Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
  • C10L3/101—Removal of contaminants
  • C10L3/102—Removal of contaminants of acid contaminants
  • C10L3/103—Sulfur containing contaminants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
  • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

• the present invention relates to a composition useful for scavenging hydrogen sulphide and organic compounds comprising at least one sulfhydryl group.
• Said composition comprises a particular triazine compound and an amine.
• the present invention also relates to the use of such a composition for scavenging hydrogen sulphide and/or organic compounds comprising at least one sulfhydryl group in a liquid or gaseous stream.
• the invention also relates to the use of an amine for improving the efficiency of triazine compounds in scavenging hydrogen sulphide and organic compounds comprising at least one sulfhydryl group in a liquid or gaseous stream.
• the present invention also relates to a method for scavenging hydrogen sulphide and/or organic compounds comprising at least one sulfhydryl group comprising contacting a hydrocarbon stream such as crude oil, fuel or natural gas with the composition of the invention.
• Hydrogen sulphide is a colourless and fairly toxic, flammable and corrosive gas which has a characteristic odour at a very low concentration. Hydrogen sulphide dissolves in liquid and gaseous streams such as hydrocarbon and water streams and can also be present in the vapour phase above liquid streams as well as in hydrocarbon gas such as LPG and natural gas. The hydrogen sulphide emissions can be harmful to workers operating in the drilling, production, transport, storage, and processing of such streams. It would therefore be desirable for the workers' comfort and safety to reduce or even eliminate the hydrogen sulphide emissions during the handling of said products.
• a variety of chemical scavengers are available to reduce the concentration of hydrogen sulphide and sulfhydryl-containing compounds in liquid and gaseous streams containing them, in particular aqueous streams and hydrocarbon streams such as gas, crude oils and refined products.
• Some of the most common methods for treating hydrogen sulphide consist in contacting them with a chemical scavenger such as compounds containing a triazine group, glyoxal, as well as metal-based scavengers.
• Glyoxal has been used extensively as hydrogen sulphide scavenger but suffers from a major drawback since aqueous glyoxal solutions are highly corrosive and cannot be used for a gas tower application.
• Triazines have recently become more common chemical scavengers used for treating hydrogen sulphide from hydrocarbon streams.
• the present invention relates to a composition useful for scavenging hydrogen sulphide and mercaptans in hydrocarbon streams, said composition comprising:
• composition of the present invention allows achieving an improved scavenging of hydrogen sulphide and organic compounds comprising at least one sulfhydryl group in a short contact time.
• the improvement can be seen when the remaining amount of sulphur compounds in the stream is reduced and/or when the speed of the scavenging of sulphur compounds is increased when contacting the composition according to the invention with said stream.
• composition of the present invention allows a faster and more efficient scavenging, i.e. the amount of sulphur compounds is decreased more rapidly and in a greater amount than with prior art scavenging compositions.
• the present invention also relates to the use of such a composition for scavenging hydrogen sulphide and/or organic compounds comprising at least one sulfhydryl group in a liquid or gaseous stream.
• the invention also relates to the use of at least one amine for improving the efficiency of compounds of formula (I) in scavenging hydrogen sulphide and organic compounds comprising at least one sulfhydryl group in a liquid or gaseous stream.
• the present invention also relates to a method for scavenging hydrogen sulphide and/or mercaptans comprising contacting a hydrocarbon stream such as crude oil, fuel or natural gas with the scavenging composition of the invention.
• C N compound or group designates a compound or a group containing in its chemical structure N carbon atoms.
• composition of the invention comprises at least one compound having the general formula (I): wherein:
• R' represents CH 3 .
• R is different from -CHOH-CH 3 .
• R' represents CH 3 and R is different from -CHOH-CH 3 .
• a “hydrocarbyl group” is a linear, branched or cyclic group that can be aliphatic or aromatic and when it is a cyclic group, the cycle(s) can be substituted by linear or branched groups.
• the hydrocarbyl group comprises carbon atoms and hydrogen atoms and optionally heteroatoms selected from oxygen, sulfur, halogen, silicon, nitrogen, preferably selected from oxygen, sulfur, halogen, silicon.
• R is selected from: R 1 -OH, R 1 -[O-R 2 ]p-OH, optionally substituted benzyl, R 1 -NR 3 R 4 , R 5 , R 1 -[N(H)-R 2 ] n -NR 3 R 4 , R 1 -[O-R 2 ] p -NR 3 R 4 , R 1 -Q, R 1 -[N(H)-R 2 ] n -Q, R 1 -[O-R 2 ] p -Q, R 1 -N(R 3 -Q)(R 4 -Q) wherein:
• R is selected from: R 1 -OH, R 1 -O-R 2 -OH, optionally substituted benzyl, R 1 -NR 3 R 4 , R 5 , R 1 -N(H)-R 2 -NR 3 R 4 , R 1 -O-R 2 -O-R 2 -NR 3 R 4 , R 1 -Q, R 1 -N(H)-R 2 -Q, R 1 -O-R 2 -O-R 2 -Q, R 1 -N(R 3 -Q) 2 wherein:
• R is selected from: R 1 -OH, R 1 -O-R 2 -OH, benzyl, R 1 -NR 3 R 4 , R 5 , R 1 -N(H)-R 2 -NR 3 R 4 , R 1 -O-R 2 -O-R 2 -NR 3 R 4 , R 1 -Q, R 1 -N(H)-R 2 -Q, R 1 -O-R 2 -O-R 2 -Q, R 1 -N(R 3 -Q) 2 wherein:
• an alkyl group is a saturated group consisting in carbon atoms and hydrogen atoms, that can be linear, branched or cyclic.
• an alkenyl group is an unsaturated group consisting in carbon atoms and hydrogen atoms, that can be linear, branched or cyclic.
• the alkenyl group can be mono-unsaturated or poly-unsaturated.
• R 3 is identical to R 4 .
• the compound(s) of formula (I) is (are) chosen from the following compounds, and mixtures thereof:
• preferred compound for use in the present invention are selected from compound I-A, compound I-B, compound I-C, compound I-D, compound I-E-, compound I-F, compound I-G, compound I-H, compound I-I, compound I-K, compound I-L, and mixtures thereof.
• Compounds I-A, I-G, I-L and I-N and mixtures thereof are particularly preferred.
• the compound(s) of formula (I) is (are) present in an amount ranging from 50 to 99% by weight, preferably from 60 to 90% by weight, more preferably from 70 to 80% by weight, relative to the total weight of the composition.
• the compound(s) selected from compound I-A, compound I-B, compound I-C, compound I-D, compound I-E-, compound I-F, compound I-G, compound I-H, compound I-I, compound I-K, compound I-L, and mixture thereof is (are) present in a total amount ranging from 50 to 99% by weight, preferably from 60 to 90% by weight, more preferably from 70 to 80% by weight, relative to the total weight of the composition.
• the compound(s) selected from compounds I-A, I-G, I-L and I-N is (are) present in a total amount ranging from 50 to 99% by weight, preferably from 60 to 90% by weight, more preferably from 70 to 80% by weight, relative to the total weight of the composition.
• composition of the invention comprises at least one amine.
• the amines may be chosen from primary, secondary and tertiary amines.
• primary amine within the meaning of the invention, is generally meant a compound comprising at least one primary amine function.
• secondary amine within the meaning of the invention, is generally meant a compound comprising at least one secondary amine function.
• tertiary amine within the meaning of the invention, is generally meant a compound comprising at least one tertiary amine function and preferably comprising only tertiary amine functions.
• the at least one amine ischosen from alkanolamines.
• an "alkanolamine” is an amine comprising at least one hydroxyalkyl group bonded to the nitrogen atom.
• the hydroxyalkyl group comprises from 1 to 10 carbon atoms, more preferably from 2 to 6 carbon atoms.
• the alkanolamines may be chosen from primary, secondary, or tertiary alkanolamines.
• primary alkanolamines are chosen from monoalkanolamines.
• secondary alkanolamines are chosen from dialkanolamines, or alkyl alkanol amines.
• tertiary alkanolamines are chosen from trialkanolamines, alkyldialkanolamines or dialkylalkanolamines.
• Alkanolamines useful in the present invention may be chosen from 2-aminoethanol (monoethanolamine, MEA), N,N-bis(2-hydroxyethyl) amine (diethanolamine, DEA), N,N,-bis(2-hydroxypropyl) amine (diisopropanolamine, DIPA), tris(2-hydroxyethyl)amine (triethanolamine, TEA), tributanolamine, bis(2-hydroxyethyl)-methylamine (N-methyldiethanolamine, MDEA), 2-diethylaminoethanol (diethylethanolamine, DEEA), 2-dimethylaminoethanol ( dimethylethanolamine, DMEA), 3-dimethylamino-1-propanol (N,-dimethylpropanolamine), 3-diethylamino-1-propanol, 2-diisopropylaminoethanol (DIEA), N,-bis(2-hydroxypropyl)methylamine (methyldiisopropanolamine, MD
• the amine(s) is (are) chosen from alkanolamines, more preferably from 2-aminoethanol (monoethanolamine, MEA), N,N-bis(2-hydroxyethyl) amine (diethanolamine, DEA), bis(2-hydroxyethyl)-methylamine (N-methyldiethanolamine, MDEA), and mixtures thereof.
• 2-aminoethanol monoethanolamine, MEA
• N,N-bis(2-hydroxyethyl) amine diethanolamine, DEA
• bis(2-hydroxyethyl)-methylamine N-methyldiethanolamine, MDEA
• said amine(s) is (are) present in an amount ranging from 0.5 to 30% by weight, preferably from 1 to 20% by weight, more preferably from 5 to 10% by weight, relative to the total weight of the composition.
• the composition contains at least one alkanolamine in an amount ranging from 0.5 to 30% by weight, preferably from 1 to 20% by weight, more preferably from 5 to 10% by weight, relative to the total weight of the composition.
• the composition contains at least one alkanolamine chosen from monoethanolamine, diethanolamine, N-methyldiethanolamine and mixtures thereof in an amount ranging from 0.5 to 30% by weight, preferably from 1 to 20% by weight, more preferably from 5 to 10% by weight, relative to the total weight of the composition.
• the weight ratio between the total amount of compound(s) of formula (I) and the total amount of amine(s) is comprised between 1 and 30, preferably between 5 and 15.
• the weight ratio between the total amount of compound I-A, compound I-B, compound I-C, compound I-D, compound I-E-, compound I-F, compound I-G, compound I-H, compound I-I, compound I-K, compound I-L, and mixtures thereof on one hand and the total amount of alkanolamine(s) on the other hand is comprised between 1 and 30, preferably between 5 and 15.
• the weight ratio between the total amount of compound I-A, compound I-B, compound I-C, compound I-D, compound I-E-, compound I-F, compound I-G, compound I-H, compound I-I, compound I-K, compound I-L, and mixture thereof and the total amount of compound(s) chosen from monoethanolamine, diethanolamine, N-methyldiethanolamine and mixtures thereof on the other hand is comprised between 1 and 30, preferably between 5 and 15.
• the weight ratio between the total amount of compound(s) I-A, I-G, I-L and I-N and mixtures thereof the total amount of compound(s) chosen from monoethanolamine, diethanolamine, N-methyldiethanolamine and mixtures thereof is comprised between 1 and 30, preferably between 5 and 15.
• the composition of the invention further contains one or more liquid solvent(s).
• liquid it is meant a solvent which is in liquid form at ambient temperature (20°C) and atmospheric pressure (1,013.10 5 Pa).
• the solvent(s) is (are) selected from water and organic liquid solvents different from the amines described above.
• the solvent(s) is (are) selected from organic liquid solvents different from said amines.
• Such solvents may in particular be chosen from poly oxyalkyl ethers, aliphatic hydrocarbons such as alkanes, aromatic solvents such as aromatic hydrocarbons and aromatic hetero-compounds, naphtas, and mixtures thereof.
• Preferred organic solvents are chosen from aromatic solvents, such as N-methylpyrrolidone, xylene, toluene, benzene; and poly oxyalkyl ethers such as butyl carbitol (diethylene glycol monobutyl ether); as well as mixtures thereof.
• aromatic solvents such as N-methylpyrrolidone, xylene, toluene, benzene
• poly oxyalkyl ethers such as butyl carbitol (diethylene glycol monobutyl ether); as well as mixtures thereof.
• organic solvents include those derived from biomass, such as oils of vegetable origin.
• a particularly preferred solvent is cashew nutshell liquid, also known as CSNL, which is a widely available vegetable oil derived from cashew nut shell.
• CSNL cashew nutshell liquid
• CNSL can be used as a mixture with any other solvent such as those described herein.
• the choice of the solvent mainly depends on the final use of the composition.
• water may be a solvent of choice.
• an organic solvent will be preferred.
• a solvent having a dual solubility i.e. a water solubility and a solubility in hydrocarbons
• Poly alkyl ethers such as butyl carbitol are preferred solvents since they have such a dual solubility.
• composition of the invention advantageously contains an amount of solvent ranging from 5 to 50% by weight, preferably from 10 to 40%wt, more preferably from 15 to 30%wt, relative to the total weight of the composition.
• composition of the invention may further comprise art least one defoamer, preferably at least one silicone-based defoamer.
• the defoamers are preferably chosen from polydimethylsiloxane polymers, more preferably from grafted polydimethylsiloxane polymers.
• composition of the invention advantageously contains an amount of defoamer ranging from 0.1 to 2% by weight, relative to the total weight of the composition.
• the present invention also encompasses the use of a composition as described above for scavenging hydrogen sulphide and/or organic compounds comprising at least one sulfhydryl group in a liquid or gaseous stream.
• the organic compounds comprising at least one sulfhydryl group are especially chosen from mercaptans, thiocarboxylic acids and dithiocarboxylic acids.
• the liquid or gaseous stream may be a monophasic stream such as in particular an aqueous stream or an organic stream, or a multiphasic stream containing both water and hydrocarbons (such as for instance oil/water or oil/water/gas or gas/water).
• the composition of the invention is used for scavenging hydrogen sulphide (H 2 S) and mercaptans (compounds of formula RSH) in a hydrocarbon containing stream.
• the mercaptans which are eliminated are typically those of formula RSH wherein R is an alkyl or alkenyl group containing from 1 to 8, preferably from 1 to 6 and more preferably from 1 to 4 carbon atoms.
• the hydrocarbon containing streams are typically selected from crude petroleum oils, hydrocarbon fractions and residues deriving from the distillation thereof, light petroleum gas (LPG) and natural gas, as well as mixtures thereof with aqueous phases such as brine.
• LPG light petroleum gas
• natural gas as well as mixtures thereof with aqueous phases such as brine.
• Such streams contain H 2 S and/or mercaptans in total amounts which may range for example from 1 to 10 000 ppm by weight.
• the present invention also concerns the use of amine(s), preferably of alkanolamine(s), as defined above for improving the efficiency of compound(s) of formula (I) for scavenging hydrogen sulphide (H 2 S) and/or mercaptans in hydrocarbon streams.
• amine(s) preferably of alkanolamine(s), as defined above for improving the efficiency of compound(s) of formula (I) for scavenging hydrogen sulphide (H 2 S) and/or mercaptans in hydrocarbon streams.
• the present invention also relates to a method for scavenging hydrogen sulphide and/or organic compounds comprising at least one sulfhydryl group such as mercaptans in a liquid or gaseous stream comprising contacting said stream with the composition of the invention.
• the liquid or gaseous stream may be monophasic such as in particular an aqueous stream or an organic stream, or multiphasic such as a stream containing both water and hydrocarbons (such as for instance oil/water or oil/water/gas or gas/water).
• the stream contains hydrocarbons.
• the stream may be especially selected from crude petroleum oils, hydrocarbon fractions and residues deriving from the distillation thereof such as in particular fuel oils and heavy fuel oils, light petroleum gas (LPG) and natural gas, as well as mixtures thereof with aqueous compositions such as brine.
• LPG light petroleum gas
• the amount of composition used per amount of stream depends on the concentration of said compound(s) of formula (I) and of amine(s) in the composition as well as the total content of hydrogen sulphide and/or organic compounds comprising at least one sulfhydryl group in the liquid or gaseous stream, as explained above.
• composition is contacted with the liquid or gaseous stream for a time sufficient to achieve an effective scavenging of hydrogen sulphide and of organic compounds comprising at least one sulfhydryl group.
• compositions A1 to A24 (according to the invention) and C1 to C10 (comparative) were prepared by mixing the above ingredients in the amounts detailed in Table (I) below: Table (I) I-A I-G I-L I-N MEA DEA MDEA Solvent A1 70 - - - 5 - - - - - 25 A2 70 - - - - 10 - - - - 20 A3 70 - - - - - 5 - - - 25 A4 70 - - - - - - 10 - - 20 A5 70 - - - - - - - - 5 - 25 A6 70 - - - - - - - - 10 20 A7 - 70 - - 5 - - - - - - - - - 10 A7 - 70 - - 5 - - - - - - 25 A8 - 70 -
• the test was carried out at room temperature.
• a 250 mL glass purger was charged with 100 mL of an inert solvent.
• a gas consisting of N 2 containing H 2 S at a concentration of 50 ppm was released by a bubbling tube at a flow rate of 0.4 mL/min into the solvent contained in said purger.
• the solvent was continuously agitated by using a magnetic stirrer.
• the gas exiting the solvent and leaving the purger was conveyed to a H 2 S detector.
• the gas H 2 S in N 2 at a concentration of 50 ppm
• the H 2 S detector started recording the H 2 S concentration at the outlet of the purger.
• the scavenging composition (1ml of said composition is mixed with 2ml of butyl carbitol to ensure proper injection into the reactor) to be tested was quickly injected into the purger.
• the H 2 S concentration was recorded at every 5 sec time interval.
• compositions A1 to A24 according to the invention allow a faster and more efficient scavenging of hydrogen sulfide, than comparative compositions C1 to C10.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Citations (5)

• 2024
  • 2024-05-30 EP EP24305853.4A patent/EP4656706A1/de active Pending

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