TW200848502A - Antioxidant blends for fatty acid methyl esters (biodiesel) - Google Patents

Antioxidant blends for fatty acid methyl esters (biodiesel) Download PDF

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Publication number
TW200848502A
TW200848502A TW097110658A TW97110658A TW200848502A TW 200848502 A TW200848502 A TW 200848502A TW 097110658 A TW097110658 A TW 097110658A TW 97110658 A TW97110658 A TW 97110658A TW 200848502 A TW200848502 A TW 200848502A
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TW
Taiwan
Prior art keywords
tertiary
phenylenediamine
butylphenol
butyl
oil
Prior art date
Application number
TW097110658A
Other languages
Chinese (zh)
Inventor
Vincent J Gatto
Gangkai Zhao
Emily R Schneller
Original Assignee
Albemarle Corp
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Filing date
Publication date
Application filed by Albemarle Corp filed Critical Albemarle Corp
Publication of TW200848502A publication Critical patent/TW200848502A/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1835—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

This invention provides stabilized biodiesels comprising (1) biodiesel, such as fatty acid methyl ester (FAME), (2) mono- or bis-hindered phenolic derived from 2, 6-di-tert-butylphenol, and (3) N, N' -di-substituted para-phenylene diamine. Also methods of stabilizing biodiesel are provided involving adding (2) and (3) to (1).

Description

200848502 九、發明說明： 【發明所屬之技術領域】 本發明係提供一種安定的生質柴油組成物，及其製備 之方法。 【先前技術】 隨著全世界能源需求持續地增加以及化石燃料的儲存 下降’能源的多樣化變得越來越重要。生質柴油係一種達 成多樣化的方式。生質柴油係爲從可再生脂質來源，像是 植物油、動物油或使用過的烹調油及脂肪，衍生之長鏈脂 肪酸單-烷基酯的屬名。生質柴油燃料依照使用於製造其之 原料而有許多的名稱，例如：脂肪酸甲基酯（fame )、油 菜籽甲基酯（RME )、使用過的植物油甲基酯（UVOME )、 大豆油（SOME )或者棕櫚油甲基酯（POME )。生質柴油 的原料在其脂肪酸組成物（鏈長及飽和）上有很大的不同。 生質柴油係通常於催化劑存在時，以植物油或者動物 脂肪與醇類（例如甲醇）反應來生產甲基酯（該生質柴油）以 及甘油。氫氧化鉀爲最普遍使用的催化劑，其係用於廣範 圍之油類與脂肪類的轉酯化反應，該油類與脂肪類之範圍 係從植物到動物，從未使用過到使用過的，以及包含最高 酸含量。如此製造的生質柴油可蒸餾以移除過多的醇類以 及其它雜質。其他生質柴油的生產方法係爲已知。 新鮮生產的植物油因所存在的天然抗氧化劑（例如生 育酚類）氧化而被保護。然而，生質柴油的製造程序傾向去 移除一些該天然抗氧化劑，而剩下的該燃料因氧化降解作 200848502 用受到較少的保護。另外，生質柴油的蒸餾主要傾向去移 除全部的天然抗氧化劑，而剩下的該燃料則因氧化降解作 用甚至更不受保護。生質柴油的氧化係藉由與空氣以及金 屬表面接觸，其導致氫過氧化物的形成。此誘發了自由基 的鏈鎖反應，使得分解成低分子量且高氧化物種（醛類、 丙酮類、酸類）以及高分子量聚合物材料（膠類）。這些 膠類傾向導致不充足的燃燒以及其它引擎問題，像是沈積 於注射器與活塞。高分子量且不可溶的膠類存在通常會使 燃料過濾器堵塞。 對於生質柴油氧化安定性的量測，RANCIMAT試驗係 爲廣泛接受的方法。這個試驗是由氣泡空氣通過已加熱至 1 1 0°C的生質柴油所構成。存在於餾出液之短鏈酸（脂肪酸 氧化的裂解產物）數量係爲生質柴油氧化安定性的直接指 示。在歐洲與巴西，不管生質柴油的老化，在生產工廠以 及充燃料補充車輛泵送時，生質柴油必須符合 6小時 RANCIMAT試驗要件。其他國家可會g制定相似的規定。雖 然新鮮生產的生質柴油可能顯示出超過6小時的氧化安定 性（利用RANCIMAT方法量測），但若沒有抗氧化劑存在， 在一般的儲存狀態下，這個數値將隨時間而減少。 爲了增加氧化安定性，在烴化物燃料中使用抗氧化 劑。生質柴油的氧化安定性亦可藉由添加抗氧化劑來增 加。然而，假如相對年輕的生質柴油燃料與烴化物燃料相 比，生質柴油的抗氧化技術還未發展良好。 因此，有在生質柴油燃料中使用之經改良抗氧化組成 200848502 物的需求以及經濟上適合於商業中使用的含該抗氧化組成 物之生質柴油組成物的需求。 【發明內容】 本發明提供由生質柴油、2，6 ·二-三級-丁基酚衍生之單 -或雙-受阻酚以及N，N ·-二-取代之對苯二胺所衍生之組成 物以符合上文所述之需求，其中以生質柴油爲基準，單-或 雙-受阻酚與Ν，Ν·-二-取代之對苯二胺的相加量爲約50ppm 至約5000ppm。此外，所提供的該組成物，其中該生質柴 油係爲粗生質柴油、以及其中該粗生質柴油係取自大豆 油、菜籽油（canola oil)、棕櫚油、椰子油、油菜籽油（rapeseed oil)、玉米油或使用過的植物油、以及其中該粗生質柴油係 爲S曰肪酸甲基酯。所提供的該組成物，其中該生質柴油係 爲蒸餾的生質柴油、以及其中該蒸餾的生質柴油係取自大 丑油、菜籽1油（canola oil)、棕櫚油、椰子油、油菜好油 (rapeseed oil)、玉米油或使用過的植物油。並且，所提供 的該組成物，其中以生質柴油爲基準，單-或雙-受阻酣與 N，N 二-取代之對苯二胺的相加量爲約1 〇 〇 p p m至約 25 00ppm。並且，所提供的該組成物，其中單-或雙_受阻酣 對Ν，Ν·-二-取代之對苯二胺之重量比爲約10:1至約η ι〇， 特別是從約5 : 1至約1 : 5的變化。同樣地提供由生質柴 油、2,4,6-三·三級-丁基酚及N，Nf-二·取代之對苯二胺所衍 生之組成物，其中該2,4,6-三-三級-丁基酚對該N,N、= _取 代之對苯二胺之重量比爲約1 0 : 1至約1 : 1 〇的變化。本發 明亦提供藉由結合、或包含生質柴油、2,6-二-三級-丁基酣 200848502 衍生之單-或雙-受阻酚及Ν，Ν·-二-取代之對苯二胺而製備 之組成物’其中以生質柴油爲基準’該單-或雙_受阻酸粗 該Ν，Ν·-二-取代之對苯二胺的相加量爲約5〇ppm至約 5000ppm 〇 本發明亦提供改善含有生質柴油之組成物氧化安定性 的方法，其係藉由結合該組成物以及2，6 -二-三級-丁基酌衍 生之單-或雙-受阻酚、以及Ν，Ν·-二-取代之對苯二胺，以生 質柴油爲基準，該單-或雙-受阻酚與該Ν，Ν，-二-取代之對苯 二胺的相加量爲約5 0 p p m至約5 0 0 0 p p m。同樣地所提供的 該方法，其中該生質柴油爲粗生質柴油、以及其中該生質 柴油係取自大豆油、菜好油（canola oil)、棕櫚油、椰子油、 油菜籽油（r a p e s e e d q i 1)、玉米油或使用過的植物油、以及 其中該粗生質柴油爲脂肪酸甲基酯。同樣地所提供的該方 法’其中該生質柴油爲蒸餾的生質柴油、以及其中該蒸餾 的生質柴油係取自大豆油、菜籽油（can〇la 011)、棕櫚油、 椰子油、油菜籽油（rapeseed oil)、玉米油或使用過的植物 油。並且，所提供的該方法，以生質柴油爲基準，該單-或 雙-受阻酚與該N，N ·-二·取代之對苯二胺的相加量爲約 lOOppm至約25 00ppm。此外，所提供的該方法，其中該單_ 或雙-受阻酚對N，N 1 -二-取代之對苯二胺之重量比爲從約 1 〇: 1至約1 : 10的變化，特別是從約5 : 1至約1 : 5的變 化。同樣地所提供改善包含生質柴油之組成物氧化安定性 的方法，其係藉由結合該組成物、2,4,6_三-三級-丁基酸、 以及N，N 1 -二-取代之對苯二胺，其中該2，4，6 -三-三級-丁基 200848502 酣對該N，N’-二-取代之對苯二胺之重量比係從約5 : 1至約 1 : 5的變化。 在本發明中，由2,6_二-三級-丁基酚衍生之該單-或雙-受阻酸可包括：鄰-三級-丁基酚、2,6_二-三級-丁基酚、2,4,6_ 三-三級-丁基酹、4,4·-亞甲基雙（2,6-二-三級-丁基酚）、 3，5 - — -二級-丁基-4 -經基苯基氫桂皮酸甲基酯、3，5 _二-三級 -丁基-4-羥基苯基氫桂皮酸C7-C9分枝烷基酯、2,6-二-三級 -丁基-α-二甲胺-對甲酚；丁基化羥基甲苯，或2,4,6-三-三級-丁基酚；以及Ν，Ν，-二-取代之對苯二胺可以至少包 括：Ν，Ν’-二-二級-丁基-對苯二胺、ν，Ν，-二異丙基-對苯二 胺或Ν，Ν、雙-(1,4-二甲基戊基）·對苯二胺。 在某些本發明的組成物及/或方法中，其中該2,4,6-三-三級-丁基酚對該Ν，ΙΤ-二-取代之對苯二胺之重量比爲大於 約1 ;在某些具體實施例中大於約1.25 ;以及在其他具體 實施例中大於約1.5。 專業用語之詞彙註解提供於申請專利範圍之前。 我們驚訝的發現，本發明所提供的生質柴油，其氧化 安定性顯著的增加。我們沒有理由會預期到如本文所敘述 以及所主張之生質柴油與抗氧化劑的該結合會提供如本文 提供之實例所顯示出的好處。 16-二-三級·丁基酚衍生之單·或雙-受阻酚類 由2,6-二-三級-丁基酚衍生之適當的單·或雙-受阻酚 類可包括：2,6-二-三級-丁基酚（例如以ETHANOX 470 1商 標販賣含有2,6-二-三級-丁基酚的產品）；2,4,6-三-三級-丁 200848502 基酚；由鄰-三級-丁基酚、2,6-二-三級-丁基酚、以及2,4,6- 三-三級-丁基酚的組合（例如以ETHANOX 47 3 3商標販賣含 有鄰-三級-丁基酚、2,6-二-三級·丁基酚、以及2,4,6-三-三 級-丁基酚的產品）；2,6-二-三級-丁基酚與2,4,6-三-三級- 丁基酚的組合（例如以ETHANOX 47 3 5商標販賣含有2,6-二 -三級-丁基酚以及2,4,6-三-三級-丁基酚的產品）；4,4·-亞甲 基雙（2,6-二-三級-丁基酚）（例如以ETHANOX 4702商標 販賣含有4,4'-亞甲基雙（2,6-二-三級-丁基酚）的產品）； 3,5-二-三級-丁基-4-羥基苯基氫桂皮酸甲基酯（例如以 ETHANOX 4750商標販賣含有3，5 -二-三級-丁基-4 -羥基苯 基氫桂皮酸甲基酯的產品）；3，5 -二-三級-丁基-4 -羥基苯基 氫桂皮酸C7-C9分枝烷基酯（例如以ETHANOX 4716商標販 賣含有3,5-二-三級-丁基-4-羥基苯基氫桂皮酸C7-C9分枝 院基酯的產品）；2，6 -二-三級-丁基-α -二甲胺-對甲酣（例如 以ETHANOX 4703商標販賣含有2,6-二-三級-丁基-α -二甲 r 胺-對甲酚的產品）；丁基化羥基甲苯（ΒΗΤ);實質上 v 100%2,4,6-三-三級-丁基酚（1^^);或其組合。本發明中’ 由2,6-二·三級-丁基酚衍生之該單-或雙-受阻酚的濃度可 爲總生質柴油的約0.0025重量百分比（wt%)至約0.25重量 百分比（wt%)。 取代之對苯二胳類 適當的N，N ’ -二-取代之對苯二胺類可包括：N，N、二_ 二級-丁基-對苯二胺（PDA)、ν,Ν，-二異丙基-對苯二胺、n，N，-雙-(1，4-二甲基戊基）_對苯二胺、或其組合。本發明中，該 -10- 200848502 N，N’-二-取代之對苯二胺的濃度可爲總生質柴油的約 0.0025重量百分比（wt%)至約0.25重量百分比（wt%)。 生質柴油類 除非其他不同的區別，本文所謂之生質柴油類包括：粗 、 生質柴油、蒸餾的生質柴油或者兩者中之任一個別化學成 分。粗生質柴油包括由植物或動物來源取得之8個碳至22 個碳飽和、單-未飽和、二-未飽和、或三-未飽和甲基酯、 或脂肪酸甲基酯。生產粗生質柴油之方法係爲該技術領域 f ' V 中所習知。脂肪酸甲基酯的個別化學成分之例子包含硬脂 酸甲酯（正-十八酸甲基酯）、油酸甲酯（9 -十八烯酸甲基 酯）、反1卜十八烯酸甲基酯（methyl vaccenate)(l卜十八烯酸 甲基酯）、亞麻油酸甲酯（9,12-十八碳二烯酸甲基酯）、或次 亞麻油酸甲酯（9,12,15-十八碳三烯酸甲基酯）、辛酸甲基 酯、癸酸甲基酯、月桂酸甲基酯、肉豆蔻酸甲基酯、軟脂 酸甲基酯、花生脂酸甲基酯、蘿酸甲基酯、月桂烯酸甲基 酯、肉豆蔻油酸甲基酯、軟脂油酸甲基酯、反油酸甲基酯、200848502 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention provides a stable biomass diesel composition and a method of preparing the same. [Prior Art] As the world's energy demand continues to increase and fossil fuel storage declines, the diversification of energy is becoming more and more important. Biodiesel is a way of achieving diversity. Biodiesel is a generic name for long-chain fatty acid mono-alkyl esters derived from renewable lipid sources such as vegetable oils, animal oils or used cooking oils and fats. Biodiesel fuels have many names depending on the materials used to make them, such as fatty acid methyl esters (fame), rapeseed methyl esters (RME), used vegetable oil methyl esters (UVOME), soybean oil ( SOME) or palm oil methyl ester (POME). Raw materials for biodiesel vary greatly in their fatty acid composition (chain length and saturation). The biodiesel is usually produced by reacting vegetable oil or animal fat with an alcohol (e.g., methanol) in the presence of a catalyst to produce a methyl ester (the biomass diesel) and glycerin. Potassium hydroxide is the most commonly used catalyst for a wide range of transesterification of oils and fats. The range of oils and fats ranges from plants to animals, never used or used. And contains the highest acid content. The biodiesel thus produced can be distilled to remove excess alcohol and other impurities. The production methods of other biodiesel are known. Freshly produced vegetable oils are protected by oxidation of the natural antioxidants (e.g., phenols) present. However, the manufacturing process for biodiesel tends to remove some of the natural antioxidants, while the remaining fuel is less protected by oxidative degradation for 200848502. In addition, the distillation of biodiesel is primarily intended to remove all of the natural antioxidants, while the remaining fuel is even more unprotected by oxidative degradation. Oxidation of the biodiesel is caused by contact with air and metal surfaces, which leads to the formation of hydroperoxides. This induces a chain reaction of free radicals, which causes decomposition into low molecular weight and high oxide species (aldehydes, acetones, acids) and high molecular weight polymer materials (gels). These gums tend to cause insufficient combustion and other engine problems, such as deposits on syringes and pistons. The presence of high molecular weight and insoluble gums typically occludes the fuel filter. The RANCIMAT test is a widely accepted method for measuring the oxidation stability of biodiesel. This test consisted of bubbling air through biodiesel that had been heated to 110 °C. The amount of short chain acid (the cleavage product of fatty acid oxidation) present in the distillate is a direct indication of the oxidation stability of the biodiesel. In Europe and Brazil, biodiesel must meet the 6-hour RANCIMAT test requirements, regardless of the ageing of biodiesel, in production plants and in fuel-filled vehicles. Other countries may formulate similar regulations. Although freshly produced biodiesel may exhibit more than 6 hours of oxidation stability (measured by the RANCIMAT method), in the absence of an antioxidant, this number will decrease over time under normal storage conditions. In order to increase oxidation stability, an antioxidant is used in the hydrocarbon fuel. The oxidation stability of biodiesel can also be increased by the addition of antioxidants. However, if relatively young biodiesel fuels are compared to hydrocarbon fuels, the antioxidant technology of biodiesel has not developed well. Accordingly, there is a need for a modified antioxidant composition 200848502 for use in biodiesel fuels and a biodiesel composition containing the antioxidant composition that is economically suitable for commercial use. SUMMARY OF THE INVENTION The present invention provides a mono- or di- hindered phenol derived from biodiesel, 2,6-di-tertiary-butylphenol, and N,N-di-substituted p-phenylenediamine. The composition meets the requirements described above, wherein the addition amount of mono- or di- hindered phenol to hydrazine, Ν·-di-substituted p-phenylenediamine is from about 50 ppm to about 5000 ppm based on biodiesel. . Further, the composition is provided, wherein the biomass diesel is crude fuel, and wherein the crude diesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed Rapeseed oil, corn oil or used vegetable oil, and wherein the crude diesel oil is S fatty acid methyl ester. The composition provided, wherein the biomass diesel is distilled diesel fuel, and wherein the distilled biodiesel is obtained from large oil, canola oil, palm oil, coconut oil, Rapeed oil, corn oil or used vegetable oil. Further, the composition is provided, wherein the addition amount of the mono- or double-blocked oxime to the N,N di-substituted p-phenylenediamine is from about 1 〇〇ppm to about 255 ppm based on the raw diesel fuel. . Further, the composition is provided, wherein the weight ratio of the mono- or double-blocked ruthenium, Ν·-di-substituted p-phenylenediamine is from about 10:1 to about η 〇, especially from about 5 : 1 to about 1: 5 changes. Similarly, a composition derived from biodiesel, 2,4,6-tris-tert-butylphenol, and N,Nf-di-substituted p-phenylenediamine is provided, wherein the 2,4,6-three The weight ratio of the third-butyl phenol to the N,N,=_substituted p-phenylenediamine is from about 10:1 to about 1:1. The present invention also provides a mono- or bis-hindered phenol derived from a combination of or containing biodiesel, 2,6-di-tertiary-butyl hydrazine 200848502, and fluorene, fluorene-di-substituted p-phenylenediamine The prepared composition 'in which the mono- or double-blocked acid is crude based on the raw material diesel oil, the added amount of the Ν·-di-substituted p-phenylenediamine is from about 5 〇 ppm to about 5000 ppm 〇 The present invention also provides a method for improving the oxidation stability of a composition containing biodiesel by combining the composition with a 2,6-di-tertiary-butyl-derived mono- or di-hindered phenol, and Ν,Ν·-di-substituted p-phenylenediamine, based on biodiesel, the addition amount of the mono- or di-hindered phenol to the fluorene, fluorene,-di-substituted p-phenylenediamine is about 5 0 ppm to approximately 5 0 0 ppm. Also provided is the method wherein the biomass diesel is crude diesel, and wherein the biomass diesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil (rapeseedqi) 1) corn oil or used vegetable oil, and wherein the crude biomass diesel is a fatty acid methyl ester. Also provided is the method wherein the biomass diesel is distilled biodiesel, and wherein the distilled biodiesel is derived from soybean oil, canola oil (can〇la 011), palm oil, coconut oil, Rapeed oil, corn oil or used vegetable oil. Further, the method is provided, wherein the addition amount of the mono- or di-hindered phenol to the N,N·-di-substituted p-phenylenediamine is from about 100 ppm to about 2500 ppm based on the raw diesel. Further, the method is provided wherein the weight ratio of the mono- or di- hindered phenol to the N,N 1 -di-substituted p-phenylenediamine is from about 1 〇:1 to about 1:10, in particular It is a change from about 5:1 to about 1:5. Also provided is a method for improving the oxidation stability of a composition comprising biodiesel by combining the composition, 2,4,6-tri-tertiary-butyl acid, and N,N 1 -di- Substituted p-phenylenediamine, wherein the weight ratio of the 2,4,6-tris-tertiary-butyl 200848502 oxime to the N,N'-di-substituted p-phenylenediamine is from about 5:1 to about 1 : 5 changes. In the present invention, the mono- or di- hindered acid derived from 2,6-di-tertiary-butylphenol may include: o-tris-butylphenol, 2,6-di-tris-butyl Phenol, 2,4,6_ tri-tertiary-butyl fluorene, 4,4·-methylene bis(2,6-di-tertiary-butyl phenol), 3,5 - - - 2 - Butyl-4-phenylphenylhydrocinnamate methyl ester, 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched alkyl ester, 2,6-di - tertiary-butyl-α-dimethylamine-p-cresol; butylated hydroxytoluene, or 2,4,6-tri-tertiary-butylphenol; and ruthenium, rhodium, and di-substituted pairs The phenylenediamine may include at least: ruthenium, Ν'-di-di-butyl-p-phenylenediamine, ν, Ν,-diisopropyl-p-phenylenediamine or hydrazine, hydrazine, bis-(1,4) -Dimethylpentyl)·p-phenylenediamine. In certain compositions and/or methods of the invention, wherein the weight ratio of the 2,4,6-tris-tertiary-butylphenol to the oxime, fluorene-di-substituted p-phenylenediamine is greater than about 1; in certain embodiments greater than about 1.25; and in other embodiments greater than about 1.5. Vocabulary notes for professional terms are provided before the scope of the patent application. We have surprisingly found that the biodiesel provided by the present invention has a marked increase in oxidation stability. There is no reason to expect that this combination of biodiesel and antioxidant as described herein and claimed will provide the benefits as exemplified by the examples provided herein. 16-di-tertiary·butylphenol-derived mono- or di- hindered phenols Suitable mono- or di- hindered phenols derived from 2,6-di-tertiary-butylphenol may include: 6-di-tertiary-butyl phenol (for example, a product containing 2,6-di-tertiary-butyl phenol sold under the trademark ETHANOX 470 1); 2,4,6-tri-tertiary-butyl 200848502 phenol a combination of o-tris-butylphenol, 2,6-di-tertiary-butylphenol, and 2,4,6-tris-tertiary-butylphenol (for example, sold under the trademark ETHANOX 47 3 3) a product containing o-tris-butylphenol, 2,6-di-tris-butylphenol, and 2,4,6-tris-tertiary-butylphenol; 2,6-di-three a combination of butyl phenol and 2,4,6-tris-tertiary-butyl phenol (for example, ETHANOX 47 3 5 trademark containing 2,6-di-tertiary-butyl phenol and 2,4,6- a product of tris-tertiary-butyl phenol); 4,4·-methylenebis(2,6-di-tertiary-butylphenol) (for example, 4,4'-sub-armor sold under the trademark ETHANOX 4702 a product of bis(2,6-di-tertiary-butylphenol); 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamate methyl ester (for example sold under the trademark ETHANOX 4750) Contains 3,5-di-tertiary-butyl-4-hydroxybenzene a product of hydrogen cinnamic acid methyl ester); 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched alkyl ester (for example, sold under the trademark ETHANOX 4716, 3,5- a product of a di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched tertyl ester); 2,6-di-tris-butyl-α-dimethylamine-p-methylhydrazine ( For example, the product containing 2,6-di-tris-butyl-α-dimethylr-p-cresol is sold under the trademark ETHANOX 4703; butylated hydroxytoluene (ΒΗΤ); substantially v 100% 2,4 , 6-tris-tertiary-butylphenol (1^^); or a combination thereof. In the present invention, the concentration of the mono- or bis-hindered phenol derived from 2,6-di-tertiary-butylphenol may be from about 0.0025 weight percent (wt%) to about 0.25 weight percent of the total biodiesel ( Wt%). Suitable N,N ' -di-substituted p-phenylenediamines for substituted benzodiazepines may include: N,N, di-di-butyl-p-phenylenediamine (PDA), ν, Ν, -diisopropyl-p-phenylenediamine, n,N,-bis-(1,4-dimethylpentyl)-p-phenylenediamine, or a combination thereof. In the present invention, the concentration of the -10-200848502 N,N'-di-substituted p-phenylenediamine may be from about 0.0025 weight percent (wt%) to about 0.25 wt% (wt%) of the total biodiesel. Biodiesel Unless otherwise different, the so-called biodiesel category includes: crude, biodiesel, distilled biodiesel or any of the individual chemical components. Crude biomass diesel includes 8 carbon to 22 carbon saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl esters, or fatty acid methyl esters obtained from vegetable or animal sources. The process for producing crude biomass diesel is well known in the art. Examples of individual chemical constituents of fatty acid methyl esters include methyl stearate (methyl-n-octadecanoate), methyl oleate (methyl 9-octadecenoate), and anti-dodecanoic acid Methyl ester (methyl vaccenate) (methyl l-octadecenoate), methyl linoleate (methyl 9,12-octadecadiate), or methyl linolenate (9, 12,15-octadecatrienoic acid methyl ester), octanoic acid methyl ester, methyl decanoate, methyl laurate, methyl myristate, methyl palmitate, arachidonic acid Base ester, methyl carboxylic acid ester, methyl laurate, methyl myristate methyl ester, methyl palmitate, methyl oleate,

C 鳕油酸甲基酯、花生油酸甲基酯、以及芥子酸甲基酯等等。 蒸餾的生質柴油包括粗生質柴油，該粗生質柴油係經 (例如）移除過量醇類、殘餘甘油、及其他雜質之至少一個 蒸餾步驟，以及包含取自粗生質柴油的蒸餾過程中所產生 之特定餾分（cut)或餾分（fraction)的生質柴油。蒸餾粗生質 柴油的方法係爲該技術領域中所習知。 粗生質柴油可自任何適合的植物或動物來源取得，包 含如大豆油、低芥子酸油菜籽油（菜籽油）、高芥子酸油菜 -11 - 200848502 籽油、棕櫚油、使用過的烹調油、植物油、椰子油、玉米 油、棉籽油、紅花子油、葵花子油、花生油、甘蔗油、豬 油、獸脂（tallow)、家禽脂肪、以及黃牛油等等。粗生質柴 油中的脂肪酸甲基酯可依熟習該項技術者所熟悉的來生 產，例如：藉由利用催化劑於一種植物或動物類之三酸甘油 脂與甲醇間的轉酯化反應。 粗生質柴油或蒸餾的生質柴油可經額外的化學處裡 (例如）減少未飽和。 < 組合（Combinations) 根據本發明之組成物，其係包括生質柴油、2,6-二-三 級-丁基酚衍生之單-或雙-受阻酚（組份（2))以及Ν，Ν^二-取 代之對苯二胺（組份（3))、或係經結合該組成而製備。以該 生質柴油的量爲基準，該組成物可包含約50ppm至約 5000ppm的組份（2)及（3)、或可經結合該組份（2)及（3)而製 備；以及以該生質柴油的量爲基準，該組成物可包含約 f 10〇PPm至約2500ppm的組份2)及（3)、或可經結合該組份成 (2)及（3)而製備。 根據本發明改善生質柴油氧化安定性的方法，其係可 包括結合該生質柴油以及從約50ppm至約5000ppm之抗氧 化劑組份，該組份係包含2，6 -二-三級-丁基酚衍生之單-或 雙·受阻酚以及N，N'-二-取代之對苯二胺。該方法亦可包括 結合該生質柴油組份以及從約100ppm至約2500ppm之抗氧 化劑組份，該抗氧化劑組份係包含2，6 _二-三級-丁基酚衍生 之單-或雙-受阻酚以及N，N，-二-取代之對苯二胺。 -12- 200848502 【實施方式】 下述的實例係說明本發明的原理。不論是在實例 本專利申請案的其他部分，應明暸本發明不受限於任 個本文作爲例子之特定具體實施例。 總結於表一之每個實例中，確定的生質柴油樣品 氧化劑組成物被合倂。在某些比較實例中，沒有抗氧 組成物加入於確定的生質柴油。在生質柴油被蒸餾過 例中，生質柴油係使用熟習該項技術者所知的標準技 蒸餾。在每個實例中，組合（或者只是某些比較實例中 質柴油）的氧化安定性，其係使用 RANCIMAT測試法 EN 141 12)之RAN CIM AT試驗來檢驗。在每個例子中， 大小爲3克、溫度爲1 1 0°C、空氣來源爲純淨的乾空氣 該流率爲1 〇升/小時。表一的數據清楚地顯示出本發 優點。例如：對沒有添加抗氧化劑的蒸餾的大豆油甲 而言，最高的RANCIMAT結果爲1.7小時（見比較實 3 3 - 3 9號）；而對根據本發明添加抗氧化劑的蒸餾的大 甲基酯而言，最高的RANCIMAT結果範圍從3.87小 11.19小時（見實例第1-22號）。對無添加抗氧化劑且無 之大豆油甲基酯而言，最高的RANCIMAT結果爲4.63 (見比較實例第4 0及4 1號）；而對根據本發明添加抗氧 的無蒸餾之大豆油甲基酯而言’最高的RANCIMAT結 圍從6.46小時至9.28小時（見實例第23 -32號）。比較 組第42及44號，兩者皆顯示結合大豆油甲基酯、蒸 及300ppm ETHANOX 47 3 3與lOOppm不是本發明的組 或是 何一 與抗 化劑 的實 術來 的生 (DIN 樣品 以及 明的 基酯 例第 豆油 時至 蒸餾 小時 化劑 果範 實例 餾以 份之 -13- 200848502 抗氧化劑組成物的結果；本發明的實例第1、3、5及6號， 每個皆顯示結合大豆油甲基酯、蒸餾以及低於300ppm ΕΤΗ ANOX 4733與PDA之抗氧化劑組成物的結果。以比較 實例第42及44號對實例第1、3、5及6號相比，顯示每 個實例第1、3、5及6號（分別爲8 · 7 6小時、9.5 3小時、6.9 1 小時以及5.8 9小時）的較每個比較實例第4 2及4 4號（分別 爲2.94小時以及2.88小時）有較佳的RANCIMAT結果。比 較實例第4 3、4 5及4 6號’每個皆顯示結合大豆油甲基酯、 f ^ 蒸餾以及300ppm ETHANOX 4702與lOOppm不是本發明的 組份之抗氧化劑組成物的結果；本發明的實例第2號，顯 示結合大豆油甲基酯、蒸餾以及200ppm ETHANOX 4702與 2 0 0ppm PDA之抗氧化劑組成物的結果。以比較實例第43、 45及46號對實例第2號相比，顯示實例第2號（10.52小時） 較任一個比較實例第4 3、4 5及4 6號（分別爲3.6小時、3.8 7 小時以及4.06小時）有較佳的RANCIM AT結果。比較實例 第50、51及52號，每個皆顯示結合大豆油甲基酯、無蒸C oleic acid methyl ester, peanut oleic acid methyl ester, and sinapic acid methyl ester and the like. The distilled biodiesel comprises crude biomass diesel which is subjected to, for example, at least one distillation step of removing excess alcohol, residual glycerin, and other impurities, and a distillation process comprising crude oil from crude oil. Biodiesel of a specific cut or fraction produced in the feed. Methods for distilling crude biomass diesel are well known in the art. Crude biomass diesel can be obtained from any suitable plant or animal source, including, for example, soybean oil, canola oil rapeseed oil (canola oil), high erucic acid rapeseed-11 - 200848502 seed oil, palm oil, used cooking Oil, vegetable oil, coconut oil, corn oil, cottonseed oil, safflower oil, sunflower oil, peanut oil, sugar cane oil, lard, tallow, poultry fat, and yellow butter. Fatty acid methyl esters in crude biomass oil can be produced by those skilled in the art, for example, by transesterification of a plant or animal triglyceride with methanol using a catalyst. Crude diesel or distilled biodiesel can be reduced in additional chemistry (for example) to reduce unsaturation. < Combinations The composition according to the present invention includes biodiesel, 2,6-di-tertiary-butylphenol-derived mono- or di-hindered phenol (component (2)), and hydrazine. , Ν^di-substituted p-phenylenediamine (component (3)), or prepared by combining the components. The composition may comprise from about 50 ppm to about 5000 ppm of components (2) and (3), or may be prepared by combining the components (2) and (3), based on the amount of the biomass diesel; Based on the amount of the biodiesel, the composition may comprise from about 10 10 ppm to about 2500 ppm of components 2) and (3), or may be prepared by combining the components into (2) and (3). A method for improving the oxidation stability of biodiesel according to the present invention, which may comprise combining the biodiesel and from about 50 ppm to about 5000 ppm of an antioxidant component comprising 2,6-di-tris-butyl A phenol-derived mono- or di-hindered phenol and an N,N'-di-substituted p-phenylenediamine. The method can also include combining the biodiesel component and from about 100 ppm to about 2500 ppm of an antioxidant component comprising 2,6-di-tertiary-butylphenol derived mono- or double - hindered phenols and N,N,-di-substituted p-phenylenediamines. -12- 200848502 [Embodiment] The following examples illustrate the principles of the present invention. It is to be understood that the invention is not limited to the specific embodiments disclosed herein. As summarized in each of the examples in Table 1, the identified oxidant composition of the biodiesel sample was combined. In some comparative examples, no antioxidant composition was added to the identified biodiesel. In the case where the biodiesel is distilled, the biodiesel is distilled using standard techniques known to those skilled in the art. In each of the examples, the oxidation stability of the combination (or just some of the comparative examples of the diesel fuel) was tested using the RAN CIM AT test of the RANCIMAT test method EN 141 12). In each case, the size was 3 gram, the temperature was 110 ° C, and the air source was pure dry air. The flow rate was 1 liter per hour. The data in Table 1 clearly shows the advantages of this invention. For example, for distilled soybean oil without the addition of antioxidants, the highest RANCIMAT result is 1.7 hours (see Comparative 3 3 - 39); and for the addition of antioxidants, the addition of large methyl esters according to the invention In terms of the highest RANCIMAT results ranged from 3.87 to 11.19 hours (see Example No. 1-22). For the soybean oil methyl ester without added antioxidant, the highest RANCIMAT result is 4.63 (see Comparative Examples Nos. 40 and 41); and for the addition of antioxidant-free distilled soybean oil according to the present invention For the base ester, the highest RANCIMAT balance was from 6.46 hours to 9.28 hours (see Examples Nos. 23-32). Comparison group Nos. 42 and 44, both of which showed that combined with soybean oil methyl ester, steamed and 300 ppm ETHANOX 47 3 3 and 100 ppm were not the group of the present invention or the actual production of the inhibitor (DIN sample) And the results of the example of the present invention, the first, third, fifth and sixth examples of the present invention are shown in the examples of the present invention. The results of combining soybean oil methyl ester, distillation, and an antioxidant composition of less than 300 ppm ΕΤΗ ANOX 4733 with PDA. Each of Comparative Examples Nos. 42 and 44 is shown for Examples Nos. 1, 3, 5, and 6. Examples Nos. 1, 3, 5, and 6 (8 · 7 6 hours, 9.5 3 hours, 6.9 1 hours, and 5.8 9 hours, respectively) were compared to No. 4 2 and No. 4 of each comparative example (2.94 hours and 2.88 hours) have better RANCIMAT results. Comparative Examples Nos. 4 3, 4 5 and 46 ' each show combined soybean oil methyl ester, f ^ distillation and 300 ppm ETHANOX 4702 and 100 ppm are not components of the invention The result of the antioxidant composition; the example of the present invention No. 2, Results of combining soybean oil methyl ester, distillation, and antioxidant composition of 200 ppm ETHANOX 4702 and 2000 ppm PDA. Example No. 2 (10.52) is shown in Comparative Example Nos. 43, 45, and 46 for Example No. 2. Hour) Better RANCIM AT results for any of Comparative Examples Nos. 4 3, 4 5 and 4 6 (3.6 hours, 3.8 7 hours and 4.06 hours, respectively). Comparative Examples Nos. 50, 51 and 52, each Both show that combined with soybean oil methyl ester, no steaming

U • 餾以及不同量（200ppm至600ppm) TTBP之抗氧化劑組成物 的結果；本發明的實例第27 - 3 2號，每個皆顯示結合大豆 油甲基酯、無蒸餾以及少於或等於200ppm TTBP與PDA之 抗氧化劑組成物的結果。以比較實例第5 0、5 1及5 2號對 實例第27 -3 2號相比，顯示每個實例第27 -3 2號（分別爲8.1 小時、9.2 8小時、8.3 8小時、7.7 7小時、6.9 5小時以及6.4 6 小時）較任一個比較實例第50、51及52號（分別爲5.28小 時、5.53小時以及5.84小時）有較佳的RANCIM AT結果。 -14- 200848502 特別是，以比較實例第50號（與200ppm TTBP的抗氧化劑 組成物以及5.28小時的RANCIMAT結果）與本發明之實例 第28號（與2 00ppm ΤΤΒΡ及200ppm PDA的抗氧化劑組成物 以及9.28小時的RANCIMAT結果）相比，可看出本發明所 提供的重大優點。一個相似的比較，基於以ETHAN OX 4703 的抗氧化劑組成物比較包含ΕΤΗANOX 4703的本發明抗氧 化劑組成物，該比較可在比較實例第48號與本發明之實例 第3、7、8以及9號之間完成。比較實例第47號顯示出與 蒸餾生質柴油使用如抗氧化劑之381 ppm PDA，其產生6.39 小時之RANCIMAT結果。雖然本發明的某些實例，其係和 單-或雙-受阻酚使用蒸餾生質柴油以及PDA的抗氧化劑， 顯示較低的RANCIMAT結果，但這些實例並沒有使用接近 3 8 lppm PDA。根據本發明，與酚類能夠使用少量的PDA， 將使相對高單價的PDA、以及相對低單價的酚類有助益， 並且還得到可接受的RANCIMAT結果。見（例如）本發明的 實例第2及3號（與蒸餾的生質柴油），實例第2及3號與酚 類只有使用200ppm PDA以及取得8.76小時與10.52小時之 RANCIMAT結果。此外，在每個呈現低於 6.39小時 RANCIMAT結果之使用蒸餾生質柴油、PDA的抗氧化劑以 及酚的本發明實例中，抗氧化劑中的該酚係爲ETHANOX 473 3，以及最低的該RANCIMAT結果爲3.87小時。以這個 實例比上比較實例第4 2及4 4號（2.9 4小時以及2 · 8 8小時的 RANCIMAT結果），其中ETHANOX 4733係使用不是本發明 之胺類，顯示用本發明之抗氧化劑組成物所改善的結果。 -15- 200848502 比較實例第49號顯示和生質柴油（無蒸餾的）使用作爲抗氧 化劑之200ppm PDA，該比較實例產生9.01小時RANCIMAT 結果。比較實例第50號顯示和生質柴油（無蒸餾的）使用如 抗氧化劑之 200ppm TTBP，該比較實例產生 5.28小時 RANCIMAT結果。當使用本發明之l〇〇PPm TTBP與lOOppm PDA的組合作爲抗氧化劑，該組合與生質柴油（無蒸餾的） 取得 8.1小時 RANCIMAT結果（實例第 27號）。使用 TTBP/PDA的組合之8.1小時結果係顯著地較單獨使用 1 TTBP取得之5.28小時佳。此外，使用TTBP/PDA的組合之 8 . 1小時結果係稍微低於單獨使用PDA所取得之9.0 1小時 以及已經提供商業上顯著的價格優點。雖然本發明的某些 實例係與單-或雙-受阻酚使用生質柴油（無蒸餾的）以及 PDA的抗氧化劑，而該實例顯示出較低的RANCIMAT結 果，但這些實例並沒有使用接近200ppm PDA。 -16- 200848502 表一 實例號碼 生質柴油樣品 抗氧化劑組成物(ppm， 以生質柴油爲基準） 結果(小時） 1 大豆油甲基酯， 蒸餾 200 ppm ETHANOX 4733，200 ppm PDA 8.76 2 大豆油甲基酯， 蒸餾 200 ppm PDA，200 ppm ETHANOX 4702 10.52 3 大豆油甲基酯， 蒸餾 200 ppm PDA，200 ppm ETHANOX 4703 9.53 4 大豆油甲基酯， 蒸餾 85 ppm ETHANOX 4733 ^ 295ppm PDA 5.85 5 大豆油甲基酯， 蒸餾 183 ppm ETHANOX 4733，206 ppm PDA 6.91 6 大豆油甲基酯， 蒸餾 296 ppm ETHANOX 4733，98 ppm PDA 5.89 7 大豆油甲基酯， 蒸餾 318 ppm PDA，104 ppm ETHANOX 4703 9.3 8 大豆油甲基酯， 蒸餾 204 ppm PDA，202 ppm ETHANOX 4703 7.88 9 大豆油甲基酯， 蒸餾 105 ppm PDA，297 ppm ETHANOX 4703 6.56 10 大豆油甲基酯， 蒸餾 100 ppm ETHANOX 4733 » 100 ppm PDA 4.45 11 大豆油甲基酯， 蒸餾 200 ppm ETHANOX 4733，200 ppm PDA 6.5 12 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4733，300 ppm PDA 8.35 13 大豆油甲基酯， 蒸餾 150 ppm ETHANOX 4733，50 ppm PDA 3.87 14 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4733 ^ 100 ppm PDA 5.47 15 大豆油甲基酯， 蒸餾 450 ppm ETHANOX 4733，150 ppm PDA 6.78 16 大豆油甲基酯， 蒸餾 100 ppm ETHANOX 4733，100 ppm PDA 4.34 17 大豆油甲基酯， 蒸餾 200 ppm ETHANOX 4733，200 ppm PDA 6.54 18 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4733，300 ppm PDA 8.42 -17- 200848502 19 大豆油甲基酯， 蒸餾 400 ppm ETHANOX 4733，400 ppm PDA 9.69 20 大豆油甲基酯， 蒸餾 500 ppm ETHANOX 4733，500 ppm PDA 11.19 21 大豆油甲基酯， 蒸餾 375 ppm ETHANOX 4733 » 125 ppm PDA 6.15 22 大豆油甲基酯， 蒸餾 375 ppm ETHANOX 4733，125 ppm PDA 6.07 23 大豆油甲基酯， 無蒸餾 100 ppm ETHANOX 4733，100 ppm PDA 7.74 24 大豆油甲基酯， 無蒸餾 200 ppm ETHANOX 4733，200 ppm PDA 9.04 25 大豆油甲基酯， 無蒸餾 150 ppm ETHANOX 4733 » 50 ppm PDA 6.82 26 大豆油甲基酯， 無蒸餾 300 ppm ETHANOX 4733，100 ppm PDA 8.3 27 大豆油甲基酯， 無蒸餾 100 ppm PDA，100 ppm TTBP 8.1 28 大豆油甲基酯， 無蒸餾 200 ppm PDA，200 ppm TTBP 9.28 29 大豆油甲基酯， 無蒸餾 100 ppm PDA，300 ppm TTBP 8.38 30 大豆油甲基酯， 無蒸餾 100 ppm PDA，100 ppm TTBP 7.77 31 大豆油甲基酯， 無蒸餾 75 ppm PDA»75 ppm TTBP 6.95 32 大豆油甲基酯， 無蒸餾 50 ppm PDA，50 ppm TTBP 6.46 33 (比較） 大豆油甲基酯， 蒸餾 M 1.57 34 (比較） 大豆油甲基酯， 蒸餾 M j\\\ 1.58 35 仳較） 大豆油甲基酯， 蒸餾 M j \ \\ 1.7 36 (比較） 大豆油甲基酯， 蒸餾 M 1.58 37 (比較） 大豆油甲基酯， 蒸餾 M 1.56 38 (比較） 大豆油甲基酯， 蒸餾 >fnT ΤΠΤΓ J\\\ 1.59 -18- 200848502 fU • Distillation and results for different amounts (200 ppm to 600 ppm) of the TTBP antioxidant composition; examples of the invention Nos. 27-3, each showing a combination of soybean oil methyl ester, no distillation, and less than or equal to 200 ppm The result of the antioxidant composition of TTBP and PDA. Comparing Examples Nos. 50, 5, and 5 to Example No. 27-32, each example No. 27-32 was displayed (8.1 hours, 9.2 8 hours, 8.3 8 hours, 7.7 7 respectively). Hours, 6.9 5 hours, and 6.4 6 hours) Better RANCIM AT results for any of Comparative Examples Nos. 50, 51, and 52 (5.28 hours, 5.53 hours, and 5.84 hours, respectively). -14- 200848502 In particular, Comparative Example No. 50 (with antioxidant composition of 200 ppm TTBP and RANCIMAT results of 5.28 hours) and Example No. 28 of the present invention (with antioxidant composition of 200 ppm hydrazine and 200 ppm PDA) The significant advantages provided by the present invention can be seen in comparison to the 9.28 hour RANCIMAT results. A similar comparison is based on comparing the antioxidant composition of the present invention comprising ΕΤΗANOX 4703 with an antioxidant composition of ETHAN OX 4703, which can be compared to Comparative Example No. 48 and Examples 3, 7, 8, and 9 of the present invention. Completed between. Comparative Example No. 47 shows the use of a 381 ppm PDA such as an antioxidant with distilled biodiesel, which produced a RANCIMAT result of 6.39 hours. Although some examples of the present invention, and mono- or di-hindered phenols use distilled biodiesel and PDA antioxidants, exhibiting lower RANCIMAT results, these examples do not use nearly 380 lppm PDA. In accordance with the present invention, the ability to use small amounts of PDA with phenols will help to make relatively high monovalent PDAs, as well as relatively low monovalent phenols, and also achieve acceptable RANCIMAT results. See, for example, Examples 2 and 3 of the present invention (with distilled biodiesel), Examples 2 and 3 with phenols using only 200 ppm PDA and obtaining RANCIMAT results of 8.76 hours and 10.52 hours. Further, in each of the examples of the present invention using distillate biomass diesel, antioxidants of PDA, and phenol presenting a RANCIMAT result of less than 6.39 hours, the phenolic system in the antioxidant is ETHANOX 473 3, and the lowest RANCIMAT result is 3.87 hours. In this example, Comparative Examples Nos. 4 2 and 4 (2.9 4 hours and 2 · 8 8 hours of RANCIMAT results), wherein ETHANOX 4733 is an amine which is not an amine of the present invention, shows the antioxidant composition of the present invention. The result of the improvement. -15- 200848502 Comparative Example No. 49 shows that biodiesel (without distillation) uses a 200 ppm PDA as an antioxidant, and this comparative example yielded a 9.01 hour RANCIMAT result. Comparative Example No. 50 shows that biodiesel (without distillation) uses 200 ppm TTBP such as an antioxidant, and this comparative example yielded 5.28 hours of RANCIMAT results. When the combination of l〇〇PPm TTBP of the present invention and lOOppm PDA was used as an antioxidant, the combination and biodiesel (no distillation) were obtained for 8.1 hours RANCIMAT results (Example No. 27). The 8.1 hour results using the combination of TTBP/PDA were significantly better than the 5.28 hours achieved with 1 TTBP alone. In addition, the 8.1 hour results using the combination of TTBP/PDA were slightly lower than the 9.0 1 hour achieved with the PDA alone and the commercially significant price advantage has been provided. Although some examples of the invention use biodiesel (no distillation) and PDA antioxidants with mono- or di-hindered phenols, and this example shows lower RANCIMAT results, these examples do not use nearly 200 ppm. PDA. -16- 200848502 Table 1 Example Number Biomass Diesel Sample Antioxidant Composition (ppm, based on Biodiesel) Results (hours) 1 Soybean Oil Methyl Ester, Distillation 200 ppm ETHANOX 4733, 200 ppm PDA 8.76 2 Soybean Oil Methyl ester, distilled 200 ppm PDA, 200 ppm ETHANOX 4702 10.52 3 Soybean oil methyl ester, distilled 200 ppm PDA, 200 ppm ETHANOX 4703 9.53 4 Soybean oil methyl ester, distilled 85 ppm ETHANOX 4733 ^ 295ppm PDA 5.85 5 Soybean oil Methyl ester, distillation 183 ppm ETHANOX 4733, 206 ppm PDA 6.91 6 Soybean oil methyl ester, distillation 296 ppm ETHANOX 4733, 98 ppm PDA 5.89 7 Soybean oil methyl ester, distilled 318 ppm PDA, 104 ppm ETHANOX 4703 9.3 8 large Methyl Bean Oil, Distillation 204 ppm PDA, 202 ppm ETHANOX 4703 7.88 9 Soybean Oil Methyl Ester, Distillation 105 ppm PDA, 297 ppm ETHANOX 4703 6.56 10 Soybean Oil Methyl Ester, Distillation 100 ppm ETHANOX 4733 » 100 ppm PDA 4.45 11 Soybean oil methyl ester, distilled 200 ppm ETHANOX 4733, 200 ppm PDA 6.5 12 soybean oil methyl ester, distilled 300 ppm ETHANOX 4733, 300 ppm PDA 8.35 13 large Oil methyl ester, distillation 150 ppm ETHANOX 4733, 50 ppm PDA 3.87 14 soybean oil methyl ester, distillation 300 ppm ETHANOX 4733 ^ 100 ppm PDA 5.47 15 soybean oil methyl ester, distillation 450 ppm ETHANOX 4733, 150 ppm PDA 6.78 16 Soybean oil methyl ester, distilled 100 ppm ETHANOX 4733, 100 ppm PDA 4.34 17 soybean oil methyl ester, distillation 200 ppm ETHANOX 4733, 200 ppm PDA 6.54 18 soybean oil methyl ester, distillation 300 ppm ETHANOX 4733, 300 ppm PDA 8.42 -17- 200848502 19 Soybean oil methyl ester, distillation 400 ppm ETHANOX 4733, 400 ppm PDA 9.69 20 soybean oil methyl ester, distillation 500 ppm ETHANOX 4733, 500 ppm PDA 11.19 21 soybean oil methyl ester, distillation 375 ppm ETHANOX 4733 » 125 ppm PDA 6.15 22 Soybean oil methyl ester, distilled 375 ppm ETHANOX 4733, 125 ppm PDA 6.07 23 Soybean oil methyl ester, no distillation 100 ppm ETHANOX 4733, 100 ppm PDA 7.74 24 Soybean oil methyl ester, no distillation 200 Ppm ETHANOX 4733, 200 ppm PDA 9.04 25 Soybean oil methyl ester, no distillation 150 ppm ETHANOX 4733 » 50 ppm PDA 6.82 26 Soybean oil methyl ester, no distillation 300 ppm ETHANOX 4733, 100 ppm PDA 8.3 27 Soybean oil methyl ester, no distillation 100 ppm PDA, 100 ppm TTBP 8.1 28 soybean oil methyl ester, no distillation 200 ppm PDA, 200 ppm TTBP 9.28 29 soybean oil methyl ester, No distillation 100 ppm PDA, 300 ppm TTBP 8.38 30 soybean oil methyl ester, no distillation 100 ppm PDA, 100 ppm TTBP 7.77 31 soybean oil methyl ester, no distillation 75 ppm PDA»75 ppm TTBP 6.95 32 soybean oil methyl ester , no distillation 50 ppm PDA, 50 ppm TTBP 6.46 33 (comparative) soybean oil methyl ester, distillation M 1.57 34 (comparative) soybean oil methyl ester, distillation M j\\\ 1.58 35 )) soybean oil methyl ester , distillation M j \ \\ 1.7 36 (comparative) soybean oil methyl ester, distillation M 1.58 37 (comparative) soybean oil methyl ester, distillation M 1.56 38 (comparative) soybean oil methyl ester, distillation > fnT ΤΠΤΓ J \\\ 1.59 -18- 200848502 f

39 (比較） 大豆油甲基酯， 蒸餾 Μ 1.61 40 (比較） 大豆油甲基酯， 無蒸飽 Μ 4.63 41 (比較） 大豆油甲基酯， 無蒸餾 Μ y \ 4.49 42 (比較） 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4733,100 ppm二癸甲基胺 2.94 43 (比較） 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4702，100 ppm二癸甲基胺 3.6 44 (比較） 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4733,100 ppm硫代二丙酸 二月桂酯 2.88 45 (比較） 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4702，100 ppm硫代二丙酸 二月桂酯 3.87 46 (比較） 大豆油甲基酯， 蒸餾 300 ppm ETHANOX 4702，100 ppm N，N’ 二亞 柳基丙二胺 4.06 47 (比較） 大豆油甲基酯， 蒸餾 381 ppm PDA 6.39 48 (比較） 大豆油甲基酯， 蒸餾 471 ppm ETHANOX 4703 3.14 49 (比較） 大豆油甲基酯， 無蒸餾 200 ppm PDA 9.01 50 (比較） 大豆油甲基酯， 無蒸餾 200 ppm TTBP 5.28 51 (比較） 大豆油甲基酯， 無蒸餾 400 ppm TTBP 5.53 52 (比較） 大豆油甲基酯， 無蒸餾 600 ppm TTBP 5.84 其應瞭解者，在說明書或申請專利範圍中任何地方以 化學名稱或化學式所指之反應物和各成分，不論其所指爲 單數或複數，均被認定其係存在於與另一以化學名稱或化 學形式（例如另一反應物或溶劑等）指稱之物質結合或進入 接觸之前。不管是何種化學變化、轉變及/或反應，若有任 何一者，其發生於所成之結合、溶液或反應介質中者，如 -19- 200848502 該變化、轉變及/或反應均爲所謂根據本揭示之條件使各特 定反應物或組成共同獲得的自然結果。因此該反應物或組 份被認定是實行所需化學反應’或形成用於進行所需反應 之結合而在一起之成分。此外，即使如以下之申請專利範 圍，可以視爲現在式（「包括」或「爲」等）之物質、組份 (components)及/或成分（ingredients)，其所引申之意義中乃 爲根據本揭示之物質、組份及/或成分存在於恰與另一或多 種其他物質、組份及/或成分初次接觸、組合、摻合或混合 / ' % 之前者。無論什麼轉變，若有任何一者，其如所引導反應 之原地發生處，係爲申請專利範圍所要覆蓋的。因此事質 上，物質、組份或成分可能在接觸、組合、摻合或混合的 過程中，經一個化學反應或轉變，而遺失其原始特性（若根 據本揭露、該常識的應用以及化學家熟知之技巧進行），因 而係對準確地瞭解、真實意義的正確評價、本揭露的物質 以及此處的申請專利範圍完全不重要。 雖然已經就一個或多個較佳具體實施例說明本發明， 但須了解可未偏離如下申請專利範圍所陳述之本發明之範 圍作出其他修改。 詞彙表 生質柴油係包括粗生質柴油、蒸餾的生質柴油、或兩 者之中任一個別化學組份。 粗生質柴油係包括8個碳至22個碳之飽和、單-不飽 和、二-不飽和、或三-不飽和甲基酯、或自植物或動物來 源衍生之脂肪酸甲基酯。 -20- 200848502 蒸餾的生質柴油係包括粗生質柴油，該粗生質柴油經 至少一次蒸餾步驟，像是移除過量的醇類、殘餘的甘油、 和其他雜質、以及包含取自於粗生質柴油的蒸餾過程中所 產生特定餾分（cut)或餾分（fraction)之生質柴油TTBP實質 上包括100% 2,4,6-三-三級·丁基酚。 【圖式簡單說明】 無。 【主要元件符號說明】 ί' 無。 -21-39 (Comparative) Soybean oil methyl ester, distilled Μ 1.61 40 (Comparative) Soybean oil methyl ester, no steaming Μ 4.63 41 (Comparative) Soybean oil methyl ester, no distillation Μ y \ 4.49 42 (Comparative) Soybean oil Methyl ester, distilled 300 ppm ETHANOX 4733, 100 ppm dimethylamine 2.94 43 (comparative) Soybean oil methyl ester, distilled 300 ppm ETHANOX 4702, 100 ppm dimethylamine 3.6 44 (comparative) soybean oil methyl Ester, distillation 300 ppm ETHANOX 4733, 100 ppm dilauryl thiodipropionate 2.88 45 (comparative) Soybean oil methyl ester, distilled 300 ppm ETHANOX 4702, 100 ppm dilauryl thiodipropionate 3.87 46 (comparative) Soybean oil methyl ester, distilled 300 ppm ETHANOX 4702, 100 ppm N, N' dilinalyl propylene diamine 4.06 47 (comparative) soybean oil methyl ester, distillation 381 ppm PDA 6.39 48 (comparative) soybean oil methyl ester , Distillation 471 ppm ETHANOX 4703 3.14 49 (Comparative) Soybean oil methyl ester, no distillation 200 ppm PDA 9.01 50 (comparative) Soybean oil methyl ester, no distillation 200 ppm TTBP 5.28 51 (comparative) Soybean oil methyl ester, none Distillation 400 ppm TTBP 5. 53 52 (Comparative) Soybean oil methyl ester, no distillation 600 ppm TTBP 5.84 It should be understood that the reactants and ingredients referred to by chemical name or chemical formula, wherever indicated in the specification or the scope of the patent application, Singular or plural, it is assumed that it is present in conjunction with or in contact with another substance referred to by chemical name or chemical form (eg, another reactant or solvent, etc.). No matter what kind of chemical change, transformation and/or reaction, if any, it occurs in the combination, solution or reaction medium, such as -19- 200848502, the change, transformation and / or reaction are so-called The natural result obtained by the combination of specific reactants or compositions according to the conditions of the present disclosure. Thus, the reactants or components are considered to be the ones that carry out the desired chemical reaction' or form a combination that is used to carry out the desired reaction. In addition, the substance, components and/or ingredients of the present formula ("including" or "for", etc.) are considered to be based on the meaning of the following claims. The materials, components and/or ingredients of the present disclosure are present prior to initial contact, combination, blending or mixing/% with respect to one or more other substances, components and/or ingredients. No matter what the change, if any one of them, the place where the induced reaction occurs, is covered by the scope of the patent application. Therefore, in substance, a substance, component or component may lose its original characteristics through a chemical reaction or transformation during contact, combination, blending or mixing (if according to the disclosure, the application of the common sense and the chemical The well-known skills are carried out, and thus the correct evaluation of the true meaning, the substance of the disclosure, and the scope of the patent application here are completely unimportant. Although the present invention has been described in terms of one or more preferred embodiments, it is understood that other modifications may be made without departing from the scope of the invention as set forth in the appended claims. Glossary Biodiesel consists of crude diesel, distilled biodiesel, or any of the individual chemical components. The crude biomass diesel fuel includes saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl esters of 8 carbons to 22 carbons, or fatty acid methyl esters derived from plant or animal sources. -20- 200848502 Distilled biodiesel system includes crude biomass diesel oil subjected to at least one distillation step, such as removal of excess alcohol, residual glycerin, and other impurities, and inclusion from coarse The biodiesel TTBP which produces a specific cut or fraction during the distillation of the biomass diesel substantially comprises 100% 2,4,6-tris-tert-butylphenol. [Simple description of the diagram] None. [Main component symbol description] ί' None. -twenty one-

Claims (1)

200848502 十、申請專利範圍： 1. 一種由生質柴油、2,6-二-三級-丁基酚衍生之單-或雙-受阻酚以及N，N’-二-取代之對苯二胺所衍生之組成物， 其中以生質柴油爲基準，單-或雙-受阻酚與N，N’-二-取 代之對苯二胺的相加量爲約5〇百萬分之一（ppm)至約 5 000百萬分之一（ppm)。 2. 如申請專利範圍第1項之組成物，其中 (a )生質柴油主要由粗生質柴油所組成； P ( b) 2,6-二-三級-丁基酚衍生之單-或雙-受阻酚包括： (i)鄰-三級-丁基酚、 (ii ) 2,6-二-三級-丁 基酚、 (iii) 2,4,6-三-三級-丁基酚、 (iv) 4,4’-亞甲基雙（2,6-二-三級-丁基酚）、 (v) 3,5-二-三級-丁基-4-羥基苯基氫桂皮酸甲基 酯、 (vi) 3,5 -二-三級-丁基-4-經基苯基氫桂皮酸 」 C7-C9分枝烷基酯、 (vii) 2,6-二-三級-丁基-α-二甲胺-對甲酚、或 (viii ) 丁基化羥基甲苯、以及 (c) N，Nf-二-取代之對苯二胺包括： (i) N，N、二-二級-丁基-對苯二胺、 (ii) N，N’·二異丙基-對苯二胺、或 (iii) N，N、雙_(1，4-二甲基戊基）-對苯二胺。 3 ·如申請專利範圍第2項之組成物，其中粗生質柴油係取 -22- 200848502 自大Η油、菜好油（canola oil)、棕櫚油、椰子油、油菜 籽油（rapes eed oil)、玉米油或使用過的植物油。 4 .如申請專利範圍第2項之組成物，其中粗生質柴油爲脂 肪酸甲基酯。 5 .如申請專利範圍第1項之組成物，其中 (a )生質柴油主要由蒸餾的生質柴油所組成·， (b) 2,6-二-三級-丁基酚衍生之單-或雙-受阻酚包括： (i )鄰-三級-丁基酚、 f ( ii ) 2,6-二-三級-丁 基酚、 (Π〇 2,4,6-三-三級-丁基酚、 (iv) 4,4’-亞甲基雙（2,6-二-三級-丁基酚）、 (v) 3,5-二-三級·丁基-4-羥基苯基氫桂皮酸甲基 酯、 (vi) 3,5-二-三級-丁基-4-羥基苯基氫桂皮酸 C7-C9分枝烷基酯、 (乂^)2,6-二-三級-丁基-〇1-二甲胺-對甲酚、或 k ( viii) 丁基化羥基甲苯、以及 (c) Ν，Ν’-二·取代之對苯二胺包括： (i) Ν，Ν’·二-二級·丁基-對苯二胺、 (ii) Ν，Ν’-二異丙基·對苯二胺、或 (iii ) N，Nf-雙-(1，4-二甲基戊基）-對苯二胺。 6.如申請專利範圔第5項之組成物，其中蒸餾的生質柴油 係取自大豆油、菜籽油（canola oil)、棕櫚油、椰子油、 油菜籽油（raPe seed oil)、玉米油或使用過的植物油。 -23- 200848502 7 ·如申請專利範圍第1項之組成物，其中以生質柴油爲基 準，單-或雙-受阻酚與Ν,Ν’ — 二_取代之對苯二胺的相加 量爲約100百萬分之一（ppm)至約2500百萬分之一 (ppm) ° 8·如申請專利範圍第丨項之組成物，其中2,4,6_三-三級· 丁基酣對N，N’-二-取代之對苯二胺之重量比爲 a) 大於約1 ; b) 大於約1 .25 ;或 c) 大於約1 · 5。 9.一種由生質柴油、2,4,6-三-三級-丁基酚及N，N，-二-取代 之對苯二胺所衍生之組成物，其中2,4,6-三-三級·丁基 酚對N，N’-二·取代之對苯二胺之重量比爲a)大於約1。 1 0 .如申請專利範圍第9項之組成物，其中2，4，6 -三-三級_ 丁基酚對N，Nf-二-取代之對苯二胺之重量比爲約1〇:1 至約1 : 1 〇。 1 1 ·一種結合生質柴油、2,6-二-三級-丁基酚衍生之單-或雙 £ \ -受阻酚及N，Nf-二-取代之對苯二胺所製備之組成物，其 中以生質柴油爲基準，單-或雙-受阻酚與N，N’-二-取代 之對苯二胺的相加量爲約5〇百萬分之一（ppm)至約50〇〇 百萬分之一（ppm)。 1 2 .如申請專利範圍第1 1項之組成物，其中 (a )生質柴油主要由粗生質柴油所組成； (b) 2,6-二-三級-丁基酚衍生之單-或雙-受阻酚包括： (i )鄰-三級-丁基酚、 -24- 200848502 (ii ) 2,6-二-三級-丁 基酚、 (iii ) 2,4,6-三-三級-丁基酚、 (iv ) 4,4’-亞甲基雙（2,6-二-三級-丁基酚）、 (v) 3,5-二-三級-丁基-4-羥基苯基氫桂皮酸甲基 酯、 (vi )3,5-二-三級-丁基-4-羥基苯基氫桂皮酸C7-C9 分枝烷基酯、 (vii) 2,6-二-三級-丁基-α-二甲胺-對甲酚、或 (viii ) 丁基化羥基甲苯、以及 (c ) N，N’-二-取代之對苯二胺至少包括： (i ) N，Nf-二-二級-丁基-對苯二胺、 (ii ) Ν，Ν·-二異丙基-對苯二胺、或 (iii) Ν，Ν’-雙-(1，4-二甲基戊基）-對苯二胺。 1 3 .如申請專利範圍第1 1項之組成物，其中 (a )生質柴油主要由蒸餾的生質柴油所組成； (b) 2,6-二-三級-丁基酚衍生之單-或雙-受阻酚包括： (i )鄰-三級-丁基酚、 (ii ) 2,6-二-三級-丁 基酚、 (iii) 2,4,6-三-三級-丁基酚、 (iv) 4,4_-亞甲基雙（2,6-二-三級-丁基酚）、 (v )3,5-二-三級·丁基-4-羥基苯基氫桂皮酸甲基酯、 (vi ) 3,5-二-三級-丁基-4-羥基苯基氫桂皮酸C7-C9 分枝烷基酯、 (vii) 2,6-二-三級-丁基-α-二甲胺-對甲酚；或 -25- 200848502 (V i i i ) 丁基化羥基甲苯、以及 (c ) N，N’-二-取代之對苯二胺包括： (i ) N，N’-二-二級-丁基-對苯二胺、 (ii) N，N’-二異丙基-對苯二胺、或 (iii) N，N’-雙- (ι，4-二甲基戊基）_對苯二胺。 14· 一種含有生質柴油、2,4,6-三-三級·丁基酚及N，N，-二-取代之對苯二胺之組成物，其中2，4，6 _三-三級-丁基酚 f ' 對N，N’_二•取代之對苯二胺之重量比爲a)大於約1。 1 5 ·如申請專利範圍第1 4項之組成物，其中2，4，6 -三·三級- 丁基酌對N，N，·二-取代之對苯二胺之重量比爲約10:1 至約1 : 1 0。 16 · —種改善含有生質柴油組成物氧化安定性之方法，係將 該組成物結合2,6-二-三級-丁基酚衍生之單-或雙-受阻 酣以及N，N’-二-取代之對苯二胺，其中以生質柴油爲基 準’單-或雙-受阻酚與N，N’_二-取代之對苯二胺的相加 量爲約50百萬分之一（ppm)至約5000百萬分之一 (ppm) ° 1 7 ·如申請專利範圍第丨6項之方法，其中 (a )生質柴油主要由粗生質柴油所組成； (b ) 2,6-二-三級-丁基酚衍生之單-或雙-受阻酚包括： (i )鄰-三級-丁基酚、 (Π ) 2,6-二-三級-丁基酚、 (iii ) 2,4,6-三-三級-丁基酚、 (iv ) 4,4’-亞甲基雙（2,6-二-三級-丁基酚）、 -26- 200848502 (V )3，5 _二-三級-丁基-4-羥基苯基氫桂皮酸甲基酯、 (乂〇3,5-二-三級-丁基-4-羥基苯基氫桂皮酸07-09 分枝院基酯、 (vii) 2,6·二-三級-丁基-α-二甲胺-對甲酚、或 (viii ) 丁基化羥基甲苯、以及 (c) N，Nf-二-取代之對苯二胺包括： (i ) N，N’-二-二級-丁基-對苯二胺、 (ii) N，Nf-二異丙基-對苯二胺、或 (iii) Ν，Ν·-雙- (1,4 -二甲基戊基）-對苯二胺。 18.如申請專利範圍第17項之方法，其中粗生質柴油係取 自大豆油、菜籽油（canola oil)、棕櫚油、椰子油、油菜 籽:油（r a P e s e e d 〇 i 1)、玉米油或使用過的植物油。 1 9 .如申請專利範圍第1 7項之方法，其中粗生質柴油爲脂 肪酸甲基酯。 2 0 .如申請專利範圍第1 6項之方法，其中 (a )生質柴油主要由蒸餾的生質柴油所組成； (b ) 2,6-二-三級-丁基酚衍生之單-或雙-受阻酚包括： (i )鄰-三級-丁基酚、 (ii ) 2,6-二-三級-丁 基酚、 (iii ) 2,4,6-三·三級-丁基酚、 (iv ) 4,4^亞甲基雙（2,6-二-三級-丁基酚）、 (v)3,5-二-三級-丁基-4-羥基苯基氫桂皮酸甲基酯、 (vi ) 3,5-二-三級-丁基-4-羥基苯基氫桂皮酸C7-C9 分枝院基酯、 -27- 200848502 (vii) 2,6-= -三級-丁基·α_二甲胺-對甲酚、或 (viii ) 丁基化羥基甲苯、以及 (e ) IN’-二-取代之對苯二胺包括： (i) Ν,Ν、：：：-二級-丁基-對苯二胺、 (ii ) Ν，Ν’-二異丙基-對苯二胺、或 (iii) Ν，Ν·-雙- (1，4-二甲基戊基）-對苯二胺。200848502 X. Patent application scope: 1. A mono- or double-hindered phenol derived from biodiesel, 2,6-di-tertiary-butylphenol and N,N'-di-substituted p-phenylenediamine a composition derived from which the addition amount of mono- or di-hindered phenol and N,N'-di-substituted p-phenylenediamine is about 5 parts per million (ppm) based on biodiesel. ) to approximately 5,000 parts per million (ppm). 2. For the composition of claim 1 of the patent scope, wherein (a) the raw diesel is mainly composed of crude diesel; P (b) 2,6-di-tertiary-butylphenol derived mono- or Bis-hindered phenols include: (i) o-tris-butylphenol, (ii) 2,6-di-tertiary-butylphenol, (iii) 2,4,6-tris-tertiary-butyl Phenol, (iv) 4,4'-methylenebis(2,6-di-tertiary-butylphenol), (v) 3,5-di-tertiary-butyl-4-hydroxyphenylhydrogen Methyl cinnamate, (vi) 3,5-di-tertiary-butyl-4-transphenylene hydrogen cinnamic acid" C7-C9 branched alkyl ester, (vii) 2,6-di-three Grade-butyl-α-dimethylamine-p-cresol, or (viii) butylated hydroxytoluene, and (c) N,Nf-di-substituted p-phenylenediamine include: (i) N,N, Di-secondary-butyl-p-phenylenediamine, (ii) N,N'.diisopropyl-p-phenylenediamine, or (iii) N,N, bis-(1,4-dimethylpentyl) Base)-p-phenylenediamine. 3 · The composition of the second paragraph of the patent application, wherein the crude diesel oil is -22-200848502 from large oyster sauce, canola oil, palm oil, coconut oil, rapeseed oil (rapes eed oil) ), corn oil or used vegetable oil. 4. The composition of claim 2, wherein the crude biomass diesel is a fatty acid methyl ester. 5. The composition of claim 1 wherein (a) the raw diesel is mainly composed of distilled biodiesel, (b) 2,6-di-tertiary-butylphenol derived mono- Or bis-hindered phenols include: (i) o-tris-butylphenol, f(ii) 2,6-di-tertiary-butylphenol, (Π〇2,4,6-tris-tertiary) Butylphenol, (iv) 4,4'-methylenebis(2,6-di-tertiary-butylphenol), (v) 3,5-di-tris-butyl-4-hydroxybenzene Methyl hydrogen cinnamate, (vi) 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched alkyl ester, (乂^) 2,6-di- Tertiary-butyl-indole 1-dimethylamine-p-cresol, or k (viii) butylated hydroxytoluene, and (c) fluorene, Ν'-di-substituted p-phenylenediamine include: (i) Ν,Ν'·di-secondary·butyl-p-phenylenediamine, (ii) hydrazine, Ν'-diisopropyl-p-phenylenediamine, or (iii) N,Nf-bis-(1,4 - dimethylpentyl)-p-phenylenediamine. 6. The composition of claim 5, wherein the distilled biodiesel is obtained from soybean oil, canola oil, palm oil, Coconut oil, rapeseed oil (raPe seed oil), corn oil or Used vegetable oil. -23- 200848502 7 · The composition of the first paragraph of the patent application, which is based on biodiesel, mono- or double-hindered phenol and hydrazine, Ν'-di-substituted terephthalic acid The addition amount of the amine is from about 100 parts per million (ppm) to about 2500 parts per million (ppm). 8. The composition of the third aspect of the patent application, wherein 2, 4, 6_three - The weight ratio of the tertiary butyl group to the N,N'-di-substituted p-phenylenediamine is a) greater than about 1; b) greater than about 1.25; or c) greater than about 1.25. 9. A composition derived from biodiesel, 2,4,6-tris-tertiary-butylphenol and N,N,-di-substituted p-phenylenediamine, wherein 2,4,6-three The weight ratio of the third-stage butyl phenol to the N,N'-di-substituted p-phenylenediamine is a) greater than about 1. 10. The composition of claim 9 wherein the weight ratio of 2,4,6-tris-tertiary butyl phenol to N,Nf-di-substituted p-phenylenediamine is about 1 〇: 1 to about 1: 1 〇. 1 1 · A composition prepared by combining biodiesel, 2,6-di-tertiary-butylphenol-derived mono- or double-h--hindered phenol and N,Nf-di-substituted p-phenylenediamine Wherein the addition amount of the mono- or di- hindered phenol and the N,N'-di-substituted p-phenylenediamine is from about 5 parts per million (ppm) to about 50 以 based on the biomass diesel. One millionth (ppm). 1 2 . The composition of claim 1 of the patent scope, wherein (a) the biomass diesel is mainly composed of crude diesel; (b) the 2,6-di-tertiary-butylphenol derived mono- Or bis-hindered phenols include: (i) o-tris-butylphenol, -24- 200848502 (ii) 2,6-di-tertiary-butylphenol, (iii) 2,4,6-tri- Tertiary-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tertiary-butylphenol), (v) 3,5-di-tertiary-butyl-4 -hydroxyphenylhydrocinnamate methyl ester, (vi) 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched alkyl ester, (vii) 2,6- Di-tertiary-butyl-α-dimethylamine-p-cresol, or (viii) butylated hydroxytoluene, and (c) N,N'-di-substituted p-phenylenediamine include at least: N,Nf-di-di-butyl-p-phenylenediamine, (ii) hydrazine, hydrazine-diisopropyl-p-phenylenediamine, or (iii) hydrazine, Ν'-bis-(1, 4-dimethylpentyl)-p-phenylenediamine. 1 3. The composition of claim 1 of the patent scope, wherein (a) the raw diesel oil is mainly composed of distilled biodiesel; (b) the 2,6-di-tertiary-butylphenol derived single - or bis-hindered phenols include: (i) o-tris-butylphenol, (ii) 2,6-di-tertiary-butylphenol, (iii) 2,4,6-tris-tertiary Butylphenol, (iv) 4,4--methylenebis(2,6-di-tertiary-butylphenol), (v) 3,5-di-tris-butyl-4-hydroxyphenyl Hydrogen cinnamic acid methyl ester, (vi) 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched alkyl ester, (vii) 2,6-di-three -butyl-α-dimethylamine-p-cresol; or -25- 200848502 (V iii ) butylated hydroxytoluene, and (c) N,N'-di-substituted p-phenylenediamine include: (i N,N'-di-di-butyl-p-phenylenediamine, (ii) N,N'-diisopropyl-p-phenylenediamine, or (iii) N,N'-double- ( , 4-dimethylpentyl)-p-phenylenediamine. 14· A composition comprising biodiesel, 2,4,6-tris-tert-butylphenol and N,N,-di-substituted p-phenylenediamine, wherein 2,4,6 _ tri-three The weight ratio of the grade-butylphenol f' to N,N'_di-substituted p-phenylenediamine is a) greater than about 1. 1 5 · The composition of claim 14 of the patent scope, wherein the weight ratio of 2,4,6-three-third-butyl to N,N,·di-substituted p-phenylenediamine is about 10 :1 to about 1: 1 0. 16 - A method for improving the oxidation stability of a biodiesel-containing composition by combining the composition with 2,6-di-tertiary-butylphenol-derived mono- or double-blocked anthracene and N,N'- Di-substituted p-phenylenediamine, wherein the addition amount of 'mono- or bis-hindered phenol and N,N'-di-substituted p-phenylenediamine is about 50 parts per million based on biodiesel (ppm) to about 5,000 parts per million (ppm) ° 1 7 · The method of claim 6, wherein (a) the raw diesel is mainly composed of crude diesel; (b) 2, 6-di-tertiary-butylphenol-derived mono- or di-hindered phenols include: (i) o-tris-butylphenol, (Π) 2,6-di-tertiary-butylphenol, ( Iii ) 2,4,6-tris-tertiary-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tertiary-butylphenol), -26- 200848502 (V 3,5 _di-tertiary-butyl-4-hydroxyphenylhydrocinnamate methyl ester, (乂〇3,5-di-tris-butyl-4-hydroxyphenylhydrocinnamic acid 07-) 09 branched ester, (vii) 2,6·di-tertiary-butyl-α-dimethylamine-p-cresol, or (viii) butylated hydroxytoluene, and (c) N,Nf- Two-substituted pair Phenylenediamines include: (i) N,N'-di-di-butyl-p-phenylenediamine, (ii) N,Nf-diisopropyl-p-phenylenediamine, or (iii) ruthenium, iridium - bis-(1,4-dimethylpentyl)-p-phenylenediamine. 18. The method of claim 17, wherein the crude biomass diesel is derived from soybean oil, canola oil (canola oil) ), palm oil, coconut oil, rapeseed: oil (ra P eseed 〇i 1), corn oil or used vegetable oil. 1 9. The method of claim 17 wherein the crude biomass is a fatty acid Methyl ester. 20. The method of claim 16 wherein (a) the biodiesel is mainly composed of distilled biodiesel; (b) 2,6-di-tertiary-butylphenol The derived mono- or bis-hindered phenols include: (i) o-tris-butylphenol, (ii) 2,6-di-tertiary-butylphenol, (iii) 2,4,6-tri. Tertiary-butylphenol, (iv) 4,4^methylenebis(2,6-di-tertiary-butylphenol), (v) 3,5-di-tris-butyl-4- Hydroxyphenylhydrocinnamate methyl ester, (vi) 3,5-di-tertiary-butyl-4-hydroxyphenylhydrocinnamic acid C7-C9 branched tertyl ester, -27- 200848502 (v Ii) 2,6-=-tertiary-butyl·α-dimethylamine-p-cresol, or (viii) butylated hydroxytoluene, and (e) IN'-di-substituted p-phenylenediamine include : (i) Ν, Ν, ::::-di-butyl-p-phenylenediamine, (ii) hydrazine, Ν'-diisopropyl-p-phenylenediamine, or (iii) Ν, Ν·- Bis-(1,4-dimethylpentyl)-p-phenylenediamine. 2 1 ·如申請專利範圍第2 0項之方法，其中蒸餾的生質柴油 係取自大丑油、菜好油（c a η ο 1 a 〇 i 1 )、棕櫚油、椰子油、 油菜籽油（rape seed oil)、玉米油或使用過的植物油。 2 2 ·如申請專利範圍第1 6項之方法，其中以生質柴油爲基 準，單-或雙-受阻酚與N，N，-二·取代之對苯二胺的相加 量爲約1〇〇百禹分之一（ppm)至約2500百萬分之一 (ppm) ° 23·如申請專利範圍第U項之方法，其中2,4,6_三-三級_ 丁基酚對Ν，Ν·-二-取代之對苯— 、丄μ仏 、匕平一妝之重星比爲a)大於約2 1 · The method of claim 20, wherein the distilled biodiesel is taken from large oil, vegetable oil (ca η ο 1 a 〇i 1 ), palm oil, coconut oil, rapeseed oil (rape seed oil), corn oil or used vegetable oil. 2 2 · For the method of claim 16th, wherein the addition amount of mono- or di-hindered phenol and N, N,-di-substituted p-phenylenediamine is about 1 based on biodiesel One hundredth (ppm) to about 2500 parts per million (ppm) ° 23. The method of claim U, wherein 2, 4, 6_ tri-tertiary _ butyl phenol pair Ν, Ν·-di-substituted benzene-, 丄μ仏, 匕平一一的重星 ratio is a) greater than about 2 4 ·如申請專利範圍第1 6項之方卞去 丁基酚對 N，N，-二- 取代之對 ’其中2,4,6·三-三級_ 胺之重量比爲約1〇:1 至約1 : 1 〇。 -28- 200848502 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： Μ 〇 J V ΝΝ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無02 4 ·If the scope of patent application is not limited to 1〇, the weight ratio of butyl phenol to N,N,-di-substituted pair of 2,4,6·3-tris-amine is about 1〇 :1 to about 1: 1 〇. -28- 200848502 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 J V ΝΝ 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention:
TW097110658A 2007-03-28 2008-03-26 Antioxidant blends for fatty acid methyl esters (biodiesel) TW200848502A (en)

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