TW201326381A - 提升低硫柴油效能之燃料添加劑 - Google Patents
提升低硫柴油效能之燃料添加劑 Download PDFInfo
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- TW201326381A TW201326381A TW101134391A TW101134391A TW201326381A TW 201326381 A TW201326381 A TW 201326381A TW 101134391 A TW101134391 A TW 101134391A TW 101134391 A TW101134391 A TW 101134391A TW 201326381 A TW201326381 A TW 201326381A
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- Prior art keywords
- fuel
- reaction product
- group
- diesel
- hydrocarbyl
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- 239000011593 sulfur Substances 0.000 title claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 24
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- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- VTALQOYOTZKULH-UHFFFAOYSA-N undecyl nitrate Chemical group CCCCCCCCCCCO[N+]([O-])=O VTALQOYOTZKULH-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
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Abstract
本發明提供一種柴油、柴油添加劑濃縮劑及用以提升柴油機之燃料噴射器效能的方法。該柴油包括一主要量具有硫含量15ppm(以重量計)或較少之中級蒸出液燃料;及一(a)經烴基取代的二羧酸或酐與(b)下式之胺化合物或其鹽的反應產物:□其中R係選自於氫或包含約1至約15個碳原子的烴基,及R1係選自於氫或包含約1至約20個碳原子的烴基,其中該反應產物包括每分子反應產物少於一當量的胺基三唑基團,及其中所存在反應產物的量足以提升柴油機之直接及/或間接的燃料噴射器效能。
Description
本揭示係有關某些柴油添加劑及關於包含該添加劑的柴油及柴油添加劑濃縮劑。特別是,本揭示係有關一種有效提高柴油機(特別是,低硫及超低硫柴油)的燃料噴射器效能之柴油添加劑。
長期想要最大化在柴油動力車輛中的燃料經濟、動力及駕駛性能,同時提高加速、減少排放物及防止停頓。雖然已知藉由使用分散劑保持閥及燃料噴射器乾淨來提高汽油動力引擎的效能,此汽油分散劑在柴油應用中未必有效。此不可預測性的理由在於在柴油機與汽油引擎的操作間有許多差異及在柴油與汽油間之化學差異。
再者,低硫柴油、超低硫柴油及高壓共軌(HPCR)引擎現在於市場上常見。”低硫”柴油意謂著具有硫含量50 ppm(以重量計)或較少的燃料(以該燃料之總重量為基準)。”超低硫”柴油(ULSD)意謂著具有硫含量15 ppm(以重量計)或較少的燃料(以該燃料之總重量為基準)。與較老型式的引擎及燃料噴射系統比較,在HPCR引擎中的燃料噴射器係在更高的壓力及溫度下運轉。低硫或ULSD與HPCR引擎之組合已對現在於市場中找到的噴射器沈積型式及噴射器沈積形成頻率造成改變。
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柴油之分散劑組成物包括一可包含聚伸
烷基琥珀醯亞胺類(其係聚伸烷基琥珀酸酐與胺之反應產物)的組成物。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,在新引擎技術中,所使用的含低硫柴油或ULSD之柴油組成物經常仍然在柴油機噴射器中產生不想要的沈積。所以,想要一可防止沈積積聚、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將效能恢復至先前”如新”的狀態之相同組成物,在試圖減低空氣運送的廢氣排放上係相等地想要及有用。
根據本揭示,範例性具體實例提供一種柴油、柴油添加劑濃縮劑,及提供一種用以提升柴油機的燃料噴射器效能之方法。該柴油包括一主要量具有硫含量50 ppm(以重量計)或較少的中級蒸出液燃料;及一(a)經烴基取代的二羧酸或酐與(b)下式之胺化合物或其鹽的反應產物:
其中R係選自於氫及包含約1至約15個碳原子的烴基;及R1係選自於氫及包含約1至約20個碳原子的烴基,其中該反應產物包括每分子反應產物少於一當量的胺基三唑基團,及其中該反應產物的存在量足以提升柴油機直接及/或間接的燃料噴射器之效能。
本揭示的另一個具體實例提供一種提升燃料噴射柴
油機的噴嘴效能之方法。該方法包括在一燃料組成物上操作該柴油機,其中該燃料組成物包含一主要量具有硫含量50 ppm(以重量計)或較少的柴油;及一較少量來自(a)下式的烴基羰基化合物:
其中R2係具有數量平均分子量範圍約200至約3000的烴基;與(b)下式的胺化合物或其鹽之反應產物:
其中R係選自於氫及包含約1至約15個碳原子的烴基,及R1係選自於氫及包含約1至約20個碳原子的烴基。該反應產物之特徵為FTIR光譜在約1630公分-1至約1645公分-1的區域中具有一波峰強度,其範圍係在約1500公分-1至約1800公分-1的區域中之其它波峰的波峰強度之約5至約45%。
本揭示的進一步具體實例提供一種清潔燃料噴射柴油機的燃料噴射器之方法。該方法包括在一燃料組成物上操作該柴油機,其中該燃料組成物包括一主要量具有硫含量50 ppm(以重量計)或較少的柴油;及一較少量來自(a)下式的烴基羰基化合物:
其中R2係具有數量平均分子量範圍約200至約3000的烴基;與(b)下式的胺化合物或其鹽之反應產物:
其中R係選自於氫及包含約1至約15個碳原子的烴基;及R1係選自於氫及包含約1至約20個碳原子的烴基。該反應產物包括每分子反應產物少於一當量的胺基三唑基團。
於本文描述的燃料添加劑之優點為該添加劑可不僅減少在直接及/或間接柴油噴嘴上形成的沈積量,且該添加劑亦可有效清潔髒的燃料噴射器。
本揭示的額外具體實例及優點某種程度上將在下列詳細說明中提出,及/或可藉由實施本揭示而學習。要瞭解前述的一般描述及下列詳細說明二者皆係範例性及僅用於解釋及非為限制如所主張的揭示。
本申請案的組成物可以較少量使用在主要量的柴油中,及可藉由讓下式的胺化合物或其鹽:
其中R係選自於由氫及包含約1至約15個碳原子的烴基所組成之群,及R1係選自於由氫及包含約1至約20個碳原子的烴基所組成之群;與下式之烴基羰基化合物反應而製得:
其中R2係具有數量平均分子量範圍約200至約3000的烴基,其中該反應產物包括每分子反應產物少於一當量的胺基三唑基團。該反應產物之特徵為FTIR光譜在約1630公分-1至約1645公分-1的區域中具有一波峰強度,其範圍係在約1500公分-1至約1800公分-1的區域中之其它波峰的波峰強度之約5至約45%。
為了比較的目的,第1圖顯示出以烴基羰基對胺的大約莫耳比率範圍約1:1至約1:2.5所製得之化合物的FTIR光譜。咸信在約1636公分-1處的波峰係胺基三唑波峰。比較上,根據所揭示的具體實例製得之反應產物具有如顯示在第2圖的FTIR光譜,其中在約1636公分-1處的波峰強度係實質上小於在約1500公分-1至約1800公分-1的區域中之其它波峰的波峰強度。例如,根據本揭示的反應產物在1630公分-1至約1645公分-1之區域中具有一波峰強度,其範圍係在約1500公分-1至約1800公分-1的區域中之其它波峰的波峰強度之約5至約45%。在其它具體實例中,該反應產物在1630公分-1至約1645公分-1的範圍內具
有一特徵波峰強度,其不超過在約1500公分-1至約1800公分-1的範圍內之其它波峰的強度之30%,例如,不超過25%及一般不超過10%。
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)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,其中該環經由該分子的另一部分完成(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,包含非烴基團的取代基,其中該非烴基團在於此描述的上下文中不改變該顯著的烴取代基(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);(3)雜取代基,也就是說,在此描述的上下文中,於由碳原子構成的環或鏈中包含除了碳外的原子,同時具有顯著的烴特徵之取代基。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,在烴基中將無非烴取代基。
如於本文中所使用,用語”主要量”經了解意謂著量
大於或等於50重量%,例如,約80至約98重量%(相對於該組成物的總重量)。再者,如於本文中所使用,用語”較少量”經了解意謂著量少於50重量%(相對於該組成物的總重量)。
下式之合適的胺化合物:
可選自於胍類及胺基胍類或其鹽,其中R及R1如上述定義。因此,該胺化合物可選自於胍類的無機鹽,諸如胍類的鹵化物、碳酸鹽、硝酸酯、磷酸鹽及正磷酸鹽。用語”胍類”指為胍及胍衍生物,諸如胺基胍。在一個具體實例中,該用於添加劑之製備的胍化合物係胺基胍碳酸氫鹽。胺基胍碳酸氫鹽可從商業來源容易地獲得,或可以熟知方式製備。
該添加劑的烴基羰基反應物化合物可係具有烴基部分及羰基部分的任何合適化合物,及其能與該胺化合物鍵結而形成本揭示的添加劑。合適的烴基羰基化合物之非為限制的實施例包括(但不限於)經烴基取代的琥珀酸酐類、經烴基取代的琥珀酸類及經烴基取代的琥珀酸類之酯。
在某些態樣中,該烴基羰基化合物可係具有下列式的聚伸烷基琥珀酸酐反應物:
其中R2係烴基部分,諸如例如,具有數量平均分子量約100至約5,000的聚烯基。例如,R2的數量平均分子量範圍可係約200至約3,000,如藉由GPC測量。除非其它方面指示出,在本專利說明書中的分子量係數量平均分子量。
該R2烴基部分可包含一個以上選自於線性或分枝烯基單元的聚合物單元。在某些態樣中,該烯基單元可具有約2至約10個碳原子。例如,該聚烯基可包含一個以上選自於下列的線性或分枝聚合物單元:乙烯基團、丙烯基團、丁烯基團、戊烯基團、己烯基團、辛烯基團及癸烯基團。在某些態樣中,該R2聚烯基可呈例如均聚物、共聚物或三元共聚物形式。在一個態樣中,該聚烯基係異丁烯。例如,該聚烯基可係包含約10至約60個異丁烯基團(諸如,約20至約30個異丁烯基團)的聚異丁烯之均聚物。可藉由任何合適的方法形成使用來形成該R2聚烯基的聚烯法化合物,諸如藉由習知的烯類之催化寡聚化。
在額外的態樣中,該烴基部分R2可衍生自線性烯烴或藉由在技藝中熟知的方法來寡聚化乙烯所製得之酸異構化的烯烴。這些烴基部分的範圍可為約8個碳原子至超過40個碳原子。例如,此型式的烯基部分可來自線性C18或C20-24烯烴之混合物或來自酸異構化的C16
烯烴。
在某些態樣中,可使用具有相當高比例具有終端亞乙烯基之聚合物分子的高反應性聚異丁烯類來形成該R2基團。在一個實施例中,至少約60%(諸如約70%至約90%)的聚異丁烯類包含終端烯系雙鍵。工業的一般趨勢為轉換成高反應性聚異丁烯類,及熟知的高反應性聚異丁烯類係揭示例如在美國專利案號4,152,499中,此揭示其全文於此以參考方式併入本文。
該烴基羰基化合物的特定實施例包括此化合物,如十二碳烯基琥珀酸酐類、C16-18烯基琥珀酸酐及聚異丁烯基琥珀酸酐(PIBSA)。在某些具體實例中,該PIBSA可具有一亞乙烯基含量範圍約4%至大於約90%的聚異丁烯部分。在某些具體實例中,在該烴基羰基化合物中之羰基數目對烴基部分數目的莫耳比率範圍可係約0.5:1至約5:1。
在某些態樣中,大約一莫耳馬來酸酐可與每莫耳聚伸烷基反應,如此所產生的聚烯基琥珀酸酐具有每個聚伸烷基取代基約0.8至約1個琥珀酸酐基團。在其它態樣中,琥珀酸酐基團對伸烷基的莫耳比率範圍可係約0.5至約3.5,諸如約1至約1.1。
該烴基羰基化合物可使用任何合適的方法製造。用來形成烴基羰基化合物的方法在技藝中熟知。已知用以形成烴基羰基化合物的方法之一個實施例包括摻合一聚烯烴與馬來酸酐。將該聚烯烴與馬來酸酐反應物加熱至溫度例如約150℃至約250℃,選擇性,使用觸媒(諸如,
氯或過氧化物)。另一種製造該聚伸烷基琥珀酸酐的範例性方法係描述在美國專利案號4,234,435中,其全文以參考之方式併入本文。
上述的烴基羰基與胺化合物可在合適之條件下混合在一起以提供本揭示之想要的反應產物。在本揭示的一個態樣中,該反應物化合物可以範圍約1:0.5至約1:1.5之烴基羰基化合物對胺的莫耳比率混合在一起。例如,該反應物的莫耳比率範圍可係約1:0.5至約1:0.95。
在大氣壓下之合適的反應溫度範圍可係約130℃至低於約200℃。例如,該反應溫度範圍可係約140℃至約160℃。可使用任何合適的反應壓力,諸如包括次大氣壓或超大氣壓。但是,該溫度範圍可與所列出在非大氣壓下進行反應的那些不同。該反應可在約1小時至約8小時的範圍內進行一段時間,較佳為在約2小時至約6小時的範圍內。
在本申請案的某些態樣中,本申請案的分散劑產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(Hcnly)等人發佈的美國專利案號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,其說明於此全文以參考方式併入本文。
在其它態樣中,本申請案的組成物可不包括載劑。例如,本申請案之某些組成物可不包括礦物油或氧化物,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,該燃料可包括習知量的鯨蠟烷促進劑、腐蝕抑制劑、低溫流動促進劑(CFPP添加劑)、傾注點抑制劑、溶劑、去乳化劑、潤滑添加劑、摩擦力改質劑、胺安定劑、燃燒促進劑、分散劑、抗氧化劑、熱穩定劑、導電度促進劑、金屬去活化劑、標誌染料、有機硝酸酯燃燒加速劑、環基三羰基合錳(cyclomatic manganese tricarbonyl)化合物及其類似物。在某些態樣中,以該添加劑濃縮劑的總重量為基準,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。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日所發佈的美國專利案號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,其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。
當調配此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柴油機中形成沈積。在某些態樣中,該燃料可包括較少量上述控制或減少引擎沈積形成之反應產物,例如,在柴油機中的噴嘴沈積。例如,
本申請案的柴油可包含(以活性成份為基底)每公斤燃料範圍約5毫克至約200毫克的反應產物之反應產物量,諸如每公斤燃料範圍約20毫克至約120毫克的反應產物。在各態樣中,若使用載劑時,該燃料組成物可包含(以活性成份為基底)每公斤燃料範圍約1毫克至約100毫克載劑之載劑量,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剩餘在其中之聚伸烷基化合物,及(ii)在反應產物之製造時(在其形成期間或之後,但是若使用載劑的話,則在加入載劑之前所使用的溶劑(若有的話)。
可將本申請案之添加劑,其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,各別地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(當呈添加劑濃縮劑形式時,如此利用藉由成份之組合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。
本申請案之柴油可應用於固定式柴油機(例如,使用在電能產生裝置、抽水站等等中的引擎)及移動式柴油機(例如,使用在汽車、卡車、道路修平(road-grading)設備、軍用車輛等等中作為原動機的引擎)二者之操作。例如,該燃料可包括任何及全部中級蒸出液燃料、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 liquid)(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個碳原子者。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,本申請案的態樣針對一種減低柴油機的噴嘴沈積量之方法,其中該柴油機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,該改良亦可在間接柴油噴嘴中觀察到。在某些態樣中,該方法包括經由該柴油機的噴嘴將一以烴為基礎包含本揭示的反應產物添加劑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。對本申請案的目的來說,用語”基本上無”定義為在噴嘴潔淨或沈積形成上具有實質上無法測量的效應之濃度。
在本申請案的更其它態樣中,該燃料添加劑可係無或實質上無1,2,4-三唑類。例如,該組成物可實質上無式II之三唑類:
其中R4及R5各自獨立地選自於氫及烴基,其限制為R4及R5之至少一個不為氫。該烴基的實施例包括C2至C50線性、分枝或環烷基;C2至C50線性、分枝或環烯基;及經取代或未經取代的芳基,諸如苯基、甲苯基及茬基。
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。
將950分子量的聚丁烯基琥珀酸酐(295克)與86克(2當量)胺基胍碳酸氫鹽(AGBC)及416克芳香族溶劑150混合。在真空下將該混合物加熱至165℃及保持在此溫度下
約4小時,移除水及二氧化碳。過濾所得的混合物。產物的FTIR光譜在1636公分-1處顯示出一波峰,其在1500公分-1至1800公分-1的區域之波峰中佔主要地位,如顯示在第1圖中。
在一燒瓶中充入950分子量的聚丁烯基琥珀酸酐(553克)、芳香族溶劑150(210克)、胺基胍碳酸氫鹽(AGBC)(79.5克,1當量)及甲苯(145克)。將該反應混合物加熱至最高145℃及保持約2小時。經由共沸蒸餾不再有水被移除。移除樣品及以約相等重量的庚烷稀釋。讓所得的混合物過濾過塞里塑料512及藉由旋轉蒸發器濃縮以提供想要的產物,如為褐色油。該產物的FTIR光譜在1724、1689、1637、1588公分-1處顯示出波峰,其中在1637公分-1處的波峰最小。
在下列實施例中,使用如在下列描述的習知柴油機燃油噴嘴測試在柴油機上進行噴嘴沈積測試。
使用DW10測試(其已由歐洲協調委員會(Coordinating European Council)(CEC)所研發)來闡明燃料導致燃油噴嘴弄髒的傾向,及亦使用來闡明某些燃料添加劑防止或控制這些沈積之能力。對直接噴射型共軌柴油機噴嘴焦炭化測試來說,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嘴焦炭化測試。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分類的DI壓電式噴嘴。
該核心方法程序由透過一循環運轉該引擎8小時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,取得引擎動力測量同時在評估的條件下操作該引擎。燃料的噴嘴弄髒傾向之特徵係觀察到所評估的動力在該測試循環之開始與結束間不同。
測試製備包括在移除噴嘴前沖洗來自引擎之先前測試的燃料。檢查、清潔測試噴嘴,及將其重新裝配在引擎中。若選擇新噴嘴時,新噴嘴完成16小時適應(break-in)循環。其次,使用想要的測試循環程式開始該引擎。一旦引擎經暖機,在4000 RPM及最大負載下測量動力以檢查在清洗噴嘴後之最大動力恢復。若動力測量在規格內,則開始測試循環。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。
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)之超低硫柴油測試多種燃料添加劑。由僅有基礎燃料不含添加劑組成的”弄髒”階段開始,接著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小時乾淨,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。藉由下列式測量動力恢復百分比:
動力恢復百分比=(DU-CU)/DUx100其中DU為在沒有添加劑的弄髒階段結束時之動力損失百分比,CU為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。習知的琥珀醯亞胺分散劑通常根據美國專利案號5,752,989之揭示製得。
1引擎運轉16小時沒有添加劑及16小時含有添加劑
2引擎運轉32小時沒有添加劑及32小時含有添加劑
如由前述實施例顯示出,運轉5-9的反應產物在超低硫柴油弄髒後,提供實質上較比較例1之反應產物為大的動力恢復。結果驚人且全部出乎意料。此外,咸信如於本文所描述的反應產物可有效保持柴油機的燃料噴射器表面乾淨及清潔髒的燃料噴射器。
要注意的是,當使用在此專利說明書及附加的申請專利範圍中時,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”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,如此在列出項目中的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,否則表示出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附加的申請專利範圍中所提出之數字參數係近似值,其可依由本揭示企圖獲得之想要的性質而變化。起碼及不作為限制與申請專利範圍的範圍同等之應用原理的企圖,每個數字參數應該至少按照數字所報導的有效數字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,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、改質、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、改質、變化、改良及實質上同等物。
第1圖係先前技術之產物的FTIR光譜之一部分;及第2圖係根據本揭示的反應產物之FTIR光譜的一部分。
Claims (28)
- 一種用於燃料噴射的柴油,其包含:一主要量具有硫含量50 ppm(以重量計)或較少的中級蒸出液燃料;及一(a)經烴基取代的二羧酸、酐或酯與(b)下式之胺化合物或其鹽的反應產物:
- 如申請專利範圍第1項之柴油,其中該反應產物的特徵為FTIR光譜在約1630公分-1至約1645公分-1的區域中具有一波峰強度,其範圍係在約1500公分-1至約1800公分-1的區域中之其它波峰的波峰強度之約5至約45%。
- 如申請專利範圍第1項之柴油,其中在該反應產物中的(a)對(b)之莫耳比率範圍係約1:0.5至約1:1.5。
- 如申請專利範圍第1項之柴油,其中該烴基二羧酸、酐或酯係選自於經烴基取代的琥珀酸酐類、經烴基取代的琥珀酸類及經烴基取代的琥珀酸類之酯。
- 如申請專利範圍第4項之柴油,其中該烴基二羧酸、 酐或酯的烴基具有數量平均分子量約200至約3,000。
- 如申請專利範圍第5項之柴油,其中該柴油包含一用於直接燃料噴射引擎的燃料。
- 如申請專利範圍第5項之柴油,其中該烴基二羧酸、酐或酯的烴基包含一聚異丁烯基團,其衍生自具有至少60%或更多終端烯系雙鍵的高反應性聚異丁烯類。
- 如申請專利範圍第1項之柴油,其中該胺包含胍的無機鹽。
- 如申請專利範圍第1項之柴油,其中該胺包含胺基胍的鹽。
- 如申請專利範圍第1項之柴油,其中該胺包含胺基胍碳酸氫鹽。
- 一種提升燃料噴射柴油機的噴嘴效能之方法,其包括在一燃料組成物上操作該柴油機,該燃料組成物包含一主要量具有硫含量50 ppm(以重量計)或較少的柴油及一較少量來自(a)下式的烴基羰基化合物及其酸或酯:
- 如申請專利範圍第11項的方法,其中在該反應產物中的(a)對(b)之莫耳比率範圍係約1:0.5至約1:1.5。
- 如申請專利範圍第11項的方法,其中R2係具有數量平均分子量約200至約3,000的聚異丁烯。
- 如申請專利範圍第11項的方法,其中該燃料噴射柴油機包含直接燃料噴射柴油機。
- 如申請專利範圍第11項的方法,其中該反應產物包括每分子反應產物少於一當量的胺基三唑基團。
- 如申請專利範圍第11項的方法,其中該胺係胺基胍碳酸氫鹽。
- 一種清潔燃料噴射柴油機的燃料噴射器之方法,其包括在一燃料組成物上操作該柴油機,其中該組成物包含一主要量具有硫含量50 ppm(以重量計)或較少的柴油及一較少量衍生自(a)下式之烴基羰基化合物及其酸或酯:
- 如申請專利範圍第17項的方法,其中R2係具有數量平均分子量約200至約3,000的聚烯烴基團。
- 如申請專利範圍第17項的方法,其中該燃料噴射柴油機係直接燃料噴射柴油機。
- 如申請專利範圍第17項的方法,其中在該反應產物中的(a)對(b)之莫耳比率範圍係約1:0.5至約1:1.5。
- 如申請專利範圍第17項的方法,其中該胺係胺基胍碳酸氫鹽。
- 一種加入至低硫柴油用以提升柴油機的燃料噴射器效能之燃料添加劑濃縮劑,其包含一來自(a)下式的烴基羰基化合物及其酸或酯:
- 如申請專利範圍第22項之添加劑濃縮劑,其中R2係一具有數量平均分子量約500至約1,300道耳吞的聚烯烴基團。
- 如申請專利範圍第23項之添加劑濃縮劑,其中該聚烯烴基團係一聚異丁烯基團。
- 如申請專利範圍第24項之添加劑濃縮劑,其中該聚異丁烯基團係衍生自具有至少60%或更多終端烯系雙鍵的高反應性聚異丁烯類。
- 如申請專利範圍第24項之添加劑濃縮劑,其中該胺包含胺基胍的無機鹽。
- 如申請專利範圍第22項之添加劑濃縮劑,其中該柴油機包括直接燃料噴射柴油機。
- 一種柴油,其具有15ppm(以重量計)或較少之硫含量,以及一量足以提供每公斤燃料約5毫克至約200毫克的反應產物之如申請專利範圍第22項的添加劑濃縮劑。
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CN106118763B (zh) * | 2016-07-01 | 2018-07-13 | 盛世昆仲(北京)科技发展有限公司 | 一种复合型柴油添加剂及制备方法 |
US11312915B2 (en) | 2019-07-19 | 2022-04-26 | Afton Chemical Corporation | Methods to reduce frequency of diesel particulate filter regeneration |
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