Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil

Definitions

• 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
• H 2 S hydrogen sulfide
• mercaptans a compound that has a typical, very unpleasant odor, which is perceived by the human sense of smell even at very low concentrations.
• 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
• 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.
• H 2 S scavengers 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
• 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
• 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.
• 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.
• 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
• 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
• 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.
• US-A-5000835 discloses the use of oil-soluble metal carboxylates for reducing the release of H 2 S.
• 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
• 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.
• certain spinels US-A-4690806
• zeolites zeolites
• 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.
• 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 .-%
• suspensions are stabilized.
• the suspensions are at room temperature
• 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.
• 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
• i) is admixed with a composition containing at least one, hydrophobically coated hydrotalcite dispersed in an organic solvent, and
• coated hydrotalcite is mixed with the H 2 S contained in the mineral oil and / or the mercaptans sufficient time, and
• 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
• Preferred compounds having hydrotalcite structure have the general formula
• X is a number from 0.1 to 0.6
• Suitable divalent metal ions are, for example, Mg, Zn, Co, Mn, Fe 2+ , Cd 2+ , Ca 2+ , Cu 2+ and Ni 2+ .
• the divalent metal ion is Mg 2+ .
• 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
• Suitable trivalent metal ions are, for example, Al, Fe, Cr, Mn, Co, Ga 3+ and ln 3+ .
• the trivalent metal ion is Al 3+ .
• 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
• 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" .
• 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.
• magnesium-aluminum-hydroxy-carbonates of the formula (2)
• hydrotalcites are compounds of the formula
• LHDs suitable according to the invention can be natural or synthetic
• calcined hydrotalcites are used because they have an increased adsorption capacity for H 2 S.
• 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
• 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.
• 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.
• the storage stability of the dispersion is improved because agglomeration of the hydrotalcite is suppressed in the additive or at least reduced.
• 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
• 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.
• 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.
• the monocarboxylic acids carry an aliphatic hydrocarbon radical.
• the aliphatic hydrocarbon radical can be linear, branched or cyclic.
• 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
• the hydrotalcite is coated with a fatty acid having 8 to 24 carbon atoms.
• 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 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.
• 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.
• 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
• 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.
• linear alkyl and alkenyl radicals having 8 to 40 carbon atoms and in particular having 10 to 28 carbon atoms.
• 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.
• anhydrides of polycarboxylic acids are useful as hydrophobizing agents. So have yourself
• 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
• 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.
• 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
• 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, ⁇ , ⁇ - Diethylaminoethanol, N, N-dimethylaminopropanol, ⁇ , ⁇ -diethylaminopropanol and
• Suitable amines for the preparation of partial amides are secondary amines such as dimethylamine,
• 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,
• 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,
• Iso-octadecanoic acid icosanoic acid, docosanoic acid and tetracosanoic acid
• suitable dicarboxylic acids are dodecenylsuccinic acid, tetradecenylsuccinic acid,
• Eicosenylsuccinic acid poly (isobutenyl) succinic acid and their anhydrides.
• carboxylic acids or carboxylic acid mixtures for the process according to the invention are also suitable tall oil fatty acid and resin and
• 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.
• 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.
• 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
• 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.
• alkali and ammonium salts of said carboxylic and sulfonic acids are useful as hydrophobizing agents.
• alkali salts are the sodium and potassium salts.
• ammonium salts which have proven useful, in particular, are those derived from amines of the formula (8),
• 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
• 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,
• 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.
• the corresponding salts of trimethylamine 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.
• the corresponding salts of trimethylamine trimethylamine
• 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.
• hydrophobizing the hydrotalcite 0.5 to 10 wt .-%, particularly preferably 1 to 7 wt .-% and in particular 1, 5 to 5 wt .-%
• the hydrophobic coating makes it possible to disperse the per se hydrophilic hydrotalcite in organic solvents.
• 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.
• 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
• 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.
• 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.
• suitable aromatics are alkylbenzenes and alkylnaphthalenes. So are
• aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures for example, aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for.
• 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
• the organic solvent may also contain polar components such as.
• polar components such 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.
• 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
• 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.
• 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, CocosölfettTexremethylester and their
• 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.
• 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
• 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
• the mixture has high shear rates of preferably at least 10 3 s -1 and especially of at least 10 5 s -1 as
• 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
• 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.
• 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.
• 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
• 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.
• 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.
• 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.
• Hydrocarbon observed on SO 2 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 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 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
• Determination of the H 2 S content can be carried out by known methods such as ASTM D6021, UOP163, ASTM D3227 or IP 399.
• 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.
• 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.
• 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 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.
• T M 85 ° C
• bitumen 150 ° C
• Table 1 formulations. The measured values given are each the average of three measurements. Table 1: Characterization of the additives used
• 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
• Tables 6 and 7 show the time required for lowering the H 2 S content.
• 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.
• 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.
• 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Lubricants (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=48790342

Family Applications (1)

Country Status (2)

Citations (8)

Family Cites Families (1)

• 2012
  • 2012-07-20 DE DE102012014473.3A patent/DE102012014473A1/de not_active Withdrawn
• 2013
  • 2013-07-11 WO PCT/EP2013/002068 patent/WO2014012640A2/fr not_active Ceased

Patent Citations (9)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events