CN104190193B - A kind of method of sack cleaner inter-sync desulfur denitrate dust collecting - Google Patents
A kind of method of sack cleaner inter-sync desulfur denitrate dust collecting Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000428 dust Substances 0.000 title claims abstract description 28
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- 239000003546 flue gas Substances 0.000 claims abstract description 133
- 238000001914 filtration Methods 0.000 claims abstract description 77
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- 239000003500 flue dust Substances 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 45
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
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- 239000011572 manganese Substances 0.000 claims description 135
- 239000007787 solid Substances 0.000 claims description 106
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 72
- 239000007788 liquid Substances 0.000 claims description 59
- 229940099596 manganese sulfate Drugs 0.000 claims description 41
- 235000007079 manganese sulphate Nutrition 0.000 claims description 41
- 239000011702 manganese sulphate Substances 0.000 claims description 41
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 41
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 239000000779 smoke Substances 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 229910001437 manganese ion Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 230000010349 pulsation Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002817 coal dust Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 18
- 230000023556 desulfurization Effects 0.000 abstract description 16
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- 239000011149 active material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 235000019738 Limestone Nutrition 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
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- 229910010413 TiO 2 Inorganic materials 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method of sack cleaner inter-sync desulfur denitrate dust collecting, it is characterized in that: take sack cleaner as reaction unit, coal-fired flue-gas after electric precipitation is introduced in sack cleaner by connecting pipe, in connecting pipe, inject Mn oxide, make Mn oxide carry out desulphurization denitration to coal-fired flue-gas; Complete Mn oxide, desulphurization denitration product and the flue dust of unreacted enters in the filter bag of sack cleaner with coal-fired flue-gas, and is trapped within filter bag surface and forms filtering layer; In the coal-fired flue-gas entering sack cleaner, spray into ammonia, residual nitrogen Reduction of Oxide in coal-fired flue-gas is nitrogen by ammonia; To carrying out regeneration process after filtering layer material recycle, the Mn oxide of acquisition recycles to injection connecting pipe.The present invention, using sack cleaner as core apparatus, using Mn oxide as active material, and is processed by a series of separation, regeneration and is recycled, realizing the synchronous and integrated of flue gas desulfurization denitration dust-removing in sack cleaner.
Description
One, technical field
The present invention relates to Air Pollution Control field, be specifically related to the method for a kind of flue gas synchronized desulfuring and denitrifying dedusting.
Two, background technology
Thermal power plant produces a large amount of SO in high-temp combustion process
2, NO
x, the pollutant such as flue dust, the nitrogen oxide in air forms fine particle PM2.5 main source, and thermal power plant is the rich and influential family of discharge nitrogen oxide.Therefore, power plant's denitration, reduces PM2.5 concentration, imperative, very urgent.Nitrogen oxide also can cause the Regional Environmental Pollution such as photochemical fog and depletion of the ozone layer problem.Due to SO
2, NO
xdischarge has caused the city in the whole nation 81.6% to occur acid rain, and the bad weathers such as nationwide haze increase, and bring have a strong impact on industrial and agricultural production, people's lives, health.
Current flue gas desulfurization is implemented at national Thermal generation unit, generally adopt lime or lime stone as sulfur removal material dry method or wet desulphurization, flue gas ash removal generally adopts electric precipitation, desulfurization and dust removing effects can reach emission request substantially, but in order to ensure atmosphere quality, also need to further develop new green technology, improve desulfurization, efficiency of dust collection, cut down sulfur dioxide and smoke discharge amount.
Flue gas NO
xenvironmental capacity, i.e. denitrating flue gas, comprise absorption process, absorption method, non-selective catalytic reduction (SNCR) and SCR (SCR) etc.SCR technology has higher denitration efficiency with it and abroad Flue Gas Denitrification Engineering obtains applying more widely.SCR method be using ammonia or urea as reducing agent under catalyst action selectively the NO in flue gas
xreduction becomes N
2.At present, the commercial denitrating catalyst WO of domestic power plant Introduced From Abroad
3-V
2o
5/ TiO
2and technology is promoted.The weak point of such catalyst is: one is that catalysis preparation cost is higher, and toxicity is comparatively strong, and during installation, workman will be with breathing mask, and the service life of catalyst is 3 years, more difficult after catalyst failure; Two is the V on catalyst
2o
5for SO
2be oxidized to SO
3reaction has catalytic action, the SO of generation
3with NH
3nH is generated with the steam reaction in flue gas
4hSO
4, e-quipment and pipe resulting in blockage lower than condensing in time its dew point (300 ~ 330 DEG C) and corrodes.Three is reaction temperatures higher (300 ~ 400 DEG C) of such catalyst denitration requirement, is not suitable for the actual conditions that temperature after the existing means of flue gas desulfurization of power plant of China, dedusting is on the low side.
Exploitation low temperature catalyst can make reaction at a lower temperature (about 200 DEG C) carry out, this not only can reduce energy consumption of reaction, reduce costs; Reduce after it is also conceivable to take SCR device to be placed on ESP (electric precipitation) or get rid of SO completely
2on the impact of catalyst.The low temperature SCR denitration catalyst mentioned in domestic and foreign literature is the MnO for preparing of infusion process mainly
x/ TiO
2, MnO
x/ AC, MnO
x/ Al
2o
3, MnO
x/ attapulgite, MnO
x, there is higher activity and the activity influence of steam to catalyst is less, but SO in flue gas
2larger side effect, especially MnO can be produced to reactivity
xcatalyst.It is the preparation of carrier impregnation load Mn, V, Cu, Co, Fe oxide low-temperature SCR catalyst that domestic publication (CN101352681) discloses with activated carbon; It is carrier impregnation load MnO that publication (CN101011659) discloses with activated carbon
x/ CeO
2the preparation of low-temperature SCR catalyst.Be that catalytic benefits prepared by carrier is that specific area that absorbent charcoal carrier enriches is conducive to the dispersion of active component with activated carbon, and there is certain anti-SO
2performance, but in activating and regenerating process, active carbon high-temp ablation is too serious, causes catalyst attrition excessive.Steam power plant of Shandong Province uses rare earth catalyst, flue gas nitrogen oxide concentration 450 milligrams/Nm
3, dropped to 90 milligrams/Nm
3below, clearance reaches 80%.But these technology all can not realize the integrated of desulfurization and denitration.
Along with the research and development of flue gas desulfurization, denitration, dedusting technology, recognize that the trend that integration is future development is moved towards in desulfurization and denitration gradually, the flow process of gas pollution control can have been reduced, reduced desulphurization denitration investment and gas pollution control cost.
Mn oxide had both had very high desulphurizing activated from the current study, also had very high SCR denitration active.With Mn oxide be desulphurization denitration active material select be applicable to mode realize synchronized desulfuring, denitration, the low dust concentration of a step-down of going forward side by side is very promising technology.
Three, summary of the invention
The present invention is directed to Problems existing in the smoke pollution comprehensive regulation, invented a kind of method of sack cleaner inter-sync desulfur denitrate dust collecting, be intended to realize synchronized desulfuring, denitration, the low dust concentration of a step-down of going forward side by side.
Technical solution problem of the present invention, adopts following technical scheme:
The method of sack cleaner inter-sync desulfur denitrate dust collecting of the present invention, is characterized in:
Take sack cleaner as reaction unit, coal-fired flue-gas after electric precipitation is introduced in sack cleaner by connecting pipe, Mn oxide is injected in described connecting pipe, make Mn oxide remove most of sulfur dioxide in coal-fired flue-gas and form manganese sulfate, and remove part nitrogen oxide formation manganese nitrate; The Mn oxide that manganese sulfate, manganese nitrate, unreacted are complete and flue dust are (when initial, here flue dust is remaining flue dust in coal-fired flue-gas after electric precipitation just, after the circulation of Mn oxide, here namely flue dust to comprise after electric precipitation remaining flue dust in coal-fired flue-gas, also comprise when recycling using solid I as Mn oxide simultaneously, flue dust in solid I) enter in sack cleaner with coal-fired flue-gas, and the filter bag surface being trapped within sack cleaner forms filtering layer; The Mn oxide that unreacted is complete in filtering layer continues and sulfur dioxide residual in coal-fired flue-gas reacts; In the coal-fired flue-gas entering sack cleaner, spray into ammonia, in filtering layer the Mn oxide that unreacted is complete catalytic action under, residual nitrogen Reduction of Oxide in coal-fired flue-gas is nitrogen by ammonia;
Along with thickness of filter bed increases, sock filtration resistance increases, when filter bag internal drop reaches 800 ~ 900Pa, remove filtering layer by the mode of electromagnetic rapping or pulsation winding-up and collect filtering layer material, to carrying out regeneration process after filtering layer material recycle, the Mn oxide obtained recycles to injection connecting pipe.
The method of sack cleaner inter-sync desulfur denitrate dust collecting of the present invention, its feature is also:
The quality of the Mn oxide injected in connecting pipe is 2:1 ~ 5:1 with the mass ratio of the coal-fired flue-gas sulfur dioxide being transported to connecting pipe.
The ammonia quality sprayed in the coal-fired flue-gas of sack cleaner is 1:1 ~ 1:1.15 with the mass ratio of nitrogen oxide in the coal-fired flue-gas entering sack cleaner.
Before coal-fired flue-gas enters sack cleaner, regulate coal-fired flue-gas temperature to make in sack cleaner coal-fired flue-gas temperature stabilization at 150 ~ 220 DEG C, with the safe handling requirement of the temperature requirement and filter bag that ensure denitration reaction.
Method filtering layer material being carried out regenerating to process acquisition Mn oxide is: the water adding 3 ~ 10 times of quality in filtering layer material, obtain solidliquid mixture I, obtain the solid I be made up of Mn oxide and flue dust after Separation of Solid and Liquid is carried out to solidliquid mixture I and by manganese sulfate and the water-soluble liquid I formed of manganese nitrate;
By liquid I ammonia neutralization to pH value in 8 ~ 9 scopes, then aeration aerating makes divalent manganesetion be oxidized to tetravalent manganese ion, obtain solidliquid mixture II, Separation of Solid and Liquid is carried out to solidliquid mixture II, obtain the solid II be made up of Mn oxide and the liquid II being rich in ammonium sulfate and ammonium nitrate;
Solid I is mixed to obtain with solid II and reclaims Mn oxide slurry, or in air atmosphere, with 300 ~ 500 DEG C of fluidized bed roastings or rotary kiln baking, be oxidized 10-40min after being mixed with solid II by solid I, obtain and reclaim Mn oxide powder; Using described recovery Mn oxide slurry or described recovery Mn oxide powder as described Mn oxide, spray to join coal-fired flue-gas from the connecting pipe be connected between electric cleaner and sack cleaner and recycle.
The method of sack cleaner inter-sync desulfur denitrate dust collecting of the present invention, take following operating procedure:
A, first coal-fired flue-gas is removed most of flue dust through electric cleaner, when burning high sulfur coal powder causes that in coal-fired flue-gas, sulfur content is higher than 800PPm, use again after first adding the agstone accounting for high-sulfur quality of pc 1-3% in high-sulfur coal dust;
B, the coal-fired flue-gas after electric precipitation to be introduced before sack cleaner by connecting pipe, regulate coal-fired flue-gas temperature, to make in sack cleaner coal-fired flue-gas temperature stabilization at 150 ~ 220 DEG C, with the safe handling requirement of the temperature requirement and filter bag that ensure denitration reaction;
C, in the coal-fired flue-gas in the connecting pipe between electric cleaner and sack cleaner spray add Mn oxide, make the sulfur dioxide fast reaction in Mn oxide and coal-fired flue-gas, remove most of sulfur dioxide in coal-fired flue-gas and form manganese sulfate, and with the part reaction of nitrogen oxides in coal-fired flue-gas, slough nitrogen oxide formed manganese nitrate; The Mn oxide that manganese sulfate, manganese nitrate, unreacted are complete and flue dust enter in sack cleaner with coal-fired flue-gas, and the filter bag surface being trapped within sack cleaner forms filtering layer; The complete Mn oxide of unreacted in filtering layer continues to react with residual sulfur dioxide in coal-fired flue-gas; The quality of the Mn oxide added be 2:1 ~ 5:1 with the mass ratio of sulfur dioxide in the coal-fired flue-gas being transported to connecting pipe;
D, in the coal-fired flue-gas entering sack cleaner, spray into ammonia, in the filtering layer of filter bag surface, unreacted Mn oxide is as selective catalytic reduction catalysts, play efficient denitration catalyst effect 150 DEG C ~ 220 DEG C temperature provinces, make ammonia be nitrogen by residual nitrogen Reduction of Oxide in coal-fired flue-gas; The ammonia quality sprayed in the coal-fired flue-gas of sack cleaner is 1:1 ~ 1:1.15 with the mass ratio of nitrogen oxide in the coal-fired flue-gas entering sack cleaner;
E, along with filter bag surface thickness of filter bed increases, sock filtration resistance increases, and when filter bag internal drop reaches 800 ~ 900Pa, by the mode of the rapping apparatus rapping of Electromagnetic Control or pulsation winding-up, filtering layer material on filter bag is come off and enters ash bucket;
F, the filtering layer material collected in ash bucket, and the manganese sulfate added in filtering layer material in the water-soluble solution filtering layer material of 3 ~ 10 times of quality and manganese nitrate, obtain solidliquid mixture I, obtain the solid I be made up of Mn oxide and flue dust after Separation of Solid and Liquid is carried out to solidliquid mixture I and by manganese sulfate and the water-soluble liquid I formed of manganese nitrate;
G, liquid I ammonia neutralization to liquid pH value in 8 ~ 9 scopes, then aeration aerating oxidation divalent manganesetion is tetravalent manganese ion, obtain solidliquid mixture II, Separation of Solid and Liquid is carried out to solidliquid mixture II, obtains the solid II be made up of Mn oxide and the liquid II being rich in ammonium sulfate and ammonium nitrate;
H, solid I mixed to obtain with solid II and reclaims Mn oxide slurry, or in air atmosphere, with 300 ~ 500 DEG C of fluidized bed roastings or rotary kiln baking, be oxidized 10-40min after being mixed with solid II by solid I, obtain and reclaim Mn oxide powder; Using described recovery Mn oxide slurry or described recovery Mn oxide powder as step c Mn oxide used, spray to join coal-fired flue-gas from connecting pipe and recycle.
Liquid II condensing crystallizing filtering layer material being carried out to regeneration process generation obtains solid ammonium sulfate and ammonium nitrate.
Along with filtering layer material gained solid I after water-soluble solution constantly circulates, the flue dust component in solid I is caused to accumulate, flue dust proportion increases, when smoke content in solid I higher than 90% time, solid I is directly abandoned the 5-20% of quality, and in remaining solid I, supplement the new Mn oxide dividing equal in quality with discarded part, then use with solid II mixing Posterior circle.
Filtering layer material gained solid I after water-soluble solution constantly circulates, the flue dust component in solid I is caused to accumulate, when smoke content in solid I higher than 85% time, remove the flue dust in solid I as follows, and then recycle: solid I is injected in connecting pipe as Mn oxide, make the sulfur dioxide in coal-fired flue-gas and nitrogen oxide that the tetravalent manganese ion in solid I is reduced to divalent manganesetion completely, generate manganese sulfate and manganese nitrate, manganese sulfate, manganese nitrate and flue dust enter in the filter bag of sack cleaner with coal-fired flue-gas, and be trapped within filter bag surface formation filtering layer, remove filtering layer by the mode of electromagnetic rapping or pulsation winding-up and collect filtering layer material, through water-soluble solution, solidliquid mixture is obtained to filtering layer material, after Separation of Solid and Liquid, gained liquid is by manganese sulfate and the water-soluble liquid formed of manganese nitrate, gained solid is flue dust, reclaims by manganese sulfate and the water-soluble liquid that forms of manganese nitrate and is regenerated as Mn oxide, abandoning flue dust, after removing the flue dust in solid I in this way, again recycle, the amount adding solid I is 0.9:1 ~ 1:1 according to the mol ratio of sulfur dioxide in wherein tetravalent manganese and coal-fired flue-gas.
Mn oxide initially used is manganese nodule powder, natural high-grade manganese oxide ore powder, commercial silica manganese powder body.
Compared with the prior art, innovation of the present invention and acquired effect are embodied in:
The present invention, using sack cleaner as core apparatus and reactor, using Mn oxide as active material, and is processed by a series of separation, regeneration and is recycled, realizing the synchronous and integrated of flue gas desulfurization denitration dust-removing in sack cleaner.
After sack cleaner of the present invention is arranged in electric precipitation, electric precipitation eliminates the soot dust granule thing of the overwhelming majority in coal-fired flue-gas, not only reduce the load of sack cleaner, play the effect that sack cleaner supplements depositing dust, simultaneously, the content of flue dust in Mn oxide recycle stock can be reduced, reduce Mn oxide separation, regeneration, circulatory system handled thing doses, reduce processing cost.
Manganese is valence variation element, bivalent manganese, tetravalent manganese state is mainly presented under air ambient, tetravalent manganese has very strong oxidisability, be easy to this kind of reducing substances of oxidize sulfur dioxide, divalent manganesetion simultaneously in water is easy to oxidation by air and becomes tetravalent manganese under neutrality, alkali condition, or the precipitation of bivalent manganese heats in atmosphere and is easy to oxide tetravalent manganese oxide, the present invention utilizes this characteristic of manganese element and compound thereof, not only realizes desulfurization but also realizes the regeneration of Mn oxide very easily.
Mn oxide slurry or powder is sprayed in the connecting pipe be connected between electric dust collector and sack cleaner, utilize the high activity of Mn oxide and oxidizing sulfur dioxide reduction reaction, sulfur dioxide (reactional equation 1) in fast eliminating flue gas, Mn oxide also has the effect (reactional equation 2) that oxidation nitrogen oxides in effluent forms manganese nitrate.
As shown in Figure 1, filter bag had both retained desulfurization product manganese sulfate, denitration product manganese nitrate, unreacted Mn oxide completely, retained again remaining soot dust granule thing in coal-fired flue-gas, supplementing as electric precipitation, improved dust removing effects.The layer of particulate matter being rich in Mn oxide that filter bag surface is formed simultaneously is again the catalyst (reactional equation 3) of catalyze ammonia reduction denitration, present invention utilizes the outstanding feature that Mn oxide has desulphurization denitration activity simultaneously.
Mn oxide direct oxidation sulfur dioxide, nitrogen oxide form sulfate and nitrate, and reactional equation is as follows:
MnO
2+SO
2＝＝＝＝＝MnSO
4(1)
2NO+O
2+MnO
2＝＝＝＝＝Mn(NO
3)
2(2)
Mn oxide is as the nitrogen oxide in catalyst ammonia reduction flue gas
6NO+4NH
3＝＝＝＝＝5N
2+6H
2O(3)
Filtering layer mainly flue dust, Mn oxide and desulfurization and denitrification reaction product thereof on filter bag, when filter bag pressure drop exceedes requirement, the mode of being jetted by general electromagnetic rapping or pulsation is made filtering layer come off and enters ash bucket.In order to regenerate and reclaim Mn oxide, the material in ash bucket is extracted manganese sulfate through water-soluble solution, and Separation of Solid and Liquid obtains solid I and liquid I.Solid I is unreacted Mn oxide and flue dust completely mainly.Mainly manganese sulfate and manganese nitrate in liquid I, reclaim solid oxides of manganese II and liquid II through ammonia neutralization, aerating oxidation, Separation of Solid and Liquid.Liquid II is the mixed solution of ammonium sulfate and ammonium nitrate, can recycle further.Solid I and solid II being mixed into slurry or mixing rear roasting becomes powder to be stored in feed bin, again by spray regime, Mn oxide is joined synchronized desulfuring and denitrifying dedusting in flue gas.By a series of process to filter bag filtering layer material, Mn oxide obtains regeneration, recovery realization recycles (as shown in Figure 2).
In order to eliminate the accumulation of flue dust material in Mn oxide and affect the efficiency that Mn oxide is cycled to used in desulphurization denitration, by reducing the amount of spraying Mn oxide in flue gas, the mol ratio of measuring than changing sulfur dioxide in tetravalent manganese and coal-fired flue-gas in Mn oxide into is 0.9:1 ~ 1:1, and stop adding ammonia in flue gas, only carry out flue gas desulfurization, the Mn oxide added is impelled to change manganese sulfate into completely, the lime-ash that filter bag reclaims is after water-soluble extraction manganese sulfate, undissolved solid mainly flue dust, as refuse process, eliminate flue dust accumulation in Mn oxide circulation slurry in this way.
Because Mn oxide slurry or powder jetting enter flue gas stream, utilize smoke power rapid mixing, dispersion becomes fine particle shape, at suspended state and SO 2 from fume, nitrogen oxide generation redox reaction, retained by filter bag to be formed after filtering layer wherein unreacted Mn oxide continue with by the sulfur dioxide in filtering layer gas, nitrogen oxide generation redox reaction, overcome lime stone dry desulfurization efficiency low, the defect that feeding lime stone ratio is large, also can overcome wet desulphurization reduces more to the temperature of flue gas, can not meet denitration temperature requirement, be unfavorable for a difficult problem for denitration.
The present invention using filter bag as core reaction device, both make use of the surface area that filter bag is high, reduce unit are flue gas load, retain again and reclaimed desulphurization denitration product, unreacted Mn oxide is as SCR catalyst simultaneously, namely filter bag becomes the carrier of catalyst fixed bed layer, and the beds lost efficacy removed by the rapping apparatus of Electromagnetic Control, and regenerates.
Four, accompanying drawing explanation
Fig. 1 is the principle schematic utilizing sack cleaner to realize the dedusting of flue gas synchronized desulfuring and denitrifying;
Fig. 2 is coal-fired flue-gas synchronized desulfuring and denitrifying dust collecting process technology path schematic diagram.
Five, specific embodiment
Embodiment 1
As depicted in figs. 1 and 2, the present embodiment illustrates the method for sack cleaner inter-sync desulfur denitrate dust collecting of the present invention, and concrete steps are:
A, by coal dust burning produce coal-fired flue-gas remove most flue dust through electric cleaner, sulfureous in flue gas content is approximately 550PPm;
Coal-fired flue-gas temperature after b, adjustment electric precipitation, makes it be stabilized between 200 ~ 210 DEG C; The coal-fired flue-gas temperature entering sack cleaner like this can be stabilized in 200 ~ 210 DEG C, had both met the temperature requirement of catalyze ammonia reduction denitrating flue gas, and met again the requirement in filter bag use safety and guarantee life-span in this temperature.
C, in the connecting pipe between electric cleaner and sack cleaner, spray commercial silica manganese powder body, make the sulfur dioxide fast reaction in Mn oxide and coal-fired flue-gas, remove most of sulfur dioxide in coal-fired flue-gas and form manganese sulfate, and with the part reaction of nitrogen oxides in coal-fired flue-gas, slough nitrogen oxide formed manganese nitrate; The Mn oxide that manganese sulfate, manganese nitrate, unreacted are complete and flue dust enter in the filter bag of sack cleaner with coal-fired flue-gas, and are trapped within filter bag surface formation filtering layer, and purifying smoke is discharged through filter bag; The complete Mn oxide of unreacted in filtering layer continues to react with residual sulfur dioxide in coal-fired flue-gas; The quality of the Mn oxide added and be transported to connecting pipe coal-fired flue-gas in the mass ratio of sulfur dioxide be 3:1;
D, in the coal-fired flue-gas of sack cleaner, spray into ammonia, in the filtering layer of filter bag surface, unreacted Mn oxide is as selective catalytic reduction catalysts, plays efficient denitration catalyst effect, makes ammonia be nitrogen by residual nitrogen Reduction of Oxide in coal-fired flue-gas; The ammonia quality sprayed into is 1:1 with the mass ratio of nitrogen oxide in the coal-fired flue-gas entering filter bag;
E, along with filter bag surface filtering layer (being made up of flue dust, Mn oxide and desulfurization and denitrification reaction product manganese sulfate thereof and manganese nitrate) thickness increase, sock filtration resistance increases, when filter bag internal drop reaches 800Pa, by the rapping apparatus rapping of Electromagnetic Control, filtering layer material on filter bag is come off and enter ash bucket;
F, the filtering layer material collected in ash bucket, and the manganese sulfate added in filtering layer material in the water-soluble solution filtering layer material of 5 times of quality and manganese nitrate, obtain solidliquid mixture I, obtain the solid I be made up of Mn oxide and flue dust after Separation of Solid and Liquid is carried out to solidliquid mixture I and by manganese sulfate and the water-soluble liquid I formed of manganese nitrate;
G, liquid I ammonia neutralization in liquid pH value 8 ~ 9 scope, and aeration aerating oxidation divalent manganesetion is tetravalent manganese ion, obtain solidliquid mixture II, Separation of Solid and Liquid is carried out to solidliquid mixture II, obtain the solid II be made up of Mn oxide and the liquid II being rich in ammonium sulfate and ammonium nitrate;
H, solid I mixed to obtain with solid II and reclaims Mn oxide slurry, be stored in Mn oxide feed bin, to reclaim Mn oxide slurry as step c Mn oxide used, spray to join coal-fired flue-gas from connecting pipe and recycle.
I, filtering layer material gained solid I after water-soluble solution constantly circulates, the flue dust component in solid I is caused to accumulate, when smoke content in solid I higher than 85% time, remove the flue dust in solid I as follows, and then recycle: solid I is used step c (amount adding solid I is 0.9:1 according to the mol ratio of sulfur dioxide in wherein tetravalent manganese and coal-fired flue-gas) as Mn oxide, the ammonia not carrying out steps d adds step, make the sulfur dioxide in coal-fired flue-gas and nitrogen oxide that the tetravalent manganese ion in solid I is reduced to divalent manganesetion completely, generate manganese sulfate and manganese nitrate, manganese sulfate, manganese nitrate and flue dust enter in the filter bag of sack cleaner with coal-fired flue-gas, and be trapped within filter bag surface formation filtering layer, automatic detection device monitors after discharge sulfur dioxide in flue gas concentration exceedes emission request, by the rapping apparatus of Electromagnetic Control, the filtering layer material on filter bag is come off and enter ash bucket, material in ash bucket is dissolved according to the ratios with water of solid-liquid mass ratio 1:5 the manganese sulfate extracted wherein, manganese nitrate, Separation of Solid and Liquid obtains solid and liquid, gained liquid is by manganese sulfate and the water-soluble liquid formed of manganese nitrate, gained solid is flue dust, solid is directly abandoned as refuse, liquid I ammonia neutralization to liquid pH value 8 ~ 9 and aeration aerating oxidation divalent manganesetion be tetravalent manganese, Separation of Solid and Liquid reclaims Mn oxide and obtains solid and liquid, solid is stored in feed bin for subsequent use, complete after Mn oxide material once circulates and substantially eliminate flue dust accumulation in material, return to step c-h operation again.
Can realize desulfuration efficiency according to the present embodiment mode and be greater than 90%, denitration efficiency is greater than 85%.
Embodiment 2
A, coal-fired flue-gas remove most flue dust through electric cleaner, and sulfureous in flue gas content is approximately 550PPm;
Coal-fired flue-gas temperature after b, adjustment electric precipitation, makes it be stabilized between 150 ~ 160 DEG C;
C, in the connecting pipe between electric cleaner and sack cleaner, spray natural high-grade manganese oxide ore powder, make the sulfur dioxide fast reaction in Mn oxide and coal-fired flue-gas, remove most of sulfur dioxide in coal-fired flue-gas and form manganese sulfate, and with the part reaction of nitrogen oxides in coal-fired flue-gas, slough nitrogen oxide formed manganese nitrate; The Mn oxide that manganese sulfate, manganese nitrate, unreacted are complete and flue dust enter in the filter bag of sack cleaner with coal-fired flue-gas, and are trapped within filter bag surface formation filtering layer, and purifying smoke is discharged through filter bag; The complete Mn oxide of unreacted in filtering layer continues to react with residual sulfur dioxide in coal-fired flue-gas; The quality of the Mn oxide added and be transported to connecting pipe coal-fired flue-gas in the mass ratio of sulfur dioxide be 5:1;
D, in the coal-fired flue-gas of sack cleaner, spray into ammonia, in the filtering layer of filter bag surface, unreacted Mn oxide is as selective catalytic reduction catalysts, plays efficient denitration catalyst effect, makes ammonia be nitrogen by residual nitrogen Reduction of Oxide in coal-fired flue-gas; The ammonia quality sprayed into is 1:1.5 with the mass ratio of nitrogen oxide in the coal-fired flue-gas entering filter bag;
E, along with filter bag surface filtering layer (being made up of flue dust, Mn oxide and desulfurization and denitrification reaction product manganese sulfate thereof and manganese nitrate) thickness increase, sock filtration resistance increases, when filter bag internal drop reaches 900Pa, by the rapping apparatus rapping of Electromagnetic Control, filtering layer material on filter bag is come off and enter ash bucket;
F, the filtering layer material collected in ash bucket, and the manganese sulfate added in filtering layer material in the water-soluble solution filtering layer material of 8 times of quality and manganese nitrate, obtain solidliquid mixture I, obtain the solid I be made up of Mn oxide and flue dust after Separation of Solid and Liquid is carried out to solidliquid mixture I and by manganese sulfate and the water-soluble liquid I formed of manganese nitrate;
G, liquid I ammonia neutralization to liquid pH value in 8 ~ 9 scopes, then aeration aerating oxidation divalent manganesetion is tetravalent manganese ion, obtain solidliquid mixture II, Separation of Solid and Liquid is carried out to solidliquid mixture II, obtains the solid II be made up of Mn oxide and the liquid II being rich in ammonium sulfate and ammonium nitrate;
H, solid I is mixed with solid II after in air atmosphere, with 450 DEG C of fluidized bed roastings or rotary kiln baking, be oxidized 30min, obtain and reclaim Mn oxide powder; Recovery Mn oxide powder is joined in Mn oxide feed bin, as step c Mn oxide used, joins coal-fired flue-gas from connecting pipe injection and recycle.
J, filtering layer material gained solid I after water-soluble solution constantly circulates, and causes the flue dust component in solid I to accumulate, when smoke content in solid I higher than 85% time, remove the flue dust in solid I by the mode that embodiment 1 is identical, and then recycle.
Can realize desulfuration efficiency according to the present embodiment mode and be greater than 90%, denitration efficiency is greater than 90%.
Claims (10)
1. a method for sack cleaner inter-sync desulfur denitrate dust collecting, is characterized in that:
Take sack cleaner as reaction unit, coal-fired flue-gas after electric precipitation is introduced in sack cleaner by connecting pipe, Mn oxide is injected in described connecting pipe, make Mn oxide remove most of sulfur dioxide in coal-fired flue-gas and form manganese sulfate, and remove part nitrogen oxide formation manganese nitrate; The Mn oxide that manganese sulfate, manganese nitrate, unreacted are complete and flue dust enter in sack cleaner with coal-fired flue-gas, and the filter bag surface being trapped within sack cleaner forms filtering layer; The Mn oxide that unreacted is complete in filtering layer continues and sulfur dioxide residual in coal-fired flue-gas reacts; In the coal-fired flue-gas entering sack cleaner, spray into ammonia, in filtering layer the Mn oxide that unreacted is complete catalytic action under, residual nitrogen Reduction of Oxide in coal-fired flue-gas is nitrogen by ammonia;
Along with thickness of filter bed increases, sock filtration resistance increases, when filter bag internal drop reaches 800 ~ 900Pa, remove filtering layer by the mode of electromagnetic rapping or pulsation winding-up and collect filtering layer material, to carrying out regeneration process after filtering layer material recycle, the Mn oxide obtained recycles to injection connecting pipe.
2. the method for sack cleaner inter-sync desulfur denitrate dust collecting according to claim 1, is characterized in that:
The quality of the Mn oxide injected in connecting pipe is 2:1 ~ 5:1 with the mass ratio of the coal-fired flue-gas sulfur dioxide being transported to connecting pipe.
3. the method for sack cleaner inter-sync desulfur denitrate dust collecting according to claim 1, is characterized in that:
The ammonia quality sprayed in the coal-fired flue-gas of sack cleaner is 1:1 ~ 1:1.15 with the mass ratio of nitrogen oxide in the coal-fired flue-gas entering sack cleaner.
4. the method for sack cleaner inter-sync desulfur denitrate dust collecting according to claim 1, is characterized in that:
Before coal-fired flue-gas enters sack cleaner, regulate coal-fired flue-gas temperature to make in sack cleaner coal-fired flue-gas temperature stabilization at 150 ~ 220 DEG C, with the safe handling requirement of the temperature requirement and filter bag that ensure denitration reaction.
5. the method for sack cleaner inter-sync desulfur denitrate dust collecting according to claim 1, is characterized in that:
Method filtering layer material being carried out regenerating to process acquisition Mn oxide is: the water adding 3 ~ 10 times of quality in filtering layer material, obtain solidliquid mixture I, obtain the solid I be made up of Mn oxide and flue dust after Separation of Solid and Liquid is carried out to solidliquid mixture I and by manganese sulfate and the water-soluble liquid I formed of manganese nitrate;
By liquid I ammonia neutralization to pH value in 8 ~ 9 scopes, then aeration aerating makes divalent manganesetion be oxidized to tetravalent manganese ion, obtain solidliquid mixture II, Separation of Solid and Liquid is carried out to solidliquid mixture II, obtain the solid II be made up of Mn oxide and the liquid II being rich in ammonium sulfate and ammonium nitrate;
Solid I is mixed to obtain with solid II and reclaims Mn oxide slurry, or in air atmosphere, with 300 ~ 500 DEG C of fluidized bed roastings or rotary kiln baking, be oxidized 10-40min after being mixed with solid II by solid I, obtain and reclaim Mn oxide powder; Using described recovery Mn oxide slurry or described recovery Mn oxide powder as described Mn oxide, spray to join coal-fired flue-gas from the connecting pipe be connected between electric cleaner and sack cleaner and recycle.
6. the method for sack cleaner inter-sync desulfur denitrate dust collecting according to claim 1, is characterized in that taking following operating procedure:
A, first coal-fired flue-gas is removed most of flue dust through electric cleaner, when burning high sulfur coal powder causes that in coal-fired flue-gas, sulfur content is higher than 800PPm, use again after first adding the agstone accounting for high-sulfur quality of pc 1-3% in high-sulfur coal dust;
B, the coal-fired flue-gas after electric precipitation to be introduced before sack cleaner by connecting pipe, regulate coal-fired flue-gas temperature, to make in sack cleaner coal-fired flue-gas temperature stabilization at 150 ~ 220 DEG C, with the safe handling requirement of the temperature requirement and filter bag that ensure denitration reaction;
C, in the coal-fired flue-gas in the connecting pipe between electric cleaner and sack cleaner spray add Mn oxide, make the sulfur dioxide fast reaction in Mn oxide and coal-fired flue-gas, remove most of sulfur dioxide in coal-fired flue-gas and form manganese sulfate, and with the part reaction of nitrogen oxides in coal-fired flue-gas, slough nitrogen oxide formed manganese nitrate; The Mn oxide that manganese sulfate, manganese nitrate, unreacted are complete and flue dust enter in sack cleaner with coal-fired flue-gas, and the filter bag surface being trapped within sack cleaner forms filtering layer; The complete Mn oxide of unreacted in filtering layer continues to react with residual sulfur dioxide in coal-fired flue-gas; The quality of the Mn oxide added be 2:1 ~ 5:1 with the mass ratio of sulfur dioxide in the coal-fired flue-gas being transported to connecting pipe;
D, in the coal-fired flue-gas entering sack cleaner, spray into ammonia, in the filtering layer of filter bag surface, unreacted Mn oxide is as selective catalytic reduction catalysts, play efficient denitration catalyst effect 150 DEG C ~ 220 DEG C temperature provinces, make ammonia be nitrogen by residual nitrogen Reduction of Oxide in coal-fired flue-gas; The ammonia quality sprayed in the coal-fired flue-gas of sack cleaner is 1:1 ~ 1:1.15 with the mass ratio of nitrogen oxide in the coal-fired flue-gas entering sack cleaner;
E, along with filter bag surface thickness of filter bed increases, sock filtration resistance increases, and when filter bag internal drop reaches 800 ~ 900Pa, by the mode of the rapping apparatus rapping of Electromagnetic Control or pulsation winding-up, filtering layer material on filter bag is come off and enters ash bucket;
F, the filtering layer material collected in ash bucket, and the manganese sulfate added in filtering layer material in the water-soluble solution filtering layer material of 3 ~ 10 times of quality and manganese nitrate, obtain solidliquid mixture I, obtain the solid I be made up of Mn oxide and flue dust after Separation of Solid and Liquid is carried out to solidliquid mixture I and by manganese sulfate and the water-soluble liquid I formed of manganese nitrate;
G, liquid I ammonia neutralization to liquid pH value in 8 ~ 9 scopes, then aeration aerating oxidation divalent manganesetion is tetravalent manganese ion, obtain solidliquid mixture II, Separation of Solid and Liquid is carried out to solidliquid mixture II, obtains the solid II be made up of Mn oxide and the liquid II being rich in ammonium sulfate and ammonium nitrate;
H, solid I mixed to obtain with solid II and reclaims Mn oxide slurry, or in air atmosphere, with 300 ~ 500 DEG C of fluidized bed roastings or rotary kiln baking, be oxidized 10-40min after being mixed with solid II by solid I, obtain and reclaim Mn oxide powder; Using described recovery Mn oxide slurry or described recovery Mn oxide powder as step c Mn oxide used, spray to join coal-fired flue-gas from connecting pipe and recycle.
7. the method for the sack cleaner inter-sync desulfur denitrate dust collecting according to claim 5 or 6, is characterized in that: liquid II condensing crystallizing filtering layer material being carried out to regeneration process generation obtains solid ammonium sulfate and ammonium nitrate.
8. the method for the sack cleaner inter-sync desulfur denitrate dust collecting according to claim 5 or 6, it is characterized in that: along with filtering layer material gained solid I after water-soluble solution constantly circulates, the flue dust component in solid I is caused to accumulate, flue dust proportion increases, when smoke content in solid I higher than 90% time, solid I is directly abandoned the 5-20% of quality, and in remaining solid I, supplement the new Mn oxide dividing equal in quality with discarded part, then use with solid II mixing Posterior circle.
9. the method for the sack cleaner inter-sync desulfur denitrate dust collecting according to claim 5 or 6, it is characterized in that: filtering layer material gained solid I after water-soluble solution constantly circulates, the flue dust component in solid I is caused to accumulate, when smoke content in solid I higher than 85% time, remove the flue dust in solid I as follows, and then recycle: solid I is injected in connecting pipe as Mn oxide, make the sulfur dioxide in coal-fired flue-gas and nitrogen oxide that the tetravalent manganese ion in solid I is reduced to divalent manganesetion completely, generate manganese sulfate and manganese nitrate, manganese sulfate, manganese nitrate and flue dust enter in the filter bag of sack cleaner with coal-fired flue-gas, and be trapped within filter bag surface formation filtering layer, remove filtering layer by the mode of electromagnetic rapping or pulsation winding-up and collect filtering layer material, through water-soluble solution, solidliquid mixture is obtained to filtering layer material, after Separation of Solid and Liquid, gained liquid is by manganese sulfate and the water-soluble liquid formed of manganese nitrate, gained solid is flue dust, reclaims by manganese sulfate and the water-soluble liquid that forms of manganese nitrate and is regenerated as Mn oxide, abandoning flue dust, after removing the flue dust in solid I in this way, again recycle, the amount adding solid I is 0.9:1 ~ 1:1 according to the mol ratio of sulfur dioxide in wherein tetravalent manganese and coal-fired flue-gas.
10. the method for sack cleaner inter-sync desulfur denitrate dust collecting according to claim 1 and 2, is characterized in that: Mn oxide initially used is manganese nodule powder, natural high-grade manganese oxide ore powder, commercial silica manganese powder body.
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| WO2018158184A1 (en) * | 2017-03-02 | 2018-09-07 | Haldor Topsøe A/S | Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant |
| WO2018158183A1 (en) * | 2017-03-02 | 2018-09-07 | Haldor Topsøe A/S | Process for the removal of sulphur oxides and nitrogen oxides contained in off-gas from an industrial plant |
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| CN108355451B (en) * | 2018-05-03 | 2019-05-24 | 河北雅威环保科技有限公司 | A kind of flue dust desulfurization and denitrification integral deduster |
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