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
  • C10L1/196—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
  • C10L1/196—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
  • C10L1/1966—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 poly-carboxylic

Definitions

• the invention relates to mineral oils, in particular crude oils, vacuum gas oils or residual oils with improved flow behavior.
• the cold behavior of petroleum and petroleum products is decisively influenced by the paraffins they contain.
• the paraffins crystallize on cooling. As a result, the fluidity of the oils is reduced or completely prevented.
• the paraffins generally dissolve in the oil matrix when heated.
• the dewaxing of the oils can be used to improve the low-temperature flow properties.
• pour point improvers From an empirical point of view, the mode of action of such pour point improvers appears to be linked to the presence of certain structural elements, namely sufficiently long alkyl groups to grow from nucleation Paraffin crystals to be installed and the presence of side chains or side groups at greater distances to disrupt the crystal growth. (See Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 20, Verlag Chemie 1981, p. 548 ff).
• the scarcity of resources leads to an increasing exploitation of oil deposits, the processing of which poses greater technological problems than a few years or decades ago. Some of these problems are related to the overall higher, but different, paraffin content of the individual crude oil sources. It has therefore proven to be increasingly difficult to provide additives which control the properties of the crude oils in the desired sense in at least a representative majority of the deposits. If possible, these additives should be inexpensive to manufacture and should be usable within the framework of the usual technologies.
• the present invention is therefore based on the object of providing flow improvers for crude oils in the broadest sense, for vacuum gas oils or residual oils places that, in relation to certain characteristics of these oils, reliably meet the requirements for flow improvers for these oils.
• the paraffins contained in the oils crystallize on cooling while releasing heat.
• the heat released can be recorded by means of differential thermal analysis (DTA) or preferably differential scanning calorimetry (DSC) as an exothermic peak and thus the start of paraffin crystallization can be correctly determined, while the determinations based on visual observation of the "wax appearance point" or the "cloud point””generally fail with dark products and residues.
• DTA differential thermal analysis
• DSC differential scanning calorimetry
• the determination of the start of the paraffin crystallization of the mineral oils is expediently carried out by means of "differential scanning calorimetry (DSC)".
• DSC differential scanning calorimetry
• the standard condition used, under which the start of paraffin crystallization at ⁇ 30 degrees C was determined, is a cooling rate of the oil sample of 10 o K / min.
• the cloud point of a 0.1% solution (% by weight) of the polymer in isooctane is defined according to DIN 51 597 used.
• the polyalkyl (meth) acrylates or polydialkyl fumarates P are examples of the polyalkyl (meth) acrylates or polydialkyl fumarates P.
• the polyalkyl (meth) acrylates PI to be used according to the invention differ on the basis of the definition made from the customary polyalkylacrylates of the prior art (see above) with C18-C24-alkyl radicals whose association temperature (start of crystallization) is approximately 20 degrees C.
• the polyalkyl (meth) acrylates required according to the invention with an association temperature ⁇ 15 degrees C are polymers of esters of acrylic or methacrylic acid with longer-chain alkanols (from C8 and up to C40), including those with C16-C24-alkyl radicals, but the selection is taken such that said criterion of the association temperature is met.
• the following selection criteria can be used: - Polymerization or copolymerization of esters of acrylic acid with alkyl radicals ⁇ 18 C atoms, in particular 12 to 18 C atoms. - Polymerization or copolymerization of esters of meth acrylic acid instead of acrylic acid, especially with C12 - C40 alkyl radicals. - Copolymerization with monomers that are not capable of side chain crystallization, in particular with alkyl radicals ⁇ C10 or branched alkyl radicals with C3 to C40.
• polymers PI or P-II are generally in the range from 5,000 to 1,000,000, preferably from 10,000 to 500,000. In general, compliance with the molecular weight range is ensured by using regulators known per se, for example of the sulfur regulator type . (See Th. Völker, H.
• Mercaptans such as dodecyl mercaptan in amounts of 0.01 to 2% by weight, based on the monomers, are particularly mentioned.
• the molecular weights are determined by means of gel permeation chromatography, using polymethyl methacrylate as the calibration substance (see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed Ed. 18, pg. 209 749, J. Wiley 1982).
• the polydialkyl fumarates P-II which are also to be used according to the invention, correspond in terms of their preparation and molecular weight to those used in the prior art (cf. T. Otsu et al., Mem.Fac.Eng., Osaka, City Univ. 23 , 79-91 (1982); Y. Murata et al., Chem. Econom., Eng. Rev. 17 (10) 18-22 (1985).
• the alkyl radicals correspond to those customary for the (meth) acrylic acid esters, ie those with up to 40 C atoms, preferably 8-40 C atoms, in particular 18-40 C atoms.
• the starting monomers are known per se or they can be prepared in a manner known per se, for example by transesterification of lower (meth) acrylates such as, for example, the methyl or ethyl ester with the higher alcohols.
• the polymers can be prepared following the radical polymerization processes of the prior art. (See H. Rauch-Puntigam, TH. Völker, Acryl- und Methacryl für n-silicon, Springer-Verlag, Berlin 1967).
• An inert medium is preferred as the polymerization medium, preferably of the mineral oil type itself, for example 100 N oil.
• Possible reaction vessels are those which are usually used and which are expediently equipped with a stirrer, heating device, thermometer, reflux condenser and metering line; preferably one works under an inert gas such as carbon dioxide.
• the usual free radical initiators are preferably peresters, peroxides or azo compounds, for example tert. Butyl perbenzoate, tert. Butyl perpivalate in the usual Concentrations, for example 0.1-5% by weight, preferably 0.3-1% by weight, based on the total amount of monomers.
• the process is started at elevated temperature, preferably from 60 degrees C, in particular at 70 ⁇ 5, whereupon initiator is added and the temperature reaches a peak which can be above 80 degrees C, for example 140 ⁇ 10 degrees C. If necessary, a temperature range suitable for postpolymerization can be achieved by heating and / or adding initiator. In general, the polymerization is completed in about 5 hours.
• the mineral oils are The mineral oils.
• the mineral oils or mineral oil products are by definition those in which the start of paraffin crystallization is at a temperature of less than / equal to 30 degrees C.
• the mineral oils to be used according to the invention are understood to mean, for example: - Raw oils - Vacuum gas oils with a boiling point of 320 to 500 degrees C at normal pressure (true boiling point) - Residual oils (distillation residues that would distill over 350 degrees C). (See Winnacker-kuchler, Chemische Technologie, Volume 5, 4th edition, Carl Hanser Verlag, Kunststoff 1981).
• the mineral oils in the polymers P are 1 - 10,000, preferably 50 to 2,000 ppm, in adaptation to the provenances, whose diligence properties need to be improved.
• the polymers P can advantageously be diluted with a suitable compatible solvent, for example a hydrocarbon such as xylene, toluene, kerosene, SHELLSOL®.
• a suitable compatible solvent for example a hydrocarbon such as xylene, toluene, kerosene, SHELLSOL®.
• the solution thus obtained can then be used in the preparation of the mineral oil mixtures. In special cases, this solution can be added to the crude oil directly at the probe head or in the pipeline.
• the polymers P are mixed, preferably in the form of the solutions mentioned, the mineral oils such as crude oils, Vacuum gas oils or residual oils expediently at an elevated temperature, for example at 40 to about 80 degrees C. The effect of the flow-improving additives is retained over the period that is normally required.
• a 0.1% by weight solution of the polyalkyl (meth) acrylate or the polydialkyl fumarate P in isooctane is prepared at 80 ° C. and transferred to a sample vessel with a jacket vessel. The solution is cooled by placing it in a temperature-controlled cooling bath. At intervals of 1 degree C, a check is carried out to see whether the solution becomes cloudy. Upon the occurrence of the very first light haze of the onset of crystallization of the polymers is reached.
• the measurement is started at 80 - 100 degrees C.
• the cooling rate is 10 K / min.
• the start of crystallization is the temperature at which the exothermic peak begins, the so-called "onset" temperature.
• the sample was taken from the cold bath at intervals of 1 degree C and opened Flowability checked.
• the fixed points are the temperatures at which the oil stops flowing.
• the automatic measuring device from Herzog, Lauda (Federal Republic of Germany) can advantageously be used.
• 100 N oil is understood to mean a base oil with a viscosity of 4 mm2 / sec at 100 degrees C, as is customary in public circles.
• the viscosity ⁇ sp / c is determined in accordance with DIN 1342 or 51 562 in chloroform at 20 degrees C.
• the cloud point (CP) determination was given above.
• the polymers PI-1 to PI-4 and VI-1 and VI-2 were added as a 10% stock solution in xylene to the crude oils at 80 degrees C. All dosages relate to polymer.
• the fixed points were determined in accordance with DIN 51 597 using an automatic measuring device from Herzog, Lauda.
• the start of paraffin crystallization (CP) of the crude oils was determined by means of DSC at a cooling rate of 10 K / min.
• North Sea crude oil with an n-alkane content of 14.7% has a CP of 47 degrees C, i.e. greater than 30 degrees C.
• Benchmark without addition + 27 + 1000 ppm PI-1 + 26 + 1000 ppm PI-2 + 27 + 1000 ppm PI-3 + 27 + 1000 ppm VI-2 ⁇ 0

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Emergency Medicine (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Fats And Perfumes (AREA)

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• 1988
  • 1988-05-31 DE DE19883818438 patent/DE3818438A1/de not_active Ceased
• 1989
  • 1989-05-26 EP EP89109550A patent/EP0344644A3/fr not_active Withdrawn
  • 1989-05-31 CA CA 601332 patent/CA1325396C/fr not_active Expired - Fee Related
  • 1989-05-31 JP JP13626989A patent/JPH0229494A/ja active Pending

Patent Citations (4)

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