Electrochemical Flow Reactor

Abstract

The present invention relates to electrochemical flow reactors, such as continuous flow electrochemical tubular reactors. The present invention also relates to processes, systems and methods comprising electrochemical flow reactors. An electrochemical flow cell may include a reaction chamber, a first static mixer electrode, a second pair of electrodes and a diaphragm disposed between the first electrode and the second electrode.

Description

Technical Field

[0001] The present invention relates to electrochemical flow reactors, such as continuous flow electrochemical tubular reactors. The present invention also relates to processes, systems and methods involving electrochemical flow reactors. Background Art

[0002] Continuous flow reactors typically comprise a reaction chamber into which reactant fluids are continuously fed to undergo a chemical reaction to form a product that is provided as a continuous output flow from the reaction chamber. The reaction chamber is typically immersed in a heating / coolant fluid, such as in a shell and tube heat exchanger configuration, to facilitate heat transfer to / from the reaction.

[0003] Continuous flow reactors may use packed bed reaction chambers, where the reaction chambers are filled with solid catalyst particles that provide a catalytic surface on which chemical reactions can occur. Static mixers may be used for premixing of fluids 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 reactor tubes. Static mixers comprise solid structures that interrupt the flow of fluids to promote mixing of reactants prior to reaction in the packed bed reaction chambers and to promote desired heat and mass transfer patterns downstream of these chambers.

[0004] Electrochemical flow reactors have been used to treat fluid streams to remove dissolved metals by electrodeposition of dissolved metal ions to form solid metal products on the surfaces of electrodes housed in the electrochemical flow reactor. Electrochemical flow reactors for water treatment have involved low flow systems with high surface area electrodes for high efficiency and controlled removal of dissolved metals from aqueous fluid streams having dilute / low concentrations of dissolved metal ions. Electrochemical flow reactors have also been used for the electrosynthesis of various products, particularly for forming reactants or intermediates.

[0005] There is a need for alternative or improved electrochemical flow reactors that provide efficient mixing, high mass transfer and / or multi-purpose operation for industrial applications.

[0006] It should be appreciated that the reference to any prior art publications herein does not constitute an admission that any of those documents forms part of the common general knowledge in the art, in Australia or any other country. Summary of the invention

[0007] The inventors have studied and developed alternative electrochemical flow reactors and have recognized that static mixers can be configured to operate as electrodes within an electrochemical flow reactor to achieve effective mixing, high mass transfer and / or multi-purpose operation for industrial applications. The electrochemical flow reactor can include a static mixer electrode separated from a counter electrode by a permeable membrane. The static mixer electrode can be configured to provide effective performance while enhancing mass transfer and chaotic advection. The static mixer electrode can be an electrode that includes a static mixer portion.

[0008] In one aspect, there is provided an electrochemical flow cell comprising:

[0009] Reaction chamber;

[0010] a first electrode;

[0011] a second electrode; and

[0012] a separator disposed between the first electrode and the second electrode, the separator at least partially defining a first channel within the reaction chamber and a second channel within the reaction chamber, the first channel being configured to receive a first fluid flow in contact with the first electrode, the second channel being configured to receive a second fluid flow in contact with the second electrode,

[0013] wherein the separator comprises a permeable membrane that allows ionic communication between the first electrode and the second electrode via the fluid stream while restricting fluid exchange between the fluid streams, and

[0014] Wherein, the first electrode includes a static mixer portion, the static mixer portion defining a plurality of flow splitting structures, the plurality of flow splitting structures splitting the first fluid flow into a plurality of sub-flows at a plurality of locations along the length of the first electrode.

[0015] In one embodiment, the electrochemical flow cell is a continuous flow tubular reactor.

[0016] In one embodiment, the diameter of the static mixer portion of the first electrode may be substantially equal to the diameter of the first channel. The first electrode may be arranged to contact the separator. The separator and the second electrode may be arranged to be concentric and coaxial with the central longitudinal axis of the first electrode. The separator and the second electrode may be substantially cylindrical. The second electrode may form at least a portion of a wall of the reaction chamber.

[0017] In one embodiment, a first electrode including a static mixer portion may be configured for enhancing mass transfer and chaotic advection by defining a plurality of flow splitting structures that split the fluid flow into a plurality of sub-flows at a plurality of locations along the length of the first electrode.

[0018] In one embodiment, adjacent splitting structures of the static mixer section may be arranged at different rotational angles about the central longitudinal axis of the static mixer section. The static mixer section may include a plurality of substantially similar structural modules arranged continuously along the length of the static mixer section. The first electrode comprising the static mixer section may be configured to split the first fluid flow by more than 200 m -1 The chaotic advection is enhanced by a factor corresponding to the number of times the first fluid flow is split within a given length of the static mixer portion along the first electrode.

[0019] In another embodiment, the first electrode comprising a static mixer portion is configured to operate at a Peclet (Pe) number of at least about 10,000. The first electrode comprising a static mixer portion may be configured to operate at a pressure drop (in Pa / m) of between about 100 and 100,000 across the first electrode. The first electrode comprising a static mixer portion may be configured to operate within the first channel to provide a volumetric flow rate of at least about 0.1 ml / min for the first fluid stream.

[0020] In another aspect, an electrochemical flow system is provided, comprising at least one first electrochemical flow cell according to any aspect, embodiment or example of an electrochemical flow cell as described herein.

[0021] In one embodiment, the electrochemical flow system comprises first and second electrochemical flow cells according to any aspect, embodiment or example of the electrochemical flow cells described herein. A plurality of flow lines may be provided to connect the first electrochemical flow cell to the second electrochemical flow cell such that the first channel of the first electrochemical flow cell is in fluid communication with the second channel of the second electrochemical flow cell, and the second channel of the first electrochemical flow cell is in fluid communication with the first channel of the second electrochemical flow cell.

[0022] In one embodiment, the electrochemical flow system further comprises:

[0023] a pump for providing fluid flow of the fluid stream;

[0024] a power source for controlling the current through the electrodes or the voltage applied to the electrodes;

[0025] A controller is used to control one or more parameters of the system, the one or more parameters comprising concentration, flow rate, temperature, pressure and residence time.

[0026] In another aspect, a method for electrochemical treatment of a fluid stream is provided, the method comprising an electrochemical flow cell according to any aspect, embodiment or example of an electrochemical flow cell, reactor or system thereof as described herein. The method can be used to treat wastewater, remove dissolved metal ions from a fluid stream, or recover metals from a fluid stream.

[0027] In one embodiment of the method, the electrochemical flow cell comprises a first electrode, the first electrode comprises a static mixer portion, the electrochemical flow cell is operable to provide at least one of:

[0028] Splitting the first fluid stream over 200 m -1 to enhance chaotic advection corresponding to the number of times the first fluid flow is split within a given length of the static mixer portion along the first electrode;

[0029] A Peclet (Pe) number of at least about 10,000;

[0030] a voltage drop of about 100 to 100,000 (in Pa / m) across the first electrode;

[0031] a volumetric flow rate of the first fluid stream of at least about 0.1 ml / min;

[0032] About 1μA·m -2 About 1000A·m -2 The current density on the first and second electrodes.

[0033] The method may include operation of first and second electrochemical flow cells according to any aspect, embodiment, or example of electrochemical flow cells as 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 the second channel of the first electrochemical flow cell is in fluid communication with the first channel of the second electrochemical flow cell.

[0034] In another aspect, a method for electrochemical synthesis of a product is provided, comprising an electrochemical flow cell according to any aspect, embodiment, or example of an electrochemical flow cell, reactor, or system thereof described herein.

[0035] In another aspect, a method for removing a substance from a fluid stream is provided, comprising an electrochemical flow cell, a reactor, or a system thereof according to any aspect, embodiment, or example described herein. The substance may be a metallic substance dissolved in the fluid stream.

[0036] It should be understood that other aspects, embodiments, and examples of electrochemical flow cells, reactors, or systems are described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Preferred embodiments of the present invention are further described and illustrated below, by way of example only, with reference to the accompanying drawings, in which:

[0038] Figure 1 shows a schematic diagram of an electrochemical flow cell according to some embodiments;

[0039] Figure 2 shows a schematic diagram of an electrochemical flow cell with a separator according to some embodiments;

[0040] Figure 3A shows a perspective view of a static mixer electrode according to some embodiments;

[0041] Figure 3B Shown (isolated) Figure 3A A perspective view of a static mixer portion of a static mixer electrode;

[0042] Figure 3C Shown (isolated) Figure 3A a cross-sectional view of a static mixer portion of a static mixer electrode;

[0043] Figure 3D Shown (isolated) Figure 3A a side view of a static mixer portion of a static mixer electrode;

[0044] Figure 4A shows a perspective view of an electrochemical flow cell according to some embodiments;

[0045] Figure 4B Shows Figure 4A A perspective view of a flow battery in an exploded configuration;

[0046] Figure 4C Shows Figure 4A A cross-sectional view of a flow battery;

[0047] Figure 5 Shows Figure 4A A perspective view of an end cap of a flow battery;

[0048] Figure 6 shows a schematic diagram of an electrochemical flow system comprising two electrochemical flow cells according to some embodiments;

[0049] Figure 7Shown are the chronoamperometric responses over 100 s at constant potentials of (a) -1.4 V, (b) -1.6 V, (c) -1.8 V, and (d) -2 V (0.001 M K3[Fe(CN)6]) with 50 s intervals in static mode and 50 s intervals at constant flow rates from 10 to 400 mL min-1;

[0050] Figure 8 The chronoamperometric responses over 100 s at constant potentials of (a) -1.4 V, (b) -1.6 V, (c) -1.8 V, and (d) -2 V (0.01 M K3[Fe(CN)6]) are shown, with intervals of 50 s in static mode and 50 s at constant flow rates from 10 to 400 mL min-1;

[0051] Fig. 9 Shown are the chronoamperometric responses over 100 s at constant potentials of (a) -1.4 V, (b) -1.6 V, (c) -1.8 V, and (d) -2 V (0.1 M K3[Fe(CN)6]) with intervals of 50 s in static mode and 50 s at constant flow rates from 10 to 400 mL min-1;

[0052] Fig.10 The results show that the Cu 2+ Electrochemical flow cell efficiency for removal of copper ions from 0.01 M sulfuric acid solution at 40 °C;

[0053] Fig.11 Shows (a) optical images of the static mixer working electrode before and after treatment, (b) EDS analysis and (ce) SEM images of the static mixer electrode after 5 hours of electrolysis; and

[0054] Fig.12 Copper concentration versus time over 24 hours of operation according to a split configuration embodiment of an electrochemical flow cell is shown. DETAILED DESCRIPTION

[0055] The present invention describes the following various non-limiting embodiments, and it relates to research to identify the electrochemical flow reactor that can provide effective mixing, high mass transfer and / or multi-purpose operation for industrial applications. Surprisingly found that the electrode comprising the static mixer part can be configured in the electrochemical flow cell to realize effective mixing, high mass transfer and / or multi-purpose operation for industrial applications. It is also found that an effective electrochemical reactor can be provided, wherein the electrode comprising the static mixer part is configured to enhance mass transfer and chaotic advection. By configuring a separator between the electrode comprising the static mixer part and the counter electrode to provide each electrode in ion communication and a separate fluid channel, further surprising advantages about system operation and performance have been identified.

[0056] the term

[0057] Throughout the specification, references to a single step, composition of matter, group of steps, or group of compositions of matter are to be understood to include both one and a plurality (i.e., one or more) of those steps, compositions of matter, group of steps, or group of compositions of matter, unless specifically stated otherwise or the context requires otherwise. In addition, as used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to "a" includes a single as well as two or more; reference to "an" includes a single as well as two or more; reference to "the" includes a single as well as two or more, etc.

[0058] The term "and / or", such as "X and / or Y", means "X and Y" or "X or Y", and is to be construed as meaning both or either of these meanings.

[0059] As used herein, unless otherwise indicated, the term "about" generally means + / - 10%, eg, + / - 5%, of a specified value.

[0060] Throughout the specification, the word "comprise" or variations such as "comprises" or "comprising" will be understood to imply the inclusion of stated elements, integers or steps, or groups of elements, integers or steps, but not the exclusion of any other elements, integers or steps, or groups of elements, integers or steps.

[0061] Those skilled in the art will appreciate that the invention herein may be varied and modified in addition to the specific description. It should be understood that the present invention includes all such variations and modifications. The present invention also includes, individually or collectively, all steps, features, compositions and compounds mentioned or indicated in this specification, as well as any and all combinations or any two or more of the steps or features.

[0062] Unless otherwise specifically stated, each example of the present invention described herein will apply to each other example with necessary modifications. The scope of the present invention is not limited by the specific embodiments described herein, which are only used for illustrative purposes. As described herein, functionally equivalent products, compositions and methods are clearly within the scope of the present invention.

[0063] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those of ordinary skill in the art to which the invention belongs. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described below. In the event of a conflict, the definitions included in this specification shall prevail. In addition, the materials, methods and embodiments are illustrative only and not restrictive.

[0064] Electrochemical Flow Reactor

[0065] An electrochemical flow cell may be provided that includes: a reaction chamber; a first electrode that includes a static mixer portion; a second electrode; and a separator disposed between the first electrode and the second electrode.

[0066] The separator can at least partially limit a first channel in the reaction chamber to accommodate a first fluid flow in contact with the first electrode, and limit a second channel in the reaction chamber to accommodate a second fluid flow in contact with the second electrode. It should be understood that the separator allows ions to be communicated via fluid flow between the first and second electrodes. The separator can be a permeable membrane that limits the fluid exchange between the fluid flows. The static mixer portion can define a plurality of shunt structures that divide the fluid flow into a plurality of sub-streams at a plurality of positions along the length of the first electrode. It should be understood that the static mixer portion as a part of an electrode is conductive. Other embodiments and details of the electrochemical flow cell are described below.

[0067] refer to Figure 1 , the electrochemical flow cell 100 (separator not shown) comprises a reaction chamber 102 containing a first electrode 104 and a second electrode 106. The second electrode 106 may form at least a portion of a wall of the reaction chamber 102, such as Figure 1 As shown. The first electrode 104 may include a static mixer. The second electrode 106 may include a static mixer. The first and second electrodes 104, 106 may be arranged concentrically, one around the other, or arranged side by side.

[0068] The power source 110 can be connected to the first and second electrodes 104, 106 via respective first and second electrical conductors or cables 114, 116 to apply a potential difference or voltage across the electrodes 104, 106. In some embodiments, the first electrode 104 can function as an anode and the second electrode 106 can function as a cathode. In some embodiments, the first electrode 104 can function as a cathode and the second electrode 106 can function as an anode. In some embodiments, a negative potential can be applied to the first electrode 104 and a positive potential can be applied to the second electrode 106. In some embodiments, a positive potential can be applied to the first electrode 104 and a negative potential can be applied to the second electrode 106.

[0069] The first and second electrodes 104, 106 may be formed of a conductive material or may include a conductive surface coating. Further characteristics of the electrodes 104, 106 are described below according to various embodiments and examples.

[0070] The pump 120 may be arranged to flow a fluid into the reaction chamber 102 via the first fluid flow line 124 through a first inlet 134 in the reaction chamber 102, so that the fluid flows through or around the first electrode 104. The pump 120 may also be arranged to flow a fluid into the reaction chamber 102 via the second fluid flow line 126 through a second inlet 136 in the reaction chamber 102, so that the fluid flows between the first electrode 104 and the second electrode 106. The fluid may then flow out of the reaction chamber 102 via a first outlet 144 adjacent to the first electrode 104 and a second outlet 146 closer to the second electrode 106.

[0071] In some embodiments, the first and second flow lines 124, 126 can be supplied with fluid independently of the first pump 120 and the second pump 122, such as Figure 2 In some embodiments, first and second flow lines 124, 126 can provide different fluids to reaction chamber 102. For example, flow lines 124, 126 can include pipes or tubes.

[0072] Reference Figure 2 , according to some embodiments, an electrochemical flow cell 200 is provided (with a separator shown). The flow cell 200 is similar to the Figure 1 The flow battery 100 described above is similar to the flow battery 100 described above, and the same reference numerals are used for the same components. In addition to the components shown and described above in the flow battery 100, the flow battery 200 includes a separator 202. Figure 2 The separator in the illustrated embodiment at least partially separates a first fluid in, around, or near the first electrode 104 from a second fluid adjacent to the second electrode 106 between the first electrode 104 and the second electrode 106. The separator 202 can cooperate with the wall of the reaction chamber 102 to define a first channel 204 and a second channel 206. The first electrode 104 can be disposed in the first channel 204 and the second electrode 106 can be disposed in or form a wall of the second channel 206. The inlet 134, 136 and the outlet 144, 146 can be configured such that the first fluid flows through the first channel 204 and the second fluid flows through the second channel 206. In some embodiments, the ratio between the transverse cross-sectional areas of the first channel 204 and the second channel 206 can be, for example, in the range of 0.01 to 100, 0.1 to 10, 0.5 to 5, 0.3 to 1, 0.5 to 0.9, 0.5 to 1.5, or 0.8 to 1.2.

[0073] Separator 202 can allow charge to flow between electrodes 104, 106, but restricts most of the fluid from passing through separator 202. In some embodiments, separator 202 can allow ions between first and second electrodes 104, 106 to communicate. For example, ions can be allowed to flow from first channel 204 to channel fluid 206, or from second channel 206 to first channel 204, while other components of the fluid can be prevented or substantially restricted from passing through separator 202. In some embodiments, a small amount of fluid can pass through separator 202, although separator 202 can be configured to substantially prevent fluid from flowing through separator 202. In some embodiments, separator 202 can include a permeable membrane, a semipermeable membrane, or a selectively permeable membrane. The characteristics of separator 202 are described in more detail below according to various embodiments.

[0074] In some embodiments, the separator 202 and the wall of the reaction chamber 102 can be arranged to define the channels 204, 206 in a side-by-side relationship. The separator 202 can be substantially flat extending between the channels 204, 206. In some embodiments, the channels 204, 206 can extend substantially in parallel. In some embodiments, the second channel 206 can partially surround the first channel 204. In some embodiments, the first and second channels 204, 206 can be arranged concentrically. In some embodiments, the first channel 204 can be completely defined by the inner surface of the separator 202. In some embodiments, the separator 202 and the chamber 102 can be substantially cylindrical. In some embodiments, the chamber 102 can be substantially coaxial with the separator 202. In some embodiments, the second electrode 106 can be substantially coaxial with the first electrode 104. In some embodiments, the walls of the chamber 102 and the separator 202 can all be substantially cylindrical and coaxial with the central longitudinal axis of the first electrode 104.

[0075] In some embodiments, the separator 202 may define surface variations or undulations to increase the surface area of ​​the separator 202. In some embodiments, the separator 202 may be corrugated. In some embodiments, the separator 202 may be generally cylindrical with longitudinal corrugations. In some embodiments, the separator 202 may be generally cylindrical with circumferential corrugations.

[0076] The first electrode 104 (and / or the second electrode 106) may include a static mixer portion (e.g., a static mixer element or SME) that defines a structure having a geometry configured to promote mixing of the fluid flowing through the static mixer between the bulk of the fluid and the electrode surface and within the fluid itself. The first electrode may be a static mixer electrode. The static mixer electrode 104 may be configured to split the flow at a plurality of different split locations along the length of the electrode 104 so as to promote thorough mixing via chaotic advection.

[0077] This static mixer can limit a plurality of shunting structures, and these shunting structures are arranged at the shunting position to shunting flow.These shunting structures can be arranged at the different azimuths of different positions to shunting with different angles.In some embodiments, the shunting structure can be configured to divide flow into two substreams at each shunting position.In some embodiments, the shunting structure can be configured to split flow into at least three substreams, such as three, four, five, six, seven or eight substreams at each shunting position.

[0078] The geometry of the static mixer can be configured to enhance chaotic advection based on the characteristics of a particular fluid. The structure of the static mixer can comprise a network of elements including one or more of: intersecting blades or vanes, struts, asperities, undulations and protrusions, spirals, corrugated plates, open configurations, closed configurations, holes, channels, pores, tubes, and multi-layer designs.

[0079] The geometry may repeat regularly along the length of the mixer, or it may vary in size, type, and / or shape. The characteristic length of the geometry may also vary from the scale of the mixer to nanometers, and features may be provided at all length scales therebetween.

[0080] Reference Figures 3A to 3D , shows a static mixer electrode 104 according to some embodiments. The electrode 104 includes a static mixer portion 304 extending between a first end 334 and a second end 344. The ends 334, 344 may define a tube or conduit to direct fluid through the static mixer.

[0081] The first end 334 may define the first inlet 134 of the flow battery and the second end 344 may define the first outlet 144 of the flow battery, such as described above with respect to Figure 1 and Figure 2 The flow batteries 100 , 200 are described. The ends 334 , 344 may also provide electrical contact areas to connect the electrode 104 to the power source 110 .

[0082] According to some embodiments, Figures 3B to 3D334, 344 to more clearly illustrate the geometry. The static mixer portion 304 comprises a plurality of straight flow-dividing structures arranged in a repeating module, wherein each subsequent module rotates 90° relative to the previous module about the central longitudinal axis of the static mixer portion extending from one end to the other. The static mixer portion 334 promotes chaotic advection of the fluid flowing through the static mixer portion 334 in the general direction along the central longitudinal axis by splitting and recombining flows at a plurality of flow-dividing positions along the length of the static mixer portion 334. These flow-dividing structures split the flow into a plurality of sub-flows at each flow-dividing position, and these sub-flows are subsequently recombined before being split by the next flow-dividing structure at the next flow-dividing position.

[0083] Each time the flow is split and recombined, it causes a different fluid packet from a large portion of the flow to contact the surface of the electrode 104, and splitting the flow multiple times along the length of the static mixer increases the amount of fluid in contact with the electrode 104.

[0084] In some embodiments, the diameter of the static mixer electrode 104 can be close to the inner diameter of the separator 202. That is, the first electrode 104 can fit tightly within the separator 202. The outer envelope of the static mixer geometry of the first electrode 104 can substantially completely occupy the internal volume defined by the separator 202. In some embodiments, the volume of the first electrode 104 can be in the range of 1% to 99%, optionally 10% to 90%, 20% to 80%, 30% to 70%, or 40% to 60% of the internal volume of the channel 204. In some embodiments, the volume of the first electrode 104 can be at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, or 99% of the internal volume of the channel 204. Further features of the static mixer are described below according to various embodiments.

[0085] Reference FIG. 4A to FIG. 4C , according to some embodiments, the electrochemical flow cell 400 is shown in an assembled configuration ( Figure 4A )、Disassembly Configuration( Figure 4B ) and cross-section ( Figure 4C ). Like components are denoted by like reference numerals and may include any features of flow batteries 100, 200 and any features of the flow batteries 100, 200. Figure 1 and 2 Describing the parts or Figures 3A to 3D A static mixer electrode 104 is depicted.

[0086] The flow battery may include a first electrode 104, a second electrode 106, and a separator 202 disposed between the first electrode 104 and the second electrode 106. For example, the first electrode 104 may include a separator 202 as described above. Figures 3A to 3D A static mixer electrode 104 is depicted.

[0087] The separator 202 may include a permeable, semi-permeable, or selectively permeable membrane that is substantially cylindrical and closely surrounds the static mixer portion 304 of the first electrode 104. The separator 202 and the first electrode 104 may cooperate to define a first channel 204 along which a fluid may flow, contact the first electrode 104, and be mixed by the static mixer portion 304 (see Figure 4C ).

[0088] The second electrode 106 may also be substantially cylindrical and define an outer wall of the reaction chamber 102 surrounding 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 Figure 4C ).

[0089] The separator 202 and the second electrode 104 may be disposed substantially concentrically and / or coaxially with a central longitudinal axis of the first electrode 104 .

[0090] According to some embodiments, the separator 202 and the electrodes 104, 106 are held in place by two opposing end caps 500. Figure 5 Each end cap 500 includes a body 501 defining a separator seat 502, a first electrode seat 504 and a second electrode seat 506.

[0091] The second electrode seat 506 is defined by an annular recess in the body 501 that is configured to receive at least a portion of one end of the second electrode 106. The flow battery 400 may include a second electrode gasket 426 disposed between the second electrode 106 and each end cap 500 to form a seal between the second electrode 106 and the second electrode seat 506 (see Figure 4B ).

[0092] The separator seat 502 is defined by an annular recess (or in some embodiments, a circular recess) that is configured to receive the first end 232 or the second end 242 of the separator 202, respectively (see Figure 4B The body 501 defines an opening 516 between the separator seat 502 and the second electrode seat 506 and a passage from the opening 516 to define the second outlet 136 or the second inlet 146, respectively.

[0093] The first electrode seat 504 is defined by a cylindrical bore or passage configured to receive the respective ends 334, 344 of the first electrode 104. The first electrode seat 504 can be surrounded by a chamfer 514 on one side of the body 501 to help position the first electrode 104 in the first electrode seat 504. The passage can extend from the chamfer 514 to the first electrode seat opening 524 on the other side of the body 501 (see Figure 4B ). The first and second ends 334, 344 of the first electrode 104 may extend through the passage and opening 524 and define a first inlet 134 or a first outlet 144, respectively.

[0094] A seal may be formed between the end portions 334, 344 and the end cap 500 using a sealing plate or gland 410 and a first electrode gasket 424 (see Figure 4B ). The gland 410 may define an electrode opening 414 to allow at least a portion of the ends 334, 344 to pass therethrough, 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 corresponding plurality of fastener recesses 512 configured to receive the fasteners 412. The fasteners 412 may engage (e.g., by threads) the fastener recesses 512 to pull the gland 410 against the end cap 500, thereby compressing the first electrode gasket 424 between the end cap 500 and the gland 410 and against the ends 334, 344, thereby forming a seal between the first electrode 104 and the end cap 500.

[0095] The end caps 500 may be held together by a plurality of tie rods 440 extending between the end caps 500 and through a corresponding plurality of tie rod openings 542 defined in the body 501 of each end cap 500. The tie rods 440 may be configured to receive a tie rod fastener 442 at each end of each tie rod 440 to pull the end caps 500 toward each other and hold the separator 202 and the first and second electrodes 104, 106 between the end caps to define the reaction chamber 102 and the flow cell 400.

[0096] Compared to conventional electrochemical flow cells, the electrochemical flow cells 100, 200 and 400 can improve the efficiency of electrochemical reactions because the static mixer geometry of the first electrode 104 (and / or the second electrode 106) promotes enhanced mixing of the fluid, such as by chaotic advection, to increase the volume of the fluid in contact with the first electrode 104 and / or the second electrode 106.

[0097] Electrochemical flow cells 200 and 400 can provide further advantages because the fluid streams can remain substantially separated in channels 204, 206 on either side of separator 202. This allows independent input fluids to remain substantially separated while still allowing electrochemical reactions to occur. For example, in some processes, specific species such as metal ions can be deposited on the surface of one of electrodes 104, 106 via electrodeposition.

[0098] Reference Figure 6 , shows an electrochemical flow system 600 according to some embodiments. The system 600 includes a first flow battery 200a and a second flow battery 200b arranged in series and powered by two power sources 110a and 110b, respectively. Although, in some embodiments, a single power source 110 can power both flow batteries 200a, 200b. The electrochemical flow batteries 200a, 200b can be substantially similar to the flow batteries 200 or 400 and include the above-mentioned Figures 2 to 5 Any feature of a component described.

[0099] The system 600 may include a first pump 120 that supplies a first fluid from a first source (input 1) into a first inlet 134a of the first flow battery 200a via a first flow line 124a of the first flow battery 200a, and a second pump 122 that supplies a second fluid from a second source (input 2) into a second inlet 136a of the first flow battery 200a via a second flow line 126a of the first flow battery 200a. The first and second electrodes 104b, 106b of the second flow battery 200b may be provided with a voltage of opposite polarity to the voltage applied to the first and second electrodes 104a, 106a of the first flow battery 200a.

[0100] The system 600 may be configured such that a first fluid flowing into the first inlet 134a of the first flow battery 200a flows through the first channel 204a and flows out through the first outlet 144a of the first flow battery 200a; then enters the second inlet 136b of the second flow battery 200b via the second flow line 126b; flows out through the second channel 206b of the second flow battery 200b and flows out through the second outlet 146b into the first reservoir (output 1). The system 600 may be further configured such that a second fluid flowing into the second inlet 136a of the first flow battery 200a flows through the second channel 206a and flows out through the second outlet 146a of the first flow battery 200a; then enters the first inlet 134b of the second flow battery 200b via the first flow line 124b; flows out through the first channel 204b of the second flow battery 200b and flows out through the first outlet 144b into the second reservoir (output 2).

[0101] For example, the first fluid source may include contaminant metals, such as copper, and it may be desirable to remove the contaminants from the first fluid source and transfer the contaminants to the second fluid. When flowing through the system 600, the contaminants will be deposited from the first fluid onto the first electrode 104a of the first flow cell 200a, and if there are any contaminants left in the first fluid after passing through the first flow cell 200a, the contaminants will also be deposited onto 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 will pass through the second channel 206a of the first flow cell 200a and the first channel 204b of the second flow cell 200b to allow electrical contact and complete the current loop of each flow cell 200a, 200b.

[0102] In conventional systems, when contaminants have accumulated on electrodes via electrodeposition, the electrodes are removed from the system and the deposited contaminants are mechanically removed from the surfaces of the electrodes. However, when using system 600, it is not necessary to remove the electrodes.

[0103] Once the contaminants have been deposited 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 way, the contaminants will be removed from the surfaces of the first electrode 104a of the first flow cell 200a and the second electrode 106b of the second flow cell 200b, and more contaminants will be removed from the first fluid and deposited on the second electrode 106a of the first flow cell 200a and the first electrode 104b of the second flow cell 200b.

[0104] Electrochemical flow system 600 allows electrochemical reactions to proceed indefinitely with relatively short interruptions to switch fluid paths, compared to conventional systems that require physical removal and replacement of electrodes when material deposited on the electrodes has reached a certain threshold.

[0105] Electrochemical Tubular Reactor

[0106] An electrochemical flow reactor, such as the electrochemical flow cell described above, may be provided in the form of a continuous flow electrochemical tubular reactor. The continuous flow electrochemical tubular reactor may be provided according to any embodiment or example as described herein for an electrochemical flow cell.

[0107] It should be understood that tubular reactors of various shapes, elongations and configurations can be provided. For example, a tubular reactor may include a reactor chamber of circular or non-circular shape, or wherein the reactor chamber comprises one or more fluid channels of circular or non-circular circumferential shape. Examples of non-circular shapes may include rectangles, isosceles triangles, ellipses, trapezoids and hexagons. In one embodiment, the tubular reactor or reactor chamber is substantially circular or cylindrical.

[0108] The continuous flow electrochemical tubular reactor may include a reactor housing defining a reactor chamber for accommodating at least one static mixer electrode spaced apart from at least one counter electrode. The static mixer electrode may be provided by an electrode comprising a static mixer portion or a static mixer element as described herein. It should be understood that at least a portion of the static mixer portion or static mixer element, or any coating thereon, may be conductive. The reactor also includes a permeable membrane used as a separator, which is used to separate the static mixer electrode from the counter electrode fluid while providing electrical connection between the electrodes. The reactor may provide a fluid channel for accommodating the static mixer electrode, which is separated from the fluid channel for accommodating the counter electrode. The pair of electrodes may provide a cathode and anode pair for driving an electrochemical reaction in a tubular reactor. Depending on the current in the electrochemical cell, the static mixer electrode and the counter electrode may be a cathode or an anode. For example, the electrode pair may be reversed by switching the current. The static mixer electrode may also be configured to enhance mass transfer and chaotic advection.

[0109] It will be appreciated that the tubular reactor is configured to allow at least the first fluid stream to flow through the static mixer electrodes to undergo chaotic advection and electrochemical reaction before exiting at the outlet. It will also be appreciated that each fluid channel in the tubular reactor may have at least one inlet and at least one outlet.

[0110] The reactor may comprise one or more chamber sections in fluid communication with each other. The static mixer electrode may be configured as a replaceable electrode for insertion into a continuous flow electrochemical reactor or as a permanent electrode. One or more reactors, or one or more chamber sections of a reactor, may be configured for operation in series or in parallel.

[0111] The length of reaction chamber 102, separator 202 and electrodes 104, 106 can be in the range of 2mm to 100m, 10mm to 10m, 50mm to 1m, 100mm to 500mm, or 200mm to 300mm. The diameter of the reactor housing or chamber can be between 5mm and 5m, wherein the size of the counter electrode and the working electrode is determined 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.

[0112] Separator

[0113] Separator 202 may comprise any porous material that allows ion transport but prevents fluid flow. The separator may comprise a permeable membrane, a semipermeable membrane, or a selectively permeable membrane. In some embodiments, separator 202 may be formed from any one or more of the following materials: nonwoven fibers (cotton, nylon, polyester, glass), polymer membranes (polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride), ceramics, and naturally occurring substances (rubber, asbestos, wood). In some embodiments, separator 202 may comprise a membrane having less than The separator 202 may be formed using dry and / or wet manufacturing processes. The nonwoven separator 202 may include a manufactured sheet, web, or mat of oriented or randomly oriented fibers.

[0114] In some embodiments, separator 202 may comprise a supported liquid membrane including a solid phase and a liquid phase contained within a microporous structure.

[0115] In some embodiments, separator 202 may include a polymer electrolyte that forms a complex with an alkali metal salt, which produces an ionic conductor that functions as a solid electrolyte. The solid ionic conductor may function as both a separator and an electrolyte.

[0116] The separator 202 may be formed from a single layer or multiple layers of material.

[0117] In some embodiments, the separator 202 can be made by sintering powdered materials such as ceramics, glass, plastics, cermets, and combinations thereof into a membrane structure.

[0118] In some embodiments, separator 202 can be configured to allow ions to pass through while preventing fluid flow. In some embodiments, separator 202 can allow a small amount of fluid to pass through.

[0119] The separator 202 can have an inner diameter configured to fit tightly around the first electrode 104. For example, the inner diameter of the separator 202 can be in a range of 0.5 mm to 5 mm, 5 mm to 1 m, or 5 mm to 10 mm.

[0120] The thickness of the separator 202 may vary depending on its porosity. For nanoporous separators, the thickness may be between 1 micron and 100 microns, and for microporous membranes, the thickness may be between 100 microns and 10 mm. The average pore size within the separator material may be between 100 microns and 10 mm. Varies between 1 and 100 microns.

[0121] It should be understood that permeable membranes generally establish separate fluid channels for each of static mixer electrodes and counter electrodes while maintaining the electrical connection required for electrochemical flow cells. Permeable membranes generally inhibit fluid flow through the membrane while allowing ion transport. For example, if during operation the static mixer electrode operates as a negative electrode (i.e., cathode) and the counter electrode operates as a positive electrode (i.e., anode), the cathode electrolyte stream for flowing through the static mixer electrode (i.e., cathode) can be prepared for a specific application different from the anolyte stream for flowing through the positive counter electrode (i.e., anode). In other words, a permeable membrane allows the ions between the two electrodes to be communicated to provide an electrical connection while separating the two separate fluid streams flowing through each cathode and anode, which provides performance advantages and process flexibility.

[0122] A permeable membrane may be positioned concentrically along the tubular reactor to separate the static mixer electrode from the counter electrode. The reactor may include an inner coaxial flow passage accommodating one electrode and an outer concentric flow passage accommodating the other electrode. The static mixer electrode may be accommodated in the inner coaxial flow passage, the outer concentric flow passage, or in both the inner coaxial flow passage and the outer concentric flow passage. The flow passages may also be referred to herein as fluid channels.

[0123] The separator can be a semipermeable membrane. The semipermeable membrane can be a porous tubular membrane, a porous ceramic filter tube, or a porous plastic tube that tightly surrounds the static mixer electrode. It should be understood that the semipermeable membrane substantially restricts the passage of fluid through the membrane while allowing ions to be transported through the membrane to maintain electrical communication between the separated static mixer electrode and the counter electrode.

[0124] The separator can be a selectively permeable membrane. A selectively permeable membrane can provide selectivity in allowing transport through the membrane, such as specific fluids or ions. It should be understood that the selectively permeable membrane selectively limits what can pass through the membrane while enabling specific ions to be transported through the membrane to maintain electrical communication between the separated static mixer electrode and the counter electrode.

[0125] It will be appreciated that each individual flow path is provided with at least one inlet and at least one outlet. Separate fluid flows may be provided for the inner coaxial flow path and the outer concentric flow path. For example, a catholyte fluid flow may be provided for the inner coaxial flow path accommodating the static mixer electrode, and an anolyte fluid flow may be provided for the outer concentric flow path accommodating the counter electrode. As previously described, the static mixer electrodes may also be substantially coaxially aligned along the axis of the tubular reactor.

[0126] Static mixer electrodes

[0127] As described above, the first electrode 104 or the second electrode 106 or the first and second electrodes 104, 106 may include a static mixer portion defining a geometry to promote mixing of fluids flowing through or around the static mixer portion. This may be referred to as a static mixer electrode or SME.

[0128] The reactor may comprise more than one static mixer electrode and / or more than one counter electrode. The counter electrode may also be provided by a static mixer electrode, for example the cathode and anode in an electrochemical flow reactor may each be provided by a separate static mixer electrode. The static mixer electrode may be concentrically contained within the inner coaxial flow passage and the counter electrode may be contained within the outer concentric flow passage.

[0129] It should be understood that the static mixer electrode may include a conductive surface. The static mixer electrode can operate as an anode or cathode, depending on the direction of the applied current. For electrochemical flow cells, it is generally understood that the anode is the positive electrode where oxidation occurs and electrons are released by a reactant, and the cathode is the negative electrode where reduction occurs and electrons are consumed by another reactant.

[0130] The static mixer electrodes can be made of a material capable of providing 1 μA m at either electrode. -2 About 1000A m -2 The static mixer electrode or its support may comprise a conductive material, for example a conductive carbon material such as graphite, glassy carbon or boron-doped diamond, a metal, an alloy or an intermetallic compound such as a powder, sheet, rod or billet, a semimetal or a doped or low bandgap semiconductor, a metal-coated particle, a conductive ceramic. Alternatively, the support may be made of a non-conductive material and subsequently coated with an electrical conductor. The non-conductive material may be a granular non-conductor such as a plastic, ceramic, glass or mineral, a thermosetting resin, a thermoplastic resin, 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 of any conductive material as described above.

[0131] The static mixer electrodes can be produced by: subtractive manufacturing, using one or a combination of processing techniques such as: milling, cutting, drilling, turning, spinning, bending and twisting, by casting, molding or forging, by extrusion, by pressing, by micro-electromechanical systems machining (MEMS), additive manufacturing processes, laser or electron beam welding, selective laser sintering, selective laser melting, direct metal laser sintering, laser engineered mesh forming, material extrusion, sheet lamination, polymerization and photopolymerization, material or binder jetting and printing.

[0132] In some embodiments, the body or support of the static mixer electrode can be conductive, such as a metal or metal alloy, such as nickel, titanium or stainless steel. In some embodiments, a conductive coating can be applied to the electrode surface, such as a titanium support coated with platinum. The coating can be formed by a metal, a semi-metal or a doped or low bandgap semiconductor, a conductive ceramic or compound, a conductive form of carbon (e.g., graphite, graphene or doped carbon material), a conductive polymer (e.g., polyaniline), or a combination thereof. The coating can be applied to the surface by one or more of the following methods: electrochemical methods, metal spraying, cold spraying, chemical or physical vapor deposition, dip coating, spraying, spin coating, sintering or other thermal treatment, or any such method that results in a thin layer of a suitable material being applied.

[0133] Static mixer electrodes can be configured to enhance mixing, including heat and mass transfer characteristics for redistributing fluids in a direction transverse to the main flow, such as in radial and tangential or azimuthal directions relative to the central longitudinal axis of the static mixer electrodes. In particular, static mixer electrodes can be configured to enhance chaotic advection, thereby reducing the restriction on the reaction rate imposed by diffusion. Static mixer electrodes can be configured to ensure that as much surface area as possible is presented to the flow to promote electrochemical reactions and improve flow mixing, so that reactant molecules contact the surface of the static mixer electrodes more frequently. Static mixer electrodes can be provided with various geometric configurations or aspect ratios for being associated with specific applications. Static mixer electrodes can be configured to enhance the turbulence, mixing and mass transfer characteristics of fluid flows. These configurations can also be designed to improve efficiency, the degree of chemical or electrochemical reactions, or other characteristics, such as pressure drop (while maintaining a predetermined flow rate), residence time distribution, or heat and mass transfer coefficients.

[0134] The static mixer electrode may comprise an electrically conductive integral support defining a plurality of passage segments configured to enhance mass transfer and turbulent advection, for example by splitting a fluid flow flowing between each of the passage segments. A major portion of the support surface may be electrically conductive.

[0135] The static mixer electrode may be configured to extend coaxially along the length and transversely across the diameter of the flow passage. In one example, the envelope of the static mixer electrode may be configured to extend coaxially along the length of the internal coaxial flow passage and transversely across the diameter of the internal coaxial flow passage to substantially occupy the internal coaxial flow passage.

[0136] The first electrode 104 can have an outer diameter configured to fit tightly within the separator 202. For example, the outer diameter of the first electrode 104 can be in the range of 0.5 mm to 5 mm, 5 mm to 1 m, or 5 mm to 10 mm. FIG. 4A to FIG. 4CIn the depicted embodiment of the flow battery 400 in which the first electrode and the second electrode are arranged concentrically and coaxially with each other, the inner diameter of the second electrode 106 may be in the range of 0.5 mm to 5 mm, 5 mm to 1 m, or 10 mm to 20 mm.

[0137] For example, the ratio between the inner diameter of the separator 202 and the inner diameter of the second electrode 106 can be in a range of 0.02 to 0.99, 0.1 to 0.9, 0.3 to 0.7, or 0.4 to 0.6.

[0138] The conductive monolithic support of the static mixer electrode may include a contiguous network of solid conductive elements distributed throughout the internal coaxial flow passage and configured to induce chaotic advection of the fluid flowing through the internal coaxial flow passage. The contiguous network of solid conductive elements may be provided by a grid of interconnected segments configured to define a plurality of apertures for inducing chaotic advection of the fluid flowing through the internal coaxial flow passage.

[0139] The static mixer electrodes may be provided in a configuration selected from one or more of the following general non-limiting example configurations:

[0140] ·Open configuration with a spiral;

[0141] · Open configuration with blades;

[0142] Corrugated sheet;

[0143] Multi-layer design;

[0144] A closed configuration with channels or holes;

[0145] An interlocking network of pillars, asperities, undulations and protrusions.

[0146] In one embodiment, a support for a static mixer electrode may be provided in a grid configuration having a plurality of integral cells defining a plurality of passages configured to facilitate mixing of one or more fluid reactants.

[0147] In another embodiment, the static mixer electrode may include a support provided by a grid of interconnected segments configured to define a plurality of holes, the plurality of orifices being used to promote mixing of fluids flowing through the reactor chamber. The support may also be configured to promote heat and mass transfer and fluid mixing.

[0148] In some embodiments, the static mixer electrode can be configured to enhance chaotic advection, and for example turbulent mixing, such as cross-sectional, transverse (relative to the flow) or local turbulent mixing. The geometry of the static mixer electrode or its support can be configured to change the local flow direction or split the flow more than a certain number of times within a given length along the longitudinal axis of the static mixer element, such as greater than 100 m.-1 , optionally greater than 200m -1 , optionally greater than 400m -1 , optionally greater than 800m -1 , optionally greater than 1500m -1 , optionally greater than 2000m -1 , optionally greater than 2500m -1 , optionally greater than 3000m -1 , optionally greater than 5000m -1 Static mixer electrodes, the geometry or configuration of which supports can contain more than a certain number of flow splitting structures within a given volume of the static mixer, such as more than 100m -3 , optionally more than 1000m -3 , optionally more than 1×10 4 m -3 , optionally more than 1×10 6 m -3 , optionally more than 1×10 9 m -3 , optionally greater than 1×10 10 m -3 .

[0149] The geometry or configuration of the static mixer electrode or its support can be configured to accompany the passage of the reactor cell (such as a tubular reactor). As mentioned above, it should be understood that the term "tubular" includes non-circular configurations, such as elliptical. The static mixer electrode or its support may be formed by or include multiple segments. Some or all of these segments may be straight segments. Some or all of these segments may include polygonal prisms, such as, for example, rectangular prisms. The support may include multiple flat surfaces. The straight segments may be angled relative to each other. The straight segments may be arranged at multiple different angles relative to the longitudinal axis of the support, such as, for example, two, three, four, five or six different angles. The static mixer electrode or its support may include a repeating structure. The static mixer electrode or its support may include multiple similar structures that are periodically repeated along the longitudinal axis of the support. The geometry or configuration may be consistent along the length of the static mixer electrode or its support. The geometry may change along the length of the static mixer electrode or its support. The straight segments may be connected by one or more curved segments. The static mixer electrode or its support may comprise one or more helical segments. The static mixer electrode or its support may generally define a helical surface. The static mixer electrode or its support may comprise a helical surface including a plurality of holes in the surface of the helical surface.

[0150] The size 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 static mixer electrode or the reactor tube may for example have a diameter (in mm) in the range of 1 to 5000, 2 to 2500, 3 to 1000, 4 to 500, 5 to 150 or 10 to 100. The static mixer electrode or the reactor tube may for example have a diameter (in mm) of at least about 1, 5, 10, 25, 50, 75, 100, 250, 500 or 1000. The static mixer electrode or the reactor tube may for example have a diameter (in mm) of less than about 5000, 2500, 1000, 750, 500, 250, 200, 150, 100, 75 or 50. The aspect ratio (L / d) of the static mixer electrode or the reactor chamber comprising the static mixer electrode may be provided in the range of the industrial scale flow rate suitable for a particular reaction. The aspect ratio may be, for example, in the range of about 1 to 1000, 5 to 750, 10 to 500, 25 to 250, 50 to 150, or 75 to 125. The aspect ratio may 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 may be, for example, greater than about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100. The aspect ratio may be provided within a range of any two of the above “less than” and “greater than” values.

[0151] The static mixer electrodes may be configured to enhance properties, such as mixing and heat and mass transfer, for laminar flow rates or turbulent flow rates. It will be appreciated that for Newtonian fluids flowing in hollow tubes, the association of laminar and turbulent flow with Reynolds number (Re) values ​​will typically provide, laminar flow rates where Re≤2300; transients where 2300≤Re≤4000; and typically turbulent flows where Re≥4000. It will be appreciated that the static mixer electrodes reduce these typical Re values ​​for generating turbulence. The static mixer electrodes may be configured for laminar or turbulent flow rates to provide one or more enhanced properties selected from mixing, degree of reaction, heat and mass transfer, chaotic advection, and pressure drop. It will be appreciated that further enhancement of a particular type of electrochemical reaction will require its own specific considerations. For flow in a tube, the Reynolds number may be defined as Re=ρuD H / μ(ρ is the density of the fluid, in kg.m -3 u is the average velocity of the fluid, in ms -1 D H is the hydraulic diameter of the pipe in meters, and μ is the dynamic viscosity of the fluid in Pa.s).

[0152] In one embodiment, the static mixer electrodes can be configured to operate at Re of 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, 1 00, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, or 15000. The static mixer electrode may be configured for operation in a Re range of about 0.1 to 2000, 1 to 1000, 10 to 800, or 20 to 500. The static mixer electrode may be configured for operation in a Re range of about 1000 to 15000, 1500 to 10000, 2000 to 8000, or 2500 to 6000. The static mixer electrode can be configured for operation at a Re in a range between any two of the above-noted “at least” values.

[0153] In some embodiments, the static mixer electrodes can be described by the Péclet number (Pe), which is another type of dimensionless number related to transport phenomena in continuous media. The Péclet number provides the ratio of the advection rate of a physical quantity caused by the flow to the diffusion rate of the same quantity driven by an appropriate gradient. In terms of material or mass transfer, the Péclet number is the product of the Reynolds number (Re) and the Schmidt number (Sc). In the case of thermal fluids, the thermal Péclet number is equal to the product of the Reynolds number (Re) and the Prandtl number (Pr). The Péclet number is defined as: Pe = convective transport rate / diffusion transport rate. For mass transfer, it is defined as: Pe L =Lu / D=Re L .Sc. For heat transfer, it is defined as PeL=Lu / α=Re L .Pr, where α = k / ρc p L is the characteristic length, u is the local velocity, D is the mass diffusion coefficient, α is the thermal diffusivity, ρ is the density, and c p is the heat capacity. The static mixer electrode can be configured to provide a higher Péclet value to enhance chaotic advection over diffusion to provide a more uniform residence time distribution and reduce dispersion. In other words, at least according to some embodiments and examples described herein, the configuration of the static mixer electrode that provides a higher Péclet value can provide improved performance and process control.

[0154] In one embodiment, the static mixer electrodes may be configured to be used to mix at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 500000, 10 6 , or 10 7 The static mixer electrodes may be configured to operate at a Péclet (Pe) value of less than about 10 8 , 10 7 , 10 6 The static mixer element may be configured to operate at a Peclet (Pe) value of about 10 3 Up to 10 8 , 10 3 Up to 10 7 , or 10 4 Up to 10 6 The static mixer element may be configured to operate within a Pe range between any two of the above upper and / or lower limits.

[0155] The volume displacement % of the static mixer electrode relative to the flow path containing the electrode can be in the range of about 1 to 90, 5 to 70, 10 to 30, or 5 to 20. The volume displacement % of the static mixer electrode relative to the flow path containing the electrode can be less than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5%. The volume displacement % of the static mixer electrode relative to the flow path containing the electrode can be greater than 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, or 80%. The volume displacement % can be provided within the range of any two of the above "less than" and "greater than" values.

[0156] The configuration of the static mixer electrodes can be provided to enhance the heat and mass transfer properties in the reactor, such as a reduced temperature difference at the outlet cross section. The heat and mass transfer of the static mixer electrodes can, for example, provide a cross-sectional or transverse temperature profile with 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.

[0157] The static mixer electrode or its support can be configured so that in use, the pressure drop (i.e., pressure difference 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 (or 1 MPa / m), including any value or range therebetween. For example, the pressure drop (in Pa / m) across the static mixer electrode can be less than about 500,000, 250,000, 100,000, 50,000, 10,000, 5,000, 1,000, 750, 500, 250, 100, 75, 50, 25, 20, 15, 10, or 5 Pa / m. For example, the pressure drop (in Pa / m) at both ends of the static mixer electrode can be at least about 10, 100, 1000, 5,000, 10,000, 50,000, 100,000 or 250,000. The pressure drop (in Pa / m) at both ends of the static mixer electrode can be provided within the range of any two of the above-mentioned upper and / or lower limits. For example, in one embodiment, the pressure drop (in Pa / m) at both ends of the static mixer electrode can be between about 10 and 250,000, 100 and 100,000 or 1,000 and 50,000. The static mixer electrode can be configured to provide a lower pressure drop relative to a specific flow rate. In this regard, the static mixer electrode, reactor, system and method as described herein can have 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.

[0158] In one embodiment, the static mixer electrode can be configured to operate at a volume 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 volume 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 a range provided by any two of these upper and / or lower values, such as a range between approximately 50 and 400, 10 and 200, or 20 and 200.

[0159] The static mixer electrode may be configured as a modular plug-in for a continuous flow electrochemical reactor or chamber thereof. The static mixer electrode may be configured for use with an online continuous flow electrochemical reactor or chamber thereof. The online continuous flow electrochemical reactor may be a circulating loop reactor or a single pass reactor.

[0160] The configuration of the static mixer electrodes may be determined using computational fluid dynamics (CFD) software, which may be used to enhance the configuration of reactant mixing to enhance contact and activation of the reactants at the surfaces of the static mixer electrodes.

[0161] The static mixer electrode can be an additively manufactured static mixer electrode. Additive manufacturing of static mixer electrodes, optionally with catalytic and / or corrosion-resistant coatings, can provide static mixer electrodes configured for effective mixing, heat and mass transfer, electrochemical reactions, or additional catalytic reactions. The additive manufacturing process allows the static mixer electrode to be physically tested for reliability and performance, and optionally further redesigned and reconfigured using additive manufacturing (e.g., 3D printing) technology. Additive manufacturing provides flexibility for preliminary design and testing, as well as further redesign and reconfiguration of static mixer electrodes. An electron beam 3D printer or a laser beam 3D printer can 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., 45-105 micron diameter range); cobalt-chromium alloy-based powders (e.g., FSX-414 or Stellite S21); or stainless steel or aluminum silicon alloys or any nickel-based alloys (e.g., Inconel, Hastelloy). The powder diameter associated with laser beam printers is generally lower than that associated with electron beam printers. Alternatively, the support may be additively manufactured from an inert material such as plastic or glass and then coated with a suitable conductive material. In addition to the conductive surface, the static mixer electrode or its support may optionally further comprise a catalytic material, depending on the specific reaction or application desired.

[0162] Counter electrode

[0163] It should be understood that the counter electrode is conductive. The counter electrode can operate as an anode or cathode, depending on the direction of the applied current. The counter electrode can be composed or configured according to any embodiment or example described above for the static mixer electrode.

[0164] It should be understood that the counter electrode may comprise a conductive surface. The counter electrode may be a conductive surface capable of providing 1 μA m -2 About 1000A m -2The counter electrode may comprise a conductive material, for example a conductive carbon material such as graphite, glassy carbon or boron-doped diamond, a metal, an alloy or an intermetallic compound such as a powder, sheet, rod or billet, a semimetal or a doped or low bandgap semiconductor, a metal-coated particle, a conductive ceramic. The counter electrode may be made of a non-conductive material and coated with an electrical conductor. The non-conductive material may be a granular non-conductor such as a plastic, ceramic, glass or mineral, a thermosetting resin, a thermoplastic resin, 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 described above for the counter electrode or static mixer electrode.

[0165] Reactor and end cap configuration

[0166] The reactor can be provided as an assembly comprising a reactor housing, a first electrode, a second electrode, a separator, and one or two optional end caps. The end caps can be configured to seal the reactor housing, and further can be optionally configured to be associated with one or more of the first electrode, the second electrode, and the separator for structural and alignment support during assembly and operation of the reactor.

[0167] In one embodiment, the tubular reactor may include first and second end caps each cooperatively configured to secure opposite ends of the reactor housing and support an arrangement of a static mixer electrode, a counter electrode, and a separator in the reactor.

[0168] The end caps may be an integral part of the static mixer electrode and / or the counter electrode (e.g., the end caps may be made as part of one of the electrodes). The end caps 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 made by an additive manufacturing process).

[0169] The end cap may be provided according to any other embodiment or example thereof as described herein.

[0170] Electrochemical Flow Systems

[0171] According to any one or more aspects, embodiments, or examples described herein, a system for providing a continuous flow electrochemical reaction may include an electrochemical flow cell or an electrochemical tubular reactor.

[0172] The system may further include a pump for providing a fluid flow through the reactor for one or more fluid reactants and any product thereof. The system may further include an electrical unit for providing and controlling a voltage applied to an electrode or an electric current flowing through an electrode for driving an electrochemical reaction at an interface of a fluid stream and an electrode. The system may further include a controller for controlling one or more parameters of the system, one or more parameters being selected from concentration, flow rate, temperature, pressure and residence time of one or more fluid reactants or its source or product.

[0173] The reactor system may comprise one flow cell assembly, or multiple assemblies arranged in parallel or in series. The polarity of the electrodes in each device may be connected in the same manner in each cell or in an alternating manner, with the outer electrodes alternately being anode, cathode, anode, cathode ... (or vice versa), and the inner electrodes alternatively being cathode, anode, cathode, anode ... (or vice versa). The system may be set up with any combination of these polarities. The magnitude of the voltage or current applied to each cell in the system may be the same or may vary, and the pumping speed through the cells in the system may be the same or may vary.

[0174] The reactor system can be constructed and controlled to accept a time-varying power input, such as from a renewable energy source. For example, the reactant flow rate can be varied according to the power available for electrolysis so that the flow reactor remains operational when the power source fluctuates.

[0175] The aspect ratio of the reactor may, for example, be similar to those previously described for the static mixer electrodes, such that the static mixer electrode module may be configured for insertion into the reactor.

[0176] The reactor may contain an optional heat exchanger for controlling the temperature of the reactor, chamber sections, static mixers, or fluid components thereof. The heat exchanger may be of a shell and tube heat exchanger design or configuration.

[0177] The present invention also provides a system for a continuous flow electrochemical reaction process, the system comprising:

[0178] A continuous flow electrochemical reactor comprising one or more static mixer electrodes according to any embodiment or example described herein;

[0179] a pump for providing fluid flow through the reactor for one or more fluid reactants and any products thereof;

[0180] A control device for controlling one or more parameters of the system, the one or more parameters being selected from reactant concentration, flow rate, current, applied voltage, pressure and residence time.

[0181] The system may include an optional heat exchanger for controlling the temperature of the reactor or its fluid components.

[0182] The system may further include a spectrometer that can be used to identify and determine the concentration of any one or more of the fluid reactants or their products.

[0183] One or more of the reactor, reactor chamber, chamber part and static mixer electrode can be provided in modular form for their complementary association. The system can include multiple reactors, and these reactors can have similar or different internal and / or external configurations. The reactor can be connected in series or in parallel, or a combination of the two. It should be understood that the system, reactor or each chamber part can include one or more inlets and outlets to provide a supply of reactants, obtain products, or recycle various reactants and / or products.

[0184] It will also be appreciated that the reactor or system can be designed to recycle various reactants, reactant sources, intermediate products, or desired products provided to and produced in the chamber portion. The reactor or system can be provided in various designs and forms, such as in the form of a tubular reactor. In another embodiment, the reactor is a once-through reactor.

[0185] The systems and processes may also be integrated into more complex systems, such as those including coal gasifiers, water purification and reticulation, electrolyzers and / or natural gas reformers, chemical synthesis and purification, and the like.

[0186] Electrochemical Applications

[0187] According to any embodiment or example described herein, the electrochemical flow reactor, electrochemical flow cell or continuous flow electrochemical tubular reactor can be used in various applications including metal recovery, recovery of heavy and precious metals from wastewater and mine wastewater, wastewater treatment, water disinfection or purification (e.g., drinking water), and from solid waste (e.g., sludge, tailings, and treated waste), and electrosynthesis of various products (e.g., gas generation, energy storage and conversion, reagent regeneration, and polymerization).

[0188] Reactors comprising static mixer electrodes can be used in continuous flow electrochemical reaction systems and processes. The process can be an online continuous flow process. The online continuous flow process can be a recirculation loop or a single pass process. In one embodiment, the online continuous flow process is a single pass process.

[0189] As mentioned above, the electrochemical reactor comprising a static mixer electrode can react in a continuous manner. The electrochemical reactor can use a single-phase or multiphase feed and product stream. In one embodiment, a substrate feed (comprising one or more reactants) can be provided as a continuous fluid stream, such as a liquid stream, which contains: a) a substrate as a solute in a suitable solvent, or b) a liquid substrate with or without a co-solvent. It should be understood that the fluid stream can be provided by one or more gas streams, such as hydrogen or its source. Pressure-driven flow is used, for example, by means of a pump, the substrate feed is pumped into the reactor. In another embodiment, the substrate feed can be provided by a solid suspended in the fluid stream, and in yet another embodiment, the reactant fluid stream can include solids, liquids and gases.

[0190] In one embodiment, a method for electrochemically treating a fluid stream is provided, the method comprising an electrochemical flow cell or a continuous flow electrochemical tubular reactor according to any embodiment or example thereof as described herein.

[0191] The above method can be used to remove dissolved metal ions from a fluid stream by applying a direct current through a static mixer electrode and a counter electrode to form a solid deposit comprising metal and / or a metallic compound on the surface of the static mixer electrode. The method can be used to recover metals from a fluid stream obtained from a tailing. The method can include parallel and / or series operations as described above for a reactor system. In one embodiment, the method is operated in series.

[0192] In one embodiment, the method comprises at least first and second continuous flow electrochemical tubular reactors, each reactor being configured such that a permeable membrane separates a static mixer electrode from a counter electrode to define an inner coaxial flow passage accommodating one electrode and an outer concentric flow passage accommodating the other electrode, each flow passage having at least one inlet and at least one outlet. The method can enable metal to be loaded onto the static mixer electrode of the first tubular reactor while providing a second reactor in series with reversed electrode polarity to remove metal previously loaded onto the static mixer electrode of the second tubular reactor.

[0193] In another embodiment of the above method, the first fluid stream can be introduced into the inner coaxial flow passage of the first tubular reactor and its output introduced into the outer concentric flow passage of the second tubular reactor. The second fluid stream can be simultaneously introduced into the outer concentric flow passage of the first tubular reactor and its output introduced into the inner coaxial flow passage of the second tubular reactor. The first tubular reactor can be operated to place the first static mixer electrode in a reducing state to accumulate solid metal species, and the second tubular reactor can be operated to place the second static mixer electrode in an oxidizing state to remove any metal species present thereon.

[0194] 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 removal and replacement of the cathode, and provides the flexibility of operating in series or reverse mode by switching the current and switching different fluid flows to remove the metal, metal compound or other metal-containing products formed on the static mixer electrode serving as the cathode during the reduction reaction.

[0195] The present invention also provides a process for synthesizing a product by reacting one or more fluid reactants, the process comprising the following steps:

[0196] Providing a continuous flow electrochemical reactor comprising a static mixer electrode or system according to any embodiment or example described herein;

[0197] providing at least a first fluid reactant to the reactor via a reactant inlet;

[0198] operating the reactor or its controls to provide flow and reaction of at least a first fluid reactant through the static mixer electrodes; and

[0199] An output stream comprising a reaction product of at least the first reactant is obtained.

[0200] It should be understood that the various parameters and conditions used in the process, such as current, pressure, and concentration / amount of materials and reactants, can be selected depending on the variable range of the process, including the product to be synthesized, the electrochemical reaction or the mechanism involved, the source of reactants, or the type of reactor used and the materials and their configuration. For example, there will be differences when one or more fluid reactants or cosolvents (e.g., inert carriers), etc. are gases, liquids, solids, or combinations thereof.

[0201] Electrochemical flow reactors can be used with 1 μAm -2 To about 1000Am -2 The current density (in Am -2 The current density (in A m) may be, for example, less than about 1000, 500, 200, 100, 50, 20, 10, 5.0, 2.0, 1.0, 0.5, 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, 0.002, 0.001, 0.0005, 0.0002, 0.0001, 0.00005, 0.00002, 0.00001, 0.000005, 0.000002, or 0.000001. -2The current density may be, for example, greater than about 0.000002, 0.000005, 0.00001, 0.00002, 0.00005, 0.0001, 0.0002, 0.00005, 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, 10, 20, 50, 100, 200, or 500. The current density may be provided in any range of two values ​​selected from any of the above values. It should be understood that various applications and configurations may apply different current densities.

[0202] In some embodiments, the voltage applied across the electrode may be less than about 2.0, 1.8, 1.6, 1.4, 1.2, 1.0, 0.8, 0.6, 0.4, or 0.2. In some embodiments, the voltage applied across the electrode may be at least about 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, or 1.8. The voltage may be within a range provided by any two of these upper and / or lower limits.

[0203] In one embodiment, the operating performance of the electrochemical flow reactor can be measured by its recovery efficiency. Recovery efficiency relates to the amount of material (e.g., pollutant) present in the fluid, such as dissolved metal species, which can be removed from the fluid by the electrochemical flow cell. In one embodiment, the recovery efficiency measured with the % of the pollutant recovered (or removed) from the fluid is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99. In some embodiments, any recovery efficiency can be provided by continuous operation (e.g., recirculation in a circulation loop reactor) within a duration of less than about 48 hours, 36 hours, 24 hours, 12 hours, 6 hours, 3 hours, 2 hours, or 1 hour. In another embodiment, material (e.g., pollutant) can be removed from fluid, such as dissolved metal material (e.g., copper material), wherein the material is present in fluid with a concentration less than about (in mol / L) 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, 0.0001, 0.00005 or 0.00001. In another embodiment, material (e.g., pollutant) can be removed from fluid, such as dissolved metal material, wherein the material is present in fluid with a concentration greater than about (in mol / L) 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1 or 0.5. The concentration of the removed material can be between any two of these upper and / or lower limits. The above-mentioned recovery efficiency and / or cycle duration can be applicable to any of these material (e.g., pollutant) concentrations. For example, the operating performance of the reactor, system or its method can provide a recovery efficiency of at least about 50% of the dissolved metal species recovered from a fluid having an initial concentration of less than about 0.01 mol / L. In another embodiment, the recovery efficiency can 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 can 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 can 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, the recovery efficiency can be at least about 90% of the dissolved metal species from a fluid having an initial concentration of less than about 0.0001 mol / L.

[0204] In another embodiment, a substance (e.g., a contaminant), such as a dissolved metal substance (e.g., a copper substance), can be removed from a fluid, wherein the substance is present in the fluid at an initial concentration of about or less than about (in ppm) 1000, 750, 500, 250, 100, 75, 50, 25, 10, 5, or 1. In another example, a substance (e.g., a contaminant), such as a dissolved metal substance (e.g., a copper substance), can be removed from a fluid, wherein the substance is present in the fluid at an initial concentration of about or greater than about (in ppm) 5, 10, 25, 50, 75, 100, 250, 500, 750, or 1000. The removed substance can be at an initial concentration in the fluid between any two of these upper and / or lower ranges. In one embodiment, the recovery efficiency measured as % of pollutants recovered (or removed) from the fluid is at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98 or 99. In some embodiments, any recovery efficiency can be provided by continuous operation (e.g., recirculation in a circulating loop reactor) within a duration 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 cycle durations can be applicable to any of these material (e.g., pollutant) concentrations. For example, the operating performance of a reactor, system or method thereof can provide a recovery efficiency of at least about 50% of the dissolved metal species recovered from a fluid having an initial concentration of about 100 ppm dissolved metal species during less than about 3 hours of continuous operation. In another example, the recovery efficiency can be at least about 95% of dissolved metal species from a fluid having an initial concentration of about 100 ppm over a continuous operation period of less than about 24 hours.

[0205] The temperature (° C.) associated with the process may be in the range between -50 and 400, or any integer or any integer range therebetween. For example, the temperature (° C.) may be at least about -50, -25, 0, 25, 50, 75, 100, 150, 200, 250, 300, or 350. For example, the temperature (° C.) may be less than about 350, 300, 250, 200, 150, 100, or 50. The temperature may also be provided in the range of about any of these values ​​or between any 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.

[0206] In one embodiment, the process is operable to provide an Re of 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, 1 00, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, or 15000. The process may be operated at a Re range of about 0.1 to 2000, 1 to 1000, 10 to 800, or 20 to 500. The process may be operated at a Re range of about 1000 to 15000, 1500 to 10000, 2000 to 8000, or 2500 to 6000. The process may be operated at a Re range provided by any two of the above "at least" values.

[0207] In one embodiment, the process may be operated at a Peclet (Pe) value of at least 100, 1000, 2000, 5000, 10000, 15000, 20000, 25000, 50000, 75000, 100000, 250000, 500000, 10 6 , or 10 7 The process can be operated at a Péclet (Pe) value of less than about 10 8 , 10 7 , 10 6 , 500,000, 250,000, 100,000, 75,000, 50,000, 25,000, 20,000, 15,000, 10,000, 5,000, 2,000, or 1,000. The process may be performed at about 10 3 Up to 10 8 , 10 3 Up to 10 7 , or 10 4 Up to 10 6 The process can be operated in a Pe range between any two of the above upper and / or lower limits.

[0208] The process can provide a pressure drop (or back pressure) (in Pa / m) across the static mixer electrodes in the range of about 0.1 to 1,000,000 Pa / m (or 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 (in Pa / m) across the static mixer electrodes can be at least about 10, 100, 1000, 5,000, 10,000, 50,000, 100,000, or 250,000. The pressure drop (in Pa / m) at both ends of the static mixer electrode can be provided within the range of any two of the above-mentioned upper and / or lower limits. For example, in one embodiment, the pressure drop (in Pa / m) at both ends of the static mixer electrode can be between about 10 and 250,000, 100 and 100,000, or 1,000 and 50,000. In this regard, the static mixer electrode, reactor, system and method as described herein can have parameters suitable for industrial applications. The above-mentioned pressure drop or its range can be provided, wherein the volume 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.

[0209] In one embodiment, the following volume flow rate 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, the following volume flow rate can be provided: less than about 1000, 900, 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, 150, 100, 75, 50, 40, 30, 20, 10, or 5 ml / min. The flow rate can be a range provided by any two of these upper and / or lower values, such as a range between approximately 50 and 400, 10 and 200, or 20 and 200.

[0210] The process can be related to the average residence time of about 0.1 second to about 60 minutes in a static mixer or reactor. The average residence time can 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 can 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 can be provided as any two scopes selected from these aforementioned values. For example, the average residence time can be in the range of 5 seconds to 10 minutes, 1 second to 5 minutes or 1 minute to 60 minutes.

[0211] The process can provide a Faradaic efficiency (% of charge passing through 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 can provide a Faradaic efficiency (% of charge passing through 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 can provide a Faradaic efficiency (% of charge passing through that participates in the reaction of interest) within a range provided by any two of the above upper and / or lower limits.

[0212] The anolyte and / or catholyte streams may include any suitable solvent, electroactive material, and supporting electrolyte. The concentration of dissolved substances may vary from a few parts per billion to their solubility limits (tens of moles per liter). In addition to dissolved substances, the fluid stream may also contain any combination of multiple phases: undissolved solids (e.g., solids suspended in the fluid stream), immiscible liquids, and gases. Therefore, the fluid stream may contain aqueous or non-aqueous solvents, molecular solvents, molten salts, ionic liquids, supercritical solvents, or mixtures of these. The dissolved substances may be ionic, molecular, or substantially ion-paired in the solution. They may be dissolved solids, gases, miscible liquids, or mixtures thereof. The other phases present may be suspended solids or gels, organic or inorganic polymers, natural products, or mixtures of these. They may be gases or vapors intentionally introduced or generated by the action of flow and / or electrochemical activity. In another embodiment, the fluid is a liquid or a complex liquid, such as a dissolved and / or suspended liquid containing a solid.

[0213] In one embodiment, a method for removing a substance from a fluid stream may be provided, the method comprising an electrochemical flow cell or system thereof according to any aspect, embodiment or example thereof as described herein. The substance may be a metallic substance dissolved in the fluid stream. It should be understood that any of the above embodiments or examples relating to the performance of the electrochemical flow cell may be applied to this embodiment.

[0214] Example

[0215] The present invention is further described by the following embodiments. It should be understood that the following description is only for the purpose of describing specific embodiments and is not intended to limit the above description.

[0216] Embodiment 1:

[0217] Prepare an electrochemical flow reactor, the electrochemical flow reactor comprising a separator 200 ( Figure 2 ) and included a peristaltic pump (Masterflex L / S variable speed drive w / Remote I / O; 600 rpm) 120 to control the flow of electrolyte into the cell and a power supply 110 (Autolab 302N potentiostat, purchased from Metrohmautolab BV, Utrecht, The Netherlands) to control the applied electrochemical potential / current flowing through the cell.

[0218] The additively manufactured metal static mixer electrodes (SME) 104, 204 as working electrodes fit tightly within a tubular porous polymer separator 202 (GenPore Reading, USA) in a separation mode configuration defining a working compartment. Two ports at either end of the electrode are incorporated into the design to provide connections for fluid flow. The fluid enters the working compartment through these tubes. As with all static mixers, the momentum of the solution causes mixing as it flows through the many angled faces of the mixer surface. In this particular experiment, an inert tubular counter electrode made of glassy carbon surrounds the working compartment at a small distance from the separator, creating a low volume counter compartment and forming the housing of the battery. Two end caps 500 ( Figure 4A , 4B and 4C) to seal the entire assembly. Port 144 machined into the end cap provides fluid flow into the counter electrode compartment. This configuration allows different fluids to be used in the two compartments if the experiment requires.

[0219] The efficiency with which the cell operates can be assessed by comparing the limiting current measured at different flow rates with the results from a rotating disk electrode (RDE) in the same solution. These comparisons are useful indicators of performance and are not used to draw any conclusions about the fluid dynamic conditions at the static mixer surface.

[0220] In order to evaluate the performance of the two configurations of the electrochemical flow reactor of the present invention, a series of experiments were conducted using 0.5 M potassium chloride as the supporting electrolyte and a platinum-coated static mixer electrode (i.e., the working electrode (10 -3 -10 -1 M)) and glassy carbon tubes (i.e., anodes), and studied ferrocyanide ([Fe(CN)6] 3+ Solution (10 -3 -10 -1 Electrochemical reduction of M). A typical reduction reaction on a split configuration of the reactor is performed as follows.

[0221] Chronoamperometric measurements were performed by applying potential steps of −1.4 V, −1.6 V, −1.8 V, and −2 V to the cell over 100 s, with the cell operating in static mode (i.e., 0 mL min) for the first 50 s interval. -1 ) operation, and at intervals of 10 and 400 mL / min -1 Constant flow rate operation between Figure 7-9 ). Steady-state currents were observed for all flow rates, and the recorded currents increased at all potential steps by increasing the flow rate. Although the recorded currents increased with increasing potential, some 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, all but [Fe(CN)6] 3+ In addition to the reduction, hydrogen evolution also occurs at the cathode, which complicates the analysis.

[0222] The experimental results show that at lower electroactive ion concentrations, the reaction is limited by mass transport (i.e., [Fe(CN)6] 3+ At higher concentrations (i.e., 0.1 M [Fe(CN)6] 3+ ), where the reaction is controlled by mass transport and kinetic factors (mixing control), the increase in reaction rate is smaller and faster when using static mixer electrodes, ranging from 1.5 to 3.7.

[0223] Embodiment 2:

[0224] In a split configuration embodiment of an electrochemical flow cell, a stainless steel static mixer electrode (i.e., working electrode) and a glassy carbon tube (i.e., anode) were used to generate a flow cell at 10-1000 mL min -1 The electrochemical flow cell was evaluated at a flow rate of 10-100 ppm Cu in 0.01 MH2SO4. 2+ The efficiency of removing copper ions from acidic contaminated solution. Fig.10 As shown, by increasing the flow rate above 50 mL min -1, the removal efficiency is reduced, which is due to the reduced residence time of the electroactive ions on the working electrode surface to complete the reduction reaction ( Fig.10 (a) and 10(b)). On the other hand, by increasing the flow rate, the charge passing through the working electrode has increased and the current recovery increases accordingly. However, increasing the flow rate is effective because it reduces the residence time of the electroactive ions on the electrode surface.

[0225] Embodiment 3:

[0226] Exhaustive electrolysis experiments were also performed to show how the electrochemical flow cell can effectively remove copper ions from a fixed volume of contaminated aqueous solution. -1 Two liters of copper-contaminated aqueous solution (i.e., 100 ppm CuSO4.4H2O in 0.01 M H2SO4) was treated at a constant flow rate of 2.5 % for 24 hours. Optical images and SEM / EDS results confirmed the deposition of copper ions on the working electrode of the static mixer ( Fig.11 ) and ICP-MS results showed that in a split configuration of an electrochemical flow cell, a 99.7% reduction in copper concentration was achieved within 24 hours ( Fig.12 ).

Claims

1. A continuous flow tubular reactor comprising: Reaction chamber; a first electrode; a second electrode; as well as a separator disposed between the first electrode and the second electrode, the separator at least partially defining a first channel within the reaction chamber and a second channel within the reaction chamber, the first channel being configured to receive a first fluid flow in contact with the first electrode, the second channel being configured to receive a second fluid flow in contact with the second electrode, wherein the separator comprises a permeable membrane that allows electrical communication between the first electrode and the second electrode via the fluid stream while restricting fluid exchange between the fluid streams, and wherein the first electrode is a static mixer electrode, the static mixer electrode comprising an electrically conductive integral support provided by a grid of interconnected segments, the integral support defining a plurality of flow splitting structures that split the first fluid flow into a plurality of sub-flows at a plurality of locations along the length of the first electrode; Wherein the separator and the second electrode are arranged concentrically and coaxially with a central longitudinal axis of the first electrode.

2. The continuous flow tubular reactor according to claim 1, wherein the integral support is a metal or a metal alloy.

3. The continuous flow tubular reactor according to claim 1 or 2, wherein: The integral stent includes a conductive coating.

4. The continuous flow tubular reactor according to claim 1 or 2, wherein: The integral support defines a plurality of passage sections configured for enhanced mass transfer and turbulent advection.

5. The continuous flow tubular reactor according to claim 1 or 2, wherein the diameter of the integral support of the first electrode is equal to the diameter of the first channel.

6. The continuous flow tubular reactor according to claim 1 or 2, wherein the first electrode is arranged in contact with the separator.

7. The continuous flow tubular reactor of claim 1 or 2, wherein the separator and the second electrode are substantially cylindrical.

8. The continuous flow tubular reactor of claim 1 or 2, wherein the second electrode forms at least a portion of a wall of the reaction chamber.

9. The continuous flow tubular reactor of claim 1 or 2, wherein the first electrode comprising the integral support is configured to operate within the first channel to provide a volumetric flow rate of at least 0.1 ml / min for the first fluid flow.

10. A continuous flow system comprising at least one first continuous flow tubular reactor, wherein the first continuous flow tubular reactor is the continuous flow tubular reactor according to any one of claims 1 to 9.

11. The continuous flow system according to claim 10 further comprises: a second continuous flow tubular reactor, the second continuous flow tubular reactor being the continuous flow tubular reactor described in any one of claims 1 to 9; and a plurality of flow pipelines connecting the first continuous flow tubular reactor to the second continuous flow tubular reactor, so that the first channel of the first continuous flow tubular reactor is in fluid communication with the second channel of the second continuous flow tubular reactor, and the second channel of the first continuous flow tubular reactor is in fluid communication with the first channel of the second continuous flow tubular reactor.

12. The continuous flow system according to claim 10 or 11, further comprising: a pump for providing 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 is used to control one or more parameters of the system, including concentration, flow rate, temperature, pressure and residence time.

13. A method for electrochemical treatment of a fluid stream, applied to the continuous flow tubular reactor of any one of claims 1 to 9 or to the continuous flow system of any one of claims 10 to 12.

14. The method according to claim 13, wherein: The first fluid stream and the second fluid stream contain a liquid.

15. A method according to claim 13 or claim 14 for treating waste water, removing dissolved metal ions from a fluid stream, or recovering metals from a fluid stream.

16. A method according to claim 13 or claim 14 for removing dissolved metallic species from a first fluid stream, wherein removal of the metallic species occurs on the surface of the static mixer portion of the first electrode.

17. The method of claim 13 or claim 14, wherein the continuous flow tubular reactor comprises the first electrode, the first electrode comprises the static mixer section, the continuous flow tubular reactor is operated to separate the first fluid stream by splitting the first fluid stream by more than 200 m -1 To enhance chaotic advection, corresponding to the number of times the first fluid flow is split within a given length along the integral support of the first electrode.

18. The method of claim 13 or claim 14, wherein the continuous flow tubular reactor comprises the first electrode, the first electrode comprises the static mixer section, the continuous flow tubular reactor being operated to provide a Peclet (Pe) number of at least 10,000.

19. A method according to claim 13 or claim 14, wherein the continuous flow tubular reactor is operated to provide a volumetric flow rate of the first fluid stream of at least 0.1 ml / min.

20. The method of claim 13 or claim 14, wherein the first fluid stream comprises dissolved metal species at a concentration of less than 0.01 mol / L.

21. The method of claim 13 or claim 14, wherein the continuous flow tubular reactor is operated to provide a recovery efficiency of at least 90% of the contaminants or metallic species initially present in the first fluid stream.

22. The method of claim 13 or claim 14, wherein the continuous flow tubular reactor is operated to provide a voltage in the range of 1 μA·m to the static mixer electrode and the counter electrode. -2 Up to 1000A·m -2 of current density.

23. The method according to claim 13 or claim 14 comprises operating a first continuous flow tubular reactor and a second continuous flow tubular reactor, wherein a plurality of flow lines connect the first continuous flow tubular reactor to the second continuous flow tubular reactor, such that the first channel of the first continuous flow tubular reactor is in fluid communication with the second channel of the second continuous flow tubular reactor, and the second channel of the first continuous flow tubular reactor is in fluid communication with the first channel of the second continuous flow tubular reactor.

24. A method for electrochemical synthesis of products, applied to the continuous flow tubular reactor according to any one of claims 1 to 9 or to the continuous flow system according to any one of claims 10 to 12.

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