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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
• • 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
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof 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
  • C10L1/18—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
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

• the present invention relates to fuel oils, middle distillates and copolymers contain from ethylene and esters of unsaturated carboxylic acids, and the one show improved cold flow behavior.
• Crude oils and middle distillates obtained by distilling crude oils such as gas oil, Diesel oil or heating oil contain different ones depending on the origin of the crude oils Amounts of n-paraffins which, when the temperature is lowered, are platelet-shaped Crystallize crystals and partially agglomerate with the inclusion of oil. This leads to a deterioration in the flow properties of these oils or distillates, which means, for example, during extraction, transport, storage and / or use of mineral oils and mineral oil distillates can occur. With mineral oils, this crystallization phenomenon can occur during transport Pipelines, especially in winter, to build up deposits on the pipe walls Individual cases, e.g. if a pipeline is at a standstill, even to completely block it to lead.
• the flow and cold behavior of mineral oils and mineral oil distillates is determined by Specification of the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116). Both parameters are in ° C measured.
• Typical flow improvers for crude oils and middle distillates are copolymers of Ethylene with carboxylic acid esters of vinyl alcohol. So you bet after the DE-A-11 47 799 petroleum distillate fuels with a boiling point between about 120 and 400 ° C oil-soluble copolymers of ethylene and Vinyl acetate with a molecular weight between about 1,000 and 3,000. Copolymers which contain about 60 to 99% by weight of ethylene and about are preferred Contain 1 to 40 wt .-% vinyl acetate. They are particularly effective when passed through radical polymerization in an inert solvent at temperatures of about 70 to 130 ° C and pressures of 35 to 2,100 atü (DE-A-19 14 756).
• polymers used as flow improvers contain, in addition to ethylene and vinyl acetate, for example hexene-1 (cf. EP-A-0 184 083), diisobutylene (cf. EP-A-0 203 554) or an isoolefin of the formula wherein R and R 'are the same or different and are hydrogen or C 1 -C 4 alkyl radicals (EP-A-0 099 646).
• Copolymers of ethylene, alkenecarboxylic acid ester and / or vinyl ester and vinyl ketone are also used as pour point depressants and to improve the flow behavior of crude oils and middle distillates of the crude oils (EP-A-0 111 888).
• copolymers based on ⁇ , ⁇ -unsaturated Compounds and maleic anhydride used as flow improvers.
• DE-196 45 603 describes copolymers of 60 to 99 mol% of ethylene derived structural units and 1 to 40 mol% of structural units that are derived from maleic acid, its anhydride or its imides.
• DE-1 162 630 discloses copolymers of ethylene and vinyl esters of straight chain fatty acids with 4 to 18 carbon atoms as Pour point lowering additive for distillate fuels of medium boiling point such as Hot oil or diesel oil.
• EP-A-0 217 602 discloses ethylene copolymers with vinyl esters bearing C 1 to C 18 alkyl radicals as flow improvers for mineral oil distillates with boiling ranges (90-20)% below 100 ° C.
• EP-A-0 493 769 discloses terpolymers which consist of ethylene, vinyl acetate and neononane or Neodecanoic acid vinyl esters are produced, and their use as Additives for mineral oil distillates.
• EP-A-0 746 598 discloses copolymers of ethylene and di-alkyl fumarates in Mix with mineral oils that have a cloud point below -10 ° C.
• the effectiveness of the known additives to improve the properties of mineral oil fractions includes depending on the origin of the mineral oil from which they were obtained and, in particular, from its composition. Additives that are used to set certain property values of fractions of a Crude oils are ideally suited for distillates of crude oils of other origin lead to completely unsatisfactory results.
• Corresponding diesel fuels are characterized by a very low Sulfur content of less than 500 ppm and in particular less than 100 ppm, a low aromatic content and a low density of less than 0.86, in particular less than 0.84 g / ml. They can be used with conventional Do not add or only insufficiently add flow improvers. Problems arise especially those made for use under arctic conditions Winter qualities of diesel fuels with their extreme cold properties, such as e.g.
• a cloud point below -8 ° C and especially below -15 ° C very narrow Distillation cuts with boiling ranges from 20 to 90 vol .-% below 120 ° C, in particular less than 100 ° C and sometimes also less than 80 ° C, and one Distillation volume of 95 vol% at temperatures below 360 ° C, in particular below 350 ° C and especially below 330 ° C.
• the cold properties of such distillates can currently only by adding low-boiling, low paraffin Components such as Kerosene, can be improved satisfactorily.
• composition caused by narrow distillation cuts and low boiling points is problematic for the response behavior of flow improvers to these oils: these oils have a paraffin distribution with a maximum at around C 12 to C 14 and contain only insignificant amounts of the n-paraffins with hydrocarbon chains that crystallize from conventional grades longer as C 18 .
• the cloud points and CFPP values are so low, especially for the winter qualities, that conventional flow improvers do not respond and the cold properties have to be adjusted by diluting with kerosene.
• the task was therefore to create new fuel oils with one compared to the stand the technology to develop improved flowability in the cold.
• the sulfur content of the mineral oils mentioned under A) is preferably less than 500, especially less than 300 ppm, especially less than 100 ppm.
• Your cloud point is preferably below -15 ° C.
• the boiling ranges (90-20%) of the Distillation cuts are preferably less than 100 ° C, especially less than 80 ° C.
• the use of mineral oils with a 95% distillation point is preferred below 360 ° C, especially below 350 ° C, especially below 330 ° C.
• R 1 is preferably hydrogen.
• R 3 preferably represents a linear or branched C 5 -C 24 alkyl radical, particularly preferably a linear or branched C 8 -C 18 alkyl radical.
• R denotes a neoalkyl radical with 7 to 11 carbon atoms, in particular a neoalkyl radical with 8, 9 or 10 carbon atoms.
• the neoalkyl acids from which the above-mentioned neoalkyl radicals can be derived are described by the formula (3):
• R and R are linear alkyl radicals with a total of preferably 5 to 9, in particular 6, 7 or 8, carbon atoms.
• the vinyl ester used for the copolymerization therefore has the formula (4):
• Other suitable comonomers are those which can be derived from acrylic acid:
• Preferred radicals R 3 are, for example, butyl, tert-butyl, pentyl, neopentyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and behenyl.
• the fuel oil compositions according to the invention preferably contain Copolymers in which the comonomers B1) with 85 to 97 mol% and the Comonomers B2) with 3 to 15 mol% are contained. 4 to are particularly preferred 10 mol% B2) and 90 to 96 mol% B1).
• the copolymers mentioned under B) are by the usual copolymerization processes such as suspension polymerization, Solvent polymerization, gas phase polymerization or high pressure bulk polymerization producible.
• High-pressure bulk polymerization is preferred at pressures of preferably 50 to 400, in particular 100 to 300 MPa and Temperatures of preferably 50 to 300, in particular 100 to 250 ° C.
• the Reaction of the monomers is caused by free radical initiators (Radical chain starter) initiated.
• This class of substances includes e.g.
• Oxygen, Hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, Dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-Butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
• the initiators are made individually or as a mixture two or more substances in amounts of 0.001 to 20% by weight, preferably 0.01 to 10 wt .-%, based on the monomer mixture, used.
• the copolymers mentioned under B) preferably have melt viscosities 140 ° C from 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
• the desired melt viscosity of these copolymers is given the composition of the monomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
• Hydrogen, saturated or unsaturated hydrocarbon e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g.
• the moderators become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture, applied.
• the copolymers mentioned under B) can contain up to 4% by weight of vinyl acetate or up to Contain 5 wt .-% of other comonomers.
• Such comonomers can for example vinyl esters, vinyl ethers, acrylic acid alkyl esters, methacrylic acid alkyl esters or higher olefins with at least 5 carbon atoms.
• Preferred as higher Olefins are hexene, 4-methylpentene, octene or diisobutylene.
• the high pressure mass polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tubular reactors, carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, Benzene or toluene can be contained in the reaction mixture. The is preferred solvent-free mode of operation.
• the Polymerization is the mixture of the monomers, the initiator and, if provided used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed.
• the monomer streams be composed differently (EP-A-0 271 738).
• the copolymers mentioned under B) become the mineral oils mentioned under A) or mineral oil distillates in the form of solutions or dispersions.
• This Solutions or dispersions preferably contain 1 to 90, in particular 10 to 80% by weight of the copolymers.
• Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g.
• the fuel oils according to the invention preferably contain 0.001 to 2, in particular 0.005 to 0.5 wt .-% copolymer, based on the Distillate.
• the fuel oils according to the invention can contain further oil-soluble co-additives contain the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
• co-additives are Copolymers containing vinyl acetate or terpolymers of ethylene, polar Compounds that cause paraffin dispersion (paraffin dispersants), as well as comb polymers.
• Oil-soluble polar compounds with ionic ones have been found as paraffin dispersants or polar groups, e.g. Amine salts and / or amides proven by reaction aliphatic or aromatic amines, preferably long-chain aliphatic Amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (cf. US Pat. No. 4,211,534).
• Other Paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be reacted (cf.
• EP-A-0 154 177 the reaction products of alkenyl spirobislactones with amines (cf. EP-A-0 413 279) and according to EP-A-0 606 055, reaction products of Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkenyl ethers of lower unsaturated Alcohols.
• Comb polymers are polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers - Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf.
• EP-A-0 153 176 copolymers of a C 6 -C 24 - ⁇ -olefin and an NC 6 - to C 22 -alkylmaleimide (cf. EP- A-0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
• the new fuel oils can contain other additives, for example Dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives or sludge inhibitors.
• Table 3 shows the effectiveness of the additives as flow improvers for mineral oil distillates using the CFPP test (Cold Filter Plugging Test according to EN 116) in various distillates from Scandinavian refineries.
• the additives are used as 50% solutions in solvent naphtha.
• EVA copolymer ethylene-vinyl acetate copolymer
• V1 melt viscosity V 140 of 125 mPas
• V2 melt viscosity
• Test oil 1 Test oil 3
• Test oil 4 Test oil 5
• Test oil 6 Start of boiling 195 ° C 127 ° C 190 ° C 192 ° C 183 ° C 20% 226 ° C 193 ° C 219 ° C 218 ° C 226 ° C 90% 280 ° C 318 ° C 291 ° C 288 ° C 330 ° C 95% 300 ° C 330 ° C 311 ° C 306 ° C 347 ° C Cloud point -30 ° C -23 ° C -24 ° C -27 ° C -9 ° C CFPP -31 ° C -23 ° C -29 ° C -34 ° C -12 ° C Pour point -30 ° C -42 ° C -27 ° C -27 ° C -21 ° C CFPP-PP -1 ° C 19 ° C -2 ° C -7 ° C 9 ° C Density (15 °)
• the CFPP is determined according to EN116, the PP according to ISO 3016 with an automatic device (Herzog MC 852).

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• Liquid Carbonaceous Fuels (AREA)
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• 1997
  • 1997-07-08 DE DE19729055A patent/DE19729055C2/de not_active Expired - Fee Related
• 1998
  • 1998-06-26 AT AT98111799T patent/ATE262021T1/de active
  • 1998-06-26 DE DE59810973T patent/DE59810973D1/de not_active Expired - Lifetime
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