TW201321495A - 改良燃料直噴引擎效能之燃料添加劑 - Google Patents
改良燃料直噴引擎效能之燃料添加劑 Download PDFInfo
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- TW201321495A TW201321495A TW101137044A TW101137044A TW201321495A TW 201321495 A TW201321495 A TW 201321495A TW 101137044 A TW101137044 A TW 101137044A TW 101137044 A TW101137044 A TW 101137044A TW 201321495 A TW201321495 A TW 201321495A
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- Prior art keywords
- fuel
- quaternary ammonium
- ammonium salt
- engine
- hydrocarbon group
- Prior art date
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- 239000000446 fuel Substances 0.000 title claims abstract description 140
- 239000002816 fuel additive Substances 0.000 title description 10
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 21
- 230000004580 weight loss Effects 0.000 claims abstract description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 32
- 239000000654 additive Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 26
- -1 phenates Chemical class 0.000 claims description 26
- 238000012360 testing method Methods 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 24
- 238000002347 injection Methods 0.000 claims description 24
- 239000007924 injection Substances 0.000 claims description 24
- 150000002430 hydrocarbons Chemical group 0.000 claims description 23
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- 150000001412 amines Chemical class 0.000 claims description 18
- 238000002485 combustion reaction Methods 0.000 claims description 18
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- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
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- 125000004122 cyclic group Chemical group 0.000 claims description 8
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- 239000002585 base Substances 0.000 description 7
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- 239000003039 volatile agent Substances 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical group CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
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- AGDYNDJUZRMYRG-UHFFFAOYSA-N hexyl nitrate Chemical group CCCCCCO[N+]([O-])=O AGDYNDJUZRMYRG-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LRMHVVPPGGOAJQ-UHFFFAOYSA-N methyl nitrate Chemical compound CO[N+]([O-])=O LRMHVVPPGGOAJQ-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
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- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
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- RCZLVPFECJNLMZ-UHFFFAOYSA-N n,n,n',n'-tetraethylpropane-1,3-diamine Chemical group CCN(CC)CCCN(CC)CC RCZLVPFECJNLMZ-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical group CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- XWAKKPDDQPWGAQ-UHFFFAOYSA-N n,n-dimethylbut-1-en-1-amine Chemical compound CCC=CN(C)C XWAKKPDDQPWGAQ-UHFFFAOYSA-N 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- KNTHOUBUFWWKBF-UHFFFAOYSA-N n,n-dimethyloct-1-en-1-amine Chemical compound CCCCCCC=CN(C)C KNTHOUBUFWWKBF-UHFFFAOYSA-N 0.000 description 1
- NXBBFAKHXAMPOM-UHFFFAOYSA-N n,n-dimethylprop-1-en-1-amine Chemical compound CC=CN(C)C NXBBFAKHXAMPOM-UHFFFAOYSA-N 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- UUHHOIMXURPAAJ-UHFFFAOYSA-N nitric acid oxolane Chemical group O[N+]([O-])=O.C1CCOC1 UUHHOIMXURPAAJ-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- TXQBMQNFXYOIPT-UHFFFAOYSA-N octyl nitrate Chemical group CCCCCCCCO[N+]([O-])=O TXQBMQNFXYOIPT-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QKOHYQVZNLEAJH-UHFFFAOYSA-N oxomethylidenemanganese Chemical class O=C=[Mn] QKOHYQVZNLEAJH-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- RWRBSYOTDDOXKC-UHFFFAOYSA-N pentan-2-yl nitrate Chemical group CCCC(C)O[N+]([O-])=O RWRBSYOTDDOXKC-UHFFFAOYSA-N 0.000 description 1
- WQZKKVJFBZPJSU-UHFFFAOYSA-N pentan-3-yl nitrate Chemical group CCC(CC)O[N+]([O-])=O WQZKKVJFBZPJSU-UHFFFAOYSA-N 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OTRMXXQNSIVZNR-UHFFFAOYSA-N prop-2-enyl nitrate Chemical compound [O-][N+](=O)OCC=C OTRMXXQNSIVZNR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical class CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- JNTOKFNBDFMTIV-UHFFFAOYSA-N propyl nitrate Chemical compound CCCO[N+]([O-])=O JNTOKFNBDFMTIV-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- HSBSUGYTMJWPAX-HNQUOIGGSA-N trans-2-hexenedioic acid Chemical compound OC(=O)CC\C=C\C(O)=O HSBSUGYTMJWPAX-HNQUOIGGSA-N 0.000 description 1
- YHGNXQAFNHCBTK-OWOJBTEDSA-N trans-3-hexenedioic acid Chemical compound OC(=O)C\C=C\CC(O)=O YHGNXQAFNHCBTK-OWOJBTEDSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- VTALQOYOTZKULH-UHFFFAOYSA-N undecyl nitrate Chemical group CCCCCCCCCCCO[N+]([O-])=O VTALQOYOTZKULH-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
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- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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- C10L10/00—Use of additives to fuels or fires for particular purposes
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Abstract
一種用於燃料直噴柴油機的燃料組成物、一種用以改良燃料噴射器的效能之方法及一種用以清潔柴油機之燃料噴射器的方法。該燃料組成物包含一主要量的燃料及一較少之有效量在350℃下具有熱解重量分析(TGA)重量損失大於50重量%的四級銨鹽。存在於該燃料中的四級銨鹽量，與已燃燒不包含該四級銨鹽的燃料組成物之此引擎的效能比較，係足以改良已燃燒該組成物之燃料直噴柴油機的效能。
Description
本揭示係關於一種燃料添加劑，及關於一種對改良燃料直噴引擎效能有用的添加劑，及一種包含該添加劑的添加劑濃縮劑。特別是，本揭示係關於一種有效提高柴油機用之直接燃料噴射器的效能之燃料添加劑。
已長期想要在柴油動力車輛中最大化燃料經濟、動力及駕駛性能，同時提高加速、減少排放物及防止停頓。雖然已知使用分散劑來保持在燃料噴射引擎埠中的閥及燃料噴射器乾淨以提高汽油動力引擎的效能，但此汽油分散劑未必對燃料直噴柴油機有效。此不可預言性的理由在於在該燃料直接及間接噴射柴油機與合適於此引擎之燃料間的許多差異。
例如，在燃料間噴柴油機與更現代的高壓共軌(high pressure common rail)(HPCR)、燃料直噴柴油機間有引人注目的差異。同樣地，低硫柴油及超低硫柴油現在在市場中常見用於此引擎。”低硫”柴油意謂著具有以重量計硫含量50 ppm或較少的燃料，以該燃料之總重量為基準。”超低硫”柴油(ULSD)意謂著具有以重量計硫含量15 ppm或較少的燃料，以該燃料的總重量為基準。與較舊型的引擎及燃料噴射系統比較，在HPCR引擎中的燃料噴射器於更高的壓力及溫度下執行。低硫或ULSD與HPCR
引擎之組合已對現在在市場中發現的噴射器沈積型式及噴射器沈積形成頻率產生改變。
用於柴油的分散劑組成物已經發展超過數年。在技藝中已知使用於燃料之分散劑組成物包括一可包含聚伸烷基琥珀醯亞胺、聚胺及經聚烷基取代的曼尼期(Mannich)化合物之組成物。該分散劑合適於將煤灰及淤泥保持懸浮在流體中，但是一旦已在表面上形成沈積時，該分散劑對清潔表面未特別有效。
因此，用於燃料直噴柴油機之燃料組成物經常在引擎中產生不想要的沈積。此外，想要一種可防止沈積積聚、對車輛壽命維持”如新的”潔淨之改良組成物。理想上，可清潔髒的燃料噴射器而將效能恢復至先前”如新的”狀態之相同組成物將同等想要及有用地試圖減低空氣運送的廢氣排放及改良引擎的動力效能。
根據本揭示的範例性具體實例提供一種用於內燃機的柴油組成物，其包括一種用以改良內燃機的燃料噴射器效能之方法及一種用以清潔燃料噴射器之方法。該燃料組成物包括一主要量的柴油及一較少之有效量的四級銨鹽，其在350℃下具有熱解重量分析(TGA)重量損失大於50重量%。與已燃燒不包含該四級銨鹽的燃料組成物之此引擎的效能比較，存在於該燃料中的四級銨鹽量足以改良已燃燒該組成物的燃料直噴柴油機之效能。
本揭示的另一個具體實例提供一種改良燃料直噴柴油機的噴射器效能之方法。該方法包括在一燃料組成物
上操作該引擎，其中該組成物包含一主要量的燃料及以該燃料的總重量為基準，以重量計約5至約200 ppm的四級銨鹽，其在350℃下具有熱解重量分析(TGA)重量損失大於50重量%。當根據用於直接噴射的CEC F-98-08協定測量時，該存在於燃料中的四級銨鹽改良該引擎的噴射器效能至少約80%。
本揭示的進一步具體實例提供一種操作燃料直噴柴油機的方法。該方法包括在引擎中燃燒一燃料組成物，其中該組成物包含一主要量的燃料及以該燃料的總重量為基準，以重量計約5至約200 ppm的四級銨鹽，其在350℃下具有熱解重量分析(TGA)重量損失大於50重量%。在進一步具體實例中，該TGA重量損失大於70重量%，諸如大於80重量%，特別是大於90重量%的重量損失。
本揭示的另一個具體實例提供一種用於使用在直噴柴油引擎的燃料之添加劑濃縮劑。該添加劑濃縮劑包含一在350℃下具有熱解重量分析(TGA)重量損失大於50重量%的四級銨鹽，及至少一種選自於由下列所組成之群的組分：稀釋劑、相容劑、腐蝕抑制劑、低溫流動改良劑(CFPP添加劑)、傾點下降劑、溶劑、去乳化劑、潤滑添加劑、摩擦力改質劑、胺安定劑、燃燒改良劑、分散劑、抗氧化劑、熱安定劑、導電度改良劑、金屬去活化劑、標記染料、有機硝酸鹽燃燒加速劑及環基三羰基合錳(cyclomatic manganese tricarbonyl)化合物。
於本文中所描述的燃料添加劑之優點為該添加劑可不僅減少在直接燃料噴射器上形成的沈積量，而且該添
加劑亦可有效清潔髒的燃料噴射器至足以對該引擎提供改良的動力恢復。
接下來將在某種程度上對本揭示的額外具體實例及優點提出詳細說明，及/或其可藉由本揭示的實行而學習。要瞭解前述一般描述及下列詳細說明二者皆係範例性及僅有解釋用而非如所主張般限制本揭示。
本申請案之燃料添加劑組分可以較少量使用在主要量的燃料中且可直接加入至燃料或以添加劑濃縮劑之組分加入至燃料。可藉由廣泛多種熟知的反應技術以胺或聚胺製得特別合適於改良內燃機之操作的燃料添加劑組分。例如，此添加劑組分可藉由讓下式之三級胺，其中R1、R2及R3每個係選自於包含1至50個碳原子的烴基：
與一四級化試劑反應，以提供下式化合物而製得：
其中R1、R2、R3及R4每個係選自於包含1至50個碳原子的烴基，其中R1、R2、R3及R4之至少一個且不多於三個係包含1至4個碳原子的烴基，及R1、R2、R3及R4之至少一個係包含8至50個碳原子的烴基，M-係選自於由下列所組
成之群：羧酸鹽、硝酸鹽、氮化物、亞硝酸鹽、次硝酸鹽、酚鹽、胺基甲酸鹽、碳酸鹽、鹵化物、硫酸鹽、亞硫酸鹽、硫化物、磺酸鹽、磷酸鹽、膦酸鹽及其類似物。在一個具體實例中，R1、R2、R3及R4每個係選自於包含1至20個碳原子的烴基，其限制為R1、R2、R3及R4之至少一個包含8至20個碳原子。在另一個具體實例中，R1、R2、R3及R4每個係選自於烷基或烯基。
合適的四級化試劑可選自於由下列所組成之群：經烴基取代的羧酸鹽、碳酸鹽、環狀碳酸鹽、酚鹽、環氧化合物或其混合物。在一個具體實例中，該四級化試劑可來自經烴基或烷基取代的碳酸鹽。在另一個具體實例中，該四級化試劑可選自於經烴基取代的環氧化合物。在另一個具體實例中，該四級化試劑可選自於經烴基取代的羧酸鹽。在一個具體實例中，該羧酸鹽四級化試劑排除草酸鹽。
如於本文中所使用，用語”烴基團”或”烴基”以其由熟習該項技術者熟知的普通觀念使用。特別是，其指為一具有碳原子直接接附至一分子的剩餘者且具有顯著的烴特徵之基團。該烴基的實施例包括：(1)烴取代基，也就是說，脂肪族(例如，烷基或烯基)、脂環族(例如，環烷基、環烯基)之取代基、及經芳香族、脂肪族及脂環族取代的芳香族取代基、和環狀取代基，其中該環透過該分子的另一個部分完成(例如，二個取代基一起形成一脂環族基團)；(2)經取代的烴取代基，也就是說，包含非烴基團(例
如，鹵基(特別是氯及氟)、羥基、烷氧基、巰基、烷基巰基、硝基、亞硝基、胺基、烷基胺基及亞碸基)的取代基，其中該非烴基團在描述於本文的上下文中不改變該主要的烴取代基；(3)雜取代基，也就是說，在此描述的上下文中，在其它方面由碳原子組成的環或鏈中包含除了碳外的其它原子，同時具有主要的烴特徵之取代基。該雜原子包括硫、氧、氮，及包括諸如吡啶基、呋喃基、噻吩基及咪唑基之取代基。通常來說，在該烴基中每十個碳原子將存在不超過二個，或作為進一步實施例，不超過一個非烴取代基；在某些具體實例中，將在該烴基中無非烴取代基。
如於本文中所使用，用語”主要量”經了解意謂著相對於該組成物的總重量，該量大於或等於50重量%，例如約80至約98重量%。再者，如於本文中所使用，用語”較少量”經了解意謂著相對於該組成物的總重量，該量少於50重量%。
用以製得四級銨鹽之方法包括，但不限於，藉由離子交換反應或藉由三級胺或聚胺的直接烷基化。直接烷基化可包括以羧酸甲酯來甲基化三級胺，諸如吡啶及異喹啉，或以烴基環氧化合物以一或二步驟反應來烷基化三級胺。
在一個具體實例中，包含單胺及聚胺的三級胺可與四級化試劑反應。可使用下式之合適的三級胺化合物：
其中R1、R2及R3每個係選自於包含1至50個碳原子的烴基。R1至R3每個烴基可各自獨立地係線性、分枝、經取代、環狀、飽和、不飽和或包含一個以上的雜原子。合適的烴基可包括，但不限於，烷基、芳基、烷基芳基、芳基烷基、烷氧基、芳氧基及其類似基團。特別合適的烴基可係線性或分枝的烷基。可被四級化以產生本發明之化合物的胺反應物之某些典型實施例有：三甲基胺、三乙基胺、三正丙基胺、二甲基乙基胺、二甲基月桂基胺、二甲基油烯基胺、二甲基硬脂基胺、二甲基廿烷基胺、二甲基十八烷基胺、N-甲基哌啶、N,N’-二甲基哌、N-甲基-N’-乙基哌、N-甲基嗎福啉、N-乙基嗎福啉、N-羥乙基嗎福啉、吡啶、三乙醇胺、三異丙醇胺、甲基二乙醇胺、二甲基乙醇胺、月桂基二異丙醇胺、硬脂基二乙醇胺、二油基乙醇胺、二甲基異丁醇胺、甲基二異辛醇胺、二甲基丙烯基胺、二甲基丁烯基胺、二甲基辛烯基胺、乙基雙十二烯基胺、二丁基廿碳烯基胺、三伸乙基二胺、六亞甲基四胺、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基丙二胺、N,N,N’,N’-四乙基-1,3-丙二胺、甲基二環己基胺、2,6-二甲基吡啶、二甲基環己基胺、經C10-C22-烷基或烯基取代的醯胺基丙基二甲基胺、經C10-C22-烷基或烯基取代的琥珀酸-醯亞胺基丙基二甲基胺及其類似物。
若該胺僅僅包含一級或二級胺基時，必需在四級化該胺之前，將該一級或二級胺基之至少一個烷基化成三級胺基。在一個具體實例中，一級胺及二級胺或含有三級胺的混合物之烷基化可全部在一個步驟中徹底或部分烷基化成三級胺及進一步烷基化成四級鹽。若使用一個步驟反應時，會需要合適地說明在氮上的氫及提供如所需要的鹼或酸(例如，烷基化最高至三級胺需要從該烷基化產物移除(中和)的氫(質子))。若使用諸如鹵烷或硫酸二烷酯之烷基化試劑時，一級或二級胺之烷基化產物係一經質子化的鹽及需要一鹼來源來釋放出該胺及繼續進行至四級鹽。此烷基化試劑需要烷基化該三級胺，及該產物係四級銨鹵化物或硫酸單甲酯。相較之下，環氧化合物作為烷基化試劑進行烷基化及中和二者，如此該中間烷基化產物已經係該自由態胺。為了使用環氧化合物繼續進行至四級鹽，需要提供一當量的酸以對羥基提供質子及對鹽提供抗衡陰離子。
合適於將三級胺轉換成四級氮化合物的四級化試劑可選自於由下列所組成之群：經烴基取代的羧酸鹽、碳酸鹽、環狀碳酸鹽、酚鹽、環氧化合物、胺基甲酸鹽、鹵化物、硫酸鹽、亞硫酸鹽、硫化物、磺酸鹽、磷酸鹽、膦酸鹽或其混合物。可衍生出該四級銨化合物的陰離子之經烴基取代的酚鹽具有許多不同型式。例如，該經烴基取代的酚鹽可衍生自下式之酚：
其中n=1、2、3、4或5，其中R20可係氫、或經取代或未經取代的烷基、環烷基、烯基、環烯基或芳基。該烴基團可藉由酮基或硫酮基鍵結至苯環。再者，該烴基團可經由氧或氮原子鍵結。此酚的實施例包括鄰-甲酚；間-甲酚；對-甲酚；2,3-二甲基酚；2,4-二甲基酚；2,3,4-三甲基酚；3-乙基-2,4-二甲基酚；2,3,4,5-四甲基酚；4-乙基-2,3,5,6-四甲基酚；2-乙基酚；3-乙基酚；4-乙基苯基；2-正丙基酚；2-異丙基酚；4-異丙基酚；4-正丁基酚；4-異丁基酚；4-二級丁基酚；4-三級丁基酚；4-壬基酚；2-十二烷基酚；4-十二烷基酚；4-十八烷基酚；2-環己基酚；4-環己基酚；2-烯丙基酚；4-烯丙基酚；2-羥基二苯基；4-羥基二酚；4-甲基-4-羥基二苯基；鄰-甲氧基酚；對-甲氧基酚；對-苯氧基酚；及4-羥基苯基二甲基胺。
亦包括下式之酚：
其中R20及R21可相同或不同且如上述對R20之定義，及m及n係整數，且對每個m或n大於1來說，R20與R21每個可相同或不同。
此酚的實施例包括2,2-二羥基-5,5-二甲基二苯基甲烷；5,5-二羥基-2,2-二甲基二苯基甲烷；4,4-二羥基-2,2-二甲基-二甲基二苯基甲烷；2,2-二羥基-5,5-二壬基二苯基甲烷；2,2-二羥基-5,5-雙十二烷基苯基甲烷；2,2,4,4-四-三級丁基-3,3-二羥基-5,5-雙十二烷基苯基甲烷；及2,2,4,4-四-三級丁基-3,3-二羥基二苯基甲烷。
該經烴基取代的碳酸鹽之烴基(或烷基)可每基團包含1至50、1至20、1至10、或1至5個碳原子。在一個具體實例中，該經烴基取代的碳酸鹽包含二個可相同或不同的烴基。合適的經烴基取代的碳酸鹽之實施例包括二甲基、二乙基、伸乙基及伸丙基碳酸鹽及其混合物。
在另一個具體實例中，該四級化試劑可係一烴基環氧化合物(如由下列式表示)與酸之組合：
其中R5、R6、R7及R8可各自獨立地係H或C1-48烴基。該烴基環氧化合物的實施例可包括(但不限於)：環氧苯乙烯、環氧乙烷、環氧丙烷、環氧丁烷、環氧己烷、環氧辛-11-烯、環氧茋及C2-50環氧化合物。
該四級銨鹽可以一個階段或二個階段製得。可以一個步驟反應伴隨著酸存在進行使用烷基環氧化合物來烷基化三級胺，如在美國專利案號4,814,108、4,675,180中
提出般；或以二個步驟方法來進行，其包括在極性媒體中烷基化該三級胺，然後混合該烷基化產物與酸。例如，1莫耳的胺可於超過由該反應之化學計量所需要的過量水存在下，以X莫耳的氧化烯烴處理(其中X係在該胺分子中之三級氮的數目)。
至於進一步實施例，吡啶(1莫耳)可在水(>1莫耳)中以氧化烯烴(1莫耳)處理。三伸乙基二胺(1莫耳)可在水(>2莫耳)中以氧化烯烴(2莫耳)處理。六亞甲四胺(1莫耳)可在水(>4莫耳)中以氧化烯烴(4莫耳)處理。
但是，若需要或想要時，該氧化烯烴可過量使用，然後，讓該過量的氧化烯烴與氫氧化四級銨反應。如上述指示出，可使用任何量的水，只要其顯示出超過由該反應的化學計量所需要之量。
該反應可藉由在反應容器中讓該胺與氧化烯烴接觸及混合而進行，其中將水加入至該反應混合物。水的加入速率不影響最後產物的品質，但是可使用慢慢加入水來控制放熱反應。
再者，該胺可與水在反應容器中混合，然後將氧化烯烴加入至該攪拌的反應混合物。該氧化烯烴可以下列形式加入：氣體，純的或經惰性載劑(例如，氮氣)稀釋；液體；在水中的溶液；或在水可溶混的有機溶劑(例如，甲醇或乙醇)中之溶液。氧化烯烴的加入速率對最後產物的品質非為關鍵性，但是可使用慢慢的加入速率來控制放熱反應。
在另一個可替代的反應程序中，該氧化烯烴可在反
應容器中與水混合及將胺加入至該反應混合物。該胺可以下列形式加入：如為純的氣體、液體或固體；在水中的溶液；在可溶於水的有機溶劑中之溶液。如該氧化烯烴及水之加入般，可使用慢慢的加入該胺來控制放熱反應。
為了促進該反應，可在所提供的溫度下一起加熱該混合的反應物，同時以足以維持穩定的反應速率及可控制的反應溫度之速率加入第三反應物。再者，可在壓力容器中加熱該反應物，但是，當加熱該反應物以促進反應時，想要避免溫度高於100℃以防止氫氧化四級銨分解。該反應程序的第二階段包括以有機酸中和在第一階段中形成的氫氧化四級銨。
通常來說，讓足夠的酸與從第一階段獲得的溶液混合以中和該氫氧化四級銨。但是，若需要的話，可使用過量的酸，如例如當僅欲中和多元酸的一個羧酸基團時。該中和反應可於下列狀態下進行：在缺乏任何溶劑下；於醇存在下，例如，甲醇、乙醇、異丙醇、2-乙氧基乙醇、2-乙基己醇或乙二醇；於任何其它極性有機溶劑存在下，例如，丙酮、甲基乙基酮、氯仿、四氯化碳或四氯乙烷；於烴溶劑存在下，例如，己烷、庚烷、石油溶劑、苯、甲苯或二甲苯；或於上述任何溶劑之混合物存在下。
可使用在該反應的第二階段中因此形成在四級銨鹽中的陰離子之有機酸可例如係羧酸、酚、硫化的酚或磺酸。
該中和反應可在周溫下進行，但是通常使用高溫。當反應完成時，可藉由在真空下加熱該反應產物來移除所使用的水及任何溶劑。該產物通常以礦物油、柴油、煤油或惰性烴溶劑稀釋，以防止產物太黏。
在另一個具體實例中，該四級化試劑可係經烴基取代的羧酸鹽，亦已知為羧酸的酯。該羧酸鹽的相應酸可選自於單、二及多羧酸。該單羧酸可包括下式的酸：
R-COOH其中R係氫、或包含1至50個碳原子之經取代或未經取代的烷基、環烷基、烯基、環烯基或芳基。此酸的實施例包括蟻酸、醋酸、丙酸、丁酸、戊酸、棕櫚酸、硬脂酸、環己烷羧酸、2-甲基環己烷羧酸、4-甲基環己烷羧酸、油酸、亞麻油酸、次亞麻油酸、環己-2-烯酸、苯甲酸、2-甲基苯甲酸、3-甲基苯甲酸、4-甲基苯甲酸、水楊酸、2-羥基-4-甲基苯甲酸、2-羥基-4-乙基水楊酸、對-羥基苯甲酸、3,5-雙三級丁基-4-羥基苯甲酸、鄰-胺基苯甲酸、對-胺基苯甲酸、鄰-甲氧基苯甲酸及對-甲氧基苯甲酸。
該二羧酸可包括下式之酸：HOOC-(CH2)n-COOH其中n係零或整數，包括例如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸及辛二酸。亦包括下式的酸：
其中x係零或整數，y係零或整數及x與y可相同或不同；及R係氫或如上所述包含1至50個碳原子之經取代或未經
取代的烷基、環烷基、烯基、環烯基或芳基。此酸的實施例包括烷基或烯基琥珀酸、2-甲基丁二酸、2-乙基戊二酸、2-正十二烷基丁二酸、2-正十二碳烯基丁二酸、2-苯基丁二酸及2-(對-甲基苯基)丁二酸。亦包括多取代的烷基二羧酸，其中如上所述的其它R基團可在烷基鏈上經取代。實施例包括2,2-二甲基丁二酸；2,3-二甲基丁二酸；2,3,4-三甲基戊二酸；2,2,3-三甲基戊二酸；及2-乙基-3-甲基丁二酸。
該二羧酸亦包括下式的酸：HOOC-(CrH2r-2)COOH其中r係整數2或更大。實施例包括馬來酸、反丁烯二酸、戊-2-烯二酸、己-2-烯二酸；己-3-烯二酸、5-甲基己-2-烯二酸；2,3-二甲基戊-2-烯二酸；2-甲基丁-2-烯二酸；2-十二烷基丁-2-烯二酸；及2-多異丁基丁-2-烯二酸。
該二羧酸亦包括芳香族二羧酸，例如酞酸、異酞酸、對酞酸及下式之經取代的酞酸：
其中R如上述所定義及n=1、2、3或4及當n>1時，則R基團可相同或不同。此酸的實施例包括3-甲基苯-1,2-二羧酸；4-苯基苯-1,3-二羧酸；2-(1-丙烯基)苯-1,4-二羧酸、及3,4-二甲基苯-1,2-二羧酸。
對以羧酸烷酯來烷基化而言，想要該羧酸鹽的相應
酸具有pKa小於4.2。例如，該羧酸鹽的相應酸可具有pKa小於3.8，諸如小於3.5，且pKa小於3.1特別想要。合適的羧酸鹽之實施例可包括(但不限於)順丁烯二酸鹽、檸檬酸鹽、反丁烯二酸鹽、酞酸鹽、1,2,4-苯三羧酸鹽、1,2,4,5-苯四羧酸鹽、硝基苯甲酸鹽、菸鹼酸鹽、草酸鹽、胺基醋酸鹽及水楊酸鹽。
在另一個具體實例中，該四級銨鹽可藉由離子交換反應來製備，諸如：
其中X係鹵化物、R如上述所定義及Ar係芳香基團。該四級亦可藉由直接烷基化三級胺或聚胺來製備。該烷基化試劑包括，但不限於，鹵烷、碳酸烷酯、硫酸烷酯、環狀碳酸鹽、烷基環氧化合物、羧酸烷酯及胺基甲酸烷酯。
在本申請案的某些態樣中，本申請案的四級銨鹽組
成物可與柴油可溶的載劑組合著使用。此載劑可係多種型式，諸如液體或固體，例如，蠟。該液體載劑的實施例包括，但不限於，礦物油及氧化物，諸如液體聚烷氧基化的醚類(亦已知為聚伸烷基二醇或聚伸烷基醚)、液體聚烷氧基化的酚類、液體聚烷氧基化的酯類、液體聚烷氧基化的胺類及其混合物。該氧化物載劑的實施例可在1998年5月19日由漢利(Henly)等人發布的美國專利案號5,752,989中找到，其載劑之說明全文於此以參考方式併入本文。該氧化物載劑的額外實施例包括經烷基取代的芳基聚烷氧基化物，其由克魯希(Colucci)等人描述在2003年7月17日公告之美國專利公告案號2003/0131527，其說明全文於此以參考方式併入本文。
在其它態樣中，該四級銨鹽組成物可不包含載劑。例如，本申請案之某些組成物可不包含礦物油或氧化物，諸如上述的那些氧化物。
可在所揭示的具體實例之燃料組成物中存在一種以上的額外選擇性化合物。例如，該燃料可包含習知量的十六烷改良劑、腐蝕抑制劑、低溫流動改良劑(CFPP添加劑)、傾點下降劑、溶劑、去乳化劑、潤滑添加劑、摩擦力改質劑、胺安定劑、燃燒改良劑、分散劑、抗氧化劑、熱安定劑、導電度改良劑、金屬去活化劑、標記染料、有機硝酸酯燃燒加速劑、環基三羰基合錳化合物及其類似物。在某些態樣中，於本文中所描述的組成物可包含約10重量百分比或較少之一種以上的上述添加劑，或在其它態樣中，約5重量百分比或較少，以該添加劑濃縮劑
的總重量為基準。類似地，該燃料可包括合適量的習知燃料摻合組分，諸如甲醇、乙醇、二烷基醚及其類似物。
在所揭示的具體實例之某些態樣中，可使用包括脂肪族或環脂族硝酸酯之有機硝酸酯燃燒加速劑，其中該脂肪族或環脂族基團係飽和及包含最高約12個碳。可使用的有機硝酸酯燃燒加速劑之實施例有硝酸甲酯、硝酸乙酯、硝酸丙酯、硝酸異丙酯、硝酸烯丙酯、硝酸丁酯、硝酸異丁酯、硝酸二級丁酯、硝酸三級丁酯、硝酸戊酯、硝酸異戊酯、硝酸2-戊酯、硝酸3-戊酯、硝酸己酯、硝酸庚酯、硝酸2-庚酯、硝酸辛酯、硝酸異辛酯、硝酸2-乙基己酯、硝酸壬酯、硝酸癸酯、硝酸十一烷酯、硝酸十二烷酯、硝酸環戊酯、硝酸環己酯、硝酸甲基環己酯、硝酸環十二烷酯、硝酸2-乙氧基乙酯、硝酸2-(2-乙氧基乙氧基)乙酯、硝酸四氫呋喃酯及其類似物。亦可使用此材料之混合物。
在本申請案的組成物中有用之合適的選擇性金屬去活化劑之實施例揭示在1984年11月13日所發布的美國專利案號4,482,357中，此揭示其全文於此以參考方式併入本文。此金屬去活化劑包括例如亞柳基-鄰-胺基酚、二亞柳基乙二胺、二亞柳基丙二胺及N,N’-二亞柳基-1,2-二胺基丙烷。
可使用在本申請案的組成物中之合適的選擇性環基三羰基合錳化合物包括例如環戊二烯基三羰基合錳、甲基環戊二烯基三羰基合錳、茚基三羰基合錳及乙基環戊二烯基三羰基合錳。合適的環基三羰基合錳化合物之更
其它實施例係揭示在1996年11月19日發佈的美國專利案號5,575,823，及1962年1月2日發佈的美國專利案號3,015,668中，此二揭示其全文於此以參考方式併入本文。
當調配本申請案的燃料組成物時，該添加劑可以足夠量使用，以減低或抑制在燃料系統或引擎的燃燒室及/或曲軸箱中形成沈積。在某些態樣中，該燃料可包含較少量之上述可控制或減少引擎形成沈積之反應產物，例如，在柴油機中的噴射器沈積。例如，以活性成份為基底，本申請案的柴油可包含一定量的四級銨鹽，其範圍在每公斤燃料約5毫克至約200毫克的反應產物，諸如範圍在每公斤燃料約10毫克至約150毫克或範圍在每公斤燃料約30毫克至約100毫克的四級銨鹽。在該等態樣中，若使用載劑時，以活性成份為基底，該燃料組成物可包含的載劑量範圍係每公斤燃料約1毫克至約100毫克載劑，諸如每公斤燃料約5毫克至約50毫克載劑。該活性成份基底排除下列之重量：(i)未反應的組分，諸如與如所製造及所使用的產物相關及殘餘在其中者，及(ii)在產物之製造時，在其形成期間或之後，但是若使用載劑的話，則是在加入載劑前，如果有使用之溶劑。
可將本申請案之包括上述反應產物及在調配本發明的燃料時所使用的選擇性添加劑之添加劑各別或以多種次組合摻合進該基礎柴油中。在某些具體實例中，可將本申請案的添加劑組分摻合進該柴油中，同時發生使用添加劑濃縮劑，如此利用藉由當呈添加劑濃縮劑形式時之成份的組合所獲得的相互相容性及方便性。同樣地，
使用濃縮劑可減少摻合時間及減輕摻合誤差的可能性。
本申請案的燃料可應用至柴油機操作。該引擎包括固定式引擎(例如，使用在發電裝置、幫浦站等等中的引擎)及移動式引擎(例如，使用作為在汽車、卡車、道路修平(road-grading)設備、軍用車輛等等中的原動機之引擎)二者。例如，該燃料可包括任何及全部汽油及中級蒸出液燃料、柴油、生物性可再生(biorenewable)燃料、生質柴油、氣轉油(gas-to-liquid)(GTL)燃料、噴射燃料、醇類、醚類、煤油、低硫燃料、合成燃料，諸如費雪-特羅普希(Fischer-Tropsch)燃料、液體石油氣體、燃料油、煤轉油(coal-to-liquids)(CTL)燃料、生物質轉油(BTL)燃料、高瀝青質燃料、衍生自煤的燃料(天然、乾淨的及石油焦(petcoke))、基因工程生質燃料及農作物及由彼之萃取物、及天然氣。如於本文中所使用，”生物性可再生燃料”經了解意謂著來自非石油來源的任何燃料。此來源包括，但不限於，穀物、玉蜀黍、大豆類及其它農作物；青草，諸如柳枝稷(switchgrass)、芒屬植物(miscanthus)及雜交草；藻類、海藻、蔬菜油；天然脂肪；及其混合物。在一個態樣中，該生物性可再生燃料可包含單羥基醇，諸如包含1至約5個碳原子的那些。合適的單羥基醇之非為限制的實施例包括甲醇、乙醇、丙醇、正丁醇、異丁醇、三級丁基醇、戊醇及異戊基醇。
此外，本申請案的態樣係針對一種減低引擎的噴射器沈積量之方法，其中該引擎具有至少一個燃燒室及一個以上與該燃燒室流體連接的直接燃料噴射器。在另一
個態樣中，於本文中所描述的四級銨鹽可與具有一或多個聚烯烴基團之相當高分子量的四級銨鹽(諸如聚單烯烴、聚烴基琥珀醯亞胺之四級銨鹽)、聚烴基曼尼期化合物(聚烴基醯胺類及酯類)結合，其中”相當高分子量”意謂著具有數量平均分子量大於600道耳吞。前述四級銨鹽可揭示例如在美國專利案號3,468,640；3,778,371；4,056,531；4,171,959；4,253,980；4,326,973；4,338,206；4,787,916；5,254,138：7,906,470；7,947,093；7,951,211；美國公告案號2008/0113890；歐洲專利申請案案號EP 0293192；EP 2033945；及PCT申請案案號WO 2001/110860中。
在某些態樣中，該方法包括經由該柴油機的噴射器將一以烴為基礎包含本揭示的四級銨鹽之壓縮燃燒燃料噴射進該燃燒室中，及燃燒該壓縮燃燒燃料。在某些態樣中，該方法亦可包括將至少一種上述選擇性額外成份混合進該柴油中。
在一個具體實例中，本申請案的柴油基本上可無，諸如缺乏，習知的琥珀醯亞胺分散劑化合物。在另一個具體實例中，該燃料基本上無烴基琥珀醯亞胺的四級銨鹽或具有數量平均分子量大於600道耳吞的烴基曼尼期化合物(Mannich compound)之四級銨鹽。對本申請案的目的來說，用語”基本上無”定義為在噴射器潔淨或沈積形成上具有實質上無法測量的效應之濃度。
下列實施例闡明本揭示的範例性具體實例。在這些
實施例中和在本申請案中的別處，全部的份及百分比皆以重量計，除非其它方面有指示出。想要顯現出這些實施例僅用於闡明目的及不想要限制本發明於此揭示的範圍。
從數量平均分子量950的聚異丁烯琥珀酸酐(PIBSA)與四伸乙基五胺(TEPA)(以PIBSA/TEPA=1/1之莫耳比率)的反應製造一添加劑。使用US 5,752,989之經修改的程序。在氮氣環境中，將PIBSA(551克)稀釋在200克芳香族150溶劑中。將該混合物加熱至115℃。然後，透過添加漏斗加入TEPA。以額外50克溶劑芳香族150溶劑沖洗該添加漏斗。在慢慢的氮流動下，將該混合物加熱至180℃約2小時。在汀-史達克(Dean-Stark)捕集器中收集水。所獲得的產物係褐色油。
如在比較例1中般製備PIBSI，除了使用二甲基胺基丙基胺(DMAPA)取代TEPA外。讓所產生的PIBSI(PD，約210克)與36.9克1,2-環氧己烷(E6)、18.5克醋酸(18.5克)及82克2-乙基己醇反應最高90℃ 3小時。在減壓下移除揮發物以提供想要的四級鹽(四級)。
在50克芳香族溶劑150中，於150℃下使來自比較例2的PIBSI(146克)與13.3克草酸二甲酯反應約2小時。所產生的產物係褐色油。
讓氯化三辛基甲基銨(70克)與130克庚烷混合。以70克醋酸鈉(於水中約16重量%)萃取該混合物五次。在減壓下從所產生的有機層移除揮發物以提供四級醋酸鹽。FTIR在1578及1389公分-1處顯示出強波峰，此係羧酸鹽的特徵。
真空蒸餾商業四級銨產物(C12)2NMe2+NO2 -以移除揮發物，以提供想要的產物。
在惰性環境中，將C18-N-Me2(118克)、39克1,2-環氧己烷、26克醋酸與76克2-乙基己醇的混合物慢慢加熱至90℃。在90℃下加熱該混合物1.5小時。然後，在減壓下移除揮發物以提供想要的產物。
在下列實施例中，使用如描述在下列的工業標準柴油機燃油噴射器測試(CEC F-98-08(DW10))，在柴油機上進行噴射器沈積測試。
使用DW10測試(其已由歐洲協調委員會(Coordinating European Council)(CEC)發展)來闡明燃料導致燃油噴射器弄髒的傾向，及亦使用來闡明某些燃料添加劑防止或控制這些沈積的能力。對直接噴射型共軌柴油機噴射器焦炭化測試來說，使用CEC F-98-08方法來評估添加劑。對寶獅(Peugeot)DW10柴油機裝置使用引擎測功計測試架來進行噴射器焦炭化測試。該引擎係具有四汽缸的2.0升引擎。每個燃燒室具有四個閥及該燃料噴
射器係具有Euro V等級的DI壓電式噴射器。
該核心方法程序由透過一循環8小時運轉該引擎及允許該引擎環境適應(關掉引擎)規定的時間量組成。重覆前述順序四次。在每小時的最後時取得引擎動力測量，同時在評估的條件下操作該引擎。以觀察到在該測試循環之開始與結束間所評估的動力差異來標出該燃料的噴射器弄髒傾向特徵。
測試製備包括在移除噴射器前從引擎中沖洗掉先前測試的燃料。檢查、清潔該測試噴射器，及將其重新裝配在引擎中。若選擇新噴射器時，新噴射器完成16小時適應(break-in)循環。其次，使用想要的測試循環程式來啟動該引擎。一旦該引擎經暖機，測量在4000 RPM及最大負載下的動力，以檢查在清洗噴射器後之最大動力恢復。若該動力測量係在規格內時，則開始該測試循環。下列表1提供DW10焦炭化循環之表示，其使用來評估根據本揭示的燃料添加劑。
表1-DW10焦炭化循環的一小時表示。
使用前述引擎測試程序，以包含新癸酸鋅、硝酸2-乙基己酯及脂肪酸酯摩擦力改質劑(基礎燃料)之超低硫柴油來測試多種燃料添加劑。由僅有基礎燃料而不含添加劑組成的”弄髒”階段開始，接著為由含有添加劑的基礎燃料組成的”潔淨”階段。全部運轉皆進行8小時弄髒及8小時潔淨，除非其它方面有指示出。使用在”弄髒”階段結束時的動力測量與在”潔淨”階段結束時的動力測量來計算動力恢復百分比。藉由下列式來測量動力恢復百分比：動力恢復百分比=(DU-CU)/DUx100其中DU係在沒有添加劑的弄髒階段結束時之動力損失百分比，CU係在含有燃料添加劑的潔淨階段結束時之動
力百分比，及根據CEC F98-08 DW10測試來測量動力。
遵從ISO-4154進行熱解重量分析(TGA)。特別是，在流速每分鐘60毫升的氮氣環境中，以每分鐘增加溫度20℃的速率，從50℃至900℃進行測試。為了比較目的，亦在XUD9引擎測試中測量所測試的組成物之氣流保持百分比，如顯示在表3中。設計出該XUD9測試方法，以評估一燃料控制在間接噴射柴油機的噴射器噴嘴上形成沈積之能力。根據XUD9測試方法的測試運轉結果係就在不同噴嘴針升起點處的氣流損失百分比來表示。以氣流測試台(airflow rig)遵從ISO 4010達成氣流測量。
在進行測試前，清潔及檢查該噴射器噴嘴在0.05，0.1、0.2、0.3及0.4毫米升起處的氣流。若該氣流於0.1毫米升起處係在250毫升/分鐘至320毫升/分鐘之範圍外時，摒棄該噴嘴。將噴嘴組合進該噴射器主體中及該開口壓力設定至115±5巴。亦將副(slave)組的噴射器安裝至該引擎。從該系統中排出先前的測試燃料。運轉該引擎25分鐘以透過該燃料系統沖洗。在此時間期間，全部溢
出燃料皆摒棄且不回用。然後，將引擎設定至測試速度及負載，且檢查及將全部具體指定的參數調整至測試規格。然後，以測試單元置換副噴射器。測量在測試前及後之氣流。使用在0.1毫米升起處之4個噴射器流動的平均來計算弄髒百分比。氣流保持程度=100-弄髒百分比。結果顯示在下列表中。
如由前述實施例(運轉4、5及6)顯示出，在燃料直噴引擎中，所揭示的具體實例之四級銨鹽在例如比運轉1-3更低的處理比例下優於運轉1-3的習知分散劑及四級銨鹽。由於根據XUD9測試，運轉4及5的相同四級銨鹽在燃料間噴引擎中具有相對差的效能，其結果令人意外。換句話說，在燃料間噴引擎中評估多種四級銨鹽將不導致所揭示的四級銨鹽之選擇改良在燃料直噴引擎中的效能。再者，咸信所揭示的四級銨鹽如於本文中所描述可有效保持引擎之燃料噴射器表面乾淨及可使用來清潔髒的燃料噴射器。
要注意的是，當在此專利說明書及所附加的申請專
利範圍中使用時，單一形式”一”、”一種”及”該”包括複數個指示對象，除非明確且毫不含糊地限制至一個指示對象。因此，例如，參照至”一抗氧化劑”包括二種以上的不同抗氧化劑。如於本文中所使用，用語”包括”及其合乎文法的變體想要非為限制，如此在列出中的項目之列舉不排除可取代或加入所列出的項目之其它類似的項目。
對此專利說明書及附加的申請專利範圍之目的來說，除非其它方面有指示出，否則表示在本專利說明書及申請專利範圍中所使用的量、百分比或比例、及其它數值之全部數字經了解在全部例子中係如由用語”約”修飾。此外，除非相反地指示出，在下列專利說明書及所附加的申請專利範圍中所提出之數字參數皆係近似值，其可依由本揭示企圖獲得之想要的性質而變化。起碼及不企圖將同等物之原理應用限制至申請專利範圍的範圍，每個數字參數應該至少按照所報導的有效數字之數目及藉由施加普通的捨入技術解釋。
雖然已經描述出特別的具體實例，但可由申請人或熟練技藝之人士產生係或可係目前預料之外的代用品、修改、變化、改良及實質上同等物。此外，如所提出及如它們可修訂的附加申請專利範圍想要包括全部此代用品、修改、變化、改良及實質上同等物。
Claims (22)
- 一種用於燃料直噴柴油機之燃料組成物，其包含：一主要量的燃料；及一較少之有效量的四級銨鹽，其在350℃下具有熱解重量分析(TGA)重量損失大於50重量%，其中存在於該燃料中的四級銨鹽量與已燃燒不包含該四級銨鹽的燃料組成物之該引擎的效能比較，係足以改良已燃燒該組成物的燃料直噴柴油機之效能。
- 如申請專利範圍第1項之燃料組成物，其中該燃料具有以重量計硫含量50 ppm或較少。
- 如申請專利範圍第1項之燃料組成物，其中該四級銨鹽包含下式之化合物：
- 如申請專利範圍第3項之燃料組成物，其中每個烴基 各自獨立地係線性、分枝、經取代、環狀、飽和、不飽和或包含一個以上的雜原子。
- 如申請專利範圍第3項之燃料組成物，其中R1、R2、R3及R4每個係選自於包含1至20個碳原子的烴基，其限制為R1、R2、R3及R4之至少一個包含8至20個碳原子。
- 如申請專利範圍第5項之燃料組成物，其中該烴基係選自於烷基、烯基及烷醇基團。
- 如申請專利範圍第1項之燃料組成物，其中以該燃料的總重量為基準，該四級銨鹽在該燃料中的量範圍係以重量計約5至約200 ppm。
- 如申請專利範圍第1項之燃料組成物，其中以該燃料的總重量為基準，該四級銨鹽在該燃料中的量範圍係以重量計約10至約150 ppm。
- 如申請專利範圍第1項之燃料組成物，其中以該燃料的總重量為基準，該四級銨鹽在該燃料中的量範圍係以重量計約30至約100 ppm。
- 如申請專利範圍第1項之燃料組成物，其中當根據CEC F98-08 DW10測試來測量時，該改良的引擎效能包括引擎動力恢復至少約80%。
- 如申請專利範圍第1項之燃料組成物，其中當根據CEC F98-08 DW10測試來測量時，該改良的引擎效能包括引擎動力恢復至少約90%。
- 如申請專利範圍第1項之燃料組成物，其中當根據CEC F98-08 DW10測試來測量時，該改良的引擎效能包括 引擎動力恢復至少約100%。
- 一種改良燃料直噴柴油機的噴射器效能之方法，包括以一燃料組成物操作該引擎，其中該組成物包含一主要量的燃料及以該燃料的總重量為基準，以重量計約5至約200 ppm(以該燃料的總重量為基準)之在350℃下具有熱解重量分析(TGA)重量損失大於50重量%的四級銨鹽，其中當根據CEC F98-08 DW10測試來測量時，存在於該燃料中之四級銨鹽改良該引擎的噴射器效能至少約80%。
- 如申請專利範圍第13項的方法，其中該引擎包含一燃料直噴柴油機。
- 如申請專利範圍第13項的方法，其中該四級銨鹽包含下式之化合物：
- 如申請專利範圍第15項的方法，其中每個烴基各自獨 立地係線性、分枝、經取代、環狀、飽和、不飽和或包含一個以上的雜原子。
- 一種操作燃料直噴柴油機的方法，包括在該引擎中燃燒一燃料組成物，其中該組成物包含一主要量的燃料及以該燃料的總重量為基準，以重量計約5至約200 ppm之在350℃下具有熱解重量分析(TGA)重量損失大於50重量%的四級銨鹽。
- 如申請專利範圍第17項的方法，其中該四級銨鹽包含下式之化合物：
- 如申請專利範圍第18項的方法，其中每個烴基各自獨立地係線性、分枝、經取代、環狀、飽和、不飽和或包含一個以上的雜原子。
- 一種用於燃料以使用在燃料直噴柴油機中之添加劑濃縮劑，其包含一在350℃下具有熱解重量分析(TGA) 重量損失大於50重量%之四級銨鹽及至少一種選自於由下列所組成之群的組分：稀釋劑、載劑流體、相容劑、十六烷改良劑、腐蝕抑制劑、低溫流動改良劑(CFPP添加劑)、傾點下降劑、溶劑、去乳化劑、潤滑添加劑、摩擦力改質劑、胺安定劑、燃燒改良劑、分散劑、抗氧化劑、熱安定劑、導電度改良劑、金屬去活化劑、標記染料、有機硝酸鹽燃燒加速劑、及環基三羰基合錳化合物。
- 如申請專利範圍第20項之添加劑濃縮劑，其中該四級銨鹽包含下式之化合物：
- 如申請專利範圍第21項之添加劑濃縮劑，其中每個烴基各自獨立地係線性、分枝、經取代、環狀、飽和、不飽和或包含一個以上的雜原子。
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- 2012-10-09 KR KR1020120111651A patent/KR101475119B1/ko not_active IP Right Cessation
- 2012-10-18 DE DE102012020501.5A patent/DE102012020501B4/de active Active
- 2012-10-31 BE BE2012/0741A patent/BE1021421B1/fr active
- 2012-11-08 SG SG2012082756A patent/SG190527A1/en unknown
- 2012-11-08 GB GB1220148.9A patent/GB2496514B/en active Active
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Cited By (1)
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| TWI648464B (zh) * | 2017-02-08 | 2019-01-21 | 康廷 熊 | 動力系統的優化裝置以及優化方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE1021421B1 (fr) | 2015-11-19 |
| KR20130052507A (ko) | 2013-05-22 |
| CN103102998A (zh) | 2013-05-15 |
| US9574149B2 (en) | 2017-02-21 |
| AU2012227347B2 (en) | 2014-04-17 |
| SG190527A1 (en) | 2013-06-28 |
| AU2012227347A1 (en) | 2013-05-30 |
| AU2012227347C1 (en) | 2015-08-13 |
| DE102012020501A1 (de) | 2013-05-16 |
| US20130118062A1 (en) | 2013-05-16 |
| KR101475119B1 (ko) | 2014-12-22 |
| DE102012020501B4 (de) | 2016-05-12 |
| CN103102998B (zh) | 2015-07-15 |
| GB201220148D0 (en) | 2012-12-26 |
| GB2496514B (en) | 2014-07-09 |
| TWI521055B (zh) | 2016-02-11 |
| GB2496514A (en) | 2013-05-15 |
| MY179415A (en) | 2020-11-05 |
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