EP0938534B1 - Use of an additive to improve the properties of heavy oil - Google Patents

Use of an additive to improve the properties of heavy oil Download PDF

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Publication number
EP0938534B1
EP0938534B1 EP97912206A EP97912206A EP0938534B1 EP 0938534 B1 EP0938534 B1 EP 0938534B1 EP 97912206 A EP97912206 A EP 97912206A EP 97912206 A EP97912206 A EP 97912206A EP 0938534 B1 EP0938534 B1 EP 0938534B1
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Prior art keywords
acid
component
weight
carbon atoms
additive
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English (en)
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EP0938534A1 (fr
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Günther Hertel
Michael Feustel
Hakan Byström
Geoffrey Richards
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Clariant Produkte Deutschland GmbH
BYCOSIN AB
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Clariant GmbH
BYCOSIN AB
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    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms 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, 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1885—Carboxylic acids; metal salts thereof resin acid
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1888—Carboxylic acids; metal salts thereof tall oil
    • 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
    • C10L1/238—Macromolecular compounds obtained otherwise than 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic 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, 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
    • C10L1/26—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 invention relates to the use of an additive to improve the Properties of heavy oils and heavy oils with this additive.
  • Heavy oils are used in the processing of petroleum (Crude oils) preserved and are residues of Processing processes such as distillation under Atmospheric pressure or vacuum, thermal or catalytic cracking and the like. Chemically speaking are these residual fuels or Residual fuels (bunker C oils) essentially from paraffinic, naphthenic and aromatic Hydrocarbons of partially high molecular weight Structure.
  • the high molecular components, too Called asphaltenes are not solved, but in a more or less dispersed form from what several problems result.
  • Heavy oils especially in the form of heavy heating oils (Marine Fuel Oils) and mixtures of heavy Heating oils and heavy distillates (Inter Fuel Oils) are used in large quantities mainly as fuel Industrial plants and power plants and as fuel for slower running internal combustion engines, in particular Marine engines.
  • Marine Fuel Oils and mixtures of heavy Heating oils and heavy distillates
  • Inter Fuel Oils are used in large quantities mainly as fuel Industrial plants and power plants and as fuel for slower running internal combustion engines, in particular Marine engines.
  • FR-A-2 172 797 describes basic iron salts of organic acids and in FR-A-2 632 966 a mixture of Iron hydroxide and a basic calcium soap as Tools to improve the combustion of Heavy oils described.
  • US-A-4,129,589 highly basic and oil soluble magnesium salts from Sulphonic acids recommended as oil additives.
  • one Document EP-A-476 196 is a mixture consisting of essentially from (1) at least one oil-soluble Manganese carbonyl compound, (2) at least one oil-soluble neutral or basic alkali or Alkaline earth metal salt from an organic Acid component and (3) at least one oil-soluble Dispersants from the group of succinimides described as an oil additive.
  • US-A-5 421 993 wherein oxalkylated fatty amines and Fatty amine derivatives as corrosion inhibitors, Demulsifiers and pour point depressants for crude oils are described.
  • the amine compounds of formula (VI) and their Manufacturing are in the aforementioned US-A-5 421 993 described in detail here is involved. They are made by oxalkylation of Amines of the formulas (II) to (V) given first with Ethylene oxide and then with propylene oxide with the addition of Obtain bases such as alkali metal hydroxides. The implementation takes place in stages at a temperature of preferably 100 to 160 ° C. The amount of wagered The catalyst / base is generally 0.5 to 3.0% by weight, based on the starting amine used.
  • Preferred metals in the metal salt compound of the Component b) are the alkali or alkaline earth metals (first and second main group of the periodic table), Copper or silver (first subgroup), zinc or Cadmium (second sub-group), titanium or zircon (fourth Subgroup), molybdenum, chromium or tungsten (sixth Subgroup), iron, cobalt or nickel (eighth Subgroup) and lanthanum, cerium or ytterbium (Lanthanide group).
  • Metals are particularly preferred the alkaline earth metals such as barium, beryllium, calcium or Magnesium, copper, zinc, zircon, molybdenum, iron, Nickel, cerium or ytterbium.
  • Preferred acids in the metal salt compound of the Component b) are aliphatic carboxylic acids 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms.
  • the aliphatic rest can be straight or be branched, saturated or unsaturated.
  • the aliphatic carboxylic acids are preferably fatty acids with 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms.
  • the aliphatic carboxylic acids and Fatty acids can be synthetic or natural and as such or as a mixture of two or more acids are present.
  • octanoic acid caprylic acid
  • decanoic acid Capric acid
  • dodecanoic acid lauric acid
  • Tetradecanoic acid myristic acid
  • hexadecanoic acid Palmitic acid
  • octadecanoic acid stearic acid
  • Eicosanoic acid arachic acid
  • docosanoic acid behenic acid
  • Dodecenoic acid laauroleic acid
  • tetradecenoic acid Myristoleic acid
  • hexadecenoic acid palmitoleic acid
  • Octadecenoic acid oleic acid
  • 12-oxy-octadecenoic acid Rosin
  • octadecadienoic acid octadecadienoic acid
  • Octadecatrienoic acid lainolenic acid
  • coconut fatty acid Tallow fatty acid, palm kernel fatty acid and the like.
  • dimeric fatty acids are also preferred acid components. These dimeric fatty acids correspond to the following formula (VII) HOOC-R 2 -COOH where R 2 is a divalent hydrocarbon radical with 34 C atoms (R 2 thus represents the radical containing 34 C atoms which is formed when an unsaturated fatty acid with 18 C atoms is dimerized to form a dicarboxylic acid with a total of 36 C atoms).
  • dimerization means the union of two identical molecules to form a new molecule, the dimer, by means of an addition reaction.
  • the dimerization of C 18 fatty acids is generally carried out at a temperature of 150 to 250 ° C, preferably 180 to 230 ° C, with or without a dimerization catalyst.
  • the dicarboxylic acid obtained corresponds to the formula VII given, where R 2 is the divalent linkage formed in the dimerization of the C 18 fatty acid, which bears the two -COOH groups and has 34 C atoms.
  • R 2 is preferably an acyclic (aliphatic) or a mono- or bicyclic (cycloaliphatic) radical with 34 C atoms.
  • the acyclic radical is usually a branched (substituted) and mono- to trisaturated alkyl radical with 34 carbon atoms.
  • the cycloaliphatic radical generally also has 1 to 3 double bonds.
  • the preferred dimeric fatty acids described are generally a mixture of two or more dicarboxylic acids of the formula VII with structurally different R 2 radicals.
  • the dicarboxylic acid mixture often has a more or less large content of trimeric fatty acids, which were formed during the dimerization and were not removed during the working up of the product by distillation. Similar mixtures are also obtained from natural products, for example in the manufacture of rosin from pine extract.
  • some dimeric fatty acids are given in terms of formula, the hydrocarbon radical bearing the two -COOH groups being an acyclic, monocyclic or bicyclic radical:
  • dimeric fatty acids described are commercially available under the name "dimerized fatty acids" or “Dimer fatty acids” are available and can, as above already mentioned, a more or less high proportion of contain trimerized fatty acids.
  • Preferred acids in the metal salt compound of the Component b) are also aliphatic or aromatic Sulfonic acids with 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms, in aliphatic or aromatic radical.
  • the aliphatic The rest can be straight or branched, saturated or be unsaturated.
  • the aromatic sulfonic acid is preferably a benzenesulfonic acid with an alkyl or Alkenyl radical with 12 to 30 carbon atoms.
  • Metal soaps are particularly preferred.
  • organic metal salts can according to the state of the art Techniques described methods can be produced. there be particularly to the above Documents FR-A-2 172 797, FR-A-2 632 966, US-A-4 129 589 and EP-A-476 196, which are here be included.
  • organic metal salts are said to be oil-soluble or at least be oil dispersible. It is also a neutral or basic product, the latter is preferred.
  • basic denotes as is known such metal salts in which the metal in a stoichiometrically larger amount than the organic one Acid radical is present.
  • the invention have basic metal salt products to be used accordingly a pH of generally 7.5 to 12, preferably from 8 to 10.
  • the additive used according to the invention is produced by mixing components a) and b) together, optionally using a solution or Dispersant.
  • Suitable such means are lower or higher alcohols such as ethanol, isopropanol, Butanol, decanol, dodecanol and the like, lower or higher glycols and their mono- or dialkyl ethers such as ethylene glycol, propylene glycol, diethylene glycol, Tetraethylene glycol, tetrapropylene glycol and the like, low to medium high boiling aliphatic, aromatic or cycloaliphatic hydrocarbons such as toluene, xylene, naphtha and the like, light to medium heavy mineral oils, oil distillates, natural or synthetic oils and derivatives thereof and mixtures of two or more of these solvents.
  • the Bringing the two components together, amine compound and metal salt compound generally takes place at Atmospheric pressure and a temperature of 15 to 100 ° C, preferably 20 to 70 ° C.
  • the heavy oils are marked by a content of the additive described.
  • the effective amount of additive in heavy oil can vary widely Limits vary. Generally the oil contains 2 to 2000 ppm additive, preferably 100 to 1000 ppm.
  • the additive used according to the invention and the heavy oils with this additive have a particularly desirable one Property profile on, and this should be mostly on an unexpectedly high synergism of those used according to the invention Combination of components a) and b) are based. So lies the additive dissolved or highly distributed in the oil. Also in Oils with a high content of asphaltenes and / or other higher molecular compounds are all of these insoluble parts well emulsified or dispersed. The the same applies in the case of sludge, so that too Sludge formation largely eliminated or at least is significantly reduced.
  • the additive used according to the invention is also a highly effective combustion improver. It ensures the complete combustion of heavy Oil while reducing soot formation.
  • the heavy oils according to the invention thus fulfill the requirements mentioned in a surprising high degree.
  • improved storage stability reduced separation of insoluble components
  • improved pumpability due to low viscosity longer service life of the filter systems
  • improved Injection behavior at the combustion devices what additionally contributes to the optimization of the combustion
  • increased corrosion protection for all facilities the good corrosion inhibition of the additive are therefore, above all as fuel for industrial plants and power plants used and also as a fuel for marine engines.
  • the fatty acid used to produce product b 1 is a distilled fatty acid consisting of a mixture (blend) of distilled talc oil fatty acid and resin acid with a molecular weight of about 300 g / mol. Approach: FeCl 3 0.85 l Density 1.48 g / cm 3 NH 3 0.785 l Density 0.91 g / cm 3 fatty acid 0.22 l Density 0.94 g / cm 3 water 0.20 l Petroleum distillate 0.80 l Density 0.82 g / cm 3
  • the 0.85 l FeCl 3 , 0.22 l fatty acid, 0.20 l water and 0.80 l petroleum distillate are mixed together at room temperature (15 to 30 ° C).
  • the 0.785 l of NH 3 are slowly introduced into this mixture with stirring (exothermic reaction).
  • the mixture is heated to 80 to 90 ° C. with stirring, an aqueous and an organic phase being formed.
  • the phase formation can be completed by adding more petroleum distillate.
  • the two phases are separated from one another (decanted), whereupon the organic phase is still centrifuged to remove residual water.
  • the organic phase contains the desired iron carboxylate compound.
  • the fatty acid used to produce product b 2 is an alkylbenzenesulfonic acid with a molecular weight of approximately 322 g / mol.
  • Comparative Examples 1 to 3 the compounds a 1 , a 3 and b 1 are each used alone.
  • the three test solutions are subjected to the same test procedure as the examples according to the invention. Result: All test solutions do not meet the asphaltene dispersibility test or the combustibility improvement test.
  • the additives used therefore have a unexpectedly high effectiveness regarding dispersion of Asphaltenes in heavy oils and also with regard to combustion of heavy oils; this should come from a surprisingly high Synergism of additive components a) and b) result. Because of the beneficial effects of The oils show new additives all those properties that are essential for use in industrial plants, power plants and heavy Ship engines are particularly desired.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (8)

  1. Utilisation d'un additif constitué essentiellement
    a) de 1 à 99 % en masse d'au moins un composé aminé de formule (I) suivante
    Figure 00240001
    où
    n
    vaut 1, 2, 3 ou 4,
    A
    représente un reste de formules (II) à (V)
    Figure 00240002
    Figure 00240003
    où
    R
    représente un groupe alkyle en C6-C22 et
    m
    vaut 2, 3 ou 4,
    x
    est un entier de 5 à 120,
    R1
    représente un atome d'hydrogène, un groupe CH3 ou un atome d'hydrogène et un groupe CH3, les restes oxalkylène étant disposés statistiquement ou en blocs, et
    b) de 1 à 99 % en masse d'au moins un composé de sel métallique oléosoluble ou oléodispersable, neutre ou basique avec un métal du premier groupe principal de la Classification périodique des éléments, du deuxième groupe principal, du premier sous-groupe, du deuxième sous-groupe, du quatrième sous-groupe, du sixième sous-groupe, du huitième sous-groupe ou du groupe des lanthanides de la Classification périodique et d'un acide carboxylique, acide sulfonique, acide ester-phosphorique ou acide estersulfurique avec un reste hydrocarbure présentant à chaque fois 8 à 40 atomes de carbone en tant que composant acide,
    les pourcentages en masse étant relatifs à l'additif, en tant que qu'agent émulsifiant ou dispersant et en tant qu'agent améliorant la combustibilité des huiles lourdes.
  2. Utilisation selon la revendication 1, caractérisée en ce que le composant a) est un composé aminé de formule (VI) suivante
    Figure 00250001
    où
    n
    vaut 1, 2, 3 ou 4,
    A
    représente un reste de formules (II) à (V) indiquées,
    a
    est un nombre de 5 à 30
    b
    est un nombre de 5 à 50 et
    c
    est un nombre de 0 à 40.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le composant b) est un composé de sel métallique avec un métal pris dans le groupe comportant les métaux alcalins, les métaux alcalino-terreux, le cuivre, l'argent, le zinc, le cadmium, le titane, le zirconium, le molybdène, le chrome, le tungstène, le fer, le cobalt, le nickel, le lanthane, le cérium et l'ytterbium, et avec un acide pris dans le groupe comportant des acides carboxyliques aliphatiques présentant 8 à 40 atomes de carbone, des acides gras dimères ayant 36 atomes de carbone et des acides sulfoniques aliphatiques ou aromatiques ayant 8 à 40 atomes de carbone.
  4. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le composant b) est un composé de sel métallique, le métal étant un métal alcalino-terreux, le cuivre, le zinc, le zirconium, le molybdène, le fer, le nickel, le cérium ou l'ytterbium, et le composant acide est un acide gras présentant 8 à 40 atomes de carbone, un acide gras dimère présentant 36 atomes de carbone ou un acide sulfonique aliphatique ou aromatique présentant 8 à 40 atomes de carbone.
  5. Utilisation selon une ou plusieurs des revendications 1 ou 4, caractérisée en ce qu'elle présente une teneur de 20 à 80 % en masse en composant a) et une teneur de 20 à 80 % en masse en composant b).
  6. Utilisation selon une ou plusieurs des revendications 1 ou 4, caractérisée en ce qu'elle présente une teneur de 40 à 60 % en masse en composant a) et une teneur de 40 à 60 % en masse en composant b).
  7. Utilisation selon une ou plusieurs des revendications 1 ou 6, caractérisée en ce qu'elle présente un pH de 7,5 à 12.
  8. Utilisation d'additifs selon une ou plusieurs des revendications 1 à 7 dans des installations industrielles, centrales énergétiques ou moteurs de bateau.
EP97912206A 1996-10-30 1997-10-21 Use of an additive to improve the properties of heavy oil Expired - Lifetime EP0938534B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19643832 1996-10-30
DE19643832A DE19643832A1 (de) 1996-10-30 1996-10-30 Schwere Öle mit verbesserten Eigenschaften und ein Additiv dafür
PCT/EP1997/005793 WO1998018885A1 (fr) 1996-10-30 1997-10-21 Huiles lourdes a proprietes ameliorees et additif pour de telles huiles

Publications (2)

Publication Number Publication Date
EP0938534A1 EP0938534A1 (fr) 1999-09-01
EP0938534B1 true EP0938534B1 (fr) 2001-09-26

Family

ID=7809624

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Application Number Title Priority Date Filing Date
EP97912206A Expired - Lifetime EP0938534B1 (fr) 1996-10-30 1997-10-21 Use of an additive to improve the properties of heavy oil

Country Status (20)

Country Link
US (1) US6488724B1 (fr)
EP (1) EP0938534B1 (fr)
CN (1) CN1235629A (fr)
AR (1) AR008902A1 (fr)
AU (1) AU727164B2 (fr)
BR (1) BR9712463A (fr)
CA (1) CA2270218C (fr)
CO (1) CO4870788A1 (fr)
DE (2) DE19643832A1 (fr)
DK (1) DK0938534T3 (fr)
ES (1) ES2165031T3 (fr)
HU (1) HUP9904230A3 (fr)
ID (1) ID22062A (fr)
MY (1) MY121236A (fr)
NO (1) NO317758B1 (fr)
RU (1) RU2177980C2 (fr)
TR (1) TR199900929T2 (fr)
UA (1) UA52704C2 (fr)
WO (1) WO1998018885A1 (fr)
ZA (1) ZA979704B (fr)

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* Cited by examiner, † Cited by third party
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FR2789999B1 (fr) * 1999-02-18 2004-05-28 Arc Chimie Procede de traitement des melanges d'hydrocarbures contenant des asphaltenes
CA2424910A1 (fr) * 2002-04-23 2003-10-23 Rohm And Haas Company Produits d'addition entre une amine et un acide insature utilises comme dispersants d'asphaltenes dans du petrole brut
ITRM20020509A1 (it) * 2002-10-08 2004-04-09 Chimec Spa Additivo per olio combustibile.
US20040232043A1 (en) * 2003-05-23 2004-11-25 Ravindranath Mukkamala Amine-unsaturated acid adducts as asphaltene dispersants in crude oil
US7625466B2 (en) * 2005-05-20 2009-12-01 Value Creation Inc. System for the decontamination of asphaltic heavy oil and bitumen
CO5930080A1 (es) * 2006-12-06 2008-06-27 Ecopetrol Sa Aditivo anti-coquizante y estabilizante de asfalteno y procedimiento para su obtencion
US8876921B2 (en) * 2007-07-20 2014-11-04 Innospec Limited Hydrocarbon compositions
US9255043B2 (en) 2011-08-31 2016-02-09 Chevron Oronite Company Llc Liquid crude hydrocarbon composition
US9212330B2 (en) * 2012-10-31 2015-12-15 Baker Hughes Incorporated Process for reducing the viscosity of heavy residual crude oil during refining
KR101836946B1 (ko) * 2015-09-17 2018-04-19 이영서 온실가스, 질소산화물 및 입자상 물질 저감을 위한 연료첨가제
US10647929B2 (en) * 2016-03-18 2020-05-12 Korea Research Institute Of Chemical Technology Method for converting heavy oil by means of high asphaltene dispersion
US10781378B2 (en) 2017-12-05 2020-09-22 Fqe Chemicals Inc. Compositions and methods for dissolution of heavy organic compounds
CA3225519A1 (fr) 2021-07-16 2023-01-19 Innospec Limited Compositions de mazout et procedes et utilisations associes

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FR2172797A1 (en) * 1972-02-22 1973-10-05 Gamlen Naintre Sa Oil-sol ferric salts of org acids - for use as paint and varnish siccatives and fuel additives
DE2316230A1 (de) * 1972-04-10 1973-10-18 Drew Chem Corp Heizoel-additiv
US4129589A (en) 1976-07-15 1978-12-12 Surpass Chemicals Limited Over-based magnesium salts of sulphonic acids
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Also Published As

Publication number Publication date
DE59704734D1 (de) 2001-10-31
DK0938534T3 (da) 2001-12-17
CN1235629A (zh) 1999-11-17
NO991949L (no) 1999-04-23
NO991949D0 (no) 1999-04-23
MY121236A (en) 2006-01-28
CA2270218A1 (fr) 1998-05-07
DE19643832A1 (de) 1998-05-07
EP0938534A1 (fr) 1999-09-01
ID22062A (id) 1999-08-26
RU2177980C2 (ru) 2002-01-10
HUP9904230A2 (hu) 2000-04-28
AR008902A1 (es) 2000-02-23
AU727164B2 (en) 2000-12-07
WO1998018885A1 (fr) 1998-05-07
BR9712463A (pt) 1999-12-21
TR199900929T2 (xx) 1999-07-21
HUP9904230A3 (en) 2001-02-28
CA2270218C (fr) 2006-10-31
US6488724B1 (en) 2002-12-03
ZA979704B (en) 1998-07-27
AU4948797A (en) 1998-05-22
UA52704C2 (uk) 2003-01-15
NO317758B1 (no) 2004-12-13
ES2165031T3 (es) 2002-03-01
CO4870788A1 (es) 1999-12-27

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