WO2022256258A1 - Stripping h2s off natural gas for multiple isotope analyses - Google Patents
Stripping h2s off natural gas for multiple isotope analyses Download PDFInfo
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- WO2022256258A1 WO2022256258A1 PCT/US2022/031393 US2022031393W WO2022256258A1 WO 2022256258 A1 WO2022256258 A1 WO 2022256258A1 US 2022031393 W US2022031393 W US 2022031393W WO 2022256258 A1 WO2022256258 A1 WO 2022256258A1
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- hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60P—VEHICLES ADAPTED FOR LOAD TRANSPORTATION OR TO TRANSPORT, TO CARRY, OR TO COMPRISE SPECIAL LOADS OR OBJECTS
- B60P3/00—Vehicles adapted to transport, to carry or to comprise special loads or objects
- B60P3/005—Vehicles adapted to transport, to carry or to comprise special loads or objects for use in contaminated areas, e.g. N.B.C. intervention vehicles
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
- B01D2252/103—Water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/05—Biogas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/346—Controlling the process
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- 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
- C10L2290/08—Drying or removing water
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- 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
- C10L2290/24—Mixing, stirring of fuel components
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- 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
- C10L2290/46—Compressors or pumps
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- 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
- C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
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- 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
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
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- 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
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- 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
- C10L2290/56—Specific details of the apparatus for preparation or upgrading of a fuel
- C10L2290/567—Mobile or displaceable apparatus
Definitions
- Hydrogen sulfide is both a toxic to humans and a common component in natural gas and other hydrocarbon-bearing reservoirs having gaseous hydrocarbon content. Study of the mobility and origin of hydrogen sulfide is performed to appreciate the quality of the hydrocarbon gas with which the hydrogen sulfide is associated. More importantly, researching and understanding various aspects of hydrogen sulfide also supports safe and effective exploration and production activities as well as the protection of personnel that work with and around such gases.
- One or more embodiments may include a hydrogen sulfide scrubber system.
- the hydrogen sulfide system includes a charging chamber.
- the charging chamber is configured to be fluidly isolated from a source of gas with hydrogen sulfide, a source of an inert purge gas, and a reaction vessel.
- the hydrogen sulfide system also includes the reaction vessel.
- the reaction vessel is coupled downstream of the charging chamber.
- the reaction vessel is configured to intimately intermix the gas with hydrogen sulfide with a hydrogen sulfide reaction solution to form a hydrogen sulfide-free gas and an insoluble sulfur reaction product.
- the reaction vessel is also configured to be fluidly isolated from both the charging chamber and a treated gas trap.
- the hydrogen sulfide scrubber system also includes the treated gas trap.
- the treated gas trap is coupled downstream of the reaction vessel.
- the hydrogen sulfide scrubber system is configured to couple to the source of gas with hydrogen sulfide upstream of the charging chamber.
- the hydrogen sulfide scrubber system is also configured to couple to the source of an inert purge gas upstream of the charging chamber.
- the hydrogen sulfide scrubber system is also configured to couple to a receiver for the hydrogen sulfide-free gas downstream of the treated gas trap.
- One or more embodiments may include a mobile vehicle, vessel, or platform that includes a mobile vehicle, vessel, or platform with a mounted hydrogen sulfide scrubber system.
- the hydrogen sulfide scrubber system is configured as previously described.
- One or more embodiments may include a method of using a hydrogen sulfide scrubber system.
- the hydrogen sulfide scrubber system is configured as previously described.
- the method may include introducing a gas with hydrogen sulfide into a charging chamber of the hydrogen sulfide scrubber system.
- the method may also include operating the hydrogen sulfide scrubber system such that the gas with hydrogen sulfide is introduced into a reaction vessel from the charging chamber.
- the method may also include operating such that the gas with hydrogen sulfide is converted into an insoluble sulfur reaction product and a hydrogen sulfide-free gas using a hydrogen sulfide reaction solution contained within the reaction vessel.
- the method may also include introducing an inert purge gas into the charging chamber of the hydrogen sulfide scrubber system such that the inert purge gas sweeps any non-inert gas from the hydrogen sulfide scrubber system.
- the method may also include recovering the hydrogen sulfide-free gas and recovering the insoluble sulfur reaction product from the reaction vessel.
- FIG. 1 is a schematic of a FhS scrubbing system according to one or more embodiments.
- Figures 2A, 2B, and 2C are schematics of several useful charging chambers for the system according to one or more embodiments.
- Figures 3A and 3B are schematics of several useful reaction vessels for the system according to one or more embodiments.
- Figure 4 is a drawing of a FhS scrubbing system as part of a mobile self- propelled vehicle according to one or more embodiments.
- Figure 5 is a process flow diagram for a method of using a FhS scrubber system according to one of more embodiments.
- upstream may more generally refer to objects, units, or processes, taken before a particular unit or process.
- downstream may more generally refer to objects, units, or processes, taken after a particular unit or process.
- FIG. 1 is a schematic of a H2S scrubbing system.
- the H2S scrubbing system is a schematic of a H2S scrubbing system.
- system 100 includes a source for gas with 3 ⁇ 4S, such as feed gas canister 110, a source for inert purge gas, such as purge tank 120, and a receiver for gas without H2S, such as remainder gas canister 130.
- the feed gas canister 110 has an isolation valve 111 to permit the feed gas canister 110 to couple to the system 100.
- the purge tank 120 has an isolation valve 121 to permit the purge tank 120 to couple to the system 100.
- the remainder gas canister 130 has an isolation valve 131 to permit the remainder gas canister 130 to couple to the system 100.
- the system 100 includes a charging chamber with a fixed volume, such as charge line 140, for receiving a fixed quantity of gas with H2S.
- Charge line 140 is coupled downstream of both feed gas canister 110 by line 113 and purge tank 120 by line 123.
- a pressure gauge 141 is shown coupled to charge line 140 to monitor pressure in the charge line 140.
- a line 143 coupled downstream of the charge line 140 includes an optional orifice plate 145 and an optional flow control valve 146. In this instance, orifice plate 145 supports a flow meter 144 that permits monitoring of the flow from charge line 140.
- reactor 150 The main conversion of hydrogen sulfide in system 100 occurs in a reaction vessel, such as reactor 150.
- Reactor 150 is shown in Figure 1 coupled downstream of charge line 140 through line 143.
- the reactor 150 has an isolation valves, such as intake valve 151 and discharge valve 152, on the exterior of the reactor 150.
- the reactor 150 also has a dip tube 154 in the interior of the reactor 150 for bubbling a gas into a solution.
- Reactor 150 may contain a FhS reaction solution 160.
- the FhS reaction solution 160 may contain a FhS reaction solution 160.
- the insoluble sulfur reactor product 161 precipitates to the bottom of reactor 150.
- a line 153 downstream couples to reactor 150 at discharge valve 152 such that wet FhS-free gas 162 may pass from reactor 150.
- a pH sensor 157 couples to the reactor 150 below the liquid level.
- a pressure gauge 155 is shown coupled to line 153 to permit monitoring of the pressure within the reactor and units downstream.
- the wet HiS-frcc gas passes from reactor 150 into a treated gas trap downstream, such as post-reactor treatment vessel 170, using line 153.
- Post-reactor treatment vessel 170 shown in partial reveal in Figure 1, has two features - a back-and- forth demister section 171 and a desiccant section 172 - that the wet H2S -free gas passes through to convert it into a dry HiS-frcc gas. After passing through line 133, the dry H2S- free gas passes into remainder gas canister 130.
- the gas with hydrogen sulfide that is introduced into the 3 ⁇ 4S scrubbing system may comprise any gas or vapor that contains at least in part hydrogen sulfide.
- Non-limiting examples include, but are not limited to, dry and wet natural gas, condensate gas, associated gas, sour gas, air sample, landfill gas, coal gas, partially-refined natural gas, and cracked refinery gases, and other hydrocarbon or non-hydrocarbon-containing gases or vaporizable liquids that contains hydrogen sulfide.
- the source of the gas with hydrogen sulfide may be a portable source, such as a tank, a cylinder, a bomb, a vessel, a container, or other device, that may hold a hydrogen sulfide containing gas at atmospheric or elevated pressure.
- Figure 1 shows feed gas canister 110 with an isolation valve 111.
- Such containers may be configured to temporarily couple to an embodiment FhS scrubbing system for introducing the gas with hydrogen sulfide into the system.
- the source of gas with hydrogen sulfide may be a fixed source, such as a pipeline or process vessel, that contains a gas with hydrogen sulfide. Such a fixed source may be temporarily coupled to an embodiment to introduce a gas containing hydrogen sulfide. Such a configuration is associated with Figure 4.
- the fixed source may be a permanently coupled or connected line to the embodiment system.
- the source of the gas with hydrogen sulfide is “hard piped” or “hard lined”.
- Such a “hard” configuration where a conduit or line is coupled or connected to an embodiment system, is useful for intermittent or continuous monitoring of a single source or a set of sources.
- a laboratory associated with a gas processing facility may have one or more hard lines - one from each source - configured in an array that is coupled to an embodiment system to perform regular testing on gas with hydrogen sulfide originating from different sources, such as wells or feed pipelines.
- the source is configured to contain and withstand the pressure of the gas containing hydrogen sulfide.
- the pressure of the gas containing hydrogen sulfide in the source is in a range of from about 10 to 5000 psi (pounds per square inch), such as from about 50 to 5000 psi.
- the temperature of the gas containing hydrogen sulfide in the source is in a range of from about 0 to 200 °C.
- the inert purge gas that is introduced into the FhS scrubbing system may comprise any gas or vapor that is chemically inert to the gas with hydrogen sulfide.
- Figure 1 shows purge tank 120 has an isolation valve 121. Since it is of investigative interest to examine the resultant hydrogen sulfide-free gas, any interaction with the precursor gas with hydrogen sulfide or the hydrogen sulfide-free gas, such as confounding the isotope or chemical analysis of the gas (other than dilution by volume) is not an objective. As well, it is also not of interest to be reactive with the hydrogen sulfide reaction solution as the solution is used to extract hydrogen sulfide and form the insoluble sulfur reaction product.
- Non-limiting examples of useful inert purge gas include, but are not limited to, the noble gases, such as helium and mixtures thereof. Selection of an inert purge gas should be cognizant of the inclusion of the inert gas in any post-collection analysis of the hydrogen sulfide-free gas, such as by mass spectrometry. It is not desired to confound the analysis of the hydrogen sulfide-free gas for either compositional makeup or isotope analysis.
- the gas with hydrogen sulfide is introduced into the system by way of the charging chamber.
- a source of inert purge gas in one or more embodiments may be provided in a portable container, such as a tank, a cylinder, a bomb, a vessel, a canister, or other device, that may hold an inert purge gas at atmospheric or elevated pressure.
- the source of an inert purge gas may be provided through a pipeline or process vessel that contains an inert purge gas.
- an air separations plant or a natural gas separations plant may provide a source for such an inert purge gas.
- the source of the inert purge gas may be provided through a permanently coupled or connected line to the embodiment FhS scrubbing system.
- the source of the inert purge gas is “hard piped” to an embodiment system for intermittent or continuous use to purge an embodiment system.
- the FhS scrubbing system may include a charging chamber.
- the charging chamber may be a fixed volume vessel or a length of process pipe or line that is positioned between the source of gas with hydrogen sulfide and the reaction vessel.
- the charging chamber may be isolated such that a fixed amount of gas with hydrogen sulfide at a given pressure is confined in the charging chamber before introduction into the reaction vessel, thereby “charging” the charging chamber.
- charging line 140 has three isolation valves (112, 122, 142) that permit charging line 140 to be filled and pressurized with the gas with hydrogen sulfide from feed gas canister 110, and be fluidly isolated.
- the charging chamber may comprise a plurality of fixed volume vessels or lengths of process piping or line coupled to one another.
- the plurality of fixed volume vessels may be coupled to one another in series.
- Figures 2A, 2B, and 2C are schematics of several useful charging chambers for the system according to one or more embodiments.
- charging chamber 140A is shown with several charging chambers 140 couple in series.
- Charging chamber 140A is shown relative to the other portions of FhS scrubbing system 100.
- a valve 147 is positioned between each fixed volume vessel or length of processing pipe or line.
- Valve 147 may also permit throttling of the gas with hydrogen sulfide as it is transferred downstream between adjacent charging chambers 140 within charging chamber 140A, decreasing its pressure each time. Throttling will be described in more detail forthcoming.
- the plurality of fixed volume vessels may be coupled to one another in parallel.
- charging chamber 140B is shown with several charging chambers 140 couple in parallel. Such a configuration may permit the “charging” of charging chamber 140B and then controlled discharge of each parallel chamber 140 in turn. Such a configuration may prevent overwhelming the reactor.
- charging chamber 140C is shown with several charging chambers 140 couple in series, and several series coupled in parallel to one another. Between each fixed volume vessel or length of processing pipe or line a valve 147 is positioned.
- the configurations as shown in Figures 2A-C also permit the volume of the charging chamber during isolation to be changed, that is, to be expanded.
- the volume may be increased while still isolated within the charging chamber portion of the system by opening an isolation valve between adjacent charging chambers. This will cause the gas in the charging chamber to be depressurized in ratio to the greater volume created.
- the volume of the charging chamber before expansion to the volume of the charging chamber after expansion is in a ratio range of from about greater than 1 : 1 to 1:5, such as from greater than about 1:1 to 1:4, such as from greater than about 1:1 to 1:3, and such as greater than about 1:1 to 1:2.
- Throttling is a technique where a flow restriction is introduced in a line, such as a partially-opened flow control valve, that creates an effect where a gas passing through the valve undergoes volume expansion and a reduction in both temperature and pressure.
- An isolation or flow control valve upstream of the charging chamber may be configured such that the gas with hydrogen sulfide passes through the valve and is “throttled” such that the pressure of the gas passing into the chagrining chamber is reduced.
- valves or another flow-type restriction including, but not limited to, an orifice plate, a let down valve, or a venturi, may be used to reduce the temperature of, extract energy from, and reduce the pressure of, a stream flowing through the restriction.
- a valve or another flow-type restriction including, but not limited to, an orifice plate, a let down valve, or a venturi
- the gas with hydrogen sulfide may be introduced into the FhS scrubbing system such that a pressure equilibrium is achieved between the source of the gas with hydrogen sulfide and the charging chamber.
- the charging line 140 may be isolated from feed gas canister 110 (thereby completing the “charge”). Then, the gas with hydrogen sulfide may be introduced into reactor 150 (and “discharging” the charging line 140) at full or reduced pressure.
- the gas with hydrogen sulfide may be introduced into the FhS scrubbing system such that the charging chamber has a reduced pressure as compared to the pressure of the source of the gas with hydrogen sulfide.
- the flow between the source and the charging chamber may be throttled or otherwise the flow restricted to cause a reduction in pressure in the gas with hydrogen sulfide flowing into the charging chamber.
- the configuration of the charging chamber relative to portions of the FhS scrubbing system may be such that the gas with hydrogen sulfide passing from the charging chamber expands in volume and its pressure is reduced.
- the ratio of the volume of the charging chamber such as charging line 140 of system 100, may be in relationship to the volume of the charging chamber, the line coupling the charging chamber and the reaction vessel, such as line 143, and the reaction vessel, such as reactor 150, of Figure 1.
- the volume of the charging chamber to the combined volume of the charging chamber, a line coupling the charging chamber and the reaction vessel, and the free vapor space of the reaction vessel is in a ratio range of from about 1:2 to 1:2000, such as from about 1:1 to 1:1000, such as from about 1:1 to 1:500, such as from about 1:1 to 1:250, such as from about 1:1 to 1:100, such as from about 1:1 to 1:50, such as from about 1:1 to 1:25, such as from about 1:1 to 1:10, such as from about 1:1 to 1:5, such as from about 1:1 to 1:2.
- the FhS scrubbing system may include a pressure monitoring system, such as a pressure sensor or gauge, associated with the charging chamber.
- the pressure monitoring system is coupled to the charging chamber.
- the pressure monitoring system is coupled upstream or downstream of the charging chamber in a way the pressure within the charging chamber is detectable.
- Figure 1 shows pressure gauge 141 is configured as part of system 100 to detect the pressure in charging line 140. Such a pressure monitoring system may be useful to ensure that the operating pressure of the reaction vessel is not exceeded when the gas with hydrogen sulfide in the charging chamber is introduced into the reaction vessel.
- the contents of the charging chamber may be discharged in a continuous manner.
- the gas with hydrogen sulfide may be introduced into the reaction vessel in a continuous yet metered manner.
- an isolation or flow control valve downstream of the charging chamber such as flow control valve 146, may be a valve that is configured to “throttle”, such as has been previously described, or merely limit the flow rate of the gas with hydrogen sulfide as it passes from the charging chamber such that the gas discharges in a regulated and continuous manner.
- the contents of the charging chamber may be discharged in an intermittent manner.
- a portion of the gas with hydrogen sulfide may be discharged from the charging chamber by opening at least partially a downstream isolation or flow control valve. After a sufficient period, the charging chamber may be isolated by closing the same valve before the entire contents of the charging chamber have been discharged. This opening-and-closing process may be repeated as many times as necessary to fully discharge the contents of the charging chamber.
- Performing the introduction of the gas with hydrogen sulfide into the reaction vessel in this manner may permit the reaction vessel to process the contents of the charging chamber in a “batch-like” manner; A limited amount of gas in each intermittent discharge is introduced at any given time.
- an amount of gas with hydrogen sulfide may be introduced from the charging chamber until a visible amount of insoluble sulfur reaction product begins to form, and then the flow from the charging chamber is terminated.
- the process of introduction may be repeated and another amount of gas with hydrogen sulfide may be introduced.
- Such an intermittent introduction process may be repeated until the pressure in the charging chamber and the reaction vessel reaches equilibrium. At equilibrium, there is insufficient pressure drive in the charging chamber to motivate gas with hydrogen sulfide in the charging chamber into the hydrogen sulfide reaction solution contained in the reaction vessel.
- the FhS scrubbing system may optionally include a flow restriction downstream of the charging chamber and upstream of the reaction vessel.
- the flow restriction may be configured to limit the mass or volume flow rate of gas with hydrogen sulfide as it is introduced into the reaction vessel.
- Such a restriction may be useful to ensure that the system used to intimately intermix the gas with hydrogen sulfide and the hydrogen sulfide reaction solution avoids being overwhelmed, such as by preventing “blow through” (where a liquid is physically pushed aside by the force of a gas stream and some of the gas is able to freely move through the reaction vessel without contacting the hydrogen sulfide reaction solution) or “slugging” (where the hydrogen sulfide reaction solution is physically pushed into a vapor overhead line).
- the flow restriction may also “throttle” the gas with hydrogen sulfide from the charging chamber and cause its pressure to be reduced after the gas passes the restriction.
- a flow control valve may be coupled upstream of the reaction vessel and positioned between the charging chamber and the reaction vessel.
- a flow control valve such as flow control valve 146 of system 100, may restrict the flow of the gas with hydrogen sulfide into the reaction vessel.
- the FhS scrubbing system may include a flow rate monitoring system, such as a flow sensor or meter.
- the flow monitoring system is positioned between the charging chamber and the reaction vessel.
- the flow monitoring system is positioned such that it may detect or determine (such as by pressure differential) the flow rate of gas with hydrogen sulfide being introduced into the reaction vessel.
- flow meter 144 is configured as part of system 100 to detect a pressure drop across orifice plate 145 such that the flow rate in line 143 is determinable.
- Such a flow rate monitoring system may be useful to determine the amount of gas with hydrogen sulfide being introduced into the reaction vessel such that it is not overwhelmed with gas flow.
- the gas with hydrogen sulfide passes from the charging chamber and is introduced at least in part into the reaction vessel.
- the reaction vessel in one or more embodiments provides a volume where the gas with hydrogen sulfide may intimately intermix with a reaction solution such that hydrogen sulfide may be extracted from the gas with hydrogen sulfide, react with the disassociated ions from a metal salt, and form an insoluble sulfur reaction product that may be collected. In doing so, the gas with hydrogen sulfide is converted into a crude hydrogen sulfide-free gas. Both products, by having hydrogen sulfide chemically eliminated, are now safer to handle than the gas with hydrogen sulfide.
- Materials of construction for the reaction vessel in one or more embodiments may include materials such as metals, non-metals, and combinations thereof.
- Materials to be avoided include those that are susceptible to reactions with solubilized acid gases, such as hydrogen sulfide and carbon dioxide.
- a selected material should avoid absorbing hydrogen sulfide onto its surface.
- useful metals include pure and alloys of metals, such as, but not limited to, stainless steel and combinations thereof.
- Non-metals and composite materials that may be useful as part of the reaction vessel may include ceramics, such as laboratory-grade glass, Pyrex®, and borosilicate glass; fiberglass; and graphite-reinforced and carbon-fiber composites; and combinations thereof.
- Polymers that may be useful in reaction vessel construction may include, but are not limited to, polyvinyl chloride (PVC); chlorinated polyvinyl chloride (CPVC); polypropylene (PP) homopolymers and copolymers thereof; polyethylene (PE) homopolymers, such as high- density PE (HDPE), and copolymers thereof, such as PP/PE copolymers; ethylene-vinyl acetate (EVA) copolymers; poly acrylates, poly(meth)acrylates, and poly (alkyl (meth)acrylates), such as poly (methyl methacrylate), and other “acrylic glasses”, copolymers thereof, and combinations thereof; and fluorinated polymers, such as polytetrafluoroethylene (PTFE), and copolymers thereof; and combinations thereof.
- PVC polyvinyl chloride
- CPVC chlorinated polyvinyl chloride
- PP polypropylene
- PE polyethylene
- HDPE high- density PE
- EVA ethylene-
- the reaction vessel is configured such that at least a portion is non-opaque.
- “Non-opaque” means that visible light may be used to view the interior contents of the reaction vessel; therefore, a portion of the reaction vessel may comprise a semi-transparent or fully transparent material.
- “Semi-transparent” means that some amount of visible light is blocked but that enough transparency exists that an operator or a camera imaging visible light may discern the internal contents of the vessel. Borosilicate glass may be considered semi-transparent.
- the reaction vessel may be fully transparent.
- the reaction vessel may be comprised of two or more materials to provide for multiple useful properties.
- the reaction vessel may comprise components of stainless steel for connections, the gas with hydrogen sulfide entry tubing, and reinforcement bands against stresses induced by internal pressure.
- the body of the reaction vessel may mainly comprise a polyacrylic glass of several centimeters of thickness for strength, optical visibility of the internal activities of the reaction vessel, and reduction of weight that a polymer provides over other metal materials.
- the reaction vessel is configured to withstand an internal pressure in a range of from about 14.7 to 5000 pounds per square inch (psi), such as having a lower limit of from about 14.7, 15, 20, 30, 50, 100, and 200 psi, to having an upper limit of about 100, 200, 300, 400, 500, 750, 1000, and 5000 psi, where any lower limit may be associated with any mathematical feasible upper limit.
- psi pounds per square inch
- the reaction vessel is configured to withstand a temperature in a range of from about 0 to 200 °C, such as having a lower limit of from about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, and 55°C, to having an upper limit of about 10, 20, 30, 40, 50, 75, 100, and 200 °C, where any lower limit may be associated with any mathematical feasible upper limit.
- the internal configuration of the reaction vessel is such that it permits intimate intermixing of the gas with hydrogen sulfide and the hydrogen sulfide reaction solution.
- the intimate intermixing permits the reaction between hydrogen sulfide and the disassociated ions of the metallic salt within the hydrogen sulfide reaction solution to form the insoluble sulfur reaction product.
- a hydrogen sulfide-free gas forms that may also be further processed and recovered for analysis.
- the internal configuration of the reaction vessel may vary depending on several processing factors, including, but not limited to, pressure and temperature constraints of the reaction vessel material of construction, the volume of gas with hydrogen sulfide to be processed, the amount of hydrogen sulfide reaction solution that the reaction vessel contains, the amount of insoluble sulfur reaction product to collect, and the amount of hydrogen sulfide-free gas to be collect.
- the total weight of a reaction vessel, including insoluble sulfur reaction product, hydrogen sulfide reaction solution, and inert purge gas, and whether it may be safely handled by a human with or without mechanical assistance is another consideration in some configurations of embodiments, for example, H2S scrubbing systems for use in the field. Another consideration may also be simplicity of configuration such that if any repairs are necessary to a reaction vessel a person may be able to remedy defects in the internal configuration of the reaction vessel in the field with simple hand held tools.
- the reactor 150 has a dip tube 154 with an open end 156 that is below the liquid/gas interface of the hydrogen sulfide reaction solution.
- This design configuration not only provides for an easy indication of the appropriate internal level of hydrogen sulfide reaction solution that should be present in the reactor 150 (above the open end 156) but also ensures intimate intermixing of the hydrogen sulfide reaction solution 160 with the gas with hydrogen sulfide as the gas bubbles through the solution 160.
- Figures 3 A and 3B are schematics of several useful reaction vessels for the H2S scrubbing system.
- reactor 150 shown in Figure 1 as part of system 100
- one or more embodiments may include variations in reaction vessel configuration that may have features useful for intimately intermingling the gas with FhS with the FhS reaction solution.
- Figure 3 A shows a reactor 150A that may be a useful in one or more embodiments.
- Reactor 150A may include features such as a settling trap 380 and a sloped bottom 381.
- reactor 150A may feature a mixing paddle 382 and a motor 383 to mix the 3 ⁇ 4S reaction solution 160 with the f S containing gas as it comes from the dip tube 154.
- FIG. 3B shows another reactor 150B that may be a useful in one or more embodiments.
- Reactor 150B may include a gas sparger 384 instead of a dip tube for distributing the gas with FhS into the interior of the reactor 150B.
- a set of spray nozzles 385 distributes the FhS reaction solution into a packing structure 386.
- the packing structure 386 may be a random distribution of packing, a structured packing element, or a combination thereof. As the liquid FhS reaction solution trickles generally downward and the gas with FhS generally moves upward, the reaction removing the FhS from the gas occurs within the packing structure 386.
- a recycle line 387 conveys FhS reaction solution from below the gas sparger 384 to the spray nozzles 385.
- FhS reaction solution intimately intermixes with the gas with hydrogen sulfide are within the vision of a person of ordinary skill in the art of absorption and distillation process technology.
- one or more sensors may be coupled to the reaction vessel.
- a temperature, a pressure, or a pH sensor may be coupled to the exterior of the reaction vessel such that the conditions within the reaction vessel, including the liquid and the vapor spaces, may be detected or determined.
- a pH sensor 157 is shown coupled to the reactor 150 to detect the pH of the hydrogen sulfide reaction solution.
- reaction vessel Contained within the reaction vessel is a hydrogen sulfide reaction solution.
- the purpose of the 3 ⁇ 4S reaction solution is to selectively remove hydrogen sulfide from the gas with hydrogen sulfide without removing other components from the gas with H2S. Recovering the sulfur atom (and isotopes thereof) for analysis as a product of H2S scrubbing system is of interest.
- the resultant of the reaction - the insoluble sulfur reaction product - is non-toxic.
- the stable, non- or low-toxicity insoluble sulfur reaction product permits safe transport, storage, and handling, of the resultant sulfur compounds.
- the hydrogen sulfide reaction solution should be a relatively easy and safe material to handle and, if necessary, make in the field from raw ingredients.
- the hydrogen sulfide reaction solution is also relatively safe to handle being made of a metallic salt and water.
- the hydrogen sulfide reaction solution may be introduced into the reaction vessel before or after the reaction vessel is coupled to the system.
- the hydrogen sulfide reaction solution comprises water with a metallic salt.
- the hydrogen sulfide reaction solution may comprise metallic cations from the metallic salt.
- the metallic cations may include, but are not limited to, ions of zinc, iron, copper, silver, lead, cadmium, cobalt, magnesium, manganese, nickel, tin, mercury, and combinations thereof.
- Anions of the metallic salt that may form from the disassociation of the metallic salt may include, but are not limited to, nitrates, sulphates, phosphates, sulfites, nitrites, chlorides, bromides, iodides, fluorides, pyrophosphates and perchlorates.
- the hydrogen sulfide reaction solution comprises a metallic nitrate salt, such as silver nitrate.
- the insoluble reaction product is a metallic sulfide, such as silver sulfide.
- the concentration and amount of metallic salt in the hydrogen sulfide reaction solution is sufficient to fully extract the hydrogen sulfide from the gas with hydrogen sulfide introduced into the reaction vessel.
- the concentration of hydrogen sulfide in the gas with hydrogen sulfide may be in a range of from about 0.1 to 40 mol.% (mole percent), such as about 0.1 to 20 mol.%.
- An insufficient amount of metallic salt in the hydrogen sulfide reaction solution would defeat the purpose of the system and its method of use. In such an instance, excess hydrogen sulfide would contaminate the hydrogen sulfide-“free” gas and all the potential sulfur isotopes from the gas with hydrogen sulfide would not be collected in as metallic sulfide salts.
- the hydrogen sulfide reaction solution may have a pH in a range of from about -1.0 to 7.7 before introduction of the gas with hydrogen sulfide, such as having a lower limit of from about -1.0, 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0, to having an upper limit of about 3.0, 4.0, 5.0, 6.0, 7.0, 7.5, and 7.7, where any lower limit may be associated with a mathematical feasible of an upper limit. It is useful to have an acidic to slightly alkaline hydrogen sulfide reaction solution to prevent the absorption and conversion of carbon dioxide into carbonic acid in the hydrogen sulfide reaction solution.
- carbon dioxide may also include isotopes of carbon, such as C 13 , which also may be useful in analyzing the hydrogen sulfide-free gas for understanding aspects of the formation, such as source maturity.
- the pH of the hydrogen sulfide reaction solution is modified during operation of the system.
- an amount of an acid or acid precursor may be introduced into the hydrogen sulfide reaction solution during the operation of the system such that the pH of the hydrogen sulfide reaction solution is maintained within a pH range of -1.0 to 7.7.
- An acid precursor is a compound that upon dissolution into the aqueous medium forms an acid.
- the acid or acid precursor may be added into the hydrogen sulfide reaction solution as a liquid, such as an aqueous solution, or a solid.
- an acid or acid precursor that may be introduced into the hydrogen sulfide reaction solution includes nitric acid and acid precursors that degrade or disassociate into nitric acid.
- the hydrogen sulfide reaction solution may further comprise a buffering solution.
- a buffering solution may comprise a weak acid and its conjugate base.
- the buffering solution is to provide pH stability in the acidic to slightly alkaline range during the exposure of the hydrogen sulfide reaction solution.
- an amount of a buffering solution may be introduced into the hydrogen sulfide reaction solution during the operation of the system such that the pH of the hydrogen sulfide reaction solution is maintained within a pH range of -1.0 to 7.7.
- the weak acid and its conjugate base should not directly interfere with the composition of the gas with hydrogen sulfide, the hydrogen sulfide-free gas, or the insoluble sulfur reaction product, in the reaction vessel.
- a buffering solution may be introduced into the hydrogen sulfide reaction solution that produces nitrate ions.
- the hydrogen sulfide reaction solution may further comprise a reactive dye.
- the reactive dye may be a naturally occurring or synthetic, or both, compound that is used to visually monitor the pH of the hydrogen sulfide reaction solution during operation of the system.
- Examples of reactive dyes include halochromic compounds and the materials in Litmus paper.
- a shift in color may indicate a change in pH may require intervention, such as introduction of a buffer solution, an acid, or an acid precursor, into the reaction vessel, before additional introduction of gas with hydrogen sulfide continues.
- the reactive dye should not directly interfere with the composition of the gas with hydrogen sulfide, the hydrogen sulfide-free gas, or the insoluble sulfur reaction product, in the reaction vessel.
- a halochromic compound may be introduced into the hydrogen sulfide reaction solution.
- the reaction vessel is permanently coupled as part of the FhS scrubbing system.
- the reaction vessel is configured to be detachable from the system.
- Figure 1 shows isolation valves 151 and 152 that may be closed and decoupled from the system 100, permitting removal of reactor 150.
- the reaction vessel may be removed and replaced with another reactor, such as a “fresh” reactor (that is, one that has not been used in an embodiment process), taken out of an embodiment system for maintenance, service, or both, or for exchanging with another reactor configuration.
- a detachable reaction vessel in some instances may resemble a bomb, a small cylinder, or a glass beaker or jar.
- an embodiment of the FhS scrubbing system may include a reaction vessel configured with a settling trap for aggregating and collecting the insoluble sulfur reaction product.
- a reaction vessel configured with a settling trap for aggregating and collecting the insoluble sulfur reaction product.
- such a configuration may facilitate collection of the insoluble sulfur reaction product by having the product accumulate at least in part in the settling trap 380.
- the accumulation may be removable from the reaction vessel even during operation, such as by an isolation valve system that permits removal of solids with some liquids.
- Such a configuration may permit the reaction vessel to be used for a run where a sample of the insoluble sulfur reaction product needs to be taken quickly, where the expected build-up of insoluble sulfur reaction product may be significant as compared to the volume of the hydrogen sulfide reaction solution, or until the hydrogen sulfide reaction solution is fully depleted of metallic salts, for example.
- the reaction vessel is associated with a pressure monitoring system, such as a pressure sensor or gauge.
- the pressure monitoring system is connected to the reaction vessel.
- the pressure monitoring system is coupled upstream or downstream of the reaction vessel in a manner such that the pressure within the reaction vessel is detectable.
- pressure gauge 155 is configured as part of system 100 to detect the pressure in reactor 150 by being positioned downstream along line 153.
- Products of the reaction vessel may include the insoluble sulfur reaction product and the hydrogen sulfide-free gas.
- the insoluble sulfur reaction product may pass from the reaction vessel by use of a settling trap or other aggregation means through the lower portion of the vessel either during operation or post-operation.
- the hydrogen sulfide reaction solution may be circulated internally or externally from the reaction vessel and the insoluble sulfur reaction product may be mechanically filtered, strained, or otherwise separated, from the aqueous solution.
- the insoluble sulfur reaction product may pass from the FbS scrubbing system post-operation (sometimes along with some amount of the hydrogen sulfide reaction solution) as part of generally cleaning, refurbishing, repairing, or preparing the reaction vessel, for another operational run.
- the hydrogen sulfide-free gas passes from the reaction vessel and is introduced into the treated gas trap.
- the FbS scrubbing system may include a treated gas trap for removing water from the wet hydrogen sulfide-free gas.
- the hydrogen sulfide- free gas picks up water in the reaction vessel that was not present in the gas with hydrogen sulfide as introduced. Removing the water provides for a more accurate analysis of the residual hydrogen sulfide-free gas. After passing through the treated gas trap, the hydrogen sulfide-free gas is ready for analysis.
- the treated gas trap in one or more embodiments may include a demister.
- the demister physically aggregates any water mist or other micro-sized droplets that form an aerosol in the hydrogen sulfide-free gas into liquid droplets.
- the demister also blocks or prevents any aqueous solution carryover or blow-through from the reaction vessel from passing the treated gas trap. Any liquid droplets that form fall out of the vapor.
- system 100 has post-reactor treatment vessel 170 downstream of the reactor 150.
- the first section of the post-reactor treatment vessel 170 (shown in partial reveal) contains a back-and-forth demister section 171 for knocking water physically out of the wet hydrogen sulfide-free gas.
- the treated gas in one or more embodiments may include a desiccant.
- the desiccant chemically removes any remaining water in the hydrogen sulfide-free gas that passes through it.
- the desiccant may be made from a hydroscopic material, including, but not limited to, silica gel, silica molecular sieves, silica-alumina gel, activated alumina, alkaline metal and alkali earth salts, such as magnesium chloride, and combinations thereof.
- silica gel silica molecular sieves
- silica-alumina gel activated alumina
- alkaline metal and alkali earth salts such as magnesium chloride, and combinations thereof.
- the hydrogen sulfide-free gas passes from the treated gas tap and is introduced into the receiver for gas without hydrogen sulfide.
- a receiver for gas without hydrogen sulfide in one or more embodiments may be provided for as a portable container, such as a tank, a cylinder, a bomb, a vessel, a canister, or other device that may hold the hydrogen sulfide-free gas at atmospheric or elevated pressure.
- the receiver for gas without hydrogen sulfide may be a permanently coupled or connected line to downstream analytical equipment. In such a configuration, the receiver of the gas without hydrogen sulfide is “hard piped” to an embodiment system for intermittent or continuous use to receive gas without hydrogen sulfide from an embodiment system.
- Figure 4 is a drawing of a FhS scrubbing system mounted as part of a mobile, self-propelled vehicle, vessel, or platform.
- Figure 4 shows a mobile vehicle, such as semi- truck 405, with a FhS scrubbing system 100A mounted on its truck bed 406.
- Mobile vehicles or vessels that are self-propelled include, but are not limited to, cars, trucks, ships, and airplanes.
- One or more embodiments may be a mobile, non- self-propelled vehicle, vessel, or platform.
- a towed barge, a land- or water-borne skiff, or a land- or water-borne drilling platform or “rig”, may be useful to convey the system to locations where samples are to be taken.
- System 100A is coupled to a source for gas with FbS: a raw natural gas pipeline
- Isolation valve 411 connects to line 413, which couples with system 100A to provide gas with FbS for sample collection.
- Line 413 is shown with several additional features coupled to the line, including flow control valve 414, a pressure sensor 415, a heating element 416, a fin cooler 417, and a liquids trap 418, all upstream of a charging chamber (not shown but part of system 100A).
- one or more sensors may be coupled upstream of the charging chamber and positioned between the source of gas with hydrogen sulfide and the charging chamber.
- Figure 4 shows a pressure sensor 415 downstream of flow control valve 414, where both are upstream of the charging chamber (not shown).
- Such a combination of a flow control valve and a pressure sensor may be used to throttle the introduced gas with hydrogen sulfide flowing into the charging chamber, as previously described.
- a heater may be coupled upstream of the charging chamber and positioned between the source of gas with hydrogen sulfide and the charging chamber.
- Figure 4 shows a portion of a heating element 416 wrapped around line 413 upstream of the charging chamber (not shown).
- a heater which may be useful for warming the line to prevent the formation of hydrates after volume expansion, to vaporize any liquids that may have formed in the line, and to facilitate the gas with hydrogen sulfide for reaction with the metallic salt in the reaction vessel, may be any form of device that can transfer heat into the line. Examples include, but are not limited to, convection heaters, such as a heat exchanger and solar hydronic heaters, and radiant heaters, such as electrical tape and microwave transmitters.
- heated fluids such as exhaust gas from the operating vehicle, may be used to heat the line.
- a cooler may be coupled upstream of the charging chamber and positioned between the source of gas with hydrogen sulfide and the charging chamber.
- Figure 4 shows a portion of a condenser with a fin cooler 417 wrapped around line 413 upstream of the charging chamber (not shown).
- the cooler may be useful for cooling the line to prevent the gas with hydrogen sulfide from overheating the system, such as causing the hydrogen sulfide reaction solution to vaporize.
- the cooler may be any form of device that can extract heat from the line. Examples include, but are not limited to, convection coolers, such as a heat exchanger or a fan, and radiant coolers, such as cooling fins.
- cooling fluids such as refrigerant from the operating vehicle, may be used to chill the line.
- the line that couples the source of gas with hydrogen sulfide to the embodiment system may include a liquids trap.
- Figure 4 shows a portion of a liquid trap 418 coupled to line 413 upstream of the charging chamber (not shown).
- Liquids may form in the line to the charging chamber due to changes in temperature or pressure during movement between the source to the charging chamber, especially out in the field.
- the liquids trap may be useful to prevent any condensed liquid from entering the charging chamber.
- the liquids from the liquids trap may be collected for analysis.
- Semi-truck 405 is also shown with an additional inert purge tank 120, remainder gas canisters 130, and reactors 150.
- Such tanks, canisters, and reactors may be pre- or post use.
- one or more of the remainder gas canisters may contain dry hydrogen sulfide-free gas and one or more of the reactors may contain insoluble sulfur reaction product from prior sampling activities.
- Figure 5 is a process flow diagram for a method of using a H2S scrubber system.
- a source of gas with hydrogen sulfide may be provided.
- the method 500 includes providing a source of gas with hydrogen sulfide 505.
- the source may be a portable source, such as a tank.
- Figure 1 shows feed gas canister 110.
- the source may be a fixed source, such a pipeline.
- Figure 4 shows raw natural gas pipeline 410.
- a source of inert purge gas may be provided.
- the method 500 includes providing a source of inert purge gas 510.
- the source may be a portable source, such as a tank.
- Figures 1 and 4 both show inert purge tank 120.
- the source may be a fixed source, such as a pipeline.
- a gas with hydrogen sulfide is introduced into the hydrogen sulfide scrubber system.
- the method 500 includes introducing the gas with hydrogen sulfide into the system 515.
- the introduced gas with hydrogen sulfide may be passed from the source describe previously and introduced into the charging chamber of the system.
- the gas with hydrogen sulfide passes from feed gas canister 110 and is introduced into system 100 via charge line 140.
- Figures 2A, 2B, and 2C show alternative charging chamber configurations 140A, 140B, and 140C, respectively, that may be present in system 100 into which the gas with hydrogen sulfide may be introduced.
- the gas with hydrogen sulfide passes from raw natural gas pipeline 410 and is introduced into system 100A.
- the introduction of the gas with hydrogen sulfide is intermittent. That is, the gas with hydrogen sulfide is introduced into the charging chamber of the hydrogen sulfide scrubber system on an “as-needed” basis or on a regular, periodic basis. For example, an amount of gas is introduced such that a pressure is achieved in the charging chamber, which has a fixed volume, and then no further gas is introduced. In one or more embodiments, the introduction of the gas with hydrogen sulfide is continuous.
- the gas with hydrogen sulfide may be introduced unobstructed or may be introduced partially obstructed.
- the pressure of the gas may be reduced by throttling, such as by using a flow control valve or an isolation valve, or by permanent means, such as an orifice or a venturi.
- the pressure of the gas with hydrogen sulfide is adjusted while being introduced into the system, such as by being depressurized. In one or more embodiments, the pressure of the gas with hydrogen sulfide is not adjusted while being introduced into the system.
- the pressure of the gas with hydrogen sulfide in the charging chamber as compared to the pressure of the gas with hydrogen sulfide in the source of the gas with hydrogen sulfide is in a ratio range of from about 1:1 to 1:2000, such as from about 1:1 to 1:1000, such as from about 1:1 to 1:500, such as from about 1:1 to 1:250, such as from about 1:1 to 1:100, such as from about 1:1 to 1:50, such as from about 1:1 to 1:25, such as from about 1:1 to 1:10, such as from about 1:1 to 1:5, such as from about 1:1 to 1:2.
- the temperature of the gas with hydrogen sulfide is adjusted while being introduced into the system. In one or more embodiments, the temperature of the gas with hydrogen sulfide is not adjusted while being introduced into the system. In such one or more embodiments, the gas with hydrogen sulfide is cooled while being introduced into the system. In such one or more embodiments, the gas with hydrogen sulfide is heated while being introduced into the system.
- the hydrogen sulfide treatment system is operated such that the charging chamber is fluidly isolated after receiving the gas with hydrogen sulfide.
- the method 500 includes isolating the charging chamber 520.
- all of the isolation or control, or both, valves both upstream and downstream of the charging chamber may be closed such that there is no flow between both the source for the gas with hydrogen sulfide and the charging chamber and between the charging chamber and the reaction vessel.
- the pressure of the gas within the charging chamber may be detected, such as by using a pressure monitoring system.
- the pressure of the gas with hydrogen sulfide is the same as the pressure of the gas with hydrogen sulfide in the source.
- the pressure of the gas with hydrogen sulfide in the charging chamber is less than the pressure of the gas with hydrogen sulfide in the source.
- the pressure of the gas with hydrogen sulfide is adjusted during isolation in the charging chamber, such as by being depressurized.
- the gas with hydrogen sulfide in one charging chamber 140 may be expanded into more than one charging chamber, thereby decreasing its pressure while still isolated within the charging chamber 140A and 140C. This can prevent over-pressurization of the reaction vessel as well as provide an additive safety feature for use of the system, especially considering coupling with full-pressure sources, by manually permitting pressure letdown.
- the volume of the charging chamber before expansion to the volume of the charging chamber after expansion is in a ratio range of from about greater than 1:1 to 1:5.
- the pressure of the gas with hydrogen sulfide in the charging chamber after pressure reduction compared to the pressure before pressure reduction is in a range of from about greater than 1 : 1 to 1 :5, such as from about greater than 1:1 to 1:4, and such as from about greater than 1:1 to 1:3, such as from about greater than 1:1 to 1:2.
- the operation of the system may include repeating the intermittent introduction of the gas with hydrogen sulfide into the charging chamber and isolating the flow into the charging chamber. This process may be repeated as many times as necessary to accomplish the one or more purposes for using the hydrogen sulfide scrubber system, including, but not limited to, obtaining sufficient insoluble sulfur reaction product, hydrogen sulfide-free gas, or both, for analysis purposes.
- the hydrogen sulfide treatment system is operated such that the gas with hydrogen sulfide passes from the charging chamber and is introduced into the reaction vessel.
- the method 500 includes passing the gas with hydrogen sulfide from the charging chamber and introducing it into the reaction chamber 525.
- the gas with hydrogen sulfide passes from charging line 140 and is introduced into reactor 150.
- Figures 2A, 2B, and 2C show charging chamber configurations 140A, 140B, and 140C, respectively, that may pass gas with hydrogen sulfide into the reactor 150.
- Figures 3 A and 3B show alternative reactors 150A and 150B, respectively, that may be present in system 100 into which the gas with hydrogen sulfide may be introduced.
- reactor 150 is shown on truck bed 406 as part of system 100A.
- the introduction of the gas with hydrogen sulfide is intermittent. That is, the gas with hydrogen sulfide is introduced into the reaction vessel of the hydrogen sulfide scrubber system on an “as-needed” basis or on a periodic basis. In such an instance, the gas with hydrogen sulfide may be introduced such that an operational pressure limit for the reaction vessel is not exceeded. In another instance, gas with hydrogen sulfide is introduced until a quantity of insoluble sulfur reaction product is produced in the reaction vessel. In another instance, the gas with hydrogen sulfide is introduced until back pressure exerted by previously produced hydrogen sulfide-free gas prevents further introduction of the gas with hydrogen sulfide. Other reasons, purposes, or goals for the intermittent introduction of the gas with hydrogen sulfide may be assumed.
- the operation of the hydrogen sulfide treatment system may include repeating one or more times the intermittent introduction of the gas with hydrogen sulfide from the charging chamber into the reaction vessel and then isolating the flow between the charging chamber and the reaction vessel. This process may be repeated as many times as necessary to accomplish a one or more goals for using the hydrogen sulfide scrubber system, including, but not limited to, obtaining sufficient insoluble sulfur reaction product, hydrogen sulfide- free gas, or both, for analysis purposes.
- the introduction of the gas with hydrogen sulfide is continuous.
- the gas with hydrogen sulfide may be introduced unobstructed or may be introduced partially obstructed.
- the gas with hydrogen sulfide is depressurized while being introduced.
- the pressure of the gas may be reduced by throttling, such as by using a flow control valve or an isolation valve, or by permanent means, such as an orifice or a venturi.
- the pressure of the gas with hydrogen sulfide is adjusted while being introduced into the reactor, such as by being depressurized. In one or more embodiments, the gas with hydrogen sulfide is not adjusted while being introduced into the reactor. In such one or more embodiments, the pressure of the gas with hydrogen sulfide in the reactor to the pressure of the gas with hydrogen sulfide in the charging chamber is in a ratio range of from about 1:1 to 1:2000, such as from about 1:1 to 1:1000, such as from about 1:1 to 1:100, such as from about 1:1 to 1:10, such as about 1:1 to 1:5, and such as from about 1:1 to 1:2.
- the hydrogen sulfide treatment system is operated such that the gas with hydrogen sulfide is converted into the insoluble sulfur reaction product and the hydrogen sulfide-free gas using the hydrogen sulfide reaction solution in the reaction vessel.
- the method 500 includes converting the gas with hydrogen sulfide into the insoluble sulfur reaction product and the hydrogen sulfide-free gas 530.
- the gas with hydrogen sulfide bubbles through the hydrogen sulfide reaction solution 160 contained in reactor 150. The hydrogen sulfide is stripped from the gas and forms a wet hydrogen sulfide-free gas 162.
- the configuration of the reaction vessel for the hydrogen sulfide treatment system is one of reactors 150A and 150B as given in Figures 3 A and 3B, respectively, instead the reactor 150 provided with system 100 of Figure 1.
- a person of ordinary skill using the content of this disclosure may appreciate the engineering necessary to substitute the partial or total features of either of the reaction vessels provided for in Figures 3 A and 3B with that of the reaction vessel feature in Figure 1.
- an acid or an acid precursor is added to the hydrogen sulfide reaction solution during operation to adjust the pH of the solution.
- a buffer solution is added to the hydrogen sulfide reaction solution during operation to adjust the pH of the solution.
- the hydrogen sulfide treatment system is operated such that the hydrogen sulfide-free gas passes from the reaction vessel and is introduced into the treated gas trap.
- the method 500 includes passing the hydrogen sulfide- free gas from the reaction vessel and introducing it into the treated gas trap 535.
- the hydrogen sulfide-free gas may traverse through a demister section in the treated gas trap.
- the post-reactor treatment vessel 170 includes a back-and-forth demister section 171 for the wet hydrogen sulfide- free gas to traverse to physically remove water mist or gas-bome droplets.
- the hydrogen sulfide-free gas may traverse through a desiccant section in the treated gas trap.
- the post-reactor treatment vessel 170 includes a desiccant section 172 for the wet hydrogen sulfide-free gas to traverse to chemically remove water and form dry hydrogen sulfide-free gas.
- the hydrogen sulfide treatment system is operated such that the hydrogen sulfide-free gas passes from the H2S scrubbing system into the receiver for gas without hydrogen sulfide.
- the method 500 includes passing the hydrogen sulfide-free gas from the system 540.
- the dry hydrogen sulfide- free gas passes into remainder gas canister 130.
- a valve such as a flow control or an isolation valve, between the source for the gas with hydrogen sulfide and the charging chamber may be closed.
- no gas with hydrogen sulfide may be introduced into the system.
- isolation valve 111 or 112 may be closed to terminate the gas with hydrogen sulfide flow from feed gas canister 110.
- isolation valve 411 may be closed to terminate the gas with hydrogen sulfide from raw natural gas pipeline 410.
- an inert purge gas is introduced into the hydrogen sulfide scrubber system such that any non-inert purge gas is swept from the system.
- the method 500 includes introducing the inert purge gas into the system 545.
- the inert purge gas is introduced into the hydrogen sulfide scrubbing system through the charging chamber such that any residual gas with hydrogen sulfide in the system upstream of the reaction vessel is pushed into the reaction vessel with the inert purge gas. Any residual gas with hydrogen sulfide passing into the reaction vessel undergoes a similar conversion as previously described.
- the introduction of the inert purge gas also substantially drives all of the residual hydrogen sulfide-free gas in the system towards the receiver for gas without hydrogen sulfide.
- the agitation by the inert purge gas agitates the hydrogen sulfide reaction solution such that substantially all the insoluble sulfur reaction product suspended in the solution falls out of solution. If any post-reaction vessel treatment occurs, the hydrogen sulfide-free gas downstream of the reaction vessel is pushed through such treatment before entering the receiver for gas without hydrogen sulfide.
- the inert purge gas passes from feed gas canister 110 into system 100 and drives all gases towards remainder gas canister 130.
- the hydrogen sulfide treatment system is operated such that the receiver for gas without hydrogen sulfide is fluidly isolated.
- the method 500 includes isolating fluidly the receiver for gas without hydrogen sulfide 550.
- at least one of the valves upstream of the receiver for gas without hydrogen sulfide such as a control or isolation valve, may be closed such that there is no fluid connectivity between the receiver for gas without hydrogen sulfide and the rest of the system.
- isolation valve 131 or 173 may be closed to isolate remainder gas canister 130.
- the hydrogen sulfide treatment system is operated such that the reaction vessel is fluidly isolated.
- the method 500 includes isolating fluidly the reaction vessel 555.
- at least one of the valves upstream and at least one of the valves downstream of the reaction vessel such as a control or isolation valve, may be closed such that there is no flow between the reaction vessel and the rest of the system.
- isolation valve 142 or 155 upstream of the reactor 150 and either isolation valve 152 or 174 downstream of the reactor 150 may be closed to isolate reactor 150.
- a valve such as a control or an isolation valve, between the source for the inert purge gas and the charging chamber may be closed.
- no inert purge gas may be introduced into the system.
- isolation valve 121 or 122 may be closed to terminate the inert purge gas flow.
- the hydrogen sulfide-free gas may be recovered.
- the dry hydrogen sulfide-free gas may be recovered by decoupling the remainder gas canister 130 from the rest of system 100.
- several remainder gas canisters 130 are shown not coupled to system 100A located on the truck bed 406.
- One or more of such canisters 130 may contains hydrogen sulfide-free gas for analysis.
- the insoluble sulfur reaction product may be recovered.
- the insoluble sulfur reaction product may be recovered by decoupling the reactor 150 from the rest of system 100.
- several reactors 150 are shown not coupled to system 100A located on the truck bed 406. One or more of such reactors 150 may contains insoluble sulfur reaction product for analysis.
- post-collection analysis may be useful, such as using XRD (X-ray powder diffraction) analysis on the insoluble sulfur reaction product, to provide for managing and adapting the system and method for future collection from the same or similar sources, such as system configuration and hydrogen sulfide reaction solution composition.
- XRD X-ray powder diffraction
- this term may mean that there can be a variance in value of up to ⁇ 10%, of up to 5%, of up to 2%, of up to 1%, of up to 0.5%, of up to 0.1%, or up to 0.01%.
- substantially refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more
- Ranges may be expressed as from about one particular value to about another particular value, inclusive. When such a range is expressed, it is to be understood that another embodiment is from the one particular value to the other particular value, along with all particular values and combinations thereof within the range.
- transitional phrase “consisting essentially of’ may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non- recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter.
- transitional phrases “consisting of’ and “consisting essentially of’ may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open- ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of’ and “consisting essentially of.”
- the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of’ components A, B, and C as well as a composition “consisting essentially of’ components A, B, and C.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Organic Chemistry (AREA)
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- Gas Separation By Absorption (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17/339,499 US11826699B2 (en) | 2021-06-04 | 2021-06-04 | Stripping H2S off natural gas for multiple isotope analyses |
| US17/339,499 | 2021-06-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022256258A1 true WO2022256258A1 (en) | 2022-12-08 |
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ID=82483134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2022/031393 Ceased WO2022256258A1 (en) | 2021-06-04 | 2022-05-27 | Stripping h2s off natural gas for multiple isotope analyses |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US11826699B2 (en) |
| WO (1) | WO2022256258A1 (en) |
Citations (5)
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| EP1656983A1 (en) * | 2004-11-12 | 2006-05-17 | Institut Français du Pétrole | Process for deacidification of a gas with an absorbing solution in fractional regeneration |
| CN107021600A (en) * | 2016-04-26 | 2017-08-08 | 华中农业大学 | The technique and device of the recovery of biogas slurry ammonia nitrogen and methane purification after pig manure anaerobic fermentation |
| EP3616774A1 (en) * | 2018-09-03 | 2020-03-04 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Method and device for the removal of metal carbonyls from a gas mixture |
| US20200254387A1 (en) * | 2019-02-07 | 2020-08-13 | California Bioenergy Llc | Systems for aggregating and processing of biogas to biomethane |
| CN108722148B (en) * | 2017-04-13 | 2021-05-04 | 中国石油化工股份有限公司 | Method and device for treating hydrogen gas containing carbon dioxide and sulfureted hydrogen |
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| US3087793A (en) | 1961-06-19 | 1963-04-30 | Gen Electric | Process of oxidizing hydrogen sulfide to elemental sulfur |
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| US5407646A (en) | 1989-12-05 | 1995-04-18 | The University Of Toronto Innovations Foundation | Dual impeller method and apparatus for effecting chemical conversion |
| US5916438A (en) | 1994-07-01 | 1999-06-29 | International Fuel Cells, Llc | Removal of hydrogen sulfide from anaerobic digester gas |
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| ITMI20022705A1 (en) | 2002-12-20 | 2004-06-21 | Enitecnologie Spa | ORGANIC CHEMICAL PROCESS FOR THE DESULFURATION OF H2S CONTAINING GASEOUS CURRENTS. |
| US6893484B2 (en) | 2003-10-06 | 2005-05-17 | Desert Energy Ltd | Low operating pressure gas scrubber |
| US7704299B2 (en) | 2006-02-24 | 2010-04-27 | M-I Llc | Methods of hydrogen sulfide treatment |
| US8647497B2 (en) | 2008-01-25 | 2014-02-11 | University Of Central Florida Research Foundation, Inc. | Method and system for hydrogen sulfide removal |
| US8372365B2 (en) | 2010-10-27 | 2013-02-12 | Merichem Company | High pressure reduction-oxidation desulfurization process |
| US9028678B2 (en) | 2011-06-28 | 2015-05-12 | Phillips 66 Company | Scrubbing hydrogen sulfide from hydrotreated product |
| US9708196B2 (en) | 2013-02-22 | 2017-07-18 | Anschutz Exploration Corporation | Method and system for removing hydrogen sulfide from sour oil and sour water |
| CA2915860A1 (en) | 2015-12-18 | 2017-06-18 | Geert Versteeg | Removal of sulfur compounds from gas streams via precipitation |
| CN210001835U (en) | 2019-11-13 | 2020-01-31 | 西南石油大学 | A natural gas purification device |
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2021
- 2021-06-04 US US17/339,499 patent/US11826699B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1656983A1 (en) * | 2004-11-12 | 2006-05-17 | Institut Français du Pétrole | Process for deacidification of a gas with an absorbing solution in fractional regeneration |
| CN107021600A (en) * | 2016-04-26 | 2017-08-08 | 华中农业大学 | The technique and device of the recovery of biogas slurry ammonia nitrogen and methane purification after pig manure anaerobic fermentation |
| CN108722148B (en) * | 2017-04-13 | 2021-05-04 | 中国石油化工股份有限公司 | Method and device for treating hydrogen gas containing carbon dioxide and sulfureted hydrogen |
| EP3616774A1 (en) * | 2018-09-03 | 2020-03-04 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Method and device for the removal of metal carbonyls from a gas mixture |
| US20200254387A1 (en) * | 2019-02-07 | 2020-08-13 | California Bioenergy Llc | Systems for aggregating and processing of biogas to biomethane |
Also Published As
| Publication number | Publication date |
|---|---|
| US20220387931A1 (en) | 2022-12-08 |
| US11826699B2 (en) | 2023-11-28 |
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