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
• • 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
  • C10L1/18—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

Definitions

• the present invention relates to a method for improving the Cold flow properties of mineral oils and mineral oil distillates, at the same time the filterability of the oils is retained, an additive mixture and the additive Oils.
• 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 cloud point (determined according to ISO 3015), the pour point (determined according to ISO 3016) and the cold filter plugging point (CFPP; determined according to EN 116) described. Both parameters are measured in ° C.
• 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 4 799 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). Mixtures of copolymers are also in the prior art described as a flow improver.
• DE-A-22 06 719 discloses mixtures of ethylene / vinyl acetate copolymers with different comonomer contents to improve the cold flow behavior of middle distillates.
• US 3,961,916 discloses mixtures of various vinyl esters or Acrylic esters with one another or with one another as cold flow improvers for Middle distillates.
• DE-A-196 20 118 discloses terpolymers of ethylene, vinyl acetate and 4-methylpentene-1 as a cold flow improver for middle distillates.
• EP-A-0 796 306 discloses additives for stabilizing the CFPP in middle distillates. These additives contain mixtures of copolymers and terpolymers of ethylene and Vinyl esters. The proportion of the mixtures proposed there is disadvantageous highly crystalline polymer fractions, in particular at low oil and / or Additive temperatures during the additive the filterability of the additive oils affect.
• the percentages by weight relate to the total weight of the mixture of A) and B).
• the mixture of the copolymers preferably consists of 20 to 40% by weight of the Components A) and 60 to 80 wt .-% of component B).
• Component A) is preferably a terpolymer which contains 7 to 11 mol% of structural units which are derived from vinyl acetate.
• Component A) furthermore preferably contains 1 to 4 mol% of structural units which are derived from 4-methylpentene-1.
• the total comonomer content, ie the content of structural units a) and b) is in a preferred embodiment between 10 and 13 mol%.
• component A) contains 5 to 9 methyl groups per 100 methylene groups, with the exception of those methyl groups which originate from vinyl acetate. The number of methyl groups is determined by means of 1 H NMR spectroscopy.
• Copolymer B) is preferably an ethylene copolymer with a Comonomer content of 10 to 20 mol%, preferably 12 to 18 mol%.
• Suitable Comonomers are vinyl esters of aliphatic carboxylic acids with 2 to 15 carbon atoms.
• Preferred vinyl esters for copolymer B) are vinyl acetate, vinyl propionate, Vinyl hexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, in particular here of neononanoic acid, neodecanoic acid and neoundecanoic acid.
• acrylic acid esters are Acrylic acid esters with alcohol residues from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as methyl acrylate, Ethyl acrylate and 2-ethylhexyl acrylate.
• Suitable comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and Norbornen. Ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers are particularly preferred.
• the copolymers used for the additive mixtures are the usual ones Copolymerization processes such as suspension polymerization, Solvent polymerization, gas phase polymerization or High-pressure bulk polymerization can be produced.
• The is preferred High pressure bulk polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350, especially 100 to 250 ° C.
• the reaction of the monomers is caused by radicals initiators (radical chain initiators) initiated. To this class of substance belong 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-butyl cumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azo-bis (2-methylbutyronitrile).
• the initiators are individual or as a mixture of two or more substances in amounts from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
• the additive components preferably have melt viscosities of 140 ° C. 20 to 10,000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
• the melt viscosities of A and B can be the same or different. A> B is preferred.
• the desired melt viscosity of the mixtures is determined by Selection of the individual components and variation of the mixing ratio of the Copolymers discontinued.
• copolymers mentioned under A) and B) can contain up to 5% by weight of further comonomers.
• Such comonomers can be, for example, vinyl esters, vinyl ethers, acrylic acid alkyl esters, methacrylic acid alkyl esters with C 1 -C 20 -alkyl radicals, isobutylene and higher olefins with at least 5 carbon atoms. Hexene, isobutylene, octene and / or diisobutylene are preferred as higher olefins.
• High pressure bulk 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 additive mixtures are mineral oils or mineral oil distillates in the form of Solutions or dispersions added. These solutions or dispersions preferably contain 1 to 90, in particular 5 to 80 wt .-% of the mixtures.
• Suitable solvents or dispersing agents are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial Solvent mixtures such as Solvent Naphtha, ®Shellsoll AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and ®Shellsol D types.
• the specified Solvent mixtures contain different amounts of aliphatic and / or aromatic hydrocarbons.
• the aliphatics can be straight-chain (n-paraffins) or be branched (iso-paraffins).
• Aromatic hydrocarbons can be mono-, be di- or polycyclic and optionally one or more substituents carry.
• improved mineral oils or mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight of the mixtures, based on the distillate.
• the Mixtures also together with one or more oil-soluble co-additives are used, which alone have the cold flow properties of crude oils, Improve lubricating oils or fuel oils.
• oil-soluble co-additives are polar Compounds which effect a paraffin dispersion (paraffin dispersants), and Comb polymers.
• Paraffin dispersants reduce the size of the wax crystals and cause the paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed.
• paraffin dispersants oil-soluble polar compounds with ionic or polar groups, e.g. Amine salts and / or amides proven by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides can be obtained (U.S. 4,211,534).
• paraffin dispersants are copolymers of Maleic anhydride and, ß-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are implemented can (EP-A-0 154 177), the reaction products of alkenylspirobislactones with Amines (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. Alkylphenol-formaldehyde resins are also used as paraffin dispersants suitable.
• 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 -alkyl maleimide (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 mixing ratio (in parts by weight) of the additive mixtures with Paraffin dispersants and / or comb polymers are each 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• Middle distillates are particularly well suited as fuel components.
• Middle distillates are referred to as those mineral oils that pass through Distillation of crude oil and boiling in the range of 120 to 400 ° C, such as kerosene, jet fuel, diesel and heating oil.
• the invention Fuels preferably contain less than 350 ppm and especially less than 200 ppm sulfur.
• the content of n-paraffins determined by GC, the chain lengths of 18 carbon atoms or more is at least 8 area%, preferably with more than 10 area%.
• additive mixtures can be used alone or together with others Additives are used, for example with dewaxing aids, Corrosion inhibitors, antioxidants, lubricity additives, dehazers, Conductivity improvers, cetane number improvers or sludge inhibitors.
• the paraffin content is determined by gas chromatographic separation of the oil (detection using FiD) and calculation of the integral of the n-paraffins ⁇ C 18 in relation to the total integral.
• Test oil 1 (° C) Test oil 2 (° C) Test oil 3 (° C) Test oil 4 (° C) Test oil 5 (° C) Test oil 6 (° C) Start of boiling 180 169 183 183 184 182 20% 267 255 226 232 258 243 90% 350 350 330 358 329 351 95% 365 364 347 378 344 366 Cloud point -0.4 -1 -9 +4 -5 -3 CFPP -3 -3 -12 -4 -9 -6 (90-20)% 83 95 104 126 71 108 n-paraff.
• ⁇ C18 [area%] 11.8 10.9 9.6 10.5 8.5 11.3
• the CFPP value of the oil additized with the specified amount of flow improver was measured directly after the additivation and the rest of the sample was stored at -3 ° C, i.e. below the cloud point. At weekly intervals, the samples were heated to 12 ° C, 50 ml were taken for another CFPP measurement and the rest was stored at -3 ° C.
• CFPP stability in test oil 1 The dosing rate in test oil 1 was 800 ppm additive, 50% in kerosene CFPP (immediately) 1 week 2 weeks 3 weeks 4 weeks A1 + B1 (1: 5) -14 -13 -11 -12 -11 A1 + B2 (1: 3) -12 -14 -12 -11 -12 A2 + B3 (1: 4) -14 -12 -11 -13 -11 A3 + B2 (1: 2) -12 -12 -11 -9 -11 A4 + B3 (1: 4) -13 -12 -13 -11 -11 A1 + B2 (1: 2) -14 -14 -10 -13 -14 A1 + B1 + B2 (1: 2: 2) -14 -12 -12 -15 -12 B1 (comparison) -10 -4 -3 -4 B2 (comparison) -11 -7 -5 -4 -5 B3 (comparison) -10 -9 -7 -7 -5 CFPP stability in test oil 2
• the dosing rate in test oil 2 was 800
• An ADT value ⁇ 15 is regarded as an indication that the gas oil can be used satisfactorily in "normal" cold weather. Products with ADT values ⁇ 25 are said to be non-filterable. Solubility of the additives ADT Blank value (without additive) 3.0 A1 + B2 (1: 5) 5.8 A1 + B3 (1: 3) 6.0 A3 + B1 (1: 1) 12.5 A4 + B2 (1: 4) 8.2 B2 (comparison) 5.4 B2 + 4% EVA copolymer with 13.5% by weight vinyl acetate (according to WO 97/17905) 60 B2 + 10% EVA copolymer with 13.5% by weight vinyl acetate (according to WO 97/17905) not filterable (115 ml in 20 minutes)

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1998
  • 1998-01-24 DE DE19802689A patent/DE19802689A1/de not_active Ceased
  • 1998-12-24 DE DE59809414T patent/DE59809414D1/de not_active Expired - Fee Related
  • 1998-12-24 EP EP98124680A patent/EP0931825B1/fr not_active Expired - Lifetime
  • 1998-12-24 ES ES98124680T patent/ES2206818T3/es not_active Expired - Lifetime
• 1999
  • 1999-01-22 JP JP11014795A patent/JPH11286690A/ja not_active Withdrawn
  • 1999-01-22 US US09/235,724 patent/US6090169A/en not_active Expired - Fee Related
  • 1999-01-22 CA CA002260168A patent/CA2260168C/fr not_active Expired - Fee Related
  • 1999-01-22 NO NO990291A patent/NO990291L/no not_active Application Discontinuation

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