US20160355931A1

US20160355931A1 - Electrochemical Co-Production of Chemicals from Carbon Dioxide Using Sulfur-Based Reactant Feeds to Anode

Info

Publication number: US20160355931A1
Application number: US15/089,126
Authority: US
Inventors: Jerry J. Kaczur; Kyle Teamey
Original assignee: Ares Capital Corp
Current assignee: Avantium Knowledge Centre BV
Priority date: 2012-07-26
Filing date: 2016-04-01
Publication date: 2016-12-08
Also published as: US9708722B2; US8444844B1; US20130140187A1; US20130134048A1; US20140206894A1; US8647493B2; US20130118909A1; US20130105330A1; US8692019B2; US20130134049A1; US20140367274A1; US20140194641A1; US20130137898A1; US20140034506A1; US9303324B2; US20140124379A1; US8845875B2; US8845876B2; US20140357904A1; US20130230435A1

Abstract

The present disclosure includes a system and method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte comprising carbon dioxide, producing a first product which may include carbon monoxide or an alkli metal formate. The method may include another step of contacting the second region with an anolyte comprising a sulfur-based reactant and producing a second product including oxygen and sulfur dioxide. Further, the method may include a step for introducing the separated oxygen from second region of the electrochemical cell with a hydrogen sulfide stream in a catalyst reactor bed, converting the hydrogen sulfide to sulfur dioxide. The sulfur dioxide may then be liquefied as a product, or a portion of the sulfur dioxide may be recycled to the second region of the electrochemical cell where it may be converted to sulfuric acid. The sulfuric acid may then be reacted with another reactant, such as ammonia, to produce an ammonium sulfate product.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. §120 of U.S. patent application Ser. No. 13/724,719 filed Dec. 21, 2012, pending. The present application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 62/190,675 filed Jul. 9, 2015. Said U.S. patent application Ser. No. 13/724,719 filed Dec. 21, 2012 and U.S. Provisional Application Ser. No. 62/190,675 filed Jul. 9, 2015 are incorporated by reference in their entireties.
Said U.S. patent application Ser. No. 13/724,719 filed Dec. 21, 2012 claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/720,670 filed Oct. 31, 2012, U.S. Provisional Application Ser. No. 61/703,234 filed Sep. 19, 2012 and U.S. Provisional Application Ser. No. 61/675,938 filed Jul. 26, 2012. Said U.S. Provisional Application Ser. No. 61/720,670 filed Oct. 31, 2012, U.S. Provisional Application Ser. No. 61/703,234 filed Sep. 19, 2012 and U.S. Provisional Application Ser. No. 61/675,938 filed Jul. 26, 2012 are incorporated by reference in their entireties.
Said U.S. patent application Ser. No. 13/724,719 filed Dec. 21, 2012 also claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/703,229 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,158 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,175 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,231 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,232 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,238 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,187 filed Sep. 19, 2012. The U.S. Provisional Application Ser. No. 61/703,229 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,158 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,175 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,231 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,232 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,238 filed Sep. 19, 2012 and U.S. Provisional Application Ser. No. 61/703,187 filed Sep. 19, 2012 are hereby incorporated by reference in their entireties.
Said U.S. patent application Ser. No. 13/724,719 filed Dec. 21, 2012 incorporates by reference co-pending U.S. patent application Ser. No. 13/724,339 filed Dec. 21, 2012, now U.S. Pat. No. 9,175,407, U.S. patent application Ser. No. 13/724,878 filed Dec. 21, 2012, now U.S. Pat. No. 8,647,493, U.S. patent application Ser. No. 13/724,647 filed Dec. 21, 2012, now U.S. Pat. No. 8,845,876, U.S. patent application Ser. No. 13/724,231 filed Dec. 21, 2012, now U.S. Pat. No. 8,845,875, U.S. patent application Ser. No. 13/724,807 filed Dec. 21, 2012, now U.S. Pat. No. 8,692,019, U.S. patent application Ser. No. 13/724,996 filed Dec. 21, 2012, now U.S. Pat. No. 8,691,069, U.S. patent application Ser. No. 13/724,082 filed Dec. 21, 2012, now U.S. Pat. No. 8,821,709 and U.S. patent application Ser. No. 13/724,768 filed Dec. 21, 2012 now U.S. Pat. No. 8,444,844 in their entireties.

TECHNICAL FIELD

The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical co-production of chemicals with a sulfur-based or a nitrogen-based reactant feed to the anode.

BACKGROUND

The combustion of fossil fuels in activities such as electricity generation, transportation, and manufacturing produces billions of tons of carbon dioxide annually. Research since the 1970s indicates increasing concentrations of carbon dioxide in the atmosphere may be responsible for altering the Earth's climate, changing the pH of the ocean and other potentially damaging effects. Countries around the world, including the United States, are seeking ways to mitigate emissions of carbon dioxide.
A mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that may be stored for later use will be possible.

SUMMARY

The present disclosure includes a system and method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte comprising carbon dioxide. The method may include another step of contacting the second region with an anolyte comprising a sulfur-based reactant. Further, the method may include a step of applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region. An additional step of the method may include removing the second product and an unreacted sulfur-based reactant from the second region and recycling the unreacted sulfur-based reactant to the second region.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not necessarily restrictive of the present disclosure. The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate subject matter of the disclosure. Together, the descriptions and the drawings serve to explain the principles of the disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The numerous advantages of the disclosure may be better understood by those skilled in the art by reference to the accompanying figures in which:

FIG. 1A is a block diagram of a system in accordance with an embodiment of the present disclosure;

FIG. 1B is a block diagram of a system in accordance with an embodiment of the present disclosure;

FIG. 2A is a block diagram of a system in accordance with another embodiment of the present disclosure;

FIG. 2B is a block diagram of a system in accordance with an additional embodiment of the present disclosure;

FIG. 3A is a block diagram of a system in accordance with an additional embodiment of the present disclosure;

FIG. 3B is a block diagram of a system in accordance with an additional embodiment of the present disclosure;

FIG. 4A is a block diagram of a system in accordance with an additional embodiment of the present disclosure;

FIG. 4B is a block diagram of a system in accordance with an additional embodiment of the present disclosure;

FIG. 5 is a flow diagram of a method of electrochemical co-production of products in accordance with an embodiment of the present disclosure;

FIG. 6 is a flow diagram of a method of electrochemical co-production of products in accordance with another embodiment of the present disclosure;

FIG. 7 is a block diagram of a system in accordance with another embodiment of the present disclosure;

FIG. 8 a flow diagram of a method of electrochemical co-production of products in accordance with another embodiment of the present disclosure;

FIG. 9A is a block diagram of a system for co-production of an alkali metal formate and oxygen in accordance with an additional embodiment of the disclosure; and

FIG. 9B is a block diagram of a system for co-production of an alkali metal formate and oxygen in accordance with an additional embodiment of the disclosure.

FIG. 9C is a block diagram of a system for co-production of carbon monoxide and oxygen in accordance with an additional embodiment of the disclosure.

FIG. 9D is a block diagram of a system for co-production of carbon monoxide and oxygen in accordance with an additional embodiment of the disclosure.

DETAILED DESCRIPTION

Reference will now be made in detail to the subject matter disclosed, which is illustrated in the accompanying drawings.
Referring generally to FIGS. 1-9D, systems and methods of electrochemical co-production of products with either a sulfur-based reactant feed or a nitrogen-based reactant feed to an anode are disclosed. It is contemplated that the electrochemical co-production of products may include a production of a first product, such as reduction of carbon dioxide to sulfur-based products to include one, two, three, and four carbon chemicals, at a cathode side of an electrochemical cell with co-production of a second product, such as an oxidized sulfur-based product, at the anode of the electrochemical cell where the anolyte comprises a sulfur-based reactant. Some of the sulfur-based reactant may remain unreacted at the anode side of the electrochemical cell and this unreacted sulfur-based reactant may be recycled back to the anolyte.
A sulfur-based reactant may include an oxidizable sulfur compound. Sulfur-based reactants may include, for example, sulfur dioxide, sodium sulfide, potassium sulfide, and hydrogen sulfide. The sulfur-based reactant may comprise a waste gas from other chemical process or, for example, a coal burning power plant. One example may include hydrogen sulfide, which may come from natural gas processing and oil refinery processes.
Before any embodiments of the disclosure are explained in detail, it is to be understood that the embodiments may not be limited in application per the details of the structure or the function as set forth in the following descriptions or illustrated in the figures. Different embodiments may be capable of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of terms such as “including,” “comprising,” or “having” and variations thereof herein are generally meant to encompass the item listed thereafter and equivalents thereof as well as additional items. Further, unless otherwise noted, technical terms may be used according to conventional usage. It is further contemplated that like reference numbers may describe similar components and the equivalents thereof.
Referring to FIG. 1, a block diagram of a system 100 in accordance with an embodiment of the present disclosure is shown. System (or apparatus) 100 generally includes an electrochemical cell (also referred as a container, electrolyzer, or cell) 102, a sulfur-based reactant source 104, a carbon dioxide source 106, an absorber/gas separator 108, a first product extractor 110, a first product 113, a second product extractor 112, second product 115, and an energy source 114.
Electrochemical cell 102 may be implemented as a divided cell. The divided cell may be a divided electrochemical cell and/or a divided photoelectrochemical cell. Electrochemical cell 102 may include a first region 116 and a second region 118. First region 116 and second region 118 may refer to a compartment, section, or generally enclosed space, and the like without departing from the scope and intent of the present disclosure. First region 116 may include a cathode 122. Second region 118 may include an anode 124. First region 116 may include a catholyte whereby carbon dioxide is dissolved in the catholyte. Second region 118 may include an anolyte which may include a sulfur-based reactant, as well as unreacted sulfur-based reactant that is recycled into the anolyte after going through the second product extractor 112 and the absorber/gas separator 108. Energy source 114 may generate an electrical potential between the anode 124 and the cathode 122. The electrical potential may be a DC voltage. Energy source 114 may be configured to supply a variable voltage or constant current to electrochemical cell 102. Separator 120 may selectively control a flow of ions between the first region 116 and the second region 118. Separator 120 may include an ion conducting membrane or diaphragm material.
Electrochemical cell 102 is generally operational to reduce carbon dioxide in the first region 116 to a first product 113 recoverable from the first region 116 while producing a second product 115 recoverable from the second region 118. Cathode 122 may reduce the carbon dioxide into a first product 113 that may include one or more compounds. Examples of the first product 113 recoverable from the first region by first product extractor 110 may include CO, formic acid, formaldehyde, methanol, oxalate, oxalic acid, glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, ethylene, ethane, lactic acid, propanoic acid, acetone, isopropanol, 1-propanol, 1,2-propylene glycol, propylene, propane, 1-butanol, 2-butanol, butane, butene, butadiene, a carboxylic acid, a carboxylate, a ketone, an aldehyde, and an alcohol.
Carbon dioxide source 106 may provide carbon dioxide to the first region 116 of electrochemical cell 102. In some embodiments, the carbon dioxide is introduced directly into the region 116 containing the cathode 122. It is contemplated that carbon dioxide source may include a source of a mixture of gases in which carbon dioxide has been filtered from the gas mixture.
First product extractor 110 may implement an organic product and/or inorganic product extractor. First product extractor 110 is generally operational to extract (separate) the first product 113 from the first region 116. The extracted first product 113 may be presented through a port of the system 100 for subsequent storage and/or consumption by other devices and/or processes.
The anode side of the reaction occurring in the second region 118 may include a sulfur-based reactant, which may be a gas phase, liquid phase, or solution phase reactant. In addition, the sulfur-based reactant may also include a nitrogen based reactant. A sulfur-based reactant and a nitrogen-based reactant may both be fed to the anolyte, or only a sulfur-based or only a nitrogen-based reactant may be fed to the anolyte. The second product 115 recoverable from the second region 118 may be derived from a variety of oxidations such as the oxidation of inorganic sulfur-based compounds as well as organic sulfur compounds. Oxidations may be direct, such as the gas phase conversion of sulfur dioxide to sulfur trioxide at the anode. The oxidations also may be solution phase, such as the oxidation of sodium sulfide to sodium sulfite or sodium thiosulfate. In addition, the second product 115 recoverable from the second region 118 may be derived from a variety of oxidations such as the oxidation of inorganic nitrogen-based compounds as well as organic nitrogen compounds.
Examples are in the table below:

TABLE 1

Chemical Feed to Anode	Oxidation Product(s)

Sulfur dioxide (gas phase)	Sulfur trioxide, sulfuric acid
Sulfur dioxide (aqueous solution)	Hydrogen sulfite, sulfuric acid,
Alkali Metal Sulfides	Alkali metal sulfites, thiosulfates,
	polysulfides, sulfates
Alkali Metal Sulfites	Alkali metal sulfates, thiosulfates,
	polysulfides
Alkali Metal Bisulfites	Alkali metal sulfite, thiosulfates,
	polysulfides, sulfates
Alkali Metal Thiosulfates	Alkali metal polysulfides, sulfates
Hydrogen Sulfide	Sulfur, thiosulfate, sulfite, sulfate,
	sulfuric acid
Nitric Oxide (Nitrogen monoxide)	Nitrite, nitrate, nitric acid
Nitrous Oxide	Nitrite, nitrate, nitric acid
Nitrogen Dioxide	Nitric acid
Ammonia	N₂, nitrite, nitrate, nitric acid

Second product extractor 112 may extract the second product 115 from the second region 118. The extracted second product 115 may be presented through a port of the system 100 for subsequent storage and/or consumption by other devices and/or processes. The second product extractor 112 may also extract unreacted sulfur-based reactant 117 from the second region 118, which may be recycled back to the anolyte. It is contemplated that first product extractor 110 and/or second product extractor 112 may be implemented with electrochemical cell 102, or may be remotely located from the electrochemical cell 102. Additionally, it is contemplated that first product extractor 110 and/or second product extractor 112 may be implemented in a variety of mechanisms and to provide desired separation methods, such as fractional distillation, without departing from the scope and intent of the present disclosure.
Furthermore, the second product 115 as well as unreacted sulfur-based reactant 117 may be extracted from the second region 118 and presented to absorber/gas separator 108. The absorber/gas separator may separate the second product 115 from the unreacted sulfur-based reactant 117, as shown in FIG. 1A.
The absorber/gas separator 108 may also absorb the second product 115 in water provided by water source 121, which may form a third product 119 as shown in FIG. 1B. For example, the sulfur-based reactant source 104 may be sulfur dioxide in one embodiment, which results in the formation of sulfur trioxide as the second product 115. The second product extractor 112 may extract the second product 115 and the unreacted sulfur-based reactant 117, which is provided to absorber/gas separator 108. Water is provided to the absorber/gas separator 108 via water source 121 which may cause the second product 115 to form a third product 119. In the example, sulfur trioxide may be absorbed with the water to form sulfuric acid (third product 119). The absorber/gas separator 108 also separates the third product 119 and unreacted sulfur-based reactant 117. Unreacted sulfur-based reactant 117 may be recycled back to the second region 118 as an input feed to the second region 118 of electrochemical cell 102. It is contemplated that unreacted sulfur-based reactant 117 may be supplied as a sole or as an additional input feed to the second region 118 of the electrochemical cell 102 without departing from the scope and intent of the present disclosure.
The absorber/gas separator 108 may include an apparatus that absorbs a in input in water or another substance. The absorber/gas separator 108 may include a mechanism for separating one gas from another gas, or a gas from a liquid such as packed bed gas stripping/adsorption column or distillation column.
Through the co-production of a first product 113 and a second product 115, the overall energy requirement for making each of the first product 113 and second product 115 may be reduced by 50% or more. In addition, electrochemical cell 102 may be capable of simultaneously producing two or more products with high selectivity.
A preferred embodiment of the present disclosure may include production of organic chemicals, such as carbon dioxide reduction products, at the cathode while simultaneously using a sulfur-based reactant feed to the anode for use in the oxidation of sulfur-based products. Referring to FIG. 2A, system 200 for co-production of a first product 113 and sulfuric acid 219 is shown. In the system 200, sulfur dioxide 204 is supplied to the second region 118 where it is oxidized to produce sulfur trioxide 115. The oxidation of sulfur dioxide 204 to produce sulfur trioxide 115 is as follows:
2 SO₂+O₂→SO₃
The oxidation of the sulfur dioxide 204 in the presence of some water may produce protons that are utilized to reduce carbon dioxide at the cathode. Both the sulfur trioxide 215 and the unreacted sulfur-based reactant 117 may be fed into an absorber/gas separator 108. The sulfur trioxide 215 may be absorbed in water provided by water source 121 to produce sulfuric acid 219, according to the following reaction:
SO₃+H₂O→H₂SO₄
Any unreacted sulfur dioxide 217 may be recycled back to the second region 118. The unreacted sulfur dioxide 217 may be recycled back to the second region either as a pure anhydrous gas or in a liquid phase. The gas phase may be generally preferred in order to minimize energy requirements.
The cathode reaction may include the production of a first product 113, such as a carbon dioxide reduction product. In the example shown in FIG. 2A, the first product 113 may include acetic acid, although it is contemplated that other products may be produced at first region 116 without departing from the scope of the current disclosure. If the first product 113 is acetic acid, the cathode reaction is the formation of acetate or acetic acid as follows:
8CO₂+32H⁺+32e ⁻→4CH₃COO+4H⁺+8H₂O
Referring to FIG. 2B, a block diagram of a system 200 in accordance with an additional embodiment of the present disclosure is provided. Similar to the embodiment shown in FIG. 2A, FIG. 2B is a block diagram of a system in accordance with an additional embodiment of the present disclosure wherein a sulfur-based reactant source may be oxidized at the anode to produce inorganic alkali metal sulfur compounds and a corresponding alkali metal hydroxide at the cathode. For example, system 200 may include a sodium sulfide source 205, which may be in liquid phase such as in an aqueous solution. The sodium sulfide 205 is fed to the second region 118 where it is oxidized to produce sodium sulfite 213. The sodium sulfite 213 and any unreacted sodium sulfide 221 may be extracted from the second region 118 and separated by liquid/gas separator 108 which may also be an evaporator/crystallizer to separate the sodium sulfide from the sulfite using the water solubility differences of the two compounds in an aqueous solution. The unreacted sodium sulfide 221 may be recycled back to the second region 118. The carbon dioxide reduction product may be sodium acetate 223 when the reactant is sodium sulfide 205. Other reactants will yield different products. For example, for other alkali sulfide and inorganics, the product may be the corresponding alkali metal organic carbon compound salts.
The reaction shown in FIG. 2B may occur under alkaline conditions, and the reduction reaction in the first region 116 may utilize sodium cations produced in the oxidation reaction in order to produce the first product.
In the example shown in FIG. 2B where the sodium sulfide 205 may be fed into the anolyte in a solution, the sodium sulfide anolyte concentration may be in the range of 2 wt % to about 40 wt %, more preferably in the range of 5 wt % to 35 wt %, and more preferably in the 10 wt % to 30 wt % range.
The example shown in FIG. 2B may also be used to produce sodium thiosulfate at the anode when sodium sulfide 205 is the sulfur-based reactant source. Similarly, other alkali metal sulfides may be used instead of sodium sulfide. For example, potassium sulfide may serve as the sulfur-based reactant source at the anode in order to produce potassium sulfite, potassium thiosulfate, potassium polysulfides, and potassium sulfates. The final oxidation product(s) from the oxidation of the sulfide may depend on a number of factors including the operating pH of the anolyte, the selected anode electrocatalyst as well as the incorporation of any catalysts in the second region space, and the extent of oxidation of the reactant which may depend on the rate of flow of the reactant through the anolyte. The reaction may occur under alkaline conditions, and the reduction reaction in the first region 116 may utilize potassium cations produced in the oxidation reaction in order to produce the corresponding alkali metal carbon product, such as potassium acetate.
It is contemplated that reactions occurring at the first region 116 may occur in a catholyte which may include water, sodium bicarbonate or potassium bicarbonate, or other catholytes. The reactions occurring at the second region 118 may be in a gas phase, for instance in the case of gas phase reactant 118 such as sulfur dioxide. The reaction at the second region 118 may also occur in liquid phase, such as the case of a an alkali metal sulfide in solution.
Referring to FIGS. 3A, 3B, 4A and 4B, block diagrams of systems 300, 400 in accordance with additional embodiments of the present disclosure are shown. Systems 300, 400 provide additional embodiments to systems 100, 200 of FIGS. 1A and B and 2A and B to co-produce a first product and second product.
Referring specifically to FIG. 3A, first region 116 of electrochemical cell 102 may produce a first product of H ₂ 310 which is combined with carbon dioxide 332 in a reactor 330 which may perform a reverse water gas shift reaction. This reverse water gas shift reaction performed by reactor 330 may produce water 334 and carbon monoxide 336. Carbon monoxide 336 along with H ₂ 310 may be combined at reactor 338. Reactor 338 may cause a reaction by utilizing H ₂ 310 from the first region 116 of the electrochemical cell 102, such as a Fischer-Tropsch-type reaction, to reduce carbon monoxide to a product 340. Product 340 may include methane, methanol, hydrocarbons, glycols, olefins. Water 306 may be an additional product produced by the first region 116 and may be recycled as an input feed to the first region 116. Reactor 338 may also include transition metals such as iron, cobalt, and ruthenium as well as transition metal oxides as catalysts, that are deposited on inorganic support structures that may promote the reaction of CO with hydrogen at lower temperatures and pressures.
Second region 118 may co-produce a second product 312, such as sulfuric acid, from a sulfur-based reactant 304, such as sulfur dioxide. Unreacted sulfur-based reactant 317 may be separated from the second product 312 and recycled back as an input feed to the second region 118. It is contemplated that sulfur-based reactant 304 may include a range of sulfur-based reactants, including alkali metal sulfides, alkali metal sulfites, alkali metal bisulfites, alkali metal thiosulfates, and hydrogen sulfide while second product 312 may also refer to any type of sulfur compound that may be the oxidation product from the sulfur-based reactant, including sulfur trioxide, sulfuric acid, alkali metal sulfites, alkali metal thiosulfates as well as alkali metal polysulfides without departing from the scope or intent of the present disclosure.
Referring to FIG. 3B, it is contemplated that second region 118 may co-produce a second product 315, from a nitrogen-based reactant 305, such as nitrogen dioxide or nitric oxide to produce second product 315. Second product 315 may include nitric acid, nitrogen gas, or another product. Unreacted nitrogen-based reactant 321 may be separated from the second product 315 and recycled back as an input feed to the second region 118.
Referring to FIG. 4A, first region 116 of electrochemical cell 102 may produce a first product of carbon monoxide 410 which is combined with water 432 in a reactor 430 which may perform a water gas shift reaction. This water gas shift reaction performed by reactor 430 may produce carbon dioxide 434 and H ₂ 436. Carbon monoxide 410 and H ₂ 436 may be combined at reactor 438. Reactor 438 may cause a reaction, such as a Fischer-Tropsch-type reaction, to reduce carbon monoxide to a product 440. Product 440 may include methane, methanol, hydrocarbons, glycols, olefins by utilizing H ₂ 436 from the water gas shift reaction. Carbon dioxide 434 may be a byproduct of water gas shift reaction of reactor 430 and may be recycled as an input feed to the first region 116. Water 406 may be an additional product produced by the first region 116 and may be recycled as another input feed to the first region 116. Reactor 438 may also include transition metals such as iron and copper as well as transition metal oxides as catalysts, deposited on inorganic support structures that may promote the reaction of CO with hydrogen at lower temperatures and pressures.
Second region 118 of electrochemical cell 102 may co-produce a second product 415, such as sulfuric acid, from a sulfur-based reactant 404, such as sulfur dioxide. Unreacted sulfur-based reactant 417 may be separated from the second product 415 and recycled back as an input feed to the second region 118. It is contemplated that sulfur-based reactant 404 may include a range of sulfur-based reactants, including alkali metal sulfides, alkali metal sulfites, alkali metal bisulfites, alkali metal thiosulfates, and hydrogen sulfide while second product 415 may also refer to any type of sulfur compound that may be oxidized from the sulfur-based reactant 404, including sulfur trioxide, sulfuric acid, alkali metal sulfites and thiosulfates as well as alkali metal polysulfides without departing from the scope or intent of the present disclosure.
Referring to FIG. 4B, it is contemplated that second region 118 may co-produce a second product 413, from a nitrogen-based reactant 405, such as nitrogen dioxide or nitric oxide to produce second product 413. Unreacted nitrogen-based reactant 421 may be separated from the second product 413 and recycled back as an input feed to the second region 118.
Referring to FIG. 5 a flow diagram of a method 500 of electrochemical co-production of products in accordance with an embodiment of the present disclosure is shown. It is contemplated that method 500 may be performed by systems 100 and system 200 as shown in FIGS. 1A-B and 2A-B. Method 500 may include producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode.
Method 500 of electrochemical co-production of products may include a step of contacting the first region with a catholyte comprising carbon dioxide 510. A further step of method 500 may include contacting the second region with an anolyte comprising a sulfur-based reactant 520. The method 500 also includes the step of applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region 530. The method 500 also includes the step of removing the second product and an unreacted sulfur-based reactant from the second region 540 and recycling the unreacted sulfur-based reactant to the second region 550. Advantageously, a first product produced at the first region may be recoverable from the first region and a second product produced at the second region may be recoverable from the second region.
Referring to FIG. 6, a flow diagram of a method 600 of electrochemical co-production of products in accordance with another embodiment of the present disclosure is shown. It is contemplated that method 600 may be performed by system 100 and system 200 as shown in FIGS. 1A-B and 2A-B. Method 600 may include steps for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode.
Method 600 may include a step of receiving a feed of carbon dioxide at the first region of the electrochemical cell 610 and contacting the first region with a catholyte comprising carbon dioxide 620. Method 600 also includes the step of receiving a feed of a sulfur-based reactant at the second region of the electrochemical cell 630 and contacting the second region with an anolyte comprising the sulfur-based reactant 640. A further step of the method is to apply an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region 650. The method 600 also includes the step of removing the second product and an unreacted sulfur-based reactant from the second region 660. The method 600 also includes the step of recycling the unreacted sulfur-based reactant to the second region 670.
It is contemplated that a receiving feed may include various mechanisms for receiving a supply of a product, whether in a continuous, near continuous or batch portions.
In an additional embodiment of the present disclosure, nitrogen compounds may also be oxidized at the anode as shown in FIG. 7. System 700 depicted in FIG. 7 includes nitrogen-based reactant source 704 which is provided to the second region 118. Nitrogen-based reactant source 704 may include nitric oxide, nitrous oxide, or ammonia, as well as other nitrogen compounds. For example, the nitrogen-based reactant source may be in aqueous solution and could include an alkali metal nitrite, nitrates and their mixtures.
Nitrogen-based reactant source 704 is reacted at the anode to produce second product 715. Second product 715 may include nitrogen gas or nitric acid. Unreacted nitrogen-based reactant 717 may be separated from the second product 715 using the absorber/gas separator 108 and recycled back to the second region 118.
In one example, the nitrogen-based reactant source 704 is ammonia, which is oxidized to produce second product 715 of nitrogen as well as hydrogen. This formation of hydrogen may be useful for processes requiring hydrogen while not producing any co-current carbon dioxide.
The reaction is:
2 NH₃→N₂+3 H₂
Referring to FIG. 8 a flow diagram of a method 800 of electrochemical co-production of products in accordance with an embodiment of the present disclosure is shown. It is contemplated that method 800 may be performed by system 700 as shown in FIG. 7. Method 800 may include producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode.
Method 800 of electrochemical co-production of products may include a step of contacting the first region with a catholyte comprising carbon dioxide 810. A further step of method 800 may include contacting the second region with an anolyte comprising a nitrogen-based reactant 820. The method 800 also includes the step of applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region 830. The method 800 also includes the step of removing the second product and an unreacted nitrogen-based reactant from the second region 840 and recycling the unreacted nitrogen-based reactant to the second region 850.
It is contemplated that the structure and operation of the electrochemical cell 102 may be adjusted to provide desired results. For example, the electrochemical cell 102 may operate at higher pressures, such as pressure above atmospheric pressure which may increase current efficiency and allow operation of the electrochemical cell at higher current densities.
Additionally, the cathode 122 and anode 124 may include a high surface area electrode structure with a void volume which may range from 30% to 98%. The electrode void volume percentage may refer to the percentage of empty space that the electrode is not occupying in the total volume space of the electrode. The advantage in using a high void volume electrode is that the structure has a lower pressure drop for liquid flow through the structure. The specific surface area of the electrode base structure may be from 2 cm²/cm³to 500 cm²/cm³or higher. The electrode specific surface area is a ratio of the base electrode structure surface area divided by the total physical volume of the entire electrode. It is contemplated that surface areas also may be defined as a total area of the electrode base substrate in comparison to the projected geometric area of the current distributor/conductor back plate, with a preferred range of 2× to 1000× or more. The actual total active surface area of the electrode structure is a function of the properties of the electrode catalyst deposited on the physical electrode structure which may be 2 to 1000 times higher in surface area than the physical electrode base structure.
Cathode 122 substrate or structure may be selected from a number of high surface area electrocatalyst materials to include copper, stainless steels, transition metals and their alloys, carbon and its various forms such as graphite and graphene, and silicon, which may then be further coated with one or more layers of additional catalyst materials which may include a conductive metal, an oxide, or a semiconductor. The base structure of cathode 122 may be in the form of fibrous, metal foams, reticulated, or sintered powder materials made from metals, carbon, or other conductive materials including polymers. The materials may be a very thin plastic screen incorporated against the cathode side of the membrane to prevent the membrane 120 from directly touching the high surface area cathode structure. The high surface area cathode structure may be mechanically pressed against a cathode current distributor backplate, which may be composed of material that has the same surface composition as the high surface area cathode. The high surface area structure may also be pressed against or bonded to a polymer ion exchange separator or membrane 120.
In addition, cathode 122 may be a suitable electrically conductive electrocatalyst electrode prepared from single metals or combinations of these different metals as alloys and as coatings or layers, such as Al, Au, Ag, Bi, C, Cd, Co, Cr, Cu, Cu alloys (e.g., brass and bronze), Ga, Hg, In, Mo, Nb, Ni, NiCo₂O₄, Ni alloys (e.g., Ni 625, NiHx), Ni—Fe alloys, Pb, Pd alloys (e.g., PdAg), Pt, Pt alloys (e.g., PtRh), Rh, Sn, Sn alloys (e.g., SnAg, SnPb, SnSb), Ti, V, W, Zn, stainless steel (SS) (e.g., SS 2205, SS 304, SS 316, SS 321), austenitic steel, ferritic steel, duplex steel, martensitic steel, Nichrome (e.g., NiCr 60:16 (with Fe)), Elgiloy (e.g., Co—Ni—Cr). The electrocatalyst cathode may also include or consist of other conductive materials such as degenerately doped n-Si, degenerately doped n-Si:As, degenerately doped n-Si:B, degenerately doped n-Si, degenerately doped n-Si:As, and degenerately doped n-Si:B. Other cathode materials that may be suitable are boron-doped carbon or other forms of carbon such a graphene. Other conductive cathode electrodes may be implemented to meet the criteria of a particular application, such as in the generation of acetate, acetic acid, or CO. For photoelectrochemical reductions, cathode 122 may be a p-type semiconductor electrode, such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, p-GaInP₂and p-Si, or an n-type semiconductor, such as n-GaAs, n-GaP, n-InN, n-InP, n-CdTe, n-GaInP₂and n-Si. Other semiconductor electrodes may be implemented to meet the criteria of a particular application including, but not limited to, CoS, MoS₂, TiB, WS₂, SnS, Ag₂S, CoP₂, Fe₃P, Mn₃P₂, MoP, Ni₂Si, MoSi₂, WSi₂, CoSi₂, Ti₄O₇, SnO₂, GaAs, GaSb, Ge, and CdSe.
Additionally, cathode 122 may be produced or processed by various methods to produce a microporous high surface electrode structure or a surface structure thickness with a high porosity. An example of this may be similar in the method in which Raney nickel electrodes are produced, wherein nickel-aluminum alloys with possibly one or more additional electrocatalyst metals included, may be subjected to chemical dissolution, such as with a sodium hydroxide solution, which may dissolve the aluminum component from the alloy, producing a high porosity nickel-metal electrocatalyst structure. This high surface area structure may comprise a thin layer ranging from microns to thousands of microns in thickness of the base metal structure, or extend through the thickness of the cathode base metal structure. Additionally, one or more electrocatalyst layers of different metals or electrocatalyst materials, as described previously, may be applied or added to the high surface area cathode structure. The processing may also be done on conductive semiconductor electrodes using suitable chemical or gaseous etchants.
In another embodiment, the cathode employed may be a GDE, a gas diffusion electrode type, where the cathode construction consists of an electrocatalyst layer that has been applied onto a carbon or graphite substrate with a gas diffusion layer that may be placed physically in contact or bonded to the electrochemical cell membrane. Carbon dioxide gas may be introduced into the cathode compartment and be converted, for example to CO, at the electrocatalyst layer. Commercially available GDE constructions may be employed, such as MEA's (membrane electrode assemblies), which are extensively employed in fuel cells. In these assemblies, an electrocatalyst on a carbon support may be applied to a carbon cloth or paper and then bonded to membrane surface to act as a cathode. The carbon cloth or another gas permeable electrically conductive layer may act as gas diffusion layer used to allow the transfer of gas to the electrocatalyst in conversion of carbon dioxide to CO. A current collector may be employed which is in physical contact with the GDE, having a suitable gas flow distribution, and used to distribute or transfer the electrical current to the GDE. The current collector may be made from carbon, graphite, or suitable selected metals. Examples of electrocatalysts for the carbon dioxide conversion to CO, may be Ag and its oxides, as well as binary and ternary alloys of Ag with other metals mentioned previously, such as Bi, In, Sn, W, and the like. The electrocatalyst may optionally consist of the arrangement of layers of these metals or alloys to optimize the conversion of carbon dioxide to CO.
The catholyte may include a pH range from 1 to 12, preferably from a pH range from 4 to pH 10. The selected operating pH may be a function of any catalysts utilized in operation of the electrochemical cell 102. Preferably, catholyte and catalysts may be selected to prevent corrosion at the electrochemical cell 102. The catholyte may include homogeneous catalysts. Homogeneous catalysts are defined as aromatic heterocyclic amines and may include, but are not limited to, unsubstituted and substituted pyridines and imidazoles. Substituted pyridines and imidazoles may include, but are not limited to mono and disubstituted pyridines and imidazoles. For example, suitable catalysts may include straight chain or branched chain lower alkyl (e.g., C1-C10) mono and disubstituted compounds such as 2-methylpyridine, 4-tertbutyl pyridine, 2,6 dimethylpyridine (2,6-lutidine); bipyridines, such as 4,4′-bipyridine; amino-substituted pyridines, such as 4-dimethylamino pyridine; and hydroxyl-substituted pyridines (e.g., 4-hydroxy-pyridine) and substituted or unsubstituted quinoline or isoquinolines. The catalysts may also suitably include substituted or unsubstituted dinitrogen heterocyclic amines, such as pyrazine, pyridazine and pyrimidine. Other catalysts generally include azoles, imidazoles, indoles, oxazoles, thiazoles, substituted species and complex multi-ring amines such as adenine, pterin, pteridine, benzimidazole, phenonthroline and the like.
The catholyte may include an electrolyte. Catholyte electrolytes may include alkali metal bicarbonates, carbonates, sulfates, phosphates, borates, and hydroxides. Non-aqueous electrolytes, such as propylene carbonate, methanesulfonic acid, methanol, and other ionic conducting liquids may be used rather than water and using salt addition electrolytes such as alkali metal salts. The electrolyte may comprise one or more of Na₂SO₄, KCl, NaNO₃, NaCl, NaF, NaClO₄, KClO₄, K₂SiO₃, CaCl₂, a guanidinium cation, an H cation, an alkali metal cation, an ammonium cation, an alkylammonium cation, a tetraalkyl ammonium cation, a halide anion, an alkyl amine, a borate, a carbonate, a guanidinium derivative, a nitrite, a nitrate, a phosphate, a polyphosphate, a perchlorate, a silicate, a sulfate, and a hydroxide.
The catholyte may further include an aqueous or non-aqueous solvent. An aqueous solvent may include greater than 5% water. A non-aqueous solvent may include as much as 5% water. A solvent may contain one or more of water, a protic solvent, or an aprotic polar solvent. Representative solvents include methanol, ethanol, acetonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethylsulfoxide, dimethylformamide, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylacetaminde, dimethoxyethane, diethylene glycol dimethyl ester, butyrolnitrile, 1,2-difluorobenzene, γ-butyrolactone, N-methyl-2-pyrrolidone, sulfolane, 1,4-dioxane, nitrobenzene, nitromethane, acetic anhydride, ionic liquids, and mixtures thereof.
In one embodiment, a catholyte/anolyte flowrate may include a catholyte/anolyte cross sectional area flow rate range such as 2-3,000 gpm/ft²or more (0.0076-11.36 m³/m²). A flow velocity range may be 0.002 to 20 ft/sec (0.0006 to 6.1 m/sec). Operation of the electrochemical cell catholyte at a higher operating pressure allows more dissolved carbon dioxide to dissolve in the aqueous solution. Typically, electrochemical cells may operate at pressures up to about 20 to 30 psig in multi-cell stack designs, although with modifications, the electrochemical cells may operate at up to 100 psig. The electrochemical cell may operate the anolyte and the catholyte at the same pressure range to minimize the pressure differential on a separator 120 or membrane separating the two regions. Special electrochemical designs may be employed to operate electrochemical units at higher operating pressures up to about 60 to 100 atmospheres or greater, which is in the liquid CO₂and supercritical CO₂operating range.
In another embodiment, a portion of a catholyte recycle stream may be separately pressurized using a flow restriction with backpressure or using a pump, with CO₂injection, such that the pressurized stream is then injected into the catholyte region of the electrochemical cell which may increase the amount of dissolved CO₂in the aqueous solution to improve the conversion yield. In addition, microbubble generation of carbon dioxide may be conducted by various means in the catholyte recycle stream to maximize carbon dioxide solubility in the solution.
Catholyte may be operated at a temperature range of −10 to 95° C., more preferably 5-60° C. The lower temperature will be limited by the catholytes used and their freezing points. In general, the lower the temperature, the higher the solubility of CO₂in an aqueous solution phase of the catholyte, which would help in obtaining higher conversion and current efficiencies. The drawback is that the operating electrochemical cell voltages may be higher, so there is an optimization that would be done to produce the chemicals at the lowest operating cost. In addition, the catholyte may require cooling, so an external heat exchanger may be employed, flowing a portion, or all, of the catholyte through the heat exchanger and using cooling water to remove the heat and control the catholyte temperature.
Anolyte operating temperatures may be in the same ranges as the ranges for the catholyte, and may be in a range of 0° C. to 95° C. In addition, the anolyte may require cooling, so an external heat exchanger may be employed, flowing a portion, or all, of the anolyte through the heat exchanger and using cooling water to remove the heat and control the anolyte temperature.
Electrochemical cells may include various types of designs. These designs may include zero gap designs with a finite or zero gap between the electrodes and membrane, flow-by and flow-through designs with a recirculating catholyte electrolyte utilizing various high surface area cathode materials. The electrochemical cell may include flooded co-current and counter-current packed and trickle bed designs with the various high surface area cathode materials. Also, bipolar stack cell designs and high pressure cell designs may also be employed for the electrochemical cells.
Anode electrodes may be the same as cathode electrodes or different. For sulfur dioxide and hydrogen sulfide anode oxidation chemistry under acid conditions, the preferred electrocatalytic coatings may include precious metal oxides such as ruthenium and iridium oxides, as well as platinum and gold and their combinations as metals and oxides on valve metal substrates such as titanium, tantalum, zirconium, or niobium. Carbon and graphite may also be suitable for use as anodes in addition to boron-doped diamond films on metal or other electrically conductive substrates. For other sulfur based reactants in the anolyte such as sodium sulfide or hydrogen sulfide being oxidized under alkaline conditions, such as in a hydroxide containing electrolyte, selected anode materials may include carbon, transition metals, transitional metal oxides carbon steel, stainless steels, and their alloys and combinations which are stable as anodes. Anode 124 may include electrocatalytic coatings applied to the surfaces of the base anode structure. Anolytes may be the same as catholytes or different. The anolyte electrolytes may be the same as catholyte electrolytes or different. The anolyte may comprise solvent. The anolyte solvent may be the same as catholyte solvent or different. For example, for acid anolytes containing SO₂as the sulfur-based reactant, the preferred electrocatalytic coatings may include precious metal oxides such as ruthenium and iridium oxides, as well as platinum and gold and their combinations as metals and oxides on valve metal substrates such as titanium, tantalum, zirconium, or niobium. For other anolytes, comprising alkaline or hydroxide electrolytes, anodes may include carbon, cobalt oxides, stainless steels, transition metals, and their alloys, oxides, and combinations. High surface area anode structures that may be used which would help promote the reactions at the anode. The high surface area anode base material may be in a reticulated form composed of fibers, sintered powder, sintered screens, and the like, and may be sintered, welded, or mechanically connected to a current distributor back plate that is commonly used in bipolar cell assemblies. In addition, the high surface area reticulated anode structure may also contain areas where additional applied catalysts on and near the electrocatalytic active surfaces of the anode surface structure to enhance and promote reactions that may occur in the bulk solution away from the anode surface such as the the introduction of SO₂into the anolyte. The anode structure may be gradated, so that the suitable of the may vary in the vertical or horizontal direction to allow the easier escape of gases from the anode structure. In this gradation, there may be a distribution of particles of materials mixed in the anode structure that may contain catalysts, such as transition metal based oxides, such as those based on the transition metals such as Co, Ni, Mn, Zn, Cu and Fe as well as precious metals and their oxides based on platinum, gold, silver and palladium which may be deposited on inorganic supports within cathode compartment space 118 or externally, such as in the second product extractor or a separate reactor.
Separator 120, also referred to as a membrane, between a first region 118 and second region 118, may include cation ion exchange type membranes. Cation ion exchange membranes which have a high rejection efficiency to anions may be preferred. Examples of such cation ion exchange membranes may include perfluorinated sulfonic acid based ion exchange membranes such as DuPont Nafion® brand unreinforced types N117 and N120 series, more preferred PTFE fiber reinforced N324 and N424 types, and similar related membranes manufactured by Japanese companies under the supplier trade names such as AGC Engineering (Asahi Glass) under their tradename Flemion®. Other multi-layer perfluorinated ion exchange membranes used in the chlor alkali industry may have a bilayer construction of a sulfonic acid based membrane layer bonded to a carboxylic acid based membrane layer, which efficiently operates with an anolyte and catholyte above a pH of about 2 or higher. These membranes may have a higher anion rejection efficiency. These are sold by DuPont under their Nafion® trademark as the N900 series, such as the N90209, N966, N982, and the 2000 series, such as the N2010, N2020, and N2030 and all of their types and subtypes. Hydrocarbon based membranes, which are made from of various cation ion exchange materials may also be used if a lower the anion rejection eficiency is not as important, such as those sold by Sybron under their trade name Ionac®, AGC Engineering (Asahi Glass) under their trade name under their Selemion® trade name, and Tokuyama Soda, among others on the market. Ceramic based membranes may also be employed, including those that are called under the general name of NASICON (for sodium super-ionic conductors) which are chemically stable over a wide pH range for various chemicals and selectively transports sodium ions, the composition is Na₁+xZr₂Si_xP₃−xO₁₂, and well as other ceramic based conductive membranes based on titanium oxides, zirconium oxides and yttrium oxides, and beta aluminum oxides. Alternative membranes that may be used are those with different structural backbones such as polyphosphazene and sulfonated polyphosphazene membranes in addition to crown ether based membranes. Preferably, the membrane or separator is chemically resistant to the anolyte and catholyte.
A rate of the generation of reactant formed in the anolyte compartment from the anode reaction, such as the oxidation of sulfur dioxide to sulfur trioxide, is contemplated to be proportional to the applied current to the electrochemical cell 102. The rate of the input or feed of the sulfur-based reactant, for example sulfur dioxide, into the second region 118 should then be fed in proportion to the generated reactant. The molar ratio of the sulfur-based reactant to the generated anode reactant may be in the range of 100:1 to 1:10, and more preferably in the range of 50:1 to 1:5. The anolyte product output in this range may contain unreacted sulfur-based reactant. The operation of the extractor 112 and its selected separation method, for example fractional distillation or packed tower scrubbing, the actual products produced, and the selectivity of the wanted reaction would determine the optimum molar ratio of the sulfur-based reactant to the generated reactant in the anode compartment. Any of the unreacted components would be recycled to the second region 118.
Similarly, a rate of the generation of the formed electrochemical carbon dioxide reduction product, is contemplated to be proportional to the applied current to the electrochemical cell 102. The rate of the input or feed of the carbon dioxide source 106 into the first region 116 should be fed in a proportion to the applied current. The cathode reaction efficiency would determine the maximum theoretical formation in moles of the carbon dioxide reduction product. It is contemplated that the ratio of carbon dioxide feed to the theoretical moles of potentially formed carbon dioxide reduction product would be in a range of 100:1 to 2:1, and preferably in the range of 50:1 to 5:1, where the carbon dioxide is in excess of the theoretical required for the cathode reaction. The carbon dioxide excess would then be separated in the extractor 110 and recycled back to the first region 116.
The electrochemical cell may be easily operated at a current density of greater than 3 kA/m²(300 mA/cm²), or in suitable range of 0.5 to 5 kA/m²or higher if needed. The anode preferably may have a high surface area structure with a specific surface area of 10 to 50 cm²/cm³or more that fills the gap between the cathode backplate and the membrane, thus having a zero gap anode configuration. Metal and/or metal oxide catalysts may be added to the anode in order to decrease anode potential and/or increase anode current density. Stainless steels or nickel may also be used as anode materials with for sodium sulfide oxidation under alkaline conditions. For sulfur dioxide and hydrogen sulfide gas reactions at the anode, under acidic conditions, anodes with precious metal oxide coatings on valve metal substrates are the preferred materials, but others may also be suitable.
FIG. 9A shows a further embodiment of the present disclosure. System 900A shows an electrochemical co-production system where electrochemical cell 901 co-produces potassium formate and oxygen, and the oxygen co-product may be utilized in the conversion of a hydrogen sulfide (H₂S) input stream in an oxidation catalyst bed 916 to sulfur dioxide (SO₂). Electrochemical cell 901 includes a catholyte compartment 902, cation ion exchange membrane separator 904, and an anode compartment 906. Carbon dioxide stream 911 may be introduced into the electrochemical cell 901 catholyte stream having a potassium bicarbonate electrolyte, and may be electrochemically reduced to formate at the cathode. Catholyte disengager 910 separates excess unreacted CO₂and byproduct hydrogen gases from the exit catholyte solution stream. The formate in catholyte formate product solution 912 may then be separated and converted to downstream products, such as potassium formate, potassium oxalate, formamides, methyl formate, oxalic acid, glycolic acid, and monoethylene glycol.
Oxygen may be produced from the oxidation of water in the anolyte compartment 906 of electrochemical cell 901 utilizing a suitable anolyte, such as a sulfuric acid electrolyte or anolyte. The oxygen is separated in anoyte disengager 908, which then may pass through heat exchanger 914 to preheat the oxygen to the temperature required for the oxidation of hydrogen sulfide to SO₂in H₂S oxidation catalyst bed unit 916. H₂ S input stream 920 may also be preheated in heat exchanger 922 and may be mixed with the preheated oxygen from electrochemical cell 901 and passed into the oxidation catalyst bed 916 at flowrates and temperatures for the efficient conversion to SO₂ product 918. The 918 stream SO₂product may then be condensed to a liquid SO₂product 924, which may be the final product, or may be converted to other sulfur products such as sodium sulfite, sodium metabisulfite, or sulfuric acid. The overall reaction of the H₂S with oxygen in the catalyst bed is theorized to be as follows:
2 H₂S+3O₂→2 SO₂+2 H₂O
The catalyst in H₂ S oxidation bed 916 may include vanadium oxides and vandium oxide mixtures combined with other metal oxides, including transition metals and their oxides, precious metals, as well as alkaline earth metal oxides. The transition metal and metal oxides include those of Fe, Ni, Co, Cu, Mn, Mo, Cr, Ti, Nb, Zr, Zn, Nb, W, Ta, as well as the oxides of Ca, Ba, Si, Al, Mg, Y, and Sr and precious metals such as Pt, Au, Ag, and Au. The oxidation catalyst may also include other metals and their oxides including Ru, Ir, Rh, Sn, In, Pb, Cd, Ga, Bi, and Sb. The support for the H₂S oxidation catalysts may include carbon, titanium oxides (TiO₂), various forms of alumina (Al₂O₃), zirconium oxide (ZrO₂), yttrium oxides, cerium oxide (CeO₂), silica, and all other commercial catalyst support materials and their mixtures that may be readily available.
The operating temperature of the catalyst bed may range from about 60° C. to 400° C., and preferably between 90° C. to 350° C., and more preferably between about 100° C. to 300° C. The molar ratio of H₂S to O₂in the oxidation catalyst bed may range from about 1:1 to 1:100, preferably from about 1:2 to 1:50, and more preferably from about 1:3 to 1:30. The selection of the catalysts and the H₂S to oxygen molar reaction ratio will determine the best temperature operating range.
The mass or volumetric flowrate of the gases through the H₂ S catalyst bed 916, in terms of reaction residence time, may range from 0.1 seconds to 500 seconds, and preferably in a range from about 0.2 seconds to 300 seconds, and more preferably from about 0.3 seconds to 200 seconds. The catalyst bed may be operated in a single pass configuration or may employ a gas recirculation loop (not shown) to increase the mass transfer and conversion of the gas reactants with the catalyst in the bed, in addition to providing good heat transfer.
FIG. 9B shows a further embodiment of the present disclosure. System 900B shows an electrochemical co-production system where electrochemical cell 901 co-produces potassium formate and a selected variable amount of anolyte co-product oxygen, and the oxygen co-product and any additional oxygen from another source may be utilized in the conversion of a hydrogen sulfide (H₂S) input stream in an oxidation catalyst bed to sulfur dioxide (SO₂). The SO₂product may be condensed or liquified to an SO₂liquid, with a 0-100 percentage captured as a product, or a proportion, from 2% to 98%, that may be routed as SO₂to the anolyte compartment of electrochemical cell 901, where it is converted to sulfuric acid. The amount of co-product oxygen produced in the anolyte is proportional to the quantity of electrons that are not oxidizing SO₂to sulfuric acid in the anodic reaction, and the oxygen being produced from the oxidation of water present in the electrolyte. The sulfuric acid product produced and leaving the anolyte compartment may then be converted to produce an ammonium sulfate product 932 using an external source of ammonia 930.
Formate electrochemical cell 901 includes catholyte compartment 902, cation ion exchange membrane separator 904, and an anode compartment 906. Carbon dioxide stream 911 is introduced into the electrochemical cell 901 catholyte stream having a potassium bicarbonate electrolyte, and may be electrochemically reduced to formate at the cathode. Catholyte disengager 910 separates excess unreacted CO₂and byproduct hydrogen gases from the exit catholyte solution stream. The formate in catholyte formate product solution 912 may then be separated and converted to downstream products, such as potassium formate, potassium oxalate, formamides, methyl formate, oxalic acid, glycolic acid, and monoethylene glycol.
A Faradaic percentage of oxygen, from about 1% to 100%, or preferably from about 5% to 90%, or more preferably from about 10%-80% may be produced from the oxidation of water in the anolyte compartment of electrochemical cell 901 utilizing a sulfuric acid electrolyte or anolyte. The remainder of the anode Faradaic reaction may be the oxidation of SO₂in the anolyte compartment from SO₂feed stream 926. The anolyte oxygen, and any residual SO₂, is separated in anoyte disengager 908, which may then pass through heat exchanger 914 to preheat the oxygen to the temperature required for the oxidation of hydrogen sulfide to SO₂in H₂S oxidation catalyst bed unit 916. Additional oxygen stream 923 supplies additional oxygen to make up any oxygen that is not provided from the anolyte compartment of electrochemical cell 901. The oxygen may be from air, but is more preferably a more concentrated oxygen source containing 30% to 99% oxygen, and more preferably from about 50% to 99% oxygen. Oxygen 923 may be supplied or produced using other various commercial methods, such as by pressure swing adsorption (PSA).
The H₂S stream 920 concentration may range from about 1% to 100% by volume, and preferably from 2% to 95% by volume, and more preferably from 2% to 90% by volume. The H₂S feed may be preferably preconcentrated if the source concentration is in the 1% to 5% by volume ranges. If a volume percentage of NOx is present with the H₂S, it may be converted to nitric acid in the anolyte compartment of electrochemical cell 901. This would produce an anolyte product that may be a mixture of sulfuric acid and nitric acid going into reactor 928, producing a mixed ammonium sulfate and ammonium nitrate 932 product mixture, which may also be an excellent fertilizer product.
The sulfuric acid concentration in the anolyte circulation loop of electrochemical cell 901 may range from about 1% to 50% by weight, preferably from about 2% to 30% by weight, and more preferably from about 2% to 10% by weight. Any nitric acid that may be produced in the anolyte loop may have similar nitric acid concentrations, in the range of about 1% to 40% by weight, and more preferably in a range of 2% to 20% by weight.
The electrochemical cell 901 may also employ a platinized titanium anode, as well as other suitable anode materials such as Ebonex (Altraverda) with or without an applied platinum group metal oxide based catalyst coatings, such as Ru, Pt, and Ir. Carbon or graphite based materials with or without a platinum group metal based oxide coating may also be employed, as well as lead dioxide-based coatings on a titanium or niobium metal base substrate. Commercially available mixed metal oxides (MMO) which have mixed compositions and layers of the oxides of Ru, Ir, Au, and Pt as well as Ti and Ta on a titanium or niobium metal substate may also be suitable.
H₂ S input stream 920 is preheated in heat exchanger 922 and is mixed with the preheated oxygen from electrochemical cell 901 and external oxygen supply 923 and passed into the oxidation catalyst bed 916 at flowrates and temperatures for the efficient conversion to SO₂ product 918. The 918 stream SO₂product may then be condensed in SO₂condenser 919 to a liquid SO₂product 925, which may be the final product or may be converted to other sulfur products. A portion of the SO₂product, such as, for example, about 5% to 100%, may then be recycled and routed as stream 926 as a liquid or gas to the anolyte compartment of electrochemical cell 901, where the SO₂may be oxidized to H₂SO₄. The SO₂oxidation as an anode reaction may result in a significantly lower anode voltage. The unreacted sulfuric acid produced may then be passed to reactor 928 where an ammonia stream 930 may be added to produce an ammonium sulfate product 932. It is contemplated that the unreacted sulfuric acid may include any excess sulfuric acid which has not been reacted in the anode reaction. In addition, oxidation catalyst bed 916 may employ a separate internal heating system, utilizing steam or electrical heat to heat the catalyst bed. If the chosen reaction conditions in the oxidation catalyst bed are exothermic, then the oxidation catalyst bed may also employ a cooling mechanism, such as cooling water, to maintain the proper catalyst bed temperature. The design of oxidation catalyst bed 916 may chosen from those types commercially available.
Electrochemical cell 901 in Systems 900A and 900B as shown in FIGS. 9A and 9B may be optionally configured to produce carbon monoxide, CO, as a catholyte product instead of formate from the reduction of CO₂. These process configurations are shown in Systems 900C and 900D of FIGS. 9C and 9D. Suitable catholyte compositions may be employed when producing CO. The catholyte may need to be processed and recycled to manage the accumulation or loss of the electrolyte components as well as concentration control of the electrolyte components. For example, the concentration of an alkali metal sulfate electrolyte may accumulate or increase in the catholyte circulation loop, and may need to be removed by various suitable available methods such a crystallization, precipitation, ion exchange, membrane separation, and the like. The selection of the anode reaction and anolyte electrolyte may affect the catholyte electrolyte and must be taken into consideration in the electrolytes employed. Other factors in the catholyte recycle loop that may need to be controlled may be pH, which may controlled by various methods such as the addition of chemicals or gases, or other methods such as the utilization of small electrochemical acidification or alkalization units, or he like. Other alternative catholyte product configurations may include acetic acid, oxalate, and methanol.
In addition, Systems 900C and 900D in producing CO as a reduction product of carbon dioxide, may require separation of excess carbon dioxide and possibly the separation of hydrogen from the CO, depending on the end use of the CO product. The separation may be conducted by various suitable mechanisms commercially available, such as PSA or membrane separations.
In the present disclosure, it is understood that the specific order or hierarchy of steps in the methods disclosed are examples of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the method may be rearranged while remaining within the disclosed subject matter. The accompanying method claims present elements of the various steps in a sample order, and are not necessarily meant to be limited to the specific order or hierarchy presented.
It is believed that the present disclosure and many of its attendant advantages will be understood by the foregoing description, and it will be apparent that various changes may be made in the form, construction and arrangement of the components without departing from the disclosed subject matter or without sacrificing all of its material advantages. The form described is merely explanatory, and it is the intention of the following claims to encompass and include such changes.

Claims

What is claimed is:

1. A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of:

contacting the first region with a catholyte including carbon dioxide, the catholyte including an alkali metal bicarbonate;

contacting the second region with an anolyte including sulfuric acid;

applying an electrical potential between the anode and the cathode sufficient to produce a first product and unreacted carbon dioxide recoverable from the first region and oxygen and unreacted sulfuric acid from the second region;

separating the first product from the unreacted carbon dioxide;

recycling at least a portion of the first product to the first region and recycling the unreacted carbon dioxide to the first region;

separating the oxygen product recoverable from the second region from the anolyte;

recycling the anolyte to the second region; and

contacting the oxygen product with hydrogen sulfide in a catalyst reactor bed to convert the hydrogen sulfide to a sulfur dioxide product.

2. The method according to claim 1, wherein the first product is an alkali metal formate.

3. The method according to claim 1, wherein the first product is carbon monoxide.

4. The method according to claim 1, wherein reacting the oxygen with hydrogen sulfide to produce sulfur dioxide is performed at an operating temperature from about 90-400 degrees Celsius.

5. The method according to claim 1, wherein the alkali metal bicarbonate includes at least one of sodium bicarbonate or potassium bicarbonate.

6. The method according to claim 1, wherein the cathode and the anode are separated by an ion permeable barrier that operates at a temperature less than 600 degrees Celsius and the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.

7. The method according to claim 1, further comprising:

condensing the sulfur dioxide product to a sulfur dioxide liquid product.

8. The method according to claim 1, further comprising:

converting the sulfur dioxide to another sulfur-based product.

9. The method according to claim 7, further comprising:

recycling at least a portion of the sulfur dioxide liquid product to the second region.

10. The method according to claim 1, further comprising:

reacting unreacted sulfuric acid with ammonia to produce ammonium sulfate.

11. A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of:

contacting the second region with an anolyte including sulfuric acid;

applying an electrical potential between the anode and the cathode sufficient to produce an alkali metal formate and unreacted carbon dioxide recoverable from the first region and oxygen and unreacted sulfuric acid from the second region;

recycling the anolyte to the second region; and

12. The method according to claim 11, wherein reacting the oxygen with hydrogen sulfide to produce sulfur dioxide is performed at an operating temperature from about 90-400 degrees Celsius.

13. The method according to claim 11, further comprising:

reacting unreacted sulfuric acid with ammonia to produce ammonium sulfate.

14. The method according to claim 11, wherein the alkali metal bicarbonate includes at least one of sodium bicarbonate or potassium bicarbonate.

15. The method according to claim 11, wherein the cathode and the anode are separated by an ion permeable barrier that operates at a temperature less than 600 degrees Celsius and the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.

16. The method according to claim 11, further comprising:

condensing the sulfur dioxide product to a sulfur dioxide liquid product.

17. The method according to claim 11, further comprising:

converting the sulfur dioxide to another sulfur-based product.

18. The method according to claim 11, further comprising:

19. A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of:

contacting the first region with a catholyte comprising carbon dioxide, the catholyte including an alkali metal bicarbonate;

contacting the second region with an anolyte comprising a sulfur-based component including sulfuric acid;

applying an electrical potential between the anode and the cathode sufficient to produce a first product and unreacted carbon dioxide recoverable from the first region and an oxygen product from the second region recoverable from the second region, the first product including a carbon monoxide;

separating the first product from the unreacted carbon dioxide;

recycling the anolyte to the second region; and