CATALYTIC POROUS POLYMER FOR SELECTIVE CAPTURE AND REDUCTION OF CARBON DIOXIDE

Abstract

A catalytic carbon capture material is provided. The catalytic carbon capture material includes a microporous polymer including a Tröger's base moiety, and a transition metal is coordinated within the microporous polymer. The catalytic carbon capture material selectively captures carbon dioxide (CO.sub.2) and also is a catalyst that simultaneously converts the captured carbon dioxide into one or more carbon dioxide-based products. A method of making the catalytic carbon capture material and a method of selective carbon dioxide capture and conversion are also provided.

Claims

1. A catalytic carbon capture material comprising: a microporous polymer including a Tröger's base moiety; and a transition metal coordinated within the microporous polymer; wherein the catalytic carbon capture material selectively captures carbon dioxide (CO.sub.2) and also is a catalyst that simultaneously converts the captured carbon dioxide into one or more carbon dioxide-based products.

2. The catalytic carbon capture material of claim 1, wherein the transition metal is one selected from the group consisting of ruthenium (Ru), iridium (Ir), iron (Fe), copper (Cu), zirconium (Zr), nickel (Ni), and rhodium (Rh).

3. The catalytic carbon capture material of claim 1, wherein the catalytic carbon capture material includes a metal chloride that comprises the transition metal.

4. The catalytic carbon capture material of claim 1, wherein the microporous polymer is formed of: (i) one of diaminotoluene or spirobi[fluorene] diamine precursors; and (ii) dimethoxymethane precursors.

5. The carbon capture material of claim 1, wherein the catalytic carbon capture material has a specific surface area in the range of approximately 500 to 700 m.sup.2/g.

6. The catalytic carbon capture material of claim 1, wherein the catalytic carbon capture material is in the form of one of a pellet or powder.

7. The catalytic carbon capture material of claim 1, wherein the catalytic carbon capture material is in the form of a membrane.

8. A method of selective carbon dioxide capture and conversion, the method comprising: providing the catalytic carbon capture material of claim 1; introducing carbon dioxide gas to the catalytic carbon capture material; wherein carbon dioxide gas is adsorbed by the catalytic carbon capture material and simultaneously converted into a carbon dioxide-based product while adsorbed by the catalytic carbon capture material.

9. The method of claim 8, wherein the step of converting the carbon dioxide gas into a carbon dioxide-based product includes introducing a hydrogen source to the catalytic carbon capture material to hydrogenate the carbon dioxide.

10. The method of claim 9, wherein the carbon dioxide-based product is one of formic acid, formate, dimethylcarbonate, or furandicarboxylic acid.

11. The method of claim 8, wherein the catalytic carbon capture material selectively adsorbs carbon dioxide over nitrogen gas (N.sub.2) and methane (CH.sub.4).

12. The method of claim 8, wherein the process is carried out at a temperature in the range of approximately 25° C. to 40° C. and a total pressure of up to approximately 60 to 100 bar.

13. The method of claim 8, wherein the catalytic carbon capture material is in the form of one of a pellet, powder, or a membrane.

14. A method of making the catalytic carbon capture material of claim 1, the method including: forming the microporous polymer in solution; filtering the solution to isolate the microporous polymer; rinsing and drying the microporous polymer; dispersing the microporous polymer in an alcohol for purification; dispersing the microporous polymer in a solution of metal chloride hydrate in an alcohol to coordinate the metal chloride with the microporous polymer; and filtering, rinsing, and drying the microporous polymer coordinated with the metal chloride.

15. The method of claim 14, wherein the microporous polymer is formed of: (i) one of diaminotoluene or spirobi[fluorene] diamine precursors; and (ii) dimethoxymethane precursors.

16. The method of claim 16, wherein the metal chloride hydrate is one of a ruthenium, rhodium, iron, copper, nickel, or iridium chloride hydrate.

Description

BRIEF DESCRIPTION OF THE DRAWING

[0026] FIG. 1 is a schematic illustration of a method of selective, simultaneous carbon dioxide capture and conversion in accordance with some embodiments of the disclosure;

[0027] FIG. 2 is a schematic illustration of the synthetic method of material and conversion pathway of selective, simultaneous carbon dioxide capture and conversion in accordance with specific embodiments of the disclosure;

[0028] FIG. 3 is a graph of the selectivity and capacity up to 10 bar of a hybrid-porous polymer catalyst carbon capture material (mmol/g) in accordance with some embodiments of the disclosure;

[0029] FIG. 4 is a graph of the adsorption and desorption of the hybrid-porous polymer carbon capture material for surface area and porosity analysis;

[0030] FIG. 5 is a graph of the adsorption and desorption of the hybrid-porous polymer catalyst carbon capture material with the ruthenium catalyst coordinated for surface area and porosity analysis;

[0031] FIG. 6 is a graph of the selectivity and capacity of the hybrid-porous polymer catalyst carbon capture material without the catalyst; and

[0032] FIG. 7 is a graph of the carbon dioxide uptake (mg/g) of the hybrid-porous polymer carbon capture material at high pressure and 40° C.

DETAILED DESCRIPTION OF THE CURRENT EMBODIMENTS

[0033] As discussed herein, the current embodiments relate to a catalytic carbon capture material, a method of making a catalytic carbon capture material, and a method of selective carbon dioxide capture and conversion. The catalytic carbon capture material includes a microporous polymer. The microporous polymer has intrinsic microporosity due to its contorted shape and fused ring structure that provides a rigid polymer backbone, forming a continuous network of interconnected intermolecular voids each being less than approximately 2 nm in width. The microporous polymer includes a Tröger's base moiety (basic tertiary amine) that is embedded into the backbone of the polymer and has a bent-ring structure including two tertiary nitrogen atoms in the ring. The Tröger's base unit included within the microporous polymer provides considerable affinity of carbon dioxide due to the presence of the amine, and the size of the micropores provides significantly enhanced capacity. For example, the microporous polymer with the Tröger's base moieties may have a high specific surface area in the range of 500 to 700 m.sup.2/g.

[0034] A transition metal is coordinated within the microporous polymer. Particularly, the transition metal may form coordinate bonds with the nitrogen atoms in the Tröger's base. The transition metal may be, for example, ruthenium (Ru), iridium (Ir), iron (Fe), copper (Cu), zirconium (Zr), nickel (Ni), and rhodium (Rh), or any other metal that is capable of catalyzing the conversion of carbon dioxide into products (e.g., carbon dioxide is used as a reactant in the production of useful end products). Choice of the transition metal may be dependent upon the desired carbon-dioxide-derived end product. For example, when ruthenium is used as the transition metal, the carbon capture material exhibits high efficiency for conversion of carbon dioxide into formic acid or formate. The amine unit of the Tröger's base provides close molecular proximity of transition metal ions with the captured carbon dioxide while also provided catalytic carbon dioxide bond activation, thereby enabling simultaneous capture and chemical conversion of carbon dioxide.

[0035] The catalytic carbon capture material is made by combining two or monomer components in solution, wherein the polymerization occurs in solution over a period of time (hours, days, e.g., 40 hours, approximately 2 days, and the like). After polymerization is complete, the solution is filtered to isolate the solid microporous polymer, which is rinsed and dried. Next, the dried microporous polymer is dispersed in alcohol, and the polymer/alcohol solution is added to a solution of a metal hydrate in alcohol, whereby the metal forms coordinate bonds with the nitrogen of the microporous polymer. The resulting hybrid microporous polymer catalyst is filtered out of the solution, and the isolated hybrid microporous polymer catalyst is rinsed and finally dried to obtain the final catalytic carbon capture material.

[0036] As shown in FIGS. 1 and 2, to selectively capture and convert carbon dioxide to useful products, the carbon capture material can be integrated into a filtration system. For example, the carbon dioxide capture material may be formed into pellets that are loaded into a fluidized bed, or the catalytic carbon capture material may be formed into an integrated moving bed. A stream of gas including carbon dioxide, such as a flow of ambient air (e.g., direct air capture of carbon) or an industrial exhaust stream, is passed through the catalytic carbon capture material. The catalytic carbon capture material adsorbs the carbon dioxide present in the gas stream. Simultaneously, a stream of reactant such as hydrogen gas is also introduced to the catalytic carbon capture material, and the adsorbed carbon dioxide reacts with the reactant via the presence of the transition metal catalyst in the catalytic carbon capture material. In this example, carbon dioxide and hydrogen react to form formic acid. However, by changing the reactant and/or the catalyst metal, other products such as but not limited to dimethylcarbonate, furandicarboxylic acid, or formate may be obtained.

[0037] The present hybrid-porous polymer catalyst carbon capture material advantageously serves the dual purpose as both an active carbon dioxide getter (by capturing CO.sub.2) and a passive catalytic site support for the conversion of CO.sub.2 into other useful chemical compounds. For example, 270 mg (6 mmol) of CO.sub.2 may be captured for every gram of the carbon capture catalyst material. The porosity of the carbon capture catalyst allows for rapid diffusion of CO.sub.2 to the active sites and hence permits the use of the catalyst at lower temperatures and intermediate pressures such as, but not limited to, 30° C. and 60 bar total pressure of CO.sub.2 plus H.sub.2. In some embodiments, the catalytic hybrid-porous polymer carbon capture material can be used as a powder, while in other embodiments it can be pelletized and included in fluidized beds for continuous processes.

[0038] As shown in FIG. 3, the hybrid-porous polymer catalyst carbon capture material demonstrated selective capture of CO.sub.2 over N.sub.2 (e.g., 26:1 of CO.sub.2:N.sub.2) as well as over CH.sub.4 (which makes the present catalyst useful in filtering byproducts such as those found in natural gas combustion processes).

[0039] The ability to produce formic acid from captured carbon dioxide with the addition of hydrogen at low temperature and pressure is industrially advantageous. Current production processes for formic acid involve the reaction of toxic carbon monoxide and methanol, which also requires the separation of impurities. Due to the expense and impurity of the obtained formic acid, many industrial applications using formic acid, e.g. as a silage additive for cattle and chicken feed, for deicing of planes, for enhanced oil recovery and so on, have moved to other cheaper but inefficient processes. Further, conventional production of formic acid emits about 3076 kg CO.sub.2 per ton of formic acid obtained, whereas only 100 kg CO.sub.2 is emitted in the present carbon dioxide hydrogenation process using the hybrid-porous carbon capture catalyst material.

[0040] In addition to the formation of formic acid, metals other than Ru can be used at the catalytic site and the conditions changed (e.g., feed material, temperature, pressure) to green-produce other chemicals such as formate, dimethylcarbonate, or furandicarboxylic acid from the source of carbon dioxide that is captured. Conventional synthetic pathways for dimethylcarbonate and furandicarboxylic acid are extremely toxic and expensive, yet these compounds are used in the production of polymers and fuel additives, making the present hybrid-porous polymer catalyst carbon capture material a green alternative to conventional synthesis methods.

Example

[0041] The present method is further described in connection with the following laboratory example, which is intended to be non-limiting.

[0042] All materials were used as purchased without further purification. 1 g (8.2 mmol; 1 eq.) of 2,6-diaminotoluene was charged into a dry, round bottom flask under an argon atmosphere and dissolved in 75.3 mL (984 mmol; 120 eq.) of trifluoroacetic acid. The solution was cooled to 0° C. while stirring. 3.6 mL (40.9 mmol; 5 eq.) of dimethoxymethane was added dropwise to the solution over a time period of 30 minutes. The solution was then allowed to warm to room temperature (in the range of approximately 20° C. to 25° C.) and became viscous over the course of 40 hours. In a separate Erlenmeyer flask, a solution of 100 mL water and 100 mL of 35% aqueous ammonia was prepared. The reaction mixture was quenched by adding it to the ammonia solution while vigorously stirring, and then allowed to stabilize for 4 hours. The resulting solid in the solution was isolated by filtration, and subsequently washed with 100 mL each of water and acetone. The solid polymer was then dissolved in 100 mL of chloroform and reprecipitated with methanol, which was repeated twice. The solid polymer was again isolated by filtration and dried under vacuum at 40° C. The obtained polymer with intrinsic microporosity (PIM) and including a Tröger's base (TB) was an off-white to pale yellow color, and had a yield of around 95%.

[0043] Next, 572 mg (2 mmol) of RuCl.sub.3*3H.sub.2O was dissolved in 30 mL of ethanol. Separately, 250 mg of the polymer obtained above was stirred in 20 mL of ethanol to form a solution that was then added dropwise to the ruthenium solution. The resulting mixture was stirred overnight and then filtered and washed three times with 20 mL of ethanol each. The obtained solid was dried on the filter and subsequently placed in a vacuum at 60° C. for 12 hours. The yield of the resulting PIM-MB-TB-metal(Ru) was 100%.

[0044] With reference to FIGS. 4 and 5, surface area and pore analysis of the resulting PIM-MB-TB and PIM-MB-TB-Ru was conducted on a Micromeritics 2020 Plus. Samples were degassed under helium while heating to 120° C. for 8 hours. Isotherms were collected under nitrogen gas. The CO.sub.2, methane, and nitrogen capacity and selectivity of the resulting PIM-MB-TB and PIM-MB-TB-Ru was also analyzed by an Intelligent Gravimetric Analyzer from Hiden Analytical Limited, UK was used to determine the sample sorption capacity and selectivity, the results of which are shown in FIGS. 3 and 6 respectively, up to 10 bar. Approximately 80 mg of sample was loaded into a quartz bucket cell and evacuated to 0.1 bar for 6 hours at 150° C. to degas and dry prior to measurement. The mass uptake (corrected for buoyancy and density of material) was measured as a function of pressure (0-10 bar at 25° C.) to obtain the absorption isotherm. Desorption isotherms were subsequently acquired by measuring the mass as a function of decreasing pressure to ensure that the solubility behavior was reversible and to test for hysteresis effects. The solubility was calculated from the slope of the adsorption isotherm in the low carbon dioxide concentration regime. In addition, the carbon dioxide uptake (mg/g) of the PIM-MB-TB at high pressure (up to 80 bar) at 40° C. is shown in FIG. 7 as measured on a Rubotherm.

[0045] The above description is that of current embodiments of the invention. Various alterations and changes can be made without departing from the spirit and broader aspects of the invention as defined in the appended claims, which are to be interpreted in accordance with the principles of patent law including the doctrine of equivalents. This disclosure is presented for illustrative purposes and should not be interpreted as an exhaustive description of all embodiments of the invention or to limit the scope of the claims to the specific elements illustrated or described in connection with these embodiments. For example, and without limitation, any individual element(s) of the described invention may be replaced by alternative elements that provide substantially similar functionality or otherwise provide adequate operation. This includes, for example, presently known alternative elements, such as those that might be currently known to one skilled in the art, and alternative elements that may be developed in the future, such as those that one skilled in the art might, upon development, recognize as an alternative. Further, the disclosed embodiments include a plurality of features that are described in concert and that might cooperatively provide a collection of benefits. The present invention is not limited to only those embodiments that include all of these features or that provide all of the stated benefits, except to the extent otherwise expressly set forth in the issued claims. Any reference to claim elements in the singular, for example, using the articles “a,” “an,” “the” or “said,” is not to be construed as limiting the element to the singular.