CN1607354A - Sulfur removal method and desulfurizer in fluidized bed device - Google Patents
Sulfur removal method and desulfurizer in fluidized bed device Download PDFInfo
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- CN1607354A CN1607354A CN 200410100515 CN200410100515A CN1607354A CN 1607354 A CN1607354 A CN 1607354A CN 200410100515 CN200410100515 CN 200410100515 CN 200410100515 A CN200410100515 A CN 200410100515A CN 1607354 A CN1607354 A CN 1607354A
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- Prior art keywords
- fluidized bed
- sulphur content
- filter cake
- bed plant
- desulfurizing agent
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- 238000000034 method Methods 0.000 title claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 7
- 239000011593 sulfur Substances 0.000 title abstract description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 69
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 69
- 239000004571 lime Substances 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 63
- 239000000446 fuel Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000011575 calcium Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims description 64
- 239000005864 Sulphur Substances 0.000 claims description 59
- 239000012530 fluid Substances 0.000 claims description 43
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 241000196324 Embryophyta Species 0.000 description 36
- 239000000203 mixture Substances 0.000 description 19
- 239000003245 coal Substances 0.000 description 18
- 238000006477 desulfuration reaction Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 235000019738 Limestone Nutrition 0.000 description 11
- 239000006028 limestone Substances 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 10
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000021552 granulated sugar Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000016068 Berberis vulgaris Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003473 refuse derived fuel Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- -1 briquet Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-N sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Fluidized-Bed Combustion And Resonant Combustion (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Industrial Gases (AREA)
Abstract
The invention provides a method for removing sulfur in a fluidized bed device and a desulfurizing agent. The method of the present invention is a method for removing sulfur content in gas generated in a fluidized bed furnace in which fuel and/or raw material is burned by fluidized bed combustion, characterized in that a desulfurizing agent containing a lime cake is charged into the fluidized bed furnace. Preferably, the particle size of the lime cake is 0.08mm or more, and the calcium content of the desulfurizing agent is 0.5 to 7 (molar ratio) with respect to the sulfur content of the fuel and/or the raw material.
Description
Technical field
The present invention relates to sulphur content removal method and desulfurizing agent in the fluidized bed plant.
Background technology
Often contain the sulphur composition in fossil fuel such as oil and coal and trade waste, the municipal refuse the like waste, be the incinerator of fuel with them or be in the gas generator of raw material, must remove harmful oxysulfide (SO such as sulfur dioxide that the burning owing to sulphur produces, sulfur oxide with them
x), after reaching the concentration that meets environment protectment protection, again burning gases are discharged.
In the past, the employed sulfur method of these stoves can be divided into following 2 kinds substantially.
(1) desulfuration in furnace method
This method is that desulfurizing agent is dropped in the stove, adsorbs, removes the method for oxysulfide.Usually, use lime stone or dolomite as desulfurizing agent, this method is mainly used in fluid bed furnace.
(2) exhaust gas desulfurization method
This method is the contact layer (tower) that desulfurizing agent and waste gas are set in the part of the flue behind stove, the method for removing the oxysulfide in the waste gas by the neutralization reaction of oxysulfide and desulfurizing agent.In this method, oxysulfide with become gypsum as the lime stone generation neutralization reaction of desulfurizing agent, can effectively be utilized.
In above-mentioned desulfuration in furnace method, what be used as desulfurizing agent is that the utilization rate of the lime stone of main component or dolomite is very low with calcium, for example, in normal pressure bubbling type fluid-bed combustion furnace, obtain the occasion of the desulfurization degree more than 90%, the utilization rate of lime stone is about 15-25%, in the circular form fluid-bed combustion furnace, its utilization rate is 25-35%.
Therefore, for sulphur content contained in fuel or the raw material is removed fully, must drop into a large amount of desulfurizing agents.This be because, desulphurization reaction only takes place in lime stone about average grain diameter 200 μ m in its surface, the inside of particle and unreacted, a large amount of calcium do not obtain utilizing and left behind.
In order to address this problem, people have inquired into a kind of method, that is, the also good desulfurizing agent of, reactivity big as the more tiny or utilizable surface area ratio of particle diameter uses calcium oxide (CaO) or calcium hydroxide (Ca (OH)
2) method of the particulate that waits.
Summary of the invention
But, in this method, make the lime stone carbon dioxide removal and make CaO or Ca (OH)
2Need to consume a large amount of energy, economy is poor, and CaO that generates in the manufacture process or Ca (OH)
2The particle diameter of particle is very little, has only below the 50 μ m, and therefore, the desulfurizing agent particle of input does not fully carry out desulphurization reaction as yet just along with the air-flow of burnt gas is discharged to outside the stove, and utilization rate is very low.
The present invention In view of the foregoing finishes, and the objective of the invention is, and the removal method and the desulfurizing agent of the sulphur composition in the burning gases in the fluid bed furnace is provided.
In order to realize above-mentioned task, the inventor has carried out deep research repeatedly, found that, use lime filter cake (ラ イ system ケ-キ) very effective as desulfurizing agent, thus the present invention finished.
According to the present invention, the desulfurizing agent that will contain the lime filter cake in fluid bed furnace drops in the stove, by be that the oxidation reaction (burning), gasification, thermal decomposition etc. of fuel or raw material are removed the sulphur content in the gas of generation in the stove with oil or coal etc.
The lime filter cake is in the manufacture process of granulated sugar, by removing the material of discharging in the process of impurity such as wherein contained organic matter and pigment in the liquid glucose of separating out as dissolving in the beet of raw material.In general, in this technical process, with CaO or Ca (OH)
2Particulate sneak in the liquid glucose and then mixed C O
2Gas makes impurity attached to precipitating on this particle, and the liquid glucose that purity is high separates with sediment.With the product after the sediment dehydration of discharging in this technical process is exactly the lime filter cake.That is, the composition of lime filter cake is the CaCO by finely particulate
3Mixture with the organic matter formation.
The contained organic matter that derives from beet in the lime filter cake plays atomic CaCO when sediment is dewatered
3Therefore the effect of the binding agent of bonding, condenses into argillaceous through the lime filter cake that dewaters, and the air dry rear section forms particle.
The particle diameter of lime filter cake depends on organic ratio and drying regime, and its particle diameter distributes than broad in general, and maximum particle diameter is 5-50mm, and minimum grain size is original C aCO
3Minimum grain size be about 5-50 μ m.In the present invention, particularly preferably be part and be a granulated into big particle diameter.
According to the present invention, sulphur content removal method and fluid bed furnace desulfurizing agent in the fluidized bed plant below providing.
1. the sulphur content removal method in the fluidized bed plant, this method is the method for removing the sulphur content in the gas that produces in the fluid bed furnace in fluidized bed plant, it is characterized in that, the desulfurizing agent that will contain the lime filter cake drops in the fluid bed furnace.
2. the sulphur content removal method in above-mentioned the 1st in the fluidized bed plant of record is characterized in that described desulfurizing agent is the lime filter cake.
3. the sulphur content removal method in the above-mentioned the 1st or the 2nd in the fluidized bed plant of record is characterized in that with respect to the sulphur content in fuel and/or the raw material, the calcium branch in the described desulfurizing agent is 0.5-7 (mol ratio).
4. the sulphur content removal method in the above-mentioned 1-3 item in the fluidized bed plant of each record is characterized in that, with respect to the sulphur content in fuel and/or the raw material, the calcium branch in the described desulfurizing agent is 0.5-5 (mol ratio).
5. the sulphur content removal method in the above-mentioned 1-4 item in the fluidized bed plant of each record is characterized in that, described desulfurizing agent is the above lime filter cake of maximum particle diameter 0.08mm.
6. the sulphur content removal method in the above-mentioned 1-5 item in the fluidized bed plant of each record is characterized in that, the above-mentioned desulfurizing agent that contains the lime filter cake is mixed in fuel and/or the raw material drops in the fluid bed furnace.
7. the sulphur content removal method in the above-mentioned 1-5 item in the fluidized bed plant of each record, it is characterized in that, described fluidized bed plant is the outer loop fluidized bed plant, and described desulfurizing agent is below the moisture 35 weight % and is a granulated into the above lime filter cake of maximum particle diameter 0.08mm.
8. the sulphur content removal method in the above-mentioned 1-5 item in the fluidized bed plant of each record, it is characterized in that, described fluidized bed plant is bubbling type fluidized bed plant or inner loop fluidized bed plant, and described desulfurizing agent is below the moisture 35 weight % and is a granulated into the above lime filter cake of maximum particle diameter 0.1mm.
9. the sulphur content removal method in above-mentioned the 7th or 8 in the fluidized bed plant of record is characterized in that, utilizes air-flow to carry above-mentioned lime filter cake is directly dropped in the fluid bed furnace.
10. the sulphur content removal method in above-mentioned the 7th or 8 in the fluidized bed plant of record is characterized in that, utilizes air-flow to carry described lime filter cake is delivered in the feed path of fuel and/or raw material, drops in the fluid bed furnace with fuel and/or raw material.
11. the sulphur content removal method in the above-mentioned 1-5 item in the fluidized bed plant of each record, it is characterized in that, the moisture of described desulfurizing agent is more than the 20 weight %, and is the lime filter cake of argillaceous or paste-like, and this lime filter cake is directly dropped in the fluid bed furnace.
12. the sulphur content removal method in above-mentioned the 11st in the fluidized bed plant of record is characterized in that, in the feed path of fuel and/or raw material above-mentioned lime filter cake is mixed with fuel and/or raw material or drops in the fluid bed furnace together.
13. the sulphur content removal method in above-mentioned the 11st or 12 in the fluidized bed plant of record is characterized in that, in the method that above-mentioned lime filter cake is dropped in the fluid bed furnace, uses the mechanical type feeding machine that it is dropped in the fluid bed furnace.
14. contain the desulfurizing agent of lime filter cake.
According to the present invention, can provide the desulfurized effect in the fluid bed furnace good sulphur content removal method and desulfurizing agent.
The specific embodiment
An embodiment of the invention are described with reference to the accompanying drawings.
Fig. 1 is the employed outer loop type of an embodiment fluidized bed plant of the sulphur content removal method in fluid bed furnace of the present invention.
In the figure, the 1st, coal hopper, the 2nd, feeder, the 3rd, the air supply pipe road, the 4th, preheater, the 5th, the air supply pipe road is used in primary combustion, the 6th, dispersion plate, the 7th, lime filter cake hopper, the 8th, the air supply pipe road is used in second-time burning, the 9th, fluid bed furnace, 10 is cyclone separators (cyclone), the 11st, the particle displacer, the 12nd, secondary cyclone separator, the 13rd, storage container, the 14th, gas cooler, the 15th, gas analyzer, the 16th, bag hose, the 17th, air blast.
The following describes the operational circumstances of this outer loop type fluidized bed plant.
The fuel (coal) that is imported in the fluid bed furnace 9 by coal hopper 1 burns in fluid bed furnace 9, and the gas of burning rises in combustion furnace 9. At this moment, the sulphur content in the fuel is transformed into oxysulfide. On the other hand, be imported in the fluid bed furnace 9 by lime filter cake hopper 7 as the lime filter cake of desulfurizing agent, utilize calcium component contained in the lime filter cake in fluid bed furnace 9 and cyclone separator 10 interior absorption, remove oxysulfide.
In the present embodiment, what fluidized bed plant used is outer loop type fluidized bed plant, but, also can use inner loop type fluidized bed plant in the present invention.In addition, replace outside or inner loop type fluidized bed plant, can also use the fluidized bed plant of bubbling type fluidized bed plant or compression type, normal pressure type.
Have again, in the present embodiment, just desulfurizing agent is dropped in the fluid bed furnace, but, also desulfurizing agent can be mixed in fuel and/or the raw material in the present invention or drop in the fluid bed furnace together with it.According to the shape of desulfurizing agent, can adopt air-flow to carry or use mechanical type feeding machines such as piston pump, plunger displacement pump, screw feeder, swivel feeding device that it is dropped in the fluid bed furnace.
Used the desulfurizing agent that contains the lime filter cake in the method for the invention.This desulfurizing agent can only be made of the lime filter cake, also can contain some lime filter cake.
Composition in the desulfurizing agent beyond the contained lime filter cake for example can be enumerated lime stone, dolomite, calcium oxide, contain the growing concrete sludge of calcium.
Ratio for lime filter cake contained in the desulfurizing agent has no particular limits, can based on fuel or the kind of raw material suitably adjust.
In the method for the invention, in the fluid bed furnace of fluidized bed plant, drop into desulfurizing agent, usually, the Ca of desulfurizing agent is divided reach 0.5-7 (mol ratio), in stove, carry out desulfurization.Above-mentioned mol ratio is lower than at 0.5 o'clock, sometimes reacts insufficient; Otherwise, be higher than at 7 o'clock, though can obtain high reactivity, the growing amount of residue can increase sometimes, grey treating capacity increases.Therefore, preferably in the ratio input of 1-5 (mol ratio), in stove, carry out desulfurization and suit.
In addition, preferably drop into desulfurizing agent in the present invention, make the Ca in the desulfurizing agent be divided into 0.5-5 (mol ratio), be more preferably 1.0-5 (mol ratio) with respect to the sulphur content in fuel and/or the raw material.
The lime filter cake that uses among the present invention, can directly use the lime filter cake that in the granulated sugar manufacture process, obtains with slurry state, perhaps the lime filter cake that obtains is used in the dehydration back in the granulated sugar manufacture process with the clay state, perhaps also can be with air dry again behind this lime cake dewatering, then with re-using after the sieve adjustment particle size range.
Using the occasion of lime filter cake in the present invention with paste-like or argillaceous, when making the lime cake dewatering that obtains in the granulated sugar process, moisture is adjusted to more than 20% (weight), is preferred for the operations such as conveying of lime filter cake.As the method for carrying this lime filter cake, can use mechanical type loaders such as piston pump, plunger displacement pump, screw feeder, swivel feeding device.
The occasion of using after the particle size range adjustment of the lime filter cake that uses in the present invention preferably is adjusted into the particle size that is not easy to disperse from fluidized system, preferred maximum particle diameter is more than 0.08mm.Specifically, for bubbling type fluidized bed plant and inner loop type fluidized bed plant, maximum particle diameter is 0.1-50mm, and preferably 1-40mm is more preferably 2-20mm; For outer loop type fluidized bed plant, maximum particle diameter is 0.08-50mm, and preferably 0.5-25mm is more preferably 1-20mm.In addition, for the efflorescence that particle is not easy owing to flow with disperse, preferably by dewatering and air dry is adjusted to its moisture below the 35 weight %.
In the present invention, the lime filter cake directly can be used as desulfurizing agent, but also can with its be used as desulfurizing agent after above-mentioned its composition mixes.When mixing its composition, adjust the particle diameter of other compositions, carry out mixingly, dry as adhesive with clay minerals such as kaolin, montmorillonites, make with sieve adjustment particle diameter then.
In the system Solid fuel of processes such as RDF (refuse derived fuel) and RPF (refuse paper and plasticfuel), honeycomb briquette, briquet, coal briquette, charcoal processing and CWM (coalwater mixture), CWP approximate fluid fuels such as (coal water paste) etc., that desulfurizing agent and fuel is pre-mixed use during use method of the present invention, preferably the lime filter cake is mixed in the fuel, drops in the fluid bed furnace then.In this occasion, its mixed proportion preferably as previously described, for the sulphur content in the fuel, the Ca branch (mol ratio) in the lime filter cake reaches the ratio of 0.5-5.
In the method for the invention, consider that fuel or raw material as burning or gasification, thermal decomposition, partial oxidation produce sulfur dioxide, sulfur oxide or other oxysulfides (SO from purpose of the present invention
x) fuel that contains sulphur content or the raw material that wait be suitable for, solid fuels such as coal, petroleum coke, oil sand, organism for example; In coal compounding the similar fluid fuel of water or wet goods; Liquid fuels such as heavy oil, kerosene, alcohol mixture; Gaseous fuels such as LPG, LNG, plant gas; Rubbish, mud, plastics, mud, tire the like waste; Perhaps be selected from least 2 kinds mixture in the above-mentioned material.
In the method for the invention, reaction in the various fluidized bed plants such as fluid-bed combustion furnace, fluidized bed coal gas producer, fluid bed heat dore furnace, fluid bed part gas generator, preferably in 500-2000 ℃ temperature range, carry out, in order further to improve desulfuration efficiency, consider preferably under 600-1000 ℃ temperature, to carry out from the angle that improves reactivity.
In the present invention preferably, be not to use the good CaCO of reaction of formation
3Intact particulate, can not fly out immediately in order to make it to enter in the stove, preferably use and contain the desulfurizing agent that these particulate part granulations is increased the lime filter cake of particle diameter.
Like this, when the lime filter cake that the part granulation is formed big particle diameter imported in the fluidized system, desulfurizing agent can not disperse outside stove immediately, can be trapped in for a long time in the system, so desulfuration in furnace was fully carried out, thereby had improved desulfuration efficiency.
Embodiment
Specifically describe the present invention below by embodiment and comparative example, but the present invention is not subjected to the restriction of following embodiment.
Embodiment 1
To have the lime filtration cakes torrefaction that the Japan sugaring Co., Ltd. of proterties shown in the table 1 makes, and be adjusted into then below the maximum particle diameter 2mm, average grain diameter 1.2mm mixes with the bunker coal with proterties shown in the table 2 below being ground into 2mm.Being prepared into the sulphur content in coal the Ca in the lime filter cake divides and counts 4 kinds of mixtures of 0,1,2,3 with mol ratio (Ca/S).The gained mixture is burnt, the SO of analytic combustion outlet in CFBC stove shown in Figure 1
xConcentration is obtained desulfurization degree by following computational methods, the results are shown in the table 3.
Desulfurization degree (%)=(a/b) * 100
SO during a=[coal independent (Ca/S=0) burning
xDischarge concentration]-(SO
xDischarge concentration)
SO during b=only (Ca/S=0) burning
xDischarge concentration
In addition, the burning condition of above-mentioned test is ignition temperature: 850 ℃, and combustion pressure: 1atm, air ratio: 1.2, fuel drops into speed: 4kg/h.
Comparative example 1
Be adjusted into below the maximum particle diameter 2mm, the lime stone of average grain diameter 1.2mm (order father produces, Pacific Ocean セ メ Application ト company make) mixes with the bunker coal with proterties shown in the table 2 below being ground into 2mm.Ca branch the sulphur content of preparation in coal in the lime stone is counted 4 kinds of mixtures of 0,1,2,3 with mol ratio (Ca/S).The gained mixture is burnt, the SO of analytic combustion outlet in fluid bed furnace shown in Figure 1
xConcentration is obtained desulfurization degree.The calculating of experimental condition and desulfurization degree is carried out similarly to Example 1.The results are shown in the table 3.
Comparative example 2
Maximum particle diameter is adjusted into the Ca (OH) of 20 μ m
2Particulate (JIS-K8575, purity are more than 95%) the bunker coal with table 2 shown in proterties following with being ground into 2mm mixes.Ca (OH) the sulphur content of preparation in coal
2Calcium in the particulate divides counts 4 kinds of mixtures of 0,1,2,3 with mol ratio (Ca/S).The gained mixture is burnt, the SO of analytic combustion outlet of still in fluid bed furnace shown in Figure 1
xConcentration is obtained desulfurization degree.The calculating of experimental condition and desulfurization degree is carried out similarly to Example 1.The results are shown in the table 3.
Table 1
| Filter mud | |||
| Industrial Analysis | Moisture wt% | Air-dry | ????2.7 |
| Ash content wt% | Air-dry | ????55.0 | |
| Volatile matter wt% | Air-dry | ????29.9 | |
| Fixed carbon wt% | Air-dry | ????12.4 | |
| Elementary analysis | Carbon wt% | Anhydrous ashless | ????29.83 |
| Hydrogen wt% | Anhydrous ashless | ????1.64 | |
| Nitrogen wt% | Anhydrous ashless | ????1.16 | |
| Sulphur wt% | Anhydrous ashless | ????0.05 | |
| Oxygen wt% | Anhydrous ashless | ????67.32 | |
| Total sulfur wt% | Anhydrous | ????0.03 | |
| Chlorine mg/kg | Anhydrous | ????17 | |
| Fluorine mg/kg | Anhydrous | ????11 | |
| Fuel ratio | ????0.41 | ||
| The composition (weight %) of ash | Acid | ????SiO 2 | ????0.00 |
| ????Al 2O 3 | ????0.97 | ||
| ????TiO 2 | ????0.00 | ||
| Alkalescence | ????Fe 2O 3 | ????0.18 | |
| ????CaO | ????92.61 | ||
| ????MgO | ????2.64 | ||
| ????Na 2O | ????0.13 | ||
| ????K 2O | ????0.00 | ||
| Other | ????P 2O 5 | ????3.01 | |
| ????MnO | ????0.02 | ||
| ????V 2O 5 | ????0.00 | ||
| ????SO 3 | ????0.04 | ||
Table 2
| Coal | ||
| Industrial Analysis is air-dry | Moisture wt% | 7.4 |
| Ash content wt% | 10.0 | |
| Volatile matter wt% | 25.8 | |
| Fixed carbon wt% | 56.8 | |
| Elementary analysis is anhydrous ashless | Carbon wt% | 81.27 |
| Hydrogen wt% | 4.67 | |
| Nitrogen wt% | 1.67 | |
| Sulphur wt% | 0.65 | |
| Oxygen wt% | 11.74 | |
| Total sulfur wt% | 0.60 | |
| Chlorine ppm | 2316 | |
| Fuel ratio | 2.20 | |
| The composition of ash | ?SiO 2 | 53.82 |
| ?Al 2O 3 | 31.92 | |
| ?TiO 2 | 1.60 | |
| ?Fe 2O 3 | 5.92 | |
| ?CaO | 0.56 | |
| ?MgO | 0.45 | |
| ?Na 2O | 0.84 | |
| ?K 2O | 0.45 | |
| ?P 2O 5 | 0.36 | |
| ?MnO | 0.01 | |
| ?V 2O 5 | 0.05 | |
| ?SO 3 | 0.41 | |
Table 3
| Ca/S | ?0 | ?1 | ?2 | ?3 | |
| Embodiment 1 | The lime filter cake | ?0 | ?60.1 | ?90.1 | ?97.2 |
| Comparative example 1 | Lime stone | ?0 | ?19.2 | ?36.3 | ?58.1 |
| Comparative example 2 | Ca(OH) 2 | ?0 | ?20.4 | ?48.2 | ?77.1 |
By the result of table 3 as can be seen, with use lime stone, Ca (OH)
2Comparative example 1 as desulfurizing agent is compared with 2, uses the lime filter cake to demonstrate very high desulphurizing ability as the embodiment 1 of desulfurizing agent under the condition of lower Ca/S ratio.This is because the lime filter cake is by tiny CaCO
3Be condensed into, its specific area is very big.
Method of the present invention goes for burning, gasification, thermal decompositions such as ore fuel, discarded object, organism such as coal, heavy oil, utilizes the energy field and the offal treatment field of the waste gas that generates.
Claims (20)
1. the sulphur content removal method in the fluidized bed plant, this method is the method for removing the sulphur content in the gas that produces in the fluid bed furnace in fluidized bed plant, it is characterized in that, the desulfurizing agent that will contain the lime filter cake drops in the fluid bed furnace.
2. the sulphur content removal method in the described fluidized bed plant of claim 1 is characterized in that, described desulfurizing agent is the lime filter cake.
3. the sulphur content removal method in the described fluidized bed plant of claim 1 is characterized in that, with respect to the sulphur content in fuel and/or the raw material, it is 0.5-7 that the calcium of described desulfurizing agent divides with molar ratio computing.
4. the sulphur content removal method in the described fluidized bed plant of claim 2 is characterized in that, with respect to the sulphur content in fuel and/or the raw material, it is 0.5-7 that the calcium in the described desulfurizing agent divides with molar ratio computing.
5. the sulphur content removal method in the described fluidized bed plant of claim 3 is characterized in that, with respect to the sulphur content in fuel and/or the raw material, it is 0.5-5 that the calcium in the described desulfurizing agent divides with molar ratio computing.
6. the sulphur content removal method in the described fluidized bed plant of claim 4 is characterized in that, with respect to the sulphur content in fuel and/or the raw material, it is 0.5-5 that the calcium in the described desulfurizing agent divides with molar ratio computing.
7. the sulphur content removal method in the described fluidized bed plant of claim 2 is characterized in that, described desulfurizing agent is the above lime filter cake of maximum particle diameter 0.08mm.
8. the sulphur content removal method in each described fluidized bed plant among the claim 1-7 is characterized in that, the above-mentioned desulfurizing agent that contains the lime filter cake is mixed in fuel and/or the raw material drops in the fluid bed furnace.
9. the sulphur content removal method in the described fluidized bed plant of claim 1, it is characterized in that, described fluidized bed plant is the outer loop fluidized bed plant, and described desulfurizing agent is below the moisture 35 weight % and is a granulated into the above lime filter cake of maximum particle diameter 0.08mm.
10. the sulphur content removal method in the described fluidized bed plant of claim 2, it is characterized in that, described fluidized bed plant is the outer loop fluidized bed plant, and described desulfurizing agent is below the moisture 35 weight % and is a granulated into the above lime filter cake of maximum particle diameter 0.08mm.
11. the sulphur content removal method in the described fluidized bed plant of claim 1, it is characterized in that, described fluidized bed plant is bubbling type fluidized bed plant or inner loop fluidized bed plant, and described desulfurizing agent is below the moisture 35 weight % and is a granulated into the above lime filter cake of maximum particle diameter 0.1mm.
12. the sulphur content removal method in the described fluidized bed plant of claim 2, it is characterized in that, described fluidized bed plant is bubbling type fluidized bed plant or inner loop fluidized bed plant, and described desulfurizing agent is below the moisture 35 weight % and is a granulated into the above lime filter cake of maximum particle diameter 0.1mm.
13. the sulphur content removal method among the claim 9-12 in each described fluidized bed plant is characterized in that, utilizes air-flow to carry above-mentioned lime filter cake is directly dropped in the fluid bed furnace.
14. the sulphur content removal method among the claim 9-12 in each described fluidized bed plant, it is characterized in that, utilize air-flow to carry above-mentioned lime filter cake is transported in the feed path of fuel and/or raw material, drop in the fluid bed furnace with fuel and/or raw material.
15. the sulphur content removal method in the described fluidized bed plant of claim 1 is characterized in that, the moisture of described desulfurizing agent is more than the 20 weight %, and is the lime filter cake of argillaceous or paste-like, and this lime filter cake is directly dropped in the fluid bed furnace.
16. the sulphur content removal method in the described fluidized bed plant of claim 2 is characterized in that, the moisture of described desulfurizing agent is more than the 20 weight %, and is the lime filter cake of argillaceous or paste-like, and this lime filter cake is directly dropped in the fluid bed furnace.
17. the sulphur content removal method in the described fluidized bed plant of claim 15 is characterized in that, in the feed path of fuel and/or raw material above-mentioned lime filter cake is mixed with fuel and/or raw material or drops in the fluid bed furnace together.
18. the sulphur content removal method in the described fluidized bed plant of claim 16 is characterized in that, in the feed path of fuel and/or raw material above-mentioned lime filter cake is mixed with fuel and/or raw material or drops in the fluid bed furnace together.
19. the sulphur content removal method among the claim 15-18 in each described fluidized bed plant is characterized in that, in the method that above-mentioned lime filter cake is dropped in the fluid bed furnace, uses the mechanical type feeding machine that it is dropped in the fluid bed furnace.
20. contain the fluid bed desulfurizing agent of lime filter cake.
Applications Claiming Priority (4)
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| JP2003313712 | 2003-09-05 | ||
| JP313712/2003 | 2003-09-05 | ||
| JP100913/2004 | 2004-03-30 | ||
| JP2004100913A JP4625265B2 (en) | 2003-09-05 | 2004-03-30 | Method for removing sulfur in fluidized bed apparatus and desulfurizing agent |
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| CN100483026C CN100483026C (en) | 2009-04-29 |
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| JP (1) | JP4625265B2 (en) |
| CN (1) | CN100483026C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102145253A (en) * | 2010-12-31 | 2011-08-10 | 东莞理文造纸厂有限公司 | Gas desulfurization system in recirculating fluidized bed boiler |
| CN101952661B (en) * | 2008-02-28 | 2012-08-29 | 三菱重工环境·化学工程株式会社 | Circulation type fluidized-bed furnace, treating system equipped with circulation type fluidized-bed furnace, and method of operating circulation type fluidized-bed furnace |
| CN114514060A (en) * | 2019-11-05 | 2022-05-17 | 乐佧本有限股份公司 | Pretreatment desulfurization method for bunker fuel oil by using pretreatment desulfurizing agent |
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| JP2010008040A (en) * | 2003-09-05 | 2010-01-14 | Idemitsu Kosan Co Ltd | Sulfur content eliminating method and desulfurizer for fluidized bed apparatus |
| JP5164051B2 (en) * | 2005-06-22 | 2013-03-13 | 北海道石灰化工株式会社 | Smoke exhaust treatment method and method for producing smoke treatment agent |
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| JP4957371B2 (en) * | 2007-05-11 | 2012-06-20 | 王子製紙株式会社 | Method for removing sulfur in fluidized bed combustor |
| FI122469B (en) * | 2010-05-17 | 2012-02-15 | Foster Wheeler Energia Oy | Process for Binding Flue Sulfur Oxides by a Circulating Swirl Bed Oxygen Combustion Boiler (CFB) |
| JP2012121734A (en) * | 2010-12-06 | 2012-06-28 | Taki Chem Co Ltd | Method for producing granular lime cake |
| JP6224903B2 (en) * | 2012-07-31 | 2017-11-01 | 出光興産株式会社 | Method for removing sulfur in pulverized coal combustion equipment |
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| CN104896494B (en) * | 2015-06-19 | 2017-07-28 | 山西大学 | A kind of waste-heat recovery device applied to dry desulfurizing process |
| CN113332851B (en) * | 2021-02-24 | 2023-08-29 | 薛援 | Dry flue gas desulfurization method for moving bed |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907674A (en) * | 1974-04-24 | 1975-09-23 | Dorr Oliver Inc | Fluid bed incineration of wastes containing alkali metal chlorides |
| CN1058004A (en) * | 1991-08-15 | 1992-01-22 | 常州飞机制造厂技术开发服务部 | Method with preparing high-purity calcium oxide from calcium carbide dregs |
| DE4300751C2 (en) * | 1993-01-14 | 1994-10-27 | Bernhard Reintanz | Device for spraying liquid, in particular of a lime milk suspension in flue gases from flue gas desulfurization plants of power plants and waste incineration plants of power plants and waste incineration plants |
| CN1033493C (en) * | 1994-03-21 | 1996-12-11 | 秦效敏 | Fume desulfurization dust catching apparatus |
| JP3384435B2 (en) * | 1997-03-28 | 2003-03-10 | 出光興産株式会社 | Fluidized bed furnace exhaust gas desulfurization method |
| TR200401879T1 (en) * | 1999-05-17 | 2005-08-22 | Mitsubishi Heavy Industries, Ltd. | A method for removing flue gas desulfurization and a system for removing flue gas desulfurization. |
-
2004
- 2004-03-30 JP JP2004100913A patent/JP4625265B2/en not_active Expired - Lifetime
- 2004-09-03 CN CNB2004101005155A patent/CN100483026C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952661B (en) * | 2008-02-28 | 2012-08-29 | 三菱重工环境·化学工程株式会社 | Circulation type fluidized-bed furnace, treating system equipped with circulation type fluidized-bed furnace, and method of operating circulation type fluidized-bed furnace |
| CN102145253A (en) * | 2010-12-31 | 2011-08-10 | 东莞理文造纸厂有限公司 | Gas desulfurization system in recirculating fluidized bed boiler |
| CN102145253B (en) * | 2010-12-31 | 2012-12-12 | 东莞理文造纸厂有限公司 | Gas desulfurization system in recirculating fluidized bed boiler |
| CN114514060A (en) * | 2019-11-05 | 2022-05-17 | 乐佧本有限股份公司 | Pretreatment desulfurization method for bunker fuel oil by using pretreatment desulfurizing agent |
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| Publication number | Publication date |
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| JP2005098673A (en) | 2005-04-14 |
| CN100483026C (en) | 2009-04-29 |
| JP4625265B2 (en) | 2011-02-02 |
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