Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
  • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
  • C10G9/16—Preventing or removing 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1983—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyesters

Definitions

• the present invention relates to a process for reducing the fouling of liquid hydrocarbons during their processing at higher levels
• Temperatures such as in refinery processes.
• hydrocarbons such as crude oil and petroleum refinery intermediates, but also petrochemicals and petrochemical intermediates are generally heated to temperatures between 100 ° C and 550 ° C, often between 200 ° C and 550 ° C. Even in heating and heat exchange systems used as heat transfer hydrocarbons are exposed to such temperatures. In virtually all of these cases, the hydrocarbons used at elevated temperatures form undesirable decomposition or byproducts that can settle and accumulate on the hot surfaces of the heat exchangers. The formation of this
• the crude oils used for this purpose generally contain constituents which carry deposits such as alkali and alkaline earth salts, compounds containing transition metals or complexes such as iron sulfide or porphyrins, sulfur-containing compounds such as mercaptans, nitrogen-containing compounds such as pyrroles,
• fouling deposits The deposits forming in the processing of the hydrocarbons at elevated temperatures and settling on the surfaces in contact with the liquid are called fouling (soiling deposits). They form, in particular, on the hot inner sides of
• the deposits described above are usually higher molecular weight materials, which can range in consistency from tar to gum and popcorn to coke, and their composition can vary in nature and, in many cases, can not be analyzed in detail carbonaceous phases of
• metal compounds can accelerate the hydrocarbon oxidation rate by promoting degenerative chain branching.
• the resulting free radicals can in turn oxidation and
• the petrochemical processes include, for example, the production of ethylene or propylene or the purification of chlorinated hydrocarbons. Also in the processing of biogenic
• Oil-soluble, polar nitrogen compounds are often used to prevent the formation of deposits. These are mainly about
• WO-2011/014215 discloses the use of mono- and bis-imides of polyamines and C10 to Ceo alkyl or alkenyl succinic anhydrides to prevent deposits in mineral oil refining equipment.
• US-5342505 discloses the use of reaction products
• Alkenyl succinic anhydrides, polyols, hydroxyl-bearing amines, polyalkylene succinimides, and polyoxyalkylene amines to reduce deposits upon heating of liquid hydrocarbons.
• dicarboxylic acids react in the condensation with primary amines preferably to form imides and form no or only minor proportions of diamides.
• primary amines preferably to form imides and form no or only minor proportions of diamides.
• EP-0809623 discloses oligomeric and polymeric bis-esters of alkyl or
• Preferred polyhydric alcohols are glycerol and oligomeric glycerols.
• WO-2008/059234 discloses oligo- and polyesters based on
• Hydroxyl groups and their use as emulsifiers. These polymers are also suitable in the oil field as a foaming agent in
• Foam drilling fluids as kinetic gas hydrate inhibitors and as
• Alkenylsuccinic anhydrides, polyols and fatty acids to lower the pour point of hydrocarbon oils. These polymers are the
• Alkenylsuccinic anhydrides, polyols having at least 4 OH groups and Fatty acids for lowering the pour point of hydrocarbon oils Preferably, the stoichiometry of the reactants used for the condensation is selected so that the number of moles of OH groups and carboxyl groups is the same, that is, there is essentially complete esterification.
• WO-2011/076338 discloses cold additives for middle distillates, the polycondensates of a polyol containing two primary OH groups and at least one secondary OH group, with a dicarboxylic acid or its anhydride or esters thereof, which have a Ci 6 - to C 4 o- Alkyl radical or a Ci 6 - to C 4 o-alkenyl carries.
• Heat exchange systems Preferably, these should be nitrogen-free. Specifically, this need exists in the distillation of crude oils and in the further processing of remaining in distillation processes fractions of the
• Ci6-C 4 oo-alkyl or Ci 6 -C 40 o-alkenyl-bearing dicarboxylic acids or anhydrides and polyols the stated tasks.
• higher molecular condensates having a substantially linear polymer backbone have proven particularly useful.
• the invention accordingly is the use of a
• Hydroxyl tendencystenden polyester by polycondensation of a Polyol, which contains two primary OH groups and at least one secondary OH group, with a dicarboxylic acid or its anhydride or esters thereof, which bears a C16 to C 4 oo-alkyl radical or a C16 to C 4 oo-alkenyl radical can be produced , as an antifoulant in the thermal treatment of liquid hydrocarbon media in the temperature range of 100 to 550 ° C.
• Another object of the invention is a method for reducing fouling in a liquid hydrocarbon medium during the thermal treatment of the medium at temperatures between 100 ° C and 550 ° C, wherein the liquid hydrocarbon before and / or during the thermal
• Treatment is added to a hydroxyl-bearing polyester obtained by polycondensation of a polyol containing two primary OH groups and at least one secondary OH group, with a dicarboxylic acid or its anhydride or esters thereof, a Ci6- to C 4 oo-alkyl radical or a Ci6- to C 40 o-alkenyl carries, can be produced.
• Another object of the invention is a method for extending the life of plants for the thermal treatment of liquid
• Hydrocarbon media in the temperature range of 100 to 550 ° C in which to be processed in the plant liquid hydrocarbon medium before and / or during the thermal treatment, a hydroxyl-bearing polyester is added by polycondensation of a polyol, which has two primary OH groups and at least one contains secondary OH group, with a dicarboxylic acid or its anhydride or esters thereof, which carries a Ci6- to C 40 o-alkyl radical or a Ci 6 - to C 40 o-alkenyl radical, can be produced.
• Ci6-C 40 o-alk (en) ylrest carrying dicarboxylic acid with the primary hydroxyl groups of the polyol. It is preferred that the secondary OH groups remain substantially unesterified.
• the preferred structure of the hydroxyl-bearing polyester can therefore be represented, for example, in accordance with formula (A): wherein
• radicals R 1 to R 4 are a Ci6-C 4 oo-alkyl or alkenyl group and the remainder of radicals R 1 to R 4 independently of one another, hydrogen or an alkyl radical having 1 to 3 carbon atoms
• R 5 for a CC bond or an alkylene radical
• n is a number from 1 to 100
• one of the radicals R 1 to R 4 is a Ci6-C 4 oo-alkyl or alkenyl radical and the rest of the radicals R 1 to R 4 independently of one another represent hydrogen or an alkyl radical having 1 to 3 C atoms and
• R 5 for a CC bond or an alkylene radical
• one of the radicals R 1 to R 4 is a Ci6-C 4 oo-AlkyI- or -Alkenylrest, one for a methyl group and the remaining hydrogen.
• one of the radicals R 1 to R 4 is a
• R 5 is a CC single bond.
• one of the radicals R 1 to R 4 is a Ci6-C 40 o-alkyl or alkenyl radical, the remaining radicals R to R 4 is hydrogen and R 5 is a
• the preparation of the dicarboxylic acids or their anhydrides bearing alkyl and / or alkenyl radicals can be carried out by known processes. For example, they can be prepared by heating ethylenically unsaturated dicarboxylic acids with olefins or with chloroalkanes. Preference is given to the thermal addition of olefins to ethylenically unsaturated dicarboxylic acids or their
• Dicarboxylic acids and dicarboxylic acid anhydrides can be hydrogenated to dicarboxylic acids carrying dicarboxylic acids and dicarboxylic anhydrides.
• Preferred dicarboxylic acids and their anhydrides are maleic acid and particularly preferably maleic anhydride. Also suitable are itaconic acid, citraconic acid and their anhydrides and the esters
• one of the radicals R 1 to R 4 is a linear C 6 -C 0 alkyl or alkenyl.
• alk (en) yl radicals carrying dicarboxylic acids or their anhydrides are preferred Olefins having 16 to 40 carbon atoms and especially with 18 to 36 carbon atoms such as 19 to 32 carbon atoms used.
• Olefins having 16 to 40 carbon atoms and especially with 18 to 36 carbon atoms such as 19 to 32 carbon atoms used.
• olefins having 18 to 36 carbon atoms are preferably used, such as mixtures of olefins in the range C20-C22, C20-C24, C24-C28, C26-C28, C 3 oC 3 6.
• olefin mixtures may also contain minor proportions of over the specified range of shorter and / or longer chain olefins such as hexene, heptene, octene, nonene, decene, undecene, dodecene, tetradecene and / or olefins having more than 40 carbon atoms.
• the proportion of shorter and longer-chain olefins in the olefin mixture is preferably not more than 10% by weight.
• Olefins which are particularly preferred for the preparation of the dicarboxylic acids or their anhydrides carrying C -16-C 4 o-alk (en) yl radicals have a linear or at least substantially linear alkyl chain.
• linear or largely linear is meant that at least 50 wt .-%, preferably 70 to 99 wt .-%, in particular 75 to 95 wt .-% such as 80 to 90 wt .-% of olefins a linear portion with 16 to 40 C atoms and especially with 18 to 36 carbon atoms such as having 19 to 32 carbon atoms.
• olefins have in particular technical
• Alkene mixtures proven. These preferably contain at least 50 wt .-%, particularly preferably 60 to 99 wt .-% and in particular 70 to 95 wt .-% such as 75 to 90 wt .-% terminal double bonds ( ⁇ -olefins).
• minor amounts of technical secondary components such as paraffins present be, but preferably not more than 5 wt .-%. Particularly preferred
• Olefin mixtures containing at least 75% by weight of linear ⁇ -olefins having a C chain length in the range of C 2 o to C24.
• one of the radicals R 1 to R 4 is a C 4 -C 4 oo-alkyl or alkenyl radical and especially a C 50 to C 300 such as, for example, a C 5 to C 20 alkyl or alkenyl.
• this alk (en) yl radical is branched.
• these C 4 rC 4 oo-alk (en) yl radicals derived from polyolefins which can be prepared by polymerization of monoolefins having 3 to 6 and in particular having 3, 4 or 5 carbon atoms.
• Particularly preferred monoolefins as the main body of the polyolefins are propylene and isobutene, from which poly (propylene) and poly (isobutene) are formed as polyolefins.
• Preferred polyolefins have an alkylvinylidene content of at least
• alkylvinylidene content is meant the content of the polyolefins to structural units, the
• R 6 or R 7 is methyl, ethyl or propyl and especially methyl, and the other group is an oligomer of the C 3 -C 6 -olefin.
• the alkylvinylidene content can be determined, for example, by means of 1 H-NMR spectroscopy.
• the number of carbon atoms in the polyolefin is between 41 and 400. In a preferred embodiment of the invention, the number of carbon atoms is between 50 and 3000 and in particular between 55 and 200.
• the C 4 iC 0 o-alkyl or alkenyl underlying polyolefins for example, by ionic polymerization accessible and available as commercial products (eg. B Glissopal ®, BASF polyisobutenes of different
• Alkylvinylidene contents and molecular weights are also suitable according to the invention, these being, for example, with respect to the underlying monomers, the molecular weights and / or the alkylvinylidene content.
• Preferred hydroxyl-bearing polyesters can be prepared by reacting a C 16 -C 40 -alkyl- or alkenyl-bearing alkyl or alkenylsuccinic acids and / or their anhydrides with polyols which carry two primary and at least one secondary hydroxyl group.
• Preferred polyols may be monomeric, oligomeric or polymeric structure.
• Polymers and oligomers are collectively referred to herein as polymers.
• R 16 in formula A) preferably represents a radical of the general formula (2)
• r and s independently represent a number from 1 to 9 and
• n in formula A) is 1.
• Preferred monomeric polyols have from 3 to 10 and especially from 4 to 6 carbon atoms. Furthermore, they have at least one and preferably 1 to 6, such as, for example, two to four secondary OH groups, but at most one OH group per C atom.
• Suitable monomeric polyols are, for example, glycerol, 1, 2,4-butanetriol, 1, 2,6-trihydroxyhexane and reduced carbohydrates and mixtures thereof.
• Reduced carbohydrates are here understood to mean polyols derived from carbohydrates and carrying two primary and two or more secondary OH groups. Particularly preferred reduced carbohydrates have 4 to 6 carbon atoms.
• n in formula A) is from 2 to 100, preferably from 2 to 50, more preferably from 3 to 25, and especially from 4 to 20.
• Preferred polymeric polyols have six to 150, especially eight to 100 and in particular nine to 50 carbon atoms. They carry at least one, preferably two to 50 and especially three to 15 secondary
• Polymeric polyols which are suitable according to the invention can be prepared, for example, by polycondensation of polyols having two primary and at least one secondary OH group.
• Preferred polymeric polyol is poly (glycerin).
• Under poly (glycerol) are understood in particular by glycerol derivable structures by polycondensation.
• the degree of condensation according to the invention preferred poly (glycerol) is between 2 and 50, more preferably between 3 and 25 and
• the preparation of poly (glycerol) is well known in the art. It can be carried out, for example, via addition of 2,3-epoxy-1-propanol (glycidol) to glycerol. Furthermore, the preparation of the poly (glycerol) can be carried out by per se known polycondensation of glycerol.
• the reaction temperature in the polycondensation is generally between 150 and 300 ° C, preferably between 200 and 250 ° C.
• the polycondensation of glycerin is normally carried out at atmospheric pressure. As catalyzing acids are
• the catalysts are preferably added to the reaction mixture in amounts of from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, based on the weight of the reaction mixture.
• the polycondensation of glycerol can be carried out solvent-free as well as in the presence of solvent. If the polycondensation takes place in the presence of solvent, its proportion in the reaction mixture is preferably from 0.1 to 70% by weight, for example from 10 to 60% by weight.
• Preferred organic solvents are the dicarboxylic acid which is also used for the condensation of the alk (en) yl radicals, their anhydride or their ester and solvent used with the polyol.
• the polycondensation of glycerol generally takes 3 to 10 hours. This method is analogously applicable to the polycondensation of other polyols.
• the reaction of the alk (en) yl residues-bearing dicarboxylic acid, its anhydride or its ester with the polyol to the hydroxyl-bearing polyester preferably takes place in a molar ratio of 1: 2 to 2: 1, particularly preferably in a molar ratio of 1: 1, 5 bis 1, 5: 1 and especially in the molar ratio of 1: 1.2 to 1, 2: 1 such as equimolar.
• the reaction is carried out with an excess of polyol.
• the polycondensation of the dicarboxylic acid carrying the alkyl radicals, their anhydride or their ester with the polyol is preferably carried out by heating C 16 -C 400 -alkyl- or -alkenyl-substituted dicarboxylic acid or its anhydride or ester with the polyol at temperatures above 100 ° C. and preferably
• Temperatures between 120 and 320 ° C such as at temperatures between 150 and 290 ° C.
• Preferred solvents for the polycondensation of the alk (en) yl radicals-bearing dicarboxylic acid, its anhydride or its ester with the polyol are higher-boiling, low-viscosity organic solvents. Especially preferred
• Solvents are aliphatic and aromatic hydrocarbons and mixtures thereof. Aliphatic hydrocarbons preferred as solvents have 9 to 20 C atoms and in particular 10 to 16 C atoms. They can be linear, branched and / or cyclic. Preferably, they are saturated or at least largely saturated. As solvent preferred aromatic
• Hydrocarbons have 7 to 20 carbon atoms and especially 8 to 16 such as 9 to 13 carbon atoms.
• Preferred aromatic hydrocarbons are mono-, di-, tri- and polycyclic aromatics. These carry in one preferred embodiment one or more such as two, three, four, five or more substituents. With several substituents they may be the same or different.
• Preferred substituents are alkyl radicals having 1 to 20 and in particular having 1 to 5 C atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl , n-pentyl, iso-pentyl, tert-pentyl and neo-pentyl.
• suitable aromatics are examples of suitable aromatics.
• Alkylbenzenes and alkylnaphthalenes For example, aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for. B.
• Benzine 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 particularly suitable.
• solvents based on mineral oils are also based on renewable raw materials and synthetic solvents
• Hydrocarbons which are obtainable, for example, from the Fischer-Tropsch process, are suitable as solvents. Also mixtures of the mentioned
• Solvents are suitable. If the polycondensation in the presence of
• Solvent is carried out, the proportion of the reaction mixture is preferably 1 to 75 wt .-% and especially 10 to 70 wt .-%, such as 20 to 60 wt .-%.
• the condensation is preferably carried out solvent-free.
• catalysts acidic inorganic, organometallic or organic catalysts and mixtures of several of these catalysts are preferred.
• acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel and acid
• Aluminum compounds of the general formula Al (OR 15 ) 3 and titanates of the general formula Ti (OR 15 ) 4 can be used as acidic inorganic catalysts, where the radicals R 5 can each be identical or different and independently are selected from one another from C 1 -C 10 -alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
• the radicals R 15 in Al (OR 15 ) 3 or Ti (OR 15 ) 4 are preferably identical and selected from isopropyl, butyl and 2-ethy
• Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides (R 15 ) 2 SnO, where R 15 is as defined above.
• R 15 dialkyltin oxides
• a particularly preferred representatives of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called Oxo-tin or as Fascat ® mark.
• Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Contain particularly preferred sulfonic acids
• aromatic sulfonic acids and especially alkylaromatic monosulfonic acids having one or more C 1 -C -alkyl radicals and, in particular, those containing C 3 -C 22 -alkyl radicals.
• alkylaromatic monosulfonic acids having one or more C 1 -C -alkyl radicals and, in particular, those containing C 3 -C 22 -alkyl radicals.
• Suitable examples are methanesulfonic acid, butanesulfonic acid,
• Benzenesulfonic acid p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, dodecylbenzenesulfonic acid,
• Ion exchangers can be used as acidic organic catalysts, for example poly (styrene) resins carrying sulfonic acid groups, which can be treated with about
• Catalysts are used according to the invention 0.01 to 10 wt .-%, preferably 0.02 to 2 wt .-% catalyst. In a specific embodiment, the condensation takes place without the addition of catalysts.
• Cie-monocarboxylic acids preferably C 2 - to Ci6-monocarboxylic acids, and especially C 3 - to C 4 monocarboxylic acids such as C 4 - to Ci2 monocarboxylic acids replaced.
• C 3 - to C 4 monocarboxylic acids such as C 4 - to Ci2 monocarboxylic acids replaced.
• Dicarboxylic acids whose anhydrides or their esters replaced by one or more monocarboxylic acids. Furthermore, minor amounts such as up to 10 mol% and in particular 0.01 to 5 mol% of the
• Alk (en) ylsuccinic acids or their anhydrides also by further dicarboxylic acids such as succinic acid, glutaric acid, maleic acid and / or
• Fumaric acid are replaced.
• the hydroxyl-bearing polyesters are prepared in the absence of monocarboxylic acids.
• minor amounts of the polyol are in the reaction mixture to adjust the molecular weight by Ci- to C 30 monoalcohols, preferably C 2 - to C 2 4 monoalcohols and especially C 3 - to C 18 monoalcohols such as C 4 - bis Replaced C 12 monoalcohols.
• Ci- to C 30 monoalcohols preferably C 2 - to C 2 4 monoalcohols and especially C 3 - to C 18 monoalcohols such as C 4 - bis Replaced C 12 monoalcohols.
• C 2 - to C 2 4 monoalcohols preferably C 3 - to C 18 monoalcohols such as C 4 - bis Replaced C 12 monoalcohols.
• C 3 - to C 18 monoalcohols such as C 4 - bis Replaced C 12 monoalcohols.
• the hydroxyl-bearing polyesters are prepared in the absence of monoalcohols.
• the polyol bearing two primary and at least one secondary hydroxyl group can also be replaced by minor amounts of up to 10 mole%, such as 0.01 to 5 mole%, by one or more diols. Preference is given to diols such as ethylene glycol, propylene glycol and / or
• the hydroxyl-bearing polyesters are prepared in the absence of diols.
• Suitable polyols having three or more primary OH groups are, for example
• Trimethylolethane Trimethylolpropane and pentaerythritol.
• Hydroxyl group-bearing polyester is preferably between 4 and 200, particularly preferably between 5 and 150, especially between 7 and 100 and in particular between 0 and 70 such as between 15 and 50 repeating units of dicarboxylic acid and polyol. Under the
• the degree of condensation is understood to be the sum of m + p + q according to formula (A).
• the weight-average molecular weight M w of the hydroxyl group-carrying polyester determined by GPC in THF against poly (ethylene glycol) standard is preferably between 2,000 g / mol and 600,000 g / mol. at
• Polyesters which are derived from C 16 -C 40 -alk (en) yl radicals bearing dicarboxylic acids it is particularly preferably between 2,000 and 100,000 g / mol and in particular between 3,000 and 50,000 g / mol such as between 4,000 and 20,000 g / mol.
• polyesters derived from C 4 iC 4 oo-alk (en) ylreste bearing dicarboxylic acids it is particularly preferably between 3,000 and 500,000 g / mol, in particular between 5,000 and 200,000 g / mol and especially between 8,000 and 50,000 g / mol such as between 10,000 and
• the acid number of the hydroxyl-carrying polyester is less than 40 mg KOH / g and more preferably less than 30 mg KOH / g as
• the acid value can be determined, for example, by titration of the polymer with alcoholic tetra-n-butylammonium hydroxide solution in xylene / isopropanol.
• the hydroxyl number of the polyester is between 40 and 500 mg KOH / g, particularly preferably between 50 and 300 mg KOH / g and in particular between 60 and 250 mg KOH / g.
• Hydroxyl number can be determined by reacting the free OH groups with isocyanate by means of 1 HN R spectroscopy by quantitative determination of the urethane formed.
• the hydroxyl-carrying polyesters used according to the invention are preferably nitrogen-free. Under nitrogen-free according to the invention understood that its nitrogen content below 1,000 ppm by weight and more preferably below
• the nitrogen content can be determined, for example, according to Kjeldahl.
• liquid hydrocarbon medium for various and various petroleum hydrocarbons and petrochemicals.
• petroleum hydrocarbon feedstocks including crude oils. and recoverable fractions thereof, such as naphtha, carburetor fuel, kerosene, diesel, jet fuel, fuel oil, gas oil, vacuum residue, and the like. covered by this definition.
• petrochemicals are olefinic or
• Hydrocarbon used hydrocarbons such as anneliator and / or substituted aromatics from the term "liquid hydrocarbon media”. Furthermore, biogenic raw materials as well as by processing of
• biogenic raw materials accessible products such as animal and vegetable oils and fats and their derivatives such as
• liquid hydrocarbon media may contain non-hydrocarbon ingredients such as salts, minerals, and organometallic compounds
• polyesters used in the invention are the liquid
• Hydrocarbon media are preferably added in amounts of from 0.5 to 5,000 ppm by weight, more preferably from 1, 0 to 1,000 ppm by weight, for example from 2 to 500 ppm by weight.
• the polyesters can be in the liquid
• Hydrocarbon medium dispersed or dissolved Preferably, they are solved.
• polyesters used according to the invention become better
• Preferred solvents are the solvents and solvent mixtures already mentioned as solvents for the condensation reaction between dicarboxylic acid and polyol. Particularly preferred are aromatic solvents.
• the proportion of the polyester in the concentrate is preferably from 5 to 95% by weight, particularly preferably from 10 to 80% by weight and in particular from 20 to 70% by weight, for example from 25 to 60% by weight.
• the addition of the polyester to the liquid hydrocarbon medium preferably takes place before its thermal treatment. It can be carried out discontinuously, for example in the storage container of the liquid hydrocarbon medium or continuously in the supply line to the heat treatment plant. Preferably, it takes place at a point at which the temperature of the liquid hydrocarbon medium at least 10 ° C and especially at least 20 ° C such as at least 50 ° C below the maximum temperature of
• Hydrocarbon media has often been found to aid in the incorporation of the polyester into the liquid hydrocarbon medium by means of static or dynamic mixing devices. Particularly advantageous are the use according to the invention of hydroxyl-bearing polyesters and the process using them in the processing or treatment of liquid hydrocarbon media above 100.degree. C., especially between 150 and 500.degree. C. and in particular between 200.degree. C. and 480.degree. C., for example between 250.degree C and 450 ° C.
• polyesters used according to the invention can be used together with one or more further additives.
• Preferred further additives are pour point depressants and demulsifiers, the latter in particular based on alkoxylated alkylphenol-aldehyde resins.
• the inventive method is generally suitable for reducing and often suppressing fouling in the processing of liquid hydrocarbon media at higher temperatures.
• Heating media used on the 'hot side' of hydrocarbons used by heating and heat exchange systems are used by heating and heat exchange systems.
• the suitability of the additives used according to the invention for suppressing or at least reducing the fouling of liquid hydrocarbons during their thermal treatment can be measured, for example, using commercially available HLPS devices (Hot Liquid Process Simulation).
• the oil to be thermally treated is continuously pumped through a capillary in which a heating element is located. Fouling gradually forms deposits on the heating element, which affect the heat transfer and lead to a pressure drop across the capillary.
• the extent of fouling can be assessed, for example, by the drop in temperature at the outlet of the capillary. A strong drop in temperature during the test period indicates the occurrence of fouling.
• Such measurements are generally considered to be a measure of the tendency of an oil to foul in heat exchangers.
• the acid value of the polymer was 6.5 mg KOH / g, the hydroxyl number was 195 mg KOH / g and the weight average molecular weight was 8,700 g / mol.
• Amounts of poly (isobutenyl) succinic anhydride (prepared by thermal condensation of maleic anhydride with poly (isobutene) having an average molecular weight Mn of 1,000 g / mol and a
• the acid value of the polymer was 8.6 mg KOH / g, the hydroxyl value was 47 mg KOH / g and the weight-average molecular weight was 14,000 g / mol.
• Proportions of poly (isobutenyl) succinic anhydride prepared by thermal condensation of maleic anhydride with poly (isobutene) having an average molecular weight Mn of 2,300 g / mol and a
• Heating rod was about 400 ° C) reached maximum temperature of the oil at the outlet of the stainless steel capillary registered (T1). On the other hand, the temperature of the oil was registered in the same place after a test time of 5 hours (T2). Since the deposits formed by fouling on the heating rod have a poor thermal conductivity, the initial maximum temperature reached correlates indirectly (low initial temperature T1 implies immediate onset of fouling) and the difference in temperatures T2 and T1 directly with the extent of fouling.
• Stainless steel capillary oil (T2) adhering temperature recorded and the experiment ended.
• the determination of the viscosity was carried out according to ASTM D-445, the determination of the density according to DIN EN ISO 12185.
• the pour point was determined according to ASTM D-97.
• the asphaltene content was determined in accordance with IP 143.
• Target temperature of the oil is specified, the inventive method also leads to energy savings.

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• 2013
  • 2013-01-29 BR BR112014011956A patent/BR112014011956A2/pt not_active Application Discontinuation
  • 2013-01-29 WO PCT/EP2013/000254 patent/WO2013113491A1/de active Application Filing
  • 2013-01-29 CN CN201380003891.XA patent/CN104066820B/zh not_active Expired - Fee Related
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  • 2013-01-29 KR KR20147012858A patent/KR20140128289A/ko not_active Application Discontinuation
  • 2013-01-29 EP EP13701920.4A patent/EP2809750A1/de not_active Withdrawn
  • 2013-01-29 CA CA2863267A patent/CA2863267A1/en not_active Abandoned
  • 2013-01-29 EA EA201400774A patent/EA025207B9/ru not_active IP Right Cessation
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