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WO1993011070A1 - Carbonatation a sec de trona - Google Patents

Carbonatation a sec de trona Download PDF

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Publication number
WO1993011070A1
WO1993011070A1 PCT/US1992/006321 US9206321W WO9311070A1 WO 1993011070 A1 WO1993011070 A1 WO 1993011070A1 US 9206321 W US9206321 W US 9206321W WO 9311070 A1 WO9311070 A1 WO 9311070A1
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WO
WIPO (PCT)
Prior art keywords
reaction
gas stream
trona
water
sodium bicarbonate
Prior art date
Application number
PCT/US1992/006321
Other languages
English (en)
Inventor
Anthony J. Falotico
Original Assignee
Church & Dwight Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Church & Dwight Company, Inc. filed Critical Church & Dwight Company, Inc.
Publication of WO1993011070A1 publication Critical patent/WO1993011070A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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

Definitions

  • Impure trona ore is generally comprised of mixtures of trona (Na 2 CO 3 .NaHCO-_2H 2 0) with other materials, e.g., alkali minerals such as sodium chloride and sodium sulfate, as well as shales and clays.
  • the invention also relates to such a process for the production of sodium bicarbonate useful in the desulfurization of flue gas.
  • the conventional technique utilized in the commercial production of sodium bicarbonate is the solution process.
  • soda ash is dissolved in spent reaction liquor from prior reaction, consisting of water and small quantities of dissolved soda ash and sodium bicarbonate.
  • the solution is then carbonated to precipitate crystals of sodium bicarbonate.
  • the sodium bicarbonate crystals are separated from the liquor and dried to yield highly purified, high density crystals.
  • Disadvantages of the conventional method are that the procedure requires several steps, and necessitates the use of separation equipment, drying of the product, and the handling of large volumes of liquids.
  • U.S. Pat. No 3,647,365 (Saeman) teaches a process in which hollow sodium bicarbonate beads of low density are prepared in a multistage reactor from hydrated soda ash, small amounts of water and carbon dioxide. This process requires several steps and must proceed slowly, with carbonation times exceeding one hour and drying times up to eight hours. The soda ash must first be hydrated in a separate step, and the reaction must occur at a temperature above 95.7°F. to produce commercially acceptable reaction rates.
  • Krieg et al. (U.S. Pat. No. 4,459,272, owned by the assignee of the present invention) described a process for the preparation of sodium bicarbonate by the reaction of a solid, particulate sodium carbonate-containing material with liquid water in a carbon dioxide-rich atmosphere.
  • the particulate mass is mixed with the water and carbon dioxide in an internally agitated or externally rotated or vibrated reactor.
  • the reaction is carried out at temperatures of from 125°F. to 240°F. under atmospheres containing from 20% to 90% carbon dioxide by volume.
  • the process is carried out under reduced water vapor partial pressures to promote evaporation of water from the surfaces of the reacting carbonate particles, and to maintain high carbon dioxide partial pressures in the reactor atmosphere.
  • Sodium bicarbonate has also been produced, as well as utilized, in dry sorbent injection processes for removing sulfur dioxide emissions from the combustion gases of fossil fuel-fired burners. Such techniques have commanded considerable attention recently, particularly because they present the lowest "first cost” alternative for removing potentially dangerous sulfur dioxide from flue gases.
  • Sodium bicarbonate has been demonstrated to be a very effective sorbent in the dry sorbent injection process.
  • the cost of pharmaceutical grade sodium bicarbonate, as currently produced is a major drawback to its use for such purpose.
  • U.S. Pat. Nos. 3,846,535 (Fonseca) and 4,385,039 (Lowell et al.) disclose methods for regenerating sodium bicarbonate from sulfate-containing solid waste formed by dry sorbent injection with sodium bicarbonate.
  • the Fonseca regeneration step is carried out by forming an aqueous solution of the sodium sulfate-containing waste, and treating such solution with ammonium bicarbonate to precipitate sodium bicarbonate.
  • the sodium bicarbonate is then separated, dried and recycled for further use.
  • Lowell et al. disclose a regeneration step which involves dissolving the solid desulfurization reaction product in a basic liquor, which contains borate ions and/or ammonia. Carbonation of this liquor results in a sodium bicarbonate precipitate.
  • the Fonseca and Lowell et al. processes thus both suffer from the use of complicated and capital intensive solution operations.
  • a further object of the invention is to provide such a process which may be readily employed to produce bicarbonate sorbent employed in the desulfurization of flue gases, more efficiently and economically than possible utilizing previously proposed techniques.
  • a process for the dry carbonation of trona which comprises:
  • reaction zone e.g., an internally agitated or externally rotated or vibrated reactor
  • gas stream containing from about 12% to 100% carbon dioxide by volume, any remaining percentage of the gas stream being an inert gas such as air or nitrogen, the gas stream being heated to a temperature within the range of about 140°F. to about 160°F. [about 60° to about 71.1 ⁇ C], preferably about 150°F. to about 155°F. [about 65.6° to about 68.3°C.];
  • step (c) initiating the reaction by introducing water into the reaction zone to form a gas mixture of water vapor and the gas stream from step (b) , so that the water vapor content of the gas mixture reaches essentially 100% of saturation at the temperature of the gas stream from step (b);
  • the operation is best carried out under atmospheric pressure or higher than atmospheric pressure in the range of about 14.7 to about 25 pounds per square inch absolute. Although higher or lower pressure may be employed, higher pressures are generally better, particularly when the process is utilizing low C0 2 concentrations, in order to increase the C0 2 partial pressure and to drive the reaction. For example, 23 psia pressure has been successfully used with 12% C0 2 concentration to increase the C0 2 partial pressure and drive the reaction.
  • the starting material is natural trona (which need not be calcined) , not the more expensive processed sodium sesquicarbonate.
  • the C0 2 content of the gas stream is less than 100%, intermittent injections of water into the reactor may be required to maintain the reaction, depending upon the balance of the stoichiometry/C0 2 partial pressure.
  • Dry carbonated trona can be screened or air classified in order to reduce insolubles.
  • the final product is more free flowing and/or has less of a tendency to cake than bicarbonate produced from pure sodium sesquicarbonate.
  • the sodium bicarbonate of the invention is novel because of these unique properties. While not wishing to be bound by any particular theory for the superior properties of the novel sodium bicarbonate of the invention, certain differences can be emphasized.
  • the morphology of the novel sodium bicarbonate shown in FIGS. 5a and 5b is unique.
  • the surface area of the novel sodium bicarbonate is greater than prior art sodium bicarbonates.
  • the dry carbonation process hereof is utilized in connection with desulfurizing low carbon dioxide-content flue gas streams, wherein the flue gas is contacted with a sodium bicarbonate-containing sorbent to react with sulfur dioxide in the flue gas, and the resulting solid waste is separated and removed from the gas stream.
  • the cleansed gas stream, from which the solid waste has been removed is cooled (to a temperature as low as about 140°F. [60°C.]), water is injected into the gas stream, and the gas stream is thoroughly mixed with a particulate trona in the manner indicated above and then utilized to contact the hot flue gas for further desulfurization thereof.
  • FIG. 1 is a schematic flow diagram of one embodiment of the process of the invention.
  • FIG. 2 is a graph of the results from continuous reactions in accordance with the invention. The graph shows the relationship between the lbs. NaHC0 3 /min.-ft. 3 made and the CO- partial pressure (pounds per square inch absolute) in the exit gas from the reactor.
  • FIG. 3 is a graph of the results of two batch reactions of trona with a gas mixture containing 12% C0 2 .
  • the percent of NaHCO- in the product (insoluble-free basis) is plotted against the reaction time in hours. For comparison purposes, a data point from a 150 lbs./hr. continuous reaction ' is also shown.
  • FIGS. 4a and 4b show the surfaces of trona feed samples enlarged to 5,000 and 10,000 times magnifications respectively.
  • FIGS. 5a and 5b show the surfaces of sodium bicarbonate product samples enlarged to 2,000 and 10,000 times magnifications respectively.
  • the process of the invention can be conducted in a batch or continuous manner. For most purposes, the continuous manner will be preferred.
  • FIG. 1 is a schematic flow diagram of one embodiment of the invention.
  • Dry trona particles are fed from hopper 1 through feed conduit 2 having an in-line flow valve to heat traced and insulated plow blender 3, which has an internal agitator, not shown, that is rotated about its axis by motor 4, which preferably rotates the agitator at a slow speed on the order of 50 to 70 rpm.
  • the rpm is a function of the diameter of the plow blender 3 and may be optimized to produce a "falling curtain" of powder inside the plow blender 3.
  • the plow blender 3 is heated to maintain the temperature of the trona particles within the range of about 140° to about 160°F. [60° to 71.1°C], preferably about 150° to about 155°F.
  • the particulate trona reactant employed in the present process may comprise any trona (and need not be calcined) .
  • the materials used are impure ores, or mixtures of trona (Na 2 CO-.NaHCO-.2H 2 0) with other materials, e.g., alkali minerals such as sodium chloride and sodium sulfate, as well as shales and clays.
  • alkali minerals such as sodium chloride and sodium sulfate
  • shales and clays e.g., sales and clays.
  • the process of the invention will be illustrated in connection with the preferred carbonation of trona. It will, however, be understood that the invention is not limited to the use of trona, as any of the other sodium carbonate-containing ores that contain excess water of hydration can be employed therein.
  • the trona feed has particles generally of sizes in the range of about 200 to 20 mesh with more than 95 cumulative percent of the particles being retained on 40, 60 and 100 mesh, U.S. sieve size.
  • CO- at temperature T 1 from scrubber 6 is introduced to the plow blender 3 through conduit 7 by blower 8.
  • an inert gas such as air or nitrogen, may be included in the gas mixture in an amount up to about 88 percent by volume.
  • the initial water injection and any subsequent intermittent water injection that may be needed to maintain the reaction is made through conduit containing an in-line valve. That water and some of the C0 2 react with the carbonate on the surface of the trona feed to yield a relatively dry bicarbonate.
  • the dry bicarbonate exits the plow blender 3 through conduit 9, which contains an in-line valve.
  • Unreacted humid C0 2 at temperature T 2 exits the plow blender 3 through heat-traced and insulated conduit 10, which conducts it back to the scrubber 6.
  • Valve 15 directs steam or cooling water to heat exchanger 16.
  • Heat exchanger 16 heats or cools the recycle water from the bottom of scrubber 6 that is pumped to heat exchanger 16 by pump 17 through pipeline 18. From heat exchanger 16, the heated or cooled recycle water flows through pipeline 19 to the scrubber nozzle 20 inside at the top of scrubber 6. Water is sprayed through the scrubber nozzle 20 downward and countercurrent to the flow of C0 2 , which enters the scrubber 6 at a lower point. The water spray and the countercurrent flow of C0 2 serve to saturate the C0 2 with water vapor at temperature T
  • the carbonating-gas stream in the reactor may be maintained initially under essentially saturated conditions, i.e., the moisture content is maintained at about 100% of saturation at the reaction temperature utilized, either by feeding the carbonating gas stream solely through a saturation tank and/or by vaporizing some liquid water sprayed into the reactor. In this manner, the initial presence of sufficient water on the surfaces of the reacting particles is assured, and the carbonation reaction proceeds at commercially acceptable rates.
  • the extent of the reaction can be determined by periodically taking samples of the product being discharged from plow blender 3, analyzing the samples by pH or any other convenient analytical method to determine the percentage of sodium bicarbonate as well as by examination under the microscope to determine the nature of the product particles.
  • the continuous process of the invention can be controlled by suitable means.
  • suitable means for example, one can use temperature or pressure sensors in the control of the process. It has been convenient and simple to control the reaction with a timer and the temperature of the exhaust stream.
  • the reaction In conducting and controlling the reaction, it is desirable to stoichiometrically balance the available water from the trona with the total gas volume (i.e., % C0 2 ) to maintain a super saturated condition and a "rain storm" of condensing water inside the reactor.
  • the "rain” should equal the amount of water required to effect conversion of the sodium carbonate to sodium bicarbonate.
  • the chemical make-up of the product is, in general, sodium bicarbonate plus trona plus sodium sesquicarbonate plus insolubles. If the reaction is carried to completion, sodium bicarbonate is essentially the sole product mixed with insolubles. Differences in bulk density may, in general, be achieved by controlling the degree of reaction.
  • the water content of the product will vary depending generally on the degree of reaction. When low C0 2 concentrations are used in the reaction, from about 2 to about 4 percent by weight of the water may be present in the product sodium bicarbonate. Generally, when high C0 2 concentrations are used in the reaction, substantially no water is present in the sodium bicarbonate product.
  • Another embodiment of the invention effects thorough mixing of the gas stream and particulate trona feed in a turbulent fluidized bed under conditions which produce thorough contact between the solid and gaseous reactants with substantially complete back mixing and heat transfer therebetween.
  • Such conditions are preferably insured by mechanically fluidizing the bed.
  • the conditions can also be effected by introducing the fluidizing gas into the fluidized bed at rates varying as required by the particle size and density of the trona feed.
  • the use of fluidizing gas to effect a fluidized bed results in the undesirable "dilution" of the available water with the excess gas required to maintain fluidization. Of course, this is not a problem with mechanical fluidization.
  • Fluidizing conditions may be provided in either a conventional gas fluidized bed reactor in which the energy required to fluidize the trona particles is imparted to the carbonating-gas stream, or preferably in a mechanically fluidized bed wherein the solid particles are mechanically accelerated through the gaseous medium to effect turbulent fluidization thereof.
  • a mechanically fluidized bed the flow rate of the carbonating-gas stream must at least be equal to that necessary to supply the gaseous reactants and to remove the heat of reaction.
  • the gas feed rate In a gas fluidized bed, the gas feed rate must also be sufficient to produce turbulent fluidization; in most instances, such feed rate is significantly greater than that required for adequate feed of the reactants and heat removal.
  • the process of the present invention produces a bicarbonate of a quality which is suited for a number of applications where a U.S.P. grade is not necessary, e.g., neutralization of acidic lakes and the dry sorbent injection process for desulfurizing flue gas because its particles are coarse.
  • a U.S.P. grade is not necessary, e.g., neutralization of acidic lakes and the dry sorbent injection process for desulfurizing flue gas because its particles are coarse.
  • the use of sodium bicarbonate having such properties is desirable because the sorption of sulfur oxides is believed to be surface related.
  • the process of the invention leads to a useful increase in surface area, e.g., to about 0.3 m 2 /gm.
  • commercially produced sodium bicarbonate has a surface area of about 0.1 meter 2 /g., and a specific density of about 50-60 lb/ft 3 .
  • a preferred embodiment of the carbonation process hereof resides in the desulfurization of flue gases by the dry injection technique.
  • the invention makes possible the direct use of low carbon dioxide-content lue gas containing at least about 12%, typically about 12-17%, C0 2 by volume.
  • a boiler flue gas stream containing fly ash and sulfur dioxide is recovered from a boiler at approximately 300°F. [148.9°C.].
  • Such a stream may typically incorporate about 8-17% carbon dioxide, 2-4% oxygen, 68-77% nitrogen, 3-18% water vapor, and up to 0.5% sulfur dioxide, by volume.
  • the flue gas is mixed with a sodium bicarbonate-based sorbent which may also contain, for example, sodium carbonate and sodium sulfate, metered from a storage bin into the flue gas stream, the sorbent reacting with the sulfur dioxide in a particulate collection device.
  • a sodium bicarbonate-based sorbent which may also contain, for example, sodium carbonate and sodium sulfate, metered from a storage bin into the flue gas stream, the sorbent reacting with the sulfur dioxide in a particulate collection device.
  • Trona is metered from a storage bin into the reactor, and the gas stream is intimately mixed with the trona in the fluidized bed. As and when needed, liquid water may also be metered into the reactor, forming a film on the trona particles in the bed. Water is generally required more frequently at low CO- concentrations than with high CO- concentrations. The bicarbonate reaction product is removed, and waste gas is vented after the removal of particulates.
  • the carbonation reaction is thought to occur only when an aqueous, C0 2 containing film forms around the trona particles. Such a film forms more rapidly when liquid water is added directly to the trona particles rather than waiting for the carbonate to adsorb sufficient water from the gas stream. Accordingly, liquid water is initially sprayed or sparged into the reactor.
  • the present invention provides an efficient technique for producing a sodium bicarbonate-based sorbent in the very desulfurizing process in which the sorbent is required.
  • the cost of producing, for example, a sodium bicarbonate-based sorbent by the present technique is far below that of producing a conventional pharmaceutical grade sodium bicarbonate sorbent, since trona is the only extrinsic raw material required for use in the process.
  • the other reactants required, carbon dioxide and water are contained in the flue gas and, therefore, do not have to be purchased or added to the carbonation reaction in a separate step.
  • the bicarbonate product may thus be directly and ef iciently produced from trona with minimum processing.
  • a continuous reaction in accordance with the invention was carried out in pilot plant apparatus and in a manner similar to that illustrated in the flow diagram of FIG. 1.
  • the trona feed had the following composition:
  • the trona particles had pH values as a 1.0 percent aqueous solution at 25°C as shown in Table I. Also shown in the table are the corresponding pH values for 1% aqueous solutions of the reaction product at the times indicated. With the exception of the trona, the percents in Table I represent the amount of sodium bicarbonate in the products.
  • the trona feed rate was 8.33 pounds per minute.
  • the reactor exit gas temperature was 145°F. [62.78°C.].
  • the reactor pressure was 14.8 psia.
  • the feed gas stream consisted of essentially 100 percent C0 2 (dry basis) and a trace percent air.
  • Water was injected into the reactor at a rate of 1.328 pounds per minute for about 10 to 15 minutes to initiate the reaction.
  • the water given off in the reaction was condensed by passing some gas from the reactor through line 10 into the scrubber 6 and recycling the gas back into the reactor through line 7.
  • the blender residence time at 60% full was 104 minutes.
  • FIG. 2 is a graph of the results from continuous reactions in accordance with the invention.
  • the graph shows the relationship between the lbs. NaHC0 3 /min.-ft. 3 made and the C0 2 partial pressure (pounds per square inch absolute) in the exit gas from the reactor. It is probably possible to improve the throughput by making subtle changes in the process variables, e.g., smaller trona feed particle size, pressure, control of leaks, etc.
  • a batch reaction in accordance with the invention was carried out in pilot plant apparatus and in a manner similar to that illustrated in the flow diagram of FIG. 1.
  • the plow blender reactor and trona used were as described in Example 1.
  • the trona particles charge to the reactor was about 500 pounds.
  • the temperature of the reactor exit gas was 149°F. [65°C.].
  • the pressure was 22.3 psia.
  • the feed gas stream consisting of 12 percent C0 2 and 88 percent air (dry basis) was introduced through line 7 into the reactor at such a rate as to provide an excess of C0 2 .
  • the object was to provide the excess so that the reaction would not be C0 2 limited.
  • the reactor exit gas was passed from the reactor through line 10 into scrubber 6 and recycled to the reactor through line 7. No cooling water was used in this batch reaction because it was not required to maintain temperature.
  • the concentration of C0 2 in the recycle gas was about 12 percent on a dry basis.
  • water was injected into the reactor to maintain the reaction by pulsing the water into the reactor 0.5 minute on, 4.5 minutes off, to 0.75 minute on, 4.25 minutes off.
  • FIG. 3 is a graph of the results of two batch reactions of trona with a gas mixture containing 12% C0 2 .
  • the percent of NaHC0 3 in the product (insoluble-free basis) is plotted against the reaction time in hours. For comparison purposes, a data point from a 150 lbs./hr. continuous reaction is also shown.
  • EXAMPLE 3 Scanning Electron Micro ⁇ raphic Analysis of Trona and Dry Carbonated Trona.
  • Representative samples of trona feed for the reaction of the invention and three representative powder samples of 95% sodium bicarbonate product from the reaction were submitted for analysis to an independent laboratory. Scanning electron microscopy was chosen for the study to document the morphology of the powder.
  • Scanning electron microscopy uses a highly focused electron beam (less than lOnm diameter) which can be scanned in a raster on the sample surface. The intensity of secondary electrons produced at each point is used to form a picture of the sample. Magnification factors from 10X to 100,000X can be obtained. The depth of field is inherently quite large, which allows the micrographs to be in focus at all points across a rough surface. In addition, the SEM does not suffer from the light microscope problem of light reflecting off at odd angles and being lost from view. "
  • FIGS. 4a and 4b show the surfaces of trona feed samples enlarged to 5,000 and 10,000 times magnifications respectively.
  • FIGS. 5a and 5b show the surfaces of sodium bicarbonate product samples enlarged to 2,000 and 10,000 times magnifications respectively. The increase in surface area can readily be seen by comparing the two sets of scanning electron micrographs.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Un procédé de carbonatation à sec de trona, pour produire du bicarbonate de sodium, consiste à mélanger, dans un mélangeur lent (3), des particules de trona et un gaz contenant du CO2 sans addition d'eau sauf pour une petite quantité d'eau ajoutée à travers un conduit (5) pour amorcer la réaction et maintenir celle-ci si le gaz contient moins de 100 % de CO2. Le flux gazeux contenant le CO2 passe à travers un épurateur (6) où il est saturé d'eau et recyclé vers le mélangeur lent (3). Une nouvelle forme de bicarbonate de sodium présentant des caractéristiques uniques est ainsi obtenue. Le procédé comprend également la production d'un agent de sorbtion contenant du bicarbonate, convenant à la désulfuration des gaz de combustion provenant des gaz contenant du dioxyde de carbone eux-mêmes.
PCT/US1992/006321 1991-12-04 1992-08-04 Carbonatation a sec de trona WO1993011070A1 (fr)

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US80226291A 1991-12-04 1991-12-04
US802,262 1991-12-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8409533B1 (en) 2012-01-13 2013-04-02 Church & Dwight Co., Inc. Boundary layer carbonation of Trona
CN110759360A (zh) * 2019-11-27 2020-02-07 天津理工大学 一种蒸发天然碱液生产碳酸钠、碳酸氢钠和氯化钠的方法及系统

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3823676A (en) * 1972-10-10 1974-07-16 Warren Cook Chem Inc Method of reducing sulphur dioxide emissions from coal
US3855397A (en) * 1973-04-12 1974-12-17 Allied Chem Method of producing sodium carbonate and bicarbonate spherules from brine
EP0005981A1 (fr) * 1978-05-30 1979-12-12 Stauffer Chemical Company Procédé de préparation de bicarbonate de soude par carbonatation
US4385039A (en) * 1981-09-18 1983-05-24 Koppers Company, Inc. Process for removal of sulfur oxides from waste gases
US4459272A (en) * 1983-04-26 1984-07-10 Church & Dwight Co., Inc. Dry carbonation process
US4664893A (en) * 1985-04-04 1987-05-12 Church And Dwight Co., Inc. Method for the preparation of a bicarbonate sorbent in flue gas desulfurization
JPH02164712A (ja) * 1988-12-17 1990-06-25 Tosoh Corp 重炭酸ナトリウムの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3823676A (en) * 1972-10-10 1974-07-16 Warren Cook Chem Inc Method of reducing sulphur dioxide emissions from coal
US3855397A (en) * 1973-04-12 1974-12-17 Allied Chem Method of producing sodium carbonate and bicarbonate spherules from brine
EP0005981A1 (fr) * 1978-05-30 1979-12-12 Stauffer Chemical Company Procédé de préparation de bicarbonate de soude par carbonatation
US4385039A (en) * 1981-09-18 1983-05-24 Koppers Company, Inc. Process for removal of sulfur oxides from waste gases
US4459272A (en) * 1983-04-26 1984-07-10 Church & Dwight Co., Inc. Dry carbonation process
US4664893A (en) * 1985-04-04 1987-05-12 Church And Dwight Co., Inc. Method for the preparation of a bicarbonate sorbent in flue gas desulfurization
JPH02164712A (ja) * 1988-12-17 1990-06-25 Tosoh Corp 重炭酸ナトリウムの製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8409533B1 (en) 2012-01-13 2013-04-02 Church & Dwight Co., Inc. Boundary layer carbonation of Trona
WO2013106294A1 (fr) * 2012-01-13 2013-07-18 Church & Dwight Co., Inc. Carbonatation de couche limite de trona
US8795615B2 (en) 2012-01-13 2014-08-05 Church & Dwight Co., Inc. Boundary layer carbonation of trona
US9056780B2 (en) 2012-01-13 2015-06-16 Church & Dwight Co., Inc. Boundary layer carbonation of trona
CN110759360A (zh) * 2019-11-27 2020-02-07 天津理工大学 一种蒸发天然碱液生产碳酸钠、碳酸氢钠和氯化钠的方法及系统
CN110759360B (zh) * 2019-11-27 2023-12-01 天津理工大学 一种蒸发天然碱液生产碳酸钠、碳酸氢钠和氯化钠的方法及系统

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