EP3918036A1 - Alkoholbasierte hemiformyle zur abscheidung von schwefelwasserstoff - Google Patents

Alkoholbasierte hemiformyle zur abscheidung von schwefelwasserstoff

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Publication number
EP3918036A1
EP3918036A1 EP20708819.6A EP20708819A EP3918036A1 EP 3918036 A1 EP3918036 A1 EP 3918036A1 EP 20708819 A EP20708819 A EP 20708819A EP 3918036 A1 EP3918036 A1 EP 3918036A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
fluid
hemi
formyl
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20708819.6A
Other languages
English (en)
French (fr)
Inventor
Rafaela Carvalhal PASSOS
Geeta RANA
Simael Manuel RODRIGUES
Barbara Valente MELANDA
Julian M. GALLARDO
Jeffery Caleb CLARK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab USA Inc
Original Assignee
Ecolab USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of EP3918036A1 publication Critical patent/EP3918036A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • C10G29/24—Aldehydes or ketones
    • 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
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN

Definitions

  • the present disclosure relates generally to scavengers of sulfur-based species, such as hydrogen sulfide and mercaptans.
  • a method of sweetening a fluid includes treating the fluid with an alcohol-based hemi-formyl of formula (I): (I) R 1 -0-[-CH 2 -0-] X -H;
  • R 1 is C1-C3 alkyl; and x is from 1 to 10. In some embodiments, x is from 1 to 5 or 1 to 3. In certain embodiments, x is 1, 2 or 3.
  • the fluid is treated with the hemi-formyl of formula (I), and x is from 1 to 12. In some embodiments, x is from 1 to 5. In some embodiments, x is 1. In some embodiments, x is 2.
  • the hemi-formyl is oil-soluble.
  • the hemi-formyl of formula (I) is methanolformyl. In some embodiments, the hemi-formyl of formula (I) is ethanolformyl.
  • the fluid is selected from crude oil, naphtha, fuel, and distillate oils.
  • the method also includes adding one or more additional components, each component independently selected from the group consisting of asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, emulsifiers, dispersants, emulsion breakers, hydrogen sulfide scavengers, gas hydrate inhibitors, surfactants, solvents, and combinations thereof.
  • each component independently selected from the group consisting of asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, emulsifiers, dispersants, emulsion breakers, hydrogen sulfide scavengers, gas hydrate inhibitors, surfactants, solvents, and combinations thereof.
  • the surfactant or dispersant is selected from the group consisting of alkyl benzyl ammonium chloride, benzyl cocoalky 1(C 12- Ci8)dimethylammonium chloride, dicocoalkyl (Ci2-Ci8)dimethylammonium chloride, ditallow dimethylammonium chloride, di(hydrogenated tallow alkyl)dimethyl quaternary ammonium methyl chloride, methyl bis(2-hydroxy ethyl cocoalkyl(Ci2-Ci8) quaternary ammonium chloride, dimethyl(2-ethyl) tallow ammonium methyl sulfate, n- dodecylbenzyldimethylammonium chloride, n-octadecylbenzyldimethyl ammonium chloride, n-dodecyltrimethylammonium sulfate, soya alkyltrimethylammonium chloride, hydrogenated
  • the method also includes adding an odorant.
  • the fluid is produced or used in a coal-fired process, a waste-water process, a farm, a slaughter house, a land-fill, a municipality waste-water plant, a coking coal process, or a biofuel process.
  • the method excludes adding any nitrogen-containing compounds to the fluid.
  • compositions to sweeten a fluid comprising an alcohol-based hemi-formyl of formula (I): (I) R 1 -0-[-CH 2 -0-] X -H;
  • R 1 is C1-C3 alkyl; and x is from 1 to 10. In some embodiments, x is from 1 to 5 or 1 to 3. In certain embodiments, x is 1, 2 or 3. In some embodiments, R 1 is Ci or C2 alkyl.
  • FIG. 1 shows scavenging capacity data for different scavengers at different temperatures
  • FIG. 2 shows data for various scavengers obtained from a liquid phase reduction test.
  • the compounds and compositions are particularly useful in the control of hydrogen sulfide and/or mercaptan emissions from crude oil based, natural gas based, and coal based products and processes.
  • the compounds and compositions are applicable to both upstream and downstream processes.
  • the scavenging compounds and compositions, optionally blended with non-aqueous solvents, are useful in a wide range of climates and under a wide range of process conditions.
  • the processes for preparing the compounds and compositions of the invention are economic, waste free, and provide said compounds in quantitative yields.
  • the compounds and compositions may be obtained in anhydrous form, thereby providing use in processes where it is desirable to minimize water content (e.g., in an oil production process such as those where the oil temperature is greater than 100°C).
  • Producing the compounds and compositions in anhydrous form also allows for reduced transportation costs.
  • the anhydrous compounds and compositions can optionally be blended with hydrophilic solvents (e.g., alcohols, glycol, polyols) for non-aqueous applications.
  • the term“consisting essentially of’ means that the methods and compositions may include additional steps, components, ingredients or the like, but only if the additional steps, components and/or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
  • alkyl refers to a linear or branched hydrocarbon radical, a defined number of carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30 carbons).
  • Alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-butyl, iso-butyl, secondary -butyl, and tertiary- butyl.
  • the term“sweetening,” as used herein, may refer to a process that removes sulfur species from a gas or liquid.
  • the sulfur species may include hydrogen sulfide and mercaptans.
  • sour gas may refer to a gas that includes significant amounts of sulfur species, such as hydrogen sulfide and/or mercaptans.
  • sour liquid or“sour fluid,” as used herein, may refer to a liquid that includes significant amounts of sulfur species, such as hydrogen sulfide and/or mercaptans.
  • Compounds disclosed herein include scavengers of sulfur-based species, such as hydrogen sulfide and mercaptans.
  • compounds disclosed herein are of formula
  • R 1 -0-[-CH2-0-] X -H where R 1 is C1-C3 alkyl and x is from 1 to 10. In some embodiments, x is from 1 to 5 or 1 to 3. In certain embodiments, x is 1, 2 or 3.
  • the unit [-CH2-O-] represents a formaldehye (i.e. when x is 1)
  • the molecular weight of the compounds of formula I depends upon both the selection of R 1 as well as number of hemi-formyl units present.
  • R 1 is Ci alkyl, C2 alkyl, or C3 alkyl.
  • the compounds of formula I are not corrosive to steel or other iron alloys.
  • the compounds of formula I may be prepared by mixing an alkyl alcohol of the formula R'-OH. where R 1 is an alkyl group among the options described above, with formaldehyde in the presence of a catalyst, for example, an alkaline catalyst or an acid catalyst, such as dodecyl benzene sulfonic acid.
  • a catalyst for example, an alkaline catalyst or an acid catalyst, such as dodecyl benzene sulfonic acid.
  • the resulting hemi-formyl may have a single hemi-formyl unit where a single unit of formaldehyde reacts with the alkyl alcohol or multiple hemi-formyl units where multiple units of formaldehyde react with the alkyl alcohol and resulting hemi-formyls.
  • compositions disclosed herein include at least one compound as described above.
  • a composition disclosed herein contains a pure composition of a compound of formula I.
  • a composition disclosed herein contains a mixture of two or more structurally distinct compounds of formula I.
  • a composition comprises from about 20 to about 100 percent by weight of one or more compounds disclosed herein, or from about 20 to about 98 percent by weight of one or more compounds disclosed herein, or from about 50 to 98 percent by weight of one or more compounds disclosed herein, or from about 70 to about 98 percent by weight of one or more compounds disclosed herein.
  • compositions disclosed herein can optionally include one or more additives.
  • Suitable additives include, but are not limited to, asphaltene inhibitors, paraffin inhibitors, corrosion inhibitors, scale inhibitors, emulsifiers, dispersants, emulsion breakers, hydrogen sulfide scavengers, gas hydrate inhibitors, surfactants, solvents, and combinations thereof.
  • Suitable asphaltene inhibitors include, but are not limited to, aliphatic sulphonic acids; alkyl aryl sulphonic acids; aryl sulfonates; lignosulfonates; alkylphenol/aldehyde resins and similar sulfonated resins; polyolefin esters; polyolefin imides; polyolefin esters with alkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefin amides; polyolefin amides with alkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefin imides with alkyl, alkylenephenyl or alkylenepyridyl functional groups; alkenyl/vinyl pyrrolidone copolymers; graft polymers of polyolefins with maleic anhydride or vinyl imidazole;
  • hyperbranched polyester amides polyalkoxylated asphaltenes, amphoteric fatty acids, salts of alkyl succinates, sorbitan monooleate, polyisobutylene succinic anhydride, and combinations thereof.
  • the amount of asphaltene inhibitor present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the asphaltene inhibitor may be present in the composition in an amount of about 0 to about 30% by weight of the composition.
  • Suitable paraffin inhibitors include, but are not limited to, paraffin crystal modifiers, and dispersant/crystal modifier combinations.
  • Suitable paraffin crystal modifiers include, but are not limited to, alkyl acrylate copolymers, alkyl acrylate vinylpyridine copolymers, ethylene vinyl acetate copolymers, maleic anhydride ester copolymers, branched polyethylenes, naphthalene, anthracene, microcrystalline wax and/or asphaltenes, and combinations thereof.
  • Suitable paraffin inhibitors also include dodecyl benzene sulfonate, oxyalkylated alkylphenols, oxyalkylated alkylphenolic resins, and combinations thereof.
  • the amount of paraffin inhibitor present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the paraffin inhibitor may be present in the composition in an amount of about 0 to about 20% by weight of the composition.
  • Suitable corrosion inhibitors include, but are not limited to, amidoamines, quaternary amines, amides, phosphate esters, and combinations thereof.
  • the amount of corrosion inhibitor present in the composition is not particularly limited and may be selected by one of ordinary skill in the art. In some embodiments, the corrosion inhibitor may be present in the composition in an amount of about 0 to about 10% by weight of the composition.
  • Suitable emulsifiers include, but are not limited to, salts of carboxylic acids, products of acylation reactions between carboxylic acids or carboxylic anhydrides and amines, alkyl, acyl and amide derivatives of saccharides (alkyl-saccharide emulsifiers), and combinations thereof.
  • the amount of emulsifier present in the composition is not particularly limited and may be selected by one of ordinary skill in the art. In some embodiments, the emulsifier may be present in the composition in an amount of about 0 to about 10% by weight of the composition.
  • Suitable dispersants include, but are not limited to, aliphatic phosphonic acids with 2-50 carbons, such as hydroxy ethyl diphosphonic acid, and aminoalkyl phosphonic acids, e.g. polyaminomethylene phosphonates with 2-10 N atoms e.g. each bearing at least one methylene phosphonic acid group; examples of the latter are ethylenediamine tetra(methylene phosphonate), diethylenetriamine penta(methylene phosphonate) and the triamine- and tetramine-polymethylene phosphonates with 2-4 methylene groups between each N atom, at least 2 of the numbers of methylene groups in each phosphonate being different.
  • Other suitable dispersants include lignin or derivatives of lignin such as lignosulfonate and naphthalene sulfonic acid and derivatives, and combinations thereof.
  • the amount of dispersant present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the dispersant may be present in the composition in an amount of about 0 to about 5% by weight of the composition.
  • Suitable emulsion breakers include, but are not limited to, dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic cationic and nonionic surfactants, resins such as phenolic and epoxide resins, and combinations thereof.
  • the amount of emulsion breaker present in the composition is not particularly limited and may be selected by one of ordinary skill in the art. In some embodiments, the emulsion breaker may be present in the composition in an amount of about 0 to about 10% by weight of the composition.
  • Suitable other hydrogen sulfide scavengers include, but are not limited to, oxidants (e.g., inorganic peroxides such as sodium peroxide, or chlorine dioxide) and combinations thereof.
  • oxidants e.g., inorganic peroxides such as sodium peroxide, or chlorine dioxide
  • the amount of other hydrogen sulfide scavengers present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the other hydrogen sulfide scavengers may be present in the composition in an amount of about 0 to about 50% by weight of the composition.
  • Suitable gas hydrate inhibitors include, but are not limited to, thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors (KHI), anti-agglomerates (AA), and combinations thereof.
  • Suitable thermodynamic hydrate inhibitors include, but are not limited to, methylethyl benzoate), and combinations thereof.
  • Suitable kinetic hydrate inhibitors and anti-agglomerates include, but are not limited to, polymers and copolymers, polysaccharides (such as hydroxy-ethylcellulose (HEC), carboxymethylcellulose (CMC), starch, starch derivatives, and xanthan), lactams (such as poly vinylcaprolactam, polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidone of various molecular weights), surfactants (such as fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkyl glucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates, alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amido
  • the amount of gas hydrate inhibitor present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the gas hydrate inhibitor may be present in the composition in an amount of about 0 to about 5% by weight of the composition.
  • Suitable surfactants include, but are not limited to, anionic surfactants, cationic surfactants, nonionic surfactants, and combinations thereof.
  • Anionic surfactants include alkyl aryl sulfonates, olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl and ethoxylated alkyl phosphate esters, and mono and dialkyl sulfosuccinates and sulfosuccinamates, and combinations thereof.
  • Cationic surfactants include alkyl trimethyl quaternary ammonium salts, alkyl dimethyl benzyl quaternary ammonium salts, dialkyl dimethyl quaternary ammonium salts, imidazolinium salts, and combinations thereof.
  • Nonionic surfactants include alcohol alkoxylates, alkylphenol alkoxylates, block copolymers of ethylene, propylene and butylene oxides, alkyl dimethyl amine oxides, alkyl-bis(2-hydroxyethyl) amine oxides, alkyl amidopropyl dimethyl amine oxides, alkylamidopropyl-bis(2-hydroxy ethyl) amine oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitan esters, and alkoyl polyethylene glycol esters and diesters, and combinations thereof. Also included are betaines and sultanes, amphoteric surfactants such as alkyl amphoacetates and amphodiacetates, alkyl amphopropripionates and amphodipropionates,
  • alkyliminodiproprionate and combinations thereof.
  • the amount of surfactant present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the surfactant may be present in the composition in an amount of about 0 to about 10% by weight of the composition.
  • Suitable solvents include, but are not limited to, isopropanol, methanol, ethanol, 2- ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, xylene, and combinations thereof.
  • the solvent is toluene.
  • the solvent is naphtha.
  • Representative polar solvents suitable for formulation with the composition include, alcohols (including straight chain or branched aliphatic such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxy ethanol, etc.), glycols and derivatives (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanone, diisobutylketone), N- methylpyrrolidinone (NMP), N,N-dimethylformamide and the like.
  • alcohols including straight chain or branched aliphatic such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-but
  • non polar solvents suitable for formulation with the composition include aliphatics such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and the like; aromatics such as toluene, xylene, heavy aromatic naphtha, fatty acid derivatives (acids, esters, amides), and the like.
  • the solvent is
  • a composition disclosed herein comprises from 0 to about 80 percent by weight of one or more solvents, based on the weight of the composition. In some embodiments, a composition of the invention comprises from 0 to about 50 percent by weight of one or more solvents, based on the weight of the composition. In certain embodiments, a composition comprises 20%, 25%, 30%, 35%, 40%, 45%, or 50% by weight of one or more solvents, based on the weight of the composition.
  • a composition disclosed herein comprises an odorant, such as vanillin.
  • the amount of odorant present in the composition is not particularly limited and may be selected by one of ordinary skill in the art.
  • the odorant may be present in the composition in an amount of about 0 to about 50% by weight of the composition.
  • compositions disclosed herein may further include additional functional agents or additives that provide a beneficial property. Additional agents or additives will vary according to the particular scavenging composition being manufactured and its intend use as one skilled in the art will appreciate. According to one embodiment, the scavenging compositions do not contain any of the additional agents or additives.
  • the amount of an additional component present in the composition is not particularly limited and may be selected by one of ordinary skill in the art. In some embodiments, the additional component may be present in the composition in an amount of about 0 to about 90% by weight of the composition.
  • the compounds and compositions disclosed herein may be used for sweetening a gas or liquid, such as a sour gas or a sour liquid.
  • the compounds and compositions may be used for scavenging hydrogen sulfide and/or mercaptans from a gas or liquid stream by treating the stream with an effective amount of a compound or composition described herein.
  • the compounds and compositions can be used in any industry where it is desirable to capture hydrogen sulfide and/or mercaptans from a gas or liquid stream.
  • the compounds and compositions can be used in, condensate/oil systems/gas systems, or any combination thereof.
  • the compounds and compositions can be applied to a gas or liquid produced or used in the production, transportation, storage, and/or separation of crude oil or natural gas.
  • the compounds and compositions can be applied to a gas or liquid produced or used in the production, transportation, storage, and/or separation of crude oil or natural gas.
  • compositions can be applied to a gas stream used or produced in a coal-fired process, such as a coal-fired power plant.
  • the compounds and compositions can be applied to a gas or liquid produced or used in a waste-water process, a farm, a slaughter house, a land-fill, a municipality waste-water plant, a coking coal process, or a biofuel process.
  • the compounds and compositions may be added to any fluid or gas containing hydrogen sulfide and/or a mercaptan, or a fluid or gas that may be exposed to hydrogen sulfide and/or a mercaptan.
  • a fluid to which the compounds and compositions may be introduced may be an aqueous medium.
  • the aqueous medium may comprise water, gas, and optionally liquid hydrocarbon.
  • a fluid to which the compounds and compositions may be introduced may be a liquid hydrocarbon.
  • the liquid hydrocarbon may be any type of liquid hydrocarbon including, but not limited to, crude oil, heavy oil, processed residual oil, bitminous oil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene.
  • the gas may be a sour gas.
  • the fluid or gas may be a refined hydrocarbon product.
  • a fluid or gas treated with a compound or composition of the invention may be at any selected temperature, such as ambient temperature or an elevated temperature.
  • the fluid (e.g., liquid hydrocarbon) or gas may be at a temperature of from about 40 °C to about 250 °C. In some embodiments, the fluid or gas may be at a temperature of from
  • the fluid or gas may be at a temperature of 22 °C, 23 °C, 24 °C, 25°C, 26 °C, 27 °C, 28 °C,
  • the fluid or gas may be at a temperature of 85 °C, 86 °C, 87 °C, 88 °C,
  • the fluid or gas in which the compounds and compositions are introduced may be contained in and/or exposed to many different types of apparatuses.
  • the fluid or gas may be contained in an apparatus that transports fluid or gas from one point to another, such as an oil and/or gas pipeline.
  • the apparatus may be part of an oil and/or gas refinery, such as a pipeline, a separation vessel, a dehydration unit, or a gas line.
  • the fluid may be contained in and/or exposed to an apparatus used in oil extraction and/or production, such as a wellhead.
  • the apparatus may be part of a coal -fired power plant.
  • the apparatus may be a scrubber (e.g., a wet flue gas desulfurizer, a spray dry absorber, a dry sorbent injector, a spray tower, a contact or bubble tower, or the like).
  • the apparatus may be a cargo vessel, a storage vessel, a holding tank, or a pipeline connecting the tanks, vessels, or processing units.
  • the fluid or gas may be contained in water systems, condensate/oil systems/gas systems, or any combination thereof.
  • the compounds or compositions may be introduced into a fluid or gas by any appropriate method for ensuring dispersal of the scavenger through the fluid or gas.
  • the compounds and compositions may be injected using mechanical equipment such as chemical injection pumps, piping tees, injection fittings, atomizers, quills, and the like.
  • the compounds and compositions of the invention may be introduced with or without one or more additional polar or non-polar solvents depending upon the application and requirements.
  • the compounds and compositions may be pumped into an oil and/or gas pipeline using an umbilical line.
  • capillary injection systems can be used to deliver the compounds and compositions to a selected fluid.
  • the compounds and compositions can be introduced into a liquid and mixed.
  • the compounds and compositions can be injected into a gas stream as an aqueous or nonaqueous solution, mixture, or slurry.
  • the fluid or gas may be passed through an absorption tower comprising a compound or composition.
  • the compounds and compositions may be applied to a fluid or gas to provide a scavenger concentration of about 1 parts per million (ppm) to about 1,000,000 ppm, about 1 ppm to about 100,000 ppm, about 10 ppm to about 75,000 ppm, about 100 ppm to about 45,000 ppm, about 500 ppm to about 40,000 ppm, about 1,000 ppm to about 35,000 ppm, about 3,000 ppm to about 30,000 ppm, about 4,000 ppm to about 25,000 ppm, about 5,000 ppm to about 20,000 ppm, about 6,000 ppm to about 15,000 ppm, or about 7,000 ppm to about 10,000 ppm.
  • ppm parts per million
  • the compounds and compositions may be applied to a fluid at a concentration of about 100 ppm to about 2,000 ppm, about 200 ppm to about 1,500 ppm, or about 500 ppm to about 1000 ppm.
  • Each system may have its own requirements, and a more sour gas (e.g., containing more hydrogen sulfide) may require a higher dose rate of a compound or composition.
  • the compounds and compositions may be applied to a fluid or gas in an equimolar amount or greater relative to hydrogen sulfide and/or mercaptans present in the fluid or gas.
  • the compounds and compositions may be applied to a fluid or gas as a neat composition (e.g., the compounds and compositions may be used neat in a contact tower).
  • the hydrogen sulfide and/or mercaptan in a fluid or gas may be reduced by any amount by treatment with a compound or composition.
  • the actual amount of residual hydrogen sulfide and/or mercaptan after treatment may vary depending on the starting amount.
  • the hydrogen sulfide and/or mercaptan levels may be reduced to about 150 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media.
  • the hydrogen sulfide levels and/or mercaptan may be reduced to 100 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media.
  • the hydrogen sulfide and/or mercaptan levels may be reduced to 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media. In some embodiments, the hydrogen sulfide and/or mercaptan levels may be reduced to 20 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media. In some embodiments, the hydrogen sulfide and/or mercaptan levels may be reduced to 15 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media. In some embodiments, the hydrogen sulfide and/or mercaptan levels may be reduced to 10 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media. In some embodiments, the hydrogen sulfide and/or mercaptan levels may be reduced to 50 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media
  • the hydrogen sulfide and/or mercaptan levels may be reduced to 5 ppm by volume or less, as measured in the vapor phase, based on the volume of the liquid media. In some embodiments, the hydrogen sulfide and/or mercaptan levels may be reduced to 1 ppm by volume, as measured in the vapor phase, based on the volume of the liquid media. In some embodiments, the hydrogen sulfide and/or mercaptan levels may be reduced to 0 ppm by volume, as measured in the vapor phase, based on the volume of the liquid media.
  • a water wash may be added in an amount suitable for forming an emulsion with a hydrocarbon.
  • the water wash may be added in an amount of from about 1 to about 50 percent by volume based on the volume of the emulsion.
  • the wash water may be added in an amount of from about 1 to about 25 percent by volume based on the volume of the emulsion.
  • the wash water may be added in an amount of from about 1 to about 10 percent by volume based on the volume of the emulsion.
  • the amount of hydrocarbon may be present in an amount of from about 50 to about 99 percent by volume based on the volume of the emulsion.
  • the hydrocarbon may be present in an amount of from about 75 to about 99 percent by volume based on the volume of the emulsion. In some embodiments, the hydrocarbon may be present in an amount of from about 90 to about 99 percent by volume based on the volume of the emulsion.
  • the water wash and hydrocarbon may be emulsified by any conventional manner.
  • the water wash and hydrocarbon may be heated and thoroughly mixed to produce an oil-in-water emulsion.
  • the water wash and hydrocarbon may be heated at a temperature in a range of from about 90 °C to about 150 °C.
  • the water wash and hydrocarbon may be mixed in any conventional manner, such as an in line static mixer or an in-line mix valve with a pressure drop of about 0.2 to about 2 bar depending on the density of the hydrocarbon.
  • the emulsion may be allowed to separate, such as by settling, into an aqueous phase and an oil phase.
  • the aqueous phase may be removed.
  • the aqueous phase may be removed by draining the aqueous phase.
  • demulsifiers may be added to aid in separating water from the hydrocarbon.
  • the demulsifiers include, but are not limited to, oxyalkylated organic compounds, anionic surfactants, nonionic surfactants or mixtures of these materials.
  • the oxyalkylated organic compounds include, but are not limited to, phenolformaldehyde resin ethoxylates and alkoxylated polyols.
  • the anionic surfactants include alkyl or aryl sulfonates, such as dodecylbenzenesulfonate.
  • Figure 1 depicts the scavenging performance of ethanol hemi-formyl and methanol hemi-formyl compared to hexahydro-l,3,5-tris(hydroxyethyl)-s-triazine.
  • the triazine scavenger was tested at about 60% activity.
  • the pH of the ethanol hemi-formyl and the methanol hemi- formyl was adjusted to be near neutral, such as from about 7 to about 7.5, before testing.
  • Reactions were carried out at about 70 °C and about 120 °C.
  • the pressure inside of the reactor was set to about 10 bar.
  • Stirring was carried out inside of the reactor using a magnetic stir bar at about 500 rpm.
  • a mass flow controller was used to control the flow of CC and H2S at about 600 mL/min.
  • Scavengers were added to the reactor in an amount of about 1000 ppm.
  • a liquid phase analysis was also performed.
  • a sample of crude oil was saturated in a Hastelloy autoclave of nominal volume (about 5 L) using a gas mixture containing about 0.2% in H2S using CO2 as a balanced gas.
  • the equipment was modified with micrometric flow control valves and bubble rock in addition to a reactor valve for the sample collection. The aliquots were removed by the lower valve of the autoclave where a drain is located.
  • the bottle penicillin, 100 mL
  • the H2S liquid phase reduction assay was performed by potentiometric titration using a silver electrode coated with silver sulfide (Ag/Ag2S), where the sample containing H2S was titrated with a solution of about 0.01M silver nitrate in ammoniacal isopropanol, previously purged with nitrogen, in order to avoid oxygen as an interfering agent in the titration.
  • Ag/Ag2S silver sulfide
  • the scavenger was added and, if necessary, agitation, stirring, and/or heating may be carried out. Stirring time and temperature vary according to the conditions required for each test.
  • the BS&W (base, sediment and water) used was about 0.5%, meaning that about 99.5% of the system was crude oil.
  • compositions of the present disclosure may comprise any compound(s) or component(s) disclosed herein and the compositions may also consist of or consist essentially of any compound(s) or component(s) disclosed herein.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Gas Separation By Absorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP20708819.6A 2019-01-31 2020-01-28 Alkoholbasierte hemiformyle zur abscheidung von schwefelwasserstoff Pending EP3918036A1 (de)

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US4551239A (en) * 1983-04-11 1985-11-05 Exxon Research & Engineering Co. Water based demulsifier formulation and process for its use in dewatering and desalting crude hydrocarbon oils
CR7573A (es) * 2004-11-11 2005-06-08 Araya Brenes Mario Composicion de un combustible y/o biocombustible a base de alcohol para sustituir gasolina, diesel o aceites combustibles en motores convencionales de combustion interna y metodo para su empleo
RU2348679C2 (ru) * 2005-03-09 2009-03-10 Камиль Карамович Шакуров Способ нейтрализации сероводорода и легких меркаптанов в товарной нефти и состав смеси гемиформаля и углеводородного нитросоединения
RU2418036C1 (ru) * 2009-12-08 2011-05-10 Ахматфаиль Магсумович Фахриев Нейтрализатор сероводорода и способ его использования
US9719027B2 (en) * 2013-02-19 2017-08-01 Baker Hughes Incorporated Low viscosity metal-based hydrogen sulfide scavengers
EP3283600B1 (de) * 2015-04-16 2019-09-25 Dow Global Technologies LLC Verfahren zur reduktion der wasserstoffsulfidkonzentration in flüssigen oder gasförmigen strömen anhand von zusammensetzungen mit triazinen und anionischen tenside
US9932255B2 (en) * 2015-06-30 2018-04-03 Ecolab Usa Inc. Metal silicate and organic deposit inhibitor/dispersant for thermal recovery operations of hydrocarbon fuels
US10584286B2 (en) * 2015-09-08 2020-03-10 Ecolab Usa Inc. Hydrogen sulfide scavengers
US11530347B2 (en) * 2016-07-01 2022-12-20 Clariant International Ltd Synergized acetals composition and method for scavenging sulfides and mercaptans

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