Classifications

• • 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Toxicology (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Business, Economics & Management (AREA)
• Emergency Management (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treating Waste Gases (AREA)
• Gas Separation By Absorption (AREA)
• Catalysts (AREA)

Priority Applications (1)

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Publications (2)

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Citations (7)

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• 1987
  • 1987-08-13 DE DE19873726917 patent/DE3726917A1/de not_active Withdrawn
• 1988
  • 1988-07-27 US US07/224,972 patent/US4902408A/en not_active Expired - Fee Related
  • 1988-08-01 DE DE8888112489T patent/DE3860747D1/de not_active Expired - Lifetime
  • 1988-08-01 AT AT88112489T patent/ATE57204T1/de not_active IP Right Cessation
  • 1988-08-01 EP EP88112489A patent/EP0303882B1/fr not_active Expired - Lifetime
  • 1988-08-04 NO NO88883470A patent/NO883470L/no unknown
  • 1988-08-12 DK DK454488A patent/DK454488A/da not_active Application Discontinuation

Patent Citations (7)

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