EP2134814A1 - Procédé d'épuration des mercaptans présents dans les hydrocarbures - Google Patents

Procédé d'épuration des mercaptans présents dans les hydrocarbures

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Publication number
EP2134814A1
EP2134814A1 EP08731506A EP08731506A EP2134814A1 EP 2134814 A1 EP2134814 A1 EP 2134814A1 EP 08731506 A EP08731506 A EP 08731506A EP 08731506 A EP08731506 A EP 08731506A EP 2134814 A1 EP2134814 A1 EP 2134814A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
group
groups
quaternary ammonium
alkyl groups
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.)
Withdrawn
Application number
EP08731506A
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German (de)
English (en)
Other versions
EP2134814A4 (fr
Inventor
Timothy J. O'brien
Jerry J. Weers
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.)
Baker Hughes Holdings LLC
Original Assignee
Baker Hughes Inc
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Filing date
Publication date
Application filed by Baker Hughes Inc filed Critical Baker Hughes Inc
Priority to EP14164453.4A priority Critical patent/EP2759587B1/fr
Publication of EP2134814A1 publication Critical patent/EP2134814A1/fr
Publication of EP2134814A4 publication Critical patent/EP2134814A4/fr
Withdrawn legal-status Critical Current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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous 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
    • 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
    • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • 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
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • 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
    • C10G2300/80—Additives

Definitions

  • the present invention relates to methods and compositions for scavenging of mercaptans in hydrocarbon fluids and more particularly to the use of quaternary ammonium hydroxides and/or quaternary ammonium alkoxides as mercaptan and/or H 2 S scavengers.
  • Hydrocarbon fluids such as crude oil, crude oil emulsions, oilfield condensate, petroleum residua and even refined fuels often contain a variety of mercaptans, including mercaptans of relatively low molecular weight.
  • mercaptans of relatively low molecular weight.
  • the mercaptans encountered can cause many problems ranging from malodors to metal corrosion.
  • mercaptans of relatively low molecular weight for example, methyl mercaptan, CH3SH, ethyl mercaptan, CH 3 CH 2 SH and propyl mercaptan, CH 3 CH 2 CH 2 SH
  • Various additives have been employed in efforts to alleviate these problems.
  • choline or choline hydroxide has been found to alleviate hydrogen sulfide evolution and to scavenge mercaptans. See, for example, U.S. Pat. Nos.
  • choline and choline hydroxide are not well suited for many uses and media, such as in crude oil. Although choline and choline hydroxide might scavenge mercaptans in such media, they also form a volatile and malodorous by-product with the sulfur compounds indigenous to such media. Accordingly, the use of choline and choline hydroxide to control odors associated with light weight mercaptans is self-defeating in media such as crude oil.
  • a method for scavenging H 2 S and/or mercaptans in a hydrocarbon fluid that involves adding to the hydrocarbon fluid an effective scavenging amount of an aqueous scavenging composition.
  • the scavenging composition includes an additive selected from the group consisting of a quaternary ammonium hydroxide, a quaternary ammonium alkoxide, and mixtures thereof, in the presence of a metal in an oxidation state of 3+ or greater.
  • the additive reacts with H 2 S and/or mercaptans in the fluid.
  • the quaternary ammonium hydroxide has the formula selected from the group consisting of R 1 R 2 R 3 N + OH OH " , R 1 R 2 R 3 N + CH 2 CHR 5 OH OH " and R 1 R 2 R 3 R 4 N + OH "
  • the quaternary ammonium alkoxide has the formula R 1 R 2 R 3 R 4 N + O " , where:
  • R 1 and R 2 are independently selected from the group consisting of alkyl groups of from 1 to about 18 carbon atoms, aryl groups of from 8 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms,
  • R 3 is selected from the group consisting of alkyl groups of from 2 to about 18 carbon atoms, aryl groups of from 6 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms, provided, however, that R 2 and R 3 may be joined to form a heterocyclic ring including the N and optionally an oxygen atom, and
  • R 4 is selected from the group consisting of H, alkyl groups of from 2 to about 18 carbon atoms, alkylaryl groups of from 7 to about 18 carbon atoms, -(CH 2 CH 2 O) n H, where n is from 1 to about 18,
  • R 5 and R 6 are independently selected from the group consisting of hydrogen, alkyl groups of from 1 to about 18 carbon atoms, aryl groups of from 6 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms, and Y is a non-acidic group selected from the group consisting of -OH,
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl groups of from 1 to about 18 carbon atoms, aryl groups of from 6 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms, and
  • R 5 is selected from the group consisting of hydrogen, alkyl groups of from 1 to about 18 carbon atoms or alkylaryl groups of from 7 to about 18 carbon atoms.
  • a hydrocarbon composition that has a reduced H 2 S and/or mercaptan presence which includes a hydrocarbon fluid, H 2 S and/or mercaptans, and an effective scavenging amount of an aqueous scavenging composition.
  • the composition includes an additive selected from the group consisting of a quaternary ammonium hydroxide, a quaternary ammonium alkoxide, and mixtures thereof, in the presence of a metal in an oxidation state of 3+ or greater.
  • the quaternary ammonium hydroxide has the formula R 1 R 2 R 3 N + OH OH " R 1 R 2 R 3 N + CH 2 CHR 5 OH OH " and/or R 1 R 2 R 3 R 4 N + OH "
  • the quaternary ammonium alkoxide has the formula R 1 R 2 R 3 R 4 N + O " , where R 1 , R 2 , R 3 , and R 4 are as defined above. At least some of the additive in the hydrocarbon composition has reacted with the H 2 S and/or mercaptan.
  • mercaptans are thiols and are defined as any of a group of organic compounds resembling alcohols, but having the oxygen of the hydroxyl group replaced by sulfur.
  • Hydrogen sulfide (H 2 S) may also be scavenged by the methods and additives herein, and while not technically a mercaptan may be understood as included among the species being scavenged. It will thus be understood that when “mercaptan" is discussed, H 2 S is included as a species that will also be scavenged herein.
  • compositions, additives, and methods herein have accomplished a goal when the amounts of H 2 S and/or mercaptan are reduced as a consequence of being contacted with the compositions described herein.
  • hydroxides and alkoxides are especially surprising in view of the findings that the hydroxides are significantly more effective scavengers than compounds differing only in the counter ion (i.e., it is other than hydroxide), and that in some non-limiting cases the hydroxides are even more effective mercaptan scavengers than the corresponding internal ions (i.e., R 3 N + R 1 O " where R 3 N + R 1 OH OH " is the hydroxide).
  • the selectivity of the hydroxides reduces the waste that would otherwise be encountered in scavenging higher molecular weight mercaptans unnecessarily, and so permits scavenging of the less desirable mercaptans with relatively small amounts of the hydroxides. And, even though the European application noted above stresses the importance of the oil-solubility of its compounds to their efficacy, the superior efficacy of the hydroxides in scavenging mercaptans in hydrocarbons has been found even though the hydroxides would be expected to be significantly less oil-soluble than their corresponding internal ions.
  • the quaternary ammonium hydroxide has the formula R 1 R 2 R 3 N + OH OH " R 1 R 2 R 3 N + CH 2 CHR 5 OH OH " or R 1 R 2 R 3 R 4 N + OH "
  • the quaternary ammonium alkoxide has the formula R 1 R 2 R 3 R 4 N + O " .
  • R 1 and R 2 are independently selected from the group consisting of alkyl groups of from 1 to about 18 carbon atoms, aryl groups of from 8 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms.
  • R 3 is selected from the group consisting of alkyl groups of from 2 to about 18 carbon atoms, aryl groups of from 6 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms, provided, however, that R 2 and R 3 may be joined to form a heterocyclic ring including the N and optionally an oxygen atom.
  • R 4 is selected from the group consisting of H, alkyl groups of from 2 to about 18 carbon atoms, alkylaryl groups of from 7 to about 18 carbon atoms, -(CH 2 CH 2 O) n H, where n is from 1 to about 18,
  • m and p are independently selected from integers from 0 to about 18, except that the sum m+p is less than or equal to 18, and -CHR 5 CHR 6 Y, where R 5 and R 6 are independently selected from the group consisting of hydrogen, alkyl groups of from 1 to about 18 carbon atoms, aryl groups of from 6 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms, and Y is a non-acidic group selected from the group consisting of -OH, -SR 7 and
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl groups of from 1 to about 18 carbon atoms, aryl groups of from 6 to about 18 carbon atoms and alkylaryl groups of from 7 to about 18 carbon atoms.
  • R 4 is -(CH 2 CH 2 O) n H or -CHR 5 CHR 6 Y, where n, R 5 , R 6 and Y are defined as above.
  • R 5 may be hydrogen, alkyl groups of from 1 to about 18 carbon atoms or alkylaryl groups of from 7 to about 18 carbon atoms.
  • each of R 1 , R 2 and R 3 is methyl.
  • R 1 , R 2 and R 3 have been designated as the radical having at least two carbon atoms.
  • R 1 and R 2 are alkyl groups of eighteen or fewer carbon atoms and in other non-restrictive embodiments lower alkyl groups of six carbons or fewer, especially three carbons or fewer and, alternatively, methyl groups.
  • R 3 is a fatty group, such as from about eight to about eighteen carbon atoms, on the other hand about ten to about fourteen carbons atoms, such as a coco- group.
  • R 3 may be a benzyl group or substituted aryl groups, for example, alkylbenzyl groups such as methyl benzyl, or, less desirably, even may be an alkyl group of at least about two carbon atoms.
  • R 2 and R 3 may be joined to form a heterocyclic ring including the N and optionally an oxygen atom. In the latter case, a morpholine may be formed.
  • Such ring products have been found to be less effective than some other products and may be more difficult to prepare by oxyalkylation of a tertiary amine.
  • R 4 corresponds to the formula -(CH 2 CH 2 O) n H, where n is an integer from one to about eighteen, the formula
  • R 4 corresponds to the formula -CHR 5 CHR 6 Y, where R 5 and R 6 are hydrogen or lower alkyls of fewer than about six carbon atoms, in one non-restrictive version hydrogen, and Y is -OH.
  • the quaternary compound is prepared by reacting a tertiary amine with an alkylene oxide to form a quaternary compound where R 4 is -CH 2 CH 2 OH
  • quaternary compounds are also formed where R 4 is the ether or polyether group -(CH 2 CH 2 O) n H.
  • a composition containing quaternary compounds where R 4 is -(CH 2 CH 2 O) n H often also contains quaternary compounds where R 4 is the ether or polyether group - (CH 2 CH 2 O) n H.
  • the quaternary compound is prepared by oxyalkylating a tertiary amine
  • the amine is reacted with the alkylene oxide in a molar ratio of about 1 :1 so that, while some amine remains unreacted thereby leaving some alkylene oxide available for polyether formation, typically the ether or polyether chains that do form are short; n being mostly one, two or three.
  • the quaternary ammonium hydroxides of this invention may be pre- pared by a variety of known techniques that will be readily apparent to those of ordinary skill in the art.
  • the quaternary ammonium hydroxides may be prepared by ion exchange techniques from readily available quaternary ammonium halides, such as quaternary ammonium chlorides.
  • the quaternary ammonium halides may be passed through an ion exchange column for exposure to an ion exchange resin, exchanging the halide ion for OH " ions (or Y " ions where Y is as defined above and does not correspond to OH) from the column.
  • the halide R 1 R 2 R 3 R 4 N + Z " where R 1 , R 2 , R 3 and R 4 are as defined in the broader definition above and Z " is a halide, is brought into contact with an ion exchange resin bearing hydroxide ions to form R 1 R 2 R 3 R 4 N + OH " .
  • the quaternary ammonium hydroxides of this invention may be prepared by oxyalkylation of tertiary amines in the presence of water. Techniques for oxyalkylation of tertiary amines have been described, for example, in the European patent application noted above, but the European application requires the reaction to be carried out under anhydrous conditions.
  • the hydroxides have been discovered to be beneficial. Such compounds are formed when the oxyalkylation is carried out in the presence of water. And, surprisingly, it has been discovered that the reaction carried out in the presence of water results in yields of the quaternary ammonium hydroxide product that are significantly higher than the yields of quaternary ammonium internal ion resulting from the reaction carried out under anhydrous conditions. Moreover, carrying out the reaction in the presence of water allows the use of less oxide per amine than called for in the non- aqueous reaction of the European application of Roof et al. (that is, a 1:1 molar ratio may be employed as opposed to bubbling the oxide through the amine as called for by Roof et al.).
  • aqueous reaction proceeds much faster than does the non-aqueous reaction and so the quaternary product may be formed in much less time.
  • Y of R 4 is a non-acidic group other than OH "
  • a similar reaction may be carried out with, for example, an alkylene sulfide or alkyleneimine instead of an alkylene oxide.
  • the resulting quaternary ammonium hydroxides not only are more effective mercaptan scavengers in certain non- limiting cases than are the internal ions (the quaternary ammonium alkoxides) that would have been produced had the reaction taken place in the absence of water, but also are produced in higher yields than the internal ions would have been.
  • the hydroxide may be prepared by reacting a tertiary amine such as of the form R 1 R 2 R 3 N with an alkylene oxide, in the presence of water.
  • the alkylene oxide may be propylene oxide, but ethylene oxide is useful in one non-limiting embodiment.
  • R 4 corresponds to the formula -CHR 5 CHR 6 Y, where R 5 and R 6 are defined above and Y is a non-acidic group corresponding to the formula
  • an alkylene sulfide or alkyleneimine may be substituted for the alkylene oxide and otherwise the same procedures may be followed.
  • R 1 , R 2 and R 3 of the tertiary amine are as defined above. In one non-limiting embodiment, however, R 1 is methyl and alternatively R 2 is also methyl. Although R 2 and R 3 may be joined to form a heterocyclic ring including the N and optionally an oxygen atom, such as to form a morpholine derivative, such compositions have been found to be more difficult to oxyalkylate without the offset of producing more potent scavengers and so in some configurations, R 2 and R 3 are not joined. In one non-restrictive version, R 3 is a fatty group of from about six to about twelve carbon atoms. [0030] The reaction may be carried out in an aqueous solvent.
  • the solvent may comprise about 50% by weight to about 95%, by weight alcohol such as isopropanol or, in one useful embodiment, methanol, and about 5% by weight to about 50% by weight water.
  • a typical solvent formulation therefore, might comprise, by weight, two parts solvent to one part water.
  • the active ingredients may make up about 70% by weight of the reaction mixture (the remaining 30% being solvent).
  • the tertiary amine is stirred in the solvent and the system is pressurized with alkylene oxide added in a molar ratio of about 1:1 to the amine. Generally, the molar ratio is in the range of from about 1:1 to about 1.5:1 alkylene oxide to amine.
  • the reaction is carried out at a temperature typically under about 70 c C, in one non-limiting embodiment about 40 0 C. to about 50 0 C, with continuous stirring and its completion is signaled by a drop in pressure to about atmospheric.
  • the resulting mixture aside from unreacted solvent, is a combination of the quaternary compounds where the R 4 S are of the formulae
  • n is as defined above, unreacted amine, and glycols formed from reaction of the alkylene oxide and water.
  • CH 3 or the formula -CHR 5 CHR 6 Y where m, p, R 5 , R 6 and Y are as defined above, may be prepared by similar techniques that will be readily apparent to those of ordinary skill in the art.
  • "high oxidation state” means the metal is present in a primary valence that is capable of being reduced without forming the element. Typically this is an oxidation state of 3+ or greater for most metals of interest.
  • these metals are believed to act as catalysts in some way, but the inventors do not wish to be limited to any particular theory.
  • the metals may function as an oxidizer.
  • Metals of high oxidation state suitable to give the desired effect include, but are not necessarily limited to, Co(+3), Fe(+3), Cr(+6,+3), Ni(+3), Cu(+2), Ce (+3, +4) and combinations thereof.
  • the metals may be present as water or oil soluble salts and complexes.
  • metals suitable for use in the compositions and methods herein include, but are not limited to DBM 830, which consists of a mixture of aqueous caustic, water, dimethylethanolamine, monoethanolamine, formaldehyde, nonionic surfactants (nonyl phenol ethoxylate) and Merox catalyst (cobalt phthalocyanine complex) available from UOP.
  • DBM 830 which consists of a mixture of aqueous caustic, water, dimethylethanolamine, monoethanolamine, formaldehyde, nonionic surfactants (nonyl phenol ethoxylate) and Merox catalyst (cobalt phthalocyanine complex) available from UOP.
  • the resulting additive be it quaternary ammonium hydroxide or quaternary ammonium alkoxide may be added to the hydrocarbon fluid to be treated by standard techniques, such as by injection or simple pouring and it may be dispersed throughout the fluid by stirring or other agitation.
  • Enough of the additive should be added that is effective to scavenge at least a portion of the H 2 S and/or mercaptan.
  • the additive is incorporated at a level sufficient to scavenge the H 2 S and/or mercaptans to a desired degree and will depend on the mercaptan content of the medium and the corresponding stoichiometry.
  • typical additive levels may be on the order of about 20 to about 10,000, in one non-limiting embodiment from a lower threshold of about 100 independently to an upper threshold of about 5,000, ppm based on the weight of the medium to be treated, alternatively from a lower threshold of about 500 independently to an upper threshold of about 1000 ppm.
  • the amount of metal in the hydrocarbon fluid may range from about 10 to about 1000 ppm, alternatively up to about 500 ppm, based on the hydrocarbon fluid.
  • the formulations of the aqueous scavenging composition may have from 0.1 to 5 wt% of the additive being metal with the remainder being alkoxide/hydroxide.
  • the medium may be any hydrocarbon fluid, and a liquid is expected to be most common, although dry gas mixtures containing mercaptans may also be treated. For example, excellent results have been obtained from treatment of crude oil, petroleum residua and fuels such as kerosene.
  • hydrocarbon fluids in some cases (for example, crude oil emulsions), hydrocarbons may make up less than half of the fluid by weight.
  • the product is particularly useful for treatment of crude oil in that it does not add an additional malodorous compound as has been associated with the use of choline to treat crude oil.
  • the hydrocarbon fluids to which the method herein may be applied include, but are not limited to, crude oil, oil field condensates (e.g. naphtha, etc.), residual fuels, petroleum distillates (e.g. gasoline, kerosene, diesel, etc.) light hydrocarbons (e.g. propane, butane, etc.), aromatic solvents (e.g.
  • the hydrocarbon fluids may contain oxygenated compounds such as alcohols, esters, glycols, ethers and the like and mixtures thereof.
  • Effective scavenging may be carried out at the ambient temperature of the hydrocarbon fluid (e.g., about 20 0 C. for stored crude oil, residuum or fuel), but the performance of the scavenger has been found to be improved at higher temperatures such as about 50 0 C. to about 75 0 C.
  • the scavenger tends to decompose at even higher temperatures, such as at about 100 0 C.
  • the decomposition at such temperatures occurs relatively slowly while the time for the reaction between the scavenger and the mercaptans is relatively short, generally requiring only several hours to reduce the mercaptan level substantially.
  • the scavenger may still be employed at such elevated temperatures with good results.
  • the scavenging additives herein remove H 2 S first, and then start removing or reacting with the mercaptans.
  • the quaternary ammonium scavengers herein have been found to react selectively with the lower molecular weight mercaptans without imparting to the system an odor of its own.
  • the scavengers have been found to scavenge methyl mercaptan in preference to ethyl mercaptan and to scavenge ethyl mercaptan in preference to n-propyl mercaptan and to scavenge n-propyl mercaptan in preference to n-butyl mercaptan, and so forth. It also has been observed that the scavengers react selectively with linear mercaptans over branched mercaptans.
  • the scavengers enable removal of the most volatile mercaptans, which are the greatest contributors to odor problems, with limited waste of scavenger on side reactions with less volatile mercaptans. It is believed that adding the high oxidation state metal helps speed the scavenging of lower mercaptans as well as improves the removal of higher mercaptans (Ae. through C12 or dodecyl mercaptans).
  • the following examples describe certain specific, non-limiting embodiments of the invention. Other embodiments within the scope of the claims herein will be apparent to one skilled in the art from consideration of the specification or practice of the invention as disclosed herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow the examples. In the examples, all percentages are given on a weight basis unless otherwise indicated.
  • Mercaptan Scavenger A was made according to the methods of U.S. Pat. Nos. 5,840,177 and 6,013,175, mentioned above, assigned to Baker Hughes Incorporated. Mercaptan Scavenger A was a quaternary ammonium hydroxide prepared from dimethyl soya amine and ethylene oxide. [0043] As shown in Table I 1 Mercaptan Scavenger A was used alone and together with DBM 830, also used alone, in the indicated dosages. The initial mercaptan proportion was 533 ppm. The liquid phase mercaptan (RSH) proportion after 24 hours and after 5 days was noted.
  • RSH liquid phase mercaptan
  • the hydrocarbon used in this testing was Caspian Pipeline Crude containing an unknown mix of naturally occurring mercaptans with an additional 205 ppm of C3 mercaptan (i.e. 1-propanethiol; CH 3 CH 2 CH 2 SH) artificially added.
  • C3 mercaptan i.e. 1-propanethiol; CH 3 CH 2 CH 2 SH
  • Example 9 using 1000 ppm of Mercaptan Scavenger A reduces the headspace H 2 S from 542 ppm to 475 ppm.
  • Example 10 which uses 500 ppm of Mercaptan Scavenger A and 500 ppm of Co +3 (10% solution) reduces the headspace H 2 S from 542 ppm to 329 ppm.

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Cette invention a trait à l'épuration du sulfure d'hydrogène, des mercaptans et des mélanges gazeux présents dans les hydrocarbures en les amenant en contact étroit avec une formule épuratrice de mercaptans faite d'alcoxyde ou d'hydroxyde d'ammonium quaternaire en présence d'un métal dont l'état d'oxydation est élevé comme le cobalt, le fer, le chrome et/ou le nickel. Le métal à état d'oxydation élevé étant un oxydant, il agit comme un catalyseur lorsqu'il est combiné avec l'éthoxyde ou l'hydroxyde quaternaire pour une meilleure épuration.
EP08731506.5A 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures Withdrawn EP2134814A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14164453.4A EP2759587B1 (fr) 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US89562507P 2007-03-19 2007-03-19
US12/042,536 US20080230445A1 (en) 2007-03-19 2008-03-05 Method of scavenging mercaptans from hydrocarbons
PCT/US2008/056006 WO2008115704A1 (fr) 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures

Related Child Applications (1)

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EP2134814A1 true EP2134814A1 (fr) 2009-12-23
EP2134814A4 EP2134814A4 (fr) 2013-04-24

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EP08731506.5A Withdrawn EP2134814A4 (fr) 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures

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US (1) US20080230445A1 (fr)
EP (2) EP2759587B1 (fr)
EA (1) EA016758B1 (fr)
WO (1) WO2008115704A1 (fr)

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US7918905B2 (en) * 2007-05-17 2011-04-05 Baker Hughes Incorporated Method for improving biodiesel fuel
GB2547364B8 (en) * 2010-10-05 2017-11-29 The Queen's Univ Of Belfast Process for removing metals from hydrocarbons
US9296956B2 (en) 2010-10-28 2016-03-29 Chevron U.S.A. Inc. Method for reducing mercaptans in hydrocarbons
US20140084206A1 (en) * 2012-09-27 2014-03-27 Baker Hughes Incorporated Treating Additives for the Deactivation of Sulfur Species Within a Stream
CN103768913B (zh) * 2012-10-22 2016-04-27 中国石油化工股份有限公司 一种脱除气体中硫化氢和硫醇的方法
RU2532019C1 (ru) * 2013-07-30 2014-10-27 Ахматфаиль Магсумович Фахриев Реагент для нейтрализации сероводорода и подавления роста сульфатвосстанавливающих бактерий
CN112312994A (zh) 2018-04-18 2021-02-02 克莱恩有限公司 用于从离子液体中分离重金属和/或硫种类的方法

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Also Published As

Publication number Publication date
EA200901177A1 (ru) 2010-04-30
EP2759587A1 (fr) 2014-07-30
US20080230445A1 (en) 2008-09-25
EP2134814A4 (fr) 2013-04-24
WO2008115704A1 (fr) 2008-09-25
EP2759587B1 (fr) 2020-02-12
EA016758B1 (ru) 2012-07-30

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