WO2012096987A1 - Systèmes et procédés de production de carbonate de sodium - Google Patents

Systèmes et procédés de production de carbonate de sodium Download PDF

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Publication number
WO2012096987A1
WO2012096987A1 PCT/US2012/020815 US2012020815W WO2012096987A1 WO 2012096987 A1 WO2012096987 A1 WO 2012096987A1 US 2012020815 W US2012020815 W US 2012020815W WO 2012096987 A1 WO2012096987 A1 WO 2012096987A1
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electrochemical
solvay
carbon dioxide
mpa
ammonia solution
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PCT/US2012/020815
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English (en)
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Riyaz SHIPCHANDLER
Betty Kong Ling PUN
Michael Joseph Weiss
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Calera Corporation
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • the Solvay process also referred to as the ammonia-soda process, is an industrial process for production of soda ash (sodium carbonate).
  • the ingredients for this process may be readily available: salt brine (from inland sources or from the sea) and limestone (from mines).
  • Salt brine from inland sources or from the sea
  • limestone from mines.
  • Carbon dioxide is emitted from the use of soda ash, and is emitted during production of soda ash, depending on the industrial process used to manufacture soda ash.
  • a method to produce sodium carbonate comprising: a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to a first electrochemical process to produce sodium carbonate.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process comprising: a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to a first electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive Solvay process.
  • the method further comprises regenerating the ammonia solution using calcium oxide obtained by lime calcination.
  • the method further comprises regenerating the ammonia solution using sodium hydroxide obtained from the first or a second electrochemical process. In some embodiments of these aspects, the method does not comprise bicarbonate calcination, lime calcination, or a combination thereof. In some embodiments of these aspects, the method produces less than 80% carbon dioxide as compared to a conventional Solvay process. In some embodiments of these aspects, the method further comprises treating the sodium carbonate with calcium or magnesium ions to form calcium carbonate, magnesium carbonate, or combination thereof. In some embodiments, the calcium carbonate, magnesium carbonate, or combination thereof is a cementitious material. In some embodiments, the cementitious material comprises vaterite. In some embodiments, the cementitious material has a compressive strength of greater than lOMPa.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising: a) a Solvay system comprising an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) a first electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate.
  • the system further comprises a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution.
  • the system further comprises a lime calciner operably connected to the regenerator and configured to produce calcium oxide for regenerating the ammonia solution.
  • system further comprises a second electrochemical system operably connected to the regenerator and configured to produce sodium hydroxide for regenerating the ammonia solution.
  • system further comprises a precipitator operably connected to the first electrochemical system configured to produce calcium and/or magnesium carbonate by treating sodium carbonate with calcium and/or magnesium ions.
  • Fig. 1 provides the Solvay process for preparing soda ash.
  • Fig. 2 is an illustrative embodiment of a modification of the Solvay process incorporating electrochemical process.
  • Fig. 3 is an illustrative embodiment of another modification of the Solvay process incorporating electrochemical process.
  • Fig. 4 is an illustrative embodiment of yet another modification of the Solvay process incorporating two electrochemical processes.
  • Fig. 5 is an illustrative embodiment of a process for producing soda ash from direct capture of carbon dioxide.
  • Fig. 6 is an illustrative embodiment of a comparison of carbon dioxide emissions from the processes illustrated in Figs. 1-5.
  • Fig. 7 is an illustrative embodiment of a process for producing soda ash from alkaline brines in accordance with the existing process by Searles Valley Minerals (Overland Park, Kansas).
  • Fig. 8 is an illustrative embodiment of a modification of the Searles Valley Minerals process incorporating electrochemical process.
  • Fig. 9 is an illustrative embodiment of a process for producing soda ash from alkaline brines incorporating electrochemical process.
  • Fig. 10 is an illustrative embodiment of a comparison of carbon dioxide emissions from the processes provided in Figs. 7-9 and a direct capture of carbon dioxide.
  • Fig. 11 is an illustrative embodiment of a typical process for converting trona to soda ash.
  • Fig. 12 is an illustrative embodiment of a process for producing soda ash from trona utilizing electrochemical process.
  • Fig. 13 provides an illustrative embodiment of an electrochemical system.
  • Fig. 14 provides an illustrative embodiment of an electrochemical system.
  • Fig. 15 provides an illustrative embodiment of an electrochemical system.
  • Fig. 16 provides an illustrative embodiment of an electrochemical system.
  • Fig. 17 provides an illustrative embodiment of a Solvay system integrated with the electrochemical system.
  • Fig. 18 provides an illustrative embodiment of a processing system.
  • Fig. 19 illustrates a plot comparing the performance between 10 wt% NaOH and 1 mol/L sodium bicarbonate solution in an electrochemical cell.
  • Described herein are methods and systems to produce sodium carbonate by integrating Solvay process with electrochemical processes.
  • the methods and systems provided herein are devoid of calcination of bicarbonate and lime as found in a conventional Solvay process, thereby providing a less carbon dioxide intensive Solvay process and an environmentally friendly sodium carbonate product.
  • a "Solvay process,” as used herein, includes any process that can be used to produce sodium carbonate using ammonia and carbon dioxide.
  • About 25 per cent of the world production of soda ash may be from natural sodium carbonate bearing deposits referred to as natural processes.
  • trona (a principal ore from which natural soda ash may be made) may be calcined in a rotary kiln and chemically transformed into a crude soda ash.
  • carbon dioxide is generated in the process.
  • sodium chloride brine, limestone, coke and ammonia are the raw materials in a series of reactions leading to the production of soda ash.
  • Ammonia may be regenerated while a small amount may be lost.
  • C0 2 is generated in two calcination processes.
  • the C0 2 generated may be captured, compressed and directed to Solvay precipitating towers for consumption in a mixture of brine (aqueous NaCl) and ammonia.
  • brine aqueous NaCl
  • ammonia there is net C0 2 emitted to the atmosphere during the production of soda ash because more C0 2 is produced by calcining limestone than is stoichiometrically required for absorption.
  • the methods and systems described herein are related to the reduction of the C0 2 emission from the Solvay process by eliminating one or both of the calcining steps.
  • the calcining steps of the Solvay process may be replaced by the electrochemical processes described herein.
  • the Solvay process (as illustrated in Fig. 1) benefits from modifications comprising one or more elements of the processing and/or electrochemical systems and methods described herein.
  • some of the carbon dioxide emitted from the Solvay process may be processed in accordance with any of the C0 2 -processing methods described herein.
  • the carbon dioxide may originate from Reaction IV ("Bicarb Calcination"), Reaction II ("Lime Calcination”), or a combination thereof.
  • Reaction III Regeneration
  • calcium and/or magnesium carbonates e.g., calcite, aragonite, vaterite, amorphous calcium carbonate
  • Such calcium and/or magnesium carbonates are useful in building materials such as cement, aggregate, supplementary cementitious materials, and the like.
  • Alkaline waste and/or by-products of the Solvay process may also be used in the C0 2 -process described herein.
  • a method to produce sodium carbonate comprising a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to a first electrochemical process to produce sodium carbonate.
  • a method to produce sodium carbonate comprising a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium
  • a method to produce sodium carbonate comprising a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium bicarbonate to a first electrochemical process to produce sodium carbonate; and c) regenerating the ammonia solution using sodium hydroxide obtained from the first or a second electrochemical process.
  • the first and/or the second electrochemical processes may be any electrochemical process described herein.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process comprising a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to a first electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive Solvay process.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process comprising a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process comprising a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium bicarbonate to a first electrochemical process to produce sodium carbonate; and c) regenerating the ammonia solution using sodium hydroxide obtained from the first or a second electrochemical process, thereby resulting in a less carbon dioxide intensive Solvay process.
  • the first and/or the second electrochemical processes may be any electrochemical process described herein.
  • the method described above and herein produces less than 80% carbon dioxide as compared to a conventional Solvay process.
  • the method described above and herein produces less than 90%>; or less than 80%>; or less than 70%>; or less than 60%>; or less than 50%>; or less than 40%>; or less than 30%>; or less than 20%>; or less than 10%>; or less than 5%; or less than 5-90%>; or less than 5-80%>; or less than 5-70%>; or less than 5-60%>; or less than 5-50%>; or less than 5-40%>; or less than 5-30%>; or less than 5-20%>; or less than 5-10%; or less than 10-80%; or less than 25-80%>; or less than 50-80%>; as compared to a conventional Solvay process.
  • the methods do not include bicarbonate calcination,
  • Figs. 2-5 provide some modifications to the Solvay process of Fig. 1.
  • Fig. 2 for example, illustrates an electrochemical process in place of Reaction IV ("Bicarb Calcination").
  • the electrochemical process is as described herein. Details of such a modification, as provided in Fig. 2, show that Reaction IV of the modified process does not produce carbon dioxide, a distinct advantage over the existing Solvay process.
  • Fig. 3, for example, illustrates an electrochemical process in place of Reaction II ("Lime Calcination").
  • the electrochemical process is as described herein. Details of such a modification, as provided in Fig. 3, show that Reaction II of the modified process does not produce carbon dioxide, a distinct advantage over the existing Solvay process.
  • Fig. 5 illustrates a direct capture feature of Fig. 4 as well as a modified Reaction III ("Regeneration").
  • Regeneration a modified Reaction III
  • Some of the advantages of the modified Solvay process are lower demand for raw materials in Reactions I and III; less carbon dioxide emissions; and less energy intensive reactions (reduced or no calcinations).
  • Fig. 5 shares the same soda ash product as the Solvay process but excises Reactions II and III and completely modifies Reactions I and II. Additional advantages of the processes provided in Figs. 2-5 are provided in the Table I immediately below.
  • Figs. 2-5 are less energy intensive and have smaller carbon footprint than the conventional Solvay process of Fig. 1.
  • Fig. 6 illustrates carbon dioxide emissions in tonnes C0 2 /tonne of soda ash produced for the processes depicted in Figs. 1-5, which correspond to "Solvay w/
  • a method to produce sodium carbonate comprising a) absorbing carbon dioxide in sodium carbonate solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate.
  • a less carbon dioxide intensive method to produce sodium carbonate comprising a) absorbing carbon dioxide in sodium carbonate solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive method to produce sodium carbonate.
  • Fig. 7 illustrates a process using Searles Valley Minerals (SVM) for producing soda ash. A modification to the process is illustrated in Fig. 8.
  • Fig. 8 replaces the bicarbonate calcination step with an electrochemical step, which electrochemical step does not release carbon dioxide.
  • Fig. 9 provides a process for producing soda ash in which there is an electrochemical step replacing the bicarbonate calcination step along with recycling of acid. Additional details for the processes of Figs. 8-9 are provided in each figure. Some of the advantages of the processes provided in Figs. 8-9 are provided in the Table II below.
  • Figs. 8-9 are less energy intensive and have smaller carbon footprints than the Searles Valley Minerals process of Fig. 7.
  • Fig. 10 illustrates carbon dioxide emissions in tonnes C0 2 /tonne of soda ash produced for the processes depicted in Figs. 8-9, which correspond to "Alkaline Brines w/ Electrochemical process,” “Alkaline Brines w/ Acid Recycle,” and “Direct Capture,”
  • Fig. 11 illustrates a conventional trona ore process where trona is calcined to form soda ash.
  • Fig. 12 illustrates modification to the trona-based method for producing soda ash, modifications including, but not limited to, use of electrochemistry and/or C0 2 processing (e.g., processing waste C0 2 produced by calcination of trona).
  • Fig. 12 illustrates one such method for producing soda ash in a less carbon dioxide intensive manner.
  • soda ash may be prepared from trona (1/2 Na 2 C0 3 » NaHC0 3 » 2 H 2 0 (s)) utilizing electrochemistry in place of, or in combination with, calcination.
  • trona may be mined and/or ground, for example, to a powder that may be used directly in electrolyte (e.g. catholyte) for the electrochemical cell or system thereof (e.g. stack of electrochemical cells), or purified before electrolyte use to remove impurities.
  • electrolyte e.g. catholyte
  • Fig. 12 illustrates use of either Na 2 S0 4 or NaCl, which provide anolytes comprising H 2 S0 4 or HC1, respectively.
  • Carbonates as shown in Fig.
  • Such carbonates may be further processed including, but not limited to, liquid-solid separation, crystallization, recrystallization, and drying.
  • the system component corresponding to the mining/grinding step may comprise a mineral processor configured to comminute trona and other rocks/minerals;
  • the system component corresponding to the electrochemical step may comprise an electrochemical cell or stack of electrochemical cells;
  • the system components corresponding to crystallization and drying may comprise a liquid-solid separator, a tank or analogous vessel for
  • crystallization/recrystallization and/or a dryer (e.g., spray dryer).
  • a dryer e.g., spray dryer
  • Trona Ore w/ Electrochemical process emits less carbon dioxide (a measure of energy efficiency) than the Trona Ore process provided in Fig. 11.
  • the process of Fig. 12 has additional advantages including, but not limited to, eliminating C0 2 emissions from calcination.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system including an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) a first electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system including an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; b) a first electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate; and c) a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system including an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; b) a first electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate; c) a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution; and d) a lime calciner operably connected to the regenerator and configured to produce calcium oxide for regenerating the ammonia solution.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system including an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; b) a first electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate; c) a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution; and d) a second electrochemical system operably connected to the regenerator and configured to produce sodium hydroxide for regenerating the ammonia solution.
  • the Solvay system is any system known in the art to carry out the Solvay process.
  • the absorber in the Solvay system may be any absorber configured to absorb carbon dioxide in an ammonia solution, such as, but not limited to, absorber configured for bubbling the carbon dioxide gas, stirrers for mixing the gas in the solution, packed bed for efficient contact between the gas and the solution, etc.
  • the solution charged with C0 2 is made by parging or diffusing the C0 2 gaseous stream through an ammonia solution to make a C0 2 charged solution containing sodium bicarbonate.
  • the C0 2 gas is bubbled or parged through a solution containing ammonia in the absorber.
  • the absorber may include a bubble chamber where the C0 2 gas is bubbled through the ammonia solution. In some embodiments, the absorber may include a spray tower where the ammonia solution is sprayed or circulated through the C0 2 gas. In some embodiments, the absorber may include a pack bed to increase the surface area of contact between the C0 2 gas and the ammonia solution. In some embodiments, a typical absorber fluid temperature is 32-37°C. For some embodiments, the absorber for absorbing C0 2 in the solution may be as described in U.S. Application Serial No. 12/721,549, filed on March 10, 2010, which is incorporated herein by reference in its entirety.
  • regenerator in the system described herein may be any system that can be used for regenerating ammonia (from ammonium chloride) where the system contains the base (such as calcium oxide from lime calcinations or sodium hydroxide from electrochemical process).
  • regenerator can be a tank, or a series of tanks, or container which may contain conduits or pipes to transfer and mix the ammonium salt solution and the base to regenerate ammonia.
  • the ammonia formed may be transferred out of the tank or container using conduits or pipes.
  • the lime calciner in the system described herein may be any system that can be used for lime calcinations. Such calciners are well known in the art and are well within the scope of the invention.
  • the sodium bicarbonate solution from the Solvay plant is transferred to the electrochemical system for the generation of soda ash.
  • the sodium hydroxide from the electrochemical systems is transferred to the Solvay plant for the regeneration of the ammonia solution.
  • the electrochemical plant may be fitted close to the Solvay plant eliminating transportation cost for waste products and allowing transportation of valuable products only.
  • electrochemical process or “electrochemical system” used in the methods and systems described above and herein are described in this section. Accordingly, the methods and systems include one or more features of the electrochemical process and electrochemical cell described herein below.
  • the electrochemical process described in Fig. 3 and/or 4 is any electrochemical process described herein that produces sodium hydroxide in the catholyte.
  • the electrochemical process described in Fig. 2, 4, 5, 8, 9, and/or 12 is any electrochemical process described herein that produces sodium hydroxide in the catholyte.
  • electrochemical process described in Fig. 2, 4, 5, 8, 9, and/or 12 is any electrochemical process described herein that produces sodium hydroxide in the catholyte.
  • Described herein are electrochemical systems and methods where the electrochemical cell electrolyzes a salt solution, such as, but not limited to, sodium chloride solution to produce sodium hydroxide in the catholyte and/or sodium carbonate ions and/or sodium bicarbonate in the catholyte, and an acid in the anolyte.
  • a salt solution such as, but not limited to, sodium chloride solution to produce sodium hydroxide in the catholyte and/or sodium carbonate ions and/or sodium bicarbonate in the catholyte, and an acid in the anolyte.
  • the systems and methods are not limited to the use of sodium chloride solution as disclosed in the embodiments described herein as other salt solutions (e.g., aqueous potassium sulfate, Na 2 S0 4 (aq), etc.) can be used to produce an equivalent result.
  • water from various sources can be used including seawater, brackish water, brines or naturally occurring fresh water. In some embodiments, water may be purified
  • the electrochemical cell comprises an anode in contact with an anolyte; a cathode in contact with a catholyte; and an ion exchange membrane disposed between the catholyte and the anolyte.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system comprising an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium
  • the electrochemical system comprises an anode in contact with an anolyte, a cathode in contact with a catholyte and one or more of ion exchange membrane.
  • the alkaline solution is produced in the catholyte of an electrochemical system 100 by electrolyzing a salt solution e.g., sodium chloride solution to produce the alkaline solution, e.g., sodium hydroxide in the catholyte, and an acid, e.g., hydrochloric acid in the anolyte.
  • a salt solution e.g., sodium chloride solution
  • an acid e.g., hydrochloric acid in the anolyte.
  • the anode and the cathode may be separated by an ion exchange membrane (IEM).
  • IEM ion exchange membrane
  • the catholyte is the electrolyte in contact with the cathode and configured to receive anions e.g., hydroxide ions from the cathode upon application of a voltage across the cathode and anode.
  • the catholyte is in a cathode compartment.
  • the anolyte is an electrolyte in contact with the anode and configured to receive cations e.g., protons from the anode upon application of the voltage across the cathode and anode.
  • the anolyte is in an anode
  • the salt solution e.g., a sodium chloride solution is placed in a salt solution compartment that is separated from the cathode compartment by a cation exchange membrane 206.
  • the salt solution is separated from the anolyte compartment by an anion exchange membrane 210.
  • the cathode 201 and the catholyte 202 form the cathode compartment and the anode 204 and the anolyte 203 form the anode compartment.
  • Alkali 205 is formed in the catholyte 202 and an acid is formed in the anolyte 203.
  • a method to produce sodium carbonate by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate wherein the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, and producing a base in the catholyte and an acid in the anolyte.
  • a method to produce sodium carbonate by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to an
  • the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, producing hydrogen gas at the cathode, transferring hydrogen gas from the cathode to the anode, and producing a base in the catholyte and an acid in the anolyte.
  • the electrochemical process does not comprise producing a gas such as chlorine gas at the anode.
  • the electrochemical process comprises producing hydroxide at the cathode and hydrochloric acid (using sodium chloride as anolyte) or sulfuric acid (using sodium sulfate as anolyte) at the anode.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive Solvay process wherein the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, and producing a base in the catholyte and an acid in the anolyte.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive Solvay process wherein the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, producing hydrogen gas at the cathode, transferring hydrogen gas from the cathode to the anode, and producing a base in the catholyte and an acid in the anolyte.
  • the electrochemical process does not comprise producing a gas such as chlorine gas at the anode.
  • the electrochemical process comprises producing hydroxide at the cathode and hydrochloric acid (using sodium chloride as anolyte) or sulfuric acid (using sodium sulfate as anolyte) at the anode.
  • the alkaline solution is produced in the catholyte by reducing water at the cathode to hydroxide ions and hydrogen gas in accordance with Eq. 1 , by applying a voltage across the anode and cathode.
  • Eq. 1 concurrent with the production of hydroxide ions and hydrogen gas at the cathode, at the anode hydrogen is oxidized to protons in accordance with Eq. 2: At the cathode: 2H 2 0 + 2e " -> H 2 + 20H Eq. 1
  • hydroxide ions produced at the cathode migrate into the catholyte to produce the alkaline solution e.g., sodium hydroxide solution by combining with cations e.g., sodium ions in the catholyte.
  • alkaline solution e.g., sodium hydroxide solution
  • the protons formed at the anode in accordance with Eq. 2 migrate into the anolyte and combine with anions in the anolyte e.g., chloride ions to produce an acid, e.g., hydrochloric acid in the anolyte.
  • the anions, e.g., chloride ions are migrated into the anolyte through the anion exchange membrane from the salt solution.
  • hydrogen produced at the cathode is collected and directed to the anode for oxidation to protons as in Eq. 2.
  • the need for externally produced hydrogen is reduced thereby reducing the overall energy expended in producing the alkaline solution.
  • the alkaline solution formed in the catholyte may be used to regenerate ammonia from the spent ammonia solution (used for sequestering carbon dioxide gas).
  • the alkaline solution may be also used to sequester carbon dioxide by absorbing the carbon dioxide in the catholyte in the cathode compartment or by absorbing the carbon dioxide in a gas absorber operatively connected to the cathode compartment configured to receive the catholyte and produce a carbonate or bicarbonate solution.
  • a method to produce sodium carbonate by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate wherein the
  • electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, and producing a base in the catholyte and an acid in the anolyte; and c) regenerating the ammonia solution using calcium oxide obtained by lime calcinations or regenerating the ammonia solution using sodium hydroxide obtained from the electrochemical process.
  • a method to produce sodium carbonate by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate wherein the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, producing hydrogen gas at the cathode, transferring hydrogen gas from the cathode to the anode, and producing a base in the catholyte and an acid in the anolyte; and c) regenerating the ammonia solution using calcium oxide obtained by lime calcinations or regenerating the ammonia solution using sodium hydroxide obtained from the electrochemical process.
  • the electrochemical process does not comprise producing a gas such as chlorine gas at the anode.
  • the electrochemical process comprises producing hydroxide at the cathode and hydrochloric acid (using sodium chloride as anolyte) or sulfuric acid (using sodium sulfate as anolyte) at the anode.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive Solvay process wherein the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, and producing a base in the catholyte and an acid in the anolyte; and c) regenerating the ammonia solution using calcium oxide obtained by lime calcinations or regenerating the ammonia solution using sodium hydroxide obtained from the electrochemical process.
  • a method to modify a Solvay process to produce a less carbon dioxide intensive Solvay process by a) absorbing carbon dioxide in an ammonia solution to form sodium bicarbonate; b) subjecting the sodium bicarbonate to an electrochemical process to produce sodium carbonate, thereby resulting in a less carbon dioxide intensive Solvay process wherein the electrochemical process comprises contacting anode with an anolyte, contacting cathode with a catholyte, producing hydrogen gas at the cathode, transferring hydrogen gas from the cathode to the anode, and producing a base in the catholyte and an acid in the anolyte; and c) regenerating the ammonia solution using calcium oxide obtained by lime calcinations or regenerating the ammonia solution using sodium hydroxide obtained from the electrochemical process.
  • the electrochemical process does not comprise producing a gas such as chlorine gas at the anode.
  • the electrochemical process comprises producing hydroxide at the cathode and hydrochloric acid (using sodium chloride as anolyte) or sulfuric acid (using sodium sulfate as anolyte) at the anode.
  • the alkaline solution 205 is produced wherein the catholyte 202 is separated from the anolyte 203 by a cation exchange membranes 206 and an anion exchange membrane 210 for cations to migrate from salt solution into the catholyte 202 through the cation exchange membrane 206 to produce the alkaline solution 205 in the catholyte 202, and for anions to migrate across an anion exchange membrane 210 to produce an acid in the anolyte 203.
  • the ion exchange membranes comprising a cation exchange membrane separates the catholyte in the cathode compartment from a third electrolyte.
  • the ion exchange membrane comprises an anion exchange membrane separating the anolyte from the third electrolyte.
  • the third electrolyte comprises sodium ions and chloride ions; the system is configured to migrate sodium ions from the third electrolyte to catholyte through the cation exchange membrane, and migrate chloride ions from the third electrolyte to the anolyte through the anion exchange membrane.
  • the systems described herein may include a second cation exchange membrane (not shown in figures) that is in contact with the anode.
  • a second cation exchange membrane (not shown in figures) that is in contact with the anode.
  • an additional chamber between the anion exchange membrane and the anode such as, a gas diffusion anode (not shown in Figs).
  • the liquid chamber is in close contact with the anode and the anion exchange membrane which anion exchange membrane is further in contact with the center salt compartment.
  • the anode and the cathode of the present system may comprise a noble metal, a transition metal, a platinum group metal, a metal of Groups IVB, VB, VIB, or VIII of the periodic table of elements, alloys of these metals, or oxides of these metals.
  • Exemplary materials include palladium, platinum, iridium, rhodium, ruthenium, titanium, zirconium, chromium, iron, cobalt, nickel, palladium- silver alloys, and palladium-copper alloys.
  • the cathode and/or the anode may be coated with a reactive coating comprising a metal, a metal alloy, or an oxide, formed by sputtering, electroplating, vapor deposition, or any convenient method of producing a layer of reactive coating on the surface of the cathode and/or anode.
  • the cathode and/or the anode may comprise a coating designed to provide selective penetration and/or release of certain chemicals or hydroxide ions and/or anti-fouling protection.
  • exemplary coatings include non-metallic polymers; in specific embodiments herein, an anode fabricated from a 20-mesh Ni gauze material, and a cathode fabricated from a 100-mesh Pt gauze material was used.
  • Reduction of water at the cathode produces hydroxide ions that migrate into the catholyte.
  • the production of hydroxide ions in the catholyte surrounding the cathode may increase the pH of the catholyte.
  • the solution with the elevated pH is used in situ, or is drawn off and utilized in a separate reaction, e.g., to react with sodium bicarbonate as described herein.
  • the pH it is possible for the pH to remain the same or even decrease, as hydroxide ions are consumed in the reaction.
  • Oxidation of hydrogen gas at the anode results in production of hydrogen ions at the anode that desorb from the structure of the anode and migrate into the electrolyte surrounding the anode, resulting in a lowering of the pH of the anolyte.
  • the pH of the electrolytes in the system can be adjusted by controlling the voltage across the cathode and anode and using electrodes comprised of a material capable of absorbing or desorbing hydrogen ions.
  • the process generates hydroxide ions in solution with less than a 1 : 1 ratio of C0 2 molecules released into the environment per hydroxide ion generated.
  • the anolyte enriched with hydrogen ions i.e. an acid
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system comprising an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; and b) a first electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate wherein the electrochemical system comprises an anode in contact with an anolyte, a cathode in contact with a catholyte; one or more of ion exchange membrane; and a hydrogen gas delivery system operably connected to the cathode compartment and configured to transfer hydrogen gas from the cathode to the anode.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system comprising an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; b) a first
  • electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate
  • the electrochemical system comprises an anode in contact with an anolyte, a cathode in contact with a catholyte; one or more of ion exchange membrane; and a hydrogen gas delivery system operably connected to the cathode compartment and configured to transfer hydrogen gas from the cathode to the anode; and c) a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system comprising an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; b) a first
  • electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate
  • the electrochemical system comprises an anode in contact with an anolyte, a cathode in contact with a catholyte; one or more of ion exchange membrane; and a hydrogen gas delivery system operably connected to the cathode compartment and configured to transfer hydrogen gas from the cathode to the anode; c) a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution; and d) a lime calciner operably connected to the regenerator and configured to produce calcium oxide for regenerating the ammonia solution.
  • a system comprising a Solvay system integrated with an electrochemical system, comprising a) a Solvay system comprising an absorber configured to absorb carbon dioxide in an ammonia solution to form sodium bicarbonate; b) a first
  • electrochemical system operably connected to the Solvay system configured to convert the sodium bicarbonate to sodium carbonate
  • the electrochemical system comprises an anode in contact with an anolyte, a cathode in contact with a catholyte; one or more of ion exchange membrane; and a hydrogen gas delivery system operably connected to the cathode compartment and configured to transfer hydrogen gas from the cathode to the anode; c) a regenerator operably connected to the Solvay system configured to regenerate the ammonia solution after absorption of the carbon dioxide in the ammonia solution; and d) a second electrochemical system operably connected to the regenerator and configured to produce sodium hydroxide for regenerating the ammonia solution.
  • the first and second electrochemical processes and/or first and second electrochemical systems may be the same electrochemical systems and process or may be different electrochemical processes and systems.
  • the first electrochemical process and system may be the one described in Fig. 13 and the second electrochemical process and system may be the one described in Fig. 14, or vice versa.
  • the first electrochemical process and system may be the one described in Fig. 14 and the second electrochemical process and system may be the one described in Fig. 15, or vice versa.
  • the first electrochemical process and system may be the one described in Fig. 15 and the second electrochemical process and system may be the one described in Fig. 16, or vice versa.
  • the first electrochemical process and system may be the same such as the one described in Fig. 13, 14, 15, or 16.
  • the system includes an inlet system configured to deliver sodium bicarbonate solution (e.g. solution containing bicarbonate/carbonate ions obtained by absorbing carbon dioxide gas with ammonia solution) into the catholyte compartment.
  • sodium bicarbonate solution e.g. solution containing bicarbonate/carbonate ions obtained by absorbing carbon dioxide gas with ammonia solution
  • the cathode compartment of the electrochemical system is operably connected to an absorber that contains ammonia and is connected to carbon dioxide obtained from Solvay process or from any other plant, such as steel, cement, or power plant.
  • the ammonia solution in the absorber after absorbing the carbon dioxide forms a carbon dioxide charged solution containing bicarbonate and/or carbonate ions and a spent ammonia (such as ammonium chloride).
  • This bicarbonate and/or carbonate ion containing solution may then be transferred to the cathode compartment of the electrochemical system where the sodium hydroxide generated by the cathode may convert the remaining bicarbonate to sodium carbonate resulting in soda ash formation.
  • the sodium bicarbonate solution from the absorber may be contacted with the sodium hydroxide from the electrochemical cell, outside the electrochemical cell, such that the sodium bicarbonate solution is not administered to the cathode compartment. As such, similar reaction takes place between the sodium bicarbonate from the absorber and sodium hydroxide from the catholyte to form sodium carbonate.
  • a first electrochemical process 400 of Fig. 16 is operably connected to the absorber 500 of the Solvay system.
  • the ammonia solution in the absorber 500 absorbs carbon dioxide gas and dissolves it to form sodium bicarbonate solution (this solution may contain sodium carbonate too).
  • the sodium bicarbonate solution may be then added to the cathode compartment of the first electrochemical process where the hydroxide ions generated at the cathode convert sodium bicarbonate to sodium carbonate (soda ash).
  • the sodium bicarbonate solution may be contacted with the sodium hydroxide from the catholyte outside the electrochemical cell (not shown in the figure).
  • the spent ammonia in the absorber (e.g., NH 4 C1) may be then treated with sodium hydroxide generated at the cathode in the second electrochemical process, to regenerate ammonia solution.
  • the regenerated ammonia may be transferred back to the absorber 500.
  • the first and the second electrochemical systems may be same (as illustrated in Fig. 17) or may be different, as described herein.
  • the absorber includes a gas mixer/gas absorber that enhances the absorption of C0 2 in ammonia.
  • the gas mixer/gas absorber includes a series of spray nozzles that produce a flat sheet or curtain of liquid through which the gas is directed for absorption; in another embodiment the gas mixer/gas absorber includes spray absorber that creates a mist into which the gas is directed for absorption; other commercially available gas/liquid absorber e.g., an absorber available from Neumann Systems, Colorado, USA may be used.
  • the cathode and anode compartments are filled with electrolytes and a voltage is applied across the cathode and anode.
  • the voltage is adjusted to a level to cause production of hydrogen gas at the cathode without producing a gas, e.g., chlorine or oxygen, at the anode.
  • the system includes a cathode and an anode that facilitate reactions whereby the catholyte is enriched with hydroxide ions and the anolyte is enriched with hydrogen ions.
  • a conductive electrolyte solution can be employed as the electrolyte solution within the reservoir and in some embodiments the electrolyte solution comprises seawater, brine, or brackish water.
  • hydroxide ions are produced in the catholyte by applying a relatively low voltage, e.g., less than 3.0 V, such as less than 2.0 V, or less than 1.0 V or less than 0.8 V or less than 0.6 V or less than 0.4 V across the cathode and anode.
  • hydroxide ions are produced from water in the catholyte in contact with the cathode, and carbonate ions are produced in the catholyte by dissolving sodium bicarbonate solution in the catholyte in the catholyte compartment.
  • the electrochemical system comprises a hydrogen gas delivery system configured to direct hydrogen gas produced at the cathode to the anode.
  • the catholyte is operatively connected to the absorber configured to dissolve carbon dioxide in ammonia; the system is configured to produce a pH differential ( ⁇ ) between 0 and 14 or greater between the anolyte and catholyte.
  • ⁇ may be zero when the catholyte and anolyte are of equal pH, or ⁇ may be 14 when the catholyte is pH 14 and the anolyte is pH 0.
  • ⁇ between the anolyte and catholyte may be greater than 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13; ⁇ between the anolyte and catholyte may be less than 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1.
  • acid produced in the anolyte is utilized to dissolve a mafic mineral and/or a cellulose material.
  • a gas e.g., oxygen or chlorine is not produced at the anode; in various embodiments, hydrogen gas from an external source is provided to the anode where it is oxidized to hydrogen ions that migrate into the anolyte to produce an acid in the anolyte.
  • hydroxide ions produced at the cathode in the second catholyte compartment migrate into the catholyte and may cause the pH of the catholyte to adjust, e.g., the pH of the catholyte may increase, decrease or remain the same, depending on the rate of removal of catholyte from the system.
  • the pH of the catholyte is adjusted by producing hydroxide ions from water at the cathode, and allowing the hydroxide ions to migrate into the catholyte. The pH is also adjusted by dissolving sodium bicarbonate solution in the catholyte to produce carbonate ions.
  • the overall cell potential of the system can be determined through the Gibbs energy change of the reaction by the formula:
  • E° ce ii -AG nF
  • AG the Gibbs energy of reaction
  • n the number of electrons transferred
  • F the Faraday constant (96485 J/V » mol).
  • the Ecell of each of these reactions is pH dependent based on the Nernst equation.
  • the overall cell potential can be determined through the combination of Nernst equations for each half cell reaction:
  • E° is the standard reduction potential
  • R is the universal gas constant
  • T is the absolute temperature
  • n is the number of electrons involved in the half cell reaction
  • F is Faraday's constant (96485 J/V mol)
  • Q is the reaction quotient such that:
  • H 2 2 H + + 2 e " ,
  • E° is 0.00 V
  • n is 2
  • Q is the square of the activity of H+ so that:
  • pH a is the pH of the anolyte
  • E° is -0.83 V
  • n is 2
  • Q is the square of the activity of OH- so that:
  • pH c is the pH of the catholyte
  • the E for the cathode and anode reactions varies with the pH of the anode and catholytes.
  • the anode reaction which is occurring in an acidic environment, is at a pH of 0, then the E of the reaction is 0 V for the half cell reaction.
  • the anode pH is 0 and the cathode pH is 7 then the overall cell potential would be 0.413 V, where:
  • directing bicarbonate solution into the catholyte may lower the pH of the catholyte by producing carbonate ions in the catholyte, and also lower the voltage across the anode and cathode to produce hydroxide, carbonate and/or bicarbonate in the catholyte.
  • operation of the electrochemical cell with the cathode pH at 7 or greater may provide a significant energy savings.
  • hydroxide ions, carbonate ions and/or bicarbonate ions are produced in the catholyte when the voltage applied across the anode and cathode was less than 3.0 V, 2.9 V, 2.8 V, 2.7 V, 2.6 V, 2.5
  • the pH differential ( ⁇ ) between the anolyte and the catholyte may be between
  • ⁇ may be zero when the catholyte and anolyte are of equal pH, or ⁇ may be 14 when the catholyte is pH 14 and the anolyte is pH 0.
  • ⁇ between the anolyte and catholyte may be greater than 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13;
  • ⁇ between the anolyte and catholyte may be less than 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1.
  • the system and method are configurable for batch, semi-batch or continuous flow operation with or without the option to withdraw portions of the sodium hydroxide produced in the catholyte, or withdraw all or a portions of the acid produced in the anolyte, or direct the hydrogen gas produced at the cathode to the anode where it may be oxidized.
  • hydroxide ions, bicarbonate ions and/or carbonate ion solutions are produced in the catholyte when the voltage applied across the anode and cathode is less than 3.0 V, 2.9 V or less, 2.8 V or less, 2.7 V or less, 2.6 V or less, 2.5 V or less, 2.4 V or less, 2.3 V or less, 2.2 V or less, 2.1 V or less, 2.0 V or less, 1.9 V or less, 1.8 V or less, 1.7 V or less, 1.6 V, or less 1.5 V or less, 1.4 V or less, 1.3 V or less, 1.2 V or less, 1.1 V or less, 1.0 V or less, 0.9 V or less or less, 0.8 V or less, 0.7 V or less, 0.6 V or less, 0.5 V or less, 0.4 V or less, 0.3 V or less, 0.2 V or less, or 0.1 V or less.
  • the voltage across the anode and cathode can be adjusted such that gas will form at the anode, e.g., oxygen or chlorine, while hydroxide ions, carbonate ions and bicarbonate ions are produced in the catholyte and hydrogen gas is generated at the cathode.
  • gas e.g., oxygen or chlorine
  • hydroxide ions, carbonate ions and bicarbonate ions are produced in the catholyte and hydrogen gas is generated at the cathode.
  • hydrogen gas is not supplied to the anode.
  • the voltage across the anode and cathode will be higher compared to the embodiment when a gas does not form at the anode.
  • the anion exchange membrane and the cation exchange membrane, as described herein, can be conventional ion exchange membranes.
  • the membranes are capable of functioning in an acidic and/or basic electrolytic solution and exhibit high ion selectivity, low ionic resistance, high burst strength, and high stability in an acidic electrolytic solution in a temperature range of 0 °C to 100 °C or higher.
  • a membrane stable in the range of 0 °C to 80 °C, or 0 °C to 90 °C, but not stable above these ranges may be used.
  • Suitable membranes include a TeflonTM-based cation exchange membrane available from Asahi Kasei of
  • hydrocarbon-based cation exchange membranes can also be utilized, e.g., the hydrocarbon-based membranes available from, e.g., Membrane International of Glen Rock, NJ, and USA.
  • the electrolyte including the catholyte or the cathode electrolyte and/or the anolyte or the anode electrolyte, or the third electrolyte disposed between AEM and CEM, in the systems and methods provided herein include, but not limited to, saltwater or fresh water.
  • the saltwater includes, but is not limited to, seawater, brine, and/or brackish water.
  • Saltwater is employed in its conventional sense to refer to a number of different types of aqueous fluids, where the term “saltwater” includes, but is not limited to, brackish water, sea water and brine (including, naturally occurring subterranean brines or anthropogenic
  • subterranean brines and man-made brines e.g., geothermal plant wastewaters, desalination waste waters, etc
  • Brine is water saturated or nearly saturated with salt and has a salinity that is 50 ppt (parts per thousand) or greater.
  • Brackish water is water that is saltier than fresh water, but not as salty as seawater, having a salinity ranging from 0.5 to 35 ppt.
  • Seawater is water from a sea or ocean and has a salinity ranging from 35 to 50 ppt.
  • the saltwater source may be a naturally occurring source, such as a sea, ocean, lake, swamp, estuary, lagoon, etc., or a man-made source.
  • the systems provided herein include the saltwater from terrestrial brine.
  • the depleted saltwater withdrawn from the electrochemical cells is replenished with salt and re-circulated back in the electrochemical cell.
  • the electrolyte including the cathode electrolyte and/or the anode electrolyte and/or the third electrolyte, such as, saltwater includes water containing more than 1% chloride content, such as, NaCl; or more than 10% NaCl; or more than 20% NaCl; or more than 30%) NaCl; or more than 40% NaCl; or more than 50% NaCl; or more than 60%> NaCl; or more than 70% NaCl; or more than 80% NaCl; or more than 90% NaCl; or between 1-99% NaCl; or between 1-95% NaCl; or between 1-90% NaCl; or between 1-80% NaCl; or between 1- 70% NaCl; or between 1-60% NaCl; or between 1-50% NaCl; or between 1-40% NaCl; or between 1-30% NaCl; or between 1-20% NaCl; or between 1-10% NaCl; or between 10-99% NaCl; or between 10-95% NaCl
  • the cathode compartment may also be operatively connected to a waste gas treatment system (not illustrated) where the base solution produced in the catholyte is utilized, e.g., to sequester carbon dioxide contained in the waste gas by contacting the waste gas and the catholyte with a solution of divalent cations to precipitate hydroxides, carbonates and/or bicarbonates as described in U.S. Patent Application No. 12/344,019, filed 24 December 2008, which is incorporated herein by reference in its entirety.
  • the sodium carbonate may be treated with divalent cations, such as calcium or magnesium ions, to precipitate calcium and magnesium carbonates which may be utilized as building materials, e.g., as cements and aggregates, as described in U.S. Patent Application No. 12/126,776, filed 23 May 2008, which is incorporated herein by reference in its entirety.
  • some or all of the carbonates and/or bicarbonates are allowed to remain in an aqueous medium, e.g., a slurry or a suspension, and are disposed of in an aqueous medium, e.g., in the ocean depths.
  • the cathode and anode are also operatively connected to an off- peak electrical power-supply system that supplies off-peak voltage to the electrodes. Since the cost of off-peak power is lower than the cost of power supplied during peak power-supply times, the system can utilize off-peak power to produce a base solution in the catholyte at a relatively lower cost.
  • partially desalinated water is produced in the third electrolyte as a result of migration of cations and anions from the third electrolyte to the adjacent anolyte and catholyte.
  • the partially desalinated water is operatively connected to a desalination system (not illustrated) where it is further desalinated as described in U.S. Patent Application No. 12/163,205, filed 27 June 2008, which is incorporated herein by reference in its entirety.
  • the system produces an acid, e.g., hydrochloric acid in the anolyte.
  • the anode compartment is operably connected to a system for dissolving minerals and waste materials comprising divalent cations to produce a solution of divalent
  • the divalent cation solution may be utilized to precipitate divalent carbonates and/or bicarbonates by contacting the divalent cation solution with sodium carbonate solution.
  • the precipitates are used as building materials e.g., cement and aggregates as described in U.S. Patent application No. 12/126,776, which is incorporated herein by reference in its entirety.
  • the system includes a catholyte withdrawal and replenishing system (not illustrated) capable of withdrawing all of, or a portion of, the catholyte from the cathode compartment.
  • the system also includes a salt solution supply system (not shown) for providing a salt solution, e.g., concentrated sodium chloride, as the third electrolyte.
  • the system also includes inlet ports (not shown) for introducing fluids into the cells and outlet ports (not shown) for removing fluids from the cells.
  • the system may produce hydroxide ions in the catholyte and hydrogen gas at the cathode and hydrogen ions at the anode when less than 2.0 V is applied across the anode and cathode, in contrast to the higher voltage that is required when a gas is generated at the anode, e.g., chlorine or oxygen.
  • a gas e.g., chlorine or oxygen.
  • hydroxide ions can be produced in the catholyte with the present lower voltages.
  • alternative reactants can be utilized depending on the ionic species desired in the system.
  • a potassium salt such as potassium hydroxide or potassium carbonate
  • a potassium salt such as potassium chloride
  • sulfuric acid is desired in the anolyte
  • a sulfate such as sodium sulfate can be utilized in electrolyte.
  • the system and method described herein are integrated with a carbonate and/or bicarbonate precipitation system wherein a solution of divalent cations, when added to the catholyte containing sodium carbonate, causes formation of precipitates of divalent carbonate and/or bicarbonate compounds, e.g., calcium carbonate or magnesium carbonate and/or their bicarbonates.
  • the precipitated divalent carbonate and/or bicarbonate compounds may be utilized as building materials, e.g., cements and aggregates as described for example in U.S. Patent Application No. 12/126,776, filed 23 May 2008, which is incorporated herein by reference in its entirety.
  • the system and method described herein are integrated with a mineral and/or material dissolution and recovery system (not illustrated) wherein the acidic anolyte solution is utilized to dissolve calcium and/or magnesium-rich minerals e.g., serpentine or olivine, or waste materials, e.g., fly ash, red mud and the like, to form divalent cation solutions that may be utilized, e.g., to precipitate carbonates and/or bicarbonates as described herein.
  • the acidic anolyte solution is utilized to dissolve calcium and/or magnesium-rich minerals e.g., serpentine or olivine, or waste materials, e.g., fly ash, red mud and the like, to form divalent cation solutions that may be utilized, e.g., to precipitate carbonates and/or bicarbonates as described herein.
  • the system and method described herein are integrated with an aqueous desalination system (not illustrated) wherein the partially desalinated water of the third electrolyte of the system is used as feed-water for the desalination system, as described in U.S. Patent Application No. 12/163,205, filed 27 June 2008, which is incorporated herein by reference in its entirety.
  • the system and method described herein are integrated with a carbonate and/or bicarbonate solution disposal system (not illustrated) wherein, rather than producing precipitates by contacting a solution of divalent cations with sodium carbonate to form precipitates, the system produces a slurry or suspension comprising carbonates and/or bicarbonates.
  • the slurry or suspension is disposed of in a location where it is held stable for an extended periods of time, e.g., the slurry/suspension is disposed in an ocean at a depth where the temperature and pressure are sufficient to keep the slurry stable indefinitely, as described in U.S. Patent Application No. 12/344,019, filed 24 December 2008, which is herein incorporated by reference in its entirety.
  • the systems provided herein may include a processor to process the compositions containing bicarbonate and/or carbonate products.
  • a processor to process the compositions containing bicarbonate and/or carbonate products.
  • An illustrative example of the processor is described in Fig. 18.
  • the processor includes a reactor configured to react soda ash obtained from the electrochemical system (such as Figs. 13-17 described herein) with divalent cations from a source of divalent cations to produce compositions containing carbonate/bicarbonate products.
  • the processor may further comprise a settling tank configured for settling compositions.
  • the processor may further comprise a treatment system configured to concentrate compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates and produce a supernatant; however, in some embodiments the compositions may be used without further treatment.
  • systems may be configured to directly use compositions from the reactor (optionally with minimal post-processing) in the manufacture of building materials.
  • systems may be configured to directly inject compositions from the processor (optionally with minimal post-processing) into a subterranean site as described in U.S. Provisional Patent Application No. 61/232,401, filed 7 August 2009, which is incorporated herein by reference in its entirety.
  • the source of divalent cations may be from any of a variety of sources of divalent cations, including, but not limited to, seawater, brines, and freshwater with added minerals.
  • the source of divalent cations comprises divalent cations
  • alkaline earth metals e.g., Ca , Mg .
  • the treatment system may comprise a liquid-solid separator or some other dewatering system configured to treat processor-produced compositions to produce supernatant and concentrated compositions (e.g., concentrated with respect to carbonates and/or
  • the treatment system may further comprise a filtration system, wherein the filtration system comprises at least one filtration unit configured for filtration of supernatant from the dewatering system, filtration of the composition from the processor, or a combination thereof.
  • the filtration system comprises one or more filtration units selected from a microfiltration unit, an ultrafiltration unit, a nanofiltration unit, and a reverse osmosis unit.
  • the processing system comprises a nanofiltration unit configured to increase the concentration of divalent cations in the retentate and reduce the concentration of divalent cations in the filtrate.
  • nanofiltration unit retentate may be recirculated to a processor of the system for producing compositions described herein.
  • the calcium carbonate composition formed by the processes described herein comprises vaterite, aragonite, amorphous calcium carbonate, calcite, or combination thereof.
  • such calcium carbonate (optionally containing magnesium carbonate) forms a cementitious material.
  • the cementitous composition has elements or markers that originate from the carbon from the source of carbon used in the process.
  • composition after setting, and hardening has a compressive strength of at least 14 MPa; or at least 16 MPa; or at least 18 MPa; or at least 20 MPa; or at least 25 MPa; or at least 30 MPa; or at least 35 MPa; or at least 40 MPa; or at least 45 MPa; or at least 50 MPa; or at least 55 MPa; or at least 60 MPa; or at least 65 MPa; or at least 70 MPa; or at least 75 MPa; or at least 80 MPa; or at least 85 MPa; or at least 90 MPa; or at least 95 MPa; or at least 100 MPa; or from 14-100 MPa; or from 14-80 MPa; or from 14-75 MPa; or from 14-70 MPa; or from 14-65 MPa; or from 14-60 MPa; or from 14-55 MPa; or from 14-50 MPa; or from 14-45 MPa; or from 14-40 MPa; or from 14-35 MPa; or from 14-30 MPa; or from 14-25 MPa; or
  • MPa or from 40-90 MPa; or from 40-80 MPa; or from 40-75 MPa; or from 40-70 MPa; or from
  • MPa or from 50-65 MPa; or from 50-60 MPa; or from 50-55 MPa; or from 60-100 MPa; or from
  • 60-90 MPa or from 60-80 MPa; or from 60-75 MPa; or from 60-70 MPa; or from 60-65 MPa; or from 70-100 MPa; or from 70-90 MPa; or from 70-80 MPa; or from 70-75 MPa; or from 80-100
  • MPa or from 80-90 MPa; or from 80-85 MPa; or from 90-100 MPa; or from 90-95 MPa; or 14
  • MPa or 16 MPa; or 18 MPa; or 20 MPa; or 25 MPa; or 30 MPa; or 35 MPa; or 40 MPa; or 45
  • the composition after setting, and hardening has a compressive strength of 14 MPa to 40 MPa; or 17 MPa to 40 MPa; or 20 MPa to 40 MPa; or 30 MPa to 40 MPa; or 35 MPa to 40
  • the compressive strengths described herein are the compressive strengths after 1 day, or 3 days, or 7 days, or 28 days.
  • electrochemical cells e.g., a stack of electrochemical cells
  • electrochemical cells may be operably connected to the above described processing system configured to precipitate a precipitation material comprising bicarbonates and/or carbonates (or a processed form thereof).
  • a precipitation material comprising bicarbonates and/or carbonates (or a processed form thereof).
  • Such carbonates and/or bicarbonates comprise calcium and/or magnesium.
  • the electrochemical cell or the stack of electrochemical cells may be operably connected to a system for further processing of the anolyte, which may comprise hydrochloric acid (if NaCl(aq) is used) or sulfuric acid (if Na 2 S0 4 (aq) is used).
  • the electrochemical cell or the stack of electrochemical cells may be operably connected to a mineral-processing system comprising a mineral processor configured to dissolve minerals (e.g., mafic minerals such as olivine, serpentine, etc.) with the anolyte (e.g.,
  • the anolyte may be used for other purposes in addition to, or instead of, mineral dissolution, including use as a reactant in production of cellulosic biofuels, use in the production of polyvinyl chloride (PVC), and the like.
  • Systems appropriate for such uses may be operably connected to the stack of electrochemical cells, or the anolyte may be transported to an appropriate site for use.
  • a solvay process is performed by absorbing carbon dioxide into ammonia solution in sodium chloride.
  • the carbon dioxide is obtained from flue gas emitted by a power plant.
  • the carbon dioxide gas is bubbled into the ammonia + sodium chloride solution.
  • the carbon dioxide gas dissolves in the solution to form sodium bicarbonate and ammonium chloride is generated.
  • Sodium bicarbonate is separated from the ammonium solution and is subjected to the
  • This study demonstrates the savings in the voltage when an electrochemical cell was run with sodium hydroxide as catholyte vs. sodium bicarbonate as catholyte.
  • a voltage sweep was performed in an electrochemical cell that was containing a 3-cell system (e.g., electrochemical cell of Fig. 16) with an anode and an anode electrolyte in an anode compartment, a cathode and a catholyte in a cathode compartment, and the anode compartment and the cathode compartment separated by an anion exchange membrane and a cation exchange membrane.
  • a 3-cell system e.g., electrochemical cell of Fig. 16
  • a voltage sweep was performed in the electrochemical cell where the anode was in contact with 0.5 wt% hydrochloric acid solution, the cathode was in contact with 10 wt% sodium hydroxide solution, and sodium chloride solution was in the middle chamber between ion exchange membranes.
  • a voltage sweep was performed in the electrochemical cell that was containing anode in contact with 0.5 wt% hydrochloric acid solution, cathode in contact with 1 mol/L sodium bicarbonate solution (at pH 10), and sodium chloride solution was in the middle chamber between ion exchange membranes.
  • the 1 mol/L sodium bicarbonate solution was formed by bubbling carbon dioxide in 1 mol sodium hydroxide solution that resulted in the formation of 1 mol/L sodium bicarbonate solution.
  • Fig. 19 illustrates that significant savings in the voltage were observed by introducing sodium bicarbonate into the catholyte ( ⁇ 250mV) as compared to sodium hydroxide.
  • the sodium hydroxide generated at the cathode converted bicarbonate to carbonate.
  • the conversion of bicarbonate to carbonate depended on flow rates, current density and length of time.

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  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

La présente invention concerne des procédés et des systèmes permettant de produire du carbonate de sodium. L'intégration d'un procédé électrochimique au procédé Solvay permet de produire moins de dioxyde de carbone et donc d'obtenir un produit de carbonate de sodium de manière plus écologique.
PCT/US2012/020815 2011-01-11 2012-01-10 Systèmes et procédés de production de carbonate de sodium WO2012096987A1 (fr)

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US201161431767P 2011-01-11 2011-01-11
US61/431,767 2011-01-11
US201161446482P 2011-02-24 2011-02-24
US61/446,482 2011-02-24

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