WO1989005777A1 - Procede de preparation d'une solution aqueuse contenant du bicarbonate de potassium et du carbonate de potassium et destinee a etre utilisee pour le lavage de gaz acides - Google Patents

Procede de preparation d'une solution aqueuse contenant du bicarbonate de potassium et du carbonate de potassium et destinee a etre utilisee pour le lavage de gaz acides Download PDF

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Publication number
WO1989005777A1
WO1989005777A1 PCT/FI1988/000201 FI8800201W WO8905777A1 WO 1989005777 A1 WO1989005777 A1 WO 1989005777A1 FI 8800201 W FI8800201 W FI 8800201W WO 8905777 A1 WO8905777 A1 WO 8905777A1
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Prior art keywords
potassium
aqueous solution
reaction product
amine
solution
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PCT/FI1988/000201
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English (en)
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Veli Sarkkinen
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CATENA Oy
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CATENA Oy
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    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • C01D7/16—Preparation from compounds of sodium or potassium with amines and carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention concerns a process in accordance wit the preamble of claim 1 for the preparation of an aqueous solution containing potassium bicarbonate and potassium carbonate for washing gases, such as industrial exhaust gases, containing acid gaseous compounds.
  • the aqueous solution of suitable potassium compound is carbonated and the obtained aqueous phase containing potassium bicarbonate and some potassium carbonate is separated from the reaction mixture
  • a liquid prepared with the aid of the invention may be use in the washing of industrial exhaust gases; potassium sulphates and nitrates being obtained from the reactions between the potassium compounds of the washing solutions and the sulphur oxides and nitrogen oxides in the gases.
  • Solutions used for washing acid gases, such as flue gases, should be sufficiently alkaline to neutralize the gases. At the same time it is desirable that the reaction product formed have at least some utility value.
  • the reagents used today include, as is known, the following: aqueous ammonia solutions, sodium sulphite, sodium aluminate, sodium carbonate, potassium sulphite, potassium phosphate or potassium acetate. None of these is, however, altogether satisfactory.
  • sodium carbonate and sodium hydroxide are used sodium sulphate, which is a worthless waste product, is obtained.
  • the Atomic International process requires high temperature and pressure, which in turn results in difficult corrosion problems.
  • potassium bicarbonate products with economic valu would be obtained, such as potassium sulphate and potassium nitrate, which could be used, for example, as fertilizers.
  • Potassium bicarbonate has usually been prepared from potass carbonate by conducting carbon dioxide into a solution saturated with potassium carbonate or by bringing moist potassium carbonate into contact with carbon dioxide gas at a moderate pressure. Potassium carbonate in its turn has been obtained by carbonating electrolytically prepared potassium hydroxide.
  • a process known as the Engel process has been used, in which carbon dioxide gas is conducted under pressure into a neutral solution of magnesi carbonate or magnesium oxide and potassium chloride or potassium sulphate, whereupon potassium carbonate is collected by decomposing the produced double salt.
  • Am represents an insoluble primary, secondary or tertiary amine
  • aq stands for the aqueous, g for the gaseous, o for the organic and s for the solid phases.
  • the method of Blumberg and coworkers is well suited for th selective preparation of sodium bicarbonate. Because the solubility of sodium bicarbonate in water is relatively lo ca. 16.4 . g/l at 60°C, sodium bicarbonate is precipitated from the aqueous phase and may easily be separated.
  • magnesi hydroxide is used for regenerating the amine, which result in dilute hydrochloric acid being obtained.
  • High carbon dioxide pressure is required to remove this acid from the process at a reasonable strength, which in turn involves difficulties, including a risk of corrosion.
  • the object of the present invention is to provide a novel process for preparing a solution of potassium bicarbonate and potassium carbonate suitable for recovering acid com ⁇ pounds.
  • potassium chloride dissolved in water is used as starting compound.
  • the carbonation is performed by liquid extraction, which comprises contacting the aqueous solution of potassium chloride with an organic solvent, essentially immiscible with water, used as extracting solution.
  • the solution the reaction product of carbon dioxide and an organic amine, which is insoluable in water.
  • the resulting potassium bicarbonate is not separated from the aqueous solution.
  • the dissolved potassiu bicarbonate is partly decomposed into potassium carbonate, carbon dioxide and water.
  • the reaction product of carbon dioxide and the organic amin used consists essentially of an amine hydrogen carbonate. Some amine carbonate may also be present. However, in the following, the term “amine hydrogen carbonate” will be used to designate said reaction product.
  • potassium bicarbona and potassium carbonate By keeping the aqueous solution suitably dilute with respec to its potassium ion concentration both potassium bicarbona and potassium carbonate will stay in solution.
  • the pH of t solution of potassium bicarbonate and potassium carbonate i between 8 and 9 and the solution is well suited for the washing of gases containing, for instance, nitrogen oxides and sulphur dioxide and sulphur trioxide. Thus, even the nitrogen oxides can be bound as potassium salts into a use ⁇ ful form.
  • the amine is regenerated (3) for a new extraction cycle (1 with calcium hydroxide.
  • Potassium chloride which is used as a starting compound, a well known substance in itself. Its solubility in water 56.7 g/100 g H20 at 60°C. The properties of potassium chloride and its production are described in the literatur e.g. in Encyclopedia of Chemical Technology, Kirk-Othmer 16 (1967) , pp. 388 -.
  • the amine used for the production of potassium bicarbonate in the process can be, for instance a secondary amine, suc as diisononylamine (DINA) or a product that is commerciall available under the trade mark "Amberlite LA-2". Its gener formula is
  • R., and R_ each independently stand for a straight or branched alkyl group consisting of 1 to 10 carbon atoms.
  • the molecular weight of the amine is preferably from 270 to 290.
  • the amine can also be a tertiary amine of the formula
  • R .,, R, and R- each independently stand for an alkyl group consisting of 1 to 10 carbon atoms.
  • a preferred tertiary amine is trioctylamine having the formula
  • amine is dissolved in a non-aqeous solvent (immiscible with water) , the boiling point of which is sufficiently high, preferably above 120 ⁇ C.
  • a non-aqeous solvent is, for instance, aliphatic hydrocarbons or aromatic hydrocarbons, such as toluene or xylene.
  • R, R- and R_ are as stated above.
  • potassium hydrogen carbonate (potassium bicarbonate) is obtained, and amine hydrogen chloride sta in the extraction solution.
  • the amine is regenerated by a suitable base, such as lime or slaked lime [CaO or Ca(OH) 2 respectively], magnesium oxide, magnesium hydroxide or magnesium carbonate and either ammonia dissolved in water, alkali hydroxide or alkali carbonate.
  • Potassium bicarbonate is to a certain extent decomposed in potassium carbonate in the aqueous solution.
  • the aqueous solution of potassium bicarbonate and potassiu carbonate produced as described above can be used for washing industrial exhaust gases, flue gases and other gases.
  • Potassium bicarbonate reacts with sulphur dioxide giving potassium sulphite.
  • potassium sulphate is obtained and the reaction of potassium bicarbonate and various nitrogen oxides results in potassium nitrate or potassium nitrite, respectively.
  • potassium chloride eg. sylvite
  • the obtained liquid is a more efficient washing solution than -the solution of K 2 S0 3 and KHSO,.
  • the nitrogen oxides are recovered as nitrates in th washing process, and they can be used as such as fertilize in addition to the potassium sulphate obtained in the process.
  • the potassium chloride to be used in the process is conduc into a container 1 together with water for dissolving the potassium chloride.
  • the amine hydrogen carbonate is, in its turn, produced in a stirred tank reactor 4 by feeding carbon dioxide into an amine solution. Reaction 4 takes place in the tank reactor:
  • Unreacted carbon dioxide is recycled to the tank 4 via a demister 21, which removes droplets from the gas.
  • the potassium chloride solution is filtered in a filter 2 and fed through an intermediate container 3 to an extractio column 5, 6 of mixer-settler type.
  • the amine hydrogen carbonate withdrawn from the tank reactor 4 is fed into the extractor 5, where the following reaction (No. 5) takes place:
  • the ratio E /R is 1.5 to 4, in particula 2 to 3, 5 extractions are enough.
  • the numerator E of the phase ratio stands for the flow of the extractant and the denominator R for the flow of the aqueous phase.
  • the aqueous phase and the organic phase are separated from each other after the extraction in the settling tank 6 and the extraction solvent is regenerated by feeding it into a mixing tank 7, in which the amine is regenerated, for instance with calcium hydroxide.
  • the aqueous solution of lime may be prepared by mixing calcium oxide into water in mixed tanks 8 and 9.
  • the temperature of the extract is about 40 to 50°C, while the regeneration is carried out at 60 to 80"C. Pressure is less than 0.5 atm above atmosphe pressure during the extraction.
  • the amine solution is separated from the calcium chloride, e.g. in a settling tank 10, and re ⁇ cycled to the tank reactor 4.
  • the aqueous solution mainly containing KHC0 3
  • the aqueous solution is upon wit drawal from the extraction column 5 and separation from th organic phase conducted to a intermediate container 11 pro vided with heating means for increasing its temperature.
  • the potassium carbonate solution is fed to a scrubber, or gas washer 13, in which the gases containing S0 2 , S0 3 and NO are washed with the aqueous solution.
  • the reactions that occur in the scrubber include the following:
  • the washing solution is circulated within the scrubber 13 through intermediate containers 14 and 15.
  • the scrubber 13 to be used in the process can be of any ordinary type, for example a tower, empty or packed, at the top equipped with high-pressure or spray nozzles.
  • the scrubber can also be a tower with baffles which by causing sudden changes in direction of the gas increase the efficiency of mass transfer.
  • a preferred type of scrubber is the gas washer known as the Venturi scrubber that opera ⁇ tes according to the co-current principle.
  • the aqueous solution containing K 2 S0 3 ⁇ K 2 S0 4 -KN0 2 -KN0 3 , can upon removal from the washer be evaporated and crystallized in an evaporating and crystallizing unit (16 - 20) comprising several containers provided with heating means as well as a dryer.
  • the crystallized mass obtained after separation is dryed and the K 2 S0_ and KNO, are oxidized to K 2 S0 4 and K 0 3 by blowing air into to the dryer 19, which can be of rotary dryer type.
  • a 4 molar aqueous solution of potassium bicarbonate was obtained from the liquid extraction, the yield being 99 %.
  • the toluene solution of the amine was regenerated with calcium hydroxide at 60 C C and recycled into the mixing tank
  • the produced solution of potassium bicarbonate was diluted with water to a concentration of about 2 moles/1. Said concentration corresponds to about 200 g of KHCO- per litre.
  • Flue gas from a coal-fired power plant containing 3000 mg/ S0 2 at a temperature of 140°C, was fed into the Venturi- washer 1.4, there meeting a flow of potassium bicarbonate solution at a concentration of 200 g KHC03/1.
  • the flow rates were :
  • the concentration of sulphur dioxide in the gas leaving th washer was below 140 mg/m .
  • the solution obtained from the washer contained potassium sulphite, potassium nitrite and potassium nitrate-,
  • the crystals were separated and the potassium sulphite and the potassium nitrite were oxidized to potassium sulphate and nitrate, respectively.
  • a toluene solution of diisononylamine (DINA) was prepared.
  • the concentration of the solution was 500 g DlNA/1.
  • the DI was then carbonated by conducting carbon dioxide gas into for 15 minutes under continuous mixing.
  • a solution -of sodium chloride was then prepared, at the concentration of 95 g/1. This solution was then shaken wit the above prepared solution of DINA and bicarbonate.
  • the ratio of the organic phase (eo) to the aqueous phase (ro) was 2:1.
  • the solution was shaken for 15 min. , cleared for 30 min. Analysis results: pH el- g/1 ro 6.8 57.1 rr 8.4 5.2 rr is the removed aqueous phase.
  • a 4 M solution of potassium chloride was prepared and shake as described above with DINA-bicarbonate.
  • the aqueous phase of the sodium bicarbonate contained precipitates. This is because the solubility of NaHCO- is only 40 g/1 and, consequently, some of the NaHCO, formed had precipitated into a separate phase.

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

La présente invention se rapporte à un procédé qui sert à produire une solution aqueuse de bicarbonate de potassium. Selon ledit procédé, une solution aqueuse d'un composé de potassium approprié est saturée de gaz carbonique, puis la phase aqueuse qui contient le bicarbonate de potassium est séparée. Selon la présente invention, on utilise du chlorure de potassium comme composé de départ et on effectue la carbonatation par extraction de liquide en mettant en contact la solution aqueuse de chlorure de potassion avec un solvant organique immiscible avec l'eau qui contient le produit de réaction d'une amine organique et de dioxyde de carbone. Le bicarbonate de potassium est laissé dans la solution, ce qui permet également la formation d'une certaine quantité de carbonate de potassium. La solution aqueuse ainsi préparée est destinée à être utilisée pour le lavage de gaz acides, tels que notamment des gaz d'évacuation industriels.
PCT/FI1988/000201 1987-12-21 1988-12-21 Procede de preparation d'une solution aqueuse contenant du bicarbonate de potassium et du carbonate de potassium et destinee a etre utilisee pour le lavage de gaz acides Ceased WO1989005777A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI875638A FI79474C (fi) 1987-12-21 1987-12-21 Foerfarande foer framstaellning av en vattenloesning som innehaoller kaliumbikarbonat och kaliumkarbonat och som laempar sig foer tvaett av sura gaser.
FI875638 1987-12-21

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WO1989005777A1 true WO1989005777A1 (fr) 1989-06-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2121971C1 (ru) * 1997-02-07 1998-11-20 Пермский государственный университет Способ получения бикарбоната натрия
CN102139893A (zh) * 2011-04-15 2011-08-03 太仓沪试试剂有限公司 一种碳酸钾的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347623A (en) * 1966-11-03 1967-10-17 Kali Chemie Ag Preparation of potassium bicarbonate
US4010243A (en) * 1975-11-28 1977-03-01 Owens-Illinois, Inc. Preparation for potassium bicarbonate from potassium halide
DE2940614C2 (de) * 1979-10-06 1982-09-16 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Herstellung von Natriumhydrogencarbonat und Chlorwasserstoff

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347623A (en) * 1966-11-03 1967-10-17 Kali Chemie Ag Preparation of potassium bicarbonate
US4010243A (en) * 1975-11-28 1977-03-01 Owens-Illinois, Inc. Preparation for potassium bicarbonate from potassium halide
DE2940614C2 (de) * 1979-10-06 1982-09-16 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Herstellung von Natriumhydrogencarbonat und Chlorwasserstoff

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2121971C1 (ru) * 1997-02-07 1998-11-20 Пермский государственный университет Способ получения бикарбоната натрия
CN102139893A (zh) * 2011-04-15 2011-08-03 太仓沪试试剂有限公司 一种碳酸钾的制备方法
CN102139893B (zh) * 2011-04-15 2013-04-10 太仓沪试试剂有限公司 一种碳酸钾的制备方法

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FI875638A0 (fi) 1987-12-21
FI79474B (fi) 1989-09-29
FI875638A7 (fi) 1989-06-22
FI79474C (fi) 1990-01-10

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