WO2019032283A1 - Procédé d'élimination de composés soufrés à partir d'un flux gazeux - Google Patents

Procédé d'élimination de composés soufrés à partir d'un flux gazeux Download PDF

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WO2019032283A1
WO2019032283A1 PCT/US2018/043466 US2018043466W WO2019032283A1 WO 2019032283 A1 WO2019032283 A1 WO 2019032283A1 US 2018043466 W US2018043466 W US 2018043466W WO 2019032283 A1 WO2019032283 A1 WO 2019032283A1
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molecular weight
low molecular
containing compounds
adsorbent
sulfur containing
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Runyu TAN
Ajay N. BADHWAR
Ross E. DUGAS
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Dow Global Technologies Llc
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    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
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    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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Definitions

  • the present invention relates to a novel adsorption process for removal of sulfur compounds, including mercaptans, sulfides, disulfides, thiophenes and thiophanes from liquid and gas feed streams, and more particularly, an adsorption process for purification of hydrocarbons, petroleum distillates, natural gas and natural gas liquids, associated and refinery gases.
  • These fluid streams may be gas, hydrocarbon gases from shale pyrolysis, synthesis gas, and the like or liquids such as liquefied petroleum gas (LPG) and natural gas liquids (NGL).
  • LPG liquefied petroleum gas
  • NNL natural gas liquids
  • Removal of sulfur containing compounds is normally done in two steps.
  • the amine treatment removes hydrogen sulfide from the system.
  • Some mercaptans, part of carbon oxysulfide and of carbon dioxide may also be removed in this step. This process is related to absorption.
  • the second step is an adsorption of organic sulfur compounds, especially mercaptans, sulfides, thiophenes, thiophanes and disulfides.
  • Adsorption of sulfur-contaminated compounds is the most common method for removal of these sulfur compounds, because of the high performance and relatively low capital and operational costs. Numerous processes and adsorbents have been developed for the removal of organic sulfur compounds and hydrogen sulfide, carbon oxysulfide and carbon disulfide, from gases and liquids.
  • the most widely used physical adsorbents for these sulfur compounds are synthetic zeolites or molecular sieves.
  • USP 2,882,243 and 2,882,244 disclose an enhanced adsorption capacity of molecular sieves for hydrogen sulfide at ambient temperatures.
  • USP 3,760,029 discloses the use of synthetic faujasites as an adsorbent for dimethyl disulfide removal from n-alkanes.
  • USP 3,816,975; 4,540,842; and 4,795,545 disclose the use of standard molecular sieves as a sulfur adsorbent for the purification of liquid hydrocarbon feedstocks.
  • USP 4,098,684 discloses the use of combined beds of two or more molecular sieves.
  • EP 0781832 discloses zeolites as adsorbents for hydrogen sulfide and tetrahydrothiophene in natural gas feed streams. Regeneration of these molecular sieves requires elevated temperatures.
  • the present invention is a process for removing low molecular weight sulfur containing compounds, such as, but not limited to sulfur dioxide (SO2), carbon disulfide (CS 2 ), carbonyl sulfide (COS), or mercaptans from a gas feedstream comprising low molecular weight sulfur containing compounds comprising, consisting essentially of, consisting of the steps of: (a) providing an adsorbent bed comprising a cross-linked macroporous polymeric adsorbent media, wherein said adsorbent media adsorbs low molecular weight sulfur containing compounds; (b) passing the gas feedstream through the cross-linked macroporous polymeric adsorbent bed to provide a low molecular weight sulfur containing compounds -lean gas feedstream and a low molecular weight sulfur containing compounds-loaded cross-linked macroporous polymeric adsorbent media; (c) further treating, recovering, transporting, liquefying, or flaring the low molecular weight sulfur containing compounds
  • the cross-linked macroporous polymeric adsorbent is a polymer of a monovinyl aromatic monomer crosslinked with a polyvinylidene aromatic compound, preferably the monovinyl aromatic monomer comprises from 92% to 99.25% by weight of said polymer, and said polyvinylidene aromatic compound comprises from 0.75% to 8% by weight of said polymer.
  • the cross-linked macroporous polymeric adsorbent is a polymer of a member selected from one or more of the group consisting of styrene, vinylbenzene, vinyltoluene, ethylstyrene, divinylbenzene, and t-butylstyrene; and is crosslinked with a member selected from the group consisting of divinylbenzene, trivinylbenzene, and ethylene glycol dimethacrylate, preferably a polymer of a member selected from the group consisting of styrene, vinylbenzene, vinyltoluene, ethylstyrene, and t-butylstyrene, more preferably styrene; and is crosslinked with a member selected from the group consisting of divinylbenzene, trivinylbenzene, and ethylene glycol dimethacrylate, more preferably
  • One embodiment of the present invention is the process disclosed herein above wherein the regeneration of the loaded adsorbent is achieved by using heated gas and/or a radiant heat contact exchanger, preferably the regeneration of the loaded adsorbent media is achieved by a using a pressure swing adsorption (PSA) process, a temperature swing adsorption (TSA) process, or a combination thereof, more preferably the regeneration of the loaded adsorbent media is achieved by a using a microwave heating system.
  • PSA pressure swing adsorption
  • TSA temperature swing adsorption
  • the loaded adsorbent media is achieved by not using a heating step, preferably using a PSA process.
  • FIG. 1 shows the mercaptan breakthrough curve for Example 1, an example of the present invention.
  • FIG. 2 shows the carbon disulfide breakthrough curve for Example 1, an example of the present invention.
  • FIG. 3 shows the carbonyl sulfide breakthrough curve for Example 1, an example of the present invention.
  • Raw natural gas comes from three types of wells: oil wells, gas wells, and condensate wells. Natural gas that comes from oil wells is typically termed “associated gas”. This gas can exist separate from oil in the formation (free gas), or dissolved in the crude oil (dissolved gas). Natural gas from gas and condensate wells, in which there is little or no crude oil, is termed “non-associated gas”. Gas wells typically produce raw natural gas by itself, while condensate wells produce free natural gas along with a semi-liquid hydrocarbon condensate. Whatever the source of the natural gas, once separated from crude oil (if present) it commonly exists as methane in mixtures with other hydrocarbons;
  • Raw natural gas and sometimes treated natural gas often contain a significant amount of impurities, such as water or acid gases, for example carbon dioxide (CO2), hydrogen sulfide (H2S), hydrogen cyanide (HCN), and low molecular weight sulfur compounds, such as, but not limited to sulfur dioxide (SO2), disulfides, such as carbon disulfide (CS 2 ), sulfides, such as carbonyl sulfide (COS) and dimethyl sulfide, thiophenes, thiophanes or mercaptans as impurities.
  • impurities such as water or acid gases, for example carbon dioxide (CO2), hydrogen sulfide (H2S), hydrogen cyanide (HCN), and low molecular weight sulfur compounds, such as, but not limited to sulfur dioxide (SO2), disulfides, such as carbon disulfide (CS 2 ), sulfides, such as carbonyl sulfide (COS) and dimethyl sulfide, thioph
  • Mercaptan compounds include but not limited to methanethiol, ethanethiol, 1-propanethiol, 2- propanethiol, 1-butanethiol, 2-butanethiol, cyclohexanethiol, benzenethiol, a-toluenethiol, and disulfides include but not limited to dimethyl sulfide, diethylsulfide, methylethylsulfide, or combinations thereof.
  • gas feedstream as used in the process of the present invention includes any liquid or gas source comprising methane in mixtures with other hydrocarbons, including, but not limited to, raw natural gas or raw natural gas that has been treated one or more times to remove water and/or other impurities.
  • the process of the present invention is the use of an adsorbent to remove low molecular weight compounds, specifically sulfur dioxide (SO2), carbon disulfide (CS 2 ), carbonyl sulfide (COS), or mercaptans from a gas feedstream.
  • Suitable adsorbents are solids having a microscopic structure.
  • the internal surface of such adsorbents is preferably between 100 to 2000 m 2 /g, more preferably between 500 to 1500 m 2 /g, and even more preferably 1000 to 1300 m 2 /g.
  • the nature of the internal surface of the adsorbent in the adsorbent bed is such that C2 and heavier hydrocarbons are adsorbed.
  • Suitable adsorbent media include materials based on silica, silica gel, alumina or silica-alumina, zeolites, activated carbon, polymer supported silver chloride, copper-containing resins. Most preferred adsorbent media is a porous cross-linked polymeric adsorbent or a partially pyrolized macroporous polymer. Preferably, the internal surface of the adsorbent is non- polar.
  • the present invention is the use of an adsorbent media to remove low molecular weight sulfur containing compounds from a gas feedstream, preferably a natural gas feedstream, comprising low molecular weight sulfur containing compounds and optionally one or more impurity.
  • a gas feedstream preferably a natural gas feedstream
  • the mechanism by which the macroporous polymeric adsorbent extracts the low molecular weight sulfur containing compounds from the natural gas stream is a combination of adsorption and absorption; the dominating mechanism at least is believed to be adsorption. Accordingly, the terms "adsorption” and "adsorbent" are used throughout this specification, although this is done primarily for convenience. The invention is not considered to be limited to any particular mechanism.
  • Loaded includes a range of adsorbance from a low level of low molecular weight sulfur containing compounds up to and including saturation with adsorbed low molecular weight sulfur containing compounds.
  • Macroporous is used in the art interchangeably with “macroreticular” and refers in general to pores with diameters of about 500 A or greater.
  • Porous is characterized as pores of between 50 A and larger but less than 500 A.
  • Micropores are characterized as pores of less than 50 A. The engineered distribution of these types of pores gives rise to the desired properties of high adsorption capacity for low molecular weight sulfur containing compounds and ease of desorption of low molecular weight sulfur containing compounds under convenient/practical chemical engineering process modifications (increase in temperature or reduced pressure [vacuum]).
  • micropores, mesopores and macropores can be achieved in various ways, including forming the polymer in the presence of an inert diluent or other porogen to cause phase separation and formation of micropores by post cross-linking.
  • the adsorbent media of the present invention is a macroporous polymeric adsorbent of the present invention is a post cross-linked polymeric synthetic adsorbents engineered to have high surface area, high pore volume and high adsorption capacities as well as an engineered distribution of macropores, mesopores and micropores.
  • the macroporous polymeric adsorbent of the present invention is hypercrosslinked and/or methylene bridged having the following characteristics: a BET surface area of equal to or greater than 500 m 2 /g and preferably equal to or greater than 1,000 m 2 /g, and having a particle size of 300 microns to 1500 microns, preferably 500 to 1200 microns.
  • Examples of monomers that can be polymerized to form macroporous polymeric adsorbents useful are styrene, alkylstyrenes, halostyrenes, haloalkylstyrenes, vinylphenols, vinylbenzyl alcohols, vinylbenzyl halides, and vinylnaphthalenes. Included among the substituted styrenes are ortho-, meta-, and para-substituted compounds.
  • styrene vinyltoluene, ethylstyrene, t-butylstyrene, and vinyl benzyl chloride, including ortho-, meta-, and para-isomers of any such monomer whose molecular structure permits this type of isomerization.
  • monomers are polyfunctional compounds.
  • One preferred class is polyvinylidene compounds, examples of which are divinylbenzene, trivinylbenzene, ethylene glycol dimethacrylate, divinylsulfide and divinylpyridine.
  • Preferred polyvinylidene compounds are di- and tri vinyl aromatic compounds.
  • Polyfunctional compounds can also be used as crosslinkers for the monomers of the first group.
  • the macroporous polymeric adsorbent comprises
  • divinylbenzene wherein the divinylbenzene may comprise ethyl styrene. If ethyl styrene is present, preferably it is present in an amount of equal to or less than 40 percent, more preferably equal to or less than 20 percent.
  • One preferred method of preparing the polymeric adsorbent is by swelling the polymer with a swelling agent, then crosslinking the polymer in the swollen state, either as the sole crosslinking reaction or as in addition to crosslinking performed prior to swelling.
  • a swelling agent any pre-swelling crosslinking reaction will be performed with sufficient crosslinker to cause the polymer to swell when contacted with the swelling agent rather than to dissolve in the agent.
  • the degree of crosslinking regardless of the stage at which it is performed, will also affect the porosity of the polymer, and can be varied to achieve a particular porosity. Given these variations, the proportion of crosslinker can vary widely, and the invention is not restricted to particular ranges.
  • the crosslinker can range from about 0.25% of the polymer to about 45%. Best results are generally obtained with about 0.75% to about 8% crosslinker relative to the polymer, the remaining (noncrosslinking) monomer constituting from about 92% to about 99.25% (all percentages are by weight).
  • macroporous polymeric adsorbents useful in the practice of this invention are copolymers of one or more monoaromatic monomers with one or more nonaromatic monovinylidene monomers. Examples of the latter are methyl acrylate, methyl methacrylate and methylethyl acrylate. When present, these nonaromatic monomers preferably constitute less than about 30% by weight of the copolymer.
  • the macroporous polymeric adsorbent is prepared by conventional techniques, examples of which are disclosed in various United States patents. Examples are USP 4,297,220; 4,382,124; 4,564,644; 5,079,274; 5,288,307; 4,950,332; and 4,965,083. The disclosures of each of these patents are incorporated herein by reference in their entirety.
  • the crosslinking subsequent to swelling can be achieved in a variety of ways, which are further disclosed in the patents cited above.
  • One method is to first haloalkylate the polymer, then swell it and crosslink by reacting the haloalkyl moieties with aromatic groups on neighboring chains to form an alkyl bridge.
  • Haloalkylation is achieved by conventional means, an example of which is to first swell the polymer under non-reactive conditions with the haloalkylating agent while including a Friedel-Crafts catalyst dissolved in the haloalkylating agent.
  • haloalkylating agents are chloromethyl methyl ether, bromomethyl methyl ether, and a mixture of formaldehyde and hydrochloric acid.
  • the polymer is swelled further by contact with an inert swelling agent. Examples are dichloroethane, chlorobenzene, dichlorobenzene, ethylene dichloride, methylene chloride, propylene dichloride, and nitrobenzene.
  • a Friedel-Crafts catalyst can be dissolved in the swelling agent as well, since the catalyst will be used in the subsequent crosslinking reaction.
  • the temperature is then raised to a level ranging from about 60°C to about 85°C in the presence of the catalyst, and the bridging reaction proceeds. Once the bridging reaction is complete, the swelling agent is removed by solvent extraction, washing, drying, or a combination of these procedures.
  • the pore size distribution and related properties of the finished adsorbent can vary widely and no particular ranges are critical to the invention. In most applications, best results will be obtained at a porosity (total pore volume) within the range of from about 0.5 to about 1.5 cc/g of the polymer. A preferred range is about 0.7 to about 1.3 cc/g. Within these ranges, the amount contributed by macropores (i.e., pores having diameters of 500 A or greater) will preferably range from about 0.025 to about 0.6 cc/g, and most preferably from about 0.04 to about 0.5 cc/g.
  • the surface area of the polymer as measured by nitrogen adsorption methods such as the well-known BET method, will in most applications be within the range of about 150 to about 2100 m 2 /g, and preferably from about 400 to about 1400 m 2 /g.
  • the average pore diameter will most often range from about 10 A to about 100 A.
  • the form of the macroporous polymeric adsorbent is likewise not critical and can be any form which is capable of containment and contact with a flowing compressed air stream.
  • Granular particles and beads are preferred, ranging in size from about 50 to about 5,000 microns, with a range of about 500 to about 3,000 microns particularly preferred.
  • Contact with the adsorbent can be achieved by conventional flow configurations of the gas, such as those typically used in fluidized beds or packed beds.
  • the adsorbent can also be enclosed in a cartridge for easy removal and replacement and a more controlled gas flow path such as radial flow.
  • the macroporous polymeric adsorbent can function effectively under a wide range of operating conditions.
  • the temperature will preferably be within any range which does not cause further condensation of vapors or any change in physical or chemical form of the adsorbent.
  • Preferred operating temperatures are within the range of from 5°C to 75 °C, and most preferably from 10°C to 50°C. In general, operation at ambient temperature or between ambient temperature and 10°C to 15°C above ambient will provide satisfactory results.
  • the pressure of the gas feedstream entering the adsorbent bed can vary widely as well, preferably extending from 2 psig (115 kPa) to 1000 psig (7000 kPa). The pressure will generally be dictated by the plant unit where the product gas will be used.
  • a typical pressure range is from 100 psig (795 kPa) to 300 psig (2170 kPa).
  • the minimum residence time of the gas feedstream in the adsorbent bed will be 0.02 second and a longer residence time is recommended.
  • the space velocity of the gas feedstream through the bed will most often fall within the range of 0.1 foot per second to 5 feet per second, with a range of 0.3 foot per second to 3 feet per second preferred.
  • the relative humidity can have any value up to 100%, although a lower relative humidity is preferred.
  • crosslinked macroporous polymeric adsorbents of the present invention described herein above can be used to selectively adsorb low molecular weight sulfur containing compounds from a gas feedstream, preferably natural gas, comprising low molecular weight sulfur containing compounds.
  • the separation process of the present invention comprises passing a gas feedstream comprising low molecular weight sulfur containing compounds through an adsorber bed charged with the adsorbent(s) of the invention.
  • the low molecular weight sulfur containing compounds are adsorbed, can be readily desorbed either by increasing the temperature of the adsorber bed or more preferably by lowering the pressure resulting in a regenerated adsorbent.
  • adsorbent bed(s) there may be multiple adsorbent beds and/or the adsorbent bed(s) may be regenerated in-place as exemplified by USP 3,458,973; 5,840,099; 8,574,348, which are incorporated herein by reference in their entirety.
  • the adsorption step and/or the regeneration step of the process of the present invention may operate in as a batch process, a semi-continuous process, a continuous process, or combination thereof.
  • both the adsorption step and the regeneration step may operate in the batch mode.
  • both the adsorption step and the regeneration step may operate in the semi-continuous mode.
  • both the adsorption step and the regeneration step may operate in the continuous mode.
  • the adsorption step may operate in a batch, semi-continuous, or continuous mode while the regeneration step operates in a different mode than that of the adsorption step.
  • the adsorption step may operate in a batch mode while the regeneration step operates in a continuous mode.
  • the adsorption step may operate in a continuous mode while the regeneration step operates in a continuous mode. All possible combinations of batch, semi-continuous, and continuous modes for the adsorbent step and regeneration step are considered within the scope of the present invention.
  • Adsorption is in many situations a reversible process.
  • the practice of removing volatiles from an adsorption media can be accomplished by reducing the pressure over the media, heating, or the combination of reduced pressure and heating. In either case the desired outcome is to re -volatilize the trapped vapors, and subsequently remove them from the adsorbent so that it can be reused to capture additional volatiles.
  • the adsorption media of the present invention when regenerated, desorbs adsorbed gases in an amount equal to or greater than 75 percent of the amount adsorbed, more preferably equal to or greater than 85 percent, more preferably equal to or greater than 90 percent, more preferably equal to or greater than 95 percent, more preferably equal to or greater than 99 percent and most preferably virtually all the low molecular weight sulfur containing compounds adsorbed.
  • the separation process comprises passing a gas feedstream through an adsorber bed charged with the adsorbent(s) of the invention.
  • the low molecular weight sulfur containing compounds that are adsorbed can be readily desorbed either by lowering the pressure or by increasing the temperature of the adsorber bed resulting in a regenerated adsorbent.
  • the adsorbent so regenerated can be reused as an adsorbent for the separation of additional low molecular weight sulfur containing compounds from the same or different gas feedstream.
  • the low molecular weight sulfur containing compounds adsorption/desorption separation process of the present invention is performed within a pressure swing adsorption (PSA) vessel containing an adsorbent material comprising one or more porous cross-linked polymeric adsorbents and is followed by an adsorbent regeneration sequence comprising the steps of depressurizing/venting the adsorption vessel down to low pressure followed by repressurizing the adsorbent-containing vessel with a gas stream, preferably a portion of the purified gas feedstream back to the pressure level at which the gas feedstream was initially contacted with the adsorbent.
  • PSA pressure swing adsorption
  • the depressurization is partly performed via one or more pressure equalization steps with other PSA vessels undergoing said repressurizing.
  • the depressurizing is performed down to vacuum pressure levels by connecting the adsorption vessel to a vacuum pump (i.e. vacuum swing adsorption or VSA).
  • a vacuum pump i.e. vacuum swing adsorption or VSA.
  • the adsorbent is purged or rinsed with a portion of the purified gas feedstream subsequent to said depressurization step and prior to said repressurization step.
  • the purge step is performed at 1 atm pressure. By lowering the purge pressure to 0.1 atm, one can obtain the same degree of purging with about 10% of the gas required at 1 atm Thus the recovery penalty associated with purging is much less severe in a VSA process as opposed to a PSA process.
  • the steps of the process are performed as a continually repeating cycle of steps in a system comprising a plurality of adsorption vessels which each undergo their respective cycle of steps while collectively operated sequentially in parallel with one another.
  • the cycle time depends on the specific design but typically might be one minute per step.
  • the low molecular weight sulfur containing compounds adsorption/desorption separation process of the present invention is performed within a temperature swing adsorption (TSA) vessel containing an adsorbent material comprising one or more porous cross-linked polymeric adsorbents.
  • TSA temperature swing adsorption
  • This is a batch-wise process consisting of two basic steps which are adsorption and regeneration.
  • the adsorption step low molecular weight sulfur containing compounds are removed by being adsorbed on the adsorbent material forming a low molecular weight sulfur containing compounds lean stream.
  • the regeneration step low molecular weight sulfur containing compounds are desorbed from the adsorbent material by means of a regeneration gas.
  • any inert or easily separated gas can be used as a regeneration gas.
  • using the heated product gas can improve regeneration, for example, heating the regeneration gas to 150°C and then flowing it through the desorption chamber will heat the adsorbent media, which will cause much of the adsorbed low molecular weight sulfur containing compounds to evaporate. Keeping the desorbed gas purity high can dictate the choice of the regeneration gas.
  • the regeneration gas is a heated split stream from the desorbed gas with the only change being the temperature of the regeneration gas.
  • the regeneration step consists of two major parts: heating and cooling.
  • the heating part of the process the regeneration stream is heated to an elevated temperature (preferably between 70°C to 150°C) in one embodiment of the invention) and flows over the adsorbent material. Due to the heat of the gas, mainly used as heat of desorption, and the difference in partial pressure of the contaminants on the adsorbent material and in the regeneration gas stream, the low molecular weight sulfur containing compounds desorb from the adsorbent material and leave the unit with the regeneration gas. A cooling step is then necessary. As a result of the heating step the adsorbent material heats up.
  • the adsorbent material is cooled by means of a stream typically flowing over the adsorbent material at a temperature very close to the feed stream temperature.
  • the most basic form of a temperature swing adsorbent process unit consists of two vessels with one vessel in adsorption mode and the other vessel in regeneration mode.
  • several vessels which operate in a parallel mode, can be used.
  • the regeneration step can also be split over two vessels in a series-heat-and-cool cycle, where one of the vessels would be in the heating step and another would be in the cooling step.
  • additional steps may need to be included dependent on the pressure levels of the gas feedstream versus the regenerant stream. For instance, if adsorption is carried out at a higher pressure than regeneration (note that a lower pressure will favor desorption of contaminants from the adsorbent material), at a minimum, two additional steps are required: a depressurization step where the pressure is reduced from adsorption pressure to the regeneration pressure; and a repressurization where the pressure is increased from the regeneration pressure to adsorption pressure. Note that sometimes the opposite is true, with regeneration carried out at a higher pressure than adsorption, but in this case again a depressurization and repressurization step need to be included. If depressurization and repressurization steps are present they are typically part of the regeneration cycle.
  • the present invention is a process for separating low molecular weight sulfur containing compounds from a gas feedstream, preferably natural gas feedstream comprising methane and one or more of ethane, propane, butane, pentane, or heavier hydrocarbons, comprising the steps of: (a) providing an adsorbent bed comprising an adsorbent media comprising a porous cross-linked polymeric adsorbent, wherein said adsorbent media adsorbs low molecular weight sulfur containing compounds; (b) passing the gas feedstream through the adsorbent bed to provide a low molecular weight sulfur containing compounds lean gas feedstream and a loaded adsorbent media; (c) recovering, transporting, liquefying, or flaring the low molecular weight sulfur containing compounds lean gas feedstream, (d) regenerating the loaded adsorbent media to release the adsorbed low molecular weight sulfur containing compounds, (e) reusing the regenerated adsorb
  • the regeneration of the loaded adsorbent media is achieved by not using a heating step.
  • the steps of the process described herein above are performed as a continually repeating cycle of steps in a system comprising a plurality of adsorption vessels which each undergo their respective cycle of steps while collectively operated sequentially in parallel with one another.
  • the adsorbent media can be stationary within the adsorption/desorption system and/or the adsorbent media can be continuously moved between chambers.
  • the process further comprises a step in which feedback is provided such that the adsorption time can be quickly and easily adjusted, either manually or automatically, to control the contact time of the gas feedstream with the adsorbent media.
  • the contact time may be varied by changing the flow rate of the gas feedstream and/or the rate of the adsorbent (e.g., the speed of a moving bed).
  • Such a feedback mechanism is applicable to any suitable adsorption/desorption process, preferably to a PSA process or TSA process.
  • the regeneration system for use in the process of the present invention is able to operate in a batch, semi-continuous, or continuous process.
  • Example 1 is an adsorbent media comprising a porous cross-linked polymeric adsorbent having a high surface area equal to or greater than 1,000 m 2 /g made from a macroporous copolymer of a monovinyl aromatic monomer and a crosslinking monomer, where the macroporous copolymer has been post-crosslinked in the swollen state in the presence of a Friedel-Crafts catalyst.
  • Example 1 is dried in an oven at 70°C overnight.
  • the dried adsorbent is loaded in a 3/8 inch by 8.0 inch stainless steel column and exposed to a gas stream containing about 920 ppm mercaptan in nitrogen with a flow rate of 500 scc/min at atmospheric pressure and 25°C.
  • the mercaptan breakthrough is monitored using an Agilent 490 Micro GC equipped with an Agilent Porabond Q column. The adsorption is stopped until full breakthrough and the materials are regenerated by nitrogen purging through. Multiple cycles are repeated and the materials tested could be fully regenerated determined by essentially identical breakthrough time.
  • the breakthrough curve of the methyl mercaptan is shown in FIG. 1.
  • the carbon disulfide breakthrough for Example 1 is determined as follows:
  • Example 1 is dried in an oven at 70°C overnight.
  • the dried Example 1 is loaded in a 3/8 inch by 2.5 inch stainless steel column and exposed to a gas stream containing 1000 ppm carbon disulfide in nitrogen with a flow rate of 1000 scc/min and back pressure of 300 psig at 25°C.
  • the carbon disulfide breakthrough is monitored using an Agilent 490 Micro GC equipped with an Agilent Porabond Q column. The adsorption is stopped until full breakthrough and the materials are regenerated by nitrogen purging through. Multiple cycles are repeated and the materials tested could be fully regenerated determined by essentially identical breakthrough time.
  • the breakthrough curve of the carbon disulfide is shown in FIG. 2.
  • Example 1 The carbonyl sulfide breakthrough for Example 1 is determined as follows:
  • Example 1 is dried in an oven at 70°C overnight. Dried Example 1 is loaded in a 3/8 inch by 8 inch stainless steel column and exposed to a gas stream containing 920 ppm carbonyl sulfide in nitrogen with a flow rate of 500 scc/min and back pressure of 300 psig at 25°C. The carbon disulfide breakthrough is monitored using an Agilent 490 Micro GC equipped with an Agilent Porabond Q column. The adsorption is stopped until full breakthrough and the materials are regenerated by nitrogen purging through. Multiple cycles are repeated and the materials tested could be fully regenerated determined by essentially identical breakthrough time. The breakthrough curve of the carbonyl sulfide is shown in FIG. 3.

Abstract

L'invention concerne un procédé d'élimination de composés contenant du soufre en faible poids moléculaire à partir d'un flux d'alimentation en gaz, de préférence un flux d'alimentation en gaz naturel. Le procédé consiste à faire passer un flux d'alimentation de gaz comprenant des composés contenant du soufre en faible poids moléculaire à travers un milieu adsorbant régénérable qui adsorbe des composés contenant du soufre en faible poids moléculaire pour fournir un produit gazeux pauvre en composés contenant du soufre en faible poids moléculaire et un milieu adsorbant riche en composés contenant du soufre en faible poids moléculaire. Le milieu adsorbant régénérable de la présente invention est un milieu adsorbant polymérique macroporeux réticulé.
PCT/US2018/043466 2017-08-11 2018-07-24 Procédé d'élimination de composés soufrés à partir d'un flux gazeux WO2019032283A1 (fr)

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