CA2533657A1 - Low-sulfur diesel fuel as well as the use of fatty acid monoalkyl esters as lubricity improvers for low-sulfur diesel fuels - Google Patents
Low-sulfur diesel fuel as well as the use of fatty acid monoalkyl esters as lubricity improvers for low-sulfur diesel fuels Download PDFInfo
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- CA2533657A1 CA2533657A1 CA002533657A CA2533657A CA2533657A1 CA 2533657 A1 CA2533657 A1 CA 2533657A1 CA 002533657 A CA002533657 A CA 002533657A CA 2533657 A CA2533657 A CA 2533657A CA 2533657 A1 CA2533657 A1 CA 2533657A1
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- Prior art keywords
- fatty acid
- low
- acid monoalkyl
- monoalkyl esters
- esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 54
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 50
- 239000000194 fatty acid Substances 0.000 title claims abstract description 50
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 50
- 150000002148 esters Chemical class 0.000 title claims abstract description 38
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims description 20
- 229910052717 sulfur Inorganic materials 0.000 title claims description 20
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 21
- 235000003441 saturated fatty acids Nutrition 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001640 fractional crystallisation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004508 fractional distillation Methods 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 235000019871 vegetable fat Nutrition 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 12
- 239000003225 biodiesel Substances 0.000 abstract description 11
- -1 fatty acid ester Chemical class 0.000 abstract description 7
- 235000012424 soybean oil Nutrition 0.000 abstract description 6
- 239000005864 Sulphur Substances 0.000 abstract 3
- 239000000314 lubricant Substances 0.000 abstract 2
- 235000019484 Rapeseed oil Nutrition 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 235000019482 Palm oil Nutrition 0.000 description 8
- 239000002540 palm oil Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 239000008157 edible vegetable oil Substances 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000010499 rapseed oil Substances 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- 235000019737 Animal fat Nutrition 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- 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
Abstract
The invention relates to a low-sulphur diesel fuel containing a maximum of 0.2 wt. % sulphur and fatty acid monoalkyl esters in an amount between 10 and 50,000 ppm as lubricant improver, whereby the fatty acid ester of the fatty acid monoalkyl ester is derived from at least 50 %, in particular at least 70 % of saturated fatty acids. It has been shown that said fatty acid esters exhibit a markedly better lubricant improvement in low-sulphur fuels than biodiesel derived from rapeseed oil or soya oil.
Description
Low-Sulfur Diesel Fuel as well as the Use of Fatty Acid Monoalkyl Esters as Lubricity Improvers for Low-Sulfur Diesel Fuels The invention relates to a low-sulfur diesel fuel containing a maximum amount of 0.2% by weight of sulfur and fatty acid monoalkyl esters in an amount of between 10 and 50,000 ppm as lubricity improvers.
Legal provisions enforce a steady decrease in the content of sulfur compounds in mineral fuels. In Europe, the content of sulfur in diesel fuel has been limited to 0.05% by weight since 1996, however, in several countries, e.g. in Sweden, so-called zero-sulfur fuel having a sulfur content of less than 10 ppm is already used almost exclusively today. A
so-called city diesel having a content of 50 ppm of sulfur is frequently offered already today especially for use in congested areas.
The elimination of sulfur compounds during refining also involves a deterioration of the lubricating properties of the fuels. It has been possible to show that the elimination of sulfur compounds is also associated with a reduction of polar, oxygenated compounds and polycyclic aromatic compounds which are responsible for the actual lubricity.
Reduced lubricity may, however, lead to major damage to the fuel injection pumps of diesel engines.
For this reason, it is necessary to add appropriate additives as lubricity improvers to the diesel fuel. Conventional lubricity improvers and additives, respectively, are either synthetic petroleum products or synthetic esters of various chemical structures. As an environmentally friendly alternative, renewable raw materials such as vegetable oils or vegetable oil derivatives such as, e.g., fatty acid monoalkyl esters are today suggested in many cases as lubricating additives.
EP 0 680 506 B describes the use of esters as lubricity improvers.
EP 0 635 558 A1 describes the use of fatty acid monoalkyl esters from saturated and unsaturated fatty acid esters in an amount of from 100 to 10,000 ppm. For this application, especially methyl esters of the composition in which the fatty acids are present in vegetable oils are used without any further pretreatment or separation. A similar application can be learnt from WO 94/17160.
Legal provisions enforce a steady decrease in the content of sulfur compounds in mineral fuels. In Europe, the content of sulfur in diesel fuel has been limited to 0.05% by weight since 1996, however, in several countries, e.g. in Sweden, so-called zero-sulfur fuel having a sulfur content of less than 10 ppm is already used almost exclusively today. A
so-called city diesel having a content of 50 ppm of sulfur is frequently offered already today especially for use in congested areas.
The elimination of sulfur compounds during refining also involves a deterioration of the lubricating properties of the fuels. It has been possible to show that the elimination of sulfur compounds is also associated with a reduction of polar, oxygenated compounds and polycyclic aromatic compounds which are responsible for the actual lubricity.
Reduced lubricity may, however, lead to major damage to the fuel injection pumps of diesel engines.
For this reason, it is necessary to add appropriate additives as lubricity improvers to the diesel fuel. Conventional lubricity improvers and additives, respectively, are either synthetic petroleum products or synthetic esters of various chemical structures. As an environmentally friendly alternative, renewable raw materials such as vegetable oils or vegetable oil derivatives such as, e.g., fatty acid monoalkyl esters are today suggested in many cases as lubricating additives.
EP 0 680 506 B describes the use of esters as lubricity improvers.
EP 0 635 558 A1 describes the use of fatty acid monoalkyl esters from saturated and unsaturated fatty acid esters in an amount of from 100 to 10,000 ppm. For this application, especially methyl esters of the composition in which the fatty acids are present in vegetable oils are used without any further pretreatment or separation. A similar application can be learnt from WO 94/17160.
2 describes the production of agents for lubricity improvement by double transesterification of vegetable oils, wherein, in the first stage, fatty acid monoalkyl esters are produced which are transesterified with a polyol in a second stage.
Similar compounds are described in EP 1 088 880 A1.
Mixtures of fatty acid esters and dicarboxylic acid esters as lubricity improvers are described in DE 19955354.
US 5,891,203 describes the use of a mixture of biodiesel and diethanolamine derivatives as lubricity improvers in low-sulfur fuels. Hereby, fatty acid amides from diethanolamine and fatty acids are used, wherein especially oleic acid is used as the preferred fatty acid.
In Energy and Fuels (2001, 15, 106-I 12), the use of biodiesel produced from various raw materials such as sunflower oil, corn oil, olive oil and used edible oils as an additive for lubricity improvement is described, wherein it has been possible to detect a distinct effect with all products, without being able to detect any differences with the individual raw materials.
By means of the directive of the European Commission, the amount of biofuels in the EU is meant to rise to an amount of 5.75% by the year 2010. In order to be able to achieve that amount, it will be necessary especially in the field of biodiesel to fully exploit the potential of possible raw materials. This means that raw materials such as used edible oils, animal fats or palm oil will increasingly have to be used as raw material sources.
A substantial obstacle against using those raw materials as biofuels is the poor low-temperature behaviour of the fatty acid monoalkyl esters produced therefrom, whereby the application as a biodiesel in a 100% form and also as a mixing component is presently still highly restricted.
The present invention starts here, which has as its object to provide an improved low-sulfur diesel fuel having a maximum amount of 0.2% by weight of sulfur, which diesel fuel contains fatty acid monoalkyl esters in an amount of between 10 and 50,000 ppm as lubricity improvers and with which the above-mentioned problem is diminished.
The low-sulfur diesel fuel according to the invention contains a maximum amount of 0.2%
by weight of sulfur and fatty acid monoalkyl esters in an amount of between 10 and 50,000 ppm as lubricity improvers and is characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%, with the fatty acid monoalkyl esters preferably being provided as fatty acid methyl esters.
The present invention is based on the surprising realization that the lubricating ability of fatty acid monoalkyl esters apparently depends on the content of saturated fatty acid derivatives. For instance, it has been possible to show that fatty acid esters having a content of more than 50% of saturated fatty acids show a substantially higher lubricity improvement in a low-sulfur diesel fuel than a biodiesel made of rape oil or soy bean oil.
Via fractional crystallization and distillation, the amounts of esters comprising unsaturated fatty acids can be separated off. Thus, in particular the fatty acid ester fractions which are obtained by fractional crystallization or distillation and are characterized by a high content of saturated fatty acids are particularly well suited as lubricity improvers.
The fatty acid monoalkyl esters contained in the diesel fuel according to the invention are preferably produced from vegetable fats and/or oils. Possible raw materials are all natural vegetable or animal oils and/or fats whose content of saturated fatty acids already amounts to more than 50%, or corresponding products which were produced by enrichment or separation of the saturated fatty acids from the respective oils and fats.
Preferably, appropriate fractions from the processing of palm oil (palm stearin) or animal fat fractions are used.
A further embodiment of the diesel fuel according to the invention is characterized in that it additionally contains one or more additives for improving the cetane number or for improving the low-temperature behaviour.
Furthermore, the invention relates to an agent for improving the lubricity of diesel fuels containing fatty acid monoalkyl esters which is characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%.
Furthermore, the invention relates to a process for the production of a fatty acid monoalkyl ester whose fatty acid moieties originate from saturated fatty acids by at least SO%, in particular by at least 70%, which process is characterized in that a fatty acid monoalkyl ester whose fatty acid moieties originate from saturated and unsaturated fatty acids is subjected to fractional crystallization or distillation.
Similar compounds are described in EP 1 088 880 A1.
Mixtures of fatty acid esters and dicarboxylic acid esters as lubricity improvers are described in DE 19955354.
US 5,891,203 describes the use of a mixture of biodiesel and diethanolamine derivatives as lubricity improvers in low-sulfur fuels. Hereby, fatty acid amides from diethanolamine and fatty acids are used, wherein especially oleic acid is used as the preferred fatty acid.
In Energy and Fuels (2001, 15, 106-I 12), the use of biodiesel produced from various raw materials such as sunflower oil, corn oil, olive oil and used edible oils as an additive for lubricity improvement is described, wherein it has been possible to detect a distinct effect with all products, without being able to detect any differences with the individual raw materials.
By means of the directive of the European Commission, the amount of biofuels in the EU is meant to rise to an amount of 5.75% by the year 2010. In order to be able to achieve that amount, it will be necessary especially in the field of biodiesel to fully exploit the potential of possible raw materials. This means that raw materials such as used edible oils, animal fats or palm oil will increasingly have to be used as raw material sources.
A substantial obstacle against using those raw materials as biofuels is the poor low-temperature behaviour of the fatty acid monoalkyl esters produced therefrom, whereby the application as a biodiesel in a 100% form and also as a mixing component is presently still highly restricted.
The present invention starts here, which has as its object to provide an improved low-sulfur diesel fuel having a maximum amount of 0.2% by weight of sulfur, which diesel fuel contains fatty acid monoalkyl esters in an amount of between 10 and 50,000 ppm as lubricity improvers and with which the above-mentioned problem is diminished.
The low-sulfur diesel fuel according to the invention contains a maximum amount of 0.2%
by weight of sulfur and fatty acid monoalkyl esters in an amount of between 10 and 50,000 ppm as lubricity improvers and is characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%, with the fatty acid monoalkyl esters preferably being provided as fatty acid methyl esters.
The present invention is based on the surprising realization that the lubricating ability of fatty acid monoalkyl esters apparently depends on the content of saturated fatty acid derivatives. For instance, it has been possible to show that fatty acid esters having a content of more than 50% of saturated fatty acids show a substantially higher lubricity improvement in a low-sulfur diesel fuel than a biodiesel made of rape oil or soy bean oil.
Via fractional crystallization and distillation, the amounts of esters comprising unsaturated fatty acids can be separated off. Thus, in particular the fatty acid ester fractions which are obtained by fractional crystallization or distillation and are characterized by a high content of saturated fatty acids are particularly well suited as lubricity improvers.
The fatty acid monoalkyl esters contained in the diesel fuel according to the invention are preferably produced from vegetable fats and/or oils. Possible raw materials are all natural vegetable or animal oils and/or fats whose content of saturated fatty acids already amounts to more than 50%, or corresponding products which were produced by enrichment or separation of the saturated fatty acids from the respective oils and fats.
Preferably, appropriate fractions from the processing of palm oil (palm stearin) or animal fat fractions are used.
A further embodiment of the diesel fuel according to the invention is characterized in that it additionally contains one or more additives for improving the cetane number or for improving the low-temperature behaviour.
Furthermore, the invention relates to an agent for improving the lubricity of diesel fuels containing fatty acid monoalkyl esters which is characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%.
Furthermore, the invention relates to a process for the production of a fatty acid monoalkyl ester whose fatty acid moieties originate from saturated fatty acids by at least SO%, in particular by at least 70%, which process is characterized in that a fatty acid monoalkyl ester whose fatty acid moieties originate from saturated and unsaturated fatty acids is subjected to fractional crystallization or distillation.
Finally, the invention relates to the use of fatty acid monoalkyl esters as lubricity improvers for low-sulfur diesel fuels, with the fatty acid moieties of the fatty acid monoalkyl esters originating from saturated fatty acids by at least 50%, in particular by at least~70%.
As a measuring method for determining lubricity, the HFRR wear test as per CEC
96 was used in accordance with international standards. Here, lubricity is determined by way of the abrasion of a rotating ball. In this method, an abrasion of 460 pm is regarded as the threshold value. The reference fuel used for tl'e tests was a sulfur-free, non-additivated diesel fuel having an abrasion value of 569 p.m.
When using different biodiesel samples (made of animal fat, rape oil, soy bean oil and used edible oil), it was surprisingly possible to detect that, when added in an amount of 0.5%, all biodiesel samples did indeed result in an enhancement of lubricating properties but that only by means of the agent according to the invention it was possible to substantially fall below the threshold value of 460 pm. Only when 1.0% was used, the biodiesel samples from rape oil and used edible oil were also able to fall below the threshold value whereas, in case of biodiesel from soy bean oil, even an addition of 2.0% did not result in the threshold value being fallen short o~
Various palm oil samples and palm oil fatty acids, respectively, having high contents of saturated fatty acids were also used for the production of fatty acid methyl esters. All samples had a content of saturated fatty acids of more than 50%. With all samples, it was possible to fall below the threshold value of 460 pm at least when 1.0% was used.
According to European Standard EN 590, an additivation by 5.0% is permitted in a mineral diesel fuel. Since, if additives are used, the price of the additive plays a decisive role and conventional lubricity improvers are available at very low prices, the use of fatty acid alkyl esters is interesting from an economic point of view only if the lowest possible amount of additive is used.
Thus, fatty acid monoalkyl esters having a content of saturated fatty acids of more than 50%
constitute ideal additives for improving the lubricating properties of sulfur-free diesel fuels.
By means of the following examples, preferred embodiments of the invention are illustrated further.
Example 1 The starting product was an animal fat having the following fatty acid composition:
Lauric acid:0.2%
Myristic 1.86%
acid:
Palmitic 25.17%
acid:
Stearic acid:14.47%
Oleic acid: 42.98%
Linoleic 9.24%
acid:
According to known methods, said fat was converted with methanol and potassium hydroxide into the corresponding fatty acid methyl esters. Via fractional crystallization, the fatty acid methyl esters obtained were separated into two fractions at low temperatures, wherein the fraction having a high content of saturated fatty acids was used as a lubricant additive. The fatty acid composition of said fraction was as follows:
Lauric acid:2.06%
Myristic 0.44%
acid:
Palmitic 33.75%
acid:
Stearic acid:35.00%
Oleic acid: 21.26%
Linoleic 2.62%
acid:
Mixtures of said fraction with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
By way of comparison, different biodiesel samples produced from rape oil, soy bean oil and used edible oil were likewise assessed by the same test.
Methyl ester 0.5% 1.0% 2.0%
sample Methyl ester 443 420 321 from animal fat after fract.
crystallization Rape oil 509 359 320 Used edible oil 521 375 322 Soy bean oil 540 483 487 HFRR abrasion values in Vim; reference value of non-additivated fuel: 569 ~.m Example 2 A technical fatty acid distillate made of palm oil and having the following fatty acid composition was used as a raw material for the production of fatty acid methyl esters:
Myristic 1.59%
acid:
Palmitic 52.07%
acid:
Stearic acid:3.93%
Oleic acid: 33.80%
Linoleic 8.37%
acid:
Said fatty acid mixture was converted with the aid of methanol and concentrated sulfuric acid as a catalyst, whereby the corresponding fatty acid methyl esters were obtained.
Mixtures of said fatty acid methyl esters with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
Amount of methyl 0.5% 1.0%
ester HFRR abrasion values in ~.m; reference value of non-additivated fuel: 569 ~m Example 3 Palm stearin produced by fractional crystallization from palm oil and having the following fatty acid composition was used as a raw material for the production of fatty acid methyl esters:
Myristic 1.3%
acid:
Palmitic 73.83%
acid:
Stearic acid:4.84%
Oleic acid: 16.56%
Linoleic 3.52%
acid:
With the aid of methanol and potassium hydroxide as a catalyst, palm stearin was subjected to multistage transesterification, whereby the corresponding fatty acid methyl esters were obtained.
Mixtures of said fatty acid methyl esters with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
Amount of methyl 0.5% 1.0%
ester HFRR abrasion values in ~,m; reference value of non-additivated fuel: 569 pm Example 4 Raw palm oil having the following fatty acid composition was used as a raw material for the production of fatty acid methyl esters:
Myristic acid: 1.07%
Palmitic acid: 44.23%
Stearic acid: 4.68%
Oleic acid: 38.28%
Linoleic acid: 11.74%
With the aid of methanol and potassium hydroxide as a catalyst, said palm oil was subjected to multistage transesterification, whereby the corresponding fatty acid methyl esters were obtained.
Mixtures of said fatty acid methyl esters with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
Amount of methyl 0.5% 1.0%
ester HFRR ~ 477 ~ 456 HFRR abrasion values in Vim; reference value of non-additivated fuel: 569 ~m
As a measuring method for determining lubricity, the HFRR wear test as per CEC
96 was used in accordance with international standards. Here, lubricity is determined by way of the abrasion of a rotating ball. In this method, an abrasion of 460 pm is regarded as the threshold value. The reference fuel used for tl'e tests was a sulfur-free, non-additivated diesel fuel having an abrasion value of 569 p.m.
When using different biodiesel samples (made of animal fat, rape oil, soy bean oil and used edible oil), it was surprisingly possible to detect that, when added in an amount of 0.5%, all biodiesel samples did indeed result in an enhancement of lubricating properties but that only by means of the agent according to the invention it was possible to substantially fall below the threshold value of 460 pm. Only when 1.0% was used, the biodiesel samples from rape oil and used edible oil were also able to fall below the threshold value whereas, in case of biodiesel from soy bean oil, even an addition of 2.0% did not result in the threshold value being fallen short o~
Various palm oil samples and palm oil fatty acids, respectively, having high contents of saturated fatty acids were also used for the production of fatty acid methyl esters. All samples had a content of saturated fatty acids of more than 50%. With all samples, it was possible to fall below the threshold value of 460 pm at least when 1.0% was used.
According to European Standard EN 590, an additivation by 5.0% is permitted in a mineral diesel fuel. Since, if additives are used, the price of the additive plays a decisive role and conventional lubricity improvers are available at very low prices, the use of fatty acid alkyl esters is interesting from an economic point of view only if the lowest possible amount of additive is used.
Thus, fatty acid monoalkyl esters having a content of saturated fatty acids of more than 50%
constitute ideal additives for improving the lubricating properties of sulfur-free diesel fuels.
By means of the following examples, preferred embodiments of the invention are illustrated further.
Example 1 The starting product was an animal fat having the following fatty acid composition:
Lauric acid:0.2%
Myristic 1.86%
acid:
Palmitic 25.17%
acid:
Stearic acid:14.47%
Oleic acid: 42.98%
Linoleic 9.24%
acid:
According to known methods, said fat was converted with methanol and potassium hydroxide into the corresponding fatty acid methyl esters. Via fractional crystallization, the fatty acid methyl esters obtained were separated into two fractions at low temperatures, wherein the fraction having a high content of saturated fatty acids was used as a lubricant additive. The fatty acid composition of said fraction was as follows:
Lauric acid:2.06%
Myristic 0.44%
acid:
Palmitic 33.75%
acid:
Stearic acid:35.00%
Oleic acid: 21.26%
Linoleic 2.62%
acid:
Mixtures of said fraction with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
By way of comparison, different biodiesel samples produced from rape oil, soy bean oil and used edible oil were likewise assessed by the same test.
Methyl ester 0.5% 1.0% 2.0%
sample Methyl ester 443 420 321 from animal fat after fract.
crystallization Rape oil 509 359 320 Used edible oil 521 375 322 Soy bean oil 540 483 487 HFRR abrasion values in Vim; reference value of non-additivated fuel: 569 ~.m Example 2 A technical fatty acid distillate made of palm oil and having the following fatty acid composition was used as a raw material for the production of fatty acid methyl esters:
Myristic 1.59%
acid:
Palmitic 52.07%
acid:
Stearic acid:3.93%
Oleic acid: 33.80%
Linoleic 8.37%
acid:
Said fatty acid mixture was converted with the aid of methanol and concentrated sulfuric acid as a catalyst, whereby the corresponding fatty acid methyl esters were obtained.
Mixtures of said fatty acid methyl esters with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
Amount of methyl 0.5% 1.0%
ester HFRR abrasion values in ~.m; reference value of non-additivated fuel: 569 ~m Example 3 Palm stearin produced by fractional crystallization from palm oil and having the following fatty acid composition was used as a raw material for the production of fatty acid methyl esters:
Myristic 1.3%
acid:
Palmitic 73.83%
acid:
Stearic acid:4.84%
Oleic acid: 16.56%
Linoleic 3.52%
acid:
With the aid of methanol and potassium hydroxide as a catalyst, palm stearin was subjected to multistage transesterification, whereby the corresponding fatty acid methyl esters were obtained.
Mixtures of said fatty acid methyl esters with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
Amount of methyl 0.5% 1.0%
ester HFRR abrasion values in ~,m; reference value of non-additivated fuel: 569 pm Example 4 Raw palm oil having the following fatty acid composition was used as a raw material for the production of fatty acid methyl esters:
Myristic acid: 1.07%
Palmitic acid: 44.23%
Stearic acid: 4.68%
Oleic acid: 38.28%
Linoleic acid: 11.74%
With the aid of methanol and potassium hydroxide as a catalyst, said palm oil was subjected to multistage transesterification, whereby the corresponding fatty acid methyl esters were obtained.
Mixtures of said fatty acid methyl esters with a non-additivated sulfur-free diesel fuel were produced and the lubricity was determined by evaluating the HFRR wear test as per CEC F-06-A-96.
Amount of methyl 0.5% 1.0%
ester HFRR ~ 477 ~ 456 HFRR abrasion values in Vim; reference value of non-additivated fuel: 569 ~m
Claims (7)
1. A low-sulfur diesel fuel containing a maximum amount of 0.2% by weight of sulfur and fatty acid monoalkyl esters in an amount of between 10 and 50,000 ppm as lubricity improvers, characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%.
2. A diesel fuel according to claim 1, characterized in that the fatty acid monoalkyl esters are provided as fatty acid methyl esters.
3. A diesel fuel according to any of claims 1 or 2, characterized in that the fatty acid monoalkyl esters were produced from vegetable fats and/or oils.
4. A diesel fuel according to one or several of claims 1 to 3, characterized in that it additionally contains one or more additives for improving the cetane number or for improving the low-temperature behaviour.
5. An agent for improving the lubricity of diesel fuels containing fatty acid monoalkyl esters, characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%.
6. A process for the production of a fatty acid monoalkyl ester whose fatty acid moieties originate from saturated fatty acids by at least 50%, in particular by at least 70%, characterized in that a fatty acid monoalkyl ester whose fatty acid moieties originate from saturated and unsaturated fatty acids is subjected to fractional crystallization or distillation.
7. The use of fatty acid monoalkyl esters as lubricity improvers for low-sulfur diesel fuels, characterized in that the fatty acid moieties of the fatty acid monoalkyl esters originate from saturated fatty acids by at least 50%, in particular by at least 70%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0119403A AT504745B1 (en) | 2003-07-28 | 2003-07-28 | SULPHIDED DIESEL FUEL AND USE OF FATTY ACID MONOGENOES AS A LUBRICITY AMPLIFIER FOR SULFUR ARMS DIESEL FUEL |
| ATA1194/2003 | 2003-07-28 | ||
| PCT/AT2004/000214 WO2005010130A1 (en) | 2003-07-28 | 2004-06-22 | Low-sulphur diesel fuel and use of fatty acid monoalkyl esters as lubricant improvers for low-sulphur diesel fuels |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2533657A1 true CA2533657A1 (en) | 2005-02-03 |
Family
ID=34085018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002533657A Abandoned CA2533657A1 (en) | 2003-07-28 | 2004-06-22 | Low-sulfur diesel fuel as well as the use of fatty acid monoalkyl esters as lubricity improvers for low-sulfur diesel fuels |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20060213118A1 (en) |
| EP (1) | EP1648984A1 (en) |
| CN (1) | CN1860209B (en) |
| AT (1) | AT504745B1 (en) |
| AU (1) | AU2004259773B2 (en) |
| CA (1) | CA2533657A1 (en) |
| HK (1) | HK1097567A1 (en) |
| NZ (1) | NZ545545A (en) |
| WO (1) | WO2005010130A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1674552A1 (en) * | 2004-12-24 | 2006-06-28 | Shell Internationale Researchmaatschappij B.V. | Fuel compositions |
| MY142383A (en) * | 2005-06-10 | 2010-11-30 | Malaysian Palm Oil Board Mpob | Palm- based biodiesel formulation |
| FR2894978B1 (en) * | 2005-12-21 | 2012-06-08 | Total France | COMPONENT ENHANCING CETANE FOR DIESEL FUELS AND DIESEL FUELS CONTAINING IT |
| FR2894977A1 (en) * | 2005-12-21 | 2007-06-22 | Total France Sa | Component improving cetane in diesel fuels and useful to prepare diesel fuels, comprises a stearic acid ester comprised e.g. in (a pure state added with a mixture of) vegetable or animal oil esters in crude or partially hydrogenated form |
| FR2912932B1 (en) | 2007-02-23 | 2011-06-10 | Total France | AQUEOUS SOLUTION FOR THE TREATMENT OF EXHAUST GASES FROM DIESEL ENGINES |
| EP2175010A1 (en) * | 2008-10-10 | 2010-04-14 | Eco Air S.r.l. | Use of fatty acid esters as descaling and lubricating agents |
| CN102295961B (en) * | 2011-07-21 | 2013-09-04 | 淄博润博化工销售有限公司 | Lubricity additive of low-sulfur diesel oil and preparation method thereof |
| CN102311838A (en) * | 2011-08-08 | 2012-01-11 | 华东理工大学 | Low-sulfur diesel oil lubrication additive and preparation method and application thereof |
| CN102977945B (en) * | 2012-11-12 | 2015-07-08 | 黄河三角洲京博化工研究院有限公司 | Diesel oil lubricity improving agent |
| AT513799B1 (en) | 2012-12-18 | 2020-02-15 | Mag Schell Klaus | Process for producing a bio-diesel fuel with a specially designed reactor and quasi-catalytically effective nanoscale structured material surface of the reactor |
| RU2642080C1 (en) * | 2016-08-12 | 2018-01-24 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Вятский государственный университет" | Fuel composition |
| CN107177398B (en) * | 2017-06-07 | 2020-01-31 | 上海鑫灵精细化工有限公司 | Diesel antiwear agent and preparation method thereof |
| CN112779064B (en) * | 2019-11-11 | 2022-12-13 | 中国石油化工股份有限公司 | Low-acid diesel antiwear agent and preparation method and application thereof |
| US11732628B1 (en) | 2020-08-12 | 2023-08-22 | Old World Industries, Llc | Diesel exhaust fluid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4920691A (en) * | 1989-05-22 | 1990-05-01 | Fainman Morton Z | Fuel additive |
| GB9301119D0 (en) * | 1993-01-21 | 1993-03-10 | Exxon Chemical Patents Inc | Fuel composition |
| IT1270954B (en) * | 1993-07-21 | 1997-05-26 | Euron Spa | DIESEL COMPOSITION |
| US5891203A (en) * | 1998-01-20 | 1999-04-06 | Ethyl Corporation | Fuel lubricity from blends of a diethanolamine derivative and biodiesel |
| DE10111857A1 (en) * | 2001-03-08 | 2002-09-12 | Wolfram Radig | Multifunctional additive, for desulfurized mineral diesel fuel, comprises saturated fatty acid esters of lower alcohols and methylated dihydroxybenzenes |
| FI111380B (en) * | 2001-06-08 | 2003-07-15 | Forchem Oy | Process for the preparation of fuel additive and an additive |
| JP5129426B2 (en) * | 2001-09-07 | 2013-01-30 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Diesel fuel, its production and use |
| US20040231234A1 (en) * | 2003-05-19 | 2004-11-25 | May Choo Yuen | Palm diesel with low pour point for climate countries |
-
2003
- 2003-07-28 AT AT0119403A patent/AT504745B1/en not_active IP Right Cessation
-
2004
- 2004-06-22 AU AU2004259773A patent/AU2004259773B2/en not_active Ceased
- 2004-06-22 CN CN2004800281298A patent/CN1860209B/en not_active Expired - Fee Related
- 2004-06-22 CA CA002533657A patent/CA2533657A1/en not_active Abandoned
- 2004-06-22 WO PCT/AT2004/000214 patent/WO2005010130A1/en active Search and Examination
- 2004-06-22 NZ NZ545545A patent/NZ545545A/en unknown
- 2004-06-22 EP EP04737103A patent/EP1648984A1/en not_active Ceased
-
2006
- 2006-01-27 US US11/341,259 patent/US20060213118A1/en not_active Abandoned
-
2007
- 2007-03-09 HK HK07102628.9A patent/HK1097567A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AT504745B1 (en) | 2010-07-15 |
| AU2004259773A1 (en) | 2005-02-03 |
| CN1860209A (en) | 2006-11-08 |
| AU2004259773B2 (en) | 2010-02-11 |
| US20060213118A1 (en) | 2006-09-28 |
| WO2005010130A1 (en) | 2005-02-03 |
| AT504745A1 (en) | 2008-07-15 |
| NZ545545A (en) | 2010-06-25 |
| EP1648984A1 (en) | 2006-04-26 |
| CN1860209B (en) | 2010-12-15 |
| HK1097567A1 (en) | 2007-06-29 |
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