# US 2014/0154174 A1 · Process and zeolitic materials for the separation of gases > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0154174 A1 - Document ID: US20140154174A1 - Status: Published application - Kind: A1 - Application number: 13/897,870 - Filed: 2013-05-20 - Published: 2014-06-05 - Earliest claimed: 2006-06-26 - Inventors: Angela CARATI; Caterina Rizzo; Marco Tagliabue; Luciano Cosimo Carluccio; Cristina Flego; Liberato Giampaolo Ciccarelli - Web page: https://patentgrep.com/patent/US20140154174A1 ## CPC - B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing} - B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} - B01J 20/186: {Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity} - C01B 3/56: by contacting with solids; Regeneration of used solids - C01B 39/48: using at least one organic template directing agent - C10L 3/10: Working-up natural gas or synthetic natural gas - B01D 53/047: Pressure swing adsorption - B01D 2253/108: Zeolites - B01D 2253/11: Clays - C01B 2203/042: Purification by adsorption on solids - C01B 2203/047: the impurity being carbon monoxide - C01B 2203/0475: the impurity being carbon dioxide - C01B 2203/048: the impurity being an organic compound - Y02C 20/40: of CO2 - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - 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 - Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG] ## Abstract The present invention relates to a process for the separation of gases which comprises putting a mixture of gases in contact with a zeolite of the ESV type to obtain the selective adsorption of at least one of the gases forming the gaseous mixture. The present invention also relates to particular zeolitic compositions suitable as adsorbents. ## Claims ### Claim 1 A process for the separation of gases which comprises putting a mixture of gases in contact with a zeolite for selectively adsorbing at least one of the gases forming the mixture, characterized in that the zeolite is a zeolite of the ESV type. ### Claim 2 (depends on 1) The process according to claim 1 comprising a desorption step of the gases adsorbed. ### Claim 3 (depends on 1, 2) The process according to claim 1 or 2, wherein the zeolite is an ERS-7 zeolite. ### Claim 4 (depends on 3) The process according to claim 3, wherein the zeolite is a zeolite of the ERS-7 type having in the calcined and anhydrous form the following general formula (I): M2/nO.Al2O3.xSiO2 wherein M is a cation having a valence n selected from H+, metallic cations of the IA group, metallic cations of the IIA group and their mixtures, n=1 or 2, and x has a value ranging from 15 to 30. ### Claim 5 (depends on 4) The process according to claim 4, wherein M is at least a cation selected from H+, Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+. ### Claim 6 (depends on 5) The process according to claim 5, wherein M is Na++ or Na and H+, optionally mixed with one or more cations selected from Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+. ### Claim 7 (depends on 6) The process according to claim 6, wherein the zeolite of the ERS-7 type is in the form directly deriving from the synthesis, after drying and calcination, containing sodium ions and H+ ions. ### Claim 8 (depends on 4, 5, 6, 7) The process according to claim 4, 5, 6 or 7 wherein M is at least partly a sodium ion and is in a quantity ranging from 0.2 and 1 expressed as a molar ratio Na/Al. ### Claim 9 (depends on 1) The process according to claim 1, wherein the zeolite is used in bound form with an inorganic binder selected from inorganic materials such as clays, oxides of silicon, aluminum, titanium, zirconium and mixtures thereof. ### Claim 10 (depends on 9) The process according to claim 9, wherein the zeolite is used in bound form and in a quantity ranging from 50 to 95% by weight with respect to the total weight of the product formed by the zeolite and binder. ### Claim 11 (depends on 10) The process according to claim 10, wherein the zeolite is in a quantity ranging from 60 to 90% by weight. ### Claim 12 (depends on 1) The process according to claim 1, wherein the ESV zeolite is contained in a membrane. ### Claim 13 (depends on 1, 2) The process according to claim 1 or 2, effected by means of adsorption cycles. ### Claim 14 (depends on 13) The process according to claim 13, effected by means of adsorption cycles of the pressure swing adsorption (PSA), thermal swing adsorption (TSA), vacuum swing adsorption (VSA), pressure-thermal swing adsorption (PTSA), or pressure-vacuum swing adsorption (PVSA. type. ### Claim 15 (depends on 14) The process according to claim 14, wherein the process is effected by means of adsorption cycles of the PSA or PTSA type. ### Claim 16 (depends on 15) A process of the PSA type according to claim 15 comprising the following steps: a. putting a mixture of gases in contact at a high pressure with a zeolite of the ESV type, to selectively adsorb at least one of the gases forming the mixture and collecting or discharging the remaining gaseous components of the mixture; b. interrupting the flow of gaseous mixture and optionally reducing the pressure; c. desorbing the gas or gases adsorbed in step a), by partial pressure reduction of the gas or gases adsorbed, and collecting or discharging them; d. repressurizing the system with the mixture of gases fed. ### Claim 17 (depends on 15) A process of the PTSA type according to claim 15 comprising the following steps: a. putting a mixture of gases in contact at a high pressure with a zeolite of the ESV type to selectively adsorb at least one of the gases forming the mixture and collecting or discharging the remaining gaseous components of the mixture; b. interrupting the flow of gaseous mixture and optionally reducing the pressure; c. desorbing the gas or gases adsorbed in step a), by raising of the temperature of the zeolite and partial pressure reduction of the gas or gases adsorbed, and collecting or discharging them; d. repressurizing the system with the mixture of gases fed. ### Claim 18 (depends on 1) The process according to claim 1, wherein the gaseous mixture is natural gas containing one or more pollutants selected from nitrogen, CO2, H2S, water, which are adsorbed. ### Claim 19 (depends on 1) The process according to claim 1, wherein the gaseous mixture is hydrogen containing carbon dioxide, carbon monoxide and hydrocarbons which are adsorbed. ### Claim 20 (depends on 16, 18) The process according to claim 16 or 18 for the separation of carbon dioxide, and, if present, H2S, from a gaseous mixture containing them together with methane comprising the following steps: a. putting said gaseous mixture in contact, at a high pressure, with a zeolite of the ESV type, to selectively adsorb carbon dioxide and, if present, H2S, and collecting the remaining gaseous component containing methane; b. interrupting the flow of gaseous mixture and optionally reducing the pressure; c. desorbing the carbon dioxide and, if present, H2S, adsorbed in step (a), by partial pressure reduction of the gas or gases adsorbed, and collecting or discharging them; d. repressurizing the system with the mixture of gases fed. ### Claim 21 (depends on 17, 18) The process according to claim 17 or 18 for the separation of carbon dioxide, and, if present, H2S, from a gaseous mixture containing them together with methane comprising the following steps: a. putting said gaseous mixture in contact, at a high pressure, with a zeolite of the ESV type, to selectively adsorb carbon dioxide and, if present, H2S, and collecting the remaining gaseous component containing methane; b. interrupting the flow of gaseous mixture and optionally reducing the pressure; c. desorbing the carbon dioxide and, if present, H2S, adsorbed in step (a), by raising the temperature of the zeolite and partial pressure reduction of the gas or gases adsorbed, and collecting or discharging them; d. repressurizing the system with the mixture of gases fed. ### Claim 22 (depends on 1, 16, 17, 20, 21) The process according to claim 1, 16, 17, 20 or 21, wherein the adsorption is carried out at a temperature ranging from 0 to 40° C. and a pressure ranging from 10 to 90 bara. ### Claim 23 (depends on 22) The process according to claim 22, wherein the adsorption is carried out at an adsorption pressure ranging from 10 to 40 bara. ### Claim 24 (depends on 2, 16, 20) The process according to claim 2, 16 or 20, wherein the desorption step is carried out at a pressure ranging from 0.5 to 10 bara and a temperature ranging from 0 to 40° C. ### Claim 25 (depends on 2, 17, 21) The process according to claim 2, 17 or 21, wherein the desorption step is carried out at a pressure ranging from 0.5 to 10 bara and a temperature ranging from 50 to 200° C. ### Claim 26 (depends on 25) The process according to claim 25, wherein the temperature ranges from 60 to 100° C. ### Claim 27 (depends on 16, 17, 20, 21) The process according to claim 16, 17, 20 or 21 wherein the zeolite is ERS-7. ### Claim 28 (depends on 2, 16, 17) The process according to claim 2, 16 or 17, wherein the desorption step is followed by washings with a gas selected from N2, CH4, air or hydrogen. ### Claim 29 Zeolites of the ERS-7 type having in the calcined and anhydrous form the following general formula (I): M2/nO.Al2O3.xSiO2 wherein M is at least a cation having a valence n selected from Li, Mg, Ca, Sr, Ba, optionally mixed with one or more cations selected from H+ and Na+, n=1 or 2, and x has a value ranging from 15 to 30. ### Claim 30 A process for preparing zeolites of the ERS-7 type having in the calcined and anhydrous form the following general formula (I): M2/nO.Al2O3.xSiO2 wherein M is a cation having a valence n selected from H+, metallic cations of the IA group, metallic cations of the IIA group and their mixtures, n=1 or 2, and x has a value ranging from 15 to 30, which comprises: a. reacting sodium silicate, aluminum sulfate, N,N-dimethylpiperidinium halide or hydroxide, under hydrothermal conditions, so that there are the following molar ratios in the reagent mixture: SiO2/Al2O3 15-30 R/SiO2 0.2-0.4 H2O/SiO2 30-50 Na/Al2O3 10-30 OH−/SiO2 0.3-0.6 wherein R is N,N-dimethylpiperidinium, at a temperature ranging from 150 to 200° C. for a period of time varying from 5 to 15 days; b. discharging the resulting mixture from which a solid is separated, by means of filtration, which, after washing with demineralized water and drying at a temperature ranging from 120 to 150° C. has the following composition (II): yR2O.mM2O.Al2O3.xSiO2 (II) wherein 0