EP0058238A1 - Method for assembling membrane electrolytic cells - Google Patents

Method for assembling membrane electrolytic cells Download PDF

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Publication number
EP0058238A1
EP0058238A1 EP81108943A EP81108943A EP0058238A1 EP 0058238 A1 EP0058238 A1 EP 0058238A1 EP 81108943 A EP81108943 A EP 81108943A EP 81108943 A EP81108943 A EP 81108943A EP 0058238 A1 EP0058238 A1 EP 0058238A1
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EP
European Patent Office
Prior art keywords
frames
frame
membrane
placing
stack
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP81108943A
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German (de)
English (en)
French (fr)
Inventor
Morton S. Kircher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Olin Corp
Original Assignee
Olin Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/230,230 external-priority patent/US4367134A/en
Application filed by Olin Corp filed Critical Olin Corp
Publication of EP0058238A1 publication Critical patent/EP0058238A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type

Definitions

  • This invention relates to a method of assembling electrolytic cells and particularly to a method for assembling membrane-type electrolytic cells.
  • Electrolytic cells have been developed which are based on the design principles used in the unit operation of "filter presses” used to filter solids from liquids. These "filter press” cells have followed the practice originated with filter presses of assembling plates or frames housing electrodes with intermediate membranes into a "bank” of frames supported with the frames in a vertical plane on a filter press skeleton structure. In general, this is a convenient method of assembling since the frames may be stored in place and may be shifted back and forth as the cell is assembled or dismantled. In the filtration field, presses are commercially available that shift frames automatically according to a program. Such presses are generally used with filter press electrolytic cells in order to simplify repairs by providing easier access to individual membranes and electrodes in the cell bank.
  • This technique of using a long cell bank and a shifting press has several disadvantages.
  • it is difficult to hold a membrane which may be wet, slippery, heavy, fraglie and soaked with caustic soda, while trying to simultaneously hold the electrode frames in a spaced position to provide enough space between the electrode for fitting the membrane between the two spaced vertical frames and between any cross-frames or other device used to space the frames to obtain a satisfactory seal or fit.
  • the membranes which are very expensive compared to conventional diaphragms, may tear or "bag” out of shape or even fail to seal on all gasket surfaces.
  • treating or conditioning the membranes is essential if the electrolytic cell is to operate at optimal efficiency after assembly.
  • the membranes are received in a nonionic state and must be converted to an ionic conductive form.
  • failure to treat or condition the membrane prior to cell assembly will cause excessive swelling or shrinkage of the membrane after the membranes are emplaced within the cell and operation of the cell begun.
  • Excessive swelling causes wrinkling in the membrane after cell assembly. This wrinkling creates a crease that generally bears against the anode and is attached by chlorine. Apparently the crease from the wrinkle becomes hardened and splits along its top. Alternately, where excessive shrinkage occurs, cracking or rupturing in the membrane will occur.
  • a solution to these and other problems is achieved with the present invention by providing a method of assembling a monopolar filter press-type electrolytic cell by treating or conditioning the membranes, assembling a vertical stack of horizontal electrode frames with a horizontal membrane sheet between each pair of opposed frames, applying pressure to the opposite vertical ends of said stack to vertically compress the stack, rotating the compressed vertical stack from a vertical orientation through approximately 90° and connecting and operating the assembled cell in an electrolytic circuit.
  • FIGURE 1 is a side, elevational view showing a stack 10 of anode frames 12 and cathode frames 14 with a spacer 16 and membrane 18 located between each opposite pair of anode and cathode frames 12, 14.
  • FIGURE 1 also shwos an optional jig 11 which can be used for purposes of guiding and holding stack 10 during assembly according to the method of the invention.
  • Other guiding and support structures such as, for example, the preferred assembly area of FIGURES 5-6 could be utilized so long as it is still possible to properly align frames 12,14 in stack 10 during assembly.
  • Jig 11 is shown to be connected temporarily to an endplate 37 upon which stack 10 rests.
  • FIGURE 2 also shows the same stack of frames held by columns 38 and cross members 40 and 42.
  • the same reference numbers in FIGURES 1-4 refer to the same parts, unless otherwise indicated.
  • Each frame 12 or 14 has external lifting eyes 36 which, when the frame is assembled in stack 10, are used to lift the frame. Eyes 36 are adapted to receive lifting hooks (not shown).
  • FIGURES 1 and 2 Although eight eyes 36 are shown attached to each frame in FIGURES 1 and 2, any number of eyes could be utilized if desired. Eight eyes are preferred because this number allows a hook to be located at the end of each side of frames 12 and 14 so as to minimize the amount of unsupported frame during lifting and to avoid interference of the guides with bus bars of monopolar cell frame necessary to connect the connector rods to a current source for electrolysis to occur.
  • Each frame 12 also includes a pair of spaced, planar . foraminous mesh surfaces 20 and 22 between which lie a plurality of substantially horizontal conductor rods 24.
  • each frame 14 includes a pair of spaced, planar foraminous surfaces 28 and 30 between which lies a plurality of substantially horizontal conductor rods 26.
  • each frame 12 includes a solid outer border portion 25 and each frame 14 includes a frame-like outer border portion 29. Border portions 25 and 29 support and space the mesh surfaces 22, 24, 28, and 30 while rods 24 and 26 conduct electricity from the outside of the cell to mesh surfaces 20,22 and 28,30, respectively.
  • Each frame 12 is provided with an outlet pipe 34 while each frame 14 is provided with an outlet pipe 32.
  • pipe 32 would serve as a hydrogen gas outlet while pipe 34 would serve as a chlorine gas outlet.
  • Pipes 32 and 34 connect respectively, to disengagers 56 and 54 (see FIGURES 3 and 4).
  • stack 10 shown in FIGURES 1 and 2 is termed a monopolar stack since each frame has a single polarity. If desired, stack 10 could be made in a bipolar configuration in which each frame should have one anode side and one cathode side electrically connected to each other. If each stack 10 was made of bipolar frames, conductor rods 24 and 26 would not be present since bipolar electrode frames conventionally have internal conductors from anode surface to cathode surface.
  • the stacking operation could be accomplished through use of overhead cranes and slings which could be remotely controlled to lift and move and position the frames into and out of jig 11 during assembly or disassembly.
  • Membranes 18 could be conveniently stored in a flat, plastic-lined box filled with hydrolyzing liquid so that they could be readily moved atop the frames during the stacking operation.
  • Frames 12, 14 and spacers 16 could be conveniently stored in a cabinet 11 8 .
  • FIGURES 5 and 6 show an assembly area 100 designed for use in efficiently vertically stacking a pack 110 of frames preparatory to compression and use in the cell 46,48 as previously described. Reference will be made below to membranes 16 and spacers 18 and other items shown in FIGURES 1-4.
  • Area 110 comprises a stack support framework 112, an elevated work platform 114, a membrane storage box 116, a frame storage cabinet 118, and a spacer storage cabinet 142 which is attached to box 116 and thus placed adjacent a side of framework 112.
  • Stack 110 of FIGURES 5-6 is similar to stack 10 of FIGURES 1-2 except that it is free-standing so as to avoid the need to lift membranes 18 over a jig 11, since membranes 18 could be damaged during such lifting unless proper care was taken. With a free-standing stack 110, the membranes 18 and spacers 16 (see FIGURES 1-2) can be slid laterally directly onto the top of stack 110 without lifting.
  • Framework 112 comprises a U-shaped guide rack 119, a rack holder 120 and four or more air cylinders 122.
  • U-shaped rack 119 has a bottom portion and two recessed vertical member 124, 126 each having recess 128 adapted to align and restrain the outer ends of rods 24 and 26.
  • Air cylinders 122 are connected to a floor 130 upon which the assembly area is constructed and to the bottom portion 123 and are used to raise or lower rack 119 so as to position the top of stack 110 at the best levels for the addition of each membrane spacer and frame.
  • Air cylinders 122 are preferably remotely controlled by assembly workers 132,134 as they assemble stack 110. A conventional remote control system could be used for this purpose.
  • Membrane storage box 116 is supported from a building wall (not shown) adjacent area 100, but could be supported in any other desired fashion which would not interfere with the assembly procedure.
  • Box 116 comprises a conditioning tank 136 and a pair of "s q ueegies" or wipers 138.
  • the conditioning box 116 can serve multiple purposes. Where a hydrolyzing fluid is utilized, the box will serve to hydrolyze the membrane (i.e. converting a salt from the ion exchange group to the active acid form) so that the membranes are in their ion conductive form.
  • the conditioning box also can serve to contain a fluid that, either separately or concurrently with the hydrolysis, equilibrates the membranes with the solution in the box so that the solution pressure of the water molecules on the membrane is at the desired level when the membranes are assembled in the cell.
  • the conditioning box 116 also serves the purpose of storing the membranes in their hydrolyzed and/or equilibrated states until they are used during the stacking procedure.
  • the membranes be . prepositioned in box 116 prior to the actual assembly operation so that the membranes can most rapidly be removed from the box 116 onto the top 140 of stack 110 during assembly.
  • the membranes could easily be transferred directly from a shipping box into box 116 if the membrane was precut into sheets of proper size.
  • top 140 of stack 110 is adjusted by use of air cylinders 122 so that top.140 is at the level of the particular membrane which is to be slid from box 116 onto stack 110.
  • An operator then grabs the rod which has been passed through loops in one end of the membrane as described above, and then pulls the membrane from box 116 laterally directly onto the top 140 of stack 110. In this way, the stresses on'the membrane during assembly are minimized.
  • Box 116 is elevated so that stack 110 will not have moved a great deal and so that box 116 is at a convenient level for the operator 132, 134.
  • the squeegies 138 are provided to remove the hydrolyzing or conditioning liquid from the membranes as they are withdrawn from box 116.
  • Cabinet 118 is also elevated at a convenient level for operators 132, 134.
  • Cabinet 118 is provided with a shelf for each frame of the cell to be constructed.
  • the frames are stored in cabinet 118 until needed for the assembly operation.
  • cabinet 118 is inspected to see that the frames are in proper position for the stacking operation. It will be appreciated that the frames will be inserted into and stored within cabinet 118 with their conductor rods pointing in the appropriate direction so that there is no need to rotate or flip the frames during the stacking operation.
  • FIGURE 5 shows operators 132 and 134 in position for sliding frames from cabinet 118 onto the top 140 of stack 110. Lines 144 show the position of one of the frames as removed from cabinet 118 just before it is placed atop stack 110.
  • Platform 114 is a conventional elevated work floor of any suitable material. Platform 114 is elevated in order that the stack 110 can be lowered to a position below the level of operators 132 and 134 and so that air cylinders 122 can be provided underneath rack 119 without raising rack 119 to an awkwardly high position.
  • FIGURES 5 and 6 show operators. 132 and 134 manipulating frames
  • the frames could also be handled by a bridge crane, a sling, a hoist, a fork lift, or some other handling device, such as for example, slide bars extendable from cabinet 118, if the sizes of the frames were or the frames were heavy enough to make it undersirable to move them manually.
  • this vertical stacking assembly is designed for use with a membrane-type electrolytic cell which is rather high in comparison with conventional "filter press" cells. Special cell designs are under development which should allow the construction of frames of sufficient size that manual operation might become undesirable.
  • a vibrator could be used to jiggle the membranes and sheets sufficiently to make them lie flat after such alignment operations.
  • a carpenter's level (not shown) would be used to vertically align the frames during stacking and to check the top 140 of the stack 110 to be sure that top 140 is horizontal to confirm that the frames are properly seated on their gaskets so that the cell will be properly sealed when it is later compressed.
  • the stack 110 is preferably "preconditioned” following completion of the stacking operation by passing warm, moist air through the frames in order to put the frames at operating temperature.
  • This "preconditioning" is desirable so that there is a minimum of dimensional change from the time stacking is compressed to the time that the cell is at operating condition during normal operation of the cell. If the cell is not preconditioned, larger forces are required to compress the cell, heavier frame construction is needed and the greater forces may tend to damage the gaskets. Preconditioning softens the gaskets.
  • the tie bolts which compress stack 110 following vertical assembly would be tightened by application of limited torque in order to put the stack at a predetermined dimension which has been previously calculated to provide adequate seating but yet not compress the gaskets so much that they are damaged.
  • the membranes which are preferred for use in stack 110 are ion exchange membranes having sulfonic acid or carboxylic acid or moieties as the active ion exchange group. Such membranes are commercially available under the trademark Nafion from E. I. duPont De Nemours and Company or alternatively are available under the trademark Flemion from Asahi Glass Co. Ltd.
  • the anode frames 12 are preferably made of titanium with the mesh surfaces 20,22 being coated with a catalytic anode coating such as a mixed crystal of ruthinium oxide or titanium oxide. Other anode materials could also be used.
  • the cathode frames 14 are preferably made of nickel with a catalytic coating such as Raney nickel layer or some other catalytic coating.
  • Frames 12 and 14 could be built of non- metallic materials so long as the mesh surfaces 20, 22, 28, and 30 are made of conductive materials suitable for use as electrode surfaces.
  • Platform 114 can be built of wood, iron, or any other desired material.
  • Air cylinders 122 would be of conventional design and would be provided with a conventional remote control so that operators 132, 134 could remotely operate air cylinders 122 during stacking.
  • Box 116 and cabinet 118 could be made of steel, plastic or any other suitable material; however, a chlorine resistant material would be preferred since it is expected that these structures will be exposed to the environment of a chlor-alkali plant which necessarily produces highly corrosive products.
  • the cell which is vertically stacked, -rotated, through approximately 90° and then connected can be much larger than conventional cells and yet can be easily inspected for integrity of gaskets and cells because all sides of the frame are readily visible during assembly by merely having an operator work around the perimeter of the vertical stack 110 and check the gaskets on the top 140 of the stack 110.
  • the procedure is also very rapid because box 116 and cabinet 118 can be positioned at a proper height to allow rapid sliding of the various layers of stack 110 onto one another.
  • stack 10 Prior to actual operation of stack 10 as an electrolytic cell, it is necessary to connect rods 24 and 26 to terminals or bus bars or intercell connectors, so that current can be passed from cell to cell in an electrical circuit of such cells. Before operation of the cell, it is also necessary to connect stack 10 to product supply and withdrawal conduits so that raw materials can be fed to the cell and products can be removed from the cell. In particular, this requires connection of each frame 12 and 14 to a source of raw materials and a product withdrawal line.
  • FIGURE 3 shows a pair of cells 46 and 48, each of which includes a stack 10 (see FIGURES 1 and 2) of electrode frames which have been vertically stacked and then rotated 90 degrees to become a horizontal stack of vertical frames and which has been connected electrically and fluidly so that it can operate as an electrolytic cell.
  • Each cell 46 and 48 is provided with an anode terminal on the right and a cathode terminal on the left.
  • Intercell connectors 80 serve to electrically connect the cathode terminal of cell 48 with the anode terminal of cell 46 so that cells 46 and 48 form an electrical series. It will be understood that any number of cells similar to cells 46 and 48 could be included within this electrical series circuit but that only two cells are shown for simplicity.
  • Each cell 46 and 48 is provided with an anolyte disengager 54 and a catholyte disengager 56; although if frames 12 and 14 were sufficiently thick for disengagement to occur therewith, the disengagers could be omitted.
  • Disengagers 54 and 56 serve to separate or "disengage" hydrogen gas and chlorine gas from caustic catholyte and anolyte brine, respectively.
  • the disengaged hydrogen passes from disengager 56 upwardly through an outlet line 68 to hydrogen-removal line 72 while disengaged chlorine passes upwardly through an outlet line 66 to a chlorine-removal line 70.
  • Disengager 54 receives fresh anolyte through line 62 and depleted anol y te is removed from disengager 54 through line 64.
  • gas-containing anolyte is produced within frames 12 and flows from frames 12 to disengager 54 through pipes 34 while disengaged anolyte is recirculated, if desired, down through a downpipe 76 to the bottom of frames 12 so as to increase the upward flow rate of anolyte through frames 12.
  • gas-containing catholyte is produced within frames 14 during electrolysis and is fed through pipes 32 upwardly to disengagers 56 while disengaged liquid catholyte is recirculated, if desired, downwardly through a downpipe 74 to the bottom of frames 14 so as to increase the upward flow rate of catholyte through frames 14 during electrolysis.
  • an end frame 52 can be placed under stack 10 preceding vertical stacking. If frames 52 are placed under stack 10 during assembly, then end plate 37 of FIGURES 1-2 , and end frame 52 of FIGURES 3-4 are the same item. End plates 37 could alternatively be a pan-type end electrode frame in addition to frames 52 and would be extra support for the cell.
  • a vibrator could be utilized to assist in the vertical assembly of the stack by causing a vibration of the frames such that the membranes and spacers are better seated. Also, the vibrations tend to smooth out any wrinkles in the membrane during stacking.
  • the method of the invention is particularly useful for cells having large frames.
  • “large” frames is meant frames having dimensions in the plane of the electrode greater than about 4 feet.
  • the method of the invention is also particularly useful for cells in which the thickness of the horizontal stack does not exceed about twice the height of the cell.
  • the large frames and limited thickness to height ratio are particularly desirable economically in order to minimize the amount of conductive material which is needed and to maximize the amount of useful part per unit area of producer space of any cell plant utilizing the invention.
  • the number of frames which may be stacked is within the range from about 2 up to about 50 and preferably within the range of from about 5 up to about 40 and more preferably within the range of from about 10 up to about 30 frames.
  • the method may be used for bipolar cells as well as for monopolar cells.
  • the size of the frame which may be used depends more on the requirement of other limitations of cell design than with limitations of the present method.
  • Bipolar cells through the use of the method of the invention, can be designed practicably for sizes from about 2 feet up to about 30 feet in the horizontal direction transverse to current flow, and from about 2 feet to up.to about 15 feet in the vertical direction transverse to current flow.
  • the lesser length is an advantage rather than a disadvantage because it eliminates the need for filter presses to manipulate individual frames since the cell length is made sufficiently small through use of the present invention to enable the cells to be removed from the circuit by use of jumper switches of economical size without disrupting current flow through the remaining cells.
  • Monopolar cells of extremely large size would also be practical within the same ranges with the added limitation that one direction must be limited to about 10 feet maximum because of the economic limitations upon the length of current conductors such as conductor rods 24 and 26.
  • the size of frames given in the Example below, approximately 5 feet by 7 feet, are convenient and comparatively large in comparison with current technology; however, as is indicated above, the present invention makes larger sizes practical.
  • the frames and membranes Prior to application of pressure to the vertical stack, the frames and membranes can be advantageously preconditioned by passing warm moist fluid, such as air, through the frames for a preset time so as to stabilize the frames at operating temperature.
  • warm moist fluid such as air
  • the pressure can be applied to compress the stack the desired amount.
  • the membranes may need to be held at a controlled humidity, once they have been hydrolyzed, in order to prevent irreparable damage, although the vertical assembly method is preferably fast enough that drying can be avoided.
  • a cell having 70 square meters of electrode surface with a rated capacity of 150 KA was assembled using a vertical stacking method. Electrode frames with gaskets cemented in place were laid horizontal and vertically stacked in a pile, in inverse order of assembly. Each frame was approximately 80" X 60" X 2". There were twelve anode frames, eleven cathode frames, and two end cathode frames which had cathode mesh surface on one side and a fluid tight surface on the other. On the adjacent side of the rectangular space defining the work area, a flat plastic lined box was laid containing ion exchange membranes, hydrolyzed, wet with hydrolyzing liquid. The box contained twenty-four membranes approximately 80" X 60".
  • a structural end frame (80" X 60") constructed of 6" steel channels having 10 projecting lugs for anchoring tie rods was leveled on a platform at the center of the work area.
  • the stack was built in the order: end cathode, membrane, anode, membrane, cathode, membrane ... etc. to the final end cathode and second structural end frame.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP81108943A 1981-02-02 1981-10-26 Method for assembling membrane electrolytic cells Withdrawn EP0058238A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US230230 1981-02-02
US06/230,230 US4367134A (en) 1980-04-21 1981-02-02 Method for assembling membrane electrolytic cells

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EP0058238A1 true EP0058238A1 (en) 1982-08-25

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EP81108943A Withdrawn EP0058238A1 (en) 1981-02-02 1981-10-26 Method for assembling membrane electrolytic cells

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EP (1) EP0058238A1 (ja)
JP (1) JPS57134583A (ja)
BR (1) BR8106573A (ja)
CA (1) CA1161788A (ja)
MX (1) MX150769A (ja)
ZA (1) ZA815034B (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0133792A1 (en) * 1983-08-01 1985-03-06 Olin Corporation Replacement of a structurally damaged membrane in an electrolytic cell
US4541911A (en) * 1983-07-19 1985-09-17 Imperial Chemical Industries Plc Method of assembling a filter press type electrolytic cell
US4824542A (en) * 1986-10-30 1989-04-25 Imperial Chemical Industries Plc Filter press structure or cell and method of assembling same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2150638A4 (en) * 2007-05-10 2011-08-31 Martinrea Internat Inc electrolyzer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2179761A1 (en) * 1972-04-12 1973-11-23 Solvay Bipolar element - for multicell alkali halide electrolysis plant
GB1348419A (en) * 1970-07-16 1974-03-20 Chemech Eng Ltd Inclined bipolar electrolytic cell
EP0038445A1 (en) * 1980-04-21 1981-10-28 Olin Corporation Method for assembling and operating membrane electrolytic cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1348419A (en) * 1970-07-16 1974-03-20 Chemech Eng Ltd Inclined bipolar electrolytic cell
FR2179761A1 (en) * 1972-04-12 1973-11-23 Solvay Bipolar element - for multicell alkali halide electrolysis plant
EP0038445A1 (en) * 1980-04-21 1981-10-28 Olin Corporation Method for assembling and operating membrane electrolytic cells

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4541911A (en) * 1983-07-19 1985-09-17 Imperial Chemical Industries Plc Method of assembling a filter press type electrolytic cell
EP0133792A1 (en) * 1983-08-01 1985-03-06 Olin Corporation Replacement of a structurally damaged membrane in an electrolytic cell
US4824542A (en) * 1986-10-30 1989-04-25 Imperial Chemical Industries Plc Filter press structure or cell and method of assembling same

Also Published As

Publication number Publication date
JPS57134583A (en) 1982-08-19
MX150769A (es) 1984-07-12
JPS6212313B2 (ja) 1987-03-18
BR8106573A (pt) 1983-04-05
ZA815034B (en) 1982-08-25
CA1161788A (en) 1984-02-07

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