OA18421A - Composition and method for scavenging sulfides and mercaptans. - Google Patents
Composition and method for scavenging sulfides and mercaptans. Download PDFInfo
- Publication number
- OA18421A OA18421A OA1201700375 OA18421A OA 18421 A OA18421 A OA 18421A OA 1201700375 OA1201700375 OA 1201700375 OA 18421 A OA18421 A OA 18421A
- Authority
- OA
- OAPI
- Prior art keywords
- group
- composition according
- formula
- métal
- carboxylate
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims description 22
- 230000002000 scavenging effect Effects 0.000 title claims description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title description 51
- 150000003568 thioethers Chemical class 0.000 title 1
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- -1 carboxylate anion Chemical class 0.000 claims abstract description 35
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
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- 150000002500 ions Chemical class 0.000 claims abstract description 8
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
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- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
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- IVQCQIORBPXQGP-UHFFFAOYSA-N 3-(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)NC(=O)N(CO)C1=O IVQCQIORBPXQGP-UHFFFAOYSA-N 0.000 description 1
- HMMSZUQCCUWXRA-UHFFFAOYSA-N 4,4-dimethyl valeric acid Chemical compound CC(C)(C)CCC(O)=O HMMSZUQCCUWXRA-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- VBHRLSQLJDHSCO-UHFFFAOYSA-N 5,5-dimethylhexanoic acid Chemical compound CC(C)(C)CCCC(O)=O VBHRLSQLJDHSCO-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- GXBPIJOAHZFSJY-UHFFFAOYSA-N 7,7-dimethyloctanoic acid zinc Chemical compound [Zn].CC(C)(C)CCCCCC(O)=O GXBPIJOAHZFSJY-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- AAOISIQFPPAFQO-UHFFFAOYSA-N 7:0(6Me,6Me) Chemical compound CC(C)(C)CCCCC(O)=O AAOISIQFPPAFQO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- HHICRQHZPBOQPI-UHFFFAOYSA-L diazanium;zinc;dicarbonate Chemical compound [NH4+].[NH4+].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O HHICRQHZPBOQPI-UHFFFAOYSA-L 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- JMOLZNNXZPAGBH-UHFFFAOYSA-N hexyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCC JMOLZNNXZPAGBH-UHFFFAOYSA-N 0.000 description 1
- 229950004531 hexyldecanoic acid Drugs 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Abstract
This invention relates to a composition comprising 1.) a metal carboxylate, wherein the métal M is selected from the group consisting of Ag, Cn, Hg, Pb, Sn, Ni, Co, Ca, Fe, Zn and Mn, those metals being present as ions in a +2 or +3 charge state, and wherein the carboxylate anion is derived from a hydrocarbyl monocarboxylic acid having 5 to 20 carbon atoms, or a mixture of such acids, 2.) a solvent selected from the group consisting of water, glycol ethers having from 4 to 15 carbon atoms, alkyl alcohols having from 1 to 10 carbons, and aromatic hydrocarbon solvents having from 6 to 30 carbons, and 3.) an emulsion breaker which is a polymeric nonionic surfactant.
Description
COMPOSITION AND METHOD FOR SCAVENGING SULFIDES AND MERCAPTANS z
FIELD OF THE INVENTION
The invention relates to a process for scavenging hydrogen sulfide from liquids and/or gas by use of métal carboxylates in combination with a solvating agent and émulsion breaker package as part of a multifunctional formulation. The formulations containing the inventive mixture hâve particular applicability in scavenging hydrogen sulfide and/or mercaptans yet at the same time prevent the formation of unwanted émulsions and/or déposition of unwanted by products often associated with using chemistries and/orformulations ofthe prior art.
BACKGROUND OF THE INVENTION
The presence of sulfhydryl compounds and particularly hydrogen sulfide pose challenges in many industries. Their presence can create a sîgnificant health, safety and environmental challenge. There are many different types of sulfhydryl compounds, but the most commonly encountered molécules include hydrogen sulfide (H2S), organo-sulfur compounds containing S-H groups (also called mercaptans), thiol carboxylic acids RC(O)SH, dithio acids RC(S)SH, and related compounds.
In the oil and gas industry the H2S content of crude oil and natural gas in many areas of the world is high enough to présent environmental and safety hazards. Hydrogen sulfide is a flammable, corrosive, and highly toxic gas. H2S is the most reduced form of sulfur and is produced by sulfate reducing bacteria (SRB) that are often found in the anaérobie conditions encountered in oil réservoirs and is highly soluble in crude oil. As oil is produced, it is depressurized and the H2S is released and can then be transferred to, for exàmple, oil based drilling fluid during the drilling process and this can become a hazard as the drilling fluid is recirculated from the well to the surface. During the production phase H2S gas can create a sîgnificant integrity risk-where it is présent at as little as >0.01 psig partial pressure as it is an acid gas and upon'dissolving into produced water créâtes a very corrosive environment and requires to somehow be removed in order for the fluids to be safely processed.
The odor of sulfhydryl compounds is also a challenge in, for example, métal working environments, but equally in water treatment processes, either municipal (e.g. waste water treatment) or industrial (recycling of.mining water). SRB are often présent in the recirculatingfiùid'systems.'andlhoughThe-bacteriacan usually be controlled by the use of biocidal compositions, it is easy to lose control of the biology in the system which results in the production of hazardous H2S in the system. Furthermore biocides are inefficient at removing H2S after it forms and only anecdotally scavenge, via either oxidation (e.g.
sodium hypochlorite application) or due to the release of low levels of aldéhyde during their breakdown (e.g. with glutaraldehyde). Sulfhydryl compounds and particularly H2S can présent environmental, toxicity and integrity challenges in gaseous phases in confined spaces, as for instance in sewage treatment facilities and particularly in shipping and storage containers for moisture sensitive materials that may émit H2S which can sit in the gaseous headspace. It would be désirable to hâve a scavenger that could reduce the H2S concentrations in such locations. It would be particularly advantageous to hâve such a scavenger that is active in the absence of an aqueous phase. Furthermore it is désirable to hâve a scavenger that does not produce unwanted by-products or form émulsions that can inadvertently contaminate the very Systems they are treating.
A number of methods hâve been proposed to scavenge hydrogen sulfide and control sulfhydryl odors in hydrocarbon containing Systems:
WO-98/02501 describes the use of bisoxazolidines prepared by the reaction of 1, 2 or 1, 3 amino alcohols containing 3 to 7 carbon atoms with aldéhydes containing 4 or fewer 20 carbon atoms. The relative oil and water solubility of these products can be controlled through the correct choice of starting materials. These bisoxazolidines react with sulfhydryl compounds présent in oil and gas streams to neutralize and therefore scavenge them.
EP-A-2650314 teaches the use of a copolymer, comprising
a) 0.1 to 10 mol-%, based on the weight ofthe copolymer, of structural units derived from vinylphosphonic acid or of a sait thereof,
b) 40 to 80 mol-%, based on the weight of the copolymer, of structural units derived from compounds ofthe formula (1)
H2C = CH (1) c=o
HN-C(CH3)2-CH2-SO®X®
c) 1 to 50 mol-%, based on the weight of the copolymer, of structural units derived from compounds of the formula (5)
H2C = CH
I c = o
X in which X is OH or NR3R4, and R3 and R4, independently of one another, are H or CrC4-alkyl, for the inhibition and/or dispersion of inorganic sulphide scales.
US-6239081 teaches a water-based drilling fluid which comprises at least one alkali métal carboxylate and at least one soluble boron compound. It further relates to the use of boron compounds in drilling fluids which comprise alkali métal carboxylates to decrease the corrosivity of these drilling fluids.
US-5347004 teaches the use of reaction products of alkoxyalkylene amine, ammonia, and dialkylamines with aldéhydes. These products are used to remove H2S from gas streams which are sparged into water solutions of the products.
There are multiple patents published in the art that teach the use of triazine chemistry for the control of H2S in the oilfield environment. US-4978512 teaches a method for reducing H2S and organic sulfides from gaseous and/or liquid hydrocarbon streams by using a reaction product of a lower alkanolamine comprising 1 to about 6 carbons with a lower aldéhyde comprising 1 to about 4 carbons. A preferred embodiment is the reaction product of monoethanolamine and formaldéhyde which is perhaps one ofthe most ubiquitously used triazine chemistries in the oil and gas industry today to scavenge H2S.
US-5128049 teaches a unique application method for scavenging agents whereby a dilute solution of a scavenging agent, such as triazine, is injected into an H2S containing fluid, followed by équilibration and a second injection of dilute solution of scavenging agent to further reduce the H2S content of the treated fluid.
EP-0636675 teaches the further use of a scavenging compound comprising a substantially formaldéhyde free 1,3,5-trimethyl-hexahydro-1,3,5-triazine to scavenge gas or liquid hydrocarbon streams containing H2S and/or mercaptans. The compound described is preferably prepared by the reaction of methylamine and formaldéhyde.
US-8512449 teaches a method for formulating an oil-soluble triazine sulfide scavenger comprising a liquid sulfide-scavenging composition comprising from about 25 to 80 % by volume of a triazine, from about 15 to 50 % by volume of a glycol ether, and from about 5 to 40 % by volume of an alcohol, with a maximum water content of about 15 % by volume, and being oil soluble. The triazine used is a reaction product of a to C6 alkanolamine and a Ci to C6 aldéhyde, where the Ci to C6 moiety in each instance is a straight or branched chain alkyl group.
WO-2014/031537 teaches the use of an aldéhyde releasing compound, preferably hydantoins, to remove sulfhydryl compounds from hydrocarbon fluids.
US-3928211 describes the use of inorganic zinc salts (most preferably zinc carbonate) preferably dispersed into aqueous or non-aqueous oil well drilling fluids with an organic dispersant such as lignin containing materials.
US-4147212 teaches the use of a water soluble zinc ammonium carbonate complex used to remove hydrogen sulfide from oils and gases by contact with aqueous solutions of the complex.
US-6599472 discloses the use of métal sait carboxylic acids that are soluble in hydrocarbon oils and are used to inactivate odor producing sulfhydryl compounds. Preferred embodiments are zinc neodecanoic acid but equally claimed are carboxylic acids of naphthenic acids, neoacids, isoacids and Guerbet acids and mixtures thereof.
WO-2014/130503 teaches the use of zinc carboxylates, preferably zinc octoate or zinc 2ethyl hexanoic acid in combination with viscosity improver selected from the group consisting of glycol ethers having from about 4 to about 15 carbon atoms, and/or alkyl alcohols having from about 1 to about 10 carbons, and/or with additional hydrocarbons from about 7 to about 30 carbons. The résultant formulations are used to scavenge hydrogen sulfide gas.
WO-2013/181056 teaches the synergistic hydrogen sulfide scavenging obtained when use of a métal sait, preferably selected from zinc chloride, zinc acetate, zinc octanoate, and zinc salts containing at least one hydrocarbyl group of at least 4 carbon atoms in combination with an oil soluble amine formaldéhyde reaction product (triazine).
US-2015/0025258 discloses the use of particulate zinc oxide salts blended in a mixture of two or more carboxylic acids selected from the group consisting of acetic acid, oleic acid, isobutyric acid, lineoleic acid and neodecanoic acid, for the scavenging of hydrogen sulfide.
The object of the invention was to provide formulations which can be used for scavenging of sulfhydryl compounds in crude oil, preferably, but not limited to H2S and/or mercaptans. The formulations of the invention should hâve particular applicability in scavenging sulfhydryl compounds and should be notable for improved performance compared to the formulations and chemistries of the prior art.
It has been found that a ternary composition that comprises a métal carboxylate, an organic solvent and an émulsion breaker molécule will scavenge sulfhydryl compounds very effectively, while at the same time not induce any émulsion challenges due to the précipitation of insoluble byproducts. Deposits of sulfide scales can be a signîficant challenge during the use of métal carboxylate scavengers. Typically carboxylates of zinc are used which results in the déposition of ZnS. This can create signîficant challenges as ZnS is highly insoluble and can create flow assurance challenges due to blockages in pipes and process equipment as well as exacerbate water in oil émulsions and therefore déhydration of the crude oil.
In a first aspect, the présent invention provides a composition, useful as a sulfhydryl scavenger for application in oilfield operations, comprising
1. ) a métal carboxylate, wherein the métal M is selected from the group consisting of
Ag, Cn, Hg, Pb, Sn, Ni, Co, Ca, Fe, Zn and Mn, those metals being présent as ions in a +2 or +3 charge state, and wherein the carboxylate anion is derived from a hydrocarbyl monocarboxylic acid having 5 to 20 carbon atoms, or a mixture of such acids,
2. ) a solvent selected from the group consisting of water, glycol ethers having from 4 to 15 carbon atoms, alkyl alcohols having from 1 to 10 carbons, and aromatic hydrocarbon solvents having from 6 to 30 carbons, and
3. ) an émulsion breaker which is a polymeric nonionic surfactant.
In a second aspect, the présent invention provides the use of the composition of the first aspect as a sulfhydryl scavenger for application in oilfield operations and process Systems.
In a third aspect, the présent invention provides a process for scavenging sulfhydryl molécules in oilfield operations and process Systems, the process comprising adding to a system susceptible to production of sulfhydryl compounds the composition of the first aspect.
In a preferred embodiment, the composition comprises additionally at least one additional hydrogen sulfide scavenger as component from group 4.
In another preferred embodiment, the composition comprises additionally at least one scale inhibitor and/or at least one corrosion inhibitor as component from group 5.
In another preferred embodiment, the composition comprises additionally both at least one additional hydrogen sulfide scavenger as component from group 4 and at least one scale inhibitor and/or at least one corrosion inhibitor as component from group 5.
Group 1
In group 1, the carboxylates are the ones ofthe metals Ag, Cn, Hg, Pb, Sn, Ni, Co, Ca, Fe, Zn and Mn in their +2 or +3 charge state which means that the metals are présent as respectively charged ions.
The compounds of group 1 comprise oil soluble sulfhydryl compound scavengers which in a preferred embodiment are sait compositions ofthe formula (1)
Ma+(R-CO2)b(OH)c.b (1) wherein
M is selected from the group consisting of silver, copper, mercury, lead, tin, nickel, cobalt, cadmium, iron and manganèse, a is2or3, b is 1,2 or 3, c is (a-b), and
R is a hydrocarbyl radical containing from 4 to 19 carbon atoms, or mixtures of such carboxylates.
The métal ions used to préparé the carboxylate salts of this invention are chosen on the basis that the sulfide salts ofthe said métal ions are water insoluble or sparinglysoluble. Preferably the métal sulfides hâve solubility in water less than 0.01 wt.-% meaning less than 0.01 g sait/100 cm3 water. The métal sulfides are the sulfides of silver, copper, mercury, lead, tin, nickel, cobalt, cadmium, iron, zinc and manganèse. Even more preferred are sulfides of zinc, lead and iron, particularly zinc and iron, and most preferred is zinc sulfide.
The most preferred embodiment for the métal carboxylate is thus a zinc carboxylate. It is known that zinc carboxylates may occur as cyclic structures that correspond to the formula (Zn)n(O2CR)(2n-2)(O)[ri]/4 instead of Zn(R-CO2)b (OH)(c-b). Mostly, zinc carboxylate will correspond to the formula Ζη4(Ο2ΟΡ)6Ο.
The carboxylic acids used to préparé the compositions of this invention contain from 5 to 20 carbon atoms, and are preferably chosen from those which form oil soluble salts with the métal ions of this invention. The preferred oil solubility is a log Pow of >1 but more preferably >2 where log Pow is measured using the OECD 117 method.
In one preferred embodiment, the acids from which the métal salts of group 1 are formed are liquid below 100 °C, more preferably below 50 °C, most preferably below 25 °C.
In another preferred embodiment, the métal salts according to formula (1) hâve a viscosity of less than 20,000 cP at standard room température and pressure (STP), more preferably below 15,000 cP, most preferably below 10,000 cP. Ail viscosity measurements were performed at STP using a Brookfield viscometer and a constant rotational speed and spindle type.
The formation of low melting salts typically requires that the carboxylic acids used to synthesize the final product hâve highly branched structures. Examples of suitable acids include:
1. Neoacids of the formula (2)
R1
R2---C---COOH (2)
R3 wherein
R1, R2, and R3 are each independently alkyl groups containing 1 to 16 carbon atoms, with the total number of carbon atoms contained in R1, R2, and R3 being from 3 to 18.
Readily available and suitable neoacids include, but are not limited to, neopentanoic acid, neoheptanoic acid, neooctanoic acid, neononanoic acid, neodecanoic acid, and neotridecanoic acid. Neoacids with up to a total average of 20 carbon atoms are also available as mixtures of chain lengths and isomers, and are also suitable, as are mixtures of any of the described neoacids in any proportions. A preferred neoacid is neodecanoic acid as it is readily available and forms low viscosity salts.
2. Isoacids of formula (3)
R4---CH2--COOH (3) wherein
R4 is an aliphatic, branched hydrocarbyl group containing from 2 to 20 carbon atoms, wherein branched means that R4 includes at least one methyl group at a position other than the terminal carbon atom.
Readily available isoacids are usually mixtures of isomers which differ in the number and position of the methyl substitutions. Preferred isoacids include isopentanoic acid, isoheptanoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, and isotridecanoic acid.
3. Guerbet acids of formula (4)
R6
R5--CH--COOH (4) wherein
R5 is a hydrocarbyl group containing from 2 to 8 carbon atoms, and
R6 is a hydrocarbyl group containing from 4 to 10 carbon atoms.
Preferred Guerbet acids include 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-hexyldecanoic acid, and 2-octyldodecanoic acid. Most preferred is 2-ethylhexanoic acid.
Group 2
This group comprises hydrocarbon solvents used to deliver the Group 1 métal carboxylate component. The métal carboxylate is delivered as a composition having the métal carboxylate and a solvent. The solvent may be any solvent suitable, for example, for dissolving or suspending the métal carboxylate. In preferred embodiments, the solvent is water, alcohol, a non-alcoholic organic solvent, and/or any combination thereof. The alcohol may include any alcohol suitable as a solvent and for use with oil recovery operations. Preferred are alkyl alcohols having from 1 to 10 carbon atoms, e.g. isopropyl alcohol, methanol, éthanol, propanol, butanol. Another preferred type of alcohols is glycol ethers having from 4 to 15 carbon atoms. Examples of suitable glycol ethers include ethylene glycol, propylene glycol, butylène glycol, oligoethylene glycols, oligopropylene glycols, isopropyl alcohol or any combination thereof. Oligoethylene glycols and oligopropylene glycols preferably hâve a number average molecular weight between 200 and 1000 g/mol.
According to another preferred embodiment, the organic solvent includes aromatic compounds, either alone or in any combination with the foregoing. In an embodiment, the aromatic compounds hâve a molecular weight from about 70 to about 400, preferably from 5 about 100 to about 200 g/mol. Examples of suitable aromatic compounds include toluene, xylene, naphthalene, ethylbenzene, trimethylbenzene, and aromatic naphtha (AN), other suitable aromatic compounds, and any combination of the foregoing. It is to be understood that the amount of métal carboxylate in the composition in relation to the solvent may vary in some embodiments depending upon factors such as température, time, and type of métal carboxylate. For instance a higher ratio of métal carboxylate to solvent may be used if a faster reaction time is desired.
Group 3
This group comprises émulsion breakers, or demulsifiers or non-emulsifiers. The purpose of having these compounds présent is to prevent the formation of émulsions caused by the reaction products of métal carboxylate from Group 1. The métal carboxylate reaction product with sulfhydryl compounds is the corresponding métal sulfide. These métal sulfides are highly oil wetting and as a resuit they are attracted to the oil/water interface and cause émulsion stability. The purpose of the demulsifier molécule is to break the oil/water émulsion by creating a preferentially water wet surface on the métal sulfide and also to modify the surface tension at the oil/water interface which is stabilized by the métal sulfides to one allowing coalescence of the émulsion.
Examples of suitable polymeric nonionic surfactants include polysorbates, fatty alcohols such as cetyl alcohol and oleyl alcohol, polymers comprising ethylene oxide, polymers comprising propylene oxide, ethylene oxide-propylene oxide copolymers, alkyl polyglucosides such as decyl maltoside, alkylphenol polyethylene oxide, alkyl polyethylene oxide, and ethoxylated and/or propoxylated alkyl phenol-formaldehyde resins.
In preferred embodiments, the émulsion breaker components refer to components or additives that may be added as part of the composition comprising the instant invention and can be described as polymeric nonionic surfactants. Without limitation, examples of 35 suitable polymeric nonionic surfactants include polysorbates, fatty alcohols such as cetyl alcohol and oleyl alcohol, polymers comprising ethylene oxide, polymers comprising propylene oxide, ethylene oxide-propylene oxide copoymers, alkyl polyglucosides such as decyl maltoside, alkylphenol polyethylene oxide, alkyl polyethylene oxide, dodecylbenzenesulfonic acid, and ethoxylated and/or propoxylated alkyl phenolformaldehyde resins.
In a preferred embodiment, the émulsion breaker is a compound according to the formula (5)
wherein
R7 is C2 to C4 alkylene
R8 is C] to C18 alkyl k is a number from 1 to 200 m is a number from 1 to 100
In a preferred embodiment R7 is an ethylene or a propylene group. R7 may respect mixtures of different C2 to C4 alkylene groups, preferably ethylene and propylene groups.
In another preferred embodiment, R8 is a C4 to C]2 alkyl group, more preferably a tertiary butyl group or an iso-nonyl group.
In formula (5), R7, R8 and k may be the same in each of the repeating units, or they may differ from unit to unit.
In another preferred embodiment k is a number from 1 to 20.
In another preferred embodiment m is a number from 3 to 20.
In another spécifie preferred embodiment the émulsion breaker is dodecylbenzenesulfonic acid:
(6)
In another preferred embodiment, the demulsifier is a mixture of at least one compound of formula (5) and at least one compound of formula (6). Such mixture preferably contains (5) and (6) in a weight ratio of from 5:1 to 1:5, more preferably in a weight ratio of from 3:1 to 1:3.
The polymeric nonionic surfactant is preferably dissolved or suspended in a solvent. Any solvent suitable for dissolving or suspending a polymeric nonionic surfactant may be used. Examples of suitable solvents include water, butylglycol, ethylene glycol, propylene glycol, butylène glycol, oligoethylene glycols, oligopropylene glycols, ethers, alcohols, toluene, xylene, aromatic naphtha, or any combination thereof. The alcohol may include any alcohol suitable for use with oil recovery and for dissolving the polymeric nonionic surfactant and is preferably selected from the group consisting of isopropyl alcohol, methanol, éthanol, propanol, butanol or any combination thereof.
Group 4
The addition of a further hydrogen sulfide scavenger serves a two-fold purpose. Firstly it scavenges any residual H2S not scavenged by the Group 1 components, and secondly, there may be a synergy created in scavenging in terms of rate of H2S uptake.
Additional scavengers that can be included in the formulation include triazine compounds, described by the formula (7):
(7)
wherein each R9 is independently selected from the group consisting of Ct to C20 straight or branched alkyl groups, or-R10OH, where R10 is a Ci to C2o straight or branched alkylene group. Preferably, at least one R9 group is a Ci to C20 straight or branched alkyl group and at least one R9 group is -R10OH.
Further, the scavenger can be selected from a range of hemi-acetal compounds, described by the general formula R11R12C(OH)OR13 wherein R11, R12 or R13 are hydrogen and/or Ci to C20 straight or branched alkyl group. ln a preferred embodiment, R11, R12, R13 ali are Ci to C20 straight or branched alkyl groups.
Further, the scavenger compound may be selected from hydantoins. Exemplary hydantoins include, but are not limited to hydroxyalkylhydantoins, bis(hydroxyalkyl)hydantoins, and dialkylhydantoins, where the alkyl group is generally a Ci to C6 alkyl group. Exemplary hydroxyaklyhydantoins useable as the aldehyde-releasing compound include, but are not limited to, 1-hydroxymethyl-5,5-dimethyl-hydantoin also known as monomethylol-dimethylhydantoin (MDMH), 3-hydroxymethyl-5,5dimethylhydantoin. Exemplary bis (hydroxyl-alkyl) hydantoins useable as the aldehydereleasing compound include, but are not limited to, 1,3-bis(hydroxymethyl)-5,5dimethylhydantoin as known as dimethyloldimethylhydantoin (DMDMH). Exemplary dialkylhydantoins useable as the aldehyde-releasing compound include, but are not limited to, 5,5-dimethylhydantoin. In addition, mixtures ofthe hydantoins mayalso be used.
Glyoxal (or ethandial) is a dialdéhyde that has been shown in the art to scavenge hydrogen sulfide gas (e.g. US-4,680,127) and may also be used in the présent invention to scavenge any hydrogen sulfide when contained in a formulation comprising group 1, group 2 and group 3 components.
One preferred embodiment of the current invention is to use 1,3,5 Hexahydrotriethanol-1,
3, 5 Triazine to scavenge hydrogen sulfide gas:
(8)
Another preferred embodiment of the current invention is to use the hemiacetal (ethylenedioxy) dimethanol (EDDM):
(9)
Yet another preferred embodiment of the current invention is to use
1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin as known as dimethyloldimethylhydantoin (DMDMH):
(10)
Group 5
Scale and/or corrosion inhibitors may be added to the target system separately and/or in association with the compounds described in group 1, 2 and 3. The addition of these Group 5 components serves to add functionality to the overall product.
Adding a scale inhibitor can prevent either the déposition of unwanted solids that may resuit from mixing of incompatible waters. Furthermore, the reaction of métal carboxylates with sulfhydryl compounds very often leads to the précipitation of insoluble sulfide scale, for example the reaction of zinc neodecanoate will inevitably lead to the précipitation of highly water insoluble zinc sulfide.
The corrosion inhibitor serves to reduce the overall corrosivity of the treatment, protecting the tubulars and production equipment that oilfield fluids into which the instant invention is deployed into.
Conventîonal scale inhibitors which may be added to the water to be treated in conjunction with the présent invention include, but are not limited to, 1-hydroxyethane-1,1diphosphonates, diethylenetriamine penta(methylene phosphonic acid), nitrilo(methylene phosphonic acid), methacrylic diphosphonate homopolymer, polymaleates, polyacrylates, polymethacrylates, polyphosphates, phosphate esters, acrylic acid-allyl ethanolamine diphosphonate copolymer, sodium vinyl sulfonate-acrylic acid-allyl ammonia diphosphonate terpolymer, acrylic acid-maleic acid-diethylene triamine) allyl phosphonate terpolymer and polycarboxylates, ail added to the formulation so that the conventîonal scale inhibitor présent in the water to be treated ranges from 20 to 50 mg/L.
Conventîonal corrosion inhibitors which may be added to the water to be treated in conjunction with the présent invention include, but are not limited to soluble zinc salts, nitrates, sulfites, benzoate, tannin, lignin sulfonates, benzotriazoles and mercaptobenzothiazoles amines, imidazolines, quaternary ammonium compounds, resins and phosphate esters, ali added to the formulation so that the conventîonal corrosion inhibitor présent in the water to be treated ranges from 50 to 100 mg/L.
One preferred embodiment of the current invention is to use amino trisfmethylene phosphonic acid) as scale inhibitor
O
Another preferred embodiment of the current invention is to use a copolymer, comprising
a) 0.1 to 10 mol-% of structural units derived from vinylphosphonic acid and/or of a sait thereof,
b) 40 to 90 mol-%, of structural units derived from compounds of the formula (12)
H2C = CH
C=O
HN-C(CH3)2-CH2-SO3°Y® (12) wherein Y is a cation, preferably selected from the group consisting of H+, alkali métal ions or NH4 +, and
c) 1 to 50 mol-% of structural units derived from compounds of the formula (13)
H2C = CH I c = o
X (13) in which
X is OH or NR14R15, and R14 and R15, independentiy of one another, are H or
CrC4-alkyl.
Molar percentages are to be understood as relating to the total copolymer composition.
In one preferred embodiment, the copolymer comprises additionally 1 to 10 mol-%, based on the total copolymer composition, of structural units of formula (14)
H2C = CH i
O (14) in which n is 1, 2, 3, 4 or 5, preferably 1.
In one preferred embodiment, the copolymer comprises addîtionally 1 to 10 mol-%, based on the total copolymer composition, of structural units of formula (15)
H2C = CH
I
N-R16 (15)
O = C - R17 in which
R16 and R17, independently of one another, are hydrogen or C1-C4-alkyl, preferably R16 and R17 are both hydrogen.
In ail embodiments ofthe invention, monomers comprising an olefinically unsaturated hydrocarbon substituted ammonium sait group, wherein the expression hydrocarbon encompasses groups containing oxygen, are présent in the copolymer in an amount of preferably below 1 mol-%, particularly 0.001 to 1 mol-%, especially 0.001 to 0.1 mol-%. They are particularly preferably completely absent.
In ali embodiments of the invention, the molar proportion of vinylphosphonic acid or salts thereof is preferably from 0.8 to 6, especially from 1 to 4 mol-%. Suitable salts of vinylphosphonic acid are preferably the alkali métal or ammonium (NH4 +) salts thereof.
In a preferred embodiment, the molar proportion of structural units which are derived from compounds of the formula (12) in ail embodiments of the invention is preferably from 45 to 70, especially from 50 to 65 mol-%.
The molar proportion of structural units which are derived from compounds of the formula (13) is preferably from 5 to 45 mol-%, especially from 10 to 40 mol-%. Formula (13) preferably represents acrylic acid and/or acrylamide. If formula (13) represents only acrylamide, the proportion thereof is preferably from 5 to 45 mol-%, especially from 10 to 40 mol-%. If formula (13) represents a mixture of acrylic acid and acrylamide, the proportion of acrylic acid is preferably from 1 to 10 mol-%, especially from 2 to 5 mol-%, and the proportion of acrylamide provides for the différence up to the total molar amount as described above.
The molar proportion of structural units which are derived from compounds of the formula (15) is preferably from 1 to 10 mol-%, particularly from 2 to 8 mol-%, especially from 3 to 7 mol-%.
The molar proportion of structural units which are derived from compounds of the formula (14) is preferably from 1 to 10 mol-%, particularly from 2to 8 mol-%, especially from 3 to 7 mol-%.
Particular examples of suitable copolymers comprise (molar %).
% AMPS, 38 % Acrylic Amide, 2 % n-Vinyl Formamide, 2 % Vinyl Phosphonic Acid.
% AMPS, 28 % Acrylic Amide, 2 % n-Vinyl Formamide, 2 % Vinyl Phosphonic Acid.
% AMPS, 5 % n-Vinyl Pyrrolidone, 5 % n-Vinyl Formamide, 5 % Acrylic Amide, 2 % Vinyl Phosphonic Acid.
The monomer units may be in any sequence in the copolymers. They may be either random polymers or block polymers.
The molecularweights (number average) ofthe copolymers according to the invention are preferably from 100,000 to 10,000,000 g/mol, in particular from 500,000 to 5,000,000 g/mol. Molecular weight is to be determined by GPC against polyacrylic acid as standard.
The copolymers according to the invention can be prepared by copolymerization of vinyl phoshonic acid and compounds ofthe formulae (12), (13) and optionally (14), (15) in the stated molar ratios.
The copolymers according to the invention can be prepared by the conventional polymerization methods, such as solution polymerization, mass polymerization, émulsion polymerization, inverse émulsion polymerization, précipitation polymerization or gel polymerization. They are preferably the product of a free-radical copolymerization of vinyl phosphonic acid and the compounds oftheformulae (12), (13) and optionally(14), (15).
Yet another preferred embodiment of the current invention is to use tallow alkyl amine ethoxylate as corrosion inhibitor °Vh (16) wherein p is a number from 4 to 10.
Yet another preferred embodiment of the current invention is to use coconut alkyl dimethyl benzyl ammonium chloride as corrosion inhibitor
R18
(17) ίίΊ wherein
R18 is C8 to C18 alkyl.
The composition may additionally contain biocides, for example, formaldéhyde or glutaraldehyde, water dispersants, antifoams, oxygen scavengers and/or flocculants. There may also be added to the water to be treated oxygen scavengers, flocculants such as polyacrylamide dispersants, antifoams such as acetylenic diols, silicones or polyethoxylated antifoams.
The composition of one embodiment of the présent invention is preferably prepared by combining:
0.1 to 80wt.-% ofthe métal carboxylate species described above in group 1, preferably between 60 and 80 wt.-%, to 50 wt.-% of the solvent species described above in group 2, preferably between 5 and 25 wt.-%,
0.1 to 10 wt.-% of at least one émulsion breaker species described above in group 3, preferably between 0.5 and 2 wt.-%, to 20 wt.-% of the scavenger species described above in Group 4, preferably between 5 and 15 wt.-%, and
0.1 to 5 wt.-% ofthe scale and/or corrosion inhibitor species described above in Group 6, preferably between 0.2 and 2 wt.-%.
Furthermore, any balance remaining after addition of the 5 components described above is preferably made up with water and/or glycol and/or alcohol based solvents. The alcohols and solvents are preferably selected from, but not limited to, methanol, éthanol, propan-1-ol, propan-2-ol, monoethylene glycol, triethylene glycol, propylene glycol and / or 2-butoxyethanol.
The inventive composition is preferably applied to a production system where significant sulfhydryl compounds are présent in concentrations between 0.1 and 10,000 mg/L based on oil production. The exact concentration will preferably dépend on the formulation activity itself, the type of sulfhydryl compounds required to be scavenged, static conditions, materials of construction of the medium being treated, quality of the materials being used to make up the inventive solution, température ofthe system and salinity of the system. At this concentration range, the inventive system can provide substantial scavenging of sulfhydryl compounds from the produced liquids in order to maintain the flowability of hydrocarbon production and the quality of the hydrocarbon produced product as it is transported to market.
The présent invention also includes a process for applications using the compositions above for application to be deployed in scavenging of sulfhydryl compounds présent in the drilling and the production cycle, particularly as a component of well work-over, well intervention, production enhancement and flow assurance packages.
The injection fluid containing the composition of the instant invention may additionally contain other ingrédients known to those familiar with the art. Such other ingrédients include acids, dispersants, viscosifiers, lubricity agents, scale inhibitors, friction reducers, crosslinker, surfactants, scavenger, pH adjuster, iron control agents, breakers; this is especially true if any produced water (or recycled water) is in contact with the compositions ofthe instant invention.
Employing the embodiments ofthe instant invention improves the scavenging of sulfhydryl compounds while not causing formation of complex and difficult to treat émulsions. Furthermore the embodiments ofthe instant invention will not corrode the oilfield equipment that it cornes into contact with, nor will it allow the déposition of unwanted solids, such as métal sulfide scales, so often found with applications of the prior art. Other applications of the embodiments of the instantaneous invention include treating water for downhole injection for pressure support, treatment of drilling and work-over operations, wettability alteration and well cleanout.
EXAMPLES
In the whole spécification, ail référencés to percentages are meant to be weight percent relative to the respective whole composition, except if noted otherwise.
Example 1 : Scavenger performance
In order to demonstrate the efficiency of the instant invention in removing sulfhydryl compounds as exhibited by components comprising Group 1, testing was performed focusing on removal of H2S from an oil/water mixture. Ail testing was performed at 117 °F (47 °C) by sparging 200 ppm and 1,000 ppm H2S gas (in a nitrogen matrix) at 0.15 liters per minute through 300 mL of oil (Eagle Ford condensate) and water (in a 50:50 volume ratio of oil to water) while magnetically stirring at 400 rpm. Five different dose rates of the various scavenger chemicals tested were added to the oil/water mixture at 250, 500, 1,000, 2,000 and 4,000 mg/L.
Efficacy was determined as the time required to measure the same concentration of H2S exiting the test fluid than that entering, i.e. the time required for the scavenger to be 100 % spent and loaded with H2S. The longer the time the more efficient the scavenger. The results hâve been summarized in Table 1.
Table 1 : H2S scavenger efficiency testing of components that comprise the instant invention and comparative examples from the prior art
| Example | Chemical | 200 ppm H2S (min-sec) | 1,000 ppm H2S (min-sec) | |||
| 250 PPm | 500 PPm | 1000 PPm | 2000 PPm | 4000 PPm | ||
| 1 (C) | 1.3,5 Hexahydrotriethanol-1, 3, 5 Triazine | 1’50 | 3’42” | 11’22” | 2’12” | 5’17 |
| 2(C) | 1, 3, 5-trimethylhexahydro- 1,3, 5-triazine | T45” | 3’37 | 11’05 | 2’03” | 5’03” |
| 3(0 | a, a, a -Trimethyl-1, 3, 5triazine-1, 3, 5(2H, 4H, 6H)-triethanol | 1’48” | 3’40” | 11’15 | 2’07” | 5’10 |
| 4(0 | 1, 6-dihydroxy-2, 5dioxahexane | 2’15 | 4’58 | 14’24” | 2’44 | 6’31 |
| 5(0 | 1,3-Dimethylol-5,5dimethylhydantoin | 2’04 | 4’32 | 12’49 | 2’24 | 5’53 |
| 6(0 | Zinc neodecanoate | 3’21 | 8’21 | 25’50” | 3’04” | 7’48” |
| 7(0 | Zinc 2-ethylhexanoate | 3’15” | 8’05 | 24’58” | 2’52 | 7’31 |
| 8 | Instant Invention Formulation | 3’25” | 8’29 | 26’02” | 3’17” | 7’59 |
The inventive formulation of example 8 was as follows: 75 % zinc-neodecanoate, 24.3 % heavy aromatic naphtha, 0.3 % of DDBSA (as described in formula (6)), 0.2 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group and an approximate molecular weight of 3,500 g/mol as described in formula (5), and 0.2 % Group 5 Copolymer (58 % AMPS, 38 % Acrylic Amide, 2 % n-Vinyl Formamide, 2 % Vinyl Phosphonic Acid).
It can be seen that ail the triazine compounds that comprised comparative examples 1 (C), 2 (C), and 3 (C) performed very similarly. Comparative examples 4 (C) and 5 (C) performed better than the triazine examples but the raw scavengers of this instant invention in examples 6 and 7 outperformed the comparative examples in terms of H2S loading efficacy.
Example 2: Viscosity profiles
The purpose of this testing was to détermine the effect that Group 2 components had on the viscosity of compositions of the instant invention. Viscosity was measured using a Brookfield viscometer at a constant of 71 °F (22 °C) and ambient pressure. The results 5 hâve been displayed in Table 2.
Table 2: Viscosity measurements of the instant invention and comparative examples
| Example | Chemistry / Formulation | Viscosity (cP) |
| 1(C) | Zinc neodecanoate | 9,000 |
| 2(0 | Zinc 2-ethylhexanoate | 8,500 |
| 3(0 | 75 % Zinc neodecanoate + 25 % MEG | 732 |
| 4(0 | 75 % Zinc 2-ethylhexanoate + 25 % MEG | 711 |
| 5(0 | 75 % Zinc neodecanoate + 25 % 2-BE | 766 |
| 6(0 | 75 % Zinc 2-ethylhexanoate + 25 % 2-BE | 728 |
| 7(0 | 75 % Zinc neodecanoate + 25 % HAN | 93 |
| 8(0 | 75 % Zinc 2-ethylhexanoate + 25 % HAN | 86 |
| 9(0 | 75 % Zinc neodecanoate + 25 % butanol | 624 |
| 10(0 | 75 % Zinc 2-ethylhexanoate + 25 % butanol | 586 |
| 11(0 | 75 % Zinc neodecanoate + 25 % toluene | 137 |
| 12(0 | 75 % Zinc 2-ethylhexanoate + 25 % toluene | 124 |
| 13 | Instant Invention Formulation | 139 |
The inventive formulation of example 13 was 1 as follows: 75 % zinc-neodecanoate, 24.3 % heavy aromatic naphtha, 0.3 % of DDBSA (as described in formula (6)), 0.2 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group and an approximate molecular weight of 3,500 g/mol as described in formula (5), and 0.2 % Group 5 Copolymer (58 % AMPS, 38 % Acrylic Amide, 2 % n-Vinyl Formamide, 2 % Vinyl
Phosphonic Acid).
In Table 2 MEG is monoethylene glycol, 2-BE is 2-butoxyethanol, and HAN is heavy aromatic naphtha. It can be seen that viscosity can be dramatically reduced by adding relatively low amounts of solvent compared to the two comparative Group 1 examples. The most effective Group 2 components to add to the Group 1 components for viscosity réduction were heavy aromatic naphtha and/or toluene.
Example 3: Emulsion testing
It is well known to one skilled in the art that solids in an oil/water mixture can cause sîgnificant émulsion stability especially if those solids are liable to oil wet and sit on the oil/water interface. This is the case with zinc sulfide and as this is a reaction product of preferred embodiments of the instant invention, the test work presented here shows how Group 3 émulsion breaker components assist with the resolution of émulsions caused by use of the Group 1 components.
The testing was performed using the standard bottle test, well known to one skilled in the art. This involved taking 100 mL of different ratios of crude oil and synthetic brine in a prescription bottle and agitating them on a mechanical shaker in order to induce émulsions. Ail tests were performed at a température of 140 °F (60 °C) and séparation observed for 10 minutes. For tests that contained ZnS, the ZnS was added as a substance in a known concentration. The time taken for émulsion resolution was recorded as water drop rate, crude oil déhydration and interface quality. Water drop rate is the rate at which water volumetrically séparâtes from the crude oil. It is désirable for this to be as quick as possible, achieving a maxima in under 5 minutes is more désirable in oilfield operations. The crude oil déhydration is measured as base sédiment and water % (BS&W %) which in this test is the water content that remains in the oil at the end of the test. This gives a secondary indication of performance because while water drop is one désirable feature of a good demulsifier, the remaining water left in the crude oil is ideally <2 %, more désirable is <1 %. Finally the quality of the interface is important. A clean interface, i.e. a very uniform layer existing between the oil and water, rather than a baggy, or inhomogeneous interface is most désirable. This is because the way oilfield séparation process equipment Works requires a clean interface to be most efficient. These tests were performed using comparative components and preferred embodiments of the instant invention to show how inclusion of Group 3 components significantly enhanced the resolution of émulsions and that examples from the known art cause substantial challenges with respect to émulsion formation. The results hâve been summarized in Tables 3 and 4 which show formulations and performance data respectively.
Table 3:
Formulations tested for émulsion resolution
| Example | Formulation |
| 1(C) | Zinc-neodecanoate |
| 2(0 | 75 % zinc-neodecanoate, 25 % HAN |
| 3 | 75 % zinc-neodecanoate, 24 % HAN, 1 % DDBSA as described in formula (6) |
| 4 | 75 % zinc-neodecanoate, 24 % HAN, 1 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group and an approximate molecular weight of 3,500 g/mol as described in formula (5) |
| 5 | 75 % zinc-neodecanoate, 24 % HAN, 0.5 % DDBSA as described in formula (6) and 0.5 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group and an approximate molecular weight of 3,500 g/mol as described in formula (5) |
Table 4: Emulsion resolution testing of the instant invention and comparative examples
| Ex. (from Table 3) | Oil (vol.-%)1 | ZnS content (wt.-%) | Water Drop (mL) | BS&W (%) | Interface Quality | |||||
| 1 min | 2 min | 3 min | 4 min | 5 min | 10 min | |||||
| 50 | 0 | 35 | 41 | 48 | 50 | 50 | 50 | 3.2 | Good, sharp | |
| 1(C) | 50 | 0.5 | 21 | 24 | 27 | 31 | 33 | 41 | 6.3 | Poor, baggy |
| 70 | 0 | 12 | 18 | 26 | 30 | 30 | 30 | 2.8 | Good, sharp | |
| 70 | 0.5 | 6 | 8 | 10 | 13 | 14 | 19 | 5.9 | Poor, baggy |
| 2(C) | 50 | 0 | 37 | 42 | 50 | 50 | 50 | 50 | 2.9 | Good, sharp |
| 50 | 0.5 | 22 | 23 | 29 | 34 | 36 | 44 | 6.1 | Poor, baggy | |
| 70 | 0 | 14 | 19 | 28 | 30 | 30 | 30 | 2.4 | Good, sharp | |
| 70 | 0.5 | 7 | 8 | 12 | 14 | 16 | 21 | 5.7 | Poor, baggy | |
| 3 | 50 | 0 | 43 | 48 | 50 | 50 | 50 | 50 | 1.4 | Good, sharp |
| 50 | 0.5 | 34 | 38 | 42 | 44 | 47 | 50 | 2.3 | Good, sharp | |
| 70 | 0 | 22 | 29 | 30 | 30 | 30 | 30 | 0.9 | Good, sharp | |
| 70 | 0.5 | 16 | 21 | 27 | 29 | 30 | 30 | 1.9 | Good, sharp | |
| 4 | 50 | 0 | 42 | 47 | 49 | 50 | 50 | 50 | 1.6 | Good, sharp |
| 50 | 0.5 | 32 | 36 | 40 | 43 | 46 | 50 | 2.7 | Good, sharp | |
| 70 | 0 | 21 | 28 | 30 | 30 | 30 | 30 | 1.0 | Good, sharp | |
| 70 | 0.5 | 14 | 20 | 26 | 28 | 30 | 30 | 2.1 | Good, sharp | |
| 5 | 50 | 0 | 48 | 50 | 50 | 50 | 50 | 50 | 0.3 | Good, sharp |
| 50 | 0.5 | 46 | 49 | 50 | 50 | 50 | 50 | 0.3 | Good, sharp | |
| 70 | 0 | 27 | 29 | 30 | 30 | 30 | 30 | 0.1 | Good, sharp | |
| 70 | 0.5 | 24 | 28 | 30 | 30 | 30 | 30 | 0.2 | Good, sharp |
1 The remainder of the 100 % is brine
It can be seen that the presence of ZnS in the oil/water mixtures causes séparation issues via émulsion formation. The presence of small concentrations of émulsion breaker bases helps to résolve these émulsions, in Example 5 which is a preferred embodiment of the instant invention, a formulated émulsion breaker package was used to show how complété émulsion resolution can be obtained that could be used as a field solution in order to résolve the challenges caused by the prior art examples.
Example 4: Breakdown product inhibition
A further preferred embodiment of the instant invention is to inhibit the formation of undesirable solids. An example is the inhibition of ZnS solids caused by the reaction of preferred embodiments from Group 1 with H2S. Preferred embodiments from Group 5 were included with a preferred embodiment formulation comprising components from Group 1, 2 and 3 and tested for inhibition of undesirable solid formation.
The various formulations were tested at various concentrations in a 50:50 oil/water mixture (as described in Example 1 ). At the end of the test the total fluids were filtered through a 0.45 pm filter and the solids captured weighted and characterized. A high amount of solids measured indicated poor inhibition of ZnS, and the composition confirmed using x-ray diffraction. The results of this testing has been summarized in Table 5 and 6 which show the formulations tested and performance of these formulations respectively.
Table 5: Formulations tested for ZnS solids déposition potential
| Example | Formulation |
| 1 (C) | Zinc-neodecanoate |
| 2(C) | 75 % zinc-neodecanoate, 25 % HAN |
| 3 | 75 % zinc-neodecanoate, 24 % HAN, 1 % DDBSA as described in formula (6) |
| 4 | 75 % zinc-neodecanoate, 24 % HAN, 1 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group as described in formula (5) . |
| 5 | 75 % zinc-neodecanoate, 24 % HAN, 0.5 % DDBSA as described in formula (6) and 0.5 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group and an approximate molecular weight of 3,500 g/mol as described in formula (5) |
| 6 | 75 % zinc-neodecanoate, 24.3 % heavy aromatic naphtha, 0.3 % of DDBSA (as described in formula (6)), 0.2 % Nonyl acid catalyzed resin with up to 5 mol ethylene oxide (EO) per OH group and an approximate molecular weight of 3,500 g/mol as described in formula (5), and 0.2 % Group 5 Copolymer (58 % AMPS, 38 % Acrylic Amide, 2 % n-Vinyl Formamide, 2 % Vinyl Phosphonic Acid). |
Table 6: Results of ZnS solids déposition control
| Example (from table 5) | Table 5 Formulation Concentration (ppm) | Mass of Solids (g) | Composition of Inorganic Component of Solids |
| KO | 1,000 | 0.0171 | Zinc sulfide |
| 5,000 | 0.0867 | Zinc sulfide | |
| 10,000 | 0.1682 | Zinc sulfide | |
| 2(0 | 1,000 | 0.0160 | Zinc sulfide |
| 5,000 | 0.0649 | Zinc sulfide | |
| 10,000 | 0.1269 | Zinc sulfide | |
| 3 | 1,000 | 0.0127 | Zinc sulfide |
| 5,000 | 0.0627 | Zinc sulfide | |
| 10,000 | 0.1247 | Zinc sulfide | |
| 4 | 1,000 | 0.0149 | Zinc sulfide |
| 5,000 | 0.0635 | Zinc sulfide | |
| 10,000 | 0.1245 | Zinc sulfide | |
| 5 | 1,000 | 0.0148 | Zinc sulfide |
| 5,000 | 0.0630 | Zinc sulfide | |
| 10,000 | 0.1252 | Zinc sulfide | |
| 6 | 1,000 | 0.0027 | Zinc sulfide |
| 5,000 | 0.0131 | Zinc sulfide | |
| 10,000 | 0.03468 | Zinc sulfide |
It can be seen that the amount of zinc sulfide byproduct formed upon sparging through excess H2S in the comparative examples is significant when compared to the inventive example number 6 which shows clear dispersion of ZnS solids.
Claims (21)
1. Composition comprising
1. ) a métal carboxylate, wherein the métal M is selected from the group consisting of
Ag, Hg, Pb, Sn, Ni, Co, Ca, Fe, Zn and Mn, those metals being présent as ions in a +2 or +3 charge state, and wherein the carboxylate anion is derived from a hydrocarbyl monocarboxylic acid having 5 to 20 carbon atoms, or a mixture of such acids,
2. ) a solvent selected from the group consisting of water, glycol ethers having from 4 to 15 carbon atoms, alkyl alcohols having from 1 to 10 carbons, and aromatic hydrocarbon solvents having from 6 to 30 carbons,
3. ) an émulsion breaker which is selected from the group consisting of a polymeric nonionic surfactant and dodecylbenzene sulfonic acid.
2. Composition according to claim 1, wherein the métal carboxylate corresponds to formula (1)
Ma+(R-CO2)b(OH)c.b (1) wherein
M is selected from the group consisting of silver, mercury, lead, tin, nickel, cobalt, cadmium, iron and manganèse, a Is2or3, b is 1,2 or 3, c is (a-b), and
R is a hydrocarbyl radical containing from 4 to 19 carbon atoms, or mixtures of such carboxylates.
3. Composition according to claim 1, wherein the métal carboxylate is zinc carboxylate.
4. Composition according to claim 3, wherein the zinc carboxylate corresponds to formula Zn4(O2CR)6O, wherein R is a hydrocarbyl radical containing from 4 to 19 carbon atoms, or mixtures of such carboxylates.
5. Composition according to one or more of claims 1-4, wherein the métal carboxylate is oil-soluble.
6. Composition according to one or more of claims 1-5, wherein the acids R-COOH, from which the métal carboxylate is derived, are liquid below 100 °C.
7. Composition according to one or more of claims 1, 2, 5 and/or 6, wherein M is Fe.
8. Composition according to one or more of claims 1-7, wherein the métal carboxylate of formula (1) is the sait of a neoacid of the formula (2)
R1
I
R2--C--COOH (2)
R3 wherein
R1, R2, and R3 are each independently alkyl groups containing 1 to 16 carbon atoms, with the total number of carbon atoms contained in R1, R2, and R3 being from 3 to 18.
9. Composition according to one or more of claims 1-7, wherein the métal carboxylate of formula (1) is a sait of an isoacid of formula (3)
R4--CH2--COOH (3) wherein
R4 is an aliphatic, branched hydrocarbyl group containing from 2 to 20 carbon atoms.
10. Composition according to one or more of claims 1-7, wherein the métal carboxylate of formula (1 ) is a sait of a guerbet acid of formula (4)
R6
R5--CH--COOH (4) wherein
R5 is a hydrocarbyl group containing from 2 to 8 carbon atoms, and
R6 is a hydrocarbyl group containing from 4 to 10 carbon atoms.
11. Composition according to one or more of claims 1-10, wherein the solvent is selected from the group consisting of isopropyl alcohol, methanol, éthanol, propanol, butanol. ethylene glycol, propylene glycol, butylène glycol, oligoethylene glycols, oligopropylene glycols, isopropyl alcohol, toluene, xylene, naphthalene, ethylbenzene, trimethylbenzene, and aromatic naphtha (AN).
12. Composition according to one or more of claims 1-11, wherein the émulsion breaker is a compound of formula (5) wherein
R7 is C2 to C4 alkylene
R8 is C] to C18 alkyl k is a number from 1 to 200 and m is a number from 1 to 100.
13. Composition according to one or more of claims 1-11, wherein the émulsion breaker is dodecylbenzene sulfonic acid.
14. Composition according to one or more of claims 1-13, wherein, as an additional H2S scavenger, a compound selected from the group consisting of triazines according to formula (7) (7) wherein each R9 is independently selected from the group consisting of Ci to C20 straight or branched alkyl groups, or-R10OH, where R10 is a Ci to C20 straight or branched alkylene group, hemi-acetal compounds ofthe general formula R11R12C(OH)OR13 wherein R11, R12 or R13 are hydrogen and/or O to C20 straight or branched alkyl group, hydroxyalkylhydantoins, bis(hydroxyalkyl)hydantoins, and dialkylhydantoins, wherein the alkyl group is a Q to C6 alkyl group, and glyoxal are présent
15. Composition according to one or more of claims 1-14, wherein a scale inhibitor selected from the group consisting of 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine penta(methylene phosphonic acid), nitrilo(methylene phosphonic acid), methacrylic diphosphonate homopolymer, polymaleates, polyacrylates, polymethacrylates, polyphosphates, phosphate esters, acrylic acid-allyl ethanolamine diphosphonate copolymer, sodium vinyl sulfonate-acrylic acid-allyl ammonia diphosphonate terpolymer, acrylic acid-maleic acid-diethylene triamine) allyl phosphonate terpolymer and polycarboxylates is présent.
16. Composition according to one or more of claims 1-14, wherein a scale inhibitor is présent which is copolymer, comprising
a) 0.1 to 10 mol-% of structural units derived from vinylphosphonic acid and/or of a sait thereof,
b) 40 to 90 mol-%, of structural units derived from compounds of the formula (12)
c) 1 to 50 mol-% of structural units derived from compounds of the formula (13)
H2C = CH
X in which
X is OH or NR14R15, and R14 and R15, independently of one another, are H or Ci-C4-alkyl.
17. Composition according to one or more of daims 1-16, comprising
0.1 to 80 wt.-% of the métal carboxylate,
1 to 50 wt.-% of the solvent
0.1 to 10 wt.-% of at least one émulsion breaker.
18. Composition according to one or more of daims 11 -17, comprising the additional H2S scavenger in an amount of 1 to 20 wt.-%.
19. Composition according to one or more of daims 15-18, comprising the scale inhibitor in an amount of 0.1 to 5 wt.-%.
20. Use of the composition according to one or more of daims 1 -19 as a sulfhydryl scavenger for application in oilfield operations and process Systems.
21. Process for scavenging sulfhydryl molécules in oilfield operations and process Systems, the process comprising adding to a system susceptible to production of sulfhydryl compounds the composition according to one or more of daims 1-19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/712547 | 2015-05-14 | ||
| EP15170013.5 | 2015-06-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA18421A true OA18421A (en) | 2018-11-02 |
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