（22) 第二階段反應器之間的管線9 8中。與第一階段反應器類 似，反應器1 0 0亦具有一再生導管或裝置1 0 2及液體 過濾器1 0 4，具有氣體管線1 0 6用於將HC S觸媒再 生氣體導入再生裝置內及具有濾液管1 0 8用於使由淤漿 所移出的烴液體通過以便藉由一或多個轉化作業作更進一 步的處理和升級。H C S反應及觸媒再生的氣態產品係向 上通入氣體空間112內及經由管線114由反應器移出 當作第二階段尾氣。以相同於第一階段H C S反應器的方 式，使該尾氣通往至少一個冷卻和氣-液分離階段。因此 第二階段尾氣係通過間接熱交換器116及冷卻至約 1 0 0 - 3 0 0 °F的溫度，而凝結出水蒸氣的霧氣及一部 分的烴類當作液體，且氣-液混合物係經由管線ί 1 8通 入氣—液分離器1 2 0內。經由管線1 2 2由分離器移出 凝結的烴液體及送往更進一步的處理，同時經由管線 1 2 4由分離器移出含和其它水溶性化合物的第二階段水 及通往管線1 4，於該處它與來自第一階段反應器的廢氣 溶液作合倂，及通入容器1 2內。經由管線1 2 6由分離 器所移出的剩餘尾氣係含有未反應的Η 2和C 0，倂隨著甲 烷、氮和C〇2，其可用當作低價値燃料或通入容器1 2內 或通入合成氣發生器2 0內。 依本發明的H C S方法所製造的烴類係典型地被升級以 成爲更有價値的產品，其係藉使全部或一部分的C5 +烴類 分餾及/或轉化。轉化係意味一或多個作業，其中改變至 少一部分的烴之分子結構，且包括非催化性處理（例如蒸 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) · I ί am— ί ϋ ϋ ϋ 一 1 1 mm— I t n 1 I # 487695 κτ ____Β7_ 五、發明說明（23 ) (請先閱讀背面之注意事項再填寫本頁) 汽裂解），及催化性處理（例如催化裂解），其中餾份與 適當的觸媒接觸。若氫當作反應物存在，則該處理步驟係 指加氫轉化，且例如包括加氫異構化、氫化裂解、氫化除 鱲、氫化精煉及更嚴重的氫化精煉如氫化處理，其皆在烴 進料（包括富含烷屬烴的烴進料）之加氫轉化的文獻中所 熟知的條件下進行。轉化所形成的更有價値之產品的說明 性但非限制性的例子係包括一或多種合成粗油、液體燃料 、烯烴、溶劑、潤滑油、工業油或藥用油、蠟烴、含氮和 氧的化合物等等。液體燃料包括一或多種發動機汽油、柴 油燃料、噴射機燃料及煤油，而潤滑油例如包括汽車、噴 射機、渦輪機和金屬加工油。工業油包括鑿井流體、農用 油、熱傳遞流體等等。 經濟部智慧財產局員工消費合作社印製 雖然已經使藉一使用處理過的天然氣當作發生器的烴進 料之F B S G合成氣發生器、淤漿H C S單元、將合成氣 中的氰化氫水解成氨等等來特別詳細地說明本發明，但是 本發明的實施係不限制這些特定的實施例，如熟悉技藝者 將知道和了解的。因此，可將任何適當且方便的合成氣來 源送入合成氣發生器，且可使用合成氣產生方法，如流體 觸媒床或固定觸媒床、非淤漿H CS方法。 茲了解熟悉技藝者在不脫離上述本發明的精神與範疇內 可明顯了解且可容易作出本發明實施中的各種不同的其它 實施例和修飾例。因此，所附的申請專利範圍不欲限制於 恰如上述的說明內，而是申請專利範圍意欲涵蓋所有屬於 本發明的新穎可專利之特徵，包括熟悉技藝者在本發明內 本紙張尺度.適用中國國家標準（CNS)A4規格（210 X 297公釐) 487695 A7 B7 五、發明說明（24 )所作的均等處理之特徵和實施例 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作往印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）A7 B7 V. Description of the invention (12) (Please read the precautions on the back before filling out this page) Gou Intellectual Property of the Ministry of Economic Affairs (Other water-soluble compounds produced by industrial and consumer cooperatives (eg, oxygenates such as acids) , Alcohols, aldehydes, etc.). In the embodiment shown, the catalyst is regenerated at the site, which produces ammonia-containing waste gas, and the reactor is producing hydrocarbons. As shown, in this embodiment, The exhaust gas of the regeneration process is combined with the tail gas of the HCS reactor, and the combined stream is cooled to condense at least a part of the water, which forms an ammonia solution with ammonia and other water-soluble compounds, which is passed into the FBSG. The natural gas stream extracts these water-soluble compounds from the downstream water vapor and passes into the syngas generator with the gas, where they are destroyed by heating and by the equilibrium control conditions in the generator, and therefore they are effectively disposed of. From these The water obtained from the stripping of water-soluble compounds (which has been defined above as clean water) flows out from the bottom of the container via line 16 and passes through heat exchanger 17, where it is cooled It then enters the scrubber 60 through line 19, where it comes into contact with the hydrolyzed syngas, from which most of the HC Ν and Ν Η 3 have been removed, as a washing chain or finishing step to remove any HC Ν and Ν Η 3 remaining in the gas to the extent of less than 5 0 ν ppb, and preferably less than 10 vppb. At least 95% from water vapor, preferably at least 98%, and more preferably at least 9 9 % Ammonia and any residual hydrogen cyanide to produce clean water. This water will typically contain less than 100 mg / L of ammonia and less than 1 mg / L (e.g. 0- < 1 mg / L ) Hydrogen cyanide. Optionally, a reboiler (not shown) can be located at the bottom or outside of the tower 12. As known to those skilled in the art, this reboiler can be used to heat a portion of clean water to Manufacture steam, if necessary, ensure that the hydrocarbon feed stripping gas is at the desired humidity. This steam will pass through the tower with the hydrocarbon feed gas. Water-saturated natural gas is passed from the humidifier through a pipeline i 8 Paper size applies Chinese National Standard (CNS) A4 specification (210X297 meal) 487695 κτ Β7 ___ printed by the company V. Description of the invention (13) The gas generator 12 enters the synthesis gas generator 20. The synthesis gas generator may further include more than one container, as known to those skilled in the art. It may be, for example, The fluid bed syngas generator (FBSG), self-heating generator, and partial oxidation unit may be a fixed catalyst bed connected to the fluidized catalyst bed, as disclosed in U.S. Patent No. 5,421,850. And these units The advantages are discussed in, for example, U.S. Patent Nos. 3,44,370 and 5,244,641. In the FBSG, partial oxidation occurs in the presence of a fluidized bed of steam reforming catalyst particles. A typical steam reforming catalyst system includes a catalytic nickel component on alpha alumina, as disclosed in U.S. Patent 5,395,406. FBSG has excellent heat transfer characteristics, and fluidized catalyst beds can also contain high temperature and heat resistant materials, such as alpha alumina, as known. For the purpose of illustration, the synthesis gas generating unit 20 will be considered as a type of FBSG unit. Typical conditions in FBSG include a pressure range of about 10-50 atmospheres, preferably 10-40 atmospheres, and more preferably 20-40 atmospheres, and the temperature range will be essentially non-catalytic hot particles Within about 50 ° F of the softening point, preferably from about 1650 ° F to about 2000 ° F, and more preferably from about 1 700 T to about 180 ° T. If needed, additional water vapor or steam can be sent into the FBSG through line 22, and oxygen or oxygen-containing gas (such as air, oxygen diluted by N2 or steam, etc.), preferably oxygen, is passed through the line 24 into the FBSG. In FBSG, the hydrocarbons in natural gas, including most of the methane and typically accompanied by a small amount of C 2 -C 8 hydrocarbons, are partially oxidized and recombined by catalytic steam to produce a type containing H 2 and C. A mixture of syngas. The ammonia system proposed by the water in the water enters this paper standard and applies the Chinese National Standard (CNS) A4 specification (210 X 297 meals)-(Please read the precautions on the back before filling this page) One Pack ------ — — Order ---! ιι · /: ν, 487695 Β7 V. Description of the invention (14). — — 1 — — — — — — — — I-(Please read the precautions on the back before filling this page) In FBSG, among others The concentration is adjusted by the equilibrium state to effectively dispose of ammonia. The organic matter extracted from the humidified water in 12 was also destroyed in the generator. Due to the high temperature in the synthesis gas generator, the synthesis gas leaving the unit via line 24 is passed through the first cyclone and the second cyclone (not shown) and optionally passes through the heat exchanger 2 6 (or A member of the Intellectual Property Bureau of the Ministry of Economic Affairs, X-Consumer, printed turbines for power generation), which may be a steam generator that cools it to a temperature below 100 ° F, and then enters the pipeline via line 28. The energy gas-water contact device is used in this description, which is a Fenqiuli scrubber 30. If a heat exchanger is not used, contact the water in the scrubber to cool the gas. Venturi scrubbers are well known and need no explanation. Other forms of high-energy contact devices include cyclonic scrubbers, impact plate scrubbers, mechanical scrubbers such as Roto-Clone (American Air Filter Corporation), and the like. Syngas contains a small amount of particulate matter from FBSG (such as catalysts and fine solids for heat transfer). When it passes downward through the Fenqiuli scrubber, it and the water that enters Fenqiuli through pipeline 36 In contact, it cools the gas to about 300-400 ° F and also removes particulate matter from the gas. The washed gas and water containing particulate matter enter the separator-demister 34 through the conduit 32, and the fine particles containing water are separated from the gas. The crimped metal wires, metal wire nets, loose fillings, etc. in the upper part of the device (not shown) can remove the particle-containing mist formed in the Fenqiuli scrubber, which coalesces in the containing In the particle water, this water is combined with a large amount of particle-containing water that enters the device through the scrubber. The ammonia water taken out by the separator 5 6 through the line 5 8 enters the top of 3 4 and flows down through the defogging device, where it contacts the coalesced mist and upstream gas to ensure that the gas leaves the paper scale. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ΓΤΤ- 487695 A7 B7 V. Description of the invention (15) The separator-demister does not contain particles before. Optionally, all or part of the water entering the top of 34 may come from the line 61 of the scrubber 60 and it contains a very small amount of dissolved HCN and NH3. The separator-demister removes the particulate-free and defogged syngas via line 38, and passes it into another heat exchanger 40, where it is cooled to about 400 ° F for use In the subsequent catalytic hydrolysis step. The water phase is taken out from the container 34 through the line 42, and a part is recycled back to the Fenqiuli scrubber through the line 44, and the rest is sent out for disposal through the line 44. Optionally, a part of the water that normally enters the scrubber of Fenqiuli may include the ammonia water separated in 56 or the water from scrubber 60. The cold air system leaving the heat exchanger is passed through the line 46 into the hydrolysis reactor 48. This reactor contains a hydrolysing zone which includes a fixed bed of catalyst for the hydrolysis of HCN to NH3. The catalyst in the HCN hydrolysis zone preferably comprises an oxide of at least one metal selected from the group consisting essentially of Group VI metals, Group I VB metals and mixtures thereof, and especially A 1 and Mo and T Oxides of at least one of i, as disclosed in European Patent Publication EP 0 5 7 969 A. The catalyst uses a composite oxide including about > 0 to 30% by weight of Mo as an oxide, preferably 10 to 20% by weight, and the amount of titanium dioxide present is about > 0 to 30% by weight, preferably 4 To 20% by weight, more preferably 8 to 16% by weight (for example, 8% by weight), and the balance is alumina. An appropriate source of molybdenum and titanium is deposited on an alumina support, after, for example, dipping or incipient wetting techniques, and then indignified at a temperature of about 250-500 ° C, and preferably at 3 50 — 450 ° C to produce oxide forms. A temperature of about 200-600 ° C is preferred, and 230-550 is preferred. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)- Outfit! 1111 Revision II --- 1ΙΛ Printed by Consumption of Intellectual Property of the Ministry of Economic Affairs X Consumption 487695 ΚΓ B7 V. Description of the invention (16) ° C, treat the catalyst with hydrogen for 1 to 24 hours. Alumina can be any alumina that can be used as a catalyst support and is typically one having a surface area of about 1,000 to 400 square meters per gram. The amount of HCN to be hydrolyzed and to be removed from the synthesis gas is typically very small (e.g. < 5000 vppb). Water is typically present in an amount of about 5-25% by volume, but the actual amount of water present may be greater or less, and this amount of water is sufficient to hydrolyze a relatively small amount of H C N present in the synthesis gas. During the hydrolysis reaction, HC N reacts with water and is converted into NH 3 and C 0. At least about 95%, typically at least 98%, and even more than 99% of the HCN lines are converted to NH3. The natural gas includes about 9 6% of the A hospital and 4% of nitrogen. It is catalyzed by partial oxidation and steam recombination in FBSG operated at about 1800 卞 and 400ps ia to produce a synthesis gas with an equilibrium limited amount of about 5 p pm of HCN. And about 3 0 p pm of NH3. Water can be used in the Fenqiuli scrubber to remove some of the NH3 and a small amount of HCN from the gas. The temperature, pressure, and space velocity in the HCN hydrolysis zone 48 can be in a wide range of about 100-400 ° C, 1-100 mt, and 2000- 50000 GHSV. The hydrolysis temperature is selected so that the hydrolysis rate achieved in the hydrolysis reactor is sufficient to convert at least 95%, preferably at least 98%, and still more preferably at least 99% of HCN into NH3, depending on the HCN content in the gas and It depends on the hydrolysis temperature in the reactor, while avoiding unfavorable side reactions, such as the methanation of CO in the synthesis gas. The hydrolyzed synthesis gas leaves the reactor 48 via line 50, and then passes through heat exchanger 52, where it is cooled to about 120 ° F and condenses most of the water vapor in the gas, which contains the paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) · I ϋ nnn i_Bi ϋ < -Iy-487695 A7, B7 V. Description of the invention (17) N Η 3. The liquid water produced by this condensation contains most (for example ~ 90%) ΝΗ3, leaving very little ΝΗ3 in the gas. In one experiment, a sample containing 43% Η2, 21.2% CO, 7% CO2, 8.8% 6% N2, 5.4% CH4, 15% H2O, and 34% (by volume% basis) was used. The synthesis gas of vppm NH3 and 6.4vppm HCN passes through the HCN hydrolysis zone at 25 ° C and 26 · 4a tm at a space velocity of 12,000 hours-1, where it contacts the HCN hydrolysis catalyst, which catalyst includes oxidation Aluminum and titanium dioxide support material, impregnated with ammonium heptamolybdate and calcined as described above. The HCN concentration of the synthesis gas leaving the reactor is less than 20 vpp b, which represents removal of more than 99% of H CN. Repeat this experiment, using a more sensitive analytical procedure, revealing that it is less than 10 ν ppb. Operating the hydrolysis reactor for 1 2 7 days, no reduced HCN was detected Removal of activity. In another experiment, the same as the above experiment, but the temperature of the hydrolysis reactor was 16 5 ° C, and the HCN concentration of the leaving synthesis gas was 269 vppb, indicating that 95. 8% of 11 CN was in the reactor. Conversion. After hydrolysis and water washing, the synthesis gas can be passed through one or more beds containing HCN and NH3 adsorbents such as alumina or activated carbon, and the downstream of the HC S reactor is monitored to prevent the concentration of HCN and NH3 in the synthesis gas. Breakthrough. Although the catalytic hydrolysis of HCN to ΝΗ3 is shown in this preferred embodiment, the catalytic hydrogenation of HCN to Ν 亦可 3 can also be used, for example, as disclosed in European Patent Publication EP 〇 0 6 7 1 3 7 Α and British Patent Application Case GB 2 267 048 A. Then the gas and ammonia water formed in the heat exchanger are passed into the gas-liquid separator 56 through the line 54, which may be a simple separation barrel, the paper size of which is generally used in China National Standard (CNS) A4 Specification (2 10 X 297 mm) (Please read the notes on the back before filling out this page)-· 1 III II I Order! 11! · Jingqi spfe »Yue Hui Property Gou 11 Xiao Fei Ke Cha i-ZU- 487695 ΚΓ Β7 V. Description of the invention (18) (Please read the notes on the back before filling out this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumption method printed in the ammonia solution is separated from the gas and returned to the container 3 via line 5 4 as washing water. The advantage of converting H C N to N Η 3 is that N Η 3 is extremely water-soluble, but H C Ν cannot be sufficiently dissolved in water in order to remove H C Ν from the gas to a desired level. When the natural gas is sent into the syngas generator and the above-mentioned hydrolysis catalyst and conditions are used, the amount of HCN remaining in the syngas after hydrolysis is < 20 vppb. The synthesis gas leaving the separator 56 enters the scrubber 60 through the line 58. The scrubber is a cap and a tray tower, and a high-surface area radon filling such as a radon ring radon filling tower, etc. . Wash water is a kind of clean water recovered from the container 12. It is cooled to a temperature of about 50 ° C by passing directly through the heat exchanger 17 and enters the top of the scrubber via line 19 and flows downward to contact Upstream synthesis gas and substantially all ammonia in the gas to produce a washed synthesis gas, the NH3 content of this synthesis gas is less than 20vppb, preferably less than 10vppb of NH3, and about 10vppb of HCN . Although the scrubber is operated at 50 ° C in this example, it may be operated at a temperature of about 25-120 ° C. Remove the effluent water containing the removed N Η 3 from the scrubber via line 33, and dispose of it in any convenient manner, including recycling back to the syngas generation step, separator-demister, high-energy contact device , Using nitrogen or fuel gas to strip NH3, and purge it into the fuel beam, or for biological treatment. The washed synthesis gas leaves the scrubber via line 6 2 and passes into the adsorption zone shown in container 63, where it is connected to one or more solid adsorbents which are selected to adsorb HC Ν and ΝΗ 3 Non-limiting illustrative examples in the presence of Co, Co2, 〇2, and Η20 include zeolite molecular sieves, activated carbon, Z η 0, alumina, etc.-This paper applies China National Standard (CNS) A4 specification (210 X 297 mm) 487695 κτ _Β7 _____ V. Description of the invention (19) (Please read the notes on the back before filling this page), etc. Among them, activated alumina and activated carbon are preferred . Adsorption of residual HCN and NH3 is performed at a temperature of 25 to 120 ° C, a pressure of 1 to 100 atm, and a space velocity of about 2000 to 2000 s c f / hr. The synthesis gas produced by this adsorption step will contain less than 50, preferably less than 20, and more preferably less than 10 vppb of the combined total of HCN and NH3, and it is suitable for use in Fisher-Nepal hydrocarbons and methanol. Synthesis. However, in this embodiment, after leaving 6 4 via line 6 3, the gas passes through a sulfur absorber 65, which contains an appropriate sulfur absorbent such as zinc oxide, which removes sulfur compounds in the gas at least less than 50 vppb, and more preferably less than 10 vppb. This produces a synthesis gas that is essentially free of HCN, NH3, and sulfur, which can then be used in Fisher-One synthesis to reduce the passivation of the catalyst. The member of Economic Village Intellectual Property Bureau X. Consumption combined with fi is printed in the illustrated embodiment. This synthesis gas then enters the bottom of the first stage hydrocarbon synthesis reactor 6 8 via line 66 and passes through the slurry (not shown in the figure). ) Gas distribution device at the bottom (not shown), the top of the slurry is represented by 70. In the reactor, the synthesis gas rises into the slurry with bubbles, and H2 and C0 react in the presence of solid particles, that is, the granular Fe / Snow catalyst is suspended or dispersed in the slurry to produce hydrocarbons. Class, which is at least partially liquid under reaction conditions. The H C S reaction also produces water vapor (steam) ', C 0 2 and some hydrocarbons, which are gaseous under the reaction conditions. Synthetic hydrocarbons (which are liquid under reaction conditions) include slurry liquids, which are separated from the catalyst particles and removed from the reactor by a suitable device, as simple as by one or more boxes 7 6 The illustrated liquid filter, hydrocarbons leave the reactor via line 7 8 for upgrading. Synthetic gas has only a small amount of catalyst passivation. This paper size applies the Zhongguanjia Standard (CNS) A4 specification (210 X 297 meals). Fee: First: £ 487695 __Β7_ 5. Description of the Invention (2G) This produces a very pure hydrocarbon liquid that can be easily fractionated and can be upgraded by one or more hydroconversion operations without the need to process the compound There exists the required processing. This is because nitrogen compounds poison the hydrotreating catalyst, which means that if sulfur is present, the hydrotreating must be performed at high temperature and pressure. This is more selective for gases and less for liquid products. Sexual (compared to low temperature and low pressure). The gaseous reaction products, including a large amount of water vapor or steam, pass through the slurry upward with the unreacted gas, enter the gas space 72 above the slurry, and then leave the reactor as a tail gas via a line 74. The HCS catalyst regeneration device 80, as disclosed in the prior art, has a duct with two ends open, which is immersed in the slurry and the top portion extends upward into the gas space 72. The gas line 82 injects an HCS catalyst regeneration gas containing hydrogen into the inside of the device 80. The rising regeneration gas acts as an upward gas, which makes the slurry cycle rise, then leaves the device, and at the same time, regenerates the passivated catalyst particles that rise with the rise of the slurry cycle, leaves the top, and then returns to the main slurry body of the reactor. The regeneration of the catalyst produces an ammonia-containing exhaust gas, which rises and leaves the device, enters the gas space 72 shown by the arrow 8 4 and exits through the line 74, and the accompanying gas uses the H C S reaction product as a part of the reactor tail gas. This tail gas passes through an indirect heat exchanger 86 through line 74, which cools the gas, thereby condensing part of the gaseous hydrocarbons into a hydrocarbon liquid and condensing most of the water vapor produced by the HCS reaction into liquid water, which contains Catalyst passivation and oxygenation. The remaining tail gas mixture, hydrocarbon liquid, and reaction water pass from line 8 8 to a separation barrel or separation vessel 90 at a temperature range of about 100 to 300 ° F. In container 90, liquid and gas are separated and the paper size. Applicable to China National Standard (CNS) A4 (210x297 mm) '• -'--', H * ^ 1 ϋ n ϋ n «^ 1 a— I k _1 ϋ i_i n ϋ ϋ 』0, · I ma— II —fli ϋ I. (Please read the precautions on the back before filling this page) 487695 A7 One B7 V. Description of the invention (21) (Please read the back first Please note that please fill in this page again.) Member X of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed two layers of consumer cooperation, one layer is condensed HCS reaction water, which now contains ammonia and other water-soluble compounds, and the other layer is a condensed hydrocarbon liquid. The hydrocarbon liquid is removed from the separation vessel via line 92 and sent to further processing and upgrading operations. An aqueous solution containing ammonia and oxygenates is passed into the vessel 12 via lines 9 4 and 14 where it is in contact with a natural gas stream which strips ammonia and oxygenates from the water to form clean water and separates them Taken into the syngas generator 20, where they are consumed. Then, the clean water produced by the stripping is passed into the gas-liquid contact container 60 through a pipeline 16 or the like, in which it dissolves substantially all the residual catalyst passivation (such as ammonia) in the syngas. When regeneration is performed in a container separate from the HCS reactor, the exhaust gas from the regeneration process is combined with the H C S reactor tail gas and passed through the heat exchanger and into the gas-liquid separator container. After the gas-liquid separation, at least one stage of heat exchange cooling is used to treat the tail gas of each H C S reactor stage as shown. Then, two or more cooling stages can be used. For example, if two stages are used, the temperature of the cooled liquid and gas in the second stage will be lower than those in the first stage, and the aqueous solution will be recovered from each combined stage and sent to the container 12. The first stage HC S reactor is operated at less than 100% CO conversion (for example ~ 80%), and the unreacted plutonium 2 and C 0, reduced water, hydrocarbon liquid are contained via line 9 8 The first stage tail gas of ammonia, ammonia and other water-soluble compounds goes to the second HCS reactor 100. Therefore, the purified first-stage tail gas is the feed to the second-stage HCS reactor, and is passed upwardly into the second-stage reactor 100 by the same method and device as those used in the first-stage reactor 68. Inside the slurry. Depending on the situation, a compressor and a CO2 removal device (not shown) can be installed in the separator 90 and this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumer Cooperative of the Property Bureau 487695 A7 B7 V. Description of the invention (22) The pipeline 9 between the second stage reactors. Similar to the first-stage reactor, the reactor 100 also has a regeneration duct or device 102, a liquid filter 104, and a gas line 106, which is used to introduce the regeneration gas of the HC S catalyst into the regeneration device. And a filtrate pipe 108 for passing the hydrocarbon liquid removed from the slurry for further processing and upgrading by one or more conversion operations. The gaseous product of the H C S reaction and the catalyst regeneration is passed upward into the gas space 112 and removed from the reactor through the line 114 as the second stage exhaust gas. In the same way as the first stage H C S reactor, this tail gas is passed to at least one cooling and gas-liquid separation stage. Therefore, the exhaust gas in the second stage is passed through the indirect heat exchanger 116 and cooled to a temperature of about 100-300 ° F. The mist of the water vapor and a part of the hydrocarbons are regarded as liquids, and the gas-liquid mixture is passed through The line ί 18 is passed into the gas-liquid separator 1 2 0. The condensed hydrocarbon liquid was removed from the separator via line 1 2 2 and sent to further processing, while the second stage water containing and other water-soluble compounds was removed from the separator via line 1 2 4 and passed to line 14. Here it is combined with the exhaust gas solution from the first-stage reactor and is passed into the container 12. The remaining tail gas removed by the separator via line 1 2 6 contains unreacted plutonium 2 and C 0, which can be used as low-cost plutonium fuel with methane, nitrogen, and C 0 2 or passed into container 12 Or pass into the syngas generator 20. Hydrocarbons produced in accordance with the H C S process of the present invention are typically upgraded to more expensive products by fractionating and / or converting all or a portion of the C5 + hydrocarbons. Conversion means one or more operations, in which the molecular structure of at least a portion of the hydrocarbons is changed, and includes non-catalytic treatment (for example, the size of the steamed paper is applicable to China National Standard (CNS) A4 (210 X 297 mm)) Read the notes on the back and fill in this page) · I ί am— ϋ ϋ 1 1 1 mm— I tn 1 I # 487695 κτ ____ Β7_ V. Description of the invention (23) (Please read the notes on the back before filling in this Page), steam cracking), and catalytic treatments (such as catalytic cracking), in which the distillate is contacted with the appropriate catalyst. If hydrogen is present as a reactant, this processing step refers to hydroconversion and includes, for example, hydroisomerization, hydrocracking, hydrodehydration, hydrorefining, and more severe hydrorefining such as hydrotreating, which are all in The hydroconversion of feeds, including paraffinic hydrocarbon-rich hydrocarbon feeds, is performed under conditions well known in the literature. Illustrative but non-limiting examples of more expensive products formed by conversion include one or more synthetic crude oils, liquid fuels, olefins, solvents, lubricants, industrial or pharmaceutical oils, wax hydrocarbons, nitrogen-containing and Oxygen compounds and so on. Liquid fuels include one or more of engine gasoline, diesel fuel, jet fuel, and kerosene, while lubricants include, for example, automobiles, jet engines, turbines, and metalworking oils. Industrial oils include well drilling fluids, agricultural oils, heat transfer fluids, and more. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, although the FBSG synthesis gas generator, slurry HCS unit, and hydrocyanide in the synthesis gas have been borrowed from a FBSG synthesis gas generator that uses processed natural gas as a hydrocarbon feed. Ammonia and the like are used to explain the present invention in particular detail, but the implementation of the present invention is not limited to these specific embodiments, as those skilled in the art will know and understand. Therefore, any suitable and convenient source of syngas can be sent to the syngas generator, and syngas generation methods such as fluid catalyst beds or fixed catalyst beds, non-slurry H CS methods can be used. It is understood that those skilled in the art can obviously understand and easily make various other embodiments and modifications in the practice of the present invention without departing from the spirit and scope of the present invention. Therefore, the scope of the attached patent application is not intended to be limited to the description just above, but the patent application scope is intended to cover all the novel patentable features of the present invention, including those skilled in the art in this paper. Applicable China National Standard (CNS) A4 Specification (210 X 297 mm) 487695 A7 B7 V. Features and Examples of Equal Treatment by Invention Description (24) (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Bureau's consumer cooperation to print this paper The size of the paper applies to China National Standard (CNS) A4 (210 X 297 mm)