Patent Application
20210053871
Ammonium chloride and ammonium sulfate are produced as low value byproducts of chemical processes. Ammonium chloride can be a waste product of sodium bicarbonate or sodium carbonate production processes, such as the Solvay Process. Ammonium chloride and/or ammonium sulfate are produced as chemical byproducts during the recovery or removal of ammonia using acid scrubbing, where ammonia or ammonia species may be scrubbed or removed from ammonia laden gas or liquid streams. Acid scrubbing may use acids which react strongly with ammonia, such as sulfuric acid, hydrochloric acid, or nitric acid, to remove ammonia from gas or liquid streams, which may include, but are not limited to, one or more or a combination of the following: wastewater, coke oven gases, ammonia-laden freshwater or marine water, urine, feces, biomass, anerobic digestion water, landfill leachate, fertilizer production, or purge gases.
Ammonium sulfate can also be produced as a byproduct from the following CO2 conversion or sequestration reaction:
(NH4)2CO3(aq)+CaSO4(s)(NH4)2SO4(aq)+CaCO3(s)
The above reaction may be an advantageous method for sequestering carbon dioxide, especially if the ammonia source is renewable or the ammonia can be economically recovered from the ammonium sulfate. In prior art, ammonium sulfate and/or ammonium chloride is sold as a low-cost fertilizer or is discarded. It would be desirable if these and other waste or byproducts could be used efficiently in other processes. It would be desirable if ammonia could be recovered from these and other waste or byproducts in an efficient or effective manner. Advantageously, the processes of the instant application use such byproducts cost-effectively and in an ecofriendly manner.
In one embodiment, a process comprises reacting ammonium chloride with zinc oxide to form a zinc chloride, ammonia, and water. The zinc chloride is reacted with sulfuric acid to form a zinc sulfate and hydrochloric acid. The zinc sulfate is thermally decomposed to produce zinc oxide.
In another embodiment a process comprises reacting sodium chloride with ammonia, carbon dioxide, and water to form sodium bicarbonate and ammonium chloride. The ammonium chloride is reacted with zinc oxide to form zinc chloride, ammonia, and water. The zinc chloride is then reacted with sulfuric acid to form zinc sulfate and hydrochloric acid. The zinc sulfate may then be decomposed to produce zinc oxide.
Example Figure Keys
Free Ammonia: Free ammonia may comprise ammonia which may be unreacted or unaltered. Free ammonia may comprise gaseous, liquid, or solid ammonia. Free ammonia may comprise ammonia dissolved in water or one or more or a combination of solvents.
Lean: ‘Lean’ may represent the concentration of a reagent relative to the concentration of the same reagent at another point in a process. ‘Lean’ represents a relatively lower concentration.
Rich: ‘Rich’ may represent the concentration of a reagent relative to the concentration of the same reagent at another point in a process. ‘Rich’ represents a relatively greater concentration.
Filling: In some embodiments, ‘filling’ may involve the addition of reactants to a reactor.
Reacting: In some embodiments, ‘reacting’ may involve reactants in a reactor undergoing one or more or a combination of reactions which may result in one or more or a combination of reaction products.
Emptying: In some embodiments, ‘emptying’ may involve the removal or transfer of one or more or a combination of products from one or more or a combination of reactors.
Low Carbon or Net Carbon Emission Negative Ammonia Production and/or Sodium Bicarbonate or Sodium Carbonate Production
Background
Ammonium chloride and ammonium sulfate are produced as low value byproducts of chemical processes. Ammonium chloride can be a waste product of sodium bicarbonate or sodium carbonate production processes, such as the Solvay Process. Ammonium chloride and/or ammonium sulfate are produced as chemical byproducts during the recovery or removal of ammonia using acid scrubbing, where ammonia or ammonia species may be scrubbed or removed from ammonia laden gas or liquid streams. Acid scrubbing may use acids which react strongly with ammonia, such as sulfuric acid, hydrochloric acid, or nitric acid, to remove ammonia from gas or liquid streams, which may include, but are not limited to, one or more or a combination of the following: wastewater, coke oven gases, ammonia-laden freshwater or marine water, urine, feces, biomass, anerobic digestion water, landfill leachate, fertilizer production, or purge gases.
Ammonium sulfate can also be produced as a byproduct from the following CO2 conversion or sequestration reaction:
(NH4)2CO3(aq)+CaSO4(s)(NH4)2SO4(aq)+CaCO3(s)
The above reaction may be an advantageous method for sequestering carbon dioxide, especially if the ammonia source is renewable or the ammonia can be economically recovered from the ammonium sulfate.
In prior art, ammonium sulfate and/or ammonium chloride is sold as a low-cost fertilizer or is discarded.
In sodium carbonate or sodium bicarbonate production, such as the Solvay process, ammonia is recovered from the ammonium chloride byproduct by reacting the ammonium chloride with calcium oxide or calcium hydroxide. Both calcium oxide and calcium hydroxide are produced in the very energy and CO2 emission intensive process of calcining, where CaCO3 is heated to an elevated temperature and decomposed into CaO and CO2. Due to the nature of the chemistry of calcining, it emits significant amounts of CO2 not only due to its thermal energy demands (which are generally powered by the burning of coal), but also or mostly due to the CO2 directly released from the decomposition of CaCO3 into CaO and CO2. In addition to the high cost, energy and CO2 emission intensive nature of recovering ammonia by reacting it with calcium oxide, the resulting calcium chloride byproduct is also generally a waste product, usually disposed by discarding into the ocean.
An example present embodiment may involve converting ammonium chloride and/or ammonium sulfate, which may be waste products or low cost, into valuable free ammonia (for example: ammonium hydroxide solution or gaseous ammonia or anhydrous ammonia). Free ammonia may be used within a chemical process (for example, which may include, but is not limited to, a process for production sodium bicarbonate or sodium carbonate) or sold or used various applications for ammonia. The present embodiment may also be employed in small-scale ammonia production, or medium scale ammonia production, or large scale ammonia production.
It is important to note Embodiment 1, for example, may consume 233 kJ/mol of heat to produce a mole of ammonia; compared to 410.6 kJ/mole of heat to produce a mole of ammonia from natural gas using the Haber-Bosch Process. It is important to note the present embodiments may not require a solid catalyst to operate, which is a unique distinction because other ammonia production processes require solid catalysts. It is important to note the present embodiments may be suited for producing value from excess or low-cost natural gas or flare gases by using the heat from flaring to produce valuable ammonia and hydrochloric acid. Ammonia may be compressed or liquified and may be sold, if desired.
The hydrochloric acid is a valuable byproduct. For example, hydrochloric acid may be employed in the production of chlorinated chemicals or polymers, such as PVC. For example, hydrochloric acid which is a required chemical in some oil & gas production operations. The present embodiments, for example, when employed on oil & gas drilling sites may comprise ‘hydrochloric acid generators’. Ammonium chloride is much easier and lower cost to ship than concentrated hydrochloric acid. The ammonia product produced by the present embodiment may be, for example, transported and/or sold to nearby farms and/or used in other applications requiring ammonia. For an upstream oil production operation, the present embodiments may transform two loss driving components of their business (gas flaring and purchasing hydrochloride acid) into a profit driver for their business (use of flare gas heat to power simultaneous ammonia and hydrochloride acid, wherein hydrochloric acid is consumed onsite and ammonia is sold and/or used onsite). It may be desirable to convert ammonia into other chemicals, which may include, but are not limited to, urea, chloramine, amines, polymers, methylamine, ethylamine, or other ammonia derivatives, or a combination thereof.
Reaction 1 Further Description and Proof:
Reaction 1 may involve reacting ammonium chloride and zinc oxide at a relatively elevated temperature to form zinc chloride, water vapor, and ammonia gas. The reaction may involve decomposing ammonium chloride and passing the resulting gas mixture over heated or unheated zinc oxide. The reaction may involve heating a mixture of ammonium chloride (which may be, at least initially, at a solid phase) and zinc oxide (which may be at a solid phase) and forming zinc chloride, ammonia gas, and according to Reaction 1. It may be preferred to react a mixture of ammonium chloride and zinc oxide because the solid mixture has been shown to produce reaction products with lower temperature requirement (210° C. for mixture vs. 338° C. for ammonium chloride alone) and lower heat input requirement (+116.33 kJ/mol NH3 for mixture vs. +228.55 kJ/mole NH3 for ammonium chloride alone). An embodiment of the reaction shown in reaction 1 has been demonstrated in literature in the article ‘Reaction of zinc oxide with ammonium chloride’ by Borisov et al. Borisov et al found the reactants initially form ammonium chlorozincates ((NH4)3ZnCl4) at 150° C., with the evolution of NH3(g) and H2O(g). Borisov et al found the mixture of ammonium chloride and zinc oxide completely converts into products shown in reaction 1 at about 210° C. Borisov et al found a stoichiometric amount of NH3 formed and the presence of zinc did not cause the NH3 to decompose.
The present reaction may be conducted in a low diatomic oxygen atmosphere or environment. Low diatomic oxygen may involve a volumetric concentration of diatomic oxygen less than 20 vol %, or less than 19 vol %, or less than 18 vol %, or less than 17 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, or less than 19 vol %. Low diatomic oxygen concentration may involving filling a vessel or container with ammonium chloride and zinc oxide such that less than 10%, or less than 20%, or less than 30%, or less than 40%, or less than 50%, or less than 60%, or less than 70%, or less than 80%, or less than 90%, or a combination thereof of the space in said vessel or container is occupied by oxygen or a gas comprising oxygen. Low diatomic oxygen concentration may involve ensuring the total mass of ammonia in a reactor or mass of ammonium chloride in a reactor or the total mass of ammonia in the form of ammonium chloride in a reactor exceeds the total mass of diatomic oxygen gas in said reactor by at least 2× or 200%, or 3× or 300%, or 4× or 400%, or 5× or 500%, or 6× or 600%, or 7× or 700%, or 8× or 800%, or 9× or 900%, or 10× or 1,000%, or 25× or 2,500%, or 50× or 5,000%, or 100× or 10,000%, or 200× or 20,000%, or a combination thereof.
It is important to note that zinc oxide may be recycled internally from Reaction 3 to Reaction 1.
It is important to note metals other than or in addition to zinc may be employed, which may include, but are not limited to, one or more or a combination of the following: iron, lead, copper, cobalt, nickel, manganese, chromium, silver, scandium, vanadium, titanium, aluminum, magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium, Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium, Unununium, or Ununbium.
Reaction 2 Further Description and Proof:
Reaction 2 may involve reacting zinc chloride with sulfuric acid form zinc sulfate and hydrochloric acid. The enthalpy of Reaction 2 may be strongly exothermic and favorable and sulfuric acid may be a stronger acid than hydrochloric acid. Reaction 2 may require cooling. Said cooling may involve recovering heat. Recovered heat may be employed to facilitate removal or distillation of excess water or separate residual zinc sulfate or zinc chloride from hydrochloric acid. Depending on the concentration of sulfuric acid, zinc chloride may be placed in sufficient water to ensure there is enough water for the product hydrochloric acid to fully dissolve and form hydrochloric acid, as hydrochloric acid may require stoichiometrically more water than sulfuric acid to remain in solution. Alternatively, or additionally, a portion of hydrochloric acid may form as a gas, and may be condensed or recovered or converted into an aqueous solution or a combination thereof. Zinc chloride or zinc sulfate may be present primarily at the solid phase due to, for example, limited amount of relative water and/or the salting-out effects of HCl or H2SO4 in solution. Residual zinc chloride or zinc sulfate may comprise, including, but not limited to, one or more or a combination of the following: a membrane-based process, a solid membrane, distillation, electrodialysis, ion exchange, crystallization, crydesalination, freezing desalination, cooling precipitation, precipitation, salting-out′, or a common-ion effect.
Reaction 3 Further Description and Proof:
Reaction 3 may involve decomposing zinc sulfate into zinc oxide and sulfur trioxide or sulfur dioxide and O2 or both. According to ‘Kinetics of the Thermal Decomposition of Zinc Sulfate’ by Ibanez et al, zinc sulfate decomposes into zinc oxide and sulfur trioxide or sulfur dioxide or O2 or a combination thereof starting at about 920° C. Zinc oxide may be transferred or employed or both to Reaction 1 and sulfur trioxide or sulfur dioxide or O2 or a combination thereof may be employed in Reaction 4.
Reaction 4 Further Description and Proof:
Reaction 4 may involve the formation of sulfuric acid from sulfur trioxide or sulfur oxides which may be converted into sulfur trioxide or sulfuric acid. Reaction 4 is well known in industry to produce sulfuric acid and may be conducted using one or more or a combination of methods for producing sulfuric acid in the art. Reaction 4 is highly exothermic and heat from the reaction may be recovered as, for example, steam. It may be possible to employ heat from Reaction 4 to power a portion of the thermal duty of Reaction 1. Sulfuric acid product may be employed in Reaction 2.
Heat from reaction 4 may be utilized to produce steam or heat produced may supplement heat requirements of reaction ‘(1)’.
Note: One or more reaction steps may be conducted in separate locations or separate facilities from one or more other reactions steps if desired. It may be desirable to conduct certain reactions where certain facilities exist. It may be desirable to conduct certain reactions where certain economic factors (for example: cost of energy or availability of feedstocks or market/application locations) are relatively more favorable. If desired, reactions may be split into one or more sub-reactions. Additional treatment steps, such as water addition or removal or membrane base purification or precipitation or cooling or heating, may be conducted between or during reaction steps.
Note: In the present example embodiment, it may be desirable for ammonium sulfate (if, for example, ammonium sulfate is a low-cost feedstock for ammonia) to be converted into ammonium chloride, for example, by reacting it with calcium chloride or other low cost chloride salt. For example, the following reaction may be employed:
(NH4)2SO4(aq)+CaCl2)(aq)2NH4Cl(aq)+CaSO4(s)
The CaSO4 solid may be sold or used, for example, as Gypsum or precipitated Gypsum.
As with other reactions described herein, it is important to note the above reaction to convert (NH4)2SO4(aq) into 2NH4Cl(aq) may be conducted in a different location from one or more other reactions in the present embodiments, if desired. Alternatively, or additionally, reactions may be conducted in the same location or facility.
Note: It is important to note the present embodiments may consume less energy in their endothermic reaction steps than is required during the production of ammonia from natural gas. The production of ammonia from natural gas (not including the additional energy required to separate nitrogen and compress gases and ammonia) requires 410.625 kJ/mol of NH3 produced according to the following equations:
Energetic Value of Methane in Natural Gas (energetic value of methane→CO2 if not transformed into CO2 using steam reforming and WGS):
CH4(g)+O2(g)CO2(g)+H2O(g) (−889 kJ/mol) (1)
CH4(g)+H2O(g)CO(g)+3H2(g) (+206 kJ/mol, 700-1100° C.) (2)
CH4(g)+H2O(g)CO(g)+3H2(g) (−41 kJ/mol, 200-250° C.) (3)
1.5H2(g)+0.5N2(g)NH3(g) (−45.9 kJ/mol) (4)
206 kJ/mol+889 kJ/mol=1095 kJ/mol (5)
(6) 1095 kJ/mol*1.5/4=410.625 kJ/mol NH3 Produced
For example, the endothermic reactions of Example Embodiment 1 consume 233 kJ per mole of NH3 produced, which is 177 kJ or 43% less energy than is required to produce ammonia using the Haber Bosch Process with a natural gas feedstock. It is also important to note that the reactions in Example Embodiment 1 operate at lower temperatures, there are fewer total reactions, and there is no energy requirement for compression (which was not included in the 410.625 kJ energy value for NH3 production in Haber Bosch Process with natural gas feedstock). Example Embodiment 1 may also not require expensive catalysts, which are required in the Haber Bosch Process, and/or also may not require high purity gaseous feedstocks, which are also required in the Haber Bosch Process.
(1) (NH4)2SO4(aq)+CaCl2(aq)2NH4Cl(aq)+CaSO4(s)
(2) 2NH4Cl(aq) may be concentrated using FO with CaCl2 as draw solution and the 2NH4Cl(aq) may be precipitated as 2NH4Cl(s). ‘2)’ comprise a cycle wherein (a) NH4Cl(aq) is mildly heated; and/or (b) concentrated using forward osmosis with CaCl2 draw solution; and/or (c) concentrated NH4Cl(aq) may be cooled to precipitate a portion of the NH4Cl; and/or (d) the remaining NH4Cl(aq) solution separated from the NH4Cl(s) precipitate may be mixed with incoming solution and/or returned to step (a). NH4Cl(s) precipitate may be transferred to reaction
(3) Because CaCl2 is deliquescent in contact with air (absorbs water from the air) it may be desirable for the CaCl2(aq) draw solution to comprise CaCl2(s) which has absorbed water from the air to form concentrated CaCl2(aq) brine. In some embodiments, it may be desirable for NH4Cl(s) to be formed by distillation of a portion of water and cooling crystallization or precipitation of NH4Cl(s) from an NH4Cl(aq) solution. In some embodiments, it may be desirable for NH4Cl(s) to be formed by solventing-out′ NH4Cl(s) from an NH4Cl(aq) solution using a regenerable water soluble organic solvent, such as a volatile organic solvent or a liquid-liquid phase transition organic solvent.
Reaction 1 Further Description and Proof:
Ammonium sulfate solid or aqueous and calcium chloride may be mixed to form ammonium chloride aqueous, ammonium chloride solid, calcium sulfate solid, minimal concentrate of aqueous calcium sulfate (due to minimal solubility), or a combination thereof. Calcium sulfate solid may form due to insolubility or relatively low solubility in water. Calcium sulfate solid may form in a step prior to the formation or generation of ammonium chloride solid. Calcium sulfate solid may be separated prior to further processing of the remaining solution to produce ammonium chloride solid.
Reaction 2 Further Description and Proof:
CaCl2 may have a greater osmotic pressure and/or higher solubility in water than NH4Cl at their saturated concentration in water, which may enable using CaCl2 input as a draw solution to concentrate remaining NH4Cl(aq) using forward osmosis (FO). After concentrating, NH4Cl(aq) may be cooled, which may result in the precipitation of a portion of NH4Cl(s). The remaining solution, which may be lean in NH4Cl(aq), may be concentrated using CaCl2 draw solution, which may occur in one or more additional cycles before other NH4Cl(aq) concentrating and/or NH4Cl(s) precipitation steps. Alternatively, or additionally, NH4Cl(aq) may be concentrated and/or NH4Cl(s) may be separated using one or more or a combination of the following: cryodesalination, freezing desalination, anti-solvent precipitation, regenerable anti-solvent precipitation, solventing-out, cooling precipitation, distillation, common-ion effect, or other separations described herein.
Alternatively to FO, the NH4Cl may be concentrated by using the difference in partial vapor pressure of water over NH4Cl vs. CaCl2) solution, which may be conducted using, for example, including, but not limited to, one or more or a combination of the following: carrier gas distillation, carrier gas evaporation, vapor gas membrane, pervaporation, membrane distillation, distillation, mechanical vapor compression distillation, vacuum distillation, headspace water vapor gas transfer, stripping gas water vapor transfer, or distillation.
It is important to note that alternatives to FO or other membrane-based processes may be beneficial because residual CaSO4 (which dissolves at low concentrations in water due to limited but existent solubility) may scale membranes. In some embodiments, distillation of a portion water and/or crystallization or precipitation of ammonium chloride may be conducted.
In some embodiments, ammonium sulfate may be directly added to a solution comprising ammonium chloride and calcium chloride, which may result in the formation of calcium sulfate precipitate. Some embodiments may conduct said ammonium sulfate addition step at warmer temperatures, such as, greater than 0° C., or 10° C., or 20° C., or 30° C., or 40° C., or 50° C., or 60° C., or 70° C., or 80° C., or 90° C. Calcium sulfate precipitate may be separated form the remaining solution. The remaining solution may be cooled, which may result in the precipitation of at least a portion of ammonium chloride solid. Said ammonium chloride solid may be separated. The remaining solution, which may be ‘lean’ in ammonium chloride, may be mixed with input calcium chloride, which may produce a solution comprising ammonium chloride and calcium chloride. Said solution may be transferred to the first step of the present embodiment of ‘Reaction 1’ and/or ‘Reaction 2’. The present embodiment may comprise a combination of ‘Reaction 1’ and ‘Reaction 2’.
In an example embodiment, (a) ammonium sulfate solid may be mixed with a calcium chloride—ammonium chloride solution, resulting in the formation of additional ammonium chloride from the ammonium sulfate and calcium sulfate precipitate. To prevent ammonium chloride from precipitating at the same time as calcium sulfate, the concentration of the resulting more concentrated ammonium chloride solution may desirably be less than the maximum solubility or saturation concentration of ammonium chloride in solution at the temperature which the calcium sulfate precipitating reaction is conducted. (b) Calcium sulfate precipitate may be separated and may be further washed to, for example, remove any residual ammonium chloride. (c) The remaining concentrated ammonium chloride solution after calcium sulfate precipitation removal may undergo further treatment to facilitate the precipitation of a portion of the ammonium chloride. For example, said treatment may involve systems and methods for precipitating salts from solutions, which may include, but are not limited to: cooling precipitation, antisolvent precipitation, thermally switchable antisolvent precipitation, solventing out, salting out, or a combination thereof (d) Precipitated ammonium chloride may be separated and transferred to Reaction 3. (e) The remaining ammonium chloride solution following ammonium chloride precipitation and precipitate separation may be mixed with calcium chloride, forming an ammonium chloride—calcium chloride solution. To prevent ammonium chloride precipitation or facilitate calcium chloride dissolution during this step, the solution may be heated before or during calcium chloride dissolution and/or any antisolvents which may have been added may be removed. The resulting ammonium chloride—calcium chloride solution may be transferred to step ‘(a)’.
Reaction 1 and/or Reaction 2 may comprise one or more or a combination of the systems and methods described thereof or herein.
Reaction 3 Further Description and Proof:
Reaction 3 may involve reacting ammonium chloride and zinc oxide at a relatively elevated temperature to form zinc chloride, water vapor, and ammonia gas. The reaction may involve decomposing ammonium chloride and passing the resulting gas mixture over heated or unheated zinc oxide. The reaction may involve heating a mixture of ammonium chloride (which may be, at least initially, at a solid phase) and zinc oxide (which may be at a solid phase) and forming zinc chloride, ammonia gas, and according to Reaction 3. It may be preferred to react a mixture of ammonium chloride and zinc oxide because the solid mixture has been shown to produce reaction products with lower temperature requirement (210° C. for mixture vs. 338° C. for ammonium chloride alone) and lower heat input requirement (+116.33 kJ/mol NH3 for mixture vs. +228.55 kJ/mole NH3 for ammonium chloride alone). An embodiment of the reaction shown in Reaction 3 has been demonstrated in literature in the article ‘Reaction of zinc oxide with ammonium chloride’ by Borisov et al. Borisov et al found the reactants initially form ammonium chlorozincates ((NH4)3ZnCl4) at 150° C., with the evolution of NH3(g) and H2O(g). Borisov et al found the mixture of ammonium chloride and zinc oxide completely converts into products shown in reaction 1 at about 210° C. Borisov et al found a stoichiometric amount of NH3 formed and the presence of zinc did not cause the NH3 to decompose.
It is important to note that zinc oxide may be recycled internally from Reaction 5 to Reaction 3.
It is important to note metals other than or in addition to zinc may be employed, which may include, but are not limited to, one or more or a combination of the following: iron, lead, copper, cobalt, nickel, manganese, chromium, silver, scandium, vanadium, titanium, aluminum, magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium, Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium, Unununium, or Ununbium.
Reaction 4 Further Description and Proof:
Reaction 4 involves reacting zinc chloride with sulfuric acid form zinc sulfate and hydrochloric acid. The enthalpy of Reaction 4 may be strongly exothermic and favorable and sulfuric acid may be a stronger acid than hydrochloric acid. Reaction 4 may require cooling. Said cooling may involve recovering heat. Recovered heat may be employed to facilitate removal or distillation of excess water or separate residual zinc sulfate or zinc chloride from hydrochloric acid. Depending on the concentration of sulfuric acid, zinc chloride may be placed in sufficient water to ensure there is enough water for the product hydrochloric acid to fully dissolve and form hydrochloric acid, as hydrochloric acid may require stoichiometrically more water than sulfuric acid to remain in solution. Alternatively, or additionally, a portion of hydrochloric acid may form as a gas, and may be condensed or recovered or converted into an aqueous solution or a combination thereof. Zinc chloride or zinc sulfate may be present primarily at the solid phase due to, for example, limited amount of relative water and/or the salting-out effects of HCl or H2SO4 in solution. Residual zinc chloride or zinc sulfate may comprise a membrane-based process, a solid membrane, distillation, electrodialysis, ion exchange, crystallization, cryodesalination, freezing desalination, cooling precipitation, precipitation, ‘salting-out’, common-ion effect, or a combination thereof.
Reaction 5 Further Description and Proof:
Reaction 5 involves decomposing zinc sulfate into zinc oxide and sulfur trioxide or sulfur dioxide and O2 or a combination thereof. According to ‘Kinetics of the Thermal Decomposition of Zinc Sulfate’ by Ibanez et al, zinc sulfate decomposes into zinc oxide and sulfur trioxide or sulfur dioxide or O2 or a combination thereof starting at about 920° C. Zinc oxide may be transferred or employed or both to Reaction 3 and sulfur trioxide or sulfur dioxide or O2 or a combination thereof may be employed in Reaction 6.
Reaction 6 Further Description and Proof:
Reaction 6 may involve the formation of sulfuric acid from sulfur trioxide or sulfur oxides which may be converted into sulfur trioxide or sulfuric acid. Reaction 6 is well known in the art to produce sulfuric acid and may be conducted using one or more or a combination of methods for producing sulfuric acid in the art. Reaction 6 is highly exothermic and heat from the reaction may be recovered as, for example, steam. It may be possible to employ heat from Reaction 6 to power a portion of the thermal duty of Reaction 1. Sulfuric acid product may be employed in Reaction 4.
Background: Sodium carbonate and sodium bicarbonate are produced by either mining or the Solvay process. The Solvay process produces over 75% of the world's sodium carbonate today.
In the Solvay process, ammonia is recovered from the ammonium chloride byproduct by reacting the ammonium chloride with calcium oxide or calcium hydroxide. Both calcium oxide and calcium hydroxide are produced in the very energy and CO2 emission intensive process of calcining, where CaCO3 is heated to an elevated temperature and decomposed into CaO and CO2. Due to the nature of the chemistry of calcining, it emits significant amounts of CO2 not only due to its thermal energy demands (which are generally powered by the burning of coal), but also or mostly due to the CO2 directly released from the decomposition of CaCO3 into CaO and CO2. The resulting calcium chloride byproduct is also generally a waste product, usually disposed by discarding into the ocean.
Some of the example embodiments may comprise a process for producing sodium bicarbonate or sodium carbonate, which may be net CO2 negative (both for producing sodium bicarbonate and/or sodium carbonate), may not calcine calcium carbonate, produces HCl byproduct, may not require an electrolyzer, and/or may be more profitable than the Solvay Process. Example Embodiment 3, for example, may:
Calculations for the above CO2 and cost values may be shown in tables herein.
Reaction 1 Further Description and Proof:
Reaction 1 may comprise the first reaction of the Solvay process and the Hou Debang modified Solvay process.
Reaction 2 Further Description and Proof:
Reaction 2 may employ the Hou Debang process method for precipitation of NH4Cl.
Reaction 3 Further Description and Proof:
Reaction 3 may involve reacting ammonium chloride and zinc oxide at a relatively elevated temperature to form zinc chloride, water vapor, and ammonia gas. The reaction may involve decomposing ammonium chloride and passing the gas mixture over heated or unheated zinc oxide. The reaction may involve heating a mixture of ammonium chloride and zinc oxide and forming zinc chloride and ammonia according to Reaction 3. It may be preferred to react a mixture of ammonium chloride and zinc oxide because the solid mixture has been shown to produce reaction products with lower temperature requirement (210° C. for mixture vs. 338° C. for ammonium chloride alone) and lower heat input requirement (+116.33 kJ/mol NH3 for mixture vs. +228.55 kJ/mole NH3 for ammonium chloride alone). The reaction shown in reaction 3 has been demonstrated in literature in the article ‘Reaction of Zinc Chloride with Zinc Oxide’ by Borisov et al. Borisov et al found the reactants initially form ammonium chlorozincates ((NH4)3ZnCl4) at 150° C., with the evolution of NH3(g) and H2O(g). Borisov et al found the mixture of ammonium chloride and zinc oxide completely converts into products shown in reaction 3 at about 210° C. Borisov et al found a stoichiometric amount of NH3 formed and the presence of zinc did not cause the NH3 to decompose.
It is important to note that zinc oxide may be recycled internally from Reaction 3.
It is important to note metals other than or in addition to zinc may be employed, which may include, but are not limited to, one or more or a combination of the following: iron, lead, copper, cobalt, nickel, manganese, chromium, silver, scandium, vanadium, titanium, aluminum, magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium, Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium, Unununium, or Ununbium.
Reaction 4 Further Description and Proof:
Reaction 4 involves reacting zinc chloride with sulfuric acid form zinc sulfate and hydrochloric acid. The enthalpy of Reaction 4 may be strongly exothermic and favorable and sulfuric acid may be a stronger acid than hydrochloric acid. Reaction 4 may require cooling. Said cooling may involve recovering heat. Recovered heat may be employed to facilitate removal or distillation of excess water or separate residual zinc sulfate or zinc chloride from hydrochloric acid. Depending on the concentration of sulfuric acid, zinc chloride may be placed in sufficient water to ensure there is enough water for the product hydrochloric acid to fully dissolve and form hydrochloric acid, as hydrochloric acid may require stoichiometrically more water than sulfuric acid to remain in solution. Alternatively, or additionally, a portion of hydrochloric acid may form as a gas, and may be condensed or recovered or converted into an aqueous solution or a combination thereof. Zinc chloride or zinc sulfate may be present primarily at the solid phase due to, for example, limited amount of relative water and/or the salting-out effects of HCl or H2SO4 in solution. Residual zinc chloride or zinc sulfate may comprise a membrane-based process, a solid membrane, distillation, electrodialysis, ion exchange, crystallization, cryodesalination, freezing desalination, cooling precipitation, precipitation, ‘salting-out’, common-ion effect, or a combination thereof.
Reaction 5 Further Description and Proof:
Reaction 5 involves decomposing zinc sulfate into zinc oxide and sulfur trioxide or sulfur dioxide and O2 or both. According to ‘Kinetics of the Thermal Decomposition of Zinc Sulfate’ by Ibanez et al, zinc sulfate decomposes into zinc oxide and sulfur trioxide or sulfur dioxide or O2 or a combination thereof starting at about 920° C. Zinc oxide may be transferred or employed or both to Reaction 3 and sulfur trioxide or sulfur dioxide or O2 or a combination thereof may be employed in Reaction 6.
Reaction 6 Further Description and Proof:
Reaction 6 may involve the formation of sulfuric acid from sulfur trioxide or sulfur oxides which may be converted into sulfur trioxide or sulfuric acid. Reaction 6 is well known in industry to produce sulfuric acid and may be conducted using one or more or a combination of methods for producing sulfuric acid in the art. Reaction 6 is highly exothermic and heat from the reaction may be recovered as, for example, steam. It may be possible to employ heat from Reaction 6 to power a portion of the thermal duty of Reaction 1. Sulfuric acid product may be employed in Reaction 4.
Comparison of Example Embodiment 3 to Process Involving Recovering Ammonia with Calcium Oxide—Energy Balance, CO2 Emissions Balance, and Value of Byproducts
Energy Consumption:
½ CaO + ½ CO2
NH3(g) +
½ ZnO(s) + ½
½ Ca(OH)2
½
CO2 Emissions:
Note: CO2 emissions savings/net CO2 sequestration is not due to fuel switching.
½ CaO + ½ CO2
0.261
0.226
0.166
½ CaO + ½ CO2 (½
0.261 CO2 +
0.226 CO2 (−89
0.166 CO2 +
NaHCO3(s) +
NaHCO3(s) +
½ CaO + ½ CO2 (½ mole
0.261 CO2 +
0.226 CO2 (−89
½ Na2CO3 + ½ CO2 + ½
½ Na2CO3 + ½ CO2 + ½
0.166 CO2 +
NaHCO3(s) +
NaHCO3(s) +
Value of Byproducts (Table):
Calcium Oxide Production without Calcining Calcium Carbonate
Background: Calcium oxide is an essential component of cement and quicklime. It is produced in excess of 300 million tons per year for use in quicklime and produced in excess of 2 billion tons per year for use in the production of cement. Calcium oxide is currently produced using the highly CO2 emitting and energy intensive process of calcining calcium carbonate, which involves heating calcium carbonate to an elevated temperature and decomposing calcium carbonate into calcium oxide and carbon dioxide. Due to the nature of the chemistry of calcining calcium carbonate, it emits significant amounts of CO2 not only due to its thermal energy demands (which are generally powered by the burning of coal), but also or mostly due to the CO2 directly released from the decomposition of CaCO3 into CaO and CO2. Calcining CaCO3 comprises over 8% of global anthropogenic CO2 emissions.
Summary of Example Embodiments: Example embodiments may involve producing calcium oxide during the production of phosphoric acid from calcium phosphate. Example embodiments may enable the production of calcium oxide without the calcining of calcium carbonate and while producing valuable phosphoric acid.
Reaction 1 and 2 Further Description and Proof:
Reactions 1 and 2 may involve the first two reactions or steps of the Odda Process or the Nitrophosphate Process.
Reaction 3 Further Description and Proof:
Reaction 3 may involve the thermal decomposition of calcium nitrate or hydrates of calcium nitrate or both or a combination thereof. According to a research paper on the thermal decomposition of calcium nitrate, ‘A kinetic and mechanistic study of the thermal decomposition of calcium nitrate’ by Ettarh et al, calcium nitrate melts and simultaneously decomposes in a temperature range around 562° C., proceeding to form the reaction products described in reaction 3.
The resulting calcium oxide may be employed for applications of calcium oxide and may comprise a valuable byproduct. The nitrogen oxides and oxygen produced may be employed, for example, in reaction 4 to produce nitric acid, which may be recycled internally.
Reaction 4 Further Description and Proof:
Reaction 4 may involve forming nitric acid from nitrogen oxides, oxygen, and water. The nitrogen oxides and oxygen may form internally (for example: reaction 3) and the resulting nitric acid may be recycled or used internally (for example: reaction 1). The process for nitric acid production may be simplified in reaction 4. For example, nitrogen monoxide is often produced and must be oxidized to nitrogen dioxide and re-introduced to water. The steps involved with producing nitric acid from nitric oxides may follow steps and procedures known in the art for nitric acid production, such as the steps and procedures performed by the Ostwald Process. The production of nitric acid from nitrogen oxides and water may be highly exothermic and heat may be recovered from said reaction and utilized internally or externally in other processes or both.
Further Notes:
Note: Any excess water may be removed from system. Similarly, water may be added to the system if desired. Water removal may be conducted by for example, including, but not limited to, one or more or a combination of the following: forward osmosis, decanter, separatory funnel, coalescer, centrifuge, filter, switchable solvent, cyclone, semi-permeable membrane, nanofiltration, organic solvent nanofiltration, reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration, hot ultrafiltration, distillation, membrane distillation, flash distillation, multi-effect distillation, mechanical vapor compression distillation, or hybrid systems.
Note: Sodium Bicarbonate may be decomposed to form Sodium Carbonate, Sodium hydroxide, Sodium Sesquicarbonate, or a combination thereof, or other sodium—carbon dioxide or sodium bicarbonate derivative chemicals.
Note: Separation Devices may include, but are not limited to, one or more or a combination of the following: decanter, separatory funnel, coalescer, centrifuge, filter, switchable solvent, cyclone, semi-permeable membrane, nanofiltration, organic solvent nanofiltration, reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration, hot ultrafiltration, distillation, membrane distillation, flash distillation, multi-effect distillation, mechanical vapor compression distillation, or hybrid systems
Note: The temperature of recovered heat may be increased using a heat pump or a refrigeration cycle, if, for example, higher temperature heat is required for one or more process steps or one or more applications. For example, if recovered heat is in the form of steam, said steam may be compressed to a greater pressure, which may enable said steam to condense at a higher temperature and/or supply higher temperature heat.
Note: Heat sources may include, but are not limited to, one or more or a combination of the following: flare gas heat, natural gas combustion, nuclear heat, Waste Heat, Ambient Temperature Changes, Diurnal Temperature Variation, Thermocline liquid body, thermocline solid body, thermocline gaseous body, Thermocline of a water body, halocline, heat pump, solar thermal, solar thermal pond, light, electricity, steam, combustion, compression, pressure increase, geothermal, radiative heat, condensation, exothermic dissolution, exothermic precipitation, exothermic formation of more liquid phases, exothermic formation of less liquid phases, exothermic phase change, or other heat sources described herein.
Note: Systems and methods described herein may be batch, semi-batch, or continuous, or a combination thereof.
Note: Metals other than or in addition to zinc may be employed, which may include, but are not limited to, one or more or a combination of the following: iron, lead, copper, cobalt, nickel, manganese, chromium, silver, scandium, vanadium, titanium, aluminum, magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium, Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium, Ununnilium, Unununium, or Ununbium.
Note: Reactions or systems and methods, steps, or a combination thereof herein may comprise a batch, semi-batch, semi-continuous, continuous stirred reactor (CSTR), continuous, or a combination thereof.
Note: The dissolution of calcium chloride in one or more embodiments may pre-heat or provide supplemental heating to an ammonium chloride—lean aqueous solution. Said dissolution and/or resulting pre-heating may occur before a solution comprising calcium chloride and ammonium chloride is reacted with ammonium sulfate. Calcium chloride dissolution is generally exothermic and said exothermic dissolution may provide at least a portion of the heat required to ensure the solution is at a sufficiently high temperature before reaction with ammonium sulfate. A sufficiently high temperature may be beneficial, as a greater temperature may enable greater solubility of ammonium chloride and/or ammonium sulfate during the reaction. A sufficiently high temperature may enable ammonium chloride to remain dissolved during the reaction between calcium chloride and ammonium sulfate, which may enable the formation of a precipitate comprising mostly or entirely calcium sulfate. A sufficiently high temperature may enable ammonium chloride to remain dissolved during the reaction between calcium chloride and ammonium sulfate (which forms additional ammonium chloride as a product), which may enable the formation of a precipitate comprising mostly or entirely calcium sulfate. After separation of calcium sulfate precipitate, the remaining solution may be rich in ammonium chloride(aq) and may be cooled to precipitate a portion of ammonium chloride(s). After the ammonium chloride precipitate is separated, the remaining solution may comprise ammonium chloride—lean aqueous solution and may be employed to the first step.
Note: Depending on the operating conditions, phases of inputs, concentrations, or a combination thereof, heating or cooling or both may be required in one or more or a combination of the steps or parts of one or more or a combination of embodiments.
Note: The present invention may employ other carbonate or bicarbonate salts as feedstocks, which may include, but are not limited to, sodium and potassium carbonates or bicarbonates.
Note: May employ materials compatible with one or more or a combination of the following: SO2, CO2, or H2O or one or more of the fuels (if any) employed in heating and/or their combustion products. It may be desirable for said materials to be compatible at temperature ranges which the materials will be operating
Note: Advantageous, the present invention does not require an air separation unit or post-combustion CO2 capture to produce pure CO2. Also advantageously, pure CO2 may be produced at a high pressure and/or relatively low temperature and/or with relatively low water vapor concentration.
Note: It may be desirable for the CaCO3 or SO2 or CaSO3 or CaO or a combination thereof in an oxygen-free or very low oxygen environment. An oxygen-free or very low oxygen environment may, for example, prevent the oxidation of SO2 or CaSO3 or other SO3 salt into a SO4 salt.
Note: The present invention may be employed to regenerate CaO from CaCO3 or similar carbonate or bicarbonate molecules in a CO2 capture process. For example, the present invention may be employed in a device to capture CO2 from the air.
Note: The SO2 may be substituted with nitric acid (HNO3). Ca(NO3)2 (which may be a resulting byproduct) can be thermally decomposed in a similar manner to CaSO3 to form CaO and NOx or O2 or NO2 or NO or a combination thereof. NOx, NO2, or NO may be converted back into nitric acid through reaction with water in, for example, the NOx+O2 and NOx+H2O reaction steps of the Ostwald process, regenerating the nitric acid in the present embodiment. Advantageously, Ca(NO3)2 does not oxidize in the presence of O2, which may enable the process to operate in an environment with the presence of O2, if desired.
Note: The carrier gas may comprise a reactive gas if desired. For example, steam may be employed as a carrier gas. Advantageously, steam may condense following calcination and the heat generated may be recoverable and the heat generated may exceed initial heat input to generate steam due to, for example, the exothermic dissolution of SO2 in the condensed steam (water) and/or the exothermic reaction of H2O with CaO to produce calcium hydroxide. It is important to note that calcium hydroxide may be a byproduct of this version of the present invention.
Note: Any excess water may be removed from system. Similarly, water may be added to the system if desired. Water removal may be conducted by for example, including, but not limited to, one or more or a combination of the following: forward osmosis, decanter, separatory funnel, coalescer, centrifuge, filter, switchable solvent, cyclone, semi-permeable membrane, nanofiltration, organic solvent nanofiltration, reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration, hot ultrafiltration, distillation, membrane distillation, flash distillation, multi-effect distillation, mechanical vapor compression distillation, or hybrid systems.
Note: Sodium salts may be employed. Sodium Bicarbonate may be decomposed to form Sodium Carbonate, Sodium hydroxide, Sodium Sesquicarbonate, or a combination thereof, or other sodium—carbon dioxide or sodium bicarbonate derivative chemicals.
Note: Separation Devices may include, but are not limited to, one or more or a combination of the following: decanter, separatory funnel, coalescer, centrifuge, filter, switchable solvent, cyclone, semi-permeable membrane, nanofiltration, organic solvent nanofiltration, reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration, hot ultrafiltration, distillation, membrane distillation, flash distillation, multi-effect distillation, mechanical vapor compression distillation, or hybrid systems
Note: Heat sources may include, but are not limited to, one or more or a combination of the following: flare gas heat, natural gas combustion, nuclear heat, Waste Heat, Ambient Temperature Changes, Diurnal Temperature Variation, Thermocline liquid body, thermocline solid body, thermocline gaseous body, Thermocline of a water body, halocline, heat pump, solar thermal, solar thermal pond, light, electricity, steam, combustion, compression, pressure increase, geothermal, radiative heat, condensation, exothermic dissolution, exothermic precipitation, exothermic formation of more liquid phases, exothermic formation of less liquid phases, exothermic phase change, or other heat sources described herein.
Note: Systems and methods described herein may be batch, semi-batch, or continuous, or a combination thereof.
Note: Sodium bicarbonate may be thermally decomposed into at least a portion carbon dioxide to, for example, produce sodium carbonate or sodium sesquicarbonate. Said carbon dioxide may be recycled internally, for example, to a carbon dioxide absorption step. Said carbon dioxide, may improve absorption characteristics including, but not limited to, one or more or a combination of the following: absorption rate, maximum carbon dioxide loading, absorption capacity, solution carrying capacity, sodium bicarbonate recovery yield, sodium bicarbonate recovery rate, or sodium bicarbonate recovery rate per a unit volume or mass of solution. Said carbon dioxide may increase the concentration of carbon dioxide in one or more or a combination of parts of the system, for example, which may be related, including, but not limited to, one or more or a combination of the following: carbon dioxide solutions, carbon dioxide gases, carbon dioxide absorption, bicarbonate salts, salts.
Note: Solutions may be passed or cycled or recycled or recirculated through a step more than once. Said ‘passed or cycled or recycled or recirculated’ may be conducted before, for example, proceeding to a next step. Said solutions may comprise, for example, absorption solutions or solutions undergoing precipitation.
Note: Magnesium chloride may be an input in the system. For example, magnesium chloride may be employed in addition to or instead of calcium chloride in one or more or a combination of the embodiments.
Note: One or more or a combination of the embodiments described herein may be employed as a net carbon dioxide emission negative method for permanently or semi-permanently sequestering carbon dioxide. For example, the sodium bicarbonate, or sodium sesquicarbonate, or sodium carbonate or a combination thereof produced by one or more embodiments may be dissolved in the ocean. Adding net carbon dioxide emission negative sodium bicarbonate, or sodium sesquicarbonate, or sodium carbonate or a combination thereof to the ocean may have multiple benefits, which may include, but are not limited to, one or more or a combination of the following: permanent or semi-permanent sequestration of carbon dioxide in the ocean; increasing the pH of ocean water; increasing the concentration of carbonate ions in the ocean; buffering ocean acidification, restoring coral reefs; restoring marine life; local rejuvenation of marine life; local rejuvenation of coral; rejuvenation of coral.
Note: To ensure full mixing of ammonium chloride and zinc oxide, aqueous ammonium chloride may be mixed with finely ground or dispersed solid zinc oxide. Water may be evaporated or distilled from said aqueous ammonium chloride while said aqueous ammonium chloride is in contact with said zinc oxide, which may result in the formation of a relatively evenly distributed mixture of ammonium chloride and zinc oxide.
Note: ‘Chloride’ may be provides as an example anion. Other anions may be employed. For example, other halogens may be employed in addition to or instead of chloride or chlorine, which may include, but are not limited to, one or more or a combination of the following: fluoride or fluorine, bromide or bromine, or iodide or iodine.
Note: Cooling and/or heating may be conducted at addition or different temperatures and/or at additional or different locations than described herein.
Note: Any excess water may be removed from system. Similarly, water may be added to the system if desired. Water removal may be conducted by for example, including, but not limited to, one or more or a combination of the following: forward osmosis, decanter, separatory funnel, coalescer, centrifuge, filter, switchable solvent, cyclone, semi-permeable membrane, nanofiltration, organic solvent nanofiltration, reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration, hot ultrafiltration, distillation, membrane distillation, flash distillation, multi-effect distillation, mechanical vapor compression distillation, or hybrid systems.
Note: Sodium salts may be employed. Sodium Bicarbonate may be decomposed to form Sodium Carbonate, Sodium hydroxide, Sodium Sesquicarbonate, or a combination thereof, or other sodium—carbon dioxide or sodium bicarbonate derivative chemicals.
Note: Separation Devices may include, but are not limited to, one or more or a combination of the following: decanter, separatory funnel, coalescer, centrifuge, filter, switchable solvent, cyclone, semi-permeable membrane, nanofiltration, organic solvent nanofiltration, reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration, hot ultrafiltration, distillation, membrane distillation, flash distillation, multi-effect distillation, mechanical vapor compression distillation, or hybrid systems, freezing desalination, cryodesalination
Note: Heat sources may include, but are not limited to, one or more or a combination of the following: flare gas heat, natural gas combustion, nuclear heat, Waste Heat, Ambient Temperature Changes, Diurnal Temperature Variation, Thermocline liquid body, thermocline solid body, thermocline gaseous body, Thermocline of a water body, halocline, heat pump, solar thermal, solar thermal pond, light, electricity, steam, combustion, compression, pressure increase, geothermal, radiative heat, condensation, exothermic dissolution, exothermic precipitation, exothermic formation of more liquid phases, exothermic formation of less liquid phases, exothermic phase change, or other heat sources described herein.
Note: Systems and methods described herein may be batch, semi-batch, or continuous, or a combination thereof.
Note: One or more or a combination of embodiments of the present invention may comprise a retrofit to pre-existing processes for producing sodium bicarbonate or sodium carbonate or other carbonate or bicarbonate salts. For example, some embodiments of the present invention may enable the production of ammonia from ammonium chloride, without the calcination of calcium carbonate or using calcium oxide. For example, some embodiments of the present invention may enable the production of ammonia and/or hydrochloric acid from ammonium chloride, which may provide greater value than an ammonium chloride byproduct.
Note: One or more or a combination of embodiments of the present invention may require solid handling or solid transfer or solid storage. Solid transfer may include, but is not limited to, conveyor belts, screw conveyors, bucket elevators, belt conveyors, pneumatic conveyors, or a combination thereof. Solid storage or transport or a combination thereof may include, but is not limited to, bin, or silo, hopper cars, bulk sacks, or other solids shipping containers, or a combination thereof.
Note: Temperatures in one or more parts of one or more embodiments may include, but are not limited to, greater than, equal to, or less than one or more or a combination of the following in degrees Celsius: −50, −40, −30, −20, −10, 0, 5, 10, 15, 20, 25, 30 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1080, 1090, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1600, 1700, 1800, 1900, 2000, 2250, 2500, 2750, 3000
Note: Sodium may be provided as an example alkali. Other alkali metal salts or cations may be employed instead of or in addition to sodium. For example, potassium or lithium or rubidium or cesium or a combination thereof may be employed.
Note: Ammonia may be provided as an example weak base. Other weak bases or weak base gases may be employed instead of or in addition to ammonia. For example, said other weak bases may include, but are not limited to, one or more or a combination of the following: amines, ammonia derivatives, imines, azines, CO2 capture absorbent cations, CO2 capture absorbents, or a combination thereof, or other weak bases, or other weak gases.
Note: CO2 sources may include, but are not limited to, one or more or a combination of the following: Power Plant (Natural gas, coal, oil, petcoke, biofuel, municipal waste), Cement production, chemical production, Waste Water Treatment, Landfill gas, Air, Metal production/refining (such as Iron, Steel, Aluminum, etc.), Glass production, Oil refineries, LNG liquification, HVAC, Transportation vehicles (ships, boats, cars, buses, trains, trucks, airplanes), Natural Gas, Biogas, Alcohol fermentation, Volcanic Activity, Decomposing leaves/biomass, Septic tank, Respiration, Manufacturing facilities, Fertilizer production, or Geothermal processes where CO2(g) releases from a well or wells.
Note: Input CO2 vol % concentration may be greater than or equal to one or more or a combination of the following volume percent concentrations: 0%, or 0.001%, or 0.1%, or 0.5%, or 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%, or 4%, or 4.5%, 5%, or 5.5%, or 6%, or 6.5%, or 7%, or 7.5%, or 8%, or 8.5%, or 9%, or 9.5%, or 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15%, or 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90%, or 100%.
Note: A gas stream comprising CO2 may be concentrated to a greater concentration of CO2 or a greater partial pressure of CO2 before being absorbed in one or more or a combination of embodiments of the present invention. Said concentrating may be conducted using including, but not limited to, one or more or a combination of the following: gas membrane, or absorption/desorption CO2 capture, or adsorption/desorption CO2 capture, or recirculated CO2, or desorption CO2, or CO2 from one or more or a combination of higher concentration CO2 sources, or condensation of non-CO2 gas, or cooling, or heating, or deposition, or deposition/sublimination, or cryogenic separation, or compression, or pressurization, electrochemical process, or ion exchange, or electrodialysis, or fuel cell, or a combination thereof.
Note: Absorption of a gas into a solution containing ammonia and/or absorption of ammonia into a solution may result in the formation of a residual or remaining gas stream comprising residual ammonia. Said residual or remaining gas stream may comprise, for example, remaining unabsorbed gases or inert gases. One or more or a combination of embodiments herein may employ an ammonia recovery or ammonia abatement cycle or system. Alternately or additionally, ammonia may be removed to ultra-low concentrations (e.g. single or double digit PPM concentrations) using hydrochloric acid (which may be produced by some embodiments herein), and/or ammonia or hydrochloric acid or both may be recovered from the resulting ammonium chloride using one or more or a combination of embodiments herein.
Note: Ammonia losses may occur within one or more or a combination of embodiments described herein. Makeup ammonia may be provided, for example, as needed.
Note: In some embodiments, ammonia may form at elevated temperatures. In some embodiments, if oxygen is present, some ammonia may undergo combustion. Ammonia combustion products, even at residual or low concentrations, may be present in one or more gases or liquids or solids or a combination thereof in one or more or a combination of embodiments. Said ammonia combustion products may comprise, including, but not limited to, nitrogen oxides, or nitrogen, or nitric acid, or a derivative thereof, or a combination thereof. Systems and methods for detecting, treating, removing, economically using, recovering, or a combination thereof said ammonia combustion products may be employed.
Note: Filling, or reacting, or emptying, or a combination thereof may be conducted simultaneously if desired.
reacting ammonium chloride with zinc oxide to form a zinc chloride, ammonia, and water;
reacting the zinc chloride with sulfuric acid to form a zinc sulfate and hydrochloric acid; and
thermally decomposing the zinc sulfate to produce zinc oxide.
This application claims priority to U.S. provisional application No. 62/895,557 filed Sep. 4, 2019 and U.S. provisional application No. 63/042,397 filed Jun. 22, 2020. The application also claims priority to U.S. application Ser. No. 16/944,850 filed Aug. 11, 2020. The application also claims priority to U.S. provisional application No. 62/890,254 filed Aug. 22, 2020. All applications are incorporated by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62895557 | Sep 2019 | US | |
| 63042397 | Jun 2020 | US | |
| 62890254 | Aug 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16944850 | Jul 2020 | US |
| Child | 16998397 | US |
