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Supported Poly(allyl)amine and Derivatives for CO2 Capture from Flue Gas or … — Georgia Tech Research Corporation (US20240024849A1)

ABSTRACT

Abstract

Supported amine polymer adsorbents based on polymers containing only or primarily primary amines sites are to be used as regenerable adsorbents for CO 2 capture from ultra-dilute gas streams, such as ambient air, or from mixtures of gases containing preferably at least I 0% oxygen. and can also be useful for use at the moderate gas pressures found in typical post-combustion capture processes, such as flue gas from large point sources such as coal-fired power plants. Preferred supported solid amine adsorbents of this invention are based on poly(allylamine) (“PAA”) and poly(vinyl amine) (“PVAm”), both of which are linear polymers, and their derivatives, containing substantially all primary amine groups, supported on substrates. Preferred such substrates include silica mesocellular foam (MCF) and mesoporous-.gamma.-alumina, as well on mesoporous-.gamma.-alumina coated throughout the pores of MCF, most preferably of monolithic structure. Preferred derivatives include the guanidinylated and cross-linked poly(allylamine) materials.

Description

CLAIM OF PRIORITY

This divisional application claims the priority of its co-pending parent application, application Ser. No. 17/373,759, filed on Jul. 12, 2021, which application is a divisional application of application Ser. No. 14/063,850, filed on Oct. 25, 2013; and the priority of its ultimate parent application, provisional Application No. 61/718,267, filed Oct. 25, 2012. The disclosures of the above applications are herein incorporated by reference as if repeated herein verbatim, and the priority of its parent application. It should be noted, however, that if there are any differences or distinctions between the disclosure herein and the disclosures of the aforesaid incorporated patent application disclosures, the present updated and further refined disclosure expressly set forth herein shall be considered the proper disclosure for the support of (a) the claims set forth herein, as well as (b) the claims of patent eventuating from the present application, and including, without limitation, (c) the claims of future co-pending continuing or divisional applications.

BACKGROUND OF THE INVENTION

It is generally acknowledged that CO 2 plays an important role in global climate change and much effort has been devoted to developing technologies for efficient capture and sequestration of CO 2 . Currently, large-scale separation of CO 2 by liquid phase amine-based absorption is in commercial operation throughout the world in natural gas separations. The technology also represents the benchmark methodology for CO 2 capture from flue gas (post-combustion CO 2 capture). Meanwhile adsorption processes based on solid adsorbents are also being evaluated by many research groups.

Low molecular weight, branched poly(ethylenimine) (PEI), has been previously proposed for CO 2 capture from flue gas, and for ambient air capture. This branched PEI, when impregnated into a porous host such as silica, gives an effective CO 2 adsorbent for extraction of CO 2 from flue gas (10% CO 2 ) or the ambient air (400 ppm CO 2 ) CO 2 adsorption from ultra-dilute gas streams (<1% CO 2 by volume) such as ambient air (350-450 ppm CO 2 by volume) requires adsorbents tuned to bind CO2 very strongly. Solid amine-functionalized materials are known to effectively bind CO 2 and extract it from gas streams. One class of adsorbents, which we shall refer to as “class I” supported amine adsorbents, composed of polymeric amines impregnated onto a porous support, is well known to be an effective adsorbent for CO 2 capture from moderately dilute flue gas streams (5-20% CO 2 by volume). The most commonly used polymer is poly(ethyleneimine) (PEI), which contains a mixture of primary, secondary and tertiary amines. It is known that adsorbents with a higher heat of adsorption will have a steeper adsorption isotherm, leading to materials with larger adsorption capacities at low target gas partial pressures. It is known that primary amines generally have higher heats of adsorption with CO 2 than secondary and tertiary amines.

Accordingly, it is an objective of the present invention to provide an adsorbent that is readily supportable on a solid substrate. It is a further objective of the present invention to provide an adsorbent that has a high proportion of primary amines and lower sensible heat when heated. It is a further objective of the present invention to provide an adsorbent that is less susceptible to oxidative deterioration.

SUMMARY OF THE INVENTION

In accordance with this invention, supported amine polymer adsorbents based on polymers containing only or primarily primary amines sites are to be used as regenerable adsorbents for CO 2 capture from ultra-dilute gas streams, such as ambient air, and can also be useful for use at the moderate gas pressures found in typical post-combustion capture processes, such as flue gas from large point sources such as coal-fired power plants.

The preferred supported solid amine adsorbents of this invention are based on poly(allylamine) (“PAA”) and poly(vinyl amine) (“PVAm”), both of which are linear polymers, and their derivatives, all of which can be effective adsorbents for the reversible adsorption of CO 2 from ultra-dilute gas streams (400 ppm CO 2 ) and moderately dilute gas streams (10% CO 2 ), with their performance under ultra-dilute conditions being competitive with or exceeding the prior state-of-the-art adsorbents based on supported PEI. The amine groups in both PAA and in PVAm are substantially all primary amine groups. Such derivatives include cross-linked poly(allylamine) prepared by crosslinking of poly(allylamine) with epichlorohydrin (PAAEPI), branched poly(allylamine) prepared by branching of poly(allylamine) with divinylbenzene (PAADVB) and guanidinylated poly(allylamine) (PAAPAG). These derivatives can all be supported on and within silica mesocellular foam (MCF), and on mesoporous-.gamma.-alumina, as well as on mesoporous-.gamma.-alumina coated throughout the pores of MCF. The structural formulae of these adsorbents are shown in FIGS. 1 ( a )-( d ) .

It has been found that for adsorbents to be sufficiently supportable on a porous solid support, the adsorbent should be capable of being held within the pores of the support in sufficient quantity to be able to adsorb relatively large quantities of CO 2 . In order to be easily placed within the pore structure of porous supports, it has been found that the adsorbent have a relatively low molecular weight, and therefore have a small enough molecular size as to be capable of ready placement within the pores without blocking access to the gas mixture to be treated. For this reason poly(allylamine) materials are therefore most preferred because they are available in sufficiently low molecular weights to permit ready impregnation into the pores of the porous substrate, whereas the poly(vinylamine) polymers are not often prepared with sufficiently low molecular weights. Generally, the molecular weights of the poly(allylamine) material, including the cross-linked and guanidinylated derivatives, should be less than about 3000 Daltons, preferably less than about 2500 Daltons, and most preferably in the range of about 1000 to about 2200 Daltons.

Although the poly(allylamine) materials are generally well suited for adsorption of CO 2 from ambient air as well as from higher concentration CO 2 materials, the guanidinylated and cross-linked poly(allylamine) materials have been found to have a greater resistance to higher temperatures, and are preferred for the direct adsorption of CO 2 from high temperature flue gases which may contain upwards of 15% CO 2 , but only about 5% CO 2 , as well as the treatment of ultra-dilute gases such as ambient air, which contain 400 ppm O 2 , but 21% O 2 . When the regeneration of the sorbent occurs at higher temperatures and the heated sorbent is then exposed to the ambient air, the greater resistance to oxidative degradation at the higher temperatures becomes significant. This is also the case for mixtures of flue gas and ambient air having an O 2 content of at least 10-15% O 2 . It is noted that linear poly(allylamine) materials also have greater resistance to oxidative degradation at the higher temperatures and especially at the higher O 2 levels in ambient air.

After multiple regenerations in ambient air or flow gas/air mixtures having oxygen contents of greater than 10%, and especially if greater than 15%, the CO 2 adsorption capacity (mol/kg sorbent) and amine efficiency (mol CO 2 /mol amine) of linear poly(allylamine) (PAA), and its deriviatives (cross-linked poly(allylamine), prepared by crosslinking of poly(allylamine) with epichlorohydrin (PAAEPI), and guanidinylated poly(allylamine) (PAAPAG), prepared by reacting PAA with guanidine supported on silica mesocellular foam (MCF), can be greater than the corresponding supported linear or branched poly(ethyleneimine), making the poly(allylamine) compounds especially useful solid adsorbents with high capacity for CO 2 . Their effectiveness, initially, is comparable to that of adsorbents based on supported PEI, including branched and linear low molecular weight PEI, but have been found to have greater durability, most significantly resistance to oxidative degeneration, after many regeneration cycles, followed by exposure to ambient air after each regeneration. The PAA and PVAm, in addition, both have a minimal amount of carbon atoms that add unwanted sensible heat to adsorbents used in this type of process.

In order to be commercially useful, an adsorbent must be capable of remaining active for thousands of cycles, i.e., adsorption and regeneration, during its lifetime. Although it has been generally found that PAA and PVAm behave similarly with regard to their ability to capture CO 2 , especially at the highly dilute levels of CO 2 such as existing in ambient air, PAA was found to be preferred due to a greater ease and lower cost of synthesis (using presently known processes) as compared to PVAm: PAA can be made directly from the allylamine hydrochloride monomer at the desired molecular weight, whereas PVAm requires two steps, synthesis of Poly(N-Vinyl formamide) (PNVF) that is then base or acid hydrolyzed into PVAm (See FIG. 2 ), and has not been readily formed at the desired molecular weight size to fit within the pores of the available porous substrates.

The resistance to oxidative degeneration is present whether the PAA or PVAm polymers are supported on and in a silica mesocellular foam (“MFC”) substrate or on and in a mesoporous γ-alumina substrate. Such impregnated substrates are prepared by impregnating a pre-synthesized, amine-containing organic polymer, e.g., PAA, PAAPAG or PAAEPI, into the pores of the supporting substrate. For such materials, of suitably low molecular weight, the amine loading scales with the pore volume of the support substrate.

SUMMARY DESCRIPTION OF DRAWINGS

FIGS. 1 ( a )-( b ) show the structural formulae for the prior art Polyethelamine materials used for the adsorption of carbon dioxide, and items FIGS. 1 ( c ), ( d ), ( e ) and ( f ) are the structural formulae for the Poly(allylamine) and Poly(vinylamine) and their two derivatives of the Polyallylamines the crosslink Polymer with epichlorhydrin (“PAAEPI”) and the guanidinylated Poly(allylamine) material (“PAAPAG”);

FIG. 1 ( g ) is a Schematic diagram of a PAA linear polymer at high loading, supported on MCF, to form a Class 1 supported adsorbent;

FIG. 2 shows the structural formulas for preparation reactions to form Poly(vinylamine) with the intermediate formation of Poly(N-Vinylformamide);

FIG. 3 shows the structural formula for the crosslinking reaction to form Poly(allylamine);

FIG. 4 shows the structural formula for the crosslinking reaction with epichlorhydrin to form Poly(allylamine)epi (“PAAEPI);

FIG. 5 shows the structural formula for the guanidinylation of Poly(allylamine), to form PAAPAG;

FIG. 6 . is a graph showing the Amine efficiency of PEI branched, PEI linear and PAA linear at different organic loadings at 400 ppm conditions;

FIG. 7 . is a graph showing the CO 2 sorption performances of PAAEPI-loaded MCF of different organic loadings in 10% CO 2 ;

FIG. 8 . is a graph showing the Amine efficiency of PAAEPI-loaded MCF of different organic loadings in 10% CO 2 ;

FIG. 9 is a graph showing the CO 2 sorption performances of PAAEPI-loaded MCF of different loading at 400 ppm CO 2 ;

FIG. 10 is a graph showing the Amine efficiency of PAAEPI-loaded MCF of different organic loadings in 400 ppm CO 2 ;

FIG. 11 is a graph showing the CO 2 sorption of PAAPAG-loaded MFC of different organic loadings in 10% CO 2 ;

FIG. 12 is a graph showing the Amine efficiency of PAAPAG-loaded MFC of different organic loadings in 10% CO 2 ;

FIG. 13 is a graph showing the CO 2 sorption performances of PAAPAG-loaded MFC of different organic loadings in 400 ppm CO 2 ;

FIG. 14 is a graph showing the Amine efficiency of PAAPAG-loaded MFC of different organic loadings in 400 ppm CO 2 ;

FIG. 15 is a graph showing the summary of CO 2 adsorption capacities of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanidinylated PAAPAG in 10% CO 2 ;

FIG. 16 is a graph showing the summary of amine efficiency of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanlinylated PAAPAG in 10% CO 2 ;

FIG. 17 is a graph showing the summary of CO 2 adsorption capacities of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanidinylated PAAPAG in 400 ppm CO 2 ; and

FIG. 18 is a graph showing the summary of amine efficiency of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanidinylated PAAPAG in 400 ppm CO 2 .

DETAILED EXAMPLES OF THE INVENTION

The following are preferred examples of the present invention.

Materials

The following chemicals were used as received from the supplier: Allylamine hydrochloride (AAHCI, TCI), Isopropanol anhydrous (IPA, 99.5%, Al

CLAIM OF PRIORITY

This divisional application claims the priority of its co-pending parent application, application Ser. No. 17/373,759, filed on Jul. 12, 2021, which application is a divisional application of application Ser. No. 14/063,850, filed on Oct. 25, 2013; and the priority of its ultimate parent application, provisional Application No. 61/718,267, filed Oct. 25, 2012. The disclosures of the above applications are herein incorporated by reference as if repeated herein verbatim, and the priority of its parent application. It should be noted, however, that if there are any differences or distinctions between the disclosure herein and the disclosures of the aforesaid incorporated patent application disclosures, the present updated and further refined disclosure expressly set forth herein shall be considered the proper disclosure for the support of (a) the claims set forth herein, as well as (b) the claims of patent eventuating from the present application, and including, without limitation, (c) the claims of future co-pending continuing or divisional applications.

BACKGROUND OF THE INVENTION

It is generally acknowledged that CO 2 plays an important role in global climate change and much effort has been devoted to developing technologies for efficient capture and sequestration of CO 2 . Currently, large-scale separation of CO 2 by liquid phase amine-based absorption is in commercial operation throughout the world in natural gas separations. The technology also represents the benchmark methodology for CO 2 capture from flue gas (post-combustion CO 2 capture). Meanwhile adsorption processes based on solid adsorbents are also being evaluated by many research groups.

Low molecular weight, branched poly(ethylenimine) (PEI), has been previously proposed for CO 2 capture from flue gas, and for ambient air capture. This branched PEI, when impregnated into a porous host such as silica, gives an effective CO 2 adsorbent for extraction of CO 2 from flue gas (10% CO 2 ) or the ambient air (400 ppm CO 2 ) CO 2 adsorption from ultra-dilute gas streams (<1% CO 2 by volume) such as ambient air (350-450 ppm CO 2 by volume) requires adsorbents tuned to bind CO2 very strongly. Solid amine-functionalized materials are known to effectively bind CO 2 and extract it from gas streams. One class of adsorbents, which we shall refer to as “class I” supported amine adsorbents, composed of polymeric amines impregnated onto a porous support, is well known to be an effective adsorbent for CO 2 capture from moderately dilute flue gas streams (5-20% CO 2 by volume). The most commonly used polymer is poly(ethyleneimine) (PEI), which contains a mixture of primary, secondary and tertiary amines. It is known that adsorbents with a higher heat of adsorption will have a steeper adsorption isotherm, leading to materials with larger adsorption capacities at low target gas partial pressures. It is known that primary amines generally have higher heats of adsorption with CO 2 than secondary and tertiary amines.

Accordingly, it is an objective of the present invention to provide an adsorbent that is readily supportable on a solid substrate. It is a further objective of the present invention to provide an adsorbent that has a high proportion of primary amines and lower sensible heat when heated. It is a further objective of the present invention to provide an adsorbent that is less susceptible to oxidative deterioration.

SUMMARY OF THE INVENTION

In accordance with this invention, supported amine polymer adsorbents based on polymers containing only or primarily primary amines sites are to be used as regenerable adsorbents for CO 2 capture from ultra-dilute gas streams, such as ambient air, and can also be useful for use at the moderate gas pressures found in typical post-combustion capture processes, such as flue gas from large point sources such as coal-fired power plants.

The preferred supported solid amine adsorbents of this invention are based on poly(allylamine) (“PAA”) and poly(vinyl amine) (“PVAm”), both of which are linear polymers, and their derivatives, all of which can be effective adsorbents for the reversible adsorption of CO 2 from ultra-dilute gas streams (400 ppm CO 2 ) and moderately dilute gas streams (10% CO 2 ), with their performance under ultra-dilute conditions being competitive with or exceeding the prior state-of-the-art adsorbents based on supported PEI. The amine groups in both PAA and in PVAm are substantially all primary amine groups. Such derivatives include cross-linked poly(allylamine) prepared by crosslinking of poly(allylamine) with epichlorohydrin (PAAEPI), branched poly(allylamine) prepared by branching of poly(allylamine) with divinylbenzene (PAADVB) and guanidinylated poly(allylamine) (PAAPAG). These derivatives can all be supported on and within silica mesocellular foam (MCF), and on mesoporous-.gamma.-alumina, as well as on mesoporous-.gamma.-alumina coated throughout the pores of MCF. The structural formulae of these adsorbents are shown in FIGS. 1 ( a )-( d ) .

It has been found that for adsorbents to be sufficiently supportable on a porous solid support, the adsorbent should be capable of being held within the pores of the support in sufficient quantity to be able to adsorb relatively large quantities of CO 2 . In order to be easily placed within the pore structure of porous supports, it has been found that the adsorbent have a relatively low molecular weight, and therefore have a small enough molecular size as to be capable of ready placement within the pores without blocking access to the gas mixture to be treated. For this reason poly(allylamine) materials are therefore most preferred because they are available in sufficiently low molecular weights to permit ready impregnation into the pores of the porous substrate, whereas the poly(vinylamine) polymers are not often prepared with sufficiently low molecular weights. Generally, the molecular weights of the poly(allylamine) material, including the cross-linked and guanidinylated derivatives, should be less than about 3000 Daltons, preferably less than about 2500 Daltons, and most preferably in the range of about 1000 to about 2200 Daltons.

Although the poly(allylamine) materials are generally well suited for adsorption of CO 2 from ambient air as well as from higher concentration CO 2 materials, the guanidinylated and cross-linked poly(allylamine) materials have been found to have a greater resistance to higher temperatures, and are preferred for the direct adsorption of CO 2 from high temperature flue gases which may contain upwards of 15% CO 2 , but only about 5% CO 2 , as well as the treatment of ultra-dilute gases such as ambient air, which contain 400 ppm O 2 , but 21% O 2 . When the regeneration of the sorbent occurs at higher temperatures and the heated sorbent is then exposed to the ambient air, the greater resistance to oxidative degradation at the higher temperatures becomes significant. This is also the case for mixtures of flue gas and ambient air having an O 2 content of at least 10-15% O 2 . It is noted that linear poly(allylamine) materials also have greater resistance to oxidative degradation at the higher temperatures and especially at the higher O 2 levels in ambient air.

After multiple regenerations in ambient air or flow gas/air mixtures having oxygen contents of greater than 10%, and especially if greater than 15%, the CO 2 adsorption capacity (mol/kg sorbent) and amine efficiency (mol CO 2 /mol amine) of linear poly(allylamine) (PAA), and its deriviatives (cross-linked poly(allylamine), prepared by crosslinking of poly(allylamine) with epichlorohydrin (PAAEPI), and guanidinylated poly(allylamine) (PAAPAG), prepared by reacting PAA with guanidine supported on silica mesocellular foam (MCF), can be greater than the corresponding supported linear or branched poly(ethyleneimine), making the poly(allylamine) compounds especially useful solid adsorbents with high capacity for CO 2 . Their effectiveness, initially, is comparable to that of adsorbents based on supported PEI, including branched and linear low molecular weight PEI, but have been found to have greater durability, most significantly resistance to oxidative degeneration, after many regeneration cycles, followed by exposure to ambient air after each regeneration. The PAA and PVAm, in addition, both have a minimal amount of carbon atoms that add unwanted sensible heat to adsorbents used in this type of process.

In order to be commercially useful, an adsorbent must be capable of remaining active for thousands of cycles, i.e., adsorption and regeneration, during its lifetime. Although it has been generally found that PAA and PVAm behave similarly with regard to their ability to capture CO 2 , especially at the highly dilute levels of CO 2 such as existing in ambient air, PAA was found to be preferred due to a greater ease and lower cost of synthesis (using presently known processes) as compared to PVAm: PAA can be made directly from the allylamine hydrochloride monomer at the desired molecular weight, whereas PVAm requires two steps, synthesis of Poly(N-Vinyl formamide) (PNVF) that is then base or acid hydrolyzed into PVAm (See FIG. 2 ), and has not been readily formed at the desired molecular weight size to fit within the pores of the available porous substrates.

The resistance to oxidative degeneration is present whether the PAA or PVAm polymers are supported on and in a silica mesocellular foam (“MFC”) substrate or on and in a mesoporous γ-alumina substrate. Such impregnated substrates are prepared by impregnating a pre-synthesized, amine-containing organic polymer, e.g., PAA, PAAPAG or PAAEPI, into the pores of the supporting substrate. For such materials, of suitably low molecular weight, the amine loading scales with the pore volume of the support substrate.

SUMMARY DESCRIPTION OF DRAWINGS

FIGS. 1 ( a )-( b ) show the structural formulae for the prior art Polyethelamine materials used for the adsorption of carbon dioxide, and items FIGS. 1 ( c ), ( d ), ( e ) and ( f ) are the structural formulae for the Poly(allylamine) and Poly(vinylamine) and their two derivatives of the Polyallylamines the crosslink Polymer with epichlorhydrin (“PAAEPI”) and the guanidinylated Poly(allylamine) material (“PAAPAG”);

FIG. 1 ( g ) is a Schematic diagram of a PAA linear polymer at high loading, supported on MCF, to form a Class 1 supported adsorbent;

FIG. 2 shows the structural formulas for preparation reactions to form Poly(vinylamine) with the intermediate formation of Poly(N-Vinylformamide);

FIG. 3 shows the structural formula for the crosslinking reaction to form Poly(allylamine);

FIG. 4 shows the structural formula for the crosslinking reaction with epichlorhydrin to form Poly(allylamine)epi (“PAAEPI);

FIG. 5 shows the structural formula for the guanidinylation of Poly(allylamine), to form PAAPAG;

FIG. 6 . is a graph showing the Amine efficiency of PEI branched, PEI linear and PAA linear at different organic loadings at 400 ppm conditions;

FIG. 7 . is a graph showing the CO 2 sorption performances of PAAEPI-loaded MCF of different organic loadings in 10% CO 2 ;

FIG. 8 . is a graph showing the Amine efficiency of PAAEPI-loaded MCF of different organic loadings in 10% CO 2 ;

FIG. 9 is a graph showing the CO 2 sorption performances of PAAEPI-loaded MCF of different loading at 400 ppm CO 2 ;

FIG. 10 is a graph showing the Amine efficiency of PAAEPI-loaded MCF of different organic loadings in 400 ppm CO 2 ;

FIG. 11 is a graph showing the CO 2 sorption of PAAPAG-loaded MFC of different organic loadings in 10% CO 2 ;

FIG. 12 is a graph showing the Amine efficiency of PAAPAG-loaded MFC of different organic loadings in 10% CO 2 ;

FIG. 13 is a graph showing the CO 2 sorption performances of PAAPAG-loaded MFC of different organic loadings in 400 ppm CO 2 ;

FIG. 14 is a graph showing the Amine efficiency of PAAPAG-loaded MFC of different organic loadings in 400 ppm CO 2 ;

FIG. 15 is a graph showing the summary of CO 2 adsorption capacities of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanidinylated PAAPAG in 10% CO 2 ;

FIG. 16 is a graph showing the summary of amine efficiency of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanlinylated PAAPAG in 10% CO 2 ;

FIG. 17 is a graph showing the summary of CO 2 adsorption capacities of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanidinylated PAAPAG in 400 ppm CO 2 ; and

FIG. 18 is a graph showing the summary of amine efficiency of PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, and guanidinylated PAAPAG in 400 ppm CO 2 .

DETAILED EXAMPLES OF THE INVENTION

The following are preferred examples of the present invention.

Materials

The following chemicals were used as received from the supplier: Allylamine hydrochloride (AAHCI, TCI), Isopropanol anhydrous (IPA, 99.5%, Alfa Aesar), Methanol (MeOH, 99.5%, Sigma Aldrich), 2,2-Azobisiobutyric acid dimethyl ester (MAIB, 98%, AK Scientific), 2,2′-Azobisisobutyronitrile (AIBN, 98%), Epichlorohydrin (EPI, 99.5%, Sigma Aldrich), Strongly basic ion exchange resin (Ambersep 900 OH form, Sigma-Aldrich), Poly(acrylamide) GC standards (PAM2950, PAM15K, PAMI00K, American polymer standards), Water for GPC (TraceSelect, Sigma Aldrich), pluronic P123 EO-PO-EO triblock copolymer (P-123, Sigma-Aldrich), 1,3,5-trimethylbenzene (TMB, 97%, Sigma-Aldrich), tetraethyl orthosilicate (TEOS, 98%, Sigma-Aldrich), ammonium fluoride (NH4F, >96%, AlfaAesar), hydrochloric acid (HCl, cone. 37%, J. T. Baker), Poly(ethylenimine) branched, Mw 800 Da (PEI branched, Sigma-Aldrich), Poly(ethylenimine) linear, Mw 2,500 Da (PEI linear, Polyscience). IH-pyrazole-Icarboxamidine monohydrochloride (PC, 99%, ACROS), Phosphate buffer (PBS, pH 7.4, AMRESCO); pseudobomite (Catapal B, 74.3% Al.sub.2O.sub.3, anhydrous isopropanol (99.5%, Alfa Aesar), methanol (200 proof, J. T. Baker), ethanol (99.5%, ACROS), strongly basic ion-exchange resin (Ambersep®-900-(OH), Fluka), nitric acid (68%, J. T Baker).

Synthesis of Polymers

Synthesis of Poly(vinylamine), PVAm

The synthesis route toward PVAm involved free-radical polymerization of (N-vinyl) formamide, to yield poly(N-Vinyl formamide), PNVF, that was base or acid hydrolyzed into PVAm ( FIG. 2 ).

Synthesis of Poly(N-Vinyl Formamide), PNVF Intermediate

A mixture of (N-vinyl) formamide 2.00 g (0.03 mol), 2- propanol 10 mL and AIBN 0.36 mg (18 wt % relative to the monomer) were degassed by three freeze-pump-thaw cycles (77K). The polymerization was carried out in an oil bath at 65.degree. C. for 18 h under argon atmosphere. The polymer was precipitated by excess acetone two times to remove unreacted monomer then dried under vacuum for 24 h to give PNVF 1.8 g (90%). HNMR (D20, ppm) 1.57 (2H, —CH2-), 3.79 (IH, —CH—), 7.90 (IH, HCO—).

Hydrolysis of PNVF to PVAm

The solution of PNVF, 1.5 gin 73.0 g of 2N NaOH (2 wt % polymer concentration) was degassed by argon purging for I hour. Then the solution was kept at constant temperature 75.degree. C. for 64 hours to reach complete hydrolysis with 100% conversion [See Bromberg, L.; Hatton, T. A; Polymer, 2007, 48, 7490-7498.]. After cooling to room temperature, the resulting PVAm polymer was acidified with concentrated HCl to precipitate the PVAm-HCl salt. The precipitate was washed with methanol to neutral pH and dried under vacuum to give 1.3 g (90%). sup.IR NMR (D20, ppm): 2.16 (2H, —CH2-), 3.74 (IH, —CH—) as shown in FIG. 2 .

PVAm was obtained by using a strongly basic ion exchange resin to remove the salt. Additional degassed deionized water (30 ml) and 16 g strongly basic ion exchange resin (Amberlyst 900) were added to the mixture and stirred for I h. The solution of PVAm polymer at pH 12.0, was filtered, the solvents was removed by vacuum and it was dried under vacuum for 24 h to give 1.40 g product (90%).

Synthesis of Poly(allylamine), PAA (FIG. 3 )

The solution of allyl amine hydrochloride 6 g (0.06 mol), isopropanol 3.99 g and MAIB 0.79 g (3.43 mmol) was deaerated by argon purging for I h. The free radical polymerization was carried out at a constant temperature of 60.degree. C. for 48 h. The resulting polymer was washed with excess methanol to remove unreacted monomer. PAA-HCl was recovered by filtration and dried under vacuum at room temperature for 24 h to give 4.50 g of white powder (70%). HNMR (D20, ppm): 1.35 (2H, —CH2-), 1.89 (IH, —CH—), 2.85 (2H, —CH2-). IR (KBr): ˜3500 cm and 3300 cm ((N—H) of NH2), two sharp peaks consistent with primary amines, ˜2,700 cm −1 (sp 3 C—H stretching of CH2), 1600 and 1480 cm −1 (N—H of NH3+), ˜1390 cm −1 (C—H bending of CH2). A broad band in the range ˜1000 cm −1 (out-of-plane bending of N—H).

PAA was obtained by using a strongly basic ion exchange resin to remove the salt. Additional degassed deionized water (30 ml) and 16 g strongly basic ion exchange resin (Amberlyst 900) were added to the mixture and stirred for 1 h. The resulting polymer solution (pH 12) was filtered, the solvent was removed by vacuum and the polymer dried under vacuum for 24 h to give 4.0 g of product (60%). 1 H NMR (D20,ppm): 1.10 (2H, —CH2-), 1.51 (IH, —CH—), 2.55 (2H, —CH2-). The weight average molecular weight was measured to be 1412 Da.; PDI was about ca. I.

Synthesis of Soluble Cross-Linked Poly(Allylamine) Using Epichlorohydrin, PAAEPI

The synthesis route of PAAEPI is shown in FIG. 4 . A 20% w/v solution of linear PAA-HCl was prepared under argon atmosphere. PAA-HCl 2.0 g (0.02 mol) and degassed H.sub.2O 8 g were mixed. NaOH 0.72 g was added. When the temperature of the solution dropped to ambient temperature (the dissolution of NaOH is exothermic), EPI 84 uL (1.07 mmol) was added. The reaction mixture was vigorously stirred for 16 h and slowly stirred for an additional 2 h. The soluble cross-linked PAAEPI was obtained by using the strongly basic ion exchange resin to remove the salt. Additional degassed deionized water 30 ml and 16 g strongly basic ion exchange resin (Amberlyst 900) were added to the mixture and it was stirred for I h. The resulting solution of cross-linked PAA polymer, pH 14.0, was filtered, the solvent was removed by vacuum and the polymer was dried under vacuum for 24 h to give 1.8 g product (90%). 1 H NMR (D 2 O, ppm): 1.15 (2H, —CH2-), 1.56 (IH, —CH—), 2.65 (2H, —CH2-). IR (KBr): ˜3300 cm −1 ((N—H stretching) of NH 2 ), ˜2900 cm −1 (sp 3 C—H stretching of CH2), ˜1600 cm −1 and 1490 cm −1 (N—H bending of NH2), ˜1400 cm −1 (C—H bending of CH2). The weight average molecular weight was measured to be 1000 Da.; PDI was about ca.1. 1 Note that the lowest Mn and Mw standard used here is poly(acrylamide) of ca.2765 and 3350 Da, respectively. Many polymers produced here are of lower molecular weight, hence, molecular weight data are often extrapolated outside the calibration range. Given this fact and that the calibration polymers are of different type [poly(acrylamide)], the molecular weight and PDI data are not rigorously quantitative and should be viewed as a very rough estimate.

Synthesis of Guanidinylated Poly(Allylamine), PAAPAG

The synthesis of PAAPAG is shown in FIG. 5 . PAAI 0.00 g (0.017 mol) was dissolved in 50 mL of PBS and then 0.40 g (2.728 mmol) of PC was added. The molar ratio of PAA and PC, which contributes the guanidinylated group, is 6.4:1. The guanidinylation reaction was performed under weakly basic conditions, pH 9.5, at room temperature for 60 h. Then 16 g strongly basic ion exchange resin (Amberlyst 900) was added to the mixture and it was stirred for I h to remove the salt. The solvent was removed by vacuum and the polymer was dried under vacuum for 24 h. 1

1 H NMR (D20, ppm): 1.20 (2H, —CH2-), 1.55 (IH, —CH—), 2.65 (2H, —CH2-), 3.17 (2H, —CH2-). IR (KBr): ˜3500 cm-I ((N—H) of NH2, ˜2900 cm-I (wide and strong overlapping peak from (N—H) of NH2 and (sp 3 C—H stretching) of CH2, ˜1500 cm −1 (N—H bending of NH2), ˜1400 cm −1 (C—H bending of CH2). The weight average molecular weight was measured to be 1000 Da.; PDI was about ca. I.

TABLE 1

Molecular weight distributions from GPC.

Retention

Sample

time

ID

(min)

Mn

Mw

PDI

PAM2590

54.54

2765

3350

1.21

PAM15K

49.57

12800

15500

1.21

PAMI00K

43.15

50000

99000

1.98

PAA

57.53

1412

1412

1.00

PAAEPI

58.65

1000

1000

1.00

PAAPAG

58.56

1047

1047

1.00

Synthesis of Silica Mesocellular Foam, MCF

A solution of PI23 16.0 g, water 260 g and 47.4 g of concentrated HCl were stirred for 24 h to complete copolymer dissolution. The flask was then transferred to a 40.degree. C. oil bath and TMB 1.6 g was added. The mixture was stirred at 40.degree. C. for 2 h, then TEOS 34.6 g was added. The solution was stirred additional for 5 min and then left quiescent for 20 h at 40.degree. C. A solution of NH4F 0.184 gin deionized water 20 mL was added as a mineralization agent—and the mixture was swirled for 5 min before aging at constant temperature of 100° C. for 24 h. The resulting precipitate was filtered, washed with excess water, dried, and calcined in air at 550° C. for 6 h (1.2° C./min ramp). A typical silica MCF was obtained, 15 g (95%).

Synthesis of Mesoporous γ-Alumina

Gamma alumina was synthesized according to earlier reported procedure by surfactant P-123@ mediated self-assembly of pseudoboehmite nano particles. In a typical procedure, 13.75 g of commercial pseudoboehmite from Sasol North America (Catapal B, 74.3% Al 2 O 3 ) was peptized in a mixture of 1.27 g nitric acid (Fischer Scientific, ˜70%) and 200 mL deionized water. The suspension obtained was further sonicated for 90 min at room temperature. The sonicated suspension was then stirred at 60° C. for 17 h after which it was cooled to room temperature. The peptized alumina thus obtained was slowly added to a solution of 15.30 g Pluronic P123@ in 200 mL ethanol (200 proof). The resulting solution was further stirred at room temperature of 24 h. Subsequently the solvent was evaporated completely at 60.degree. C. The resulting P-123@-alumina composite was further dried at 75° C. for 24 h. The white sol-gel derived mesoporous γ-alumina was obtained by calcination of this composite at 700° C. for 4 h with a heating ramp of 1° C./min and an intermediate step of 150° C. for 1 h to remove the water and ethanol.

Impregnation of Amine Polymers in MCF

The amine polymer-loaded MCF samples in different weight percentage loadings were prepared by a wet impregnation method. In a typical preparation, the desired amount of amine polymer was dissolved in methanol under stirring for about 15 min while purging the mixture with argon gas, until the polymer dissolved completely. Then, the necessary amount of calcined MCF was added to the mixture. The resulting mixture was stirred for 16 h under an argon atmosphere. The mass ratio of methanol:MCF was always maintained constant at 28: I for each sample, while the ratio of MCF:polymer was varied in each case. The resulting final solid was recovered by removal of the solvent under vacuum and drying under vacuum at ambient temperature for 24 h. The as-prepared adsorbent were denoted as X_MCF_Y, where X represents the amine polymer, Y represents the polymer weight percentage in the sample. PEI branched, PEI linear, PAA linear, cross-linked PAAEPI, guanidinylated PAAPAG are referred to as PEI0.8KBR, PEI2.5KLN, PAA1.4KLN, PAAEPII.0KCL, PAAPAGI.0K, respectively.

Characterization of Amine Polymer Loaded MFC Materials

The polymer structure was characterized using solution 1 H NMR. The measurements were performed using a Mercury Vx 400 MHz with D20 as solvent. FT-IR spectroscopy was performed using a Bruker Vertex 80v (KBr). Molecular weights of the polymers were determined by Gel Permeation Chromatography, GPC, at 30° C. The GPC system was comprised of a Shimadzu LC-20AD pump, a Shimadzu RID-I OA RI detector, a Shimadzu SPD-20A UV detector, a Shimadzu CTO-20A column oven, and Vise tek TSK Viscogel PWXL Guard, G3000, G4000, and G6000 columns mounted in series. The mobile phase consisted of 0.05 M NaNO3 and the flow rate was maintained at 0.4 mL/min. Poly(acrylamide) standards were used (Mw 3350, 15500, 99000), (Mn 2765, 12800, 45600). The surface area, total pore volume and pore size distributions were determined by N2 adsorption-desorption isotherm measurements at 77 K using a Micromeritics TRISTAR2002. The samples were degassed under vacuum at 100° C. overnight before the adsorption measurements. The surface area was determined by the Brunauer-Emmett-Teller (BET) method. Total pore volume, and cell and window pore size were calculated using the Broekhoff-de Boer method with the Frenkel-Halsey-Hill (BdB-FHH) modification. Total pore volume was calculated from the amount of absorbed N2 at P/Po=0.99. The organic loading of the materials was characterized by combustion using a Netzsch STA409 TGA under a flowing nitrogen diluted air stream. About 10 mg of the sample was heated from 27-740° C. at a rate of IO.degree. C./min.

CO 2 Adsorption on Amine Polymer Loaded MFC Materials

The CO 2 adsorption characteristics of the amine polymer-loaded MCF materials were characterized using a TA Q500 thermogravimetric analyzer. A sample weight of about 20 mg of sorbent was loaded in a platinum vessel and tested for CO 2 adsorption performance. The initial activation of the sample was carried out at 120.degree. C. for 3 h after heating to that temperature at 5° C./min rate under an Ar flow of a 100 ml/min. Then, the temperature was decreased to 25° C. and held for 1 h at that temperature before introducing CO 2 . Adsorption was then initiated by exposing the samples to the dry target gas of desired concentration (400 ppm CO 2 or 10% CO 2 balanced with Ar) at a flow rate of 100 ml/min. The adsorption experiment was performed until the pseudo-equilibrium capacity was reached, which was determined to be the time when the weight gains from adsorbed CO 2 changed by less than 0.0001%/min. The adsorption runs were conducted for 12 h for 400 ppm gas experiments and 3 h for 10% CO 2 experiments. Table 1 displays molecular weight distributions obtained from GPC experiments.

Impregnation of Poly(Allyamine) (PAA) and Branched Poly(Ethyleneimine) (PEI) Amine Polymers in Mesoporous Alumina

Poly(allylamine) PAA-, and branched poly(ethyleneimine) PEI-=impregnated mesoporous alumina sorbents were prepared by wet impregnation of method described previously (see Oxidative Stability of Amino Polymer-Alumina Hybrid Adsorbents for Carbon Dioxide Capture, by Bali et al., Energy Fuels 2013, 27, 1547-1554. In a typical synthesis, 1.0 g of alumina support was dispersed in 15.0 mL of methanol (sigma Aldrich, ACS reagent). To the resulting suspension was added drop wise a solution of the calculated amount of polymer (branched-PEI/PAA) in 20 mL of methanol. The resulting solution was stirred at room temperature for another 24 h after which the methanol was evaporated on a rotary evaporator. The obtained PEI/PAA impregnated sorbents were further dried in high vacuum line (˜20 mtorr) at room temperature.

Oxidation of PAA and PEI Amine Polymer Loaded Mesoporous Alumina Materials

The evaluation of the oxidative stability of the synthesized sorbent materials was carried out in a fixed bed contactor. In a typical oxidation experiment, the PAA and PEI impregnated alumina sorbents (400 mg) were packed into a Pyrex tube, 1 cm in diameter, with a frit at the center to allow the flow of gas through the sample without loss of the adsorbent from the reactor. To remove residual water from the system, the sorbent was treated at 110° C. under flowing nitrogen at 15 mL/min 2 h prior to switching it to oxidation gas stream. The temperature was then set to the desired oxidation temperature (110° C., 70° C.), and the flow was switched to the desired O 2 concentration (21% and 5% by volume in N 2 ) for the predetermined time of oxidation of 20 h. The oxidation gas was maintained at 15 mL/min through the reactor during the course of oxidation, after which the reactor was cooled and the adsorbent samples were recovered for further characterization and CO 2 uptake experiments using TGA. The oxidized alumina impregnated PAA/PEE samples have been designated as ALPAA/PEE_PercentOxygen_Temperature of oxidation.

Characterization of Amine Polymer Loaded Mesoporous Alumina Materials

The organic loading relative to alumina support was determined by TGA analysis. The TGA analysis was performed on the adsorbents using a Netzsch STA409PG thermogravimetric analyzer (TGA). The organic groups (amines) on the inorganic support alumina were combusted while measuring the change in total mass. The ramp rate was 10° C./min under a mixed gas stream comprising of air flowing at 90 mL/min and nitrogen flowing at 30 mL/min. Nitrogen physisorption measurements were carried out on a Micromeritics Tristar II 3020 instrument. Before the measurement the samples were degassed under vacuum at 110° C. for at least 15 h. Surface areas, pore diameters, and pore volumes were calculated from the collected isotherm data. Surface areas were calculated using the Brunauer Emmett Teller (BET) method, and pore diameters and pore volumes were calculated using the Broekhoff-de Boer-Frenkel Halsey Hill (BdB-FHH) method. Powder X-ray diffraction (XRD) patterns were collected on a PANalytical X'pert diffractometer with a Cu—K-alpha X-ray source. The 13 C cross-polarization magic angle spinning (CP-MAS) solid-state nuclear magnetic resonance (NMR) measurements were carried out on a Bruker DSX-300 spectrometer. The samples were spun at a frequency of 10 kHz, and 16000-18000 scans were taken for each sample.

CO 2 Adsorption on Fresh and Oxidized Amine Polymer Loaded Mesoporous Alumina Materials

A TA Instruments Q500 TGA was used to measure the adsorption capacities of the materials under dry CO 2 capture conditions. The adsorbent materials were loaded into the platinum sample pan and helium was flowed through the sample chamber, while its temperature was ramped to 110° C. The temperature was held constant at 110° C. for 3 h to remove residual water, and CO 2 potentially adsorbed from the atmosphere. The sample chamber was then cooled to 50° C. After stabilization at 50° C. for 1 h, the gas flow was switched to 10% CO 2 in helium, and the subsequent weight gain because of adsorption of CO 2 was measured. The adsorption was done for 6 h to approach equilibrium capacities for all the tested adsorbents.

Results and Discussion

Resulting of Discussion Regarding Amine Polymer Loaded MFC Materials

The thermochemical and physical properties of MCF and the organic loading in the composite adsorbents were measured by TGA. For the bare MCF material after template removal through calcination, thermogravimetric analysis showed a negligible mass loss of 1.0% attributable to a small amount of silanol condensation. This small mass loss has negligible effect on subsequent thermogravimetric analyses of the polymer loaded mesoporous materials that are used to assess the organic loadings in the composites. For PAA, the significant mass loss occurred when the samples were heated from 27-740° C. The PAA-loaded MCF samples displayed a mass loss of about 10% over the 27° C. to 160° C. range. This can be attributed to desorption of moisture. No obvious mass loss occurred from 160-300° C. The PAA in MCF began to decompose above 300° C. with in all samples. At 740° C., the PAA was completely decomposed and fully removed as volatile species. These results indicate the maximum stability temperature of these samples under these conditions is about 300.degree. C. Other samples were measured in a similar manner.

TABLE 2

Textural properties of MCF materials

before and after polymer loading.

Adsorp-

Desorp-

tion

tion

BET

Cell

Pore

Pore

surlace

diam-

Win-

volume

volume

area

eter

dow

(cm 3

(cm 3

(cm 2

Sample ID

(nm)

(nm)

g− 1 )

g− 1 )

g− 1 )

MCF

39

17

2.7

2.7

660

PEI0.8KBR_MCF 25

39

17

2.1

2.1

330

PEI0.8KBR_MCF 35

39

17

1.5

1.5

221

PEI0.8KBR_MCF 45

39

17

0.8

0.8

118

PEI2.5KLN_MCF 25

39

17

2.1

2.1

365

PEI2.5KLN_MCF 35

39

17

1.8

1.8

300

PEI2.5KLN_MCF 45

39

17

1.5

1.5

226

PAA1.4KLN_MCF 25

39

17

1.5

1.5

258

PAA1.4KLN_MCF_35

39

17

1.2

1.2

190

PAA1.4KLN_MCF 45

39

17

0.8

0.8

129

PAAEPII.OKCL MCF

39

17

1.9

1.9

334

20

PAAEPII.OKCL MCF

39

17

1.4

1.4

235

27

PAAEPII.OKCL MCF

39

17

1.1

1.1

173

34

PAAPAGI.OK MCF 14

39

17

1.3

1.3

272

PAAPAGI.OK MCF 18

39

17

1.2

1.2

253

PAAPAGI.OK MCF 22

39

17

1.1

1.1

214

The surface area, cell diameter, window and pore volume of MCF and the amine polymer-loaded MCF samples were investigated by nitrogen adsorption/desorption isotherms. The textural properties of MCF and all the composite samples prepared in this work are summarized in Table 2. All samples exhibit type IV isotherms according to the IUPAC classification. The isotherms demonstrate a significant reduction in total pore volume and surface area with composites containing different polymer percentages. The BET surface area, cell diameter, and window and pore volumes of the bare MCF are 660 m 2 /g, 39 nm, 17 nm and 2.7 cm 3 /g, respectively. The surface area and pore volume of the composites decrease significantly with increasing polymer loadings. The polymer may be largely contained within the pores, although some part of it could be also outside the pores on the external surface. It appears there is less porosity loss when loading higher molecular weight and linear polymers compared to branched polymers, which is consistent with increased difficulty in all of these polymers into the pores of the support. Together with the TGA results, the data confirm that the amine polymers are loaded into the pore channels of the MCF support.

TABLE 3

Capacity and amine efficiency in 10% CO 2 of synthesized samples.

CLAIMS

Claims ( 5 )

1 . A supported adsorbent comprising a porous substrate on and in which is infused an active adsorbent for CO 2 selected from the group consisting of poly(allylamine), cross-linked poly(allylamine) with epichlorhydrin and guanidylated poly(allylamine), wherein the porous substrate is silica mesocellular foam in monolithic shape.

2 . The supported adsorbent of claim 1 , wherein the CO 2 adsorbent has an average molecular weight of not greater than about 5000 Daltons.

3 . The supported adsorbent of claim 1 , wherein the adsorbent is poly(allylamine), having an average molecular weight of not greater than about 3000 Daltons.

4 . The supported adsorbent of claim 1 , wherein the adsorbent is a cross-linked poly(allylamine) cross-linked with epichlorhydrin.

5 . The supported adsorbent of claim 1 , wherein the average molecular weight of the poly(allylamine) material, is in the range of from about 500 to about 2200 Daltons.

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