Electrochemical Flow Reactor

Abstract

The present disclosure relates to electrochemical flow reactors, such as continuous flow electrochemical tubular reactors. The present disclosure also relates to processes, systems, and methods that include the electrochemical flow reactors. The electrochemical flow cell may include a reaction chamber, a first static mixer electrode, a second counter electrode, and a separator disposed between the first electrode and the second electrode.

Description

[Technical field]

[0001] The present disclosure relates to electrochemical flow reactors, such as continuous flow electrochemical tubular reactors. The present disclosure also relates to processes, systems, and methods that include electrochemical flow reactors. [Background technology]

[0002] A continuous flow reactor typically comprises a reaction chamber into which reactant fluids are continuously fed, where chemical reactions take place to form products, and where the products are provided in a continuous effluent stream from the reaction chamber. The reaction chamber is typically submerged in a heating / cooling fluid, for example in a shell-and-tube heat exchanger configuration, to facilitate heat transfer to / from the reaction.

[0003] Continuous flow reactors may use packed bed reaction chambers, which pack the reaction chamber with solid catalyst particles that provide a catalytic surface over which chemical reactions can occur. Static mixers may be used to premix fluid streams prior to contact with the packed bed reaction chambers and downstream of these chambers to transfer heat between the central and outer regions of the reaction tubes. Static mixers comprise solid structures that block the flow of fluids, which promotes mixing of reactants prior to reaction in the packed bed reaction chambers and promotes desirable patterns of heat and mass transfer downstream of these chambers.

[0004] Electrochemical flow reactors have been used in fluid stream treatment to remove dissolved metals by electrochemical deposition of dissolved metal ions onto the surfaces of electrodes contained within the electrochemical flow reactor to form solid metal products. Electrochemical flow reactors for water treatment are directed to low flow rate systems with high surface area electrodes that provide high efficiency and control for the removal of dissolved metals from aqueous fluid streams having dilute / low concentrations of dissolved metal ions. Electrochemical flow reactors are also used for the electrosynthesis of various products, specifically the formation of reactants or intermediate products.

[0005] Alternative or improved electrochemical flow reactors are needed to provide efficient mixing, high mass transfer, and / or versatile operation in industrial applications.

[0006] It is to be understood that any prior art publications mentioned in this specification are not an admission that any of these documents form part of the general knowledge in the art in Australia or any other country. Summary of the Invention

[0007] The present inventors have undertaken research and development of alternative electrochemical flow reactors and have determined that a static mixer can be configured to act as an electrode in an electrochemical flow reactor to achieve efficient mixing, high mass transfer, and / or versatile operation for use in industrial applications. The electrochemical flow reactor may comprise a static mixer electrode separated from a counter electrode by a permeable membrane. The static mixer electrode may be configured to provide effective performance while improving mass transfer and chaotic advection. The static mixer electrode may be an electrode that comprises a static mixer section.

[0008] In one aspect, A reaction chamber; A first electrode; A second electrode; An electrochemical flow cell is provided, comprising a separator disposed between a first electrode and a second electrode; the separator at least partially defines a first channel within the reaction chamber configured to receive a first fluid stream in contact with the first electrode and a second channel within the reaction chamber configured to receive a second fluid stream in contact with the second electrode; the separator comprises a permeable membrane that allows ionic communication between the first electrode and the second electrode via the fluid streams while simultaneously limiting fluid exchange between the fluid streams; The first electrode includes a static mixer portion defining a plurality of dividing structures that divide the first fluid stream into a plurality of substreams at a plurality of locations along the length of the first electrode.

[0009] In one embodiment, the electrochemical flow cell is a continuous flow tubular reactor.

[0010] In one embodiment, the diameter of the static mixer portion of the first electrode may be approximately equal to the diameter of the first channel. The first electrode may be disposed in contact with the separator. The separator and the second electrode may be disposed concentrically and coaxially with a central longitudinal axis of the first electrode. The separator and the second electrode may be generally cylindrical. The second electrode may form at least a portion of a wall of the reaction chamber.

[0011] In one embodiment, a first electrode comprising a static mixer portion may be configured to enhance mass transfer and chaotic advection by defining multiple dividing structures that divide the fluid flow into multiple substreams at multiple locations along the length of the first electrode.

[0012] In one embodiment, adjacent split structures of the static mixer section may be disposed at different rotation angles about a central longitudinal axis of the static mixer section. The static mixer section may comprise a plurality of substantially similar structural modules disposed in series along a length of the static mixer section. The first electrode comprising the static mixer section may be 200 mm long. -1 The chaotic advection may be enhanced by dividing the first fluid flow by more, and may be up to 200 m -1 corresponds to the number of times the first fluid stream splits within a given length along the static mixer portion of the first electrode.

[0013] In another embodiment, the first electrode with the static mixer portion is configured to operate at a Peclet (Pe) number of at least about 10,000. The first electrode with the static mixer portion may be configured to operate at a pressure drop across the first electrode of about 100 to 100,000 (in Pa / m). The first electrode with the static mixer portion may be configured to operate providing a volumetric flow rate of the first fluid stream in the first channel of at least about 0.1 ml / min.

[0014] In another aspect, there is provided an electrochemical flow system comprising at least a first electrochemical flow cell according to any aspect, embodiment, or example of the electrochemical flow cell described herein.

[0015] In one embodiment, an electrochemical flow system comprises a first electrochemical flow cell and a second electrochemical flow cell according to any aspect, embodiment, or example of an electrochemical flow cell described herein. A plurality of flow lines may be provided 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 a first channel of the second electrochemical flow cell.

[0016] In one embodiment, the electrochemical flow system further comprises: a pump for providing a fluid flow of the fluid stream; a power supply that controls the current through or the voltage applied to the electrodes; a controller for controlling one or more parameters of the system, including concentration, flow rate, temperature, pressure, and residence time; Equipped with.

[0017] In another aspect, there is provided a method of electrochemical processing of a fluid stream comprising an electrochemical flow cell according to any aspect, embodiment, or example of an electrochemical flow cell, reactor, or system thereof described herein. The method may be for performing wastewater treatment, removal of dissolved metal ions from a fluid stream, or metal recovery from a fluid stream.

[0018] In one embodiment of the method, an electrochemical flow cell including a first electrode with a static mixer portion includes: 200m -1 Chaotic advection by dividing the first fluid flow by more than 200 m -1 is the chaotic advection, which corresponds to the number of times the first fluid flow splits within a given length along the static mixer section of the first electrode; A Peclet number of at least about 10,000; a pressure drop across the first electrode of about 100 to 100,000 (in Pa / m); a volumetric flow rate of the first fluid stream of at least about 0.1 ml / min; Approximately 1μA m -2 ~about 1000A m -2 current density of the first electrode and the second electrode; The signal may be operable to provide at least one of:

[0019] The method may include operation of a first electrochemical flow cell and a second electrochemical flow cell according to any aspect, embodiment, or example of an electrochemical flow cell described herein, wherein a plurality of flow lines connect 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 such that the second channel of the first electrochemical flow cell is in fluid communication with a first channel of the second electrochemical flow cell.

[0020] In another aspect, there is provided a method of 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.

[0021] In another aspect, there is provided a method for removing a particle species from a fluid stream comprising an electrochemical flow cell, a reactor, or a system thereof according to any aspect, embodiment, or example thereof described herein. The particle species can be a metal species dissolved in the fluid stream.

[0022] It will be appreciated that other aspects, embodiments, and examples of electrochemical flow cells, reactors, or systems are described herein.

[0023] Preferred embodiments of the present disclosure will now be further described and illustrated, by way of example only, with reference to the accompanying drawings in which: [Brief description of the drawings]

[0024] [Figure 1] 1 shows a schematic diagram of an electrochemical flow cell, according to some embodiments. [Diagram 2] FIG. 1 shows a schematic diagram of an electrochemical flow cell having a separator, according to some embodiments. [Figure 3A] 1 illustrates a perspective view of a static mixer electrode according to some embodiments. [Figure 3B] 3B shows a perspective view of the static mixer portion of the static mixer electrode of FIG. 3A (in isolation); [Figure 3C] 3B shows a cross-sectional view of the static mixer portion of the static mixer electrode of FIG. 3A (in isolation). [Figure 3D] 3B shows a side view (isolated) of the static mixer portion of the static mixer electrode of FIG. 3A. [Figure 4A] FIG. 1 shows a perspective view of an electrochemical flow cell according to some embodiments. [Figure 4B] FIG. 4B shows a perspective view of the flow cell of FIG. 4A in an exploded configuration. [Figure 4C] 4B shows a cross-sectional view of the flow cell of FIG. 4A. [Diagram 5] FIG. 4B shows a perspective view of the end cap of the flow cell of FIG. 4A. [Figure 6] FIG. 1 shows a schematic diagram of an electrochemical flow system including two electrochemical flow cells, according to some embodiments. [Figure 7] Chronoamperometric responses of 100 s at constant potentials of (a) -1.4 V, (b) -1.6 V, (c) -1.8 V, and (d) -2 V in static mode for 50 s and constant flow rates of 10–400 mL min−1 for 50 s are shown (0.001 M K3[Fe(CN)6]). [Figure 8] Chronoamperometric responses of 100 s at constant potentials of (a) -1.4 V, (b) -1.6 V, (c) -1.8 V, and (d) -2 V in static mode for 50 s and constant flow rates of 10–400 mL min−1 for 50 s are shown (0.01 M K3[Fe(CN)6]). [Figure 9]Chronoamperometric responses of 100 s at constant potentials of (a) -1.4 V, (b) -1.6 V, (c) -1.8 V, and (d) -2 V in static mode for 50 s and constant flow rates of 10–400 mL min−1 for 50 s are shown (0.1 M K3[Fe(CN)6]). [Figure 10] Electrochemical flow cell efficiency for removing copper ions from 0.01 M sulfuric acid solution at three different concentrations of Cu2+ is shown. [Figure 11] (a) Optical images of the static mixer working electrode before and after the process, (b) EDS analysis, and (c)–(e) SEM images of the static mixer electrode after 5 h of electrolysis are shown. [Figure 12] 1 shows copper concentration versus time over 24 hours of operation according to an embodiment of a separation configuration of an electrochemical flow cell. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The present disclosure describes various non-limiting embodiments below related to research conducted to identify electrochemical flow reactors that can provide efficient mixing, high mass transfer, and / or versatile operation for industrial applications. Surprisingly, it has been found that electrodes with static mixers can be configured to achieve efficient mixing, high mass transfer, and / or versatile operation for use in industrial applications in electrochemical flow cells. It has also been found that efficient electrochemical reactors can be provided when electrodes with static mixers are configured to enhance mass transfer and chaotic advection. Further surprising advantages in system operation and performance have been identified by configuring a separator between the electrodes with static mixers and a counter electrode to provide each of the electrodes in ionic communication with separate fluidic channels.

[0026] term Throughout this specification, unless specifically stated otherwise or the context requires otherwise, references to a single step, configuration of events, steps, or configurations of events shall be construed as including one and the plurality (i.e., one or more) of that step, configuration of events, steps, or configurations of events. Thus, as used herein, the singular forms "a," "an," and "the" include plural aspects unless the context clearly dictates otherwise. For example, reference to "a" includes the singular as well as two or more, reference to "an" includes the singular as well as two or more, reference to "the" includes the singular as well as two or more, etc.

[0027] The term "and / or", e.g., "X and / or Y", means either "X and Y" or "X or Y", and should be interpreted as explicitly including both meanings or either meaning.

[0028] The term "about" as used herein, unless otherwise specified, typically refers to + / - 10%, for example + / - 5% of the specified value.

[0029] It will be understood that throughout this specification the word "comprise" or variations such as "comprises" or "comprising" are meant 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.

[0030] Those skilled in the art will understand that the disclosure herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all of the steps, features, compositions, and compounds referred to or shown in the present specification, individually or collectively, as well as any and all combinations of such steps or features, or any two or more of such steps or features.

[0031] Each embodiment of the present disclosure described herein shall apply mutatis mutandis to every other embodiment unless specifically stated otherwise. The present disclosure is not intended to be limited in scope by the specific embodiments described herein, and such specific examples are intended for illustrative purposes only. Functionally equivalent products, compositions, and methods are expressly within the scope of the disclosure described herein.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. Methods and materials similar or equivalent to those described herein can be used in the practice or testing of this invention, but suitable methods and materials are described below. In case of conflict, the present specification, including definitions, will take precedence. In addition, the materials, methods, and examples are merely illustrative and are not intended to be limiting.

[0033] Electrochemical Flow Reactor An electrochemical flow cell can be provided that includes a reaction chamber, a first electrode with a static mixer portion, a second electrode, and a separator disposed between the first electrode and the second electrode.

[0034] The separator may at least partially define a first channel in the reaction chamber that accommodates a first fluid stream in contact with the first electrode and a second channel in the reaction chamber that accommodates a second fluid stream in contact with the second electrode. It will be understood that the separator allows ionic communication between the first and second electrodes via the fluid stream. The separator may be a permeable membrane that limits fluid exchange between the fluid streams. The static mixer portion may define a plurality of dividing structures that divide the fluid stream into a plurality of branches at a plurality of positions along the length of the first electrode. It will be understood that the static mixer portion that is part of the electrode is electrically conductive. Further embodiments and details of the electrochemical flow cell are described below.

[0035] 1, an electrochemical flow cell 100 (separator not shown) comprises a reaction chamber 102 including 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 electrode 104 and the second electrode 106 may be arranged concentrically, one surrounding the other, or in a side-by-side configuration.

[0036] A power source 110 may be connected to the first electrode 104 and the second electrode 106 via respective first and second conductors or cables 114, 116 and 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.

[0037] The first electrode 104 and the second electrode 106 may be formed of a conductive material or may include a conductive surface coating. Further features of the electrodes 104, 106 are described below according to various embodiments and examples.

[0038] The pump 120 may be configured to force fluid into the reaction chamber 102 through a first inlet 134 of the reaction chamber 102 via a first fluid flow line 124, and through or around the first electrode 104. The pump 120 may also be configured to force fluid into the reaction chamber 102 through a second inlet 136 of the reaction chamber 102 via a second fluid flow line 126, and 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 proximate the second electrode 106.

[0039] In some embodiments, the first flow line 124 and the second flow line 126 may be supplied with fluids separately from a first pump 120 and a second pump 122, as shown in Figure 2. In some embodiments, the first flow line 124 and the second flow line 126 may provide different fluids to the reaction chamber 102. The flow lines 124, 126 may include, for example, pipes or tubes.

[0040] Referring to FIG. 2, an electrochemical flow cell 200 according to some embodiments is provided (separator shown). The flow cell 200 is similar to the flow cell 100 described in connection with FIG. 1, and similar reference numbers are used for similar components. In addition to the components shown in the flow cell 100 and listed above, the flow cell 200 comprises a separator 202. The separator in the embodiment shown in FIG. 2 at least partially separates a first fluid in, around, or adjacent to 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 separator 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 within the first channel 204, and the second electrode 106 may be disposed within or form the wall of the second channel 206. The inlets 134 and 136 and outlets 144, 146 can be configured such that a first fluid flows through the first channel 204 and a second fluid flows through the second channel 206. In some embodiments, the cross-sectional area ratio of the first channel 204 to the second channel 206 can be in the range of, for example, 0.01-100, 0.1-10, 0.5-5, 0.3-1, 0.5-0.9, 0.5-1.5, or 0.8-1.2.

[0041] The separator 202 may allow charge flow between the electrodes 104, 106, but restrict a majority of the fluid from passing through the separator 202. In some embodiments, the separator 202 may allow ionic communication between the first electrode 104 and the second electrode 106. For example, ions may pass from the first channel 204 to the second channel 206, or from the second channel 206 to the first channel 204, but other components of the fluid may be prevented or substantially restricted from passing through the separator 202. In some embodiments, the separator 202 may be configured to substantially prevent fluid from flowing through the separator 202, although a small amount of fluid may pass through the separator 202. In some embodiments, the separator 202 may include a permeable membrane, a semi-permeable membrane, or a selectively permeable membrane. The properties of the separator 202 are described in more detail below according to various embodiments.

[0042] In some embodiments, the separator 202 and the walls of the reaction chamber 102 may be configured to define channels 204, 206 in a side-by-side relationship. The separator 202 may be generally planar extending between the channels 204, 206. In some embodiments, the channels 204, 206 may extend generally parallel. In some embodiments, the second channel 206 may partially surround the first channel 204. In some embodiments, the first channel 204 and the second channel 206 may be concentrically disposed. In some embodiments, the first channel 204 may be generally defined by an inner surface of the separator 202. In some embodiments, the separator 202 and the reaction chamber 102 may be generally cylindrical. In some embodiments, the reaction chamber 102 may be generally coaxially disposed with the separator 202. In some embodiments, the second electrode 106 may be generally coaxially disposed with the first electrode 104. In some embodiments, the walls of the reaction chamber 102 and the separator 202 may all be substantially cylindrical and disposed substantially coaxially with the central longitudinal axis of the first electrode 104 .

[0043] In some embodiments, separator 202 may define surface variations or undulations to increase the surface area of ​​separator 202. In some embodiments, separator 202 may be corrugated. In some embodiments, separator 202 may be generally cylindrical with longitudinal corrugations. In some embodiments, separator 202 may be generally cylindrical with circumferential corrugations.

[0044] The first electrode 104 (and / or the second electrode 106) may comprise a static mixer portion (e.g., a static mixer element or SME) that defines a structure having a shape configured to promote mixing of the fluid flowing through the static mixer that exists between the bulk 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 multiple different split locations along the length of the electrode 104 to promote thorough mixing by chaotic advection.

[0045] The static mixer may define a plurality of splitting structures disposed at splitting locations to split the flow. The splitting structures may be disposed at different locations and at different azimuth angles to split the flow at different angles. In some embodiments, the splitting structures may be configured to split the flow into two branches at each splitting location. In some embodiments, the splitting structures may be configured to split the flow into at least three branches, e.g., three, four, five, six, seven, or eight branches, at each splitting location.

[0046] 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 include a network of elements including one or more of intersecting blades or vanes, struts, irregularities, undulations and protrusions, spirals, corrugated plates, open configurations, closed configurations, pores, channels, holes, tubes, and multi-layer designs.

[0047] The features may be repeated periodically along the length of the mixer, or may vary in size, type, and / or shape. The features may also vary in their characteristic length from the mixer scale down to nanometers, with features provided at all length scales in between.

[0048] 3A-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 pipe that passes fluid through the static mixer.

[0049] 1 and 2, 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. The ends 334, 344 may also provide electrical contact areas for connecting the electrode 104 to the power source 110.

[0050] According to some embodiments, in Figures 3B-3D, the static mixer section 304 is shown without ends 334, 344 to show the shape more clearly. The static mixer section 304 has multiple linear split structures arranged in a repeating modular form, with each subsequent module rotated 90 degrees relative to the previous module about a central longitudinal axis of the static mixer section that extends from one end to the other. The static mixer section 304 encourages chaotic advection of the fluid flowing through the static mixer section 304 in a general direction along the central longitudinal axis by splitting and recombining the flow at multiple split locations along the length of the static mixer section 304. The split structures split the flow into multiple tributaries at each split location, which then recombine before being split by the next split structure at the next split location.

[0051] Each time the flow splits and recombines, a different fraction of the flow comes into contact with the surface of the electrode 104; by splitting the flow multiple times along the length of the static mixer, the amount of fluid in contact with the electrode 104 is increased.

[0052] In some embodiments, the diameter of the static mixer electrode 104 may closely approximate the inner diameter of the separator 202. That is, the first electrode 104 may closely fit within the separator 202. The static mixer-shaped outer membrane of the first electrode 104 may almost completely occupy the interior volume defined by the separator 202. In some embodiments, the volume of the first electrode 104 may range from 1% to 99%, optionally 10% to 90%, 20% to 80%, 30% to 70%, or 40% to 60% of the interior 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 interior volume of the channel 204. Further characteristics of the static mixer are described below according to various embodiments.

[0053] 4A-4C, an electrochemical flow cell 400 according to some embodiments is shown in an assembled configuration (FIG. 4A), an exploded configuration (FIG. 4B), and a cross-sectional view (FIG. 4C). Like components are indicated with like reference numbers and may include any of the components of the flow cells 100, 200 and described in connection with FIGS. 1 and 2, or the features of the static mixer electrode 104 described in connection with FIGS. 3A-3D.

[0054] 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. The first electrode 104 may include a static mixer electrode 104, for example, as described in connection with Figures 3A-3D.

[0055] The separator 202 may include a permeable, semi-permeable, or selectively permeable membrane that is generally cylindrical and closely surrounds a static mixer portion 304 of the first electrode 104. The separator 202 and the first electrode 104 may cooperate to define a first channel 204 along which fluid may flow, contact the first electrode 104, and be mixed by the static mixer portion 304 (see FIG. 4C).

[0056] The second electrode 106 may also be generally cylindrical and define an outer wall of the reaction chamber 102 that surrounds the separator 202 and the first electrode 104. The separator 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).

[0057] The separator 202 and the second electrode 106 may be disposed generally concentrically and / or generally coaxially with respect to a central longitudinal axis of the first electrode 104 .

[0058] According to some embodiments, the separator 202 and electrodes 104, 106 are held in place by two opposing end caps 500, shown in more detail in Figure 5. Each end cap 500 comprises a body 501 defining a separator mounting portion 502, a first electrode mounting portion 504, and a second electrode mounting portion 506.

[0059] The second electrode mounting portion 506 is defined by an annular recess in the body 501 configured to receive at least a portion of an end of the second electrode 106. The flow cell 400 may include a second electrode gasket 426 disposed between the second electrode 106 and each end cap 500, which forms a seal between the second electrode 106 and the second electrode mounting portion 506 (see FIG. 4B).

[0060] The separator mounting portion 502 is defined by an annular recess (or in some embodiments a circular recess) configured to receive the first end 232 or second end 242 of the separator 202, respectively (see FIG. 4B). The body 501 defines an opening 516 disposed between the separator mounting portion 502 and the second electrode mounting portion 506, and a passageway from the opening 516 that defines the second outlet 136 or second inlet 146, respectively.

[0061] The first electrode mounting portion 504 is defined by a cylindrical bore or passage configured to receive the respective ends 334, 344 of the first electrode 104. On one side of the body 501, the first electrode mounting portion 504 may be surrounded by a chamfer 514 to aid in positioning the first electrode 104 on the first electrode mounting portion 504. The passage may extend from the chamfer 514 to a first electrode mounting opening 524 on the opposite side of the body 501 (see FIG. 4B). The first and second ends 334, 344 of the first electrode 104 may extend through the passage and opening 524 to define the first inlet 134 and first outlet 144, respectively.

[0062] The seal plate or gland 410 and the first electrode gasket 424 may form a seal between the ends 334, 344 and the end cap 500 (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 a plurality of fasteners 412. The body 501 of the end cap 500 may define a plurality of corresponding fastener recesses 512 configured to receive the fasteners 412. The fasteners 412 may engage (e.g., by threads) with the fastener recesses 512 to draw the gland 410 against the end cap 500 and compress 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.

[0063] The end caps 500 may be held together by a plurality of drawbars 440 that extend between the end caps 500 and through a plurality of corresponding drawbar openings 542 defined in the body 501 of each end cap 500. The drawbars 440 may be configured to receive drawbar fasteners 442 at each end of each drawbar 440 to draw the end caps 500 toward each other and hold the separator 202, first electrode 104, and second electrode 106 between the end caps to define the reaction chamber 102 and the flow cell 400.

[0064] The electrochemical flow cells 100, 200, and 400 may enable improved efficiency of electrochemical reactions compared to conventional electrochemical flow cells by facilitating enhanced fluid mixing, such as by chaotic advection, which increases the amount of fluid in contact with the first electrode 104 and / or second electrode 106, due to the static mixer geometry of the first electrode 104 (and / or second electrode 106).

[0065] The electrochemical flow cells 200 and 400 may provide an additional advantage in that the fluid streams may be kept substantially separated in the channels 204, 206 on either side of the separator 202. This allows independent input fluids to be kept substantially separated while still allowing electrochemical reactions to occur. For example, in some processes, certain substances, such as metal ions, may be deposited on the surface of one of the electrodes 104, 106 by electrodeposition.

[0066] Referring to Figure 6, an electrochemical flow system 600 according to some embodiments is shown. The system 600 comprises a first flow cell 200a and a second flow cell 200b arranged in series and powered by two power sources 110a and 110b, respectively. However, in some embodiments, a single power source 110 may power both flow cells 200a, 200b. The electrochemical flow cells 200a, 200b may be substantially similar to the flow cells 200 or 400 and may include any of the component features previously described in connection with Figures 2-5.

[0067] The system 600 may include a first pump 120 that supplies a first fluid from a first source (inlet 1) through a first flow line 124a of the first flow cell 200a to a first inlet 134a of the first flow cell 200a, and a second pump 122 that supplies a second fluid from a second source (inlet 2) through a second flow line 126a of the first flow cell 200a to a second inlet 136a of the first flow cell 200a. The first electrode 104b and the second electrode 106b of the second flow cell 200b may be supplied with a voltage of opposite polarity with respect to the voltage applied to the first electrode 104a and the second electrode 106a of the first flow cell 200a.

[0068] The system 600 can 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, exits through the first outlet 144a of the first flow cell 200a, then flows via the second flow line 126b into the second inlet 136b of the second flow cell 200b, flows through the second channel 206b of the second flow cell 200b, and exits through the second outlet 146b to the first reservoir (outlet 1). The system 600 may further be configured such that a second fluid flowing into the second inlet 136a of the first flow cell 200a flows through the second channel 206a, exits through the second outlet 146a of the first flow cell 200a, then flows via the second flow line 124b into the first inlet 134b of the second flow cell 200b, flows through the first channel 204b of the second flow cell 200b, and exits through the first outlet 144b to a second reservoir (Outlet 2).

[0069] For example, the first fluid source may contain a contaminating metal such as copper, and it may be desired to remove contaminants from the first fluid source and transfer the contaminants to the second fluid. Contaminants are deposited on the first electrode 104a of the first flow cell 200a as they flow through the system 600, and if contaminants remain in the first fluid after passing through the first flow cell 200a, they are also 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 200b. The second fluid passes through the second channel 206a of the first flow cell 200a and the first channel 204b of the second flow cell 200b, allowing electrical contact and completing the galvanic circuit of each flow cell 200a, 200b.

[0070] In conventional systems, when contaminants accumulate on the electrode by electrodeposition, the electrode is removed from the system and the accumulated contaminants are mechanically removed from the surface of the electrode. However, when system 600 is used, there is no need to remove the electrode.

[0071] When contaminants accumulate on the first electrode 104a of the first flow cell 200a and the second electrode 106b of the second flow cell 200b, the fluid sources can be switched by swapping the flow lines 124a, 126a or using in-line valves or gates (not shown) so that the first fluid flows through the second channel 206a of the first flow cell 200a 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 200b. In this manner, contaminants are 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 are 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 200b.

[0072] Compared to conventional systems that require physical removal and replacement of electrodes when material buildup on the electrodes reaches a certain threshold, electrochemical flow system 600 allows electrochemical reactions to proceed indefinitely with relatively short interruptions to switch fluid pathways.

[0073] 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 described herein with respect to the electrochemical flow cell.

[0074] It will be appreciated that the tubular reactor may be provided in a variety of shapes, extensions, and configurations. For example, the tubular reactor may include a circular or non-circular reaction chamber, or the reactor chamber comprises one or more fluid channels that are circular or non-circular circumferential shapes. Examples of non-circular shapes may include rectangular, isosceles, elliptical, trapezoidal, and hexagonal. In one embodiment, the tubular reactor or reactor chamber is generally circular or cylindrical.

[0075] 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 with a static mixer section or static mixer element as described herein. It will be understood that at least a portion of the static mixer section or static mixer element, or any coating present thereon, may be electrically conductive. The reactor also comprises a permeable membrane that acts as a separator that fluidically separates the static mixer electrode from the counter electrode while providing an electrical connection between the electrodes. The reactor may provide a fluid channel housing the static mixer electrode that is separate from the fluid channel housing 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 a cathode or an anode depending on the current flow in the electrochemical cell. For example, the electrode pair may be reversed by switching the current flow. The static mixer electrodes may also be configured to enhance mass transfer and chaotic advection.

[0076] It will be appreciated that the tubular reactor is configured to allow at least a first fluid stream to flow across the static mixer electrodes and undergo chaotic advection and electrochemical reactions before exiting the outlet. It will also be appreciated that each fluid channel of the tubular reactor may have at least one inlet and at least one outlet.

[0077] The reactor may include one or more chamber sections in fluid communication with each other. The static mixer electrodes may be configured as replaceable electrodes for insertion into the continuous flow electrochemical reactor or may be configured as permanent electrodes. One or more reactors, or one or more chamber sections of a reactor, may be configured for serial or parallel operation.

[0078] The lengths of the reaction chamber 102, separator 202, and electrodes 104, 106 can range from 2 mm to 100 m, 10 mm to 10 m, 50 mm to 1 m, 100 mm to 500 mm, or 200 mm to 300 mm. The reactor housing or chamber can be 5 mm to 5 m in diameter, with the counter and working electrodes sized to maintain an effective electrochemical arrangement. In some embodiments, the aspect ratio (L / d) of the reactor can be at least about 5, 10, 15, 20, 25, 30, 40, 50, 60, 75, or 100.

[0079] Separator The separator 202 may include any porous material that allows ion transport but impedes fluid flow. The separator may include a permeable, semi-permeable, or selectively permeable membrane. In some embodiments, the separator 202 may be formed from any one or more of the following materials: non-woven fibers (cotton, nylon, polyester, glass), polymer films (polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride), ceramics, and naturally occurring materials (rubber, asbestos, wood). In some embodiments, the separator 202 may include a polymeric material with pores less than 20 Å. The separator 202 may be formed using dry and / or wet manufacturing processes. The non-woven separator 202 may include a sheet, web, or mat made of unidirectionally or randomly oriented fibers.

[0080] In some embodiments, separator 202 can include a supported liquid membrane that includes a solid or liquid phase contained within a microporous structure.

[0081] In some embodiments, separator 202 may include a polymer electrolyte that is complexed with an alkali metal salt to produce an ionic conductor that functions as a solid electrolyte. The solid ionic conductor may function as both a separator and an electrolyte.

[0082] Separator 202 may be formed of a single layer of material or multiple layers of material.

[0083] In some embodiments, the separator 202 can be fabricated by sintering powdered materials, such as ceramics, glasses, plastics, cermets, and combinations thereof, into a membrane structure.

[0084] In some embodiments, the separator 202 may be configured to allow ions to pass while simultaneously impeding fluid flow, hi some embodiments, the separator 202 may allow a small amount of fluid to pass.

[0085] The separator 202 can have an inner diameter configured to fit closely around the first electrode 104. For example, the inner diameter of the separator 202 can be in the range of 0.5 mm to 5 mm, 5 mm to 1 mm, or 5 mm to 10 mm.

[0086] The thickness of the separator 202 can vary depending on its porosity. For nanoporous separators, the thickness can be from 1 micron to 100 microns, and for microporous membranes, the thickness can be from 100 microns to 10 mm. The average pore size within the separator material can vary from 10 Å to 100 microns.

[0087] It will be appreciated that the permeable membrane typically establishes separate fluid channels to each of the static mixer electrode and the counter electrode while maintaining the electrical connections required for the electrochemical flow cell. The permeable membrane typically inhibits fluid flow through the membrane while allowing ion transport. For example, if in operation the static mixer electrode acts as a negative electrode (i.e., cathode) and the counter electrode acts as a positive electrode (i.e., anode), the catholyte fluid stream flowing across the static mixer electrode (i.e., cathode) may be prepared for a particular application different from the anolyte fluid stream flowing across the positive counter electrode (i.e., anode). In other words, the permeable membrane separates the two separate fluid streams flowing through the cathode and anode, respectively, while allowing ionic communication between the two electrodes to provide electrical connection, thereby providing performance advantages and process flexibility.

[0088] The permeable membrane may be concentrically positioned along the tubular reactor to separate the static mixer electrode from the counter electrode. The reactor may include an inner coaxial flow passage that houses one electrode and an outer concentric flow passage that houses the other electrode. The static mixer electrodes 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 passages may also be referred to herein as fluid channels.

[0089] The separator may be a semi-permeable membrane. The semi-permeable membrane may be a porous tubular film, a porous ceramic filter tube, or a porous plastic tube that closely surrounds the static mixer electrode. It will be appreciated that the semi-permeable membrane substantially restricts fluid from passing through the membrane while allowing ion transport across the membrane to maintain electrical communication between the separated static mixer electrode and the counter electrode.

[0090] The separator may be a selectively permeable membrane. A selectively permeable membrane may provide selectivity for what is permitted to be transported through the membrane, such as, for example, certain fluids or ions. It will be appreciated that a selectively permeable membrane selectively restricts what can pass through the membrane while allowing transport of certain ions across the membrane to maintain electrical communication between the separated static mixer electrode and the counter electrode.

[0091] It will be appreciated that each separate flow passage is provided with at least one inlet and at least one outlet. Separate fluid flows may be provided to the inner coaxial flow passage and the outer concentric flow passage. For example, the inner coaxial flow passage housing the static mixer electrode may be provided with a catholyte fluid flow, and the outer concentric flow passage housing the counter electrode may be provided with an anolyte fluid flow. As previously mentioned, the static mixer electrodes may also be generally coaxially aligned along the axis of the tubular reactor.

[0092] Static Mixer Electrode As discussed above, the first electrode 104, or the second electrode 106, or both the first electrode 104 and the second electrode 106 may include a static mixer portion that defines a shape that promotes mixing of fluids flowing through or around the static mixer portion, which may be referred to as a static mixer electrode, or SME.

[0093] The reactor may comprise two or more static mixer electrodes and / or two or more counter electrodes. The counter electrodes may also be provided with static mixer electrodes, for example the cathode and anode in an electrochemical flow reactor may each be provided with a separate static mixer electrode. The static mixer electrodes may be concentrically housed within an inner coaxial flow channel and the counter electrodes may be housed within an outer concentric flow channel.

[0094] It will be understood that the static mixer electrodes may include a conductive surface. The static mixer electrodes may operate as an anode or a cathode depending on the direction of the applied current. In the case of an electrochemical flow cell, it will be generally understood that an anode is a positive electrode where oxidation occurs and electrons are released by a reactant, and a cathode is a negative electrode where reduction occurs and electrons are absorbed by another reactant.

[0095] The static mixer electrodes are connected to either electrode at a current of 1 μA m -2 ~about 1000A m -2 The static mixer electrode or its skeleton may be made of a material capable of providing a current density in the range of 0.1 to 1.0 V. The static mixer electrode or its skeleton may comprise a conductive material, such as a conductive carbon material, such as graphite, glassy carbon, or boron-doped diamond, a metal, alloy, or intermetallic compound, a semimetal, or a doped or low band gap semiconductor, metal-coated particles, or a conductive ceramic in powder, sheet, rod, or billet form. Alternatively, the skeleton may be made of a non-conductive material and then coated with a conductor. The non-conductive material may be a particulate non-conductor, such as a plastic, ceramic, glass, or mineral, a thermoset, a thermoplastic, or a natural product, such as rubber and wood. The conductive coating may be formed of a metal, a metal alloy, an intermetallic compound, a conductive compound, or any of the conductive materials mentioned above.

[0096] Static mixer electrodes may be manufactured by subtractive manufacturing using one or a combination of processing techniques such as milling, cutting, drilling, turning, spinning, bending, twisting, by casting, molding, or forging, by extrusion, by pressure forming, by microelectromechanical systems machining (MEMS), additive manufacturing processes, laser or electron beam welding, selective laser sintering, selective laser melting, direct metal laser sintering, laser machining net forming, material extrusion, sheet lamination, polymerization and photopolymerization, material or binder jetting, and printing.

[0097] In some embodiments, the body or skeleton of the static mixer electrode may be electrically conductive, e.g., 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, e.g., a titanium skeleton coated with platinum. The coating may be formed from a metal, semi-metal, or doped or low band gap semiconductor, a conductive ceramic or compound, a conductive form of carbon (e.g., graphite, graphene, or doped carbon materials), a conductive polymer (e.g., polyaniline), or a combination thereof. The coating may be applied to the surface by one or more of electrochemical processes, metal spray, cold spray, chemical or physical vapor deposition, dip coating, spray coating, spin coating, sintering or other heat treatment, or any such process that results in the application of a thin layer of a suitable material.

[0098] Static mixer electrodes may be configured to improve mixing, including heat and mass transfer properties that redistribute fluids in directions across the main flow, e.g., radial and tangential or azimuthal directions relative to the central longitudinal axis of the static mixer electrodes. In particular, static mixer electrodes may be configured to improve chaotic advection, thereby reducing the reaction rate limitations imposed by diffusion. Static mixer electrodes may be configured to ensure that as much surface area as possible is exposed to the flow, promoting electrochemical reactions, and to improve mixing of the flow, so that reactant molecules come into contact with the static mixer electrode surfaces more frequently. Static mixer electrodes may be provided with a variety of geometric configurations or aspect ratios that are correlated with the particular application. Static mixer electrodes may be configured to improve turbulence, mixing, and mass transfer properties of the fluid flow. Configurations may also be designed to improve efficiency, extent of chemical or electrochemical reactions, or other properties such as pressure drop (while maintaining a given flow rate), residence time distribution, or heat and mass transfer coefficients.

[0099] The static mixer electrode can comprise an electrically conductive monolithic skeleton defining a plurality of passage segments configured to enhance mass transfer and chaotic advection, e.g., by dividing a fluid flow between each of the passage segments. A substantial portion of the surface of the skeleton can be electrically conductive.

[0100] The static mixer electrode may be configured to extend coaxially along the length of the flow passage and across a diameter of the flow passage. In one embodiment, the outer membrane of the static mixer electrode may be configured to extend coaxially along the length of the inner coaxial flow passage and across a diameter of the inner coaxial flow passage to substantially occupy the inner coaxial flow passage.

[0101] The first electrode 104 can have an outer diameter configured to fit closely within the separator 202. For example, the outer diameter of the first electrode 104 can range from 0.5 mm to 5 m, 5 mm to 1 m, or 5 mm to 10 mm. In embodiments such as the flow cell 400 described in connection with Figures 4A-4C, where the first and second electrodes are arranged concentrically and coaxially with one another, the inner diameter of the second electrode 106 can range from 0.5 mm to 5 m, 5 mm to 1 m, or 10 mm to 20 mm.

[0102] The ratio of the inner diameter of separator 202 to the inner diameter of second electrode 106 can be, for example, 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.

[0103] The conductive monolithic skeleton of the static mixer electrode may comprise a contiguous network of solid conductive elements distributed throughout the inner coaxial flow passage and configured to induce chaotic advection of fluid flowing through the inner coaxial flow passage. The contiguous network of solid conductive elements may be provided with a lattice of interconnected segments configured to define a plurality of apertures for inducing chaotic advection of fluid flowing through the inner coaxial flow passage.

[0104] The static mixer electrodes may be provided in a configuration selected from one or more of the following general, non-limiting, exemplary configurations: Open configuration with helix Open configuration with blades ·Corrugated Plate ·Multi-layer design Closed configuration with channels or holes An interlocking network of posts, bumps, undulations, and protrusions

[0105] In one embodiment, the skeleton of the static mixer electrode may be provided in a mesh configuration having a plurality of integral units defining a plurality of passages configured to facilitate mixing of one or more fluid reactants.

[0106] In another embodiment, the static mixer electrode may comprise a scaffold provided by a lattice of interconnected segments configured to define a plurality of apertures that facilitate mixing of the fluids flowing through the reactor chamber. The scaffold may also be configured to facilitate heat and mass transfer and fluid mixing.

[0107] In some embodiments, the static mixer electrodes may be configured to enhance chaotic advection and turbulent mixing, e.g., cross-sectional, transverse (with respect to the flow), or localized turbulent mixing. The geometry of the static mixer electrodes or their skeleton may be configured to redirect the local flow or split the flow more than a certain number of times within a given length along the longitudinal axis of the static mixer element, e.g., 100 m. -1 More, optionally 200m -1 More, optionally 400m -1 More, optionally 800m -1 More, optionally 1500m -1 More, optionally 2000m -1 More, optionally 2500m -1 More, optionally 3000m -1 More, optionally 5000m -1 The static mixer electrode, its skeleton shape or configuration may provide more than a certain number of split structures within a given volume of the static mixer, e.g., 100 m -3 More, optionally 1000m -3 More, optionally 1×10 4 m -3 More, optionally 1×10 6 m -3 More, optionally 1×10 9 m -3 More, optionally 1×10 10 m -3 More flow splitting structures may be provided.

[0108] The shape or configuration of the static mixer electrode or its skeleton may be configured to accompany the channels of a reactor cell, such as a tubular reactor. As previously mentioned, it will be understood that the term "tubular" includes non-circular configurations, such as, for example, elliptical. The static mixer electrode or its skeleton may be formed from or comprise multiple segments. Some or all of the segments may be straight segments. Some or all of the segments may include polygonal prisms, such as, for example, rectangular prisms. The skeleton may include multiple planar surfaces. The straight segments may be disposed at an angle relative to one another. The straight segments may be disposed at several different angles, such as, for example, two, three, four, five, or six different angles, relative to the longitudinal axis of the skeleton. The static mixer electrode or its skeleton may comprise a repeating structure. The static mixer electrode or its skeleton may comprise a plurality of similar structures that are periodically repeated along the longitudinal axis of the skeleton. The shape or configuration may be consistent along the length of the static mixer electrode or its skeleton. The shape may vary along the length of the static mixer electrode or its skeleton. Straight segments may be connected by one or more curved segments. The static mixer electrode or its skeleton may include one or more helical segments. The static mixer electrode or its skeleton may generally define a helix. The static mixer electrode or its skeleton may include a helix including a plurality of apertures in a surface of the helix.

[0109] The dimensions of the static mixer electrode may vary depending on the application. The static mixer electrode, or the reactor comprising the static mixer electrode, may be tubular. The diameter of the tube of the static mixer electrode or reactor may range, for example, from 1 to 5000, 2 to 2500, 3 to 1000, 4 to 500, 5 to 150, or 10 to 100 (in mm). The diameter of the tube of the static mixer electrode or reactor may be, for example, at least about 1, 5, 10, 25, 50, 75, 100, 250, 500, or 1000 (in mm). The diameter of the tube of the static mixer electrode or reactor may be, for example, less than about 5000, 2500, 1000, 750, 500, 250, 200, 150, 100, 75, or 50 (in mm). The aspect ratio (L / d) of the static mixer electrode, or the reactor chamber comprising the static mixer electrode, can be provided in a range suitable for industrial-scale flow rates for a particular reaction. The aspect ratio can be, for example, in the range of about 1-1000, 5-750, 10-500, 25-250, 50-150, or 75-125. 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 can be provided in any two of the above ranges of "less than" and "greater than" values.

[0110] The static mixer electrodes may be configured to enhance properties such as mixing and heat and mass transfer for laminar or turbulent flow rates. It will be appreciated that for Newtonian fluids flowing in hollow pipes, the correlation between laminar and turbulent flow and Reynolds number (Re) values ​​typically results in laminar flow rates when Re is less than 2300, transient flow rates when Re is greater than 2300 and less than 4000, and turbulent flow rates when Re is greater than 4000. It will be appreciated that the static mixer electrodes reduce these typical Re values ​​that produce turbulent flow. The static mixer electrodes may be configured to provide enhancements in properties selected from one or more of mixing, reactivity, heat and mass transfer, chaotic advection, and pressure drop for laminar or turbulent flow rates. It will be appreciated that further enhancements of certain types of electrochemical reactions require their own specific considerations. For flow in a tube, the Reynolds number is Re=ρuD H / μ (ρ is kg.m -3 is the fluid density in units of m -1 is the fluid mean velocity in units of D H is the hydraulic diameter of the pipe in meters and μ is the fluid dynamic viscosity in Pa.s).

[0111] In one embodiment, the static mixer electrodes are 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, 2000, 2200, 2400, 2600, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2 The static mixer electrodes may be configured to operate at Re of about 0.1 to 2000, 1 to 1000, 10 to 800, or 20 to 500. The static mixer electrodes may be configured to operate at Re of about 1000 to 15000, 1500 to 10000, 2000 to 8000, or 2500 to 6000. The static mixer electrodes may be configured to operate with Re in the range between any two of the "at least" values ​​set forth above.

[0112] In some embodiments, the static mixer electrodes may be described by the Peclet number (Pe), another class of dimensionless number related to transport phenomena in continua. The Peclet number provides the ratio of the advection rate of a physical quantity due to a flow to the diffusion rate of the same quantity driven by a suitable gradient. For the transfer of particle species or mass, the Peclet number is the product of the Reynolds number (Re) and the Schmidt number (Sc). For thermal fluids, the thermal Peclet number is equal to the product of the Reynolds number (Re) and the Prandtl number (Pr). The Peclet number is defined as Pe=advective transport rate / diffusive transport rate. For mass transfer, Pe L =Lu / D=Re L .Sc. In heat transfer, PeL=Lu / α=Re L .Pr is defined as α=k / ρc p where L is the characteristic length, u is the local flow velocity, D is the mass diffusion coefficient, α is the thermal diffusivity, ρ is the density, and c pis the heat capacity. Static mixer electrodes can be configured to provide higher Peclet values ​​to improve chaotic advection relative to diffusion, provide a more uniform residence time distribution, and reduce variability. In other words, static mixer electrode configurations that provide higher Peclet values ​​can result in improved performance and process control, at least according to some embodiments and examples described herein.

[0113] In one embodiment, the static mixer electrodes are at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 500000, 10 6 , or 10 7 The static mixer electrodes can be configured to operate at a Peclet (Pe) value of about 10 8 , 10 7 , 10 6 , 500000, 250000, 100000, 75000, 50000, 25000, 20000, 15000, 10000, 5000, 2000, or 1000 Peclet (Pe) values. 3 ~10 8 , 10 3 ~10 7 , or 10 4 ~10 6 The static mixer element may be configured to operate in a Pe range between any two of the above upper and / or lower limits.

[0114] The volumetric displacement % of the static mixer electrode relative to the flow path containing the electrode may be in the range of about 1-90, 5-70, 10-30, or 5-20. The volumetric displacement % of the static mixer electrode relative to the flow path containing the electrode may be less than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5%. The volumetric displacement % of the static mixer electrode relative to the flow path containing the electrode may be greater than 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, or 80%. The volumetric displacement % may be provided in any two of the ranges of "less than" and "greater than" values ​​above.

[0115] The static mixer electrode configuration may provide for improved heat and mass transfer characteristics within the reactor, such as reducing the temperature difference at the exit cross section. The static mixer electrode heat and mass transfer may provide, for example, a cross-sectional or transverse temperature profile having a temperature difference of less than about 20° C. / mm, 15° C. / mm, 10° C. / mm, 9° C. / mm, 8° C. / mm, 7° C. / mm, 6° C. / mm, 5° C. / mm, 4° C. / mm, 3° C. / mm, 2° C. / mm, or 1° C. / mm.

[0116] The static mixer electrode or scaffold thereof may be configured such that, in use, the pressure drop (i.e., pressure differential or back pressure) across the static mixer electrode (in Pa / m) is in the range of about 0.1 to 1,000,000 Pa / m (i.e., 1 MPa / m), including any value or range of values ​​therebetween. For example, the pressure drop across the static mixer electrode (in Pa / m) may 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 across the static mixer electrode may be at least about 10, 100, 1000, 5,000, 10,000, 50,000, 100,000, or 250,000 (in Pa / m). The pressure drop across the static mixer electrode (in Pa / m) may be provided in any two of the upper and / or lower limits listed above. For example, in one embodiment, the pressure drop across the static mixer electrode may be in the range of about 10 to 250,000, 100 to 100,000, or 1,000 to 50,000 (in Pa / m). The static mixer electrode may be configured to provide a lower pressure drop for a particular flow rate. In this regard, the static mixer electrodes, reactors, systems, and processes described herein may be provided with parameters suitable for industrial applications. The above pressure drops can 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.

[0117] In one embodiment, the static mixer electrodes 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 can 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 can be within the range provided by any two of these upper and / or lower limits, for example, within a range of about 50-400, 10-200, or 20-200.

[0118] The static mixer electrode may be configured as a modular insert of a continuous flow electrochemical reactor or its chamber. The static mixer electrode may be configured for use with an in-line continuous flow electrochemical reactor or its chamber. The in-line continuous flow electrochemical reactor may be a recycle loop reactor or a single pass reactor.

[0119] The configuration of the static mixer electrodes can be determined using computational fluid dynamics (CFD) software, and the reactant mixing configuration can be improved using the CFD software to improve contact and activation of the reactants at the surfaces of the static mixer electrodes.

[0120] The static mixer electrode may be an additively manufactured static mixer electrode. Additive manufacturing of the static mixer electrode, optionally with a catalytic and / or corrosion resistant coating, may provide a static mixer electrode configured for efficient mixing, heat and mass transfer, electrochemical reactions, or further catalytic reactions. The additive manufacturing process allows for physically testing the reliability and performance of the static mixer electrode, and optionally, further redesigning and reconfiguring the static mixer electrode using additive manufacturing (e.g., 3D printing) techniques. Additive manufacturing provides flexibility in preliminary design and testing, and further redesigning and reconfiguring the static mixer electrode. An electron beam 3D printer or a laser beam 3D printer may be used. The additive material for 3D printing can be, for example, pure metals such as iron, cobalt, nickel, copper, zinc, or alloys such as titanium alloy-based powders (e.g., in the diameter range of 45-105 micrometers), cobalt chromium alloy-based powders (e.g., FSX-414 or Stellite S21), or stainless steel or aluminum silicon alloys, or any of the nickel-based alloys (e.g., Inconel, Hastelloy). The powder diameters associated with laser beam printers are typically smaller than those used in electron beam printers. Alternatively, the scaffold can be additively manufactured from an inert material such as plastic or glass, and then coated with a suitable conductive material. In addition to the conductive surface, the static mixer electrode or its scaffold can optionally further include a catalytic material, depending on the particular reaction or application desired.

[0121] Counter electrode It will be appreciated that the counter electrode is electrically conductive. The counter electrode may act as an anode or a cathode depending on the direction of the applied current. The counter electrode may be made of materials or may be configured according to any of the embodiments or examples previously described with respect to the static mixer electrodes.

[0122] It will be appreciated that the counter electrode may comprise a conductive surface. The counter electrode may be configured to deliver 1 μA m -2 ~about 1000A m -2The counter electrode may be made of a material capable of providing a current density in the range of 0.1 to 1.0 V. The counter electrode may comprise a conductive material, such as a conductive carbon material, such as graphite, glassy carbon, or boron-doped diamond, a metal, alloy, or intermetallic compound, a semi-metal, or a doped or low band gap semiconductor, metal-coated particles, a conductive ceramic, in powder, sheet, rod, or billet form. The counter electrode may be made of a non-conductive material and coated with a conductor. The non-conductive material may be a particulate non-conductor, such as a plastic, ceramic, glass, or mineral, a thermoset, a thermoplastic, and a natural product, such as rubber and wood. The conductive coating may be formed of a metal, a metal alloy, an intermetallic compound, a conductive compound, or any of the conductive materials previously described with respect to the counter electrode or static mixer electrode.

[0123] Reactor and End Cap Configuration The reactor may be provided as an assembly including a reactor housing, a first electrode, a second electrode, a separator, and one or two optional end caps. The end caps may be configured to seal the reactor housing and, optionally, to couple with one or more of the first electrode, the second electrode, and the separator to aid in the structure and arrangement of the assembly and operation of the reactor.

[0124] In one embodiment, the tubular reactor may include a first end cap and a second end cap, each of which is cooperatively configured to secure opposite ends of the reactor housing and support the placement of the static mixer electrode, the counter electrode, and the separator within the reactor.

[0125] 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 fabricated as part of one of the electrodes), or the end cap may be provided as an integral part of the electrochemical flow cell or continuous flow electrochemical tubular reactor (e.g., the entire electrochemical flow cell is fabricated by additive manufacturing).

[0126] The end caps may be provided according to any other embodiment or example thereof described herein.

[0127] Electrochemical Flow System A system for providing a continuous flow electrochemical reaction may comprise an electrochemical flow cell or an electrochemical tubular reactor according to any one or more aspects, embodiments, or examples described herein.

[0128] The system may further comprise a pump to provide fluid flow of one or more fluid reactants and any products thereof through the reactor. The system may further comprise an electric unit to provide and control the voltage applied to or current flowing through the electrodes to drive the electrochemical reaction at the interface between the fluid stream and the electrodes. The system may further comprise a controller to control one or more parameters of the system selected from the concentration, flow rate, temperature, pressure, and residence time of the one or more fluid reactants or their sources or their products.

[0129] The reactor system may comprise one flow cell assembly, or multiple assemblies set up in parallel or series. The polarity of the electrodes in each setup may be connected in the same way in each cell, or in an alternating way where the outer electrodes are alternately anode, cathode, anode, cathode, ... (or vice versa) and the inner electrodes are alternately 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 varied, and the pump speeds through the cells in the system may be the same or varied.

[0130] The reactor system can be constructed and controlled to accept a time-varying power input, for example from a renewable energy source, for example, the flow rate of reactants can vary depending on the power available for electrolysis, so that the flow reactor continues to operate even when the power source fluctuates.

[0131] The aspect ratio of the reactor can be, for example, similar to the aspect ratios described above with respect to the static mixer electrodes, such that the static mixer electrode module can be configured to be inserted into the reactor.

[0132] The reactor may include any heat exchanger for controlling the temperature of the reactor, chamber section, static mixer, or fluid components thereof. The heat exchanger may be of shell-and-tube heat exchanger design or configuration.

[0133] The present disclosure 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 of the embodiments or examples described herein; a pump for providing a fluid flow of one or more fluid reactants and any products thereof through the reactor; a control means for controlling one or more of the parameters of the system selected from reactant concentration, flow rate, current flow, applied voltage, pressure, and residence time; Equipped with.

[0134] The system may include an optional heat exchanger for controlling the temperature of the reactor or its fluid components.

[0135] The system may further include a spectrometer, which may be used to identify and determine the concentration of any one or more of the fluid reactants or their products.

[0136] One or more of the reactors, reactor chambers, chamber sections, and static mixer electrodes may each be provided in a modular form for complementary coupling thereof. The system may include multiple reactors that may be of similar or different internal and / or external configurations. The reactors may be operated in series or parallel, or a combination of both. It will be appreciated that the system, reactors, or each chamber section may include one or more inlets and outlets for providing a supply of reactants to obtain products, or for recirculating various reactants and / or products.

[0137] It will also be appreciated that the reactor or system may be designed to recycle various reactants, reactant sources, intermediate products, or desired products provided to and produced in the chamber sections. The reactor or system may be provided in a variety of designs and configurations, for example, in the form of a tubular reactor. In another embodiment, the reactor is a single pass reactor.

[0138] The systems and processes may also be integrated into more complex systems, such as systems and processes including coal gasifiers, water purification and reticulation, electrolyzers and / or natural gas reformers, chemical synthesis and purification, and the like.

[0139] Electrochemical Applications The electrochemical flow reactor, electrochemical flow cell, or continuous flow electrochemical tubular reactor according to any embodiment or example described herein may be used in a variety of applications including metal recovery, heavy and precious metal recovery from wastewater and mine drainage, wastewater treatment, water disinfection or purification (e.g., drinking water), and metal recovery from solid waste (e.g., sludge, tailings, and waste products), and electrosynthesis of various products (e.g., gas generation, energy storage and conversion, reagent regeneration, and polymerization).

[0140] The reactor with static mixer electrodes may be for use 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 process or a single pass process. In one embodiment, the in-line continuous flow process is a single pass process.

[0141] As described above, electrochemical reactors with static mixer electrodes are capable of carrying out reactions continuously. Electrochemical reactors may use single-phase or multi-phase feed and product streams. In one embodiment, the substrate feed (including one or more reactants) may be provided as a continuous fluid stream, for example, a) as a liquid stream containing the substrate as a solute in a suitable solvent, or b) as a liquid stream containing the solution substrate with or without a co-solvent. It will be understood that the fluid stream may be provided by one or more gas streams or sources thereof, such as hydrogen gas. The substrate feed is injected into the reactor using a pressure-driven flow, for example by a pump. In another embodiment, the substrate feed may be provided in solids suspended within the fluid stream, and in yet another embodiment, the reactant fluid stream may include solids, liquids, and gases.

[0142] In one embodiment, there is provided a method for electrochemical processing of a fluid stream comprising an electrochemical flow cell or a continuous-flow electrochemical tubular reactor according to any embodiment or example thereof described herein.

[0143] The method may be for removing 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 metals and / or metal compounds on a surface of the static mixer electrode. The method may be for recovering metals from a fluid stream obtained from mine tailings. The method may include operating in parallel and / or series as described above with respect to the reactor system. In one embodiment, the method is performed in series.

[0144] In one embodiment, the method includes at least a first continuous flow electrochemical tubular reactor and a second continuous flow electrochemical tubular reactor, each reactor configured such that a permeable membrane separates a static mixer electrode from a counter electrode and defines an inner coaxial flow passage containing one electrode and an outer concentric flow passage containing the other electrode, each flow passage having at least one inlet and at least one outlet. The method may allow for loading metal onto the static mixer electrode of the first tubular reactor while simultaneously providing a second reactor in series of opposite electrode polarity to remove metal previously loaded onto the static mixer electrode of the second tubular reactor.

[0145] In a further embodiment of this above method, a first fluid stream may be introduced into the inner coaxial passage of the first tubular reactor and its outlet into the outer concentric passage of the second tubular reactor. A second fluid stream may be simultaneously introduced into the outer concentric passage of the first tubular reactor and its outlet into the inner coaxial passage of the second tubular reactor. The first tubular reactor may be operated to bring the first static mixer electrode to a reducing state to accumulate solid metal species, and the second tubular reactor may be operated to bring the second static mixer electrode to an oxidizing state to remove any metal species present on the surface.

[0146] Another advantage of the electrochemical flow reactor and its system according to various embodiments or examples described herein is that the electrochemical flow cell or tubular reactor does not require disassembly to replace the cathode and provides the flexibility to operate in series or reverse mode by switching the current and switching in different fluid flows to remove metals, metal compounds, and other metal-containing products formed on the static mixer electrode, which is the cathode of the reduction reaction.

[0147] The present disclosure also provides a process for synthesizing a product by reaction of one or more fluid reactants, the process comprising: Providing a continuous flow electrochemical reactor comprising a static mixer electrode or system according to any of the embodiments or examples described herein; providing at least a first fluid reactant to the reactor via a reactant inlet; operating the reactor or its control means to effect flow and reaction of at least a first fluid stream reactant through the static mixer electrode; obtaining an effluent stream comprising a product of the reaction of at least a first reactant; The steps include:

[0148] It will be appreciated that the various parameters and conditions used in the process, such as current flow, pressure, and concentrations / amounts of materials and reactants, may be selected depending on the range of process variations, including the products to be synthesized, the electrochemical reactions or mechanisms involved, the reactant sources, or the type of reactor used, and its materials and configuration. Differences exist, for example, when one or more of the fluid reactants or co-solvents (e.g., inert carriers), etc., are gases, liquids, solids, or combinations thereof.

[0149] The electrochemical flow reactor was designed to operate at 1 μA m -2 ~about 1000A m -2 The current density can be, for example, 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 (A m -2 The current density can be, for example, less 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 (A m -2 The current density may be provided in any range between two values ​​selected from any of the above values. It will be appreciated that different applications and configurations may apply different current densities.

[0150] In some embodiments, the voltage applied across the electrodes can 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 can 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 can be within a range provided by any two of these upper and / or lower limits.

[0151] In one embodiment, the operational performance of an electrochemical flow reactor can be measured by its recovery efficiency. Recovery efficiency includes the amount of particulate species (e.g., contaminants), such as dissolved metal species, present in the fluid that can be removed from the fluid by the electrochemical flow cell. In one embodiment, the recovery efficiency, measured in % of contaminants 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 of the recovery efficiencies can be provided by continuous operation (e.g., recirculation in a recycle loop reactor) for a period of less than about 48 hours, 36 hours, 24 hours, 12 hours, 6 hours, 3 hours, 2 hours, or 1 hour. In another example, a particle species (e.g., a contaminant), such as a dissolved metal species (e.g., a copper species), may be removed from a fluid if the particle species is present in the fluid at a concentration less than about 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, 0.0001, 0.00005, or 0.00001 (in mol / L). In another example, a particle species (e.g., a contaminant), such as a dissolved metal species, may be removed from a fluid if the particle species is present in the fluid at a concentration greater than 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, or 0.5 (in mol / L). Particle species may be removed at concentrations between any two of these upper and / or lower ranges. The above recovery efficiencies and / or recirculation periods may apply to any of these particle species (e.g., contaminant) concentrations. For example, the operational performance of the reactor, system, or method may 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 a 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 a 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 the dissolved metal species from a fluid having an initial concentration of less than about 0.0005 mol / L.In another embodiment, from fluids having an initial concentration of less than about 0.0001 mol / L, recovery efficiency can be at least about 90% of the dissolved metal species.

[0152] In another example, a particle species (e.g., a contaminant), such as a dissolved metal species (e.g., a copper species), may be removed from a fluid if the particle species is present in the fluid at an initial concentration of about 1000, 750, 500, 250, 100, 75, 50, 25, 10, 5, or 1 (in ppm) or less. In another example, a particle species (e.g., a contaminant), such as a dissolved metal species, may be removed from a fluid if the particle species is present in the fluid at an initial concentration of about 5, 10, 25, 50, 75, 100, 250, 500, 750, or 1000 (in ppm) or more. A particle species may be removed at an initial concentration in the fluid between any two of these upper and / or lower ranges. In one embodiment, the recovery efficiency, measured in percent of contaminants 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 of the recovery efficiencies may be provided by continuous operation (e.g., recirculation in a recycle loop reactor) for a period of less than about 48 hours, 36 hours, 24 hours, 12 hours, 6 hours, 3 hours, 2 hours, or 1 hour. The above recovery efficiencies and / or recirculation periods may apply to any of these particle species (e.g., contaminant) concentrations. For example, the operational performance of the reactor, system, or method may provide at least about 50% recovery efficiency of dissolved metal species from a fluid having an initial concentration of about 100 ppm of dissolved metal species during less than about 3 hours of continuous operation. In another example, recovery efficiency can be at least about 95% of the dissolved metal species from a fluid having an initial concentration of about 100 ppm during continuous operation for less than about 24 hours.

[0153] The temperature (°C) associated with the process can be in the range of -50 to 400, or any integer or range of integers therebetween. For example, the temperature (°C) can be at least -50, -25, 0, 25, 50, 75, 100, 150, 200, 250, 300, or 350. For example, the temperature (°C) can be less than about 350, 300, 250, 200, 150, 100, or 50. The temperature can also be provided at about any of these values, or in any range of these values, such as in the range of about 0 to 250°C, about 25 to 200°C, or about 50 to 150°C.

[0154] In one embodiment, the process is 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, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200 The process may be operated to provide a Re of 0, 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 in a Re range of about 0.1-2000, 1-1000, 10-800, or 20-500. The process may be operated in a Re range of about 1000-15000, 1500-10000, 2000-8000, or 2500-6000. The process may be operated in a Re range provided by any two of the "at least" values ​​above.

[0155] In one embodiment, the process is performed at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 500000, 10 6 , or 10 7 The process can operate at Peclet (Pe) values ​​of about 10 8 , 10 7 , 10 6, 500000, 250000, 100000, 75000, 50000, 25000, 20000, 15000, 10000, 5000, 2000, or 1000 Peclet (Pe) values. 3 ~10 8 , 10 3 ~10 7 , or 10 4 ~10 6 The process may operate in a Pe range between any two of the upper and / or lower limits listed above.

[0156] Depending on the process, the pressure drop (i.e., back pressure) (in Pa / m) across the static mixer electrodes can be in the range of about 0.1 to 1,000,000 Pa / m (i.e., 1 MPa / m), including any value or range of values ​​therebetween. For example, the pressure drop (in Pa / m) across the static mixer electrodes 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 across the static mixer electrodes can be at least about 10, 100, 1000, 5,000, 10,000, 50,000, 100,000, or 250,000 (in Pa / m). The pressure drop across the static mixer electrodes (in Pa / m) can be provided within any two of the upper and / or lower limits listed above. For example, in one embodiment, the pressure drop across the static mixer electrode may be in the range of about 10 to 250,000, 100 to 100,000, or 1,000 to 50,000 (in Pa / m). In this regard, the static mixer electrodes, reactors, systems, and processes described herein may be provided with parameters suitable for industrial applications. The above pressure drops or ranges thereof may be provided 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, 100, 500, 1000 ml / min.

[0157] In one embodiment, volumetric flow rates can 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, volumetric flow rates can be provided at 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 can be within the range provided by any two of these upper and / or lower limits, for example, within a range of about 50-400, 10-200, or 20-200.

[0158] The process may involve an average residence time in a static mixer or reactor ranging from 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 in a range selected from any two of these above 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.

[0159] The process may provide a faradaic efficiency (% charge passed that participates in the reaction of interest) of 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 may provide a faradaic efficiency (% charge passed that participates in the reaction of interest) of 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 may provide a faradaic efficiency (% charge passed that participates in the reaction of interest) in a range provided by any two of the upper and / or lower limits above.

[0160] The anolyte and / or catholyte streams may contain any suitable solvent, electroactive species, and supporting electrolyte. The concentration of dissolved particle species may vary from parts per billion to the solubility limit of the particle species (tens of moles per liter). In addition to dissolved particle species, the fluid stream may also contain multiple phases in any combination of undissolved solids (e.g., solids suspended within the fluid stream), immiscible liquids, and undissolved gases. Thus, the fluid stream may contain aqueous or non-aqueous solvents, molecular solvents, molten salts, ionic liquids, supercritical solvents, or mixtures thereof. The dissolved particle species may be ions, molecules, or substantially ion-pairs within the liquid. They may be dissolved solids, gases, miscible liquids, or mixtures thereof. Other phases present may be suspended solids or gels, organic or inorganic polymers, natural products, or mixtures thereof. These may be gases or vapors intentionally introduced or generated by the action of the flow and / or electrochemical activity. In another example, the fluid is a liquid or a complex liquid, such as a liquid that contains dissolved and / or suspended solids.

[0161] In one embodiment, a method of removing particle species from a fluid stream may be provided that includes an electrochemical flow cell, or a system thereof, according to any aspect, embodiment, or example thereof described herein. The particle species may be a metal species dissolved in the fluid stream. It will be understood that any of the above embodiments or examples relating to the performance of an electrochemical flow cell may be applied to this embodiment. EXAMPLES

[0162] The present disclosure is further illustrated by the following examples. It should be understood that the following descriptions are merely for the purpose of illustrating certain embodiments, and are not intended to be limiting with respect to the above descriptions.

[0163] Experimental Example 1 An electrochemical flow reactor was prepared, which included a separator 200 (FIG. 2), as well as liquid supply lines containing peristaltic pump(s) 120 (Masterflex L / S variable speed drive with remote I / O, 600 rpm) that controlled the electrolyte flow into the cell, and a power supply 110 (Autolab 302N potentiostat, Metrohm Autolab BV, Utrecht, The Netherlands) that controlled the applied electrochemical potential / current flowing through the cell.

[0164] An additively manufactured metal static mixer electrode (SME) 104, 204 as the working electrode was closely mounted within a tubular porous polymer separator 202 (GenPore Reading, USA) in a separation mode configuration that defines the working compartment. To connect the fluid flow, two ports at either end of the electrode are built into the structure. Through these tubes, the fluids enter the working compartment. As in all static mixers, the driving force of the solution flows through the multiple angled faces of the mixer surface, causing mixing. An inert tubular counter electrode 102 made of glassy carbon in this particular experiment surrounded the working zone at a short distance from the separator, creating a low volume counter electrode compartment and forming the outer housing of the cell. The whole assembly is sealed using two end caps 500 (Figures 4a, 4b, and 4c). Ports 144 machined into the end caps provide fluid flow within the counter electrode compartment. This configuration allows the use of different fluids in the two zones if required by the experiment.

[0165] The working efficiency of the cell can be evaluated by comparing the limiting currents measured at various flow rates with rotating disk electrode (RDE) results for the same solutions. These comparisons are a useful indication of performance and are not used to draw any conclusions about the hydrodynamic conditions at the static mixer surface.

[0166] To evaluate the performance of the two configurations of our electrochemical flow reactor, a platinum-coated static mixer electrode (i.e., working electrode) and a glassy carbon tube (i.e., anode) were used to measure the electrochemical reaction of ferricyanide ([Fe(CN)6]6) in 0.5 M potassium chloride as the supporting electrolyte. 3+ ) solution (10 -3 ~10 -1 A series of experiments was carried out to investigate the electrochemical reduction of M. A typical reduction reaction in a separate reactor configuration was carried out as follows:

[0167] Chronoamperometric measurements were performed with potential steps of −1.4 V, −1.6 V, −1.8 V, and −2 V applied to the cell for 100 s, with the cell in quiescent mode (i.e., 0 mL min−1) for the first 50 s. -1 ) and then at a constant flow rate of 10 to 400 mL min-1 for the last 50 s (Figures 7 to 9). Steady-state currents were observed at all flow rates, and by increasing the flow rate, the recorded current increased at all potential steps. The recorded current increased with increasing potential, although some air bubbles were observed in the solution exiting the flow cell when -1.8 V and -2 V were applied. At these higher potentials in this experimental setup, [Fe(CN)6] 3+ In addition to the reduction of H2O, hydrogen evolution occurs at the cathode, which can complicate the analysis.

[0168] Experimental results indicate that at low concentrations of electroactive ions (i.e., 0.001 and 0.01 M [Fe(CN)6]) the reaction is mass-transfer limited. 3+ ), the electrochemical flow cell configuration has been shown to significantly enhance the reaction rate. At high concentrations (i.e., 0.1M [Fe(CN)6]) where the reaction is controlled by mass transport and kinetic factors (mixing control), 3+ ) the reaction rate is 1.5 to 3.7 times faster when a static mixer electrode is used, and the improvement in reaction rate is small.

[0169] Experimental Example 2 10-100ppm Cu in 0.01M H2SO4 2+The efficiency of the electrochemical flow cell in removing copper ions from an acidic contaminated solution containing 10 to 1000 mL min 2 was measured using a stainless steel static mixer electrode (i.e., working electrode) and a glassy carbon tube (i.e., anode) in a separate configuration embodiment of the electrochemical flow cell. -1 As shown in Figure 10, flow rates ranging from 50 mL min -1 Increasing the flow rate beyond 100% reduced the removal efficiency due to the reduced residence time of the electroactive ions on the surface of the working electrode to complete the reduction reaction (Figure 10a). On the other hand, increasing the flow rate increased the charge passing through the working electrode and the current recovery increased accordingly (Figure 10b). However, increasing the flow rate is efficient up to the point where the efficiency decreases due to the reduced residence time of the electroactive ions on the electrode surface.

[0170] Experimental Example 3 A comprehensive electrolysis experiment was also carried out to demonstrate how effectively the electrochemical flow cell can remove copper ions from a volume of contaminated aqueous solution. A 2-liter solution of copper-contaminated aqueous solution (i.e., 100 ppm CuSO4.4H2O in 0.01 M H2SO4) was electrolyzed at 50 mL min for 24 h using the electrochemical flow cell. -1 The optical images and SEM / EDS results confirmed the deposition of copper ions on the static mixer working electrode (Figure 11), and the ICP-MS results showed that a 99.7% copper concentration reduction was achieved in 24 h in the separation structure of the electrochemical flow cell (Figure 12).

Claims

1. A reaction chamber; A first electrode; A second electrode; and a separator disposed between the first electrode and the second electrode, the separator at least partially defines a first channel in the reaction chamber configured to receive a first fluid stream in contact with the first electrode and a second channel in the reaction chamber configured to receive a second fluid stream in contact with the second electrode; the separator comprises a permeable membrane that allows electrical communication between the first electrode and the second electrode via the fluid streams while simultaneously limiting fluid exchange between the fluid streams; the first electrode being a static mixer electrode comprising an electrically conductive monolithic framework provided by a lattice of interconnected segments defining a plurality of dividing structures that divide the first fluid stream into a plurality of substreams at a plurality of dividing locations along a length of the first electrode; the electrochemical flow cell is a continuous flow tubular reactor; the separator and the second electrode are disposed concentrically and coaxially about a central longitudinal axis of the first electrode; Electrochemical flow cell.

2. The electrochemical flow cell of claim 1 , wherein the static mixer electrode has a conductive coating.

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

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

5. The electrochemical flow cell of any one of claims 1 to 4, wherein the separator and the second electrode are substantially cylindrical.

6. 6. The electrochemical flow cell of claim 1, wherein the second electrode forms at least a part of a wall of the reaction chamber.

7. An electrochemical flow cell as described in any one of claims 1 to 6, wherein the first electrode having a static mixer portion is configured to operate to provide a volumetric flow rate of the first fluid stream in the first channel of at least 0.1 ml / min.

8. An electrochemical flow system comprising at least a first electrochemical flow cell according to any one of claims 1 to 7.

9. A first electrochemical flow cell according to any one of claims 1 to 7; A second electrochemical flow cell according to any one of claims 1 to 7; a plurality of flow lines connecting 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; An electrochemical flow system comprising:

10. a pump for providing a fluid flow of said fluid stream; a power source for controlling the current through the electrodes or the voltage applied to the electrodes; a controller for controlling one or more parameters of the system, including concentration, flow rate, temperature, pressure, and residence time; 10. The electrochemical flow system of claim 8 or 9, further comprising:

11. A method for electrochemical processing of a fluid stream comprising an electrochemical flow cell according to any one of claims 1 to 7 or a system according to any one of claims 8 to 10.

12. The method of claim 11 , wherein the first fluid stream and the second fluid stream comprise a liquid.

13. 13. The method of claim 11 or 12 for wastewater treatment, removal of dissolved metal ions from a fluid stream, or recovery of metals from a fluid stream.

14. The method according to any one of claims 11 to 13, 200m －１ 2. Improving chaotic advection by splitting the first fluid flow more, －１ corresponds to the number of times the first fluid stream splits within a given length along the static mixer portion of the first electrode; providing a Peclet (Pe) number of at least 10,000; providing a volumetric flow rate of said first fluid stream of at least 0.1 ml / min; the first fluid stream comprising a concentration of dissolved metal species less than 0.01 (mol / L); providing a recovery efficiency of contaminants or metal species in the first fluid stream of at least 90% of the contaminants or metal species initially present in the first fluid stream; and 1 μAm for the static mixer electrode and counter electrode －２ ~1000Am －２ To provide a current density in the range of wherein the electrochemical flow cell operates to provide one or more of:

15. The method according to any one of claims 11 to 14, The method includes operating a first electrochemical flow cell and a second electrochemical flow cell according to any one of claims 1 to 7, 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.

16. A method for the electrochemical synthesis of a product comprising an electrochemical flow cell according to any one of claims 1 to 7 or a system according to any one of claims 8 to 10.

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