阅读说明：本技术 电化学流动反应器 (Electrochemical flow reactor ) 是由 M·D·霍恩 B·巴亚特萨尔马迪 T·罗多普洛斯 J·特沙那昔地 D·R·古纳加拉姆 C· 于 2019-08-07 设计创作，主要内容包括：本发明涉及电化学流动反应器,诸如连续流动电化学管式反应器。本发明还涉及包含电化学流动反应器的工艺、系统和方法。一种电化学流动电池可以包含反应室、第一静态混合器电极、第二对电极和布置在第一电极和第二电极之间的隔膜。(The present invention relates to electrochemical flow reactors, such as continuous flow electrochemical tubular reactors. The invention also relates to processes, systems, and methods involving the electrochemical flow reactor. An electrochemical flow cell may include a reaction chamber, a first static mixer electrode, a second pair of electrodes, and a separator disposed between the first electrode and the second electrode.)

1. An electrochemical flow cell, comprising:

a reaction chamber;

a first electrode;

a second electrode; and

a membrane disposed between the first and second electrodes, the membrane at least partially defining a first channel within the reaction chamber configured to receive a first fluid flow in contact with the first electrode and a second channel within the reaction chamber configured to receive a second fluid flow in contact with the second electrode,

wherein the membrane comprises a permeable membrane that allows electrical communication between the first and second electrodes via the fluid streams while limiting fluid exchange between the fluid streams, and

wherein the first electrode comprises a static mixer portion defining a plurality of flow splitting structures that split the first fluid flow into a plurality of sub-flows at a plurality of locations along a length of the first electrode.

2. The electrochemical flow cell of claim 1, wherein the electrochemical flow cell is a continuous flow tubular reactor.

3. The electrochemical flow cell of claim 1 or 2, wherein the diameter of the static mixer portion of the first electrode is approximately equal to the diameter of the first channel.

4. The electrochemical flow cell of any one of claims 1-3, wherein the first electrode is disposed in contact with the separator.

5. The electrochemical flow cell of any one of claims 1-4, wherein the separator and second electrode are disposed concentric and coaxial with a central longitudinal axis of the first electrode.

6. The electrochemical flow cell of any one of claims 1-5, wherein the separator and the second electrode are substantially cylindrical.

7. The electrochemical flow cell of any one of claims 1-6, wherein the second electrode forms at least a portion of a wall of the reaction chamber.

8. The electrochemical flow cell of any one of claims 1-7, wherein adjacent flow splitting structures of the static mixer portion are disposed at different angles of rotation about a central longitudinal axis of the static mixer portion.

9. The electrochemical flow cell of any one of claims 1-8, wherein the static mixer portion comprises a plurality of substantially similar structural modules disposed in series along a length of the static mixer portion.

10. The electrochemical flow cell of any one of claims 1-9, wherein the first electrode comprising the static mixer portion is configured by splitting the first fluid stream by more than 200m^-1To enhance chaotic advection, corresponding to the number of times the first fluid stream is divided within a given length along the static mixer portion of the first electrode.

11. The electrochemical flow cell of any one of claims 1-10, wherein the first electrode comprising the static mixer portion is configured for operation at a peclet (pe) number of at least about 10,000.

12. The electrochemical flow cell of any one of claims 1-11, wherein the first electrode comprising the static mixer portion is configured for operation at a pressure drop (in Pa/m) across the first electrode of between about 1000 to 100,000.

13. The electrochemical flow cell of any one of claims 1-12, wherein the first electrode comprising the static mixer portion is configured for operation within the first channel so as to provide a volumetric flow rate for the first fluid flow of at least about 0.1 ml/min.

14. An electrochemical flow system comprising at least one first electrochemical flow cell according to any one of claims 1 to 13.

15. The electrochemical flow system of claim 14, further comprising:

a second electrochemical flow cell according to any one of claims 1 to 13; and

a plurality of flow lines connecting the first electrochemical flow cell to the second electrochemical flow cell such that a first channel of the first electrochemical flow cell is in fluid communication with a second channel of the second electrochemical flow cell and the second channel of the first electrochemical flow cell is in fluid communication with the first channel of the second electrochemical flow cell.

16. The electrochemical flow system of claim 14 or 15, further comprising:

a pump for providing a fluid flow of the fluid stream;

a power supply for controlling the current through or voltage applied to the electrodes;

a controller for controlling one or more parameters of the system, the parameters including concentration, flow rate, temperature, pressure, and residence time.

17. A method for electrochemical treatment of a fluid stream comprising an electrochemical flow cell according to any one of claims 1 to 13 or a system according to any one of claims 14 to 16.

18. A method according to claim 17 for treating wastewater, removing dissolved metal ions from a fluid stream, or recovering metals from a fluid stream.

19. The method for removing dissolved metallic species from a first fluid stream of claim 17, wherein the removal of the metallic species occurs on a surface of the static mixer portion of the first electrode.

20. The method of any one of claims 17 to 19, wherein the electrochemical flow cell comprises the first electrode comprising the static mixer portion, the electrochemical flow cell being operated to split the first fluid stream by more than 200m^-1To enhance chaotic advection, corresponding to the number of times the first fluid stream is divided within a given length along the static mixer portion of the first electrode.

21. The method of any one of claims 17-20, wherein the electrochemical flow cell comprises the first electrode comprising the static mixer portion, the electrochemical flow cell being operated to provide a peclet (pe)) number of at least about 10,000.

22. The method of any one of claims 17 to 21, wherein the electrochemical flow cell comprises the first electrode comprising the static mixer portion, the electrochemical flow cell being operated to provide a pressure drop (Pa/m) across the first electrode of between about 1000 and 100,000.

23. The method of any one of claims 17 to 22, wherein the electrochemical flow cell is operated to provide a volumetric flow rate of the first fluid stream of at least about 0.1 ml/min.

24. The method of any one of claims 17 to 23, wherein the first fluid stream comprises a dissolved metal species concentration of less than about 0.01 (in mol/L).

25. The method of any one of claims 17 to 24, wherein the electrochemical flow cell is operated to provide a recovery efficiency of at least about 90% of contaminants or metal species originally present in the first fluid stream.

26. The method of any one of claims 17 to 25, wherein the electrochemical flow cell is operated to provide a range from 1 μ Α -m on the static mixer electrode and the counter electrode^-2To about 1000 A.m^-2The current density of (1).

27. The method of any one of claims 17 to 26, comprising operating the first and second electrochemical flow cells of any one of claims 1 to 13, wherein a plurality of flow lines connect the first electrochemical flow cell to the second electrochemical flow cell such that the first channel of the first electrochemical flow cell is in fluid communication with the second channel of the second electrochemical flow cell and the second channel of the first electrochemical flow cell is in fluid communication with the first channel of the second electrochemical flow cell.

28. A method for electrochemical synthesis of a product comprising the electrochemical flow cell of any one of claims 1 to 13 or the system of any one of claims 14 to 16.

29. The method of claim 28, comprising reacting a first fluid stream comprising one or more reactants in the first channel of the electrochemical flow cell and obtaining an output stream comprising reaction products.

Technical Field

The present invention relates to electrochemical flow reactors, such as continuous flow electrochemical tubular reactors. The invention also relates to processes, systems, and methods involving the electrochemical flow reactor.

Background

Continuous flow reactors typically comprise a reaction chamber in which a reactant fluid is continuously fed to perform a chemical reaction to form a product provided as a continuous output stream from the reaction chamber. The reaction chamber is typically immersed in a heating/coolant fluid, such as in a shell and tube heat exchanger configuration, to facilitate heat transfer to/from the reaction.

Continuous flow reactors may use a packed bed reaction chamber, wherein the reaction chamber is filled with solid catalyst particles that provide a catalytic surface on which chemical reactions can occur. Static mixers may be used for premixing of fluids to transfer heat between the central and outer regions of the reactor tube prior to contact with the packed bed reaction chambers and downstream of these chambers. Static mixers comprise solid structures in which fluid flow is interrupted to promote mixing of reactants prior to reaction in a packed bed reaction chamber and to promote a desired heat and mass transfer pattern downstream of these chambers.

Electrochemical flow reactors have been used to treat fluid streams to remove dissolved metals by electrodeposition of dissolved metal ions to form solid metal products on the surfaces of electrodes housed in the electrochemical flow reactor. Electrochemical flow reactors for water treatment have involved low flow systems with high surface area electrodes for high efficiency and controlled removal of dissolved metals from aqueous fluid streams with dilute/low concentrations of dissolved metal ions. Electrochemical flow reactors are also used for the electrosynthesis of various products, particularly for the formation of reactants or intermediates.

There is a need for alternative or improved electrochemical flow reactors for providing efficient mixing, high mass transfer and/or multi-purpose operation for industrial applications.

It will be understood that any prior art publication mentioned herein does not constitute an admission that any of these documents forms part of the common general knowledge in the art, in australia or in any other country.

Disclosure of Invention

The present inventors have conducted research and development on alternative electrochemical flow reactors, and have recognized that static mixers may be configured to operate as electrodes within an electrochemical flow reactor to achieve efficient mixing, high mass transfer, and/or multi-purpose operation for industrial applications. The electrochemical flow reactor may comprise a static mixer electrode separated from a counter electrode by a permeable membrane. The static mixer electrodes can be configured to enhance mass transfer and turbulent advection while providing efficient performance. The static mixer electrode may be an electrode comprising a static mixer portion.

In one aspect, there is provided an electrochemical flow cell comprising:

a reaction chamber;

a first electrode;

a second electrode; and

a membrane disposed between the first electrode and the second electrode, the membrane at least partially defining a first channel within the reaction chamber configured to receive a first fluid flow in contact with the first electrode and a second channel within the reaction chamber configured to receive a second fluid flow in contact with the second electrode,

wherein the separator comprises a permeable membrane that allows ionic communication between the first electrode and the second electrode via the fluid streams while limiting fluid exchange between the fluid streams, and

wherein the first electrode comprises a static mixer portion defining a plurality of flow splitting structures that split the first fluid flow into a plurality of sub-flows at a plurality of locations along the length of the first electrode.

In one embodiment, the electrochemical flow cell is a continuous flow tubular reactor.

In one embodiment, the diameter of the static mixer portion of the first electrode may be substantially equal to the diameter of the first passageway. The first electrode may be arranged in contact with the membrane. The diaphragm and the second electrode may be disposed concentric and coaxial with a central longitudinal axis of the first electrode. The diaphragm and the second electrode may be substantially cylindrical. The second electrode may form at least a portion of a wall of the reaction chamber.

In one embodiment, a first electrode comprising a static mixer section may be configured for enhanced mass transfer and chaotic advection by defining a plurality of flow splitting structures that split a fluid stream into a plurality of sub-streams at a plurality of locations along the length of the first electrode.

In one embodiment, adjacent splitting structures of the static mixer portion may be disposed at different angles of rotation about the central longitudinal axis of the static mixer portion. The static mixer section may comprise a plurality of substantially similar structural modules disposed in series along the length of the static mixer section. The first electrode comprising the static mixer portion may be configured to be formed by splitting the first fluid flow by more than 200m^-1To enhance chaotic advection, pairCorresponding to the number of times the first fluid flow is divided within a given length of the static mixer section along the first electrode.

In another embodiment, the first electrode comprising the static mixer portion is configured for operation at a peclet (pe) number of at least about 10,000. The first electrode comprising the static mixer portion may be configured for operation at a pressure drop (in Pa/m) across the first electrode of between about 100 and 100,000. The first electrode comprising the static mixer portion may be configured for operation within the first channel to provide a volumetric flow rate for the first fluid flow of at least about 0.1 ml/min.

In another aspect, an electrochemical flow system is provided that includes at least a first electrochemical flow cell according to any aspect, embodiment or example of an electrochemical flow cell as described herein.

In one embodiment, the electrochemical flow system comprises first and second electrochemical flow cells according to any aspect, embodiment or example of an electrochemical flow cell described herein. A plurality of flow lines may be provided to connect the first electrochemical flow cell to the second electrochemical flow cell such that the first channel of the first electrochemical flow cell is in fluid communication with the second channel of the second electrochemical flow cell and the second channel of the first electrochemical flow cell is in fluid communication with the first channel of the second electrochemical flow cell.

In one embodiment, the electrochemical flow system further comprises:

a pump for providing fluid flow of the fluid stream;

a power supply for controlling the current through or voltage applied to the electrodes;

a controller for controlling one or more parameters of the system, the one or more parameters including concentration, flow rate, temperature, pressure, and residence time.

In another aspect, there is provided a method for the flow-electrochemical treatment of a fluid, the method comprising an electrochemical flow cell according to any aspect, embodiment or example of an electrochemical flow cell, reactor or system thereof described herein. The process may be used to treat wastewater, remove dissolved metal ions from a fluid stream, or recover metals from a fluid stream.

In one embodiment of the method, the electrochemical flow cell comprises a first electrode comprising a static mixer portion, the electrochemical flow cell operable to provide at least one of:

splitting a first fluid flow over 200m^-1To enhance chaotic advection, corresponding to the number of times the first fluid stream is divided within a given length along the static mixer portion of the first electrode;

a peclet (pe) number of at least about 10,000;

a voltage drop (in Pa/m) across the first electrode of about 100 to 100,000;

a volumetric flow rate of the first fluid stream of at least about 0.1 ml/min;

about 1 μ A. m^-2To about 1000 A.m^-2Current density on the first and second electrodes.

The method may comprise operation of first and second electrochemical flow cells according to any aspect, embodiment or example of an electrochemical flow cell as described herein, wherein the plurality of flow lines connect the first electrochemical flow cell to the second electrochemical flow cell such that the first channel of the first electrochemical flow cell is in fluid communication with the second channel of the second electrochemical flow cell and the second channel of the first electrochemical flow cell is in fluid communication with the first channel of the second electrochemical flow cell.

In another aspect, there is provided a method for electrochemical synthesis of a product, comprising an electrochemical flow cell according to any aspect, embodiment or example of an electrochemical flow cell, reactor or system thereof described herein.

In another aspect, there is provided a method for removing a substance from a fluid stream comprising an electrochemical flow cell, reactor or system thereof according to any aspect, embodiment or example described herein. The substance may be a metallic substance dissolved in the fluid stream.

It is to be understood that other aspects, embodiments, and examples of an electrochemical flow cell, reactor, or system are described herein.

Drawings

Preferred embodiments of the present invention will now be further described and illustrated, by way of example only, with reference to the accompanying drawings, in which:

fig. 1 shows a schematic diagram of an electrochemical flow cell according to some embodiments;

fig. 2 shows a schematic of an electrochemical flow cell with a separator according to some embodiments;

fig. 3A illustrates a perspective view of a static mixer electrode according to some embodiments;

FIG. 3B shows a perspective view of a static mixer portion of the static mixer electrode of FIG. 3A (in isolation);

FIG. 3C shows a cross-sectional view of a static mixer portion of the static mixer electrode of FIG. 3A (in isolation);

FIG. 3D shows a side view of the static mixer portion of the static mixer electrode of FIG. 3A (in isolation);

fig. 4A illustrates a perspective view of an electrochemical flow cell according to some embodiments;

FIG. 4B shows a perspective view of the flow cell of FIG. 4A in an exploded configuration;

fig. 4C shows a cross-sectional view of the flow cell of fig. 4A;

FIG. 5 shows a perspective view of an end cap of the flow cell of FIG. 4A;

fig. 6 shows a schematic of an electrochemical flow system including two electrochemical flow cells, according to some embodiments;

FIG. 7 shows the results at (a) -1.4V, (b) -1.6V, (c) -1.8V and (d) -2V (0.001M K)₃[Fe(CN)₆]) At a constant potential of 100 seconds, with 50 seconds intervals in the quiescent mode and 50 seconds intervals at a constant flow rate of 10 to 400mL min "1;

FIG. 8 shows the results at (a) -1.4V, (b) -1.6V, (c) -1.8V and (d) -2V (0.01M K)₃[Fe(CN)₆]) At constant potential ofTimed current response over 100 seconds with 50 seconds intervals in static mode and 50 seconds intervals at constant flow rate of 10 to 400mL min "1;

FIG. 9 shows the results at (a) -1.4V, (b) -1.6V, (c) -1.8V and (d) -2V (0.1M K)₃[Fe(CN)₆]) At a constant potential of 100 seconds, with 50 seconds intervals in the quiescent mode and 50 seconds intervals at a constant flow rate of 10 to 400mL min "1;

FIG. 10 shows Cu at three different concentrations²⁺Electrochemical flow cell efficiency for removing copper ions from a 0.01M sulfuric acid solution;

FIG. 11 shows (a) optical images of the static mixer working electrode before and after treatment, (b) EDS analysis and (c-e) SEM images of the static mixer electrode after 5 hours of electrolysis; and

fig. 12 shows copper concentration versus time in 24 hour operation according to a separation configuration embodiment of an electrochemical flow cell.

Detailed Description

The present invention describes various non-limiting embodiments that relate to studies conducted to identify electrochemical flow reactors capable of providing efficient mixing, high mass transfer, and/or multi-purpose operation for industrial applications. It has been surprisingly discovered that electrodes comprising a static mixer portion can be configured within an electrochemical flow cell to achieve efficient mixing, high mass transfer, and/or multi-purpose operation for industrial applications. It has also been found that an efficient electrochemical reactor can be provided in which the electrode comprising the static mixer section is configured to enhance mass transfer and chaotic advection. Further surprising advantages with respect to system operation and performance were identified by configuring a separator between an electrode comprising a static mixer portion and a counter electrode to provide each electrode in ionic communication and separate fluid channels.

Term(s) for

Throughout this specification, unless specifically stated otherwise or the context requires otherwise, reference to a single step, composition of matter, group of steps or group of compositions of matter shall be taken to include one or more (i.e., one or more) of those steps, compositions of matter, group of steps or group of compositions of matter. Furthermore, as used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to "a" includes a single as well as two or more; references to "a" or "an" include the singular as well as two or more; reference to "the" includes a single as well as two or more, etc.

The term "and/or", for example "X and/or Y" means "X and Y" or "X or Y" and is to be understood in both or whichever sense.

As used herein, unless otherwise specified, the term "about" generally refers to +/-10%, e.g., +/-5%, of the specified value.

Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

Those skilled in the art will appreciate that the invention herein may be subject to variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications. The invention also includes all of the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations or any two or more of said steps or features.

Unless specifically stated otherwise, each example of the invention described herein applies mutatis mutandis to each other example. The scope of the present invention is not limited by the specific embodiments described herein, which are intended to be exemplary only. Functionally equivalent products, compositions and methods are clearly within the scope of the present invention, as described herein.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Electrochemical flow reactor

An electrochemical flow cell can be provided comprising: a reaction chamber; a first electrode comprising a static mixer portion; a second electrode; and a separator disposed between the first electrode and the second electrode.

The membrane may at least partially define a first channel within the reaction chamber to accommodate a first fluid flow in contact with the first electrode and a second channel within the reaction chamber to accommodate a second fluid flow in contact with the second electrode. It should be appreciated that the membrane allows ionic communication between the first and second electrodes via the fluid flow. The membrane may be a permeable membrane that restricts fluid exchange between fluid streams. The static mixer portion may define a plurality of flow dividing structures that divide the fluid flow into a plurality of sub-flows at a plurality of locations along the length of the first electrode. It should be understood that the portion of the static mixer that is part of the electrode is electrically conductive. Other embodiments and details of the electrochemical flow cell are described below.

Referring to fig. 1, an electrochemical flow cell 100 (separator not shown) includes a reaction chamber 102 containing a first electrode 104 and a second electrode 106. The second electrode 106 may form at least a portion of a wall of the reaction chamber 102, as shown in fig. 1. The first electrode 104 may comprise a static mixer. The second electrode 106 may comprise a static mixer. The first and second electrodes 104, 106 may be concentrically arranged, one surrounding the other, or arranged side-by-side.

The power supply 110 may be connected to the first and second electrodes 104, 106 via respective first and second electrical conductors or cables 114, 116 to apply a potential difference or voltage across the electrodes 104, 106. In some embodiments, the first electrode 104 may function as an anode and the second electrode 106 may function as a cathode. In some embodiments, the first electrode 104 may function as a cathode and the second electrode 106 may function as an anode. In some embodiments, a negative potential may be applied to the first electrode 104, and a positive potential may be applied to the second electrode 106. In some embodiments, a positive potential may be applied to the first electrode 104 and a negative potential may be applied to the second electrode 106.

The first and second electrodes 104, 106 may be formed of an electrically conductive material or may include an electrically conductive surface coating. Further characteristics of the electrodes 104, 106 are described below in accordance with various embodiments and examples.

The pump 120 may be arranged to flow fluid into the reaction chamber 102 via the first fluid flow line 124 through a first inlet 134 in the reaction chamber 102 to flow fluid through or around the first electrode 104. The pump 120 may also be arranged to flow fluid into the reaction chamber 102 via the second fluid flow line 126 through a second inlet 136 in the reaction chamber 102 to flow fluid between the first electrode 104 and the second electrode 106. The fluid may then exit the reaction chamber 102 via a first outlet 144 adjacent the first electrode 104 and a second outlet 146 closer to the second electrode 106.

In some embodiments, the first and second flow lines 124, 126 may be supplied with fluid independently of the first and second pumps 120, 122, as shown in fig. 2. In some embodiments, the first and second flow lines 124, 126 may provide different fluids to the reaction chamber 102. For example, the flow lines 124, 126 may comprise pipes or tubes.

Referring to fig. 2, an electrochemical flow cell 200 (in which a separator is shown) is provided according to some embodiments. Flow cell 200 is similar to flow cell 100 described with respect to fig. 1, and like reference numerals are used for like components. In addition to the components shown in the flow cell 100 and described above, the flow cell 200 includes a separator 202. The membrane in the embodiment shown in fig. 2 at least partially separates a first fluid in, around or near the first electrode 104 from a second fluid adjacent to the second electrode 106 between the first electrode 104 and the second electrode 106. The membrane 202 may cooperate with the walls of the reaction chamber 102 to define a first channel 204 and a second channel 206. The first electrode 104 may be disposed in the first channel 204 and the second electrode 106 may be disposed in or form a wall of the second channel 206. The inlets 134, 136 and outlets 144, 146 may be configured such that the first fluid flows through the first channel 204 and the second fluid flows through the second channel 206. In some embodiments, the ratio between the lateral cross-sectional areas of the first channel 204 and the second channel 206 may be in the range of, for example, 0.01 to 100, 0.1 to 10, 0.5 to 5, 0.3 to 1, 0.5 to 0.9, 0.5 to 1.5, or 0.8 to 1.2.

The membrane 202 may allow charge to flow between the electrodes 104, 106, but restrict most fluid flow through the membrane 202. In some embodiments, the membrane 202 may allow ionic communication between the first and second electrodes 104, 106. For example, ions may be allowed to flow from the first channel 204 to the channel fluid 206, or from the second channel 206 to the first channel 204, while other components of the fluid may be prevented or substantially restricted from passing through the membrane 202. In some embodiments, a small amount of fluid may pass through the diaphragm 202, although the diaphragm 202 may be configured to substantially prevent fluid flow through the diaphragm 202. In some embodiments, the membrane 202 may comprise a permeable membrane, a semi-permeable membrane, or a selectively permeable membrane. The properties of the diaphragm 202 are described in more detail below according to various embodiments.

In some embodiments, the membrane 202 and the walls of the reaction chamber 102 may be arranged to define channels 204, 206 in a side-by-side relationship. The diaphragm 202 may be substantially flat extending between the channels 204, 206. In some embodiments, the channels 204, 206 may extend substantially parallel. In some embodiments, the second channel 206 may partially surround the first channel 204. In some embodiments, the first and second channels 204, 206 may be concentrically arranged. In some embodiments, the first channel 204 may be defined entirely by an inner surface of the septum 202. In some embodiments, the diaphragm 202 and the chamber 102 may be substantially cylindrical. In some embodiments, the chamber 102 may be substantially coaxial with the separator 202. In some embodiments, the second electrode 106 may be substantially coaxial with the first electrode 104. In some embodiments, the walls of the chamber 102 and the diaphragm 202 may both be substantially cylindrical and coaxial with the central longitudinal axis of the first electrode 104.

In some embodiments, the septum 202 may define surface variations or undulations to increase the surface area of the septum 202. In some embodiments, the diaphragm 202 may be corrugated. In some embodiments, the diaphragm 202 may be generally cylindrical with longitudinal corrugations. In some embodiments, the septum 202 may be generally cylindrical with circumferential corrugations.

The first electrode 104 (and/or the second electrode 106) may include a static mixer portion (e.g., a static mixer element or SME) that defines a structure having a geometry configured to promote mixing of the fluid flowing through the static mixer between the body of the fluid and the electrode surface, as well as within the fluid itself. The first electrode may be a static mixer electrode. The static mixer electrode 104 may be configured to split the flow at a plurality of different split locations along the length of the electrode 104 to promote thorough mixing via chaotic advection.

The static mixer may define a plurality of flow splitting structures arranged at splitting locations to split the flow. The flow dividing structures may be arranged at different azimuthal angles at different locations to divide the flow at different angles. In some embodiments, the flow splitting structure may be configured to split the flow into two sub-flows at each splitting location. In some embodiments, the flow splitting structure may be configured to split the flow into at least three sub-flows, such as three, four, five, six, seven or eight sub-flows, at each splitting location.

The geometry of the static mixer may be configured to enhance chaotic advection based on the characteristics of a particular fluid. The structure of the static mixer may comprise a network of elements including one or more of: intersecting blades or vanes, struts, microprotrusions, undulations and protrusions, spirals, corrugated sheets, open configurations, closed configurations, pores, channels, pores, tubes, and multilayer designs.

This geometry may be repeated regularly along the length of the mixer, or it may vary in size, type and/or shape. The feature length of the geometry may also vary from the scale of the mixer to nanometers, and features may be provided at all length scales in between.

Referring to fig. 3A through 3D, a static mixer electrode 104 is shown according to some embodiments. The electrode 104 includes a static mixer portion 304 extending between a first end 334 and a second end 344. The ends 334, 344 may define a tube or conduit to direct fluid through the static mixer.

The first end 334 may define the first inlet 134 of the flow cell and the second end 344 may define the first outlet 144 of the flow cell, such as the flow cells 100, 200 described above with respect to fig. 1 and 2. The ends 334, 344 may also provide electrical contact areas to connect the electrode 104 to the power source 110.

According to some embodiments, the static mixer portion 304 is shown without the ends 334, 344 in fig. 3B to 3D to more clearly illustrate the geometry. Static mixer section 304 contains a plurality of linear flow splitting structures arranged in repeating modules, with each subsequent module being rotated 90 ° relative to the previous module about the central longitudinal axis of the static mixer section extending from one end to the other. Static mixer section 334 promotes chaotic advection of fluid flowing through static mixer section 334 in a general direction along the central longitudinal axis by splitting and recombining the flow at a plurality of split locations along the length of static mixer section 334. The flow splitting structures split the flow into sub-flows at each splitting location, and the sub-flows are subsequently recombined before being split by the next splitting structure at the next splitting location.

Each flow is split and recombined, which brings a large portion of the different fluid packets from the flow into contact with the surface of the electrode 104, and splitting the flow multiple times along the length of the static mixer increases the amount of fluid in contact with the electrode 104.

In some embodiments, the diameter of the static mixer electrode 104 may be close to the inner diameter of the septum 202. That is, the first electrode 104 may fit closely within the diaphragm 202. The outer envelope of the static mixer geometry of the first electrode 104 may substantially completely occupy the interior volume defined by the diaphragm 202. In some embodiments, the volume of the first electrode 104 may be in a range of 1% to 99%, optionally 10% to 90%, 20% to 80%, 30% to 70%, or 40% to 60% of the internal volume of the channel 204. In some embodiments, the volume of the first electrode 104 may be at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, or 99% of the internal volume of the channel 204. Further features of the static mixer are described below in accordance with various embodiments.

Referring to fig. 4A-4C, an electrochemical flow cell 400 is shown in an assembled configuration (fig. 4A), a disassembled configuration (fig. 4B), and a cross-section (fig. 4C), according to some embodiments. Like components are denoted with like reference numerals and may include any features of the flow cell 100, 200 as well as the components described with respect to fig. 1 and 2 or the static mixer electrode 104 described with respect to fig. 3A through 3D.

The flow cell may include a first electrode 104, a second electrode 106, and a separator 202 disposed between the first electrode 104 and the second electrode 106. For example, the first electrode 104 may include a static mixer electrode 104 as described with respect to fig. 3A-3D.

The membrane 202 may comprise a permeable, semi-permeable, or selectively permeable membrane that is substantially cylindrical and closely surrounds the static mixer portion 304 of the first electrode 104. The membrane 202 and the first electrode 104 can cooperate to define a first channel 204 along which a fluid can flow, contact the first electrode 104, and be mixed by the static mixer portion 304 (see fig. 4C).

The second electrode 106 may also be substantially cylindrical and define an outer wall of the reaction chamber 102 surrounding the diaphragm 202 and the first electrode 104. The diaphragm 202 and the second electrode 106 may cooperate to define a second channel 206, along which a fluid may flow and contact the second electrode 106 (see fig. 4C).

The diaphragm 202 and the second electrode 104 may be disposed substantially concentric and/or coaxial with a central longitudinal axis of the first electrode 104.

According to some embodiments, the diaphragm 202 and electrodes 104, 106 are held in place by two opposing end caps 500, which are shown in more detail in fig. 5. Each end cap 500 comprises a body 501 defining a diaphragm seat 502, a first electrode seat 504 and a second electrode seat 506.

The second electrode holder 506 is defined by an annular recess in the body 501 configured to receive at least a portion of one end of the second electrode 106. The flow cell 400 can include a second electrode gasket 426 disposed between the second electrode 106 and each end cap 500 to form a seal between the second electrode 106 and the second electrode holder 506 (see fig. 4B).

The diaphragm seat 502 is defined by an annular recess (or circular recess in some embodiments) configured to receive the first end 232 or the second end 242 (see fig. 4B) of the diaphragm 202, respectively. The body 501 defines an opening 516 between the diaphragm seat 502 and the second electrode seat 506 and a passageway from the opening 516 to define the second outlet 136 or the second inlet 146, respectively.

The first electrode holder 504 is defined by a cylindrical bore or passageway configured to receive the respective ends 334, 344 of the first electrode 104. The first electrode holder 504 may be surrounded by a chamfer 514 on one side of the body 501 to help position the first electrode 104 in the first electrode holder 504. The passageway may extend from the chamfer 514 to a first electrode holder opening 524 on the other side of the body 501 (see fig. 4B). The first and second ends 334, 344 of the first electrode 104 may extend through the passageway and the opening 524 and define the first inlet 134 or the first outlet 144, respectively.

A seal may be formed between the ends 334, 344 and the end cap 500 using a sealing plate or gland 410 and a first electrode gasket 424 (see fig. 4B). The gland 410 may define an electrode opening 414 to allow passage of at least a portion of the ends 334, 344 and a plurality of fastener apertures (not shown) to receive the plurality of fasteners 412. The body 501 of the end cap 500 may define a corresponding plurality of fastener recesses 512 configured to receive the fasteners 412. The fastener 412 may engage (e.g., by threading) the fastener recess 512 to pull the gland 410 against the end cap 500, compressing the first electrode gasket 424 between the end cap 500 and the gland 410 and against the ends 334, 344, thereby forming a seal between the first electrode 104 and the end cap 500.

The end caps 500 may be held together by a plurality of tie rods 440 that extend between the end caps 500 and through a corresponding plurality of tie rod openings 542 defined in the body 501 of each end cap 500. Tie bars 440 may be configured to receive tie bar fasteners 442 at each end of each tie bar 440 to draw end caps 500 toward each other and retain membrane 202 and first and second electrodes 104, 106 between the end caps to define reaction chamber 102 and flow cell 400.

The electrochemical flow cells 100, 200, and 400 may improve the efficiency of the electrochemical reaction compared to conventional electrochemical flow cells, as the static mixer geometry of the first electrode 104 (and/or the second electrode 106) promotes enhanced mixing of the fluid, such as, for example, by chaotic advection, to increase the volume of fluid in contact with the first electrode 104 and/or the second electrode 106.

Electrochemical flow cells 200 and 400 may provide further advantages in that the fluid streams may remain substantially separated in channels 204, 206 on either side of membrane 202. This allows the independent input fluids to remain substantially separated while still allowing the electrochemical reactions to occur. For example, in some processes, a particular species, such as a metal ion, may be deposited on a surface of one of the electrodes 104, 106 via electrodeposition.

Referring to fig. 6, an electrochemical flow system 600 is shown, according to some embodiments. The system 600 includes a first flow battery 200a and a second flow battery 200b arranged in series and powered by two power sources 110a and 110b, respectively. Although, in some embodiments, a single power source 110 may supply power to both flow cells 200a, 200 b. The electrochemical flow cell 200a, 200b may be substantially similar to the flow cell 200 or 400 and include any of the features of the components described above with respect to fig. 2-5.

The system 600 may include: a first pump 120 that supplies a first fluid from a first source (input 1) into a first inlet 134a of a first flow cell 200a via a first flow line 124a of the first flow cell 200 a; and a second pump 122 that supplies a second fluid from a second source (input 2) into the second inlet 136a of the first flow cell 200a via a second flow line 126a of the first flow cell 200 a. The first and second electrodes 104b, 106b of the second flow cell 200b may be provided with a voltage of opposite polarity to the voltage applied to the first and second electrodes 104a, 106a of the first flow cell 200 a.

The system 600 may be configured such that a first fluid flowing into the first inlet 134a of the first flow cell 200a flows through the first channel 204a and out through the first outlet 144a of the first flow cell 200 a; and then into the second inlet 136b of the second flow cell 200b via the second flow line 126 b; through the second channel 206b of the second flow cell 200b and out through the second outlet 146b into the first reservoir (output 1). The system 600 may be further configured such that the second fluid flowing into the second inlet 136a of the first flow cell 200a flows through the second channel 206a and out through the second outlet 146a of the first flow cell 200 a; and then into the first inlet 134b of the second flow cell 200b via the first flow line 124 b; through the first channel 204b of the second flow cell 200b and out through the first outlet 144b into the second reservoir (output 2).

For example, the first fluid source may include a contaminant metal, such as copper, and it may be desirable to remove contaminants from the first fluid source and transfer the contaminants to the second fluid. When flowing through the system 600, contaminants will be deposited from the first fluid onto the first electrode 104a of the first flow cell 200a, and if any contaminants remain in the first fluid after passing through the first flow cell 200a, contaminants will also be deposited on the second electrode 106b of the second flow cell 200b as the first fluid flows through the second channel 206b of the second flow cell 200 b. The second fluid will pass through the second channel 206a of the first flow cell 200a and the first channel 204b of the second flow cell 200b to allow electrical contact and complete the current loop for each flow cell 200a, 200 b.

In conventional systems, when contaminants have accumulated on the electrode via electrodeposition, the electrode is removed from the system and the deposited contaminants are mechanically removed from the surface of the electrode. However, when using the system 600, the electrodes do not have to be removed.

Once contaminants have deposited on the first electrode 104a of the first flow cell 200a and the second electrode 106b of the second flow cell 200b, the source of the fluid may be switched by exchanging the flow lines 124a, 126a or using an in-line valve or gate (not shown) such that the first fluid flows through the second channel 206a of the first flow cell 20a and the first channel 204b of the second flow cell 200b, and the second fluid flows through the first channel 204a of the first flow cell 200a and the second channel 206b of the second flow cell 200 b. In this way, contaminants will be removed from the surfaces of the first electrode 104a of the first flow cell 200a and the second electrode 106b of the second flow cell 200b, and more contaminants will be removed from the first fluid and deposited on the second electrode 106a of the first flow cell 200a and the first electrode 104b of the second flow cell 200 b.

Electrochemical flow system 600 allows electrochemical reactions to proceed indefinitely with relatively short interruptions to switch fluid paths, as compared to conventional systems, which require physical removal and replacement of electrodes when the material deposited on the electrodes has reached a certain threshold.

Electrochemical tubular reactor

An electrochemical flow reactor, such as the electrochemical flow cell described above, may be provided in the form of a continuous flow electrochemical tubular reactor. The continuous flow electrochemical tubular reactor may be provided according to any embodiment or example as described herein for an electrochemical flow cell.

It will be appreciated that tubular reactors of various shapes, elongations and configurations may be provided. For example, a tubular reactor may comprise a reactor chamber of circular or non-circular shape, or wherein the reactor chamber comprises one or more fluid channels of circular or non-circular circumferential shape. Examples of non-circular shapes may include rectangular, isosceles triangular, elliptical, trapezoidal, and hexagonal. In one embodiment, the tubular reactor or reactor chamber is substantially circular or cylindrical.

The continuous flow electrochemical tubular reactor may comprise a reactor housing defining a reactor chamber for housing at least one static mixer electrode spaced apart from at least one counter electrode. The static mixer electrode may be provided by an electrode comprising a static mixer portion or a static mixer element as described herein. It should be understood that at least a portion of the static mixer portion or static mixer element, or any coating thereon, may be electrically conductive. The reactor also contains a permeable membrane that acts as a membrane for fluidly separating the static mixer electrode from the counter electrode while providing an electrical connection between the electrodes. The reactor may provide a fluid channel for receiving the static mixer electrode, the fluid channel being separate from the fluid channel receiving the counter electrode. The pair of electrodes may provide a cathode and anode pair for driving the electrochemical reaction in the tubular reactor. The static mixer electrode and the counter electrode may be either the cathode or the anode, depending on the current in the electrochemical cell. For example, the electrode pair may be reversed by switching the current. The static mixer electrodes can also be configured to enhance mass transfer and chaotic advection.

It should be understood that the tubular reactor is configured to allow at least the first fluid stream to flow past the static mixer electrode before exiting at the outlet to undergo chaotic advection and electrochemical reactions. It will also be understood that each fluid channel in a tubular reactor may have at least one inlet and at least one outlet.

The reactor may comprise one or more chamber sections in fluid communication with each other. The static mixer electrode may be configured as a replaceable electrode for insertion into a continuous flow electrochemical reactor or as a permanent electrode. One or more reactors, or one or more chamber sections of a reactor, may be configured for series or parallel operation.

The length of the reaction chamber 102, the membrane 202, and the electrodes 104, 106 may be in the range of 2mm to 100m, 10mm to 10m, 50mm to 1m, 100mm to 500mm, or 200mm to 300 mm. The diameter of the reactor housing or chamber may be between 5mm and 5m, with the counter and working electrodes being dimensioned to maintain an efficient electrochemical arrangement. In some embodiments, the length to diameter ratio (L/d) of the reactor can be at least about 5, 10, 15, 20, 25, 30, 40, 50, 60, 75, or 100.

Diaphragm

The membrane 202 may comprise any porous material that allows ion transport but prevents fluid flow. The membrane may comprise a permeable membraneA membrane, a semi-permeable membrane, or a selectively permeable membrane. In some embodiments, the septum 202 may be formed from any one or more of the following materials: non-woven fibers (cotton, nylon, polyester, glass), polymeric films (polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride), ceramics and naturally occurring substances (rubber, asbestos, wood). In some embodiments, the septum 202 may include a septum having a diameter less thanThe pore of (a). The diaphragm 202 may be formed using dry and/or wet fabrication processes. The nonwoven membrane 202 may comprise a fabricated sheet, web, or mat of oriented or randomly oriented fibers.

In some embodiments, the membrane 202 may comprise a supported liquid membrane, including a solid phase and a liquid phase contained within a microporous structure.

In some embodiments, the separator 202 may include a polymer electrolyte that forms a complex with an alkali metal salt, which results in an ionic conductor that functions as a solid electrolyte. The solid ionic conductor can serve as both a separator and an electrolyte.

The diaphragm 202 may be formed from a single layer or multiple layers of material.

In some embodiments, the diaphragm 202 may be made by sintering a powder material, such as ceramic, glass, plastic, cermet, and combinations thereof, into a film structure.

In some embodiments, the membrane 202 may be configured to allow ions to pass through while preventing fluid flow. In some embodiments, the septum 202 may allow a small amount of fluid to pass through.

The diaphragm 202 may have an inner diameter configured to fit closely around the first electrode 104. For example, the inner diameter of the septum 202 may be in the range of 0.5mm to 5m, 5mm to 1m, or 5mm to 10 mm.

The thickness of the membrane 202 may vary depending on its porosity. For nanoporous membranes, the thickness may be between 1 micron and 100 microns, and for microporous membranes, the thickness may be between 100 microns and 10 mm. The average pore size within the separator material may be withinAnd 100 microns.

It will be appreciated that the permeable membrane typically establishes separate fluid channels for each of the static mixer electrode and the counter electrode, while maintaining the electrical connections required for the electrochemical flow cell. Permeable membranes generally inhibit fluid flow through the membrane while allowing ion transport. For example, if during operation the static mixer electrode is operated as a negative electrode (i.e., cathode) and the counter electrode is operated as a positive electrode (i.e., anode), the catholyte stream for flow through the static mixer electrode (i.e., cathode) can be prepared for a particular application different from the anolyte stream for flow through the positive counter electrode (i.e., anode). In other words, the permeable membrane allows ionic communication between the two electrodes to provide an electrical connection while separating the two separate fluid streams flowing through each cathode and anode, which provides performance advantages and process flexibility.

The permeable membrane may be positioned concentrically along the tubular reactor to separate the static mixer electrode from the counter electrode. The reactor may comprise an inner coaxial flow path housing one electrode and an outer concentric flow path housing the other electrode. The static mixer electrode may be housed in the inner coaxial flow passage, the outer concentric flow passage, or both the inner coaxial flow passage and the outer concentric flow passage. The flow path may also be referred to herein as a fluid channel.

The membrane may be a semi-permeable membrane. The semi-permeable membrane may be a porous tubular membrane, a porous ceramic filter tube or a porous plastic tube that tightly surrounds the static mixer electrode. It will be appreciated that the semi-permeable membrane substantially restricts the passage of fluid through the membrane, while enabling transport of ions across the membrane to maintain electrical communication between the separated static mixer electrode and the counter electrode.

The membrane may be a selectively permeable membrane. A permselective membrane may provide selectivity while allowing transport through the membrane, such as a particular fluid or ion. It will be appreciated that a permselective membrane selectively restricts what can pass through the membrane while enabling transport of specific ions through the membrane to maintain electrical communication between the separated static mixer electrode and the counter electrode.

It will be appreciated that each individual flow path is provided with at least one inlet and at least one outlet. Separate fluid flows may be provided for the inner coaxial flow path and the outer concentric flow path. For example, a catholyte fluid flow may be provided to an inner concentric flow passage housing the static mixer electrode, and an anolyte fluid flow may be provided to an outer concentric flow passage housing the counter electrode. As previously mentioned, the static mixer electrodes may also be substantially coaxially aligned along the axis of the tubular reactor.

Static mixer electrode

As described above, the first electrode 104 or the second electrode 106 or the first and second electrodes 104, 106 may comprise a static mixer portion defining a geometry to facilitate mixing of the fluid flowing through or around the static mixer portion. This may be referred to as a static mixer electrode or SME.

The reactor may comprise more than one static mixer electrode and/or more than one counter electrode. The counter electrode may also be provided by a static mixer electrode, for example the cathode and anode in an electrochemical flow reactor may each be provided by a separate static mixer electrode. A static mixer electrode may be concentrically received within the inner concentric flow passage and a counter electrode may be received within the outer concentric flow passage.

It should be understood that the static mixer electrode may comprise a conductive surface. The static mixer electrode may operate as an anode or a cathode depending on the direction of the applied current. For electrochemical flow cells, it is generally understood that the anode is the positive electrode where oxidation occurs and electrons are released from the reactant, and the cathode is the negative electrode where reduction occurs and electrons are consumed by another reactant.

The static mixer electrode may be made of a material capable of providing 1 μ A m on either electrode^-2To about 1000A m^-2Materials with current densities in the range. The static mixer electrode or its support may comprise an electrically conductive material, for example an electrically conductive carbon material such as graphite, glassy carbon or boron doped diamond, a metal,alloys or intermetallic compounds such as powders, sheets, rods or billets, semi-metals or doped or low bandgap semiconductors, metal coated particles, conductive ceramics. Alternatively, the stent may be made of a non-conductive material and subsequently coated with an electrical conductor. The non-conductive material may be particulate nonconductors such as plastics, ceramics, glass or minerals, thermosetting resins, thermoplastic resins, and natural products such as rubber and wood. The conductive coating may be formed from a metal, metal alloy, intermetallic compound, conductive compound, or from any conductive material as described above.

The static mixer electrode may be produced by: subtractive manufacturing using one or a combination of processing techniques such as: milling, cutting, drilling, turning, spinning, bending and twisting, by casting, molding or forging, by extrusion, by pressing, by micro-electro-mechanical systems machining (MEMS), additive manufacturing processes, laser or electron beam welding, selective laser sintering, selective laser melting, direct metal laser sintering, laser engineered mesh forming, material extrusion, sheet lamination, polymerization and photopolymerization, material or adhesive spraying and printing.

In some embodiments, the body or support of the static mixer electrode may be electrically conductive, for example a metal or metal alloy, such as nickel, titanium or stainless steel. In some embodiments, a conductive coating may be applied to the electrode surface, such as a platinum coated titanium stent. The coating may be formed of a metal, semi-metal or doped or low bandgap semiconductor, a conductive ceramic or compound, a conductive form of carbon (e.g., graphite, graphene or doped carbon material), a conductive polymer (e.g., polyaniline), or a combination thereof. The coating may be applied to the surface by one or more of the following methods: electrochemical methods, metal spraying, cold spraying, chemical or physical vapor deposition, dip coating, spray coating, spin coating, sintering or other thermal treatment, or any such method that results in the application of a thin layer of a suitable material.

The static mixer electrode may be configured for enhanced mixing including heat and mass transfer characteristics for redistributing the fluid in a direction transverse to the main flow, e.g., in radial and tangential or azimuthal directions relative to a central longitudinal axis of the static mixer electrode. In particular, the static mixer electrode may be configured to enhance chaotic advection, thereby reducing the limitation on the reaction rate imposed by diffusion. The static mixer electrode may be configured to ensure that as much surface area as possible is presented to the flow to facilitate the electrochemical reaction and improve flow mixing so that the reactant molecules contact the surface of the static mixer electrode more frequently. The static mixer electrodes may be provided with various geometric configurations or aspect ratios for association with a particular application. The static mixer electrodes may be configured to enhance the turbulent, mixing, and mass transfer characteristics of the fluid flow. These configurations may also be designed to improve efficiency, the extent of chemical or electrochemical reactions, or other characteristics such as pressure drop (while maintaining a predetermined flow rate), residence time distribution, or heat and mass transfer coefficients.

The static mixer electrode may comprise an electrically conductive monolithic support defining a plurality of passage sections configured to enhance mass transfer and chaotic advection, for example, by splitting a fluid flow flowing between each of the passage sections. A major portion of the surface of the support may be electrically conductive.

The static mixer electrode may be configured to extend coaxially along the length and traverse the diameter of the flow passage. In one example, the envelope of the static mixer electrode may be configured to extend coaxially along the length of the inner coaxial flow passage and transversely across the diameter of the inner coaxial flow passage to substantially occupy the inner coaxial flow passage.

The first electrode 104 may have an outer diameter configured to fit closely within the diaphragm 202. For example, the outer diameter of the first electrode 104 may be in the range of 0.5mm to 5m, 5mm to 1m, or 5mm to 10 mm. In embodiments of the flow cell 400 such as described with respect to fig. 4A-4C, where the first and second electrodes are arranged concentrically and coaxially with each other, the inner diameter of the second electrode 106 may be in the range of 0.5mm to 5m, 5mm to 1m, or 10mm to 20 mm.

For example, the ratio between the inner diameter of the septum 202 and the inner diameter of the second electrode 106 may be in the range of 0.02 to 0.99, 0.1 to 0.9, 0.3 to 0.7, or 0.4 to 0.6.

The conductive monolithic support of the static mixer electrode may comprise a contiguous network of solid conductive elements distributed throughout the inner coaxial flow passage and configured for inducing chaotic advection of a fluid flowing through the inner coaxial flow passage. The contiguous network of solid conductive elements may be provided by a grid of interconnected segments configured to define a plurality of holes for causing chaotic advection of fluid flowing through the inner coaxial flow passage.

The static mixer electrodes may be provided in a configuration selected from one or more of the following general non-limiting example configurations:

an open configuration with a helix;

an open configuration with vanes;

corrugated board;

a multi-layer design;

closed configurations with channels or pores;

interlocking network of struts, roughness, undulations and protrusions.

In one embodiment, the support of the static mixer electrode may be provided in a grid configuration having a plurality of integral units defining a plurality of passageways configured to facilitate mixing of the one or more fluid reactants.

In another embodiment, the static mixer electrode may comprise a support provided by a grid of interconnected segments configured to define a plurality of apertures for facilitating mixing of the fluid flowing through the reactor chamber. The holder may also be configured to promote heat and mass transfer and fluid mixing.

In some embodiments, the static mixer electrodes can be configured to enhance chaotic advection, as well as, for example, turbulent mixing, such as cross-sectional, lateral (with respect to flow), or local turbulent mixing. The geometry of the static mixer electrode or its support may be configured to change the local flow direction or split the flow more than a certain number of times within a given length along the longitudinal axis of the static mixer element, such as more than 100m^-1Optionally greater than 200m^-1Optionally greater than400m^-1Optionally greater than 800m^-1Optionally greater than 1500m^-1Optionally greater than 2000m^-1Optionally greater than 2500m^-1Optionally greater than 3000m^-1Optionally greater than 5000m^-1. Static mixer electrodes, the geometry or configuration of the support of which may comprise more than a certain number of flow-dividing structures, such as more than 100m, within a given volume of the static mixer^-3Optionally more than 1000m^-3Optionally more than 1X 10⁴m^-3Optionally more than 1X 10⁶m^-3Optionally more than 1X 10⁹m^-3Optionally greater than 1X 10¹⁰m^-3。

The geometry or configuration of the static mixer electrode or its support may be configured to accompany the channel of a reactor cell, such as a tubular reactor. As previously mentioned, it should be understood that the term "tubular" includes non-circular configurations, such as elliptical. The static mixer electrode or its holder may be formed from or comprise a plurality of segments. Some or all of these sections may be straight sections. Some or all of these sections may comprise polygonal prisms, such as, for example, rectangular prisms. The stent may comprise a plurality of planar surfaces. The straight sections may be angled with respect to each other. The straight sections may be arranged at a plurality of different angles relative to the longitudinal axis of the stent, such as, for example, two, three, four, five, or six different angles. The static mixer electrode or its support may comprise a repeating structure. The static mixer electrode or its stent may comprise a plurality of similar structures that repeat periodically along the longitudinal axis of the stent. The geometry or configuration may be uniform along the length of the static mixer electrode or its support. The geometry may vary along the length of the static mixer electrode or its support. The straight sections may be connected by one or more curved sections. The static mixer electrode or its support may comprise one or more helical sections. The static mixer electrode or its support may generally define a helicoid. The static mixer electrode or its support may comprise a helicoid, comprising a plurality of holes in the surface of the helicoid.

The size of the static mixer electrodes may vary depending on the application. The static mixer electrode or the reactor containing the static mixer electrode may be tubular. The static mixer electrodes or reactor tubes may, for example, have a diameter (in mm) in the range of 1 to 5000, 2 to 2500, 3 to 1000, 4 to 500, 5 to 150, or 10 to 100. The static mixer electrode or reactor tube may, for example, have a diameter (in mm) of at least about 1, 5, 10, 25, 50, 75, 100, 250, 500, or 1000. The static mixer electrodes or reactor tubes may, for example, have a diameter (in mm) of less than about 5000, 2500, 1000, 750, 500, 250, 200, 150, 100, 75, or 50. The aspect ratio (L/d) of the static mixer electrode or the reactor chamber containing the static mixer electrode may be provided in a range suitable for industrial scale flow rates for a particular reaction. The aspect ratio may, for example, be in the range of about 1 to 1000, 5 to 750, 10 to 500, 25 to 250, 50 to 150, or 75 to 125. The aspect ratio can be, for example, less than about 1000, 750, 500, 250, 200, 150, 125, 100, 75, 50, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, or 2. The aspect ratio can be, for example, greater than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100. The aspect ratio may be provided within a range of any two of the above "less than" and "greater than" values.

The static mixer electrodes may be configured to enhance characteristics for laminar or turbulent flow rates, such as mixing and heat and mass transfer. It will be appreciated that for Newtonian fluids flowing in hollow tubes, the correlation of laminar and turbulent flow with Reynolds number (Re) values will generally provide, laminar flow rates where Re ≦ 2300; instantaneous, where 2300 is equal to or greater than Re is equal to or less than 4000; and is typically turbulent, with Re ≧ 4000. It will be appreciated that static mixer electrodes reduce these typical values of Re for creating turbulence. The static mixer electrodes may be configured for laminar or turbulent flow rates to provide enhanced characteristics selected from one or more of mixing, degree of reaction, heat and mass transfer, turbulent advection, and pressure drop. It will be appreciated that further enhancement of a particular type of electrochemical reaction will require specific considerations of its own. For in-tube flow, the reynolds number may be defined as Re ═ ρ uD_Hμ ([ rho ] is the density of the fluid in kg.m.)^-3In terms of u is the average velocity of the fluid in m.s^-1Meter, D_HIs the hydraulic diameter of the pipe in meters and μ is the dynamic viscosity of the fluid in pa.s).

In one embodiment, the static mixer electrode may be configured to operate at Re: at least 0.01, 0.1, 1, 5, 50, 100, 150, 200, 250, 300, 350, 400, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, or 15000. The static mixer electrode may be configured for operation in the Re range of about 0.1 to 2000, 1 to 1000, 10 to 800, or 20 to 500. The static mixer electrode may be configured for operation in the Re range of about 1000 to 15000, 1500 to 10000, 2000 to 8000, or 2500 to 6000. The static mixer electrode can be configured to operate at Re in a range between any two of the above "at least" values.

In some embodiments, the static mixer electrodes may be described by the peclet number (Pe), which is another type of dimensionless number associated with transmission phenomena in continuous media. The paclet number provides the ratio of the advection rate of a physical quantity caused by flow to the diffusion rate of the same quantity driven by an appropriate gradient. In terms of mass or mass transfer, the P é clet number is the product of the Reynolds number (Re) and the Schmidt number (Sc). In the case of hot fluids, the thermal peclet number is equal to the product of the reynolds number (Re) and the prandtl number (Pr). The Beclet number is defined as: pe-convective transport rate/diffusive transport rate. For mass transfer, it is defined as: pe_L＝Lu/D＝Re_LSc. For heat transfer, it is defined as PeL ═ Lu/α ═ Re_LPr, where α ═ k/ρ c_p. L is the characteristic length, u is the local flow velocity, D is the mass diffusion coefficient, and α is the thermal diffusivity, ρ is the density, and c_pIs the heat capacity. The static mixer electrode may be configured to provide a higher value of pclet to enhance chaotic advection over diffusion to provide a more uniform residence time distribution and reduce dispersion. In other words, toIn accordance with at least some embodiments and examples described herein, configurations of static mixer electrodes that provide higher values of pclet may provide improved performance and process control.

In one embodiment, the static mixer electrode may be configured for application at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 500000, 10⁶Or 10⁷Operate at the value of (P clet), (pe). The static mixer electrode may be configured for use at less than about 10 deg.f⁸、10⁷、10⁶500000, 250000, 100000, 75000, 50000, 25000, 20000, 15000, 10000, 5000, 2000, or 1000. The static mixer element may be configured for use at about 10 deg.f³To 10⁸、10³To 10⁷Or 10⁴To 10⁶Operating in the Pe range of (c). The static mixer element may be configured for operation within a Pe range between any two of the above-mentioned upper and/or lower values.

The% volume displacement of the static mixer electrode relative to the flow path housing the electrode may be in the range of about 1 to 90, 5 to 70, 10 to 30, or 5 to 20. The% volume displacement of the static mixer electrode relative to the flow path housing the electrode may be less than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or 5%. The% volume displacement of the static mixer electrode relative to the flow path housing the electrode can be greater than 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, or 80%. The volume displacement% may be provided within a range of any two of the above "less than" and "greater than" values.

A configuration of static mixer electrodes may be provided to enhance heat and mass transfer properties in the reactor, such as a reduced temperature difference at the outlet cross section. The heat and mass transfer of the static mixer electrode may for example provide a cross-sectional or transverse temperature profile with the following temperature differences: less than about 20 deg.C/mm, 15 deg.C/mm, 10 deg.C/mm, 9 deg.C/mm, 8 deg.C/mm, 7 deg.C/mm, 6 deg.C/mm, 5 deg.C/mm, 4 deg.C/mm, 3 deg.C/mm, 2 deg.C/mm, or 1 deg.C/mm.

The static mixer electrode or its support may be configured such that, in use, the pressure drop (i.e. the pressure differential or back pressure) (in Pa/m) across the static mixer electrode is in the range of about 0.1 to 1,000,000Pa/m (or 1MPa/m), including any value or range therebetween. For example, the pressure drop (in Pa/m) across the static mixer electrode can be less than about 500,000, 250,000, 100,000, 50,000, 10,000, 5,000, 1,000, 750, 500, 250, 100, 75, 50, 25, 20, 15, 10, or 5 Pa/m. For example, the pressure drop (in Pa/m) across the static mixer electrode can be at least about 10, 100, 1000, 5,000, 10,000, 50,000, 100,000, or 250,000. The pressure drop (in Pa/m) across the static mixer electrode may be provided within a range of any two of the upper and/or lower values noted above. For example, in one embodiment, the pressure drop (in Pa/m) across the static mixer electrode may be between about 10 and 250,000, 100 and 100,000, or 1,000 and 50,000. The static mixer electrode may be configured to provide a lower pressure drop relative to a particular flow rate. In this regard, the static mixer electrodes, reactors, systems, and methods as described herein may have parameters suitable for industrial applications. The above pressure drop may be maintained when the volumetric flow rate is at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 ml/min.

In one embodiment, the static mixer electrode can be configured to operate at a volumetric flow rate of at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1000 ml/min. In another embodiment, the volumetric flow rate may be less than about 1000, 900, 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, 150, 100, 75, 50, 40, 30, 20, 10, or 5 ml/min. The flow rate may be in a range provided by any two of these upper and/or lower values, such as in a range between about 50 and 400, 10 and 200, or 20 and 200.

The static mixer electrode may be configured as a modular insert for a continuous flow electrochemical reactor or chamber thereof. The static mixer electrode can be configured for use with an in-line continuous flow electrochemical reactor or chamber thereof. The in-line continuous flow electrochemical reactor may be a recycle loop reactor or a single pass reactor.

The configuration of the static mixer electrode may be determined using Computational Fluid Dynamics (CFD) software that may be used to enhance the configuration of the reactant mixing to enhance contact and activation of the reactants at the surface of the static mixer electrode.

The static mixer electrode may be an additive manufactured static mixer electrode. Additive manufacturing of the static mixer electrode, optionally with a catalytic and/or corrosion-resistant coating, can provide a static mixer electrode configured for efficient mixing, heat and mass transfer, electrochemical reactions, or additional catalytic reactions. The additive manufacturing process allows for physical testing of the reliability and performance of the static mixer electrodes, and optionally further redesigned and reconfigured using additive manufacturing (e.g., 3D printing) techniques. Additive manufacturing provides flexibility in preliminary design and testing, as well as further redesign and reconfiguration of static mixer electrodes. An electron beam 3D printer or a laser beam 3D printer may be used. The additive material for 3D printing may be, for example: pure metals such as iron, cobalt, nickel, copper, zinc; or alloys, such as titanium alloy based powders (e.g., 45-105 micron diameter range); cobalt chromium alloy based powders (e.g. FSX-414 or Stellite S21); or stainless steel or an aluminum-silicon alloy or any nickel-based alloy (e.g., Inconel, Hastelloy). The powder diameter associated with laser beam printers is typically lower than the powder diameter associated with electron beam printers. Alternatively, the stent may be additively manufactured from an inert material, such as plastic or glass, and then coated with a suitable conductive material. In addition to the electrically conductive surface, the static mixer electrode or its support may optionally further comprise a catalytic material, depending on the particular reaction or application desired.

Counter electrode

It should be understood that the counter electrode is electrically conductive. The counter electrode may operate as an anode or a cathode depending on the direction of the applied current. The counter electrode may be composed or configured of a material according to any of the embodiments or examples described above for the static mixer electrode.

It should be understood that the counter electrode may comprise a conductive surface. The counter electrode may be formed by providing 1 μ A m on either electrode^-2To about 1000A m^-2Materials with current densities in the range. The counter electrode may comprise a conductive material, for example a conductive carbon material such as graphite, glassy carbon or boron doped diamond, a metal, alloy or intermetallic compound such as a powder, sheet, rod or blank, a semi-metal or doped or low bandgap semiconductor, metal coated particles, a conductive ceramic. The counter electrode may be made of a non-conductive material and coated with an electrical conductor. The non-conductive material may be particulate nonconductors such as plastics, ceramics, glass or minerals, thermosetting resins, thermoplastic resins, and natural products such as rubber and wood. The conductive coating may be formed from a metal, metal alloy, intermetallic compound, conductive compound, or from any of the conductive materials described above for the counter electrode or static mixer electrode.

Reactor and end cap arrangement

The reactor may be provided as an assembly comprising a reactor shell, a first electrode, a second electrode, a membrane, and one or two optional end caps. The end caps may be configured to seal the reactor shell and further optionally configured for association with one or more of the first electrode, the second electrode, the membrane, for structural and alignment support in assembly and operation of the reactor.

In one embodiment, the tubular reactor may comprise first and second end caps each cooperatively configured for securing opposing ends of the reactor shell and supporting the arrangement of the static mixer electrode, counter electrode and membrane in the reactor.

The end cap may be an integral part of the static mixer electrode and/or the counter electrode (e.g., the end cap may be made part of one of the electrodes). The end caps may be provided as an integral part of an electrochemical flow cell or a continuous flow electrochemical tubular reactor (e.g., the entire electrochemical flow cell is made by an additive manufacturing process).

The end cap may be provided according to any other embodiment or example thereof as described herein.

Electrochemical flow system

According to any one or more aspects, embodiments, or examples described herein, a system for providing a continuous flow electrochemical reaction may comprise an electrochemical flow cell or an electrochemical tubular reactor.

The system may further comprise a pump for providing fluid flow through the reactor for the one or more fluid reactants and any products thereof. The system may further comprise an electrical unit for providing and controlling a voltage applied to the electrodes or a current flowing through the electrodes for driving an electrochemical reaction at the interface of the fluid flow and the electrodes. The system may further comprise a controller for controlling one or more parameters of the system, the one or more parameters selected from the group consisting of concentration, flow rate, temperature, pressure and residence time of one or more fluid reactants or sources or products thereof.

The reactor system may comprise one flow cell module, or a plurality of modules arranged in parallel or in series. The polarity of the electrodes in each device may be connected in the same manner or in an alternating manner in each cell, with the outer electrodes being alternately the anode, cathode, anode, cathode … (or vice versa) and the inner electrodes optionally being the cathode, anode, cathode, anode … (or vice versa). The system may be set up with any combination of these polarities. The magnitude of the voltage or current applied to each cell in the system may be the same or may vary, and the pumping speed through the cells in the system may be the same or may vary.

The reactor system may be configured and controlled to accept time-varying power input, for example from a renewable energy source. For example, the reactant flow rate may vary depending on the power available for electrolysis, so that the flow reactor remains operational when the power supply fluctuates.

The aspect ratio of the reactor may, for example, be similar to those previously described for the static mixer electrode, such that the static mixer electrode module may be configured for insertion into the reactor.

The reactor may comprise an optional heat exchanger for controlling the temperature of the reactor, chamber section, static mixer, or fluidic components thereof. The heat exchanger may be a shell and tube heat exchanger design or configuration.

The present invention also provides a system for a continuous flow electrochemical reaction process, the system comprising:

a continuous flow electrochemical reactor comprising one or more static mixer electrodes according to any embodiment or example described herein;

a pump for providing a fluid flow through the reactor for the one or more fluid reactants and any products thereof;

a control means for controlling one or more parameters of the system, the one or more parameters selected from the group consisting of reactant concentration, flow rate, current, applied voltage, pressure and residence time.

The system may comprise an optional heat exchanger for controlling the temperature of the reactor or fluid components thereof.

The system may further comprise a spectrometer that can be used to identify and determine the concentration of any one or more of the fluid reactants or products thereof.

One or more of the reactor, reactor chamber, chamber portion and static mixer electrode may each be provided in modular form for their complementary association. The system may comprise a plurality of reactors that may have similar or different internal and/or external configurations. The reactors may be operated in series or in parallel, or a combination of both. It will be appreciated that the system, reactor or each chamber section may include one or more inlets and outlets to provide supplies of reactants, obtain products, or recycle various reactants and/or products.

It will also be understood that the reactor or system may be designed to recycle the various reactants, reactant sources, intermediate products, or desired products provided to and produced in the chamber section. The reactor or system may be provided in various designs and forms, for example in the form of a tubular reactor. In another embodiment, the reactor is a single pass reactor.

The systems and processes may also be integrated into more complex systems, such as systems and methods including coal gasifiers, water purification and reticulation, electrolyzers and/or natural gas reformers, chemical synthesis and purification, and the like.

Electrochemical applications

According to any of the embodiments or examples described herein, the electrochemical flow reactor, electrochemical flow cell, or continuous flow electrochemical tubular reactor may be used for a variety of applications, including metal recovery, recovery of heavy and precious metals from wastewater and mine wastewater, wastewater treatment, water disinfection or purification (e.g., drinking water), and electrosynthesis of various products from solid waste (e.g., sludge, tailings, and processed waste). (e.g., gas generation, energy storage and conversion, reagent regeneration, and polymerization).

Reactors containing static mixer electrodes can be used in continuous flow electrochemical reaction systems and processes. The process may be an in-line continuous flow process. The in-line continuous flow process may be a recycle loop or a single pass process. In one embodiment, the in-line continuous flow process is a single pass process.

As described above, the electrochemical reactor comprising the static mixer electrode is capable of performing the reaction in a continuous manner. The electrochemical reactor may use single or multi-phase feed and product streams. In one embodiment, the substrate feed (comprising one or more reactants) may be provided as a continuous fluid stream, such as a liquid stream, comprising: a) as a substrate for a solute in a suitable solvent, or b) a liquid substrate with or without a co-solvent. It will be appreciated that the fluid stream may be provided by one or more gas streams, such as hydrogen or a source thereof. The substrate feed is pumped into the reactor using a pressure driven flow, for example by means of a pump. In another embodiment, the substrate feed may be provided by a solid suspended in a fluid stream, and in yet another embodiment, the reactant fluid stream may comprise a solid, a liquid, and a gas.

In one embodiment, there is provided a method for electrochemically treating a fluid stream, the method comprising an electrochemical flow cell or a continuous-flow electrochemical tubular reactor according to any embodiment or example thereof as described herein.

The above-described method may be used to remove dissolved metal ions from a fluid stream by applying a direct current across a static mixer electrode and a counter electrode to form a solid deposit comprising metal and/or metal compounds at the surface of the static mixer electrode. The process may be used for recovering metals from a fluid stream obtained from tailings. The process may comprise parallel and/or series operation as described above for the reactor system. In one embodiment, the process is operated in series.

In one embodiment, the method comprises at least first and second continuous flow electrochemical tubular reactors, each reactor configured such that a permeable membrane separates a static mixer electrode from a counter electrode to define an inner coaxial flow path housing one electrode and an outer concentric flow path housing the other electrode, each flow path having at least one inlet and at least one outlet. The method may enable loading of metal onto the static mixer electrode of the first tubular reactor while providing the second reactor in series with reversed polarity of the electrodes to remove metal previously loaded onto the static mixer electrode of the second tubular reactor.

In another embodiment of the above method, the first fluid stream may be introduced into the inner concentric flow path of the first tubular reactor and its output into the outer concentric flow path of the second tubular reactor. The second fluid stream may be simultaneously introduced into the outer concentric flow path of the first tubular reactor and its output introduced into the inner concentric flow path of the second tubular reactor. The first tubular reactor is operable to place the first static mixer electrode in a reducing state to accumulate solid metallic species, and the second tubular reactor is operable to place the second static mixer electrode in an oxidizing state to remove any metallic species present thereon.

Another advantage of the electrochemical flow reactor and system thereof according to various embodiments or examples described herein is that the electrochemical flow cell or tubular reactor does not require the removal and replacement of the cathode, and provides flexibility to operate in series or reverse mode by switching the current and switching the different fluid flows to remove metals, metal compounds, or other metal-containing products formed on the static mixer electrode as the cathode in the reduction reaction.

The present invention also provides a process for the synthesis of a product by reaction of one or more fluid reactants, the process comprising the steps of:

providing a continuous-flow electrochemical reactor comprising a static mixer electrode or system according to any embodiment or example described herein;

providing at least a first fluid reactant to the reactor via the reactant inlet;

operating the reactor or a control means thereof to provide flow and reaction of at least a first fluid reactant through the static mixer electrode; and is

An output stream of reaction products comprising at least the first reactant is obtained.

It will be appreciated that the various parameters and conditions used in the process, such as current, pressure and concentration/amount of materials and reactants, may be selected depending on the process's variable ranges, including the product to be synthesized, the electrochemical reaction or mechanisms involved, the source of reactants or type of reactor used, as well as the materials and configuration thereof. For example, differences will exist when one or more of the fluid reactants or co-solvents (e.g., inert carriers), etc., are gases, liquids, solids, or combinations thereof.

The electrochemical flow reactor may be operated at 1 μ A m^-2To about 1000A m^-2Current density operation at any electrode within the range. Current density (at A m)^-2Meter) can be, for example, less than about 1000, 500, 200, 100, 50, 20, 10, 5.0, 2.0, 1.0, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, 0.001, 0.0005, 0.0002, 0.0001, 0.00005, 0.00002, 0.00001, 0.000005, 0.000002, or 0.000001. Current density (at A m)^-2Meter) can be, for example, greater than about 0.000002, 0.000005, 0.00001, 0.00002, 0.00005, 0.0001, 0.0002, 0.0005, 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, 10, 20, 50, 100, 200, or 500. The current density can be inAny range of two values selected from any of the above values is provided. It should be understood that various applications and configurations may employ different current densities.

In some embodiments, the voltage applied across the electrodes may be less than about 2.0, 1.8, 1.6, 1.4, 1.2, 1.0, 0.8, 0.6, 0.4, or 0.2. In some embodiments, the voltage applied across the electrodes may be at least about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, or 1.8. The voltage may be within a range provided by any two of these upper and/or lower values.

In one embodiment, the operational performance of an electrochemical flow reactor can be measured by its recovery efficiency. Recovery efficiency relates to the amount of species (e.g., contaminants) present in the fluid, such as dissolved metal species, that can be removed from the fluid by the electrochemical flow cell. In one embodiment, the recovery efficiency, measured as% of the contaminant recovered (or removed) from the fluid, is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99. In some embodiments, any recovery efficiency may be provided by continuous operation (e.g., recirculation in a circulating loop reactor) for a duration of less than about 48 hours, 36 hours, 24 hours, 12 hours, 6 hours, 3 hours, 2 hours, or 1 hour. In another embodiment, a substance (e.g., a contaminant), such as a dissolved metal substance (e.g., a copper substance), can be removed from a fluid, where the substance is present in the fluid at a concentration of less than about (in moles/L) 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, 0.0001, 0.00005, or 0.00001. In another embodiment, a substance (e.g., a contaminant), such as a dissolved metal substance, can be removed from a fluid, where the substance is present in the fluid at a concentration greater than about (in moles/L) 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, or 0.5. The concentration of the species removed may be between any two of these upper and/or lower limits. The recovery efficiency and/or cycle duration described above may be applied to any of these species (e.g., contaminant) concentrations. For example, the operational performance of the reactor, system, or method thereof can provide a recovery efficiency of at least about 50% of the dissolved metal species from a fluid having an initial concentration of less than about 0.01 mol/L. In another embodiment, the recovery efficiency may be at least about 60% of the dissolved metal species from the fluid having an initial concentration of less than about 0.005 mol/L. In another embodiment, the recovery efficiency may be at least about 70% of the dissolved metal species from the fluid having an initial concentration of less than about 0.001 mol/L. In another embodiment, the recovery efficiency may be at least about 80% of dissolved metal species from the fluid having an initial concentration of less than about 0.0005 mol/L. In another embodiment, the recovery efficiency may be at least about 90% of the dissolved metal species from the fluid having an initial concentration of less than about 0.0001 mol/L.

In another embodiment, a substance (e.g., a contaminant), such as a dissolved metal species (e.g., a copper species), can be removed from a fluid, where the substance is present in the fluid at an initial concentration of about or less than about (in ppm) 1000, 750, 500, 250, 100, 75, 50, 25, 10, 5, or 1. In another example, a substance (e.g., a contaminant), such as a dissolved metal species (e.g., a copper species), can be removed from a fluid, where the substance is present in the fluid at an initial concentration of about or greater than about (in ppm) 5, 10, 25, 50, 75, 100, 250, 500, 750, or 1000. The removed species may be at an initial concentration in the fluid between any two of these upper and/or lower ranges. In one embodiment, the recovery efficiency, measured as% of the contaminant recovered (or removed) from the fluid, is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99. In some embodiments, any recovery efficiency may be provided by continuous operation (e.g., recirculation in a circulating loop reactor) for a duration of less than about 48 hours, 36 hours, 24 hours, 12 hours, 6 hours, 3 hours, 2 hours, or 1 hour. The recovery efficiency and/or cycle duration described above may be applied to any of these species (e.g., contaminant) concentrations. For example, the operational performance of the reactor, system, or method thereof can provide a recovery efficiency of at least about 50% of the dissolved metal species from a fluid having an initial concentration of about 100ppm of the dissolved metal species during less than about 3 hours of continuous operation. In another example, the recovery efficiency may be at least about 95% of the dissolved metal species from the fluid at an initial concentration of about 100ppm during less than about 24 hours of continuous operation.

The temperature (. degree.C.) associated with the process may be in the range between-50 and 400, or any integer or range of integers therebetween. For example, the temperature (. degree. C.) can be at least about-50, -25, 0, 25, 50, 75, 100, 150, 200, 250, 300, or 350. For example, the temperature (C.) may be less than about 350, 300, 250, 200, 150, 100, or 50. The temperature may also be provided at about any of these values or within a range between any of these values, such as within a range of about 0 to 250 ℃, about 25 to 200 ℃, or about 50 to 150 ℃.

In one embodiment, the process is operable to provide the following Re: at least 0.01, 0.1, 1, 5, 50, 100, 150, 200, 250, 300, 350, 400, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, or 15000. The process may be operated at a Re in the range of about 0.1 to 2000, 1 to 1000, 10 to 800, or 20 to 500. The process may operate at a Re in the range of about 1000 to 15000, 1500 to 10000, 2000 to 8000 or 2500 to 6000. The process can operate at a Re range provided by any two of the above "at least" values.

In one embodiment, the process may operate at the following values of perclet (pe): at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 500000, 10⁶Or 10⁷. The process may operate at values less than the following peclet (pe): about 10⁸、10⁷、10⁶500000, 250000, 100000, 75000, 50000, 25000, 20000, 15000, 10000, 5000, 2000, or 1000. The process may be at about 10³To 10⁸、10³To 10⁷Or 10⁴To 10⁶Operating in the Pe range of. The process can be operated at a Pe range between any two of the above upper and/or lower limits.

The process can provide a pressure drop (or back pressure) (in Pa/m) across the static mixer electrodes in the range of about 0.1 to 1,000,000Pa/m (or 1MPa/m), including any value or range of values therebetween. For example, the pressure drop (in Pa/m) across the static mixer electrode can be less than about 500,000, 250,000, 100,000, 50,000, 10,000, 5,000, 1,000, 750, 500, 250, 100, 75, 50, 25, 20, 15, 10, or 5 Pa/m. For example, the pressure drop (in Pa/m) across the static mixer electrode can be at least about 10, 100, 1000, 5,000, 10,000, 50,000, 100,000, or 250,000. The pressure drop (in Pa/m) across the static mixer electrode may be provided within a range of any two of the upper and/or lower values noted above. For example, in one embodiment, the pressure drop (in Pa/m) across the static mixer electrode may be between about 10 and 250,000, 100 and 100,000, or 1,000 and 50,000. In this regard, the static mixer electrodes, reactors, systems, and methods as described herein may have parameters suitable for industrial applications. The pressure drop or range thereof can be provided, wherein the volumetric flow rate is at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 100, 500, 1000 ml/min.

In one embodiment, the following volumetric flow rates may be provided: at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 75, 100, 125, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1000 ml/min. In another embodiment, the following volumetric flow rates may be provided: less than about 1000, 900, 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, 150, 100, 75, 50, 40, 30, 20, 10, or 5 ml/min. The flow rate may be in a range provided by any two of these upper and/or lower values, such as in a range between about 50 and 400, 10 and 200, or 20 and 200.

The process may involve an average residence time in the static mixer or reactor of about 0.1 seconds to about 60 minutes. The average residence time may be, for example, less than about 60 minutes, 45 minutes, 30 minutes, 15 minutes, 10 minutes, 5 minutes, 1 minute, 30 seconds, 10 seconds, or 5 seconds. The average residence time may be, for example, greater than about 1 second, 5 seconds, 10 seconds, 30 seconds, 1 minute, 5 minutes, 10 minutes, 15 minutes, 30 minutes, or 45 minutes. The average residence time may be provided as a range selected from any two of these aforementioned values. For example, the average residence time may be in the range of 5 seconds to 10 minutes, 1 second to 5 minutes, or 1 minute to 60 minutes.

The process can provide the following faradaic efficiencies (% charge passed participating in the reaction of interest): at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99. The process can provide the following faradaic efficiencies (% charge passed participating in the reaction of interest): less than 99, 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10. The process can provide a faradaic efficiency (% charge passed to participate in the reaction of interest) in the range provided by any two of the above upper and/or lower values.

The anolyte and/or catholyte streams may include any suitable solvent, electroactive species, and supporting electrolyte. The concentration of dissolved species can vary from parts per billion to their solubility limit (tens of moles per liter). In addition to dissolved substances, the fluid stream may contain multiple phases in any combination: undissolved solids (e.g., solids suspended in a fluid stream), immiscible liquids, and gases. Thus, the fluid stream may comprise an aqueous or non-aqueous solvent, a molecular solvent, a molten salt, an ionic liquid, a supercritical solvent, or a mixture of these. The dissolved species may be ionic, molecular, or substantially ion-paired in solution. They may be dissolved solids, gases, miscible liquids or mixtures thereof. The other phases present may be suspended solids or gels, organic or inorganic polymers, natural products or mixtures of these. They may be gases or vapors intentionally introduced or generated by the action of flow and/or electrochemical activity. In another embodiment, the fluid is a liquid or complex liquid, such as a dissolved and/or suspended liquid containing solids.

In one embodiment, there may be provided a method for removing a substance from a fluid stream, the method comprising an electrochemical flow cell or system thereof according to any aspect, embodiment or example thereof as described herein. The substance may be a metallic substance dissolved in the fluid stream. It will be appreciated that any of the above embodiments or examples relating to the performance of an electrochemical liquid flow cell may be applied to this embodiment.

Examples

The invention is further described by the following embodiments. It is to be understood that the following description is for the purpose of describing particular embodiments only and is not intended to be limiting of the above description.

Example 1:

an electrochemical flow reactor was prepared containing a membrane 200 (fig. 2), and including a peristaltic pump (Masterflex L/S variable speed drive w/Remote I/O; 600rpm)120 to control the flow of electrolyte into the cell and a power supply 110(Autolab 302N potentiostat, available from metrohmautalab BV, dutch aldehler (urtht)) to control the applied electrochemical potential/current flowing through the cell.

An additively manufactured metallic Static Mixer Electrode (SME)104, 204 as a working electrode fits tightly within a tubular porous polymer membrane 202(GenPore Reading, usa) in a split mode configuration defining a working compartment. Two ports at either end of the electrode were incorporated into the design to provide connections for fluid flow. Through which the fluid enters the working compartment. As with all static mixers, the momentum of the solution causes mixing as it flows over many angled surfaces of the mixer surface. In this particular experiment, an inert tubular counter electrode 102 made of glassy carbon surrounds the working compartment at a small distance from the membrane, creating a low volume counter compartment and forming the housing of the cell. Two end caps 500 (fig. 4a, 4b and 4c) are used to seal the entire assembly. A port 144 machined into the end cap provides fluid flow into the counter electrode compartment. This configuration allows for the use of different fluids in the two compartments if required for the experiment.

The efficiency of cell operation can be assessed by comparing the limiting currents measured at different flow rates with the results from a Rotating Disk Electrode (RDE) in the same solution. These comparisons are useful indicators of performance and are not used to draw any conclusions about the hydrodynamic conditions at the static mixer surface.

To evaluate the performance of the electrochemical flow reactor of the invention in both configurations, a series of experiments were conducted using a platinum-coated static mixer electrode (i.e., working electrode (10)) with 0.5M potassium chloride as the supporting electrolyte^-3-10^-1M)) and a glassy carbon tube (i.e., anode), ferricyanide ([ Fe (CN))₆]³⁺Solution (10)^-3-10^-1M) electrochemical reduction. A typical reduction reaction in a separate configuration of the reactor proceeds as follows.

Chronoamperometric measurements were performed by applying potential steps of-1.4V, -1.6V, -1.8V, and-2V to the cell over 100 seconds, with the cell in quiescent mode (i.e., 0mL min) at the first 50 second intervals^-1) Run at 10 and 400mL min at the last 50 second interval^-1With constant flow rate (fig. 7-9). Steady state currents were observed for all flow rates and by increasing the flow rate, the recorded currents increased in all potential steps. Although the recorded current increased with increasing potential, some bubbles were observed in the solution exiting the flow cell when-1.8V and-2V were applied. At these higher potentials of the experimental setup, except [ Fe (CN)₆]³⁺In addition to the reduction, hydrogen evolution occurs at the cathode, which complicates the analysis.

Experimental results indicate that at lower electroactive ion concentrations, the reaction is mass transport limited (i.e., [ Fe (CN))₆]³⁺At concentrations of 0.001 and 0.01M), the configuration of the electrochemical flow cell significantly improves the reaction rate. At higher concentrations (i.e., 0.1M [ Fe (CN))₆]³⁺) Where the increase in reaction rate is small, faster when using static mixer electrodes, between 1.5 and 3.7, by mass transport and kinetic factor controlled reaction (mixing control).

Example 2:

in the electrochemical flow cell separation configuration embodiment, the use of stainless steel static mixer electrode (i.e. working electrode) and carbon glass tube (i.e. anode), in 10-1000mL min^-1Evaluation of electrochemical flow cell at a flow rate of 0.01M H₂SO₄Contains Cu 10-100ppm²⁺The efficiency of removing copper ions in the acidic contaminated solution. As shown in FIG. 10, by increasing the flow rate over 50mL min^-1The removal efficiency is reduced due to the reduced residence time of the electroactive ions on the surface of the working electrode to complete the reduction reaction (fig. 10a and 10 b). On the other hand, by increasing the flow rate, the charge through the working electrode has increased and the current recovery increases accordingly (fig. 10c and 10 d). However, increasing the flow rate is effective because the residence time of the electroactive ions at the electrode surface is reduced.

Example 3:

extensive electrolysis experiments were also performed to show how electrochemical flow cells effectively remove copper ions from a fixed volume of contaminated aqueous solution. Use electrochemical flow cell at 50mL min^-1Two liters of copper contaminated aqueous solution (i.e., 100ppm CuSO) was treated at a constant flow rate₄.4H₂O is 0.01M H₂SO₄Solution in (c) for 24 hours. Optical images and SEM/EDS results confirmed the deposition of copper ions on the static mixer working electrode (fig. 11) and ICP-MS results show that in the isolated configuration of the electrochemical flow cell, a 99.7% reduction in copper concentration was achieved within 24 hours (fig. 12).