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
  • C10L1/1966—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
• • 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
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • 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
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
  • C10L10/16—Pour-point depressants
• • 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
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes
• • 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
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
• • 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
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
• • 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
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/10—Specifically adapted fuels for transport, e.g. in pipelines as a gas hydrate slurry

Definitions

• the present invention relates to copolymers comprising C 14 - to C 50 -olefins and at least two different Olefindicarbonklareestern and optionally maleic acid or maleic acid derivatives.
• the olefinic acid esters are on the one hand esters with linear C 18 - to C 50 -alkyl groups and on the other hand esters with short-chain linear, branched or cyclic alkyl groups or esters with aromatic groups.
• the invention further relates to a process for the preparation of such copolymers and their use as a pour point depressant for crude oil, mineral oil and / or mineral oil products, preferably as a pour point depressant for crude oil.
• the reservoir temperature of oil reservoirs is usually above room temperature, for example at 40 ° C to 100 ° C. From such deposits crude oil is still warm, and it cools during or after the pumping naturally more or less quickly to room temperature or at appropriate climatic conditions to temperatures below.
• Crude oils have different proportions of long-chain n-paraffins depending on their origin.
• the proportion of such paraffins may typically be from 1 to 30% by weight of the crude oil. They are often referred to as waxes.
• the paraffins can usually crystallize on cooling when falling below a certain temperature in the form of platelets. The precipitated paraffins significantly affect the fluidity of the oil.
• the platy n-paraffin crystals can form a kind of house structure that encloses the crude oil so that the crude stagnates, although the majority is still liquid. Failed paraffins can continue to clog filters, pumps, pipelines and other equipment or deposit in tanks, causing such a high level of cleaning.
• the lowest temperature at which a sample of oil just flows on cooling is called the pour point. Standardized measuring methods are used to measure the pour point. Crude oils can have pour points above room temperature. Such crude oils may solidify during or after conveying.
• suitable additives prevent the formation of said card house-like structures and thus lower the temperature at which the crude oil solidifies. Furthermore, additives can promote the formation of fine, well-crystallized, non-agglomerating paraffin crystals, so that a trouble-free oil transport is ensured. Such additives are referred to as pour-point depressants or flow improvers.
• Paraffin inhibitors or wax inhibitors are those substances which are said to prevent the deposition of paraffins or paraffin waxes on surfaces in contact with crude oils or other wax-containing oils and / or mineral oil products.
• copolymers of olefins and esters of ethylenically unsaturated dicarboxylic acids It is also known to use for this purpose copolymers of olefins and esters of ethylenically unsaturated dicarboxylic acids.
• GB 1 468 588 discloses a middle oil distillate containing an MSA-olefin copolymer esterified with C 18 to C 44 alcohols to improve low temperature properties.
• An example discloses a copolymer of MSA, C 22/28 ⁇ -monoolefins, and behenyl alcohol.
• US 2,542,542 discloses copolymers of dedecene, tetradecene, hexadecene or octadecene and maleic anhydride as an additive to lubricating oils.
• EP 214 786 A1 discloses the use of copolymers of straight chain olefins, for example, 1-octene, 1-decene, 1-dodecene, 1-tetradecene or 1-octadecene and maleic acid esters to improve the low temperature properties of fuels.
• the alcohols used for the esterification have at least 10 carbon atoms and they can be linear or branched. The document discloses that a mixture of linear and simple methyl branched alcohols can be used.
• EP 1 746 147 A1 discloses the use of copolymers of olefins and esters of ethylenically unsaturated dicarboxylic acids to lower the cloud point of fuel oils and lubricants.
• the copolymers comprise as monomers C 3 to C 50 olefins, preferably C 8 to C 88 olefins and C 1 to C 40 mono- or diesters of ethylenically unsaturated dicarboxylic acids, in particular of maleic acid.
• the C 1 - to C 40 -hydrocarbon radicals of the ester groups are preferably linear or branched C 1 - to C 40 -alkyl radicals.
• Copolymers which comprise both linear and branched alkyl radicals are not disclosed and the document contains no information on the molecular weight of the products obtained.
• the copolymers described are prepared by first reacting the olefins with maleic anhydride to give an olefin-MSA copolymer and, in a second step, in o-xylene (flash point about 30 ° C.) as solvent with alcohols. In this case, the ring of polymerized MSA units is opened. The o-xylene can be removed after completion of the reaction.
• the document further describes additive packages in which the said copolymers, optionally with further components, are formulated in suitable diluents. Diluents may be, for example, aliphatic or aromatic solvents or alkoxyalkanols.
• copolymers for use as pour-point depressants are usually carried out in chemical production facilities and the products are transported from there to the place of use, for example to an oil field or to an offshore platform. Such places of use can be in cold regions of the earth.
• concentrates of the copolymers are usually prepared in hydrocarbons. Such concentrates can be formulated by the users on site in the desired manner to ready-to-use formulations. For example, it is possible to dilute with solvent and / or add further additives.
• Particularly advantageous pour point depressants can be obtained by using C 20 - to C 24 -olefins and C 16 - to C 28 -alcohols for the preparation of said copolymers.
• Ready-to-use formulations may comprise, for example, about 20% by weight of said copolymers in high boiling organic solvents.
• High-boiling organic solvents are used because they also have a high flash point. In particular, solvents having a flash point of at least 60 ° C. are frequently used.
• Such formulations have the disadvantage that they can solidify when handled in a cold environment, for example in an Arctic environment, which is highly undesirable. The problem could be solved for example by the use of formulations with a lower concentration of polymers. As a result, however, larger amounts of solvents are needed, so that this solution must of course be more expensive. Higher costs also result in changes to the infrastructure, such as heated pipes.
• the formulations should have a lower solidification temperature, while having a substantially constant action as a pour point depressant, than known formulations.
• composition of the copolymer described (X) and organic solvents (Y), in particular hydrocarbons having a flash point ⁇ 60 ° C was found.
• copolymers (X) were found, obtainable by means of the method described.
• the novel copolymers (X) are synthesized from ethylenically unsaturated monomers. They comprise as monomers at least one ⁇ -olefin (A) and at least two different Olefindicarbonklareester (B1) and (B2).
• A ⁇ -olefin
• B1 Olefindicarbon Acidester
• B2 Olefindicarbon Acidester
• optionally maleic acid, maleic anhydride, or the corresponding methyl-substituted derivatives and / or further ethylenically unsaturated monomers, in particular monoethylenically unsaturated monomers may be copolymerized into the copolymer (X).
• R 1 is a linear, cyclic or branched, aliphatic and / or aromatic hydrocarbon radical having 14 to 50, in particular 16 to 30 carbon atoms, preferably 18 to 30 carbon atoms and particularly preferably 18 to 28 carbon atoms.
• linear or branched alkyl radicals are preferably linear or branched alkyl radicals, particularly preferably linear alkyl radicals having 14 to 50 carbon atoms, in particular linear alkyl radicals having 16 to 30 carbon atoms, preferably 18 to 30 carbon atoms, particularly preferably 18 to 28 carbon atoms and for example 18 to 24 carbon atoms.
• mixtures may be used which comprise at least two, preferably at least three, ⁇ -olefins having alkyl radicals R 1 , preferably linear alkyl radicals R 1 having 16 to 30 carbon atoms, preferably 18 to 24 carbon atoms.
• the mixtures may in particular be technical mixtures of linear aliphatic ⁇ -olefins.
• Such technical mixtures contain as main constituents aliphatic ⁇ -olefins having an even number of carbon atoms.
• the monomers (B) are monoethylenically unsaturated dicarboxylic acids or derivatives. According to the invention, the monomers (B) are at least two different monomers (B1) and (B2). In addition, optionally monomers (B3) may be present. In addition to (B1), (B2) and, if appropriate, (B3), no further monomers (B) are present.
• R 5 and R 6 are each H or methyl, preferably, in R 5 and R 6 each are H.
• R 2 is a linear n-alkyl radical having 16 to 36 carbon atoms, preferably 16 to 32 carbon atoms, in particular 16 to 26 carbon atoms.
• radicals examples include n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tetracosyl, n-hexacosyl, n- Octacosyl or n-tricontyl radicals.
• R 2 is at least one linear n-alkyl radical having 16 to 22 carbon atoms.
• R 2 is at least one linear n-alkyl radical having 22 to 26 carbon atoms.
• R 3 is at least one radical selected from the group of R 3a , R 3b , R 3c and R 3d , preferably selected from R 3b and R 3c .
• R 3a are linear 1-alkyl radicals having 1 to 10 carbon atoms, preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms.
• linear 1-alkyl radicals R 3a examples include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl radicals; preference is given to n- Propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, particularly preferred are ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl radicals and very particularly preferred are n-butyl radicals.
• R 3b are branched and / or secondary alkyl radicals having 4 to 36 carbon atoms, preferably 4 to 30, particularly preferably 4 to 17 carbon atoms.
• Branched alkyl radicals can be mono- or polysubstituted.
• branched alkyl radicals R 3b include i-butyl, t-butyl, 2,2'-dimethylpropyl, 2-ethylhexyl, 2-propylheptyl, i-nonanol, i-decyl, i-tridecyl, i Heptadecylreste, preferred are t-butyl, 2-ethylhexyl and 2-Propylheptylreste.
• secondary alkyl radicals examples include 2-butyl, 2-propyl, 2-hexyl, 2-heptyl or 2-dodecyl radicals.
• R 3c are unsubstituted or alkyl-substituted, cyclic alkyl radicals having 5 to 18 carbon atoms, preferably 6 to 10 carbon atoms. In particular, they are unsubstituted or alkyl-substituted cyclic alkyl radicals containing 5, 6 or 7 rings. It may also be bicyclic radicals. Examples of R 3c radicals include cyclopentyl, cyclohexyl, cycloheptyl, bornyl or myrthanyl radicals. Preferably, R 3c may be a cyclohexyl radical.
• R 3d is unsubstituted or alkyl-substituted aromatic hydrocarbon radicals having 6 to 36 carbon atoms.
• aromatic hydrocarbon radicals having 6 to 36 carbon atoms.
• examples of such radicals include phenyl, benzyl or toluyl radicals.
• R 4 in the formulas (B1) and (B2) are each a radical selected from the group of H, R 2 and R 3 , where R 2 and R 3 have the meaning defined above, with the proviso that that in each case 50 mol%, preferably at least 75 mol% and particularly preferably at least 95 mol% of the radicals R 4 is H. In one embodiment of the invention, all radicals R 4 are H.
• R 4 in (B1) or (B2) is H, then (B1) and (B2) are monoesters. If R 4 in (B1) or (B2) is R 2 or R 3 , it is diester.
• the monomers (B1) and (B2) comprise COOH groups.
• the COOH groups may be dissociated, and they may also be present in salt form as - COO- 1 / m X m + , where X m + is an m-valent cation.
• X m + may be alkali metal ions such as Na + , K + or ammonium ions.
• the proportion of the monomers (B1) + (B2) with respect to the sum of all monomers (B) is at least 50 mol%, preferably at least 80 mol%, Particularly preferably at least 95 mol% and very particularly preferably exclusively monomers (B1) and (B2) are present.
• the proportion of the radicals R 3 with respect to the sum of the radicals R 2 and R 3 is 1 mol% to 49 mol%, in particular 5 mol% to 45 mol%, preferably 20 mol% to 45 mol% and for example 30 mol% to 40 mol%.
• It may be only one monomer (B1), or it may be several different monomers (B1) with different radicals R 2 .
• It can be only one monomer (B2), or it can be several different monomers (B2) with different radicals R 3 .
• radicals R 3 are radicals R 3a .
• radicals R 3 are radicals R 3b and / or radicals R 3c .
• radicals R 3 are radicals R 3b .
• radicals R 3 are radicals R 3c .
• radicals R 3 are radicals R 3d .
• monomers (C) may optionally be present.
• ⁇ -olefins (A) different ⁇ -olefins such as methyl undecenoate.
• vinyl ethers, vinyl esters, N-vinyl comonomers such as vinylpyrrolidones, vinylcaprolactams, isobutene, diisobutene or polyisobutene.
• the proportion of the monomers (A) with respect to the amount of all monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol% and for example 48 to 52 mol%.
• the proportion of the monomers (B) with respect to the amount of all monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol%, and for example 48 to 52 mol%.
• the amount of additional monomers (C) is not more than 20 mol%, preferably not more than 10 mol%, more preferably not more than 5 mol%, and most preferably no further monomers (C) are present ,
• the weight-average molecular weight M w of the copolymers (X) is, according to the invention, 2000 g / mol to 25000 g / mol, preferably 4000 g / mol to 20 000 g / mol and, for example, 10 000 to 20 000 g / mol.
• this embodiment involves copolymers (X) which contain at most small amounts of maleic anhydride and / or maleic acid or the corresponding methyl derivatives, and in which the olefinic acid ester units are mainly monoesters.
• composition comprising olefin-olefinic acid ester copolymers (X) and hydrocarbons
• copolymers (X) according to the invention and preferred embodiments of the copolymers (X) have already been described above, so that reference is made at this point only to the above description.
• the organic solvents (Y) may in principle be any organic solvents, provided that the copolymers (X) are soluble therein. Preference is given to using solvents which have a flash point ⁇ 60 ° C.
• Organic solvents (Y) may be hydrocarbons.
• hydrocarbons include aliphatic, cycloaliphatic and / or aromatic solvents.
• organic solvents comprising functional groups for example alcohols or esters.
• the organic solvents are nonpolar solvents (Y1) comprising saturated aliphatic hydrocarbon groups, preferably those which have a flash point ⁇ 60 ° C.
• solvents (Y1) include saturated aliphatic alcohols or esters of saturated aliphatic ones Carboxylic acids and saturated aliphatic alcohols, with the proviso that the solvents preferably each have a flash point ⁇ 60 ° C.
• esters include esters of saturated fatty acids having at least 8 carbon atoms with saturated aliphatic alcohols, such as methyl laurate or stearic acid methyl ester. Technical mixtures of various aliphatic esters are commercially available.
• the solvents used may be esters of aliphatic or cycloaliphatic dicarboxylic acids, for example dialkyl esters of cyclohexane-1,2-dicarboxylic acid, such as cyclohexane-1,2-dicarboxylic acid diisononyl ester.
• the organic solvents (Y) are saturated aliphatic hydrocarbons (Y1) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons.
• Hydrocarbons (Y1) are preferably high-boiling aliphatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. Suitable hydrocarbons with a flash point ⁇ 60 ° C include, for example, n-undecane (flash point 60 ° C, boiling point 196 ° C) or n-dodecane (flash point 71 ° C, boiling point 216 ° C).
• hydrocarbons for example mixtures of paraffinic hydrocarbons, mixtures of paraffinic and naphthenic hydrocarbons or mixtures of isoparaffins. It is clear to the person skilled in the art that technical mixtures may still contain small residues of aromatic or unsaturated hydrocarbons.
• Technical mixtures of saturated aliphatic solvents are commercially available, for example technical mixtures of the Shellsol® D series or the Exxsol® D series.
• the organic hydrocarbons (Y) are aromatic hydrocarbons (Y3) or mixtures thereof.
• Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C.
• Suitable aromatic hydrocarbons having a flash point ⁇ 60 ° C include, for example, naphthalene.
• technical mixtures of aromatic hydrocarbons can be used.
• Technical blends of aromatic solvents are commercially available, for example, technical blends of the Shellsol® A series or the Solvesso® series.
• the organic solvents (Y) are preferably aromatic hydrocarbons (Y3).
• the concentration of the copolymers (X) in the composition according to the invention is chosen by the person skilled in the art according to the desired properties of the composition.
• the concentration of the copolymers (X) may be 15 to 75 wt .-%, preferably 15 to 45 wt .-%, particularly preferably 15 wt .-% to 30 wt .-%, for example 17 to 25 wt .-% or 18 to 22 wt .-%, each based on the sum of all components of the composition.
• the composition comprises at least one copolymer (X) and at least one aromatic hydrocarbon (Y3) having a boiling point of at least 175 ° C and a flash point ⁇ 60 ° C, wherein the Concentration, the concentration of the copolymers (X) is 15 to 30 wt .-%, preferably 17 wt .-% to 25 wt .-% and for example 18 to 22 wt .-% with respect to the sum of all components of the composition.
• the novel copolymers (X) can be prepared by free-radically polymerizing the said monomers (A), (B) and optionally (C) in the desired ratio. Radical polymerization techniques are known to those skilled in the art. In this technique, therefore, previously prepared monomers (B1) and (B2) are used for the polymerization.
• the preparation is carried out by means of an at least two-stage process, wherein in a first process step I provides a polymeric starting material from olefins and maleic anhydride or the corresponding methyl-substituted derivatives thereof and in a second process step II the maleic anhydride of the provided educt in a polymer-analogous reaction with alcohols esterified.
• a first process step I provides a polymeric starting material from olefins and maleic anhydride or the corresponding methyl-substituted derivatives thereof and in a second process step II the maleic anhydride of the provided educt in a polymer-analogous reaction with alcohols esterified.
• This procedure results in the formation of monomers (B1) and (B2) derived repeating units of the copolymer (X) thus only in the course of the polymer-analogous reaction.
• a polymeric starting material is provided. This is a copolymer of the olefins (A), a monomer (B3b) and optionally further monomers (C). Preference is given to using maleic anhydride as monomer (B3b).
• the proportion of the monomers (A) with respect to the amount of all the monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol%, and for example 48 to 52 mol%.
• the proportion of the monomers (B3b) with respect to the amount of all the monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol%, and for example 48 to 52 mol%.
• the proportion of optional monomers (C), if present at all, is not more than 20 mol%, preferably not more than 10 mol%, more preferably not more than 5 mol%, and very particularly preferably no further monomers (C ) available.
• the number-average molecular weight M n of the polymeric educt of olefin (A) and monomer (B3b) is usually from 1000 g / mol to 15000 g / mol.
• Olefin-maleic anhydride copolymers having such number average molecular weights M n are known in the art in principle and are commercially available.
• the preparation can be carried out in a manner known in principle by radical polymerization of the ⁇ -olefins (A) and the maleic anhydride or the methyl-substituted derivatives (B3b) in the desired amounts.
• A ⁇ -olefins
• B3b methyl-substituted derivatives
• the in EP 214 786 A1 in particular pages 6, lines 1 to 14 described procedure can be used. It can be polymerized both in bulk and using solvents.
• Suitable solvents are aprotic solvents such as xylene, aliphatics, alkanes, benzene or ketones.
• the solvents are at least one organic solvent (Y), in particular a hydrocarbon, preferably hydrocarbons or hydrocarbon mixtures which have a flash point ⁇ 60 ° C.
• the hydrocarbons may be, for example, saturated aliphatic hydrocarbons (Y 2) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons. Hydrocarbons (Y 2) are preferably high-boiling aliphatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y2), reference is made to the above description of the hydrocarbons (Y2).
• the hydrocarbons may also be aromatic hydrocarbons (Y3) or mixtures thereof.
• Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y3), reference is made to the above description of the hydrocarbons (Y3).
• the radical polymerization can be carried out using conventional, thermally decomposing initiators at 80 ° C to 200 ° C, preferably at 100 ° C to 180 ° C and especially at 130 ° C to 170 ° C.
• the amount of initiator is usually from 0.1 to 10% by weight, based on the amount of the monomers, preferably from 0.2 to 5% by weight and more preferably from 0.5 to 2% by weight.
• the polymerization time is usually 1 to 12 hours.
• the person skilled in the art knows how to set the desired range of the number average molecular weight M n .
• the molecular weight can in principle known manner by the choice of polymerization temperature (the lower, the higher M n ) or by the choice of the reaction medium (aromatic solvents regulate more, ie lower M n , aliphatic regulate less, ie higher M n , without Solvent even higher M n ) are controlled.
• the resulting polymeric starting materials are obtained without solvent or as a solution.
• the copolymer (X) can of course be isolated from the solvent by methods known to those skilled in the art and used as such for process step II.
• the person skilled in the art selects a suitable concentration of the monomers in the solvent for the polymerization. For example, a concentration of the monomers in the solvent of from 20 wt.% To 80 wt.%, For example, 30 wt.% To 60 wt.% Can be selected.
• the provided polymeric educts of olefins and maleic anhydride or methylmaleic anhydride and / or dimethylmaleic anhydride are esterified in a second step with at least one alcohol R 2 OH and at least one alcohol R 3 OH polymer analogous.
• the rings of the copolymerized anhydride groups are opened and the corresponding dicarboxylic acid monoesters or dicarboxylic acid diesters are formed in a polymer-analogous reaction, depending on the amount of the alcohols and the reaction conditions.
• the alcohols R 2 OH are linear aliphatic alcohols and R 2 is a linear 1-alkyl radical having 16 to 36 carbon atoms, preferably 16 to 32 carbon atoms, particularly preferably 16 to 26 carbon atoms.
• alcohols R 2 OH examples include n-hexadecyl alcohol, n-octadecyl alcohol, n-nonadecyl alcohol, n-eicosyl alcohol, n-heneicosyl alcohol, n-docosyl alcohol, n-tetracosyl alcohol, n-hexacosyl alcohol, n-octacosyl alcohol or n-tricontyl alcohol.
• Particularly preferred are alcohols selected from the group of n-docosyl alcohol, n-tetracosyl alcohol and n-hexacosyl alcohol.
• a mixture of at least three alcohols R 2 OH which comprises at least 1-docosyl alcohol, 1-tetracosyl alcohol and 1-hexacosyl alcohol.
• the amount of said three alcohols is preferably at least 70% by weight, preferably at least 80% by weight, with respect to the amount of all the alcohols R 2 OH used.
• alcohols R 3a OH include ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, preferred are n-propanol, n-butanol , n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, particularly preferably ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol and very particularly preferably n butanol.
• Examples of branched and / or secondary alcohols R 3b OH include i-butanol, t-butanol, 2,2'-dimethylpropanol-1, 2-ethylhexanol-1,2-propylheptanol-1, i-nonanol, i-decanol, i Tridecanol or i-heptadecanol, 2-butanol, 2-heptanol, 2-hexanol, 2-octanol or 2-decanol, preferred are t-butanol, 2-ethylhexanol-1 and 2-propylheptanol-1 and i-heptadecanol.
• alcohols R 3c OH examples include cyclopentanol, cyclohexanol, cycloheptanol, borneol, isoborneol, menthol, neomemthol, isomenthol, neoisomenthol, or myrthanol.
• alcohols R 3d examples include phenol, toluene or benzyl alcohol.
• the alcohols R 3 OH are alcohols R 3a OH.
• the alcohols R 3 OH are alcohols R 3b OH and / or alcohols R 3c OH.
• the alcohols R 3 OH are alcohols R 3b OH.
• the alcohols R 3 OH are alcohols R 3c OH.
• the alcohols R 3 OH are alcohols R 3d OH.
• the proportion of the alcohols R 3 OH with respect to the sum of the alcohols used for the esterification R 2 OH and R 3 OH 1 mol% to 49 mol%, preferably 5 mol% to 45 mol%, 20 mol% to 45 mol% and, for example, 30 mol% to 40 mol%.
• the amount of the alcohols R 2 OH and R 3 OH used together is 0.5 to 1.5 mol / mol of anhydride units in the copolymer (X), preferably 0.8 to 1.2 mol / mol, particularly preferably 0, 9 to 1.1 mol / mol, very particularly preferably 0.95 to 1.05 mol / mol.
• the polymeranloge esterification is usually carried out at a temperature of 130 ° C to 180 ° C, preferably 140 ° C to 160 ° C.
• the esterification can be carried out in bulk or in the presence of inert solvents.
• the reaction mixture should remain liquid and homogeneous at the reaction temperature to ensure homogeneous reaction.
• the reaction can be carried out without pressure or under pressure.
• the alcohols can be completely charged or added sequentially.
• the esterification can be carried out for example in the presence of esterification catalysts such as para-toluenesulfonic acid, methanesulfonic acid or sulfuric acid.
• esterification catalysts such as para-toluenesulfonic acid, methanesulfonic acid or sulfuric acid.
• a suitable procedure is for example in the WO 2014/095408 A1 disclosed.
• the amount may be 0.05 to 0.5 mol% based on the alcohols.
• process step I is carried out in solvents, it is advantageously possible to use a solution of the polymeric starting materials obtained in process step II for process step II. Otherwise, the polymeric starting materials for process step II are dissolved in suitable inert solvents.
• the esterification is preferably carried out in hydrocarbons, preferably in hydrocarbons or hydrocarbon mixtures with a flash point ⁇ 60 ° C. In this procedure, the esterification directly gives the composition according to the invention of at least one copolymer (X) and at least one hydrocarbon.
• the hydrocarbons may be, for example, saturated aliphatic hydrocarbons (Y 2) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons.
• the hydrocarbons may also be aromatic hydrocarbons (Y3) or mixtures thereof.
• Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y3), reference is made to the above description of the hydrocarbons (Y3).
• process step II is carried out in solution and the amount of hydrocarbons used is such that a composition of at least one copolymer (X) and at least one hydrocarbon in a concentration of 15 to 85 wt .-% is formed. It can be prepared equal to a ready-to-use composition in the concentrations as described above or it can be a concentrate, for example, produced at a concentration of 50 to 70 wt .-%, which then has to be further diluted on site to the ready-to-use concentration.
• the invention further relates to copolymers (X) which are obtainable by the process just described.
• copolymers (X) which are obtainable by the process just described.
• process parameters reference is made to the method just described.
• copolymers (X) according to the invention can be used as pour-point depressants for crude oil, mineral oil and / or mineral oil products by adding at least one of the described copolymers (X) to the crude oil, the mineral oil and / or the mineral oil products.
• the copolymers (X) according to the invention are used as pour point depressants for crude oil by adding to the crude oil at least one of the copolymers (X) described above.
• pour point depressants reduce the pour point of crude oils, mineral oils and / or mineral oil products.
• the term "pour point” refers to the lowest temperature at which a sample of oil just flows when it cools down. Standardized measuring methods are used to measure the pour point.
• the copolymers (X) can be used as such.
• the copolymers (X) according to the invention are preferably used in the form of a solution.
• formulations of the copolymers (X) can be used, which may contain other components in addition to solvents.
• the copolymers (X) according to the invention should be homogeneously dispersed in the solvents used, preferably dissolved therein. In principle, all solvents which meet these requirements are suitable. Of course, mixtures of different solvents can be used.
• it is at least one organic solvent (Y), preferably an organic solvent having a flash point ⁇ 60 ° C.
• the organic solvents are nonpolar solvents (Y1) comprising saturated aliphatic hydrocarbon groups, preferably those which have a flash point ⁇ 60 ° C.
• solvents (Y1) include saturated aliphatic alcohols or esters of saturated aliphatic carboxylic acids and saturated aliphatic alcohols, with the proviso that the solvents preferably each have a flash point ⁇ 60 ° C.
• esters include esters of saturated fatty acids having at least 8 carbon atoms with saturated aliphatic alcohols, such as methyl laurate or stearic acid methyl ester. Technical mixtures of various aliphatic esters are commercially available.
• the solvents used may be esters of aliphatic or cycloaliphatic dicarboxylic acids, for example dialkyl esters of cyclohexane-1,2-dicarboxylic acid, such as cyclohexane-1,2-dicarboxylic acid diisononyl ester.
• the organic solvents are saturated aliphatic hydrocarbons (Y 2) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons. Hydrocarbons (Y 2) are preferably high-boiling aliphatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y2), reference is made to the above description of the hydrocarbons (Y2).
• the organic solvents are aromatic hydrocarbons (Y3) or mixtures thereof.
• Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y3), reference is made to the above description of the hydrocarbons (Y3).
• compositions of copolymers (X) and organic solvents (Y), preferably hydrocarbons may be used.
• such compositions can be obtained by using hydrocarbons, in particular hydrocarbons or hydrocarbon mixtures having a flash point ⁇ 60 ° C., for the preparation of the copolymers (X), likewise as described above.
• Ready-to-use formulations of the copolymers (X) may of course comprise further components.
• additional wax dispersants to the formulation.
• Wax dispersants stabilize formed paraffin crystals and prevent them from sedimenting.
• wax dispersants for example, alkylphenols, alkylphenol-formaldehyde resins or organic sulfonic acids such as dodecylbenzenesulfonic acid can be used.
• the concentration of the copolymers (X) in ready-to-use formulations can be from 0.5 to 45% by weight, preferably from 15 to 45% by weight, particularly preferably from 15% by weight to 30% by weight, for example from 17 to 25% by weight. -% or 18 to 22 wt .-%, each based on the sum of all components of the composition.
• the preparation of copolymers (X) and optionally of a concentrate of the copolymers (X) in solvents naturally takes place in a chemical plant
• the preparation of the ready-to-use formulation can be made as close as possible to the point at which the formulation is to be injected.
• the crude oil, mineral oil and / or mineral oil products preferably the crude added amount of copolymers of the invention (X) is measured by the expert so that the desired reduction of the pour point is achieved, where it is natural for the skilled person that the necessary amount depends on the type of crude oil. On the other hand, it is desirable for economic reasons to use as little as possible pour-point depressant.
• the copolymers (X) in an amount of from 50 to 1500 ppm with respect to the crude oil, mineral oil and / or mineral oil products.
• the amount is 100 to 1000 ppm, more preferably 250 to 600 ppm and for example 300 to 600 ppm.
• the amounts indicated relate to the copolymer (X) itself.
• the oil is crude oil.
• copolymers (X) or their solutions or formulations are added to the crude oil before the precipitation of waxes has begun, ie. at a temperature above the pour point.
• the addition may be made at a temperature not lower than 10 ° C above the pour point.
• the location of the addition of the copolymers (X) to the crude oil is suitably selected by the person skilled in the art.
• the addition can be made, for example, in the formation, downhole, wellhead, or pipeline.
• copolymers (X) or their solutions or formulations are injected into a crude oil pipeline.
• the injection may be on the oil field, i. at the beginning of the crude oil pipeline, but the injection can of course also take place at another location.
• it may be a pipeline that leads from an offshore platform to the mainland.
• the copolymers (X) can prevent pipelines from clogging if the crude cools during transportation in the pipeline. This danger is inherently particularly pronounced when it is a pipeline in a cold environment, e.g. in arctic environment.
• the copolymers (X) or their solutions or formulations are injected into a production well.
• a production well may be an offshore production well.
• the injection can be made approximately at the point where oil from the formation flows into the production well. In this way, the solidification of the crude oil in the production well and in downstream transport pipelines can prevent excessive increase of its viscosity as well as the cross-sectional constriction of pipes by paraffin deposits.
• the injection may be umbilical.
• a flexible rod comprising at least one pipe and optionally electrical lines or control lines in a protective sheath is introduced axially into a borehole or a pipeline.
• the formulation of the copolymers (X) can be injected exactly at the desired location.
• copolymers (X) according to the invention can also be used for other purposes.
• the above-described copolymers (X) or their solutions or formulations are used to prevent wax deposits on surfaces which are in contact with crude oil, mineral oil and / or mineral oil products. They are preferably surfaces which are in contact with crude oil.
• the use takes place by adding at least one of the copolymers (X) or their solutions or formulations to the crude oil, mineral oil and / or the mineral oil products.
• Preferred solutions and formulations have already been mentioned and also the nature of the use is analogous to the use as a pour point depressant.
• copolymers (X) By the partial replacement of long-chain, linear alkyl groups by short linear alkyl groups, branched alkyl groups, cyclic alkyl groups or hydrocarbon groups, copolymers (X) are obtained which can be processed into formulations, in particular about 20% formulations which have lower solidification points than those corresponding formulations of unmodified copolymers, ie exclusively copolymers comprising linear alkyl groups. As a result, the handling of such formulations is facilitated, especially in colder environment, such as Arctic environment.
• C 20/24 olefins Commercially available mixture of ⁇ -olefins, main components C 20 , C 22 and C 24 olefins C 18 ⁇ 3% by weight C 20 35 to 55% by weight C 22 25 to 45% by weight C 24 10 to 26% by weight C 26 ⁇ 2% by weight > C 26 ⁇ 0.1% by weight
• the solids content was determined by drying the products at 120 ° C, 2 h in a vacuum oven.
• the mass-average molecular weights and polydispersities are measured with a GPC system at 35 ° C.
• the system includes two columns as well as refractive index detector and UV detector.
• the eluant used is THF with 0.1% trifluoroacetic acid.
• the pour point determination was performed according to ASTM D 5853 Test Method for Pour Point of Crude Oils.
• the pour point is the minimum temperature at which a sample of a tested oil is just flowable.
• ASTM D 5853 a sample of the oil is cooled in 3 ° C increments and the flowability is tested after each step.
• a crude oil from the "Landau" oil field in southwestern Germany (Wintershall Holding GmbH) with an API grade of 37 and a pour point of 27 ° C was used.
• the polymers to be tested were used for the oil in a concentration of 300 ppm of polymer based on the crude oil.
• the pour point of a 20% strength solution of the polymer according to the invention itself was measured.
• the resulting solutions were diluted to a concentration of 20% by weight using Solvesso® 150.
• the pour point is the minimum temperature at which the 20% solution is just still flowable.
• the 20% pour point was determined according to ASTM D5985-02 (approved Jan. 1, 2014).
• the no-flow point of a 20% strength solution of the polymer according to the invention itself was measured.
• the resulting solutions were diluted to a concentration of 20% by weight using Solvesso® 150.
• the no-flow point is the temperature at which the 20% solution is just no longer flowable.
• the 20% pour point was determined according to ASTM D 7346-15 (approved July 1, 2015).
• copolymer I and 11.71 g of isoheptadecanol are melted at an external temperature of 85 ° C and after melting 20.54 g of Solvesso® 150 and 10 mg of para-toluenesulfonic acid are added. Heat to 150 ° C outside temperature and stir for 2 hours. Then 25.45 g of alcohol mixture I (C 16/22 -alcohols) are added and the mixture is stirred for a further 4 h.
• Comparative Experiment 1 (Table 1) a product according to the prior art was used, namely a product based on the MSA-olefin copolymer I, in which the MSA units are opened only with a linear C 16/22 alcohol.
• the copolymer lowers the pour point of the crude oil tested from 27 ° C to 9-12 ° C; the 20% solution solidifies at about 6.5 ° C and the pour point of the 20% solution is 9 ° C.
• Examples 3, 4 and V2 show the effect of partially replacing the linear alcohol with cyclohexanol (30, 40 and 50 mol%).
• the temperature at which the 20% solution solidifies becomes lower and lower.
• the solidification temperature of the 20% solution is -5 ° C / -5.8 ° C for the product with 50 mol% cyclohexanol (Comparative Experiment 2)
• the effect as a pour point depressant for crude oil decreases markedly (only one more) Reduction from 27 ° C to 18 ° C, instead of 27 ° C to 9 to 12 ° C as in the unmodified product).
• the amount of cyclohexanol should accordingly be less than 50 mol%.

Landscapes

• 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)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Lubricants (AREA)
• Liquid Carbonaceous Fuels (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=55068744

Family Applications (1)

Country Status (8)

Families Citing this family (10)

Family Cites Families (13)

• 2016
  • 2016-11-17 SG SG11201804366RA patent/SG11201804366RA/en unknown
  • 2016-11-17 EA EA201891271A patent/EA035184B1/ru not_active IP Right Cessation
  • 2016-11-17 WO PCT/EP2016/077935 patent/WO2017089212A1/de active Application Filing
  • 2016-11-17 CN CN201680068135.9A patent/CN108291163B/zh active Active
  • 2016-11-17 EP EP16797890.7A patent/EP3380589B1/de active Active
  • 2016-11-17 US US15/778,723 patent/US10781385B2/en active Active
  • 2016-11-17 ES ES16797890T patent/ES2769078T3/es active Active
  • 2016-11-17 CA CA3003953A patent/CA3003953C/en active Active
• 2020
  • 2020-08-14 US US16/993,668 patent/US11236282B2/en active Active

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events