WO2014012640A2

WO2014012640A2 - Method for lowering the hydrogen sulphide content of mineral oils and residues of the mineral oil destillation

Info

Publication number: WO2014012640A2
Application number: PCT/EP2013/002068
Authority: WO
Inventors: Michael Brauchle; Gabriela CANTANOIU; Michael Feustel; Matthias Krull; Rainer Albert RAKOCZY
Original assignee: Clariant International Ltd
Priority date: 2012-07-20
Filing date: 2013-07-11
Publication date: 2014-01-23
Also published as: DE102012014473A1; WO2014012640A3

Abstract

The invention relates to the use of compositions which contain at least one hydrophobically coated hydrotalcite dispersed in an organic solvent, for lowering the mineral oil content and residues of mineral oil distillation of H₂S and thiols.

Description

description

Method for lowering the hydrogen sulfide content of mineral oils and residues of mineral oil distillation

The present invention relates to a process for reducing the content of mineral oils and residues of mineral oil distillation of hydrogen sulfide and sulfides. Crude oils and the products made from them in refineries

usually larger amounts of hydrogen sulfide (H ₂ S) and mercaptans. The problem here is especially the accumulating in the gas space above the oil H ₂ S, which is released, for example, during loading operations and in the breath even at concentrations of about 100 ppm can endanger employees. Furthermore, H ₂ S as well as mercaptans have a typical, very unpleasant odor, which is perceived by the human sense of smell even at very low concentrations. Furthermore owns

Hydrogen sulphide, especially when combined with water, has highly corrosive properties that may affect the functionality and safety of storage, transport and processing equipment. Therefore, great efforts are being made in industry to reduce the content of raw and

Residue oils as well as mineral oil distillates to reduce H2S, on the one hand to limit the environmental impact and on the other hand to ensure safe handling of these oils. Against this background, the legislature admits the permissible levels in mineral oil products

Hydrogen sulfide regulated and lowered further and further. Thus, according to ISO / FDIS 8217: 2010 (E), only 2 ppm H ₂ S in bunker oils will be permitted in the future, and such measures are also being discussed for other residues of mineral oil distillation such as bitumen. Consequently, these trends also call for adequate measures to lower the H ₂ S content. An additional problem often arises with heavy and viscous crude oils, residual oils and mineral oils containing crude oils such as mazut, heavy fuel oils and bunker oils. These are often stored at elevated temperatures of 70 ° C and more such as 90 ° C and more, to facilitate their handling; Bitumen is often stored even at temperatures above 150 ° C and partially above 80 ° C. Under these conditions, it is often observed that the content of hydrogen sulfide, which has been set to specification-compliant values according to known methods, increases again after a short storage period of the oils. The reason for this is likely to be accelerated reactions of the sulfur compounds contained in the oil, such as cyclic or

be aromatic hydrocarbons with bound sulfur, mercaptans and also elemental sulfur to H2S. This from oil components at

Heating replicated H ₂ S, which is also referred to as inherent H ₂ S in the context of this invention, must also be bound, which requires over the entire storage life of the oil cross-cutting measures.

A common method for lowering the H ₂ S content of mineral oils is their treatment with H ₂ S-binding, designated as H ₂ S scavengers

chemical additives. Regenerative systems are used in many cases in which the H ₂ S of an adsorbent (the terms adsorbent and adsorption in the context of this application in a broad sense

and also includes absorbent) such as an alkanolamine, poly (ethylene glycol) or hindered amine extracted from the oil and the adsorbent is regenerated in a second step for reuse. There are also non-regenerative processes in which

H ₂ S scavengers such as formaldehyde, whose reaction products with amines such as triazines, glyoxal, metal oxides, metal sulfonates and other organometallic compounds with H ₂ S to difficult to volatilize

Connections react. A common method for the separation of smaller amounts of H ₂ S is the treatment of H ₂ S-containing mineral oils with a scavenger based on 3,5-trialkyl-substituted triazines. Triazines, which are condensation products of amines such as Monoethanolamine or monomethylamine with formaldehyde, contain nitrogen, which at higher amounts, especially in crude oils

Can cause problems in certain refineries. In addition, formaldehyde-containing scavengers are unpopular in terms of health and environmental protection. The alternatively used Glyoxal is also harmful to health and also corrosive. In addition, formaldehyde, triazines and also glyoxal in raw and residual oils often have an unsatisfactory effectiveness. In particular, they are relatively volatile and thermostable only to a limited extent, so that they are not suitable for binding the inherent H ₂ S which is gradually replicated during prolonged warm storage.

Widely used in residual oils and especially in bitumen

H ₂ S scavengers are transition metals and their oxides and salts, which react with H ₂ S to form highly volatile and often also slightly soluble sulfides. Thus, US-A-5000835 discloses the use of oil-soluble metal carboxylates for reducing the release of H ₂ S. WO-A-2009/105444

Transition metal borate complexes for the same purpose. Also the

Metal carboxylates often show only limited efficiency in residual oils. Often, they can also release the inherent H ₂ S at longer

Do not effectively suppress storage at high temperatures.

Also, certain salts and oxides containing elements of the second main group of the Periodic Table of the Elements such as magnesium and aluminum have a high affinity for hydrogen sulfide and mercaptans. For example, certain spinels (US-A-4690806), zeolites

(US-A-2006/0043001) and also LDHs (layered double hydroxides;

US-A-5951851, US-A-6027636) as H ₂ S scavengers.

US-A-5951851 and US-A-6027636 disclose processes for removing elemental sulfur and mercaptans from liquid hydrocarbons by contacting sulfur-containing liquid hydrocarbons with hydrotalcite. The treatment of the hydrocarbon takes place at room temperature or slightly elevated temperatures by adding, for example, powder or pellets to the oil followed by filtration or by means of a solid bed through which the hydrocarbon flows.

EP-A-2155359 discloses a process for the deacidification of natural gas in which natural gas containing H ₂ S and / or mercaptans is contacted with an aqueous suspension of a layered double hydroxide.

Both the required high dosage rates as well as the low

Reaction rate of hydrotalcite with H2S or mercaptans, however, are often unsatisfactory. Presumably, the polar surface in mineral oils is only partially accessible and / or the surface of the pellets too small.

EP 1329419 A discloses dispersions of hydrotalcite in polar organic solvents. By coating with higher fatty acids, partial esters of

Phosphoric acid, with silanes, titanates or aluminates, the properties of the dispersions can be improved.

EP 63631 A discloses suspensions of hydrotalcite in non-polar organic solvents. By coating the hydrotalcite with 1 - 10 wt .-%

surface-active anionic substances such as alkali salts of higher fatty acids (soaps) and / or hydrocarbon radicals bearing sulfonic acids, the suspensions are stabilized. The suspensions are at room temperature

stable for at least 2 months. They are used in combination with overbased agents as detergent-dispersant additives for lubricating and fuel oils.

It was now the task of providing a means that the content of mineral oils and in particular of residues of the

Lowering mineral oil distillation of hydrogen sulphide and volatile mercaptans at low dosing rates. It should reduce the salary

Hydrogen sulfide and volatile mercaptans to the lowest possible values and in particular values below the relevant relevant

Specification limits may be possible. In addition, the fastest possible achievement of these values desirable. Furthermore, the content of free H ₂ S, even with prolonged storage of the additivierten oil such as mehrtätiger and in particular several weeks of storage at elevated temperatures such

remain low, for example, above 80 ° C and especially above 120 ° C and especially above 150 ° C without replenishment of the agent. In particular, with mineral oil distillates, it would also be desirable to simultaneously

Lower the sulfur content of the oil in order to adjust the low specification levels required for marketable fuel oils. Surprisingly, it has been found that by adding a dispersion of hydrophobically coated hydrotalcite in organic solvent to mineral oils, and in particular to residues of mineral oil distillation, a very fast, efficient and also permanent reduction of the content of H2S and

Mercaptans is enabled. Both the reaction rate of the hydrotalcite and its scavenger capacity are significantly greater than in the previously used powder or pellet form. In addition, inherent H ₂ S released during storage at high temperatures is efficiently bound for long periods of time. In addition, the sulfur content in mineral oil distillates can be lowered by removing the mineral oil distillate-insoluble adduct of hydrotalcite with H ₂ S and / or mercaptans therefrom.

The invention relates to the use of compositions containing at least one hydrophobically coated hydrotalcite dispersed in an organic solvent for lowering the content of mineral oils and residues of mineral oil distillation on H ₂ S and mercaptans.

Another object of the invention is a method for lowering the content of mineral oils and residues of mineral oil distillation of H ₂ S and mercaptans by the mineral oil or the residue of the mineral oil distillation is added to a composition containing at least one in a

organic solvent dispersed, hydrophobically coated hydrotalcite contains. Another object of the invention are mineral oils and residues of mineral oil distillation containing at least one hydrophobically coated hydrotalcite.

It is also an object of the invention to reduce the total sulfur content of mineral oils. This can be achieved according to the invention by adding after the addition of hydrophobic coated hydrotalcite

Separation of the resulting, insoluble in mineral oil adduct in addition to the H ₂ S content and the S content is lowered.

Another object of the invention is therefore a method for lowering the sulfur content of mineral oils, wherein the H ₂ S and / or mercaptans

containing mineral oil

i) is admixed with a composition containing at least one, hydrophobically coated hydrotalcite dispersed in an organic solvent, and

ii) the mineral oil thus treated for one for the implementation of the hydrophobic

coated hydrotalcite is mixed with the H ₂ S contained in the mineral oil and / or the mercaptans sufficient time, and

iii) the mineral oil-insoluble adduct is separated off.

Hydrotalcite is generally understood here to mean compounds which have a hydrotalcite structure. Thus, in addition to naturally occurring also synthetically producible variants of this mineral includes. These compounds have hybrid layer structures and are referred to in the Anglo-Saxon as layered double hydroxides (LDH). Hydrotalcite is a mineral from the mineral class of carbonates (and related) that is derived from the crystal structure of brucite Mg (OH) ₂ . While the layers formed by metal hydroxide in brucite are electroneutral, isomorphous substitution of divalent Mg cations with trivalent cations such as Al ³⁺ ions results in a positive overall charge of the mixed metal hydroxide layers. This positive charge of the metal hydroxide layers is due to carbonate ions in intermediate layers, which continue to stabilize the crystal structure Contain water molecules, neutralized. LDHs thus have alternating

Metal (2+) - Metal (3+) - Hydroxide layers and anions-water layers on. Crystal structure and current classification of LDHs are described, for example, in Bulgarian Geological Society, Annual Scientific Conference "Geology 2004" 16-17.12.2004.

Preferred compounds having hydrotalcite structure have the general

Formula (1) [M ²⁺ _1-x M ³⁺ _x (OH) _2] ^{x +} [(A ⁿ -) x / _n - (H ₂ 0) _m] (1) wherein

M ²⁺ for at least one divalent metal ion,

M ³⁺ for at least one trivalent metal ion,

A ^{n "} for at least one anion with the valency of n,

X is a number from 0.1 to 0.6,

n for 1 or 2, and

m stands for a number between 0 and 1. Suitable divalent metal ions are, for example, Mg, Zn, Co, Mn, Fe ²⁺ , Cd ²⁺ , Ca ²⁺ , Cu ²⁺ and Ni ²⁺ . In a preferred embodiment, the divalent metal ion is Mg ²⁺ . In a further preferred embodiment, the hydrotalcite contains, as the divalent metal ion, Mg.sup.2 ⁺ which is 0 to 60 mol%, more preferably 0.1 to 50 mol%, and especially 0.5 to 30 mol%, such as 1, for example to 20 mol% is replaced by at least one other divalent metal ion. Preferred further divalent metal ions are

for example Zn ⁺ , Co ²⁺ , Mn ²⁺ , Fe ²⁺ , Cd ²⁺ , Ca ²⁺ , Cu ²⁺ and Ni ²⁺ .

Suitable trivalent metal ions are, for example, Al, Fe, Cr, Mn, Co, Ga ³⁺ and ln ³⁺ . In a preferred embodiment, the trivalent metal ion is Al ³⁺ . In a further preferred embodiment, the hydrotalcite trivalent metal ion contains Al ³⁺ which is 0 to 50 mol% and especially 0.1 to 30 mol%, for example 1 to 20 mol%, by at least one other trivalent Metal ion is replaced. Preferred further trivalent metal ions are

for example Fe ³⁺ , Cr ³⁺ , Mn ³⁺ , Co ³⁺ Ga ³⁺ and ln ³⁺ .

Suitable anions A ^{n "} are, for example, OH ^" , Cl ^" , CO ₃ ^{2 ~} , SO ₄ ^{2 ~} , NO ₃ ^" , SO ₃ ^{2 "} , S ₂ O ₃ ^2" , HPO ₄ ^{2 "} , PO ₄ ^3" , HPO ₃ ^{2 "} , PO ₃ ^3" , P0 ₂ ^" , H ² BO ₃ ^" , SiO ₃ ^{2 '} , HSi ₂ 0 ₅ ^" , Si ₂ O ₅ ^{2 ~} and organic anions A particularly preferred anion is CO ₃ ^2" .

Preferably, x is a number from 0.12 to 0.50, more preferably from 0.15 to 0.40 and especially from 0.2 to 0.33.

In a particularly preferred embodiment, these are magnesium-aluminum-hydroxy-carbonates of the formula (2)

[Mg _1-x Al _x (OH) ₂ ] ²⁺ [(CO ₃ ) _y (A ⁿ -) z. (H ₂ O) _m ] (2) wherein

x, n and m have the meanings given above,

A ^{n "} , for at least one anion with the valency of n with the exception of CO ₃ ^2" and

(2y + nz) stands for a number between 0.9 and 1.5x.

Examples of particularly preferred hydrotalcites are compounds of the

Formulas (3) to (7). Mg ₄ Al 2 (OH) ₁ 3 ₁ 2 (CO ₃ ) o _{> 4} * H ₂ O (3)

Mg ₅ Al ₂ (OH) ₁₄ (CO ₃ ) .4H ₂ O (4)

Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O (5)

Mg8Al2 (OH) i9,6 (C03) i, 2 · 2 H ₂ O (6)

Al ₄ Mg ₆ Zn ₂ (OH) ₂₄ (CO ₃ ) ₂ · 10 H ₂ O (7)

LHDs suitable according to the invention can be natural or synthetic

Be of origin. Particularly preferred calcined hydrotalcites are used because they have an increased adsorption capacity for H ₂ S. When using of synthetic hydrotalcites whose production process for the use according to the invention as well as for the inventive method of secondary importance. For example, by coprecipitation with the addition of soda to aqueous solutions of magnesium and

Aluminum nitrate or chloride and subsequent hydrothermal treatment (calcination) of the precipitate produced hydrotalcites successfully used. Further suitable production methods are described, for example, in Appl. Organometallic chemistry. Chem. 2009, 23, 335-346. The volumetric particle size distribution of the hydrophobically coated hydrotalcite in the dispersion is preferably such that at least 90% of the particles (D90) have a size below 200 .mu.m and more preferably between 10 nm and 100 .mu.m. Specifically, at least 90% of the particles have a particle size between 0.1 pm and 50 pm. The mean volumetric particle size (D50) is preferably between 0.1 pm and 100 pm and especially between 0.5 pm and 75 pm. While smaller particles do not show sufficient stability, larger particles are difficult to disperse. The particle size is determined by laser light scattering (laser diffraction, low angle laser light scattering, LALLS) on the dispersion of the hydrophobically coated hydrotalcite in the organic solvent. The surface area of the hydrotalcites used for the preparation of the dispersion determined by the BET method is preferably between 0.1 and 500 m ² / g, more preferably between 1 and 350 m ² / g, especially between 2 and 200 m ² / g and in particular between 3 and 100 m ² / g such as between 5 and 50 m ² / g.

The hydrophobic coating of the hydrotalcite used according to the invention and used in the process according to the invention makes it possible on the one hand to disperse the hydrotalcite in organic solvents and thus to meter in flowable additives. In addition, the storage stability of the dispersion is improved because agglomeration of the hydrotalcite is suppressed in the additive or at least reduced. In addition, the hydrophobic coating leads to a very homogeneous distribution of hydrotalcite in the additized hbS-containing mineral oils and in particular the H ₂ S-containing residues of mineral oil distillation.

The hydrotalcite used according to the invention is preferably hydrophobicized with an anionic, surface-active compound. Especially preferred

Hydrophobizing agents are optionally substituted

Carbon hydrogen radicals with 4 to 200 carbon atoms bearing carboxylic acids and their salts and optionally substituted hydrocarbon radicals having 4 to 40 carbon atoms bearing sulfonic acids and their salts. Suitable substituents of the hydrocarbon radicals are, for example, hydroxyl groups and their ethers with C 1 -C ₁₀ -alcohols and their esters with C 1 -C ₁₀ -carboxylic acids, and nitro groups and halogens such as, for example, chlorine and fluorine. Also mixtures of different hydrophobizing agents are suitable. Carboxylic acids preferred as hydrophobizing agents have one or more, such as, for example, two, three or more carboxyl groups. Preferred monocarboxylic acids carry an optionally substituted

Hydrocarbon radical having 4 to 40 carbon atoms, particularly preferably having 5 to 30 carbon atoms and in particular having 7 to 24 carbon atoms such as 9 to 20 carbon atoms. They can be natural or synthetic. The hydrocarbon radical can also contain heteroatoms such as, for example, oxygen, nitrogen, phosphorus and / or sulfur, but preferably not more than one heteroatom per 3 C atoms. In a preferred embodiment, the monocarboxylic acids carry an aliphatic hydrocarbon radical. The aliphatic hydrocarbon radical can be linear, branched or cyclic. The

Carboxyl group may be bonded to a primary, secondary or tertiary carbon atom. It is preferably bound to a primary carbon atom. The hydrocarbon radical may be saturated or unsaturated. unsaturated

Hydrocarbon radicals preferably contain one or more

C = C double bonds and more preferably one, two or three

C = C-double bonds. In a specific embodiment, the hydrotalcite is coated with a fatty acid having 8 to 24 carbon atoms. In a further preferred embodiment, aryl radicals are carrying

Ci-C6 monocarboxylic acids used. Aliphatic C to C ₆ monocarboxylic acids and in particular aliphatic cis bis are preferred

C ₃ monocarboxylic acids. These can carry an aryl radical at any point on the alkyl chain; it is preferably in the 2- or 3-position of the alkyl radical. Preferred aryl radicals have 2 or 3 aromatic rings. The aromatic rings may contain heteroatoms such as nitrogen, oxygen and / or sulfur. Examples of suitable aryl radicals are phenyl, naphthyl and pyridyl radicals. The aryl radicals may in turn carry one or more substituents such as, for example, C 1 -C ₈ -alkyl radicals, C 1 -C ₈ -oxyalkyl radicals and hydroxyl groups. However, they preferably do not carry more than 3 and in particular not more than 2 substituents per aromatic ring.

Other preferred carboxylic acids for hydrophobization are

Alkylarylcarboxylic acids such as alkylphenylcarboxylic acids. These are aromatic carboxylic acids in which the aryl group carrying the carboxyl group additionally carries at least one alkyl or alkenyl radical having one or two to 50 carbon atoms. The aryl radical may be one or more, such as two, three or more aromatic systems, and 6 to

Contain 50 carbon atoms. It preferably contains an aromatic system. Also particularly advantageous are alkylbenzoic acids containing at least one alkyl radical having 1 to 50 carbon atoms, preferably having 2 to 20 carbon atoms and

in particular carry 3 to 18 carbon atoms. In a further preferred embodiment, as

Hydrophobizing agent polycarboxylic acids and particularly preferred

Dicarboxylic acids used. Aliphatic dicarboxylic acids which carry an alkyl or alkenyl radical having 8 to 200 carbon atoms and in particular having 0 to 150 carbon atoms, for example 12 to 120 carbon atoms, have proven particularly useful. The alkyl or alkenyl radical can be linear or branched.

Particularly preferred are linear alkyl and alkenyl radicals having 8 to 40 carbon atoms and in particular having 10 to 28 carbon atoms. Further preferred are branched alkyl and alkenyl radicals having 12 to 200 carbon atoms and in particular 20 to 150 C atoms, such as having 50 to 120 carbon atoms.

Likewise, the anhydrides of polycarboxylic acids, and especially dicarboxylic acids, are useful as hydrophobizing agents. So have yourself

for example, by addition of linear α-olefins having 8 to 40 carbon atoms and in particular having 10 to 28 carbon atoms to maleic acid or maleic anhydride producible succinic acids and succinic anhydrides as

Hydrophobization agent especially proven. Furthermore, have proven particularly useful by addition of branched olefins having 12 to 200 carbon atoms and in particular having 20 to 150 carbon atoms such as 50 bis

120 C-atoms of maleic acid or maleic anhydride producible

Succinic and succinic anhydrides. Preferred branched olefins are obtainable, for example, by oligomerization of lower olefins having 3 to 5 C atoms, such as propene, n-butene, isobutene and / or pentene.

Furthermore, partial esters and partial amides of polycarboxylic acids and in particular of dicarboxylic acids with alcohols or amines, which carry an optionally substituted hydrocarbon radical having 1 to 40 carbon atoms and in particular having 2 to 24 carbon atoms such as 3 to 12 carbon atoms as hydrophobizing agent proven. Preferred partial esters and amides have at least one free carboxyl or carboxylate group per

Molecule. Examples of suitable alcohols for the preparation of partial esters are methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol and fatty alcohols having 10 to 24 carbon atoms and tertiary amino-carrying alcohols such as N, N-dimethylaminoethanol, Ν, Ν- Diethylaminoethanol, N, N-dimethylaminopropanol, Ν, Ν-diethylaminopropanol and

1- (2-hydroxyethyl) piperidine. Examples of suitable amines for the preparation of partial amides are secondary amines such as dimethylamine,

Diethylamine, dibutylamine, di (2-ethylhexyl) amine and N-methylbutylamine. Such partial esters and amides can be prepared, for example, by reacting the corresponding acid anhydrides with an approximately equimolar amount of alcohol or amine. Suitable carboxylic acids are, for example, pentanoic acid, iso-pentanoic acid, pivalic acid, phenylacetic acid, (methoxyphenyl) acetic acid,

(Dimethoxyphenyl) acetic acid, 2-phenylpropionic acid, 3-phenylpropionic acid, 3- (4-hydroxyphenyl) propionic acid, 4-hydroxyphenoxyacetic acid, indoleacetic acid, the various isomers of pyridinoacetic acid, hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, neononanoic acid, decanoic acid,

Neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid,

Tridecanoic acid, iso-tridecanoic acid, tetradecanoic acid, 12-methyltridecanoic acid, pentadecanoic acid, 13-methyltetradecanoic acid, 12-methyltetradecanoic acid,

Hexadecanoic acid, 14-methylpentadecanoic acid, heptadecanoic acid,

5-methylhexadecanoic acid, 14-methylhexadecanoic acid, octadecanoic acid,

Iso-octadecanoic acid, icosanoic acid, docosanoic acid and tetracosanoic acid,

Myristolein, palmitoleic, hexadecadiene, delta-9-cis-heptadecene, oil,

Petroselen, Vaccene, Linol, Linolen, Gadolein, Gondo, Icosadien, Arachidone, Cetolein, Eruca-, Docosadien- and Tetracosensic Acid, 5-Hydroxyhexanoic Acid, 2-Hydroxyoctanoic Acid, 2-Hydroxytetradecanoic Acid, 15-Hydroxypentadecanoic Acid , 6-hydroxyhexadecanoic acid and 12-hydroxystearic acid, decylbenzoic acid, dodecylbenzoic acid, tetradecylbenzoic acid, hexadecylbenzoic acid and octadecylbenzoic acid and mixtures thereof. Further suitable and preferred are natural fats and oils such as

Cottonseed, coconut, peanut, safflower, corn, palm kernel, rapeseed, olive, mustard, soya, sunflower and tallow, bone and fish oil derived carboxylic acid mixtures. Examples of suitable dicarboxylic acids are dodecenylsuccinic acid, tetradecenylsuccinic acid,

Hexadecenyl succinic acid, octadecenyl succinic acid,

Eicosenylsuccinic acid, poly (isobutenyl) succinic acid and their anhydrides. As carboxylic acids or carboxylic acid mixtures for the process according to the invention are also suitable tall oil fatty acid and resin and

Naphthenic acids.

Sulfonic acids preferred as hydrophobizing agents have at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical with 4 to 40 C atoms and preferably with 6 to 24 C atoms. In addition to aliphatic

Sulfonic acids are especially preferred aromatic sulfonic acids and especially alkyl aromatic sulfonic acids. The aryl radical may contain one or more, for example two, three or more aromatic systems and 6 to 50 carbon atoms. It preferably contains an aromatic system. Also particularly advantageous are alkylaromatic sulfonic acids, the

at least one alkyl radical having 1 to 36 carbon atoms, preferably 2 to

24 C atoms and in particular 3 to 18 carbon atoms on the aryl radical wear. Suitable examples are benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid,

2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid and mixtures thereof.

Likewise, the alkali and ammonium salts of said carboxylic and sulfonic acids are useful as hydrophobizing agents. Examples of alkali salts are the sodium and potassium salts. In addition to the salts derived from the ammonia, the ammonium salts which have proven useful, in particular, are those derived from amines of the formula (8),

NR ¹ R ² R ³ (8) wherein

R ¹ represents an optionally substituted hydrocarbon radical having 1 to 50 carbon atoms, in particular d- to C ₂ o alkyl, C ₃ - to C ₂ o-alkenyl, C ₆ - to C ₂ o-aryl or for at least one Hydroxyl-bearing hydrocarbon radical having 1 to 10 carbon atoms and in particular having 2 to 8 carbon atoms or a group of the formula - (B-0) _p -R ⁴ and

R ² , R ^{3 are} independently hydrogen or R ¹ or

R ¹ and R ² or R ² and R ³ together for a cyclic hydrocarbon radical having 4 to 10 carbon atoms and

B is an alkylene radical having 2 to 6 C atoms, preferably 2 or

3 C atoms,

p is a number from 1 to 50, preferably from 2 to 20, in particular from 3 to 10 and especially for 1 or 2 and

R ^{4 is} hydrogen, a hydrocarbon radical having 1 to 50 C atoms,

in particular C 1 to C 20 alkyl, C ₂ to C 20 alkenyl, C 6 to C 18 aryl or a group of the formula B-NH ₂ .

For example, sodium, potassium and ammonium stearate, sodium, potassium and ammonium oleate, sodium, potassium and ammonium palmitate, sodium and potassium linolates, sodium potassium and ammonium laurylbenzenesulfonate and sodium, potassium and ammonium butyl naphthylsulfonate have proven particularly useful. Furthermore, the corresponding salts of trimethylamine,

Triethylamine, ethanolamine, diethanolamine triethanolamine,

Ν, Ν-dimethylaminoethanol, N, N-diethylaminoethanol,

N, N-Dimethylaminopropanols Ν, Ν-Diethylaminopropanols and of 1- (2-hydroxyethyl) piperidine particularly proven.

The hydrophobic coating of the hydrotalcite is carried out by known methods such as, for example, by jointly grinding hydrotalcite with the hydrophobizing agent or by adding an aqueous suspension of the hydrotalcite with the hydrophobizing agent or an aqueous solution thereof, then removing the solvent and drying the thus coated hydrotalcite.

Preference is given to hydrophobizing the hydrotalcite 0.5 to 10 wt .-%, particularly preferably 1 to 7 wt .-% and in particular 1, 5 to 5 wt .-%

- Based on the mass of the hydrotalcite to be coated - on

Hydrophobization agent used.

The hydrophobic coating makes it possible to disperse the per se hydrophilic hydrotalcite in organic solvents. Preferred organic solvents are aliphatic and aromatic hydrocarbons and mixtures thereof. Particular preference is given to solvents having a low solidification point (pour point, in accordance with ASTM D97) of preferably below 0 ° C. and in particular between -10 ° C. and -60 ° C., for example between -15 ° C. and -50 ° C. Preferably, the onset of boiling of the organic solvent is above the pour point of the oil to be treated and in particular 10 ° C and especially at least 25 ° C above the pour point of the oil to be treated.

Preferred solvents also have a kinematic viscosity at 40 ° C (according to ASTM D445) of more than 2 mm ² / s and in particular between 3 and 100 mm ² / s, for example between 5 and 50 mm ² / s.

Aliphatic hydrocarbons preferred as solvents have 9 to

24 C atoms and in particular 10 to 20 C atoms. They can be linear, branched and / or cyclic. They may also be saturated or unsaturated, preferably they are saturated or at least largely saturated. When

Solvents preferred aromatic hydrocarbons have 7 to 20 C-atoms and in particular 8 to 16 such as 9 to 13 C-atoms. Preferred aromatic hydrocarbons are mono-, di-, tri- and polycyclic aromatics. In a preferred embodiment, these carry one or more, for example two, three, four, five or more substituents. With several substituents they may be the same or different. preferred

Substituents are alkyl radicals having 1 to 20 and in particular having 1 to 5 C atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl and neo-pentyl. Examples of suitable aromatics are alkylbenzenes and alkylnaphthalenes. So are

for example, aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for. As gasoline fractions, kerosene, decane, pentadecane or commercial solvent mixtures such as solvent naphtha, Shellsoll ^® AB, Solvesso ^® 150, Solvesso ^® 200, Exxsol ^® , ISOPAR ^® and Shellsol ^® D types suitable. The specified solvent mixtures contain different amounts of aliphatic and / or aromatic hydrocarbons. Particularly useful as solvents are partially hydrogenated naphthenic oils having a content of naphthenic carbons determined in accordance with ASTM D2140-08 of more than 10% by weight and in particular between 15 and 70% by weight

for example, between 20 and 60 wt .-%. Such solvents are

for example, under the brand Nytex ^® available. Optionally, the organic solvent may also contain polar components such as. As alcohols, organic acids, ethers and / or esters of organic acids or alcohols or consist of these. Preferred polar constituents have 4 to 24 C atoms, particularly preferably 6 to 18 and in particular 8 to 16 C atoms. Examples of suitable polar constituents are 2-ethylhexanol, decanol, iso-decanol, iso-tridecanol, nonylpenol, benzoic acid, oleic acid, dihexyl ether, dioctyl ether, 2-ethylhexyl acid butyrate, ethyl octanoate, ethylhexanoate, butyl 2-ethylhexylate and 2-ethylhexyl butyrate and higher ethers and / or or higher esters such as di (2-ethylhexyl) ether, 2-ethylhexylic acid 2-ethylhexyl ester and 2-ethylhexyl stearate. Further preferred polar constituents are alkoxylated C ₄ -C ₄ o-fatty alcohols and alkoxylated

C ₄ -C ₄ o-fatty acids. These alkoxilates contain preferably 1 to 100 mol and in particular 2 to 50 mol such as, for example, 3 to 20 mol of alkylene oxide per mole of fatty alcohol or fatty acid. Preferred alkylene oxides are ethylene oxide, propylene oxide and mixtures thereof.

In addition to the mineral oil based solvents are also on

renewable raw materials such as, for example, based on plant and / or animal oils solvents and the derived from C to C ₅ alkyl esters and especially the methyl esters (biodiesel) such as rapeseed, methyl sunflower, Cocosölfettsäuremethylester and their

Mixtures suitable. Synthetic hydrocarbons which are obtainable, for example, by the Fischer-Tropsch process or by hydrodeoxygenation of renewable raw materials have also been used successfully as solvents. Mixtures of the solvents mentioned are also suitable.

The compositions (dispersions) used according to the invention preferably contain from 10 to 60% by weight and especially from 15 to 50% by weight as is

For example, 20 to 40 wt .-% of at least one hydrophobic coated hydrotalcite. The proportion of dispersions of organic solvent is preferably between 40 and 90 wt .-%, and especially between 50 and 85 wt .-%, such as between 60 and 80 wt .-%. The dispersions are usually prepared by mixing hydrophobically coated hydrotalcite and organic solvent

Temperatures between 20 and 60 ° C and subsequent homogenization. For homogenization, it has been proven that the mixture has high shear rates of preferably at least 10 ³ s ^-1 and especially of at least 10 ⁵ s ^-1 as

For example, at least 10 ⁶ s ^" suspend, as for example by means of stirrers, jet mixers, sprocket dispersers (eg Ultra-Turrax ^® ) or high-pressure homogenizers with classic or preferably crooked

Channel architecture (Microfluidizer ^® ) can be generated. Also by cavitron, ultrasound and special mills such as ball mills and

Agitator ball mills are suitable shear rates achievable. During homogenization often takes place a reduction in the size of the particles used. It has often been found useful to add further emulsifiers and / or rheology-modifying substances to the dispersions of the invention used to further prevent the settling of dispersed particles.

Preferred emulsifiers are anionic, cationic and nonionic oil-soluble surfactants. In a preferred embodiment, as further emulsifiers the anionic, surface-active compounds described for the hydrophobization of the hydrotalcite are used, wherein

Hydrophobizing agent and other emulsifier may be the same or different. In a preferred embodiment, the dispersions used according to the invention comprise from 0.1 to 10% by weight and in particular from 0.2 to 7% by weight and in particular from 0.5 to 5% by weight of at least one further emulsifier.

Preferred rheology-modifying substances are amphiphilic organic compounds such as hydrogenated castor oil derivatives, natural and synthetic oil-soluble polymers such as poly (olefins), as well as in organic solvents swellable clay minerals such as

organophilic bentonite or silicas. In a preferred embodiment, the dispersions used according to the invention contain from 0.01 to 5% by weight and in particular from 0.1 to 2% by weight of at least one rheology-modifying substance. According to the process of the invention, the dispersion of the hydrophobically coated hydrotalcite is mixed into the mineral oil to be treated or the mineral oil distillation residue to be treated. Preferably, the dispersion is added above the pour point of the mineral oil or the mineral oil distillation residue to be treated, more preferably at least 10 ° C and especially from 20 to 70 ° C such as 30 to 50 ° C above the pour point of the oil. The temperature of the dispersion can vary within wide limits. It is preferably used at temperatures at which it is pumpable. Thus, it has proven useful to use the dispersion at temperatures between -20 ° C and +60 ° C and preferably between 0 ° C and +50 ° C such as between +10 ° C and +40 ° C.

The use according to the invention and the method according to the invention are particularly suitable for lowering the content of H 2 S and / or

Mercaptans in liquid or viscous hydrocarbons. Often it is a simultaneous lowering of the content of the liquid or viscous

Hydrocarbon observed on SO ₂ . In particular, they are suitable for the treatment of crude oil and residues of crude oil distillation at atmospheric pressure as well as in vacuum such as for bunker oils and for residues of the visbreaker. Specifically, they are suitable for the treatment of bitumen.

The use according to the invention and the method according to the invention are also suitable for lowering the H ₂ S and / or mercaptan content of fuel oils such as jet fuel, kerosene, gasoline, diesel and heating oils. Since the remaining in the fuel oil, derived from hydrotalcite solid ingredients in the further use of fuel oils are undesirable, they must be removed, which for example by

Decantation, filtration or centrifugation can be done. In this way, at the same time, the total sulfur content of the treated oil is lowered.

The metering rates of the at least one in an organic solvent used in the inventive use and inventive method dispersed, hydrophobically coated hydrotalcite-containing compositions are preferably between 2 and 30 ppm by weight and more preferably between 3 and 20 ppm by weight such as between 5 and 15 ppm by weight of the composition per ppm by weight H ₂ S in the oil , The

Determination of the H ₂ S content can be carried out by known methods such as ASTM D6021, UOP163, ASTM D3227 or IP 399.

With the method according to the invention, the content of mineral oils and in particular of residual oils to H ₂ S and mercaptans is lowered rapidly and efficiently. The hydrophobic coating of the LDH facilitates its distribution in the most viscous mineral oils and in particular in residual oils such as bitumen, which leads to a significant acceleration of the lowering of the H ₂ S content. Due to the fast conversion rate that is

inventive method especially advantageous where the residence time of H ₂ S-containing oils is limited. For example, it has proven to be successful on off-shore platforms, where space is limited and thus only short contact times between oil and H ₂ S scavengers are available before the transfer point.

The adsorption capacity of the invention used

Compositions for H ₂ S are significantly higher than those of currently used scavengers. While the latter are often used with a high overdose in order to reduce the H ₂ S content to a specification-compliant level, last but not least, the short reaction times of the process according to the invention also allow a significantly lower dosage of the additive.

The adsorption capacity of hydrotalcite in mineral oils and residual oils is retained even when the additive oils are stored at elevated temperatures over long periods of time, so that inherent H ₂ S which is also reproduced gradually by aging processes of the oil is intercepted. In addition, since the formed adducts of hydrotalcite with H ₂ S and / or mercaptans have an extremely high stability at the high storage temperatures used in residual oils, a low H ₂ S content is ensured in the long term and reliably by means of the process according to the invention. Examples The experiments were carried out by co-milling with fatty acids or

Sulfonic acids hydrophobically coated hydrotalcites used according to Table 1. These were slurried in the organic solvent and at room temperature for two minutes by means of Ultra-Turrax ^® T45 with tool S25N-25F

Sheared 10,000 rpm. The organic solvent used was a hydrocarbon with a 45% fraction of naphthenic C atoms (according to ASTM D 2140), a boiling point above 250 ° C. and a pour point of -55 ° C.

The determination of the particle size and its distribution in the dispersion were carried out by means of laser scattering using a Mastersizer 2000 device from Malvern Instruments. The determined volumetric diameters D (50) and D (90) each indicate the percentage of particles smaller than the specified value.

To determine the efficacy of H ₂ S scavengers, the

Hydrogen sulfide content of the oils characterized in Tables 2 and 3 based on IP 570 at a temperature T _M of 85 ° C (HFO) or 150 ° C (bitumen) in the liquid phase in ppm (w / w) determined. The in the

Tables 4 to 8 indicated in each case refer to the in

Table 1 formulations. The measured values given are each the average of three measurements. Table 1: Characterization of the additives used

na = not applicable Table 2: Characterization of the heavy fuel oil used (HFO)

Test oil HFO

Density @ 20 ° C [g / cm ³ ] 0.94

Pour Point [° C] 18

Flash point [° C] 110

Conradson Carbon Residue [wt%] 5.6

Viscosity @ 80 ° C [cSt] 12

H ₂ S [ppm] 70

Table 3: Characterization of the bitumen used

Test oil bitumen

Penetration @ 25 ° C [0.1 mm] 82

Softening Point R & B [° C] 47

Density, 25 ° C [kg / m ³ ] 1, 030

Viscosity @ 135 ° C [mm ² / s] 350

H ₂ S [ppm] 22

Lowering the H ₂ S content

Tables 4 and 5 show the efficiency of lowering the H ₂ S content by addition of various scavengers at oil temperatures TM after a reaction time tR of 30 minutes. Table 4: Lowering of the H ₂ S content in HFO (t _R

Table 5: Reduction of H ₂ S content in bitumen (tR

Example TM additive dosing rate H ₂ SH ₂ S reduction

[° C] [ppm] [ppm] [%]

13 150 - 0 22 0

14 150 A1 220 1, 6 93

15 150 A1 180 3.5 84 16 150 A2 220 1, 9 91

17 150 A3 220 1, 9 91

18 150 A4 220 1, 7 92

19 (Cf.) 150 A5 220 12 45

20 (Cf.) 150 A6 220 13 41

21 (Cf.) 150 A6 350 4.4 80

22 (Cf.) 150 A7 220 13 41

23 (Cf.) 150 A7 350 1, 5 93

24 (Cf.) 150 A8 220 18 18

Tables 6 and 7 show the time required for lowering the H ₂ S content. For the analysis of the kinetics of the H ₂ S reduction, 10 ml aliquots of the HFO mixed with 700 ppm scavenger A and of bitumen offset with 220 ppm scavenger A were measured for their reaction times t _R of 30 min, 60 min and 120 minutes H ₂ S analyzed.

Table 6: Kinetics of lowering the H ₂ S content in HFO

Example additive TM H ₂ S content [° C] t _R = 30 min tR = 60 min t _R = 120 min

25-85 70 70 70

26 A1 85 0.7 <0.5 <0.5

27 A2 85 1, 0 0.7 <0.5

28 A3 85 1, 0 0.6 <0.5

29 A4 85 0.8 <0.5 <0.5

30 (Cf.) A5 85 5.1 3.0 2.1 31 (See) A6 85 4,1 2,8 1, 9

32 (See) A7 85 3.0 1, 9 1, 3

33 (Cf.) A8 85 56 54 50

Table 7: Kinetics of lowering the H ₂ S content in bitumen

34 - 150 22 22 22

35 A1 150 1, 6 <0.5 <0.5

36 A2 150 1, 9 1, 4 <0.5

37 A3 150 1, 9 1, 2 <0.5

38 A4 150 1, 7 1, 0 <0.5

39 (See) A5 150 12 5.0 3.1

40 (See) A6 150 13 10 8.4

41 (See) A7 150 13 8,3 5,7

42 (Cf.) A8 150 18 16 15 Long-term effect of the additive

In sulfur-containing mineral oils and residues of mineral oil distillation often takes place during storage at elevated temperatures, a replication of H ₂ S instead (inherent H ₂ S). In order to test the sustainability of the lowering of the H ₂ S content, the H ₂ S content of bituminized bituminum was monitored during storage at 150 ° C. (bitumen) over a period † L of altogether 7 days. The storage was carried out in a virtually completely filled, closed pressure vessel to prevent the escape of H ₂ S. Table 8: Sustainability of reduction of H ₂ S content in bitumen

The examples show that hydrophobically coated hydrotalcite reduces the content of mineral oils and in particular of residues of mineral oil distillation significantly more efficiently or at lower metering rates than is possible with known derivatives of formaldehyde. In addition, the lowering of the H ₂ S content is much faster than with uncoated hydrotalcite and also the release of inherent H ₂ S is effectively suppressed. This will be the

H ₂ S content kept permanently low even under the usual for residual oils such as bunker oil and bitumen high or even further elevated storage temperatures. The latter is not possible with minerals such as zeolite.

Claims

claims:

1. Use of compositions containing at least one, dispersed in an organic solvent, hydrophobically coated hydrotalcite to reduce the content of mineral oils and residues of mineral oil distillation of H ₂ S and mercaptans.

2. Use according to claim 1, wherein the hydrotalcite corresponds to the general formula (1)

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +}

(1) wherein

M ²⁺ for at least one divalent metal ion,

M ³⁺ for at least one trivalent metal ion,

A ^n_ for at least one anion with the valency of n,

x for a number from 0.1 to 0.6,

n for 1 or 2, and

m stands for a number between 0 and 1.

3. Use according to claim 1 and / or 2, wherein the material used for the hydrophobic coating of the hydrotalcite is a surface-active compound. 4. Use according to claim 3, wherein the surface-active compound contains an optionally substituted hydrocarbon radical having from 4 to 200 carbon atoms bearing carboxylic acid or its salt.

5. Use according to claim 3, wherein the surface-active compound contains an optionally substituted hydrocarbon radical having 4 to 40 carbon atoms monocarboxylic acid or its salt.

6. Use according to claim 3, wherein the surface-active compound contains a dicarboxylic acid or its salt which carries an optionally substituted hydrocarbon radical having 8 to 200 carbon atoms. 7. Use according to claim 3, wherein the surface-active compound contains an optionally substituted hydrocarbon radical having 4 to 40 carbon atoms bearing sulfonic acid or its salt.

8. Use according to one or more of claims 4 to 7, wherein the salt of the carboxylic acid is selected from alkali metal salts, ammonium salts and amines of the formula (8)

NR ¹ R ² R ³ (8)

wherein

R ^{1 represents} an optionally substituted hydrocarbon radical having 1 to 50 carbon atoms, or a hydrocarbon radical having 1 to 10 carbon atoms bearing at least one hydroxyl group or a group of the formula - (B-O) _p -R ⁴ and

R ² , R ^{3 are} independently hydrogen or R or

R and R ² or R ² and R ³ together represent a cyclic hydrocarbon radical having 4 to 10 C atoms and

B is an alkylene radical having 2 to 6 C atoms,

p is a number from 1 to 50, and

R ^{4 is} hydrogen, a hydrocarbon radical having 1 to 50 C atoms, or a group of the formula -B-NH ₂ ,

derived salts.

9. Use according to claim 8, wherein R ^{1 is} C to C ₂₀ alkyl, C ₂ - to C ₂ o-alkenyl or C ₆ - to C ₃₀ -aryl.

10. Use according to claim 8, wherein R ^{1 is} a hydrocarbon radical carrying at least one hydroxyl group, the 2 to 8

Contains carbon atoms.

1 1. Use according to claim 8, 9 or 10, wherein B is an alkylene radical having 2 or 3 C-atoms. 12. Use according to claim 8, 9, 10 or 11, wherein p is 1 or 2.

13. Use according to claim 8, 9, 10, 11 or 12, wherein R ^{4 is} C to C ₂ o-alkyl, C ₂ - to C ₂₀ -alkenyl or C ₆ - to C ₈ -aryl. 14. Use according to one or more of claims 3 to 13, wherein the hydrotalcite with 0.5 to 10 wt .-% of at least one surface-active

Compound is coated.

15. Use according to one or more of claims 1 to 14, wherein the dispersions of hydrotalcite in an organic solvent a

have volumetric particle size distribution, in which at least 90% of the particles are smaller than 200 μιη.

16. Use according to one or more of claims 1 to 15, wherein the organic solvent has a pour point of below 0 ° C. 7. Use according to one or more of claims 1 to 16, wherein the boiling point of the organic solvent is above the pour point of the mineral oil to be treated or residue of mineral oil distillation.

18. Use according to one or more of claims 1 to 17, wherein the mineral oil is crude oil. 9. Use according to one or more of claims 1 to 17, wherein the residue of the mineral oil distillation bunker oil, heavy fuel oil or bitumen.

20. A method for lowering the content of mineral oils and residues of mineral oil distillation of H ₂ S and mercaptans, characterized in that the mineral oil or the residue of the mineral oil distillation a

A composition containing at least one dispersed in an organic solvent, hydrophobically coated hydrotalcite is added.

A method according to claim 20, wherein a composition as defined in claims 2 to 12 is added to the mineral oil or the residue of the mineral oil distillation.

22. The method according to claim 20 or 21, wherein the mineral oil is crude oil.

23. The method according to claim 20 or 21, wherein the residue of the

Mineral oil distillation is bunker oil, heavy fuel oil or bitumen.

24. mineral oils and residues of mineral oil distillation containing at least one hydrophobically coated in an organic solvent

Hydrotalcite included. 25. mineral oils according to claim 24, wherein the mineral oil is crude oil.

26. Residues of the mineral oil distillation according to claim 24, wherein the residue of the mineral oil distillation is bunker oil, heavy fuel oil or bitumen. Mineral oils and residues of mineral oil distillation according to claims 24 to 26, wherein the mineral oils and residues of mineral oil distillation contain a composition as defined in claims 2 to 15.

28. A method for lowering the sulfur content of mineral oils, wherein the H ₂ S and / or mercaptans-containing mineral oil

i) is admixed with a composition containing at least one, hydrophobically coated hydrotalcite dispersed in an organic solvent, and ii) the mineral oil treated in this way is mixed for a time sufficient for the reaction of the hydrophobically coated hydrotalcite with the H ₂ S contained in the mineral oil and / or the mercaptans, and

iii) the mineral oil-insoluble adduct is separated off.

A process according to claim 28, wherein a composition as defined in claims 2 to 17 is added to the mineral oil.

30. The method of claim 28 and / or 29, wherein the mineral oil a

Mineral oil distillate is.