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Pelletized immobilized amine sorbent for CO2 capture — U.S. Department Of Energy (US10603654B1)

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The disclosure describes a pelletized sorbent comprising a first component comprising Basic Immobilized Amine Sorbent, a second component comprising inorganic strength additive, and a third component comprising polymer binder, where the Basic Immobilized Amine Sorbent and solid inorganic strength … Pelletized immobilized amine sorbent for CO2 capture — U.S. Department Of Energy (US10603654B1)

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ABSTRACT

Abstract

The disclosure describes a pelletized sorbent comprising a first component comprising Basic Immobilized Amine Sorbent, a second component comprising inorganic strength additive, and a third component comprising polymer binder, where the Basic Immobilized Amine Sorbent and solid inorganic strength additive are interconnected by the polymer binder. The pelletized sorbent is useful for removing CO2 from a gaseous mixture such as a post combustion gas stream.

Description

RELATION TO OTHER APPLICATIONS

This patent application is a continuation-in-part of and claims priority from nonprovisional patent application Ser. No. 15/156,773 filed May 17, 2016, which issued as U.S. Pat. No. 10,065,174 and claims the benefit of provisional application 62/233,493 filed Sep. 28, 2015, which are hereby incorporated by reference.

GOVERNMENT INTEREST

The United States Government has rights in this invention pursuant to the employer-employee relationship of the Government to the inventors as U.S. Department of Energy employees and site-support contractors at the National Energy Technology Laboratory.

FIELD OF THE INVENTION

The disclosure provides a pelletized sorbent for removal of carbon dioxide from a gaseous mixture. The pelletized sorbents are comprised of Basic Immobilized Amine Sorbent in particle or pellet form, inorganic strength additive, and a polymer binder.

BACKGROUND OF THE INVENTION

Carbon sequestration is a viable alternative to reducing the emissions of the greenhouse gas carbon dioxide (CO 2 ) from large point sources. It holds the potential to provide deep reductions in greenhouse gas emissions. Carbon sequestration is a two-step process where the capture of carbon dioxide from a gas stream is followed by permanent storage. The capture step for carbon dioxide represents a major cost in the overall process.

Of particular interest are power generation point sources that use fossil fuels. Since nearly one-third of the anthropogenic CO 2 emissions are produced by these facilities, conventional coal-burning power plants and advanced power generation plantsâsuch as integrated gasification combined cycleâpresent opportunities where carbon can be removed and then permanently stored. At the current time, pulverized coal-fired-base steam cycles have been the predominant electric power generation technology. These will continue to be used predominantly in the near future. Technologies for capturing CO 2 will need to be applied to new more efficient coal-fired facilities and will need to be retrofitted onto existing plants.

For coal-fired power plants, the conventional scrubbing system that is currently the comparative baseline for all other capture technologies is monoethanolamine (MEA) scrubbing. This wet scrubbing process removes the CO 2 in an absorber and then regenerates the spent scrubbing liquor in a vessel by indirectly heating the solution with plant steam. Although there have been large scale commercial demonstrations of this technology, the process has several disadvantages, such as a high heat of reaction, low working capacity, corrosiveness of the solution, the susceptibility of being poisoned, and most notably, its need to be in an aqueous solution. This latter disadvantage results in a large energy need to regenerate the spent solution, especially the sensible heating of the water, which is a minimum of 70 wt % of the solution. The water is recognized as an inert carrier between the absorption and regeneration steps. Another energy loss while regenerating the spent MEA solution includes evaporative heat loss of vaporizing liquid water.

One type of novel CO 2 capture technology that can be applied to various gas streams has, as a basis, dry regenerable solid sorbents. Examples of these types of sorbents are zeolites, activated carbon, alkali/alkaline earth metals, immobilized amines, metal organic framework, etc. A specific sorbent category that shows significant advancement are amine-based solid sorbents, such as Basic Immobilized Amine Sorbents (hereinafter BIAS). BIAS consist of amines (primary, secondary, tertiary, or a combination thereof) deposited onto a porous support. The manner of deposition can be random or structured deposition of the amine onto this support (silica, polymer, etc.). When used in the industrial setting, the dry solid sorbent process may act in a similar fashion to the wet scrubbing process in that the sorbent would be transported between an adsorption step and a regeneration step and in that the sorbent is regenerated by a temperature-swing application.

One of the main benefits in using the solid sorbent is the elimination of the sensible heat for the liquid water as compared to MEA. A secondary benefit lies in the lower heat capacity for the solid versus the liquid solvent, also serving to lower the sensible heat required. More CO 2 can be adsorbed on a weight or volume basis with the amine-based solid sorbents, so the sorbent system is capable of a significant decrease in the heat duty for the regeneration step. A lower cost of energy service for process involving BIAS as compared to amine wet scrubbing may also result. Thus amine-based solid sorbents have the capability to improve the overall energetics of CO 2 capture.

Effective amine-based solid sorbent methodologies are needed for carbon dioxide capture from a gaseous mixture, whether the capture occurs in combustion or gasification power generation systems from flue gas, or in other applications such as natural gas sweetening. Because of the high concentration of carbon dioxide in any of these feed streams, a large quantity of the gas will be reacting with the sorbent and thus produce considerable amounts of exothermic heat. This heat must be removed from the sorbent to prevent temperature instability within the reactor, to assure the sorbent will operate at optimum temperature, and to eliminate the potential degradation of the sorbent because of high temperature excursions.

Unfortunately, reactor designs which are amenable to flowing solid sorbents present issues with management of those mobile solid sorbent. For example, sorbents of a particle size capable of efficient CO 2 adsorption are often easily aerosolized, carried into a flue stream, and progressed further through the reactor system where they cause damage to downstream components and are overall lost. Sorbent particles of sufficient size not to be at risk for being aerosolized are significantly less efficient at sorption per unit mass, which leads to an increase in the mass of sorbent required. Further, sorbent particles themselves are vulnerable in industrial processes as they do not have the structural integrity necessary for prolonged use in reactors. Where the sorbent has low structural integrity and readily breaks down, greater material investment is required and the sorbent becomes less economical to utilize over other competing materials and methods.

Basic Immobilized Amine Sorbents (BIAS or sorbents) and their associated processes are among the most widely studied solid sorbents to mitigate post-combustion carbon dioxide (CO 2 ) emissions. BIAS are organized into three classes (1-3) according to their preparation procedure and amine immobilization mechanisms. Class 1 sorbents are generally prepared by dry or wet impregnation of a support, namely different grades of silica, with a polyamine/hydrophilic solvent (methanol, ethanol, etc.) mixture. Principal polyamines employed are tetraethylenepentamine (TEPA), polyethylenimine (PEI), and generally various linear or branched polyamines that possess different ratios of âNH 2 (primary)/âNH (secondary)/âN (tertiary) amine groups that can potentially adsorb CO 2 . These polyamines are bound to the supports by SiâOHâNH 2 hydrogen bonding and also ionic SiO â . . . âNH 2 + /âNH â interactions. Primary and secondary amines can capture CO 2 under dry and wet conditions while tertiary amines primarily capture CO 2 only under humid conditions. The manner of amine deposition to the support can be random or structured deposition of the amine onto the support. In addition to silica, other supports may include clays, polymers, activated carbons, zeolites, and others.

Class 2 sorbents are typically prepared by wet impregnation of a mixture of a reactive aminosilane and anhydrous hydrophobic solvent, usually toluene, onto a dry, pre-treated silica support. Strict control of the H 2 O content within the system is maintained to manipulate the subsequent grafting reaction between the aminosilane and the silica support. The grafted aminosilanes are immobilized to the silica support via covalent SiâOâSi linkages. These SiâOâSi linkages are also responsible for immobilizing the aminosilane within the bulk of the pore via polymerization.

BIAS sorption capacity is typically calculated either on a weight-percent-of-sorbent basis or mmol CO 2 /g-sorbent basis. For weight percent basis, the weight of adsorbed CO 2 is divided by the weight of sorbent and multiplied by 100. For the mmol CO 2 /g-sorbent basis, the weight of adsorbed CO 2 is divided by the molecular weight of CO 2 (44 g/g-mole), multiplied by 1,000, and divided by the sorbent weight. The sorption capacity of a pelletized sorbent is best measured by exposing the pellet to a CO 2 concentration of ppm level to 100% CO 2 at 0 to 120Â° C. for a period of time until the maximum amount of CO 2 is adsorbed by the sorbent, usually less than or equal to 1 hour. Preferential determination of pellet CO 2 capture capacity involves placing the pellet in a thermogravimetric analyzer (TGA) or fixed bed reactor and exposing the pellet to 10-15 vol % of flowing CO 2 with a balance of either air or inert He or N 2 at 40-75Â° C. The CO 2 concentration range and adsorption temperature here are either in the range of coal-fired power plant flue gas, or can be achieved with minimal process modification. The pellet is first heated at 100-110Â° C. for 10-60 min under flowing air or an inert gas to remove any pre-adsorbed water or CO 2 (from the environment). To determine the CO 2 capture capacity of the pellet in the case of the TGA system, the final weight of the sorbent after CO 2 adsorption is subtracted from the initial weight of the sorbent after pre-treatment, and the weight difference is used to calculate the CO 2 capture capacity. In the case of the fixed bed, CO 2 gas concentration profiles from an effluent measuring device, such as a mass spectrometer, are analyzed and used to calculate the CO 2 capture capacity of the pellet.

Advancements in reactor design from batch, fixed-bed systems to continuous circulating fluidized bed, rotating disk, and moving bed systems, and development of a steam-stable sorbent under practical conditions are promising milestones towards commercialization. However, the aforementioned inherent difficulties in the application of such a small particle-size sorbent to industry scale processes remain. For example, BIAS degrades structurally over time as the material is moved from one industrial environment to another. Additionally, the light BIAS can be picked up by and carried into a gas stream, leading to loss of the material and degradation of components downstream. Further, the current amine based sorbent technology utilized in CO 2 separation is that the impregnated liquid amines of the BIAS sorbents are vulnerable to leaching from the sorbent pores by condensed steam during practical CO 2 adsorption-desorption testing under humidified conditions. The deleterious effect of steam on the CO 2 capture of BIAS materials is widely seen in the literature, and was attributed to, in part, amine leaching from the sorbents. Additional difficulties with small particle sorbents include high energy costs to overcome large pressure drop across sorbent beds and failure of, specifically, internal moving parts (valves, conveyors, etc.) by agglomerated or aerosolized particles. Because of these issues, pelletization of immobilized amine sorbents is advantageous for their large scale application. It would be advantageous to provide a pelletized sorbent for CO 2 capture using an amine-based solid sorbent, where the pelletized sorbent is capable of efficient CO 2 sorption while maintaining an appropriate mass and structural integrity for use in a post-combustion separation system. Such a pelletized sorbent would achieve acceptable CO 2 adsorption while being of an optimized volume and mass for incorporation of large loads of the sorbent into a post-combustion reactor system. Additionally, the pelletized sorbent would more easily provide for integration with existing power or fuel production facilities than current solid sorbents. Thus, through utilization of the pelletized sorbent, increases in CO 2 capture capability while minimizing energy and infrastructure requirements is realized.

Accordingly, it is an object of this disclosure to provide a pelletized sorbent for CO 2 capture comprising: a Basic Immobilized Amine Sorbent, an inorganic strength additive, and a polymer binder.

These and other objects, aspects, and advantages of the present disclosure will become better understood with reference to the accompanying description and claims.

SUMMARY OF THE INVENTION

The disclosure describes a pelletized sorbent comprising a Basic Immobilized Amine Sorbent particle, an inorganic strength additive, and a polymer binder. The pelletized sorbent is useful for removing CO 2 from a gaseous mixture such as a post combustion gas stream.

As illustrated in FIG. 1 , the pelletized sorbent comprises at least the three components Basic Immobilized Amine Sorbent particle, an inorganic strength additive depicted (as fly ash (FA)), and a polymer binder. The polymer binder interconnects the Basic Immobilized Amine Sorbent particles and inorganic strength additive to form an agglomerated pellet capable of CO 2 sorption. The interconnection is a result of both physical binding of the constituents as well as chemical bonding of the polymer binder to the Basic Immobilized Amine Sorbent and inorganic strength additive, thus providing added strength to the pelletized sorbent. The pelletized sorbent features high crush strength, high attrition resistance, good CO 2 capture, and hydrophobicity for use in gas separation operations.

The pelletized sorbents may remove CO 2 from a gaseous mixture where the gaseous mixture necessarily comprises either pure CO 2 or a mixture of CO 2 and at least one other gas. An exemplary gaseous mixture is a post-combustion gas stream from power generation. Such a flue gas stream would comprise N 2 and CO 2 as its primary constituents. Removal in another exemplary gaseous mixture is the sweetening of raw natural gas, where a stream of raw piped gas primarily comprising primarily NH 4 , varying amounts of other hydrocarbons, and CO 2 is sweetened by removal of the CO, such removal accomplished by the pelletized sorbent.

The pelletized sorbents separate CO 2 from the gaseous mixture by sorption of the CO 2 . The pelletized sorbents primarily absorb the CO 2 by first external diffusion of CO 2 from the bulk gas stream to the surface of the pellet; followed by diffusion of CO 2 into the bulk pellet structure; then pore diffusion into the BIAS particles comprising the pellet; and subsequent reaction of CO 2 with BIAS amine groups. Reaction of CO 2 with the amines will primarily form ammonium-carbamate ion pairs, and potentially carbamic acid and bicarbonate (in the presence of H 2 O).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 . Illustrates the internal structure of a pelletized sorbent.

FIG. 2 . Illustrates the effect of fly ash content on the (a) mechanical crush strengths and (b) CO 2 capture capacities of pelletized sorbent.

FIG. 3 : Illustrates the pelletized sorbent (a) structure and (b) H-bonding mechanisms.

FIG. 4 Illustrates use of (a) a cross-linker and (b) the structure of cross-linked material using a diamine for poly (vinyl chloride) (PVC) and a dialdehyde for poly(vinyl alcohol) (PVA).

FIG. 5 : Illustrates an exemplary preparation procedure of a pelletized sorbent comprising BIAS/fly-ash/PVC.

FIG. 6 . Illustrates IR absorbance intensity profiles for (a) âNH 2 + and (b) âNH 3 + species generated during in situ degradation at

RELATION TO OTHER APPLICATIONS

GOVERNMENT INTEREST

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

Accordingly, it is an object of this disclosure to provide a pelletized sorbent for CO 2 capture comprising: a Basic Immobilized Amine Sorbent, an inorganic strength additive, and a polymer binder.

These and other objects, aspects, and advantages of the present disclosure will become better understood with reference to the accompanying description and claims.

SUMMARY OF THE INVENTION

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 . Illustrates the internal structure of a pelletized sorbent.

FIG. 2 . Illustrates the effect of fly ash content on the (a) mechanical crush strengths and (b) CO 2 capture capacities of pelletized sorbent.

FIG. 3 : Illustrates the pelletized sorbent (a) structure and (b) H-bonding mechanisms.

FIG. 4 Illustrates use of (a) a cross-linker and (b) the structure of cross-linked material using a diamine for poly (vinyl chloride) (PVC) and a dialdehyde for poly(vinyl alcohol) (PVA).

FIG. 5 : Illustrates an exemplary preparation procedure of a pelletized sorbent comprising BIAS/fly-ash/PVC.

FIG. 6 . Illustrates IR absorbance intensity profiles for (a) âNH 2 + and (b) âNH 3 + species generated during in situ degradation at 105Â° C. under N 2 flow for FA/EI 423 (20/80) based pelletized sorbents having PVC 62 and PPD-PVC 62 binders.

FIG. 7 . Illustrates an exemplary preparation procedure for pelletized sorbents comprising BIAS/fly-ash/PC.

FIG. 8 : Illustrates the cyclic CO 2 capture capacities of a pelletized sorbent comprising EI 423 /fly-ash/PC.

FIG. 9 . Illustrates CO 2 adsorption of a pelletized sorbent comprising 12.2 wt % PC prepared from binder solutions having different mixing times and of the fresh particle E100/S sorbent.

FIG. 10 . Illustrates the cyclic CO 2 capture capacities of a pelletized sorbent comprising E100-S/fly-ash/PC.

FIG. 11 . Illustrates the effect of different polymer binders on the CO 2 capture capacity and structural integrity.

FIG. 12 . Illustrates the CO 2 capture capacity of a PEI/E3/SIO 2 sorbent.

FIG. 13 . Illustrates a strategy for pelletized sorbent synthesis.

FIG. 14 . Illustrates a comparison of CO 2 capture capacity plus PCR and OCR values of pellets with different ratios of E3/amine (E100 or PEI).

FIG. 15 . Illustrates a comparison of PCR value with increasing antioxidant content.

DETAILED DESCRIPTION OF THE INVENTION

The following description is provided to enable any person skilled in the art to use the invention and sets forth the best mode contemplated by the inventor for carrying out the invention. Various modifications, however, will remain readily apparent to those skilled in the art, since the principles of the present invention are defined herein specifically to provide a pelletized sorbent for CO 2 capture comprising Basic Immobilized Amine Sorbent particles, an inorganic strength additive, and polymer binder.

The pelletized sorbent is an agglomeration of the constituent materials comprising at least Basic Immobilized Amine Sorbent particles, an inorganic strength additive, and polymer binder. The pelletized sorbent may further compromise additives such as amines, dispersants, and non-ionic surfactants or other like materials to enhance structural integrity or CO 2 migration throughout the pellet. Preferred BIAS for pelletization include Class 1, Class 2, or hybrid class 1/ class 2 sorbent (as also known as Class 4) types. Preferred sorbents have silica as the support and amine species that possess any combination of primary and secondary amines, and tertiary amines. BIAS may also include an epoxy-based chemical cross-linker which covalently joins the amines together to enhance their thermal and H 2 O stability. Further, BIAS will include an inorganic antioxidant, such as NaCO 3 or K 2 CO 3 , or organic antioxidant as in phenylenediamine, which serves to inhibit amine oxidation. These sorbents are all capable of being pelletized using the combination of inorganic strength additives and polymer binder as disclosed herein.

Chemical characteristics of BIAS supports such as silica and zeolite promote binding of sorbent pellet constituents. For example, the SiâOH groups of amine/silica supported sorbents and AlâOH groups of amine/zeolite sorbents interact chemically with aromatic benzene. These aromatic groups are present on polymer binders such as polystyrene, with the resulting polymer-BIAS interactions serving to increase the mechanical and structural integrity of the final pelletized sorbents.

Preferred porous supports of the BIAS is any grade of silica with an amorphous, crystalline, or combination of amorphous and crystalline structure. Preferred types and structures of silica include precipitated, fumed, gel, SBA-15, and those with ordered mesoporous structures such as MCM-41. Preferred physical properties of the BIAS silica support include a surface area (BET) between 0 and 2,000 m 2 /g, and a pore volume (BJH) between 0 and 5 cm 3 /g.

Preferred amines for the BIAS are polyamines that contain more than one as well as any combination of the following amine groups: primary (âNH 2 ), secondary (âNH), and tertiary (âN) amines. These polyamines could be nearly pure single components or a combination of different polyamines. Examples of some polyamines used in the BIAS include the following: ethylenimine oligomer mixture (EI 423 , linear/branched mixture, âN/âNH/âNH 2 ratio of 1.3:1:2.2), polyethylenimine with molecular weights between 400 and 20,000 (PEI, âN/âNH/âNH 2 ratio of 1.3:1:1.7 for PEI 800 ), E100 (linear, cyclic, branched mixture), tetraethylenepentamine (TEPA, linear, âN/âNH/âNH 2 ratio of 0:1:0.7), pentaethylenehexamine, and hexaethyleneheptamine. Furthermore, these examples of amines and other potential amines should have but are not limited to a molecular weight (MW) range between 180 and 20,000 g/g-mole to avoid excessive loss from the BIAS at CO 2 desorption temperatures (100 to 110Â° C.) (lower MW values) and to minimize CO 2 diffusion limitations (higher MW values). Preferentially, BIAS sorbents may possess an amine loading between 1 and 65 wt %. Preferred BIAS sorbents possess an amine loading between 20 and 45 wt %. More preferred BIAS sorbents possess an amine loading between 45 and 65 wt %.

BIAS may be functionalized for CO 2 sorption either prior to, or after, palletization. Example 1, for example, provides a method for palletization using BIAS particles requiring only grinding to the desired size for final pellet formation. In Examples 7 and 8, BIAS is functionalized by amine impregnation after pelletization. Accordingly, BIAS includes unfunctionalized BIAS particles during pellet formation.

Chemically cross-linking polymeric amines further increases their molecular weight, increases their viscosity, and generally reduces their H 2 O solubility, all of which enhance the H 2 O stability of their associated immobilized amine sorbents. A key feature herein is the combination of an NâN-diglycidyl-4-glycidyloxyaniline (E3) tri-epoxide (3 epoxide groups per molecule) cross-linker with higher molecular weight polymer amine species (>400 g/g-mol) containing primarily branched structures, or branched structures mixed with aliphatic and aromatic. Higher molecular weight branched structures, name polyethylenimine (PEI 800 ), give greater H 2 O-stability than lower molecular aliphatic species for immobilized amine sorbents due to their higher viscosity which is partially attributed to the physical entanglement of the polymer chains and dense hydrogen bonding among large branched chains.

The combination of branched polyethylenimine with the branched NâN-diglycidyl-4-glycidyloxyaniline was shown to produce a highly porous and H 2 O-insoluble polymer network upon the reaction of these species in a porogen at 105Â° C. after 3 hours. A porous network was also formed when the E3 linker was mixed with aliphatic tetraethylenepentamine (TEPA). A porous network was not obtained when the E3 tri-epoxide linker was substituted with bisphenol A-based D.E.R 332 di-epoxide (2 epoxide groups per molecule), and mixed with either TEPA or PEI 800 . The superiority of the E3 linker over the bisphenol A is due to (i) faster reaction kinetics imparted by the higher concentration of epoxide groups on the E3 tri-epoxide molecule compared to Bisphenol A-based epoxides; (ii) more effective reactions for E3 than for bisphenol A-based linkers with amines due to more easily and more quickly accessed epoxide groups of the smaller and lighter E3 cross-linker compared to the bulkier and heavier bisphenol A-based linkers; (iii) better thermodynamic compatibility of the E3 linker than bisphenol A-based linkers with amines facilitated, in part, by less aromatic groups on the E3 molecule and the tertiary amine group (nitrogen atom bonded to three functional groups and containing no hydrogen atoms) on the E3 molecule; (iv) ability of the E3 linker to capture CO 2 under humid conditions via the tertiary amine group, which is widely known to capture CO 2 in the presence of water vapor. The combination of a bisphenol A-based di-epoxide (EPON) and aliphatic TEPA were used elsewhere in an immobilized amine sorbent. A mono-epoxide, 1,2-epoxybutane, was also used in combination with PEI to make other immobilized amine sorbents. The reasons herein described prove a novel and superior application of the combination of a branched tri-epoxide with a branched polymeric amine or with a mixture of branched polymeric amine/aliphatic amine/cyclic amine for an immobilized amine sorbent. This novel combination described herein was proven to increase the H 2 O stability of immobilized amine sorbents in both particle and pellet form. Other tri-epoxide species, like commercially available Heloxy 48 (aliphatic triglycidyl ether-based; Trimethyol Propane Triglycidyl Ether-based) and also tetra-epoxide species like 4,4â²-methylenebis(N,N-diglycidylaniline) may be used. Preferentially, BIAS sorbents contain between 0.01 and 50 wt % epoxy-based cross-linker. To give both the amine species and the polymer binder resistance to oxidative degradation, antioxidants are incorporated into the BIAS pellet formulation. Antioxidants serve, in place of the amines, as sacrificial electron donors or as electron acceptors towards oxygen radicals. The combination of polymer amines, such as polyethylenimine, with antioxidants, preferably K 2 CO 3 , has a distinct advantage over a similar combination of aliphatic amine/antioxidant. Whereby, greater oxygen diffusion limitations are imparted to the sorbent by branched PEI's relatively high viscosity than by the relatively low viscosity of a linear amine. These diffusion limitations slow the rate of oxygen transport into and oxygen concentration within the sorbent pores, resulting in slower reaction kinetics with the antioxidant. The solubility of the Group 1 carbonates in water at 10-20Â° C. follow as: 1.4 g/100 mL, Li 2 CO 3 <16.4 g/100 mL, Na 2 CO 3 <112 g/100 ml, K 2 CO 3 <260.5 g/100 mL, Cs 2 CO 3 . Higher solubility of carbonates in water lends to a higher ratio of MeOH/H 2 O that can be used in the impregnation solution, resulting in lower solvent evaporation energy costs for particle sorbents and pellets. Preferred concentrations of antioxidant in BIAS sorbents is between 0.01 and 10 wt %.

An extension of the pellet impregnation solution containing polyamine, epoxide linkers, and or K 2 CO 3 antioxidant is towards a pellet coating. The coating solution would contain any of the herein described polyamines, polyepoxides, and antioxidants in any weight ratio relative to each other component of the solution, with a total concentration in solvent between 0.001 wt % and 99.99 wt %. The solvent could be any single liquid or combination of these polar and nonpolar liquids: water, methanol, ethanol, propanol, ethylacetate, diethyl ether, toluene, benzene, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), dioxanes, acetonitrile, chloroform, hexane, dichloromethane, and others. The coating would be applied by suspending the amine (plus other components)-functionalized pellet sorbent in the coating solution and removing the solvent in the rotary-evaporator set-up. This would deposit a coating of the non-volatile materials on the pellets outer surface and provide added water resistance/amine leach resistance.

The BIAS in the pelletized sorbent are the primary constituents responsible for the CO 2 capture of the pelletized sorbents. Preferred CO 2 capture capacity of the starting BIAS particles before pelletization is from about 0.1 to about 1.0 mmol CO 2 /g. More preferred CO 2 capture capacity of the BIAS before palletization is from about 1.0 to about 2.8 mmol CO 2 /g. Most preferred BIAS possess CO 2 capture capacity before pelletization greater than about 2.8 mmol CO 2 /g.

The physical characteristics of the BIAS are critical to their incorporation into the pelletized sorbent. The BIAS powders are preferentially 1 nm to 25 Î¼m in diameter. Further, BIAS particles may be ground prior to pelletization. Such grinding serves to process the particles into a size preferential for incorporation into a pellet as well as expose a greater number of functional groups for CO 2 capture.

Inorganic Strength Additives:

In addition to the Basic Immobilized Amine Sorbents, the pelletized sorbents comprise one or more inorganic strength additives. The inorganic strength additive provides a single or plurality of solid substrate which primarily serve to provide structural support to the pellet. As discussed supra, BIAS, when used directly in gas separation operations, presents difficulties when used at an industrial scale. Thus, addition of an inorganic strength additive, in part, facilitates the structural integrity of the basic immobilized amine sorbent based pellet thereby structural degradation and material loss is avoided.

Ideal inorganic strength additives are available in large quantity, inexpensive, do not drastically decrease the CO 2 capture capacity of the sorbents, and provide a medium capable of increasing the structural integrity of the pellet. Additionally, inorganic strength additives ideally are able to bond either chemically or physically to the other constituents of the pelletized sorbent. Exemplary inorganic strength additives, in addition to fly ash, include bottom ash; clays; activated carbon; and oxide materials themselves typically comprising fly ash, namely silicon dioxide, aluminum oxide, and calcium oxide.

In one embodiment, the inorganic strength additive is fly ash. Fly ash, also known as pulverized fuel ash, is commonly produced as a solid product of coal combustion where the fly ash is carried by and later captured from the flue gas. Fly ash is available in a variety of dimensions and compositions.

Fly ash compositions include functional groups on the surfaces of the fly ash particles which promote agglomeration by chemical bonding. For example, select polymer binders may hydrogen bond to fly ash to promote the formation of pellets and increase their end crush strength. Exemplary functional groups on the fly ash include hydroxyl groups, carboxylic acid groups, and oxides.

As shown in Table 1, fly ash as used in pelletized sorbents is primarily comprised of silica and alumina. However, as a product of primarily coal combustion, the exact composition of other potential fly ash materials may vary depending on the combustion source. Advantageously, both silica and alumina can hydrogen bond to the amine groups of the sorbents and the polymer binder to promote the formation of pelletized sorbent. Therefore, it is expected that other fly ash sources are capable of assisting pellet formation for the sorbents.

TABLE 1

Fly ash major oxides content as wt % and mol %.

Components

wt. %

mol. %

Al 2 O 3

25.59

17.92

CaO

1.55

1.97

Fe 2 O 3

5.02

2.24

K 2 O

2.92

2.21

MgO

0.79

1.4

MnO

0.05

Na 2 O

0.56

0.65

P 2 O 5

0.07

0.04

SiO 2

61.02

72.52

TiO 2

1.11

0.99

Loss on Ignition

1.33

The dimensions (particle size) of the inorganic strength additive allow greater incorporation of the strength additive into the other materials comprising the pellet sorbent. Denser packing of smaller inorganic strength additive particles between larger sorbent particles could strengthen the pelletized sorbent as previously stated. Inorganic strength additive sizes range from about 1 nm to about 25 Î¼m. In a preferred embodiment, inorganic strength additive particle sizes range from about 1 nm to about 2.0 Î¼m.

FIG. 2 shows the effect of the inorganic strength additive fly ash on the average crush strengths (MPa in P crush ) of pellets prepared from a BIAS sorbent containing 50 wt % ethylenimine, MW=423/silica, labeled EI 423 -S, or 50 wt % tetraethylenepentamine (TEPA)/silica, labeled TEPA-S. Crush strength of the final pelletized sorbent (pellets) is an accurate measure of the structural integrity and mechanical strength of the material. Crush strength is defined and calculated as the pellet crush weight divided by the cross-sectional area of the pellet (area=diameter times length). The crush weight is represented as an average of three crush tests, where the standard deviation is less than 15%. In FIG. 2 , the fly ash content is reported as X/Y (Y=100âX), where X/Y is the wt % ratio of FA/sorbent in the dry mixture (FA plus sorbent). This X/Y ratio does not include the content of the polymer binder, or additional amine added together with the polymer binder to the pellet. Overall the final composition of the pellets in FIG. 2 includes 10 wt % polymer binder (poly (vinyl chloride), PVC), 5 wt % of added amine (TEPA), and between 8 wt % (X/Y=10/90) and 35 wt % (X/Y=40/60) fly ash. Increasing the strength additive (fly ash, average particle diameter=1.7 nm) content from X/Y=0 to 40 wt % for EI 423 -S-based and TEPA-S-based sorbent pellets enhanced their mechanical strength by a factor of 1.9 and 3.1, respectively. Furthermore, dense packing of smaller strength additive (fly ash) particles (D P,avg. =1.7 Î¼m) between larger sorbent particles strengthened the pellet by mechanically interlocking the particles, and also reducing voids that would weaken the pellet.

In the final pelletized sorbents (pellets), the inorganic strength additive may range from about 5 wt % to about 37 wt % of total dry pelletized sorbent weight. Preferentially, the inorganic strength additive ranges from about 8 wt % to about 37 wt % of total pelletized sorbent. More preferentially, the fly ash composition is from about 18 wt % to about 37 wt % of total pelletized sorbent.

Polymer Binders:

In the pelletized sorbent, the Basic Immobilized Amine Sorbents and inorganic strength additives are agglomerated via at least one polymer binder. Polymer binders serve to interconnect the respective components to form a rigid network suitable for structurally stabilizing the pellet through chemical, physical, or a combination of chemical and physical bonding. In one example, the polymer binder polyvinyl chloride (PVC) operates by way of introducing a polymer network which physically entraps the BIAS and inorganic strength additive particles.

Pelletized sorbents may further comprise more than one polymer binder. As in Example 1, a single polymer binder such as PVC may be utilized. However, more than one polymer binder may be utilized. In Example 8, a combination of poly (chloroprene) latex and polyethylenimine is utilized.

The mechanism responsible for the agglomeration may be physical, chemical, or both physical and chemical. In physical agglomeration, the agglomerated components are physically intertwined by the polymer binder. The binding polymer interactions, in part, create a network of physical cross-links which contribute to the pellet strength.

With respect to chemical bonding, the polymer binder functions primarily through two types of chemical interactions, hydrogen bonding (H-bonding) and covalent bonding (cross-linking). Hydrogen bonding in general involves the electrostatic interactions between H atoms attached to electronegative atoms such as N, O, and other electronegative atoms attached to molecules in close proximity. FIG. 3 ( a ) shows the interconnected network of the BIAS pellets comprised of BIAS and fly ash as strength additives dispersed within a polymer binder. The schematic of FIG. 3 ( b ) shows that three different H-bonding mechanisms within the pellet are possible. Mechanisms (1) and (2) involve interactions between functional groups of the polymer binder chains and the surface hydroxyl groups (âOH) of either a silica-type support of the BIAS sorbent or the fly ash particles. The polymer binder possess functional groups, such as chlorine (âCl) groups for PVC or poly (chloroprene) (PC), hydroxyl groups (âOH) for PVA, urethane (âNHCOOâR) groups for polyurethane (PU), or other electronegative atoms that interact with the H atoms of the fly ash or silica âOH groups to adhere the polymer binder to the fly ash and sorbent.

The long polymer binder chains of the polymer binder entangle through intermolecular or intramolecular H-bonding which further contributes to the pellet strength. Mechanism (3) of FIG. 3( b ) involves H-bonding interactions between the polymer binder and the amines coated of the BIAS. Polymer binders, in addition to PVC and PC may adhere the pellets through hydrogen bonding of their various functional groups.

In one embodiment, the polymer binders are hydrophobic. Hydrophobic polymers can be described generally in three different ways, which are not wetted by water, i.e. the contact angle of a small droplet is greater than zero, not soluble in water, or minimally absorbing or adsorbing adsorb. In contrast, materials that are wetted by water, dissolve in water, or absorb water are considered hydrophilic. Hydrophobic polymers accompany material such as the poly(chloroprene) (PC), PVC, polystyrenes, polyurethanes, and epoxies. Hydrophobic polymers are one method by which to impart the necessary hydrophobicity to the pellets. In another embodiment, the polymers are hydrophilic; wetted by water, dissolve in water, or absorb/adsorb water. These polymers can include poly (vinyl alcohol), poly (vinylpyrrolidone), and poly (acrylamide). To impart hydrophobicity to the pellet, a hydrophobic additive such as those polymers previously mentioned would be included in the BIAS. In general, pellets can be prepared either with a hydrophobic sorbent and a hydrophilic polymer binder, or a hydrophilic sorbent and a semi-hydrophobic polymer binder.

Preferred polymer binders include the following polymers, preferred functional groups of these and of modified versions of these polymers include the following: F (fluorine atom)-poly(vinylidene fluoride), poly(tetrafluoroethylene); acetal (RCOR)-poly(vinyl acetate); Cl (chlorine atom)-isoprene, polyisoprene, chlorinated polyethylene; ether (ROR)-poly(vinylbutyral), poly(vinylbutyral-co-vinylalcohol-co-vinylacetate), poly(vinyl chloride-co-vinyl acetate-co-vinyl alcohol), poly(ethyl vinyl ether), poly(vinyl formal); ester (RCOOR)-polyester poly(tert-butyl acrylate), poly(vinyl cinnamate); carbonate (RCOO â )-polycarbonate, polypropylene carbonate); carboxylic acid (RCOOH)-poly(vinyl chloride-co-acrylic-acid); nitrile-poly(acrylonitrile), and poly(acrylonitrile-co-butadiene); imide (RCO) 2 NR; and amide (RCONR). Polymers containing any of these preferred functional groups is included. Co-polymers comprised of more than one of these preferred polymers is also included.

Another preferred polymer binder and modified versions thereof is poly(chloroprene) latex (PC latex). PC latex differs from poly(chloroprene) pure polymers in the following ways: (1) PC latex is a suspension (emulsion) of nano-sized solid particles in water; therefore, it lends a slightly different binding mechanism to the pelletized sorbent than pure PC polymer; (2) being that PC is in emulsion form it does not have to be dissolved into any solvent because it is already in a usable form, which is in contrast to the pure PC that has to be ground from large chunks into small particles and then dissolved in a solvent to make the polymer binder solution; and (3) the PC latex is largely hydrophobic but contains hydrophilic functional groups that allow it to exist in the latex/emulsion state and these groups help the PC latex be more compatible to impregnated polyamines in comparison to pure PC. To summarize, although used in the same way as the pure PC, the PC latex has a slightly different binding mechanism than the pure PC and more importantly it dramatically simplifies the pellet synthesis process because it does not require any special preparation of its corresponding polymer binder solution; no special grinding or heating in toxic solvent steps.

In one example, poly (vinyl alcohol) (PVA), which has âOH groups and poly (vinyl acetate) (PVAc), which has âOCâOâ groups, are alternatives to PVC that can hydrogen bond to fly ash and BIAS to form pelletized sorbents. The aryl groups of polystyrenes can interact with SiâOH groups of amine/silica sorbents and also AlâOH groups of zeolite.

Physical modification of the constituents also promotes pelletization via increasing bonding among the polymer binder. Physically grinding the BIAS before pelletization exposes bulk amine groups previously inside the sorbent pores. In one instance, the exposed, high-viscosity EI 423 of the pellets in FIG. 2 would interact with the PVC binder and resist the compressive force during crush testing. In other words, available âNH 2 and âNH groups of viscous immobilized amines, in general, play an increased role in binding the pelletized sorbents. Furthermore, the strength additive can also be ground for providing added pellet strength.

Polymer binders may also be modified to include functional groups which enhance CO 2 sorption. In one embodiment, polymer binders are modified to comprise amine functional groups. During experimental studies, pelletized sorbents comprising PVC formed ammonium ions while heating at the CO 2 desorption temperature of 105Â° C. for 100 min. Ammonium ions were formed via protonation of the amines by HCl, which was generated, in part, by the elimination reaction of PVC with highly basic aliphatic amines of the BIAS sorbent or binder solution. These protonated amines cannot absorb CO 2 which decreases overall CO 2 capture capacity during long term cycling. Modification of PVC with a less basic aromatic amine, for example p-phenylenediamine (PPD), before pelletizing favors the substitution reaction to form âNH groups, which capture CO 2 , and reduce the chlorine content of PVC. Reduced chlorine in the modified exemplary PPD-PVC binder discourages the formation of harmful HCl during cycling of the pelletized sorbent. Additional species that may be used to modify the PVC binder in addition to PPD include aniline, o-toluidine, diaminotoluenes, n-methylaniline, and diphenylamine.

PVC may also be modified by reacting it with a strong organic or inorganic base or nucleophile in the liquid or solid phase, utilizing the elimination reaction, where the resulting PVC will be dechlorinated to form HCl. This HCl can then be neutralized by rinsing the modified PVC (initially solid or precipitated from solution) with an aqueous inorganic base solution. Organic nucleophiles may include linear polyamines such as ethylenediamine, tetraethylenepentamine, and poly(ethylenimine), and choline hydroxide. Inorganic nucleophiles/bases include sodium carbonate, sodium hydroxide, other metal-hydroxide species, potassium thiocyanate, sodium iodide.

Preferentially, pelletized sorbents comprise those polymer binders with chlorine groups such as PVC and PC. Other polymer binders include the hydroxyl group polymer PVA, followed by PVAc (acetate groups) then polystyrene (aromatic benzyl groups).

The pelletized sorbents are typically comprised of 1 to 15 weight % of the total dry pelletized sorbent as polymer binder. Preferential weight percent . . . 5 to 8 wt %. Most preferential weight percent 8 to 15 wt %.

Additives:

In one embodiment, the pelletized sorbents contain additives. A cross-linker additive introduces covalent bonding as a pellet binding mechanism, attaching two or more polymer chains within the network together via the cross-linker. As shown in FIG. 4 , polymer binder chains are interconnected via chemical bonds with a cross-linker having at least two reactive functional groups, one each bond to a polymer binder. Cross-linkers act beneficially to increase pellet mechanical strength and also increase hydrophobicity. FIG. 4 ( b ) illustrates that pellets bound with PVC are cross-linked with a diamine (NH 2 âRâNH 2 ), where each of the primary amine groups (âNH 2 ) chemically react with and join different PVC chains. Exemplary amine molecules possessing two or more âNH 2 groups may include tetraethylenepentamine, polyethylenimine, phenylenediamine, and 1,6-hexanediamine.

Alternatively, pellets preferentially bound with PVA or a combination of PVA and polyethylenimine (PEI) are cross-linked with a dialdehyde (OHCâRâCHO), where each aldehyde (âCHO) group reacts with different PVA chains via two hydroxyl (âOH) groups on each chain to form the interconnected polymer network. A dicarboxylic acid could cross-link PVA. Exemplary dialdehydes may include linear glutaraldehyde and aromatic, hydrophobic terephthalaldehyde.

Other preferred cross-linking compounds are molecules bearing more than one epoxy group, such as different forms of bisphenol A diglycidylether (di-epoxy), N,N-Diglycidyl-4-glycidyloxyaniline (tri-epoxy), and 4,4â²-Methylenebis(N,N-diglycidylaniline) (quart-epoxy groups). These epoxies covalently join multiple amine molecules together to form a network. These amine molecules could be those of the BIAS sorbents being pelletized, or could be additional amine species added together with the epoxy in the polymer binder solution. Other preferred cross-linkers include aminosilanes (with amine groups) or alkoxysilanes (without amine group) and possessing methoxy/ethoxy (ROCH 3 /ROCH 2 CH 3 ) group, such as-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, N-(3-(trimethoxylsilyl)propyl)ethylenediamine, tetraethyeleorthosioicate. Commonly known cyanate/isocyanate (ROCN/RNCO), and acrylate and cyanoacrylate can also be used with a polyol (multiple âOH groups of an alcohol) molecule to covalent bind the pellet sorbent.

In one embodiment, loaded amines are additives to the pelletized sorbents. The loaded amines are introduced to the pelletized sorbent composition during manufacturing as a part of the polymer binder solution. The loaded amines are present throughout the pelletized sorbent and serve to increase final CO 2 sorption capacity. Loaded amines may be present in the pelletized sorbent from up to about 8 wt % of the total pelletized sorbent. Other preferred additives include the following: (i) antioxidants such as sodium carbonate, sodium bicarbonate, potassium carbonate, other water-soluble metal-carbonates, phenylenediamine, and various aminoacids, (ii) CO 2 adsorption enhancers such as ethylene glycol, poly (ethylene glycol), and non-ionic surfactants. One or more of these additives may be incorporated within the pelletized sorbent's base constituents to promote characteristics such as porosity, stability, or CO 2 migration through the pellet and also incorporated within the binder solution.

Pelletized Sorbent Composition:

<div id="p-0079" num="

CLAIMS

Claims ( 7 )

We claim:

1. A pelletized sorbent for separation of CO 2 from a gaseous mixture, said pelletized sorbent comprising:

a first component comprising a Basic Immobilized Amine Sorbent;

a second component comprising an inorganic strength additive; and

a third component comprising a polymer binder wherein the polymer binder is poly(vinyl chloride), poly(chloroprene), or poly(chloroprene) latex, and wherein the Basic Immobilized Amine Sorbent and inorganic strength additive are interconnected by the polymer binder.

2. A pelletized sorbent for separation of CO 2 from a gaseous mixture, said pelletized sorbent comprising:

a first component comprising a Basic Immobilized Amine Sorbent wherein the Basic Immobilized Amine Sorbent comprises an epoxy-based crosslinker;

a second component comprising an inorganic strength additive; and

a third component comprising a polymer binder,

wherein the Basic Immobilized Amine Sorbent and inorganic strength additive are interconnected by the polymer binder.

3. A pelletized sorbent for separation of CO 2 from a gaseous mixture, said pelletized sorbent comprising:

a first component comprising a Basic Immobilized Amine Sorbent wherein the Basic Immobilized Amine Sorbent comprises an antioxidant;

a second component comprising an inorganic strength additive; and

a third component comprising a polymer binder,

wherein the Basic Immobilized Amine Sorbent and inorganic strength additive are interconnected by the polymer binder.

4. The pelletized sorbent of claim 3 wherein the antioxidant is an inorganic antioxidant.

5. A pelletized sorbent for separation of CO 2 from a gas mixture, said pelletized sorbent comprising:

a first component comprising a Basic Immobilized Amine Sorbent (BIAS),

wherein the Basic Immobilized Amine Sorbent is a Class 1, Class 2, or hybrid Class 1/Class 2 BIAS, and

wherein the Basic Immobilized Amine Sorbent is present in the range from about 68% to about 85% of the total dry pelletized sorbent weight;

a second component comprising an inorganic strength additive,

wherein the inorganic strength additive is fly ash,

wherein the inorganic strength additive is present in the range from about 5% to about 37% of the total dry pelletized sorbent weight;

a third component comprising a polymer binder wherein the polymer binder is poly(chloroprene) latex and wherein the Basic Immobilized Amine Sorbent and the inorganic strength additive are interconnected by the polymer binder and;

a CO 2 sorbent capacity greater than 1.7 mmol/g;

a crush strength equal to or greater than 1.0 MPa or attrition value less than 1% after 24 hrs;

and a PCR value greater than 50%.

6. A pelletized sorbent for separation of CO 2 from a gas mixture, said pelletized sorbent comprising:

a first component comprising a Basic Immobilized Amine Sorbent,

wherein the Basic Immobilized Amine Sorbent is a Class 1, Class 2, or hybrid Class 1/Class 2 BIAS,

wherein the BIAS comprises an antioxidant, and

wherein the Basic Immobilized Amine Sorbent is present in the range from about 68% to about 85% of the total dry pelletized sorbent weight;

a second component comprising inorganic strength additive,

wherein the inorganic strength additive is fly ash,

wherein the inorganic strength additive is present in the range from about 5% to about 37% of the total dry pelletized sorbent weight;

a third component comprising a polymer binder,

wherein the Basic Immobilized Amine Sorbent and the inorganic strength additive are interconnected by the polymer binder;

a fourth component comprising an epoxy-based crosslinker,

a CO 2 sorbent capacity greater than 1.7 mmol/g;

a crush strength equal to or greater than 1.0 MPa or attrition value less than 1% after 24 hrs; and

a PCR value greater than 50%.

7. A pelletized sorbent for separation of CO 2 from a gas mixture, said pelletized sorbent comprising:

a first component comprising a Basic Immobilized Amine Sorbent (BIAS),

wherein the Basic Immobilized Amine Sorbent comprises an epoxy-based cross-linker,

wherein the Basic Immobilized Amine Sorbent is a Class 1, Class 2, or hybrid Class 1/Class 2 BIAS, and

wherein the Basic Immobilized Amine Sorbent is present in the range from about 68% to about 85% of the total dry pelletized sorbent weight;

a second component comprising inorganic strength additive,

wherein the inorganic strength additive is fly ash,

wherein the inorganic strength additive is present in the range from about 5% to about 37% of the total dry pelletized sorbent weight;

a third component comprising a polymer binder,

wherein the Basic Immobilized Amine Sorbent and the inorganic strength additive are interconnected by the polymer binder;

a CO 2 sorbent capacity greater than 1.7 mmol/g;

a crush strength equal to or greater than 1.0 MPa or attrition value less than 1% after 24 hrs; and

a PCR value greater than 50%.

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