ELECTROCHEMICAL METHODS TO GENERATE HYDROGEN AND SEQUESTER CARBON DIOXIDE

1 . A method of generating renewable hydrogen and sequestering gaseous carbon dioxide comprising:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one water electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode, wherein the hydroxide ions are present in the form of a base;

d) collecting the hydrogen gas product;

e) collecting the oxygen gas product;

f) removing some or all of the acid from the anode region;

g) removing some or all of the base from the cathode region; and

h) contacting the hydroxide ions in the base with a source of gaseous carbon dioxide to sequester carbon dioxide in solution as bicarbonate or carbonate or a mixture thereof.

2 . The method according to claim 1 , wherein the source of gaseous carbon dioxide is atmospheric carbon dioxide.

3 . The method according to claim 1 , wherein the source of gaseous carbon dioxide is a gas stream.

4 . The method according to claim 1 , further comprising isolating bicarbonate or carbonate from the solution.

5 . The method according to claim 4 , wherein isolating bicarbonate or carbonate from the solution comprises precipitating bicarbonate or carbonate from the solution.

6 . The method according to claim 4 , further comprising the step of concentrating the solution.

7 . The method according to claim 1 , further comprising chilling the solution to a temperature ranging from about 0° C. to about 10° C. to precipitate carbonate or bicarbonate from the solution.

8 . The method according to claim 1 , further comprising adding a salt comprising calcium ions to isolate calcium carbonate from the solution.

9 . The method according to claim 1 , further comprising adding a salt comprising magnesium ions to isolate magnesium carbonate from the solution.

10 . The method according to claim 1 , further comprising spraying the solution to precipitate carbonate or bicarbonate from the solution.

11 . The method according to claim 1 , further comprising applying to the water electrolysis cell a counter-current flow adapted to introduce concentrated electrolyte into a central feed chamber separated by semi-permeable membranes from the anode and cathode regions, such that the direction of flow of the electrolyte is opposite to the direction of flow of acid and base produced at the anode and cathode regions.

12 . The method according to claim 1 , further comprising maintaining a separate anode and cathode region by providing at least one ion selective membrane positioned between the anode region and the cathode region of the electrolysis cell.

13 . The method according to claim 1 , further comprising maintaining a separate anode and cathode region by providing at least one non-selective, semi-permeable membrane positioned between the anode region and the cathode region of the electrolysis cell.

14 . The method according to claim 1 , further comprising continuously supplying fresh electrolyte to the electrolysis cell.

15 . The method according to claim 1 , further comprising supplying fresh electrolyte to the electrolysis cell in a batch-wise manner.

16 . The method according to claim 1 , further comprising maintaining a pH difference between the anode region and the cathode region of at least 6 pH units.

17 . The method according to claim 1 , wherein the electricity supplied from the source ranges from about 1.2 to about 10.0 volts.

18 . The method according to claim 1 , wherein the voltage supplied from the energy source is at least 1.2 volts.

19 . The method according to claim 1 , wherein a pH of the base produced at the cathode region ranges from about pH=8 to about pH=14.

20 . The method according to claim 1 , further comprising applying positive pressure to the electrolysis cell to remove the acid from the anode region and the base from the cathode region.

21 . The method according to claim 1 , further comprising applying a gravity feed to the electrolysis cell to remove the acid from the anode region and the base from the cathode region.

22 . The method according to claim 1 , further comprising continuously pumping acid from the anode region to an acid storage region and the base from the cathode region to a base storage region.

23 . The method according to claim 1 , wherein the electrical source is a renewable energy source.

24 . The method according to claim 23 , further comprising recycling the hydrogen gas to the renewable energy source to be utilized as a fuel.

25 . The method according to claim 23 , wherein the renewable energy source is a fuel cell powered by renewable hydrogen, a synthetic fuel, biomass, or biofuel.

26 . The method according to claim 23 , wherein the renewable energy source is any one of a wind turbine, solar cell, hydroelectric generator, biofuel, geothermal, or oceanic.

27 . The method according to claim 1 , further comprising recycling the hydrogen gas to generate renewable electricity.

28 . The method according to claim 1 , further comprising recycling the hydrogen gas and the oxygen gas to regenerate water and electricity supplied to the electrolysis unit.

29 . The method according to claim 1 , wherein the source does not consume fossil based fuels.

30 . The method according to claim 1 , wherein the electrical source is a nuclear generator.

31 . The method according to claim 1 , wherein the aqueous electrolyte comprises an alkali salt substantially free of chloride ions.

32 . The method according to claim 1 , wherein the aqueous electrolyte comprises a sodium salt substantially free of chloride ions.

33 . The method according to claim 1 , wherein the aqueous electrolyte is selected from the group consisting of sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, potassium nitrate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, calcium carbonate, and magnesium carbonate.

34 . The method according to claim 1 , wherein the electrolyte is saturated in solution.

35 . The method according to claim 1 , further comprising maintaining a saturated electrolyte solution.

36 . The method according to claim 1 , wherein the aqueous electrolyte is sodium sulfate or potassium sulfate.

37 . The method according to claim 1 , further comprising regenerating electrolyte supplied to the electrolysis unit by reacting the acid removed from the anode region of the electrolysis cell with sodium chloride to produce hydrochloric acid and the original electrolyte salt.

38 . The method according to claim 1 , further comprising collecting and concentrating the base.

39 . A base produced according to the method of claim 1 .

40 . A building material comprising carbonate produced according to the method of claim 1 , wherein the building material is any one of a dry wall product, filled polyvinyl chloride, tile, grout, synthetic stone, filled resin, or an adhesive.

41 . The method according to claim 1 , further comprising contacting the acid produced at the anode region with a mineral compound to form a carbon dioxide sequestering material.

42 . The method according to claim 42 , wherein the mineral compound is any one of talc, clay mineral sepiolite, clay minerals, serpentine, asbestos, or mining byproducts.

43 . The method according to claim 1 , further comprising contacting the acid produced at the anode region with the gaseous carbon dioxide in an electrochemical cell to produce reduced carbon compounds having a general formula of CmHxO 2 n, wherein m an integer between 1 and 6, x is an integer between 0 and 24, and n is an integer between 0 and 6.

44 . The method according to claim 43 , wherein the reduced carbon compound is any one of formic acid, oxalic acid, formaldehyde, or methanol.

45 . The method according to claim 1 , further comprising chemically reducing carbon dioxide by reacting hydrogen gas produced by the system with carbon dioxide trapped by the system to produce carbon monoxide, a precursor for other synthetic processes.

46 . The method according to claim 1 , wherein an amount of carbon dioxide sequestered is greater than an amount of carbon dioxide generated by the electrical source.

47 . The method according to claim 1 , wherein a difference of at least 6 pH units is maintained between the anode region and cathode region by supplying electrolyte utilizing bi-direction flow.

48 . The method according to claim 1 , wherein a difference of at least 6 pH units is maintained between the anode region and cathode region utilizing convection currents generated by rising hydrogen gas in the cathode region and rising oxygen gas in the anode region.

49 . The method according to claim 1 further comprising concentrating cations from the electrolyte and delivering the cations to the cathode region.

50 . The method according to claim 1 further comprising concentrating anions from the electrolyte and delivering the anions to the anode region.

51 . A process of producing renewable hydrogen from water and bicarbonate from gaseous carbon dioxide comprising:

supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

producing hydrogen gas and hydroxide ions at the cathode region;

removing some or all of the base comprising hydroxide ions from the cathode region of the electrolysis cell; and

contacting the hydroxide ions with gaseous carbon dioxide to produce a solution comprising bicarbonate, carbonate or a mixture thereof; and

isolating bicarbonate from the solution.

52 . A process of producing renewable hydrogen from water and carbonate from gaseous carbon dioxide comprising:

supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

producing hydrogen gas and a base comprising hydroxide ions at the cathode region;

removing some or all of the base comprising hydroxide ions from the cathode region;

contacting the hydroxide ions with gaseous carbon dioxide to produce a solution comprising bicarbonate, carbonate, or a mixture thereof; and

isolating carbonate from the solution.

53 . A method of producing renewable hydrogen and carbon dioxide neutral or carbon dioxide negative acid comprising:

a) supplying a direct current from a renewable electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the cathode region, wherein the protons are present in the form of an acid;

c) removing some or all of the acid from anode region;

d) collecting the acid in a reservoir; and

e) concentrating the acid.

54 . The method according to claim 53 , wherein a pH of the cathode region ranges from about pH=0 to about pH=5.

55 . The method according to claim 53 , wherein the acid is sulfuric acid.

56 . A method of producing renewable hydrogen and a carbon dioxide neutral or carbon dioxide negative base comprising:

a) supplying a renewable electric current from a source to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

c) removing some or all of the base from the cathode region;

d) collecting the base in a reservoir; and

e) concentrating the base.

57 . The method according to claim 56 , wherein a pH of the base region ranges from about pH=8 to about pH=14.

58 . The method according to claim 56 , wherein the base is sodium or potassium hydroxide.

59 . A method of generating and maintaining separate regions of concentrated hydronium ions and concentrated hydroxide ions comprising:

a) contacting a cathode region including at least one cathode adapted to generate hydrogen gas and hydroxide ions and an anode region including at least one anode adapted to generate oxygen gas and hydronium with an aqueous electrolyte;

b) applying a DC voltage between 1.2 and 10 volts to the anode and cathode;

c) removing the hydrogen gas and hydroxide ions from the cathode region; and

d) removing the oxygen gas and hydronium ions from the anode region.

60 . The method of claim 60 , further comprising the step of supplying the cathode and anode regions with fresh electrolyte utilizing bi-directional flow.

61 . The method of claim 60 further comprising the step of creating convection currents within the anode and the cathode regions.

62 . The method of claim 60 , further comprising the step of separating the anode and the cathode region with a porous glass frit.

63 . A method of generating renewable hydrogen and producing a carbon dioxide sequestering compound comprising the steps of:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, the anode and the cathode regions electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) removing some or all of the acid from the anode region;

d) concentrating the acid, wherein the acid has a pH ranging from about pH=0 to about pH=5; and

e) contacting the acid with a material that when exposed to a strong acid is converted to a carbon dioxide sequestering solution.

64 . The method according to claim 63 , wherein the material is any one of a mineral clay sepiolite, serpentine, talc, asbestos, or a mining byproduct.

65 . The method according to claim 63 , wherein the acid is sulfuric acid.

66 . The method according to claim 63 , further comprising the step of adding base to the carbon dioxide sequestering solution.

67 . The method according to claim 63 , further comprising the step of contacting the carbon dioxide sequestering solution with a source of gaseous carbon dioxide.

68 . The method according to claim 67 , further comprising the step of precipitating and processing magnesium salts from the carbon dioxide sequestering solution.

69 . A method of generating renewable hydrogen and producing pressurized carbon dioxide gas from atmospheric or gas stream carbon dioxide comprising:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base comprising hydroxide ions with gaseous carbon dioxide to produce a solution comprising bicarbonate, carbonate, or a mixture thereof;

g) contacting the solution with acid produced at the anode region of the cell to produce carbon dioxide gas under pressure; and

h) collecting the pressurized carbon dioxide gas.

70 . The method according to claim 69 , further comprising producing super critical carbon dioxide from the collected pressurized carbon dioxide gas.

71 . A method of generating renewable hydrogen and producing urea fertilizer, the method comprising the steps of:

a) supplying an electric current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base with a gaseous source of carbon dioxide to produce a feedstock comprising bicarbonate or carbonate or a mixture thereof;

g) contacting the acid produced at the anode region with the feedstock to produce carbon dioxide gas; and

h) contacting the carbon dioxide gas with a source of anhydrous ammonia under pressure to produce urea.

72 . A method of generating renewable hydrogen and producing urea fertilizer, the method comprising the steps of:

a) supplying an electric current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base with a gaseous source of carbon dioxide to produce a feedstock comprising bicarbonate or carbonate or a mixture thereof;

g) contacting the acid produced at the anode region with the feedstock to produce carbon dioxide gas; and

h) reacting the carbon dioxide gas and hydrogen produced at the cathode with nitrogen gas in an electrochemical process to produce urea.

73 . A method of generating renewable hydrogen and producing carbon dioxide neutral or carbon dioxide negative agricultural lime comprising the steps of:

a) supplying a direct current from a renewable or nuclear electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base having a pH of greater than about pH=10 with gaseous carbon dioxide to produce a carbonate enriched feedstock;

g) contacting the feedstock with an aqueous composition comprising calcium ions; and

h) precipitating calcium carbonate from the feedstock to produce agricultural lime.

74 . A method of generating renewable hydrogen and producing carbon dioxide neutral or carbon dioxide negative quick lime comprising:

a) supplying a direct current from a renewable or nuclear electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base having a pH of greater than about pH=10 with gaseous carbon dioxide to produce a carbonate enriched feedstock;

g) contacting the carbonate enriched feedstock with an aqueous solution comprising calcium ions to generate calcium carbonate;

h) applying heat to the calcium carbonate to produce quick lime.

75 . The method according to claim 74 , wherein carbon dioxide released from applying heat to the calcium carbonate is contacted with base to regenerate the carbonate feedstock.

76 . The method according to claim 74 , wherein carbon dioxide released from applying heat to the calcium carbonate is sequestered and pressurized for use as supercritical carbon dioxide.

77 . A method of generating renewable hydrogen and producing carbon monoxide from atmospheric or gas stream carbon dioxide comprising:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base with gaseous carbon dioxide to produce a solution comprising bicarbonate or carbonate or a mixture thereof;

g) contacting the solution with acid produced in the anode region of the cell to produce carbon dioxide gas under pressure;

h) collecting the pressurized carbon dioxide gas; and

i) reducing a portion of the carbon dioxide gas with a portion of the hydrogen gas generated at the cathode to produce carbon monoxide.

78 . A method of generating renewable hydrogen and producing formic acid from atmospheric or gas stream carbon dioxide comprising:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base with a gaseous carbon dioxide to produce a solution comprising bicarbonate or carbonate or a mixture thereof;

g) contacting the solution with acid produced in the anode region of the cell to produce carbon dioxide gas under pressure;

h) collecting the pressurized carbon dioxide gas;

i) reducing a portion of the carbon dioxide gas with a portion of hydrogen gas generated at the cathode to produce carbon monoxide; and

j) reacting a portion of the carbon monoxide with methanol in the presence of the base produced at the cathode having a pH of at least 10 to produce methyl formate; and

k) hydrolyzing the methyl formate to produce formic acid.

79 . A method of generating renewable hydrogen and producing formic acid from atmospheric or gas stream carbon dioxide comprising:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base having a with gaseous carbon dioxide to produce a solution comprising cesium bicarbonate; and

g) electrolyzing cesium bicarbonate to form formic acid.

80 . A method of generating renewable hydrogen and producing formic acid from atmospheric or gas stream carbon dioxide comprising:

a) supplying a direct current from an electrical source at a predetermined voltage to a water electrolysis unit having at least one electrolysis cell including an aqueous electrolyte substantially free of chloride ions and an anode region adapted to generate oxygen gas and protons separated from a cathode region adapted to generate hydrogen gas and hydroxide ions, wherein the anode and the cathode regions are electrically connected by the electrolyte;

b) producing oxygen gas and protons at the anode region, wherein the protons are present in the form of an acid;

c) producing hydrogen gas and hydroxide ions at the cathode region, wherein the hydroxide ions are present in the form of a base;

d) removing some or all of the acid from the anode region;

e) removing some or all of the base from the cathode region;

f) contacting the base with gaseous carbon dioxide to produce a solution comprising bicarbonate or carbonate or a mixture thereof; and

g) hydrogenating the bicarbonate in the presence of a catalyst to produce formic acid.