DE102004028495A1 - Cold flow improver compositions in naphthalene-lean solvent naphtha - Google Patents

Abstract

The invention relates to a composition comprising DOLLAR AA) solvent naphtha having a naphthalene content of less than 1% by weight, DOLLAR AB) a middle distillate cold flow improver and DOLLAR AC) a solvent-imparting additive selected from aliphatic or alicyclic C¶1¶- to C¶22¶ alcohols, cycloaliphatic hydrocarbons and monocyclic aromatic hydrocarbons.

Description

The The present invention relates to compositions containing a cold flow improver for mineral oils or mineral oil distillates solved in naphthalene solvent naphtha (SN), and a solubilizer contain.

SN is a product obtained from the refining of crude oil. It is generally a fraction with the following typical characteristics: Density at 15 ° C (according to ASTM D1298) 0.86-0.905 g / ml Initial boiling point (according to AST> M D1078) 150 ° C Boiling ends (according to ASTM D1078) 305 ° C Color according to Saybolt (according to ASTM D156) +25 to +30 Doctor Test (according to ASTM D235) negative Pensky Closed Flash Test (to ASTM D93) 40 ° C - 100 ° C Aromatic content (HPLC) > 90% by weight

SN so far had a high naphthalene content, at 10 and more Could be percent by weight. Since naphthalene is suspected, To be carcinogenic, the compositions that are more than 1 wt .-% naphthalene, with regard to their possible carcinogenic property subject to classification. This has to Consequence that SN are produced with low naphthalene becomes.

SN is a common one solvent for middle distillate cold flow improvers. For example, EP-A-0 733 694 discloses middle distillate cold flow improver compositions, which in addition to alcohols and the cold flow improver also contain SN.

The restriction However, the naphthalene content of SN has the consequence that the solvent properties change from SN. So it was found that the solvent properties SN with less than 1 wt% naphthalene for middle distillate cold flow improvers are significantly worse than those of SN, which is not low in naphthalene is.

There SN a frequently used solvent for cold flow improvers is, was the one to be solved Task in it, a Lösevermittler to find the deteriorated solvent properties of naphthalene SN for middle distillate cold flow improvers so far improved that appropriate solutions remain manageable. Another task was to use the solver, the pour point of these solutions lower.

Surprisingly it was found that the addition of alcohols and / or certain cyclic hydrocarbons the solvent properties of naphthalinarmem SN for Middle distillate cold flow improvers improves and leads to a pour point reduction.

• A) Solvent Naphtha mit einem Naphthalingehalt von weniger als 1 Gew.-%,
• B) einen Mitteldestillat-Kaltfließverbesserer und
• C) ein lösevermittelndes Additiv, ausgewählt aus aliphatischen oder alicyclischen C₁- bis C₂₂-Alkoholen, cycloaliphatischen Kohlenwasserstoffen und monocyclischen aromatischen Kohlenwasserstoffen.

The invention thus relates to a composition containing

• A) Solvent naphtha with a naphthalene content of less than 1% by weight,
• B) a middle distillate cold flow improver and
• C) a solubilizing additive selected from aliphatic or alicyclic C ₁ - to C ₂₂ -alcohols, cycloaliphatic hydrocarbons and monocyclic aromatic hydrocarbons.

Another object of the invention is the use of aliphatic or alicyclic C ₁ - to C ₂₂ alcohols, cycloaliphatic hydrocarbons or monocyclic aromatic hydrocarbons as a solubilizer and pour point depressant in solutions of solvent naphtha with less than 1 wt .-% naphthalene content and middle distillate cold flow improvers.

The invention further provides a process for the preparation of solutions of middle distillate cold flow improvers in solvent naphtha containing less than 1% by weight of naphthalene by mixing the mixture of these two ingredients with a solubilizing additive selected from aliphatic or alicyclic C ₁ to C ₂₂ - Alcohols, cycloaliphatic hydrocarbons and monocyclic aromatic hydrocarbons, added.

Another object of the invention is the use of solutions of middle distillate Kaltfließverbesserern in solvent naphtha with less than 1 wt .-% naphthalene, containing aliphatic or alicyclic C ₁ - to C ₂₂ alcohols, cycloaliphatic hydrocarbons or monocyclic aromatic hydrocarbons, as cold additives in Middle distillates, biofuel oils or mixtures thereof.

at Component C) of the composition according to the invention they are preferably monohydric alcohols. In a preferred embodiment have the hydrocarbon radicals of the alcohols 1 to 12, in particular 1 to 10 carbon atoms. The hydrocarbon radicals are aliphatic or alicyclic. Examples of suitable alcohols are methanol, ethanol, 2-ethylhexanol and cyclohexanol.

In a further preferred embodiment Component C) is cycloaliphatic hydrocarbons. These are mono- or polycyclic hydrocarbons that are not are aromatic. The cycloaliphatic compounds can be saturated or unsaturated be. They preferably comprise 4 to 18, in particular 6 to 12 Carbon atoms. You can Substituents such as amino, carboxy, keto or aldehyde groups wear. By way of example here cyclohexane, norbornane, norbornene and derivatives thereof called become.

In a further preferred embodiment Component C) is monocyclic aromatic Links. these can Substituents such as hydroxy, amino, carboxy, keto or aldehyde groups. To name a few are the isomers Nonylphenols, hydroxybenzenes and salicylaldehyde.

When Component B) come the usual cold flow improvers for middle distillates in question.

Examples such cold flow improvers are polar compounds that cause paraffin dispersion (Paraffin dispersants), alkylphenol-aldehyde resins, polymeric cold flow improvers as well as oil-soluble amphiphiles.

So are as cold flow improvers those polymers are suitable which contain 10 to 40% by weight of vinyl acetate and 60 to 90 wt .-% ethylene. According to a further embodiment of Invention is used as component B) ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, Ethylene / vinyl acetate / vinyl neononanoate terpolymers and / or ethylene vinyl acetate / vinyl neodecanoate terpolymers. The terpolymers of vinyl 2-ethylhexanoate, vinyl neononanoate or the neodecanoic acid vinyl ester contain except ethylene 8 to 40 wt .-% of vinyl acetate and 1 to 40 wt .-% of the respective long-chain Vinylesters. Further preferred copolymers contain in addition to ethylene and 10 to 40% by weight of vinyl esters and / or 1 to 40% by weight of long-chain Vinyl ester still 0.5 to 20 wt .-% of olefin having 3 to 10 carbon atoms, such as e.g. Isobutylene, diisobutylene, propylene, methylpentene or norbornene.

The paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds having ionic or polar groups, for example amine salts, imides and / or amides. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 8 to 36 carbon atoms, in particular dicoco fatty amine, ditallow fatty amine and distearylamine. Paraffin dispersants which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ). Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds which can optionally be reacted with primary and / or secondary monoalkylamines and / or aliphatic alcohols (see EP-A-0 154 177), the reaction products of alkenyl spiro-bis-lactones with amines (US Pat. see EP-A-0 413 279 B1) and according to EP-A-0 606 055 A2 reaction products of terpolymers based on α, β-unsaturated dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.

When Component B) esters are also suitable. These esters are derived of polyols having 3 or more OH groups, in particular of glycerol, Trimethylolpropane, pentaerythritol and the resulting from condensation accessible Oligomers having 2 to 10 monomer units, e.g. Polyglycerol. The Polyols are generally preferred with from 1 to 100 moles of alkylene oxide 3 to 70, in particular 5 to 50 mol of alkylene oxide reacted per mole of polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. The alkoxylation is carried out by known methods.

The fatty acids suitable for the esterification of the alkoxylated polyols preferably have 8 to 50, in particular 12 to 30, especially 16 to 26 C-atoms. Suitable fatty acids are, for example, lauric, tride can, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachinic and behenic, oleic and erucic acid, palmitoleic, myristolein, ricinoleic acid, and fatty acid mixtures derived from natural fats and oils. Preferred fatty acid mixtures contain more than 50% fatty acids with at least 20 C atoms. Preferably, less than 50% of the fatty acids used for esterification contain double bonds, in particular less than 10%; specifically, they are largely saturated. Under largely saturated here is an iodine value of the fatty acid used of up to 5 g I per 100 g fatty acid are understood. The esterification can also be carried out starting from reactive derivatives of fatty acids such as esters with lower alcohols (for example methyl or ethyl esters) or anhydrides.

For the esterification of the alkoxylated polyols, it is also possible to use mixtures of the above fatty acids with fat-soluble, polybasic carboxylic acids. Examples of suitable polybasic carboxylic acids are dimer fatty acids, alkenylsuccinic acids and aromatic polycarboxylic acids and derivatives thereof such as anhydrides and C ₁ - to C ₅ -esters. Alkenylsuccinic acids and their derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred. Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride. The polybasic carboxylic acids are preferably used to lower levels of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.

ester and fatty acid be for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups in the ratio of 1.5: 1 to 1: 1.5, preferably 1.1: 1 to 1: 1.1, in particular equimolar. The paraffin-dispersing Effect is particularly pronounced if with an acid excess of up to 20 mol%, especially up to 10 mol%, especially up to to 5 mol% is worked.

The esterification is carried out by conventional methods. Has proven particularly useful the reaction of polyol with fatty acid, optionally in the presence of catalysts such as para-toluenesulfonic acid, C ₂ - to C ₅₀ -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers. The separation of the water of reaction can be carried out by distillation by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or higher boiling mixtures such as ^® Shellsol A, Shellsol B, Shellsol AB or solvent naphtha or naphthalene (<1 wt .-%) variants of the solvent naphtha take place. The esterification is preferably carried out completely, ie for the esterification 1.0 to 1.5 moles of fatty acid are used per mole of hydroxyl groups. The acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.

Other preferred paraffin dispersants suitable as component B) are prepared by reacting compounds containing an acyl group with an amine. This amine is a compound of the formula NR ⁶ R ⁷ R ⁸ , in which R ⁶ , R ⁷ and R ^{8 may be} identical or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ - C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ -alkyl, C ₁₂ -C ₂₄ -alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ -alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A 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 ₃₀ -aryl, and n is 2, 3 or 4, and Y and Z are each independently H, C ₁ -C ₃₀ - Alkyl or - (AO) _x . By acyl group is meant here a functional group of the following formula: > C = O

Alkylphenol-aldehyde resins are also suitable as constituent B). Alkylphenol-aldehyde resins are known in principle and, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351ff. described. The alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They may be linear or preferably branched, wherein the branch may contain secondary as well as tertiary structural elements. Preference is given to n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and tripropenyl, Tetrapropenyl, pentapropenyl and polyisobutenyl to C ₂₄ . The alkylphenol-aldehyde resin may also contain up to 20 mole% of phenol units and / or alkylphenols with short alkyl chains such as butylphenol. For the alkylphenol-aldehyde resin, the same or different alkylphenols may be used.

Of the Aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4 carbon atoms and may carry further functional groups. It is preferably an aliphatic aldehyde, more preferably he is formaldehyde.

The molecular weight of the alkylphenol-aldehyde resins is preferably 350 to 10,000, in particular 400 to 5000, g / mol. This preferably corresponds to a condensation degree n of 3 to 40, in particular of 4 to 20. The prerequisite here is that the resins are oil-soluble.

sind, worin R^A für C₆-C₂₄-Alkyl oder -Alkenyl, R^B für OH oder O-(A-O)_x-H mit A = C₂-C₄-Alkylen und x = 1 bis 50, und n für eine Zahl von 2 bis 50, insbesondere 5 bis 40 steht.In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula

wherein R ^{A is} C ₆ -C ₂₄ alkyl or alkenyl, R ^{B is} OH or O- (AO) _x -H with A = C ₂ -C ₄ alkylene and x = 1 to 50, and n is a number from 2 to 50, in particular 5 to 40 stands.

The Preparation of the alkylphenol-aldehyde resins takes place in a known manner by basic catalysis, with condensation products of the resol type arise, or by acid catalysis, with condensation products arise from the novolac type.

The condensates obtained by both types are for the compositions according to the invention suitable. Preferably, the condensation is in the presence of acidic Catalysts.

to Preparation of the alkylphenol-aldehyde resins becomes an alkylphenol with 6 - 24, preferably 8-22, in particular 9 - 18 C atoms per alkyl group, or mixtures thereof and at least one Aldehyde reacted with each other, wherein per mole of alkylphenol compound about 0.5 - 2 mol, preferably 0.7 - 1.3 mol and in particular equimolar Amounts of aldehyde can be used.

Suitable alkylphenols are in particular n- and iso-hexylphenol, n- and iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyI (isobutenyl) phenol -C _24th

The Alkylphenols are preferably para-substituted. The alkylphenols can carry one or more alkyl radicals. Preferably, they are at most 5 mol%, in particular at most 20 mol% and especially at most 40 mol% substituted with more than one alkyl group. Prefers carry at most 40 mol%, in particular at most 20 mol% of the alkylphenols used in the ortho position an alkyl radical. specially the alkylphenols are not ortho to the hydroxyl group with tertiary Substituted alkyl groups.

Of the Aldehyde can be a mono- or dialdehyde and other functional Wear groups like -COOH. Particularly suitable aldehydes are formaldehyde, Acetaldehyde, butyraldehyde, glutaric dialdehyde and glyoxylic acid is formaldehyde. The formaldehyde may be in the form of paraformaldehyde or in the form of preferably 20-40% by weight aqueous formalin be used. It can also appropriate amounts of trioxane can be used.

Finally, comb polymers are used as constituent B) in a further embodiment of the invention. This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30% of the monomers have side chains (compare Comb-like Polymers-Structure and Properties, NA Platé and VP Shibaev, J. Polym, Sci Macromolecular Revs 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1 ), Copolymers of a C ₆ -C ₂₄ α-olefin and a NC ₆ -C ₂₂ alkylmaleimide (see EP-A-0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

beschrieben werden. Darin bedeuten
A R', COOR', OCOR', R''-COOR' oder OR';
D H, CH₃, A oder R;
E H oder A;
G H, R'', R''-COOR', einen Arylrest oder einen heterocyclischen Rest;
M H, COOR'', OCOR'', OR'' oder COOH;
N H, R'', COOR'', OCOR, COOH oder einen Arylrest;
R' eine Kohlenwasserstoffkette mit 8-150 Kohlenstoffatomen;
R'' eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;
m eine Zahl zwischen 0,4 und 1,0; und
n eine Zahl zwischen 0 und 0,6.Comb polymers may, for example, be represented by the formula

to be discribed. Mean in it
A R ', COOR', OCOR ', R''-COOR' or OR ';
DH, CH _3, A or R;
EH or A;
GH, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
MH, COOR '', OCOR '', OR '' or COOH;
NH, R ", COOR", OCOR, COOH or an aryl radical;
R 'is a hydrocarbon chain of 8-150 carbon atoms;
R '' is a hydrocarbon chain of 1 to 10 carbon atoms;
m is a number between 0.4 and 1.0; and
n is a number between 0 and 0.6.

component A is low-naphthalene SN. It preferably contains less than 1, in particular at most 0.1 Wt .-% naphthalene. The aromatic content of the SN is preferably at more than 90 wt .-%, in particular more than 95 wt .-%. Be Boiling range is preferably between 160 and 230 ° C.

Preferably contains the composition of the invention 1 - 80 % By weight of ingredient B), 0.1 to 5% by weight of ingredient C) and component A) ad 100% by weight.

Preferably contains the composition of components A), B), and C), and optionally other ingredients usually added to middle distillates, a total of less than 1, in particular at most 0.1 wt .-% naphthalene.

Next the middle distillate cold flow improvers can the compositions according to the invention further Contain ingredients that are usually added to middle distillates. Such ingredients are, for example, dewaxing aids, Corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, Dehazer and additives for lowering the cloud point.

Tabelle 2: Charakterisierung der SN-Qualitäten

Various cold flow improvers specified in Table 1 were dissolved in low-naphthalene and non-naphthalene SN and the pour point (PP) of the solution was determined. Table 1: Characterization of the cold flow improvers

Table 2: Characterization of SN qualities

Table 3 shows the results of the PP determination obtained with the middle distillate cold flow improvers indicated in Table 1 in the SN grades indicated in Table 2. Table 3: Pour Points (PP) without the addition of ingredient C)

Table 4 shows the pour point results obtained with various components C) in Solvent Naphtha A150 ND. Table 4: Pour Point Effectiveness of Various Ingredients C) Constituent A was always SN A150 ND

Claims (13)

A composition comprising A) solvent naphtha having a naphthalene content of less than 1% by weight, B) a middle distillate cold flow improver and C) a solubilizing additive selected from aliphatic or alicyclic C ₁ to C ₂₂ alcohols, cycloaliphatic hydrocarbons and monocyclic aromatic hydrocarbons. A composition according to claim 1, wherein component C) is a monohydric alcohol. A composition according to claim 1 and / or 2, wherein Component C) methanol, ethanol, 2-ethylhexanol and / or cyclohexanol is. A composition according to claim 1, wherein component C) a mono- or polycyclic hydrocarbon having 6 to 12 Carbon atoms. A composition according to claim 4, wherein component C) is cyclohexane, norbornane or norbornene. A composition according to claim 1, wherein component C) one of the isomeric nonylphenols, hydroxybenzenes and / or salicylaldehyde is. Composition according to one or more of claims 1 to 6, wherein component B) is a polymer having from 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene. Composition according to one or more of claims 1 to 6, wherein component B) is an ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymer, ethylene / vinyl acetate / vinyl neononanoate terpolyme and / or ethylene-vinyl acetate / vinyl neodecanoate terpolymers. Composition according to one or more of claims 1 to 6, wherein component B) is a copolymer which in addition to ethylene and 10 to 40% by weight of vinyl esters and / or 1 to 40% by weight of long-chain Vinyl ester still contains 0.5 to 20 wt .-% of olefin having 3 to 10 carbon atoms. Composition according to one or more of claims 1 to 6, wherein component B is an amine salt, imide or amide of secondary fatty amines with 8 to 36 carbon atoms is. Composition according to one or more of claims 1 to 10, wherein component A) solvent naphtha with at most 0.1 wt .-% naphthalene content is. Composition according to one or more of claims 1 to 10, wherein component A) solvent naphtha with more than 90 wt .-% Aromatic content is. Use of solutions of middle distillate cold flow improvers in solvent naphtha with less than 1% by weight naphthalene content, containing aliphatic or alicyclic C ₁ to C ₂₂ alcohols, cycloaliphatic hydrocarbons or monocyclic aromatic hydrocarbons, as cold additives in middle distillates, biofuel oils or mixtures thereof.