US20100282614A1 - Process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate - Google Patents
Process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate Download PDFInfo
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- US20100282614A1 US20100282614A1 US12/811,643 US81164309A US2010282614A1 US 20100282614 A1 US20100282614 A1 US 20100282614A1 US 81164309 A US81164309 A US 81164309A US 2010282614 A1 US2010282614 A1 US 2010282614A1
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- sodium bicarbonate
- sodium
- sodium carbonate
- electrodialyser
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 168
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 title claims abstract description 126
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 69
- 229910000030 sodium bicarbonate Inorganic materials 0.000 title claims abstract description 63
- 235000017557 sodium bicarbonate Nutrition 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 27
- 235000010755 mineral Nutrition 0.000 title claims abstract description 27
- 239000011707 mineral Substances 0.000 title claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000012528 membrane Substances 0.000 claims abstract description 36
- 125000002091 cationic group Chemical group 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 230000004907 flux Effects 0.000 claims abstract description 12
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 5
- -1 hydroxyl ions Chemical class 0.000 claims abstract description 3
- 241001625808 Trona Species 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 18
- 239000012452 mother liquor Substances 0.000 claims description 15
- 239000010448 nahcolite Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000003385 sodium Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 72
- 235000017550 sodium carbonate Nutrition 0.000 description 51
- 229940001593 sodium carbonate Drugs 0.000 description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 2
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000006351 Leucophyllum frutescens Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000002625 Salsola soda Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/10—Preparation of bicarbonates from carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/38—Purification; Separation by dialysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
- C01D7/126—Multi-step processes, e.g. from trona to soda ash
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/32—Purification by dialysis
Definitions
- This invention relates to a process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate, in particular from trona, nahcolite or from other mineral underground ores, rich in sodium bicarbonate values, such as Wegscheiderite or Decemite.
- Nahcolite is an ore consisting primarily of sodium bicarbonate. There are for instance vast quantities of nahcolite in the Piceance Creek Basin in Northwestern Colorado, which deposits are in the form of beds and disseminated crystals in the Saline Zone of the Green River formation.
- Trona ore is a mineral that contains about 90-95% sodium sesquicarbonate (Na 2 CO 3 .NaHCO 3 .2H 2 O).
- a vast deposit of mineral trona is found in southeastern Wyoming near Green River. This deposit includes beds of trona and mixed trona and halite (rock salt or NaCl). By conservative estimates, the major trona beds contain about 75 billion metric tons of ore. The different beds overlap each other and are separated by layers of shale. The quality of the trona varies depending on its particular location in the stratum.
- the sodium sesquicarbonate found in trona ore is a complex salt that is soluble in water and dissolves to yield approximately 5 parts by weight sodium carbonate (Na 2 CO 3 ) and 4 parts sodium bicarbonate (NaHCO 3 ), as shown in the above analysis.
- the trona ore is processed to remove the insoluble material, the organic matter and other impurities to recover the valuable alkali contained in the trona.
- trona The most valuable alkali produced from trona is sodium carbonate.
- Sodium carbonate is one of the largest volume alkali commodities made in the United States. In 1992, trona-based sodium carbonate from Wyoming comprised about 90% of the total U.S. soda ash production. Sodium carbonate finds major use in the glass-making industry and for the production of baking soda, detergents and paper products.
- a common method to produce sodium carbonate from trona ore is known as the “monohydrate process”.
- crushed trona ore is calcined (i.e., heated) into crude sodium carbonate which is then dissolved in water.
- the resulting water solution is purified and fed to a crystallizer where pure sodium carbonate monohydrate crystals are crystallized.
- the monohydrate crystals are separated from the mother liquor and then dried into anhydrous sodium carbonate.
- This process is however very energy intensive, mainly due to the calcination step, which requires the use of large quantities of coal, fuel, gas or mixtures thereof.
- sodium bicarbonate is a product with a wide range of interesting properties and a very wide range of applications from high tech ingredients for the pharma industry to the human food and animal feed, and to the use in flue gas treatment.
- flue gas treatment sodium bicarbonate is most likely among the most efficient chemicals for the removal of a wide range of pollutants (most notably the acidic one), and its use is limited only by the competition of less efficient but much cheaper chemicals such as lime or even limestone.
- the production of sodium bicarbonate is currently almost entirely made by the carbonation of sodium carbonate.
- the carbonation is usually made in situ in the soda ash plants from CO 2 coproduced during the production of soda ash (mainly the CO 2 generation in the lime kilns).
- the carbonation is usually made in separate plants which purchase independently the soda ash and the CO 2 and combine them. Because of the nature of this most important process, the production cost of the sodium bicarbonate is even above the cost of the sodium carbonate.
- U.S. Pat. No. 4,636,289 discloses a method for recovering sodium carbonate from trona and other mixtures of sodium carbonate and sodium bicarbonate.
- sodium hydroxide is produced in electrodialytic cells and used to solution mine the mineral ore.
- this process requires the introduction of sodium sulfates into the acid compartments of the electrodialysers, which appears to be difficult to put into practice in a cost effective and efficient way.
- the invention aims at producing sodium carbonate and/or sodium bicarbonate from ore minerals, in a simple, economical way, avoiding the large energy consumption of the known processes.
- the invention concerns a process to produce sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate according to which:
- a solution comprising sodium bicarbonate is optionally extracted from the less basic compartments.
- FIG. 1 illustrates one particular embodiment of a process according to the invention.
- a bipolar membrane is an ion exchange membrane comprising one cationic face—permeable for the cations and impermeable for the anions and an other anionic face—permeable for the anions and impermeable for the cations.
- Such membrane can be produced by the juxtaposition of two monopolar membranes. Under a sufficient electric field, and in aqueous solution, the only possible reaction is the splitting of water at the interface between the two monopolar membranes into H + and OH ⁇ which then cross respectively the cationic and anionic monopolar membrane and exit the membrane into the adjacent compartments. It is recommended that the bipolar membranes are produced by the process as described in the patent application WO 01/79335 in the name of SOLVAY, in particular as described in its claims.
- the electrodialyser contains at least two types of compartments and two types of membranes, cationic and bipolar. In some embodiments it can contain additional types of compartments and anionic membranes.
- the electodialyser comprises only two types of compartments and only cationic and bipolar membranes.
- each compartment is thus delimited on one side by a cationic membrane, and on the other side by a bipolar membrane.
- the sodium hydroxide reacts with the sodium bicarbonate contained in the mineral ore.
- the resulting sodium carbonate thanks to its high solubility is easily solubilized from the ore, which allows to extract efficiently the sodium values of the mineral ore.
- the reaction solution comprises advantageously at most 120 g/kg, preferably at most 100 g/kg sodium hydroxide and at most 40 g/kg preferably 30 g/kg sodium carbonate. It is nevertheless preferable that the reaction solution comprises at least 40 g/kg, more preferably 50 g/kg sodium hydroxide.
- reaction solution will be made by mixing the solution comprising sodium hydroxide which is extracted from the more basic compartments with fresh water or recycle waters, in order to dilute it.
- the solution comprising sodium hydroxide can be advantageously used as such to form the reaction solution and put directly into contact with the mineral ore.
- the output from the more basic compartments will have to be reintroduced in their input, in order to get the best sodium hydroxide concentration.
- the control of the composition of the reaction solution allows to regulate the composition of the produced solution. It is advantageous that the produced solution comprises advantageously at least 200 g/kg, preferably 250 g/kg sodium carbonate.
- At least part of the produced solution is evaporated in order to produce a suspension comprising sodium carbonate crystals, which are separated and valorized.
- the evaporation can be made as in the monohydrate process, preferably by using mechanical vapor recompression.
- the sodium carbonate monohydrate crystals are then preferably processed into dense soda ash.
- a production solution comprising sodium carbonate is introduced into the less basic compartments of the electrodialyser. Due to the flux of Na + ions through the cationic membrane and an incoming flux of H + ions, at least part of the entering sodium carbonate is transformed into sodium bicarbonate, forming an output solution comprising sodium bicarbonate.
- sodium bicarbonate is converted into carbon dioxide at the output of the less basic compartments of the cell.
- the carbon dioxide can then be reacted with sodium carbonate solutions at other stages of the process, in order to produce sodium bicarbonate crystals.
- a solution comprising sodium bicarbonate is extracted from the less basic compartments of the electrodialyser, this solution being afterwards cooled in order to produce a suspension comprising sodium bicarbonate crystals.
- the suspension is separated into sodium bicarbonate crystals to be valorized and a sodium bicarbonate mother liquor.
- the mother liquor is then preferably debicarbonated, in order to produce on one side a gas comprising CO 2 and on the other side a debicarbonated solution depleted in sodium bicarbonate and enriched in sodium carbonate.
- the debicarbonated solution contains preferably not more than 60 g/kg, more preferably 50 g/kg, most preferably 40 g/kg sodium bicarbonate.
- the debicarbonated solution can be mixed with the production solution and introduced into the electrodialyser. It can also be mixed with the produced solution in order to form the reaction solution.
- the debicarbonation can be performed by vapor or preferably by air stripping.
- the more basic compartments can be advantageously fed by introducing into them the debicarbonated solution produced in the recommended embodiment described just above.
- it can be fed by a diluted sodium carbonate solution, containing advantageously at least 20 g/kg sodium carbonate, but at most 70 g/kg, preferably at most 50 g/kg sodium carbonate.
- the more basic compartments are not fed by any solution coming from the outside.
- the more basic compartments contain only NaOH produced in situ into those compartments by combination of Na + and OH ⁇ ions (crossing the cationic membranes and the anionic faces of the bipolar membranes), the input flow to the compartments being taken from their output (recirculation), with only supply of water, if necessary.
- even the supply of external water is avoided, the less basic compartments being only fed by water passing through the ion exchange membranes into them.
- the process according to the invention can be run with only one electrodialyser. It is however possible to use several electrodialysers, the output from some of them being used as input for others.
- the solution comprising sodium bicarbonate which is extracted from the less basic compartments of the electrodialyser is introduced into the less basic compartments of another electrodialyser.
- the mother liquor is then introduced into the other electrodialyser.
- the concentration in sodium carbonate of the solution comprising sodium bicarbonate which is introduced into the other electrodialyser is sufficiently low so as to generate CO 2 gas into the less basic compartments of this other electrodialyser.
- any additional flux of Na + ions passing through those membranes has the consequence of destroying sodium bicarbonate into CO 2 and water.
- the generated CO 2 gas is then advantageously used to react with part of the sodium carbonate solution produced through the contact with the mineral ores, in order to produce sodium bicarbonate crystals.
- This reaction can be performed in gas-liquid contactors suitable for the carbonation of sodium carbonate solutions.
- the sodium carbonate solution can be first concentrated by any suitable means, before its carbonation.
- the sodium hydroxide is produced in the electrodialyser out of a sodium carbonate solution and the sodium carbonate solution is in turn very simply obtained by using part of the solution produced by the reaction of the sodium hydroxide with the sodium bicarbonate part of the mineral ore.
- Different mineral ores can be utilized and the mineral ores can be put into contact with the reaction solution in very different ways, for instance in surface equipments using excavated mineral ores. The simplicity of this process allows to use it at large industrial scale. It is particularly interesting to introduce the reaction solution underground and put it into contact with subterranean mineral ore deposits.
- the solution comprising sodium carbonate is then formed underground and extracted by conventional solution mining techniques. This embodiment is suited to Trona, Nahcolite, Wegscheiderite or Decemite mineral underground ores.
- the mineral ore comprising sodium bicarbonate is an underground trona or nahcolite ore mineral.
- FIG. 1 illustrates a particular embodiment of the invention.
- a production solution 1 comprising sodium carbonate is introduced into the less basic compartments of an electrodialyser 2 comprising alternating less basic and more basic compartments.
- a solution 3 comprising sodium bicarbonate is extracted from the less basic compartments and a solution 4 comprising sodium hydroxide is extracted from the more basic compartments of the electrodialyser.
- the solution 3 is cooled in the crystallizer 5 , resulting in sodium bicarbonate crystals 6 and a mother liquor 7 .
- the mother liquor 7 is debicarbonated by air stripping in the contactor 8 , resulting in CO 2 gas 9 and debicarbonated mother liquor 10 , part of which ( 10 ′) is sent back to the electrodialyser and part of which is mixed with the solution 4 comprising sodium hydroxide together with fresh water 11 , to form the reaction solution 12 .
- the reaction solution 12 is injected into a subterranean trona mine 13 .
- a solution comprising sodium carbonate 14 is extracted from the trona mine.
- a produced solution 14 ′ is taken out of this solution 14 and sent to an evaporator (not represented), wherein sodium carbonate monohydrate crystals are formed. Those crystals are thereafter valorized, for instance by transformation into dense soda ash.
- the remaining part of the solution 14 is sent to the electrodialyser, constituting after mixing with debicarbonated mother liquor 10 ′ the production solution 1 .
- the process illustrated by the FIG. 1 is operated in the following way.
- a quantity of 0.024 m 3 /h of a production solution comprising 110 g/kg sodium carbonate and 32 g/kg sodium bicarbonate is introduced at a temperature of 29° C. into the less basic compartments of an electrodialyser.
- the electrodialyser comprise bipolar membranes produced by ASTOM, model NEOSEPTA BP-1E and cationic membranes NAFION® 324, produced by DuPont.
- a current density of 1 kA/m 2 is applied to the elementary cell.
- a solution 3 comprising 117 g/kg sodium bicarbonate and 20 g/kg sodium carbonate at a temperature of 65° C.
- a solution 4 comprising 357 g/kg of sodium hydroxide is extracted from the more basic compartments of the electrodialyser at a flow rate of 0.002 m 3 /h and a temperature of 65° C.
- a reaction solution comprising 68 g/kg NaOH and 27 g/kg Na 2 CO 3 is introduced at a flow rate of 0.012 m 3 /h and at a temperature of 50° C. into a trona mine comprising trona ore having the composition described in the introductory part of this specification, the temperature of the ore being approximately 25° C.
- a solution 14 comprising 280 g/kg Na 2 CO 3 is extracted from the mine at a flow rate of 0.014 m 3 /h and a temperature of approximately 30° C.
- a part of 0.008 m 3 /h is subtracted from this solution 14 for evaporation and sodium carbonate crystallization.
- the remaining flow rate is mixed with 0.02 m 3 /h of debicarbonated mother liquor 10 ′ containing 50 g/kg sodium carbonate and 43 g/kg sodium bicarbonate.
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Abstract
In a process to produce sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate, a production solution comprising sodium carbonate is introduced into less basic compartments of an electrodialyser comprising alternating less basic and more basic adjacent compartments separated from each other by cationic membranes, the more basic compartments being delimited by anionic faces of bipolar membranes on one side and by the cationic membranes on the other side; a solution comprising sodium hydroxide is produced into the more basic compartments by combination of sodium ions flux crossing the cationic membrane and hydroxyl ions flux crossing the anionic face of the bipolar membranes, and is then extracted from the electrodialyser to be used as a reaction solution; the reaction solution is put into contact with the mineral ore to form a solution comprising sodium carbonate; and the solution comprising sodium carbonate is divided into a part used as the production solution and a remaining part used as a produced solution.
Description
- The present application is a U.S. national stage application under 35 U.S.C. §371 of International Application No. PCT/EP2009/050075 filed Jan. 6, 2009, which claims the priority benefit of European Application No. 08150104.1 filed Jan. 8, 2008, the whole content of such application being incorporated herein by reference for all purposes.
- This invention relates to a process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate, in particular from trona, nahcolite or from other mineral underground ores, rich in sodium bicarbonate values, such as Wegscheiderite or Decemite.
- Nahcolite is an ore consisting primarily of sodium bicarbonate. There are for instance vast quantities of nahcolite in the Piceance Creek Basin in Northwestern Colorado, which deposits are in the form of beds and disseminated crystals in the Saline Zone of the Green River formation.
- Trona ore is a mineral that contains about 90-95% sodium sesquicarbonate (Na2CO3.NaHCO3.2H2O). A vast deposit of mineral trona is found in southwestern Wyoming near Green River. This deposit includes beds of trona and mixed trona and halite (rock salt or NaCl). By conservative estimates, the major trona beds contain about 75 billion metric tons of ore. The different beds overlap each other and are separated by layers of shale. The quality of the trona varies depending on its particular location in the stratum.
- A typical analysis of the trona ore mined in Green River is as follows:
-
TABLE 1 Constituent Weight Percent Na2CO3 43.6 NaHCO3 34.5 H2O (crystalline and free moisture) 15.4 NaCl 0.01 Na2SO4 0.01 Fe2O3 0.14 Insolubles 6.3 - The sodium sesquicarbonate found in trona ore is a complex salt that is soluble in water and dissolves to yield approximately 5 parts by weight sodium carbonate (Na2CO3) and 4 parts sodium bicarbonate (NaHCO3), as shown in the above analysis. The trona ore is processed to remove the insoluble material, the organic matter and other impurities to recover the valuable alkali contained in the trona.
- The most valuable alkali produced from trona is sodium carbonate. Sodium carbonate is one of the largest volume alkali commodities made in the United States. In 1992, trona-based sodium carbonate from Wyoming comprised about 90% of the total U.S. soda ash production. Sodium carbonate finds major use in the glass-making industry and for the production of baking soda, detergents and paper products.
- A common method to produce sodium carbonate from trona ore is known as the “monohydrate process”. In that process, crushed trona ore is calcined (i.e., heated) into crude sodium carbonate which is then dissolved in water. The resulting water solution is purified and fed to a crystallizer where pure sodium carbonate monohydrate crystals are crystallized. The monohydrate crystals are separated from the mother liquor and then dried into anhydrous sodium carbonate. This process is however very energy intensive, mainly due to the calcination step, which requires the use of large quantities of coal, fuel, gas or mixtures thereof.
- On the other side, sodium bicarbonate is a product with a wide range of interesting properties and a very wide range of applications from high tech ingredients for the pharma industry to the human food and animal feed, and to the use in flue gas treatment. In flue gas treatment sodium bicarbonate is most likely among the most efficient chemicals for the removal of a wide range of pollutants (most notably the acidic one), and its use is limited only by the competition of less efficient but much cheaper chemicals such as lime or even limestone.
- The production of sodium bicarbonate is currently almost entirely made by the carbonation of sodium carbonate. In Europe, the carbonation is usually made in situ in the soda ash plants from CO2 coproduced during the production of soda ash (mainly the CO2 generation in the lime kilns). In USA, the carbonation is usually made in separate plants which purchase independently the soda ash and the CO2 and combine them. Because of the nature of this most important process, the production cost of the sodium bicarbonate is even above the cost of the sodium carbonate.
- Attempts to reduce the energy consumption for the production of sodium carbonate and bicarbonate have been made, by the use of electrodialytic methods. U.S. Pat. No. 4,636,289 discloses a method for recovering sodium carbonate from trona and other mixtures of sodium carbonate and sodium bicarbonate. In U.S. Pat. No. 4,636,289, sodium hydroxide is produced in electrodialytic cells and used to solution mine the mineral ore. However, this process requires the introduction of sodium sulfates into the acid compartments of the electrodialysers, which appears to be difficult to put into practice in a cost effective and efficient way.
- The invention aims at producing sodium carbonate and/or sodium bicarbonate from ore minerals, in a simple, economical way, avoiding the large energy consumption of the known processes.
- In consequence, the invention concerns a process to produce sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate according to which:
-
- a production solution comprising sodium carbonate is introduced into the less basic compartments of an electrodialyser comprising alternating less basic and more basic adjacent compartments separated from each other by cationic membranes, the more basic compartments being delimited by the anionic faces of bipolar membranes on one side and by the cationic membranes on the other side;
- a solution comprising sodium hydroxide is produced into the more basic compartments, by combination of the flux of sodium ions crossing the cationic membrane and the flux of hydroxyl ions crossing the anionic face of the bipolar membranes;
- the solution comprising sodium hydroxide is extracted from the more basic compartments of the electrodialyser and used to constitute a reaction solution;
- the reaction solution is put into contact with the mineral ore comprising sodium bicarbonate in order to form a solution comprising sodium carbonate;
- the solution comprising sodium carbonate is divided into a part which is used to constitute the production solution and a remaining part which constitutes a produced solution.
- In the process according to the invention, a solution comprising sodium bicarbonate is optionally extracted from the less basic compartments.
-
FIG. 1 illustrates one particular embodiment of a process according to the invention. - A bipolar membrane is an ion exchange membrane comprising one cationic face—permeable for the cations and impermeable for the anions and an other anionic face—permeable for the anions and impermeable for the cations. Such membrane can be produced by the juxtaposition of two monopolar membranes. Under a sufficient electric field, and in aqueous solution, the only possible reaction is the splitting of water at the interface between the two monopolar membranes into H+ and OH− which then cross respectively the cationic and anionic monopolar membrane and exit the membrane into the adjacent compartments. It is recommended that the bipolar membranes are produced by the process as described in the patent application WO 01/79335 in the name of SOLVAY, in particular as described in its claims.
- In the process according to the invention, the electrodialyser contains at least two types of compartments and two types of membranes, cationic and bipolar. In some embodiments it can contain additional types of compartments and anionic membranes.
- In a preferred embodiment of the process, the electodialyser comprises only two types of compartments and only cationic and bipolar membranes. In this embodiment, wherein the less basic and more basic compartments of the electrodialyser are separated by an alternation of cationic and bipolar membranes, each compartment is thus delimited on one side by a cationic membrane, and on the other side by a bipolar membrane.
- In the process according to the invention, the sodium hydroxide reacts with the sodium bicarbonate contained in the mineral ore. The resulting sodium carbonate, thanks to its high solubility is easily solubilized from the ore, which allows to extract efficiently the sodium values of the mineral ore. The reaction solution comprises advantageously at most 120 g/kg, preferably at most 100 g/kg sodium hydroxide and at most 40 g/kg preferably 30 g/kg sodium carbonate. It is nevertheless preferable that the reaction solution comprises at least 40 g/kg, more preferably 50 g/kg sodium hydroxide.
- Usually, the reaction solution will be made by mixing the solution comprising sodium hydroxide which is extracted from the more basic compartments with fresh water or recycle waters, in order to dilute it.
- However, the solution comprising sodium hydroxide can be advantageously used as such to form the reaction solution and put directly into contact with the mineral ore. Depending on the particular circumstances, the output from the more basic compartments will have to be reintroduced in their input, in order to get the best sodium hydroxide concentration.
- The control of the composition of the reaction solution allows to regulate the composition of the produced solution. It is advantageous that the produced solution comprises advantageously at least 200 g/kg, preferably 250 g/kg sodium carbonate.
- In a recommended embodiment of the process according to the invention, at least part of the produced solution is evaporated in order to produce a suspension comprising sodium carbonate crystals, which are separated and valorized. The evaporation can be made as in the monohydrate process, preferably by using mechanical vapor recompression. The sodium carbonate monohydrate crystals are then preferably processed into dense soda ash.
- In the process according to the invention, a production solution comprising sodium carbonate is introduced into the less basic compartments of the electrodialyser. Due to the flux of Na+ ions through the cationic membrane and an incoming flux of H+ ions, at least part of the entering sodium carbonate is transformed into sodium bicarbonate, forming an output solution comprising sodium bicarbonate.
- Depending on the concentrations in sodium carbonate and sodium bicarbonate of the first production solution, it can also happen in advantageous embodiments, that sodium bicarbonate is converted into carbon dioxide at the output of the less basic compartments of the cell. The carbon dioxide can then be reacted with sodium carbonate solutions at other stages of the process, in order to produce sodium bicarbonate crystals.
- In a recommended embodiment of the process, a solution comprising sodium bicarbonate is extracted from the less basic compartments of the electrodialyser, this solution being afterwards cooled in order to produce a suspension comprising sodium bicarbonate crystals. The suspension is separated into sodium bicarbonate crystals to be valorized and a sodium bicarbonate mother liquor. The mother liquor is then preferably debicarbonated, in order to produce on one side a gas comprising CO2 and on the other side a debicarbonated solution depleted in sodium bicarbonate and enriched in sodium carbonate. The debicarbonated solution contains preferably not more than 60 g/kg, more preferably 50 g/kg, most preferably 40 g/kg sodium bicarbonate. The debicarbonated solution can be mixed with the production solution and introduced into the electrodialyser. It can also be mixed with the produced solution in order to form the reaction solution. The debicarbonation can be performed by vapor or preferably by air stripping.
- In order to produce a solution comprising sodium hydroxide into the more basic compartments of the electrodialyser, it is necessary to limit the flux of sodium bicarbonate which could be introduced into those compartments. In fact, the maximum flux of HCO3− ions entering into the more basic compartments is limited by the flux of OH− ions and Na+ ions introduced into them through the bipolar and cationic membranes. The more basic compartments can be advantageously fed by introducing into them the debicarbonated solution produced in the recommended embodiment described just above. Alternatively, it can be fed by a diluted sodium carbonate solution, containing advantageously at least 20 g/kg sodium carbonate, but at most 70 g/kg, preferably at most 50 g/kg sodium carbonate.
- In a preferred embodiment, the more basic compartments are not fed by any solution coming from the outside. In this embodiment, the more basic compartments contain only NaOH produced in situ into those compartments by combination of Na+ and OH− ions (crossing the cationic membranes and the anionic faces of the bipolar membranes), the input flow to the compartments being taken from their output (recirculation), with only supply of water, if necessary. In a variant of this embodiment, even the supply of external water is avoided, the less basic compartments being only fed by water passing through the ion exchange membranes into them.
- The process according to the invention can be run with only one electrodialyser. It is however possible to use several electrodialysers, the output from some of them being used as input for others.
- For instance, in a recommended embodiment of the process according to the invention, the solution comprising sodium bicarbonate which is extracted from the less basic compartments of the electrodialyser is introduced into the less basic compartments of another electrodialyser. In this embodiment, it is preferable first to cool the solution comprising sodium bicarbonate extracted from the less basic compartments of the first electrodialyser and separate the sodium bicarbonate crystal which appears due to the cooling. The mother liquor is then introduced into the other electrodialyser. Additionally, in this embodiment, it is recommended that the concentration in sodium carbonate of the solution comprising sodium bicarbonate which is introduced into the other electrodialyser is sufficiently low so as to generate CO2 gas into the less basic compartments of this other electrodialyser. Indeed, when all the sodium carbonate entering the less basic compartments has been transformed into sodium bicarbonate as a consequence of Na+ ions passing the cationic membranes, any additional flux of Na+ ions passing through those membranes has the consequence of destroying sodium bicarbonate into CO2 and water. The generated CO2 gas is then advantageously used to react with part of the sodium carbonate solution produced through the contact with the mineral ores, in order to produce sodium bicarbonate crystals. This reaction can be performed in gas-liquid contactors suitable for the carbonation of sodium carbonate solutions. Depending on the circumstances, the sodium carbonate solution can be first concentrated by any suitable means, before its carbonation.
- According to the invention, the sodium hydroxide is produced in the electrodialyser out of a sodium carbonate solution and the sodium carbonate solution is in turn very simply obtained by using part of the solution produced by the reaction of the sodium hydroxide with the sodium bicarbonate part of the mineral ore. Different mineral ores can be utilized and the mineral ores can be put into contact with the reaction solution in very different ways, for instance in surface equipments using excavated mineral ores. The simplicity of this process allows to use it at large industrial scale. It is particularly interesting to introduce the reaction solution underground and put it into contact with subterranean mineral ore deposits. The solution comprising sodium carbonate is then formed underground and extracted by conventional solution mining techniques. This embodiment is suited to Trona, Nahcolite, Wegscheiderite or Decemite mineral underground ores. In a particularly preferred embodiment, the mineral ore comprising sodium bicarbonate is an underground trona or nahcolite ore mineral.
- Depending on the circumstances, it can also be advantageous to mix part of the reaction solution with a solution comprising sodium bicarbonate already at hand, in order to convert at least part of the sodium bicarbonate into sodium carbonate.
- The annexed
FIG. 1 illustrates a particular embodiment of the invention. Aproduction solution 1 comprising sodium carbonate is introduced into the less basic compartments of anelectrodialyser 2 comprising alternating less basic and more basic compartments. Asolution 3 comprising sodium bicarbonate is extracted from the less basic compartments and asolution 4 comprising sodium hydroxide is extracted from the more basic compartments of the electrodialyser. Thesolution 3 is cooled in thecrystallizer 5, resulting insodium bicarbonate crystals 6 and amother liquor 7. Themother liquor 7 is debicarbonated by air stripping in thecontactor 8, resulting in CO2 gas 9 anddebicarbonated mother liquor 10, part of which (10′) is sent back to the electrodialyser and part of which is mixed with thesolution 4 comprising sodium hydroxide together withfresh water 11, to form thereaction solution 12. Thereaction solution 12 is injected into asubterranean trona mine 13. A solution comprisingsodium carbonate 14 is extracted from the trona mine. A producedsolution 14′ is taken out of thissolution 14 and sent to an evaporator (not represented), wherein sodium carbonate monohydrate crystals are formed. Those crystals are thereafter valorized, for instance by transformation into dense soda ash. The remaining part of thesolution 14 is sent to the electrodialyser, constituting after mixing withdebicarbonated mother liquor 10′ theproduction solution 1. - Details and particularities of the invention will appear from the description of the following example.
- The process illustrated by the
FIG. 1 is operated in the following way. A quantity of 0.024 m3/h of a production solution comprising 110 g/kg sodium carbonate and 32 g/kg sodium bicarbonate is introduced at a temperature of 29° C. into the less basic compartments of an electrodialyser. The electrodialyser comprise bipolar membranes produced by ASTOM, model NEOSEPTA BP-1E and cationic membranes NAFION® 324, produced by DuPont. A current density of 1 kA/m2 is applied to the elementary cell. Asolution 3 comprising 117 g/kg sodium bicarbonate and 20 g/kg sodium carbonate at a temperature of 65° C. is extracted from the less basic compartments of the electrodialyser at a flow rate of 0.023 m3/h. This solution is cooled to 30° C. in a crystallizer, resulting in a production of 0.78 kg/h of sodium bicarbonate crystals. Asolution 4 comprising 357 g/kg of sodium hydroxide is extracted from the more basic compartments of the electrodialyser at a flow rate of 0.002 m3/h and a temperature of 65° C. After mixing with 0.007 m3/h water and 0.003 m3/hdebicarbonated mother liquor 10″, a reaction solution comprising 68 g/kg NaOH and 27 g/kg Na2CO3 is introduced at a flow rate of 0.012 m3/h and at a temperature of 50° C. into a trona mine comprising trona ore having the composition described in the introductory part of this specification, the temperature of the ore being approximately 25°C. A solution 14 comprising 280 g/kg Na2CO3 is extracted from the mine at a flow rate of 0.014 m3/h and a temperature of approximately 30° C. A part of 0.008 m3/h is subtracted from thissolution 14 for evaporation and sodium carbonate crystallization. - The remaining flow rate is mixed with 0.02 m3/h of
debicarbonated mother liquor 10′ containing 50 g/kg sodium carbonate and 43 g/kg sodium bicarbonate.
Claims (10)
1. A process to produce sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate, comprising:
introducing a production solution comprising sodium carbonate into less basic compartments of an electrodialyser comprising alternating less basic and more basic adjacent compartments separated from each other by cationic membranes, the more basic compartments being delimited by anionic faces of bipolar membranes on one side and by the cationic membranes on the other side;
optionally extracting a solution comprising sodium bicarbonate from the less basic compartments;
producing a solution comprising sodium hydroxide into the more basic compartments, by combination of flux of sodium ions crossing the cationic membrane and flux of hydroxyl ions crossing the anionic face of the bipolar membranes;
extracting the solution comprising sodium hydroxide from the more basic compartments of the electrodialyser and using such solution to constitute a reaction solution;
putting the reaction solution into contact with the mineral ore comprising sodium bicarbonate in order to form a solution comprising sodium carbonate; and
dividing the solution comprising sodium carbonate into a part which is used to constitute said production solution and a remaining part which constitutes a produced solution.
2. The process according to claim 1 , wherein the produced solution is evaporated in order to produce a suspension comprising sodium carbonate crystals, which are separated and valorized.
3. The process according to claim 1 , wherein a solution comprising sodium bicarbonate is extracted from the less basic compartments of the electrodialyser, this sodium bicarbonate-comprising solution being afterwards cooled in order to produce a suspension comprising sodium bicarbonate crystals, and the suspension being separated into valorized sodium bicarbonate crystals and a sodium bicarbonate mother liquor.
4. The process according to claim 3 , wherein the sodium bicarbonate mother liquor is debicarbonated and introduced into the less basic compartments of the electrodialyser
5. The process according to claim 3 , wherein the sodium bicarbonate mother liquor is debicarbonated and introduced into the more basic compartments of the electrodialyser.
6. The process according to claim 3 , wherein the sodium bicarbonate mother liquor is introduced into the less basic compartments of another electrodialyser.
7. The process according to claim 6 , wherein the concentration in sodium carbonate of the sodium bicarbonate mother liquor is sufficiently low so as to generate CO2 gas into the less basic compartments of the other electrodialyser.
8. The process according to claim 7 , wherein the generated CO2 is put into contact with at least part of the produced solution comprising sodium carbonate, in order to produce sodium bicarbonate crystals.
9. The process according to claim 1 , wherein part of the reaction solution comprising sodium hydroxide is mixed with a solution comprising sodium bicarbonate, in order to convert at least part of the sodium bicarbonate into sodium carbonate.
10. The process according to claim 1 , wherein the mineral ore comprising sodium bicarbonate is an underground trona or nahcolite ore mineral.
Applications Claiming Priority (3)
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EP08150104.1 | 2008-01-08 | ||
EP08150104A EP2078697A1 (en) | 2008-01-08 | 2008-01-08 | Process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate |
PCT/EP2009/050075 WO2009087145A1 (en) | 2008-01-08 | 2009-01-06 | Process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate |
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US20110217227A1 (en) * | 2008-07-23 | 2011-09-08 | Fze Engsl | Combined solid waste, carbon dioxide quicklime sparging, brine water, and reverse osmosis/ion exchange processes for the production of soda chemicals |
WO2012096987A1 (en) * | 2011-01-11 | 2012-07-19 | Calera Corporation | Systems and methods for soda ash production |
EP2607314A1 (en) | 2011-12-23 | 2013-06-26 | Solvay SA | Solution mining of ore containing sodium carbonate and bicarbonate |
WO2014042781A3 (en) * | 2012-09-14 | 2014-05-08 | Liquid Light, Inc. | Process and high surface area electrodes for the electrochemical reduction of carbon dioxide |
US8821709B2 (en) | 2012-07-26 | 2014-09-02 | Liquid Light, Inc. | System and method for oxidizing organic compounds while reducing carbon dioxide |
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US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
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FR2926027A1 (en) | 2008-01-07 | 2009-07-10 | Solvay | PROCESS FOR THE PRODUCTION OF SODIUM BICARBONATE FOR THE DEULFURATION OF SMOKE. |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3953073A (en) * | 1974-05-17 | 1976-04-27 | Kube Wolfram H | Process for the solution mining of subterranean sodium bicarbonate bearing ore bodies |
US4044097A (en) * | 1976-06-17 | 1977-08-23 | Allied Chemical Corporation | Recovery of soda values from sodium carbonate crystallizer purge liquors |
US4238305A (en) * | 1979-10-29 | 1980-12-09 | Allied Chemical Corporation | Electrodialytic process for the conversion of impure soda values to sodium hydroxide and carbon dioxide |
US4584077A (en) * | 1984-08-13 | 1986-04-22 | Allied Corporation | Process for recovering sodium carbonate from trona and other mixtures of sodium carbonate and sodium bicarbonate |
US4636289A (en) * | 1983-05-02 | 1987-01-13 | Allied Corporation | Solution mining of sodium minerals with acids generated by electrodialytic water splitting |
US5308455A (en) * | 1992-03-09 | 1994-05-03 | Solvay (Societe Anonyme) | Process for the manufacture of sodium hydroxide |
US6221225B1 (en) * | 1997-01-23 | 2001-04-24 | Archer Daniels Midland Company | Apparatus and process for electrodialysis of salts |
US6924318B2 (en) * | 2000-04-19 | 2005-08-02 | Solvay (Societe Anonyme) | Method for making a bipolar membrane and use of resulting bipolar membrane |
US20090288957A1 (en) * | 2006-07-07 | 2009-11-26 | Solvay (Societe Anonyme) | Process for the Production of Sodium Bicarbonate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3834807A1 (en) * | 1988-10-13 | 1990-05-10 | Kali Chemie Ag | METHOD FOR PRODUCING CARBONIC SALTS OF ALKALI METALS |
-
2008
- 2008-01-08 EP EP08150104A patent/EP2078697A1/en not_active Withdrawn
-
2009
- 2009-01-06 US US12/811,643 patent/US20100282614A1/en not_active Abandoned
- 2009-01-06 WO PCT/EP2009/050075 patent/WO2009087145A1/en active Application Filing
- 2009-01-06 EP EP09701448.4A patent/EP2240408B1/en active Active
- 2009-01-06 CN CN2009801018989A patent/CN101918316B/en not_active Expired - Fee Related
- 2009-01-06 ES ES09701448.4T patent/ES2625298T3/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3953073A (en) * | 1974-05-17 | 1976-04-27 | Kube Wolfram H | Process for the solution mining of subterranean sodium bicarbonate bearing ore bodies |
US4044097A (en) * | 1976-06-17 | 1977-08-23 | Allied Chemical Corporation | Recovery of soda values from sodium carbonate crystallizer purge liquors |
US4238305A (en) * | 1979-10-29 | 1980-12-09 | Allied Chemical Corporation | Electrodialytic process for the conversion of impure soda values to sodium hydroxide and carbon dioxide |
US4636289A (en) * | 1983-05-02 | 1987-01-13 | Allied Corporation | Solution mining of sodium minerals with acids generated by electrodialytic water splitting |
US4584077A (en) * | 1984-08-13 | 1986-04-22 | Allied Corporation | Process for recovering sodium carbonate from trona and other mixtures of sodium carbonate and sodium bicarbonate |
US5308455A (en) * | 1992-03-09 | 1994-05-03 | Solvay (Societe Anonyme) | Process for the manufacture of sodium hydroxide |
US6221225B1 (en) * | 1997-01-23 | 2001-04-24 | Archer Daniels Midland Company | Apparatus and process for electrodialysis of salts |
US6924318B2 (en) * | 2000-04-19 | 2005-08-02 | Solvay (Societe Anonyme) | Method for making a bipolar membrane and use of resulting bipolar membrane |
US20090288957A1 (en) * | 2006-07-07 | 2009-11-26 | Solvay (Societe Anonyme) | Process for the Production of Sodium Bicarbonate |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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US20110217227A1 (en) * | 2008-07-23 | 2011-09-08 | Fze Engsl | Combined solid waste, carbon dioxide quicklime sparging, brine water, and reverse osmosis/ion exchange processes for the production of soda chemicals |
US8986533B2 (en) | 2009-01-29 | 2015-03-24 | Princeton University | Conversion of carbon dioxide to organic products |
US8845877B2 (en) | 2010-03-19 | 2014-09-30 | Liquid Light, Inc. | Heterocycle catalyzed electrochemical process |
US10119196B2 (en) | 2010-03-19 | 2018-11-06 | Avantium Knowledge Centre B.V. | Electrochemical production of synthesis gas from carbon dioxide |
US9970117B2 (en) | 2010-03-19 | 2018-05-15 | Princeton University | Heterocycle catalyzed electrochemical process |
US9222179B2 (en) | 2010-03-19 | 2015-12-29 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US9309599B2 (en) | 2010-11-30 | 2016-04-12 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
WO2012096987A1 (en) * | 2011-01-11 | 2012-07-19 | Calera Corporation | Systems and methods for soda ash production |
EP2607313A1 (en) | 2011-12-23 | 2013-06-26 | Solvay SA | Solution mining of ore containing sodium carbonate and bicarbonate |
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US9010869B2 (en) | 2011-12-23 | 2015-04-21 | Solvay Sa | Solution mining of ore containing sodium carbonate and bicarbonate |
US8845876B2 (en) | 2012-07-26 | 2014-09-30 | Liquid Light, Inc. | Electrochemical co-production of products with carbon-based reactant feed to anode |
US9303324B2 (en) | 2012-07-26 | 2016-04-05 | Liquid Light, Inc. | Electrochemical co-production of chemicals with sulfur-based reactant feeds to anode |
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US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
US9175409B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Multiphase electrochemical reduction of CO2 |
US8858777B2 (en) | 2012-07-26 | 2014-10-14 | Liquid Light, Inc. | Process and high surface area electrodes for the electrochemical reduction of carbon dioxide |
US9267212B2 (en) | 2012-07-26 | 2016-02-23 | Liquid Light, Inc. | Method and system for production of oxalic acid and oxalic acid reduction products |
US9085827B2 (en) | 2012-07-26 | 2015-07-21 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
US8845875B2 (en) | 2012-07-26 | 2014-09-30 | Liquid Light, Inc. | Electrochemical reduction of CO2 with co-oxidation of an alcohol |
US9708722B2 (en) | 2012-07-26 | 2017-07-18 | Avantium Knowledge Centre B.V. | Electrochemical co-production of products with carbon-based reactant feed to anode |
US11131028B2 (en) | 2012-07-26 | 2021-09-28 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
US8821709B2 (en) | 2012-07-26 | 2014-09-02 | Liquid Light, Inc. | System and method for oxidizing organic compounds while reducing carbon dioxide |
US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
US10287696B2 (en) | 2012-07-26 | 2019-05-14 | Avantium Knowledge Centre B.V. | Process and high surface area electrodes for the electrochemical reduction of carbon dioxide |
WO2014042781A3 (en) * | 2012-09-14 | 2014-05-08 | Liquid Light, Inc. | Process and high surface area electrodes for the electrochemical reduction of carbon dioxide |
US9873951B2 (en) | 2012-09-14 | 2018-01-23 | Avantium Knowledge Centre B.V. | High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide |
Also Published As
Publication number | Publication date |
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EP2240408B1 (en) | 2017-03-15 |
CN101918316B (en) | 2012-07-18 |
CN101918316A (en) | 2010-12-15 |
WO2009087145A1 (en) | 2009-07-16 |
EP2078697A1 (en) | 2009-07-15 |
ES2625298T3 (en) | 2017-07-19 |
EP2240408A1 (en) | 2010-10-20 |
WO2009087145A8 (en) | 2010-08-05 |
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