CN1004258B - Process for removing gaseous sulfur compunds, such as sulfur dioxide, from flue gases of furnace - Google Patents
Process for removing gaseous sulfur compunds, such as sulfur dioxide, from flue gases of furnace Download PDFInfo
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- CN1004258B CN1004258B CN85107964.4A CN85107964A CN1004258B CN 1004258 B CN1004258 B CN 1004258B CN 85107964 A CN85107964 A CN 85107964A CN 1004258 B CN1004258 B CN 1004258B
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- stove
- flue gas
- sulfur dioxide
- carbonate
- calcium
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000003546 flue gas Substances 0.000 title claims description 56
- 239000011593 sulfur Substances 0.000 title abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 7
- 230000008569 process Effects 0.000 title description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000007921 spray Substances 0.000 claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000292 calcium oxide Substances 0.000 abstract description 15
- 238000002485 combustion reaction Methods 0.000 abstract description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000395 magnesium oxide Substances 0.000 abstract description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 abstract description 4
- 239000001095 magnesium carbonate Substances 0.000 abstract description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 239000000428 dust Substances 0.000 description 7
- 239000004579 marble Substances 0.000 description 6
- 238000007667 floating Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 235000010261 calcium sulphite Nutrition 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LWNKHILEJJTLCI-UHFFFAOYSA-J calcium;magnesium;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mg+2].[Ca+2] LWNKHILEJJTLCI-UHFFFAOYSA-J 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 this Chemical compound 0.000 description 1
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
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/464—Sulfates of Ca from gases containing sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Geology (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
- Chimneys And Flues (AREA)
Abstract
The present invention relates to a method for removing sulfur dioxide from effluent gases of a stove. In the present invention which is on the basis of and superior to the original techniques, powdery oxides or the carbonate of calcium carbonate and magnesium carbonate are added to the stove (1) besides fuels (4) containing sulfur and gases (5) containing oxygen. The powdery oxides or the carbonate of calcium carbonate and magnesium carbonate are added by a slightly excessive amount according to a corresponding proportion to the amount of sulfur dioxide in a combustion chamber; water is respectively sprayed into the effluent gases which come into the combustion chamber to enter a separator (2) and contain calcium oxide or magnesium oxide. The present invention has another method which can be selected that the powdery oxides [6+[']] are directly added to the effluent gases leaving the stove (1).
Description
The invention relates to from combustion of sulfur fuel, remove gaseous sulphide in the flue gas of the stove of coal or oil, as the method for sulfur dioxide.
Formerly just know that the combustion chamber that calcium oxide, calcium carbonate or some other acid compound can be added to stove reduces the content of sulfur dioxide in the flue gases of furnace.In a fluid bed stove that has a circulation fluidized bed, when furnace maneuver within the temperature range that is suitable for most chemical reaction, promptly 800-1000 ℃ the time, might adopt to add the amount of sulfur dioxide that contains that calcium reduces flue gas and reach 90%.Sulfur dioxide just is absorbed and forms gypsum and stay on the stove with floating dust like this.
On other stove, when being necessary to adopt and above-mentioned higher temperature.Because＜〉relation, the time of staying of additive can expect that reducing sulfur dioxide of flue gases content is about 50% very in short-term, and in fact still very low or less, therefore this technology can not apply to such stove on commercial scale.
On the other hand, the various absorption techniques of also known employing outside stove reduce the content of sulfur dioxide of flue gases, and this technology itself is known, promptly is so-called spray-on process or semidry method, and in this method, flue gas is left stove and is imported in the separate reactor.Simultaneously, by special nozzle calcium hydroxide slurry being sprayed into droplet enters in this reactor.This reactor generally is bigger container, and the speed of flue gas can reduce therein, sprays to the bottom and slurries are tops of container from then on.The about 50-80 of temperature ℃ of reactor at this moment, the spraying that control calcium hydroxide slurry this moment is crucial, and this is because excessive drop can become liquid and stay reactor bottom.The denseness of calcium hydroxide slurry should remain on such level, promptly the heat of flue gas can will enter the water evaporates of reactor go out, thereby adsorbed product can be reclaimed with the form of dry powder.Adopt this technology might remove 90% sulfur dioxide, but the shortcoming of this technology is a spray nozzle clogging, needs extra preparation and the proportioner that increases calcium hydroxide, (these can increase investment) and the problem that when spraying, has control drop size.
The purpose of this invention is to provide and a kind ofly from the flue gas of stove, remove gaseous sulphide, method as sulfur dioxide, this method is to change gaseous sulphide into solid-state sulfide, and can easily separate it from the * body, so this is a kind of simple economy is removed gaseous sulphide again effectively from flue gases of furnace a method.
Principal character of the present invention is seen claim.
The method according to this invention can be reacted with gaseous sulphide a kind of, particularly can join in this technology respectively with the compound of sulfur dioxide reaction and water and go, so can avoid the preparation of slurries, storage * charging concrete grammar.
A, except adding sulfurous fuels (4) and oxygen-containing gas (5) in the stove, the compound that also pulverous alkali metal oxide and/or alkaline earth oxide and/or * carbonate (6) one classes can be changed corresponding oxide in stove adds in the stove (1), also above-mentioned oxide powder can be added in the flue gas that contains sulfur dioxide that discharge from stove.
B, be water and/or steam to join respectively to go in the stove and/or join in the flue gas to go, be hydroxide so that make oxygenate conversion, and react with sulfur dioxide, last
C, solids, promptly contain the sulfate of alkali metal or alkaline-earth metal, may also have sulphite from gas, to separate.
Basic thought of the present invention is such, promptly from removing the viewpoint of sulfur dioxide, the oxide of calcium and magnesium, be inactive, only ability available water and/or steam make its activation in flue gas, and make it be converted into corresponding hydroxide, and react with sulfur dioxide, thereby form the sulfate/sulphite mixture of solid, this mixture can be borrowed physical separation method afterwards, effectively removes from flue gas.
The Powdered oxidation in the adding stove combustion chamber and/or the amount of carbonate are the sulfur contents according to flue gas, the amount that promptly adds alkali metal and/or alkaline-earth metal at least should be with suitable according to the mole number of sulphur in the reaction equation, but preferably high than the desired amount of reaction.Because the oxide and/or the carbonate powder that add are to enter the combustion chamber respectively, or this oxide directly adds in the flue pipe and goes, do not need to add with the slurries form by nozzle, therefore the obstruction of nozzle and extra preparation slurries and proportioner all can omit, on the contrary, add entry by nozzle and steam is uncomplicated and easy.
Water or steam are joined in the flue gas, and this operation is actually and carries out in 50-800 ℃ of temperature range, and the temperature range of preferentially selecting for use is 90-200 ℃.If the absorption product that wish to reclaim is when being dry powder substantially, water consumption should be and the reaction heat of flue gas and the heat of itself, can be enough to make it evaporation, and perhaps the outside from system adds the additional heat that a spot of energy is used as reaction heat.
Consult following accompanying drawing, can illustrate in greater detail the present invention.Represented to be applicable to enforcement in the accompanying drawing according to device of the present invention, (1) is stove on figure.The sulfurous fuels that burns (4), general through the oxygen-containing gas (5) of preheating and the oxide (6) of calcium and/or magnesium, and/or these materials of carbonate (6) according to the combustion chamber in the proportional amount of formed sulfur dioxide, preferably more excessive, the combustion chamber of adding stove (1).The connotation of said here " excessive " speech is to add the calcium magnesium amount that reacts with all sulphur in the combustion chamber, or the calcium magnesium amount that in the oxide of calcium and/or magnesium and/or carbonate, exists, should be greater than theoretical value, this theoretical value calculates by reaction equation.
Carbonate is decomposed into oxide and carbon dioxide after entering stove in stove.The part of oxide can react with sulfur dioxide, at first forms sulphite, is reoxidised into sulfate subsequently.Because the time that stops in stove is very short, have only the free and sulfur dioxide of partial oxide under sufficiently high temperature, to react, so, contain and have residue of combustion and unabsorbed sulfur dioxide leave stove by flue pipe (7) combustion chamber in calcium oxide and/or the magnesian flue gas (8).In addition, powdered oxide (6) can directly enter flue pipe (7) or enter the reactor (2) of back.
In fact, the temperature of flue gas (8) is very low, and the reacting phase between calcium and/or magnesia and the sulfur dioxide is when faint, so from removing the angle of sulphur, oxide is quite inactive under these conditions.Yet, can be used to the air that heating enters stove (1) by heat exchange (12) flue gas (8).
The flue gas (8) that contains calcium and/or magnesia and sulfur dioxide is come out from stove (1), directly enter reactor (2) then, for activate calcium and or magnesium, water (9) or steam spray in the flue gas in reactor (2), water or steam and calcium and/or magnesia just react, and form suitable hydroxide.The part of this hydroxide and the reaction of remaining sulfur dioxide in flue gas (8), and form corresponding sulphite in the presence of aerobic, have further oxidation and become corresponding sulfate of part at least.
The water (9) that adds reactor (2) is adjusted to low like this amount, and promptly the heat of flue gas (8) enough will enter the water evaporation of reaction (2).So the same product of this dried floating dust just can be as other floating dust, the floating dust separator (2) by routine is removed.The flue gas (11) of being come out by separation graph directly enters flue (13), and floating dust of separating (12) and product might further directly be handled.
The method that water or steam and powdered oxide add is to be provided with strict order, for example, water or steam can add stove, and powdered oxide then can only add the aft section of stove, it can be added in the flue, also can be added in the reactor that is connected on the back and go.According to technology provided by the invention, another advantage be in fact this technology applicable to the stove that has the various forms burner.The size of stove does not limit yet, do not need calcium and/or magnesium oxide in the burning indoor circulation yet, avoided adopting the expensive circulation fluidized bed that has complicated EGR, also avoided because operating principle causes circulation fluidized bed that the shortcomings such as separation of excessive dust and dust are arranged simultaneously.Compare with the spray art known to original, water or steam are sprayed into reactor (2) can reduce its complexity widely, in addition, spray slurries and cause spray nozzle clogging easily and mix difficulty, and the injection of water or steam is more or less freely.Another advantage is exactly that burning is a less expensive to carbonate in the stove inner combustion chamber in addition.
Be described in more detail the present invention with following example.
Example 1
The coal that contains 1.4% sulphur with 70 tons/time flow be added in the fine coal stove that thermal power is 600 megawatts, stove carries out full load operation.Add excessive combustion air, oxygen content is 4% in the flue gas like this, and the then available calcium carbonate of calcium, marble or calcium oxide add in the stove, as being that its amount is to change according to the ratio of sulfur content in the fuel gas in 90% the calcium carbonate adding stove with calcium carbonate content.In theory its aequum be about 3.4 tons/time calcium carbonate.
（1）CaCO
3→CaO+CO
2
Calcium carbonate just is decomposed into calcium oxide and carbon dioxide when being in the high temperature furnace, and it leaves stove with flue gas, and partial oxidation calcium in stove and the sulfur dioxide in the flue gas react and forms sulfuric acid or calcium sulfite.
（2）CaO+SO
2+1/2O
2→CaSO
4
CaO+SO
2→CaSO
3
CaSO
3+1/2O
2→CaSO
4
The water and/or the steam that spray into flue gas can spray in the stove, also can spray in the flue pipe, perhaps spray in the separator of flue pipe back.
On the viewpoint of saving the energy, most economical method is to spray water to enter to improve containing of flue gas of warm measuring to reclaim all surface heats in the separate reactor.
Improve containing warm amount and can make the calcium oxide that in stove, can not react form incidental calcium hydroxide in the flue gas.
（3）CaO+H
2O→Ca（OH）
Ca（OH）
2+SO
2→CaSO
3+H
2O
Calcium hydroxide can be rapidly and the sulfur dioxide in the flue gas react.It is high more to contain the temperature amount in the flue gas, and the effect of removing sulfur dioxide from flue gas is just good more.Yet from economizing the angle of about energy, be operating as in such a way, that is: the heat that chemical reaction discharged satisfies the water yield that evaporation adds, if require to improve the end temperature of flue gas, adopts external heat again or with hot flue gas stream.
The calcium carbonate or the marble that add when arriving conversion zone, become oxide shape, this be the most basic a bit.
Listed in the following table, the result who obtains according to the present invention during the calcium carbonate of different amounts, removes the percentage of sulfur dioxide of flue gases in adding stove.The amount of the calcium carbonate here is with the calcium content in the powder calcium carbonate content of sulphur in the flue gas to be represented with mole ratios.The temperature of flue gas is to measure in the place of the front, entrance that nestles up water or steam.Having only when temperature is 800 ℃, is an exception, and at this moment water or steam are only in the direct adding stove.
A) water and steam add in the stove,
B) place before the water entry and then,
Example 2
According to the method for example 1, containing 45% calcium carbonate (CaCO
3), 45% magnesium carbonate (MgCO
3) and the marble of 10% impurity join in the powder coal stove, and adopt same operating parameter, according to chemical balance, in the ratio of sulfur content add about 6.8 tons of marmorean amount/time.
Calcium carbonate that marble contained in stove and magnesium carbonate are decomposed into calcium oxide, and magnesia and carbon dioxide also leave stove with flue gas.In stove, the carbon dioxide reaction in partial oxide and the flue forms sulfate or sulphite.
In the flue gas that water and/or steam are injected in the stove or flue pipe is interior, or spray in the flue tube of separate reactor back appropriate point.Responseless oxide in stove and since improved the temperature amount of containing at this point side's hydroxide that just can form hydroxide, part react the pulverous product of formation with the sulfide that is present in the flue gas.
When adopting marble, the active high calcium hydroxide magnesium hydroxide lower than reactivity takes place easily react earlier.If the calcium amount is enough like this, by the almost not reaction of magnesium hydroxide of reactor.Because the design of this technology only considers that the calcium in the marble reacts, so above-mentioned equivalent numerical value can reach.When calcium was at least 1 to the mole ratio of sulphur, then the method for this technology was to accord with the listed numerical value of table 1 basically.
Example 3
The calcium oxide that will contain 10% impurity joins in the stove according to example 1 method and adopts corresponding operation parameter.According to reaction, by the sulfur content that enters the fuel gas in the stove, the theoretical equivalent value that calculates required calcium oxide be about 1.9 tons/time.
In stove, the sulfur dioxide reaction of depositing in partial oxidation calcium and the flue gas forms calcium sulfate or calcium sulfite.
Water and/or steam are sprayed in the flue gas in the stove or in the flue pipe, perhaps spray into the flue pipe that is arranged in the separate reactor back.
Owing to improved moisture content, calcium oxide forms the calcium hydroxide of high response, promptly with the sulfur dioxide reaction of the remnants of flue gas.The temperature amount of containing of flue gas is high more, and the efficient of removing sulfur dioxide from flue gas is also high more.Yet from energy-conservation viewpoint, it is favourable operating in such a way, i.e. the water that the heat of chemical reaction release enough is used for adding evaporates.
When adding calcium with the form of calcium oxide, the amount of adding is by with recently the calculating of the gram molecule of sulphur, and the listed data of table 1 are consistent in its result and the example 1.
Table 1
Claims (9)
1, a kind ofly remove gaseous sulphide from the flue gas of stove, the method as sulfur dioxide is characterized in that:
A) also can be simultaneously except sulfurous fuels (4) and oxygen-containing gas (5) with powdery alkali metal and/or alkaline earth oxide and/or resemble carbonate (6) one classes can change corresponding oxide in stove compound and add in the stove (1), also above-mentioned oxide powder can be added in the flue gas that contains sulfur dioxide that discharge from stove.
B) water (9) and/or water vapour are sprayed into respectively in stove (1), reactor (2) and/or the flue gas (8), so that it is make oxygenate conversion be the hydroxide that can react with sulfur dioxide, last
C) obtaining a kind of sulfate that contains alkali metal and/or alkaline-earth metal as product, also may be the solid (10) of sulphite, and it is separated from gas (11) in separator (3).
2,, it is characterized in that more excessive than the amount of the sulphur that exists in the flue gas in proportion described powder compounds (6,6 ') is added according to the method for claim 1.
3,, it is characterized in that the temperature when flue gas is 50-800 ℃, and when being preferably 90-200 ℃, spray into water (9) and/or water vapour according to the method for claim 1.
4,, it is characterized in that it is the amount that flue gas and the heat energy that produced thereof can make its evaporation that water (9) is sprayed into maximum in the flue gas (8) in reaction according to claim 1 method.
5,, it is characterized in that before flue gas being carried out the solid separation, the energy that will add on a small quantity from the outside adds the reactor according to the method for claim 1.
6, according to the method for any one claim in the aforesaid right requirement, it is characterized in that the powdered compounds that is added is a calcium carbonate, calcium carbonate-magnesium carbonate and/or corresponding oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI851622A FI78845B (en) | 1984-11-09 | 1985-04-24 | FOERFARANDE FOER AVLAEGSNANDE AV GASFORMIGA SVAVELFOERENINGAR, SAOSOM SVAVELDIOXID FRAON ROEKGASERNA FRAON EN PANNA. |
| NL851622 | 1985-04-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85107964A CN85107964A (en) | 1986-12-31 |
| CN1004258B true CN1004258B (en) | 1989-05-24 |
Family
ID=8520717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85107964.4A Expired CN1004258B (en) | 1985-04-24 | 1985-11-07 | Process for removing gaseous sulfur compunds, such as sulfur dioxide, from flue gases of furnace |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS61287419A (en) |
| CN (1) | CN1004258B (en) |
| BA (1) | BA97189B1 (en) |
| BE (1) | BE903596A (en) |
| CH (1) | CH672266A5 (en) |
| CS (1) | CS274269B2 (en) |
| DD (1) | DD239126A5 (en) |
| DE (1) | DE3539349A1 (en) |
| DK (1) | DK515385A (en) |
| ES (1) | ES8700308A1 (en) |
| FR (1) | FR2580949B1 (en) |
| HU (1) | HU202423B (en) |
| LT (1) | LT2549B (en) |
| LV (1) | LV5587A3 (en) |
| PL (1) | PL148178B1 (en) |
| RO (1) | RO93450A (en) |
| SU (1) | SU1711658A3 (en) |
| YU (1) | YU44270B (en) |
| ZA (1) | ZA858475B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19711529A1 (en) * | 1997-03-19 | 1998-09-24 | Sueddeutsche Kalkstickstoff | Process for removing acidic pollutants from exhaust gases |
| JP5591910B2 (en) * | 2010-03-02 | 2014-09-17 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for removing sulfur compounds from castable |
| BE1021596B9 (en) * | 2013-06-25 | 2018-06-18 | Lhoist Rech Et Developpement Sa | METHOD AND DEVICE FOR TREATING GAS BY INJECTION OF PULVERULENT COMPOUND. |
| JP6153258B2 (en) * | 2013-09-30 | 2017-06-28 | 太平洋セメント株式会社 | Cement kiln extraction gas processing method and chlorine bypass system |
| CN107462077A (en) * | 2016-06-06 | 2017-12-12 | 成都市新力设备制造有限责任公司 | A kind of tunnel kiln smoke-gas desulphurization system UTILIZATION OF VESIDUAL HEAT IN and pre- sulfur method |
| CN107816731A (en) * | 2017-11-21 | 2018-03-20 | 无锡市洗选设备厂 | A kind of coal particles drying process device |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS499471A (en) * | 1972-05-24 | 1974-01-28 | ||
| JPS50150675A (en) * | 1974-05-25 | 1975-12-03 | ||
| DE2539500B2 (en) * | 1975-09-05 | 1980-06-19 | Heinz Ing.(Grad.) 4390 Gladbeck Hoelter | Process for separating dust and gaseous pollutants from hot exhaust gases and device for carrying out the process |
| JPS5644023A (en) * | 1979-09-13 | 1981-04-23 | Mitsubishi Heavy Ind Ltd | Exhaust gas purifying method |
| CA1152294A (en) * | 1980-10-08 | 1983-08-23 | Xuan T. Nguyen | Fluidized bed sulfur dioxide removal |
| DE3136914A1 (en) * | 1981-09-17 | 1983-03-31 | Hölter, Heinz, Dipl.-Ing., 4390 Gladbeck | "Process for the cleaning of flue gas downstream of power stations, producing gypsum at the same time in a dry process" |
| JPS5851924A (en) * | 1981-09-24 | 1983-03-26 | Sumitomo Cement Co Ltd | Method for desulfurizing and cooling exhaust gas |
| AT372876B (en) * | 1981-11-19 | 1983-11-25 | Oesterr Draukraftwerke | METHOD AND DEVICE FOR THE DESCULATION OF FLUE GAS DESULFURING COAL BURNERS AFTER THE DRY ADDITIVE METHOD |
| DE3232080C2 (en) * | 1982-08-28 | 1986-10-16 | Rheinisch-Westfälisches Elektrizitätswerk AG, 4300 Essen | Process for the dry removal of sulfur dioxide and other pollutants from flue gases |
| DE3235341A1 (en) * | 1982-09-24 | 1984-03-29 | Deutsche Babcock Anlagen Ag, 4200 Oberhausen | METHOD FOR PURIFYING EXHAUST GASES |
-
1985
- 1985-10-22 JP JP60236245A patent/JPS61287419A/en active Pending
- 1985-10-24 HU HU854100A patent/HU202423B/en not_active IP Right Cessation
- 1985-10-24 DD DD85282040A patent/DD239126A5/en not_active IP Right Cessation
- 1985-10-28 ES ES548286A patent/ES8700308A1/en not_active Expired
- 1985-11-04 FR FR858516280A patent/FR2580949B1/en not_active Expired - Lifetime
- 1985-11-04 CH CH4723/85A patent/CH672266A5/de not_active IP Right Cessation
- 1985-11-05 ZA ZA858475A patent/ZA858475B/en unknown
- 1985-11-06 YU YU1730/85A patent/YU44270B/en unknown
- 1985-11-06 DE DE19853539349 patent/DE3539349A1/en not_active Ceased
- 1985-11-06 SU SU853971542A patent/SU1711658A3/en active
- 1985-11-06 BE BE0/215831A patent/BE903596A/en not_active IP Right Cessation
- 1985-11-07 CN CN85107964.4A patent/CN1004258B/en not_active Expired
- 1985-11-08 CS CS807985A patent/CS274269B2/en not_active IP Right Cessation
- 1985-11-08 RO RO85120718A patent/RO93450A/en unknown
- 1985-11-08 PL PL1985256162A patent/PL148178B1/en unknown
- 1985-11-08 DK DK515385A patent/DK515385A/en not_active Application Discontinuation
-
1992
- 1992-12-29 LV LV920549A patent/LV5587A3/en unknown
-
1993
- 1993-09-28 LT LTRP1230A patent/LT2549B/en not_active IP Right Cessation
-
1997
- 1997-08-19 BA BA970189A patent/BA97189B1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE3539349A1 (en) | 1986-11-06 |
| PL256162A1 (en) | 1986-11-04 |
| ZA858475B (en) | 1986-07-30 |
| FR2580949B1 (en) | 1990-08-03 |
| DD239126A5 (en) | 1986-09-17 |
| LT2549B (en) | 1994-02-15 |
| HU202423B (en) | 1991-03-28 |
| BE903596A (en) | 1986-03-03 |
| DK515385A (en) | 1986-10-25 |
| CS274269B2 (en) | 1991-04-11 |
| ES548286A0 (en) | 1986-10-01 |
| PL148178B1 (en) | 1989-09-30 |
| YU173085A (en) | 1987-10-31 |
| FR2580949A1 (en) | 1986-10-31 |
| CH672266A5 (en) | 1989-11-15 |
| LV5587A3 (en) | 1994-05-10 |
| CN85107964A (en) | 1986-12-31 |
| CS807985A2 (en) | 1990-09-12 |
| ES8700308A1 (en) | 1986-10-01 |
| DK515385D0 (en) | 1985-11-08 |
| BA97189B1 (en) | 1999-08-02 |
| JPS61287419A (en) | 1986-12-17 |
| YU44270B (en) | 1990-04-30 |
| RO93450A (en) | 1987-12-31 |
| HUT48127A (en) | 1989-05-29 |
| SU1711658A3 (en) | 1992-02-07 |
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