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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
• • 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
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • 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
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
  • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
• • 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
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • 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
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • 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
  • C10L1/2222—(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

Definitions

• This invention relates to paraffin dispersants having lubricity effects suitable mixtures, their use in petroleum middle distillates, such petroleum middle distillates and concentrates therefor.
• Middle distillates such as gas oils, diesel oils or light heating oils, which are obtained by distillation from petroleum oils, have different contents of paraffins depending on the origin of the crude oil.
• solid paraffins are excreted (cloud point or cloud point, CP).
• the platy n-paraffin crystals form a kind of "house of cards structure" and the middle distillate stagnates, although the majority of the middle distillate is still liquid.
• the precipitated n-paraffins in the temperature range between cloud point (cloud point) and pour point (pour point) the flowability of middle distillate fuels is significantly affected;
• the paraffins clog filters and cause uneven or completely interrupted fuel supply to the combustion units. Similar disturbances occur with light fuel oils.
• Ethylene vinyl carboxylate copolymers have long been used as flow improvers.
• a disadvantage of these additives is that the precipitated paraffin crystals tend due to their relative to the liquid part higher density tend to settle more and more at the bottom of the container during storage. As a result, a homogeneous low-paraffin phase forms in the upper container part and a two-phase paraffin-rich layer at the bottom. Since the deduction of the middle distillate mostly takes place slightly above the container bottom both in the vehicle tanks and in storage or delivery tanks of the mineral oil dealer, there is a risk that the high concentration of solid paraffins leads to blockages of filters and metering devices. This danger is greater the further the storage temperature falls below the excretion temperature of the paraffins, since the amount of paraffin precipitated increases with decreasing temperature.
• wax dispersants can reduce these problems.
• EP-A-0 398 101 describes reaction products of aminoalkylene polycarboxylic acids with long-chain secondary amines as paraffin dispersants for petroleum middle distillates.
• the effect is not sufficient in all petroleum middle distillate compositions, especially if they have a low sulfur content of less than 500 ppm.
• DE-A-11 49 843 describes the use of maleamic acids and their amine salts of primary amines and maleic anhydride as corrosion inhibitors and stability improvers for petroleum distillates as well as for the prevention of sedimentation.
• EP-A-0 106 234 describes the use of amine salts of maleamic acids from primary amines and maleic anhydride as corrosion inhibitors for the storage and transport of crude oils.
• lubricity additives can improve the lubricity of low-sulfur diesel fuels.
• the effectiveness is determined according to the standard CEC F-06-A-96 with the HFRR test (High Frequency Reciprocating Rig-Test) by determining the wear size WS1.4 in ⁇ m at 60 ° C; the smaller the WS1.4, the lower the wear and the better the lubricity.
• WO-A-9 746 640 describes a mixture comprising (a) 10 to 90% by weight of at least one imide of a copolymer based on an ⁇ -olefin and an ethylenically unsaturated dicarboxylic acid and a polyamine and (b) 10 to 90 % By weight of at least one reaction product of a poly (C 2-20 -carboxylic acid) having at least one tertiary amino group with secondary amines, and their use as paraffin dispersants in petroleum middle distillates.
• the object was to provide improved products which ensure improved flowability of petroleum middle distillates at low temperature by having such a dispersing effect that delaying or preventing settling of precipitated paraffins and simultaneously contributing to improved lubricity of the petroleum middle distillates ,
• the invention also relates to the use of these mixtures as an additive for petroleum middle distillates, in particular as paraffin dispersant and lubricity additive.
• the invention also relates to these mixtures containing concentrates and petroleum middle distillates.
• Component (a) is a reaction product of a tertiary amino group containing poly (C 2-20 carboxylic acid) with secondary amines.
• the polycarboxylic acid preferably contains at least 3 carboxyl groups, particularly preferably 3 to 12, in particular 3 to 5, carboxyl groups.
• the carboxylic acid groups in the polycarboxylic acid preferably have 2 to 10 carbon atoms, preferably acetic acid groups.
• the carboxylic acid groups are suitably linked to the polycarboxylic acid, for example via one or more C and / or N atoms. Preferably, they are attached to tertiary nitrogen atoms, which are linked in the case of several nitrogen atoms via hydrocarbon chains.
• Component (a) is preferably an amide, amide ammonium salt, ammonium salt or a mixture thereof of aminoalkylcarboxylic acids of the formulas I and II where A is a straight-chain or branched alkylene radical having 2 to 6, preferably 2 to 4, in particular 2 or 3, carbon atoms or the radical of the formula (III) where B is a radical having 1 to 19 carbon atoms, preferably a C 1-19 -alkylene radical, particularly preferably C 1-10 -alkylene radical, in particular a methylene radical.
• A is an ethylene radical.
• the secondary amine may be selected from a variety of amines carrying hydrocarbon radicals, optionally linked together.
• the secondary amine preferably has the formula HNR 2 , wherein the radicals R are independently straight-chain aliphatic radicals, in particular alkyl radicals having 10 to 30, preferably 14 to 24 carbon atoms. They preferably have no heteroatoms or double or triple bonds. Preferably, the radicals R are the same.
• the secondary amines can be bound to the polycarboxylic acid by means of amide structures or in the form of the ammonium salts, partly also by means of amide structures and partly in the form of the ammonium salts. Preferably, there are little or no free acid groups.
• the amines are fully bonded in the form of the amide structures.
• the amides, or amide ammonium salts or ammonium salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid are prepared by reacting the acids with from 0.5 to 1.5 mol of amine, preferably from 0.8 to 1.2 mol Amine per carboxyl group.
• reaction temperatures are about 80 to 200 ° C, wherein for the preparation of the amides, a continuous removal of the resulting reaction water.
• the reaction does not have to be completely led to the amide, but may be 0 to 100 mol% of the amine used in the form of the ammonium salt.
• Especially preferred amines are dioleylamine, dipalmitinamine, dicoco fatty amine and dibehenylamine, especially ditallow fatty amine.
• mixture components (a) according to the invention and their preparation are described in EP-A-0 398 101. Particularly preferred is the reaction product of one mole of ethylenediaminetetraacetic acid and four moles of hydrogenated Ditalgfettamin.
• the mixture components (a) can still small amounts of conductivity in the form of salts, in particular of hydrocarbon-soluble carboxylic acids and sulfonic acids or their metal and ammonium salts. be added.
• the preparation of the mixture components (b) according to the invention is carried out in a manner known per se by reacting maleic anhydride with primary C 8-30 -alkylamine. Preference is given to using primary C 8 - to C 18 -alkylamines in a molar ratio of 1: 1 at from 70 to 100 ° C. according to the process described in DE-A-11 49 843 and EP-A-0 106 234.
• Suitable primary amines are all amines defined within these limits, for example straight-chain or branched octyl, nonyl, decyl, undecyl, dodecyl, tricecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylamine and mixtures these amines.
• Particularly preferred is the reaction product of one mole of maleic anhydride and one mole of tridecylamine.
• the mixtures according to the invention can be prepared by simply mixing components (a) and (b); These mixtures are added to the petroleum distillates in amounts of 10-1000 ppm, preferably 50-500 ppm.
• the proportion of component (a) is 5 to 95, preferably 30 to 95, in particular 50 to 90 wt .-%, the proportion of component (b) 5 to 95, preferably 5 to 70, in particular 10 to 50 wt .-%.
• the polymer blends of the invention are used as an additive for petroleum middle distillates, which are understood to include petroleum, light fuel oils and diesel fuels having a boiling point of about 150 to 400 ° C.
• the polymer mixtures can be added directly to the middle distillates, but preferably as a 20 to 70% by weight solution (concentrate).
• Suitable solvents are aliphatic or aromatic solvents such as xylene or mixtures thereof, furthermore high-boiling aromatic mixtures such as solvent naphtha, as well as middle distillates.
• the amount of the mixture in the petroleum middle distillates is usually 10 to 10,000, preferably 20 to 5000, and more preferably 50 to 1000 ppm.
• middle distillates still contain flow improvers, e.g. based on ethylene / vinylcarboxilate copolymers.
• middle distillates may additionally contain further additives such as conductivity improvers, anti-corrosive additives, lubricity additives, antioxidants, metal deactivators, anti-foam agents, demulsifiers, detergents, cetane number improvers and / or dyes and fragrances.
• the mixtures according to the invention in middle distillates significantly improve the flow properties in the cold by effectively keeping the precipitated paraffin crystals in suspension, so that blockages of filters and lines by sedimented paraffin do not occur. They have a good broad effect and cause so that the precipitated paraffin crystals are dispersed very well in different middle distillates; at the same time they contribute to an improved lubricity of the middle distillates.
• the mixtures according to the invention were tested in two commercial German winter diesel fuels, which correspond to the European diesel fuel standard EN 590; they are referred to as D 1 and D 2 and are characterized by the following physical data: D 1 (97/526) D 2 (96/86) Cloud Point (° C) according to ISO 3015: -6 -6 CFPP (° C) according to EN 116: -10 -8th Density at 15 ° C (kg / m 3 ) according to ASTM D 4052: 841 834 Sulfur content (ppm) according to EN 24260: 160 200 WS1.4 ( ⁇ m) according to CEC F-06-A-96: 542 Distillation according to ISO 3405: Boiling start (° C) 170 171 5% boiling point (° C) 203 193 10% boiling point (° C) 215 200 20% boiling point (° C) 235 212 50% boiling point (° C) 280 249 70% boiling point (° C) 308 282 90% boiling point (° C) 347 329 95% boiling
• the middle distillates were added with the amounts indicated in the table mixtures of the invention PD 1 to PD 4 or Examples 1 and 2 and the flow improver MDFI at 40 ° C with stirring and then cooled to room temperature.
• the additized middle distillates were placed in 500 ml glass cylinders in a room temperature refrigerated bath at a cooling rate of about 14 ° C per hour cooled to -13 ° C and stored at this temperature for 20 hours. Subsequently, the amount and appearance of the paraffin phase were determined and assessed visually.
• Table 1 Dispersing experiments in D 1, CP: -6 ° C, CFPP: -10 ° C, WS1.4: 542 ⁇ m mixture
• test results show that the mixtures according to the invention, with the same total metering, lead to a lower WS1.4 and thus to an improved lubricity of low-sulfur diesel fuels than the respective individual components.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Degasification And Air Bubble Elimination (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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• 1998
  • 1998-10-21 DE DE19848621A patent/DE19848621A1/de not_active Withdrawn
• 1999
  • 1999-10-19 EP EP99953878A patent/EP1124916B1/de not_active Expired - Lifetime
  • 1999-10-19 DK DK99953878T patent/DK1124916T3/da active
  • 1999-10-19 AT AT99953878T patent/ATE342324T1/de active
  • 1999-10-19 JP JP2000577256A patent/JP4603692B2/ja not_active Expired - Fee Related
  • 1999-10-19 KR KR1020017004888A patent/KR100693848B1/ko active IP Right Grant
  • 1999-10-19 ES ES99953878T patent/ES2275357T3/es not_active Expired - Lifetime
  • 1999-10-19 DE DE59913914T patent/DE59913914D1/de not_active Expired - Lifetime
  • 1999-10-19 CA CA002347039A patent/CA2347039C/en not_active Expired - Fee Related
  • 1999-10-19 WO PCT/EP1999/007899 patent/WO2000023541A1/de active IP Right Grant
  • 1999-10-19 US US09/830,149 patent/US6786940B1/en not_active Expired - Lifetime
• 2001
  • 2001-04-19 NO NO20011927A patent/NO329079B1/no not_active IP Right Cessation

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