EP2759587B1 - Procédé d'épuration des mercaptans présents dans les hydrocarbures - Google Patents

Procédé d'épuration des mercaptans présents dans les hydrocarbures Download PDF

Info

Publication number
EP2759587B1
EP2759587B1 EP14164453.4A EP14164453A EP2759587B1 EP 2759587 B1 EP2759587 B1 EP 2759587B1 EP 14164453 A EP14164453 A EP 14164453A EP 2759587 B1 EP2759587 B1 EP 2759587B1
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.)
Active
Application number
EP14164453.4A
Other languages
German (de)
English (en)
Other versions
EP2759587A1 (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
Baker Hughes a GE Co LLC
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 Baker Hughes Inc, Baker Hughes a GE Co LLC filed Critical Baker Hughes Inc
Publication of EP2759587A1 publication Critical patent/EP2759587A1/fr
Application granted granted Critical
Publication of EP2759587B1 publication Critical patent/EP2759587B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 quaternary ammonium internal ions 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, CH 3 SH, ethyl mercaptan, CH 3 CH 2 SH and propyl mercaptan, CH 3 CH 2 CH 2 SH
  • mercaptans of relatively low molecular weight for example, methyl mercaptan, CH 3 SH, ethyl mercaptan, CH 3 CH 2 SH and propyl mercaptan, CH 3 CH 2 CH 2 SH
  • choline or choline hydroxide has been found to alleviate hydrogen sulfide evolution and to scavenge mercaptans. See, for example, U.S. Pat. Nos. 4,594,147 to Roof et al. , 4,867,865 to Roof and 5,183,560 to Roof et al.
  • choline and choline hydroxide are not well suited for many uses and media, such as in crude oil.
  • 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.
  • European application 0 538 819 A3 to Roof et al. describes the use of oil-soluble quaternary ammonium compounds of the formula: to scavenge various sulfur compounds, including mercaptans, from certain oils, especially high boiling, heavy residual fuels.
  • These compounds, prepared under anhydrous conditions, are what are described herein as "internal ions"; i.e., the positive charge on the nitrogen and the negative charge on the oxygen result in overall electrically neutral compounds without the presence of counter ions such as halides.
  • the European application stresses the significance of the oil solubility of these compounds, noting that they are more oil soluble than choline base and so disperse through the oil being treated more thoroughly to decrease the concentration of undesirable sulfur compounds more effectively. Nevertheless, the compositions of the European application suffer from certain disadvantages. For example, compositions that are produced in higher yields, yet still at low cost, and that reduce mercaptan concentrations more effectively are still desired.
  • U.S. Pat. Nos. 5,840,177 and 6,013,175 and 4,923,596 relate to methods for scavenging mercaptans in hydrocarbon fluids using quaternary ammonium hydroxides.
  • US 4,929,340 relates to methods for treating sour hydrocarbon streams using dipolar compounds including ephedrine.
  • chemistries and methods for removing mercaptans from hydrocarbons include caustic (NaOH solutions) and cobalt with caustic (MeroxTM process of UOP, Merichem processes).
  • 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 mixtures of a quaternary ammonium hydroxide and a quaternary ammonium internal ion, 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 - , and the quaternary ammonium internal ion has the formula R 1 R 2 R 3 N + CH 2 CH 2 O - , where:
  • 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 mixtures of a quaternary ammonium hydroxide and a quaternary ammonium internal ion, 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 internal ion has the formula R 1 R 2 R 3 N + CH 2 CH 2 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 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.
  • the efficacy of the hydroxides and internal ions is 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'O - where R 3 N + R'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 - , and the quaternary ammonium internal ion has the formula R 1 R 2 R 3 N + CH 2 CH 2 O - .
  • R 1 and R 2 are independently selected from the group consisting of alkyl groups of from 1 to 18 carbon atoms, aryl groups of from 8 to 18 carbon atoms and alkylaryl groups of from 7 to 18 carbon atoms.
  • R 3 is selected from the group consisting of alkyl groups of from 2 to 18 carbon atoms, aryl groups of from 6 to 18 carbon atoms and alkylaryl groups of from 7 to 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 18 carbon atoms, alkylaryl groups of from 7 to 18 carbon atoms, -(CH 2 CH 2 O) n H, where n is from 1 to 18, where m and p are independently selected from integers from 0 to 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 18 carbon atoms, aryl groups of from 6 to 18 carbon atoms and alkylaryl groups of from 7 to 18 carbon atoms, and Y is a non-acidic group selected from the group consisting of -OH, -SR 7 and-NR 7 R 8 , where R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl groups of from 1 to 18 carbon atoms, aryl groups of from 6 to 18 carbon atoms and alkylaryl groups of from 7 to
  • R 5 may be hydrogen, alkyl groups of from 1 to 18 carbon atoms or alkylaryl groups of from 7 to 18 carbon atoms.
  • each of R 1 , R 2 and R 3 is methyl. It now has been found that if one of R 1 , R 2 and R 3 is longer than methyl, scavenging may be carried out even in crude oil without the volatile, malodorous scavenging byproducts trimethylamine generated with use of the choline base. Accordingly, R 3 has been designated as the radical having at least two carbon atoms. In some non-limiting forms, 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 eight to eighteen carbon atoms, on the other hand ten to 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 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 eighteen, the formula where m and p are integers from zero to eighteen (independently selected except that m+p is less than or equal to eighteen), or the formula -CHR 5 CHR 6 Y, where R 5 and R 6 and Y are defined as above. Inclusion of such R 4 groups in the quaternary compound has been found to increase the performance of the compound as a mercaptan scavenger significantly over that of tetra-alkyl quaternary compounds.
  • 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 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 prepared 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. Anhydrous conditions were necessary for the formation of the internal ions of the European application. This reaction gives the quaternary ammonium internal ions discovered to be useful herein.
  • Quaternary ammonium internal ions are formed when ethylene oxide is reacted with tertiary amines to give R 1 R 2 R 3 N + CH 2 CHR 4 O - where R 4 is H, and R 1 , R 2 and R 3 are as defined previously.
  • 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 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 -SR 7 or -NR 7 R 8 , an alkylene sulfide or alkyleneimine, respectively, 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 six to twelve carbon atoms.
  • 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., in one non-limiting embodiment about 40°C. to about 50°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 -CH 2 CH 2 OH and -(CH 2 CH 2 O) n H, where n is as defined above, unreacted amine, and glycols formed from reaction of the alkylene oxide and water.
  • R 4 corresponds to the formula 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.
  • the quaternary ammonium hydroxides and quaternary ammonium internal ions described herein have improved H 2 S and/or mercaptan scavenging properties when they are in the presence of a metal of a high oxidation state.
  • 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. In one non-limiting embodiment these metals are believed to act as catalysts in some way, but the inventors do not wish to be limited to any particular theory. Alternatively, 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), Ce (+3,+4) and combinations thereof.
  • the metals may be present as water or oil soluble salts and complexes.
  • Specific, non-limiting examples of 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.
  • the resulting additive 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 20 to 10,000, in one non-limiting embodiment from a lower threshold of 100 independently to an upper threshold of 5,000, ppm based on the weight of the medium to be treated, alternatively from a lower threshold of 500 independently to an upper threshold of 1000 ppm.
  • the amount of metal in the hydrocarbon fluid may range from 10 to 1000 ppm, alternatively up to 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.
  • a liquid is expected to be most common, although dry gas mixtures containing mercaptans may also be treated.
  • 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. toluene, xylene, etc.) and paraffinic solvents ( e.g. pentane, heptane, etc.), renewable fuels such as biodiesel, and mixtures thereof.
  • 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°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°C. to about 75°C.
  • the scavenger tends to decompose at even higher temperatures, such as at about 100°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 (i.e. through C12 or dodecyl mercaptans).
  • 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.
  • 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.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Claims (12)

  1. Procédé de piégeage de H2S et/ou de mercaptans dans un fluide hydrocarboné, comprenant l'ajout au fluide hydrocarboné d'une composition aqueuse de piégeage comprenant une quantité efficace pour le piégeage d'un additif choisi dans le groupe constitué de mélanges d'un ion interne ammonium quaternaire et d'un hydroxyde d'ammonium quaternaire, en présence d'un métal à un état d'oxydation de 3+ ou plus, où l'hydroxyde d'ammonium quaternaire a une formule choisie dans le groupe constitué de R1R2R3N+OH OH-, R1R2R3N+CH2CHR5OH OH- et R1R2R3R4N+OH- , et des mélanges de ceux-ci et l'ion interne ammonium quaternaire est de formule R1R2R3N+CH2CH2O -, où :
    R1 et R2 sont indépendamment choisis dans le groupe constitué de groupes alkyle allant de 1 à 18 atomes de carbone, de groupes aryle allant de 8 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone,
    R3 est choisi dans le groupe constitué de groupes alkyle allant de 2 à 18 atomes de carbone, de groupes aryle allant de 6 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone, à condition, cependant, que R2 et R3 puissent se joindre pour former un noyau hétérocyclique incluant le N et éventuellement un atome d'oxygène,
    R4 est choisi dans le groupe constitué d'hydrogène, de groupes alkyle allant de 2 à 18 atomes de carbone, de groupes alkylaryle allant de 7 à 18 atomes de carbone, de -(CH2CH2O)nH, où n va de 1 à 18,
    Figure imgb0010
    où m et p sont indépendamment choisis parmi des nombres entiers allant de 0 à 18, si ce n'est que la somme de m+p est inférieure ou égale à 18, et de-CHR5CHR6Y, où R5 et R6 sont indépendamment choisis dans le groupe constitué d'hydrogène, de groupes alkyle allant de 1 à 18 atomes de carbone, de groupes aryle allant de 6 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone, et Y est un groupe non acide choisi dans le groupe constitué de -OH, -SR7 et -NR7R8, où R7 et R8 sont indépendamment choisis dans le groupe constitué d'hydrogène, de groupes alkyle allant de 1 à 18 atomes de carbone, de groupes aryle allant de 6 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone, et
    R5 est choisi dans le groupe constitué d'hydrogène, de groupes alkyle allant de 1 à 18 atomes de carbone ou de groupes alkylaryle allant de 7 à 18 atomes de carbone.
  2. Procédé selon la revendication 1 où le fluide hydrocarboné est choisi dans le groupe constitué de pétrole brut, condensats de champ de pétrole, combustibles résiduels, distillats de pétrole, hydrocarbures légers, solvants aromatiques, courants de gaz sec, solvants paraffiniques, combustibles comprenant des composés oxygénés, biodiesel, et des mélanges de ceux-ci.
  3. Procédé selon la revendication 1 ou 2 où le métal dans un état d'oxydation de 3+ ou plus est choisi dans le groupe constitué de Co(+3), Fe(+3), Cr(+6,+3), Ni(+3), Ce(+3,+4) et des combinaisons de ceux-ci.
  4. Procédé selon la revendication 3 où la quantité d'additif dans le fluide hydrocarboné va de 20 à 10 000 ppm.
  5. Procédé selon la revendication 3 où la quantité de métal dans le fluide hydrocarboné va de 0,1 à 5 % en poids de l'additif.
  6. Procédé selon la revendication 3 où R4 est -(CH2CH2O)nH et n va de 1 à 18.
  7. Composition d'hydrocarbure ayant une présence réduite en H2S et/ou en mercaptan, la composition comprenant :
    un fluide hydrocarboné ;
    H2S et/ou des mercaptans ;
    une composition aqueuse de piégeage comprenant une quantité efficace pour le piégeage d'un additif choisi dans le groupe constitué de mélanges d'un ion interne ammonium quaternaire et d'un hydroxyde d'ammonium quaternaire, en présence d'un métal dans un état d'oxydation de 3+ ou plus, où l'hydroxyde d'ammonium quaternaire a une formule choisie dans le groupe constitué de R1R2R3N+OH OH-, R1R2R3N+CH2CHR5OH OH- et R1R2R3R4N+OH-, et des mélanges de ceux-ci et l'ion interne ammonium quaternaire est de formule R1R2R3N+CH2CH2O-, où :
    R1 et R2 sont indépendamment choisis dans le groupe constitué de groupes alkyle allant de 1 à 18 atomes de carbone, de groupes aryle allant de 8 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone,
    R3 est choisi dans le groupe constitué de groupes alkyle allant de 2 à 18 atomes de carbone, de groupes aryle allant de 6 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone, à condition, cependant, que R2 et R3 puissent se joindre pour former un noyau hétérocyclique incluant le N et éventuellement un atome d'oxygène,
    R4 est choisi dans le groupe constitué d'hydrogène, de groupes alkyle allant de 2 à 18 atomes de carbone, de groupes alkylaryle allant de 7 à 18 atomes de carbone, de -(CH2CH2O)nH, où n va de 1 à 18,
    Figure imgb0011
    où m et p sont indépendamment choisis parmi des nombres entiers allant de 0 à 18, si ce n'est que la somme de m+p est inférieure ou égale à 18, et-CHR5CHR6Y, où R5 et R6 sont indépendamment choisis dans le groupe constitué d'hydrogène, de groupes alkyle allant de 1 à 18 atomes de carbone, de groupes aryle allant de 6 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone, et Y est un groupe non acide choisi dans le groupe constitué de -OH, -SR7 et -NR7R8, où R7 et R8 sont indépendamment choisis dans le groupe constitué d'hydrogène, de groupes alkyle allant de 1 à 18 atomes de carbone, de groupes aryle allant de 6 à 18 atomes de carbone et de groupes alkylaryle allant de 7 à 18 atomes de carbone, et
    R5 est choisi dans le groupe constitué d'hydrogène, de groupes alkyle allant de 1 à 18 atomes de carbone ou de groupes alkylaryle allant de 7 à 18 atomes de carbone.
    où au moins une partie de l'additif a réagi avec le H2S et/ou le mercaptan.
  8. Composition d'hydrocarbure selon la revendication 7 où le fluide hydrocarboné est choisi dans le groupe constitué de pétrole brut, condensats de champ de pétrole, combustibles résiduels, distillats de pétrole, hydrocarbures légers, solvants aromatiques, solvants paraffiniques, courants de gaz sec, combustibles comprenant des composés oxygénés, biodiesel, et des mélanges de ceux-ci.
  9. Composition d'hydrocarbure selon la revendication 7 ou 8 où le métal dans un état d'oxydation de 3+ ou plus est choisi dans le groupe constitué de Co(+3), Fe(+3), Cr(+6,+3), Ni(+3), Ce(+3,+4) et des combinaisons de ceux-ci.
  10. Composition d'hydrocarbure selon la revendication 9 où la quantité d'additif dans le fluide hydrocarboné va de 20 à 10 000 ppm.
  11. Composition d'hydrocarbure selon la revendication 9 où la quantité de métal dans le fluide hydrocarboné va de 0,1 à 5 % en poids de l'additif.
  12. Composition d'hydrocarbure selon la revendication 9 où R4 est-(CH2CH2O)nH et n va de 1 à 18.
EP14164453.4A 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures Active EP2759587B1 (fr)

Applications Claiming Priority (4)

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

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP08731506.5A Division EP2134814A4 (fr) 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures

Publications (2)

Publication Number Publication Date
EP2759587A1 EP2759587A1 (fr) 2014-07-30
EP2759587B1 true EP2759587B1 (fr) 2020-02-12

Family

ID=39766340

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14164453.4A Active EP2759587B1 (fr) 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures
EP08731506.5A Withdrawn EP2134814A4 (fr) 2007-03-19 2008-03-06 Procédé d'épuration des mercaptans présents dans les hydrocarbures

Family Applications After (1)

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

Country Status (4)

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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7918905B2 (en) * 2007-05-17 2011-04-05 Baker Hughes Incorporated Method for improving biodiesel fuel
GB2484301B8 (en) * 2010-10-05 2017-11-22 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

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928211A (en) * 1970-10-21 1975-12-23 Milchem Inc Process for scavenging hydrogen sulfide in aqueous drilling fluids and method of preventing metallic corrosion of subterranean well drilling apparatuses
US4033860A (en) * 1975-09-10 1977-07-05 Uop Inc. Mercaptan conversion process
US4124531A (en) * 1977-01-03 1978-11-07 Uop Inc. Catalytic composite for the treatment of sour petroleum distillates
US4778617A (en) * 1984-11-27 1988-10-18 The Drackett Company Acid cleaner composition
US4594147A (en) 1985-12-16 1986-06-10 Nalco Chemical Company Choline as a fuel sweetener and sulfur antagonist
US4867865A (en) 1988-07-11 1989-09-19 Pony Industries, Inc. Controlling H2 S in fuel oils
US4923596A (en) * 1989-05-22 1990-05-08 Uop Use of quaternary ammonium compounds in a liquid/liquid process for sweetening a sour hydrocarbon fraction
US4929340A (en) * 1989-07-31 1990-05-29 Uop Catalyst and process for sweetening a sour hydrocarbon fraction using dipolar compounds
US5183560A (en) 1991-09-09 1993-02-02 Baker Hughes Incorporated Treatment of oils using choline base
US5430160A (en) * 1991-09-23 1995-07-04 Florida State University Preparation of substituted isoserine esters using β-lactams and metal or ammonium alkoxides
AU2714192A (en) 1991-10-21 1993-04-22 Baker Hughes Incorporated Treatment of oils using epoxylated tertiary amines
US5232887A (en) * 1992-04-02 1993-08-03 Uop Catalyst for sweetening a sour hydrocarbon fraction
US5413704A (en) * 1993-11-15 1995-05-09 Uop Process for sweetening a sour hydrocarbon fraction using a mixture of a supported metal chelate and a solid base
CA2133270C (fr) * 1994-03-03 1999-07-20 Jerry J. Weers Hydroxydes d'ammonium quaternaire, agents d'epuration pour mercaptans
US5744024A (en) * 1995-10-12 1998-04-28 Nalco/Exxon Energy Chemicals, L.P. Method of treating sour gas and liquid hydrocarbon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2759587A1 (fr) 2014-07-30
EA016758B1 (ru) 2012-07-30
EA200901177A1 (ru) 2010-04-30
WO2008115704A1 (fr) 2008-09-25
US20080230445A1 (en) 2008-09-25
EP2134814A1 (fr) 2009-12-23
EP2134814A4 (fr) 2013-04-24

Similar Documents

Publication Publication Date Title
US8679203B2 (en) Method of scavenging mercaptans from hydrocarbons
EP2759587B1 (fr) Procédé d'épuration des mercaptans présents dans les hydrocarbures
JP2576952B2 (ja) メルカプタン捕捉剤としての第四級アンモニウムヒドロキシド類
AU2010245644B2 (en) Method of scavenging hydrogen sulfide from hydrocarbon stream
EP2155841B1 (fr) Procédé d'amélioration du carburant biodiesel
US8048175B2 (en) Quick removal of mercaptans from hydrocarbons
EP3400087B1 (fr) Composition d'additif de fixation de sulfure d'hydrogène et procédé d'utilisation associé
EP2593533B1 (fr) Utilisation d'alpha-amino éthers pour éliminer des mercaptans contenus dans des hydrocarbures
CA2755746C (fr) Composition piegeant le mercaptan a base d'ammonium quaternaire
EP1713885B1 (fr) Hydrocarbures a niveaux reduits de mercaptans et procede et composition utiles pour leur preparation
US8211294B1 (en) Method of removing arsenic from hydrocarbons
MXPA95001180A (en) Ammonium hydroxides as mercapt depurers
MXPA98006858A (es) Hidroxidos de amonio como depuradores de mercaptano

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140411

AC Divisional application: reference to earlier application

Ref document number: 2134814

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

R17P Request for examination filed (corrected)

Effective date: 20150122

RBV Designated contracting states (corrected)

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170404

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190826

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WEERS, JERRY, J.

Inventor name: O'BRIEN, TIMOTHY, J.

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BAKER HUGHES, A GE COMPANY, LLC

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AC Divisional application: reference to earlier application

Ref document number: 2134814

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1232113

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008062135

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200512

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200512

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200612

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200705

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008062135

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1232113

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200212

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200306

26N No opposition filed

Effective date: 20201113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200306

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20220225

Year of fee payment: 15

Ref country code: DE

Payment date: 20220217

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200212

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20220217

Year of fee payment: 15

Ref country code: IT

Payment date: 20220217

Year of fee payment: 15

Ref country code: FR

Payment date: 20220218

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008062135

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20230401

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230306

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230306

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230331

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230306