CN1344236A - Method and appts. for producing fertilizer from flue gas contg. sulfur oxides - Google Patents
Method and appts. for producing fertilizer from flue gas contg. sulfur oxides Download PDFInfo
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- CN1344236A CN1344236A CN 00805292 CN00805292A CN1344236A CN 1344236 A CN1344236 A CN 1344236A CN 00805292 CN00805292 CN 00805292 CN 00805292 A CN00805292 A CN 00805292A CN 1344236 A CN1344236 A CN 1344236A
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- 238000000034 method Methods 0.000 title claims abstract description 35
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000003337 fertilizer Substances 0.000 title claims description 43
- 229910052815 sulfur oxide Inorganic materials 0.000 title abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000003546 flue gas Substances 0.000 title abstract description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 97
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000007789 gas Substances 0.000 claims abstract description 84
- 239000001103 potassium chloride Substances 0.000 claims abstract description 48
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 48
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 43
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 41
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 41
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 41
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 30
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 33
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- 239000006096 absorbing agent Substances 0.000 claims description 13
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010894 electron beam technology Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000011027 product recovery Methods 0.000 claims description 9
- 239000002912 waste gas Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011591 potassium Substances 0.000 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 39
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- 239000000843 powder Substances 0.000 description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 235000011118 potassium hydroxide Nutrition 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 235000011181 potassium carbonates Nutrition 0.000 description 10
- 239000000428 dust Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000008235 industrial water Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- -1 sulfurous acid ions Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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
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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
An method and apparatus for recovering potassium from flue gas containing sulfur oxides by using the low-cost potassium chloride. The apparatus has a gas absorbing unit wherein a flue gas is contacted with an absorption liquid having ammonia dissolved therein, an introduction means which introduces an absorption liquid from the gas absorbing unit, which has absorbed the flue gas, an introduction means which introduces potassium chloride, and a mixer/crystallizer wherein the introduced absorption liquid and potassium chloride are admixed in an aqueous system to thereby crystallize potassium sulfate. Alternatively, ammonia may be directly injected into the flue gas, and the resulting reaction product may be admixed with potassium chloride in an aqueous system in the mixer/crystallizer.
Description
Technical Field
The invention relates to a method for producing fertilizer, in particular to a method and a device for producing fertilizer by using sulfur oxide-containing waste gas to produce potassium sulfate.
Technical Field
As an apparatus for recovering a fertilizer containing potassium component from an exhaust gas, there has been proposed a method of introducing an exhaust gas containing nitrogen oxide into an oxidation vessel, increasing the oxidation degree of nitrogen oxide contained in the gas in the oxidation vessel, and then mixing the gas with potassium carbonate (K) dissolved therein2CO3Hereinafter, referred to as potassium carbonate) or potassium hydroxide (KOH, hereinafter, referred to as caustic potash) to absorb nitrogen oxides. In such an apparatus, potassium nitrate can be crystallized by recycling the alkaline absorption liquid, partially withdrawing the alkaline absorption liquid, and evaporating water from the withdrawn absorption liquid (hereinafter referred to as "withdrawn liquid").
When this apparatus is used for a sulfur oxide-containing exhaust gas, a part of the sulfur oxide is oxidized in the oxidation vessel to a higher degree, and the other part is absorbed by an alkaline aqueous solution in which the above-mentioned potassium carbonate or caustic potash is dissolved, as is the case with the nitrogen oxide, and the sulfur oxide is converted into potassium sulfate (K) in an alkaline absorption liquid2SO4Hereinafter referred to as potassium sulfate).
However, in general, caustic potash is produced by electrolytic potassium chloride (KCl, hereinafter referred to as potassium chloride), while potassium carbonate is synthesized from caustic potash and carbon dioxide, and these reactants are produced by a power-consuming process, and therefore, the unit price is high, so that the conventional techniques using these methods have a problem of high running costs.
In view of the above-described conventional techniques, an object of the present invention is to provide a method and an apparatus for producing a fertilizer capable of recovering potassium sulfate from sulfur oxide-containing exhaust gas with low running cost.
Disclosure of Invention
Namely, the present invention provides a method for producing a fertilizer, characterized by reacting an exhaust gas containing sulfur oxides with ammonia to produce a fertilizer containing ammonium sulfate [ (NH)4)2SO4Hereinafter referred to as ammonium sulfate]The reaction product of (3), mixing the reaction product with potassium chloride in water, and recovering crystallized sulfuric acid by the mixingAnd (4) potassium.
The reaction of the exhaust gas with ammonia in the fertilizer production process may be carried out by contacting the exhaust gas with an absorption liquid in which ammonia is dissolved. In addition, ammonia or a mixture of ammonia and water may be injected into the exhaust gas as it is, and in this case, the exhaust gas may be irradiated with an electron beam before or after the injection of ammonia into the exhaust gas.
Further, the present invention provides a fertilizer production apparatus comprising a gas absorber for bringing exhaustgas into contact with an absorbing liquid containing ammonia dissolved therein, an introducing means for introducing the absorbing liquid in the gas absorber after the contact with the exhaust gas, and a mixed crystallizer for introducing potassium chloride into the gas absorber, wherein the introduced absorbing liquid and potassium chloride are mixed in an aqueous system (mixed with water) to crystallize potassium sulfate.
The present invention also provides a fertilizer production apparatus comprising a gas reactor having a waste gas inlet and an ammonia injection means for injecting ammonia or ammonia mixed with water into waste gas, a product recovery means for recovering a reaction product produced in the gas reactor, and a mixed crystallizer for crystallizing potassium sulfate, wherein the mixed crystallizer comprises an introduction means for introducing the reaction product recovered by the product recovery means and an introduction means for introducing potassium chloride, and the introduced reaction product and potassium chloride are mixed in an aqueous system. A gas absorber having an inlet for introducing the exhaust gas from which the reaction product is recovered and for bringing the introduced exhaust gas into contact with an absorbent containing dissolved therein at least one of ammonia, sulfate ions and sulfite ions may be provided downstream of the product recovery apparatus, and the mixed crystallizer may be provided with an introducing means for introducing the absorbent in the gas absorber into contact with the exhaust gas.
In addition, these fertilizer production apparatuses may be provided with a separator connected to the mixer-crystallizer for separating potassium sulfate crystals from the mixer-crystallizer, and an evaporator-crystallizer for introducing the aqueous solution after the potassium sulfate is separated by the separator, evaporating the aqueous solution, and crystallizing the residual compounds, the evaporator-crystallizer being connected to the separator.
The above is the basic content of the present invention, and the details are described further below.
In the potassium source in the present invention, potassium chloride is used instead of potassium carbonate or caustic potash. In general, potassium chloride can be produced naturally as a sylvine salt or from carnallite (KCl. MgCl)2·6H2O) is crystallized and precipitated. As previously mentioned, because caustic potash is produced by electrolysis of potassium chloride, potassium carbonate is formed from caustic potash and dioxygenThe potassium chloride is synthesized by carbon, so the potassium chloride can be obtained at a remarkably lower price compared with potassium carbonate and caustic potash.
However, since the aqueous solution of potassium chloride is neutral, even if the exhaust gas comes into contact with the aqueous solution in which potassium chloride is dissolved, sulfur oxides in the exhaust gas cannot be absorbed efficiently. Therefore, it is impossible to effectively produce a fertilizer from a sulfur oxide-containing waste gas by merely replacing the aqueous solution of potassium carbonate or caustic potash with an aqueous solution of potassium chloride in the conventional apparatus.
Therefore, the present inventors have studied a method for producing potassium sulfate by reacting a reaction product produced by a removal reaction using another reactant without using a substance having potassium in the reaction for removing sulfur oxides in exhaust gas with potassium chloride, the method comprising reacting an exhaust gas containing sulfur oxides with ammonia to produce a reaction product containing ammonium sulfate, recovering the reaction product, mixing the reaction product with potassium chloride, and separating potassium sulfate.
When the reaction product containing ammonium sulfate and potassium chloride are dissolved in water together, potassium sulfate and ammonium chloride (NH) are produced from ammonium sulfate and potassium chloride in the reaction product by the following reaction formula (1)4Cl, hereinafter referred to as ammonium chloride), potassium sulfate can be crystallized out because of the difference in solubility between the two.
When the potassium sulfate thus crystallized is separated, potassium sulfate can be obtained.
Potassium chloride, which is a raw material of caustic potash and potassium carbonate as described above, and ammonia can be inexpensively synthesized from nitrogen in the air, natural gas, and the like, and thus potassium sulfate can be produced less expensively than the prior art using caustic potash and potassium carbonate.
In the mixed crystallization process, when the ratio of potassium chloride to ammonium sulfate is small, ammonium chloride and ammonium sulfate are contained in the crystallized product. Since these ammonium salts can be used as fertilizers, the crystallized products can be directly used as fertilizers. The mother liquor from which the crystallized potassium sulfate is separated contains an ammonium salt such as ammonium chloride as a main component and contains a little potassium sulfate which is not crystallized, and when water is distilled off from the mother liquor and then crystallized, a binary fertilizer containing ammoniacal nitrogen and potassium components is obtained.
It is known that potassium sulfate is most suitable as a fertilizer for growing tobacco and tea, but when used for such applications, the purity of potassium sulfate must be increased. Therefore, as one method, the ratio of potassium chloride to ammonium sulfate may be increased in the above-mentioned mixed crystallization process, but the ratio of potassium chloride to potassium sulfate in the mother liquor is increased. As a method for increasing the purity of potassium sulfate and suppressing the outflow of potassium components, there is a method in which the mixed crystallization process is divided into two stages. That is, in the first stage, the ratio of potassium chloride to ammonium sulfate is reduced to a small extent to obtain crude potassium sulfate having a low purity as an intermediate crystallized product, and then potassium chloride is added to the crude potassium sulfate to conduct crystallization in the second stage, whereby the ammonium salt mixed in the crude potassium sulfate is almost completely transferred to the mother liquor to obtain potassium sulfate having a high purity.
The potassium chloride may be dissolved in water in a dissolution tank before being mixed with the reaction product containing ammonium sulfate, and then mixed with the reaction product containing ammonium sulfate. Further, if a purification apparatus is provided 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 the potassium chloride source.
As a method for producing a reaction product containing ammonium sulfate by reacting an exhaust gas containing sulfur oxides with ammonia, there is a method of bringing an exhaust gas into contact with an absorbent containing ammonia dissolved therein. In this method, the reaction of the reaction formula (1) can be carried out by recovering the reaction product as an aqueous solution in which ammonium sulfate is dissolved, and adding potassium chloride to the aqueous solution in which the ammonium sulfate is dissolved, or adding water to the aqueous solution to dissolve the reaction product to form a diluted aqueous solution.
Further, as a method for producing ammonium sulfate by reacting sulfur oxide-containing exhaust gas with ammonia, there is a method for injecting ammonia into exhaust gas. As the method of injecting ammonia, there are a method of injecting ammonia gas, a method of spraying liquid ammonia, and a method of mixing ammonia with water and spraying and injecting. The recovery rate of sulfur oxides in the flue gas can also be improved by irradiating electron beams before or after ammonia injection. In these methods, the reaction product is an ammonium sulfate-containing aerosol, and the reaction product is recovered as a powder when a product recovery device such as a dry electric dust collector is used. When a product recovery device such as a wet electric dust collector is used, the product is recovered as an aqueous solution in which ammonium sulfate is dissolved. In addition, when the reaction product in the electric dust collector is recovered in the form of powder, the product scattered from the dust collecting plate may be dissolved in water and then transported in the form of an aqueous solution.
When the reaction product is recovered as an aqueous solution, the mixed crystallization process is as described above. When the powder is recovered, the powder and potassium chloride are dissolved in water at the same time, and the reaction of the reaction formula (1) can be caused. In addition, as described above, the potassium chloride may be dissolved in water to dissolve the ammonium sulfate-containing powder in the aqueous solution. It is also possible to dissolve the ammonium sulfate-containing powder in water and then dissolve potassium chloride in the aqueous solution.
Alternatively, potassium chloride and the ammonium sulfate-containing powder may be dissolved in water, respectively, and these aqueous solutions may be mixed.
When the electron beam irradiation isnot performed or the dose of the electron beam is small, the generation efficiency of ammonium sulfate is low, and sulfur oxide or injected ammonia remains in the exhaust gas in some cases. In this case, a gas absorber is provided, and the exhaust gas from which the reaction product is recovered is brought into contact with an absorbing solution in which ammonia, sulfate ions, sulfite ions, or the like is dissolved, whereby sulfur oxide or ammonia remaining in the exhaust gas is absorbed in the absorbing solution, and these can be recovered as ammonium sulfate. The collected absorption liquid may be sent to a mixed crystallizer together with ammonium sulfate collected by the product collection device. The composition of the absorption liquid is adjusted according to the concentration of sulfur oxides and ammonia remaining in the exhaust gas entering the gas absorber.
In the mixed crystallizer, when the concentration of the supplied aqueous solution is low, the apparatus for evaporating water contained in the aqueous solution is too large, and the energy of steam or the like required for the apparatus is also increased. Therefore, the concentration of the aqueous solution supplied to the mixing crystallizer is preferably as high as possible and the water content is preferably small.
In the case of a dry electric precipitator for a product recovery apparatus, when a gas absorber is provided downstream thereof, most of the ammonium sulfate is recovered as powder in the dry electric precipitator, and therefore the moisture content of the absorption liquid for recovering ammonium sulfate in the gas absorber does not exceed the minimum moisture content required for dissolving and recovering the total ammonium sulfate (powdery ammonium sulfate + ammonium sulfate in the absorption liquid). Therefore, the mixing crystallizer only supplies the minimum water content, and the device for evaporating the water content in the mixing crystallizer and the energyrequired by the device can be minimized.
Brief description of the drawings
FIG. 1 is a process flow diagram showing an embodiment of a fertilizer production apparatus of the present invention.
FIG. 2 is a process flow diagram showing another embodiment of the fertilizer production apparatus of the present invention.
FIG. 3 is a process flow diagram showing another embodiment of the fertilizer production apparatus of the present invention.
FIG. 4 is a process flow diagram showing another embodiment of the fertilizer production apparatus of the present invention.
Best mode for carrying out the invention
Embodiments of the present invention are described in detail below with reference to the accompanying drawings.
FIG. 1 is a process flow diagram showing an embodiment of a fertilizer production apparatus of the present invention.
In FIG. 1, a flow rate 150 generated by a heavy oil boiler 10m3(NTP) and a flue gas 11 containing about 800ppm of sulfur oxides are cooled in a gas cooler 2, introduced into a gas absorption tower 3, and brought into gas-liquid contact with an absorption liquid 13 in which ammonium sulfite and ammonia are dissolved, whereby the sulfur oxides in the flue gas 11 are absorbed by the absorption liquid 13. The absorption liquid 13 is circulated by the circulation pump 10, but a part thereofThe sulfurous acid ions in the extract are oxidized by sulfuric acid ions and then sent to a mixed crystallizer 6. There was about 7kg/h of ammonium sulfate in the solution. On the other hand, 8.1 kg/hr of crude potassium chloride 14 powder was dissolved in 16.2L/hr of industrial water 15 in the dissolution and purification apparatus 5, and after removing impurities 17, the solution was sent to the mixing crystallizer 6 as a purified aqueous solution 16 and mixed with the extract. The mixed liquid 18 withdrawn from the mixed crystallizer 6 is sent to a potassium sulfate separator 7, and approximately 7kg/h of crystals of potassium sulfate 19 crystallized in the mixed liquid are separated. The separated mother liquor 20 is sent to an evaporation crystallizer 8, and after water is evaporated, crystals such as ammonium chloride and potassium sulfate are concentrated and precipitated. The concentrated solution 21 from which crystals were crystallized was sent to a binary fertilizer separator 9, and the powdery particles of the binary fertilizer 22 mainly containing ammonium chloride and potassium sulfate crystals were recovered at about 7 kg/h.
FIG. 2 is a process flow diagram showing another embodiment of the fertilizer recovery apparatus of the present invention.
In FIG. 2, the heavy oil boiler 1 generates a flow rate of 1500m3(NTP) and a waste gas 11 containing about 800ppm of sulfur oxide are cooled in a gas cooler 2 and then introduced into a gas reactor 23. The ammonia 29 supplied from the ammonia storage tank 28 is mixed with compressed air 31 in a gas mixer 30, supplied to the two-fluid nozzle 25 provided at the inlet of the gas reactor 23, mixed with the process water 15 in the gas-liquid mixing chamber of the two-fluid nozzle 25, and sprayed into the exhaust gas. After the exhaust gas is irradiated with an electron beam generated by an electron accelerator 24, the exhaust gas is introduced into a dry electric dust collector 26, about 7kg/h of powder generated in the exhaust gas is collected, and the powder is sent to a mixer-crystallizer 6 through a duct 27. On the other hand, 8.1kg/h of the powder of the crude potassium chloride 14 was dissolved in 16.2L/h ofthe industrial water 15 in the dissolution and purification unit 5, and after removing the impurities 17, the solution was sent to the mixed crystallizer 6 to dissolve the powder 27 collected by the electric dust collector 26.
The mixed solution 18 thus obtained is sent to a potassium sulfate separator 7, an evaporation crystallizer 8, and a binary fertilizer separator 9, as in FIG. 1, and about 7 kg/hr of potassium sulfate 19 and about 7 kg/hr of binary fertilizer 22 are recovered as powder particles.
FIG. 3 is a process flow diagram showing another embodiment of the fertilizer recovery apparatus of the present invention.
In FIG. 3, the flow rate of the heavy oil boiler 1 is 1500m3(NTP) until the electron beam irradiation was performed, the exhaust gas 11 containing about 800ppm of sulfur oxides was the same as that shown in FIG. 2. However, in this figure, the reaction product generated in the reactor 23 is collected by the wet electric dust collector 26. In the wet electric dust collector 26, the industrial water is sprayed, the reaction product is dissolved in the industrial water 15, and the aqueous solution 32 containing about 7kg/h ammonium sulfate is drawn out and sent to the mixing crystallizer 6. On the other hand, in the case of a liquid,8.1 kg/hr of crude potassium chloride 14 powder was dissolved in 16.2L/hr of industrial water 15 in a dissolution and purification apparatus 5, and after removing impurities 17, the solution was sent to a mixer-crystallizer 6 and mixed with the extract 32.
The mixed solution 18 thus obtained is sent to a potassium sulfate separator 7, an evaporation crystallizer 8, and a binary fertilizer separator 9, as in FIG. 1, and about 7 kg/hr of potassium sulfate 19 and about 7 kg/hr of binary fertilizer 22 are recovered as powder particles.
FIG. 4 is a process flow diagram showing still another embodiment of the fertilizer recovery apparatus of the present invention.
In fig. 4, as in the case of fig. 2 and 3, the exhaust gas containing about 800ppm of sulfur oxides generated by the heavy oil boiler 1 is sent to the gas reactor 23 through the gas cooler 2, and the ammonia 29 supplied from the ammonia storage tank 28 is mixed with the compressed air 31 in the gas mixer 30, supplied to the two-fluid nozzle 25 provided at the inlet of the gas reactor 23, mixed with the process water 15 in the gas-liquid mixing chamber of the two-fluid nozzle 25, and then sprayed into the exhaust gas. But the gas reactor 23 does not irradiate the electron beam. The exhaust gas discharged from the reactor 23 was introduced into a dry electric dust collector 26, and about 6kg/h of powder generated in the exhaust gas was collected and sent to the mixing crystallizer 6. The exhaust gas is sent to a gas suction device 36, which is not shown in the figure but is provided with a circulation pump as in fig. 1, and a part 40 of the absorption liquid to be recycled is pumped out and sent to an oxidizer 38, and is sent to the mixing crystallizer 6 as an aqueous solution containing about 1kg/h ammonium sulfate.
In the mixed crystallizer, as in FIGS. 1 to 3, the powder 27 and the oxidized absorption liquid 40 are mixed with the purified potassium chloride aqueous solution 16, and then sent to the potassium sulfate separator 7, the evaporation crystallizer 8, and the binary fertilizer separator 9, to recover about 7 kg/hr of potassium sulfate 19 and about 7 kg/hr of binary fertilizer 22.
Claims (10)
1. A process for producing a fertilizer, characterized in that a sulfur oxide-containing waste gas is reacted with ammonia to produce a reaction product containing ammonium sulfate, which is ammonium sulfate, and the reactionproduct is mixed with potassium chloride in an aqueous system to recover potassium sulfate which is crystallized.
2. A method for producing a fertilizer as set forth in claim 1, wherein the reaction of the exhaust gas with ammonia is carried out by bringing the exhaust gas into contact with an absorbent containing dissolved ammonia.
3. A method for producing a fertilizer according to claim 1, wherein the reaction of the exhaust gas with ammonia is carried out by injecting ammonia directly into the exhaust gas or by mixing ammonia with water and injecting the mixture.
4. A method for producing a fertilizer as set forth in claim 3, wherein the exhaust gas is subjected to electron beam irradiation before or after the ammonia is injected into the exhaust gas.
5. A fertilizer production apparatus comprising a gas absorber for bringing exhaust gas into contact with an absorbing liquid containing ammonia dissolved therein, and a mixed crystallizer equipped with an introducing means for introducing the absorbing liquid into the gas absorber and contacting the exhaust gas and an introducing means for introducing potassium chloride, wherein the introduced absorbing liquid and potassium chloride are mixed in an aqueous system to crystallize potassium sulfate.
6. A fertilizer apparatus for producing, characterized by having:
the device comprises a gas reactor having an exhaust gas inlet and an ammonia injection means for injecting ammonia into the exhaust gas or mixing ammonia with water and injecting the mixture, a product recovery device for recovering a reaction product produced in the gas reactor, and a mixed crystallizer provided with an introduction means for introducing the reaction product recovered by the product recovery device and an introduction means for introducing potassium chloride, wherein the introduced reaction product and potassium chloride are mixed in an aqueous system to crystallize potassium sulfate.
7. A fertilizer production apparatus as set forth in claim 6 wherein a gas absorber having an inlet for introducing the exhaust gas after recovery of the reaction product and contacting the introduced exhaust gas with an absorbent containing at least one of ammonia, sulfate ions and sulfite ions dissolved therein is provided downstream of the product recovery unit, and the mixed crystallizer is provided with an introducing means for introducing the absorbent into the gas absorber after contacting the exhaust gas.
8. A fertilizer production apparatus as set forth in claim 6 or 7, characterized in that said gas reactor is provided with an electron beam irradiation means for irradiating an electron beam to the exhaust gas in the reactor.
9. A fertilizer production apparatus as set forth in claim 5, 6, 7 or 8, wherein a separator is connected to said mixer-crystallizer for separating potassium sulfate crystals obtained by said mixer-crystallizer.
10. A fertilizer production apparatus as set forth in claim 9, wherein an evaporation crystallizer is provided for introducing the aqueous solution from which the potassium sulfate is separated by said separator, evaporating the aqueous solution, and crystallizing and precipitating residual compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12205399 | 1999-04-28 | ||
| JP122053/99 | 1999-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1344236A true CN1344236A (en) | 2002-04-10 |
Family
ID=14826456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00805292 Pending CN1344236A (en) | 1999-04-28 | 2000-04-21 | Method and appts. for producing fertilizer from flue gas contg. sulfur oxides |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1344236A (en) |
| AU (1) | AU3842000A (en) |
| WO (1) | WO2000066516A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103547550A (en) * | 2011-04-20 | 2014-01-29 | 苏尔瓦里斯股份有限公司 | Conversion of acid gas to sulphate or phosphate-based fertilizers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020082915A (en) * | 2001-04-24 | 2002-11-01 | 김덕수 | Processed Freshwater Prawn Food |
| US10046272B2 (en) * | 2015-10-27 | 2018-08-14 | Marsulex Environmental Technologies, Corp. | Process and system for removing sulfur dioxide from flue gas |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5018392A (en) * | 1973-06-22 | 1975-02-26 | ||
| JPH0640945B2 (en) * | 1987-12-10 | 1994-06-01 | 株式会社荏原製作所 | Radiation irradiation exhaust gas treatment method |
-
2000
- 2000-04-21 WO PCT/JP2000/002621 patent/WO2000066516A1/en active Application Filing
- 2000-04-21 CN CN 00805292 patent/CN1344236A/en active Pending
- 2000-04-21 AU AU38420/00A patent/AU3842000A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103547550A (en) * | 2011-04-20 | 2014-01-29 | 苏尔瓦里斯股份有限公司 | Conversion of acid gas to sulphate or phosphate-based fertilizers |
| CN103547550B (en) * | 2011-04-20 | 2016-01-20 | 苏尔瓦里斯股份有限公司 | Sour gas is to the conversion of vitriol base manure material or phosphate base fertilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000066516A1 (en) | 2000-11-09 |
| AU3842000A (en) | 2000-11-17 |
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