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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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

Definitions

• the invention relates to mineral oils and mineral oil products with improved flow behavior, which contain a mixture of different types of polyalkyl (meth) acrylates as flow improvers.
• 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.
• Their mode of action was interpreted with the following model: Paraffin-like compounds are built into the growing paraffin crystal surfaces and thus prevent the crystals from growing further and the formation of extensive crystal groups. (See Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 20, p. 548, Verlag Chemie 1981).
• Polymers based on (meth) acrylic acid esters of long-chain alkanols are rightly considered to be effective flow improvers for crude oils (cf. DE-A 17 70 695).
• Polybehenyl acrylate can e.g. considered as a prototype of a flow improver for crude oils.
• Polybehenyl acrylate crystallizes even at a temperature of + 20 degrees C (determined in 0.1% concentration in isooctane by "cloud point" measurement according to DIN 51 597 or ASTM D 97-66), and fulfills the requirements very well to be able to interact with the long-chain paraffins in the crude oil.
• the use of polybehenyl acrylate and comparable long-chain polyacrylates does, of course, stand in the way of the high price of the starting materials.
• paraffin-containing mineral oils from the group of crude oils, vacuum gas oils and residual oils with improved flow properties are described, the mineral oils having in common that the start of the paraffin crystallization is at a temperature ⁇ 30 degrees C. and that they have a content of 1 to 10,000 ppm of at least one polymer P selected from the class of polyalkyl (meth) acrylates or polydialkyl fumarates, the start of crystallization of which is below 15 degrees C.
• the start of paraffin crystallization in the oils as a function of the temperature can be determined as a significant characteristic for determining the flow-improving effect.
• the determination methods see A. Ecker in “Petroleum and Coal” Vol. 38 (6) 281 (1985); A. Ecker, Erdöl, Erdgas 101 , 154 (1982); RL Blaine, NGLI-Spokesman, June 1976) .
• 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 two polymer components P1 and P2 are preferably in a weight ratio of 1:50 to 50: 1, in particular 1:10 to 10: 1 to one another.
• the polyalkyl (meth) acrylates P1 of type A with an association temperature above 15 degrees C will generally be formed from monomers with an alkyl radical> C18 or contain significant proportions thereof.
• Particularly suitable are the polyalkyl (meth) acrylates of C18-C26 alkanols, especially of C18-C24 alkanols, especially polybehenyl acrylate (polymer P1-a).
• the polyalkyl (meth) acrylates P2 of type B) required according to the invention with an association temperature (start of crystallization) ⁇ 15 degrees C are polymers of esters of acrylic or methacrylic acid, in particular with longer-chain alkanols (from C1, preferably from C8 and to C40) thus also those with C16-C24 alkyl radicals, but the selection is made so that said characteristic of the association temperature ( ⁇ 15 degrees C) is met.
• the following selection criteria can be used: - Polymerization or copolymerization of esters of acrylic acid with alkyl residues ⁇ 18 C atoms, in particular 12 - 18 C atoms.
• the molecular weights of the polymers P1 and P2 are generally in the range 5,000 to 1,000,000, preferably 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 H. Rauch-Puntigam, Th.
• 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. Vol. 18, pg. 209 749, J. Wiley 1982).
• 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, methyl or ethyl ester with the higher alcohols.
• the preparation of the polymers can follow the free radical polymerization processes of the prior art are carried out. (See H. Rauch-Punktigam, Th. Völker, Acryl- und Methacryl für n-Verlag, Berlin 1967).
• An inert medium preferably of the mineral oil type itself, for example 100 N oil, is recommended as the polymerization medium.
• 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 used 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 to 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 70-90, 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, the additional polymerization can be initiated by adding the initiator again and, if necessary, by heating. In general, the polymerization is completed in about 5 hours.
• the mineral oils are The mineral oils.
• mineral oils or mineral oil products their properties, in particular their temperature-dependent properties
• Flow behavior is improved by the present invention, it is mainly mineral oil products from the following groups: - 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 have been distilled above 350 degrees C).
• 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 have been distilled above 350 degrees C.
• paraffin crystallization as a function of the temperature is an important parameter for the mineral oil provenances or the petroleum products in question, the determination of which is carried out routinely by a person skilled in the art. As already mentioned, the preferred determination method is the DSC.
• the content of mineral oils in the polymers P is 1-10,000, preferably 50 to 2,000 ppm, in adaptation to the provenances, the flow properties of which need to be improved.
• the polymers P can advantageously with a suitable compatible solvent, for example a hydrocarbon such as Xylene, toluene, kerosene, SHELLSOL® can be diluted.
• a suitable compatible solvent for example a hydrocarbon such as Xylene, toluene, kerosene, SHELLSOL® can be diluted.
• 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 preferably in the form of the solutions mentioned, are advantageously mixed with the mineral oils, such as crude oils, vacuum gas oils or residual oils, 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 model concept can be developed for the unexpected interaction of the two polymer components P1 and P2, the validity of which should, however, have no influence on the present technical teaching:
• the component with the higher self-association temperature influences the crystallization of the long-chain crude oil paraffins.
• the second component with a lower self-association temperature takes effect.
• polybehenyl acrylate as component A), the following approach can be used, for example: In crude oils in which polybehenyl acrylate lowers the pour point by no more than 0 degrees C, mixed components B) with intrinsic crystallization temperatures between 0 and 15 degrees C are advantageous. In crude oils, in which the pour point can be lowered to below -5 degrees C with polybehenyl acrylate, mixed components B) with self-association temperatures ⁇ - 5 degrees C are optimal.
• behenyl acrylate e.g. (ALFOL 20 +) - acrylate (acrylic esters of C20, C22, C24 alcohol) can also be used.
• the polymers P1-a-P2-e were added as a 10% solution in xylene to the crude oils at 80 degrees C. All dosages relate to polymer.
• the pour points were determined in accordance with DIN 51 597 using an automatic measuring device from Herzog, Lauda.
• the pour points in Example 8 were determined in accordance with DIN 51 597 (ASTM 097-66).
• Example 9 Baltic crude oil, 8.6% n-alkane content, pour point without additives 12 degrees C.

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

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Citations (7)

• 1989
  • 1989-07-14 DE DE3923249A patent/DE3923249A1/de not_active Withdrawn
• 1990
  • 1990-07-06 AT AT90112914T patent/ATE75768T1/de not_active IP Right Cessation
  • 1990-07-06 EP EP90112914A patent/EP0407906B1/fr not_active Expired - Lifetime
  • 1990-07-06 DE DE9090112914T patent/DE59000113D1/de not_active Expired - Lifetime
  • 1990-07-13 JP JP2184376A patent/JP2760886B2/ja not_active Expired - Lifetime
  • 1990-07-16 CA CA002021246A patent/CA2021246C/fr not_active Expired - Lifetime

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