JP2004323830A - Demulsifier for mixture of middle distillate and fuel oil of vegetable or animal origin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a demulsifier process suitable for a mixture of a middle fraction and a biofuel oil, and a method for demulsification by addition of the emulsifier to the mixture. <P>SOLUTION: The method demulsifies a mixture composed of a major portion of mixture of (A) a middle fraction fuel oil and (B) a biofuel oil by addition of a minor component of (C) ethylene and at least 0.2-35 mole% of an oil soluble copolymer with pH value of 10-300 mg (KOH)/g containing the other olefinic unsaturated compound having at least one free hydroxy group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to the use of additives as demulsifiers for mixtures of middle distillates with vegetable or animal fuel oils and to corresponding added fuel oils.

    Increasingly interested in alternative energy sources based on renewable feedstocks, given the debate about the world's declining oil reserves and the use of fossil and mineral fuels is causing environmental destruction ing. These include natural oils and fats, especially of plant and animal origin. These generally include fatty acid triglycerides having 10 to 24 carbon atoms and a calorific value comparable to conventional fuels, but are also classified as biodegradable and environmentally friendly.

  The oils obtained from animal- or plant matter mainly comprise triglycerides of monocarboxylic acids, for example acids having 10 to 25 carbon atoms and of the formula

［式中、Ｒは１０〜２５の炭素原子を持ちそして飽和でも不飽和でもよい脂肪族基である 。］
で表される代謝生成物である。

Wherein R is an aliphatic group having 10 to 25 carbon atoms and which may be saturated or unsaturated. ]
It is a metabolic product represented by

  Generally, such oils contain glycerides consisting of a series of acids whose carbon number and type vary at the source of the oil, and which additionally contain phosphoglycerides. Such oils can be obtained by methods known from the prior art.

  Due to the sometimes unsatisfactory physical properties of triglycerides, this technique has been used to convert naturally occurring triglycerides into fatty acid esters of lower alcohols such as methanol or ethanol. The prior art also includes mixtures of middle distillates with oils of vegetable or animal origin (hereinafter also referred to as "biological oils").

  EP-B-0,665,873 describes biofuels, crude oil-based fuel oils and (a) oil-soluble ethylene copolymers or (b) comb polymers or (c) polar nitrogen compounds or (D) substantially linear at least 10 to 30 carbon atoms to provide at least one linear atom chain comprising the carbon atoms of the alkyl group and one or more non-terminal oxygen atoms; A fuel oil composition comprising a compound in which one alkyl group is bonded to a non-polymeric organic group, or (e) an additive containing one or more components (a), (b), (c) and (d) Is disclosed.

  What hinders the use of a mixture of middle distillate and biofuel is that it has a strong tendency to form a stable emulsion with water. Such emulsions cause corrosion problems in the fuel oil distribution network, and also when used in motor vehicles.

  The object of the present invention was therefore to provide suitable demulsifiers for mixtures of middle distillates and biofuels.

  We have surprisingly found that ethylene copolymers with hydrophilic substituents are excellent demulsifiers for such mixtures.

The present invention is based on
A) a mixture of distillate fuel oil and B) biofuel oil and a small portion thereof,
C) A fuel oil comprising an oil-soluble copolymer having a pH value of 10 to 300 mg (KOH) / g of ethylene and at least 0.2 to 35 mol% of another olefinically unsaturated compound containing at least one free hydroxyl group. About.

  The invention furthermore relates to the use of the copolymers defined under C) as a demulsifier in mixtures of middle distillate fuel oils and biofuel oils.

  In addition, the invention relates to a method for demulsifying a mixture of middle distillate fuel oil and biofuel oil by adding a copolymer as defined above to said mixture.

  A middle distillate fuel oil is used as component A). This refers in particular to those boiling in the range from 120 to 450 ° C. obtained by distillation of crude oil, such as kerosene, jet fuel, diesel oil and heating oil. It is advantageous to use middle distillates which contain less than 350 ppm, preferably less than 200 ppm, particularly preferably less than 50 ppm and in particular cases less than 10 ppm of sulfur. These are generally middle distillates which have been subjected to purification under hydrogenation conditions and therefore contain only small amounts of polymeric aromatics and polar compounds. This is preferably a middle distillate having a distillation point of 95% below 370 ° C., in particular below 350 ° C., in special cases below 330 ° C. This middle distillate preferably has an aromatics content of up to 28% by weight, particularly preferably up to 20% by weight.

  A biofuel oil is used as component B). In a preferred embodiment, the biofuel oil, often also referred to as "biodiesel oil" or "fuel oil", is a mixture of a fatty acid having 14 to 24 carbon atoms and an alcohol having 1 to 4 carbon atoms. It is a fatty acid alkyl ester. In general, the longer parts of the fatty acid have one, two or three double bonds. These fatty acids are particularly preferably, for example, rapeseed oil methyl ester, and especially mixtures of rapeseed oil methyl ester, sunflower oil fatty acid methyl ester and / or soybean oil fatty acid methyl ester.

  Examples of oils derived from animal or plant material and that can be used in the compositions of the present invention include rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, plum seed oil. There are oils, coconut oil, poppy seed oil, tallow, bone oil and fish oil. Other examples are oils derived from wheat, jute, sesame, shea tree nut, arachis oil and linseed oil, and which can be derived therefrom in a manner known in the art. An oil obtained by using an oil such as a frying oil can also be used. Rapeseed oil, which is a mixture of fatty acids partially esterified with glycerol, is advantageous because it can be obtained in large quantities and can be obtained in a simple manner by extraction and compression of rapeseed. In addition, the equally widely available oils of sunflower and soybean are advantageous, as are mixtures of these with rapeseed oil.

  Useful lower alkyl esters of fatty acids also include the following, for example, commercially available mixtures: fatty acids having 12 to 22 carbon atoms, such as lauric acid, myristic acid, palmitic acid, palmitolic acid, stearic acid, stearic acid, oleic acid, Ethyl, propyl, butyl and especially methyl-esters of elaidic acid, petroselinic acid, ricinoleic acid, elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadolinic acid, docosanoic acid or erucic acid. All of these have an iodine value of 50 to 150, especially 90 to 125. Mixtures of particularly advantageous properties are those which contain predominantly, ie at least 50% by weight, methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds. Preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.

  Commercial mixtures of the abovementioned type are obtained, for example, by hydrolyzing and esterifying animal and vegetable fats and oils and by transesterification with lower aliphatic alcohols. For the production of lower alkyl esters of fatty acids, it is advantageous to start with fats and oils having a high iodine value, such as sunflower oil, rapeseed oil, coriander oil, castor oil, soybean oil, cottonseed oil, peanut oil or tallow. The relatively lower alkyl esters of fatty acids based on a new class of rapeseed oil are preferred, wherein more than 80% by weight of the fatty acid component is derived from unsaturated fatty acids having 18 carbon atoms. The mixing ratio of components A and B can be varied as desired. A: B is 99.9: 0.1 to 0.1: 99.9, preferably 99: 1 to 1:99, particularly preferably 95: 5 to 5:95, for example 85:15 to 15:85 or Advantageously, it is between 80:20 and 20:80.

  Component C) is an ethylene copolymer. In one advantageous embodiment of the invention, the copolymer has an OH number of from 20 to 250 mg (KOH) / g, preferably from 25 to 200 mg (KOH) / g. In another preferred embodiment, the copolymer has an average molecular weight Mw of 700 to 10,000 g / mol.

  Olefinically unsaturated compounds present in addition to ethylene in the copolymer include vinyl esters, acrylic esters, mono- and diesters of ethylenically unsaturated carboxylic acids, methacrylic esters, alkyl vinyl ethers, and / or hydroxyalkyl, hydroxyalkenyl, Advantageously, it is an alkene having a hydroxycycloalkyl or hydroxyaryl group. These groups have at least one hydroxyl group at the desired position in the group, preferably at the chain end (ω-position) or, in the case of a ring system, in the para position.

Vinyl ester has the formula (1)
^{_{CH 2 = CH-OCOR 1 (}} 1)
Wherein R ¹ is C ₁ -C ₃₀ -hydroxyalkyl, preferably C ₁ -C ₁₂ -hydroxyalkyl, particularly preferably C ₂ -C ₆ -hydroxyalkyl and the corresponding hydroxyalkoxy group. ] Is preferable. Suitable vinyl esters include 2-hydroxyethyl vinyl ester, α-hydroxypropyl vinyl ester, 3-hydroxypropyl vinyl ester and 4-hydroxybutyl vinyl ester and diethylene glycol monovinyl ester.

The acrylate is represented by the formula (2)
_{^{CH 2 = CR 2 -COOR 3 (}} 2)
Wherein R ² is hydrogen or methyl and R ³ is C ₁ -C ₃₀ -hydroxyalkyl, preferably C ₁ -C ₁₂ -hydroxyalkyl, particularly preferably C ₂ -C ₆ -hydroxy. Alkyl and the corresponding hydroxyalkoxy groups. ]
What is represented by is advantageous. Suitable acrylates include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, hydroxyisopropyl acrylate, 4-hydroxybutyl acrylate and glycerol monoacrylate. Corresponding esters of methacrylic acid and esters of diols with ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid are likewise suitable.

The alkyl vinyl ether has the formula (3)
^{_{CH 2 = CH-OR 4 (}} 2)
Wherein R ⁴ is C ₁ -C ₃₀ -hydroxyalkyl, preferably C ₁ -C ₁₂ -hydroxyalkyl, particularly preferably C ₂ -C ₆ -hydroxyalkyl and the corresponding hydroxyalkoxy group. ]
Are preferred. Suitable alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hexanediol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and cyclohexanedimethanol-monovinyl ether.

  The alkenes are preferably monounsaturated hydroxy hydrocarbons having 3 to 30 carbon atoms, in particular 4 to 16 carbon atoms, especially 5 to 12 carbon atoms. Suitable alkenes include dimethylvinylcarbinol (= 2-methyl-3-buten-2-ol), allyloxypropanediol, 2-butene-1,4-diol, 1-buten-3-ol, 3-butene -1-ol, 2-buten-1-ol, 1-penten-3-ol, 1-penten-4-ol, 2-methyl-3-buten-1-ol, 1-hexen-3-ol, 5 -Hexen-1-ol and 7-octene-1,2-diol.

  Copolymers containing structural units derived from ethylene and vinyl alcohol are likewise suitable for use as demulsifiers. Copolymers of this type can also be prepared by partially or completely hydrolyzing copolymers containing structural units derived from ethylene and vinyl acetate.

  Copolymers derived from ethylene and a monomer having a glycidyl group, such as glycidyl (meth) acrylate or glycidyl allyl ether, may also be water, alcohols, such as methanol or glycol, or amines, such as ammonia, methylamine, ethanolamine or It can be used according to the invention after hydrolysis with diethanolamine.

Demulsification can be achieved with the method of the present invention by using an ethylene copolymer having alkoxylated acid groups. Suitable ethylene copolymers for this purpose are, for example, those containing acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride. For this purpose, these copolymers containing acid groups are alkoxylated at the acid groups with C ₁ -C ₁₀ -alkylene oxides. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. The alkoxylation is preferably carried out with 0.5 to 10 mol, particularly preferably 1 to 5 mol, particularly preferably 1 to 2 mol, of alkylene oxide per mol of acid groups.

  The molar fraction of hydroxyl-functionalized monomers in the copolymer is preferably from 0.5 to 15%, particularly preferably from 1 to 12%.

  The melt viscosity of the copolymer according to the invention at 140 ° C. is preferably 10,000 mPa.s. s or less, particularly preferably from 10 to 1000 mPa.s. s, particularly preferably 15 to 500 mPa.s. s.

  The copolymers of the present invention contain at least one hydroxyl-containing comonomer in addition to ethylene. They may also contain, for example, one, two or three further olefinically unsaturated comonomers. Such olefinically unsaturated monomers include, for example, vinyl esters, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, vinyl ethers or olefins. Particularly preferred vinyl esters are vinyl acetate, vinyl propionate and vinyl esters of neocarboxylic acids having 8, 9, 10, 11 or 12 carbon atoms. Particularly preferred acrylic and methacrylic esters are esters with alcohols having 1 to 20 carbon atoms, in particular methanol, ethanol, propanol, n-butanol, isobutanol and tert-butanol. Particularly preferred vinyl ethers are hydroxy vinyl ethers. Particularly preferred olefins are those having 3 to 10 carbon atoms, especially propylene, isobutylene, diisobutylene, norbornene, 4-methyl-pentene-1 and hexene. Particular preference is given to terpolymers consisting of ethylene, hydroxy-functionalized comonomers and vinyl acetate or vinyl esters of neocarboxylic acids having 8 to 12 carbon atoms. If the copolymer contains other comonomers, its molar fraction is preferably up to 18%, in particular up to 12%.

  The comonomers are copolymerized by known methods (for example, see Ullmanns Encyclopaedie der Technischen Chemie, 4th edition, volume 19, pages 169 to 178). The polymerization is advantageously a solution, suspension, gas phase and hot bulk polymerization. It is advantageous to use a high-pressure bulk polymerization carried out at a pressure of 50-400 MPa, preferably 100-300 MPa and at 50-350 ° C., preferably 100-300 ° C. The reaction between the comonomers is initiated by a radical polymerization initiator (radical chain initiator). This group of substances includes, for example, oxygen, hydrogen peroxide, peroxides and azo compounds, such as cumene hydroperoxide, tert-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, Tributyl maleate, tert-butyl perbenzoate, dicumyl peroxide, tert-butyl cumyl peroxide, di (tert-butyl) peroxide, 2,2′-azobis (2-methylpropanonitrile), 2,2 ′ -Azobis (2-methylbutyronitrile). These initiators are used individually or as a mixture of two or more substances in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the monomer mixture.

  In the case of the above composition of the comonomer mixture, the desired melt viscosity of the copolymer is adjusted by changing the reaction parameters of pressure and temperature and, if appropriate, by adding regulators. Useful regulators include hydrogen, saturated or unsaturated hydrocarbons such as propane, aldehydes such as propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or alcohols. For example, butanol has been demonstrated. Depending on the desired viscosity, the modifier is used in an amount of up to 20% by weight, preferably 0.05 to 10% by weight, based on the comonomer mixture.

  The high pressure bulk polymerization is carried out batchwise or continuously in known high pressure reactors, such as autoclaves or tubular reactors, and tubular reactors have proven to be particularly useful. Solvents, such as aliphatic hydrocarbons or hydrocarbon mixtures, benzene or toluene, may be present in the reaction mixture, even if solvent-free processes have proven advantageous. In one advantageous embodiment of the polymerization, a mixture of comonomer, initiator and, if used, modifier is fed to the tubular reactor from the inlet and one or more side chains of the tubular reactor. The comonomer streams may have different compositions (EP 0,271,738).

The copolymer (C) is added to the mixture consisting of A) and B) in an amount of 0.001 to 5% by weight, preferably 0.005 to 1% by weight, particularly preferably 0.01 to 0.05% by weight. These can be used as such or as solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, such as toluene, xylene, ethylbenzene, decane, pentadecane, petroleum fractions, kerosene, naphtha, diesel oil, heating oil, isoparaffin or commercial solvent mixtures, such as solvent naphtha ^{(solvent naphtha), (R)} Shellsoll AB, (R) Solvesso 150, (R) Solvesso 200, (R) Exxsol, or dissolved in ^(R) Isopar and ^(R) Shellsol D types Can be used in a distributed manner. They are preferably dissolved in animal or vegetable source fuels based on fatty acid alkyl esters. Advantageously, the additives according to the invention contain 1 to 80%, preferably 10 to 70%, particularly preferably 25 to 60% of solvent.

  The copolymer C) can be added to the oil to be added by methods known from the prior art. If more than one copolymer is to be used, such components can be introduced into the oil together or separately in the desired combination.

  In order to produce an additive package which specifically solves the problem, the copolymers C) are combined with one or more oil-soluble co-additives which themselves improve the properties of crude oils, lubricating oils or fuel oils. May be used. Examples of such co-additives include paraffin dispersions (paraffin dispersants), alkylphenol-aldehyde resins, polymeric cold flow improvers, and polar compounds that provide oil-soluble amphiphiles.

  For example, mixtures of copolymer C) with copolymers containing 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene have been found to be very useful. In one alternative embodiment of the present invention, the additive of the present invention is an ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymer for simultaneously improving the flowability and lubricity of a mineral oil or mineral oil fraction. It is used in a mixture with a polymer, ethylene / vinyl acetate / vinyl neononanoate terpolymer and / or ethylene / vinyl acetate / vinyl neodecanoate terpolymer. Apart from ethylene, terpolymers of vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate contain from 8 to 40% by weight of vinyl acetate and from 1 to 40% by weight of each long-chain vinyl ester. . Besides ethylene and 10 to 40% by weight of vinyl esters and / or 1 to 40% by weight of long-chain vinyl esters, another advantageous copolymer is 0.5 to 20% by weight of olefins having 3 to 10 carbon atoms, It also contains, for example, isobutylene, diisobutylene, propylene, methylpentene or norbornene.

  Paraffin dispersants are preferably low molecular weight or polymeric oil-soluble compounds having ionic or polar groups, such as amine salts, imides and / or amides. Particularly preferred paraffin dispersants include the reaction products of secondary aliphatic amines having 8 to 36 carbon atoms, especially coconut oil, ditallow, and distearylamine. The inventor has determined that paraffins obtained by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or anhydrides thereof. Systemic dispersants have been found to be particularly useful (see US Pat. No. 4,211,534). Other paraffin dispersants include maleic anhydride and copolymers of α, β-unsaturated compounds which can optionally react with primary monoalkylamines and / or aliphatic alcohols (EP-A-0,154). 177), the reaction products of alkenyl-spirobislactones with amines (see European Patent Application (B1) No. 0,413,279) and European Patent Application Publication (A2). According to U.S. Pat. No. 0,606,055 there are reaction products of terpolymers based on polyoxyalkylenes of .alpha.,. Beta.-unsaturated dicarboxylic anhydrides, .alpha.,. Beta.-unsaturated compounds and lower unsaturated alcohols.

  Suitable co-additives that have a paraffin dispersing effect include, for example, esters. These esters are derived from polyols having three or more OH groups, in particular from glycerol, trimethylolpropane, pentaerythritol and oligomers having 2 to 10 monomer units obtainable therefrom by condensation, such as polyglycerol. You. The polyol is generally reacted with from 1 to 100 mol, preferably from 3 to 70 mol, particularly preferably from 5 to 50 mol, of alkylene oxide per mol of said polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. The alkoxylation is performed by a known method.

  Fatty acids suitable for the esterification of alkoxylated polyols preferably have 8 to 50, particularly preferably 12 to 30, especially 16 to 26, carbon atoms. Suitable fatty acids include, for example, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid and behenic acid, oleic acid and erucic acid, palmitolic acid, myristolic acid, ricinoleic acid , And fatty acid mixtures obtained from natural fats and oils. Preferred fatty acid mixtures contain more than 50% of fatty acids of at least 20 carbon atoms. In particular, less than 50%, especially less than 10%, of the fatty acids for ester reactions contain double bonds. That is, they are particularly well saturated. In this connection, "saturated" means the iodine value of fatty acids in which up to 5 g of iodine are used per 100 g of fatty acids. Esterification can be carried out starting from reactive derivatives of fatty acids, such as esters with lower alcohols (eg methyl or ethyl esters) or acid anhydrides.

In order to esterify the alkoxylated polyol, it is also possible to use a mixture of the above fatty acids and fat-soluble polybasic carboxylic acids. Suitable polybasic example dimer fatty acids in the carboxylic acids, alkenyl succinic acids and aromatic polycarboxylic acids and their derivatives, such as acid anhydrides and C ₁ -C ₅ - is an ester. Alkenyl succinic acids having an alkyl group having 8 to 200, preferably 10 to 50 carbon atoms and derivatives thereof are preferred. For example, dodecyl-, octadecenyl- and poly (isobutenyl) succinic anhydride. It is advantageous to use the polybasic carboxylic acid in small fractions of up to 30 mol%, preferably 1 to 20 mol%, particularly preferably 2 to 10 mol%.

  Esters and fatty acids have a ratio of 1.5: 1 to 1: 1.5, preferably 1.1: 1 to 1: 1.1, based on the hydroxyl content on the one hand and on the carboxyl group on the other. They are used in a ratio, particularly preferably in equimolar amounts. The paraffin dispersing action is particularly good when the acid excess is up to 20 mol%, preferably up to 10 mol%, especially up to 5 mol%.

Esterification is carried out in a conventional manner. The catalyst optionally a polyol alkoxylate with fatty acids, for example p-toluenesulfonic acid, C ₂ -C ₅₀ - alkyl benzene sulfonic acid, it is reacted in the presence of methanesulfonic acid or an acidic ion exchange resin is particularly useful I know. The water of reaction is collected by direct condensation or especially in the presence of an organic solvent such as toluene, xylene or a high boiling mixture such as ^(R) Shellsol A, ^(R) Shellsol B, ^(R) Schellsoll AB or Solvent naphtha. It can be distilled off by boiling distillation. The esterification is preferably carried out completely, that is to say for the esterification, between 1.0 and 1.5 mol of fatty acids per mol of hydroxyl groups. The acid value of the ester is generally at most 15 mg (KOH) / g, preferably at most 10 mg (KOH) / g, especially at most 5 mg (KOH) / g.

Particularly advantageous paraffin dispersants are prepared by reacting a compound having an acyl group with an amine. This amine is a compound represented by the formula NR ⁶ R ⁷ R ⁸ . However, in the formula, R ⁶ , R ⁷ and R ⁸ may be the same or different from each other, and at least one of these groups is a C ₈ -C ₃₆ -alkyl, a C ₆ -C ₃₆ -cycloalkyl, a C ₈ -C ₆ -alkyl. C ₃₆ - alkenyl, especially C ₁₂ -C ₂₄ - alkyl, C ₁₂ -C ₂₄ - alkenyl or cyclohexyl and the remaining radicals are hydrogen atoms, C ₁ -C ₃₆ - alkyl, C ₂ -C ₃₆ - alkenyl, cyclohexyl or the formula - (a-O) _x -E or - (CH ₂₎ a group represented by _n -NYZ, a at that time is an ethylene or propylene group, x is a number from 1 to 50, E is H, C ₁ -C ₃₀ - alkyl, C ₅ ~C ₁₂ - cycloalkyl or C ₆ -C ₁₂ - cycloalkyl or C ₆ -C ₃₀ - aryl is and Y and Z independently of each H, C ₁ -C ₃₀ - alkyl or It is (A-O) _x. In the context of the present invention, an acyl group is a functional group represented by the following formula:
> C = O
The paraffin dispersants may be mixed with the copolymer C) or added separately to the middle distillate to be added.

Alkyl phenol aldehyde resins are disclosed, for example, in Roempp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pages 3351 et seq. The alkyl or alkenyl group of the alkylphenol has 6 to 24, preferably 8 to 22, particularly preferably 9 to 18, carbon atoms. These may be straight-chain or, preferably, branched, and the branches may have secondary and tertiary structures. These preferably n- and isohexyl, n- and isooctyl, n- and isononyl, n- and isodecyl, n- and isododecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and tripropenyl, tetrapropenyl, until pentapropenyl and C ₂₄ Polyisobutenyl. The alkylphenol-aldehyde resin may have up to 20 mol% of phenol units and / or alkylphenols having short alkyl chains, such as butylphenol. The same or different alkylphenols can be used for the alkylphenol-aldehyde resin.

  The aldehyde in the alkylphenol-aldehyde resin has from 1 to 10, preferably from 1 to 4, carbon atoms and may have additional functional groups. Preferred aldehydes are aliphatic aldehydes, especially formaldehyde.

  The molecular weight of the alkylphenol-aldehyde resin is preferably from 350 to 10,000, particularly preferably from 400 to 5,000 g / mol. This preferably corresponds to a degree of condensation of from 3 to 40, particularly preferably from 4 to 20. In this case, it is assumed that the resin is oil-soluble.

  In one advantageous embodiment of the invention, these alkylphenol-formaldehyde resins have the formula

［式中、Ｒ^A はＣ₆ 〜Ｃ₂₄−アルキルまたは−アルケニルであり、Ｒ^B はＯＨまたはＯ− （Ａ−Ｏ）_x −Ｈであり、その際にＡはＣ₂ 〜Ｃ₄ −アルキレン基であり、ｘは１〜５ ０でありそしてｎは２〜５０、好ましくは５〜４０の数である。］
で表される繰り返し単位を持つオリゴマーまたはポリマーである。

Wherein R ^A is C ₆ -C ₂₄ -alkyl or -alkenyl, R ^B is OH or O— (A—O) _x —H, wherein A is C ₂ -C ₄ -alkylene. X is from 1 to 50 and n is a number from 2 to 50, preferably from 5 to 40. ]
An oligomer or polymer having a repeating unit represented by

  Alkyl phenol aldehyde resins are prepared in a known manner with basic catalysts and result in resol-type condensation products or in acid-catalyzed novolak-type condensation products.

  Condensates obtained by both methods are suitable for the composition according to the invention. It is advantageous to condense in the presence of an acidic catalyst.

  To prepare an alkylphenol aldehyde resin, an alkylphenol having 6 to 24, preferably 8 to 22, particularly preferably 9 to 18 carbon atoms per alkyl group or a mixture thereof is reacted with at least one aldehyde. In this case, about 0.5 to 2 mol, preferably 0.7 to 1.3 mol, particularly preferably equimolar, of aldehyde is used per mol of alkylphenol compound.

Suitable alkylphenols are, in particular, n- and isohexylphenol, n- and isooctylphenol, n- and isononylphenol, n- and isodecylphenol, n- and isododecylphanol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosyl phenol, there is tri propenyl phenol, up tetrapropenylphenol and C ₂₄ poly (isobutenyl) phenol.

  Alkyl phenols are preferably para-substituted. Alkyl phenols may have one or more alkyl groups. The proportion substituted with more than one alkyl group is preferably at most 5 mol%, in particular at most 20 mol%, especially at most 40 mol%. Up to 40 mol%, in particular up to 20 mol%, of the alkylphenols used have an alkyl group in the ortho position. Particularly preferably, the alkylphenols are not substituted with a tertiary alkyl group ortho to the hydroxyl group.

  The aldehyde may be a mono- or dialdehyde and may have other functional groups, such as -COOH. Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde, glutaraldehyde and glyoxylic acid, preferably formaldehyde. The formaldehyde may be used in the paraformaldehyde state or preferably in the form of a 20 to 40% by weight aqueous formalin solution. It is also possible to use corresponding amounts of trioxane.

The alkyl phenol is generally reacted in the presence of an alkali catalyst, such as an alkali metal hydroxide or an alkylamine, or an acidic catalyst such as an inorganic or organic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamic acid or haloacetic acid, It is carried out in the presence of an organic solvent which forms an azeotrope with water, for example toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is heated to a temperature of 90-200C, preferably 100-160C, and the resulting water of reaction is removed during the reaction by azeotropic distillation. Solvents that do not release protons under the conditions of the condensation reaction may remain in the product after the condensation reaction. The resin may be used directly or after neutralization of the catalyst, optionally converting the solution to an aliphatic and / or aromatic hydrocarbon or hydrocarbon mixture such as petroleum fraction, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene, or solvent naphtha (solvent naphtha), it is possible to use ^{(R) Shellsoll AB, (R} ) Solvesso 150, (R) Solvesso 200, (R) Exxsol, the ^(R) ISOPAR and ^(R) Shellsol D types.

Finally, in another advantageous embodiment of the invention, the additives according to the invention are used in combination with comb polymers. These are polymers in which hydrocarbon groups having at least 8, especially at least 10 carbon atoms are attached to the polymer backbone. These are homopolymers whose alkyl side chains preferably contain at least 8, particularly preferably at least 10, carbon atoms. In the case of copolymers, the side chains have at least 20%, preferably at least 30%, of the monomers (Comb-like Polymers-Structure and Properties; NA Plate and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974). , 8, pp. 117 et seq.). Fumarate / vinyl acetate Examples of comb polymers which are suitable - the copolymer (see EP-0,153,176), C ₆ ~C ₂₄ -α- olefin and N-C ₆ ~C ₂₂ - alkyl Maleic amides (see EP-A-0,320,766) and esterified olefin / maleic anhydride copolymers, polymers or copolymers of α-olefins and esterification of styrene with maleic anhydride It is a copolymer.

  The comb polymer is, for example, of the formula

「式中、ＡはＲ’、ＣＯＯＲ’、ＯＣＯＲ’、Ｒ”−ＣＯＯＲ’またはＯＲ’であり、
ＤはＨ、ＣＨ₃ 、ＡまたはＲ" であり、
ＥはＨまたはＡであり、
ＧはＨ、Ｒ”、Ｒ”−ＣＯＯＲ’、アリール基またはヘテロ環基であり、
ＭはＨ、ＣＯＯＲ”、ＯＣＯＲ’、ＯＲ”またはＣＯＯＨであり、
ＮはＨ、Ｒ”、ＣＯＯＲ”、ＯＣＯＲ，ＣＯＯＨまたはアリール基であり、
Ｒ’は炭素原子数８〜１５０の炭化水素鎖であり、
Ｒ”は炭素原子数１〜１０の炭化水素鎖であり、
ｍは０．４〜１．０の数でありそして
ｎは０〜０．６の数である。］
で表すことができる。

"Where A is R ', COOR', OCOR ', R"-COOR' or OR ';
D is H, CH ₃ , A or R ";
E is H or A,
G is H, R ", R" -COOR ', an aryl group or a heterocyclic group,
M is H, COOR ", OCOR ', OR" or COOH;
N is H, R ", COOR", OCOR, COOH or an aryl group;
R ′ is a hydrocarbon chain having 8 to 150 carbon atoms,
R ″ is a hydrocarbon chain having 1 to 10 carbon atoms,
m is a number from 0.4 to 1.0 and n is a number from 0 to 0.6. ]
Can be represented by

  The mixing ratio (parts by weight) of the copolymer C) to the low-temperature fluidity improver, the paraffin dispersant, the comb polymer and the resin is 1:10 to 20: 1, preferably 1: 1 to 10: 1.

  The copolymers C) can be used alone or with other additives, such as other solidification or dewaxing aids, corrosion inhibitors, antioxidants, lubricating aids, sludge inhibitors, dehazers and cloud points. It may be used in combination with a reducing additive.

Example:
Characteristics of test oil:
The measurement of the CFPP value is determined according to EN 116 and the boiling characteristics are determined according to ASTM D-86 and the cloud point according to ISO 3015.

ＧＣから算出された沃素価 １１６
表２：使用した中間留分の特徴

コポリマーの特徴:
以下のコポリマーを使用した:
Ｐ１ Ｅ／ＶＡ／４−ヒドロキシビニルエーテル（４−ＨＢＶＥ）ターポリマー
Ｐ２ Ｅ／ＶｅｏＶａ-10 ／ヒドロキシプロピルアクリレート（ＨＰＡ）ターポリマーＰ３ Ｅ／ＶＡ／ヒドロキシビニルエーテル（ＨＢＶＥ）ターポリマー
Ｐ４ Ｅ／ＶＡ／ヒドロキシブチルビニルエーテル（ＨＢＶＥ）ターポリマー
Ｐ５ Ｅ／ＶＡ／ヒドロキシエチルビニルエーテル（４−ＨＥＶＥ）ターポリマー
Ｐ６ Ｅ／ＶＡ／ヒドロキシプロピルメタクリレートターポリマー
Ｐ７ Ｅ／ＶＡ／２−メチル−３−ブテン−２−オールターポリマー
Ｐ８ Ｅ／ＶＡコポリマー
Ｐ９ Ｅ／ＶＡ／ＶｅｏＶａ-10 ターポリマー
Ｐ１０ Ｅ／ＶＡ／ＶｅｏＶａ-10 ターポリマー
ＶＡ＝酢酸ビニル
ＶｅｏＶａ-10 ＝ビニルネオデカノエート
本発明の目的のために、ＯＨ−価をＤＩＮ５３２４０に従って規定した過剰量の無水酢酸と反応させそして次に生じた酢酸を滴定することによって測定した。 Table 1: Analysis of biodiesel used (hereinafter also referred to as "RME")

Iodine value calculated from GC 116
Table 2: Characteristics of middle distillate used

Copolymer features:
The following copolymers were used:
P1 E / VA / 4-hydroxyvinyl ether (4-HBVE) terpolymer P2 E / VeoVa-10 / hydroxypropyl acrylate (HPA) terpolymer P3 E / VA / hydroxyvinyl ether (HBVE) terpolymer P4 E / VA / hydroxybutyl Vinyl ether (HBVE) terpolymer P5 E / VA / hydroxyethyl vinyl ether (4-HEVE) terpolymer P6 E / VA / hydroxypropyl methacrylate terpolymer P7 E / VA / 2-methyl-3-buten-2-ol terpolymer P8 E / VA copolymer P9 E / VA / VeoVa-10 terpolymer P10 E / VA / VeoVa-10 terpolymer VA = Vinyl acetate VeoVa-10 = Vinyl neodecanoate Defining the excess and then the resulting acid is reacted with acetic anhydride in accordance with 3240 was determined by titration.

解乳化剤としての性能：
添加剤の乳化傾向はＡＳＴＭ Ｄ １０９４−８５に従って試験した。８０ｍＬのディーゼル燃料を１００ｍＬのメスシリンダー中で２５０ｍＬの試験すべき添加剤と混合しそして６０℃で１５分間加熱し、次いで攪拌する。室温に冷却した後に、２０ｍＬの緩衝溶液を添加しそしてシリンダーを２分間攪拌する。５分後にサンプルを以下の基準で視覚的に評価する：

表４：９５重量％のＦ２と５重量％の生物ディーゼル油との混合物中の解乳化剤として のコポリマーの性能

＊：たったの僅かの時間（１〜２分）の後でも顕著な相分離あり。 Table 3: Characteristics of the copolymer

Performance as demulsifier:
The emulsification tendency of the additives was tested according to ASTM D 1094-85. Mix 80 mL of diesel fuel with 250 mL of the additive to be tested in a 100 mL graduated cylinder and heat at 60 ° C. for 15 minutes, then stir. After cooling to room temperature, 20 mL of buffer solution is added and the cylinder is stirred for 2 minutes. After 5 minutes, the samples are evaluated visually according to the following criteria:

Table 4: Performance of copolymers as demulsifiers in a mixture of 95 wt% F2 and 5 wt% biodiesel oil

*: Remarkable phase separation after only a short time (1-2 minutes).

水酸基含有コポリマーの冷間流動性改善剤への影響:
−７℃のＣＦＰＰを有する中間留分およびそれと５％の記載の生物燃料との混合物（この混合物のＣＦＰＰは同様に−７℃）を、冷間流動性向上剤および水酸基含有コポリマーを用いて試験した。 Table 5: Effect of different mixing ratios between middle distillate and biofuel on emulsification performance

Effect of hydroxyl group-containing copolymer on cold flow improver:
The middle distillate having a CFPP of -7 ° C and a mixture thereof with 5% of the stated biofuel (CFPP of this mixture is likewise -7 ° C) are tested using a cold flow improver and a hydroxyl-containing copolymer. did.

流動性向上剤の存在下でのディーゼル油／生物ディーゼル油−混合物の乳化性能への水酸基含有コポリマーの影響。 Table 6: Influence on cold fluidity by hydroxyl-containing copolymer

Effect of hydroxyl-containing copolymer on the emulsification performance of diesel / biodiesel oil mixtures in the presence of flow improvers.

  The emulsifying performance of oil F4, which additionally contains 5% by weight of diesel fuel oil, is significantly changed by the addition of 10 ppm of P4 and does not show any emulsifying tendency despite the presence of 300 ppm of flow improver.

Claims (9)

Of many parts,
A) a mixture of distillate fuel oil and B) biofuel oil and a small portion thereof,
C) A fuel oil consisting of an oil-soluble copolymer of ethylene with at least 0.2 to 35 mol% of another olefinically unsaturated compound containing at least one free hydroxyl group, having a pH value of 10 to 300 mg (KOH) / g. . 2. The fuel oil according to claim 1, wherein the mixing ratio of A): B) is from 99: 1 to 1:99. 3. The fuel oil according to claim 1, wherein the OH value of the copolymer C) is from 20 to 250 mg (KOH) / g. The fuel oil according to any one of claims 1 to 3, wherein the copolymer has an average molecular weight of 700 to 10,000 g / mol. 5. The fuel oil according to claim 1, wherein the proportion of hydroxyl functional comonomer in the copolymer is from 0.5 to 15 mol%. The copolymer C), besides ethylene and at least one hydroxyl-functional comonomer, at least one other comonomer selected from the group consisting of vinyl esters, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, vinyl ethers and olefins The fuel oil according to any one of claims 1 to 5, further comprising: The fuel oil according to any one of claims 1 to 6, wherein the content of C) in the mixture consisting of A) and B) is 0.001 to 5% by weight. In addition to components A), B) and C),

Wherein R ^A is C ₆ -C ₂₄ -alkyl or -alkenyl, R ^B is OH or O- (A-O) _x -H, wherein A is C ₂ -C ₄ -alkylene. X is from 1 to 50 and n is a number from 2 to 50, especially from 5 to 40. ]
The fuel oil according to any one of claims 1 to 7, further comprising at least one alkylphenol formaldehyde resin represented by the following formula: Oil-soluble copolymers of ethylene with at least 0.2 to 35 mol% of at least one other olefinically unsaturated compound containing free hydroxyl groups, having a pH value of 10 to 300 mg (KOH) / g, a middle distillate fuel oil For use as a demulsifier in a mixture of oil and biofuel.