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WO2000066516A1 - Procede et dispositif servant a produire des engrais a partir de gaz de combustion contenant des oxydes de soufre - Google Patents

Procede et dispositif servant a produire des engrais a partir de gaz de combustion contenant des oxydes de soufre Download PDF

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Publication number
WO2000066516A1
WO2000066516A1 PCT/JP2000/002621 JP0002621W WO0066516A1 WO 2000066516 A1 WO2000066516 A1 WO 2000066516A1 JP 0002621 W JP0002621 W JP 0002621W WO 0066516 A1 WO0066516 A1 WO 0066516A1
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WO
WIPO (PCT)
Prior art keywords
exhaust gas
ammonia
gas
fertilizer production
potassium
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2000/002621
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English (en)
Japanese (ja)
Inventor
Masahiro Izutsu
Akihiko Maezawa
Ryoji Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ebara Corp
Original Assignee
Ebara Corp
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 Ebara Corp filed Critical Ebara Corp
Priority to AU38420/00A priority Critical patent/AU3842000A/en
Publication of WO2000066516A1 publication Critical patent/WO2000066516A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • 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
    • 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
    • B01D53/73—After-treatment of removed components

Definitions

  • the present invention relates to a method for producing fertilizer, and more particularly to a method and apparatus for producing fertilizer for producing potassium sulfate using exhaust gas containing sulfur oxides.
  • the exhaust gas containing nitrogen oxides is guided to an oxidation container, and the oxidation degree of nitrogen oxides contained in the gas is increased in the oxidation container.
  • potassium carbonate K 2 CO 3 , hereinafter potassium carbonate
  • potassium hydroxide KOH, potassium hydroxide
  • K2CO 3 potassium hydroxide
  • the sulfur oxides When this device is applied to an exhaust gas containing sulfur oxides, the sulfur oxides can be partially oxidized in an oxidation vessel, and some of them can remain as they are, and the carbon dioxide or caustic
  • the sulfur oxides are absorbed by the alkaline aqueous solution in which the sulfur is dissolved, and the sulfur oxides are converted to potassium sulfate (K 2 SO 4 , potassium sulfate) in the alkaline absorbing solution.
  • potassium hydroxide is produced by electrolysis of potassium chloride (KC1), and potassium carbonate is synthesized from potassium hydroxide and carbon dioxide. Since these reactants are produced by such a process that consumes electric power, the unit price is high, and therefore, the conventional technology using them has a problem that the operating cost is high.
  • the present invention provides a method for producing potassium sulfate from exhaust gas containing sulfur oxides. It is an object of the present invention to provide a fertilizer production method and a production apparatus capable of recovering fertilizer at low operating costs. Disclosure of the invention
  • an exhaust gas containing sulfur oxides is reacted with ammonium Nia and Anmoniumu sulfate [(NH 4) 2 S 0 4 , below, ammonium sulfate] to produce a reaction product containing, reaction
  • a method for producing fertilizer which comprises mixing a product with chlorinated water in water and recovering a sulfuric acid crystallization crystallized by the mixing.
  • the reaction between the exhaust gas and ammonia in this fertilizer production method can be performed by bringing the exhaust gas into contact with an absorption solution in which ammonia is dissolved.
  • an absorption solution in which ammonia is dissolved.
  • a gas absorber for bringing the exhaust gas into contact with an absorbing solution in which ammonia is dissolved, an introducing means for introducing the absorbing solution brought into contact with the exhaust gas in the gas absorber, and potassium chloride are introduced.
  • a mixed crystallizer having an introduction means, and water-based mixing (mixing via water) of the introduced absorbing solution and chlorinated acid to crystallize sulfuric acid.
  • a gas reactor having an exhaust gas inlet and an ammonia injection means for injecting ammonia or ammonia into water after mixing with water, and a product for recovering a reaction product generated in the gas reactor.
  • the present invention provides a fertilizer production apparatus having an introduction means for introducing, and wherein the introduced reaction product and chlorinated water are mixed in an aqueous system. Downstream of the product recovery device, there is an inlet for introducing the exhaust gas after the reaction product is collected, and the introduced exhaust gas is converted into at least one of ammonia, sulfate ion and sulfite ion.
  • the gas reactor can be provided with an electron beam irradiation device for irradiating the exhaust gas in the device with an electron beam.
  • a separator for separating the crystals of the sulfuric acid from the crystallizer can be provided by connecting to the mixed crystallizer.
  • An evaporative crystallizer for introducing the separated aqueous solution, evaporating the aqueous solution, and crystallizing the remaining compound can be provided subsequent to the separator.
  • potassium chloride is used instead of potassium carbonate or caustic potassium as a potassium source.
  • potassium chloride and naturally occurring as sylvite, or can kernal stone (or Kanari Tsu DOO, KC 1 ⁇ M g C 1 2 ⁇ 6 H 2 ⁇ ) also do we readily crystallized
  • caustic potash is produced by electrolysis of potassium chloride, and potassium carbonate is synthesized from caustic and carbon dioxide. It is available at a significantly lower price than power.
  • the aqueous solution of potassium chloride is neutral. Therefore, even if the exhaust gas is brought into contact with an aqueous solution in which chlorination is dissolved, the sulfur oxide in the exhaust gas cannot be efficiently absorbed. For this reason, in the conventional apparatus, simply replacing the aqueous solution of potassium carbonate or caustic force with the aqueous solution of chloride force cannot be an effective method for producing fertilizer from exhaust gas containing sulfur oxides.
  • the present inventors did not use a substance having potassium in the reaction for removing sulfur oxides from the exhaust gas, but used the reaction product generated by the removal reaction using another reactant to remove the sulfur oxide.
  • a method for producing potassium sulfate by reaction was studied, and an exhaust gas containing sulfur oxide was reacted with ammonia to produce a reaction product containing ammonium sulfate, and the reaction product was recovered. Chloride power After that, the fertilizer production method is to separate sulfuric acid.
  • reaction formula (1) shows that ammonium sulfate and potassium chloride NH 4 C 1, from potassium sulfate and potassium chloride in the reaction product, ) And potassium sulfate can be crystallized from the difference in solubility between the two.
  • the crystallized substance will contain ammonium chloride and ammonium sulfate, but since these ammonium salts are used as fertilizers, The precipitate can be used as fertilizer as it is.
  • the mother liquor after separation of the crystallized potassium sulfate is an aqueous solution mainly containing an ammonium salt such as salt salt and containing a small amount of sulfuric acid which cannot be completely crystallized. By evaporating and crystallizing again, a binary fertilizer containing ammoniacal nitrogen and natural lime is obtained.
  • Potassium sulfate is known as a fertilizer particularly suitable for tobacco and tea cultivation, but when used for such purposes, it is necessary to increase the purity of potassium sulfate.
  • One way to do this is to increase the ratio of potassium chloride to ammonium sulfate during the mixed crystallization process described above.In this case, the potassium component of potassium chloride and sulfuric acid flows out into the mother liquor. The percentage increases.
  • As a method of increasing the purity of potassium sulfate and suppressing the outflow of potassium components there is a method of dividing the mixed crystallization process into two stages. That is, in the first step, the ratio of potassium chloride to ammonium sulfate is kept low, and crude potassium sulfate having low purity is obtained as an intermediate crystal. After that, when the crude sulfuric acid was added to the chloride and the second stage of crystallization was performed, the ammonium salt mixed in the crude sulfuric acid was almost completely transferred to the mother liquor and the purity was high. Potassium sulf
  • the potassium chloride Before mixing with the ammonium sulfate-containing reaction product, the potassium chloride can be dissolved in water in a dissolving tank in advance and then mixed with the ammonium sulfate-containing reaction product. If a purification device is installed to remove impurities from the aqueous solution obtained by dissolution, raw materials such as crude potassium chloride and potassium rock salt can be used as a potassium chloride source.
  • reaction product containing ammonium sulfate As a method of producing a reaction product containing ammonium sulfate by reacting an exhaust gas containing sulfur oxides with ammonia, there is a method of bringing the exhaust gas into contact with an absorption solution in which ammonia is dissolved.
  • the reaction product is recovered as an aqueous solution in which ammonium sulfate is dissolved, and potassium chloride is dissolved in an aqueous solution in which ammonium sulfate is dissolved, or in a dilute aqueous solution obtained by adding water to the aqueous solution, whereby the reaction formula (1) is obtained.
  • a reaction can take place.
  • a method of producing ammonium sulfate by reacting an exhaust gas containing a sulfur oxide with ammonia there is a method of injecting ammonia into the exhaust gas.
  • a method of injecting ammonia there are a method of injecting ammonia gas, a method of spraying liquid ammonia, and a method of spraying ammonia after mixing ammonia with water.
  • the reaction product is converted into an aerosol containing ammonium sulfate, and the reaction product is recovered as a powder when, for example, a dry electrostatic precipitator is used as a product recovery device, and the product is recovered.
  • a dry electrostatic precipitator is used as the device, it is collected as an aqueous solution in which ammonium sulfate is dissolved.
  • an eclectic method is also possible in which the products after being removed from the dust collecting plate are transported by dissolving the products in water and in an aqueous solution state It is.
  • reaction product When the reaction product is recovered as an aqueous solution, the mixed crystallization process is as described above, but when the reaction product is recovered as a powder, the powder and potassium chloride are simultaneously dissolved in water.
  • the reaction of reaction formula (1) can be caused.
  • first dissolve potassium chloride in water as described above first dissolve potassium chloride in water as described above, The powder containing ammonium sulfate may be dissolved in the aqueous solution, or the powder containing ammonium sulfate may be dissolved in water, and the chlorination solution may be dissolved in the aqueous solution.
  • the powder containing potassium chloride and the ammonium sulfate may be separately dissolved in water, and the aqueous solutions may be mixed.
  • the recovered absorbent can be sent to a mixed crystallizer together with the ammonium sulfate recovered by the product recovery device.
  • the composition of the absorbing solution is adjusted according to the concentration of sulfur oxides and ammonia remaining in the exhaust gas entering the gas absorber.
  • the concentration of the aqueous solution supplied to the mixed crystallizer be as high as possible and the amount of water be small.
  • FIG. 1 is a process chart showing an example of embodying the fertilizer production device of the present invention.
  • FIG. 2 is a process chart showing another example of realizing the fertilizer production device of the present invention, and
  • FIG. 3 is a process diagram showing another example of realizing the fertilizer production device of the present invention.
  • FIG. 4 is a process chart showing still another example of realizing the fertilizer production device of the present invention. Preferred embodiments of the invention
  • FIG. 1 is a process chart showing an example of realizing the fertilizer production device of the present invention.
  • the exhaust gas 11 with a flow rate of 1,500 m 3 Zh (NTP) containing sulfur oxides of about 800 ppm generated from the heavy oil boiler 1 is cooled by the gas cooler 2.
  • NTP 1,500 m 3 Zh
  • the sulfur oxides in the exhaust gas 11 are absorbed into the absorption liquid 13 by being led to the gas absorber 3 and coming into gas-liquid contact with the absorption liquid 13 in which ammonium sulfite and ammonia are dissolved.
  • the absorption liquid 13 is circulated and used by the circulation pump 10, but a part is withdrawn and sent to the oxidizer 4, where the sulfite ions in the extracted liquid are oxidized to sulfate ions, and then mixed.
  • Sent to Crystallizer 6. There is an amount of about 7 kgZh as ammonium sulfate in this solution.
  • the crude potassium chloride 14 powder 8.1 kgZh is dissolved in 16.2 liters of industrial water 15 in a dissolution / purification unit 5 to remove impurities 17 and then purified.
  • the resulting aqueous solution 16 is sent to the mixed crystallizer 6 and mixed with the extracted water.
  • the mixed solution 18 extracted from the mixed crystallizer 6 is sent to the potassium sulfate separator 7, where potassium sulfate 19 crystallized in the mixed solution and about 7 kgZh crystals are separated.
  • the mother liquor 20 after the separation is sent to the evaporator and crystallizer 8, where the water is evaporated and concentrated, and crystals such as ammonium chloride and potassium sulfate are crystallized.
  • the concentrated liquid 21 in which the crystals are crystallized is sent to the binary fertilizer separator 9, and the powder and granules of the binary fertilizer 22 mainly composed of ammonium chloride and potassium sulfate crystals, about 7 kgZh, are collected. Is done.
  • FIG. 2 is a process chart showing another example of realizing the fertilizer recovery device of the present invention.
  • the exhaust gas 11 with a flow rate of 1,500 m 3 / h (NTP) containing approximately 800 ppm of sulfur oxides generated from the heavy oil boiler 1 is cooled by the gas cooler 2. After that, it is led to the gas reactor 23.
  • the ammonia 29 supplied from the ammonia storage tank 28 is mixed with the compressed air 31 by the gas mixer 30, and then supplied to the two-fluid nozzle 25 provided at the inlet of the gas reactor 23.
  • the mixture is mixed with industrial water 15 in the gas-liquid mixing chamber 5 and sprayed into the exhaust gas.
  • the exhaust gas is irradiated with an electron beam generated from an electron accelerator 24, and then guided to a dry-type electrostatic precipitator 26, where the powder generated in the exhaust gas is collected at about 7 kgZh, 27
  • the body is sent to the mixed crystallizer 6.
  • the crude potassium chloride powder (8.1 kg Zh) was dissolved in 16.2 liters / h of industrial water (15) in a dissolution purifier (5) to remove impurities (17), followed by mixed crystallization.
  • the powder 27 sent to the container 6 and collected by the electrostatic precipitator 26 is dissolved.
  • the mixture 18 thus produced is sent to the potassium sulfate separator 7, evaporator and crystallizer 8, and binary fertilizer separator 9 as in Fig. 1, and the potassium sulfate of about 7 kgZh 1.9 and Approximately 7 kg Zh of binary fertilizer 22 is recovered.
  • FIG. 3 is a process chart showing another example of realizing the fertilizer recovery device of the present invention.
  • the reaction product generated in 23 is collected by the wet electrostatic precipitator 26.
  • industrial water is sprayed, the reaction product is dissolved in the industrial water 15, and the aqueous solution 32 containing about 7 kgZh of ammonium sulfate is withdrawn. Is sent to the mixed crystallizer 6.
  • 8. lkg / h of crude potassium chloride powder was dissolved in 16.2 liters of industrial water 15 of Zh in a dissolution purifier 5 to remove impurities 17 and mixed crystallization. Sent to the vessel 6
  • FIG. 4 is a process chart showing another example of realizing the fertilizer recovery device of the present invention.
  • the exhaust gas containing about 800 ppm of sulfur oxides generated from the heavy oil boiler 1 passes through the gas cooler 2 and is sent to the gas reactor 23.
  • the ammonia 29 supplied from the ammonia storage tank 28 is mixed with the compressed air 31 by the gas mixer 30 and then supplied to the two-fluid nozzle 25 provided at the inlet of the gas reactor 23, In the gas-liquid mixing chamber of the fluid nozzle 25, it is mixed with industrial water 15 and then sprayed into the exhaust gas.
  • the gas reactor 23 is not irradiated with an electron beam.
  • the flue gas leaving the reactor 23 is led to the dry electrostatic precipitator 26, where the powder generated in the flue gas is collected at about 6 kg / h and sent to the mixed crystallizer 6, where the flue gas is Sent to inhaler 36.
  • the gas inhaler is provided with a circulating pump similar to that shown in Fig. 1. After a part of the absorbent used for circulation is extracted and sent to the oxidizer 38, The solution is sent to the mixed crystallizer 6 as an aqueous solution containing about 1 kg / h of ammonium sulfate.
  • the powder 27 and the oxidized absorbing solution 40 are mixed with the purified potassium chloride aqueous solution 16 as in FIGS. 1 to 3, and then mixed with the potassium sulfate separator 7. It is sent to the evaporative crystallizer 8 and the binary fertilizer separator 9 to recover about 7 kg / h of sulfuric acid 19 and about 7 kg / h of the binary fertilizer 22.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

Dispositif possédant un ensemble d'absorption (3) de gaz et servant à extraire du sulfate de potassium, ce qui consiste à mettre en contact un gaz de combustion avec un liquide d'absorption dans lequel est dissous de l'ammoniac. Ce dispositif possède également des moyens d'introduction permettant d'introduire le liquide d'absorption provenant de l'ensemble d'absorption (3), qui a absorbé le gaz de combustion, des moyens d'introduction servant à introduire du chlorure de potassium (16) et un mélangeur/cristalliseur (6) dans lequel le liquide d'absorption et le chlorure de potassium sont mélangés dans un milieu aqueux, de manière à cristalliser le sulfate de potassium. Dans un autre mode de réalisation, on peut injecter directement l'ammoniac dans le gaz de combustion et mélanger le produit réactionnel obtenu avec du chlorure de potassium dans un milieu aqueux contenu dans le mélangeur/cristalliseur. On peut utiliser ce dispositif, et un procédé mettant ce dernier en application, afin d'extraire du sulfate de potassium depuis un gaz de combustion au moyen de chlorure de potassium, ce qui ne représente qu'un coût de production limité.
PCT/JP2000/002621 1999-04-28 2000-04-21 Procede et dispositif servant a produire des engrais a partir de gaz de combustion contenant des oxydes de soufre Ceased WO2000066516A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38420/00A AU3842000A (en) 1999-04-28 2000-04-21 Method and apparatus for producing fertilizer from flue gas containing sulfur oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/122053 1999-04-28
JP12205399 1999-04-28

Publications (1)

Publication Number Publication Date
WO2000066516A1 true WO2000066516A1 (fr) 2000-11-09

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PCT/JP2000/002621 Ceased WO2000066516A1 (fr) 1999-04-28 2000-04-21 Procede et dispositif servant a produire des engrais a partir de gaz de combustion contenant des oxydes de soufre

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CN (1) CN1344236A (fr)
AU (1) AU3842000A (fr)
WO (1) WO2000066516A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020082915A (ko) * 2001-04-24 2002-11-01 김덕수 민물새우 가공식품
EP3368192A4 (fr) * 2015-10-27 2019-05-15 Marsulex Environmental Technologies Corporation Procédé et système pour éliminer du dioxyde de soufre à partir de gaz de carneau

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2737825A1 (fr) * 2011-04-20 2012-10-20 Carbon Solutions Incorporated Conversion de gaz corrosif en engrais a base de sulfate ou de phosphate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5018392A (fr) * 1973-06-22 1975-02-26
EP0326686A1 (fr) * 1987-12-10 1989-08-09 Ebara Corporation Méthode de traitement de gaz d'échappement par irradiation avec des faisceaux électroniques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5018392A (fr) * 1973-06-22 1975-02-26
EP0326686A1 (fr) * 1987-12-10 1989-08-09 Ebara Corporation Méthode de traitement de gaz d'échappement par irradiation avec des faisceaux électroniques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020082915A (ko) * 2001-04-24 2002-11-01 김덕수 민물새우 가공식품
EP3368192A4 (fr) * 2015-10-27 2019-05-15 Marsulex Environmental Technologies Corporation Procédé et système pour éliminer du dioxyde de soufre à partir de gaz de carneau

Also Published As

Publication number Publication date
CN1344236A (zh) 2002-04-10
AU3842000A (en) 2000-11-17

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