WO2010059055A1 - Procédé de conversion de co à la vapeur d'eau - Google Patents

Procédé de conversion de co à la vapeur d'eau Download PDF

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Publication number
WO2010059055A1
WO2010059055A1 PCT/NL2009/050709 NL2009050709W WO2010059055A1 WO 2010059055 A1 WO2010059055 A1 WO 2010059055A1 NL 2009050709 W NL2009050709 W NL 2009050709W WO 2010059055 A1 WO2010059055 A1 WO 2010059055A1
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WIPO (PCT)
Prior art keywords
gas
adsorbent
promoted
reactor
gas mixture
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Application number
PCT/NL2009/050709
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English (en)
Inventor
Paul Dean Cobden
Stéphane WALSPURGER
Rudolf Willem Van Den Brink
Hendricus Adrianus Johannes Van Dijk
Original Assignee
Stichting Energieonderzoek Centrum Nederland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Stichting Energieonderzoek Centrum Nederland filed Critical Stichting Energieonderzoek Centrum Nederland
Priority to CA2744416A priority Critical patent/CA2744416C/fr
Priority to CN200980152370.4A priority patent/CN102264633B/zh
Priority to EP09760022.5A priority patent/EP2362848B8/fr
Priority to BRPI0921995A priority patent/BRPI0921995B1/pt
Publication of WO2010059055A1 publication Critical patent/WO2010059055A1/fr
Priority to US13/112,881 priority patent/US8617512B2/en
Priority to AU2011202375A priority patent/AU2011202375B2/en
Priority to ZA2011/03815A priority patent/ZA201103815B/en

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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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Definitions

  • the invention relates to a water gas shift (WGS) process.
  • WGS water gas shift
  • the invention further relates to the use of an alkali promoted alumina based material (as adsorbent) for the removal of (multiple) acid gas components from a gas mixture.
  • adsorbents to remove SO 2 from certain gas streams.
  • US5358701 describes a process for removing noxious sulphur oxides, nitrous oxides, and chlorine from gas streams, particularly from flue gases of coal- burning power plants, using layered double hydroxide (LDH) sorbents.
  • LDH layered double hydroxide
  • the sorbents are particularly useful for SO 2 absorption at temperatures in the range of 100 0 C to less than 400 0 C.
  • the SO 2 gas absorbs into the hydrotalcite structure as SO3 2" anions by replacing most of the gallery CO3 2" anions.
  • the adsorbed SO 2 is driven-off by calcination at elevated temperatures (500 0 C) and the LDH sorbents are regenerated by hydro lyzing the calcined product optionally in the presence of CO 2 or CO3 2" .
  • WO2005102916 describes apparatus and methods for converting hydrocarbon fuels to hydrogen-rich reformate that incorporate a carbon dioxide fixing mechanism into the initial hydrocarbon conversion process.
  • the mechanism utilizes a carbon dioxide fixing material within the reforming catalyst bed to remove carbon dioxide from the reformate product.
  • the removal of carbon dioxide from the product stream shifts the reforming reaction equilibrium toward higher hydrocarbon conversion with only small amounts of carbon oxides produced.
  • Fixed carbon dioxide may be released by heating the catalyst bed to a calcination temperature.
  • a non-uniform distribution of catalysts and carbon dioxide fixing material across catalyst bed yields higher conversion rates of hydrocarbon to hydrogen-rich reformate.
  • US2004081614 describes a process for producing a high temperature CO x -lean product gas from a high temperature CO x -containing feed gas, which includes providing a sorption enhanced reactor containing a first adsorbent, a shift catalyst and a second adsorbent; feeding into the reactor a feed gas containing H 2 , H 2 O, CO and CO 2 ; contacting the feed gas with the first adsorbent to provide a CO 2 depleted feed gas; contacting the CO 2 depleted feed gas with the shift catalyst to form a product mixture comprising CO 2 and H 2 ; and contacting the product mixture with a mixture of second adsorbent and shift catalyst to produce the product gas, which contains at least 50 vol.
  • the adsorbent is a high temperature adsorbent for a Sorption Enhanced Reaction process, such as K3CO3 promoted hydrotalcites, modified layered double hydroxides, spinels, modified spinels, and magnesium oxides.
  • US6322612 describes a pressure or vacuum swing adsorption process and apparatus used for the separation and recovery of certain gaseous components, such as carbon dioxide from hot gas mixtures containing water vapour.
  • the process comprises introducing the feed gas mixture at an elevated temperature into a feed end of an adsorber column containing an adsorbent.
  • the adsorbent preferentially adsorbs at least one adsorbable component.
  • An adsorber effluent, depleted of the at least one adsorbable component is withdrawn from a product end of the adsorber column.
  • the adsorber column is depressurized below atmospheric pressure and then purged with steam to withdraw an effluent comprising a mixture of the at least one adsorbable component and H 2 O.
  • the adsorber column is pressurized by introducing a gas that is depleted of the at least one adsorbable component.
  • the steps are repeated in a cyclic manner. Further, Descamps et al (Energy 33 (2008) 874-881)) and Maurstad (8 th
  • a disadvantage of prior art processes may be that for performing the WGS process from a gas that (also) comprises H 2 S, H 2 S has to be removed from the WGS inlet gas (or starting mixture) and/or from the WGS outlet gas (or product gas), which may require a plurality of reactors.
  • a disadvantage of prior art processes may be that conventional WGS catalysts are necessary, in addition to optional CO 2 adsorbents, which may also require a plurality of reactors and/or a plurality of (mixed) beds.
  • the invention provides a water gas shift process comprising a reaction stage comprising (a) providing a gas mixture comprising CO, H 2 O and an acid gas component to a reactor containing an adsorbent, wherein the adsorbent comprises an alkali promoted alumina based material, and (b) subjecting the gas mixture to water gas shift reaction (WGSR) conditions to perform the water gas shift reaction, wherein the acid gas component may comprise H 2 S, and wherein the gas mixture may comprise a H 2 S reactor inlet concentration of at least about 200 ppm H 2 S relative to the gas mixture, more especially at least about 500 ppm. Characteristic ranges will be about 200-20.000 ppm, such as 500-20.000 ppm H 2 S.
  • the adsorbent may be suitable for the abatement (capture) of CO 2 and H 2 S in the gas, while on the other hand, the adsorbent may also have suitable water gas shift (WGS) activity.
  • WGS water gas shift
  • the adsorbent may be used as coadsorber of two or more acid gas components and/or for the catalysis of the WGS reaction.
  • An advantage of the process of the invention may be that this process may be applied in one single reactor and optionally even with one single bed.
  • the reaction stage is performed in a single reactor and especially in a single bed.
  • the adsorbent may easily be regenerated, i.e. the adsorption of CO 2 and H 2 S is reversible. Via (partial) pressure swing and/or temperature swing, the adsorbent may be regenerated.
  • the process further comprises an adsorbent regeneration stage, wherein CO 2 and optionally the acid gas component are at least partially removed from the adsorbent. Therefore, the invention also provides a cyclic process comprising a plurality of alternating reaction stages and regeneration stages.
  • advantages of the invention may be that no specific catalyst may be needed but only a sorbent, and nevertheless WGS is performed, and/or the co-capture of CO 2 with H 2 S and optionally other acid gases may be possible. Thereby, potentially costs related with traditional gas cleaning sections may be avoided.
  • the term "adsorbent” may also indicate a combination of adsorbents.
  • the adsorbent (comprising an alkali promoted alumina based material) comprises one or more alkali-promoted aluminas, wherein alkali is an element selected from the group consisting of K, Na, Li, Cs, and Rb.
  • the akali content is > 5 wt.% calculated as carbonate, preferably 5-30 wt.% calculated as carbonate, relative to the total amount of the alkali promoted alumina.
  • the adsorbent comprises one or more promoted alkali-promoted aluminas, wherein alkali is an element selected from the group consisting of K, Na, Li, Cs, and Rb ("first promoter").
  • alkali is an element selected from the group consisting of K, Na, Li, Cs, and Rb ("first promoter").
  • the alkali-promoted alumina may be further promoted, and is then indicated as "promoted alkali-promoted alumina".
  • the alkali-promoted alumina may be further promoted with one or more elements selected from the group consisting of Mg, Mn, Ti,
  • the alumina may be promoted first with the first promoter and thereafter with the second promoter, but in another embodiment, the alumina may also be promoted first with the second promoter and thereafter with the first promoter; in yet another embodiment, the alumina is promoted with the first and second promoter substantially at the same time.
  • the promoter (second promoter) content is about 5 wt.% or more calculated as oxide, preferable about 5-50 wt.% calculated as oxide, relative to the total weight of the promoted alkali-promoted aluminas.
  • Mg, Mn or Fe are used as promoter (i.e. second promoter).
  • the adsorbent comprises one or more alkali- promoted hydrotalcites, wherein alkali is an element selected from the group consisting of K, Na, Li, Cs, and Rb.
  • the hydrotalcite (herein also indicated as "HTC") may have the chemical formula: [M ⁇ (1 . x )Al ( ⁇ x )M ⁇ i ((1 . ⁇ ) X ) (OH)2][C n l( X /n).yH 2 O.zM I ( m )A m - wherein
  • M 1 is one or more selected from the group consisting of Li, Na, K, Rb and Cs
  • M ⁇ is one or more selected from the group consisting of Mg, Mn, Cu, Co, Fe, Cd and Cr
  • Al is aluminium
  • M i ⁇ is optionally one or more of the group consisting of Fe, Cr and Mn; C n ⁇ is one or more anions selected from the group consisting of N(V, SO 4 2" ,
  • a m" is one or more anions, such as selected from CO 3 2" , CH 3 CO 2” , C 2 O 4 2” , NO 3 “ , SO 4 2” , CO 3 2” , CH 3 CO 2 “ , OH “ , Cl “ , Br “ , F “ and I “ etc...
  • the alkali promoter is an element selected from the group consisting of K, Na, Li, Cs, and Rb.
  • the akali promoter content is >5 wt.% calculated as carbonate, preferably 5-30 wt.% calculated as carbonate, relative to the total amount of the alkali promoted hydrotalcite.
  • the value of z is preferably at least about 0.033 and in another embodiment preferably not more than about 0.17.
  • the adsorbent may comprise an alkali promoted hydrotalcite, such as potassium promoted hydrotalcite. Hydrotalcite may for instance be promoted with K 2 CO 3 . In such embodiment, K 2 CO 3 is applied as source of promoter material to promote the hydrotalcite.
  • the molar ratio M ⁇ :(Al+M i ⁇ ) is in the range of about 0:1 - 1 :0, preferable 30:70 -70:30.
  • the actual oxidation state of some of the M ⁇ and M i ⁇ ions can be changed during operation, e.g. Fe 11 and Fe 111 exist.
  • the elements with a 3+ oxidation state can be a mixture of Al 3+ and M i ⁇ , such as Fe 111 , Cr 111 , and Mn 111 .
  • the molar ratio of A1 3+ :M 3+ is preferably 1 :1 - 1 :0 (i.e. 0.5 ⁇ ⁇ ⁇ 1). It surprisingly appears that relatively low x values are especially advantageous.
  • x is in the range of 0.33-0.55, preferably in the range of 0.4-0.5.
  • the hydrotalcite material is low in magnesium.
  • Especially preferred systems are Mgi_ x Al( x )(OH) 2 (CO 3 ) ⁇ / 2 .
  • hydrotalcite is indicated as alumina based material, since, under the reaction conditions, hydrotalcite is at least partly converted to a mixed-metal oxide comprising alumina (more precisely, promoted alumina).
  • M 1 can be considered as first promoter and M ⁇ and M i ⁇ can be considered as second promoter.
  • a promoted alumina based material may be used as adsorbent.
  • the promoter(s) may be selected from the group consisting of K, Na, Li, Cs, Rb, Mg, Mn, Ti, Ag, Cu, Co, Pb, Fe and Cd. More than one type of promoter may be applied.
  • the adsorbent comprises a promoted alkali promoted alumina based material, wherein the alumina based material is promoted with one or more first promotors selected from the group consisting of K, Na, Li, Cs, and Rb, and one or more second promotors selected from the group consisting of Mg, Mn, Ti, Ag, Cu, Co, Pb, Fe and Cd. It appears that the second promoter advantageously (further) promotes CO 2 capture by the adsorbent.
  • the adsorbent comprises the alkali promoted hydrotalcite, as defined above.
  • thermotalcite materials over aluminas An advantage of hydrotalcite materials over aluminas is that it appears that the regeneration of the HTC materials seems easier. Hence, HTC materials may have a longer lifetime and/or be cheaper in maintenance costs and/or have a higher acid gas adsorption capacity in cost effective regenerative conditions. It further seems to appear that the promoted HTC adsorbentia, especially those low in magnesium content, may be used without an additional (conventional) WGS catalysts. Hence, the promoted hydrotalcite material alone may have the function of adsorbent and catalyst.
  • alkali is an element selected from the group consisting of K, Na, Li, Cs, and Rb
  • alkali- promoted aluminas etc. indicates that the alumina etc. may be promoted with one or more types of alkali elements.
  • promoted with one or more elements selected from the group consisting of Mg, Mn, Ti, Ag, Cu, Co, Pb, Fe and Cd indicates that the (promoted) alumina etc. may be promoted with one or more types of these elements.
  • Mg, Fe and Mn are used as promoter (i.e. second promoter).
  • Fe is used as promoter (i.e. second promoter).
  • Mg, and Mn are used as promoter (i.e. second promoter), yet even more preferably, Mg.
  • alkali-promoted alumina may also include a thermally treated alkali-promoted alumina, thermally treated promoted alkali-promoted alumina, and thermally treated alkali-promoted hydrotalcite, respectively.
  • the thermal treatment may be performed before use as adsorbent or under the reaction conditions to perform the method of the invention (see also below). Promoting the materials may be performed by mixing or impregnation of a salt of the alkali (and/or other) element with the alumina based material and thermally treating the product thus obtained.
  • Suitable salts are hydroxides, carbonates, nitrates, halides, oxalates etc., especially carbonates.
  • the thermal treatment may in an embodiment be performed in the reactor for performing the method of the invention.
  • the invention may allow the use of coal- derived syngas (synthesis gas) as feed to the WGS reactor, whereas in prior art (sweet shift) processes, coal derived syngas could not easily, or could not be used at all without further measures, as WGS reactor inlet gas.
  • no substantial sulphur deactivation such as by H 2 S, may take place, and thus no pre-desulphurization step may be necessary (although such pre-desulphurization is not excluded in an embodiment).
  • reactor inlet gas or “WGS reactor inlet gas” refer to the gas (and optionally its composition) that is provided to the reactor.
  • different components of the gas mixture might be provided within the reactor via different inlets. Therefore, the term “reactor inlet gas” or “WGS reactor inlet gas” refer to the gas (and optionally its composition) not yet adsorbed and/or reacted (including subjecting to the WGS conditions) according to the invention; or, in other words, the terms “reactor inlet gas” or “WGS reactor inlet gas” can also be indicated as starting mixture.
  • coal-derived syngas or "coal-derived synthesis gas” refer to synthesis gas derived from coal gasification, and which especially includes sulphur compounds, such as H 2 S.
  • This acid gas component may further (thus in addition to H 2 S) comprise one or more components selected from the group consisting of HCN, COS, CS 2 , NO x , SO x and HCl.
  • the total acid gas component concentration (not including CO 2 ) may be in the range of about 200-50.000 ppm, such as 500-50.000 ppm. In this concentration, CO 2 is not included; CO 2 may be present in an amount ranging from for instance 5000 - 500000 ppm.
  • the reactor may further contain a (conventional) water gas shift catalyst, wherein preferably the weight ratio of the adsorbent to catalyst is about > 5, even more preferably about > 20.
  • the weight ratio may be in the range of about 5-50, such as about 5-20, especially about 10-20, or in the range of about 20-100, such as 20-50, especially about 25-50.
  • the reactor does not contain a further (WGS) catalyst (in addition to the adsorbent as defined herein).
  • the invention provides the use of an alkali promoted alumina based material (as adsorbent) for the removal of acid gas components of a gas mixture comprising acid gas components, wherein the acid gas components comprise (a) a sulphur containing compound selected from the group consisting of H 2 S, COS, CS 2 and SO x and (b) another compound selected from the group consisting of HCN, NO x and HCl.
  • the invention provides the use of an alkali promoted alumina based material for the removal of acid gas components of a gas mixture comprising acid gas components, wherein the acid gas components comprise H 2 S and one or more components selected from the group consisting Of H 2 S, CO 2 , HCN, COS, CS 2 , NO x , SO x and HCl.
  • the acid gas components at least comprise H 2 S and CO 2 .
  • the adsorbent comprising the alkali promoted alumina based material may be used as co-adsorbent.
  • the gas mixture (thus provided) may be used for a Fischer-Tropsch reaction but also for other processes.
  • the reaction mixture, enriched in H 2 may thus be provided to a further reactor, which may for instance be a Fischer-Tropsch reactor, or a gas turbine for combustion, or a methanol synthesis reactor, or a CO preferential oxidizer for low-grade H 2 production lean in CO+CO 2 , or a PSA (pressure swing adsorber) system for high grade H 2 production, or a methanol production unit, or an ammonia synthesis reactor, etc.
  • a further reactor which may for instance be a Fischer-Tropsch reactor, or a gas turbine for combustion, or a methanol synthesis reactor, or a CO preferential oxidizer for low-grade H 2 production lean in CO+CO 2 , or a PSA (pressure swing adsorber) system for high grade H 2 production, or a methanol production unit, or an ammonia synthesis reactor, etc.
  • PSA pressure swing ads
  • the gas mixture further comprises CO and H 2 O
  • the alkali promoted alumina based material may further also be used for the simultaneous removal Of H 2 S and CO 2 and the water gas shift reaction of CO and H 2 O from the gas mixture.
  • the gas mixture may comprise coal derived syngas, to which H 2 O is added or has been added.
  • the term 'TSfO x " relates to compounds wherein x is equal to or larger than 1, such as NO, N 2 O 3 , NO 2 , N 2 O 4 , N 2 O 5 , etc., especially at least NO and/or NO 2 .
  • SO x relates to compounds wherein x is equal to or larger than 1, such as SO, S 2 O 2 , SO 2 , SO 3 , S 6 O 2 , S 7 O 2 , etc., especially at least SO 2 .
  • Figure 1 schematically depicts an embodiment of an arrangement comprising a reactor for performing the process of the invention
  • Figures 2a-2f show experimental results.
  • FIG. 1 schematically depicts an arrangement 2 comprising an embodiment of a reactor 1 for performing the process of the invention.
  • the reactor 1 in this embodiment encloses a single bed 11, which comprises an adsorbent 10 (and optionally a catalyst).
  • WGSR water gas shift reaction
  • the process of the invention is however not confined to the herein schematically depicted arrangement 2 and the schematically depicted reactor 1.
  • the term reactor may also relate to a plurality of reactors, which may especially be arranged parallel. Therefore, also the term “single reactor” may relate to a plurality of reactors arranged in parallel.
  • the process that may be applied, the water gas shift process may comprise a reaction stage comprising (a) providing a gas mixture 200 comprising CO, H 2 O and an acid gas component to reactor 1 containing adsorbent 10 and (b) subjecting the gas mixture 200 to water gas shift reaction conditions to perform the water gas shift reaction.
  • the adsorbent 10 may comprise an alkali promoted alumina based material, such as potassium promoted alumina.
  • Alumina may for instance be promoted with K2CO3.
  • promoted relates to the intimate mixture of a compound with another compound that acts like a promoter.
  • Alumina may for instance be promoted with K 2 CO 3 by mixing an (aqueous) slurry of both components and removing water by drying, and optionally calcining the dried product.
  • alkali promoted alumina based materials may for instance comprise sodium or lithium promoted aluminas.
  • the alumina may for instance comprise ⁇ alumina, but may also comprise gibbsite or gamma alumina.
  • the adsorbent 10 may also comprises an alkaline earth alkali promoted alumina.
  • the alumina is promoted with the alkaline earth element (sometimes also indicated as "earth alkaline element").
  • the adsorbent 10 may comprise a magnesium alkali promoted alumina.
  • the alumina may be potassium and magnesium promoted.
  • Alumina may for instance be promoted with K2CO3 and Mg(NOs) 2 by mixing an (aqueous) slurry of both components and removing water by drying, and optionally calcining the dried product.
  • Other alkali and alkaline earth promoted aluminas may for instance comprise aluminas promoted with one or more of potassium, sodium or lithium and promoted with one or more of magnesium, (calcium,) strontium and barium.
  • the promotion can be performed with most commonly available salt of the promoters, not necessarily carbonates, or oxides, as these may be formed under reaction conditions in any case.
  • the adsorbent 10 may comprise a transition metal promoted alumina.
  • the alumina may not only be promoted with an alkali element, and optionally with an alkaline earth element, but may optionally also be promoted with a transition metal element.
  • Such transition metal element may be selected from the groups 3-12, especially from the groups 6-11, such as for instance one or more of Mn, Fe, Co, Ni, Cu and Zn.
  • the adsorbent 10 may comprise a promoted layered double hydroxide (LDH), especially alkali promoted layered double hydroxide, and even more especially the adsorbent 10 comprises a promoted hydrotalcite, especially alkali promoted hydrotalcite.
  • LDH promoted layered double hydroxide
  • the product of a thermally treated relates to a product that has been heated at a temperature above about 200 0 C, even more especially above about 400 0 C.
  • hydrotalcite when heating this hydrotalcite in the reactor before the WGS reaction or during the WGS reaction, the hydrotalcite modifies to a promoted alumina, such as K2CO3 and MgO promoted alumina, since at elevated temperatures, the hydrotalcites may at least partially rearrange in mixed oxides while loosing hydrotalcite crystalline structure hydrotalcites and layered double hydroxide.
  • a promoted alumina such as K2CO3 and MgO promoted alumina
  • metal promoted compound refers to compounds to which these metals, in any form, are attached and/or included. The metal will in general be present on the compound as oxide and/or as hydroxide.
  • a mixed bed of a catalyst of a metal oxide and a compound may essentially consist of discrete particles (especially granules or extrudates) of the metal oxide and of the compound (respectively), whereas when a promoted compound is used in a (single) bed, the bed will essentially consist of particles (especially granules or extrudates) which comprise an intimate mixture of the compound and its promoter(s).
  • the acid gas component may comprises H 2 S, but may also (alternatively or additionally) comprise one or more components selected from the group consisting of HCN, COS, CS 2 , NO x , SO x and HCl.
  • the gas mixture 200 comprising the starting components CO and H 2 O (for the WGSR) and the acid gas components may be introduced to the reactor 1 via one or more inlets.
  • a mixture comprising at least CO and H 2 S originates from a first supply 20, for instance from a coal gasifier, an oil gasifier, a petcoke gasifier, a natural gas reformer, from biomass gasification, etc. can be introduced to a first inlet 101 to the reactor 1.
  • H 2 O for instance from a second supply 30, can be added to this mixture, either via the same supply line, such that the compete gas mixture is introduced at inlet 101, or via a separate supply line, such that H 2 O may be introduced at a second inlet 102 in the reactor 1.
  • the supply of the gas mixture 200 or gas components from first and second supplies 20, 30 may be controlled by for instance valves 21 and 32, respectively.
  • the gas mixture 200 before a reaction and before adsorption in the reactor 1 has a composition, which can be predetermined, and which composition is also indicated as "inlet composition".
  • the complete gas mixture 200 may be introduced via one supply line into reactor 1. For instance, the gas mixture may originate from supply 20.
  • one or more of the components may also be introduced to a gas mixture comprising at least CO and H 2 S before entering the reactor, such as in the example above wherein H 2 O is introduced in the gas mixture from supply 30 via valve 32.
  • one or more components of the gas mixture 200 may also be introduced to the reactor separate from the mixture 200 comprising at least CO and H 2 S, such as in the example above wherein H 2 O is introduced in the gas mixture from supply 30 via valve 31.
  • gas components of the gas mixture 200 may also introduced from a third supply 40, which may be introduced for instance in reactor 1 via opening 103 (and optional valve 41).
  • Such further supply 40 may also for instance be used to provide gasses for pressure swing, like steam (see also below).
  • gasses for pressure swing can be provided counter current to the feed stream 20.
  • compositions are indicated:
  • Examples 1-5 relate to potassium promoted hydrotalcite, Mgo.8iAlo.19(OH) 2 (COs)COgS-O-IS[K 2 COs] and example 6 relates to K promoted alumina, AI2O3.0.185[K 2 COs].
  • the first comparative example indicates a gas composition comparable to a coal derived syngas at the inlet of pre-shift section (or without pre-shift section).
  • the second comparative example shows a gas composition comparable to a coal derived syngas at the outlet of pre-shift section (or with pre-shift section).
  • the gas mixture 200 may comprise a H 2 S reactor inlet concentration of at least 200 ppm, especially at least about 500 ppm H 2 S relative to the gas mixture 200.
  • the gas mixture 200 comprises coal-derived synthesis gas.
  • the gas mixture 200 is fed to reactor 1 (or is composed at the inlets) and is subjected to water gas shift conditions (also indicated herein as WGSR conditions).
  • This may mean introducing a predetermined amount of H 2 O such that the WGSR may take place, providing the gas mixture 200 an elevated temperature or bringing the gas mixture 200 to an elevated temperature (in the reactor 1), wherein the elevated temperature is preferably at least about 300 0 C, even more preferably at least about 400 0 C, and further preferably below about 700 0 C, even more preferably below about 65O 0 C, such as equal to or below about 600 0 C.
  • the adsorbent alone already provides the WGS reaction in addition to the advantageous adsorption of CO 2 (i.e.
  • subjecting the gas mixture 200 to water gas shift reaction conditions to perform the water gas shift reaction may comprise subjecting the gas mixture 200 to a temperature in the range of 300-600 0 C.
  • the adsorbent 10 may be comprised in one or more beds 1 1 ; the schematic picture indicates one single bed 11. Further, additional catalyst may be present, in other beds or mixed with the adsorbent 10.
  • the reactor 1 further contains a WGS catalyst
  • the weight ratio of the adsorbent 10 to the catalyst is preferably > 5.
  • Conventional WGS catalysts are for instance Iron-Chromium based catalyst, high temperature shift catalysts, Copper-Zinc- Aluminium mixed oxide catalysts, low temperature shift catalysts, sulphided Cobalt Molybdenum catalysts, sour shift catalysts or any noble metal based catalyst.
  • the reactor 1 only contains the adsorbent 10 as active species (i.e. here adsorbent and WGS catalyst).
  • the reactor 1 does not contain a further catalyst (and/or no other adsorbent).
  • the reaction stage is performed in a single reactor 1 , preferably in a single bed 11.
  • reaction mixture 300 enriched in H 2
  • second reactor 400 which may for instance be a Fischer- Tropsch reactor or a gas turbine for combustion or a methanol synthesis reactor, or a CO preferential oxidizer for low-grade H 2 production lean in CO+CO 2 , or a PSA (pressure swing adsorber) system for high grade H 2 production, or a methanol production unit, or an ammonia synthesis reactor, etc.
  • Products thereof, indicated with reference 402 may be released from the second reactor 50 via outlet 402.
  • Reference 105 indicates an opening or outlet in the reactor 1, arranged to be in gaseous communication with the optional second reactor 400.
  • a valve 108 may be present in the gas channel between the reactor 1 and the optional second reactor 400.
  • Optional second reactor 400 may have an opening or inlet 401, arranged to be in gaseous contact (via the gas channel) with the reactor 1.
  • An advantage of the application of the invention may also be for instance that the downstream reactors for H 2 production may be smaller (such as a methanator, PrOx, PSA) and/or that the H 2 purity can be increased because the present invention already removes significant amounts of impurities (CO 2 , H 2 S, etc).
  • a regeneration stage may be applied.
  • the process of the invention further comprises an adsorbent regeneration stage, wherein CO 2 and optionally the acid gas component are at least partially removed from the adsorbent 10.
  • Regeneration may be applied by pressure-swing and/or thermal swing, processes known in the art. Pressure- swing herein also comprises partial pressure swing, i.e.
  • the partial pressure of a gas component is controlled.
  • steam may be provided to the adsorbent 10.
  • the partial pressure Of H 2 O may be increased in the reactor 1.
  • CO 2 and H 2 S and/or other acid gas components may substantially release from the adsorbent 1.
  • gases like N 2 or Air could also be used; in a pressure swing unit the sorbent can also be regenerated using CO 2 .
  • Combinations of two or more gasses may also be applied.
  • the off-gasses may be released from the reactor 1, for instance via an exhaust 107, such as via a further outlet 106 to exhaust 107.
  • the regeneration stage is preferably be performed at a temperature in the range of about 200-600°C, even more preferably above about 25O 0 C, yet even more preferably in a range of about 300-500 0 C.
  • the reaction stage and regeneration stage may be performed in a cyclic way, wherein the reaction stage is followed by one or more regeneration stages.
  • Outlets 105 and 106 may also be connected to a parallel reactor 1 (see above) for e.g., pressure equalisation.
  • the invention also provides the use of an alkali promoted alumina based material, i.e. adsorbent 10, for the removal of acid gas components of a gas mixture 200 comprising (a) a sulphur containing compound selected from the group consisting of H 2 S, COS, CS 2 and SO x and (b) another compound selected from the group consisting of HCN, NO x and HCl.
  • the invention provides the use of an alkali promoted alumina based material for the removal of acid gas components of a gas mixture comprising acid gas components, wherein the acid gas components comprise H 2 S and one or more components selected from the group consisting of H 2 S, CO 2 , HCN, COS, CS 2 , NO x , SO x and HCl.
  • the acid gas components at least comprise H 2 S and CO 2 .
  • the adsorbent 10 may also be used for the co-adsorption of CO 2 and H 2 S in gas mixtures. Therefore, such adsorbent 10 may be used for the purification of natural gas.
  • the adsorbent 10 may be used for the simultaneous removal of one or more sulphur containing acid gas components, especially H 2 S, and CO 2 and (for performing) the water gas shift reaction of CO and H 2 O from the gas mixture 200 comprising CO, CO 2 , H 2 O and sulphur containing acid gas components, especially H 2 S.
  • Figures 2a-2e show a number of experiments, wherein on the x-axis the number of cycles (i.e. a time scale with time on stream (T. O. S.) in minutes) is indicated, and on the y-axis the normalized response is indicated. In figure 2e, on the right y-axis, the non-normalized CO 2 -response is indicated in arbitrary units. From these data it can be concluded that there is co-adsorption of CO 2 and H 2 S. Further, it appears that the material has water gas shift activity while still having the ability to co-adsorb CO 2 and H 2 S, even after initial saturation with CO 2 .
  • the sorbent is periodically exposed to HeZH 2 SZC(VH 2 O and H 2 OZN 2 at conditions specified in the table above.
  • the responses for He, H 2 S and CO 2 are represented by 201, 202 and 203, respectively.
  • the response of the inert tracer 201 is added as reference for the hydrodynamics of the experimental reactor. From this figure it can be concluded that there is a reversible co-adsorption of CO 2 and H 2 S because of the reproducible delayed responses for 202 and 203 with respect to 201. If there was no adsorption taking place then CO 2 and H 2 S would breakthrough at the same time as the non-reactive trace gas He. This is clearly not the case. If there was no co-adsorption the CO 2 and H 2 S would breakthrough at different times relative to the tracer gas. It is clear to those skilled in the art that this is not the case.
  • experiment 2b is repeated using a halved H 2 S content.
  • H 2 S content there still is reversible co-adsorption of CO 2 and H 2 S.
  • the CO 2 and H 2 S still breakthrough at the same time relative to each other.
  • the figures 2a-2c taken together show that co-adsorption is occurring.
  • the sorbent is periodically exposed to H 2 S rich syngas and H 2 OZN 2 at conditions specified in the table above.
  • the responses for H 2 and CO are represented by 204 and 205 respectively.
  • the sorbent is active for the WGS reaction.
  • the sorbent is periodically exposed to i) syngas free of CO 2 and H 2 S and ii) H 2 OZN 2 at conditions specified in the table above.
  • the WGS reaction proceeds to completion in the period before the sorbent is saturated by CO 2 .
  • the sorbent displays some WGS activity following breakthrough of CO 2 . This is evidenced by the observation that the H 2 response is higher than in the feed, while the CO response is lower than in the feed.
  • promoted alumina based materials are for instance selected from K-Al 2 O 3 , Cs-Al 2 O 3 , K-MgO- Al 2 O 3 , Li-MgO-Al 2 O 3 , K-MnO-Al 2 O 3 , K-Fe-Al 2 O 3 Li-HTC, K-(Mn-Al)HTC, K-(Fe-Al)HTC (with HTC being hydrotalcite).
  • Alumina promoted with potassium was tested for its CO 2 capacity.
  • the alumina ( ⁇ - Al 2 O 3 ) was promoted by impregnation with a solution of potassium carbonate as follows: the material was first dried at 80 0 C for 16h and 5.O g of dried material were further impregnated by incipient wetness method with a aqueous solution containing 1.41g of K 2 CO 3 . The resulting wet powder was dried at 120 0 C for 16h. Further, alumina was also promoted with potassium and magnesium, potassium and iron or potassium and manganese according to the following procedures: - Mg 5 K-Al 2 O 3 : ⁇ -Al 2 O 3 was dried at 80 0 C for 16h.
  • ⁇ -Al 2 O 3 was dried at 80 0 C for 16 h. 8.48g Fe(NO 3 ) 3 .9H 2 O dissolved in 5.70 g deionised water were used for impregnating 9.0Og of ⁇ - Al 2 O 3 .
  • the resulting wet powder was dried at 120 0 C for 16h and further calcined at 400 0 C for 4 hours. 5.00 g of the resulting material were further impregnated by incipient wetness method with an aqueous solution containing
  • ⁇ -Al 2 O 3 was dried at 80 0 C for 16 h. 6.23g Mn(NO 3 ) 2 .4H 2 O dissolved in 5.70 g deionised water were used for impregnating 9.0Og of ⁇ - Al 2 O 3 .
  • the resulting wet powder was dried at 120 0 C for 16h and further calcined at 400 0 C for 4 hours. 5.00 g of the resulting material were further impregnated by incipient wetness method with an aqueous solution containing 1.41 g OfK 2 CO 3 . The resulting wet powder was dried at 120 0 C for 16 h.
  • the CO 2 sorption capacities were measured under the following conditions: 2 grams of the material in a U-shaped glass reactor were first treated with a flow of N 2 with 10.7% water at 400 0 C during one hour. Then, CO 2 was added to the gas mixture for 45 minutes (gas mixture: 5.8% CO 2 , 10.7% H 2 O and balance N 2 ). Desorption stage under a flow of N 2 with 10.7% water was then carried out at 400 0 C for one hour. This adsorption/desorption cycle was repeated two times, while the CO 2 flow in the outlet was continuously monitored using the mass spectrometer.
  • Table 2 shows some gas sample compositions and conditions.
  • Table 3 shows a comparison between breakthrough capacities measured when moving from Gas Composition GC3 to GC2, compared to GC3 to GCl. The materials were exposed to condition GC3 for at least 2 hours before switching to the second gas composition. All three materials show decreased CO 2 breakthrough capacities in the presence of H 2 S compared to its absence. However, the hydrotalcite based materials, HTCl and HTC2, have higher CO 2 breakthrough capacity in the presence OfH 2 S than ALOl.
  • Pellets of HTCl and HTC2 were prepared for loading in a 2m long reactor, with 38mm internal diameter.
  • the reactor was heated to 400 0 C, and the material exposed to gas compositions GC4 and GC5 in a cyclic manner for more than 1000 cycles.
  • the crush strength of the pellets was determined before and after the experiment, as shown in table 6.
  • HTCl had lost its mechanical strength and had been degraded to a powder.
  • HTC2 became weaker but still remain mechanically robust.
  • XRD x-ray diffraction spectrometry
  • the invention provides a water gas shift process comprising a reaction stage comprising (a) providing a gas mixture comprising CO, H 2 O and an acid gas component to a reactor containing an adsorbent, wherein the adsorbent comprises an alkali promoted alumina based material and (b) subjecting the gas mixture to water gas shift reaction conditions to perform the water gas shift reaction, wherein the acid gas component comprises H 2 S, and wherein the gas mixture comprises a H 2 S reactor inlet concentration of preferably at least 200 ppm H 2 S relative to the gas mixture.
  • the invention provides such process, wherein the acid gas component further comprises one or more components selected from the group consisting of HCN, COS, CS 2 , NO x , SO x and HCl.
  • subjecting the gas mixture to water gas shift reaction conditions to perform the water gas shift reaction comprises subjecting the gas mixture to a temperature in the range of 300-600 0 C.
  • the invention provides such process, wherein the adsorbent comprises potassium promoted alumina or hydrotalcite.
  • the invention provides such process, wherein the adsorbent is further promoted with one or more elements selected from the group consisting of Mg, Mn, Ag, Cu, Co, Pb, Fe and Cd, especially selected from Mg, Fe and Mn.
  • the adsorbent may comprises an alkaline earth alkali promoted alumina or hydrotalcite.
  • the invention provides such process, wherein the adsorbent comprises magnesium alkali promoted alumina or hydrotalcite.
  • the adsorbent comprises an alkali promoted hydrotalcite having the chemical formula [M ⁇ (1 . x) Al ( ⁇ x) M ⁇ i ((1 . ⁇ )x) (OH) 2 ][C n -] (x/n) .yH 2 O.zM I (m) A m - wherein
  • M 1 is one or more selected from the group consisting of Li, Na, K, Rb and Cs;
  • M ⁇ is one or more selected from the group consisting of Mg, Mn, Cu, Co, Fe, Cd and Cr;
  • Al is aluminium
  • M i ⁇ is optionally one or more of the group consisting of Fe, Cr and Mn;
  • C n ⁇ is one or more anions selected from the group consisting of N(V, SO 4 2" , CO 3 2" , CH 3 CO 2 “ , Cl “ , Br “ , F “ and I “ ;
  • a m” is one or more anions, such as selected from CO 3 2" , CH 3 CO 2” , C 2 O 4 2" ,
  • the invention provides such process, wherein the reactor further contains a water gas shift catalyst, wherein the weight ratio of the adsorbent to catalyst is > 5. In an embodiment, the reactor does not contain a further catalyst.
  • the invention further provides the use of an alkali promoted alumina based material for the removal of acid gas components of a gas mixture comprising acid gas components, wherein the acid gas components comprise H 2 S and one or more components selected from the group consisting of CO 2 , HCN, COS, CS 2 , NO x , SO x and HCl.
  • the invention further provides such use, wherein the acid gas components at least comprise H 2 S and CO 2 . Yet, the invention provides such use, wherein the gas mixture further comprises CO and H 2 O, for the simultaneous removal of H 2 S and CO 2 and the water gas shift reaction of CO and H 2 O from the gas mixture.
  • the invention provides such use, wherein the gas mixture comprises coal-derived synthesis gas.

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Abstract

L'invention porte sur un procédé de conversion de CO à la vapeur d'eau comprenant une étape de réaction. L'étapetade de réaction comprend les opérations consistant (a) acheminer un mélange gazeux comprenant CO, H2O et un composant acide gazeux à un réacteur contenant un adsorbant, et (b) soumettre le mélange gazeux à des conditions de conversion de CO à la vapeur d'eau pour effectuer la conversion de CO à la vapeur d'eau. L'adsorbant comprend une matière de type hydrotalcite avec un alcali comme promoteur. Le composant acide gazeux comprend H2S.
PCT/NL2009/050709 2008-11-21 2009-11-23 Procédé de conversion de co à la vapeur d'eau WO2010059055A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA2744416A CA2744416C (fr) 2008-11-21 2009-11-23 Procede de conversion de co a la vapeur d'eau
CN200980152370.4A CN102264633B (zh) 2008-11-21 2009-11-23 水煤气变换方法
EP09760022.5A EP2362848B8 (fr) 2008-11-21 2009-11-23 Procédé de conversion de co à la vapeur d'eau
BRPI0921995A BRPI0921995B1 (pt) 2008-11-21 2009-11-23 processo de deslocamento de gás para água , e, uso de um adsorvente.
US13/112,881 US8617512B2 (en) 2008-11-21 2011-05-20 Water gas shift process
AU2011202375A AU2011202375B2 (en) 2008-11-21 2011-05-23 Water Gas Shift Process
ZA2011/03815A ZA201103815B (en) 2008-11-21 2011-05-24 Water gas shift process

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NL1036224 2008-11-21
NL1036224A NL1036224C2 (en) 2008-11-21 2008-11-21 Water gas shift process.

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AU2011202375A Division AU2011202375B2 (en) 2008-11-21 2011-05-23 Water Gas Shift Process

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EP2407421A1 (fr) 2010-07-13 2012-01-18 Air Products And Chemicals, Inc. Procédé et appareil de production d'alimentation et d'hydrogène
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US20130209339A1 (en) * 2011-08-08 2013-08-15 Ah-Hyung Alissa Park Methods And Systems For Producing Hydrogen And Capturing Carbon Dioxide
NL2008313A (en) * 2012-02-17 2013-08-21 Stichting Energie Water gas shift process.
CN103702742A (zh) * 2011-08-03 2014-04-02 荷兰能源建设基金中心 气体吸附剂的再生
EP2716350A1 (fr) * 2012-10-08 2014-04-09 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Production de gaz de synthèse appauvri en CO2 utilisant un sorbant à base de magnésium
WO2014083517A1 (fr) 2012-11-29 2014-06-05 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de sechage de gaz humide par dessicants et de regeneration des dessicants par gaz de synthese pour mise en oeuvre de la reaction de gaz a l'eau
EP2874741A4 (fr) * 2012-07-19 2016-06-08 Res Triangle Inst Sorbant régénérable pour l'élimination de dioxyde de carbone
EP3604210A1 (fr) 2018-08-02 2020-02-05 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Production de dioxyde de carbone et d'ammoniac à partir de gaz résiduels dans l'industrie sidérurgique et métallurgique
WO2022017829A1 (fr) 2020-07-24 2022-01-27 Totalenergies Se Réduction des émissions de co et de co2 à partir d'un ccf dans une combustion partielle avec co-production de h2
EP3967653A1 (fr) 2020-09-11 2022-03-16 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Processus de conversion eau-gaz amélioré par sorption pour la formation d'un flux de produits co2 et d'un flux de produits h2
EP3967386A1 (fr) 2020-09-11 2022-03-16 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Processus d'adsorption de purge par déplacement pour séparer le co2 d'un autre gaz
EP4166216A1 (fr) 2021-10-15 2023-04-19 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Optimisation d'un processus d'adsorption modulée en pression

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EP2407421A1 (fr) 2010-07-13 2012-01-18 Air Products And Chemicals, Inc. Procédé et appareil de production d'alimentation et d'hydrogène
CN103702742B (zh) * 2011-08-03 2017-02-15 荷兰能源建设基金中心 气体吸附剂的再生
CN103702742A (zh) * 2011-08-03 2014-04-02 荷兰能源建设基金中心 气体吸附剂的再生
US20130209339A1 (en) * 2011-08-08 2013-08-15 Ah-Hyung Alissa Park Methods And Systems For Producing Hydrogen And Capturing Carbon Dioxide
CN102502493A (zh) * 2011-11-23 2012-06-20 安徽淮化股份有限公司 一种适用于co变换装置的热氮气置换系统
US9260302B2 (en) 2012-02-17 2016-02-16 Stichting Energieonderzoek Centrum Nederland Water gas shift process
KR20140126326A (ko) * 2012-02-17 2014-10-30 쉬티흐틴크 에네르지온데르조크 센트룸 네델란드 수성 가스 전환 방법
WO2013122467A1 (fr) * 2012-02-17 2013-08-22 Stichting Energieonderzoek Centrum Nederland Processus de conversion du gaz à l'eau
NL2008313A (en) * 2012-02-17 2013-08-21 Stichting Energie Water gas shift process.
KR102037212B1 (ko) 2012-02-17 2019-10-28 쉬티흐틴크 에네르지온데르조크 센트룸 네델란드 수성 가스 전환 방법
EP2874741A4 (fr) * 2012-07-19 2016-06-08 Res Triangle Inst Sorbant régénérable pour l'élimination de dioxyde de carbone
EP2716350A1 (fr) * 2012-10-08 2014-04-09 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Production de gaz de synthèse appauvri en CO2 utilisant un sorbant à base de magnésium
WO2014083517A1 (fr) 2012-11-29 2014-06-05 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de sechage de gaz humide par dessicants et de regeneration des dessicants par gaz de synthese pour mise en oeuvre de la reaction de gaz a l'eau
WO2020025815A1 (fr) 2018-08-02 2020-02-06 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Production de dioxyde de carbone et d'ammoniac à partir de gaz résiduels provenant de l'industrie de l'acier et du métal
EP3604210A1 (fr) 2018-08-02 2020-02-05 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Production de dioxyde de carbone et d'ammoniac à partir de gaz résiduels dans l'industrie sidérurgique et métallurgique
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NL1036224C2 (en) 2010-05-25
ZA201103815B (en) 2012-01-25
EP2362848A1 (fr) 2011-09-07
CN102264633B (zh) 2015-07-08
CA2744416A1 (fr) 2010-05-27
CN102264633A (zh) 2011-11-30
US8617512B2 (en) 2013-12-31
US20110293509A1 (en) 2011-12-01
EP2362848B8 (fr) 2019-05-22
BRPI0921995B1 (pt) 2019-12-17
AU2011202375B2 (en) 2013-09-05
EP2362848B1 (fr) 2019-01-23
CA2744416C (fr) 2018-11-20
AU2011202375A1 (en) 2011-06-09
BRPI0921995A2 (pt) 2016-08-23

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