CN1061915A - Process for simultaneously removing sulfur and nitrogen in furnace - Google Patents
Process for simultaneously removing sulfur and nitrogen in furnace Download PDFInfo
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- CN1061915A CN1061915A CN91105599A CN91105599A CN1061915A CN 1061915 A CN1061915 A CN 1061915A CN 91105599 A CN91105599 A CN 91105599A CN 91105599 A CN91105599 A CN 91105599A CN 1061915 A CN1061915 A CN 1061915A
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- aqueous solution
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- 238000000034 method Methods 0.000 title claims abstract description 148
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011593 sulfur Substances 0.000 title claims abstract description 42
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title claims description 116
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 151
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 75
- 239000007864 aqueous solution Substances 0.000 claims abstract description 59
- 239000003814 drug Substances 0.000 claims abstract description 58
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004202 carbamide Substances 0.000 claims abstract description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 23
- 230000001174 ascending effect Effects 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 151
- 239000007788 liquid Substances 0.000 claims description 42
- 239000010440 gypsum Substances 0.000 claims description 40
- 229910052602 gypsum Inorganic materials 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 239000000920 calcium hydroxide Substances 0.000 claims description 19
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 19
- 239000005864 Sulphur Substances 0.000 claims description 15
- 238000011084 recovery Methods 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 11
- 235000012255 calcium oxide Nutrition 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 150000003672 ureas Chemical class 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 56
- 230000023556 desulfurization Effects 0.000 abstract description 51
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 29
- 235000011116 calcium hydroxide Nutrition 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 241000196324 Embryophyta Species 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000000428 dust Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 10
- 235000019504 cigarettes Nutrition 0.000 description 9
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000013505 freshwater Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000001294 propane Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
Abstract
The simultaneously removing sulfur and nitrogen in furnace method is to be selected from a) ammonia or ammoniacal liquor and b) sulphur ammonium or its acidic aqueous solution and C) the medicament i of urea and compound powder or its aqueous solution) 700-1100 ℃ of ascending zones in stove separately respectively, 500-900 ℃ of Zhong Liu districts and＜500 ℃ of lower current areas processing; Ii) medicament separately or two kinds be blended in handle in above-mentioned 2 districts and iii) medicament be blended in above-mentioned 1 district and handle, i wherein) or ii) the time, in the main denitration of ascending zone, the main desulfurization of middle stream and lower current area and the 2nd section denitration; While desulphurization denitration in the time of iii).
Description
The invention relates to from various boilers, various heating furnace and incinerator etc. in the waste gas of the burning of discharging and remove sulfur oxide (SO simultaneously
X) and nitrogen oxide (NO
X) the method for simultaneously removing sulfur and nitrogen in furnace.
In the general desulfurization and method of denitration that China adopts, be to use ammonia as reducing agent for denitration, in the presence of catalyst, now for NO
XOptionally contact the method for reduction, and be to adopt the damp process resemble wet type lime stone-gypsum method for desulfurization.
, these methods are because area that its configuration device occupied is very big and capital cost and running are all very high by the cost of usefulness, so wish that more miniaturization is arranged, cheap implementation method.
On the other hand, having a kind of is that desulfurization medicament with lime stone etc. directly drops into direct desulfurization method in the so-called stove in the stove, can correspondingly alleviate above-mentioned capital construction cost and operating cost expense, but effective utilization of medicament etc. are below half of damp process only, and medicaments such as unreacted CaO then are discharged from.For example, when adopting in the stove direct desulfurization mode, in the cigarette ash of discharging, then contain a large amount of CaSO for coal fired boiler
4And CaO, need to carry out ash discharge simultaneously and handle.
First purpose of the present invention is in order to satisfy above-mentioned requirement, provides with low cost and has implemented, and can give play to the process for simultaneously removing sulfur and nitrogen in furnace of good desulphurization denitration performance.
Second purpose of the present invention is to provide and captures the unreacted ammonia that reclaims to come out from the pump-down process process or the sulphur ammonium of generation, and the method that can re-use.
The present invention is exactly in order to finish above-mentioned purpose, through taking off the method for meaning research, desulfurization denitration method in the time of in its first kind of stove, be will be from a) ammonia or its aqueous solution and b) aqueous solution and the c of sulphur ammonium and sour sulfur ammonium) medicament selected the powder of urea and urea compounds or the medicament group that its aqueous solution constitutes, supply with medicament with one of following three kinds of distribution methods:
ⅰ) be dispersed in the interior temperature of stove respectively individually below 1100 ℃, the ascending zone of scope, the interior temperature of stove are below 900 ℃ more than 700 ℃, the Zhong Liu district of scope more than 500 ℃ reaches in 3 districts of the lower current area below 500 ℃ from the outlet of still to the downflow temperature, at 3 phase process gases;
ⅱ) individually a kind of in these medicaments, and other two kinds be dispersed in 2 districts in above-mentioned three districts with the form of mixing, at 2 phase process gases; And
ⅲ) be dispersed in 1 district in 3 districts, at 1 phase process gas with mixed form.
With ⅰ) or during distribution method ⅱ), mainly be to carry out denitration reaction at ascending zone, in the Zhong Liu district and lower current area carry out the denitration reaction of desulphurization reaction and second section;
With ⅲ) distribution method the time, can cause desulphurization reaction and denitration reaction simultaneously.
The best embodiment of the 1st kind of process for simultaneously removing sulfur and nitrogen in furnace comprises following process:
From a) ammonia or its aqueous solution b) select at least a medicament the medicament group that forms of the aqueous solution of sulphur ammonium and sour sulfur ammonium and be dispersed in the stove temperature below 1100 ℃, in the ascending zone more than 700 ℃ in the scope, make it the process of denitration reaction and some desulphurization reactions in the 1st stage of taking place;
From a) ammonia or its aqueous solution and b) aqueous solution and the c of sulphur ammonium and sour sulfur ammonium) at least a medicament selected the powder of urea and urea compounds or the medicament group that its aqueous solution is formed, be dispersed in the interior temperature of stove below 900 ℃, in the Zhong Liu district of scope, make it to take place the process of desulphurization reaction and the 2nd stage denitration reaction more than 500 ℃; And
From a) ammonia or its aqueous solution and b) at least a medicament selected the medicament group that forms of sulphur ammonium and sour sulfur aqueous ammonium, be dispersed in from the outlet of still to the downflow temperature and in the lower current area below 500 ℃, make it the desulphurization reaction process in the 2nd stage of taking place.
The method of the 2nd kind of simultaneously removing sulfur and nitrogen in furnace of the present invention is to be made of following pump-down process process and medicament removal process.
Exhaust process promptly is with a) ammonia or its aqueous solution and b) aqueous solution and the c of sulphur ammonium and sour sulfur ammonium) medicament selected among the powder of urea and urea compounds or the medicament group that its aqueous solution is formed, supply with medicament in one of following 3 kinds of modes:
ⅰ) be dispersed in the interior temperature of stove respectively individually below 1100 ℃, the ascending zone of scope, the interior temperature of stove are below 900 ℃ more than 700 ℃, the Zhong Liu district of scope reaches in 3 districts of the lower current area below 500 ℃ from the outlet of still to the downflow temperature, at 3 phase process gases more than 500 ℃;
ⅱ) with 1 in these medicaments individually, and other 2 be dispersed in 2 districts in above-mentioned 3 districts, at 2 phase process gases with mixed form; And
ⅲ) be dispersed in 1 district in 3 districts, carry out gas treatment 1 stage with mixed form.
With ⅰ) or during distribution method ⅱ), mainly be to cause denitration reaction at ascending zone, in the Zhong Liu district and lower current area mainly be the denitration reaction that causes desulphurization reaction and the 2nd section;
With ⅲ) distribution method the time, can cause desulphurization reaction and denitration reaction simultaneously.
The medicament removal process promptly by being arranged on the exhaust decontaminating apparatus on the flow flue under the stove, captures the unreacted ammonia or the sulphur ammonium of generation or the process of sour sulfur ammonium that reclaim to come out from exhaust process.
The best embodiment of the 2nd kind of simultaneously removing sulfur and nitrogen in furnace is made of pump-down process process and medicament removal process.
Exhaust process comprises from a) ammonia or its aqueous solution and b) at least a medicament selected the medicament group that forms of sulphur ammonium and sour sulfur aqueous ammonium is dispersed in the stove temperature below 1100 ℃, in the ascending zone of scope, make it the process of denitration reaction and some desulphurization reactions in the 1st stage of taking place more than 700 ℃;
From a) ammonia or its aqueous solution and b) sulphur ammonium and sour sulfur aqueous ammonium and c) at least a medicament selected the powder of urea and urea compounds or the medicament group that its aqueous solution is formed, be dispersed in the interior temperature of stove below 900 ℃, in the Zhong Liu district of scope, make it to take place the process of desulphurization reaction and the 2nd stage denitration reaction more than 500 ℃; And
From a) ammonia or its aqueous solution and b) at least a medicament selected the medicament group that forms of the aqueous solution of sulphur ammonium and sour sulfur ammonium, be dispersed in the lower current area below 500 ℃ from the outlet of still to the downflow temperature, make it the process of the desulphurization reaction in the 2nd stage of taking place.
The medicament removal process, promptly the exhaust decontaminating apparatus of the following flow flue by being located at stove captures the unreacted ammonia that reclaims to come out from the pump-down process process, or the sulphur ammonium that generates, or the process of sour sulfur ammonium.
The 2nd kind of process for simultaneously removing sulfur and nitrogen in furnace, be preferably in the above-mentioned medicament removal process, ammonia or sulphur ammonium or sour sulfur aqueous ammonium and quick lime or the calcium hydroxide that to reclaim are set, separate out the groove internal reaction with the slurries shape at reactive crystallization, the ammonia composition is reclaimed with the gas that contains water vapour, the ammonia that gypsum is separated out in sulfate radical or sour sulfur acid group and calcium ion reaction reclaims the gypsum crystallization precipitation process.
In addition, in the 2nd kind of process for simultaneously removing sulfur and nitrogen in furnace, be preferably in above-mentioned ammonia and reclaim and the ammonia that recovery is contained water vapour is set in the gypsum crystallization precipitation process compresses and cool off and the ammoniacal liquor preparation process that obtains ammoniacal liquor.
And then, in the 2nd kind of process for simultaneously removing sulfur and nitrogen in furnace, being preferably in above-mentioned ammonia reclaims in the gypsum crystallization precipitation process, after the gypsum slurries Separation of Solid and Liquid that will reclaim is set, reclaim gypsum with solid constituent, reclaim ammoniacal liquor with liquid component, or the Separation of Solid and Liquid process of unreacted sulphur aqueous ammonium or sour sulfur aqueous ammonium.
When the 2nd kind of process for simultaneously removing sulfur and nitrogen in furnace implemented, temperature is below 900 ℃ in being equivalent to stove, the proparea in scope district is that temperature is below 1100 ℃ more than 500 ℃, more than 700 ℃ in the district of scope, and/or be equivalent to temperature back zone in scope district more than 500 ℃ below 900 ℃, promptly from the outlet of still to the downflow temperature, also can supply with medicament in the district below 500 ℃ and handle with the distribution method of the method for the 2nd kind of simultaneously removing sulfur and nitrogen in furnace.
The 1st figure represents the flow chart of combustion test.The 2nd figure represents urea/SO
2The relation of equivalent proportion and desulfurization degree.The 3rd chart temperature indicating degree and denitration rate relation.The 4th figure represents NH
+
4Scaled value and NH
+
4The relation of assay value.The relation of the 5th chart temperature indicating degree and desulfurization degree.The relation of the 6th chart temperature indicating degree and denitration rate.The 7th figure represents NH
+
4Scaled value and NH
+
4The relation of assay value.The 8th figure represents the relation of ammonia addition and desulfurization degree and denitration rate, and the 9th figure represents the relation of time and reactivity.The 10th～12 figure represents the flow chart of in-furnace desulfurization, denitration method.
Process for simultaneously removing sulfur and nitrogen in furnace of the present invention is comprised of 4 processes of following explanation.
Process 1: denitration in the stove sweetening process
1. in stove, temperature is below 1100 ℃ more than 700 ℃ in the ascending zone of scope, with a) ammonia or its aqueous solution, b) aqueous solution of sulphur ammonium and/or sour sulfur ammonium is dispersed in the stove with independent form or mixed form, makes it the process of denitration reaction and some desulphurization reactions in the 1st stage that occured.
2. in stove, at the downflow temperature of above-mentioned dispersion zone below 900 ℃ more than 500 ℃ in the Zhong Liu district of scope, with a) ammonia or its aqueous solution, b) sulphur ammonium and/or sour sulfur aqueous ammonium, c) powder or the aqueous solution of urea and/or urea compounds spreads in the stove with independent form or mixed form, carries out the process of desulphurization reaction and the denitration reaction in the 2nd stage.
3. exporting to the lower current area of dirty temperature below 500 from stove, with a) ammonia or its aqueous solution, b) aqueous solution of sulphur ammonium and/or sour sulfur ammonium is dispersed in the flue with independent form or mixed form, makes it to occur the process of the 2nd stage desulfurization reaction.
Process II: the sulphur ammonium of unreacted ammonia or steam and generation or the removal process of sour sulfur ammonium
At the lower flow flue of the dust collect plant that is attached to boiler etc. (for dust collect plant is not installed, be equivalent to chimney near the flue of porch) on, by washing cigarette device or other suitable absorption plants with water as the wet type of absorbing medium, the ammonia that will discharge from said process 1 or the water vapour that contains ammonia and sulphur ammonium or sour sulfur ammonium gas or smog gas etc. capture the process of recovery.
Process III: make at the regenerant of process II and quick lime or calcium hydroxide and react, carry out the recovery of ammonia and the process that gypsum is separated out
Separate out device at the ammoniacal liquor of process II recovery and the aqueous solution importing reactive crystallization of sulphur ammonium or sour sulfur ammonium, and to the powder that wherein adds the quick lime calcium hydroxide or its water slurry, make the sulfate radical that consists of sulphur ammonium or sour sulfur ammonium or sour sulfur acid group with the calcium ion reaction, separate out gypsum, and then the reactive crystallization precipitation process that the ammonia of this reaction generation is displaced with gas or steam form.
Process IV: the process of separating recovery and the recovery of sulphur aqueous ammonium and its circulation of the recovery of ammonia and its recirculation and gypsum
1. the ammonia that contains water vapour that the said process III has been reclaimed obtains the process of ammoniacal liquor by compression and cooling.
2. after the equipment for separating liquid from solid of the gypsum crystallization slurries after reactive crystallization being separated out by centrifugal separator etc. carries out Separation of Solid and Liquid, reclaim gypsum crystallization with the goods form, filtrate as the sulphur aqueous ammonium is mixed with above-mentioned ammonia spirit 1., the process that mixed liquor uses as the desulfurization denitrification agent recirculation of process 1.
According to the ultimate criterion of desulphurization denitration, by product is to be used for other aspects with gypsum or with sulphur aqueous ammonium form, and the combination of above-mentioned each process can some difference among the present invention:
(1) with the SO in the exhaust2After the absorption, reclaim with gypsum form. When wishing to get high desulfurization rate and high denitration rate, 1.～3. reach the process II, III, IV of process 1 make up, and the combination of 1. and 2. or the 2. and 3. combination of process 1 and process II, III, IV.
When (2) paying the next sulphur ammonium of output or sour sulfur ammonium for other purposes, process 1 1.～3., 1.～2., the combination of the combination one of in 2.～3. and process II (at this moment, sulphur ammonium or the sour sulfur aqueous ammonium that has been reclaimed by the process II, directly be recycled to process 1 and use, wherein a part is discharged outside systems as other purposes) myriad combinations of carrying out.
" desulphurization denitration test "
The reaction of each process among the present invention can be confirmed by the represented vertical corrosion chamber of the 1st figure and other glass experimental rig.
The device that is used for this test is the combustion chamber (6) of using fine breeze and is its main body with reative cell (1) that the desulphurization denitration that its rear flow side joins is used. The heap(ed) capacity of fine breeze quantity combusted is 10Kg/ hour, wherein also can be to combustion-supporting ignition temperature control, the NO that carries out with propaneXThe control of generating capacity and then injection SO2Gas flow is regulated the SO in the smoke evacuation2Concentration. During test, the mode that can only burn the multifuel combustion of propane, propane and fine breeze or only burn fine breeze, the numerical value of regulation can control and the control of supplying with the combustion air amount is reached by the quantity delivered of these fuel to the temperature of burning.
From the smoke evacuation that reative cell (1) is discharged, can pass through the cooling of air heat exchanger (4) and gas cooler (5), use again bag hose (3) dedusting, then discharged to atmosphere.
Reative cell (1) is that the stainless steel tube by internal diameter 330mm, high 4m consists of. The outside of reative cell (1) is provided with the electric heater (2) of garden tubular, so just can make the inner burning and gas-exhausting temperature of reative cell (1) be controlled at the temperature of regulation. Desulfurization denitrification agent from the top entrance (11) of reative cell along with air stream together is injected into reative cell (1).
O in the smoke evacuation2、SO
2、NO
XConcentration can be by being arranged on reative cell (1) outlet and the analysis meter (7) (8) of bag hose (3) outlet measure respectively. Namely, in these analysis meters (7) (8), use with the exhaust after self decontaminating apparatus metal sintering filter dedusting and import to infrared-type SO2Analysis is taken into account in the zirconia formula oxygen analyzer, to different local SO2And O2Analyze. In addition, further use chemiluminescence formula NO in the outlet of bag hose (3)XAnalysis meter carries out NOXAnalyze, carry out SO according to the wet type exhaust gas analysis of JIS law regulationXThe full S that analyzes and be absorbed in the absorption liquid analyzes and NH+
4Concentration analysis.
Measure the represented temperature everywhere that goes out in the 1st figure with thermocouple thermometer; For dropping into fuel quantity, during fine breeze, measure consumption with metering device, during propane, the available gas flowmeter is measured; The air capacity of burning can be measured with orifice flow meter; Capacity can be measured with Venturi type gas flowmeter (10). In addition, from fuel quantity and to drop into theoretical capacity and actual measurement capacity that air flow meter calculates consistent in certain percentage of being everlasting, confirm that thus each metrical instrument is in correct work.
As the SO in the exhaust2, add industrial SO2Gas, the adjustment addition makes the SO in the exhaust2Concentration reaches 500ppm.
(1) desulfurization and denitrification reaction of aqueous solution of urea
Urea shows denitration reaction, and this is known thing. But simultaneously also causing desulphurization reaction, is the present inventors by in addition clear and definite after testing.
These reactions can be thought and represent with following reaction equation.
(1) denitration reaction
(2) desulphurization reaction
Herein, 1. the denitration reaction of formula is reported in the literature to some extent, but 2.～3. the reaction of formula is the contemplated reaction equations of present inventors.Just can produce through sulphur ammonium after such course or sour sulfur ammonium, or urea and SO
2Directly reaction also is not very clear and definite in present stage, but as explanation later on, is to have generated sulphur ammonium or sour sulfur ammonium really.
Here, use the experimental rig of the 1st figure, from inlet (11) in reative cell (1) inside of this device, the desulfurization performance when aqueous solution of urea is blown into spray form, or the denitration performance of this moment is illustrated respectively on the 2nd figure and the 3rd figure.In the 2nd figure, transverse axis is got and is made urea and SO
2Molar equivalent get and make desulfurization degree than, the longitudinal axis, will be blown into the combustion gas temperature of position as parameter.
Can find out clearly that from this figure for desulfurization, efficient height when temperature is low is when temperature is 750 ℃, when equivalent proportion is 1.1 left and right sides, almost can carries out 100% desulfurization.
At this moment, the burning and gas-exhausting condition is as follows:
Fuel: propane
SO
2Concentration: 500ppm
NO
XConcentration: 170ppm～60ppm
*
Burning and gas-exhausting amount: 90～100NM
3/ time
Concentration of aqueous solution of urea: 25～50g/l
(notes)
*Temperature NO according to burning
XThe degree of generation also different.
In the 3rd figure, transverse axis is got the temperature, the longitudinal axis that are blown into the position and is got the denitration rate of doing.
This figure is with urea and NO
XMolar equivalent mark and draw than the data that were fixed on 5 o'clock and form.The denitration rate of the temperature that is blown into the position from the 3rd figure as can be seen more than 820 ℃ the time is about 80%, and below the temperature, along with decrease of temperature, the denitration rate has downward trend gradually at this.In addition, when the temperature that surpasses 1150 ℃, the denitration rate has downward trend, and does not express its relation in this figure.
Below, exhaust in the time of will be by this test behind the sintered filter of the outlet side of the represented bag hose (3) of the 1st figure, method according to JIS regulation washes, and obtains with the gravimetric analysis of the capacity analysis of 1/10N caustic soda titer and barium sulfate precipitate method respectively then and dissolves sulfuric acid amount and the total sulfur content that contains in this detergent remover.In addition, obtain ammonia concentration in this solution with ammonium ion electrode analysis meter.From these analysis results, obtain the SO of calculating by total sulfur content
4Measure (A), obtain the SO of calculating by sulfuric acid amount
4Amount (B) is calculated and is used for the required NH of (A-B) quantitative response
+
4Amount.And, confirm that do not exist SO in the absorption liquid this moment
--
3, all with SO
--
4Form exists.
The 4th figure represents the NH that calculates
+
4Amount and the NH that obtains by the ion electrode analysis meter
+
4The dependency relation of amount.
In the figure, reactive material is assumed to the sulphur ammonium, through after converting, is distributed in slope and is on the each point on 1, and provable its reactant is the sulphur ammonium.In addition, for the low test of the interpolation equivalent proportion of urea, be presented at the NH of the 4th figure
+
4The part that scaled value is little.At this moment, can be assumed to the sour sulfur ammonium, it is on 1/2 straight line that each point is distributed in the back slope that converts, and has proved that the reactant of this moment is the sour sulfur ammonium, clearly is the result that 2.～4. above-mentioned reaction equation acts on.
This sulphur ammonium reactant can be thought to be contained in the exhaust by bag hose and sintered filter, and products such as the sulphur ammonium in this method are to exist with smoke-like or gas shape.If these are solids, just should in this test, after operating for a long time, not see the deposit of the thing that on these surfaces, responds on the filtering surface of bag hose or observe the deposit of these reactants on the sintered filter yet.In addition, as a ring of this test,, be contained in NH in the cigarette ash by what bag hose captured even when coal dust firing, add urea water
+
4Amount, most applications also are the vestige degree.
Can find out significantly that from the above fact add that urea carries out desulphurization reaction and the material that generates is sulphur ammonium or sour sulfur ammonium, these materials are to exist with gas or smoke condition, can not trap with bag hose in the aerosol more than 100 ℃.
(2) the desulphurization denitration performance of sulphur ammonium
Because the sulphur ammonium contains SO on it is formed
--
4So when it was used as the in-furnace desulfurization, denitration agent, worry sulphur ammonium can be emitted SO when decomposing
2, therefore on general knowledge, generally do not use as desulfurization denitrification agent.
, according to present inventors' result of the test, explanation has found that clearly the sulphur ammonium can play the reagentia of desulphurization denitration as described later
(1) denitration reaction
(ⅰ) high-temperature region:
Warm area (ⅱ):
The reaction of above-mentioned 5. formula is the reaction that at high temperature takes place, and under this condition, clearly emits SO
26. the reaction of formula is the reaction that takes place under middle warm area, under this condition, denitration can take place, and does not see the desulfurization phenomenon.
(2) desulphurization reaction
In lower humidity province, even the sulphur ammonium also desulphurization reaction can take place, this can think that the sulphur ammonium is absorbing SO as the 7. reaction of formula
2The back is oxidized, in the process that forms the sour sulfur ammonium desulfidation has taken place.
In addition, can think that the sulfuric acid that generates generates the sour sulfur ammonium according to the reaction of following 9. formula in 6. formula is reacted.
In order to confirm these reactions, availablely above-mentionedly carry out desulphurization denitration with urea and test identical condition, measuring the sulphur ammonium concentration is that the aqueous solution of 40g/l supplies to the desulphurization denitration characteristic of the reative cell shown in the 1st figure (1) when interior from inlet (11) spraying.
The 5th figure has represented the SO in sulphur aqueous ammonium and the exhaust
2Molar equivalent than setting 1 o'clock the temperature and the relation of desulfurization degree of being about.
Among this figure, transverse axis is got the delivery temperature of doing on the solution eject position, and the longitudinal axis is got the desulfuration in furnace rate of doing.When desulfurization degree is represented one (negative), proved because SO has been emitted in the decomposition reaction of sulphur ammonium
2
When the 5th figure used as desulfurization denitrification agent with the sulphur aqueous ammonium as can be seen, some desulphurization reactions also took place below 800 ℃ the time in temperature, and this can think the exercising result of above-mentioned 7. formula reaction.
In the aerosol of temperature more than 900 ℃, can observe the SO that emits by the reaction of 5. formula
2, this moment, desulfurization degree showed negative value.At these denitration reactions and NO
XThe reaction intricately complexing of emitting in the intermediate temperature area of reaction 5.～8. is staggered in together, and the decentralization of data is bigger, may be exactly the reason of above-mentioned reaction complexing.More than when the desulphurization reaction phenomenon takes place, also can be observed denitration reaction.
The 6th figure has shown the denitration characteristic of this moment.
The formation of this figure is the same with the 5th figure, but the longitudinal axis is represented the denitration in the stove rate.
From the 6th figure as can be seen, for denitration reaction, when temperature is high, denitration rate height, with about 800 ℃ be boundary, when this temperature was following, the denitration rate was tending towards being fixed on 60%.
In addition, more than 800 ℃ the time, because SO is arranged simultaneously
2Emit,, during temperature below this, suppose and carry out according to the 6. reaction of formula so think that reaction carries out according to 5. formula.
Moreover shown denitration rate is when not adding the sulphur ammonium on this figure, the NO that is taken place by the propane burning
XFor benchmark, for example, the temperature that is blown into the position in the time of 1100 ℃, the NO of generation
XValue is 60ppm for 170ppm, 700 ℃ the time, respectively according to variations in temperature, and the NO of generation
XA reference value also is different.
Below, when confirming that the sulphur aqueous ammonium sprays, follow the product of desulfurization and denitrification reaction, use the same manner with above-mentioned interpolation urea, shown in the 4th figure, from conversion NH
+
4The NH that concentration value and ion electrode analysis obtain
+
4The relativeness of concentration is illustrated on the 7th figure.Can find out significantly that from this figure product is sulphur ammonium or sour sulfur ammonium, according to 7. formula and the 8. reaction of formula record, the sour sulfur ammonium when urea adds, begin just can be a large amount of generation.
Find out the sulphur aqueous ammonium significantly from the above fact, can cause desulfurization and denitrification reaction according to reaction condition, its reactant is the sour sulfur ammonium.
In addition, be and the irrelevant sulphur ammonium of 5.～8. formula reaction at the represented sulphur ammonium of the 7th figure, their unreacteds directly row outside system and be captured.
(3) the desulphurization denitration performance of ammonia
As everyone knows, ammonia has NO
XReduction, when using,, to and use with catalyst usually in order to improve reaction efficiency as denitrfying agent.
Moreover, with SO
2Gas is passed in the ammoniacal liquor, and then when dropping into excessive air, then ammonia and SO
2And O
2React at an easy rate, and generate the sulphur ammonium, this is generally known.
The reaction of this moment is as follows.
(1) denitration reaction
(2) desulphurization reaction
As the ammonia of desulfurization denitrification agent when the furnace injection, for denitration, with catalyst and time spent relatively, reaction efficiency is lower, expects better effect.
Denitration performance when adding ammonia from inlet (11) in the reative cell (1) that the 1st figure represents is illustrated on the 8th figure.
The transverse axis of this figure is got the ammonia concentration that work adds in exhaust, the longitudinal axis is got work denitration rate and desulfurization degree at that time.
Exhaust conditions during test:
Fuel: the multifuel combustion of propane and fine breeze
Burning and gas-exhausting amount: 105Nm
3/ time
The temperature of point of addition: 800 ℃
SO
2Concentration: 800ppm
NO
XConcentration: 200ppm
Can find out significantly from the 8th figure, for the denitration performance of ammonia, be 600ppm(NH at its addition
3/ NO equivalent proportion=3) during above scope, the denitration rate is 70%, and more than this, even increase addition again, the denitration rate does not increase yet, and keeps certain value.
, desulphurization reaction like that, can not take place in this moment fully in stove shown in the 8th figure, and the method for anhydrous ammonia being added to the high-temperature region is to obtain desulfurized effect.This can think because the water that there is no need exists, can not by
Formula is reacted with reaction temperature too high former thereby is caused.
As previously mentioned, have abundant water in the presence of
The reaction of formula can easily be carried out.Therefore, studied ammonia with the ammoniacal liquor form, in the low temperature part below 500 ℃, and at the i.e. desulphurization reaction of half wet type state of very wet state.The result of the test remarks of this moment is in the 8th figure.
Can find out significantly from this figure, add to by water with necessity
In the reaction of formula, then be easy to carry out desulphurization reaction with ammonia.
(4) sulphur ammonium or sour sulfur ammonium are to the absorption of water
As previously mentioned, use urea, sulphur ammonium and ammoniacal liquor to carry out by product behind the desulfurization and denitrification reaction as sulphur ammonium or sour sulfur ammonium as desulfurization denitrification agent, in 100 ℃ exhaust, they exist with smoke-like or gas shape.
In addition, they are materials very high to water-soluble, absorb capture so use with water at an easy rate as the simple wet type exhaust decontaminating apparatus of medium.
For example, the result who in above-mentioned wet analysis, uses the such simple exhaust decontaminating apparatus of absorption bottle to check, NH
+
4In the 1st absorption bottle, all be captured, almost just can't check NH from the 2nd absorption bottle
+
4Existence, its highly absorbable.
(5) separate out from the gypsum reactive crystallization of sulphur ammonium or sour sulfur ammonium
Present inventors have studied from sulphur ammonium or sour sulfur ammonium and have paid the output gypsum and reclaim the method for ammonia.
Quick lime or calcium hydroxide are put in the aqueous solution of sulphur ammonium or sour sulfur ammonium, studied its reaction.
These reactions can be supposed and undertaken by following formula.
(1) quick lime drops into generation calcium hydroxide in back in the water:
(2) calcium hydroxide and sulphur ammonium or sour sulfur ammonium reaction, separate out gypsum:
（NH
4）HSO
4+Ca（OH）
2+H
2O→
(3) ammoniacal liquor is emitted ammonia by heating with steam or gas shape.
When being cooled off, it then is reduced into ammoniacal liquor.
Here
Formula reaches
Formula is known reaction equation, and
Formula reaches
Formula is necessary to be confirmed.
Present inventors are in order to confirm
Formula reaches
The reaction of formula has been carried out reaction test by simple glass system experimental rig.In this test, sulphur aqueous ammonium 500ml is added in the flask of 1000ml capacity, after wherein dropping into calcium hydroxide, heat this solution, make it explosive evaporation, the steam of this generation is more condensing than inferior cooling tube cooling with the lining, and then this condensed liquid is injected in the dilution heat of sulfuric acid, with NH
+
4Composition is absorbed in this liquid and reaction.Per 10 minute will change once fresh dilute sulfuric acid solution to this absorption liquid this moment, changes 6 times, promptly continued 60 minutes.With ammonium ion electrode method, the absorption liquid that obtains is like this carried out NH
+
4Its reaction process is studied in component analysis.
NH is emitted in reaction thus
+
4The effluxion of amount and the relation table of its cumulant are shown among the 9th figure.
(A) and experimental condition (B) are as follows among this figure:
The reaction test condition
Project A B
Sulphur aqueous ammonium amount (ml) 500 500
Sulphur aqueous ammonium concentration (g/l) 40 40
Calcium hydroxide addition (g) 15 22
Reaction temperature (℃) 100～102 100～102
Reaction time (branch) 60 60
NH
4 +Absorb and use 30% dilute sulfuric acid
Liquid measure (ml) 50 50
(A) and (B) condition difference is that just the calcium hydroxide addition is different, and other all are to carry out under identical conditions.
Can find out significantly that from the 9th figure calcium hydroxide and sulphur ammonium react quite easily, under the situation of (A), drop into the NH of sulphur ammonium
+
4Amount about 80% at 60 minutes internal reactions, under the situation of (B), 90% all can react.
In addition, NH in the raffinate
+
4Amount and the NH that emits
+
4NH in the additive value of amount and the initial sulphur ammonium that drops into
+
4Amount is almost consistent, and revenue and expenditure is a balance.
From this result, can confirm to carry out at an easy rate
The reaction that formula is represented.In addition, this reaction is that the concentration of alkali has relation in the input amount ie in solution with calcium hydroxide, (A) of (B) when therefore dropping into 22g when dropping into 15g, and it is big that its reaction speed is wanted.
Moreover, though
The reaction of formula still be can not determine, can infer ratio theoretically
Formula has bigger reaction speed.
(6) recovery of gypsum and ammonia
With above-mentioned reacted gypsum slurries, carry out the suction strainer test with filter paper, can carry out Separation of Solid and Liquid simply.Filtrate is limpid, does not see the appearance that has solids to pass through.
In addition, in the gypsum that separation obtains, also residual have a large amount of unreacted calcium hydroxides, so it will be made goods the time, for the residual quantity that reduces calcium hydroxide or the gypsification aspect of residual calcium hydroxide, also be necessary further research.
About the recovery of ammonia, as mentioned above,, just can reclaim ammonia simply as long as reactive vapors is cooled off condensing, need not install especially, it just can be zero reclaiming loss.
In filtrate, also residual have a unreacted sulphur ammonium composition, can mix it once more with above-mentioned ammoniacal liquor, and the desulfurization denitrification agent that can be used as project (1) record reuses.
(7) summary of result of the test
The achievement in research that arrangement is above, conclusion is as follows:
(1) reaction of the in-furnace desulfurization, denitration in the process 1
ⅰ) aqueous solution of urea has good desulphurization denitration performance, as urea/SO
2Equivalent proportion be 1.1 o'clock, can give and see that 100% desulfidation is arranged.Its performance is subjected to spraying input position Temperature Influence.For denitration, in the humidity province more than 800 ℃, can obtain about 80% denitration rate, 1. the reaction equation of this moment can be assumed to～4. formula.
ⅱ) the sulphur aqueous ammonium also has desulfurization off sulfide effect.But temperature has very big influence to this, more than 800 ℃ the time, SO can take place to emit again
2Reaction.In addition, desulphurization denitration has shown opposite effect, during as if the raising denitration effect, just may be related to SO
2Emit.5. the reaction equation of this moment can be assumed to～8. formula, and these are representing their complex relationship.From this fact as can be seen the sulphur ammonium have denitration effect more than 60%.
ⅲ) ammonia has good denitration performance, for example, in the time of 800 ℃, ammonia/NO
XEquivalent proportion is 3 o'clock, can obtain 70% denitration rate.At this moment, reaction is undertaken by 10. formula.
Ammonia be can't see desulfurized effect fully when anhydrous state.When wet state, can obtain very big desulfurized effect, its reaction is pressed
Formula reaches
Formula is carried out.
IV) reaction by product above-mentioned ⅰ)～ⅲ) is sulphur ammonium or sour sulfur ammonium, they are after reaction in furnace, be present in the exhaust of burning with smoke-like or gas shape, owing in the aerosol of gas temperature more than 100 ℃, be not exist, so can not capture with dust collect plants such as bag hoses with particulate forms.
In addition, in the cigarette ash that they are produced in the time of also may being adsorbed on coal dust firing with the degree of trace, pass through dust collect plant.
(2) absorption of sulphur ammonium in the process II or sour sulfur ammonium
Product sulphur ammonium or sour sulfur ammonium as the process I are very big to the dissolubility of water, so just can all reclaim with simple decontaminating apparatus.
(3) the gypsum reactive crystallization in the process III is separated out the recovery with ammonia
Easy and the calcium hydroxide reaction of sulphur ammonium or sour sulfur ammonium can be separated out gypsum and be emitted ammonia.Can be assumed to this reaction
Formula.
Its filterability of gypsum crystallization that separate out this moment is good, easily carries out Separation of Solid and Liquid.In addition, also not having sneaking into of gypsum in the filtrate, is limpid liquid.
Moreover, for the ammonia of emitting, can easily be reclaimed by cooling off condensing operation.
(4) ammonia that is obtained by the recovery of process IV ammonia and sulphur aqueous ammonium recirculation use III mixes with sulphur aqueous ammonium in the filtrate with the ammoniacal liquor form, is used for the desulfurization denitrification agent of process I once more.
Embodiment
Below, specifically describe the present invention by embodiment with reference to the accompanying drawings.
All tests from the above description as can be seen, with urea, sulphur ammonium, sour sulfur ammonium and ammonia respectively individually or mixed form ground be ejected in the stove equably, after carrying out the in-furnace desulfurization, denitration reaction, reclaim with decontaminating apparatus again and be contained in the burning and gas-exhausting as the sulphur ammonium of by product or the gas or the smog gas of sour sulfur ammonium, and then in the above-mentioned by product aqueous solution that obtains, add quick lime or calcium hydroxide carries out the gypsum crystallization evolution reaction, reclaim gypsum, at this moment, the sulphur ammonium that is contained in the filtrate reaches owing to reacting the ammonia that produces and can use as desulfurization denitrification agent once more.
Use the method, the consumption of desulfurization denitrification agent is quite few, SO
2Finally can gypsum form reclaim.
As technology example, can be illustrated by the represented craft embodiment of inventing by present inventors of the 10th figure with above feature.
Flow chart for the 10th figure is described in detail, on the burner (22) of boiler body (21), supplies with the fine breeze that acts as a fuel.When the burning and gas-exhausting of this generation gives hot device (24) by nest of tubes (23) and waste gas, heat is fully absorbed, and behind dust collect plant (25) capture ash content, is the absorption tower through exhaust decontaminating apparatus (26), again with after inducing exhaust blower (27) guiding chimney, outside the discharge system.
In above-mentioned exhaust stream, use this process, with ammoniacal liquor and sulphur ammonium or sour sulfur aqueous ammonium with mixed form, spray equably than the nozzle (40) of higher temperature part and be dispersed in temperature in the stove below 1100 ℃ more than 700 ℃ the ascending zone of scope from being arranged on boiler body (21), the denitration in the stove that mainly carried out for the 1st stage reacts and some desulphurization reactions.Then, from being arranged on the nozzle (41) of boiler body (21), aqueous solution of urea is evenly spread in the stove temperature below 900 ℃ more than 500 ℃ in the Zhong Liu district of scope, mainly carry out the desulfuration in furnace and the denitration reaction in the 2nd stage than lower temperature part.These pay sulphur ammonium or the sour sulfur ammonium that produces by the in-furnace desulfurization, denitration reaction, owing in the burning and gas-exhausting of high temperature, exist with smoke-like or gas shape, so can give hot device (24) and dust collect plant (25) by boiler nest of tubes (23), waste gas, reclaim with aqueous solution form with exhaust decontaminating apparatus (26).
In addition, if exhaust becomes the problem of white cigarette when occurring, can on the back stream of exhaust decontaminating apparatus (26), heater be set.
To exhaust decontaminating apparatus (26), supply with fresh water (FW) in order to replenish the cooling water that evaporation loses, and, be in tower, to scatter by the watering device that is arranged on epimere for preventing the atomizing of absorption liquid.The smog of sulphur ammonium etc. or gas can be by the absorption liquids that is recycled by circulating pump (29), be dispersed in the tower from the hypomere nozzle after, be absorbed in this absorption liquid.This absorption liquid is the part of sulphur ammonium or sour sulfur aqueous ammonium, then imports to reactive crystallization and separates out in the groove (30).In this groove, further drop into quick lime or calcium hydroxide, fully above-mentioned solution is mixed with the blade (32) of mixer (31).Separate out groove (30) inside at reactive crystallization, sulphur ammonium or sour sulfur ammonium and calcium hydroxide reaction begin to separate out gypsum.At this moment,, preferably make it be in heated condition in order to separate out accelerated reaction in the groove (30) at reactive crystallization, the method for intensification, can be blown into steam or by the dress heater.
React the gypsum of separating out thus, then carry out Separation of Solid and Liquid, discharge outside the system then at equipment for separating liquid from solid (33).In addition, the filtrate of coming out by equipment for separating liquid from solid (33), after boosting by pump (34), capable of circulation re-using.
On the other hand, because the ammonia that contains water vapour that reaction produces is used compressor (35) pressurization, and then makes it to become ammoniacal liquor through supercooling condensed device (36), be stored in the container (37).After this liquid boosted through pump (38), mix with the filtrate that equipment for separating liquid from solid (33) comes out, this mixed liquor is distributed in the stove equably from nozzle (40) or nozzle (41), reuses as desulfurization denitrification agent.In addition, as required, this mixed liquor can disperse to supply to from the outlet of still to the downflow temperature the lower current area below 500 ℃, to be used for the desulphurization reaction in the 2nd stage from dirty nozzle (44) homogeneous of heat economizer (24).
Be mainly used in the above-mentioned urea that desulfurization is used, at first in being housed, the solution allocation groove (42) of mixer (39) is dissolved in the fresh water (FW), and then after pumping up, be distributed to equably in the stove by nozzle (41), carry out the above-mentioned desulfuration in furnace reaction and the denitration reaction in the 2nd stage.
At this moment, can with should be sent to nozzle (40) recirculation ammoniacal liquor one sulphur ammonium water mixed liquor a part therewith urea liquid mix, reduce the consumption of urea with this.In addition since above-mentioned recirculation mixed liquor to go to nozzle (40) different with the sendout of (41), the degree of desulfurization and denitration is changed to some extent, therefore, be necessary to set the optimum value of sendout.
As concrete application examples, the consumption of its desulphurization denitration performance and medicament etc. can be described according to the 10th figure.
In addition, put down in writing among the 10th figure＜mark, material income and expenses represented at this place.Can find out significantly that from the example of following record in this technology, desulfurization degree is 97.5%, the denitration rate is 70%, and then per hour can obtain gypsum 1297Kg, has carried out desulphurization denitration in stove very effectively.
＜1〉coal combustion and the grey gas specification that produces
The kind of coal: bold and unconstrained state coal
Burning of coal amount: 21 tons/hour
Burning and gas-exhausting amount: 212.000Nm
3/ time
Exhaust is formed
CO
2The 14.5%(volume)
O
2The 3.3%(volume)
H
2O 8.4%(volume)
SO
2800ppm
NO
X200ppm(NO
XSuppress the burning back)
＜2〉the grey gas specification behind the in-furnace desulfurization, denitration (chimney inlet)
SO
220ppm
NO
X60ppm
＜3〉the desulfurization denitrification agent specification in the 1st stage
(from the specification of nozzle (40) dispersion soln in stove)
The solution amount of supplying with: 1.2m
3/ hour
Solution composition:
Sulphur ammonium: 3.5%(weight)
Ammoniacal liquor: 14.8%(weight)
Water: 81.7%(weight)
＜4〉the desulfurization denitrification agent specification in the 2nd stage
(the solution specification of in stove, disperseing from nozzle (41))
The solution amount of supplying with: 2.5m
3/ hour
Solution composition
Urea: 7.0%(weight) (192Kg/ hour)
Sulphur ammonium: 2.8%(weight)
Ammoniacal liquor: 11.6%(weight)
Water: 81.7%(weight)
＜5〉quick lime quantity delivered: 434Kg/ hour
＜6〉steam delivery volume: about 1000Kg/ hour
＜7〉absorption liquid of supplying with to reaction partial crystallization groove
The solution amount of supplying with: 5.2m
3/ hour
Solution composition:
Sulphur ammonium: 30.8%(weight)
Water: 69.3%(weight)
＜8〉gypsum by product amount: 1297Kg/ hour (but containing 2.2% calcium hydroxide)
The 11st figure represents to be used for other craft embodiments of the present invention.Below explain the flow chart of this figure, fine breeze fuel is supplied on the burner (52) of boiler body (51).Here the burning and gas-exhausting of Fa Shenging, during by boiler nest of tubes (53) and heat economizer (54), heat fully is absorbed, behind dust collect plant (55) capture ash content, through the exhaust decontaminating apparatus (56) is the absorption tower, with inducing exhaust blower (57), guide chimney into after, outside the discharge system, giving the ash content that hot device (54) and dust collect plant (55) trap by waste gas is the cigarette ash that contains anhydrous gypsum.
In the above-mentioned exhaust stream, for this process, calcium carbonate powder in storage tank (64) is by using the air pneumatic transmission, spray equably than the nozzle (60) of higher temperature part and be distributed in the stove temperature ascending zone of scope more than 700 ℃ below 1100 ℃ by being arranged on boiler body (51), mainly is that the denitration in the stove that carried out for the 1st stage reacts and some desulphurization reactions.Then,, aqueous solution of urea is distributed in the stove temperature below 900 ℃ more than 500 ℃ in the Zhong Liu district of scope equably, mainly carries out the desulfuration in furnace and the denitration reaction in the 2nd stage from the nozzle (61) of the comparison low temperature part that is arranged on boiler body (51).This aqueous solution of urea is to dispose in the solution allocation groove (62) of mixer (69) is housed, and uses pump (63) to boost then and is the independent aqueous solution of urea.These pay the sulphur ammonium or the sour sulfur ammonium of output from the in-furnace desulfurization, denitration reaction, owing in the burning and gas-exhausting of high temperature, exist with smoke-like or gas shape, so can pass through boiler nest of tubes (53), heating by the exhaust gases pipe (54) and dust collect plant (55), by exhaust decontaminating apparatus (56), reclaim with aqueous solution form.
In addition, when exhaust becomes Bai Yanshi, can heater be set in the back of exhaust decontaminating apparatus (56).
To exhaust decontaminating apparatus (56), supply with fresh water (FW) in order to replenish the cooling water that evaporation loses, and, can this water be dispersed in the tower by the watering device that is arranged on epimere for preventing the atomizing of absorption liquid.The smog or the gas of sulphur ammonium etc., the available absorption liquid that recycles by circulating pump (59), be dispersed in the tower from the hypomere nozzle after, be absorbed in this absorption liquid.This absorption liquid is the part of sulphur ammonium or sour sulfur aqueous ammonium, be sent to by pump (65) in the nozzle (66) of nozzle (60) or this nozzle (60) top, from here, make it be distributed in the stove temperature equably below 1100 ℃ more than 700 ℃ in the ascending zone of scope.In addition, as required, this absorption liquid can be distributed to the lower current area below 500 ℃ from the outlet of still to the downflow temperature equably from the dirty nozzle (74) of heat economizer (54), is used for the desulphurization reaction in the 2nd stage.
The 12nd figure represents to use another process implementing example of the present invention.Below the flow process of this figure is described in detail, fine breeze fuel is supplied in the burner (82) of boiler body (81), when the burning and gas-exhausting that is taken place is by boiler nest of tubes (83) and heat economizer (84) here, heat is fully absorbed, behind dust collect plant (85) capture ash content, through exhaust exhaustion device (56) is the absorption tower, and after inducing exhaust blower (87) to guide chimney (88) into, row is outside system.Cigarette ash by waste gas gives hot device (84) and dust collect plant (85) capture can be sent in the gypsum reactive tank described later (95).
In the above-mentioned exhaust stream, for this process, can be with the interior calcium carbonate powder of storage tank (94), by using the air pneumatic transmission, spray equably than the nozzle (90) of higher temperature part and be distributed in the stove temperature ascending zone of scope more than 700 ℃ below 1100 ℃ from being arranged on boiler body (81), the denitration in the stove that mainly carried out for the 1st stage reacts and some desulphurization reactions.Then, with aqueous solution of urea from be arranged on boiler body (81) relatively the nozzle (91) of low temperature part be distributed in the stove temperature equably below 900 ℃ more than 500 ℃ the Zhong Liu district of scope, mainly be to carry out the desulfuration in furnace and the denitration reaction in the 2nd stage.This aqueous solution of urea is to dispose in the solution allocation groove that mixer (99) is housed, and independent aqueous solution of urea after boosting with pump (93) or this independent aqueous solution of urea and aftermentioned are from the mixed liquor of nozzle (116) aqueous dispersion in stove.Pay the sulphur ammonium or the sour sulfur ammonium of output in the in-furnace desulfurization, denitration reaction, owing in the burning and gas-exhausting of high temperature, exist with smoke-like or gas shape, so can pass through boiler nest of tubes (83), heat economizer (84) and dust collect plant (85), reclaim with aqueous solution form with exhaust decontaminating apparatus (86).
In addition, if exhaust is Bai Yanshi, can heater be set in the back of exhaust decontaminating apparatus.
Supply with fresh water (FW) so that replenish the cooling water that evaporates and lose to exhaust decontaminating apparatus (86),,, water is dispersed in the tower by being arranged on the watering device of epimere in order to prevent the absorption liquid atomizing.The absorption liquid that recycles by circulating pump (89) is dispersed in the tower from the hypomere nozzle, makes smog such as sulphur ammonium or GAS ABSORPTION in this absorption liquid.This absorption liquid is the part of sulphur ammonium or sour sulfur aqueous ammonium, is sent in the gypsum reactive tank (95) that has mixer (101), reacts at this and the cigarette ash that captures.Contain the cigarette ash of separating out gypsum two water salt by what this reaction obtained, then after equipment for separating liquid from solid (103) Separation of Solid and Liquid, be discharged to outside the system.In addition, the filtrate of being come out by equipment for separating liquid from solid (103) is stored in the storage tank (96), after then boosting with pump (104), recycles.
On the other hand, the ammonia that contains water vapour that produces owing to reaction becomes ammoniacal liquor through supercooling condensed device (106), is stored in the container (107).After boosting it and then with pump (108), mix with the filtrate of coming out from equipment for separating liquid from solid (103), and this mixed liquor is sent in the nozzle (116) that is arranged on nozzle (90) top, from disperseing to supply in the stove temperature here below 1100 ℃ more than 700 ℃ the ascending zone of scope, used again as desulfurization denitrification agent.In addition, where necessary, this mixed liquor can also be from the dirty nozzle (114) of heat economizer (84), and homogeneous is distributed to from outlet of still to the lower current area of dirty temperature below 500 ℃, is used for carrying out the desulphurization reaction in the 2nd stage.
Use process for simultaneously removing sulfur and nitrogen in furnace of the present invention,, can low-costly implement desulphurization denitration, but also can bring into play good desulphurization denitration performance as above formation.And then, can also capture the unreacted ammonia that comes out from the pump-down process process or the sulphur ammonium or the sour sulfur ammonium of generation, can supply with and re-use.
Claims (7)
1, a kind of process for simultaneously removing sulfur and nitrogen in furnace is with a) ammonia or its aqueous solution and b) sulphur ammonium and sour sulfur aqueous ammonium and c) medicament selected among the medicament group that forms of urea and urea compounds powder or its aqueous solution, supply with medicament with one of following 3 kinds of distribution methods,
I) be dispersed in individually respectively in the stove temperature below 1100 ℃ more than 700 ℃ in the ascending zone of scope, the stove temperature below 900 ℃ more than 500 ℃ the Zhong Liu district of scope reach and export to 3 districts of the lower current area of downflow temperature below 500 ℃, at 3 phase process gases from stove;
Be individually one of in these medicaments ii), and other 2 be dispersed in 2 districts in above-mentioned 3 districts with mixed form, handle gas 2 stages; And
Iii) be dispersed in 1 district in above-mentioned 3 districts, at 1 phase process gas with mixed form;
With i) or during distribution form ii), mainly be to carry out denitration reaction at ascending zone, in the Zhong Liu district and lower current area carry out the denitration reaction of desulphurization reaction and the 2nd section,
During with iii) distribution form, can carry out desulphurization reaction and denitration reaction simultaneously.
2, according to the process for simultaneously removing sulfur and nitrogen in furnace of claim 1 record, it comprises following process:
A) ammonia or its aqueous solution and b) at least a medicament selected among the medicament group that forms of sulphur ammonium and sour sulfur aqueous ammonium, be dispersed in the stove temperature below 1100 ℃ more than 700 ℃ in the ascending zone of scope, carry out the process of denitration reaction and some desulphurization reactions in the 1st stage;
A) ammonia or its aqueous solution and b) sulphur ammonium and sour sulfur aqueous ammonium and c) at least a medicament selected among the powder of urea and urea compounds or the medicament group that its aqueous solution is formed, be dispersed in the stove temperature below 900 ℃ more than 500 ℃ in the Zhong Liu district of scope, carry out the denitration reaction process in desulphurization reaction and the 2nd stage; And
A) ammonia or its aqueous solution and b) at least a medicament selected among the medicament group that forms of sulphur ammonium and sour sulfur aqueous ammonium, be dispersed in from outlet of still to the lower current area of dirty temperature below 500 ℃, carry out the desulphurization reaction process in the 2nd stage.
3, a kind of process for simultaneously removing sulfur and nitrogen in furnace, it is made up of pump-down process process and medicament removal process, the pump-down process process comprises a) ammonia or its aqueous solution and b) sulphur ammonium and sour sulfur aqueous ammonium and c) medicament selected among the powder of urea and urea compounds and the medicament group that the aqueous solution is formed thereof, supply with medicament in one of following 3 kinds of modes:
ⅰ) be dispersed in individually respectively in the stove temperature below 1100 ℃ more than 700 ℃ in the ascending zone of scope, the stove temperature below 900 ℃ more than 500 ℃ the Zhong Liu district of scope reach and export to 3 districts of the lower current area of downflow temperature below 500 ℃, at 3 phase process gases from stove;
ⅱ) one of these medicaments individually and other 2 be dispersed in 2 districts in above-mentioned 3 districts, with mixed form at 2 phase process gases; And
ⅲ) be dispersed in 1 district in above-mentioned 3 districts, at a phase process gas with admixture;
With ⅰ) or during distribution form ⅱ), mainly be to carry out the denitration reaction that denitration reaction, Zhong Liu district and lower current area carry out desulphurization reaction and the 2nd section at ascending zone,
With ⅲ) the distribution form time, cause desulphurization reaction and denitration reaction simultaneously;
The medicament removal process, i.e. the exhaust decontaminating apparatus of the lower flue by being arranged on stove, unreacted ammonia or the sulphur ammonium of generation or the process that the sour sulfur ammonium captures recovery that will come out from the pump-down process process.
4, according to the process for simultaneously removing sulfur and nitrogen in furnace of claim 3 record, it is made up of pump-down process process and medicament removal process, and exhaust process comprises:
A) ammonia or its aqueous solution and b) at least a medicament selected among the medicament group that forms of the aqueous solution of sulphur ammonium and sour sulfur ammonium, be dispersed in the stove temperature below 1100 ℃ more than 700 ℃ in the ascending zone of scope, carry out the denitration reaction in the 1st stage and some desulphurization reaction processes;
A) ammonia or its aqueous solution and b) aqueous solution and the c of sulphur ammonium and sour sulfur ammonium) at least a medicament selected among the powder of urea and urea compounds or the medicament group that its aqueous solution is formed, be dispersed in the stove temperature below 900 ℃ more than 500 ℃ in the Zhong Liu district of scope, carry out the denitration reaction process in desulphurization reaction and the 2nd stage; And
A) ammonia or its aqueous solution and b) at least a medicament selected among the medicament group that forms of the aqueous solution of sulphur ammonium and sour sulfur ammonium, be dispersed in from the outlet of still to the downflow temperature and in the lower current area below 500 ℃, carry out the process of the desulphurization reaction in the 2nd stage;
The medicament removal process is by being arranged on the exhaust decontaminating apparatus of flow flue under the stove, capturing unreacted ammonia or the sulphur ammonium of generation or the process of sour sulfur ammonium of coming out from exhaust process.
5, according to claim 3 or 4 methods of putting down in writing, in the medicament removal process, have the ammonia that will reclaim or sulphur ammonium or sour sulfur aqueous ammonium and quick lime or calcium hydroxide and separate out the groove internal reaction at reactive crystallization with pulpous state or powdery, reclaim the ammonia composition with the gas that contains water vapour, itself and sulfate radical or sour sulfur acid group and calcium ion are reacted, make it to separate out the ammonia recovery of gypsum, the gypsum crystallization precipitation process.
6, according to the method for claim 5 record, reclaim, in the gypsum crystallization precipitation process, comprise that the ammonia that contains water vapour that will reclaim through overcompression and cooling, makes it to become the ammoniacal liquor generative process of ammoniacal liquor at ammonia.
7, the method for putting down in writing according to claim 5, in ammonia recovery, gypsum crystallization precipitation process, comprise gypsum slurries carried out Separation of Solid and Liquid after, reclaim gypsum with solid constituent, reclaim the Separation of Solid and Liquid process of ammoniacal liquor or unreacted sulphur aqueous ammonium or sour sulfur aqueous ammonium with liquid component.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP185592/90 | 1990-07-13 | ||
| JP2185593A JPH0693971B2 (en) | 1990-07-13 | 1990-07-13 | Simultaneous desulfurization denitration method in furnace |
| JP185593/90 | 1990-07-13 | ||
| JP2185592A JPH0651098B2 (en) | 1990-07-13 | 1990-07-13 | Simultaneous desulfurization denitration method in furnace |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061915A true CN1061915A (en) | 1992-06-17 |
Family
ID=26503203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91105599A Pending CN1061915A (en) | 1990-07-13 | 1991-07-13 | Process for simultaneously removing sulfur and nitrogen in furnace |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR930012041B1 (en) |
| CN (1) | CN1061915A (en) |
| DE (1) | DE4123155A1 (en) |
| GB (1) | GB2246121B (en) |
| IT (1) | IT1250274B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102022712A (en) * | 2010-09-26 | 2011-04-20 | 安徽金鼎锅炉股份有限公司 | Waste incineration waste heat boiler |
| CN102824809A (en) * | 2012-09-21 | 2012-12-19 | 中冶长天国际工程有限责任公司 | Adsorption tower |
| CN103691271A (en) * | 2013-12-16 | 2014-04-02 | 山东大学 | Simultaneous gas-phase desulfurization and denitration method for smoke gas |
| CN106823721A (en) * | 2017-02-23 | 2017-06-13 | 中国石油大学(北京) | A kind of flue gas desulfurization and denitrification agent and its preparation method and application |
| CN108800147A (en) * | 2018-06-28 | 2018-11-13 | 杭州国泰环保科技股份有限公司 | Low NOx burning process and its device |
| CN109260918A (en) * | 2017-07-18 | 2019-01-25 | 吕朝妮 | A kind of flue gas desulfurization and denitrification integral method and its dedicated unit |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091995A (en) * | 1993-03-08 | 1994-09-14 | 巴布考克及威尔考克斯公司 | Use ammonia-lime stone washing accessory substance and be applied to agricultural |
| AT500744B8 (en) * | 2005-03-11 | 2007-02-15 | Montanuniv Leoben | USE OF AN AMMONIA-RELATED RESIDUE |
| DE102006016963B3 (en) | 2006-04-11 | 2007-10-04 | Forschungszentrum Karlsruhe Gmbh | Method for reducing nitrogen oxides and halogenated organic compounds in a waste gas in a combustion installation comprises removing fly ash using a dust separator, removing hydrochloric acid in a first scrubber and further processing |
| DE102016220184A1 (en) * | 2016-10-17 | 2018-04-19 | Thyssenkrupp Ag | Process and plant for the production of nitric acid |
| CN111539160B (en) * | 2020-04-14 | 2022-10-04 | 龙净科杰环保技术（上海）有限公司 | Method for calculating flow velocity of ammonia injection pipeline of urea denitration system of coal-fired unit |
| CN114835327B (en) * | 2022-05-31 | 2023-05-02 | 中冶赛迪工程技术股份有限公司 | Desulfurization wastewater and sintering machine head ash cooperative treatment method |
| CN115990401A (en) * | 2023-03-22 | 2023-04-21 | 中国恩菲工程技术有限公司 | Purification process and device for waste incineration flue gas |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4029752A (en) * | 1973-05-29 | 1977-06-14 | Exxon Research And Engineering Company | Method of producing sulfur from sulfur dioxide |
| JPS5285069A (en) * | 1976-01-07 | 1977-07-15 | Mitsugi Aoyama | Desulfurization and denitration process for decomposing and separating exhaust liquid to nonpollutants while purifying exhaust gas by adding exhaust liquid obtained by treating sulfur oxides in exhaus |
| CA1097487A (en) * | 1976-04-20 | 1981-03-17 | David W. Turner | Method and apparatus for reducing no.sub.x emission to the atmosphere |
| DE2708919C2 (en) * | 1977-03-02 | 1982-05-27 | Dr. C. Otto & Comp. Gmbh, 4630 Bochum | Process for the purification of SO ↓ 2 ↓ -containing industrial exhaust gases |
| US4853193A (en) * | 1986-01-10 | 1989-08-01 | Exxon Research And Engineering Company | Process for removing NOx and SOx from a gaseous mixture |
| ATE88372T1 (en) * | 1987-03-06 | 1993-05-15 | Fuel Tech Inc | MULTI-STEP PROCESS FOR REDUCING THE CONTAMINATION LEVEL IN AN EXHAUST STREAM. |
-
1991
- 1991-07-12 GB GB9115069A patent/GB2246121B/en not_active Expired - Fee Related
- 1991-07-12 DE DE4123155A patent/DE4123155A1/en not_active Withdrawn
- 1991-07-12 IT ITTO910547A patent/IT1250274B/en active IP Right Grant
- 1991-07-12 KR KR1019910011853A patent/KR930012041B1/en not_active IP Right Cessation
- 1991-07-13 CN CN91105599A patent/CN1061915A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102022712A (en) * | 2010-09-26 | 2011-04-20 | 安徽金鼎锅炉股份有限公司 | Waste incineration waste heat boiler |
| CN102824809A (en) * | 2012-09-21 | 2012-12-19 | 中冶长天国际工程有限责任公司 | Adsorption tower |
| CN102824809B (en) * | 2012-09-21 | 2015-05-13 | 中冶长天国际工程有限责任公司 | Adsorption tower |
| CN103691271A (en) * | 2013-12-16 | 2014-04-02 | 山东大学 | Simultaneous gas-phase desulfurization and denitration method for smoke gas |
| CN103691271B (en) * | 2013-12-16 | 2016-01-13 | 山东大学 | A kind of flue gas gas phase desulfurization denitration method simultaneously |
| CN106823721A (en) * | 2017-02-23 | 2017-06-13 | 中国石油大学(北京) | A kind of flue gas desulfurization and denitrification agent and its preparation method and application |
| CN109260918A (en) * | 2017-07-18 | 2019-01-25 | 吕朝妮 | A kind of flue gas desulfurization and denitrification integral method and its dedicated unit |
| CN108800147A (en) * | 2018-06-28 | 2018-11-13 | 杭州国泰环保科技股份有限公司 | Low NOx burning process and its device |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4123155A1 (en) | 1992-01-16 |
| GB9115069D0 (en) | 1991-08-28 |
| ITTO910547A0 (en) | 1991-07-12 |
| ITTO910547A1 (en) | 1993-01-12 |
| IT1250274B (en) | 1995-04-07 |
| KR930012041B1 (en) | 1993-12-23 |
| GB2246121B (en) | 1995-03-08 |
| GB2246121A (en) | 1992-01-22 |
| KR920002210A (en) | 1992-02-28 |
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