Electrochemical conversion of alkali sulfate into useful chemical products

Electrochemical processes to convert alkali sulfates into useful chemical products, such as syngas, alkali hydroxide, and sulfur are disclosed. An alkali sulfate is reacted with carbon to form carbon monoxide and alkali sulfide. In one embodiment, the alkali sulfide is dissolved in water and subjected to electrochemical reaction to form alkali hydroxide, hydrogen, and sulfur. In another embodiment, the alkali sulfide is reacted with iodine to form alkali iodide sulfur in a non-aqueous solvent, such as methyl alcohol. The alkali iodide is electrochemically reacted to form alkali hydroxide, hydrogen, and iodine. The iodine may be recycled to react with additional alkali sulfide. The hydrogen and carbon monoxide from both embodiments may be combined to form syngas. The alkali hydroxide from both embodiments may be recovered as a useful industrial chemical.

FIELD OF THE INVENTION

The present invention relates to the electrochemical treatment of alkali sulfate to form commercially valuable chemical products. More specifically, the present invention relates to electrochemically converting an alkali sulfate by reacting it with carbon and forming an aqueous or non aqueous metal sulfide that can be electrolyzed into useful chemical products, including alkali hydroxide, sulfur, and syngas.

BACKGROUND

Chemical products are used in a wide variety of useful applications. One problem with chemical products is that they are difficult and expensive to transport. Another problem is that they are expensive to manufacture. Many industrial applications create as a byproduct a waste stream that contains amounts of chemicals that must be contained or otherwise properly disposed of. It would be an advancement in the art to have methods and apparatuses that can create chemical products on site to reduce the need for transporting the chemicals. It would be a further advancement to be able to create useful chemical products from waste streams or other inexpensive or underutilized feed streams. Such methods and apparatuses are disclosed and claim herein.

SUMMARY OF THE INVENTION

In one embodiment, a process for electrochemically converting an alkali sulfate into useful chemical products includes reacting an alkali sulfate with carbon according to reaction (1):
M2SO4+4C4CO+M2S  (1)
The M2S may be dissolved in a liquid to form an aqueous or nonaqueous M2S. In another embodiment, the M2S may be further reacted with iodine in a methyl alcohol solvent according to reaction (2):
M2S+I22MI+S  (2)
In these reactions, M is an alkali metal such as, for example, a sodium metal, a lithium metal, a potassium metal, or other alkali metal.

An electrolytic cell comprising an alkali ion conducting membrane configured to selectively transport alkali ions may be provided. The membrane is positioned between an anolyte compartment configured with an anode and a catholyte compartment configured with a cathode. In one embodiment, aqueous or nonaqueous M2S of equation (1) may be introduced into the anolyte compartment. In another embodiment, MI in methyl alcohol from equation (2) may be introduced into the anolyte compartment. Water may then be introduced into the catholyte compartment.

In one embodiment, aqueous or nonaqueous M2S and water are electrolyzed in the electrolytic cell to form NaOH, H2and sulfur, according to reaction (3):
M2S+2H2O2MOH+S+H2(3)
In yet another embodiment, MI and water are electrolyzed in the electrolytic cell to form MOH, H2and iodine, according to reaction (4):
2MI+2H2O2MOH+I2+H2(4)
The CO from reaction (1) and H2from reaction (3) or (4) may be recovered and combined to form syngas.

DETAILED DESCRIPTION

In the following description, specific details of various embodiments are provided. However, some embodiments may be practiced without at least some of these specific details. In other instances, certain methods, procedures, components, and circuits are not described in detail for the sake of brevity and clarity, but are nevertheless understood from the context of the description herein.

In general, alkali sulfates, such as sodium sulfate and potassium sulfate, are common in industrial waste streams. This invention relates to the electrochemical treatment of alkali sulfate to form commercially valuable chemical products. Such chemical products include, but are not limited to, alkali hydroxide, sulfur, and syngas (also known as synthetic gas or synthesis gas). While the following disclosure relates to a specific alkali sulfate, sodium sulfate (Na2SO4), it is understood that the disclosed invention relates to treatment of alkali sulfates in general, and where the disclosure references sodium, other alkali metals such as lithium and potassium may also be included.

The disclosure relates to processes for converting sodium sulfate into useful chemical products. One embodiment of the Na2SO4conversion method includes the step of reacting Na2SO4with carbon to make Na2S and CO, according to Equation (5):
Na2SO4+4C4CO+Na2S  (5)

The carbon may come from a variety of sources, including but not limited to coal, charcoal, tar, lignin, etc. This reaction proceeds by heating the sodium sulfate and carbon at a temperature sufficiently high to anaerobically “burn” the carbon in the sodium sulfate. The reaction can be achieved using excess carbon in sodium sulfate solid and igniting the mixture and collecting CO gas. A stoichiometric quantity of carbon is desirable, but excess carbon can be used to be react substantially all of the sodium sulfate. The carbon monoxide gas may be recovered and used in syngas production.

The process includes the steps of dissolving Na2S in water or organic solvents, and electrolyzing aqueous Na2S solution or organic solution of Na2S to form NaOH, H2and sulfur, according to Equation (6):
Na2S+2H2O2NaOH+S+H2(6)

The electrochemical process represented by Equation 6 preferably occurs in an electrolytic cell having a sodium ion conductive membrane. The membrane can comprise virtually any suitable sodium ion conductive membrane. Some non-limiting examples of such membranes include, but are not limited to, NaSICON (sodium super ionic conductor) membranes. Where other non-sodium alkali sulfates are treated within the scope of the present invention, it is to be understood that similar alkali ion conductive membranes such as a LiSICON membrane and a KSICON membrane may be used.

FIG. 1schematically shows one possible electrolytic cell110that may be used in the electrochemical process of electrolyzing aqueous Na2S within the scope of the present invention. The electrolytic cell110uses a sodium ion conductive membrane112that divides the electrochemical cell110into two compartments: an anolyte compartment114and a catholyte compartment116. An electrochemically active anode118is housed in the anolyte compartment114where oxidation reactions take place, and an electrochemically active cathode120is housed in the catholyte compartment116where reduction reactions take place. The sodium ion conductive ceramic membrane112selectively transfers sodium ions122from the anolyte compartment114to the catholyte compartment116under the influence of an electrical potential124.

The electrolytic cell110is operated by feeding a sodium sulfide solution126into the anolyte compartment114. The sodium sulfide solution126may be aqueous or nonaqueous. The sodium sulfide solution126may be a reaction product from Equation (5). The concentration of sodium sulfide in the aqueous solution should be below its saturation limit in water. The concentration of sodium sulfide in the aqueous solution is between about 1% by weight and about 20% by weight of the solution, and more preferably between about 10% by weight and 20% by weight of the solution at ambient temperature. The weight percent may vary at different temperatures. For example at higher temperatures the weight percent of sodium sulfide can go as high as 90%. The temperature range for the operation of this electrolytic cell may be 20° C. to 150° C. In one embodiment, the temperature range for the operation is between about 30° C. and about 80° C.

Water128is fed into the catholyte compartment116. At least initially, the water128preferably includes sodium ions, which may be in the form of an unsaturated sodium hydroxide solution. The concentration of sodium hydroxide is between about 0.1% by weight and about 50% by weight of the solution. In one embodiment, the water128includes a dilute solution of sodium hydroxide. During operation, the source of sodium ions may be provided by sodium ions122transporting across the sodium ion conductive membrane112from the anolyte compartment114to the catholyte compartment116.

The anode118can comprise any suitable anode material that allows the cell to oxidize sulfide ions in the anolyte when electrical potential passes between the anode and the cathode. Some examples of suitable anode materials include, but are not limited to, stainless steel, titanium, platinum, lead dioxide, carbon-based materials (e.g., boron-doped diamond, glassy carbon, synthetic carbon, etc.), and other known or novel anode materials. Additionally, in some embodiments the anode comprises a dimensionally stable anode, which may include, but is not limited to, rhenium dioxide and titanium dioxide on a titanium substrate, and rhenium dioxide and tantalum pentoxide on a titanium substrate.

The cathode120may also be fabricated of any suitable cathode that allows the cell to reduce water in the catholyte to produce hydrogen gas. In this regard, some examples of suitable cathode materials include, without limitation, nickel, stainless steel, graphite, a nickel-cobalt-ferrous alloy (e.g., a KOVAR® alloy), and any other suitable cathode material that is known or novel.

Under the influence of electric potential124, electrochemical reactions take place at the anode118and cathode120. Oxidation of sulfur ions to sulfur occurs at the anode118, and reduction of water to form hydrogen gas130and hydroxyl ions occurs at the cathode120. The hydrogen gas30may be recovered and combined with carbon monoxide produced according to Equation (5) to form syngas, a useful chemical product.

As the reactions occur at the electrodes, sodium ions122are transported from the anolyte compartment114across the sodium ion conductive ceramic membrane112into the catholyte compartment116. The transported sodium ions122combine with the hydroxyl ions produced by the reduction of water at the cathode120to form a sodium hydroxide solution. This sodium hydroxide solution132may be removed from the catholyte compartment as a useful chemical product. Sulfur134may be recovered from the anolyte compartment114as a useful chemical product.

The chemical reactions in the electrochemical cell110are summarized below:

This embodiment of the Na2SO4conversion method further includes combining the CO and H2generated in Equations (5) and (6) respectively to form syngas (seeFIG. 3where the Electrochemical Cell depicted may be the Electrochemical Cell ofFIG. 1). Syngas refers to a gas mixture that contains varying amounts of carbon monoxide and hydrogen. Syngas may also contain carbon dioxide. It has a much lower energy density compared to natural gas and may be used as a direct fuel source or as an intermediate for the production of other fuels or chemicals.

The method or process may further include recovering the NaOH and sulfur. Sodium hydroxide is a useful industrial chemical. It may be used directly as it is removed from the catholyte compartment116or it may be further processed or concentrated as desired.

Another embodiment of the Na2SO4conversion method includes reacting Na2SO4with carbon to make Na2S and CO, according to Equation (5), above. The process includes the step of reacting the Na2S product with iodine (I2) to form sodium iodide according to Equation (7).
Na2S+I22NaI+S  (7)

This reaction preferably proceeds in a non-aqueous solvent such as methyl alcohol (CH3OH). Other non-aqueous solvents such as ethanol, acetone, liquid ammonia, liquid sulfur, dioxide, formic acid, acetonitrite, acete, formamide, acetamide, dimethylformamide, and the like may be used.

The sulfur precipitates from the methyl alcohol solution, as well any unreacted Na2SO4and carbon from Equation (5). These solids may be recovered. Unreacted Na2SO4and carbon may be recycled and further reacted according to Equation (5). The process further includes the step of electrolyzing NaI solution in methyl alcohol to generate iodine (I2) and NaOH, according to Equation (8):
2NaI+2H2O2NaOH+I2+H2(8)

The iodine remains in the methyl alcohol and can be recycled and used again in the step of reacting the Na2S product with iodine (I2) to form sodium iodide according to Equation (7).

The overall electrochemical process represented by Equation (8) preferably occurs in an electrolytic cell having a sodium ion conductive membrane. One presently preferred type of sodium ion conductive membrane includes sodium super ionic conductor (hereinafter “NaSICON”) membrane technologies. The NaSICON membranes are permeable to sodium ions and impermeable to water. Such membranes provide effective separation between the aqueous catholyte compartment and the non-aqueous anolyte compartment.

FIG. 2schematically shows one possible electrolytic cell210that may be used in the electrochemical process of electrolyzing NaI within the scope of the present invention. The electrolytic cell210uses a sodium ion conductive membrane212that divides the electrochemical cell210into two compartments: an anolyte compartment214and a catholyte compartment216. A NaSICON membrane is preferred because it is permeable to sodium ions and impermeable to water. Such membranes provide effective separation between the aqueous catholyte compartment216and the non-aqueous anolyte compartment214.

An electrochemically active anode218is housed in the anolyte compartment214where oxidation reactions take place, and an electrochemically active cathode220is housed in the catholyte compartment216where reduction reactions take place. The sodium ion conductive ceramic membrane212selectively transfers sodium ions222from the anolyte compartment214to the catholyte compartment216under the influence of an electrical potential224.

The electrolytic cell210is operated by feeding a sodium iodide in methyl alcohol226into the anolyte compartment214. The sodium iodide solution226may be a reaction product from Equation (7). The concentration of sodium iodide in the methyl alcohol solution should be below its saturation limit. The concentration of sodium iodide in methyl alcohol is between about 10% by weight and about 80% by weight of the solution, and more preferably between about 35% by weight and 50 by weight of the solution. An increase in temperature can increase the range. It will be appreciated that other non-aqueous solvents may be used besides methyl alcohol, including but not limited to, ethanol, acetone, liquid ammonia, liquid sulfur, dioxide, formic acid, acetonitrite, acete, formamide, acetamide, dimethylformamide, and the like.

Water228is fed into the catholyte compartment216. At least initially, the water228preferably includes sodium ions, which may be in the form of an unsaturated sodium hydroxide solution. The concentration of sodium hydroxide is between about 0.1% by weight and about 50% by weight of the solution. In one embodiment, the water228includes a dilute solution of sodium hydroxide. During operation, the source of sodium ions may be provided by sodium ions222transporting across the sodium ion conductive membrane212from the anolyte compartment214to the catholyte compartment216.

The anode218can comprise any suitable anode material that allows the cell to oxidize iodide ions in the anolyte when electrical potential passes between the anode and the cathode. Some non-limiting examples of suitable anode materials are discussed above in relation toFIG. 1. The cathode220may also be fabricated of any suitable cathode that allows the cell to reduce water in the catholyte to produce hydrogen gas. In this regard, some non-limiting examples of suitable cathode materials are discussed above in relation toFIG. 1.

Under the influence of electric potential224, electrochemical reactions take place at the anode218and cathode220. Oxidation of iodide ions to iodine occurs at the anode218, and reduction of water to form hydrogen gas230and hydroxyl ions occurs at the cathode220. The hydrogen gas230may be recovered and combined with carbon monoxide produced according to Equation (5) to form syngas, a useful chemical product.

As the reactions occur at the electrodes, sodium ions222are transported from the anolyte compartment214across the sodium ion conductive membrane212into the catholyte compartment216. The transported sodium ions222combine with the hydroxyl ions produced by the reduction of water at the cathode220to form a sodium hydroxide solution. This sodium hydroxide solution232may be removed from the catholyte compartment as a useful chemical product. Iodine234and methyl alcohol may be recovered from the anolyte compartment214and recycled for use in Equation (7).

The chemical reactions in the electrochemical cell210are summarized below:

This embodiment of the Na2SO4conversion method further includes the step of combining the CO and H2generated in Equations (5) and (8) to form syngas (seeFIG. 4where the Electrochemical Cell depicted may be the Electrochemical Cell ofFIG. 2). The syngas may be used as a direct fuel source or as an intermediate for the production of other fuels or chemicals. This embodiment also includes the step of recovering the NaOH. Sodium hydroxide is a useful industrial chemical. It may be used directly as it is removed from the catholyte compartment216or it may be further processed or concentrated as desired.

Additionally, the method of this embodiment may include recycling the iodine produced in Equation (8) to react with sodium sulfide according to Equation (5).

Referring now toFIG. 5, a process flow diagram is shown. In one embodiment, a process for electrochemically converting an alkali sulfate into useful chemical products, comprises reacting an alkali sulfate with carbon according to reaction (1) to produce carbon monoxide and M2S. In one embodiment, the M2S may be dissolved in water to form aqueous M2S. In another embodiment, the M2S may be dissolved in a nonaqueous solution to form nonaqueous M2S. The alkali sulfide in the aqueous or non aqueous solution may be between about 1% by weight and about 90% by weight of the solution.

An electrolytic cell of the type depicted inFIG. 1may be provided comprising an alkali ion conducting membrane configured to selectively transport alkali ions. The alkali ion conducting membrane is selected from a NaSICON membrane, a KSICON membrane, and a LiSICON membrane. The membrane is positioned between an anolyte compartment configured with an anode and a catholyte compartment configured with a cathode. The aqueous M2S is introduced into the anolyte compartment and water is introduced into the catholyte compartment. The aqueous M2S and water are electrolyzed to form MOH, H2and sulfur, according to reaction (3). In one embodiment, M is an alkali metal such as sodium, lithium, or potassium.

The CO from reaction (1) and H2from reaction (3) are recovered and combined to form syngas. The syngas may be an intermediate for the production of other fuels or chemicals. In one embodiment, the MOH from reaction (3) is recovered for later use. The MOH is concentrated by removing water. The carbon which reacts with the alkali sulfate in Equation 1 is selected from a carbon source selected from coal, charcoal, tar, lignin, and combinations thereof. In one embodiment, reaction (1) proceeds at a temperature in the range from 700 to 1600° C. and the reaction (1) proceeds under anaerobic conditions.

FIG. 5also represents the process for electrochemically converting an alkali sulfate into useful chemical products after an alkali sulfate is reacted with carbon according to reaction (1), the M2S is further reacted with iodine in a methyl alcohol solvent according to reaction (2). The process proceeds as above by providing an electrolytic cell comprising an alkali ion conducting membrane configured to selectively transport alkali ions where the membrane positioned between an anolyte compartment configured with an anode and a catholyte compartment configured with a cathode. The MI in methyl alcohol from reaction (2) is introduced into the anolyte compartment and water is introduced into the catholyte compartment. The MI and water are electrolyzed in the electrolytic cell to form MOH, H2and iodine, according to reaction (4). As discussed above, M is an alkali metal. For example, M may be sodium, lithium, potassium, or other alkali metals. The CO from reaction (1) and H2from reaction (4) are recovered and combined to form syngas, which may be used as an intermediate for the production of other fuels or chemicals.

In this embodiment, the process also includes recovering MOH from reaction (3) and concentrating it by removing water. The carbon is selected from a carbon source selected from coal, charcoal, tar, lignin and combinations thereof. The alkali ion conducting membranes are the same as discussed with earlier embodiment and the reaction (1) proceeds at similar temperatures under similar anaerobic conditions. The iodine produced in reaction (4) may be recycled to react with further alkali sulfide.

A process test including mixing 2.5 grams of Sodium sulfate with a molar excess of high surface area graphite (1:4.25) and reacted at a temperature of 800° C. in an Argon atmosphere. The duration of the heating cycle was 24 hours. The product mixture was examined by X-ray diffraction. The peaks in the X-ray pattern were identified to be sodium sulfide and residual graphite. One part of the mixture was then dispersed in methyl formamide, which selectively dissolved sodium sulfide while leaving the solid graphite which was removed by centrifugation. A second part of the mixture was reacted with an iodine solution in methanol (molar ratio of Na2S:I2::1:1) at 45° C. The reaction resulted in formation of sodium iodide product which dissolved in methanol while sulfur and carbon remained as solids which were retrieved by centrifugation. As before the solid products were identified by X-ray diffraction. The methanol solution containing sodium iodide was heater to evaporate methanol and retrieve solid sodium iodide which was also identified by X-ray diffraction.

It will be appreciated that the disclosed embodiments provide electrochemical processes to convert alkali sulfates into useful chemical products, such as syngas, alkali hydroxide, and sulfur.

While specific embodiments and examples of the present invention have been illustrated and described, numerous modifications come to mind without significantly departing from the spirit of the invention, and the scope of protection is only limited by the scope of the accompanying claims.