201040137 六、發明說明： 【發明所屬之技;財領域】 本發明係關於呈液態且因存在以不同形 而受污染之煙原料之脫汞處理的領域。更:“:而：汞 關於一種移除存在於液態煙原料中之朱物質之製程，1製 程係在用於捕捉該等汞物質之由包含至少一個硫^㈣之 有機基團或衍生物的有機_無機混合材料形成之材 下進行。 本發明之目的在於藉助於使料—液相階段之製程捕捉 存在於液態烴原料中之不同物質中之汞而不藉助於對該煙 原料之先前預處理階段，例如熱預處理階段或氫化階段。 【先前技術】 熟習此項技術者已知一些為液態或氣態之烴礦床受元素 汞污染。在此等烴之稍後處理期間，汞呈現出環境及安全 性問題。此外，其亦抑制在提純此等粗烴原料之下游所執 行之製程中所用的某些催化劑。 部分I :存在之汞物質 熟習此項技術者已知元素汞以不同化學形式存在於有機 相中。此尤其反映在藉由蒸館受污染粗烴原料所獲得之顧 份組中存在汞衍生物（P Sarrazin, C. J· Cameron，Y, Barthel, Μ. Ε. Morrison, Processes Prevent Detrimental Effects from As and Hg in Feedstocks, Oil and Gas Journal, 1993，86) °然而’且儘管許多科學出版物涉及此研究領 域’但此等物質之確切化學性質尚未被清楚地鑑別。僅證 140315.doc 201040137 實存在金屬汞（B. Edmonds, Mercury partitioning in natural gases and condensates, GPA European Chapter Meeting 1996年3月21日）。有機金屬衍生物（R-Hg-R'，其 中R及R'為烷基或苯基類型之烴基）或非水溶性離子化合 物，以及此兩個族系之可能組合之存在已有所提及（札 Tao, T. Murakami, M. Tominaga, A. Miyazaki, Mercury speciation in natural gas condensate by gas chromatography inductively coupled plasma mass spectrometry, Journal of Analytical Atomic Spectrometry, 1998，13，1085)。詳言 之，Tao及其同事教示一種測定存在於液態有機介質t之 汞物質之方法。一個目前論述之假設為汞亦可以「錯合 物」形式（以與鎳能夠形成諸如Ni卟啉之錯合物相同的方 式）存在。因此，錯合的金属Hg並不直接可獲得且其天然 反應性可因此有變化。201040137 VI. Description of the Invention: [Technology of the Invention; Financial Field] The present invention relates to the field of mercury removal treatment in a liquid state and due to the presence of contaminated tobacco materials in different shapes. Further: ": and: mercury is a process for removing the Zhu material present in the liquid smoke material, and the process is for the organic group or derivative containing at least one sulfur (4) for capturing the mercury species. The organic-inorganic hybrid material is formed under the material. The object of the present invention is to capture the mercury present in the different substances in the liquid hydrocarbon raw material by means of the process of the liquid-liquid phase without resorting to the prior preparation of the raw material of the tobacco. Processing stage, such as a thermal pretreatment stage or a hydrogenation stage. [Prior Art] It is known to those skilled in the art that some liquid or gaseous hydrocarbon deposits are contaminated with elemental mercury. During later processing of such hydrocarbons, mercury presents an environment. And safety issues. In addition, it also inhibits certain catalysts used in processes performed downstream of the purification of these crude hydrocarbon feedstocks. Part I: Mercury species present are known to the skilled artisan. Elemental mercury is known in different chemical forms. It is present in the organic phase. This is especially reflected in the presence of mercury derivatives in the group obtained by steaming the contaminated crude hydrocarbon feedstock (P Sarrazin, C. J. Cameron, Y, Barthel, Μ Mor. Morrison, Processes Prevent Detrimental Effects from As and Hg in Feedstocks, Oil and Gas Journal, 1993, 86) ° However, and although many scientific publications cover this field of study, the exact chemical nature of such substances has not been known. Identification: only 140315.doc 201040137 There are metal mercury (B. Edmonds, Mercury partitioning in natural gases and condensates, GPA European Chapter Meeting March 21, 1996). Organometallic derivatives (R-Hg-R', Wherein R and R' are alkyl or phenyl type hydrocarbyl groups or water insoluble ionic compounds, and the existence of possible combinations of the two families is mentioned (Za Tao, T. Murakami, M. Tominaga, A. Miyazaki, Mercury speciation in natural gas condensate by gas chromatography inductively coupled plasma mass spectrometry, Journal of Analytical Atomic Spectrometry, 1998, 13, 1085). In detail, Tao and his colleagues teach a determination of the presence of liquid organic medium t The method of mercury substances. A hypothesis that is currently discussed is that mercury can also be in the form of a "complex" (to be able to form with nickel) It is present in the same manner as a complex such as Ni porphyrin. Therefore, the miscible metal Hg is not directly available and its natural reactivity can be varied accordingly.
部分II 經發展用於捕捉汞之最初方法係基於金屬汞與含硫化合 物之強親和力。另外，應注意僅此特定形式之汞具有該親 和力。已觀察到該金屬汞主要處於非冷凝氣相或LPG(液化 石油氣）餾份中。此等後者為主要含有具有3及4個碳原子 之烴之烴餾份。此等烴具有在周圍狀態下呈蒸氣形式且於 弱正壓下冷凝之特性。因此’對於接近環境之溫度（30_ 70T：)而言，可根據脫汞處理進行時之壓力而以氣態或液 態形式獲得LPG餾份。因此，基本上發展了基於藉由汽相 沈積（S或H2S熱蒸氣）或藉由用水溶性硫元素之前驅體進行 140315.doc 201040137 t =潰沈積了硫之活性碳之第—吸附劑（或采捕捉材料） ㈣心淨化氣相D舉例而言，us M58,334描述一種能 夠自僅為氣相之烴館份移除汞之製程。據教示該製程具有 移除主要金屬形式之采之功能。制領域為氣體蒸氣流之 領域n使肖切捕捉材❹有將硫元素釋放至介質 中之缺點’此係由於硫並非不可逆地滞留於構成該捕捉材 料之部分的載體上。 衍生自上述用於處理氣態原料之特定製程且用於其允許 處理流體U其液體）的作用之製程亦已報導於該文獻中。 因此’專利FR 2,628,338及印2,764 214揭示允言午淨化液態 煙潑份之兩階段製程。如上文所提及，在有機介質中，元 素汞可以不與上述含硫捕捉材料具有特定親和力之非水溶 性無機鹽或有機金屬化合物之形式存在。因此，一種解決 方案在於預處理該原料以便使汞之衍生物轉化為金屬录，' 而其又可吸附於該等捕捉材料上。上述專利提出藉由在第 一階段期間使烴原料氫化來預處理該烴原料，在此之後進 仃在含硫捕捉材料上之標準「吸附」階段。然而，此預處 理階段通常要求約18(rc之高溫條件，及隨之在提純地點 存在氫，此與所有提純廠均不相容。此外，另一缺點在於 下事貫弟一卩自ί又中所用之基於硫之捕捉材料並不滞留 所有最初存在於烴餾份中之汞衍生物。 第二吸附劑族系已在文獻（us 5,223，145)中加以鑑別。 此部分由沸石組成之物質在兩階段製程之第二階段中起作 用，製程之第一階段由在不存在氫之情況下熱預處理原料 140315.doc 201040137 組成。向金屬汞之轉化係藉由熱分解初始汞衍生物來提 供°更確切而言’該吸附劑為基於FAU結構類型之銀促進 ί弗石的可再生分子篩，其根據反應/再生循環來起作用。 亦必須在每一循環後回收經吸附接著解吸附之液態汞且必 .須考慮經由合適之汽化再使用此後者。此外，汞並非不可 逆地滯留於該篩上且因此其可潛在地釋放至介質中之事實 會導致製程之中間相及過渡相中之可能污染。 〇 目前’對於液態原料之脫汞處理所提出之解決方案均使 用對游離水敏感之捕捉材料。此等材料為（例如且不完全） 基於紹基質之吸附劑、能力因水而變化之吸附劑及在水存 在下失去機械強度之活性碳。一般地’因此必須分離比游 離水’例如經由傾析器隨後聚結器，隨後才處理存在於初 始原料中之兩個相，水相及有機相中之每一者。該水事實 上常常存在於油或天然氣生產井之出口處的粗餾份中。事 實上4人所周知使用水作為輔助流體來增加存在於礦床令之 Q 烴之回收程度。因此常常有必要於井之出口處處理多相氣 體-有機液體-水性液體混合物。一些水藉由傾析而被分 離，接著再循環至井中，但一些水與所產生之液態烴一起 被淨化。必須在脫汞處理反應器之上游萃取此水。（第2屆 歐洲石化產品技術會議（2nd European PetrochemicalsPart II The initial method developed to capture mercury is based on the strong affinity of metallic mercury to contain sulfur compounds. In addition, it should be noted that only this particular form of mercury has this affinity. It has been observed that the metallic mercury is mainly in a non-condensed gas phase or an LPG (liquefied petroleum gas) fraction. These latter are hydrocarbon fractions mainly containing hydrocarbons having 3 and 4 carbon atoms. These hydrocarbons have the property of being vaporized in a surrounding state and condensing under a weak positive pressure. Therefore, for the temperature close to the environment (30_70T:), the LPG fraction can be obtained in a gaseous or liquid form depending on the pressure at the time of the mercury removal treatment. Therefore, the first adsorbent based on vapor deposition (S or H2S thermal vapor) or by using a water-soluble sulfur element precursor 140315.doc 201040137 t = crushed sulfur-deposited activated carbon (or Capture material) (4) Heart purification gas phase D For example, us M58, 334 describes a process that can remove mercury from a hydrocarbon column that is only gas phase. It is taught that the process has the function of removing the main metal form. The field of gas vapor flow is a disadvantage of the fact that the Schau trap material has a sulfur element released into the medium. This is because the sulfur is not irreversibly retained on the carrier constituting the portion of the trapping material. Processes derived from the above-described processes for treating gaseous feedstocks and for allowing them to treat fluids U its liquids have also been reported in this document. Thus, the patents FR 2,628,338 and 2,764,214 disclose a two-stage process for purifying liquid smoke in the afternoon. As mentioned above, in an organic medium, the elemental mercury may be present in the form of a non-water-soluble inorganic salt or an organometallic compound which does not have a specific affinity with the above sulfur-containing capturing material. Therefore, one solution consists in pretreating the raw material in order to convert the derivative of mercury into a metal record, which in turn can be adsorbed onto the capture material. The above patent teaches pretreating the hydrocarbon feedstock by hydrogenating the hydrocarbon feedstock during the first stage, after which it is subjected to a standard "adsorption" stage on the sulfur containing capture material. However, this pretreatment stage usually requires about 18 (the high temperature conditions of rc, and the subsequent presence of hydrogen in the purification site, which is incompatible with all purification plants. In addition, another disadvantage is that the next step is to The sulfur-based capture material used in the process does not retain all of the mercury derivatives originally present in the hydrocarbon fraction. The second adsorbent family has been identified in the literature (us 5, 223, 145). In the second phase of the two-stage process, the first stage of the process consists of thermally pretreating the raw material 140315.doc 201040137 in the absence of hydrogen. The conversion to metallic mercury is by thermal decomposition of the initial mercury derivative. Providing ° more precisely 'the adsorbent is a renewable molecular sieve based on the FAU structure type of silver-promoting glutinous stone, which acts according to the reaction/regeneration cycle. It must also be recovered after each cycle by adsorption followed by desorption. Liquid mercury must be considered for reuse by suitable vaporization. Furthermore, the fact that mercury is not irreversibly retained on the sieve and therefore potentially released into the medium can result in Potential contamination in the mesophase and transition phase. 〇The current solution for mercury removal from liquid feedstocks uses capture materials that are sensitive to free water. These materials are (eg, not completely) based on the substrate. Adsorbents, adsorbents whose capacity varies with water, and activated carbon which loses mechanical strength in the presence of water. Generally, 'it must therefore be separated than free water', for example via a decanter followed by a coalescer, before being processed in the starting material Two of the phases, the aqueous phase and the organic phase. The water is in fact often present in the crude fraction at the outlet of the oil or natural gas production well. In fact, four people are known to use water as the auxiliary fluid. Increasing the degree of recovery of Q hydrocarbons present in the deposit. It is therefore often necessary to treat the multiphase gas-organic liquid-aqueous liquid mixture at the exit of the well. Some of the water is separated by decantation and then recycled to the well, but Some of the water is purified along with the liquid hydrocarbons produced. This water must be extracted upstream of the mercury removal treatment reactor (2nd European Conference on Petrochemical Technology (2nd) European Petrochemicals
Technology Conference), EPTC 2000, Mercury and Arsenic Removal from Ethylene Plant Feedstocks, B. Didillon, L.Technology Conference), EPTC 2000, Mercury and Arsenic Removal from Ethylene Plant Feedstocks, B. Didillon, L.
Savary’ J. Cosyns，Q. Debuisschert, P. Travers)。因此，存 在於水相中之汞物質係藉由使用第一脫汞處理製程來移除 140315.doc 201040137 且彼等存在於有機相中之汞物質係藉由實施第二脫汞處理 製程來移除。應注意，存在於水相中之汞物質及存在於有 機相中之汞物質極不同，且水性溶液及有機溶液之化學性 質展示了經發展用於水相之脫汞處理與彼等經發展用於有 機相之脫汞處理不相容的許多實例。 此外，最近出現與處理植物及動物油相關之關注問題。 油來自動物（主要為海洋動物）或來自可在受來自陸上或海 上之發電站或天然氣生產地點的含有重金屬（包括汞）之廢 氣〉可染之地區生長茂盛的陸地植物。若該油為植物來源， 則汞由植物固定且保留在植物結構内，部分保留在其纖維 物質或其含油部分中。在動物生物之情況下，同樣如此， 在暴露於污染物後大部分汞固定於脂肪中。最近以替代油 為目的而引起脂肪物質來源多樣化之關注為提倡使用此等 脂肪作為燃料基質。在此情況下，能夠在轉化為燃料基質 之前處理此等脂肪物質，以便能夠由此避免汞散播至生態 系統中為較重要的。現今，並沒有已知的能夠使脂肪物質 轉化為燃料基質同時全面處理存在於原料中之采之移除的 製程。 、 【發明内容】 本發明之標的物係一種移除存在於液態烴原料中之汞物 質之製程，該製程以單階段進行且包含在至少一個固定床 反應器中ϊ吏該原#與捕捉該等汞物質之材料相接觸地置 放，該反應n經定尺寸以使得該固定床之高度大於或等於 忒床之直徑的二倍且該反應器之入口與出口之間的壓降包 140315.doc 201040137 含在0.2巴/公尺與1巴/公尺固定床之間，該捕捉材料甴包 含至少一個硫醇類型之有機基團或衍生物之有機—無機混 合材料形成且以直徑包含在1.2 mm與ι·8 mm之間的擠出物 形式存在》 本發明之移除製程所針對之汞物質尤其為金屬汞H g 〇、 諸如Hg+及Hg2+之自水溶性鹽獲得之汞離子、非水溶性離 子汞化合物、汞之有機金屬化合物及此等物質每一者之混 合物。該等存在於烴原料中之汞物質化學吸附於捕捉材料 上，該捕捉材料藉由形成Hg_S鍵而使該等物質不可逆地轉 化為辰砂。 用於實施根據本發明之製程之捕捉材料有利地由包含至 少一個有機硫醇基R-SH之有機-無機混合材料形成，其中r 較佳為具有2至5個碳原子之飽和直鏈烷基鏈。 本發明之益處 ❹ 〜根據本發明之使用包含至少_個硫醇類型之有機基困或 何生物之〇〗Η Μ (有機-無機混合材料）作為捕捉材料的製程 允許以單-階段處理其中存在不同形式之汞物質之液態煙 原料，而無需執行對該原料之早先預處理。此外，根據本 發明之製程之-優點在於其有利地於通常包含在抓與 9〇C之間的低溫下實施，此意謂該製程使用較少能量。根 據本發明之製程之另__優點在於如下事實，其不需要使用 氫且因此與在孤立地點上使用相容，例如彼等靠近炉生產 地點且無平行氫生產之地點。另一方面，在藉由化學吸附 捕捉汞期間’不可逆地固定汞，此避免汞流動的所有危險 140315.doc 201040137 以及污染所產生排出物之所右 物之所有危險。此外’根據本發明之 ’點在於其有效地移除所有存在於液相之烴 =料中之水物質，無論其化學性質如何。根據本發明之製 程產生以下本發明描述中所定義之最大捕捉效率，亦即至 少等於90%或甚至大於95%。根據本發明之製程之另一主 要優點在於該製程亦允許處理其中存在水之煙原料由該 有機-無機混合材料形成之捕捉材料對水不敏感；詳言 之，根據本發明之該製程允許同時移除不僅存在於液態烴 原料之有機相中且亦存在於該原料之水相中之汞物質此 使得不必在脫汞處理之上游進行任何水相分離階段。因 此，根據本發明之製程可有利地用於移除存在於來自鑽井 =由水性部分及有機部分形成之整個液體流出物中之果物 質此外根據本發明之該製程對於移除存在於動物或植 物來源之特定烴原料（脂肪酸甘油三醋及其與游離脂肪 酸、色素、固醇之混合物)中之采物質亦為有效的。 此外’驚人地發現，在滿^關於較床之高度、固定床 之直徑及穿過反應器之壓降的明確定義之液壓標準之固定 床反應器中使用〇臟作為以直徑包含在12腿與18随 之間的擠出物形式存在之捕捉材料引起捕捉汞之效能與藉 由在尺寸不滿^所有此等三個標準之固定床反應器中使用 同類材料（亦即0IHM)獲得的彼等效能相比而言之改良。 使用至少等於3之最小{固定床高度/固定床直徑}比率及在 0.2巴/公尺與丨巴/公尺固定床之間精確選擇之穿過反應器 的Μ降出人意料地允許獲得最佳化效能。 140315.doc -10- 201040137 【實施方式】 本發明之標的物係—種移除存在於液態烴原料中之录物 質之製程，該製程以單階段進行且包含在至少一個固定床 反應器中使該原料與捕捉該等汞物質之材料相接觸地置 纟，該反應11經定尺相使得㈣定床之高度大於或等於 . /床之直仫的一倍且該反應器之入口與出口之間的壓降包 含在0.2巴/公尺與1&/公尺固定床之間，該捕捉材料由包 〇 纟至少—個硫醇類型之有機基團或衍生物之有機·無機混 〇材料开v成且以直徑包含在〗2爪爪與丨8 之間的擠出物 形式存在。 待根據本發明之移除製程處理之存在汞物質的烴原料是 主要為液態之原料，亦即大於95體積％為液體，且該烴原 料極較佳完全呈液態。有利地，其為包含具有3至6〇個碳 原子的分子之烴原料。該液態烴原料可為粗原料或早先已 經受例如藉由蒸餾進行之分離階段且由此呈特徵為初满點 〇 及終沸點之烴餾份之形式的原料。若其為經蒸餾之原料， 則有利地使用具有包含在5。(：與3(rc之間的初沸點及包含 在200°C與550°C之間的終沸點之液態烴原料。尤其，該液 態烴原料係選自天然氣之冷凝物、原油、動物或植物油及 來自此等後者之顧出物。 該烴原料中汞物質之含量無關緊要：根據本發明之製程 允許移除汞物質，無論原料中該等物質之含量如何。用於 貫紅根據本發明之製程之捕捉材料可有效地移除汞物質， 烴原料中汞物質之濃度變化可極大且例如包含在1〇 140315.doc 201040137 與2000叫·1·1之間，較佳在30 pg.l·1與1000 pg.l1之間。 在粒子（例如存在於鑽泥中之粒子，諸如礦物質氧化鋁 或矽石粒子）存在於根據本發明之製程待處理之原料中的 可能情況下，在由根據本發明之製程實施的脫汞處理之上 游進订過濾以避免由捕捉材料形成之顆粒床之任何「堵 塞」。 根據本發明且根據本發明之製程之一特定實施例，烴原 料包3相對於總烴原料佔〇· i重量％至5重量％之水相。根 據該特疋實施例，捕捉材料可有效地藉由化學吸附同時移 除存在於待純化之烴原料之有機相及水相中的采物質，此 避免了在由根據本發明之製程實施之脫汞處理的上游進行 水相與有機相之任何分離階段。此外，水（例如呈游離水 形式之水）本身亦可存在於根據本發明之製程中而並之存 …干擾該製程之操作。尤其，水及烴可同時引入反應 Γ 在亥反應器中'、要液體-液體液壓系統與由該捕捉 材料形成之顆粒床中之處理相容，就可將該煙原料鱼捕捉 材料相接觸地置放。用於實施根據本發明之製程之固定床 反應器經定尺相使得考慮料錢施加之機械約束。 根據本發明之製程，用於實施該移除汞物質之製程之捕 捉材料藉由化學吸附存在於該液態烴原料中之不同采物質 來發揮作用。評言之’該捕捉材料能夠藉由化學吸附移除 不僅存在於液態烴原料之有德} … 叶有機相中且亦（需要時)存在於水 相中之所有汞物質。心’其尤其能夠移除金屬采Hg、 諸女Hg及Hg之來自水溶性鹽之果離子、非水溶性離子 I40315.doc 201040137 汞化合物、汞之有機金屬化合物及此等物質之每一者之混 口物。存在於烴原料中之汞物質化學吸附於藉由形成Hg_s 鍵使該等物質不可逆地轉化為辰砂之捕捉材料上。 根據本發明之製程係#由將捕捉材料置於待純化之液態 ㈣料所穿過之固定床反應器中來實施。為了改良烴原料 於捕捉材料令之擴散且最佳化該捕捉材料之效率，其應用 於尺寸促進汞物質達到該捕捉材料之活性位點上之反應器 〇 卜根據本發明，實施本發明之製程之固定床反應器經定 尺寸以便滿足液壓標準，尤其關於固定床之高度、固定床 之直仏及穿過反應器之壓降的標準，以便確保原料在該乘 捕㈣料附近之良好擴散。根據本發明，該固定床反應器 ’’·呈疋尺寸以使得固疋床之南纟大於或等於固定床之直徑的 3倍且反應器之人口與出σ之間的料Δρ包含在每公尺固 定床0.2巴與1巴此心MPa)之間。固定床之高度較佳大 2或等於固定床之直徑的5倍且甚至更佳地大於或等於固 〇 疋床之直‘的7倍。反應器之入口與出口之間的壓降ΛΡ對 應於含有果物質之烴原料在存在於固定床反應器中之捕捉 材料上的摩擦。根據本發明，該塵降有利地包含在Μ巴/ 公尺與0.7巴/公尺固定床之間。壓降為所用之捕捉材料床 之粒間工隙度的函數。若存在低粒間空隙度，則壓降高 (參見文章「les deaeteurs ehimiques」，p 〜福崎，了 p Euzen，Edition Technip，2〇〇2，第7章，第 432頁）。為了確 保烴原料在捕捉材料附近之較好分布，有可能(例如)使用 用以堵塞粒間空隙之小内部稀釋劑或亦有可能使液體高速 140315.doc -13- 201040137 穿過捕捉材料床。在於小型設備上（例如於測試台或實驗Savary’ J. Cosyns, Q. Debuisschert, P. Travers). Therefore, the mercury species present in the aqueous phase are removed by using the first mercury removal treatment process 140315.doc 201040137 and the mercury species present in the organic phase are moved by performing the second mercury removal process. except. It should be noted that the mercury species present in the aqueous phase and the mercury species present in the organic phase are very different, and the chemical properties of the aqueous solution and the organic solution demonstrate the development of the mercury removal process for the aqueous phase and their development. Many examples of incompatible mercury removal processes in organic phases. In addition, concerns related to the treatment of plant and animal oil have recently emerged. The oil comes from animals (mainly marine animals) or from terrestrial plants that can grow in contaminated areas that contain heavy metals (including mercury) from power stations or natural gas production sites on land or at sea. If the oil is of plant origin, the mercury is fixed by the plant and remains within the plant structure, partially retained in its fibrous material or its oil-containing fraction. In the case of animal organisms, too, most of the mercury is fixed in fat after exposure to contaminants. The recent focus on diversifying sources of fatty materials for the purpose of replacing oils is to promote the use of such fats as a fuel matrix. In this case, it is possible to treat such fatty substances before they are converted into a fuel matrix, so that it is more important to avoid the spread of mercury into the ecosystem. Today, there are no known processes for converting fatty materials into fuel matrices while comprehensively treating the removals that are present in the feedstock. SUMMARY OF THE INVENTION The subject matter of the present invention is a process for removing mercury species present in a liquid hydrocarbon feedstock, the process being carried out in a single stage and contained in at least one fixed bed reactor, the raw # and capturing the The material of the mercury species is placed in contact, and the reaction n is sized such that the height of the fixed bed is greater than or equal to twice the diameter of the trampoline and the pressure drop between the inlet and the outlet of the reactor is 140315. Doc 201040137 is contained between a fixed bed of 0.2 bar/meter and 1 bar/meter. The capture material is formed of an organic-inorganic hybrid material containing at least one organic group or derivative of a thiol type and is included in the diameter of 1.2. The presence of the extrudate between mm and ι·8 mm” The mercury species targeted by the removal process of the present invention are, in particular, metallic mercury H g 〇, mercury ions obtained from water-soluble salts such as Hg+ and Hg2+, non-aqueous soluble A ionic mercury compound, an organometallic compound of mercury, and a mixture of each of these materials. The mercury species present in the hydrocarbon feedstock are chemically adsorbed onto the capture material which irreversibly converts the materials into cinnabar by forming Hg_S bonds. The capture material for carrying out the process according to the invention is advantageously formed from an organic-inorganic hybrid material comprising at least one organic thiol group R-SH, wherein r is preferably a saturated linear alkyl group having 2 to 5 carbon atoms chain. Advantages of the Invention 〜 The process according to the present invention comprising at least one thiol type organic group or organic 〇 Η 有机 (organic-inorganic hybrid material) as a capture material allows for the treatment in a single-stage process Liquid smoke raw materials of different forms of mercury species without the need to perform an earlier pretreatment of the raw materials. Moreover, the process according to the invention has the advantage that it is advantageously carried out at a low temperature typically comprised between 9 C and C, which means that the process uses less energy. Another advantage of the process according to the invention lies in the fact that it does not require the use of hydrogen and is therefore compatible with use at isolated locations, e.g., where they are close to the furnace production site and where there is no parallel hydrogen production. On the other hand, mercury is irreversibly fixed during the capture of mercury by chemisorption, which avoids all hazards of mercury flow and all hazards to the right of the pollutants produced by the pollution. Further, the 'in accordance with the present invention' is that it effectively removes all of the water substances present in the hydrocarbons in the liquid phase regardless of their chemical nature. The process according to the invention produces the maximum capture efficiency as defined in the following description of the invention, i.e. at least equal to 90% or even greater than 95%. Another major advantage of the process according to the present invention is that the process also allows the processing of the capture material formed by the organic-inorganic hybrid material to be insensitive to water in the presence of water in which the water is present; in particular, the process according to the present invention allows simultaneous The removal of mercury species not only present in the organic phase of the liquid hydrocarbon feedstock but also in the aqueous phase of the feedstock makes it unnecessary to carry out any aqueous phase separation stage upstream of the mercury removal treatment. Thus, the process according to the invention can advantageously be used to remove fruit material present in the entire liquid effluent from the wellbore = formed from the aqueous portion and the organic portion. Furthermore, the process according to the invention is for the removal of the animal or plant present It is also effective to extract materials from a specific hydrocarbon feedstock of the source (fatty acid glycerin and its mixture with free fatty acids, pigments, sterols). In addition, it is surprisingly found that in the fixed bed reactors with a well-defined hydraulic standard for the height of the bed, the diameter of the fixed bed and the pressure drop across the reactor, the smear is used as a diameter in the 12-legged The capture material present in the form of an extrudate with 18 causes the ability to capture mercury and the equivalent energy obtained by using the same material (ie, 0 IHM) in a fixed bed reactor of all of these three standards. In comparison to improvement. The use of a minimum {fixed bed height/fixed bed diameter} ratio of at least 3 and a precisely selected pass through the reactor between 0.2 bar/meter and a bar/meter fixed bed unexpectedly allows for optimization efficacy. 140315.doc -10- 201040137 [Embodiment] The subject matter of the present invention is a process for removing a substance present in a liquid hydrocarbon feedstock, the process being carried out in a single stage and contained in at least one fixed bed reactor. The material is placed in contact with a material that captures the mercury species, and the reaction 11 is subjected to a fixed length such that the height of the (4) fixed bed is greater than or equal to twice the diameter of the bed and the inlet and outlet of the reactor The pressure drop between the two is between 0.2 bar/meter and a fixed bed of 1&/meter. The capture material is made of an organic/inorganic hybrid material containing at least one thiol type organic group or derivative. v is formed and is present as an extrudate having a diameter between the jaws and the jaws 8. The hydrocarbonaceous material in the presence of the mercury species to be treated in accordance with the present invention is a predominantly liquid feedstock, i.e., greater than 95% by volume liquid, and the hydrocarbon feedstock is preferably completely completely liquid. Advantageously, it is a hydrocarbon feedstock comprising molecules having from 3 to 6 carbon atoms. The liquid hydrocarbon feedstock can be a crude feedstock or a feedstock that has previously been subjected to a separation stage, such as by distillation, and thus in the form of a hydrocarbon fraction characterized by an initial point and a final boiling point. If it is a distilled raw material, it is advantageously used to have it included in 5. (: a liquid hydrocarbon feedstock with an initial boiling point between 3 and rc and a final boiling point between 200 ° C and 550 ° C. In particular, the liquid hydrocarbon feedstock is selected from the group consisting of natural gas condensate, crude oil, animal or vegetable oil And the content of the latter from the hydrocarbon feedstock. The content of the mercury species in the hydrocarbon feedstock is irrelevant: the process according to the invention allows the removal of the mercury species, regardless of the content of such materials in the feedstock. The process capture material can effectively remove mercury species, and the concentration of mercury species in the hydrocarbon feedstock can vary greatly, for example, between 1〇140315.doc 201040137 and 2000,·1·1, preferably 30 pg.l· Between 1 and 1000 pg.l1. In the case where particles (for example, particles present in the mud, such as mineral alumina or vermiculite particles) are present in the raw material to be treated according to the process of the present invention, The upstream feed filtration of the mercury removal treatment carried out in accordance with the process of the present invention avoids any "clogging" of the particle bed formed by the capture material. According to a particular embodiment of the process of the invention and in accordance with the present invention, the hydrocarbon feedstock package 3 is relatively to The total hydrocarbon feedstock comprises from 9% by weight to 5% by weight of the aqueous phase. According to this particular embodiment, the capture material can be effectively removed by chemical adsorption while present in the organic and aqueous phases of the hydrocarbon feedstock to be purified. The material is collected, which avoids any separation of the aqueous phase and the organic phase upstream of the mercury removal treatment carried out by the process according to the invention. Furthermore, water (for example in the form of free water) may itself be present in accordance with In the process of the present invention, it interferes with the operation of the process. In particular, water and hydrocarbons can be simultaneously introduced into the reaction Γ in the reactor, and the liquid-liquid hydraulic system and the particle bed formed by the capture material are The processing is compatible, and the tobacco raw material catching material can be placed in contact. The fixed bed reactor for carrying out the process according to the present invention is subjected to a fixed-size phase to make mechanical considerations in consideration of the application of the money. The capture material for performing the process of removing the mercury substance functions by chemically adsorbing different materials collected in the liquid hydrocarbon material. The review of the capture material can borrow Chemical adsorption removes not only all of the mercury species present in the organic phase of the liquid hydrocarbon feedstock but also (if needed) in the aqueous phase. The heart's ability to remove the metal from the Hg, the female Hg and Hg derived from water-soluble salt fruit ion, water-insoluble ion I40315.doc 201040137 Mercury compound, organometallic compound of mercury and a mixture of each of these substances. The mercury substance present in the hydrocarbon raw material is chemically adsorbed The substance is irreversibly converted into a capture material of cinnabar by forming a Hg_s bond. The process line according to the present invention is carried out by placing the capture material in a fixed bed reactor through which the liquid (tetra) material to be purified passes. In order to improve the efficiency of the hydrocarbon feedstock in the capture material to diffuse and optimize the capture material, it is applied to a reactor that promotes the mercury species to reach the active site of the capture material. According to the present invention, the process of the present invention is practiced. The fixed bed reactor is sized to meet hydraulic standards, especially with regard to the height of the fixed bed, the straight line of the fixed bed and the pressure drop across the reactor to ensure (Iv) materials in the multiply-catching good diffusion in the vicinity of. According to the present invention, the fixed bed reactor is sized such that the south enthalpy of the solid boring bed is greater than or equal to three times the diameter of the fixed bed and the material Δρ between the population of the reactor and the σ is contained in each Between the fixed bed of 0.2 bar and 1 bar of this heart MPa). The height of the fixed bed is preferably 2 or greater than 5 times the diameter of the fixed bed and even more preferably greater than or equal to 7 times the straightness of the fixed trampoline. The pressure drop between the inlet and outlet of the reactor corresponds to the friction of the hydrocarbon feedstock containing the fruit material on the capture material present in the fixed bed reactor. According to the invention, the dust fall is advantageously comprised between a bar/meter and a fixed bed of 0.7 bar/meter. The pressure drop is a function of the intergranularity of the bed of capture material used. If there is a low interparticle void, the pressure drop is high (see the article "les deaeteurs ehimiques", p ~ Fusaki, p Euzen, Edition Technip, 2〇〇2, Chapter 7, page 432). In order to ensure a better distribution of the hydrocarbon feedstock in the vicinity of the capture material, it is possible, for example, to use a small internal diluent to plug the interparticle voids or it is also possible to pass the liquid through the capture material bed at a high speed 140315.doc -13 - 201040137. On small devices (such as test benches or experiments)
〇又備上）測试之情況下，將較佳使用填隙稀釋劑（丨加打8出W diluent)，尤其為碳化矽Sic(金剛砂）。在較大設備之情況 下，將使用較高液體線速度來確保〇 2巴/公尺固定床之最 小壓降。 中間加熱器或冷卻器亦可用於本製程之設備中。靜態或 動態混合器亦可用在根據本發明之製程之設備的上游。類 似地，使待純化之液態烴原料分布於反應器之表面上之裝 置可存在於該使用汞捕捉材料之反應器之包封結構中。 根據本發明，無論用於實施根據本發明之製程之技術類 型為何，有利地將該液態烴原料注入含有捕捉材料之反應 器中而無特定預處理。尤其，有利地將其注入反應器中而 不經受早先熱處理及/或氫化反應。 根據本發明之移除製程係於操作條件下實施以使得溫度 在30°C與250。(：之間、較佳在”。(：與叫它之間變化。調整 壓力以便待處理之烴原料之液體含量保持95體積。/。以上。 較佳地’相對於捕捉材料之體積，待處理之原料之每小時 體積（每小時空間速度）在〇.1 h·1與10 h·1之間、較佳在〇 5 h 1與1 1Γ1之間變化。在高於150°c之溫度下實施根據本發 明之製程為有益的’因為其導致捕捉材料之較好效率而不 會觀察到存在於該捕捉材料中之硫醇類型之有機基團或衍 生物的損失。 根據本發明之製程，用於實施該移除汞物質之製程的用 於捕捉該等汞物質之材料為包含至少一個硫醇類型之有機 140315.doc 14 201040137 基團或衍生物之有機_無機混合材 之製程之最佳化實施而言，該捕捉材料呈)直?7八本發明 随與1·8 _之間的擠出物形式。較佳地；：::1·2 圓“ ‘然而，其亦可呈多葉輪廓 .以多葉輪卿式存在之㈣物具有 葉）^式° 夕p弓沾咖丄士 在h2 mm與1.8 mm 料立μ 士 ^" 寿有機-無機混合材 .Jk 貞1丌稱為無機相）及有機基團（其稱 為有機相）組成之材料。包含至少 O s , , ^ 匕3至乂一個硫醇類型之有機基 =或/何生物且根據熟習此項技術者熟知之合成方法獲得並 直徑包含在1.2随與^ mm之間的擠出物形式之任何類 型之有機-無機混合材料固體可用於實施根據本發明之制 程。包含至少一個硫醇類型之有機基圏或衍生物之有機衣 無機混合材料（諸如在本發明之製程中用作捕捉材料之彼 ，者）尤其描述於美國專利6,326,326中。該用於捕捉采物 質、用於實施根據本發明之製程之材料不能呈粉末形式。 〇 硫醇類型之有機基團或衍生物尤其意謂包含至少一個硫 醇基R-SH之有機基團或包含至少一個二硫化物基團n S-R2之有機基團。若其為包含至少一個硫醇*R_SH之有機 基團，則有機部份R-SH之基團R表示有機烷基、芳基、烷 氧基、芳基-烧基（視情況鹵化）片段，其為飽和或不餘和、 支鏈或非支鏈且帶有或不帶有一或多個有機官能基。有機 片段R之烴鏈含有至少一個碳原子、更通常1至30個碳原子 且較佳3至1 8個碳原子。烴鏈上之氫可能由鹵化物（較佳為 氯及溴且更佳為氯）取代可產生完全經取代之鏈。較佳不 140315.doc -15· 201040137 發生取代。極佳地，包含至少一個硫醇基r_SH之有機基團 使得R為具有2至5個碳原子之飽和直鏈烷基鏈，較佳尺為 丙基。若其為包含至少一個二硫化物基團r〗_S-S-R2之有機 基團’則基團R〗及R_2為相同或不同長度之具有1至5個碳原 子之飽和直鏈烷基鏈。較佳地，及r_2皆為甲基。極佳 地’該存在於用於實施根據本發明之製程之捕捉材料中的 硫醇類型之有機基團或衍生物為硫醇基。根據本發明之製 程’該硫醇類型之有機基團或衍生物捕捉存在之汞物質。 視有機-無機界面之性質而定，在文獻中定義了兩類有 ❹ 機-無機混合材料（OIHM):有機及無機組份之内聚由弱相 互作用（H鍵、凡得瓦爾（Van Der ▽⑽⑷鍵）提供之第^員 OIHM，及兩個相由強共價鍵或離子共價鍵連接之第11類 〇IHM(C. Sanchez, B. Jullian, P. Belleville, M. Popall, J. Μαία 2〇〇5, 15(35_36)，3559)。較佳地，包含硫醇 類型之有機基團或衍生物（較佳為有機硫醇基R_SH)且在本 發明之製程中用作捕捉材料之〇IHM為第π類材料。 對於該等第II類材料而言，有機基團之引入有利地由使 〇 用同時具有有機&團及可水解且可縮合基團（通常為烷醇 鹽或鹵化物類型）之前驅體引起。更特定言之，通常在文 獻中遇到兩種合成方法：直接合成，其包括在無機固體之 心膠-嘁膠合成期間在熟習此項技術者熟知之無機前驅體 存在下直接合併此有機固體；及後處理合成，其包括在第 -階段獲得無機固體且在第二階段期間藉由有機前驅體之 院醇鹽及/或齒化物基團與經基表面基團之水解_縮合反應 140315.doc •16· 201040137 (接枝技術）來使表面官能化（A. Sayari，s Ham〇udi， Κπ，2〇01，13, 3151)。與受最初形成之固體之表面狀況 限制的後處理技術相比，先引用之方法具有允許合併高含 :之有機片段的優點。另一方面’因為與產生無機構架同 合併有機部分，所以有機位點之可達性並不完全。此 外，難以想像藉由高溫熱處理使無機構架穩定。較佳地， 包含硫醇類型之有機錢或衍生物且在本發明之製財用 作捕捉材料之第Π類OIHM係根據稱為「後處理」之合成 方法獲得。 ^ 對於第II類材料而言，人帶有硫醇類型之官能之有機 基團或衍生物有利地反映在M_〇_z_R_SH鍵之形成中其 中Μ為構成所選無機氧化物基質之金屬，z為來自有機前 驅體=可水解基團之雜元素且為經選擇用來在本發明 之脫水處理製私十將固體用作捕捉材料期間給予整個固體 所要特性之有機部份。較佳地，在本發明之製程中捕捉材 料之帶有硫醇類Φ $分At U .In the case of testing, it is preferable to use a gap filler (such as W diluent), especially strontium carbide Sic (corundum). In the case of larger equipment, a higher liquid line speed will be used to ensure a minimum pressure drop of a fixed bed of 2 bar/meter. Intermediate heaters or coolers can also be used in the process equipment. Static or dynamic mixers can also be used upstream of the apparatus of the process according to the invention. Similarly, means for distributing the liquid hydrocarbon feedstock to be purified on the surface of the reactor may be present in the encapsulating structure of the reactor using the mercury capture material. According to the present invention, regardless of the type of technology used to carry out the process according to the present invention, it is advantageous to inject the liquid hydrocarbon feedstock into a reactor containing the capture material without specific pretreatment. In particular, it is advantageously injected into the reactor without undergoing an earlier heat treatment and/or hydrogenation reaction. The removal process according to the present invention is carried out under operating conditions such that the temperature is between 30 ° C and 250. (: between, preferably between.) (: change from calling it. Adjust the pressure so that the liquid content of the hydrocarbon feedstock to be treated is maintained at 95 vol. /. above. Preferably 'relative to the volume of the capture material, The hourly volume (space velocity per hour) of the treated material varies between h1 h·1 and 10 h·1, preferably between 〇5 h 1 and 1 1Γ1. At temperatures above 150 ° C It is advantageous to carry out the process according to the invention 'because it results in a better efficiency of capturing the material without observing the loss of the thiol type organic group or derivative present in the capture material. Process according to the invention The material for capturing the mercury species for performing the process for removing the mercury species is the most expensive process for the organic-inorganic hybrid material comprising at least one mercaptan type organic 140315.doc 14 201040137 group or derivative In terms of implementation, the capture material is in the form of an extrudate between the invention and the 1. 8 _. Preferably;:::1·2 circle "', however, it may also be Multi-leaf contour. (4) objects with multiple impellers have a leaf) ^ ° ° 夕 p bow H2 mm in coffee Shang persons with disabilities 1.8 mm standpipe μ ^ " life organic - inorganic hybrid material sheet referred .Jk Chen Ji inorganic phase 1) and an organic group (which is referred to as an organic phase) of. An extrudate comprising at least O s , , ^ 匕 3 to 乂 one thiol type organic group = or / organism and obtained according to a synthetic method well known to those skilled in the art and having a diameter between 1.2 and ^ mm Any type of organic-inorganic hybrid solid in the form can be used to carry out the process according to the present invention. An organic coating inorganic hybrid material comprising at least one thiol type organic hydrazine or derivative, such as the one used as a capture material in the process of the present invention, is described inter alia in U.S. Patent 6,326,326. The material used to carry out the process for carrying out the process according to the invention cannot be in powder form. The organic group or derivative of the thiol type means in particular an organic group comprising at least one thiol group R-SH or an organic group comprising at least one disulfide group n S-R2. If it is an organic group containing at least one thiol*R_SH, the group R of the organic moiety R-SH represents an organoalkyl, aryl, alkoxy, aryl-alkyl (optionally halogenated) moiety, It is saturated or unbalanced, branched or unbranched with or without one or more organic functional groups. The hydrocarbon chain of the organic moiety R contains at least one carbon atom, more usually from 1 to 30 carbon atoms, and preferably from 3 to 18 carbon atoms. Hydrogen on the hydrocarbon chain may be substituted with a halide, preferably chlorine and bromine, and more preferably chlorine to produce a fully substituted chain. Preferably not 140315.doc -15· 201040137 Replacement occurs. Excellently, the organic group containing at least one thiol group r_SH is such that R is a saturated linear alkyl chain having 2 to 5 carbon atoms, preferably a propyl group. If it is an organic group containing at least one disulfide group r _S-S-R2, then the groups R and R 2 are the same or different lengths of saturated linear alkyl chains having 1 to 5 carbon atoms. . Preferably, both r_2 are methyl. It is excellent that the organic group or derivative of the thiol type present in the capture material used to carry out the process according to the invention is a thiol group. The organic group or derivative of the thiol type captures the mercury species present in accordance with the process of the present invention. Depending on the nature of the organic-inorganic interface, two types of organic-inorganic hybrid materials (OIHM) are defined in the literature: cohesive of organic and inorganic components by weak interactions (H-bond, Van Der Val (Van Der) ▽(10)(4) key) provides the member OIHM, and the 11th class 〇IHM whose two phases are connected by strong covalent bond or ionic covalent bond (C. Sanchez, B. Jullian, P. Belleville, M. Popall, J Μαία 2〇〇5, 15(35_36), 3559). Preferably, an organic group or derivative of the thiol type (preferably an organic thiol group R_SH) is included and used as a capture in the process of the present invention. The material IHM is a π-type material. For these Class II materials, the introduction of an organic group is advantageously made by using both an organic & group and a hydrolyzable and condensable group (usually an alkanol) Salt or halide type) caused by precursors. More specifically, two synthetic methods are commonly encountered in the literature: direct synthesis, which is well known to those skilled in the art during the synthesis of inorganic solids. Directly combining the organic solid in the presence of an inorganic precursor; and post-treatment synthesis, Included in the first stage to obtain an inorganic solid and during the second stage by the hydrolysis and condensation reaction of the alkoxide and/or the dentate group of the organic precursor with the base surface group 140315.doc •16· 201040137 Branching) to functionalize the surface (A. Sayari, s Ham〇udi, Κπ, 2〇01, 13, 3151). Compared with the post-treatment technique limited by the surface condition of the initially formed solid, the method cited first It has the advantage of allowing the organic fractions of high inclusions to be combined. On the other hand, 'the accessibility of the organic sites is not complete because the organic fractions are combined with the inorganic framework. In addition, it is difficult to imagine that there is no mechanism by high temperature heat treatment. Preferably, the steroid type OIHM comprising a mercaptan type organic money or derivative and used as a capture material in the invention is obtained according to a synthesis method called "post-treatment". In the case of a material, an organic group or derivative having a thiol type functional group is favorably reflected in the formation of the M_〇_z_R_SH bond, wherein Μ is a metal constituting the selected inorganic oxide matrix, and z is derived from organic Precursor = can The heteroelement of the hydrolyzed group and is an organic moiety selected to impart the desired properties of the entire solid during use as a capture material in the dehydration treatment of the present invention. Preferably, the material is captured during the process of the present invention. With thiol Φ $ points At U .
© 此的有機基團或衍生物之雜元素Z 為石夕或麟原子且甚至更佳地Z為石夕原子。在㈣之較佳情 =，所用有機前驅體通常來自有機炫氧基 烧函化物族系，特徵為燒氧基為si(0R")(R，，=H、甲A、乙夕 基、烧基）或幽素類型較佳為氯及演且更佳為氯。 無機氧化物基質可兔畫Α羽 ^ ^ g ,,,, ，，，、‘，、自此項技術者已知之任何氧化物 或虱氧化物。無機餾份 U 其可選自由M元素之氧化物或氫 虱化物，其中Μ選自开去、m u 素週期表之第IB族、第ΠΒ族、第 IIIB族、第⑽族、m缺弟 弟…族、第VIB族、第VIib族、第vm 140315.doc 201040137 族、第IIIA族、第IVA族、第VA族、鑭族元素及婀系元素 t 九素[Handbook of Chemistry and Physics,第 55 版， 1974-1975)、屬於第IA族及第IIA族之元素之碳酸鹽、天然 或合成礦物質組成之群。此等氧化物及氫氧化物可為簡單 的’亦即僅包含單一厘元素或混合元素，亦即包含若干種 Μ元素’較佳介於2種與4種Μ元素之間。其可具有具經測 定之X射線繞射圖案之結晶晶體結構（沸石及相關固體、聚 合形式之氧化鋁）’或無結晶晶體結構（例如矽石），或非晶 相與結晶相之混合物。類似地，其可具有微孔度及/或中 孔度等級之均一組織化空間孔隙率（沸石及相關固體、中 結構固體、混合沸石/中結構化合物）或無特定週期性或尺 寸之孔隙率。較佳地，在本發明之製程中用作捕捉材料之 包含硫醇類型之有機基團或衍生物的〇ΙΗΜ之無機氧化物 基質係選自由矽石、中結構矽石、氧化鋁、二氧化鈦、二 氧化鍅組成之群且甚至更佳地選自由矽石、中結構矽石及 氧化紹組成之群。 無機基質亦可選自屬於第ΙΑ族及第„Α族之元素之碳酸 鹽。較佳使用碳酸H無機基質亦可選自天然或合成礦物 質’較佳選自滑石粉、璘灰石、石英、石膏。無機基質亦 可選自陶瓷（諸如氮化矽）、半導體，諸如矽、砷化鎵、氮 化鎵及碳化石夕。 藉由使用早先呈擠出物形式之無機氧化物基質、接著藉 由接枝處理以便引人〇ΙΗΜ之有機相或藉由進行早先與點 合劑（較佳為石夕石或氧化叙）混合之粉末形式之⑽Μ的擠 140315.doc -18- 201040137 壓來以擠出物形式獲得捕捉 體或多葉形式進行最初呈/ 確切而言，#以圓柱 呈粉末形式之OIHM之擠壓時，通 吊第步驟為於強酸（例如石、占缺、丄 (例如硝酸）中捏合黏合劑（較佳為矽石 或軋化鋁）以確保膠溶，接 將粉末形式之〇疆添加至膠 7 、膠中’接著將全部混合足夠量之時間，通 分鐘，以便獲得均勻遇合物，接著於⑽。C下將 其乾燥以移除確酸鹽。兮躜 羽 肖I 谷、該混合及該擠壓技術為熟© The hetero group element Z of the organic group or derivative is a stone or a lining atom and even more preferably Z is a stone atom. In the case of (4), the organic precursor used is usually derived from the organoxyloxy group, characterized by alkoxy groups as si(0R") (R,, =H, A, Ethyl, and The basal or phage type is preferably chlorine and more preferably chlorine. The inorganic oxide matrix can be used to draw feathers ^ ^ g , , , , , , , , , , or any oxide or cerium oxide known to those skilled in the art. The inorganic fraction U may be selected from the oxides or hydroquinones of the M element, wherein the cesium is selected from the group IB, the third group, the third group BB, the group (10), and the younger brother of the mu periodic table. Family, Group VIB, Group VIib, Group vm 140315.doc 201040137, Group IIIA, Group IVA, Group VA, steroids and lanthanides t nine [Handbook of Chemistry and Physics, 55th edition , 1974-1975), a group of carbonates, natural or synthetic minerals belonging to elements of Groups IA and IIA. These oxides and hydroxides may be simple 'i.e., containing only a single PCT element or a mixed element, i.e., containing several cerium elements', preferably between 2 and 4 cerium elements. It may have a crystalline crystal structure (zeolite and related solid, aggregated form of alumina) or a crystalline crystal structure (e.g., vermiculite) having a measured X-ray diffraction pattern, or a mixture of an amorphous phase and a crystalline phase. Similarly, it may have a uniform organized spatial porosity (zeolite and related solids, medium structural solids, mixed zeolite/medium structural compounds) of microporosity and/or mesoporosity grade or porosity without specific periodicity or size. . Preferably, the inorganic oxide matrix of ruthenium containing a thiol type organic group or derivative used as a capture material in the process of the present invention is selected from the group consisting of vermiculite, medium structure vermiculite, alumina, titania, The group of cerium oxide is formed and even more preferably selected from the group consisting of vermiculite, medium structure vermiculite and oxidized. The inorganic substrate may also be selected from carbonates belonging to the elements of the steroidal and Α Α family. The preferred use of the carbonic acid H inorganic matrix may also be selected from natural or synthetic minerals, preferably selected from talc, ash, quartz. , gypsum. The inorganic matrix may also be selected from ceramics (such as tantalum nitride), semiconductors such as germanium, gallium arsenide, gallium nitride, and carbon carbide. By using an inorganic oxide matrix that is previously in the form of an extrudate, followed by By grafting treatment to attract the organic phase or by pressing (140) squeezing 140315.doc -18- 201040137 in a powder form which is previously mixed with a point compound (preferably Shishishi or oxidized) The extrudate form is obtained in the form of a capture body or a multi-leaf form. Initially / exactly, when the OIHM is extruded in the form of a cylinder, the first step is to apply a strong acid (for example, stone, vacancies, hydrazine (such as nitric acid). a medium kneading adhesive (preferably vermiculite or rolled aluminum) to ensure peptization, and then adding the powder form to the gum 7 and the gum', and then mixing all of them for a sufficient amount of time, in order to obtain Uniform composition, then It is dried at (10) C to remove the acid salt. 兮躜 Yu Xiao I Valley, the mixing and the extrusion technique are cooked
驾此項技術者所熟知。 * 在本發明之框架内’移除存在於液態烴原料，之汞物質 有利地藉助於所謂穿透測試來模擬，該測試以與工業規模 上進行之f程相比加速的方式模擬所測試之捕捉材料之盘 時間有關的效率。該穿透測試係於較高的每小時㈣速度 :執行以便能夠在有限量的時間内再現在卫業設備中將在 右干年時期中觀察到之所測試捕捉材料的總體特性。此測 試由此模擬❹以之捕捉㈣之加速老化，且在實施比測 試中所應用之每小時空間速度大於為在卫業設備中實施製 程所應用1每小時空間速度。纟穿透測試結料，「去穿 透」測試係用有機溶劑（通常為二甲苯）來執行以確保不可 逆地收集汞物質。當在反應器之出口處之排出物中觀察到 初始汞濃度之一半時，達成捕捉材料之穿透。穿透測試允 許於特定時刻t下藉由測定於此時刻t下由捕捉材料塊收集 之汞數量來量測捕捉材料收集存在於待純化之液態烴原料 中之汞物質的能力。 如下計算該能力： 140315.doc •19- 201040137Well known to those skilled in the art. * Within the framework of the invention 'removal of the mercury species present in the liquid hydrocarbon feedstock, which is advantageously modeled by means of a so-called penetration test, which simulates the test in a manner that is accelerated compared to the f-pass on an industrial scale. Capturing the efficiency of the material's disk time. The penetration test is at a higher hourly (four) speed: performed to be able to reproduce the overall characteristics of the captured material that will be observed during the right dry years in the sanitary equipment for a limited amount of time. This test thus simulates the accelerated aging of (4), and the hourly space velocity applied in the implementation of the test is greater than the hourly space velocity applied to implement the process in the sanitary equipment. The “penetration through” test is performed with an organic solvent (usually xylene) to ensure irreversible collection of mercury. The penetration of the capture material is achieved when one half of the initial mercury concentration is observed in the effluent at the outlet of the reactor. The penetration test allows the ability of the capture material to collect the mercury species present in the liquid hydrocarbon feedstock to be purified by measuring the amount of mercury collected by the capture material block at this time t at a particular time t. Calculate this ability as follows: 140315.doc •19- 201040137
Q材料 其中v為在初始時刻與觀察到穿透之時刻之間所注射之 原料的體積’ [Hg]為原料中之水;農度，Q為捕捉材料之裝 載體積。其以pg Hg/cm3材料或g Hg/m3材料給出以用於外 推至工業規模。 由此測定所測試之捕捉材料之與時間有關的效率E。如 下計算於特定時間之捕捉效率E(以％表示）： 沢=避§3^入口-[HgL刪J 。 [Hg]反慝器入^ 根據本發明，捕捉效率至少等於9〇%且較佳至少等於 95%。 以下實例說明本發明，但不限制其範疇。 實例 實例1:在根據本發明之製程中用作捕捉材料之含有有機 硫醇官能的OIHM之製備。藉由將三甲氧基酼基丙基矽烷 (TMMPS)接枝於再經基化之中孔γ氧化銘（M1)上進行後處 理。 將20.25 g呈直徑等於16 mm且長度等於6 mm之圓柱形 擠出物之形式的中孔γ氧化鋁引入史蘭克燒瓶（Sch丨enk flask)中且於回流下在水中加熱4 h。過濾懸浮液且將再羥 基化氧化銘於40°C下於真空下乾燥4 h。接著添加250 ml經 蒸館之無水甲苯。最後，將8·4 ml經脫氣之TMMPS引入懸 浮液中。將混合物於甲苯回流下置放8天。接著過濾懸浮 1403i5.doc -20· 201040137 液且用3x50 ml經蒸餾之無水甲苯洗滌固體。接著將該固 體於40°C下於真空下乾燥丨小時3〇分，隨後在封閉蒸汽飽 和谷态中置放一晚以便水解接枝TMMps之甲氧基。用5〇 體積％(2x50 ml)水/乙醇混合物’接著用5質量％還原琉代 硫酸鈉溶液洗滌粉末以移除任何s_s橋鍵。用水/乙醇混合 物 '接著用純水洗滌允許移除任何僅剩的游離產物。將接 枝固體於30。(：下於真空下乾燥2x8 h且保存於氬氣下以結 束製備。以直徑等於丨.6 mm且長度等於6 mm之圓柱形擠 出物形式獲得捕捉材料Ml。 實例2:在根據本發明之製程中用作捕捉材料之含有有機 硫醇官能的OIHM之製備》藉由將三甲氧基巯基丙基矽烷 (TMMPS)接枝於再羥基化之中孔矽石（M2)上進行後處 理0 將20.00 g呈直徑等於16 mm且長度等於3 mm之圓柱形 擠出物形式的中孔矽石引入史蘭克燒瓶中且於回流下在水 Q 中加熱4 h。過濾懸浮液且將再羥基化矽石於周圍溫度下 於真二下乾燥4 h。接者添加250 ml經蒸顧之無水曱苯。最 後’將13.4 ml經脫氣之TMMPS引入懸浮液中。將混合物 於甲苯回流下置放8天。接著過濾懸浮液且用3 X 50 ml經蒸 館之無水甲苯洗滌固體。接著將該固體於4〇。〇下於真空下 乾燥1小時30分’隨後在封閉蒸汽飽和容器中置放一晚以 便水解該接枝TMMPS之曱氧基。用50體積％(2><5〇 ml)水/ 乙醇混合物，接著用5質量％還原硫代硫酸鈉溶液洗滌粉 末以移除任何S-S橋鍵。用水/乙醇混合物、接著用純水洗 140315.doc •21 · 201040137 滌允許移除任何僅剩的游離產物。將接枝固體於3〇(；c下於 真工下乾燥2 x 8 h且保存於氬氣下以結束製備。以直徑等 於1.6 mm且長度等於3 mm之圓柱形擠出物形式獲得捕捉 材料M2。 實例3(本發明）：由包含有機硫醇基之〇mM組成之捕捉材 料M2在移除存在於液態烴原料中之有機金屬《方面的效 能0 移除存在於液態烴原料中之汞物質有利地藉助於所謂穿 透測試來模擬，該職與卫業規模上進行之製程相比以一 種加速的方式模擬所測試之各捕捉材料之以時間為函數的 效率。該穿透測試係於較高的每小時空間速度下執行以便 能夠在有限量的時間（亦即48小時，例如3、5及8及1〇小 時，例如6及7及16小時，例如4小時）内再現在工業設備中 將在若干年時期中觀察到之所測試之捕捉材料的碑 性。此測試由此模擬所測試之各捕捉材料之加速老化且在 實施此測試中所應用之每小時空間速度大於為在卫業設備 中實施製程所應用之每小時空間速度。在各穿透測試结束 時’用有機溶劑（二甲苯）來執行「去穿透」測試以確保不 可逆地收集采物質。當在反應器之出口處之排出物中觀察 到初始汞濃度之-半時’達成捕捉材料之穿透^更確切而 言，對於以下實例之每—者而言，對與待處理之原料流相 比低體積之捕捉材料進行穿透測試。其允許於特定時刻【 下藉由測定於此時刻t下由捕捉材料塊所收集之汞數量來 量測捕捉材料之每一者收集存在於待純化之液態烴原料中 140315.doc •22· 201040137 之汞物質的能力。 如下計算該能力： C =-㈣区】原料)* Y主射-原料 Q材料 - 其中v為在初始時刻與觀察到穿透之時刻之閭所注射之 _ 原料的體積，[Hg]為原料中之汞濃度’ Q為捕捉材料之裝 載體積。其以Kg Hg/cm3材料或g Hg/m3材料給出以用於外 〇 推至工業規模。該能力通常經界定用於捕捉效率大於90% 之持續時間。 由此測疋所測試之捕捉材料每一者之與時間有關的效率 E。如下計算於特定時間下之捕捉效率E(以％表示）·· 器入口 在以下實例中，藉由原子吸附使用日本NIC公司銷售之 NIC SP3D分析器或Milestone公司銷售之DMA 80分析器來 測定存在於液態烴原料中及排出物中之汞。此為對以所有 形式存在之汞之總體測定：汞物質中之每一者並不被分別 測定。 針對移除存在於由初沸點等於l39 3〇c且終沸點事於 155.3°C之氣體冷凝物之餾份組成的原料中之有機金屬汞 來測°式實例2中製備之捕捉材料M2。該裳料包含3 2重量％ C7、C8、C9石蠟，48重量0/〇具有7、8或9個碳原子之芳族 化合物及20重量％ C7、C8、〇萘。在此原料中’ 2 ppm二 140315.doc •23- 201040137 苯汞溶解’於50°C下於攪拌下保留24小時。 該測試係在9 mm直徑之不鏽鋼反應器中、在固定床中 執行。將藉由接枝技術獲得之4· 5 cm3呈擠出物形式之捕极 材料M2饋入該反應器中。將丨_5 cm3具有小粒徑（〇 〇6 mm) 之SiC(金剛砂）引入反應器中以堵塞間隙。將由捕捉材料 (4.5 cm3’固定床高度/固定床直徑=7.5)形成之床置於反應 器中心。用具有較大粒徑（1.2 mm)之Sic填充剩餘反應器 容積（20 cm3)。於測試條件下所量測之壓降等於〇 5巴/公尺 固定床。此量測係藉助於置於反應器之入口及出口處之壓 降感應器來進行。 執行測試，於80°C之溫度、7巴之壓力及等cm3.min-丨 之原料流速下操作48小時之持續時間。定期量測反應器之 出口處之汞濃度。展示存在於反應器之出口處之排出物中 的與時間有關之汞濃度之穿透曲線（未圖示）證明捕捉材料 M2在捕捉汞方面之顯著有效性：在整個穿透測試期間反 應器之出口處之汞濃度極低且在48小時結束時反應器之出 口處之汞濃度小於20 pg.r1。只要將捕捉材料M2與原料相 接觸地置放，則捕捉效率保持最大。在48小時測試結束時 其等於98%且材料M2之能力大於900 g Hg/m3。 規定藉由FX及UV分析未偵測到反應器之出口處之排出 物中存在硫。 實例4(比較）：在固定床反應器之不利尺寸下捕捉材料m2 在移除存在於液態烴原料中之有機金屬采方面的效能。 對於本實例而言，使捕捉材料M2經受與實例3中所述相 140315.doc •24- 201040137 同之穿透測試。操作條件（丁、P、原料流速）除持續時間外 與實例3中所給出之彼等條件相同，在本實例4中持續時間 等於16小時（實例3及4中所注射之原料等質量），且液態烴 原料具有與實例3所測試者相同之組成；詳言之，其含有二 ppm二苯汞。 該測試係在9 mm直徑之不鏽鋼反應器中、在固定床中 執行。將藉由接枝技術獲得之丨5 cm3呈擠出物形式之捕捉 〇 材料M2饋入該反應器中。將由捕捉材料（1.5 cm3 ,固定床 尚度/固定床直徑=2.5)形成之床置於反應器中心。用具有 較大粒徑（1.2 mm)之SiC填充剩餘反應器容積（2〇 cm3)。於 測试條件下所量測之壓降等於〇. i巴/公尺固定床。此量測 係藉助於置於反應器之入口及出口處之壓降感應器來執 行。 定期量測反應器之出口處之汞濃度。穿透曲線（未圖示） 證明在整個穿透測試期間反應器之出口處之汞濃度極高且 〇 等於1200 μ§·1-1。在48小時結束時捕捉效率低且僅等於 40〇/〇’而材料M2的能力小於36〇gHg/m3。 規定藉由FX及UV分析未偵測到反應器之出口處之排出 物中存在硫。 實例5(比較）：在固定床反應器之不利尺寸下捕捉材料M2 在移除存在於液態烴原料中之有機金屬汞方面之效能 對於本實例而言，使捕捉材料M2經受與實例3中所述相 同之穿透測試。操作條件（τ、p、原料流速、持續時間）與 貫例3中所給出之彼等條件相同且液態烴原料具有與對於 140315.doc -25- 201040137 實例3所測試者相同之組成；詳言之，其含有2 ppm二苯 果。 該測試係在9 mm直徑之不鏽鋼反應器中、在固定床中 執行。將藉由接枝技術獲得之4.5 cm3呈擠出物形式之捕捉 材料M2饋入該反應器中。將由捕捉材料（4 5 cm3，固定床 高度/固定床直徑=7.5)形成之床置於反應器中心。用具有 較大粒徑（1.2 mm)之SiC填充剩餘反應器容積（2〇 cm3)。於 測試條件下所量測之壓降等於〇 〇5巴/公尺固定床。此量測 係藉助於置於反應器之入口及出口處之壓降感應器來執 行。 疋期量測反應态之出口處之汞濃度。穿埠曲線（未圖示） 證明在整個穿透測試期間反應器之出口處之汞濃度等於 300 pg.l·1。在48小時結束時捕捉效率等於85%，而材料河2 的能力小於800 g Hg/m3。 規定藉由FX及UV分析未偵測到反應器之出口處之排出 物中存在硫。 因此，藉由比較實例3、4及5中所提供之關於捕捉效率 及能力之效能，證明在單一階段中由呈擠出物形式且包含 至少一個硫醇類型之有機基團之有機_無機混合材料形成 的捕捉材料在用於經定尺寸以便滿足液壓標準（亦即固定 床之高度、固$床之直徑及壓降）之固定床反應器中時產 生最佳化效能值，亦即至少90%之捕捉效率。必須監測大 於或等於3之{固定床高度/固定床直徑}比率及包含在〇2巴 /公尺與1巴/公尺固定床之間的壓降之累積组合。無法滿足 H03I5.doc -26- 201040137 此等標準中之一者或兩者導致效能值大大減弱或甚至極 差，尤其關於捕捉效率。 實例6(本發明）：由包含有機硫醇基之OIHM組成之捕捉材 料M2在移除存在於液態烴原料中之汞物質方面的效能。 對於本實例而言，使實例2中製備之捕捉材料M2經受與 實例3中所述相同類型之穿透測試。 針對移除存在於下表1中給出組成之液態烴原料中之汞 物質測試該捕捉材料。該原料為自粗原料之蒸餾產生之餾 份且對應於氣體冷凝物，該蒸餾根據標準ASTM D86進 行。 ASTM蒸餾，體積％ 沸點，°C 初沸點 36 10 66 30 107 50 149 70 210 90 308 終沸點 430 該原料含有200 pg.l·1不同形式之汞；根據Tao及其同事 所教示之方法測定存在於此原料中之汞（H. Tao，T. Murakami, M. Tominaga, A. Miyazaki, Mercury speciation in natural gas condensate by gas chromatography inductively coupled plasma mass spectrometry, Journal of Analytical Atomic Spectrometry, 1998,13，1085)。其揭露存 140315.doc -27- 201040137 在於該原料中之汞物f包含6G重量％呈非水溶性離子化合 物形式之汞及40重量％呈金屬形式之汞。 該穿透測試係在9 mm直徑之不鏽鋼反應器中、在固定 床中執行。將藉由接枝技術獲得之4·5 em3呈擠出物形式之 捕捉材料M2饋入該反應器中。將15 具有小粒徑（〇 mm)之SiC(金剛砂）引入反應器中以堵塞間隙。將由捕捉材 料（4.5 cm3,固定床高度/固定床直徑=75)形成之床置於反 ^中心。用具有較大粒徑（1.2咖）之训填充剩餘反應 器容積（20 cm3)。於測試條件下所量測之壓降等於❹：巴/公 尺固定床。此量測係藉助於置於反應器之入口及出口處之 壓降感應器來執行。 執行測試，於8〇t之溫度、7巴之壓力及等於i 之原料流速下操作10小時之持續時間。穿透曲線（未圖示） 證明對存在於原料中之汞物質之混合物的最大捕捉效率。 在ίο小時測試結束時，捕捉效率仍等於91%且材料M2能力 大於120 g Hg/m3，此證明捕捉材料河2在移除以不同形式 存在於原料中之所有汞物質方面之顯著效能值。 實例7(本發明）：由包含有機硫醇基之〇mM組成之捕捉材 料Ml在移除存在於液態烴原料中之汞物質方面的效能。 對於本實例而言，使實例1令製備之呈擠出物形式之捕 捉材料m經受與實例6中所述相同之穿透測試。操作條件 與實例6中所給出之彼等條件相同且液態烴原料具有與對 實例6所測試者相同之組成；詳言之，其含有在不同物質 中之200 pg.l汞.6〇重量％呈非水溶性離子化合物形式之 140315.doc 201040137 汞及40重量％呈金屬形式之汞。 穿，曲線（未圖示）證明對存在於原料中之采物質之混合 物的最大捕捉效率。在1〇小時測試結束時，捕捉效率仍等 ;°。且材料Ml^力大於12〇 g Hg/m3，此證明捕捉材料 • 在移除以不同形式存在於原料中之所有汞物f方面之 顯考效能值。 1 (本發月）.由包含有機硫醇基之〇iHM組成之捕捉材 0料移除存在於含有含Hg、子之過飽和水相之液態 烴原料中的金屬汞方面之效能。 用於本實例之捕捉材料為根據實例2製備之捕捉材料 M2。使其經受與實例3中所述者相同之穿透測試。操作條 件與實例3中所給出之彼等條件相同，反應器及反應器之 饋料與實例3中所述相同。待處理之烴原料由初沸點等於 139.3 C且終沸點等於155.rc之氣體冷凝物之館份組成。 該原料包含32重量％C7、C8、C9石壞，料重量％具有7、8 〇 或9個碳原子之芳族化合物及20重量％ C7、C8、C9萘。將 8〇〇 gg.r1金屬汞添加至該液態烴原料中。 製備由去離子純水形成之水性溶液，向其中添加果鹽 HgCl2以便獲得水性溶液中等於1〇〇〇 丨·丨之汞濃卢。 將烴饋料以等於1 “之流速引入反使用 微型泵同時以等於50 μΐ mjn-丨之、、* $ , 士 卜 之，瓜逮（亦即相對於有機相 2·5體積％水相）引入該摻雜有Hg2+離子之水性溶液。 於反應器之出口處，每4小時抽出所有排：物以使得其 含有足夠量之水相。使抽出之每一排出物靜置Μ小時隨 140315.doc •29- 201040137 後測定有機相及水相之不同物質中之汞。在48小時測試結 束時，對於水相中所測定之汞及對於有機相中所測定之 汞，捕捉效率皆等於91 %。因此，捕捉材料M2可有效地同 時捕捉存在於存在水之液態烴原料之有機相及水相中的 物質。 7 140315.doc •30·Q material where v is the volume of the raw material injected between the initial time and the time at which the penetration is observed. [Hg] is the water in the raw material; the agricultural degree, Q is the loading volume of the capturing material. It is given in pg Hg/cm3 material or g Hg/m3 material for extrapolation to industrial scale. The time-dependent efficiency E of the captured material tested was thus determined. The capture efficiency E (expressed in %) calculated at a specific time is as follows: 沢 = avoid § 3 ^ entry - [HgL delete J. [Hg] Reversal Injector According to the present invention, the capture efficiency is at least equal to 9% and preferably at least equal to 95%. The following examples illustrate the invention without limiting its scope. EXAMPLES Example 1: Preparation of an organic thiol-functional OIHM for use as a capture material in a process according to the present invention. The post-treatment was carried out by grafting trimethoxymercaptopropyl decane (TMMPS) onto a re-enacted mesoporous γ-oxidation (M1). 20.25 g of mesoporous gamma alumina in the form of a cylindrical extrudate having a diameter equal to 16 mm and a length equal to 6 mm was introduced into a Schlank flask and heated in water for 4 h under reflux. The suspension was filtered and re-hydroxylated oxidized under vacuum at 40 ° C for 4 h. Then add 250 ml of steamed anhydrous toluene. Finally, 8.4 ml of degassed TMMPS was introduced into the suspension. The mixture was placed under reflux of toluene for 8 days. The suspension was then filtered to suspend 1403i5.doc -20·201040137 and the solid was washed with 3 x 50 ml of distilled anhydrous toluene. The solid was then dried under vacuum at 40 ° C for 3 minutes, then placed in a closed steam saturated valley for one night to hydrolyze the grafted methoxy group of TMMps. The powder was washed with 5 vol% (2 x 50 ml) water/ethanol mixture' followed by a 5 mass% reduction sodium sulphate solution to remove any s_s bridge. The water/ethanol mixture 'then washed with pure water allows removal of any remaining free product. The graft solid will be at 30. (: drying under vacuum for 2×8 h and storage under argon to complete the preparation. The capture material M1 was obtained in the form of a cylindrical extrudate having a diameter equal to 丨.6 mm and a length equal to 6 mm. Example 2: According to the invention Preparation of organic thiol-functional OIHM used as a capture material in the process" by post-processing the trimethoxymercaptopropyl decane (TMMPS) onto the re-hydroxylated mesoporphyrin (M2). 20.00 g of mesoporous vermiculite in the form of a cylindrical extrudate having a diameter equal to 16 mm and a length equal to 3 mm was introduced into a Schlenk flask and heated under reflux for 4 h in water Q. The suspension was filtered and re-hydroxyl The vermiculite was dried at ambient temperature for 4 h under the true temperature. The addition of 250 ml of anhydrous benzene was carried out. Finally, 13.4 ml of degassed TMMPS was introduced into the suspension. The mixture was refluxed under toluene. After 8 days, the suspension was filtered and the solid was washed with 3 X 50 ml of steamed anhydrous toluene. The solid was then dried at 4 Torr. under vacuum for 1 hour and 30 minutes, then placed in a closed steam-saturated vessel. One night to hydrolyze the methoxy group of the grafted TMPPS. Volume % (2 >< 5 〇 ml) water / ethanol mixture, followed by washing the powder with a 5 mass % reduced sodium thiosulfate solution to remove any SS bridge. Wash with water/ethanol mixture followed by pure water 140315.doc • 21 · 201040137 Polyester allows removal of any remaining free product. The grafted solid is dried at 3 Torr (c) for 2 x 8 h and stored under argon to complete the preparation. The diameter is equal to 1.6 mm and Capture material M2 is obtained in the form of a cylindrical extrudate having a length equal to 3 mm. Example 3 (Invention): Capture material M2 consisting of 〇 mM containing an organic thiol group is used to remove the organometallic present in the liquid hydrocarbon feedstock. Aspects of effectiveness 0 The removal of mercury species present in the liquid hydrocarbon feedstock is advantageously modeled by means of a so-called penetration test, which simulates each of the captured materials tested in an accelerated manner compared to processes performed on the scale of the health industry. The efficiency is a function of time. The penetration test is performed at a higher hourly space velocity so that it can be used for a limited amount of time (ie 48 hours, such as 3, 5 and 8 and 1 hour, for example 6 and 7 and 16 hours, examples The monumental nature of the captured material that will be observed in industrial equipment for a number of years is reproduced within 4 hours. This test thus simulates the accelerated aging of each captured material tested and is used in the implementation of this test. The hourly space velocity is greater than the hourly space velocity applied to the process in the sanitary equipment. At the end of each penetration test, the "de-penetration" test is performed with an organic solvent (xylene) to ensure irreversible collection. Substance. When the initial mercury concentration is observed in the effluent at the outlet of the reactor - half time 'reaches the penetration of the capture material ^ more precisely, for each of the following examples, the pair to be treated The feed stream was tested for penetration compared to the low volume capture material. It allows each of the capture materials to be collected in the liquid hydrocarbon feedstock to be purified by measuring the amount of mercury collected by the capture material block at this time t at a specific time. 140315.doc •22· 201040137 The ability of mercury substances. The capacity is calculated as follows: C = - (four) zone] raw material) * Y main shot - raw material Q material - where v is the volume of the raw material injected at the initial time and the time when the penetration is observed, [Hg] is the raw material The concentration of mercury in the 'Q is the loading volume of the capture material. It is given in Kg Hg/cm3 material or g Hg/m3 material for external scale push to industrial scale. This ability is typically defined to capture a duration of greater than 90% efficiency. The time-dependent efficiency E of each of the captured materials tested is thus measured. The capture efficiency E (expressed in %) at a specific time is calculated as follows. In the following example, the presence of the NIC SP3D analyzer sold by Japan NIC Corporation or the DMA 80 analyzer sold by Milestone Corporation is used to determine the presence of the atomic adsorption. Mercury in liquid hydrocarbon feedstocks and in effluents. This is an overall measure of mercury in all forms: each of the mercury species is not separately measured. The capturing material M2 prepared in the example 2 was measured for the removal of the organometallic mercury present in the raw material consisting of the fraction of the gas condensate having an initial boiling point equal to l39 3〇c and a final boiling point of 155.3 °C. The dressing contains 32% by weight of C7, C8, C9 paraffin, 48 parts by weight of 0/〇 of an aromatic compound having 7, 8 or 9 carbon atoms and 20% by weight of C7, C8, indole naphthalene. In this material, '2 ppm two 140315.doc • 23- 201040137 phenylmercury dissolved' was kept at 50 ° C for 24 hours with stirring. The test was performed in a 9 mm diameter stainless steel reactor in a fixed bed. A trapping material M2 in the form of an extrudate of 4·5 cm3 obtained by a grafting technique was fed into the reactor. SiC (5 cm3) SiC (corundum) having a small particle size (〇 〇 6 mm) was introduced into the reactor to block the gap. A bed formed of a capture material (4.5 cm3' fixed bed height / fixed bed diameter = 7.5) was placed in the center of the reactor. The remaining reactor volume (20 cm3) was filled with Sic with a larger particle size (1.2 mm). The pressure drop measured under the test conditions is equal to 〇 5 bar / meter fixed bed. This measurement is carried out by means of a pressure drop sensor placed at the inlet and outlet of the reactor. The test was carried out and operated for 48 hours at a temperature of 80 ° C, a pressure of 7 bar, and a feed flow rate of equal cm 3 .min-丨. The mercury concentration at the outlet of the reactor is measured periodically. A breakthrough curve (not shown) showing the concentration of mercury associated with the effluent present at the outlet of the reactor demonstrates the significant effectiveness of the capture material M2 in capturing mercury: the reactor during the entire penetration test The mercury concentration at the outlet is extremely low and the mercury concentration at the outlet of the reactor at the end of 48 hours is less than 20 pg.r1. As long as the capturing material M2 is placed in contact with the raw material, the capturing efficiency is kept to a maximum. At the end of the 48 hour test it was equal to 98% and the capacity of material M2 was greater than 900 g Hg/m3. It is specified that sulfur is not present in the effluent at the outlet of the reactor by FX and UV analysis. Example 4 (Comparative): Capture the effectiveness of material m2 in removing the organometallics present in the liquid hydrocarbon feedstock at the unfavorable size of the fixed bed reactor. For the present example, the capture material M2 was subjected to the penetration test as described in Example 3, 140315.doc • 24-201040137. The operating conditions (D, P, feed flow rate) were the same as those given in Example 3 except for the duration, which was equal to 16 hours in this Example 4 (quality of raw materials injected in Examples 3 and 4) And the liquid hydrocarbon feedstock had the same composition as the one tested in Example 3; in detail, it contained two ppm of diphenylmercury. The test was performed in a 9 mm diameter stainless steel reactor in a fixed bed. The 〇5 cm3 obtained by the grafting technique was captured in the form of an extrudate. The material M2 was fed into the reactor. A bed formed of a capture material (1.5 cm3, fixed bed capacity / fixed bed diameter = 2.5) was placed in the center of the reactor. The remaining reactor volume (2 〇 cm3) was filled with SiC having a larger particle size (1.2 mm). The pressure drop measured under the test conditions is equal to 〇. i bar / meter fixed bed. This measurement is performed by means of a pressure drop sensor placed at the inlet and outlet of the reactor. The mercury concentration at the outlet of the reactor is measured periodically. The breakthrough curve (not shown) demonstrates that the mercury concentration at the outlet of the reactor during the entire penetration test is extremely high and 〇 equals 1200 μ§ 1-1. The capture efficiency was low at the end of 48 hours and was only equal to 40 Å/〇' and the capacity of the material M2 was less than 36 〇gHg/m3. It is specified that sulfur is not present in the effluent at the outlet of the reactor by FX and UV analysis. Example 5 (Comparative): Efficacy of capturing material M2 at the unfavorable size of a fixed bed reactor in removing organometallic mercury present in a liquid hydrocarbon feedstock. For the present example, the capture material M2 was subjected to the same as in Example 3. The same penetration test is described. The operating conditions (τ, p, feed flow rate, duration) are the same as those given in Example 3 and the liquid hydrocarbon feedstock has the same composition as that tested for Example 3 of 140315.doc -25- 201040137; In other words, it contains 2 ppm diphenyl fruit. The test was performed in a 9 mm diameter stainless steel reactor in a fixed bed. A capture material M2 in the form of an extrudate of 4.5 cm3 obtained by a grafting technique was fed into the reactor. A bed formed of a capture material (4 5 cm3, fixed bed height / fixed bed diameter = 7.5) was placed in the center of the reactor. The remaining reactor volume (2 〇 cm3) was filled with SiC having a larger particle size (1.2 mm). The pressure drop measured under the test conditions is equal to a fixed bed of 〇 5 bar / metre. This measurement is performed by means of a pressure drop sensor placed at the inlet and outlet of the reactor. The mercury concentration at the outlet of the reaction state is measured during the flood season. The threading curve (not shown) demonstrates that the mercury concentration at the outlet of the reactor during the entire penetration test is equal to 300 pg.l·1. The capture efficiency is equal to 85% at the end of 48 hours, while the material River 2 has a capacity of less than 800 g Hg/m3. It is specified that sulfur is not present in the effluent at the outlet of the reactor by FX and UV analysis. Thus, by comparing the potency and capture efficiencies provided in Examples 3, 4, and 5, an organic-inorganic hybrid consisting of an organic group in the form of an extrudate and comprising at least one thiol type in a single stage was demonstrated. The capture material formed by the material produces an optimized performance value when used in a fixed bed reactor sized to meet hydraulic standards (ie, the height of the fixed bed, the diameter of the bed, and the pressure drop), ie, at least 90 % capture efficiency. The {fixed bed height/fixed bed diameter} ratio greater than or equal to 3 and the cumulative combination of pressure drops between the fixed bed of 〇2 bar/meter and 1 bar/meter must be monitored. Unable to meet H03I5.doc -26- 201040137 One or both of these standards result in greatly reduced or even poor performance values, especially with regard to capture efficiency. Example 6 (Invention): The effectiveness of the capture material M2 consisting of OIHM comprising an organic thiol group in removing mercury species present in the liquid hydrocarbon feedstock. For the present example, the capture material M2 prepared in Example 2 was subjected to the same type of penetration test as described in Example 3. The capture material was tested for the removal of mercury species present in the liquid hydrocarbon feedstock of the composition given in Table 1 below. The feedstock is a fraction resulting from the distillation of the crude feedstock and corresponds to a gas condensate which is carried out according to standard ASTM D86. ASTM Distillation, Volume % Boiling Point, °C Initial Boiling Point 36 10 66 30 107 50 149 70 210 90 308 Final Boiling Point 430 This material contains 200 pg.l·1 of different forms of mercury; the presence is determined according to the method taught by Tao and colleagues Mercury in this raw material (H. Tao, T. Murakami, M. Tominaga, A. Miyazaki, Mercury speciation in natural gas condensate by gas chromatography inductively coupled plasma mass spectrometry, Journal of Analytical Atomic Spectrometry, 1998, 13, 1085) . It is disclosed in the present document 140315.doc -27- 201040137 that the mercury f in the raw material contains 6 g% by weight of mercury in the form of a water-insoluble ion compound and 40% by weight of mercury in a metal form. The penetration test was performed in a 9 mm diameter stainless steel reactor in a fixed bed. The capture material M2 in the form of an extrudate obtained by the grafting technique in the form of an extrudate was fed into the reactor. 15 SiC (corundum) having a small particle size (〇 mm) was introduced into the reactor to block the gap. The bed formed by the capture material (4.5 cm3, fixed bed height / fixed bed diameter = 75) was placed at the center of the anti-^. Fill the remaining reactor volume (20 cm3) with a larger particle size (1.2 coffee). The pressure drop measured under the test conditions is equal to ❹: bar / metric fixed bed. This measurement is performed by means of a pressure drop sensor placed at the inlet and outlet of the reactor. The test was performed for a duration of 10 hours at a temperature of 8 Torr, a pressure of 7 bar, and a feed rate equal to i. The breakthrough curve (not shown) demonstrates the maximum capture efficiency for a mixture of mercury species present in the feedstock. At the end of the ίο hour test, the capture efficiency was still equal to 91% and the material M2 capacity was greater than 120 g Hg/m3, which demonstrates the significant performance value of Capture Material River 2 in removing all of the mercury species present in the feed in different forms. Example 7 (Invention): The effectiveness of the capture material M1 consisting of mM mM containing an organic thiol group in removing mercury species present in the liquid hydrocarbon feedstock. For the present example, Example 1 was prepared to subject the prepared capture material m in the form of an extrudate to the same penetration test as described in Example 6. The operating conditions were the same as those given in Example 6 and the liquid hydrocarbon feedstock had the same composition as the one tested for Example 6; in particular, it contained 200 pg.l of mercury. 6 〇 weight in different materials. % is in the form of a water-insoluble ionic compound 140315.doc 201040137 Mercury and 40% by weight of mercury in metallic form. The wear curve (not shown) demonstrates the maximum capture efficiency of the mixture of materials present in the feedstock. At the end of the 1 hour test, the capture efficiency is still equal; °. And the material Ml ^ force is greater than 12 〇 g Hg / m3, which proves that the capture material • the performance value of the removal of all mercury in various forms in the raw material f. 1 (this month). The capture material consisting of 〇iHM containing an organic thiol group removes the effectiveness of metal mercury present in a liquid hydrocarbon feedstock containing a Hg-containing supersaturated aqueous phase. The capture material used in this example was the capture material M2 prepared according to Example 2. It was subjected to the same penetration test as described in Example 3. The operating conditions were the same as those given in Example 3, and the reactor and reactor feeds were the same as described in Example 3. The hydrocarbon feedstock to be treated consists of a gas condensate with an initial boiling point equal to 139.3 C and a final boiling point equal to 155.rc. The raw material contained 32% by weight of C7, C8, C9 stone, and the weight % of the aromatic compound having 7, 8 or 9 carbon atoms and 20% by weight of C7, C8, C9 naphthalene. 8 gg.r1 of metallic mercury is added to the liquid hydrocarbon feedstock. An aqueous solution formed of deionized pure water was prepared, and a fruit salt of HgCl2 was added thereto to obtain a mercury-rich hydrate equivalent to 1 丨·丨 in an aqueous solution. Introduce the hydrocarbon feedstock at a flow rate equal to 1" to the counter-use micropump while equalizing 50 μΐ mjn-丨, * $ , 士卜之, (ie, relative to the organic phase 2. 5 vol% water phase) The aqueous solution doped with Hg2+ ions is introduced. At the outlet of the reactor, all the discharges are taken out every 4 hours so that they contain a sufficient amount of aqueous phase. Each of the discharged discharges is allowed to stand for one hour with 140315. Doc •29- 201040137 Post-measurement of mercury in different organic and aqueous phases. At the end of the 48-hour test, the capture efficiency is equal to 91% for the mercury measured in the aqueous phase and for the mercury measured in the organic phase. Therefore, the capture material M2 can effectively simultaneously capture the substances present in the organic phase and the aqueous phase of the liquid hydrocarbon material in the presence of water. 7 140315.doc •30·