WO2019006045A1 - Compositions et procédés de séparation membranaire de gaz acide à partir de gaz hydrocarboné - Google Patents

Compositions et procédés de séparation membranaire de gaz acide à partir de gaz hydrocarboné Download PDF

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WO2019006045A1
WO2019006045A1 PCT/US2018/039877 US2018039877W WO2019006045A1 WO 2019006045 A1 WO2019006045 A1 WO 2019006045A1 US 2018039877 W US2018039877 W US 2018039877W WO 2019006045 A1 WO2019006045 A1 WO 2019006045A1
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Prior art keywords
membrane
pim
mol
gas
hydrogen sulfide
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PCT/US2018/039877
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English (en)
Inventor
Shouliang Yi
William J. Koros
Ingo Pinnau
Bader Ghanem
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Georgia Tech Research Corporation
King Abdullah University Of Science And Technology
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Publication of WO2019006045A1 publication Critical patent/WO2019006045A1/fr

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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
    • B01D53/22—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 diffusion
    • B01D53/228—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 diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/05—Biogas
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L2290/548—Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates generally to membrane separation of gases. More particularly, the present invention relates to membrane separation of acid gases, including hydrogen sulfide.
  • Hydrogen sulfide is a flammable, highly toxic gas that causes nearly instant death when its concentrations are over 1000 parts per million (ppm). Even 5 ppm levels cause eyes, nose, and throat irritation.
  • H2S Hydrogen sulfide
  • Raw natural gas contains many impurities but H2S and carbon dioxide (CO2) are arguably the two most important to remove after primary dehydration.
  • CO2 carbon dioxide
  • Over 40% of proven raw natural gas reserves in the United States are termed "sour,” which means the gas contains H2S in amounts of about 4 ppm or more measured at standard temperature and pressure. In certain areas in the Middle East (e.g.
  • membranes are required having good intrinsic stability and attractive CO2 and H2S selectivities relative to CH 4 under aggressive feed conditions of 20 bar or more.
  • the hydrocarbon-based feedstock can further include carbon dioxide, and when it does, the permeate stream comprises carbon dioxide, and the retentate stream is depleted in carbon dioxide as compared to the hydrocarbon-based feedstock.
  • the retentate stream comprises carbon dioxide in an amount of less than 90 mol %.
  • the retentate stream comprises carbon dioxide in an amount of less than 10 mol %.
  • the retentate stream comprises carbon dioxide in an amount of less than 2 mol %.
  • the membrane can include an integrally- skinned asymmetric structure in flat sheet geometry.
  • the membrane can include a composite structure in flat sheet geometry.
  • the membrane can include an integrally-skinned asymmetric structure in hollow fiber geometry.
  • the membrane can include a composite structure in hollow fiber geometry.
  • the membrane can further include a hydrogen sulfide/methane selectivity of greater than about 40 at a pressure of 30 bar and a gas feed of 20 mol% H 2 S, 20 mol % C0 2 , 60 mol % CH 4 .
  • the membrane can include a hydrogen sulfide/methane selectivity of greater than about 60 at a pressure of up to 77 and a gas feed of 20 mol% H 2 S, 20 mol % C0 2 , 60 mol % CH 4 .
  • FIG. 1 A is a graph of C02/CH 4 selectivity vs. CO2 permeability (Barrer) at 35 °C and compares membranes according to embodiments disclosed herein with various known membranes.
  • FIG. 1 B is a graph of hbS/ChU selectivity vs. H2S permeability (Barrer) at 35 °C and compares membranes according to embodiments disclosed herein with various known membranes.
  • FIG. 2B is graph of H2S pure gas permeation isotherms at 35 °C for polymer membranes according to embodiments disclosed herein.
  • FIG. 3B is a graph of H2S permeability (Barrer) as a function of mixed gas feed pressure (bar) at 35 °C for a feed gas of 20 mol. % H 2 S, 20 mol. % C0 2 , and 60 mol. % CH 4 for polymer membranes according to embodiments disclosed herein and one known polymer membrane.
  • FIG. 4A is a graph of C0 2 /CH 4 selectivity as a function of mixed gas feed pressure (bar) at 35 °C for a feed gas of 20 mol. % H 2 S, 20 mol. % C0 2 , and 60 mol. % CH 4 for polymer membranes according to embodiments disclosed herein and one known polymer membrane.
  • FIG. 4B is a graph of H 2 S/CH 4 selectivity as a function of mixed gas feed pressure (bar) at 35 °C for a feed gas of 20 mol. % H 2 S, 20 mol. % C0 2 , and 60 mol. % CH 4 for polymer membranes according to embodiments disclosed herein and one known polymer membrane.
  • FIG. 5B is a graph of combined acid gas selectivity as a function of mixed gas feed pressure (bar) at 35 °C for a feed gas of 20 mol. % H 2 S, 20 mol. % C0 2 , and 60 mol. % CH 4 for polymer membranes according to embodiments disclosed herein and one known polymer membrane.
  • FIG. 6 is a graph of C0 2 and H 2 S permeabililty and C0 2 /CH 4 and H 2 S/CH 4 selectivity at 35 °C as a function of operating time for polymer membranes according to embodiments disclosed herein.
  • FIG. 7B is a graph of H 2 S/CH 4 selectivity as a function of H 2 S partial pressure at 35 °C and compares membranes according to embodiments disclosed herein with various known membranes.
  • a method for separating at least one acid gas from a mixture of gases includes contacting a hydrocarbon-based feedstock including an acid gas and a hydrocarbon gas with a membrane comprising a polymer of intrinsic microporosity (PIM) or an amidoxime-functionalized polymer of intrinsic microporosity (AO-PI M), wherein the membrane separates the hydrocarbon-based feedstock into a permeate stream that comprises at least some of the acid gas and a retentate stream that is depleted in the acid gas as compared to the hydrocarbon-based feedstock.
  • the acid gas includes hydrogen sulfide, carbon dioxide, or a combination thereof.
  • Microporous organic polymers as a group have well-defined pore structures, strong covalent bonds, and potential for use in membrane-based separation methods. But MOPs demonstrate insufficient selectivity for certain gas separations.
  • a certain group of MOPs known as polymers of intrinsic microporosity (PI Ms) have rigid and contorted backbone structures and interconnected voids.
  • PI Ms have a high Brunauer-Emmett-Teller (BET) surface area and a pore size of less than 2 nm, which allows these polymers to behave like molecular sieves.
  • BET Brunauer-Emmett-Teller
  • PIMs include polymers and copolymers of triptycene, Troger's base, ethanoanthranene, phthalocyanines, spirobisindanes, and benzidioxanes.
  • PIMs are attractive materials for membrane separations because they are solution processable and have structural diversity for gas molecules with different sizes and shapes. They also show high gas permeability, and moderate selectivity based on differences in size of diverse gases where the size difference is at least 0.5 A; however, the H 2 S/CH 4 gas pair only differs by about 0.2 A in size.
  • AO-PI Ms described herein include amidoxime-functionalized polymers and/or copolymers derived from triptycene, Troger's base, ethanoanthranene, a phthalocyanine, a spirobisindanes, or a benzidioxane.
  • an AO-PIM described herein is an amidoxime-functionalized spirobisindane-based PIM, such as AO-PI M-1 .
  • AO-PI M is an amidoxime-functionalized Troger's base-based PIM (AO-TB-PIM).
  • AO-TB-PIM amidoxime-functionalized Troger's base-based PIM
  • one exemplary AO-TB-PIM has the structure shown below.
  • an AO-PIM described herein can be formed by synthesizing a parent polymer of intrinsic microporosity and then functionalizing the parent polymer with amidoxime to form the AO-PIM.
  • AO- PI Ms can be prepared in a variety of ways known to one skilled in the art of organic synthesis or variations thereon as appreciated by those skilled in the art.
  • the AO-PI Ms can be prepared from readily available starting materials, and optimum reaction conditions may vary with the particular reactants or solvents used, but such conditions can be determined by one skilled in the art.
  • AO-PIM's described herein can be used to form membranes for selectively separating H 2 S gas.
  • membranes can be formed by dissolving an AO- PIM in an appropriate solvent, pouring a thin layer of the solution onto a smooth level surface or dipping a support such as a porous hollow fiber into a solution of the functionalized PIM and evaporating the solvent to form a vitrified film.
  • concentration of the AO-PI M solution is not critical and in some examples may be from 1 to 50 wt % AO-PI M.
  • Any solvent that can dissolve the AO-PIM may be used.
  • the solvent may be dimethylformamide, dimethylacetamide, or N- methylpyrrolidone.
  • the membrane can have an integrally-skinned asymmetric structure in a hollow fiber geometry or a composite structure in a hollow fiber geometry.
  • a membrane having a flat sheet geometry can be formed as described above.
  • a membrane having a hollow fiber geometry can be formed by extruding a polymer dope through a spinneret, as is known in the art.
  • the dope can be a solution of the AO-PIM polymer, similar to that described above for forming a vitrified film.
  • the membranes described herein have hydrogen sulfide gas permeabilities and selectivities significantly higher than any other material known for such separations.
  • the membranes have hydrogen sulfide permeabilities of at least 500 Barrer (e.g., at least 1000 Barrer, at least 3000 Barrer, or at least 4000 Barrer).
  • a method for separating an acid gas from a mixture of gases includes contacting a mixture of gases including an acid gas with a membrane, wherein the membrane comprises a hydrogen sulfide permeability of at least 500 Barrer, and wherein the membrane separates the mixture of gases into a permeate stream that comprises at least some of the acid gas and a retentate stream that is depleted in the acid gas as compared to the mixture of gases.
  • the acid gas includes hydrogen sulfide, carbon dioxide, or a combination thereof.
  • the mixture of gases further includes a hydrocarbon gas, nitrogen, oxygen, or a mixture thereof.
  • Permeability and selectivity are intrinsic material properties used to characterize membrane material productivity and separation efficiency, respectively.
  • the permeability (Pi) of penetrant i can be defined as the steady-state flux ( ) normalized by transmembrane pressure differential ( ⁇ ;) and thickness of the membrane (/),
  • the sorption coefficient S (cm 3 (STP)/cm 3 cmHg) can be deduced from the sorption-diffusion model.
  • the ideal selectivity (c3 ⁇ 4/j) is defined as the ratio of gas permeabilities for the fast gas (/) and slow gas (/),
  • Eq. 4 allows the ideal selectivity of a membrane to be decoupled into the product of mobility selectivity ( ⁇ 3 ⁇ 4) and the solubility selectivity (as).
  • a separation factor based on gas chromatographic measurement of upstream and downstream compositions indicate the membrane separation efficiency.
  • the separation factor equals to the ratio of the component mole fractions in the downstream direction, y, and upstream direction, x,
  • the separation factor equals the ratio of the mixed gas permeabilities of components / and /, based on the fugacity-based driving force of permeability is preferred
  • the permeabilities and selectivities of AO-PI M membranes were measured using fresh AO-PIM-1 membranes, aged AO-PI M-1 membranes (ambient conditions, 6 months), and rejuvenated AO-PIM-1 membranes (aged membranes soaked in methanol then hexane and dried).
  • the aged film has much lower H2S and CO2 permeabilities than the freshly cast membrane, but the rejuvenated sample exhibits H2S and CO2 permeabilities similar to those of freshly cast film.
  • the rejuvenated sample shows slightly lower H2S/CH4 and CO2/CH 4 ideal permselectivities due to a somewhat higher CH 4 permeability than in the fresh membrane. In any case, these results show that the decreased productivity in the aged AO-PIM-1 films can be significantly rejuvenated through a simple solvent treatment.
  • the membranes described herein have significantly higher permeabilities and selectivities for H2S and CO2 than membranes made from other known materials. It is known that a tradeoff exists between permeability and selectivity, where membranes having high selectivity tend to have low permeability, and vice versa.
  • the Robeson limit is an upper bound that represents the general trend in the tradeoff between permeability and selectivity for a given gas over a range of materials. While the Robeson limit is not fixed and has evolved as materials having improved properties have been developed, it is a good measure of the current state of the art.
  • FIGs. 1 A-B are pure gas permeability-selectivity trade-off curves that compare the fresh, aged, and rejuvenated AO-PIM-1 membranes with membranes made from typical glassy polymers, including cellulose acetate (C. S. K. Achoundong et ai, Silane modification of cellulose acetate dense films as materials for acid gas removal. Macro molecules 46, 5584-5594 (2013)); 6FDA-based polyimides 6 FDA- DAM :DABA 3:2 (B. Kraftschik, et ai, Dense film polyimide membranes for aggressive sour gas feed separations. J. Membr. Sci.
  • 6FDA- mPDA:6FDA-durene G. O. Yahaya, et ai , Aromatic block co-polyimide membranes for sour gas feed separations. Chem. Eng. J. 304, 1020-1030 (2016)); crosslinkable polyimide PEGMC (B. Kraftschik, W. J. Koros, Cross-linkable polyimide membranes for improved plasticization resistance and permselectivity in sour gas separations. Macro molecules 46, 6908-6921 (2013)); fluorinated polyamide-imide 6F-PAI (J. T. Vaughn, W. J.
  • FIG. 1 A also includes the published 1991 and 2008 Robeson upper bound plots for state of the art polymer membranes for CO2 separations. (L. M. Robeson, Correlation of separation factor versus permeability for polymeric membranes. J. Membr. Sci.
  • FIG. 1 B includes a solid line showing the experimental hbS/ChU upper bound between H2S permeability and hbS/ChU selectivity in typical glassy polymers. H2S permeability was measured at 1 bar feed pressure and 35 °C to avoid plasticization effects.
  • the AO-PI M membranes described herein are significantly more permeable than conventional hydroxyl functionalized polyimides, such as PIM-6FDA-OH, for which data is included in FIGs. 1A-B.
  • the amidoxime-functionalized polymers described herein offer extensive interchain and intrachain hydrogen bonding, which contributes to the tight microstructure of AO-PIMs and a balance between intrachain rigidity and intrachain spacing. This balance in properties produces the exceptional CO2 separation performance of AO-PIM-1 , which surpass the most recent 2008 Robeson upper bound of state-of-the-art polymer membranes for the C02/CH 4 separations.
  • FIG. 2A shows the onset of C02-induced plasticization around 14 bar with a CO2 permeability of about 1 100 Barrer for fresh, aged, and rejuvenated AO-PIM-1 membranes.
  • a membrane of PEGMC which is a PEG crosslinked derivative of the PI M-6 FDA-DAM : DABA, showed negligible plasticization up to 20 bar pure CO2, but the CO2 permeability was significantly lower at only 70-80 Barrer.
  • the AO- PIM-1 film After aging under ambient conditions for six months while not in use, the AO- PIM-1 film showed a drop of about 80% in diffusion coefficients for all three gases as compared with the freshly cast sample and a drop of from about 50 % to 70 % in sorption coefficients compared with the freshly cast sample.
  • the AO-PIM-1 aging response is quite different from the aging phenomena of its parent PIM-1 and other PI Ms, where the aging process is dominated by a decrease in diffusion coefficients.
  • the combined drop in both diffusion and sorption coefficients upon aging for six months under ambient conditions leads to a dramatic AO-PIM-1 permeability loss of nearly 90% relative to the freshly cast sample.
  • the rejuvenation process led to recovery and even increased diffusion coefficients while the sorption coefficients remained slightly lower in comparison with the freshly made membrane.
  • the rejuvenated AO-PIM-1 film exhibits slightly higher gas permeabilities and lower C02/CH 4 and H2S/CH4 selectivities than that in the freshly cast sample.
  • the aged sample shows higher C02/CH 4 diffusion selectivity in comparison with the freshly cast and rejuvenated films and also their parent PIM-1 .
  • such a trend may reflect generalized tightening of the AO-PIM-1 during aging.
  • the diffusion and sorption coefficients of CO2 and CH 4 for the AO-PIM-1 film are about 50 % to 60 % less than those in the parent PIM-1 .
  • the freshly-cast AO-PIM-1 film showed a remarkable increase in diffusion selectivity over the PIM-1 film. This increase in diffusion selectivity occurred simultaneously with a slight reduction in the solubility selectivity relative to the parent PIM-1 membrane.
  • a tightened structure in AO-PIM-1 may contribute to the enhanced C02/CH 4 diffusion-based discrimination over the parent PIM-1 material.
  • H2S diffusion coefficients of H2S are always smaller than that of CH 4 in all the freshly made, aged, and rejuvenated AO-PIM-1 films. This trend may seem surprising, given the smaller kinetic diameter of H2S (3.6 A) compared to CH 4 (3.8 A). This trend reflects strong hydrogen bonding of the highly polar H2S with amine and hydroxyl groups in the amidoxime moieties in AO-PIM-1 . Such a trend may lead to a lower diffusion coefficient resulting from the tendency of H2S molecules to "stick" to the sorption sites. This so called "stickiness" of H2S within the polymer matrix can lead to a higher activation energy of diffusion of H2S than expected. Based on these observations, the overall hbS/ChU selectivity of AO-PIM films is mainly contributed by the sorption selectivity, whereas C02/CH 4 selectivity is controlled by both factors, even though the diffusion selectivity is dominant.
  • FIG. 3A shows CO2 penetrant-induced plasticization did not occur below 42 bar for freshly cast AO-PI M-1 films, but occurred at about 30 bar for the aged and rejuvenated AO-PIM-1 membranes.
  • FIG. 3B shows strong hbS-induced plasticization effects were observed in the AO-PI M-1 membranes, even under the lowest feed pressure tested. H2S permeabilities were much higher than that of CO2 under the same feed pressures, suggesting that H2S in the mixed gas feeds competes more effectively than CO2 in the polymer matrix. More importantly, the hbS/ChU selectivity in all the freshly cast, aged, and rejuvenated AO-PI M-1 films does not decrease due to plasticization effects as does C02/CH 4 selectivity, as shown by FIGs. 4A-B.
  • FIG. 7A compares the overall separation performance of the AO- PI M membranes described herein, and the literature data listed in Table 2 via a combined acid gas productivity-efficiency trade-off plot.
  • FIG. 7B compares the H2S separation performance of AO-PI M membranes described herein with other polymers.
  • FIGs. 7A and 7B are PIM- 6FDA-OH, cross-linked DEGMC, cross-linked TEBMC, cellulose acetate, 6 FDA- DAM :DABA (3:2), 6F-PAI-1 ; and 6FDA-mPDA:6FDA-durene.
  • the typical rubbery polymers represented on Table 2 and FIGs. 7A and 7B are Pebax 1074, PU1 , PU2, PU3, and PU4.
  • FIGs. 7A-B proposed upper bound plots for typical glassy polymers and typical rubbery materials to reveal single H2S and combined acid gas (C02+H2S) productivity-efficiency relationships based on the data in the literature. As shown in FIGs.
  • both H2S separation performance and the overall performance of the AO-PI M membranes is located at the far upper right quadrant and well above an upper bound for typical glassy and rubbery polymers.
  • the materials and methods for separating acid gases disclosed herein are significantly better than known materials and methods.
  • DCTB 1 ,4-dicyanotetrafluorobenzene
  • TTSBI 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1 , 1 '-spirobisindane (TTSBI) (98%) was supplied by Alfa Aesar, USA.
  • DMAc ⁇ , ⁇ -Dimethylacetamide (DMAc) (99%), toluene (anhydrous, 99.8%), potassium carbonate (anhydrous, 99.5%), chloroform (99.5%), n-hexane (anhydrous, >99%), methanol (99.5%), tetrahydrofuran (99.8%), and hydroxylamine (50 wt.
  • the amidoxime-functionalized PIM-1 (AO-PI M-1 ) was prepared by dissolving 0.6 g PIM-1 powder in 40 mL tetrahydrofuran (THF) and heating to 65 °C under N 2 . Then 6.0 mL hydroxylamine was added dropwise. The mixture was then refluxed at 69 °C for 20 hrs under stirring. The resultant polymer was then cooled to room temperature and purified by addition of ethanol, filtered, thoroughly washed with ethanol, and dried at 1 10 °C for 3 h to yield AO-PIM-1 as an off-white solid.
  • THF tetrahydrofuran
  • Vacuum dried PIM-1 polymer was dissolved in chloroform to form a 2-3 wt% polymer solution and placed on a roller for at least 24 h for mixing.
  • the polymer solution was then filtered and used to prepare dense films by a solution casting method in a glove bag at room temperature to achieve slow evaporation (3-4 days).
  • the vitrified films were then removed and soaked in methanol, air-dried, and then heated at 120 C in a vacuum oven for 24 h to remove any residual solvent.
  • Vacuum dried AO-PIM-1 polymer was dissolved in DMAc to form a 2-3 % w/v concentration polymer dope. Then the polymer dope was filtered and poured onto a leveled glass plate with a stainless steel ring. The solvent was slowly evaporated at 45 °C for two days to form vitrified films, and the vitrified membranes were soaked in methanol, air-dried, and annealed at 120 °C under high vacuum to remove residual solvent trapped in the micropores.
  • Example 3 Membrane Aging
  • An AO-PIM-1 membrane of Example 2 was aged under ambient conditions (i.e., about 25-30 °C and 1 atm with a relative humidity between about 50 % and 70 %) for six months to form an aged AO-PIM-1 membrane as might be the case for storage before use in an active feed situation.
  • An aged AO-PI M-1 membrane of Example 3 was dried at 120 °C for 12 h, soaked in pure methanol for 24 h and n-hexane for another 24 h, air-dried, and then post-dried at 120 °C under vacuum for 24 h to remove residual solvents, forming a rejuvenated AO-PIM-1 membrane.
  • Dense film permeation was conducted using a constant volume/variable pressure permeation apparatus described in S. Yi, X. Ma, I. Pinnau, W. J. Koros, A high-performance hydroxyl-functionalized polymer of intrinsic microporosity for an environmentally attractive membrane-based approach to decontamination of sour natural gas. J. Mater. Chem. A 3, 22794-22806 (2015).
  • the permeation cell was additionally enclosed in a large ventilated cabinet as a secondary compartment to prevent H2S exposure if a leak was to occur in the system.
  • two pneumatically actuated valves were used in place of standard hand-operated valves and controlled by a Labview® program for additional safety.
  • the downstream actuated valve was programmed to shut down when the downstream pressure reached a certain maximum pressure to avoid over- pressurization that may damage the pressure transducers, and also to prevent unintended release of large quantities of H2S and minimize operator risk when handling H2S.
  • the retentate flow rate and upstream pressure were well maintained with the stage cut at 1 % or below using 1000 D syringe pumps (Teledyne Isco Inc., Lincoln, NE, USA) and a metering valve.
  • the stage cut represents the ratio of permeate to retentate flow.
  • the downstream composition was measured using a Varian 450-GC (Agilent Technologies, USA).
  • the permeate gas composition is tested at least three times, or until the steady state operation is confirmed.
  • Mixed gas permeation values are based on the average of at least three gas chromatograph (GC) permeate composition measurements at each pressure point up to approximately 77 bar.
  • GC gas chromatograph

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Abstract

L'invention concerne des matériaux et des procédés de séparation de sulfure d'hydrogène d'un mélange gazeux à base d'hydrocarbures par mise en contact du mélange gazeux à base d'hydrocarbures avec une membrane formée à partir d'un polymère de microporosité intrinsèque (PIM) ou d'un polymère fonctionnalisé amidoxime de microporosité intrinsèque (AO-PIM). La membrane sépare la charge d'alimentation hydrocarbonée en un courant de perméat qui comprend au moins une partie du sulfure d'hydrogène et un courant de rétentat qui est appauvri en sulfure d'hydrogène par comparaison avec le mélange gazeux à base d'hydrocarbures.
PCT/US2018/039877 2017-06-27 2018-06-27 Compositions et procédés de séparation membranaire de gaz acide à partir de gaz hydrocarboné WO2019006045A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020037246A1 (fr) * 2018-08-17 2020-02-20 The Regents Of The University Of California Polymères orientés par diversité de microporosité intrinsèque et leurs utilisations
CN112851690A (zh) * 2020-12-29 2021-05-28 郑州大学 低分子量自具微孔聚合物、制备方法与超薄有机溶剂纳滤膜及其制备方法
CN113230905A (zh) * 2021-05-12 2021-08-10 天津大学 偕胺肟基团功能化超交联微孔聚合物膜及其制备和应用
CN113413776A (zh) * 2021-06-21 2021-09-21 东华理工大学 一种基于聚偕胺肟为界层的纳滤膜的制备方法
WO2022026241A1 (fr) * 2020-07-31 2022-02-03 Battelle Memorial Institute Sorbant chimique à amine ajoutée
US11318455B2 (en) 2015-04-03 2022-05-03 The Regents Of The University Of California Polymeric materials for electrochemical cells and ion separation processes
CN114515520A (zh) * 2022-03-16 2022-05-20 浙江工业大学 一种高通量高选择性的基于特勒格碱基耐酸纳滤膜及其制备方法
US11394082B2 (en) 2016-09-28 2022-07-19 Sepion Technologies, Inc. Electrochemical cells with ionic sequestration provided by porous separators
US11545724B2 (en) 2016-12-07 2023-01-03 The Regents Of The University Of California Microstructured ion-conducting composites and uses thereof
US20230133081A1 (en) * 2021-10-28 2023-05-04 Saudi Arabian Oil Company Membranes of glassy polymer blends with peg-crosslinked intrinsic microporous polymers for gas separations
EP3983117A4 (fr) * 2019-06-11 2023-06-21 Chevron U.S.A. Inc. Membranes pour l'élimination de contaminants d'un gaz naturel et leurs procédés d'utilisation
WO2024163517A3 (fr) * 2023-01-31 2024-09-19 Massachusetts Institute Of Technology Nanofilms polymères hautement poreux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016092178A1 (fr) * 2014-12-11 2016-06-16 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé et appareil pour séparer un gaz d'alimentation contenant au moins 20% mol. de co2 et au moins 20% mol. de méthane, par condensation partielle et/ou par distillation
US20160220966A1 (en) * 2013-10-11 2016-08-04 Fujifilm Corporation Gas separation membrane and gas separation membrane module
US20160367948A1 (en) * 2014-02-27 2016-12-22 Kyoto University Crosslinked polymer, method for producing the same, molecular sieve composition and material separation membranes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160220966A1 (en) * 2013-10-11 2016-08-04 Fujifilm Corporation Gas separation membrane and gas separation membrane module
US20160367948A1 (en) * 2014-02-27 2016-12-22 Kyoto University Crosslinked polymer, method for producing the same, molecular sieve composition and material separation membranes
WO2016092178A1 (fr) * 2014-12-11 2016-06-16 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé et appareil pour séparer un gaz d'alimentation contenant au moins 20% mol. de co2 et au moins 20% mol. de méthane, par condensation partielle et/ou par distillation

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11318455B2 (en) 2015-04-03 2022-05-03 The Regents Of The University Of California Polymeric materials for electrochemical cells and ion separation processes
US11394082B2 (en) 2016-09-28 2022-07-19 Sepion Technologies, Inc. Electrochemical cells with ionic sequestration provided by porous separators
US11545724B2 (en) 2016-12-07 2023-01-03 The Regents Of The University Of California Microstructured ion-conducting composites and uses thereof
WO2020037246A1 (fr) * 2018-08-17 2020-02-20 The Regents Of The University Of California Polymères orientés par diversité de microporosité intrinsèque et leurs utilisations
US12084544B2 (en) 2018-08-17 2024-09-10 The Regents Of The University Of California Diversity-oriented polymers of intrinsic microporosity and uses thereof
EP3983117A4 (fr) * 2019-06-11 2023-06-21 Chevron U.S.A. Inc. Membranes pour l'élimination de contaminants d'un gaz naturel et leurs procédés d'utilisation
WO2022026241A1 (fr) * 2020-07-31 2022-02-03 Battelle Memorial Institute Sorbant chimique à amine ajoutée
CN112851690B (zh) * 2020-12-29 2021-12-31 郑州大学 低分子量自具微孔聚合物、制备方法与超薄有机溶剂纳滤膜及其制备方法
CN112851690A (zh) * 2020-12-29 2021-05-28 郑州大学 低分子量自具微孔聚合物、制备方法与超薄有机溶剂纳滤膜及其制备方法
CN113230905A (zh) * 2021-05-12 2021-08-10 天津大学 偕胺肟基团功能化超交联微孔聚合物膜及其制备和应用
CN113413776A (zh) * 2021-06-21 2021-09-21 东华理工大学 一种基于聚偕胺肟为界层的纳滤膜的制备方法
US20230133081A1 (en) * 2021-10-28 2023-05-04 Saudi Arabian Oil Company Membranes of glassy polymer blends with peg-crosslinked intrinsic microporous polymers for gas separations
CN114515520A (zh) * 2022-03-16 2022-05-20 浙江工业大学 一种高通量高选择性的基于特勒格碱基耐酸纳滤膜及其制备方法
WO2024163517A3 (fr) * 2023-01-31 2024-09-19 Massachusetts Institute Of Technology Nanofilms polymères hautement poreux

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