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
• • 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
  • C10L1/143—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 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
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
• • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • 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
  • C10L1/197—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 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
  • C10L1/22—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
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
  • C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic 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 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
  • C10L1/26—Organic compounds containing phosphorus
  • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
  • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only

Definitions

• the present invention relates to additives for improving the flow behavior of crude oil. These additives remain effective even under high shear loads.
• Crude oil is the crude oil that comes directly from the earth. Crude oil consists essentially of hydrocarbons, namely alkanes, cycloalkanes and alkylbenzene. In addition, it contains oxygen and sulfur-containing compounds such as naphthenic acids, phenols, aldehydes, thioethers and various heterocyclic compounds.
• the alkanes are a mixture of straight-chain unbranched paraffins having 1 to about 30 carbon atoms, the gaseous and the solid hydrocarbons being dissolved in the liquid.
• This process changes the rheological behavior of the crude oil. Its viscosity increases and its fluidity in the conveyor systems and lines is impaired accordingly. The increase in viscosity can lead to the crude oil stalling.
• the pour point (according to DIN 51 583) or the pour point (yield point; according to DIN ISO 3016) is determined. They are determined in conventional test equipment.
• paraffin inhibitors are also used, which influence the rheological properties of the extracted or transported oil and prevent the formation of paraffin crystals by incorporating them into the resulting structures or by their absorption. In both cases the crystal growth is counteracted, so that small particles are formed which do not allow the formation of networks.
• the addition of paraffin inhibitors therefore enables crude oil to be extracted and transported below the pour point temperature.
• Paraffin inhibitors or flow improvers predominantly have a paraffin-like structure and generally have polar groups in the side chains.
• these branches have the task. counteract the crystal formation of the inhibitor. Chemically, they belong to the group of polyethylenes, polymethacrylates and ethylene-vinyl acetate copolymers.
• paraffin inhibitors to crude oil are not always without side effects. For example, they can adversely affect the viscosity and pour point of the crude oil in system parts such as orifices or centrifugal pumps that are subject to severe shocks.
• This object is achieved by using 0.005 to 0.5% by weight (based on the crude oil) of a copolymer which consists of 65 to 80% by weight of ethylene units and 35 to 20% by weight of vinyl acetate units, together with 0.01 to 1.0% by weight (based on the crude oil) of an antioxidant as a flow improver for crude oil.
• a further improvement in the flowability of crude oil under the action of shear forces is achieved by adding 0.001 to 1.0% by weight (based on the crude oil) of an amine to the crude oil in addition to ethylene-vinyl acetate copolymer and antioxidant.
• the preparation of the copolymers used according to the invention is known. It is carried out by polymerizing the monomer mixture at temperatures from 100 to 350 ° C. and pressures from 1,000 to 8,000 bar in the presence of initiators which form free radicals. The polymerization does not require the presence of a solvent as the reaction medium.
• the ethylene used as comonomer is used in the purity customary for polymerization reactions of at least 99%.
• the polymerization takes place in the presence of catalytic amounts of free radical initiators, e.g. Oxygen, in amounts of 2 to 250 mol.ppm, based on the ethylene to be polymerized.
• free radical initiators e.g. Oxygen
• peroxides such as tert-butyl perbenzoate, dilauroyl peroxide, di-tert-butyl peroxide or azo-butyrononitrile in amounts of 2 to 200 mol.ppm, based on the ethylene, can also be used as initiators.
• the molecular weights are adjusted using moderators, such as aliphatic alcohols and / or carbonyl compounds, saturated, unsaturated or chlorinated hydrocarbons or hydrogen.
• copolymers used according to the invention have molecular weights of 500 to 25,000, determined according to K. Rast, Ber. 550, 1922.
• Antioxidants in the sense of the invention are understood to mean substances which prevent or inhibit undesirable processes caused by the action of oxygen in plastics. These are organic compounds of very different structures. They essentially belong to the group of amines and phenols and also include sulfur and phosphorus compounds. What they have in common is that they intervene in the antioxidation mechanism in different ways. They are mainly used as free radical scavengers, as peroxide decomposers, as metal ion deactivators and as UV absorbers.
• antioxidants have been found to be 2,6-di-tert-butyl-4-methylphenol, 4,4'-thio-bis- (3-methyl-6-tert-butylphenol), bis- (3,3- bis (4'hydroxy-3'-tert-butylphenyl) butanoic acid) glycol ester and tri- (3,4-di-tert-butylphenyl phosphite).
• a general overview can be found in Ullmann's Encyclopedia of Technical Chemistry, 4th edition, volume 8, pages 19 ff (1974); on antioxidants for plastics in the same work, volume 15, page 253 ff (1978).
• the effectiveness of the copolymer / antioxidant combination can be increased significantly by adding amines. It manifests itself in the fact that the flowability of the crude oil is hardly reduced even under high shear loads.
• Suitable amines correspond to the general formula R-NH 2 , where R represents saturated or monounsaturated, straight-chain or branched hydrocarbon radicals having 8 to 18 carbon atoms.
• the copolymer, antioxidant and optionally amine can be added to the crude oil separately, in the form of the dissolved or undissolved substances. You can also dissolve the components in a solvent and add this solution to the crude oil.
• Aromatic hydrocarbons are preferred as solvents, e.g. Aromatic mixtures which are commercially available under the name Solventnaphtha or heavy benzene.
• the pour point of Montrose and Beatrice North Sea crude oil is determined before and after shear stress. The measurement is carried out according to DIN ISO 3016.

Landscapes

• 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)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Lubricants (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (3)

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ID=6252874

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Cited By (1)

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• 1984
  • 1984-12-15 DE DE19843445811 patent/DE3445811A1/de not_active Withdrawn
• 1985
  • 1985-12-06 DE DE8585115541T patent/DE3573272D1/de not_active Expired
  • 1985-12-06 EP EP85115541A patent/EP0186009B1/fr not_active Expired

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