WO2021257344A1 - Utilizing black powder for electrolytes for flow batteries - Google Patents

Utilizing black powder for electrolytes for flow batteries Download PDF

Info

Publication number
WO2021257344A1
WO2021257344A1 PCT/US2021/036600 US2021036600W WO2021257344A1 WO 2021257344 A1 WO2021257344 A1 WO 2021257344A1 US 2021036600 W US2021036600 W US 2021036600W WO 2021257344 A1 WO2021257344 A1 WO 2021257344A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron
solution
black powder
molar
electrolyte
Prior art date
Application number
PCT/US2021/036600
Other languages
French (fr)
Inventor
Ahmad D. Hammad
Bandar A. Fadhel
Issam T. Amr
Original Assignee
Saudi Arabian Oil Company
Aramco Services Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/934,779 external-priority patent/US11495814B2/en
Application filed by Saudi Arabian Oil Company, Aramco Services Company filed Critical Saudi Arabian Oil Company
Publication of WO2021257344A1 publication Critical patent/WO2021257344A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This disclosure relates to producing electrolytes for flow batteries.
  • a flow battery is an energy storage technology that stores electrical energy as chemical energy in flowing solutions converts and and release it in a controlled manner when required. It is worth noting that the design of a flow battery allows for the separation between power and energy capacity that keeps the cost low for large scale application and also, facilitates matching with various loads/applications. Summary
  • An embodiment described herein provides a method for forming electrolyte solutions for a flow battery from black powder.
  • the method includes heating the black powder under an inert atmosphere to form Fe304, dissolving the Fe304 in an acid solution to form an electrolyte solution, and adjusting a ratio of iron (II) to iron (III) by a redox process.
  • Another embodiment described herein provides an electrolyte for a flow battery, including a solution of iron ions formed from black powder that has been heat- treated to be converted to FesCri, and dissolved in an acidic solution.
  • Another embodiment described herein provides a flow battery including a catholyte including iron ions formed from black powder that has been heat-treated to be converted to FesCri and then dissolved in an acidic solution.
  • Figure 1 A is a drawing of a flow batery using two electrolytes.
  • Figure IB is a drawing of an Fe/Fe flow batery that uses a single electrolyte solution, the catholyte, and a solid iron anode.
  • Figure 2 is bar chart that shows the typical major mineral composition a black powder without treatment.
  • Figure 3 is a process flow diagram of a method converting black powder to an iron electrolyte for use in a flow batery.
  • Figure 4 is a bar chart that shows the mineral composition of black powder after treatment at 400 °C under an inert gas.
  • Figure 5 is a bar chart that shows the mineral composition of black powder after treatment at 775 °C in air.
  • the electrolyte represents about 30 % to about 40% of the total cost of a flow batery. As electrolytes have generally been very costly, this has limited the wide spread deployment of flow bateries. Accordingly, lower cost electrolyte materials would allow for greater adoption of flow cells. Cost reduction can be achieved by utilizing low value materials as the main raw materials for electrolyte synthesis. Waste materials, such as black powder from pipelines, are present in large quantities and are underutilized.
  • black powder is a solid contaminant often found in hydrocarbon pipelines.
  • the material may be wet, for example, having a tar-like appearance.
  • the black powder be a very fine, dry powder.
  • Black powder can include mill scale, such as magnetite or FeiCri, which originates from the pipe manufacturing process as steel is oxidized at high temperatures. These types of solids strongly adhere to pipe walls and are not easily removed.
  • black powder can include flash rust, such as Fe203 and FeOOH, from water exposure during hydrotesting.
  • Black powder can also be formed by internal pipeline corrosion, such as caused by microbial action, acid gas corrosion, or both. Black powder can also be a carryover from gas gathering systems.
  • Black powder is regarded as a chronic nuisance waste that is removed from valuable process streams by the use of filter bags, separators, or cyclones, among others. Limited efforts have been exerted to utilize black powder, despite its availability in large amounts at almost no cost.
  • the black powder is tested for contamination by naturally occurring radioactive materials (NORM).
  • NORM may include decay products formed from uranium and thorium in subsurface deposits.
  • lead-210 may be present in some black powders.
  • the black powder can be used as the main raw material to synthesize iron based electrolyte solutions.
  • the electrolyte solutions may be used in Fe/V, Fe/Fe and/or Fe/V mixed chloride and sulfide flow batteries, as well as in electrolytes used in fixed installation (non-flow type) batteries.
  • FIG. 1A is a drawing of a flow battery 100 using two electrolytes.
  • the energy is stored in electrolytes 102 and 104, which are termed anolyte 102 and catholyte 104, herein.
  • the electrolytes 102 and 104 are stored in tanks 106 and 108 and are separately pumped from the tanks 106 and 108 to an electrochemical cell 110 by dedicated pumps 112.
  • an ion exchange membrane 114 is used in the electrochemical cell 110.
  • the ion exchange membrane 114 separates the electrolytes 102 and 104 to prevent energy loss by short-circuiting, while allowing protons, or other ions, to pass between the sides during charge and discharge cycles.
  • the ion exchange membrane 114 is a sulfonated tetrafluoroethylene, commercially available as NAFION® from DuPont Chemical of Wilmington Virginia.
  • the ion exchange membrane 114 generally controls the efficiency of the flow battery 100, and is a significant contributor to the cost of the flow battery 100. Accordingly, in some embodiments, the ion exchange membrane 114 is omitted and the electrolytes 102 and 104 are generally kept from mixing by laminar flow or is made unnecessary by battery design, such as if a single electrolyte solution is used.
  • the channels 116 and 118 may include a porous electrode material, such as felt, or Rainey nickel, among others, to allow ions and electrons to flow between the electrolytes 102 and 104.
  • the channels 116 and 118 may be narrow to enhance laminar flow.
  • the anolyte 102 is oxidized, losing electrons to the anode current collector 120.
  • the electrons are transferred by a line 122 to a load 124.
  • the electrons are returned to the electrochemical cell 110 by another line 126.
  • the electrons reenter the electrochemical cell 110 from the cathode current collector 128, reducing the catholyte 104.
  • the anolyte 102 and catholyte 104 are regenerated during a charging cycle when a power source 130 removes electrons from the cathode current collector 128 through a line 132, oxidizing the catholyte 104 to its initial state.
  • the electrons are provided to the anode current collector 120 from the power source 130 through another line 134, reducing the anolyte 102 to its initial state.
  • VRB vanadium redox flow battery
  • vanadium redox flow battery vanadium redox flow battery
  • vanadium ions are dissolved in an aqueous acid supporting electrolyte.
  • VRBs are often based on V 2+ /V 3+ and V 4+ /V 5+ redox couples.
  • VRBs have high costs for the vanadium-based electrolytes and for the Nafion membranes, providing incentives for lower cost materials.
  • Fe/V redox chemistry has been explored as a potential option for lowering costs for large scale energy storage, as iron is lower cost than vanadium.
  • the catholyte 104 includes Fe(III) which is reduced to Fe(II) at the cathode current collector 128 (+), while the anolyte 102 includes V(II) which is oxidized to V(III) at the anode current collector 120 (-), according to the reactions shown below:
  • FIG. IB is a drawing of an Fe/Fe flow battery 200 that uses a single electrolyte solution, the catholyte 104, and an iron anode 202.
  • iron (III) chloride in the catholyte 104 is reduced to iron (II) chloride at the cathode current collector 128.
  • iron anode 202 iron is oxidized to iron (II) chloride and dissolved into the catholyte 104.
  • the iron anode 202 also functions as the anode current collector, eliminated the need for any additional current collectors.
  • iron (0) is deposited on the surface of the iron anode 202 by the electrochemical reduction of ferrous ions, while the catholyte 104 is regenerated to iron (III) chloride.
  • the source of iron is black powder, either as FeCh directly or by the electrochemical reduction of FeCh to FeCh.
  • the Fe/Fe flow battery does not use an iron anode 202, but uses two electrolyte solutions, an anolyte that includes FeCh and a catholyte that includes FeCh and FeCh.
  • an ion exchange membrane 114 is used in the configuration shown in Figure 1 A.
  • FIG. 2 is a bar chart that shows the typical major mineral composition of black powder without treatment.
  • black powder is regenerative debris that is formed inside natural gas pipelines as a result of corrosion of the internal walls of the pipeline. It can also be collected from upstream filters or filter bags used in gas refineries.
  • the primary component in the sample is magnetite (FeiCh) at about 68.5 %.
  • the sample also includes iron oxide or hematite (Fe2Cb), at about 20.9 %, as well as quartz (SiCh), at about 10.6 %.
  • the materials including, for example, metal carbonates, metal hydroxides, and sulfide iron carbonates may be present.
  • FIG 3 is a process flow diagram of a method 300 for converting black powder to an iron electrolyte for use in a flow battery.
  • black powder is used as the iron source for iron based flow-batteries. This may be achieved by converting the iron in the black powder to iron (II) chloride or iron (III) chloride, for example, by the techniques of the method 300.
  • the method 300 begins at block 302. [0032] At block 302, the black powder is heated under an inert atmosphere to form magnetite (FesCri), as described with respect to Figure 4.
  • the resulting magnetite is dissolved in HC1 (aq), or an acid mixture that includes sulfides, sulfites, sulfates, nitrites, or nitrates, among others, to form iron (II) chloride and iron (III) chloride.
  • the concentration ratio of the iron (II) chloride to iron (III) chloride is adjusted, for example, by electrochemical reduction of iron (III) chloride.
  • Figure 4 is a bar chart that shows the mineral composition of the black powder after treatment at 400 °C under an inert gas.
  • the black powder is heat-treated at about 400 °C to about 700 °C, under nitrogen, to convert the iron content to magnetite (FeiCri).
  • the heat treatment converts the black powder to a blend of about 97.7 % magnetite (FeiCri) and about 2.3 % quartz (SiC ), as depicted in Equation 4.
  • Figure 5 is a bar chart that shows the mineral composition of black powder after treatment at 775 °C under air to form hematite or Fe203.
  • the oxygen free environment provided by the inert atmosphere (N2) is important in the black powder transformation, since treating the black powder under an oxygen containing environment, such as air, will result in the formation of ferric oxide, Fe203, which is not a good precursor for forming FeCb.
  • the electrolytes can be prepared at room temperature using deionized (DI) water. This may be performed by preparing a solution of HC1, or a mixture of acids, at a concentration of about 1 to about 6 molar (M) in the DI water.
  • DI deionized
  • the appropriate metal sources are dissolved in the HCl(aq) or acid solution.
  • VCb, VOSO4, or both is dissolved in HCl(aq) form a solution of vanadium with a concentration of about 1 M to about 4 M.
  • the magnetite powder formed by heating under an inert atmosphere is dissolved in the HCl(aq) to form an iron solution of about 1 M to about 4 M iron ions.
  • the amount of the iron (II) chloride in the solution may then be adjusted by a redox process, such as electrochemically reducing FeCb to FeCh.
  • the magnetite is dissolved in the HCl(aq) or acid solution.
  • iron (II) chloride only one electrolyte is prepared, iron (II) chloride.
  • the magnetite powder formed by heating under an inert atmosphere is dissolved in the HCl(aq) to form a solution of about 1 M to about 4 M in concentration of iron.
  • the amount of the iron (II) chloride in the solution may then be adjusted by electrochemically reducing FeCb to FeCh, such as during the operation of the flow battery.
  • An embodiment described herein provides a method for forming electrolyte solutions for a flow battery from black powder.
  • the method includes heating the black powder under an inert atmosphere to form Fe304, dissolving the Fe304 in an acid solution to form an electrolyte solution, and adjusting a ratio of iron (II) to iron (III) by a redox process.
  • the method includes analyzing the black powder for naturally occurring radioactive materials. In an aspect, the method includes discarding black powder including naturally occurring radioactive materials.
  • the method includes heating the black powder to a temperature of between about 400 °C and about 700 °C. In an aspect, the method includes heating the black powder to a temperature of about 400 °C.
  • the method includes mixing the acid solution to a concentration of about 1 molar to about 6 molar. In an aspect, the method includes mixing an HC1 solution to a concentration of about 1 molar to about 6 molar to form the acid solution. In an aspect, the method includes dissolving the FesCri in an acid solution comprising an HC1 solution to form the electrolyte solution of a concentration of about 1 molar to about 4 molar iron ions. [0043] In an aspect, the method includes adjusting the ratio of iron (II) to iron (III) by reducing iron (III) to iron (II) in an electrochemical cell.
  • the method includes adjusting the ratio of iron (III) to iron (II) in the flow battery during a recharging process.
  • the method includes dissolving a vanadium compound in a second acid solution to form an anolyte.
  • the method includes dissolving VC13, V0S04, or both in the second acid solution solution form a solution of about 1 M to about 4 M in concentration of vanadium.
  • Another embodiment described herein provides an electrolyte for a flow battery, including a solution of iron ions formed from black powder that has been heat- treated to be converted to magnetite and dissolved in an acidic solution.
  • the electrolyte includes an HC1 solution of about 1 molar to about 6 molar in concentration. In an aspect, the electrolyte includes a solution of iron (II) and iron (III) ions in a concentration of about 1 molar to about 4 molar in iron. In an aspect, the electrolyte includes a solution of iron (II) ions formed from iron (III) ions in an electrochemical cell.
  • Another embodiment described herein provides a flow battery including a catholyte including iron ions formed from black powder that has been heat-treated to be converted to FesCri and then dissolved in an acidic solution.
  • the catholyte includes an acidic solution of iron (III) ions and iron (II) ions.
  • the flow battery includes a solid iron anode.
  • the flow battery includes an anolyte including an acidic solution of iron (II) ions.

Abstract

A method and systems are provided for utilizing black powder to form an electrolyte for a flow battery. In an exemplary method the black powder is heated under an inert atmosphere to form Fe3O4. The Fe3O4 is dissolved in an acid solution to form an electrolyte solution. A ratio of iron (II) to iron (III) is adjusted by a redox process.

Description

UTILIZING BLACK POWDER FOR ELECTROLYTES FOR FLOW BATTERIES
Claim of Priority [0001] This application claims priority to Greek Patent Application No.
20200100343 filed on June 17, 2020 and U.S. Patent Application No. 16/934,779 filed on July 21, 2020, the entire contents of which are hereby incorporated by reference.
Technical Field
[0002] This disclosure relates to producing electrolytes for flow batteries. Background
[0003] Energy storage is currently one of the major challenges in the deployment of renewable energy resources and the improvement of the electrical grid efficiency. Flow batteries are among the most promising storage options and have the potential to be cheaper and more flexible than other competitors. A flow battery is an energy storage technology that stores electrical energy as chemical energy in flowing solutions converts and and release it in a controlled manner when required. It is worth noting that the design of a flow battery allows for the separation between power and energy capacity that keeps the cost low for large scale application and also, facilitates matching with various loads/applications. Summary
[0004] An embodiment described herein provides a method for forming electrolyte solutions for a flow battery from black powder. The method includes heating the black powder under an inert atmosphere to form Fe304, dissolving the Fe304 in an acid solution to form an electrolyte solution, and adjusting a ratio of iron (II) to iron (III) by a redox process.
[0005] Another embodiment described herein provides an electrolyte for a flow battery, including a solution of iron ions formed from black powder that has been heat- treated to be converted to FesCri, and dissolved in an acidic solution.
[0006] Another embodiment described herein provides a flow battery including a catholyte including iron ions formed from black powder that has been heat-treated to be converted to FesCri and then dissolved in an acidic solution. Brief Description of Drawings
[0007] Figure 1 A is a drawing of a flow batery using two electrolytes.
[0008] Figure IB is a drawing of an Fe/Fe flow batery that uses a single electrolyte solution, the catholyte, and a solid iron anode. [0009] Figure 2 is bar chart that shows the typical major mineral composition a black powder without treatment.
[0010] Figure 3 is a process flow diagram of a method converting black powder to an iron electrolyte for use in a flow batery.
[0011] Figure 4 is a bar chart that shows the mineral composition of black powder after treatment at 400 °C under an inert gas.
[0012] Figure 5 is a bar chart that shows the mineral composition of black powder after treatment at 775 °C in air.
Detailed Description
[0013] The electrolyte represents about 30 % to about 40% of the total cost of a flow batery. As electrolytes have generally been very costly, this has limited the wide spread deployment of flow bateries. Accordingly, lower cost electrolyte materials would allow for greater adoption of flow cells. Cost reduction can be achieved by utilizing low value materials as the main raw materials for electrolyte synthesis. Waste materials, such as black powder from pipelines, are present in large quantities and are underutilized.
[0014] The techniques described herein provide for the formation of iron- containing electrolytes for flow bateries using black powder has the primary raw material. As the black powder is an abundant waste material, the costs of the electrolyte are substantially reduced. [0015] As used herein, black powder is a solid contaminant often found in hydrocarbon pipelines. The material may be wet, for example, having a tar-like appearance. The black powder be a very fine, dry powder. Black powder can include mill scale, such as magnetite or FeiCri, which originates from the pipe manufacturing process as steel is oxidized at high temperatures. These types of solids strongly adhere to pipe walls and are not easily removed. Further, black powder can include flash rust, such as Fe203 and FeOOH, from water exposure during hydrotesting. Black powder can also be formed by internal pipeline corrosion, such as caused by microbial action, acid gas corrosion, or both. Black powder can also be a carryover from gas gathering systems.
[0016] Black powder is regarded as a chronic nuisance waste that is removed from valuable process streams by the use of filter bags, separators, or cyclones, among others. Limited efforts have been exerted to utilize black powder, despite its availability in large amounts at almost no cost.
[0017] In some embodiments described herein, the black powder is tested for contamination by naturally occurring radioactive materials (NORM). NORM may include decay products formed from uranium and thorium in subsurface deposits. For example, lead-210 may be present in some black powders. However, as the materials generally decay quickly and lead-210 is a long-lived isotope, most black powder deposits are relatively free of NORM. This allows the use of black powder for other applications. However, if the black powder includes lead-210, or other norm, the black powder may be discarded. [0018] Accordingly, the black powder can be used as the main raw material to synthesize iron based electrolyte solutions. The electrolyte solutions may be used in Fe/V, Fe/Fe and/or Fe/V mixed chloride and sulfide flow batteries, as well as in electrolytes used in fixed installation (non-flow type) batteries.
[0019] Figure 1A is a drawing of a flow battery 100 using two electrolytes. In the flow battery 100, the energy is stored in electrolytes 102 and 104, which are termed anolyte 102 and catholyte 104, herein. The electrolytes 102 and 104 are stored in tanks 106 and 108 and are separately pumped from the tanks 106 and 108 to an electrochemical cell 110 by dedicated pumps 112.
[0020] In some embodiments, an ion exchange membrane 114 is used in the electrochemical cell 110. The ion exchange membrane 114 separates the electrolytes 102 and 104 to prevent energy loss by short-circuiting, while allowing protons, or other ions, to pass between the sides during charge and discharge cycles. In some embodiments, the ion exchange membrane 114 is a sulfonated tetrafluoroethylene, commercially available as NAFION® from DuPont Chemical of Wilmington Virginia. The ion exchange membrane 114 generally controls the efficiency of the flow battery 100, and is a significant contributor to the cost of the flow battery 100. Accordingly, in some embodiments, the ion exchange membrane 114 is omitted and the electrolytes 102 and 104 are generally kept from mixing by laminar flow or is made unnecessary by battery design, such as if a single electrolyte solution is used.
[0021] As the electrolytes 102 and 104 are pumped through the electrochemical cell 110, they pass through channels 116 and 118. The channels 116 and 118 may include a porous electrode material, such as felt, or Rainey nickel, among others, to allow ions and electrons to flow between the electrolytes 102 and 104. In some embodiments, for example, when the ion exchange membrane 114 is omitted, the channels 116 and 118 may be narrow to enhance laminar flow.
[0022] During the production of power, the anolyte 102 is oxidized, losing electrons to the anode current collector 120. The electrons are transferred by a line 122 to a load 124. After powering the load 124, the electrons are returned to the electrochemical cell 110 by another line 126. The electrons reenter the electrochemical cell 110 from the cathode current collector 128, reducing the catholyte 104.
[0023] The anolyte 102 and catholyte 104 are regenerated during a charging cycle when a power source 130 removes electrons from the cathode current collector 128 through a line 132, oxidizing the catholyte 104 to its initial state. The electrons are provided to the anode current collector 120 from the power source 130 through another line 134, reducing the anolyte 102 to its initial state.
[0024] One of the most established technologies for flow batteries is based on vanadium redox chemistry and is termed the vanadium redox flow battery (VRB). In VRBs, vanadium ions are dissolved in an aqueous acid supporting electrolyte. VRBs are often based on V2+/V3+ and V4+/V5+ redox couples. However, VRBs have high costs for the vanadium-based electrolytes and for the Nafion membranes, providing incentives for lower cost materials. [0025] Accordingly, a flow battery based on Fe/V redox chemistry has been explored as a potential option for lowering costs for large scale energy storage, as iron is lower cost than vanadium. In an Fe/V flow battery, during the discharge cycle of the flow battery, the catholyte 104 includes Fe(III) which is reduced to Fe(II) at the cathode current collector 128 (+), while the anolyte 102 includes V(II) which is oxidized to V(III) at the anode current collector 120 (-), according to the reactions shown below:
Fe3+ + e ®Fe1+
Figure imgf000005_0001
V2+ ®V3+ +e (2)
Fe3+ + V2+ ®V3+ +Fe2+ (3)
[0026] Figure IB is a drawing of an Fe/Fe flow battery 200 that uses a single electrolyte solution, the catholyte 104, and an iron anode 202. In this embodiment, during discharge, iron (III) chloride in the catholyte 104 is reduced to iron (II) chloride at the cathode current collector 128. At the iron anode 202, iron is oxidized to iron (II) chloride and dissolved into the catholyte 104. The iron anode 202 also functions as the anode current collector, eliminated the need for any additional current collectors.
These processes are reversed during battery charging. During charging of the iron- chloride redox flow battery, iron (0) is deposited on the surface of the iron anode 202 by the electrochemical reduction of ferrous ions, while the catholyte 104 is regenerated to iron (III) chloride. As only one electrolyte solution is used, no ion exchange membrane 114 is used, further decreasing the cost. In some embodiments, the source of iron is black powder, either as FeCh directly or by the electrochemical reduction of FeCh to FeCh.
[0027] In some embodiments, the Fe/Fe flow battery does not use an iron anode 202, but uses two electrolyte solutions, an anolyte that includes FeCh and a catholyte that includes FeCh and FeCh. In these embodiments, an ion exchange membrane 114 is used in the configuration shown in Figure 1 A. [0028] EXAMPLES
[0029] Figure 2 is a bar chart that shows the typical major mineral composition of black powder without treatment. In many cases, black powder is regenerative debris that is formed inside natural gas pipelines as a result of corrosion of the internal walls of the pipeline. It can also be collected from upstream filters or filter bags used in gas refineries. The primary component in the sample is magnetite (FeiCh) at about 68.5 %. The sample also includes iron oxide or hematite (Fe2Cb), at about 20.9 %, as well as quartz (SiCh), at about 10.6 %. In other examples, the materials including, for example, metal carbonates, metal hydroxides, and sulfide iron carbonates may be present. [0030] Preparation of Black Powder for Use in an Electrolyte
[0031] Figure 3 is a process flow diagram of a method 300 for converting black powder to an iron electrolyte for use in a flow battery. As described in embodiments herein, black powder is used as the iron source for iron based flow-batteries. This may be achieved by converting the iron in the black powder to iron (II) chloride or iron (III) chloride, for example, by the techniques of the method 300. The method 300 begins at block 302. [0032] At block 302, the black powder is heated under an inert atmosphere to form magnetite (FesCri), as described with respect to Figure 4. At block 304, the resulting magnetite is dissolved in HC1 (aq), or an acid mixture that includes sulfides, sulfites, sulfates, nitrites, or nitrates, among others, to form iron (II) chloride and iron (III) chloride. At block 306, the concentration ratio of the iron (II) chloride to iron (III) chloride is adjusted, for example, by electrochemical reduction of iron (III) chloride. [0033] Figure 4 is a bar chart that shows the mineral composition of the black powder after treatment at 400 °C under an inert gas. Initially, the black powder is heat- treated at about 400 °C to about 700 °C, under nitrogen, to convert the iron content to magnetite (FeiCri). The heat treatment converts the black powder to a blend of about 97.7 % magnetite (FeiCri) and about 2.3 % quartz (SiC ), as depicted in Equation 4.
D
Black Powder ® Fe304 (4)
[0034] Figure 5 is a bar chart that shows the mineral composition of black powder after treatment at 775 °C under air to form hematite or Fe203. As this chart indicates, the oxygen free environment provided by the inert atmosphere (N2) is important in the black powder transformation, since treating the black powder under an oxygen containing environment, such as air, will result in the formation of ferric oxide, Fe203, which is not a good precursor for forming FeCb. [0035] Preparation of Anolyte and Catholyte Solutions
[0036] After the heat treatment to form the magnetite (FesCri), the electrolytes can be prepared at room temperature using deionized (DI) water. This may be performed by preparing a solution of HC1, or a mixture of acids, at a concentration of about 1 to about 6 molar (M) in the DI water. [0037] To prepare the electrolytes for an Fe/V flow battery from the black powder, the appropriate metal sources are dissolved in the HCl(aq) or acid solution. For the anolyte, VCb, VOSO4, or both is dissolved in HCl(aq) form a solution of vanadium with a concentration of about 1 M to about 4 M. For the catholyte solution, the magnetite powder formed by heating under an inert atmosphere is dissolved in the HCl(aq) to form an iron solution of about 1 M to about 4 M iron ions. The amount of the iron (II) chloride in the solution may then be adjusted by a redox process, such as electrochemically reducing FeCb to FeCh.
[0038] To prepare the catholyte for an Fe/Fe flow battery from the black powder, the magnetite is dissolved in the HCl(aq) or acid solution. In this embodiment, only one electrolyte is prepared, iron (II) chloride. The magnetite powder formed by heating under an inert atmosphere is dissolved in the HCl(aq) to form a solution of about 1 M to about 4 M in concentration of iron. The amount of the iron (II) chloride in the solution may then be adjusted by electrochemically reducing FeCb to FeCh, such as during the operation of the flow battery.
[0039] An embodiment described herein provides a method for forming electrolyte solutions for a flow battery from black powder. The method includes heating the black powder under an inert atmosphere to form Fe304, dissolving the Fe304 in an acid solution to form an electrolyte solution, and adjusting a ratio of iron (II) to iron (III) by a redox process.
[0040] In an aspect, the method includes analyzing the black powder for naturally occurring radioactive materials. In an aspect, the method includes discarding black powder including naturally occurring radioactive materials.
[0041] In an aspect, the method includes heating the black powder to a temperature of between about 400 °C and about 700 °C. In an aspect, the method includes heating the black powder to a temperature of about 400 °C.
[0042] In an aspect, the method includes mixing the acid solution to a concentration of about 1 molar to about 6 molar. In an aspect, the method includes mixing an HC1 solution to a concentration of about 1 molar to about 6 molar to form the acid solution. In an aspect, the method includes dissolving the FesCri in an acid solution comprising an HC1 solution to form the electrolyte solution of a concentration of about 1 molar to about 4 molar iron ions. [0043] In an aspect, the method includes adjusting the ratio of iron (II) to iron (III) by reducing iron (III) to iron (II) in an electrochemical cell. In an aspect, the method includes adjusting the ratio of iron (III) to iron (II) in the flow battery during a recharging process. [0044] In an aspect, the method includes dissolving a vanadium compound in a second acid solution to form an anolyte. In an aspect, the method includes dissolving VC13, V0S04, or both in the second acid solution solution form a solution of about 1 M to about 4 M in concentration of vanadium. [0045] Another embodiment described herein provides an electrolyte for a flow battery, including a solution of iron ions formed from black powder that has been heat- treated to be converted to magnetite and dissolved in an acidic solution.
[0046] In an aspect, the electrolyte includes an HC1 solution of about 1 molar to about 6 molar in concentration. In an aspect, the electrolyte includes a solution of iron (II) and iron (III) ions in a concentration of about 1 molar to about 4 molar in iron. In an aspect, the electrolyte includes a solution of iron (II) ions formed from iron (III) ions in an electrochemical cell.
[0047] Another embodiment described herein provides a flow battery including a catholyte including iron ions formed from black powder that has been heat-treated to be converted to FesCri and then dissolved in an acidic solution.
[0048] In an aspect, the catholyte includes an acidic solution of iron (III) ions and iron (II) ions. In an aspect, the flow battery includes a solid iron anode. In an aspect, the flow battery includes an anolyte including an acidic solution of iron (II) ions.
[0049] Other implementations are also within the scope of the following claims.

Claims

Claims What is claimed is:
1. A method for forming electrolyte solutions for a flow battery from black powder, comprising: heating the black powder under an inert atmosphere to form FesCri; dissolving the Fe304 in an acid solution to form an electrolyte solution; and adjusting a ratio of iron (II) to iron (III) by a redox process.
2. The method of claim 1, comprising analyzing the black powder for naturally occurring radioactive materials.
3. The method of claim 2, comprising discarding black powder comprising naturally occurring radioactive materials.
4. The method of claim 1, comprising heating the black powder to a temperature of between about 400 °C and about 700 °C.
5. The method of claim 1, comprising heating the black powder to a temperature of about 400 °C.
6. The method of claim 1, comprising mixing the acid solution to a concentration of about 1 molar to about 6 molar.
7. The method of claim 1 , comprising mixing an HC1 solution to a concentration of about 1 molar to about 6 molar to form the acid solution.
8. The method of claim 1, comprising dissolving the Fe304 in an acid solution comprising an HC1 solution to form the electrolyte solution of a concentration of about 1 molar to about 4 molar iron ions.
9. The method of claim 1, comprising adjusting the ratio of iron (II) to iron (III) by reducing iron (III) to iron (II) in an electrochemical cell.
10. The method of claim 9, comprising adjusting the ratio of iron (III) to iron (II) in the flow battery during a recharging process.
11. The method of claim 1, comprising dissolving a vanadium compound in an acid to form an anolyte.
12. The method of claim 11, comprising dissolving VCb, VOSCri, or both in an HC1 solution form a solution of about 1 M to about 4 M in concentration of vanadium.
13. An electrolyte for a flow battery, comprising a solution of iron ions formed from black powder that has been heat-treated to be converted to magnetite and dissolved in an acidic solution.
14. The electrolyte of claim 13, comprising an HC1 solution of about 1 molar to about 6 molar in concentration.
15. The electrolyte of claim 13, comprising a solution of iron (II) and iron (III) ions in a concentration of about 1 molar to about 4 molar in iron.
16. The electrolyte of claim 13, comprising a solution of iron (II) ions formed from iron (III) ions in an electrochemical cell.
17. A flow battery comprising a catholyte comprising iron ions formed from black powder that has been heat-treated to be converted to magnetite and dissolved in an acidic solution.
18. The flow battery of claim 17, wherein the catholyte comprises an acidic solution of iron (III) ions and iron (II) ions.
19. The flow battery of claim 17, comprising a solid iron anode.
20. The flow batery of claim 17, comprising an anolyte comprising an acidic solution of iron (II) ions.
PCT/US2021/036600 2020-06-17 2021-06-09 Utilizing black powder for electrolytes for flow batteries WO2021257344A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GR20200100343 2020-06-17
GR20200100343 2020-06-17
US16/934,779 US11495814B2 (en) 2020-06-17 2020-07-21 Utilizing black powder for electrolytes for flow batteries
US16/934,779 2020-07-21

Publications (1)

Publication Number Publication Date
WO2021257344A1 true WO2021257344A1 (en) 2021-12-23

Family

ID=76731078

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2021/036600 WO2021257344A1 (en) 2020-06-17 2021-06-09 Utilizing black powder for electrolytes for flow batteries

Country Status (1)

Country Link
WO (1) WO2021257344A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100261070A1 (en) * 2010-03-10 2010-10-14 Deeya Energy, Inc. Methods for the preparation of electrolytes for chromium-iron redox flow batteries
US20150048777A1 (en) * 2013-08-14 2015-02-19 Epsilor-Electric Fuel LTD. Novel flow battery and usage thereof
US20190011372A1 (en) * 2017-07-05 2019-01-10 Saudi Arabian Oil Company Detecting black powder levels in flow-lines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100261070A1 (en) * 2010-03-10 2010-10-14 Deeya Energy, Inc. Methods for the preparation of electrolytes for chromium-iron redox flow batteries
US20150048777A1 (en) * 2013-08-14 2015-02-19 Epsilor-Electric Fuel LTD. Novel flow battery and usage thereof
US20190011372A1 (en) * 2017-07-05 2019-01-10 Saudi Arabian Oil Company Detecting black powder levels in flow-lines

Similar Documents

Publication Publication Date Title
Chen et al. Separating hydrogen and oxygen evolution in alkaline water electrolysis using nickel hydroxide
Kabtamu et al. Electrocatalytic activity of Nb-doped hexagonal WO 3 nanowire-modified graphite felt as a positive electrode for vanadium redox flow batteries
CN107579235B (en) Preparation method of Mxene/S oxide compound applied to lithium-sulfur battery anode
Wang et al. A bimetallic thermally regenerative ammonia-based battery for high power density and efficiently harvesting low-grade thermal energy
Suresh et al. Realizing highly efficient energy retention of Zn–Br2 redox flow battery using rGO supported 3D carbon network as a superior electrode
US20200388857A1 (en) Redox flow batteries employing diamond
US11495814B2 (en) Utilizing black powder for electrolytes for flow batteries
US20130101920A1 (en) Catalyst, electrode, fuel cell, gas detoxification apparatus, and methods for producing catalyst and electrode
Guo et al. A novel design of an electrolyser using a trifunctional (HER/OER/ORR) electrocatalyst for decoupled H 2/O 2 generation and solar to hydrogen conversion
WO2015076873A1 (en) High-energy-density, aqueous, metal-polyiodide redox flow batteries
CN109860536B (en) Lithium-rich manganese-based material and preparation method and application thereof
Na et al. Graphite felts modified by vertical two-dimensional WO 3 nanowall arrays: high-performance electrode materials for cerium-based redox flow batteries
Zhipeng et al. Hierarchical porous carbon toward effective cathode in advanced zinc-cerium redox flow battery
Liu et al. A facile preparation of λ-MnO2 as cathode material for high-performance zinc-manganese redox flow battery
JP3163370B2 (en) Redox battery
Zhu et al. Cu 2 CoGeS 4 nanocrystals for high performance aqueous polysulfide/iodide redox flow batteries: enhanced selectively towards the electrocatalytic conversion of polysulfides
Tehrani et al. Application of electrodeposited cobalt hexacyanoferrate film to extract energy from water salinity gradients
US20200106118A1 (en) Bimetallic thermally-regenerative ammonia-based battery system, flow battery system and using methods
Duranti et al. Novel composite fuel electrode for CO2/CO-RSOCs
Liu et al. Novel CO2-tolerant Co-based double perovskite cathode for intermediate temperature solid oxide fuel cells
CN113299873B (en) Preparation method of composite cathode material of water-based zinc ion battery
KR102336084B1 (en) Sulfur management and utilization in molten metal anode solid oxide fuel cells
WO2021257344A1 (en) Utilizing black powder for electrolytes for flow batteries
KR102022447B1 (en) Method of manufacturing high-purity of vanadium electrolyte for vanadium redox flow batteries by using catalytic reactor
Jung et al. Characteristics of the all-vanadium redox flow battery using ammonium metavanadate electrolyte

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21736875

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 03/04/2023)

122 Ep: pct application non-entry in european phase

Ref document number: 21736875

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 522441746

Country of ref document: SA