CARBON CAPTURE, STORAGE, AND RECYCLING COMPOSITIONS

Abstract

The invention relates to carbon dioxide dioxaphosphetane compositions, including solid carbon dioxide dioxaphosphetane compositions. The invention includes compositions and methods for the capture, storage, and recycling of carbon, including methods of boric acid catalyzed reduction of carbonates in aqueous media and the use of phosphate solutions for capture and recycling of carbon.

Claims

1.-49. (canceled)

50. A method of capturing carbon dioxide, said method comprising the step of capturing carbon dioxide in a carbon dioxide dioxaphosphetane composition having the chemical structure ##STR00009## wherein M is a cation, aryl, or alkyl group, and wherein the carbon dioxide dioxaphosphetane composition is an liquid media.

51. The method of claim 50, wherein M is selected from the group consisting of H, Na, K, aryl, and alkyl.

52. A method of claim 50, wherein the carbon dioxide is produced from a combustion source.

53. A method of claim 50, wherein the carbon dioxide is a component of flue gas.

54. A method of claim 50, wherein the liquid media comprising the carbon dioxide dioxaphosphetane is stored.

55. A method of claim 50, wherein liquid media comprising the carbon dioxide dioxaphosphetane is precipitated or concentrated to a crystalline composition, and the crystalline composition is stored.

56. A method for reducing a carbonate, said method comprising the steps of: a. obtaining a solution comprising the carbonate; b. combining the carbonate of step a) with boric acid; c. adding sodium borohydride to the combination of step b) to reduce the carbonate to a formate.

57. The method of claim 56, wherein the method further comprises the step of stirring the combination of step b).

58. The method of claim 56, wherein the carbonate is selected from the group consisting of one or more of an ammonium carbonate, a sodium carbonate, a potassium carbonate, a rubidium carbonate, a cesium carbonate, an ammonium bicarbonate, a bisodium carbonate, a potassium bicarbonate, a rubidium bicarbonate, and a cesium bicarbonate.

59. The method of any claim 56, wherein the carbonate is an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof.

60. The method of claim 56, wherein the carbonate is a sodium carbonate, a sodium bicarbonate, or a combination thereof.

61. The method of claim 56, wherein the formate is an alkali metal formate.

62. The method of claim 56, wherein the formate is a sodium formate.

63. A method for reducing a carbonate, said method comprising the steps of: a. dissolving the carbonate in an liquid media to form a solution; b. combining the carbonate of step a) with boric acid; c. adding sodium borohydride to the combination of step b) to reduce the carbonate to a formate.

64. The method of claim 63, wherein the method further comprises the step of stirring the combination of step b).

65. The method of claim 63, wherein the carbonate is selected from the group consisting of one or more of an ammonium carbonate, a sodium carbonate, a potassium carbonate, a rubidium carbonate, a cesium carbonate, an ammonium bicarbonate, a bisodium carbonate, a potassium bicarbonate, a rubidium bicarbonate, and a cesium bicarbonate.

66. The method of claim 63, wherein the carbonate is an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof.

67. The method of claim 63, wherein the carbonate is a sodium carbonate, a sodium bicarbonate, or a combination thereof.

68. The method of claim 63, wherein the formate is an alkali metal formate.

69. The method of claim 63, wherein the formate is a sodium formate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0072] FIG. 1 shows an apparatus for capture of CO.sub.2 using food grade CO.sub.2.

[0073] FIG. 2 shows .sup.31P nmr of dioxaphosphetane of CO.sub.2.

[0074] FIG. 3 shows FTIR of dibasic sodium phosphate.

[0075] FIG. 4 shows FTIR of hydrated dioxaphosphetane of CO.sub.2.

[0076] FIG. 5 shows an apparatus for capture of CO.sub.2 from sodium carbonate.

[0077] FIG. 6 shows CO.sub.2 dioxaphosphetane in crystalline form.

[0078] FIG. 7 shows .sup.1H nmr of sodium formate from reduction taken in D2O.

[0079] FIG. 8 shows .sup.13C nmr of reduction of dioxaphosphetane to form sodium formate and sodium bicarbonate.

[0080] FIG. 9 shows .sup.1H nmr of diphenyl phosphate (sodium salt)+CO2+NaBH4.

[0081] FIG. 10 shows .sup.13C nmr of diphenyl phosphate (sodium salt)+CO2+NaBH4.

[0082] FIG. 11 shows .sup.1H nmr of dipotassium phosphate+CO2+NaBH4.

[0083] FIG. 12 shows .sup.13C nmr of dipotassium phosphate+CO2+NaBH4.

[0084] FIG. 13 shows .sup.1H nmr of dibasic ammonium phosphate+CO2+NaBH4.

[0085] FIG. 14 shows .sup.13C nmr of dibasic ammonium phosphate+CO2+NaBH4.

[0086] FIG. 15 shows .sup.1H nmr of sodium bicarbonate in the presence of potassium phosphate.

[0087] FIG. 16 shows .sup.13C nmr of reduction sodium bicarbonate in the presence of potassium phosphate.

[0088] FIG. 17 shows .sup.13C nmr of reduction of sodium bicarbonate with sodium borohydride or the reduction of sodium carbonate with sodium borohydride in the presence of monobasic potassium phosphate.

[0089] FIG. 18 shows .sup.1H nmr of reduction of sodium bicarbonate with sodium borohydride or the reduction of sodium carbonate with sodium borohydride in the presence of monobasic potassium phosphate.

[0090] FIG. 19 shows .sup.13C nmr of the reduction of sodium carbonate with sodium borohydride in the presence of boric acid. The nmr shows approximately 100% conversion of the carbonate.

[0091] Various embodiments of the invention are described herein as follows. In certain aspects described herein, a solid carbon dioxide dioxaphosphetane composition is provided. The solid carbon dioxide dioxaphosphetane composition has the chemical structure

##STR00003##

wherein M is a cation and/or an alkyl group. In some embodiments, M is selected from the group consisting of H, Na, K, aryl, and alkyl. In various embodiments, the composition is crystalline. In certain aspects, the composition is at a pH of 7 or greater. In one embodiment, the solid carbon dioxide dioxaphosphetane composition has the chemical structure

##STR00004##

[0092] In other aspects, a process for making a carbon dioxide dioxaphosphetane composition is provided. The process comprises the steps of a) combining a phosphate and water in a container; b) flushing the combination of dibasic sodium phosphate and water with carbon dioxide; c) stirring the resultant combination; and d) cooling the resultant combination to form the carbon dioxide dioxaphosphetane composition. In some embodiments, the phosphate is selected from the group consisting of ammonium phosphate, sodium phosphate, potassium phosphate, and dialkyl phosphate. In other embodiments, the carbon dioxide dioxaphosphetane composition is a crystalline composition.

[0093] In some embodiments, the stirring is for about 2 hours. In other embodiments, the stirring is for between 2 hours and 8 hours. In yet other embodiments, the stirring is for between 2 hours and 12 hours. In some embodiments, the stirring is for between 12 and 48 hours. In other embodiments, the stirring is for at least 12 hours. In various embodiments, the cooling is in an ice water bath.

[0094] A product formed by the process is also provided.

[0095] In yet another aspect, a method of reducing carbon dioxide is provided. The method comprises the steps of a) obtaining a carbon dioxide dioxaphosphetane composition, b) placing the carbon dioxide dioxaphosphetane composition in a solution; and c) combining sodium borohydride with the solution comprising carbon dioxide dioxaphosphetane to form a formate composition and reduce carbon dioxide. In some embodiments, the formate composition is sodium formate. In other embodiments, phosphate is precipitated via combination of sodium borohydride with the solution comprising carbon dioxide dioxaphosphetane. In some aspects, the method is utilized to transport carbon. In other aspects, the method is utilized to recycle carbon.

[0096] A process for reducing a carbonate is also provided. The process comprises the steps of a) dissolving the carbonate in water; b) combining the carbonate solution of step a) with boric acid; and c) adding sodium borohydride to the combination of step b) to reduce the carbonate to a formate. In certain embodiments, the process further comprises the step of stirring the combination of step b). In some embodiments, the process is performed at room temperature. In other embodiments, the carbonate is a water-soluble carbonate. In yet other embodiments, the carbonate is a metal carbonate. In some embodiments, the metal carbonate is selected from the group consisting of an ammonium carbonate, a sodium carbonate, a potassium carbonate, a rubidium carbonate, and a cesium carbonate. In other embodiments, the metal carbonate is an alkali metal carbonate. In yet other embodiments, the metal carbonate is a sodium carbonate. In some embodiments, the carbonate is a bicarbonate. In other embodiments, the bicarbonate is a sodium bicarbonate. In yet other embodiments, the formate is a sodium formate. In some embodiments, the boric acid is added in step b) at about 1 molar equivalent of boric acid to carbonate. In other embodiments, the boric acid is added in step b) at more than 1 molar equivalent of boric acid to carbonate.

[0097] In yet other embodiments, the carbonate is reduced to a formate at an efficacy of at least 90%. In some embodiments, the carbonate is reduced to a formate at an efficacy of about 90%. In other embodiments, the carbonate is reduced to a formate at an efficacy of about 95%.

[0098] In yet other embodiments, the carbonate is reduced to a formate at an efficacy between 90-100%.

[0099] In yet another aspect, a method of capturing carbon dioxide is provided. The method comprises the step of capturing carbon dioxide in a carbon dioxide dioxaphosphetane composition having the chemical structure

##STR00005##

wherein M is a cation and/or alkyl groups, and wherein the carbon dioxide dioxaphosphetane composition is an aqueous phosphate solution. In some embodiments, M is selected from the group consisting of H, Na, K, aryl, and alkyl. In various embodiments, the phosphate is selected from the group consisting of ammonium phosphate, sodium phosphate, potassium phosphate, and dialkyl phosphate.

[0100] In another aspect, a process for making a carbon dioxide dioxaphosphetane composition is provided. The process comprises the steps of a) combining a phosphate and water in a container; b) flushing the combination of step a) with carbon dioxide; and c) stirring the combination. In some embodiments, the process further comprises the step of storing the combination. In various embodiments, the phosphate is selected from the group consisting of ammonium phosphate, sodium phosphate, potassium phosphate, and dialkyl phosphate.

[0101] In some embodiments, the stirring is for about 2 hours. In other embodiments, the stirring is for between 2 hours and 8 hours. In yet other embodiments, the stirring is for between 2 hours and 12 hours. In some embodiments, the stirring is for between 12 and 48 hours. In other embodiments, the stirring is for at least 12 hours.

[0102] A product formed by the process is also provided.

[0103] In one aspect, a method of reducing carbon dioxide is provided. The method comprises the step of combining sodium borohydride with a carbon dioxide dioxaphosphetane solution to form a formate.

Example 1

Formation of CO2 Dioxaphosphetane Using Food Grade Carbon Dioxide

[0104] A 100 mL round bottom flask containing a stirring bar was charged with a 40 mL water and 2.84 g dibasic sodium phosphate to form a solution. The flask was fitted and sealed with a septum. The solution was flashed with food grade carbon dioxide (Airgas, Evansville, Ind.) according to the following protocol pursuant to Scheme 1:

##STR00006##

[0105] A long needle directly connected to the CO.sub.2 tank was inserted through the septum such that the tip of the needle was close to the surface of the solution (see FIG. 1). A shorter needle was also pushed into the septum such that the tip was just inside the flask. The gas outlet on the CO.sub.2 tank was opened while stirring the solution.

[0106] After a few minutes, the shorter needle was removed followed by the long needle with the gas tank still open. A balloon filled with CO.sub.2 and taped unto a syringe and a needle was inserted into the septum to maintain an atmosphere of CO.sub.2 in the flask. After 48 hours of stirring, the solution was cooled in an ice/water bath and filtered to produce the solid dioxaphosphetane in crystalline form.

[0107] The solid dioxaphosphetane in crystalline form was observed to have a .sup.31P nmr chemical shift of 2.9406 ppm (see FIG. 2). The chemical shift of Na.sub.2HPO.sub.4 of similar concentration taken before and after that of the dioxaphosphetane is 3.4311 ppm.

[0108] FUR of the dioxaphosphetane reveal disappearance of the P═O frequency at 1120 cm.sup.−1 and the appearance of a medium broad carbonyl peak at 1666.75 cm.sup.−1 frequency (FIG. 3 and FIG. 4).

[0109] The instant example can also he reproduced to produce a solution of dioxaphosphetane.

Example 2

Formation of Dioxaphosphetane Using Carbon Dioxide Generated from Sodium Carbonate

[0110] The CO.sub.2 receiving flask containing a 2.84 g of dibasic sodium phosphate dissolved in 40 mL deionized water was connected to the CO.sub.2 generating flask containing 5 g of sodium carbonate (see FIG. 5). CO.sub.2 was generated by injecting 10 mL of 4 M Hydrochloric acid into the generating flask. The solution in the receiving flask was stirred for 48 hours without dismantling the apparatus. The system was then dismantled and the receiving flask was cooled in an ice/water bath to produce dioxaphosphetane in crystalline form (see FIG. 6).

Example 3

Reduction of CO.SUB.2 .to Formate

[0111] Addition of sodium borohydride to a solution of the dioxaphosphetane partially reduced it to formate. The remaining dioxaphosphetane was converted to sodium carbonate (Scheme 2).

##STR00007##

[0112] Dioxaphosphetanes generally activate the phosphorus atom for nucleophilic substitution. Nucleophilic attack of the hydrides on the phosphorus produced the carbonate with a CNMR chemical shift of 163.7.

[0113] The presence of the formate was confirmed by HNMR chemical shift of 8.35 ppm (see FIG. 7) and a CNMR chemical shift of 171.2205 ppm (see FIG. 8).

Example 4

Reduction of Carbonates Using Sodium Borohydride and Boric Acid

[0114] A 250 mL volumetric flask containing a stirring bar was charged with a 15 mL water and 2 mmol (0.212 g) of dibasic sodium carbonate to form a solution at room temperature. To this solution, 2 mmol (0.124 g) of boric acid was added. Optionally, additional water may be added to ensure that all solid is dissolved. Advantageously, addition of sodium borohydride to the solution provides sodium formate in excellent yields. The method successfully reduced both bicarbonates and carbonates in water at room temperature and in an inexpensive manner. As shown below, observed yields were between 90-100%.

##STR00008##

[0115] In contrast, in the absence of boric acid, sodium carbonate provided no yield of sodium formate when it was reduced. Further, when sodium carbonate was mixed with one equivalent of monobasic sodium/potassium phosphate and reduced, only a 30-40% yield of sodium formate was achieved. Similarly, 30-40% yield of the formate was achieved when sodium bicarbonate was reduced with sodium borohydride without boric acid.

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