CN1047042A - The processing method of combustion product gases - Google Patents
The processing method of combustion product gases Download PDFInfo
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- CN1047042A CN1047042A CN90102605A CN90102605A CN1047042A CN 1047042 A CN1047042 A CN 1047042A CN 90102605 A CN90102605 A CN 90102605A CN 90102605 A CN90102605 A CN 90102605A CN 1047042 A CN1047042 A CN 1047042A
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- flue gas
- compound
- urea
- desulfurization
- inorganic agent
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 title claims abstract description 18
- 238000003672 processing method Methods 0.000 title claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000003546 flue gas Substances 0.000 claims abstract description 96
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 66
- 230000023556 desulfurization Effects 0.000 claims abstract description 66
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004202 carbamide Substances 0.000 claims abstract description 43
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 67
- 230000008569 process Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000006253 efflorescence Methods 0.000 abstract description 3
- 206010037844 rash Diseases 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 37
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 36
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 36
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000003245 coal Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 13
- 235000011941 Tilia x europaea Nutrition 0.000 description 13
- 239000004571 lime Substances 0.000 description 13
- 239000001294 propane Substances 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000002650 habitual effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- ADUFBHYKXMWOSH-UHFFFAOYSA-N [O--].[O--].[Ti+4].[V+5] Chemical compound [O--].[O--].[Ti+4].[V+5] ADUFBHYKXMWOSH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Images
Classifications
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- 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
- B01D53/68—Halogens or halogen compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Incineration Of Waste (AREA)
- Weting (AREA)
Abstract
To temperature is to feed desulfurization compound of being made up of compounds such as calcium carbonate and calcium hydroxides and the denitration compound of being made up of compounds such as ammonium bromide and urea in 600～900 ℃ the combustion product gases, as the flue gas inorganic agent.These compounds can be the forms of mixture, also can be the forms of non-mixture.The flue gas inorganic agent can be the formed aqueous slurry form of desulfurization compound and urea, or after the aqueous slurry drying with desulfurization compound and urea formation, the powdered rubber that the urea dipping desulfurization compound efflorescence that generates is obtained also can be with this powder slurryization and the paste-like material that obtains once again.
Description
Nitrogen oxide (NO in the flue gas that the present invention relates to various boilers, various heating furnace, urban refuse burner, trade waste combustion furnace and other waste combustion stove are produced
X), oxysulfide (SO
X) and hydrogen chloride (HCl) method of removing, especially relating to can be with NO
XAnd SO
XThe two while dry type removes, perhaps with NO
XSO
XReach the simple and effective flue gas processing method that HCl three's while dry type removes,
About with NO
XAnd SO
XThe method that the two removes simultaneously had NH in the past
3Absorption process, wet or facture such as acetate absorption process, nitric acid, sulfuric acid process.As for the dry process rule activated carbon method, electron beam irradiation method etc. are arranged.Although people have carried out big quantity research for above-mentioned damp process, because NO
XRemoval efficiency relatively very low, simultaneously because the economy of dry process method is still undesirable, so all fail to realize practicability so far.
In addition, though NO
X, SO
XRemove the technology that in the processing of incineration firing flue gas, is very important when reaching HCl three, but do not see that the someone studies.
As mentioned above, though the establishment meeting that said two devices or above-mentioned three is removed simultaneously technology aspect the equipment and economic aspect bring enormous benefits owing to still be unrealized at present, so NO
X, SO
XAnd removing also of HCl all carried out in different operations respectively.Certainly, because SO
XBe both sour gas with HCl, in wet processed as described later, can be removed simultaneously naturally.In addition, because NO
XReactivity very low, promptly use damp process can not with SO
XAnd HCl removes simultaneously.
As NO
XThe method of removing, be mostly with ammonia as reducing agent, use the catalytic reduction method of titanium dioxide vanadium catalyst, this method has many practical examples.In addition, feed ammonia in the also oriented high-temperature flue gas more than 900 ℃, do not use catalyst to be about to NO
XThe on-catalytic denitration method that reduction removes.In this denitration method, except that ammonia, also can use the compound that after thermal decomposition, can produce ammonia, as ammonium carbonate, urea, ammonium formate, ammonium oxalate etc.But the use amount of these reducing agents will be many more than the use amount in the above-mentioned catalytic reduction method, and however, its denitration rate is but just below 50%.Therefore, this method is seldom used in large-sized boilers such as thermal power plant, and present application is just in special occasions such as refuse burners.Though select catalytic reduction method that many practical example are arranged, saying from the equipment aspect needs catalytic reactor, and needs higher operating technology, so its economy is not so good.Therefore people wish to develop and the practical application said method beyond the method for simple and good economy performance.
On the other hand, present SO
XRemoval method in wet type lime stone-gypsum method account for main flow, be to obtain practicality, and established technology, but, cause the temperature of flue gas to drop to about 60 ℃ owing to use lime white in this method in Japan and various countries.The reduction of this temperature has suppressed the diffusion of flue gas in atmosphere.Have the shortcoming that white cigarette takes place, Wen Shifa also needs to handle water and drainage treatment equipment simultaneously, so people wish to develop very much and practical dry dry process method.In order to meet this requirement, present research directly feeds the lime insufflation of calcium carbonate and limestone powder etc. and feed lime white in flue gas in flue gas.Make the water evaporates in the slurry and method that the lime composition is reacted as solids with the sensible heat of flue gas.But the former reaction temperature needs more than 1000 ℃, and SO
XRemoval efficiency less than 50%, so still there not being at present the example of practicability, and the latter can carry out under lower temperature conditions, and SO
XRemoval efficiency can reach 60～80%, so at the existing practical example of West Germany and the U.S..
For removing of HCl, also studying the dry process method that in refuse burner, is blown into lime stone.Because HCl compares SO
XReactive height and the reaction of HCl and lime stone and the CaCl that generates
2Physical property (fusing point is lower, so not too resemble CaSO
4Such phenomenon that reaction is stopped at limestone particle sub-surface formation housing) reason can obtain higher H Cl removal efficiency.But this lime stone insufflation is not and with NO
XRemove.
Therefore, in the past at needs with NO
XAnd SO
XThe two is removed or simultaneously with NO
X, SO
XAnd HCl three is when removing simultaneously, all must carry out denitration, desulfurization respectively and take off the combination of each operation of HCl.
Combination about denitration and desulfurization has many practical examples, wherein the most generally selects the combination of catalytic reduction method and wet type lime stone-gypsum method.This being combined in can obtain high denitration rate and the high desulfurization rate this point is very superior, but this in any case method is the combination of two kinds of operations, so from the operation complexity and it adopted damp process to carry out desulfurization, a kind of desirable method of can not saying so is as for NO
X, SO
XRemoval method when reaching HCl three, existing with on-catalytic denitration method (NH in the urban refuse burner flue gas is handled
3Insufflation) and the wet type alkali absorb method (can remove SO simultaneously
XAnd HCl) the practical example that makes up, but this method also has and the same shortcoming of aforesaid denitration doctor treatment.
From above situation as can be seen, this NO
X, SO
XAnd in the removal methods of HCl, the dry process method is the most suitable.For example in this dry process of lime insufflation, reaction temperature can be further reduced, NO can be removed simultaneously
XAnd SO
X, the method that can also remove HCl when containing HCl in the flue gas simultaneously is very desirable.
The processing method of combustion product gases of the present invention is a kind of dry process method, and it is can be with NO
XAnd SO
XThe two, NO
X, SO
XReach the very simple and effective method that HCl three removes simultaneously.
Method of the present invention is to be to feed desulfurization compound of being made up of compounds such as calcium carbonate and calcium hydroxides and the denitration compound of being made up of compounds such as ammonium bromide and urea in 600～900 ℃ the flue gas to temperature, as the flue gas processing method of flue gas inorganic agent.
The form that an object lesson of the present invention is desulfurization compound and denitration compound all is microgranular, and these compounds can be the forms of mixture, also can be the form of non-mixture.The form that another object lesson of the present invention is the flue gas inorganic agent can be desulfurization compound and the formed aqueous slurry of urea, or the powdered substance that after the aqueous slurry drying that desulfurization compound and urea are formed the urea dipping desulfurization compound solid efflorescence that generates is obtained, perhaps with this powder slurryization and the paste-like material that obtains once again.
In the method, if the temperature of flue gas is lower than 600 ℃ of lower limits, owing to reaction speed low is difficult to reach desirable SO
XRemoval efficiency.If instead be higher than 900 ℃ of the upper limits, then NO
XIn fact the tendency that increase is arranged can not reach and remove NO
XPurpose.Therefore, the flue-gas temperature that is blown into the flue gas inorganic agent is defined in 600～900 ℃ scope.
(say that exactly this is SO with selection catalytic reduction method and wet type lime stone-gypsum method
XRemoval method, and when HCl exists, can remove HCl and SO simultaneously
X) combined method compare.Flue gas facture of the present invention can be handled in very low temperature range, only handles by simple one-level, can avoid the generation of white cigarette, removes NO with quite high efficient
X, SO
XAnd HCl.
Fig. 1 is the flow chart of experimental technique, Fig. 2 be Ca/S than with the relation curve of denitration rate, Fig. 3 be Ca/S than with the relation curve of desulfurization degree.
The 1st most preferred embodiment of the present invention is to feed desulfurization compound of being made up of compounds such as calcium carbonate and calcium hydroxides and the denitration compound of being made up of compounds such as ammonium bromide and urea separately respectively with the admixture line in temperature is 600～900 ℃ flue gas.
The best form of each compound is microgranular, and the best combination of desulfurization compound and denitration compound is:
A) calcium carbonate and ammonium bromide
B) calcium carbonate and urea
C) calcium carbonate and ammonium bromide and urea
D) calcium hydroxide and urea.
The 2nd most preferred embodiment of the present invention is to be to feed the desulfurization compound be made up of calcium carbonate and calcium hydroxide and the formed aqueous slurry of urea in 600～900 ℃ the flue gas as the flue gas inorganic agent to temperature.
The 3rd most preferred embodiment of the present invention be to temperature be feed the aqueous slurry drying that the desulfurization compound that will be made up of calcium carbonate and calcium hydroxide and urea forms in 600～900 ℃ the flue gas after, and then the solid substance powderization of the urea that generated dipping desulfurization compound is obtained the aqueous slurry of powdered rubber or its powder, as the flue gas inorganic agent.
The range of reaction temperature of this method is 600 ℃～900 ℃, and optimum temperature range is 700 ℃～800 ℃.
The formed aqueous slurry shape of desulfurization compound and urea flue gas inorganic agent, the paste-like flue gas inorganic agent that the Powdered flue gas inorganic agent of above-mentioned urea dipping desulfurization compound and above-mentioned powder flue gas inorganic agent obtain after slurryization once again all has same performance.Its reason be since the slurry of flue gas almost instantaneous time get final product transpiring moisture, become the particle of urea dipping desulfurization compound, become calcium oxide.
At first for removing SO with method of the present invention
XTake off bright.
In lime insufflation in the past, need the reaction temperature more than 1000 ℃, even but under such high temperature, still can not obtain very high desulfurization degree.Its reason is to form and SO on the surface of the calcium oxide particulate that the calcium carbonate decomposition generates
XThe calcium sulfate housing that reacts and generate has hindered SO
XFurther diffusion to desulfurizing agent inside has suppressed the carrying out that reacts.And use the aqueous slurry drying that desulfurization compound and urea are formed, during the flue gas inorganic agent that further the solid matter efflorescence of the urea dipping desulfurization compound that generates obtained, in the decomposable process of desulfurization compound, it and urea reaction and generate low melting point, and make the surface activation of calcium oxide.In fact, compare with the mixture of particulate denitration compound with using particulate desulfurization compound.Powder with above-mentioned urea dipping desulfurization compound has obtained higher desulfurization degree as the flue gas inorganic agent.
In the method, SO
XThe product that removes reaction is a calcium sulfate, and does not produce calcium sulfite or ammonium sulfate.
Under regard to method of the present invention and remove NO
XDescribe.
In the method, NO
XThe reaction that removes do not resemble SO
XThe reaction that removes produce the solid product like that, but make NO by the effect of denitration compound
XBe decomposed into H
2O and N
2In the past remove NO with the ammoniation on-catalytic
XOn-catalytic denitration method in, reaction temperature is the high temperature range more than 900 ℃, and in the method for the invention, reaction temperature is below 900 ℃, this is of the present invention one big characteristics.Because temperature is too high, NO takes place in the oxidizing fire of ammoniate in on-catalytic denitration method in the past
XReaction of formation, make NO on the contrary
XConcentration increase to some extent.On-catalytic denitration in the past promptly enables not taken place to reduce NO in 600 ℃～900 ℃ temperature range
XThe best denitration efficiency rate of removal efficiency, NO
XRemoval efficiency also only about 50%.And can reach high NO more than 90% with method of the present invention
XRemoval efficiency.
In addition, compare with the mixture of particulate denitration compound with using particulate desulfurization compound, the powder that floods desulfurization compound with above-mentioned urea has obtained high denitration rate as the flue gas inorganic agent.Can think that in view of the above calcium carbonate or calcium hydroxide singly are not SO
XAbsorbent, can promote NO but also have
XEffect with urea reaction.
For removing of HCl, because HCl compares SO
XReactive high, can HCl be removed with higher removal efficiency by the reaction of HCl and desulfurization compound.
In the device of reality, flue gas with discharges such as various boilers, heating furnace, urban refuse burner, waste combustion stoves, carry out heat exchange when temperature reaches 600～900 ℃ scope by heat exchanger, the flue gas inorganic agent is fed flue gas, then flue gas is cooled to the adaptable temperature of cleaner such as cyclone dust collectors or bag hose, product calcium sulfate or calcium chloride collection is removed with cleaner.
Various boilers, heating furnace and combustion furnace generally all are equipped with heat exchanger and cyclone dust collectors and bag hose, therefore just increase the device for blowing that the flue gas inorganic agent is set and just can carry out with dry process NO
X, SO
XReach removing of HCl.
Embodiment
Followingly embodiments of the invention are described with reference to accompanying drawing.Fig. 1 implements experimental provision of the present invention and production procedure.Experimental provision among the figure mainly consists of the following components: internal diameter 350mm, the combustion furnace of high 450mm (1), internal diameter 330mm, add the air heater (4) of hot-air, the gas cooler (5) of cooled flue gas and the bag hose (6) that flue gas ash removal is used with fume waste heat at the reative cell of high 4m (3).At first
At first, fine coal is chewed with the burning of combustion furnace (1) burnt.The pulverized coal friring amount of combustion furnace (1) is 10kg/ hour (when only burning coal) to the maximum, but also can use the low load coal combustion of the burning of propane rib combustion, be the mixed combustion of coal and propane, can control the temperature and the NO of reative cell (3) by the ratio of regulating this fuel
XOutput, in addition by regulating SO
2SO in the also controlled tobacco curing gas of the injection rate of gas and HCl gas
2The concentration of gas and HCl gas.
The flue gas that is taken place at combustion furnace (1) enter be located at the combustion furnace rear side in order to carry out denitration, desulfurization and to take off the reative cell (3) of HCl.The temperature of reative cell (3) is controlled with being located at its electric heater (2) on every side,
When using pulverous flue gas inorganic agent, the flue gas inorganic agent is blown in the reative cell with air stream from the supply orifice (11) that is located at reative cell (3) top, when the flue gas inorganic agent is paste-like, sprays from above-mentioned supply orifice (11) and to inject.When desulfurization compound and denitration compound were blown into respectively, a side was from supply orifice (11), and the opposing party feeds from the supply orifice (12) of bottom.The flue gas that comes out from reative cell (3) passes through air heater (4), by cooling off air recovery used heat and after cooling off, further being cooled off by cooling water through gas cooler (5).
O in the flue gas
2, NO
XAnd SO
XConcentration export by analyzer (7) that is located at reative cell (1) outlet and bag hose (6) respectively and be located at analyzer (8) and analyze.Simultaneously, NO
XAnd SO
XAnalyzer (7), (8) measured numerical value equate, confirm to be provided with between two analyzers generation NO
XAnd SO
XThe reaction that participates in.The amount of HCl is measured with the wet chemistry analyzer, but between the numerical value that records with analyzer (7) and (8) very big-difference is arranged, and the numerical value that records with analyzer (8) is lower.That is to say, the reaction of HCl and CaO may take place in temperature range, demonstrate as a whole and take off the tendency that HCl leads raising.(9) are thermometer among the figure, and (10) are flowmeter.
Comparative example 1
This comparative example is depicted as this habitual technology of lime insufflation, by relatively making the characteristics of aftermentioned embodiment more clear and definite.
With device shown in Figure 1, to flue gas, drop into levigate calcium carbonate from supply orifice (11) as the flue gas inorganic agent, desulfurization degree and denitration rate of this experiment gained are shown in table 1.In this experiment, when reaction temperature is 1300 ℃, just burn coal (10kg/ hour), and when reaction temperature was 1100 ℃ and 800 ℃, what carry out was the mixed combustion of coal and propane flammable gas.But the SO in the flue gas
2Concentration is all regulated and is about 900ppm.NO in the flue gas
XConcentration when burning coal, be about 830ppm, be O in 400～600ppm flue gas when mixing combustion
2Concentration when burning coal, be about 6%, and be 9～11% when mixing combustion.
As shown in Table 1, by selecting appropriate reaction conditions, SO
XRemoval efficiency can reach about 80%, but when reaction temperature is reduced to below 800 ℃, but show desulfurized effect hardly, certainly, on the other hand, denitration all is 0% within all scopes.
With device shown in Figure 1, in flue gas, be blown into as the calcium carbonate microparticle of flue gas inorganic agent and the mixture of ammonium bromide particulate with supply orifice (11), carried out SO
XAnd NO
XThe experiment that removes simultaneously.The equipment operating condition of present embodiment is:
Burning: propane and powder coal for mixing combustion (propane: 0.64Nm
3/ hour, coal: 3.24kg/ hour)
Air ratio: the concentration of oxygen is 9.4% in the 1.81(flue gas)
Exhaust gas volumn: 70Nm
3/ hour
NO in the flue gas
XConcentration: 260ppm
SO in the flue gas
XConcentration: 485ppm
Reaction time: 4.5 seconds
Reaction temperature: 775 ℃
The mixed proportion of calcium carbonate and ammonium bromide: 1: the 1(weight ratio)
Result of the test is as shown in table 2.As seen from table, present embodiment realized in comparative example 1, can not obtaining fully in temperature range to SO
XAnd NO
XCarrying out high efficiency removes.
With device shown in Figure 1, the mixture that is blown into calcium carbonate microparticle and urea liquid grain (one-level industry reagent) from supply orifice (11) to flue gas has carried out NO as the flue gas inorganic agent
XAnd SO
XThe time remove experiment.The equipment operating condition of present embodiment is:
Burning: propane and powder coal for mixing combustion (propane: 0.64Nm
3/ hour, coal: 2.37kg/ hour)
Air ratio: the concentration of oxygen is 11.0% in the 2.10(flue gas)
Exhaust gas volumn: 63Nm
3/ hour
NO in the flue gas
XConcentration: 209ppm
SO in the flue gas
XConcentration: 568ppm
Reaction time: 5.0 seconds
Reaction temperature: 765 ℃
The mixed proportion of calcium carbonate and urea: 1: the 1(weight ratio)
Result of the test is as shown in table 3.As seen from table, present embodiment the SO that realized in comparative example 1, can not obtaining fully in temperature range and low Ca/S molar range
XHigh removal efficiency and the habitual on-catalytic denitration method high denitration rate that can not obtain.
With device shown in Figure 1, the supply rate of flue gas inorganic agent is adjusted to 0.49kg/ hour, then only change reaction temperature, other operating conditions are identical to desulfurization degree and denitration rate are measured with embodiment 1.Reaction temperature is controlled by the electric current of the heater (2) of conditioned reaction chamber (3).
Experimental result is as shown in table 4.As seen from table, when reaction temperature is 600 ℃, compare with embodiment 1, desulfurization degree and denitration rate all descend to some extent, and when reaction temperature was 950 ℃, though desulfurization degree is very high, the denitration rate was a negative value, and promptly changing into has NO
XReaction of formation.
With device shown in Figure 1, the mixture that feeds calcium carbonate microparticle and ammonium bromide particulate from supply orifice (11) to flue gas has carried out NO as the flue gas inorganic agent
XRemove test.Fuel only is to use propane, and does not inject SO
2, so desulphurization reaction does not take place.
The denitration rate of the operating condition of present embodiment combustion furnace and gained is as shown in table 5.As seen from table, be that the denitration rate is a negative value in 1000 ℃ the test in reaction temperature, this be since in the flue gas inorganic agent burning of ammonium bromide make NO
XConcentration increases to 100ppm by 30ppm.
When reaction temperature is 765 ℃, NO
XConcentration is reduced to 25ppm by 62ppm, i.e. denitration rate is 58.3%.
With device shown in Figure 1, with embodiment 2 identical operations conditions under just the flue gas inorganic agent is changed to the mixture (the weight mixed proportion is 1: 0.5: 0.5) of calcium carbonate, ammonium bromide and urea, feed with 0.27kg/ hour supply rate.
Its result has obtained 75.7% desulfurization degree and 79.0% denitration rate.Promptly use the mixture of calcium carbonate and ammonium bromide to compare with embodiment 2, the desulfurization degree of present embodiment and denitration rate all increase.
Comparative example 2
With device shown in Figure 1, to flue gas, feed the calcium hydroxide particulate as desulfurizing agent from supply orifice (11), with comparative example 1 identical operations condition under repeated the operation of comparative example 1.
Select felicity condition, also can obtain the desulfurization degree about 80%, but when reaction temperature is reduced to 800 ℃, show desulfurized effect hardly.Denitration rate in addition also all is 0% in all scopes.
Embodiment 6
With device shown in Figure 1, the mixture (the weight mixed proportion is 1: 1) that to flue gas, feeds calcium hydroxide particulate and urea microparticles from supply orifice (11) with embodiment 1 identical operations condition under repeated the operation of embodiment 1.
Result of the test is as shown in table 6.As seen from table, present embodiment has been realized the SO in temperature range that can not obtain fully in comparative example 2
XAnd NO
XHigh efficiency remove.
Embodiment 7
In this example, desulfurizing agent injects from different supply orifices respectively with denitrfying agent.
With device shown in Figure 1, to flue gas, feed urea microparticles as the denitration compound from supply orifice (11), feed calcium hydroxide as desulfurization compound from supply orifice (12), carried out SO
XAnd NO
XThe time remove test.The operating condition of present embodiment all is 0.3kg/ hour except that the injection rate of urea and the injection rate of calcium hydroxide, and all the other are identical with the operating condition of embodiment 6.
The result of present embodiment, denitration rate are 95.0%, and desulfurization degree is 86.0%, have still realized SO in low temperature range
XAnd NO
XHigh efficiency remove.
Comparative example 3
Shown in this comparative example this habitual technology of lime insufflation, by relatively making the characteristics of embodiment described later more clear and definite.
With device shown in Figure 1, in flue gas, drop into levigate calcium carbonate as exhaust gas treating agent.The operating condition of this moment is:
Burning: propane and powder coal for mixing combustion (propane: 0.64Nm
3/ hour, coal: 3.24kg/ hour)
Air ratio: O in the 1.81(flue gas
2Concentration be 9.4%)
Exhaust gas volumn: 70Nm
3/ hour
NO in the flue gas
XConcentration: 300ppm
SO in the flue gas
XConcentration: 900ppm
Reaction time: 4～5 seconds
Result of the test is as follows.
Reaction temperature reaction time Ca/S mol ratio desulfurization degree denitration rate
1100 ℃ 4 seconds 2.1 62% 0%
800 ℃ 5 seconds 2.1 15% 0%
According to above result as can be known, when reaction temperature was 800 ℃, desulfurization degree was 15%, illustrated in such temperature range, can not obtain practical desulfurization degree with the lime insufflation, and also yes 0% for the denitration rate.
Embodiment 8
With method as follows the flue gas inorganic agent is modulated.The commercially available calcium carbonate of weighing 10kg (average grain diameter 12um) contains the large-size stainless steel basin.The urea of weighing 1kg one-level reagent adds 41 water it is dissolved on the other hand, and this aqueous solution of urea is made an addition to above-mentioned Stainless steel basin, and it is fully mixed with calcium carbonate, has obtained the paste-like material.Then Stainless steel basin is put into drier, at a dry night under 110 ℃ temperature, moisture is removed in evaporation.Slurry becomes solid matter after drying, but pulverizes than being easier to.The urea that obtains is flooded calcium carbonate with after the mortar pulverizing, and making it is the sieve of 0.3mm by mesh, and the powder that obtains so promptly is the calcium carbonate powder that contains 10% urea of having an appointment, and its flue gas inorganic agent as following test is used.
With device shown in Figure 1, the flue gas inorganic agent of modulating above feeding in flue gas has carried out SO
XAnd NO
XThe time remove test.Experimental condition is as follows, and result of the test is shown in Fig. 2 and Fig. 3 respectively.
Burning: propane and powder coal for mixing combustion (propane: 0.65Nm
3/ hour, coal: 2.12kg/ hour)
Air ratio: O in the 1.86(flue gas
2Concentration be 11.0%)
Exhaust gas volumn: 56Nm
3/ hour
NO in the flue gas
XConcentration: 200ppm
SO in the flue gas
XConcentration: 900ppm
Reaction time: 6 seconds
Reaction temperature: 800 ℃
Fig. 2 be Ca/S than with the relation of denitration rate, Fig. 3 be Ca/S than with the relation of desulfurization degree.In two figure, result of the test when curve A is to use the flue gas inorganic agent of above-mentioned modulation, curve B is to be blown into calcium carbonate that average grain diameter is 12um and urea powder (one-level reagent, particle diameter are about 10～30um) mixture (calcium carbonate: the result in the time of urea=4: 1).When using the latter, under 800 ℃ temperature conditions, also reached calcium carbonate insufflation (comparative example 3) inaccessible desulfurization degree of institute and denitration rate, but obtained the denitration rate and the desulfurization degree of better effects if when using the former.The particularly obvious increase of desulfurization degree, the denitration reaction that the method is described is different with habitual on-catalytic denitration reaction since with the interaction of calcium carbonate, obtained better effect.
Embodiment 9
With modulation flue gas inorganic agent used among the embodiment 8 slurryization again, make it become 20% water slurry, with embodiment 8 identical conditions under this slurry is sparged in the reative cell (3).Its result has obtained 55% denitration rate and 60% desulfurization degree.The Ca/S ratio of this moment is about 1.5.
Embodiment 10
Under condition substantially the same manner as Example 8, in flue gas, add HCl, the test of carried out denitration, desulfurization, taking off HCl.Used flue gas inorganic agent is the powder of modulation in embodiment 8.The difference of experimental condition and embodiment 8 is:
HCl concentration: 800ppm
SO
XConcentration: 200ppm
NO
XConcentration: 200ppm
Ca/(S+2Cl) ratio: 4
Its denitration rate as a result is 50%, and desulfurization degree is 75%, and taking off that HCl leads is 98%.In addition, carry out the result of sample analysis in the preceding conduit of this equipment bag filter (6), taking off that HCl leads is 65%.From this result as can be known, in quite low temperature range, for example under 120 ℃ temperature, also HCl can be removed.
Comparative example 4
In this comparative example, replace calcium carbonate as the flue gas inorganic agent with levigate calcium hydroxide, under the experimental condition identical, repeated the operation of comparative example 3 with comparative example 3.
Result of the test is as follows:
Reaction temperature reaction time Ca/S mol ratio desulfurization degree denitration rate
1100 ℃ 4 seconds 2.1 58% 0%
800 ℃ 5 seconds 2.1 10% 0%
When reaction temperature was 800 ℃, desulfurization degree was 10%, illustrated in such temperature range, can not obtain practical desulfurization degree with the lime insufflation, and also yes 0 for the denitration rate.
Embodiment 11
Replace calcium carbonate with commercially available calcium hydroxide (average grain diameter 20um) in the present embodiment, use the method identical, repeated the operation of embodiment 8 with embodiment 8.Result of the test as the curve A in Fig. 2 and 3 ' shown in.
As can be seen from Figure 3, the inorganic agent used with embodiment 8 is identical, and the used flue gas inorganic agent of present embodiment also demonstrates very high denitration and desulfurized effect.
Embodiment 12
Calcium hydroxide 20kg and urea 5kg are dissolved in the 75kg water, obtain the slurry material, then this paste-like flue gas inorganic agent is sparged in the reative cell (3), under the experimental condition identical, repeated the test of embodiment 8 with embodiment 8.
Its denitration rate as a result is 70%, and desulfurization degree is 83%.The Ca/S ratio of this moment is about 2.1.
Table 1
Claims (8)
1, the processing method of combustion product gases, wherein to temperature be feed the desulfurization compound formed by compounds such as calcium carbonate and calcium hydroxides in 600～900 ℃ the flue gas and the nitrated compound formed by compounds such as ammonium bromide and urea as the flue gas inorganic agent.
2, the described method of claim 1, wherein the form of desulfurization compound and denitration compound all is microgranular.
3, the described method of claim 1, wherein the flue gas inorganic agent is the mixture form of desulfurization compound and denitration compound.
4, the described method of claim 1, wherein the flue gas inorganic agent is the non-mixture form of desulfurization compound and denitration compound.
5, the process of claim 1 wherein that the flue gas inorganic agent is the formed aqueous slurry form of desulfurization compound and urea.
6, the described method of claim 1 after wherein the flue gas inorganic agent is the aqueous slurry drying that desulfurization compound and urea are formed, makes the solid substance powderization of the urea dipping desulfurization compound that is generated and the micro mist shape form that obtains.
7, the described method of claim 1, wherein the flue gas inorganic agent is to require book 6 described powder slurryization and the slurry form that obtains once again.
8, after the aqueous slurry drying that desulfurization compound and urea are formed, the flue gas inorganic agent that the solid matter micronizing of the urea dipping desulfurization compound that generates is obtained again,
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP113941/89 | 1989-05-06 | ||
| JP11394189 | 1989-05-06 | ||
| JP223682/89 | 1989-08-30 | ||
| JP22368289 | 1989-08-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1047042A true CN1047042A (en) | 1990-11-21 |
Family
ID=26452809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90102605A Pending CN1047042A (en) | 1989-05-06 | 1990-05-05 | The processing method of combustion product gases |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR920007857B1 (en) |
| CN (1) | CN1047042A (en) |
| DE (1) | DE4014388A1 (en) |
| GB (1) | GB2232972B (en) |
| IT (1) | IT1240462B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974207A (en) * | 2012-11-07 | 2013-03-20 | 环境保护部华南环境科学研究所 | Method and apparatus for cement rotary kiln flue gas denitration and desulfurization |
| CN113423990A (en) * | 2019-02-20 | 2021-09-21 | 萨普工业公司 | Method for treating flue gases from a combustion unit |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE468273B (en) * | 1990-02-07 | 1992-12-07 | Eka Nobel Ab | PROCEDURE AND DEVICE FOR CHEMICAL AND / OR PHYSICAL TREATMENT OF A FLUID |
| DE4100645A1 (en) * | 1991-01-11 | 1992-07-16 | Hansjoerg Regler | Waste gas purificn. with nitrogen basic cpds. removing acid cpds. - by adding ammonia and alkali and/or alkaline earth cpds., for foundry, alkali chloride electrolysis, blast furnace, power station, refuse and glass industry |
| DK170891A (en) * | 1991-02-19 | 1992-08-20 | Intevep Sa | PROCEDURE FOR REMOVAL OF EFFLUENTS FROM EMISSIONS GASED BY COMBUSTION OF A FUEL |
| WO1993011066A1 (en) * | 1991-11-27 | 1993-06-10 | Nalco Fuel Tech | PROCESS AND COMPOSITION FOR NOx and SOx REDUCTION |
| BE1006780A5 (en) * | 1992-02-10 | 1994-12-06 | Etienne Vansant | PRODUCTS, METHODS AND DEVICES FOR THE removal of pollutants from a fluid. |
| US5282999A (en) * | 1992-06-12 | 1994-02-01 | Intevep, S.A. | Sorbent for treatment of effluent gas stream |
| US5630991A (en) * | 1994-08-16 | 1997-05-20 | General Electric Co. | Limestone-based wet flue gas desulfurization process |
| EP1779919A1 (en) * | 2005-10-31 | 2007-05-02 | Constructions Industrielles De La Mediterranee- Cnim | Improved process for the removal of NOx, apparatus, and application to the treatment of smokes from a household waste combustion process |
| DE102010007588A1 (en) * | 2010-02-05 | 2011-08-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 80686 | Method for producing synthesis gas from biomass in fuel carburetor, involves performing high temperature cleaning, reforming high temperature tar by catalytic converter and removing high-temperature sulfur-and halogen by dry sorbents |
| US9387438B2 (en) | 2014-02-14 | 2016-07-12 | Tenneco Automotive Operating Company Inc. | Modular system for reduction of sulphur oxides in exhaust |
| KR101836047B1 (en) | 2017-09-18 | 2018-03-08 | 이철 | Desulfurization system using a catalyst for desulfurization |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3426796A1 (en) * | 1984-07-20 | 1986-01-30 | Hölter, Heinz, Dipl.-Ing., 4390 Gladbeck | Separation out of SO2 and simultaneous separation out of NOx downstream of nonferrous metal furnaces, such as anode furnaces or converter furnace plants |
| EP0190416A3 (en) * | 1984-11-30 | 1988-07-27 | Waagner-Biro Aktiengesellschaft | Process for separating pollutants from combustion gases |
| DE3513484A1 (en) * | 1985-04-16 | 1986-10-16 | Krupp Polysius Ag, 4720 Beckum | METHOD FOR REDUCING NITROGEN EMISSION FROM CEMENT PLANTING PLANTS |
| US4795586A (en) * | 1986-01-09 | 1989-01-03 | Thompson Richard E | Method and composition for utilizing lime-urea hydrates to simultaneously reduce NOx and SOx in combustion effluents |
| US4731233A (en) * | 1986-01-09 | 1988-03-15 | Thompson Richard E | Method and composition for utilizing lime-urea hydrates to simultaneously reduce NOx and SOx in combustion effluents |
| DE3705267C1 (en) * | 1987-02-19 | 1988-03-31 | Rwk Rhein Westfael Kalkwerke | Use of a reactor grain for desulphurising flue gases |
| US4851201A (en) * | 1987-04-16 | 1989-07-25 | Energy And Environmental Research Corporation | Methods of removing NOx and SOx emissions from combustion systems using nitrogenous compounds |
| DE3823223A1 (en) * | 1987-08-06 | 1989-02-16 | Rheinische Braunkohlenw Ag | Process for purifying flue gases containing sulphur oxides and nitrogen oxides |
| DK339588A (en) * | 1987-09-03 | 1989-03-04 | Smidth & Co As F L | PROCEDURE AND PLANT FOR SIMILAR CLEANING OF ROEGGAS AND FLYING BASKET FOR Sulfur Oxides and Nitrogen Oxides |
-
1990
- 1990-05-02 GB GB9009921A patent/GB2232972B/en not_active Expired - Fee Related
- 1990-05-03 IT IT67327A patent/IT1240462B/en active IP Right Grant
- 1990-05-04 KR KR1019900006318A patent/KR920007857B1/en not_active IP Right Cessation
- 1990-05-04 DE DE4014388A patent/DE4014388A1/en not_active Ceased
- 1990-05-05 CN CN90102605A patent/CN1047042A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974207A (en) * | 2012-11-07 | 2013-03-20 | 环境保护部华南环境科学研究所 | Method and apparatus for cement rotary kiln flue gas denitration and desulfurization |
| CN102974207B (en) * | 2012-11-07 | 2015-02-18 | 环境保护部华南环境科学研究所 | Method and apparatus for cement rotary kiln flue gas denitration and desulfurization |
| CN113423990A (en) * | 2019-02-20 | 2021-09-21 | 萨普工业公司 | Method for treating flue gases from a combustion unit |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1240462B (en) | 1993-12-17 |
| KR920007857B1 (en) | 1992-09-18 |
| IT9067327A0 (en) | 1990-05-03 |
| KR900017647A (en) | 1990-12-19 |
| GB2232972A (en) | 1991-01-02 |
| DE4014388A1 (en) | 1990-11-08 |
| GB9009921D0 (en) | 1990-06-27 |
| IT9067327A1 (en) | 1991-11-03 |
| GB2232972B (en) | 1993-09-15 |
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