EP0303882A1 - Process for removing hydrogen sulphide with transition metal 2-ethyl-hexanoate - Google Patents

Process for removing hydrogen sulphide with transition metal 2-ethyl-hexanoate Download PDF

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Publication number
EP0303882A1
EP0303882A1 EP88112489A EP88112489A EP0303882A1 EP 0303882 A1 EP0303882 A1 EP 0303882A1 EP 88112489 A EP88112489 A EP 88112489A EP 88112489 A EP88112489 A EP 88112489A EP 0303882 A1 EP0303882 A1 EP 0303882A1
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Prior art keywords
hydrogen sulfide
transition metal
carboxylates
carboxylate
xylene
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EP88112489A
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German (de)
French (fr)
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EP0303882B1 (en
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Günther Dr. Reichert
Christian Dr. Wegner
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Bayer AG
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Bayer AG
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/916—Odor, e.g. including control or abatement

Definitions

  • the present invention relates to the removal of hydrogen sulfide with transition metal compounds.
  • Hydrogen sulfide is often undesirable because of its toxicity, its corrosive properties and its unpleasant smell.
  • the specification for many petrochemical products stipulates that hydrogen sulfide may be contained in them at most to a few ppm.
  • a process for the removal of hydrogen sulfide has now been found, which is characterized in that the hydrogen sulfide to be removed is brought into contact with a transition metal carboxylate.
  • Carboxylates of titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc and / or manganese are suitable for the process according to the invention, it being possible for the transition metals to be present in all common oxidation states.
  • Carboxylates of divalent or trivalent iron and of divalent manganese are preferred.
  • the carboxylates can be those which are derived from mono-, di- or polycarboxylic acids.
  • the carboxylate radicals can contain, for example, 2 to 20 C atoms and 1 to 3 carboxylate groups.
  • the carbon skeleton of the carboxylate radicals can be, for example, straight-chain, branched-chain or cyclic.
  • the carboxylate residue is preferably derived from carboxylic acids whose transition metal salts dissolve well in nonpolar solvents, for example aliphatic and aromatic hydrocarbons. Examples include: oleic acid, tall oil fatty acid, linoleic acid, linolenic acid and ricinoleic acid. Straight-chain or branched C4-C14 acids such as coconut fatty acid or versatic acids are particularly preferred. Octanoate residues such as 2-ethylhexanoate are particularly preferred.
  • transition metal carboxylates can also be used, which can differ with regard to the transition metal and / or the carboxylate residue.
  • hydrogen sulfide can be removed from a wide variety of (undesirable) occurrences. It is particularly suitable for removing hydrogen sulfide from liquids containing mineral oil or liquids to be treated or produced in refineries or petrochemical plants. Also for removing hydrogen sulfide from condensed gases, e.g. condensed, volatile hydrocarbons and hydrocarbon mixtures, it is well suited.
  • the process according to the invention can be used particularly advantageously to remove hydrogen sulfide from liquids which have high contents of aromatic and / or paraffinic constituents. For example, these contents can be over 60% by weight, preferably between 70 and 100% by weight.
  • the transition metal carboxylates can be used as they are or as they are produced. In general, these are viscous liquids.
  • the transition metal carboxylates are preferably used as a solution or dispersion in a hydrocarbon (for example benzene or xylene) or a hydrocarbon mixture (for example petrol or petroleum). They are then less viscous and even lighter in the liquids distributable, which are preferably freed of hydrogen sulfide, and even better dosed.
  • the concentration of the transition metal carboxylates in hydrocarbons or hydrocarbon mixtures can be arbitrary. For example, concentrations of 0.1 to 10% by weight are suitable.
  • transition metal carboxylates to be used for the process according to the invention are not commercially available, they can be prepared in a simple manner. For example, one can proceed by neutralizing a mixture of alkalis (e.g. NaOH) and water by adding an equivalent amount of the desired carboxylic acid and then adding a, preferably water-soluble, mineral acid salt of the desired transition metal.
  • the transition metal carboxylate formed separates out as an oily phase and can thus be separated off.
  • the last step can also be carried out in the presence of a hydrocarbon or hydrocarbon mixture. A solution or dispersion of the transition metal carboxylate in the hydrocarbon or hydrocarbon mixture is then obtained, which can be used directly in this form for the removal of hydrogen sulfide according to the invention.
  • the process according to the invention has a number of surprising advantages. Hydrogen sulfide becomes quick and complete even from low concentrations removed, in particular from aromatic and / or paraffin-rich hydrocarbon mixtures in which the removal of hydrogen sulfide was previously problematic.
  • the transition metal carboxylates are not very corrosive, do not cause toxicological problems in their manufacture, storage and handling and do not require any special equipment.
  • the reaction products of transition metal carboxylates with hydrogen sulfide are very finely dispersed, so that they contain liquids which are easy to handle (eg pumpable).
  • reaction products of transition metal carboxylates and hydrogen sulfide therefore do not have to be separated off immediately after their formation; this can be carried out at a suitable point, also away from the point of origin, for example by fine filtration.
  • Good results ie complete removal of hydrogen sulfide within a short time, are already obtained if an equivalent amount of transition metal carboxylate is used, based on the amount of hydrogen sulfide to be removed.
  • an excess of transition metal carboxylate is used for the sake of safety, for example 1.1 to 5 times the amount by weight which is required by calculation in order to completely remove the hydrogen sulfide present.
  • the present invention also relates to the use of the transition metal carboxylates described above for the removal of hydrogen sulfide, in particular from liquids containing mineral oil or liquids to be processed or produced in refineries or petrochemical plants.

Abstract

Schwefelwasserstoff wird mit Übergangsmetallcarboxylaten entfernt.Hydrogen sulfide is removed with transition metal carboxylates.

Description

Die vorliegende Erfindung betrifft die Entfernung von Schwefelwasserstoff mit Übergangsmetallverbindungen.The present invention relates to the removal of hydrogen sulfide with transition metal compounds.

Schwefelwasserstoff ist wegen seiner Toxizität, seiner korrosiven Eigenschaften und seines unangenehmen Geruchs häufig unerwünscht. So beträgt die an Arbeitsplätzen zu­lässige Höchstmenge nur 10 ppm (= MAK-Wert). Außerdem schreibt die Spezifikation für viele petrochemische Pro­dukte vor, daß Schwefelwasserstoff höchstens zu einigen ppm in ihnen enthalten sein darf.Hydrogen sulfide is often undesirable because of its toxicity, its corrosive properties and its unpleasant smell. The maximum quantity allowed at workplaces is only 10 ppm (= MAK value). In addition, the specification for many petrochemical products stipulates that hydrogen sulfide may be contained in them at most to a few ppm.

Es ist bekannt Schwefelwasserstoff mit speziellen Eisen­oxiden zu entfernen (siehe z.B. US-PS 4 008 775 und 4 476 027). Dieses Verfahren erfordert relativ große Mengen an Eisenoxiden und relativ lange Kontaktzeiten. Außerdem fallen die Umsetzungsprodukte von Schwefel­wasserstoff mit Eisenoxiden in Form fester Partikel an. Diese Art der Schwefelwasserstoffentfernung ist deshalb im wesentlichen nur dort von Interesse, wo diese Nach­teile nicht stören, beispielsweise bei Bohrlöchern für die Erkundung und Gewinnung von Erdöl und/oder Erdgas.It is known to remove hydrogen sulfide with special iron oxides (see, for example, US Pat. Nos. 4,008,775 and 4,476,027). This process requires relatively large amounts of iron oxides and relatively long contact times. In addition, the reaction products of hydrogen sulfide with iron oxides are obtained in the form of solid particles. This type of hydrogen sulfide removal is therefore essentially only of interest where these disadvantages do not disturb, for example in wells for the exploration and production of oil and / or natural gas.

Bei der Weiterverarbeitung von Erdöl und Erdölprodukten in Raffinerien und petrochemischen Anlagen muß häufig aus kondensierten Gasen und/oder flüssigen Produkten und Strömen Schwefelwasserstoff entfernt werden. Hierfür werden auch beim Vorliegen von Schwefelwasserstoff in großer Verdünnung der Einsatz von wenig Hilfsmitteln, kurze Reaktionszeiten und leichte Handhabbarkeit (z.B. gute Dosierbarkeit und Vermeidung von Sedimentationen) bei praktisch vollständiger Schwefelwasserstoffentfer­nung gefordert. Diese Aufgabestellung ist bisher noch nicht befriedigend gelöst worden.When petroleum and petroleum products are processed in refineries and petrochemical plants, it is often necessary to remove hydrogen sulfide from condensed gases and / or liquid products and streams. For this purpose, even with the presence of hydrogen sulfide in a large dilution, the use of few auxiliaries, short reaction times and easy handling (e.g. good dosing and avoidance of sedimentation) with practically complete removal of hydrogen sulfide are required. This task has not yet been solved satisfactorily.

Es ist zwar bekannt, für diesen Zweck Chlordioxid oder Acrolein zu verwenden (siehe ASTM STP 641), jedoch han­delt es sich dabei um sehr toxische Substanzen, deren Handhabung spezielle Ausrüstungen erfordert. Außerdem ist Chlordioxid sehr korrosiv und bei niedrigen Schwefelwasserstoffgehalten und/oder hohen Öl-, insbe­sondere Paraffingehalten in dem zu behandelnden Substrat wenig effektiv. Auch Amine sind für diesen Zweck vorge­schlagen worden (siehe Oil and Gas Journal, Sept. 29 (1986), S. 61-65). Diese müssen jedoch mit starken Al­kalien, die ihrerseits korrosiv sind, präformiert werden und sind in Substraten mit hohen Ölgehalten auch wenig effektiv. Gleiches gilt beim Einsatz von wäßrigen Mangan(II)-Sulfatlösungen und von Acrylamiden (siehe DE-OS 27 10 529). Bei letzteren ist außerdem die Gegen­wart alkalischer Katalysatoren erforderlich. Schließ­lich ist auch die Verwendung von Maleinimiden (siehe US-PS 4 569 766) und N-Halogen-Sulfonamiden (siehe US-PS 4 374 732) unbefriedigend, insbesondere weil die Reak­tionsprodukte davon schwierig zu entfernen sind.Although it is known to use chlorine dioxide or acrolein for this purpose (see ASTM STP 641), these are very toxic substances, the handling of which requires special equipment. In addition, chlorine dioxide is very corrosive and ineffective at low hydrogen sulfide contents and / or high oil, especially paraffin contents in the substrate to be treated. Amines have also been proposed for this purpose (see Oil and Gas Journal, Sept. 29 (1986), pp. 61-65). However, these must be preformed with strong alkalis, which in turn are corrosive, and are also not very effective in substrates with high oil contents. The same applies to the use of aqueous manganese (II) sulfate solutions and acrylamides (see DE-OS 27 10 529). The latter also requires the presence of alkaline catalysts. Finally, the use of maleimides (see US Pat. No. 4,569,766) and N-halosulfonamides (see US Pat. No. 4,374,732) is also unsatisfactory, particularly because the reaction products are difficult to remove therefrom.

Es wurde nun ein Verfahren zur Entfernung von Schwefel­wasserstoff gefunden, das dadurch gekennzeichnet ist, daß man den zu entfernenden Schwefelwasserstoff mit einem Übergangsmetallcarboxylat in Kontakt bringt.A process for the removal of hydrogen sulfide has now been found, which is characterized in that the hydrogen sulfide to be removed is brought into contact with a transition metal carboxylate.

Für das erfindungsgemäße Verfahren sind beispielsweise Carboxylate des Titans, Vanadins, Chroms, Eisens, Kobalts, Nickels, Kupfers, Zinks und/oder Mangans ge­eignet, wobei die Übergangsmetalle in allen gängigen Oxidationsstufen vorliegen können. Bevorzugt sind Carboxylate des 2- oder 3-wertigen Eisens und des 2-­wertigen Mangans.Carboxylates of titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc and / or manganese, for example, are suitable for the process according to the invention, it being possible for the transition metals to be present in all common oxidation states. Carboxylates of divalent or trivalent iron and of divalent manganese are preferred.

Bei den Carboxylaten kann es sich um solche handeln, die sich von Mono-, Di- oder Polycarbonsäuren ableiten. Die Carboxylatreste können beispielsweise 2 bis 20 C-Atome und 1 bis 3 Carboxylatgruppen enthalten. Das Kohlen­stoffgerüst der Carboxylatreste kann z.B. geradkettig, verzweigtkettig oder cyclisch sein. Bevorzugt leitet sich der Carboxylatrest von Carbonsäuren ab, deren Übergangs­metallsalze sich in unpolaren Lösungsmitteln, beispielsweise aliphatischen und aromatischen Kohlenwasserstoffen, gut lösen. Beispielsweise seien genannt: Ölsäure, Tallölfettsäure, Linolsäure, Linolensäure und Ricinolsäure. Besonders bevor­zugt sind geradkettige oder verzweigte C₄-C₁₄-Säuren wie beispielsweise Kokosfettsäure oder versatic Säuren. Speziell bevorzugt sind Octanoatreste wie das 2-Ethylhexanoat.The carboxylates can be those which are derived from mono-, di- or polycarboxylic acids. The carboxylate radicals can contain, for example, 2 to 20 C atoms and 1 to 3 carboxylate groups. The carbon skeleton of the carboxylate radicals can be, for example, straight-chain, branched-chain or cyclic. The carboxylate residue is preferably derived from carboxylic acids whose transition metal salts dissolve well in nonpolar solvents, for example aliphatic and aromatic hydrocarbons. Examples include: oleic acid, tall oil fatty acid, linoleic acid, linolenic acid and ricinoleic acid. Straight-chain or branched C₄-C₁₄ acids such as coconut fatty acid or versatic acids are particularly preferred. Octanoate residues such as 2-ethylhexanoate are particularly preferred.

Selbstverständlich können auch Gemische von verschie­denen Übergangsmetallcarboxylaten eingesetzt werden, die sich hinsichtlich des Übergangsmetalls und/oder des Carboxylatrestes unterscheiden können.Of course, mixtures of different transition metal carboxylates can also be used, which can differ with regard to the transition metal and / or the carboxylate residue.

Mit dem erfindungsgemäßen Verfahren kann man Schwefel­wasserstoff aus den verschiedensten (unerwünschten) Vor­kommen entfernen. Besonders geeignet ist es zur Entfer­nung von Schwefelwasserstoff aus mineralölhaltigen Flüssigkeiten oder in Raffinerien oder petrochemischen Anlagen zu behandelnden oder dort hergestellten Flüssig­keiten. Auch zur Entfernung von Schwefelwasserstoff aus kondensierten Gasen, z.B. kondensierten, leicht flüchti­gen Kohlenwasserstoffen und Kohlenwasserstoffgemischen, ist es gut geeignet. Besonders vorteilhaft kann man mit dem erfindungsgemäßen Verfahren Schwefelwasserstoff aus Flüssigkeiten entfernen, die hohe Gehalte an aromati­schen und/oder paraffinischen Bestandteilen aufweisen. Beispielsweise können diese Gehalte über 60 Gew.-% be­tragen, vorzugsweise liegen diese bei 70 bis 100 Gew.-%.With the method according to the invention, hydrogen sulfide can be removed from a wide variety of (undesirable) occurrences. It is particularly suitable for removing hydrogen sulfide from liquids containing mineral oil or liquids to be treated or produced in refineries or petrochemical plants. Also for removing hydrogen sulfide from condensed gases, e.g. condensed, volatile hydrocarbons and hydrocarbon mixtures, it is well suited. The process according to the invention can be used particularly advantageously to remove hydrogen sulfide from liquids which have high contents of aromatic and / or paraffinic constituents. For example, these contents can be over 60% by weight, preferably between 70 and 100% by weight.

Die Übergangsmetallcarboxylate können im Rahmen der vor­liegenden Erfindung so eingesetzt werden, wie sie vor­liegen oder bei ihrer Herstellung anfallen. Im allge­meinen handelt es sich dabei um viskose Flüssigkeiten. Vorzugsweise werden die Übergangsmetallcarboxylate als Lösung oder Dispersion in einem Kohlenwasserstoff (z.B. Benzol oder Xylol) oder Kohlenwasserstoffgemisch (z.B. Fahrbenzin oder Petroleum) eingesetzt. Sie sind dann niedriger viskos, noch leichter in den Flüssigkeiten verteilbar, die vorzugsweise von Schwefelwasserstoff befreit werden, und noch besser dosierbar.In the context of the present invention, the transition metal carboxylates can be used as they are or as they are produced. In general, these are viscous liquids. The transition metal carboxylates are preferably used as a solution or dispersion in a hydrocarbon (for example benzene or xylene) or a hydrocarbon mixture (for example petrol or petroleum). They are then less viscous and even lighter in the liquids distributable, which are preferably freed of hydrogen sulfide, and even better dosed.

Die Konzentration der Übergangsmetallcarboxylate in Kohlenwasserstoffen oder Kohlenwasserstoffgemischen kann beliebig sein. Geeignet sind beispielsweise Konzentra­tionen von 0,1 bis 10 Gew.-%.The concentration of the transition metal carboxylates in hydrocarbons or hydrocarbon mixtures can be arbitrary. For example, concentrations of 0.1 to 10% by weight are suitable.

Soweit die für das erfindungsgemäße Verfahren einzu­setzenden Übergangsmetallcarboxylate nicht im Handel erhältlich sind können sie auf einfache Weise herge­stellt werden. Beispielsweise kann man dabei so ver­fahren, daß man ein Gemisch von Alkalien (z.B. NaOH) und Wasser durch Zugabe einer äquivalenten Menge der gewün­schten Carbonsäure neutralisiert und dann ein, vorzugs­weise wasserlösliches Mineralsäuresalz des gewünschten Übergangsmetalls hinzufügt. Das gebildete Übergangs­metallcarboxylat scheidet sich dabei als ölige Phase ab und kann so abgetrennt werden. Man kann den letzten Schritt auch in Gegenwart eines Kohlenwasserstoffs oder Kohlenwasserstoffgemischs durchführen. Man erhält dann eine Lösung oder Dispersion des Übergangsmetallcar­boxylats in dem Kohlenwasserstoff bzw. Kohlenwasser­stoffgemisch, die direkt in dieser Form zur erfindungs­gemäßen Schwefelwasserstoffentfernung eingesetzt werden kann.If the transition metal carboxylates to be used for the process according to the invention are not commercially available, they can be prepared in a simple manner. For example, one can proceed by neutralizing a mixture of alkalis (e.g. NaOH) and water by adding an equivalent amount of the desired carboxylic acid and then adding a, preferably water-soluble, mineral acid salt of the desired transition metal. The transition metal carboxylate formed separates out as an oily phase and can thus be separated off. The last step can also be carried out in the presence of a hydrocarbon or hydrocarbon mixture. A solution or dispersion of the transition metal carboxylate in the hydrocarbon or hydrocarbon mixture is then obtained, which can be used directly in this form for the removal of hydrogen sulfide according to the invention.

Das erfindungsgemäße Verfahren hat eine Reihe von über­raschenden Vorteilen. Schwefelwasserstoff wird auch aus niedrigen Konzentrationen heraus schnell und vollständig entfernt, insbesondere aus aromaten- und/oder paraffin­reichen Kohlenwasserstoffgemischen, bei denen bisher die Schwefelwasserstoffentfernung problematisch war. Die Übergangsmetallcarboxylate sind wenig korrosiv, verur­sachen keine toxikologischen Probleme bei ihrer Her­stellung, Lagerung und Handhabung und benötigen keine speziellen Ausrüstungen. Die Umsetzungsprodukte von Übergangsmetallcarboxylaten mit Schwefelwasserstoff fallen sehr feindispers an, so daß sie enthaltende Flüssigkeiten gut handhabbar (z.B. pumpbar) bleiben. Die Umsetzungsprodukte von Übergangsmetallcarboxylaten und Schwefelwasserstoff müssen deshalb nicht sofort nach ihrer Bildung abgetrennt werden, diese kann an geeigneter Stelle, auch entfernt vom Entstehungsort, beispielsweise durch Feinfiltration erfolgen. Gute Ergebnisse, d.h. vollständige Schwefelwasserstoffentfernung innerhalb kurzer Zeit, werden bereits erhalten, wenn man bezogen auf die abzutrennende Schwefelwasserstoffmenge eine äquivalente Menge Übergangsmetallcarboxylat einsetzt. Im allgemeinen setzt man sicherheitshalber jedoch einen Überschuß an Übergangsmetallcarboxylat ein, beispiels­weise das 1,1 bis 5-fache der Gewichtsmenge, die rechnerisch erforderlich ist, um den vorhandenen Schwe­felwasserstoff vollständig zu entfernen.The process according to the invention has a number of surprising advantages. Hydrogen sulfide becomes quick and complete even from low concentrations removed, in particular from aromatic and / or paraffin-rich hydrocarbon mixtures in which the removal of hydrogen sulfide was previously problematic. The transition metal carboxylates are not very corrosive, do not cause toxicological problems in their manufacture, storage and handling and do not require any special equipment. The reaction products of transition metal carboxylates with hydrogen sulfide are very finely dispersed, so that they contain liquids which are easy to handle (eg pumpable). The reaction products of transition metal carboxylates and hydrogen sulfide therefore do not have to be separated off immediately after their formation; this can be carried out at a suitable point, also away from the point of origin, for example by fine filtration. Good results, ie complete removal of hydrogen sulfide within a short time, are already obtained if an equivalent amount of transition metal carboxylate is used, based on the amount of hydrogen sulfide to be removed. In general, however, an excess of transition metal carboxylate is used for the sake of safety, for example 1.1 to 5 times the amount by weight which is required by calculation in order to completely remove the hydrogen sulfide present.

Die vorliegende Erfindung betrifft auch die Verwendung der zuvor beschriebenen Übergangsmetallcarboxylate zur Entfernung von Schwefelwasserstoff, insbesondere aus mineralölhaltigen Flüssigkeiten oder in Raffinerien oder petrochemischen Anlagen zu bearbeitenden oder dort her­gestellten Flüssigkeiten.The present invention also relates to the use of the transition metal carboxylates described above for the removal of hydrogen sulfide, in particular from liquids containing mineral oil or liquids to be processed or produced in refineries or petrochemical plants.

BeispieleExamples A. Beispiele zur Herstellung von Übergangsmetallcarboxy­laten (nicht erfindungsgemäß)A. Examples for the production of transition metal carboxylates (not according to the invention) Beispiel 1example 1

In einem Becherglas wurden 200 ml Wasser vorgelegt, 0,6 Mol NaOH zugegeben und 0,6 Mol 2-Ethylhexancarbon­säure zudosiert. Unter leichtem Rühren wurden dann 100 ml Xylol zugegeben. Zuletzt wurde 0,1 Mol Fe₂(SO₄)₃, gelöst in 100 ml Wasser, eingerührt. Innerhalb weniger Minuten erfolgte eine quantitative Umsetzung zu Eisen-­(III)-2-ethylhexanoat, das in die Xylol-Phase überging und zusammen mit Xylol aus dem Reaktionsgemisch abge­trennt wurde.200 ml of water were placed in a beaker, 0.6 mol of NaOH was added and 0.6 mol of 2-ethylhexane carboxylic acid was metered in. 100 ml of xylene were then added with gentle stirring. Finally, 0.1 mol of Fe₂ (SO₄) ₃, dissolved in 100 ml of water, was stirred in. Within a few minutes there was a quantitative conversion to iron (III) -2-ethylhexanoate, which passed into the xylene phase and was separated from the reaction mixture together with xylene.

Beispiel 2Example 2

Es wurde verfahren wie in Beispiel 1, jedoch wurde an­stelle von Xylol 100 ml eines aromatenarmen paraffini­schen Öls (Handelsbezeichnung: Shellsol® D 70) zuge­geben.The procedure was as in Example 1, but 100 ml of a low-aromatic paraffinic oil (trade name: Shellsol® D 70) were added instead of xylene.

Beispiel 3Example 3

0,1 Mol 2-Ethylhexancarbonsäure wurden mit 100 ml Wasser vermischt und mit 0,1 Mol NaOH versetzt. Dann wurden 100 ml Xylol zugegeben und schließlich 0,05 Mol MnSO₄ x 2 H₂O, gelöst in 100 ml Wasser. Die Xylolphase, welche das gebildete Mangan-(II)-2-ethylhexanoat ent­hielt wurde abgetrennt.0.1 mol of 2-ethylhexane carboxylic acid was mixed with 100 ml of water and mixed with 0.1 mol of NaOH. Then 100 ml of xylene were added and finally 0.05 mol of MnSO₄ x 2 H₂O, dissolved in 100 ml of water. The xylene phase, which contained the manganese (II) -2-ethylhexanoate formed, was separated off.

B. Beispiele zur Entfernung von Schwefelwasserstoff (ge­mäß der Erfindung)B. Examples of hydrogen sulfide removal (according to the invention)

Die folgenden Beispiele wurden im Labor durchgeführt und simulieren möglichst wirklichkeitsnah die Verhältnisse in einer petrochemischen Anlage.The following examples were carried out in the laboratory and simulate the conditions in a petrochemical plant as realistically as possible.

Beispiel 4Example 4

In einem Kolben wurden 500 ml Xylol bei Raumtemperatur vorgelegt und Schwefelwasserstoff eingeleitet bis es in einer Konzentration von 2640 ppm im Xylol vorhanden war. Danach wurden mittels einer Spritze 23 ml (25,8 mMol) der xylolischen Dispersion von Eisen(III)-2-ethylhexanoat zugefügt, wie sie gemäß Beispiel 1 erhalten worden war. Es bildete sich sofort ein Niederschlag von Eisensulfid. Anschließend wurde das Gemisch filtriert, das Filtrat auf Schwefelwasserstoff hin untersucht und kein Schwe­felwasserstoff mehr gefunden.500 ml of xylene were placed in a flask at room temperature and hydrogen sulfide was introduced until it was present in the xylene in a concentration of 2640 ppm. 23 ml (25.8 mmol) of the xylene dispersion of iron (III) -2-ethylhexanoate, as obtained in Example 1, were then added by means of a syringe. A precipitate of iron sulfide formed immediately. The mixture was then filtered, the filtrate was examined for hydrogen sulfide and no more hydrogen sulfide was found.

Beispiel 5Example 5

In einem 12 l-Autoklaven wurden 229 g einer 60 %igen Dispersion von Eisen(III)-2-ethylhexanoat in Xylol mit 600 ml Xylol bei Raumtemperatur vermischt. Danach wurden 10 ml flüssiger Schwefelwasserstoff zudosiert. An­schließend wurde so viel Stickstoff aufgedrückt, daß sich ein Druck von 5 bar einstellte. Nach 15 Minuten wurde eine Probe aus dem Autoklaven entnommen. In ihr konnte kein Schwefelwasserstoff mehr nachgewiesen werden.In a 12 liter autoclave, 229 g of a 60% dispersion of iron (III) -2-ethylhexanoate in xylene were mixed with 600 ml of xylene at room temperature. Then 10 ml of liquid hydrogen sulfide were added. So much nitrogen was then injected that a pressure of 5 bar was established. After 15 minutes, a sample was taken from the autoclave. No more hydrogen sulfide could be detected in it.

Beispiel 6Example 6

Es wurde verfahren wie in Beispiel 5, jedoch wurde eine entsprechende Menge Mangan-(II)-2-ethylhexanoat einge­setzt. Auch hier war nach 15 Minuten kein Schwefel­wasserstoff mehr nachweisbar.The procedure was as in Example 5, but a corresponding amount of manganese (II) -2-ethylhexanoate was used. Here, too, hydrogen sulfide was no longer detectable after 15 minutes.

Beispiel 7Example 7

In einem 12 l-Autoklaven wurden 229 g einer 60 %igen xylolischen Lösung von Eisen-(III)-2-ethylhexanoat zu­sammen mit 6 l eines Gemischs aus 10 Volumen-% Xylol und 90 Volumen-% Petroleum p.a. (Hersteller Merck, Darmstadt, max. 0,2 % Aromatenanteil) vorgelegt. Danach wurden 10 ml flüssiger Schwefelwasserstoff zugegeben. An­schließend wurde Stickstoff bis zu einem Druck von 5 bar aufgedrückt. Nach 60 Minuten wurde eine Probe entnommen. In ihr konnte kein Schwefelwasserstoff mehr nachgewiesen werden.In a 12 l autoclave, 229 g of a 60% xylene solution of iron (III) -2-ethylhexanoate together with 6 l of a mixture of 10% by volume xylene and 90% by volume petroleum p.a. (Manufacturer Merck, Darmstadt, max. 0.2% aromatic content) submitted. Then 10 ml of liquid hydrogen sulfide were added. Then nitrogen was injected up to a pressure of 5 bar. A sample was taken after 60 minutes. No more hydrogen sulfide could be detected in it.

Beispiel 8Example 8

Mit einer Strömungsgeschwindigkeit von 10 l/h wurde 18 Minuten lang Schwefelwasserstoff aus einer Stahlbombe durch eine Kaskade aus 4 Reaktorelementen geleitet, in denen sich jeweils 100 ml Petroleum (Qualität wie in Beispiel 7) und 10,7 g einer 60 %igen xylolischen Lö­sung von Eisen-(III)-2-ethylhexanoat befanden. Ein dieser Kaskade nachgeschalteter Reaktor wurde mit wäß­riger Zinkacetatlösung beschickt um festzustellen, wann Schwefelwasserstoff in der Reaktorkaskade nicht mehr aufgefangen wird. In dem nachgeschalteten, mit wäßriger Zinkacetatlösung beschickten Reaktor wurde erst ein Niederschlag von Zinksulfid be­obachtet, nachdem alles in den vier Kaskadenelementen vorhandene Eisen-(III)-2-ethylhexanoat mit Schwefel­wasserstoff zu Eisensulfid abreagiert war.At a flow rate of 10 l / h, hydrogen sulfide was passed from a steel bomb through a cascade of 4 reactor elements for 18 minutes, each containing 100 ml of petroleum (quality as in Example 7) and 10.7 g of a 60% xylene solution of Iron (III) -2-ethylhexanoate were found. A reactor downstream of this cascade was charged with aqueous zinc acetate solution to determine when Hydrogen sulfide is no longer collected in the reactor cascade. Precipitation of zinc sulfide was only observed in the downstream reactor charged with aqueous zinc acetate solution after all the iron (III) -2-ethylhexanoate present in the four cascade elements had reacted with hydrogen sulfide to give iron sulfide.

Claims (7)

1. Verfahren zur Entfernung von Schwefelwasserstoff, dadurch gekennzeichnet, daß man den zu entfernenden Schwefelwasserstoff mit einem Übergangsmetall­carboxylat in Kontakt bringt.1. A process for removing hydrogen sulfide, characterized in that the hydrogen sulfide to be removed is brought into contact with a transition metal carboxylate. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man den Schwefelwasserstoff mit Carboxylaten des Titans, Vanadins, Chroms, Eisens, Kobalts, Nickels, Kupfers, Zinks und/oder Mangans in Kontakt bringt.2. The method according to claim 1, characterized in that the hydrogen sulfide is brought into contact with carboxylates of titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc and / or manganese. 3. Verfahren nach Ansprüchen 1 und 2, dadurch gekenn­zeichnet, daß man den Schwefelwasserstoff mit Über­gangsmetallcarboxylaten in Kontakt bringt, deren Carboxylatreste sich von Mono-, Di- oder Poly­carbonsäuren ableiten, die 2 bis 20 C-Atome ent­halten.3. Process according to Claims 1 and 2, characterized in that the hydrogen sulfide is brought into contact with transition metal carboxylates whose carboxylate residues are derived from mono-, di- or polycarboxylic acids which contain 2 to 20 C atoms. 4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekenn­zeichnet, daß man Schwefelwasserstoff aus mineral­ölhaltigen Flüssigkeiten oder in Raffinerien oder petrochemischen Anlagen zu behandelnden oder dort hergestellten Flüssigkeiten entfernt.4. Process according to Claims 1 to 3, characterized in that hydrogen sulfide is removed from liquids containing mineral oil or in liquids to be treated or produced in refineries or petrochemical plants. 5. Verfahren nach Ansprüchen 1 bis 4, dadurch gekenn­zeichnet, daß man die Übergangsmetallcarboxylate als Lösung oder Dispersion in einem Kohlenwasser­stoff oder Kohlenwasserstoffgemisch einsetzt.5. Process according to Claims 1 to 4, characterized in that the transition metal carboxylates are used as a solution or dispersion in a hydrocarbon or hydrocarbon mixture. 6. Verfahren nach Ansprüchen 1 bis 5, dadurch gekenn­zeichnet, daß man das Übergangsmetallcarboxylat in der 1,1 bis 5-fachen Gewichtsmenge einsetzt, die rechnerisch erforderlich ist, um den vorhande­nen Schwefelwasserstoff vollständig zu entfernen.6. The method according to claims 1 to 5, characterized in that one uses the transition metal carboxylate in the 1.1 to 5 times the amount by weight, which is required by calculation in order to completely remove the hydrogen sulfide present. 7. Verwendung von Übergangsmetallcarboxylaten zur Entfernung von Schwefelwasserstoff.7. Use of transition metal carboxylates to remove hydrogen sulfide.
EP88112489A 1987-08-13 1988-08-01 Process for removing hydrogen sulphide with transition metal 2-ethyl-hexanoate Expired - Lifetime EP0303882B1 (en)

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AT88112489T ATE57204T1 (en) 1987-08-13 1988-08-01 PROCESS FOR REMOVAL OF HYDROGEN SULFIDE WITH TRANSITION METAL 2-ETHYLHEXANOATE.

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DE19873726917 DE3726917A1 (en) 1987-08-13 1987-08-13 METHOD FOR REMOVING SULFUR HYDROGEN WITH METAL COMPOUNDS
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US4902408A (en) 1990-02-20
NO883470D0 (en) 1988-08-04
DK454488D0 (en) 1988-08-12
NO883470L (en) 1989-02-14
DE3726917A1 (en) 1989-02-23
DK454488A (en) 1989-02-14
EP0303882B1 (en) 1990-10-03
ATE57204T1 (en) 1990-10-15

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