WO2010064121A2 - Procédé de séparation de gaz - Google Patents

Procédé de séparation de gaz Download PDF

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Publication number
WO2010064121A2
WO2010064121A2 PCT/IB2009/007618 IB2009007618W WO2010064121A2 WO 2010064121 A2 WO2010064121 A2 WO 2010064121A2 IB 2009007618 W IB2009007618 W IB 2009007618W WO 2010064121 A2 WO2010064121 A2 WO 2010064121A2
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WIPO (PCT)
Prior art keywords
process according
porous material
gases
pressure
gas
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PCT/IB2009/007618
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WO2010064121A3 (fr
WO2010064121A8 (fr
Inventor
Angela Carati
Patrizia Broccia
Caterina Rizzo
Liberato Giampaolo Ciccarelli
Marco Tagliabue
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Eni SpA
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Eni SpA
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Priority to HR20110442A priority Critical patent/HRP20110442A2/hr
Priority to AU2009323821A priority patent/AU2009323821A1/en
Publication of WO2010064121A2 publication Critical patent/WO2010064121A2/fr
Publication of WO2010064121A3 publication Critical patent/WO2010064121A3/fr
Publication of WO2010064121A8 publication Critical patent/WO2010064121A8/fr
Anticipated expiration legal-status Critical
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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
    • B01D53/02—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2253/306—Surface area, e.g. BET-specific surface
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    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2257/304—Hydrogen sulfide
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    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40028—Depressurization
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
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    • B01D53/02—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
    • 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
    • B01D53/0462—Temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/02—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
    • 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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    • B01D53/02—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
    • 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
    • B01D53/047—Pressure swing adsorption
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    • 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
    • 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
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Definitions

  • the present invention relates to a process for the separation of gases comprising putting a mixture of gases in contact with a particular porous material, containing a silica matrix in which one or more metal oxides are possibly uniformly dispersed, said metal oxides being selected from transition metals or from metals of groups IIIA, IVA and VA.
  • the process is particularly suitable for the sweetening of natural gas , mainly to remove carbon dioxide , hydrogen sulphide or mixtures thereof , from natural gas .
  • the process can also be used in the separation of hydro- gen from blends containing carbon dioxide, carbon monox- ide , hydrogen sulphide , water and hydrocarbons , such as , for example, gaseous effluents from steam methane reforming. In this case, hydrogen is the non-adsorbed component .
  • the separation of gases in a blend can be effected using various methods. For the removal of nitrogen from natural gas, for example, cryogenic processes, adsorption processes or membrane systems, can be used. In all these processes, the gas is produced at low pressure and must therefore be recompressed to be delivered.
  • cryogenic processes are also carried out at low temperatures and therefore require pre-treatment to remove the components present in the natural gas which solidify under these conditions.
  • acid gases such as CO 2 and H 2 S
  • systems respectively based on the use of amines, solvents, alkaline solutions of inorganic salts or mixtures thereof, can be used.
  • the acid gases are then eliminated from the solvent by means of high temperature stripping or depressurization.
  • mem- brane systems are used for separating carbon dioxide : the membranes consist of polymer films without pores and extremely dense, in which the carbon dioxide dissolves and is conveyed by diffusion.
  • the use is described of a membrane based on polyacrylonitrile for the separation of N 2 /CH 4 with a high selectivity, but low permeability.
  • US 6,565,626 describes a process with organic membranes permeable to CO 2 , H 2 O, H 2 S, N 2 , but with a low permeability to CH 4 .
  • the SPREX process allows the extraction of hydrogen sulphide from natural gas streams containing at least 10% by volume of H 2 S by cooling the gaseous feeding stream to -30 0 C or -60 0 C (Hydrocarbon Processing: Gas Processes 2006, Gulf Publishing Company) .
  • a stream rich in H 2 S is thus produced, suitable for being injected again into the gas well, together with a stream rich in CH 4 , destined for washing with amines for the abatement of the residual acid gases until the specification required.
  • Adsorption/desorption cycles are also known, such as, for example, those of the "pressure swing” (PSA) , “thermal swing” (TSA) , “vacuum swing” (VSA) , “pressure-thermal swing” (PTSA), “pressure-vacuum swing” (PVSA) type.
  • PSA pressure swing
  • TSA thermo swing
  • VSA vacuum swing
  • PTSA pressure-thermal swing
  • PVSA pressure-vacuum swing
  • PSA-type processes substantially comprise the following steps: a first step in which a gaseous mixture containing two or more gases is put in contact, at high pressure, with an adsorbing material and one or more of the gases forming the mixture are selectively adsorbed; the adsorption normally takes place in short times, in the order of 30 seconds to 5 minutes; - a subsequent step wherein the adsorbed gas or gases are desorbed by means of one or more of the following systems: pressure lowering, washing with gas.
  • the gas desorption is obtained in this way, and the gas is recovered by regenerating the same adsorbent; - and a last step, which concludes the cycle, in which the adsorbing bed is pressurized with the gas fed.
  • EP 758561 describes a process for nitrogen adsorption from gaseous streams containing it, by using suitably ex- changed zeolites, selected from chabazite, offretite, eri- onite, levinite, mordenite, zeolite A, zeolite T, EMC-2, ZSM-3, ZSM-18, ZK-5, zeolite L and zeolite beta.
  • zeolites selected from chabazite, offretite, eri- onite, levinite, mordenite, zeolite A, zeolite T, EMC-2, ZSM-3, ZSM-18, ZK-5, zeolite L and zeolite beta.
  • Engelhard Corporation now BASF Catalysts applied this material in a process called Molecular Gate, capable of separating nitrogen from methane (US 6,197,092, US 6,444,012) .
  • the Molecular Gate process can also be applied to the removal of carbon dioxide from methane (US 6,610,124).
  • EP 1,254,694 describes the use of zeolite X for separating CO 2 and H 2 O from air. If necessary, the de- sorption phase of gases from the adsorber can be effected by thermal treatment (TSA) , or by means of a vacuum (VSA) .
  • a process is described in WO 2008/00380 for the separation of gases which includes putting a gas mixture in contact with an ESV-type zeolite in order to obtain the selective adsorption of at least one of the gases forming the gaseous mixture .
  • "Carbogenic" adsorbents are also mentioned for gas separation.
  • a process based on “carbon molecular sieves” (CMS) is described for the purification of gaseous mixtures containing methane .
  • the characteristics of the adsorbing material are at the basis of the separation capacity of the different gas components .
  • Other variables can be important : for example the sensitivity of the adsorbent to humidity can influence the surface reactivity (the hydroxylation degree, for example) or the porosity, or an insufficient stability can prevent the thermal regeneration of the material to eliminate the accumulation of the adsorbed gas. Low recoveries of the desired gas require onerous internal recycling.
  • the remaining gases forming the mixture pass through the adsorbing
  • ERS-8 The material used in the process of the present in- vention, comprising a silica matrix in which one or more metal oxides selected from among transition metals or from among metals belonging to groups IIIA, IVA and VA and having the aforementioned characteristics, are possibly uniformly dispersed, is called ERS-8 and is described in EP 691305, EP 736323 and EP 812804.
  • These materials preferably have a surface area larger than 800 m 2 /g and a pore volume preferably between 0.3 and 0.6 ml/g.
  • a particular aspect of the present invention is that the metal oxide dispersed in the silica matrix is alumin- ium oxide: these silico-aluminas of the ERS- 8 type preferably have a SIO 2 /A1 2 O 3 molar ratio higher than 50, even more preferably ranging from 100 to 500.
  • ERS-8 a new class of microporous alumi- nosilicates
  • H. Chon, S. K. Ihm and Y. S. Uh Editors
  • Progress in Zeolite and Microporous Materials Studies in Surface Science and Catalysis, Vol. 105, 1997 Elsevier Science B. V. and in C.Rizzo et al .
  • Synthesis and tex- tural properties of amorphous silica-aluminas Studies in Surface Science and Catalysis Volume 128, 2000, Pages 613 - 622 .
  • the materials of the ERS-8 type of the present invention can be prepared as follows: (A) a solution of a tetra-alkyl orthosilicate in alcohol is subjected to hydrolysis and gelification with an aqueous solution of a hydroxide of tetra-alkyl ammonium having the formula :
  • Table 1 operating at a temperature close to the boiling point, at atmospheric pressure, of the alcohol used in the solution of tetra-alkyl-orthosilicate and of any alcohol formed as by-product of the above hydrolysis reaction, with no elimination, or without any substantial elimination of said alcohols from the reaction environment, preferably at a temperature ranging from 20 to 80 0 C;
  • the tetra-alkyl orthosilicate can be selected from tetramethyl- , tetraethyl-, tetrapropyl- , tetra-isopropyl- orthosilicate, and tetra-ethyl-orthosilicate (TEOS) is preferred.
  • the alcohol used for solubilizing the above- mentioned tetra-alkyl orthosilicate is preferably ethanol .
  • the soluble or hydrolyzable compounds of one or more metals are selected from the salts or hydrosoluble or hydro- lysable acids of the same metals. Among these, aluminium tripropoxide and triisopropoxide are preferred. In the case of liquid aluminium alkoxides, it is possible to dissolve these alkoxides in the alcohol solution instead of in the aqueous solution.
  • preparations of materials of the ERS-8 type are also described in EP 736323 and EP 812804.
  • preparations are preferred in which the hydrolysis and gelification step is effected at atmospheric pressure, using reactors equipped with reflux condensers and in the presence of a tetra-alkyl ammonium hydroxide in which at least one of the alkyl substituents contain 6 or 7 carbon atoms .
  • the materials of the ERS- 8 type in particular silico-aluminas of the ERS- 8 type, can be used in the process of the present invention in the form bound with an inorganic binder, selected, for example, from alumina, silica, clay. Binding processes which can be used are those well-known to experts in the field, such as press- ing, extrusion, granulation, drop coagulation, atomiza- tion techniques.
  • the material of the ERS-8 type and, in particular, the silico-alumina of the ERS-8 type is contained in proportions of between 50 and 100% by weight with respect to the total weight of the product, wherein the proportion of 100% refers to a formation in the absence of a binder.
  • the material of the ERS-8 type and, in particular, the silico-alumina of the ERS-8 type is preferably contained in a proportion higher than 80% by weight with respect to the total weight of the product.
  • the process for the separation of gases of the present invention which comprises putting a mixture of gases in contact with a material of the ERS-8 type, preferably a silico-alumina of the ERS-8 type, so as to have the selec- tive adsorption of at least one of the gases forming the gas mixture, can be effected by means of adsorp- tion/desorption cycles.
  • the gaseous mixture to be fractionated is put in contact with the mate- rial of the ERS-8 type, preferably a silico-alumina of the ERS-8 type, in order to selectively adsorb one or more components of the same mixture.
  • the non-adsorbed component is collected as pure product and the adsorbed components are periodically desorbed, for example by means of reduc- tion in the pressure and/or washing, and/or temperature increase, so as to avoid saturation of the adsorbing bed.
  • pressure swing adsorption after adsorption at high pressure of at least one of the gases forming the mixture, and the separation of the remaining components of the mixture, the pressure is reduced to de- adsorb the adsorbed gas and regenerate the adsorbing bed containing the material of the ERS-8 type, preferably a silico-alumina of the ERS- 8 type.
  • the desorption step is effected, instead of by reducing the pressure, by raising the temperature of the adsorbing bed containing the material of the ERS-8 type, preferably a silico-alumina of the ERS-8 type.
  • the adsorption step is carried out at high pressure, whereas the desorption step is effected by increasing the temperature of the adsorbing bed, containing the material of the ERS-8 type, preferably a silico-alumina of the ERS-8 type, and reducing the pressure .
  • the adsorption step is carried out at atmospheric pressure, or slightly higher, whereas the desorption step is effected by reducing the pressure to vacuum.
  • the adsorption step is carried out at high pressure, whereas the desorption step is effected by reducing the pressure to vacuum.
  • a process of the PVSA type is therefore a particular case of the PSA process, in which the desorption is effected under vacuum.
  • the desorption can be facilitated by the contemporaneous washing of the adsorbing bed containing, for example, silico-alumina, by partial recycling of the pure com- ponent, not adsorbed, or with inert gas not contained in the feeding .
  • the process of the present invention is preferably effected by means of "pressure swing adsorption” (PSA) o "pressure-thermal swing adsorption” (PTSA) .
  • PSA pressure swing adsorption
  • PTSA pressure-thermal swing adsorption
  • a particular aspect of the present invention is therefore a process for the separation of gases of the PSA type comprising the following steps: a) putting a mixture of gases in contact, under high pressure, with a porous material to selectively ad- sorb at least one of the gases forming the mixture and collecting or discharging the remaining gaseous components of the mixture, wherein said material includes a silica matrix in which one or more metal oxides selected from among transition metals or from among metals belonging to groups IIIA, IVA and VA, are possibly uniformly dispersed, characterized by a surface area larger than 500 m 2 /g, a pore volume between 03 and 1.3 ml/g, an average pore diameter smaller than 40 Angstrom, an X
  • Accessory operations such as recycling of the products, partial depressurization (in equi- and/or counter- current with respect to the feed) , rinsing of the adsorbing bed, well-known to experts in the field, can be added to phases (a) - (d) .
  • the material of the ERS-8 type used in step (a) is a silico- alumina of the ERS-8 type.
  • the adsorbing step (a) can be carried out at a temperature ranging from 0 to 40 0 C, preferably at room tem- perature, and at an adsorbing pressure of 10 to 90 bara, preferably 10 to 40 bara.
  • the desorption pressure can be selected from 0.1 to 10 bara, whereas the temperature ranges from 0 to 40 0 C and is preferably room temperature.
  • the desorption is chosen to be effected under vacuum, the process will be in particular of the PVSA type.
  • the adsorption step (a) is carried out under the same conditions described above, whereas the de- sorption step (c) is effected by means of an increase in the temperature of the adsorbing bed containing the material of the ERS- 8 type, preferably a silico-alumina of the ERS-8 type, and a reduction in the pressure: it is therefore preferable to operate at a pressure ranging from 0.1 to 10 bara and a temperature of 50 to 250 0 C, even more preferably between 60 and 100 0 C.
  • gas rins- ing such as, for example, N 2 , CH 4 , air or hydrogen.
  • the process of the present invention can be successfully used, in particular, for the purification of natural gas from pollutants selected from CO 2 , H 2 S, water and mixtures thereof, wherein the water is in a quantity, at the most, equal to the saturation of the gaseous mixture.
  • pollutants selected from CO 2 , H 2 S, water and mixtures thereof, wherein the water is in a quantity, at the most, equal to the saturation of the gaseous mixture.
  • the contaminants are preferably adsorbed with respect to methane.
  • the process of the present invention is used for the purification of natural gas from CO 2 and/or H 2 S.
  • a particularly preferred aspect of the present invention is a process of the PSA type for the separation of carbon dioxide, H 2 S or mixtures thereof from a gaseous mixture containing them together with methane, comprising the following steps : a) putting said gaseous mixture in contact with a porous material, at high pressure, in order to selectively adsorb carbon dioxide, H 2 S or their mixture, and collecting the remaining gaseous component containing methane, wherein said material comprises a silica matrix in which one or more metal oxides selected from transition metals or metals belonging to groups IIIA, IVA and VA, are possibly uniformly dispersed, characterized by a surface area larger than 500 m 2 /g, a pore volume ranging from 0.3 to 1.3 ml/g, an average pore diameter smaller than 40 Ang- strom, an XRD powder spectrum which does not have a crystalline structure, does not show any peak, and has a single broad diffraction line, or, in any case,
  • step (b) interrupting the flow of the gaseous mixture and possibly reducing the pressure; c) desorbing carbon dioxide, H 2 S or their mixture, adsorbed in step (a) , by reduction of the partial pres- sure of the gas or gases adsorbed, collecting or discharging them; d) re-pressurizing the system with the gas mixture fed.
  • a silico-alumina is preferably used as adsorbing material of the ERS-8 type. If the separation of carbon dioxide, H 2 S or a mixture thereof, from a gaseous mixture containing them together with methane, is carried out by means of PTSA, the desorption step (c) is effected by an increase in the temperature of the adsorb- ing bed containing the material of the ERS-8 type, preferably a silico-alumina of the ERS-8 type, and reduction of the pressure.
  • a material of the ERS-8 type preferably a silico-alumina of the ERS-8 type in a PSA process
  • the material of the ERS-8 type when used in the present gas adsorption process, in particular when used for the removal of acid gas, can be completely regenerated by isothermal depressurization and a particularly preferred as- pect of the present invention is therefore to effect the desorption step of the adsorbed gases by reducing the partial pressure of the adsorbed gas(es) , at a constant temperature .
  • ERS-8 type and, preferably, a silico-alumina of the ERS-8 type, used in the separation process of the present in- vention are capable of contemporaneously satisfying the following requirements: a) maximum quantity of adsorbable H 2 S at 5 bara and 30 0 C, higher than 120 Nml/g; b) ratio between the maximum quantity of adsorbable H 2 S and CH 4 at 5 bara and 30 0 C, higher than 8.5: c) maximum quantity of H 2 S that can be released by isothermal depressurization from 5 bara to 0.5 bara at 30 0 C, equal to at least 75% of the maximum quantity adsorbable at 5 bara.
  • the process of the present invention can also be used for the separation of hydrogen from mixtures containing carbon dioxide , carbon monoxide and hydrocarbons , such as , for example, gaseous effluents from "steam methane reforming" .
  • hydrogen is the non-adsorbed compo- nent .
  • the results of the experimental tests are expressed by using, as measurement parameter of the adsorbing properties of a material, the adsorption capacity at equilibrium q (Nml/g) , expressed as the quantity of ad- sorbed gas at equilibrium under certain conditions (T, P) and referring to the weight of the adsorbing material (specific capacity) .
  • Example 1 - synthesis of ERS- 8 silico-alumina 669.2 g of tetra-hexyl ammonium hydroxide at 40% by weight in aqueous solution are diluted with 928.4 g of water and charged into a reactor equipped with a condenser. A solution containing 1667.0 g of tetra-ethyl orthosili- cate, 2944.0 g of ethanol and 13.2 g of aluminium sec- butoxide are added at room temperature, and the whole mixture is maintained under stirring for 3 hrs . A limpid sol is obtained which is concentrated in a rotavapor until a gel is formed. The gel is dried under vacuum at 80 0 C and calcined at 550 0 C for 8 hrs.
  • Example 2 Absorption test with ERS-8 silico-alumina
  • the adsorbing material of Example 1 was pre-treated under vacuum at 350 0 C for 16 hrs and the adsorp- tion/desorption isotherms were acquired on it for H 2 S, CO 2 , CH 4 at 30 0 C.
  • the results are shown in Figure 1. From Figure 1 it can be seen that the adsorbing material synthesized according to Example 1 preferably adsorbs the acid gases (H 2 S and CO 2 ) with a high selectivity with respect to CH 4 , within a wide pressure range.
  • a high selectivity prevents the co-adsorption of various components on the same adsorbing material, thus increasing the efficiency of the separation process.
  • the quantities of CO 2 , H 2 S and CH 4 adsorbed at 5 bara and 3O 0 C are 57 Nml/g, 132 Nml/g and 14 Nml/g respectively. It follows that the ratio between the maximum quantity of CO 2 and CH 4 which can be adsorbed by the sample of Example 1 (at 5 bara and 30 0 C) is equal to 4, whereas the ratio between the maximum quantity of H 2 S and CH 4 which can be adsorbed by the sample of Example 1 (at 5 bara and 30 0 C) is equal to 9.5.
  • a tubular adsorber was charged with the adsorbing material granulated at 20-40 mesh.
  • the adsorber was degassed in situ at 350 0 C under vac- uum for 16 hrs .
  • the CO 2 adsorption referring to the weight of adsorbing material, proved to be equal to 90 Nml/g.
  • Example 2 the regeneration of the adsorbing ma- terial synthesized as described in Example 1 is indicated, by means of depressurization and washing of the adsorbing bed with CH 4 .
  • the operation was carried out by depressurization and subsequent sweeping of the adsorbing bed with CH 4 .
  • This example describes the effect of the thermal re- generation of the adsorbing material synthesized as described in Example 1.
  • Example 4 At the end of the 5 adsorption/desorption cycles, mentioned in Example 4, the adsorbing material saturated with CO 2 was treated at 350 0 C under a stream of CH 4 , in situ. At the end of the thermal regeneration, after cooling the system to room temperature, the sequence of 5 adsorption/desorption cycles was repeated with the same procedures described in Example 4.
  • the adsorbing material synthesized as described in Example 1 can be regenerated by depressurization and sweeping with CH 4 . No significant decrease in the specific capacity for CO 2 is revealed during the 1-5 cycles.
  • the adsorbing material synthesized as described in Example 1 can be regenerated by thermal treatment. No significant decrease in the specific capacity for CO 2 is revealed passing from the 5 cycles of Example 4 to the 5 cycles of Example 5.
  • Example 6 (comparative) - Adsorption test with a commer- cial adsorbent.
  • the specific capacity represents a fundamental char- acteristic for an adsorbing material to be used in a cyclic separation process.
  • high specific capacities allow less frequent regenerations of the adsorbing material used.
  • Example 7 This example describes the behaviour of the adsorbing material synthesized as described in example 1, in the competitive adsorption of H 2 S.
  • a tubular adsorber was charged with the adsorbing material granulated at 20-40 mesh.
  • the adsorber was degassed in situ at 350 0 C under vac- uum for 16 hrs .
  • the H 2 S adsorption referring to the weight of the adsorbing material, proved to be equal to 90 Nml/g.
  • This example indicates the regeneration of the adsorbing material synthesized as described in Example 1 by means of depressurization and washing of the adsorbing bed with CH 4 .
  • the operation was carried out by depressurization and subsequent sweeping of the adsorbing bed with CH 4 .
  • Table 3 indicates the quantities of H 2 S adsorbed (referring to the weight of the adsorbing material) during the cycles.

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Abstract

La présente invention concerne un procédé de séparation de gaz qui comprend la mise en contact d'un mélange de gaz avec un matériau poreux contenant une matrice de silice dans laquelle sont éventuellement uniformément dispersés un ou plusieurs oxydes métalliques qui sont sélectionnés parmi les métaux de transition ou parmi les métaux des groupes IIIA, IVA et VA, présentant une surface spécifique supérieure à 500 m²/g, un volume de pores compris entre 0,3 et 1,3 ml/g, un diamètre de pore inférieur à 40 Angströms et un spectre de diffraction des rayons X sur poudre qui ne possède pas de structure cristalline, ne présente aucun pic et possède une seule ligne de diffraction large ou, en tout cas, possède une diffusion étendue à des valeurs angulaires non supérieures à 2θ = 5 ° avec un rayonnement CuKa, sans autre phénomène de diffusion cohérent pour des valeurs angulaires supérieures. Au moyen du procédé de la présente invention, l'adsorption sélective d'au moins l'un des gaz formant le mélange gazeux est obtenue. Ces matériaux adsorbants peuvent être régénérés et sont particulièrement appropriés pour des opérations d'élimination massive des gaz acides du gaz naturel.
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WO2012118737A2 (fr) 2011-03-01 2012-09-07 Exxonmobil Research And Engineering Company Procédé d'absorption modulée en température pour la séparation d'une espèce cible d'un mélange gazeux
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