WO2002086021A1 - Traitement d'hydrocarbures a base de sulfures - Google Patents

Traitement d'hydrocarbures a base de sulfures Download PDF

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Publication number
WO2002086021A1
WO2002086021A1 PCT/US2002/012618 US0212618W WO02086021A1 WO 2002086021 A1 WO2002086021 A1 WO 2002086021A1 US 0212618 W US0212618 W US 0212618W WO 02086021 A1 WO02086021 A1 WO 02086021A1
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sulfide
hydrocarbon
substrate
potassium formate
amine
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PCT/US2002/012618
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English (en)
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Larry W. Gatlin
Wayne Mueller
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Clearwater International, LLC.
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Priority to CA002445422A priority Critical patent/CA2445422A1/fr
Priority to GB0324935A priority patent/GB2391015B/en
Publication of WO2002086021A1 publication Critical patent/WO2002086021A1/fr
Priority to NO20034771A priority patent/NO336126B1/no

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    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/06—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of alkaline solutions
    • 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
    • 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
    • C10G29/08—Metal salts, or metal salts deposited on a carrier containing the metal in the lower valency
    • 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
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/02—Odour removal or prevention of malodour

Definitions

  • This invention relates to compositions and methods for the removal or other treatment of hydrogen sulfide and other sulfides present in other compositions. It is particularly useful for the removal of sulfides from hydrocarbons, particularly oil and gas newly recovered from the earth.
  • compositions have been proposed and used for the treatment of hydrocarbons to remove or otherwise treat hydrogen sulfide and/or other sulfides present in them. See, for example, Gatlin's US Patents 5,128,049, 5,486,605, 5,488,103, and 5,498,707, US Patent 4,978,512 in the name of Dillon, and Stanchem's Canadian Patent 2,269,476.
  • the treating agents may be referred to as scavengers or sulfide scavengers in the patent literature. Frequently they are reaction products of aldehydes "and amine compounds, and may or may not contain one or more triazines or derivatives thereof. See the descriptions in columns 5-8 of Trauffler et al US Patent 5,698,171, Sullivan III et al US Patent 5,674,377, 5,674,377 and 5,744,024, Rivers et al US Patent 5,554,591, Weers et al US Patents 5,223,127, 6,024,866 and 5,284,576, Pounds et al US Patents 5,462,721 and 5,688,478, and Callaway US Patent 5,958,352. They may be contacted with the hydrocarbons in various ways as mentioned in these patents and others such as Galloway US Patent
  • Our invention may include the use of any of the sulfide scavengers recited or identified in this paragraph and the preceding one, as well as any of the sulfide scavengers described in any of the patents discussed herein, particularly those containing at least one nitrogen.
  • a product of a reaction between an aldehyde and a nitrogen compound may be used as a scavenging composition.
  • U.S. Pat. No. 2,776,870 discloses that aqueous amines and alkanolamines are useful for removing acids from a gaseous mixture.
  • Hydrogen sulfide may be selectively removed from gas streams containing carbon dioxide by use of triethanolamine or methyldiethanolamine.
  • British Published Patent Specification No. 2103645 discloses that hydrogen sulfide and carbon dioxide may be removed from a gas mixture by contacting the mixture with a solvent comprising a tertiary amine and a physical absorbent.
  • Suitable physical adsorbents include N-methylpyrrolidone and sulfolane.
  • U.S. Patent 4,112,051 discloses a process for removing acidic gases from a gaseous mixture with an amine-solvent liquid absorbent comprising (1) an amine comprised of at least about 50 mole percent of a sterically hindered aniine; and (2) a solvent for the amine mixture which is also a physical absorbent for the acid gases.
  • Suitable sterically hindered amines include various piperidine compounds.
  • Suitable solvents include sulfones and pyrrolidone and piperidone compounds, to name a few.
  • Patent 4,978,512 discloses methods for reducing the levels of hydrogen sulfide and organic sulfides in a hydrocarbon stream by contacting the stream with a composition comprising a reaction products of a lower alkanolamine with a lower aldehyde. Suitable reaction products include mixtures of triazine and bisoxazolidine compounds.
  • U.S. Patent 4,647,397 discloses a process and composition for removing hydrogen sulfide and similar sulfides from a gas stream.
  • the gas stream is contacted with a substituted aromatic nitrile having an electron-attracting substitutent on the aromatic ring at least as strong as halogen and an organic tertiary amine in an inert organic solvent, such as N-methyl-2- pyrrolidone.
  • the spent contacting solution may be regenerated by heating the solution above the decomposition temperature of the reaction products to separate the sulfides from the liquid phase absorbent solution.
  • U.S. Patent 4,775,519 discloses a continuous process for removing acid gas components from a gas stream by counter-currently contacting the stream with an aqueous solution of a mixture of N-methyldiethanolamine (MDEA) with imidazole or a methyl substituted imidazole.
  • MDEA N-methyldiethanolamine
  • U.S. Patent 4,624,838 discloses a process for removing acid gases from a gaseous stream by contacting the stream with an aqueous scrubbing solution containing a hetero nitrogen compound comprising either a five- or six- membered ring having a pKa no greater than about 8.
  • Preferred hetero nitrogen compounds include imidazole and piperazine compounds.
  • Patent 5,347,003 describes a regenerative method where an N-C-N compound is regenerated from a product of a sulfur scavenging reaction, in which said N-C-N compound removes a sulfur atom from a sulfur compound to form the original N-C-N compound.
  • U.S. Patent 3,622,273 discloses a regenerative method for the removal of hydrogen sulfide from a gaseous stream wherein the gaseous stream is contacted with a solution containing, by weight, from 0.005 to 20 percent of a ferric ion complex, from 25.0 to 99.945 percent of water and from 0.05 to 10.0 percent of a buffering agent selected from the group consisting of alkali metal carbonate.
  • Trauffer's composition includes a scavenging compound which is a reaction product of an aldehyde and an nitrogen compound.
  • Typical aldehydes include formaldehyde, paraformaldehyde, glyoxal, acetaldehyde, butyraldehyde, benzaldehyde, N-(2-hydroxyethyl)dioxazine and oleylaldehyde
  • typical amines include methylamine, ethylamine, propylamine, isopropyl amine, oleylamine, ethylene diamine, diethylene tdamine, dimethylamine, diethylamine, monoethanolamine, diethanolamine, mo holine piperazine, thiomonoethanolamine and chlorooleylamine.
  • Trauffer's sulfur scavenging compound is represented by a nitrogen compound of the formula R 1 R 2 NCHR 3 NR 4 R 5 where each of R 1 , R 2 ,R 3 R 4 and R 5 is independently selected from the group consisting of: (i) hydrogen; (ii) a substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon chain of 1 to 20 carbons; (iii) a substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon chain of 1 to 20 carbons comprising at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and halogen; (iv) a substituted or unsubstituted polymeric chain; and (v) a direct bond to any other of R 1 , R 2 ,R 3 R 4 and R 5 .
  • Trauffer's suggested scavenging compounds include various triazines, such as l,3,5-tris(2- hydroxyethyl)hexahydro-s-triazine, and trimethyl triazine, bisoxazolidines, such as N,N'-methylene bisoxazolidine, piperidines, piperazines, amines, such as methyldiethanolamine, bis(dibutylamino)methane and bis(di-2- hydroxyethylamino)methane, bis(morpholino)methane, and primary, secondary and tertiary amines.
  • triazines such as l,3,5-tris(2- hydroxyethyl)hexahydro-s-triazine, and trimethyl triazine
  • bisoxazolidines such as N,N'-methylene bisoxazolidine
  • piperidines piperazines
  • amines such as methyldiethanolamine, bis(
  • Trauffer further describes scavenging compounds as a reaction products between (a) an aldehyde of formula HCOR where R is selected from the group consisting of: (i) hydrogen; (ii) a substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon chain of 1 to 50 carbons; (iii) a substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon chain of 1 to 50 carbons comprising at least one hetero atom selected from the group consisting of nitrogen, oxygen, sulfur and halogen; (iv) a substituted or unsubstituted polymeric chain; (v) a substituted or unsubstituted dimer (vi) a mono or polyaldehyde.
  • R is selected from the group consisting of: (i) hydrogen; (ii) a substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon chain
  • aldehyde may be utilized in anhydrous or hydrated forms of the above.
  • suitable aldehydes include, but are not limited to: formaldehyde, paraformaldehyde, . glyoxal, acetaldehyde,butyraldehyde, benzaldehyde, N-(2-hydroxyethyl)dioxazine, oleylaldehyde and (b) an nitrogen compound of formula HNR°R 7 wherein R 6 and R 7 are independently selected from the group consisting of: (i) hydrogen; (ii) a substituted of unsubstituted, saturated of unsaturated, linear, branched or cyclic hydrocarbon chain of 1 to 50 carbons; (iii) a substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon chain of 1 to 50 carbons comprising at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and halogen; (i
  • nitrogen compounds include, but are not limited to methylamine, ethylamine, propylamine, isopropyl amine, oleylaniine, ethylene diamine, diethylene triamine, dimethylamine, diethylamine, monoethanolamine, diethanolamine, morpholine, piperazine, thiomonoethanolamine, chlorooleylamine.
  • the nitrogen compound and the aldehyde of Trauffer's discloure may be reacted in any molar ratio with a preferred ratio being from 1 mole aldehyde to 10 moles nitrogen compound to 10 moles aldehyde to 1 mole nitrogen compound, a more preferred ratio being from 1 mole aldehyde to 5 moles nitrogen compound to 5 moles aldehyde to 1 mole nitrogen compound, an even more preferred ratio being 1 mole aldehyde to 3 moles nitrogen compound to 3 moles aldehyde to 1 mole nitrogen compound and a most preferred ratio being 1 mole aldehyde to 1 mole nitrogen compound.
  • the scavenging compound formed from the reaction of the aldehyde and nitrogen compound are dependent upon the selected nitrogen compound, the selected aldehyde and the ratios of each selected. Similarly mixtures of the above aldehydes and nitrogen compounds may also be reacted in order to form singular or mixtures of various scavenging compounds.
  • the reaction of the nitrogen compound and the aldehyde listed above will typically result in the formation of an aminal.
  • triazines such as l,3,5-tris(2-hydroxyethyl)hexahydro-
  • Gatlin in US Patent 5,128,049, reviews the prior art partially as follows:
  • U.S. Pat. No. 4,569,766 a method is disclosed for scavenging hydrogen sulfide and mercaptans from fluids by contacting the fluids with maleimides.
  • U.S. Pat. • No. 4,680,127 a method is disclosed for reducing the amount of hydrogen sulfide in aqueous or wet gaseous mediums by adding an effective amount of glyoxal, preferably in combination with formaldehyde or glutaraldehyde.
  • U.S. Pat. No. 4,748,011 a method is disclosed for the separation and collection of natural gas comprising the use of a sweetening solution.
  • the sweetening solution consists of an aldehyde or a ketone, methanol, an amine inhibitor, sodium or potassium hydroxides and isopropanol.
  • the amine inhibitor includes alkanolamines to adjust the pH.
  • U.S. Pat. No. 4,978,512 a method is disclosed for selectively reducing the levels of hydrogen sulfide and organic sulfides present in gaseous or liquid hydrocarbon streams or mixtures thereof by contacting the streams with the reaction product of a lower alkanolamine and a lower aldehyde.
  • Gatlin goes on to disclose a two-step scavenging process utilizing scavenging agents such as hexahydro-l,3,5-tris (2-hydroxyethyl)-S-triazine; tris (hydroxymethyl) nitromethane; a mixture of 4-(2-nitrobutyl)morpholine and 4,4'- (2-ethyl-2-nitrotrimethylene)-dimorpholine; a mixture of 4,4-dimethyloxazolidine and 3,4,4-trimethyloxazolidine; hexahydro-l,3,5-triethyl-S-triazine; a mixture of sodium 2-pyridinethiol-l -oxide and hexahydro-l,3,5-tris(2-hydroxyethyl)-S- triazine; 2,2-dibromo-3-nitrilopropionamide; methanol [[[2-(dihydro-5-methyl- 3(2H)-ox
  • UNICIDE TZ-135 is marketed as a fungicide and bactericide for use, by way of example, in controlling the growth of bacteria and fungi in oil well drilling and processing fluids.
  • BIOBAN GK is also marketed as a bactericide; tris (hydroxymethyl) nitromethane is commercially available in aqueous solution from Angus Chemical Company under the tradename TRIS NITRO, and is marketed as an antimicrobial agent; a mixture of 4-(2-nitrobutyl)morpholine and 4,4'-(2-ethyl-2- nitrotrimethylene)-dimorpholine is commercially available from Angus Chemical Company under the tradenames BIOBAN P-1487 or BIOBAN FP, and is marketed as an antimicrobial agent; a mixture of 4,4-dimethyloxazolidine and 3,4,4-trimethyloxazolidine is commercially available from Angus Chemical
  • BIOBAN CS-1135 is marketed as antimicrobial agent for use in oilfield water systems, and as a corrosion inhibitor.
  • This material is also available from Cosan Chemical Corporation under the tradename COSAN 101; hexahydro-l,3,5-triethyl-S-triazine is commercially available from R. T. Vanderbilt Co., Inc. under the tradename VANICIDE TH, and is marketed as an industrial preservative; a mixture of sodium 2-pyridinethiol-
  • 1-oxide and hexahydro-l,3,5-tris(2-hydroxyethyl)-S-triazine is commercially available from Olin Chemicals under the tradename TRIADINE 10, and is marketed as an antimicrobial agent; 2,2-dibromo-3-nitrilopropionamide is commercially available from Dow Chemical U.S.A.
  • This material is also available from Cosan Chemical Corporation under the tradename COSAN 91; 2[(hydroxymethyl)amino]-2-methyl-propanol is commercially available from Troy Chemical Company under the tradename TROYS AN 192, and is marketed as a water-soluble biocide.
  • Sodium dichloro- S-triazinetrione dihydrate is commercially available from Olin Chemicals under the tradename OCI 56, and is market for use as a bleach, sanitizer or cleaning compound.
  • Solutions of l,3-bis(hydroxymethyl)-5,5-dimethylhydantoin, antibacterial preservatives, may also be used as scavenging agents.
  • Gatlin prefers to use dilute solutions of the materials described above as scavenging agents in compositions containing from about 1 to about 50 percent, and typically from about 10 to about 30 percent, of one or more of the preferred active ingredients identified above.
  • These dilute solutions of scavenging agents are preferably added to the hydrogen sulfide-containing streams at concentrations of about 0.05 to about 100 ppm of diluted scavenging agent per 1 ppm of hydrogen sulfide, and most preferably, at concentrations of from about 2 to about 10 ppm of diluted scavenging agent per 1 ppm of hydrogen sulfide.
  • the hydrogen sulfide scavengers of the Weers et al disclosure are prepared by reacting alkylenepolyamines and formaldehyde in a known manner. Where water is present, the alkylenepolyamine is selected so that the reaction product is preferably soluble both in water and hydrocarbon stock.
  • the polyamines useful in the preparation of the hydrogen sulfide scavengers useful in the method of the Weers invention are alkylenepolyamines represented by the formula H 2 NRNH(RNH) X H wherein each R is independently an alkylene radical having 2 to about 20 carbon atoms and x is 0 to about 15.
  • the alkylene radical may be straight or branched chain, e.g., ethylene, methylethylene, trimethylene, phenylethylene and may be substituted with one or more organic or inorganic radicals that do not react with formaldehyde, e.g., halo such as chloro, bromo, fluoro, alkyloxy, etc.
  • the alkylene radical is preferably a straight chain lower alkylene, e.g., ethylene or propylene and any suitable lower alkyl substituent thereon, such as methyl, ethyl, etc.
  • the alkylene radical of the polyamine may be derived from fatty materials, such as tallow.
  • Representative polyamines include ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetrabutylenepentamine, hexaethyleneheptamine, hexapentyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, decaethyleneundecamine, decahexyleneundecamine, undecaethylenedodecamine, dodecaethylenetridecamine, tridecaethylenetetradecamine, N-tallow propylenediamine and higher polyamines.
  • the scavenging compounds of the Weers et al 6.024.866 disclosure are prepared by the exothermic reaction of an alkylenepolyamine, e.g., diethylenediamine, and formaldehyde.
  • the mole ratio of polyamine to formaldehyde may range from about 1:1 to about 1:14, preferably about 1:1 to about 1:3.
  • the reaction temperature is maintained at about 50°-60°C.
  • the reaction may occur over a period of approximately an hour at a time. A temperature drop indicates the completion of the reaction.
  • the resulting reaction product is a complex mixture of compounds, including, for example, methylene- bridged diethylenetriamines.
  • R 1 , R 2 , and R 3 are independently selected from the group consisting of hydrogen and hydrocarbon groups having between about 1-8 carbon atoms, selected from the group consisting of straight, branched, and cyclic alkyl groups, aryl, alkaryl, and aralkyl groups, and heterocyclic alkyls containing oxygen or tertiary nitrogen as a ring constituent wherein none of R 1 , R 2 , or R 3 is an alkoxyalkylene substitutent.
  • R 1 , R 2 , and R 3 are methyl groups.
  • Aldehyde ammonia trimers may be manufactured by reacting acetaldehyde with aqueous ammonia in a 1:1 molar ratio.
  • the amount of water used may vary depending upon how the product will be used. For example, if the substrate will be hydrophobic, e.g., a dry oil phase, the trimer may be formulated in isopropanol rather than water. In the field, the trimer preferably should be used in a solution having an active concentration of about 2-30%, preferably about 10-20%.
  • Galloway in US Patent 5.405,591, proposes scavenging with a triazine, which is a reaction product of an alkanolamine and an aldehyde.
  • the triazine extracts sulphide(s) from sour gas to sweeten the gas by reacting with the sulphide(s) to form a solution comprised of a sulphonated component and an alkanolamine component, which substantially separates the sulphonated component from the alkanolamine component.
  • More aldehyde can be added to the alkanolamine component to form additional sulphide reactive agent. In this way, a cyclic, regenerative process is provided.
  • the make-up triazine can be produced from any of the following alkanolamines: mono, di, and tri methly amine; mono, di and tri ethyl amine; mono di, and tri n-propyl amine; iso proply amine; n, iso, sec, and tert butyl amine and ethylenediamine.
  • the make-up triazine can be produced from any of the following aldehydes: formaldehyde (methanal); acetaldehyde (ethanal); propinaldehyde (propanal); and n-butyalaldehyde (butanal).
  • Amine compounds or reactants proposed by Rivers et al include, but are not necessarily limited to, 3-methoxypropylamine (CH3OCH2CH2CH2NH2; sometimes noted as MOPA); 3-ethoxypropylamine; ammonia (NH3); methylamine (CH3NH2); dimethylamine (CH3NHCH3); 1- methoxyisopropylamine [CH3OCH2CH(NH2)CH3, also known by the product name of Jeffamine Registered TM M-89 amine sold by Texaco Chemical Co.] and mixtures thereof.
  • the amine reactants to aldehyde reactants molar ratio may range from about 10:1 to 1:10.
  • the amine to aldehyde molar ratio be in the range from about 1.2:1 to 1:1.2.
  • the molar ratio of alkoxy- alkyleneamine to all other amines used as reactants may range from about 1 :0 to 1:100, preferably from about 1:0 to 1:9.
  • the amine compound and the aldehyde compound are reacted together in a first step and then the dialdehyde is added in a second step.
  • the dialdehyde is reacting to give an unknown product or if the dialdehyde was simply blended with the reaction products of the amine compound and the aldehyde compound.
  • the dialdehyde may be added with the monoaldehyde compound in the first step for reaction with the amine compound.
  • Suitable dialdehydes for the enhanced embodiment of the invention include, but are not necessarily limited to, glyoxal; glutaraldehyde; succinic aldehyde; 1,6- hexane dialdehyde (adipic aidehyde) and mixtures thereof.
  • Glyoxal is particularly preferred.
  • Adialdehyde such as those described above, may be advantageously blended and/or reacted with known triazine H2S scavengers such as .
  • H2S scavengers such as .
  • the reaction of MEA with CH2O gives l,3,5-tris-(2-hydroxyethyl)-hexahydro-D- triazine
  • U.S. Pat. No. 5,128,049 discloses a method of using triazines as hydrogen sulfide scavengers.
  • U.S. Pat. No. 5,169,411 discloses a method for preventing liberation of H2S in crude oil or petroleum residuum medium with imines.
  • U.S. Pat. No. 5,266,185 discloses the suppression of hydrogen sulfides in a heavy hydrocarbon derived from heavy crude oil by contacting the petroleum with the reaction product of a heterocyclic aldehyde and an organic primary amine. The useful compound was described as an imine.
  • 5,284,576 discloses a process for scavenging hydrogen sulfide using a scavenger prepared by reacting an alkylenepolyamine, including diethylenetriamine, and formaldehyde.
  • U.S. Pat. No. 5,314,672 discloses a method of selectively reducing the levels of hydrogen sulfide and organic sulfides by contacting natural gas with the reaction product of ethylenediamine and 50% uninhibited aqueous formaldehyde.
  • the method requires contacting the particular stream with a composition which is a reaction product of an active primary or secondary amine with an aldehyde.
  • an aldehyde included both monoaldehydes (one carbonyl group) and dialdehydes (two carbonyl groups).
  • Pounds' preferred monoaldehydes include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde (propanal), and n-butyraldehyde (1-butanal).
  • the most preferred monoaldehyde is formaldehyde.
  • the preferred dialdehyde is ethanedial.
  • compositions that are adapted to convert hydrogen sulfide and organic sulfides to nontoxic polymers.
  • the compositions comprise amine resin solutions made by reacting sterically hindered amines such as amine heads with aldoses selected from the group consisting of D- aldoses having from 3 to 6 carbon atoms.
  • Streams containing hydrogen sulfide or organic sulfides are preferably treated by contacting such streams with from about 2 to about 4 ppm or more of the amine solution of the invention per ppm of sulfide.
  • U.S. Pat. Nos. 4,748,011 discloses a method for the separation and collection of natural gas through use of a sweetening solution comprising an aldehyde or ketone, methanol, an amine inhibitor (including alkanolamines), sodium or potassium hydroxides, and isopropanol.
  • U.S. Pat. Nos. 4,978,512 discloses a method for selectively reducing the levels of hydrogen sulfide and organic sulfides present in gaseous or liquid hydrocarbon streams or mixtures thereof by contacting the streams with a composition comprising the reaction product of a lower alkanolamine with a lower aldehyde.
  • U.S. Pat. No. 4,112,051 discloses the removal of acidic gases, including hydrogen sulfide, from normally gaseous mixtures by contacting the mixtures with an amine-solvent liquid absorbent comprising an amine having at least about 50 mol percent of a sterically hindered amine and a solvent for the amine mixtures which is also a physical absorbent for the acidic gases.
  • Gatlin's US Patent 5,486,605 a hydrogen sulfide or organic sulfide converter is provided that comprises the reaction product of sterically hindered amines such as selected aliphatic diamines, aliphatic triamines, amino alcohols, and mixtures thereof with aldoses.
  • sterically hindered amines such as selected aliphatic diamines, aliphatic triamines, amino alcohols, and mixtures thereof with aldoses.
  • a hydrogen sulfide or organic sulfide converter comprises the reaction product of amine heads with a second component comprising an aldose selected from the group consisting of D-aldoses having from three to six carbon atoms.
  • a hydrogen sulfide or organic sulfide converter is provided that comprises the reaction product of amine heads with a crude aldose mixture made by reacting formaldehyde, methanol, sodium hydroxide and water.
  • a crude aldose mixture made by reacting formaldehyde, methanol, sodium hydroxide and water.
  • a hydrogen sulfide or organic sulfide converter is made that comprises the reaction product of amine heads with a second component comprising about 70 parts of 37% formaldehyde containing about 7 weight percent methanol and about 30 parts of about 50 weight percent sodium hydroxide in water reacted together slowly while controlling the temperature between about 190o % F. and about 210 degrees F., thereafter cooled, and adjusted to a pH of between about 6 and 7 by the slow addition of 30% hydrochloric acid.
  • a hydrogen sulfide or organic sulfide converter comprises the reaction product of amine heads with an aldose in a system further comprising up to about 90 weight percent of a solvent comprising a lower alcohol.
  • a composition is provided in which the hydrogen sulfide or organic sulfide converter of the invention further comprises a solvent adapted to reduce foaming and prevent cross-linking.
  • Preferred solvents include methanol, methoxymethanol, water, and mixtures thereof.
  • a composition in which the hydrogen sulfide or organic sulfide converter of the invention is diluted with methanol, methoxymethanol, mixtures of methanol and methoxymethanol, or water, and optionally, a minor amount of a surfactant.
  • a method is provided for removing hydrogen sulfide from gaseous and liquid hydrocarbon streams by contacting such streams with a solution comprising a hydrogen sulfide converter (scavenger) of the Gatlin invention as described above.
  • compositions and methods described by Gatlin in US Patent 5,486,605 allows direct conversion of hydrogen sulfide to a stable form without liberating the hydrogen sulfide during regeneration in the manner experienced with prior art compositions and methods.
  • the complexes produced by reacting the compositions disclosed in Gatlin's US Patent 5,486,605 with hydrogen sulfide do not have to be removed from the process fluids for regeneration.
  • the complexes produced thereby are largely water soluble, and are therefore easily separated from gaseous or liquid hydrocarbon streams.
  • compositions which convert hydrogen sulfide or other organic sulfides to water soluble, nontoxic, stable complexes can be made by reacting under controlled conditions solutions of sterically hindered amines comprising amine heads, selected aliphatic diamines, aliphatic triamines, amino alcohols, and mixtures thereof, with aldehydes, aldehyde donors, or the reaction products of lower alkanolamines and lower aldehydes.
  • the complexes thus formed are easily separated from gaseous or liquid hydrocarbons.
  • compositions disclosed in Gatlin's US Patent 5,486,605 are said to be more efficient than using conventional materials, with significantly lower concentrations of the converter being required (such as from about 2 to 3 times less) in actual practice to achieve the same degree of sulfide conversion.
  • Typical application ratios for the Gatlin compositions are from about 2 to about 4 ppm of converter per ppm of hydrogen sulfide in the treated fluid. This improved conversion allows more complete removal of hydrogen sulfide at a minimal cost, often without the need for a scrubber tower, which further reduces related equipment costs.
  • compositions of Gatlin's US Patent 5,486,605 are preferably made by reacting a solution comprising free aldehyde and the reaction product of a lower aldehyde and a lower alkanolamine either with a solution comprising a sterically hindered amine, preferably amine heads, or with an activator comprising the reaction product of a amine heads and formaldehyde.
  • a particularly preferred lower aldehyde for use in making the subject compositions is formaldehyde.
  • a particularly preferred lower alkanolamine for use in making the subject compositions is monoethanolamine.
  • amine heads refers to an unrefined mixture of alkyl diamines that comprise from 4 to 6 carbon atoms.
  • alkyl diamines typically found in amine heads include aminomethylcyclopentylamine; 1,2-cyclohexanediamine (1,2- diaminocyclohexane); 1,5-pentanediamine, 2-methyl; 1,6-hexanediamine; 1H- azepine, hexahydro; and 1,4-butanediamine.
  • Amine heads is commercially available from Monsanto Company and DuPont as a byproduct in the manufacture of hexamethylenediamine. Although amine heads is a convenient and useful source of aliphatic diamines suitable for use in making the scavengers of Gatlin's
  • compositions are made by reacting the reaction product of monoethanolamine and formaldehyde with an activator comprising the reaction product of amine heads and formaldehyde.
  • an activator comprising the reaction product of amine heads and formaldehyde.
  • Another composition described by Gatlin in US Patent 5,486,605 comprises the reaction product of amine heads with a formaldehyde donor such as HMTA or hydantoin.
  • methyl-diethanolamine 2-[(hydroxymethyl)amino]ethanol, 2-amino- 2-methyl-l-propanol; methylethanol amine; 2-methyl-l-amino ethanol; 2-ethyl-l- amino ethanol; 2-tertiary butylamino ethanol, 2-tertiary butylamino ethanol; 2- amino-2-ethyl-l,3-propanediol; 2-[(hydroxymethyl)amino]-2-methyl propanol; hydantoin; 5,5-dimethyl-l-hydantoin; acetaldehyde ammonia; acetalsoxime; 2- amino-2-hydroxymethanol, 1-3-propanediol; 2-amino-l,3-propanediol; 2-amino- 2-methyl-l,3-propanediol; the reaction product of methyl pyrol and
  • Components that may be reacted with sterically hindered amines comprising amine heads, selected aliphatic diamines, aliphatic triamines, or amino alcohols to produce compositions of the Gatlin 5,486,605 patent include, for example, aldehydes, aldehyde donors, the reaction products of lower alkanolamines and lower aldehydes, and the family of D aldoses having from 3 to 6 carbon atoms.
  • Aldehydes believed to be useful for making the subject compositions are preferably selected from the group consisting of monoaldehydes and dialdehydes having from 1 to 6 carbon atoms, and mixtures thereof, with formaldehyde, acetaldehyde, glycolaldehyde, glyceraldehyde, hydroxymethyl glyceraldehyde, glyoxal, and methyl formcel (a hemi-acetal, 55 percent formaldehyde solution in methanol and methoxy-methanol or water) being particularly preferred.
  • Aldehyde donors suggested by Gatlin in US Patent 5,486,605 as useful in making scavengers are preferably selected from the group consisting of hydantoin; hexamethylenetetramine; hexamethylolmelamine; 2-
  • D-aldoses having from 3 to 6 carbon atoms also suggested as useful are preferably selected from the group consisting of D-Glyceraldehyde; D-Erythrose; D-Ribose; D-Arabinose;
  • D-Allose D-Altrose; D-Glucose; D-Mannose; D-Threose; D-Xylose; D-Lyxose;
  • D-Gulose D-Idose; D-Galactose; D-Talose; and mixtures thereof.
  • sulfide scavengers are (1) the 1,3,5-hexahydro- 1,3,5-tert-butyl triazine of Sullivan III et al US Patent 5,674,377, (2) the ono- and polyamidines of Weers et al in US Patent 5,223,127, and (3) the bisoxazolidines of Rivers in US Patent 6,117,310.
  • compositions comprising potassium formate and a sulfide scavenger and (b) methods of treating sulfide-containing hydrocarbons by contacting them with the compositions comprising potassium formate and a sulfide scavenger.
  • a sulfide scavenger we mean any of the compositions described or suggested for sulfide treatment in any of the patents reviewed in the
  • hydrocarbon substrate is meant to include unrefined and refined hydrocarbon products, including natural gas, derived from petroleum or from the liquefaction of coal, both of which contain hydrogen sulfide or other sulfur-containing compounds.
  • hydrocarbon substrate includes wellhead condensate as well as crude oil which may be contained in storage facilities at the producing field.
  • Hydrocarbon substrate also includes the same materials transported from those facilities by barges, pipelines, tankers, or tracks to refinery storage tanks, or, alternately, transported directly from the producing facilities through pipelines to the refinery storage tanks.
  • hydrocarbon substrate also includes refined products, interim and final, produced in a refinery, including distillates such as gasolines, distillate fuels, oils, and residual fuels.
  • distillates such as gasolines, distillate fuels, oils, and residual fuels.
  • hydrocarbon substrate also refers to vapors produced by the foregoing materials.
  • the scavenging agents of the present invention may be used to treat aqueous and hydrocarbon substrates that are rendered “sour” by the presence of "sulfhydryl compounds,” such as hydrogen sulfide (H2S), organosulfur compounds having a sulfhydryl (-SH) group, known as mercaptans, also known as thiols (R-SH, where R is a hydrocarbon group), thiol carboxylic acids (RCO-SH), dithio acids (RCS- SH), and related compounds.
  • H2S hydrogen sulfide
  • -SH organosulfur compounds having a sulfhydryl
  • R-SH organosulfur compounds having a sulfhydryl
  • R-SH thiol carboxylic acids
  • RCS- SH dithio acids
  • aqueous substrate refers to any “sour” aqueous substrate, including waste water streams in transit to or from municipal waste water treatment facilities, tanning facilities, and the like.
  • Our invention includes a method of treating sulfides in hydrocarbons, hydrocarbon substrates, or aqueous substrates comprising (a) contacting the hydrocarbons or substrates containing sulfides with potassium formate and (b) contacting the hydrocarbons or substrates containing sulfides with a sulfide scavenger.
  • Contacting of the sulfide-containing hydrocarbon with potassium formate may take place before the scavenger is used, substantially at the same time, or after the scavenger is used.
  • the potassium formate is preferably in an aqueous solution, but need not be.
  • the scavenger may be any effective sulfide scavenger, as the primary mechanism of our invention is that the potassium formate acts to draw water from association with the hydrocarbons, the sulfides being themselves associated with the water.
  • the use of potassium formate, whether or not initially in solution, thus tends to improve the efficiency of the scavenging process more or less regardless of the identity of the particular scavenger.
  • sulfides such as hydrogen sulfide in hydrocarbons tend to associate with whatever water is present with or in contact with the hydrocarbons.
  • Our invention utilizes the hygrosopic nature of the potassium formate to separate the water from the hydrocarbons, which causes the sulfides to come with it, thus increasing the efficiency of the scavenger when contact is made between the scavenger and the sulfide.
  • Potassium formate solutions have the additional advantage of a low freeze point. We are thus able to employ our invention in climates, remote locations, and temperatures where it is normally difficult to employ aqueous solutions.
  • Our invention includes compositions comprising combinations of potassium formate and sulfide scavengers, with or without additional potassium hydroxide, and the use of these compositions in sulfide removal from hydrocarbons.
  • our invention includes the treatment of sewage suspensions, and pulp systems in the paper industry to reduce sulfide emissions.
  • Our novel compositions may be used to treat these and other odiferous materials; also, methods similar to our hydrocarbon-treating methods may be used for sewage, pulp, and other odiferous compositions and systems, i.e. treating with potassium formate and sulfide scavengers in separate steps or at the same time.
  • any sulfide scavenger in our process and in our novel compositions including potassium formate we prefer to use amine/aldehyde condensates, and particularly the hydroxy methyl amino alcohols and other materials described in Gatlin's US Patents 5,486,605 and 5,488,103. Our invention may be used with any of these and/or any of the scavengers described in the patents mentioned in the Background of the Invention or in the Summary of the invention. Solvents and other materials which may be present with the scavengers include (without intending to be limiting in any way), water, methanol, glycols, and cellosolves.
  • aqueous potassium formate solutions and slurries we use in conjunction with sulfide scavengers may range in potassium formate concentration from 1% to 99%) by weight, but we prefer solutions from 20% to 40%, and most preferably 25-35%).
  • they may be contacted with the hydrocarbons by continuous injection or in an adsorption tower. See also the description in Gatlin US Patent 5,128,049 of "pre-treatment” and “polishing" steps (column 3, line 62 - column 4, line 36), which are also useful in the present invention. More than one injection or treatment step may be used, and different concentrations of the scavenger and the potassium formate solution may be used in each.
  • our process is particularly useful in treating gaseous hydrocarbons, in that it will tend to remove moisture from the gas and/or inhibit the absorption of water by the gaseous hydrocarbons.
  • An additional advantage of our process is that the effectiveness of the scavenger is prolonged by the alkalinity of the potassium.
  • the potassium formate content of our treating compositions can be generated in solution by the reaction of formic acid and potassium hydroxide, and this solution can be utilized more or less without additional steps; moreover, the alkalinity of the solution can be enhanced by using an excess of potassium hydroxide for the reaction. Potassium hydroxide can simply be added to an already prepared solution of potassium formate, also resulting in enhanced performance of the scavenger.
  • useful preferred compositions and ratios (separate or premixed) of the ingredients include: 1. Scavenger and potassium formate in a weight ratio in the range of
  • composition 1 examples include 35-65% scavenger to 65%-35% KCOOH.
  • Compositions 1 and 2 may, and preferably will, include water. Preferably, the water will be present in amounts to make solutions of potassium formate in concentrations of 10% to 90% by weight.
  • Compositions 1, 2, and/or 3 may include KOH, which may be present as an excess from the reaction of potassium hydroxide with formic acid to make potassium formate.
  • An aqueous solution was prepared by reacting (a) a molar amount of formaldehyde with (b) a 0.5 molar amount of monoethanolamine and a 0.5 molar amount of amine heads (the molar calculation being based on the nitrogen content.
  • An additional 10%> by weight of a 60%> by weight solution of potassium formate was introduced, and further diluted with another 15%> by weight water.
  • This solution was placed in a treating vessel including a spreader bar.
  • a gas containing varying concentrations of hydrogen sulfide evolving from water separated from a small gas well was bubbled through the solution at a rate of 300- 500 scf/day. The hydrogen sulfide was removed from the gas in amounts as high as 12,000 ppm based on the gas.
  • our invention bay be used to treat drilling fluids, particularly as they are recirculated.

Abstract

Selon l'invention, on utilise du formiate de potassium avec un fixateur de sulfure pour retirer et traiter des composés de sulfhydryle tels que du sulfure d'hydrogène présent dans des hydrocarbures et des substrats aqueux.
PCT/US2002/012618 2001-04-25 2002-04-23 Traitement d'hydrocarbures a base de sulfures WO2002086021A1 (fr)

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CA002445422A CA2445422A1 (fr) 2001-04-25 2002-04-23 Traitement d'hydrocarbures a base de sulfures
GB0324935A GB2391015B (en) 2001-04-25 2002-04-23 Treatment of hydrocarbons containing sulfides
NO20034771A NO336126B1 (no) 2001-04-25 2003-10-24 Fremgangsmåte og blanding for å fjerne eller behandle sulfider i hydrokarboner, hydrokarbonsubstrater eller vandige substrater som inneholder sulfider.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9493711B2 (en) 2012-12-19 2016-11-15 Coastal Chemical Co., L.L.C. Processes and compositions for scavenging hydrogen sulfide
WO2017201393A1 (fr) * 2016-05-19 2017-11-23 Ecolab Usa Inc. Amines lourdes utilisées comme fixateurs de sulfure d'hydrogène et de mercaptans

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7211665B2 (en) * 2001-11-09 2007-05-01 Clearwater International, L.L.C. Sulfide scavenger
US8562820B2 (en) * 2001-11-09 2013-10-22 Clearwater International, L.L.C. Sulfide scavenger
JP4085262B2 (ja) * 2003-01-09 2008-05-14 三菱瓦斯化学株式会社 レジスト剥離剤
ES2430376T3 (es) * 2005-03-10 2013-11-20 Applied Cleantech Inc. Método para reciclar fibras a partir de aguas cloacales y medios para ello
US8617281B2 (en) * 2007-08-13 2013-12-31 Applied Cleantech, Inc Methods and systems for feedstock production from sewage and product manufacturing therefrom
US7985881B2 (en) * 2007-09-12 2011-07-26 Guard Products Llc Aromatic imine compounds for use as sulfide scavengers
RU2496853C9 (ru) * 2009-01-21 2014-02-10 Ахматфаиль Магсумович Фахриев Нейтрализатор сероводорода и способ его использования
US20120012507A1 (en) * 2010-07-14 2012-01-19 Compton Dennis R Use of alpha-amino ethers for the removal of hydrogen sulfide from hydrocarbons
RU2482163C1 (ru) * 2012-03-12 2013-05-20 Ахматфаиль Магсумович Фахриев Нейтрализатор сероводорода и способ его использования
RU2485169C1 (ru) * 2012-05-03 2013-06-20 Ооо Научно-Исследовательский И Проектный Институт По Обустройству Нефтяных И Газовых Месторождений Способ очистки нефти, газоконденсата и их фракций от сероводорода и меркаптанов
WO2014031537A2 (fr) 2012-08-21 2014-02-27 Lonza, Inc. Procédé de piégeage de sulfure d'hydrogène et/ou de composés de sulfhydryle
WO2014100051A1 (fr) 2012-12-19 2014-06-26 Nalco Company Traitement de compression pour le piégeage in situ de sulfure d'hydrogène
WO2014100054A1 (fr) 2012-12-19 2014-06-26 Nalco Company Fixateurs de sulfure d'hydrogène fonctionnalisés
RU2517709C1 (ru) * 2013-02-13 2014-05-27 Ахматфаиль Магсумович Фахриев Нейтрализатор сероводорода и способ его использования
US9458393B2 (en) * 2014-04-15 2016-10-04 Ecolab Usa Inc. Hydantoins as hydrogen sulfide and mercaptan scavengers
US10655232B2 (en) 2014-09-03 2020-05-19 Baker Hughes, A Ge Company, Llc Additives to control hydrogen sulfide release of sulfur containing and/or phosphorus containing corrosion inhibitors
US20160060520A1 (en) * 2014-09-03 2016-03-03 Baker Hughes Incorporated Scavengers for sulfur species and/or phosphorus containing compounds
RU2693494C2 (ru) * 2015-01-29 2019-07-03 Курарей Ко., Лтд. Композиция для удаления серосодержащих соединений
MX2018004223A (es) * 2015-10-14 2018-08-01 Topsoe Haldor As Un proceso para retirar compuestos de azufre de corrientes de proceso.
DE102015223820A1 (de) * 2015-12-01 2017-06-01 Henkel Ag & Co. Kgaa "Leistungsstarke Haarbehandlungsmittel mit strukturstärkendem-Effekt"
WO2022099192A1 (fr) * 2020-11-09 2022-05-12 Gaps Technology, Llc Compositions chimiques et systèmes de traitement et procédés de traitement les utilisant pour remédier à h2s et à d'autres contaminants dans des mélanges de fluides contaminés
US11802246B2 (en) 2021-03-11 2023-10-31 Baker Hughes Oilfield Operations Llc Synergistic effects among mercaptan scavengers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053757A (en) * 1958-10-24 1962-09-11 Shell Oil Co Hydrocarbon sweetening process
US5488103A (en) * 1991-07-11 1996-01-30 Gatlin; Larry W. Hydrogen sulfide converter

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2149380A (en) * 1938-03-15 1939-03-07 Shell Dev Process for removing acid components from hydrocarbon solutions
US4675169A (en) * 1980-05-21 1987-06-23 Union Oil Company Of California Process for removing sox and nox compounds from gas streams
US4440649A (en) * 1982-01-28 1984-04-03 Halliburton Company Well drilling and completion fluid composition
US4978512B1 (en) * 1988-12-23 1993-06-15 Composition and method for sweetening hydrocarbons
US5128059A (en) * 1989-02-23 1992-07-07 First Chemical Corporation Ring-alkylated m-phenylene diamine blends for use in curing epoxy resins
CA2017047C (fr) * 1989-08-01 1999-08-17 Jerry J. Weers Methode d'elimination du sulfure d'hydrogene des hydrocarbures
US5486605A (en) * 1991-07-11 1996-01-23 Gatlin; Larry W. Hydrogen sulfide converter
US5223127A (en) * 1991-07-18 1993-06-29 Petrolite Corporation Hydrogen sulfide scavengers in fuels, hydrocarbons and water using amidines and polyamidines
US5347004A (en) * 1992-10-09 1994-09-13 Baker Hughes, Inc. Mixtures of hexahydrotriazines useful as H2 S scavengers
US5498707A (en) * 1993-04-22 1996-03-12 Gatlin; Larry W. Hydrogen sulfide converter
US5405591A (en) * 1994-01-27 1995-04-11 Galtec Canada, Ltd. Method for removing sulphide(s) from sour gas
US5688478A (en) * 1994-08-24 1997-11-18 Crescent Holdings Limited Method for scavenging sulfides
US5462721A (en) * 1994-08-24 1995-10-31 Crescent Holdings Limited Hydrogen sulfide scavenging process
CA2177408C (fr) * 1995-06-06 2001-12-11 Michael Callaway Elimination du sulfure d'hydrogene a l'aide de trimeres de l-aminoethanol
US5674377A (en) * 1995-06-19 1997-10-07 Nalco/Exxon Energy Chemicals, L.P. Method of treating sour gas and liquid hydrocarbon
US5744024A (en) * 1995-10-12 1998-04-28 Nalco/Exxon Energy Chemicals, L.P. Method of treating sour gas and liquid hydrocarbon
US5698171A (en) * 1996-01-10 1997-12-16 Quaker Chemical Corporation Regenerative method for removing sulfides from gas streams
US5697443A (en) * 1996-02-09 1997-12-16 Halliburton Energy Services, Inc. Method and composition for acidizing subterranean formations utilizing corrosion inhibitor intensifiers
CA2231659C (fr) * 1996-07-12 2003-12-23 Baker Hughes Incorporated Agent epurateur contenant des bisoxazolidines pour eliminer le sulfure d'hydrogene
US6136282A (en) * 1998-07-29 2000-10-24 Gas Research Institute Method for removal of hydrogen sulfide from gaseous streams

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053757A (en) * 1958-10-24 1962-09-11 Shell Oil Co Hydrocarbon sweetening process
US5488103A (en) * 1991-07-11 1996-01-30 Gatlin; Larry W. Hydrogen sulfide converter

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9493711B2 (en) 2012-12-19 2016-11-15 Coastal Chemical Co., L.L.C. Processes and compositions for scavenging hydrogen sulfide
US10626334B2 (en) 2012-12-19 2020-04-21 Coastal Chemical Co., L.L.C. Processes and compositions for scavenging hydrogen sulfide
WO2017201393A1 (fr) * 2016-05-19 2017-11-23 Ecolab Usa Inc. Amines lourdes utilisées comme fixateurs de sulfure d'hydrogène et de mercaptans

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