WO2015009429A1 - Oil soluble hydrogen sulfide scavenger - Google Patents
Oil soluble hydrogen sulfide scavenger Download PDFInfo
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- WO2015009429A1 WO2015009429A1 PCT/US2014/044559 US2014044559W WO2015009429A1 WO 2015009429 A1 WO2015009429 A1 WO 2015009429A1 US 2014044559 W US2014044559 W US 2014044559W WO 2015009429 A1 WO2015009429 A1 WO 2015009429A1
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- Prior art keywords
- acid
- zinc
- hydrogen sulfide
- complex composition
- mixture
- Prior art date
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 22
- 239000002516 radical scavenger Substances 0.000 title description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005642 Oleic acid Substances 0.000 claims abstract description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims abstract description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 6
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 230000003247 decreasing effect Effects 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000002000 scavenging effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/173—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with the aid of organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
Definitions
- the invention relates to the reduction of the concentration of hydrogen sulfide in hydrocarbons.
- the invention particularly relates scavenging hydrogen sulfide from hydrocarbons.
- H 2 S Hydrogen Sulfide
- H 2 S metal based scavengers and certain triazines and aldehydes are known to be useful for these purposes.
- glyoxal OHCCHO
- Glyoxal and other aldehydes such as acrolein and formaldehyde are known to be useful in a variety of other applications such as biocides, disinfectants, and the like.
- Aldehydes may be corrosive to metals such as aluminum, iron, and steel.
- Metal Carboxylates are known to be useful for reducing the concentration of hydrogen sulfide in hydrocarbons.
- many of the prior art metal carboxylates, especially those prepared with acetic acid, are insoluble in hydrocarbons and must be used as a dispersion or the like. It would be desirable in the art to prepare an oil soluble hydrogen sulfide inhibitor for use with hydrocarbons, especially crude oil, fuel oils, and bitumen.
- the invention is a method for preparing a zinc carboxylate oxo complex composition which is useful for scavenging hydrogen sulfide from a hydrocarbon comprising reacting particulate zinc oxide with a mixture of two or more carboxylic acids wherein: none of the acids is octanoic acid or an octanoic acid isomer, and the zinc carboxylate oxo complex composition is soluble in hydrocarbons.
- Another aspect of the invention is a method for preparing a zinc carboxylate oxo complex composition which is useful for scavenging hydrogen sulfide from a hydrocarbon comprising reacting particulate zinc oxide with a mixture of two or more carboxylic acids wherein the a zinc carboxylate oxo complex composition is soluble in hydrocarbons.
- the invention is a method for reducing the concentration of hydrogen sulfide in a hydrocarbon comprising introducing a zinc carboxylate oxo complex composition of the disclosure into the hydrocarbon.
- the disclosure is directed to a method for preparing a zinc carboxylate oxo complex composition, useful for scavenging hydrogen sulfide from a hydrocarbon.
- the zinc carboxylate oxo complex is prepared by reacting particulate zinc oxide with a mixture of two or more carboxylic acids. In this process the carboxylic acids act as both solvent and reactant. The total number of moles of carboxylic acid used in the reaction is equal to about 1 .5 times the total moles of zinc added.
- This reaction pathway leads to a final zinc product with a zinc to acid ratio of about 2:3.
- the acids chosen are miscible and of appropriate structure and proportion to result in a product which is uniform and is soluble in organic solvents.
- the acids may be selected from the group consisting of acetic acid, oleic acid, isobutyric acid, lineoleic acid, cekanoic acid, and neodecanoic acid.
- ethyl hexanoic acid may be used while in other embodiments ethyl hexanoic acid is proscribed.
- the reaction proceeds when the acid mixture is heated as zinc oxide is dissolved in the mixture.
- the reaction produces the previously mentioned zinc carboxylate oxo complex in addition to water, which is eventually distilled off to purify the zinc carboxylate oxo product.
- the resultant complex can be dissolved in an organic solvent.
- the method of the application includes synthesizing a zinc oxo complex of the formula Zn 4 0(acid) 6 in which the term "acid" refers to a carboxylate ligand with a -1 charge.
- the carboxylate ligands include two or more differing types of acid ligands and the complex is synthesized using a method in which zinc oxide is reacted neat with a liquid mixture of carboxylic acids.
- the combination of acid species as ligands causes the complex to be oil soluble and suitable for injection into hydrocarbon streams whereas a similar complex consisting of only one type of acid ligand would be less suitable for injection or potentially impossible to inject.
- the ratio of zinc atoms to total acid ligands in the complex is about 2:3, but the ratio of zinc atoms to each discrete acid ligand may range from about 4:5 to about 4: 1
- the acid ligands in this embodiment consists of two or more from the types neodecanoic acid, acetic acid, oleic acid, and linoleic acid.
- the scavenger remains soluble in the sour hydrocarbon streams due to the highly branched nature of a majority of the ligands bound to the zinc atoms.
- By synthesizing a complex which is coordinated to a mixture of acid ligands it is possible to incorporate lower molecular weight acid molecules, allowing an overall lower molecular weight complex. Decreasing the total molecular weight of the oxo zinc complex results in a complex with a higher zinc content by mass, which improves cost effectiveness of the final product with regard to H2S scavenging efficacy.
- the use of low molecular weight acids does not affect the H2S scavenging efficacy of the product, as the driving force of the scavenging reaction is the production of zinc sulfide and a protonated acid molecule:
- the hydrogen sulfide scavengers maybe employed in the process of the disclosure in any way known to be useful to those of ordinary skill in the art of producing oil and gas. For example, it may be atomized and introduced into a gas stream or directly admixed, liquid phase to liquid phase, with a crude oil stream. It may be introduced in a solvent into a viscous phase such as bitumen.
- neodecanoic acid and 3.7g of acetic acid were charged into a reactor, heated to 60°C and agitated. After reaching temperature, 20g of zinc oxide powder were slowly added to the acid mixture in small aliquots. Once all the zinc oxide powder was added and dissolved, the temperature of the reactor was increased to 100°C and agitated for one hour. Following the agitation period, the temperature of the reactor was increased again to 1 10°C and a nitrogen sparge was added in order to remove the water entrained in the reaction mixture. Following the collection of water, the reactor temperature was decreased to 80°C, at which point 27.6g of an aromatic distillate solvent was added and the reaction mixture was allowed to stir for 30 minutes.
- a test is performed using an oxo complex as prepared in Example 1 but with the acids shown in the Table.
- the additive is introduced at a concentration of 2000 ppm into a hydrocarbon, ISOPAR M (A trademark of EXXON MOBIL CHEMICALS) which has been treated with hydrogen sulfide to have a blank value of 28,000 ppm at 2 hours after treatment and 22,500 ppm at 24 hours after treatment. The results are displayed in the table.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The concentration of hydrogen sulfide in a hydrocarbon can be mitigated by intruding therein a zinc carboxylate oxo complex composition prepared by reacting particulate zinc oxide with a mixture of two or more carboxylic acids wherein the zinc carboxylate oxo complex composition is soluble in hydrocarbons. Useful acids useful include acetic acid, oleic acid, isobutyric acid, lineoleic acid, cekanoic acid, and neodecanoic acid.
Description
TITLE: OIL SOLUBLE HYDROGEN SULFIDE SCAVENGER
INVENTOR(S): POLAND, Ross
BACKGROUND
1. Field of the Disclosure
[0001] The invention relates to the reduction of the concentration of hydrogen sulfide in hydrocarbons. The invention particularly relates scavenging hydrogen sulfide from hydrocarbons.
2. Background Of The Disclosure
[0002] Hydrogen Sulfide (H2S) is often encountered in the exploration for and production of oil and natural gas. The presence of H2S is usually objectionable because it may react with other hydrocarbons or fuel system components. Another reason that the H2S is objectionable is that it may be highly corrosive. Still another reason that H2S is undesirable is that it is a cause of highly noxious odors.
[0003] One solution to these problems is to "scavenge" H2S. Metal based scavengers and certain triazines and aldehydes are known to be useful for these purposes. For example, glyoxal (OHCCHO) has been used at pH neutral as a successful scavenger. Glyoxal and other aldehydes such as acrolein and formaldehyde are known to be useful in a variety of other applications such as biocides, disinfectants, and the like.
[0004] But the use of such aldehydes can of themselves sometimes be a problem. Aldehydes may be corrosive to metals such as aluminum, iron, and steel.
[0005] Metal Carboxylates are known to be useful for reducing the concentration of hydrogen sulfide in hydrocarbons. Unfortunately, many of the prior art metal carboxylates, especially those prepared with acetic acid, are
insoluble in hydrocarbons and must be used as a dispersion or the like. It would be desirable in the art to prepare an oil soluble hydrogen sulfide inhibitor for use with hydrocarbons, especially crude oil, fuel oils, and bitumen.
SUMMARY
[0006] In one aspect, the invention is a method for preparing a zinc carboxylate oxo complex composition which is useful for scavenging hydrogen sulfide from a hydrocarbon comprising reacting particulate zinc oxide with a mixture of two or more carboxylic acids wherein: none of the acids is octanoic acid or an octanoic acid isomer, and the zinc carboxylate oxo complex composition is soluble in hydrocarbons.
[0007] Another aspect of the invention is a method for preparing a zinc carboxylate oxo complex composition which is useful for scavenging hydrogen sulfide from a hydrocarbon comprising reacting particulate zinc oxide with a mixture of two or more carboxylic acids wherein the a zinc carboxylate oxo complex composition is soluble in hydrocarbons.
[0008] In another aspect, the invention is a method for reducing the concentration of hydrogen sulfide in a hydrocarbon comprising introducing a zinc carboxylate oxo complex composition of the disclosure into the hydrocarbon.
DESCRIPTION
[0009] In one embodiment, the disclosure is directed to a method for preparing a zinc carboxylate oxo complex composition, useful for scavenging hydrogen sulfide from a hydrocarbon. The zinc carboxylate oxo complex is prepared by reacting particulate zinc oxide with a mixture of two or more carboxylic acids. In this process the carboxylic acids act as both solvent and reactant. The total number of moles of carboxylic acid used in the reaction is equal to about 1 .5 times the total moles of zinc added.
[0010] This reaction pathway leads to a final zinc product with a zinc to acid ratio of about 2:3. The acids chosen are miscible and of appropriate structure and proportion to result in a product which is uniform and is soluble in organic solvents. The acids may be selected from the group consisting of acetic acid, oleic acid, isobutyric acid, lineoleic acid, cekanoic acid, and neodecanoic acid. In some embodiments, ethyl hexanoic acid may be used while in other embodiments ethyl hexanoic acid is proscribed. The reaction proceeds when the acid mixture is heated as zinc oxide is dissolved in the mixture. The reaction produces the previously mentioned zinc carboxylate oxo complex in addition to water, which is eventually distilled off to purify the zinc carboxylate oxo product.
[0011] In some embodiments, the resultant complex can be dissolved in an organic solvent.
[0012] Stated another way, the method of the application includes synthesizing a zinc oxo complex of the formula Zn40(acid)6 in which the term "acid" refers to a carboxylate ligand with a -1 charge. The carboxylate ligands include two or more differing types of acid ligands and the complex is synthesized using a method in which zinc oxide is reacted neat with a liquid mixture of carboxylic acids. In this embodiment, the combination of acid species as ligands causes the complex to be oil soluble and suitable for injection into hydrocarbon streams whereas a similar complex consisting of only one type of acid ligand would be less suitable for injection or potentially impossible to inject. In each case, the ratio of zinc atoms to total acid ligands in the complex is about 2:3, but the ratio of zinc atoms to each discrete acid ligand may range from about 4:5 to about 4: 1 The acid ligands in this embodiment consists of two or more from the types neodecanoic acid, acetic acid, oleic acid, and linoleic acid.
[0013] While not wishing to be bound by any theory, it is nevertheless believed that the scavenger remains soluble in the sour hydrocarbon streams due to the highly branched nature of a majority of the ligands bound to the
zinc atoms. By synthesizing a complex which is coordinated to a mixture of acid ligands, it is possible to incorporate lower molecular weight acid molecules, allowing an overall lower molecular weight complex. Decreasing the total molecular weight of the oxo zinc complex results in a complex with a higher zinc content by mass, which improves cost effectiveness of the final product with regard to H2S scavenging efficacy. The use of low molecular weight acids does not affect the H2S scavenging efficacy of the product, as the driving force of the scavenging reaction is the production of zinc sulfide and a protonated acid molecule:
Zn40(acid)6 + 4 H2S - 4 ZnS + 6 H-acid + H20
[0014] The hydrogen sulfide scavengers maybe employed in the process of the disclosure in any way known to be useful to those of ordinary skill in the art of producing oil and gas. For example, it may be atomized and introduced into a gas stream or directly admixed, liquid phase to liquid phase, with a crude oil stream. It may be introduced in a solvent into a viscous phase such as bitumen.
EXAMPLES
[0015] The following examples are provided to illustrate the invention. The examples are not intended to limit the scope of the invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated.
Example 1
[0016] 53.2g of neodecanoic acid and 3.7g of acetic acid were charged into a reactor, heated to 60°C and agitated. After reaching temperature, 20g of zinc oxide powder were slowly added to the acid mixture in small aliquots. Once all the zinc oxide powder was added and dissolved, the temperature of the reactor was increased to 100°C and agitated for one hour. Following the agitation period, the temperature of the reactor was increased again to 1 10°C and a nitrogen sparge was added in order to remove the water entrained in
the reaction mixture. Following the collection of water, the reactor temperature was decreased to 80°C, at which point 27.6g of an aromatic distillate solvent was added and the reaction mixture was allowed to stir for 30 minutes.
Example 2
[0017] 26.5g of neodecanoic acid, 9.3g of acetic acid, and 17.4g of oleic acid were charged into a reactor, heated to 60°C and agitated. After reaching temperature, 20g of zinc oxide powder were slowly added to the acid mixture in small aliquots. Once all the zinc oxide powder was added and dissolved, the temperature of the reactor was increased to 100°C and agitated for one hour. Following the agitation period, the temperature of the reactor was increased again to 1 10°C and a nitrogen sparge was added in order to remove the water entrained in the reaction mixture. Following the collection of water, the reactor temperature was decreased to 80°C, at which point 27.6g of an aromatic distillate solvent was added and the reaction mixture was allowed to stir for 30 minutes.
Example 3
[0018] 23.9g of neodecanoic acid, 10.19g of acetic acid, and 18g of oleic acid were charged into a reactor, heated to 60°C and agitated. After reaching temperature, 20g of zinc oxide powder was slowly added to the acid mixture in small aliquots. Once all the zinc oxide powder was added and dissolved, the temperature of the reactor was increased to 100°C and agitated for one hour. Following the agitation period, the temperature of the reactor was increased again to 1 10°C and a nitrogen sparge was added in order to remove the water entrained in the reaction mixture. Following the collection of water, the reactor temperature was decreased to 80°C, at which point 27.6g of an aromatic
distillate solvent was added and the reaction mixture was allowed to stir for 30 minutes.
Example 4
[0019] 26.58g of neodecanoic acid, 9.27g of acetic acid, and 17.312g of linoleic acid were charged into a reactor, heated to 60°C and agitated. After reaching temperature, 20g of zinc oxide powder was slowly added to the acid mixture in small aliquots. Once all the zinc oxide powder was added and dissolved, the temperature of the reactor was increased to 100°C and agitated for one hour. Following the agitation period, the temperature of the reactor was increased again to 1 10°C and a nitrogen sparge was added in order to remove the water entrained in the reaction mixture. Following the collection of water, the reactor temperature was decreased to 80°C, at which point 27.6g of an aromatic distillate solvent was added and the reaction mixture was allowed to stir for 30 minutes.
Examples 5-8 and Comparative Examples A & B
[0020] A test is performed using an oxo complex as prepared in Example 1 but with the acids shown in the Table. The additive is introduced at a concentration of 2000 ppm into a hydrocarbon, ISOPAR M (A trademark of EXXON MOBIL CHEMICALS) which has been treated with hydrogen sulfide to have a blank value of 28,000 ppm at 2 hours after treatment and 22,500 ppm at 24 hours after treatment. The results are displayed in the table.
TABLE
Discussion of the Examples
[0021] The Examples clearly show that an effective and soluble hydrogen sulfide scavenger can be prepared.
Claims
1. A method for decreasing the concentration of hydrogen sulfide in a hydrocarbon comprising introducing a zinc carboxylate oxo complex composition prepared by reacting particulate zinc oxide with a mixture of two or more carboxylic acids, wherein the zinc carboxylate oxo complex composition is soluble in hydrocarbons.
2. The method of Claim 1 , wherein the two or more carboxylic acids are selected from the group consisting of acetic acid, oleic acid, isobutyric acid, lineoleic acid, cekanoic acid, and neodecanoic acid.
3. The method of Claim 1 or 2, wherein at least one of the carboxylic acids is acetic acid.
4. The method of Claim 1 or 2, wherein a ratio of zinc atoms to total acid ligands in the oxo complex composition is 2:3.
5. The method of Claim 4, wherein a ratio of zinc atoms to each discrete acid ligand may range from 4:5 to 4: 1 .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14825595.3A EP3022275B1 (en) | 2013-07-19 | 2014-06-27 | Oil soluble hydrogen sulfide scavenger |
| CN201480034759.XA CN105339467B (en) | 2013-07-19 | 2014-06-27 | Oil-soluble hydrogen sulfide scavenger |
| CA2915247A CA2915247C (en) | 2013-07-19 | 2014-06-27 | Oil soluble hydrogen sulfide scavenger |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/946,836 US9353026B2 (en) | 2013-07-19 | 2013-07-19 | Oil soluble hydrogen sulfide scavenger |
| US13/946,836 | 2013-07-19 |
Publications (1)
| Publication Number | Publication Date |
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| WO2015009429A1 true WO2015009429A1 (en) | 2015-01-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2014/044559 WO2015009429A1 (en) | 2013-07-19 | 2014-06-27 | Oil soluble hydrogen sulfide scavenger |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9353026B2 (en) |
| EP (1) | EP3022275B1 (en) |
| CN (1) | CN105339467B (en) |
| CA (1) | CA2915247C (en) |
| SA (1) | SA516370418B1 (en) |
| WO (1) | WO2015009429A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018207657A1 (en) | 2017-05-12 | 2018-11-15 | 株式会社クラレ | Device for removing sulfur-containing compound and method for removing sulfur-containing compound |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10577542B2 (en) * | 2013-02-19 | 2020-03-03 | Baker Hughes, A Ge Company, Llc | Low viscosity metal-based hydrogen sulfide scavengers |
| WO2016180563A1 (en) | 2015-05-14 | 2016-11-17 | Clariant International Ltd | Composition and method for scavenging sulfides and mercaptans |
| BR112017028362A2 (en) * | 2015-07-03 | 2018-09-04 | Dorf Ketal Chemicals India Private Ltd | additive compositions for the elimination of hydrogen sulfide, and the medium comprising them |
| EP3400260B1 (en) * | 2016-01-08 | 2021-06-02 | Innophos, Inc. | Scavenger compositions for sulfur species |
| US20230390170A1 (en) * | 2020-09-24 | 2023-12-07 | Firmenich Sa | Consumer products containing pro-fragrances |
| CN113372894A (en) * | 2021-06-11 | 2021-09-10 | 四川正蓉上之登科技有限公司 | Efficient and rapid soluble sulfur removal corrosion inhibitor and preparation method thereof |
| WO2023225494A1 (en) * | 2022-05-16 | 2023-11-23 | Heritage Research Group, Llc | Unrefined neodecanoic acid source as a raw material for h2s scavenging metal carboxylate |
| CN115678516A (en) * | 2022-11-11 | 2023-02-03 | 西南石油大学 | Preparation method and application of modified nano zinc oxide oil-based drilling fluid desulfurizing agent |
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| US20110139686A1 (en) | 2009-12-15 | 2011-06-16 | Compton Dennis R | Method of removing hydrogen sulfide |
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| US4830838A (en) | 1988-11-01 | 1989-05-16 | The Dow Chemical Company | Removal of hydrogen sulfide from fluid streams with minimum production of solids |
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| GB9411698D0 (en) * | 1994-06-10 | 1994-08-03 | Exxon Chemical Patents Inc | Improved basic zinc carboxylates |
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| US9278307B2 (en) * | 2012-05-29 | 2016-03-08 | Baker Hughes Incorporated | Synergistic H2 S scavengers |
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2013
- 2013-07-19 US US13/946,836 patent/US9353026B2/en not_active Expired - Fee Related
-
2014
- 2014-06-27 CN CN201480034759.XA patent/CN105339467B/en not_active Expired - Fee Related
- 2014-06-27 EP EP14825595.3A patent/EP3022275B1/en active Active
- 2014-06-27 CA CA2915247A patent/CA2915247C/en active Active
- 2014-06-27 WO PCT/US2014/044559 patent/WO2015009429A1/en active Application Filing
-
2016
- 2016-01-19 SA SA516370418A patent/SA516370418B1/en unknown
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| EP0121377B1 (en) * | 1983-03-31 | 1987-04-01 | Exxon Research And Engineering Company | Decreasing h2s emission in bitumen/sulphur mixtures |
| US5000835A (en) * | 1989-10-02 | 1991-03-19 | Exxon Chemical Patents, Inc. | Method of reducing H2 S in asphalt |
| US6599472B1 (en) | 2000-11-03 | 2003-07-29 | Surface Chemists Of Florida Inc. | Oil soluble scavengers for sulfides and mercaptans |
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| WO2018207657A1 (en) | 2017-05-12 | 2018-11-15 | 株式会社クラレ | Device for removing sulfur-containing compound and method for removing sulfur-containing compound |
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| Publication number | Publication date |
|---|---|
| EP3022275A4 (en) | 2017-03-29 |
| US9353026B2 (en) | 2016-05-31 |
| CA2915247A1 (en) | 2015-01-22 |
| EP3022275B1 (en) | 2020-04-29 |
| US20150025258A1 (en) | 2015-01-22 |
| CA2915247C (en) | 2018-02-27 |
| CN105339467A (en) | 2016-02-17 |
| CN105339467B (en) | 2017-10-24 |
| SA516370418B1 (en) | 2017-03-05 |
| EP3022275A1 (en) | 2016-05-25 |
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