TW496894B - Synthetic jet fuel and process for its production - Google Patents

Synthetic jet fuel and process for its production Download PDF

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TW496894B
TW496894B TW087101646A TW87101646A TW496894B TW 496894 B TW496894 B TW 496894B TW 087101646 A TW087101646 A TW 087101646A TW 87101646 A TW87101646 A TW 87101646A TW 496894 B TW496894 B TW 496894B
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fischer
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Robert Jay Wittenbrink
Paul Joseph Berlowitz
Bruce Randall Cook
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Exxon Research Engineering Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/08Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S208/00Mineral oils: processes and products
    • Y10S208/95Processing of "fischer-tropsch" crude

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Description

496894 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(1 ) 發明領域 本發明係有關於具有優異安定性之蒸餾物,可作爲高 潤滑噴氣式發動機燃油或作爲其摻合基,以及此噴氣式發 動機燃油之製法。更特別地,本發明係有關於由Fischer-Tropsch蠟製成噴氣式發動機燃油的方法。 發明背景 不含有硫,氮或芳族物之乾淨餾液在作爲噴氣式發動 機燃油或是摻合噴氣式發動機燃油上有極大的需求,具有 高潤滑性與高安定性的乾淨餾液特別有價値。一舨的石油 餾液並不乾淨,因爲多含有顯著量的硫,氮或芳族物。再 者,需要嚴苛的氫處理(hydrotreating)來得到具有足夠安 定性的燃油,而此將造成燃油的潤滑性低。經由嚴苛氫處 理得到由石油衍生之乾淨燃油的成本較未經氫處理者昂貴 。燃油的潤滑性爲燃油傳送系統有效率地操作所需,其可 藉由添加核准之添加劑來改善。由Fischer-Tropsch蠘製成乾 淨且高辛烷値的餾液已於公開文獻中有討論,但是這些方法 製成的餾液仍欠缺某些重要性質,例如潤滑性。所以這些 Fischer-Tropsch餾液得與其他原料摻合或是使用昂貴的添力口 劑。這些先前技藝揭7τκ對全部的Fischer-Tropsch產物(包括 整個7 0 0 °F部份)給予氫處理。此氫處理 <完全去除了噴 氣式發動機燃油中的含氧物(oxygenates)。 在本發明中,保留了少量的含氧物,所以產物具有高 潤滑性。此產物可作爲噴氣式發動機燃油或作爲摻合基與 (讀先閲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(210X 297公釐)·4 _ 496894 A7 B7 五、發明説明(2 ) 其他他低級品製成噴氣式發動機燃油。 發明簡沭 依本發明製成可作爲噴氣式發動機燃油或其摻合基之 乾淨餾液,其具有潤滑性(以Ball on Cylinder (BOCEL)測 試測量)約等於或高於高潤滑性參考燃油。且較好由 Fischer-Tropsch蠟製成,並由鈷或铑觸媒衍生。製法中係將 蠟產物分爲較重與較輕部份,公稱的分離點係爲約7 0 0 T。所以較重的部份主要含7 0 0 °F +,較輕部份主要含 7 0 0 0F -。 進一步分離較輕部份成至少兩個其他部份:(i )主 要含C 7 - C i 2醇者(ϋ )不含前述醇者,而得到餾液。 部份(U )爲5 5 0 °F +部份,較好爲5 0 0 °F +部份, 更好爲4 7 5°F +部份,而更好爲正C14 +部份。較重部 份(ϋ )之至少一部份或較好爲全部於二官能觸媒存在, 經濟部中央標準局員工消費合作社印11 (請先閱讀背面之注意事項再填寫本頁) 典型之氫異構化條件下,接受氫轉化處理(例如氫異構化 )。此部份之氫異構化可與Fischer-Tropsch蠟(即自Fischer -Tropsch反應之較重7 0 0 °F +部份)之氫異構化在相同或 分開的反應區中進行,以相同反應區較好。在任一種情況 中,將如4 7 5 °F +的一部份轉化成沸點較低的部份,如 4 7 5 °F —。然後,可與得自氫異構化之噴 < 氣式發動機冷 凍物(jet freeze)相容之物的至少一部份或較好爲全部則 與部份(i )(較好爲2 5 0 - 4 7 5 °F部份)的至少一 部份或較好爲全部合倂,且較好不用任何氫處理(如氫異 本紙張尺度適用中國國家標準(CNS) A4規格(210Χ297公釐)~ 經濟部中央標準局員工消費合作社印繁 496894 ΑΊ ____Β7 五、發明説明(3 ) 構化)。本發明之噴氣式發動機燃油或其摻合基在噴氣式 發動機燃油的範圍內沸騰且可含有在噴氣式發動機燃油的 範圍以上沸騰的烴類物(其量爲使這些額外物質可與噴氣 式發動機冷凍物(即,一 4 7 °C或以下)相容)。這些相 容物的量取決於氫異構化區的轉化率,較高的氫異構化可 有較多的相容物(即,較高分枝度的物質)。所以噴氣式 發動機燃油的範圍通常爲2 5 0 - 5 5 0 °F,較好爲 250 — 550 °F,更好爲250 — 475 °F,且可含相 容物,並具有下述性質。 得自分餾器的噴氣式發動機物質具下示性質: 石蠟 至少95wt%,較好爲至少96wt%, 更好爲至少9 7 w t %,最好爲至少 9 8 w t % 異/正比 約0.3至3.0,較好爲0.7至 2 . 0 硫 S 5 0 p p m ( w t ),較好沒有 氮 €50ppm(wt),較好$20 P P m,更好沒有 不飽和物(烯 烴與芳族物) S2 · 〇wt%,較好SI .Owt%, 更好 SO · 5wt% 含氧物 約0.005至低於約〇.5wt%氧,以 無水物爲基準 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公髮)~ (請先閲讀背面之注意事項再填寫本頁) 、1Τ 496894 A7 B7___ ... 1 -. " "" ' ~ — ~~ 五、發明説明(4 ) 異石蠟通常爲單甲基分枝,又因爲此方法使用Fischer, Tropsch蠘,所以產物不含環狀石蠘(如環己院)。 即 c
C請先閱讀背面之注意事項再填寫本百C 較輕部份(如2 5 0 — 4 7 5 °F部份)主要含 ^9 5% ’含氧物’且主要爲’如$9 5%c6 線型末端醇。 厘式簡單說明 第1圖爲本發明方法之圖示。 主_要元件對照表 1 管線 2 Fischer-Tropsch反應器 3 管線 4 管線 5 氫異構化反應器 6 熱分離器 7 4 7 5卞—物質線 經濟部中央標準局員工消費合作社印製 8 管線 9 冷分離器 1 0 管線 1 1 管線 \ 12 管線 13 蒸餾塔 1 4 7 0 〇 °F +物質線 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 496894 A7 B7 五、發明説明(5 ) 經濟部中央標準局員工消費合作社印繁 1 5 2 5 〇 - 4 7 5 °F 噴 氣 式 發 動 機 燃 油 線 1 6 C 4 * -2 5丨 0 c F石油腦物流線 1 7 C 4 ' -氣體 1 8 4 7 5 - 7 0 0 °F 柴 油 線 較 佳 具 體 例 之說 明 參 考 圖 式更 加 詳 細 說 明 本 發 明 〇 將 管 線 1內呈適當比 例 之合成 氣 體, 氫 與 —^ 氧 化 碳 饋 入 Fi scher -Tropsch反應器2 中 , 較 好 爲 游漿 反 應 器 由 管 線 3 與 4 各 回 收 7 0 0 °F + 與 7 0 0 °F 一產 物 〇 較 輕 部 份 進 入 熱 分 離 器 6而由管線8 回 收 4 7 5 -7 0 0 °F 部 份 其 與 來 白 管 線 3 的 7 0 0 °F + 物 質 合倂而 饋 入 氫 異 構 化反 應 器 5 ( 其 中約5 0 %被 轉 化成 7 0 0 °F — 物 質 ) 〇 4 7 5 °F — 物 質 進入冷分離器 9 而 由 管 線 10 回 收 C 4 - -氣體 〇 ! C 5 之4 7 5 °F部份由 管 線 1 1 回 收, 然 後 與 來 白 氫 異 構 化反 應 器 5,管線1 2 之 輸 出 物 流 合倂 〇 管 線 1 2進 入 蒸 餾 塔 1 3 產 出 C 4 一 < 2 ! 5 0 °F石腦油物 流 線 1 6 y 2 5 0 — 4 7 5 °F 噴 氣 式 發 動 機 燃油線1 5, 4 7 5 — 7 0 0 °F 柴 油 線 1 8 與 7 0 0 °F + 物質1 4。 7 0 0 T + 物質 可再 循 環 回 氫 異 構 化 反 應 器 5或是用來製 造 局 品 質 之 油。 若 氫 異 構 化 反 應 器 5 將 大 部( 份的正C i 4 + 石 蠟 轉 化 爲 異石 蠟 較 好 管 線 1 5 與 1 8 的 分段點由 4 7 5 °F 向 上調 〇 此 分 段 點 較 好 爲 5 0 0 °F ,更好爲 5 5 0 °F,只要將噴氣式發動機燃油凝固點保持在至少 (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(210X297公釐) 496894 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(6 ) 一 4 7 °C即可。 氫異構化法爲公知,下表列出其一些較寬及較佳條件 ___條件__ _寬箪B圍 較佳範圍 溫度,°F 300-800 500-750 總壓力,psig 300-2500 500-1500 氫處理速率,SCF/B 500-5000 1500-4000 幾乎任何用於氫處理(如氫異構化或選擇性氫裂解) 之由金屬氫化觸媒與酸性成份組成的二官能觸媒均適於本 案方法,以性能較佳者爲優選。例如,含承載之VI族貴金 屬(如鉑或鈀)的觸媒以及含0 . 5 — 20wt% 1或 多種VDI族非貴金屬(如鎳,鈷)之觸媒,且其亦可含 1 · 0 - 2 0wt%VI族金屬(如鉬。金屬之載體可爲任 何耐火氧化物或沸石或其混合物。較佳載體包括氧化矽, 氧化鋁,氧化矽-氧化鋁,氧化矽-氧化鋁磷酸鹽,氧化 鈦,氧化銷,氧化釩,其他m,iv,V A或vi族氧化物, 以及Y分子篩(如超安定Y分子篩)。較佳載體包括氧化 鋁及氧化矽-氧化鋁。 較佳觸媒具有之表面積爲約2 0 0 - 50 0 m2/ g, 較好爲0 · 3 5 - 0 · 8 0 m L / g (由水吸附法測出) ,整體密度爲約0 · 5 — 1 · 〇g/mL。 此觸媒包括\1族非貴金屬(如鐵、鎳)與I B族金屬 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐)-9- 丨| :-------麵-I (請先閱讀背面之注意事項再填寫本頁) 訂 496894 A7 B7 五、發明説明(7 ) (請先閱讀背面之注意事項再填寫本頁) (如銅),且承載於酸性載體上。載體較好爲不定形氧化 矽一氧化鋁,其中氧化鋁含量低於約5 0 w t %,較好爲 5 - 30wt%,更好爲10 — 20wt%。此載體亦可 含少量(如,2 0 - 3 0 w t % )結合劑,如,氧化銘, 氧化矽,IV A族金屬氧化物以及各種黏土,氧化鎂等,較 好爲氧化銘。 不定形氧化矽一氧化鋁徵球之製備於(Rylaiid,Loyd B .,Tamele, M.W., and Wilson, J.N.., Cracking Catalysts, Catalysis: volume VH , Ed. Paul H. Emmett, Reinhold Publishing Corporation,New York,I960,pp· 5·9)中有說 明。 此觸媒係如下製成:令金屬自溶液共浸漬至載體上, 100 — 150 °C乾燥,然後於200 - 500 °C空氣中 煅燒。 Μ族金屬的量爲約15wt%以下,較好爲1一12 wt%, IB族金屬含量通常更少,例如,其與權族金屬 之比例爲1 : 2至1 : 2 0。典型觸媒如下示: 經濟部中央標準局員工消費合作社印製 N i ,w t %
C t % A I2O3— S i O2 A 1 2〇3 (結合劑) 表面積 孔體積(H g ) 2 . 5 ~ 3 . 5 0.25-0.35 6 5-75 2 5 — 30 290 — 325 m2/ gm 0.3 5 — 0.4 5mL/gm 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)_ 1〇 496894 A7 B7 五、發明説明(8 )
整體密度 0.58 — 0.68g/mL 7 0 0°F +至7 0 0°F —的轉化程度爲約2 0 - 8 0 %,較好爲20-70%,更好爲約30-60%。氫異 構化時,幾乎所有的烯烴與含氧物均被氫化了。此外,大 部分的線型石蜡被異構化或裂解,使低溫特性顯著改善, 例如,噴氣式發動機凝固點。 將7 0 0 °F —物流分離成C 5 _ 4 7 5 °F物流與4 7 5 —7 0 0 °F物流,而將4 7 5 - 7 0 0 °F物流氫異構化均 使產物凝固點得到改善(如上述)但是於C 5 — 4 7 5 °F中 的含氧物具有改善潤滑性的功效,且當作爲摻合基時,可 改善習知產品之潤滑性。 經濟部中央標準局員工消費合作社印製 (请先閱讀背面之注意事項存填寫本買) 較佳 Fischer-Tropsch 法爲使用非遷移(non-shifting) 觸媒(即,不具有水氣遷移能力)者,例子有鈷或铑或其 混合物,特別是鈷,且最好爲已促進(promoted)之鈷,該 促進劑爲鉻或铑,較好爲铑。此類觸媒爲公知,且較佳觸 媒係如US 4568663與EP 0266898所 述。 ’
Fischer-Tropsch法之產物主要爲石蜡烴。铑製成之石錯 主要在餾液範圍內沸騰,即,Ci。— C2Q ;鈷觸媒通常生 成較重的烴,如,C 2 〇 +,故以鈷爲較佳Fischer-Tropsch 催化金屬。 好的噴氣式發動機油通常具有下f特性:高發煙點’ 低凝固點,高潤滑性,氧化安定性以及符合噴氣式發動機 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)~-11- 496894 A7 B7 五、發明説明(9 ) 燃油規則之物性。
(請先閱讀背面之注意事項再填寫本頁J 本發明產物可用作爲噴氣式發動機燃油本身或是與其 他較差石油或烴類(含有約相同沸騰範圍之物料)摻合。 當本發明產物作爲摻合基時,用量可較少,如,10%以 上,便可顯著改善終產物。雖然本發明產物可改善幾乎所 有的噴氣式發動機產物,較好是將其與低品質精鍊噴氣式 發動機物流摻合,特別是具有高芳族.物者。 因爲使用Fischer-Tropsch法,回收的餾液幾乎不含硫與 氮。這些雜原子化合物會毒害Fischer-Tropsch觸媒,所以早 自含甲院之天然氣中移除,該天然氣爲Fischer-Tropsch法中 便利之進料。在天然氣中含硫與氮化合物的含量極低。此 外,此法不產生芳族物,即使如一般操作亦幾乎不生成芳 族物。含有一些烯烴生成,因爲有一烯烴產製過程係經由 烯烴中間物。然而,烯烴濃度通常很低。 經濟部中央標準局員工消費合作社印装 含氧物包括醇類與某些酸,會由Fischer-Tropsch加工法 生成,但已知至少有一方法可用氫處理將產物中的含氧物 與不飽和物完全除去,'參考,例如,Shell Middle Distillate Process, Eiler,J·,Posthuma, S. A., Sie, S.T., Catalysis Letters, 1990,7,253-270 o 但是,吾人發現少量的含氧物,較好爲醇,可提供額 外的潤滑性。例如,如實例所示,高石蜡性噴氣式發動機 燃油加上少量含氧物將具有優異潤滑性,如B 0 C L E測 試(圓柱體上球之潤滑性評估儀)所^。但是若不含含氧 物時,例如,經萃取,分子篩吸收,氫處理等使其含量低 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)~-12- "~ 496894 A7 B7 五、發明説明(1〇 ) 於1 0 p p m w t氧(以無水物爲基準),潤滑性變得 相當差。 依本發明揭示的處理流程,較輕7 0 0 °F —部份的一 部份,即,2 5 0 °F - 4 7 5 °F部份並未接受任何氫處理 。因爲沒有氫處理,此部份中仍可保留少量含氧物(主要 爲線型醇),但較重部份之含氧物則由氫異構化步驟除去 。對潤滑性有價値之含氧物C 7 +,較好爲C 7 — C i 2,更 好爲C 9 — C i 2 —級醇,且較存在於未經處理之2 5 0 -4 7 5 °F部份。氫異構化亦可用來提高餾液燃油中的異石 蜡,其有助於使燃油符合凝固點之規格。 咸信含氧物會提升潤滑性,且係藉由氫鍵,此氫鍵能 大於烴結合能(一些標準參考資料中列有各種化合物之相 關能量測量);若差距愈大則潤滑效應愈大。含氧物亦具 有親脂端與親水端,故可溼潤燃油。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 當含氧物爲酸時,應知酸具腐蝕性,其係於Fischer-Tropsch加工過程中,非遷移條件下,少量地產出。酸爲二 含氧物,與較佳單含氧物(如線型醇)不同。所以,通常 用紅外線是測不到二或多含氧物,且,例如,低於約1 5 w p p m氧(以氧計)。 非遷移Fischer-Tropsch反應爲此技藝人士公知,其特徵 在於使C〇2副產物的生成最低的條件。此條件可用許多方 法達成,包括下述一個或多個:於較低C 0分壓下操作, 即,Η 2 / C〇比至少約1 · 7 / 1 ,|較好約1 · 7 / 1至 2 · 5/1,更好至少約1 · 9/1,且範圍爲1 · 9/ 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐)~^)3- 496894 A7 ________B7_ 五、發明説明(11 ) 1至約2 · 3/1,另α値至少約〇 · 88,較好至少約 0 · 91,溫度爲約175 - 225 °C,較好爲180 - (請先閱讀背面之注意事項再填寫本頁) 2 2 0 C ’以含銘或铑之觸媒作爲首要Fischer-Tropsch催化 劑。 含氧物的量,表爲無水物中之氧,很少便可達到所需 潤滑性,即,至少約0 · 0 1 w t %氧(以無水物爲基準 ),較好爲0.01 — 〇.5wt %.氧(以無水物爲基準 ),更好爲〇 · 02 - 0 · 3wt%氧(以無水物爲基準 )° 下述實例用來例示本發明而非限制本發明。 氫與—氧化碳合成氣體(H2: C0爲2 · 1 1 -2 · 1 6 )於游漿Fischer-Tropsch反應器中轉化成重石蜡。 用於此反應的觸媒爲承載於氧化鈦上之鈷/铑觸媒(已述 於US 4568663中)。反應條件爲422 — 428°F,287 — 289ps ig,線速度爲 12 — 1 7 · 5 c m /秒。Fischer-Tropsch合成步驟之α値爲 經濟部中央標準局員工消費合作社印製 0 · 9 2。然後,石蜡性Fischer-Tropsch產物以三個沸點不 同的物流來單離,如下:1 ) C 5 - 5 0 0 T沸騰部份’下 文中稱爲F — τ冷分離器液體;2 ) 5 0 0 - 7 0 0 °F沸 騰部份,下文中稱爲F—T熱分離器液體;3)700T +沸騰部份,下文中稱爲F-T反應器蜡。 實例1
I 將7〇wt%氫異構化F - T反應器蠟,16 · 8 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)· 14 - 496894 經濟部中央標準局員工消費合作社印繁 A7 B7 五、發明説明(12) wt%氫處理F-T冷分離器液體與13·2wt%氫處 理F - T熱分離器液體合倂並激烈混合。此摻合物於 2 5 〇 — 4 7 5°F沸騰的部份爲噴氣式發動機燃油a,其 係經蒸餾單離且如下製成··如U S 5 2 9 2 9 8 9與 5 3 7 8 3 4 8使用以姑與鉬促進(promote)的氧化砂一 氧化鋁觸媒之固定床單元製成氫異構化F - T反應器蠟。 氫異構化的條件爲7 0 8 °F,7 5 0 p s i g Η 2, 2 5 0 〇 S C F / Β Η 2,液體每小時空間流速(L Η S V )爲0 · 7 - 0 · 8。藉由流入固定床反應器與市售大塊 鎳觸媒製成氫處理F - T冷與熱分離器液體。氫處理的條 件爲 450°F,430ps igH2,1000SCF/ BH2,與3·0LHSV。燃油A爲此技藝公知之典型完 全氫處理鈷衍生Fischer-Tropsch噴氣式發動機燃油的代表。 實例2 將78wt%氫異構化F — T反應器鱲,12wt% 未處理F - T冷分離器液體與1 〇wt%F — T熱分離器 液體合倂並混合。此摻合物於2 5 0 - 4 7 5 °F沸騰的部 份爲噴氣式發動機燃油B,其係經蒸餾單離且如下製成: 如US 5292989與5378348使用以鈷與鉬 促進(promote)的氧化矽-氧化鋁觸媒之固定床單元製成 氫異構化F - T反應器蠟。氫異構化的條件爲6 9 0 °F, 725ps igH2,2500SCF/BH2,液體每小 時空間流速(LHSV)爲〇 · 6 — 0 · 7。燃油B爲本 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐)-15 - (請先閱讀背面之注意事項再填寫本頁} #· -訂 496894 A7 B7 五、發明説明(13 ) 發明之代表例。 實例3 爲了測量本發明與現今市售噴氣式發動機燃油的潤滑 性以及其與市售噴氣式發動機燃油的摻合功效,測試下列 燃油。燃油C爲符合市售噴氣式發動機燃油規格之市售 U · S ·噴氣式發動機燃油,且經acjapUig0US黏土處理而除 去雜質。燃油D爲40%燃油A (氫處理F - T噴氣式發 動機燃油)與6 0%燃油C (US市售噴氣式發動機燃油 )的混合物。燃油E爲40%燃油B (本發明)與60% 燃油C ( U S市售噴氣式發動機燃油)的混合物。 實例4 經濟部中央標準局員工消費合作社印繁 (請先閲讀背面之注意事項再填寫本頁) 於實例1的燃油中添加本發明燃油B中發現的典型醇 化合物,如下述:燃油F爲燃油A加上〇 · 5 w t % 1 -庚醇。燃油G爲燃油A加上〇 · 5 w t % 1 —癸醇。燃油 Η爲燃油A加上〇 · 〇5wt%l —十六院醇。燃油I爲 燃油A加上〇 · 2wt%l —十六烷醇。燃油J爲燃油A 加上0 · 5wt%l —十六院醇。 實例5 噴氣式發動機燃油A - E均以標準拖曳負載之圓柱體 上球之潤滑性評估(B〇C L E或S L B〇C L E )測試 ,該測量可參考 Lacey,P.I. “The U.S. Army Scuffing Load 本紙張尺度適用中國國家標準(CNS)A4規格(210X 297公釐)-16- 496894 A7 _______B7 五、發明説明(14 ) Wear Test’’,January 1,1994。此測試係共於 a S T M D 500 1。結果如表2所示’且表爲參考燃油2 (如 Lacey所述)之百分比,拖曳負載爲絕對克數。 表 1 燃油A - E之拖曳BOCLE結果。結果以絕對拖曳負載與參 考燃油2 (如上述參考資料所述)之百分比來表示。 &_氣式發動機燃油 拖曳負載 %參考燃油2 A 1300 19% B 2100 34% C 1600 23% D 1400 21% E 2100 33% (請先閱讀背面之注意事項再填寫本頁) 衣· 經濟部中央標準局員工消費合作社印繁 完全氫處理之燃油A具有極低潤滑性(其爲所有石蜡 燃油的典型)。燃油B含有高濃度含氧物(線型Cs — C i 4 一級醇)具有顯著優異的潤滑性。燃油C (市售u S 噴氣式發動機燃油)具有略比燃油A佳之潤滑性,但仍不 及本發明燃油B。燃油D與E顯示本發明燃油B之摻合功 效’燃油D (低潤滑燃油A與燃油C混合)之潤滑性如預 期地介於二成份間,且顯著低於本發明F - T燃油。而將 燃油B加入燃油C製成之燃油C,發現原本較差的潤滑性 已被改善成與燃油B相當(即使燃油B僅佔最終混合物之 40%)。顯示將本發明燃油摻入習知噴氣式發動機燃油 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐)-17 - 496894 A7 _____B7五、發明説明(15 ) 中可得到實質改善。 實例7 藉由將特定醇類加入低潤滑燃油Α中可顯示醇類對潤 滑性的功效。所加醇類爲本發明所述Fischer-Tropsch法中典 型產物,且可於燃油B中發現。 表 2 燃油A與F - J之拖曳B0CLE結果。結果以絕對拖曳負載 與參考燃油2 (如上述參考資料所述)之百分比來表示。 噴氣式發動機燃油 拖曳負載 %參考燃油2 A 1300 19% F 2000 33% G 2000 33% Η 2000 32% I 2300 37% J 2700 44% (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 實例8 〜 實例1 一 5之燃油以A S T: M D. 5 0 0 1 Β〇C L Ε測試步驟評定作爲飛行燃油的性能。此測試測 量球上之磨痕(mm),不同於實例6與7之拖曳負載。 示出燃油A,B,C,Ε,Η與J的測試結果,此 ASTM D 5 0 0 1 BOCLE測試之結果與拖曳負載 本紙張尺度適用中國國家標準( CNS ) A4規格(210X 297公釐)-18 - 496894 A7 ____B7 五、發明説明(16 ) 類似。 (請先閱讀背面之注意事項再填寫本頁) 表 3 燃油A,B,C,E,H,J2ASTM D 5001 BOCLE結果。如ASTM D 5Q01所述將結果 表爲磨痕直徑。 經濟部中央標準局員工消費合作社印繁 等於燃油B之性能,此結果與拖曳負載B 0 C L E測試相 同。添加少量醇類主燃油A中,並未如拖曳負載測試中般 改良潤滑性(燃油Η ),但在較高濃度可看出此改善情形 (燃油J )。 噴氣式發動機燃油 磨痕直徑 A 0.57mm B 0.5 4mm C 0.66mm E 0.53mm Η 0.57mm J 0.5 4mm 上開結果顯示本發明燃油(燃油B )較市售燃油(燃 油C )或氫處理Fischer-Tropsch燃油(燃油A )具有更優異 之性能。將潤滑性不佳之市售燃油C與燃油B摻合得到約 本紙張尺度適用中國國家標率(CNS ) Α4規格(210X297公釐)-19 ·

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  1. 496894
    告 公
    8 8 8 ABC 經濟部智慧財產局員工消費合作社印製 々、申請專利範圍 附件A :第87101 646號專利申請案 中文申請專利範圍修正本 民國9 1年5月修正 1 . 一種用作爲噴氣式發動機燃油或其摻合成份之材 料,包括得自非遷移Fischer-Tropsch法之250 — 550 T 部份,且包括 一至少95wt%石蜡,且異/正比爲〇.3至 3 ·〇, 一各S 5 0 P P m ( w t )之硫與氮, —低於1 · 0 w t %不飽和物, —0 · 0 1至低於0 . 5 w t %氧(以無水物爲基 準)。 2 .如申請專利範圍第1項之材料,其中之氧主要以 線型醇形式存在。 3 ·如申請專利範圍第1項之材料,其包括2 5 0 — 5 0 0 °F部份。 zl ·如申請專利範圍第2項之材料,其中之線型醇爲 C 7 — C 1 2 者。 5 · —種製備噴氣式發動機燃油之方法,包括 (a )將Fischer-Tropsch法之產物分離成較重部份與較 輕部份; (b )將較輕部份進一步分成至少兩個部份:(i ) 至少一種含一級C 7 - C i 2醇之部份,其一分段點幾乎排 (請先閲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(210X297公釐) 496894 8 88 8 ABCD 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 除了所有的正C i 4石蜡,(· ϋ ) 一或多個其他部份; (C )將步驟(a )較重部份之至少一部份於氫異構 化條件下予以氫異構化,回收7 〇 〇 °F -部份; (d )將(b ) ( i )部份之至少一部份與步驟(c )回收之7 0 0 °F -部份之至少一部份摻合。 6 ·如申請專利範圍第5項之方法,其中(b ) ( 11 )部份之至少一剖份被氫異構化。 7 ·如申請專利範圍第6項之方法,其中由步驟(d )摻合產物中回收2 5 0 — 5 5 〇 °F範圍沸騰之產物。 8 ·如申請專利範圍第6項之方法,其中由步驟(d )摻合產物中回收2 5 0 - 4 7 5 °F範圍沸騰之產物。 9 ·如申請專利範圍第8項之方法,其中步驟(d ) 摻合產物含〇 · 0 1至〇 . 5wt%氧(以無水物爲基準 )° 1 〇 ·如申請專利範圍第6項之方法,其中(b )( i )部份含幾乎所有的C 7 - C 1 2 —級醇。 1 1 ·如申請專利範圍第5項之方法,其中(b )( i)剖份不經氫處理。 1 2 ·如申請專利範圍第5項之方法,其中(b )( ϋ )部份爲4 7 5 °F -者。 (請先閱讀背面之注意事項再填寫本頁) .裝· 、1T_ 本紙張尺度適用中國國家標準(CNS )八4規格(2丨〇><297公釐)
TW087101646A 1997-02-07 1998-03-03 Synthetic jet fuel and process for its production TW496894B (en)

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US5766274A (en) 1998-06-16
US6669743B2 (en) 2003-12-30
JP4845938B2 (ja) 2011-12-28
KR100519145B1 (ko) 2005-10-06
WO1998034999A1 (en) 1998-08-13
KR20000070855A (ko) 2000-11-25
AR011621A1 (es) 2000-08-30
DE69806171D1 (de) 2002-07-25
DK1015530T3 (da) 2002-10-14
MY120139A (en) 2005-09-30
BR9807553A (pt) 2000-02-01
HK1025989A1 (en) 2000-12-01
PT1015530E (pt) 2002-11-29
CN1246888A (zh) 2000-03-08
CA2277974C (en) 2005-07-12
US20020005009A1 (en) 2002-01-17
ES2178822T3 (es) 2003-01-01
AU6433698A (en) 1998-08-26
JP2001511207A (ja) 2001-08-07
AU721442B2 (en) 2000-07-06
CN1097083C (zh) 2002-12-25
CA2277974A1 (en) 1998-08-13
ZA98617B (en) 1998-07-20
NO993790D0 (no) 1999-08-05
JP4272708B2 (ja) 2009-06-03
EP1015530A1 (en) 2000-07-05
NO993790L (no) 1999-10-04
EP1015530B1 (en) 2002-06-19
US6309432B1 (en) 2001-10-30
DE69806171T2 (de) 2002-10-31
JP2008291274A (ja) 2008-12-04

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