Apparatus for electrowinning multivalent metals

Claim 2

An electrolytic diaphragm cell, without means to adjust the diaphragm pore size, for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one foraminous diaphragm with a porous metal substrate and a metal coating thereon, the diaphragm being resistant to the corrosive environment within the containing means and having a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the diaphragm being adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 3

The electrolytic cell of claim 1 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.5.

Claim 4

The electrolytic cell of claim 1 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4.

Claim 5

The electrolytic cell of claim 1 wherein the flow coefficient is within the range of from about 0.1 to about 8.

Claim 6

The electrolytic cell of claim 4 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4.

Claim 7

The electrolytic cell of claim 5 including a means to insulate said diaphragm from said anode, cathode, cell body and from electric sources outside of said cell.

Claim 8

The electrolytic cell of claim 5 wherein the metal coating is electrolytically deposited cobalt.

Claim 9

The electrolytic cell of claim 5 wherein the metal coating is electrolytically deposited nickel.

Claim 10

The electrolytic cell of claim 5 wherein the substrate is commercially pure nickel.

Claim 11

The electrolytic cell of claim 5 wherein the substrate consists essentially of cobalt or nickel.

Claim 12

The electrolytic cell of claim 10 wherein the metal coating is electrolessly deposited nickel.

Claim 13

The electrolytic cell of claim 10 wherein the metal coating is electrolessly deposited cobalt.

Claim 14

The electrolytic cell of claim 12 wherein the substrate is metal screen with a mesh of from about 50 to about 250.

Claim 15

The electrolytic cell of claim 13 wherein said diaphragm is electrically insulated from electric sources outside of said anode compartment and said cathode compartment.

Claim 16

The electrolytic cell of claim 5 wherein the coating consists essentially of cobalt or nickel.

Claim 17

The electrolytic cell of claim 1 wherein the flow coefficient is within the range of from about 0.2 to about 1.

Claim 18

The electrolytic cell of claim 16 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4.

Claim 19

The electrolytic cell of claim 16 wherein the substrate is a metal screen with a mesh of from about 50 to about 250.

Claim 20

The electrolytic cell of claim 16 wherein the substrate consists essentially of cobalt or nickel.

Claim 21

The electrolytic cell of claim 16 wherein the metal coating is electrolytically deposited cobalt.

Claim 22

The electrolytic cell of claim 16 wherein the metal coating is electrolytically deposited nickel.

Claim 23

The electrolytic cell of claim 16 wherein the substrate is commercially pure nickel.

Claim 24

The electrolytic cell of claim 22 wherein the metal coating is electrolessly deposited nickel.

Claim 25

The electrolytic cell of claim 22 wherein the metal coating is electrolessly deposited cobalt.

Claim 26

The electrolytic cell of claim 24 wherein the substrate is a metal screen with a mesh of from about 50 to about 250.

Claim 27

The electrolytic cell of claim 25 wherein said diaphragm is electrically insulated from electric sources outside of said anode compartment and said cathode compartment.

Claim 28

The electrolytic cell of claim 1 wherein the substrate contains at least 50 weight percent of a metal selected from the group consisting of cobalt and nickel.

Claim 29

The electrolytic cell of claim 1 wherein the diaphragm substrate is commercially pure nickel.

Claim 30

The electrolytic cell of claim 1 wherein the metal coating is electrolytically deposited nickel.

Claim 31

The electrolytic cell of claim 1 wherein the metal coating is electrolessly deposited cobalt.

Claim 32

The electrolytic cell of claim 1 wherein the metal coating is electrolessly deposited nickel.

Claim 33

The electrolytic cell of claim 1 wherein the substrate is a metal screen with a mesh of from about 50 to about 250.

Claim 34

The electrolytic cell of claim 1 wherein the substrate is a metal screen with a mesh of from about 100 to about 200.

Claim 35

The electrolytic cell of claim 1 wherein the cell portion in contact with the electrolyte is resistant to molten salts and salt mixtures selected from the group consisting of NaCl, LiCl--KCl, LiCl--KCl--NaCl, and LiCl--KCl--CaCl 2 .

Claim 36

The electrolytic cell of claim 1 wherein the cell portion in contact with the electrolyte is resistant to a mixture of lithium chloride and potassium chloride.

Claim 37

The electrolytic cell of claim 1 including a means to exclude oxygen, nitrogen, carbon dioxide and water vapor from within the cell.

Claim 38

The electrolytic cell of claim 1 wherein said electrical energy means is electrically connected to only the anode and the cathode.

Claim 39

The electrolytic cell of claim 37 including a means to electrically insulate said anode, cathode and diaphragm from said containing body.

Claim 40

The electrolytic cell of claim 1 including a means to electrically insulate said anode, cathode and diaphragm from said containing body.

Claim 41

The electrolytic cell of claim 1 wherein said electrical energy means is electrically connected to only said anode, cathode and feed means.

Claim 42

The electrolytic cell of claim 40 wherein said anode, cathode, feed means and diaphragm are electrically insulated from said containing body.

Claim 43

The electrolytic cell of claim 1 including a means to remove metallic titanium from said cathode compartment.

Claim 44

The electrolytic cell of claim 1 wherein said diaphragm is supported by a porous member to complement the physical strength of said diaphragm during operation of the electrolytic cell at elevated temperatures.

Claim 45

The electrolytic cell of claim 1 including a means to supply a protective gas into the said anode compartment and said cathode compartment.

Claim 46

The electrolytic cell of claim 1 wherein said feed means is adapted to regulatively supply titanium tetrachloride into said cathode compartment.

Claim 47

The electrolytic cell of claim 1 wherein the distance between said anode and said diaphragm is at least 1/4 times the anode diameter.

Claim 48

The electrolytic cell of claim 1 wherein the distance between said anode and said diaphragm is within the range of from about 1/4 to about 11/2 times the anode diameter.

Claim 49

The electrolytic cell of claim 1 wherein the distance between said anode and said diaphragm is substantially equal to the anode diameter.

Claim 50

The electrolytic cell of claim 1 wherein the coating consists essentially of cobalt.

Claim 51

The electrolytic cell of claim 1 wherein the coating consists essentially of nickel.

Claim 52

An electrolytic cell for the production of metallic titanium from titanium tetrachloride in a molten lithium chloride-potassium chloride salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one woven metal diaphragm with a diaphragm coefficient with the range of from about 0.1 to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25 adapted to be at least partially immersed in the bath to space apart said anode and said cathode compartments, said diaphragm consisting essentially of a nickel substrate screen with an adherent coating layer consisting essentially of cobalt or nickel; at least one titanium tetrachloride feed means adapted to provide titanium ions to the bath; a means to remove gaseous chlorine from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 53

An electrolytic cell for the production of metallic titanium from titanium tetrachloride in a molten lithium chloride-potassium chloride salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one woven metal diaphragm with a diaphragm coefficient with the range of from about 0.1 to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25 adapted to be at least partially immersed in the bath to space apart said anode and said cathode compartments, said diaphragm consisting essentially of a nickel substrate screen with an adherent coating layer consisting essentially of cobalt or nickel; at least one titanium tetrachloride feed means adapted to provide titanium ions to the bath; a means to remove gaseous chlorine from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 54

The electrolytic cell of claim 51 wherein the distance between said anode and said diaphragm is at least about 1/4 times the anode diameter.

Claim 55

The electrolytic cell of claim 57 wherein the distance between said anode and said diaphragm is within the range of from about 1/4 to about 11/2 times the anode diameter.

Claim 56

The electrolytic cell of claim 51 wherein the distance between said anode and said diaphragm is substantially equal to the anode diameter.

Claim 57

The electrolytic cell of claim 51 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.5.

Claim 58

The electrolytic cell of claim 51 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4.

Claim 59

The electrolytic cell of claim 51 wherein the flow coefficient is within the range of from about 0.1 to about 8.

Claim 60

The electrolytic cell of claim 57 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4.

Claim 61

The electrolytic cell of claim 51 wherein the flow coefficient is within the range of from about 0.2 to about 1.

Claim 62

The electrolytic cell of claim 59 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4.

Claim 63

The electrolytic cell of claim 51 wherein the substrate screen has a mesh within the range of from about 100 to about 200.

Claim 64

A metallic diaphragm suitable to separate an anode compartment from a cathode compartment in an electrolytic cell for electrolytically producing titanium comprising a foraminous member with a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the surface of the foraminous member being coated with a metal consisting essentially of cobalt or nickel.

Claim 65

A metallic diaphragm suitable to separate an anode compartment from a cathode compartment in an electrolytic cell for electrolytically producing titanium comprising a foraminous member with a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the surface of the foraminous member being coated with a metal consisting essentially of cobalt or nickel.

Claim 66

The diaphragm of claim 62 wherein said foraminous member consists essentially of an about 50 to about 250 mesh nickel substrate screen with an adherent coating layer consisting essentially of cobalt.

Claim 67

The diaphragm of claim 62 wherein the flow coefficient is within the range of from about 0.1 to about 8.

Claim 68

The diaphragm of claim 62 wherein the flow coefficient is within the range of from about 0.2 to about 1.

Claim 69

An electrolytic diaphragm cell, without means to adjust the diaphragm pore size, for the production of a multivalent metal in a molten salt bath comprising: a body adapted to contain the bath, and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one foraminous diaphragm with a porous metal substrate and a metal coating thereon, the diaphragm being resistant to the corrosive environment within the containing means and having a diaphragm coefficient greater than zero to 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the diaphragm being adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments; at least one feed means adapted to provide multivalent metal ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit a solid multivalent metal on said cathode.

Claim 70

An electrolytic diaphragm cell, without means to adjust the diaphragm pore size, for the production of a multivalent metal in a molten salt bath comprising: a body adapted to contain the bath, and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one foraminous diaphragm with a porous metal substrate and a metal coating thereon, the diaphragm being resistant to the corrosive environment within the containing means and having a diaphragm coefficient greater than zero to 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the diaphragm being adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments; at least one feed means adapted to provide multivalent metal ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit a solid multivalent metal on said cathode.

Claim 71

The electrolytic cell of claim 66 including a means to insulate said diaphragm from said anode, cathode, cell body and electric sources outside of said cell and said diaphragm has the specified diaphragm coefficient and flow coefficient at least before operation of the cell.

Claim 72

An electrolytic diaphragm cell, without means to adjust the diaphragm pore size, for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode; at least one foraminous diaphragm with a porous metal substrate and a metal coating thereon, the diaphragm being resistant to the corrosive environment within the containing means and having a diaphragm coefficient greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the diaphragm being adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments, the diaphragm coefficient being represented by the formula ##EQU3## V s = voltage in volts in an aqueous 0.1 molar sodium chloride solution as determined by calomel measuring electrodes communicating with the solution by salt bridges with orifices to such salt bridges spaced 0.75 inch apart between silver-chloride primary electrodes spaced one inch apart I s = 0.002 amps V d+s = the voltage in volts as determined under the same conditions as for V s with the diaphragm positioned between the measuring electrodes I d+s = 0.002 amps, the flow coefficient is represented by the formula ##EQU4## where: h = a pressure head of ten inches of water at about 75° F. as measured upwardly from the centerline of a generally circular diaphragm portion, with a 30 square inch area on a single surface of the diaphragm portion, where a water flow measurement through the diaphragm is obtained, and F = the volumetric water flow rate through the diaphragm portion at about 75° F. in liters per minute.

Claim 73

An electrolytic diaphragm cell, without means to adjust the diaphragm pore size, for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode; at least one foraminous diaphragm with a porous metal substrate and a metal coating thereon, the diaphragm being resistant to the corrosive environment within the containing means and having a diaphragm coefficient greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25, the diaphragm being adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments, the diaphragm coefficient being represented by the formula ##EQU3## V s = voltage in volts in an aqueous 0.1 molar sodium chloride solution as determined by calomel measuring electrodes communicating with the solution by salt bridges with orifices to such salt bridges spaced 0.75 inch apart between silver-chloride primary electrodes spaced one inch apart I s = 0.002 amps V d+s = the voltage in volts as determined under the same conditions as for V s with the diaphragm positioned between the measuring electrodes I d+s = 0.002 amps, the flow coefficient is represented by the formula ##EQU4## where: h = a pressure head of ten inches of water at about 75° F. as measured upwardly from the centerline of a generally circular diaphragm portion, with a 30 square inch area on a single surface of the diaphragm portion, where a water flow measurement through the diaphragm is obtained, and F = the volumetric water flow rate through the diaphragm portion at about 75° F. in liters per minute.

Claim 74

The cell of claim 68 wherein the diaphragm coefficient is from about 0.1 to about 0.5.

Claim 75

An electrolytic cell for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be be at least partially immersed in the bath, disposed within said cathode compartment; at least one metallic, foraminous diaphragm, having a porous metal substrate with an electrolytically deposited cobalt coating thereon, resistant to the corrosive environment within the containing means with a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25 adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 76

An electrolytic cell for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be be at least partially immersed in the bath, disposed within said cathode compartment; at least one metallic, foraminous diaphragm, having a porous metal substrate with an electrolytically deposited cobalt coating thereon, resistant to the corrosive environment within the containing means with a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25 adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 77

An electrolytic cell for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one metal coated, foraminous diaphragm resistant to the corrosive environment within the containing means with a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25 adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments, said diaphragm being electrically insulated from electric sources outside said anode and cathode compartments; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 78

An electrolytic cell for the production of metallic titanium in a molten salt bath comprising: a body adapted to contain the bath and to separate the bath from the ambient atmosphere; an anode compartment disposed within said body; a deposition cathode compartment disposed within said body and spaced apart from said anode compartment by a diaphragm; at least one anode, adapted to be at least partially immersed in the bath, disposed within said anode compartment; at least one deposition cathode, adapted to be at least partially immersed in the bath, disposed within said cathode compartment; at least one metal coated, foraminous diaphragm resistant to the corrosive environment within the containing means with a diaphragm coefficient of greater than zero to about 0.5 and a flow coefficient within the range of from about 0.1 to about 25 adapted to be at least partially immersed in the bath to space apart said anode and cathode compartments, said diaphragm being electrically insulated from electric sources outside said anode and cathode compartments; at least one feed means adapted to provide titanium ions to the bath; a means to remove a gas from said anode compartment; and a means to provide sufficient electrical energy to said anode and said cathode to deposit solid titanium on said cathode.

Claim 79

The electrolytic cell of claim 71 wherein the coating consists essentially of cobalt.

Claim 80

The electrolytic cell of claim 72 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4 and the flow coefficient is within the range of from about 0.1 to about 8.

Claim 81

The electrolytic cell of claim 71 wherein the coating consists essentially of nickel.

Claim 82

The electrolytic cell of claim 74 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4 and the flow coefficient is within the range of from about 0.1 to about 8.

Claim 83

The electrolytic cell of claim 71 wherein the diaphragm coefficient is within the range of from about 0.1 to about 0.4 and the flow coefficient is within the range of from about 0.1 to about 8.