CN101721898B - Method and device for simultaneous desulphurization and denitration by flue gas-seawater method - Google Patents
Method and device for simultaneous desulphurization and denitration by flue gas-seawater method Download PDFInfo
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- CN101721898B CN101721898B CN200810197273.4A CN200810197273A CN101721898B CN 101721898 B CN101721898 B CN 101721898B CN 200810197273 A CN200810197273 A CN 200810197273A CN 101721898 B CN101721898 B CN 101721898B
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- 239000013535 sea water Substances 0.000 title claims abstract description 286
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000003546 flue gas Substances 0.000 claims abstract description 116
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000002253 acid Substances 0.000 claims abstract description 78
- 238000005406 washing Methods 0.000 claims abstract description 64
- 238000007599 discharging Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 168
- 229910052742 iron Inorganic materials 0.000 claims description 98
- 230000003197 catalytic effect Effects 0.000 claims description 58
- 238000011084 recovery Methods 0.000 claims description 39
- -1 iron ion Chemical class 0.000 claims description 32
- 229910000859 α-Fe Inorganic materials 0.000 claims description 23
- 238000005273 aeration Methods 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 18
- 230000000295 complement effect Effects 0.000 claims description 15
- 239000000779 smoke Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000012762 magnetic filler Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 14
- 230000003009 desulfurizing effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005422 blasting Methods 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003317 industrial substance Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005518 chemical engineering design Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241001572175 Gaza Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940075933 dithionate Drugs 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method and a device for simultaneous desulphurization and denitration by a flue gas-seawater method. The method comprises the following steps: A) catalyzing and washing the flue gas containing SO2 and NOx by seawater to remove the SO2 and the NOx in the flue gas, and then discharging the purified flue gas subjected to the desulphurization and the denitration and discharging acid seawater formed during washing; and B) recovering the quality of the seawater, namely adding the seawater into the acid seawater and blowing the air into the acid seawater, and discharging the seawater when the quality of the acid seawater is recovered to accord with the environment-friendly requirement. The method and the device for simultaneous desulphurization and denitration have the advantages that chemical raw materials are not needed, the emission reduction efficiency and reliability are high, the occupied area is small, the construction and running costs are low, and the method and the device are particularly suitable for simultaneous desulphurization and denitration for boiler flue gases of large and medium-sized heat power plants.
Description
Technical field
The present invention relates to a kind of flue gas-seawater method simultaneous SO_2 and NO removal method and device; utilize seawater to remove sulphur in flue gas and nitre simultaneously; be particularly suitable for the discharge as pollutants such as boiler minimizing sulfur dioxide and nitrogen oxide etc. such as thermal power plants; belong to atmospheric environment protection technical field, more specifically belong to flue gas and desulfurizing and denitrifying technical field (simultaneous desulfurization and denitrification), (simultaneous removing SOx andNOx).
Background technology
Due to the needs of environment protection, industrial smoke must reduce the discharge of sulfur dioxide and nitrogen oxide two kinds of important pollutants.But; respectively with traditional reduction mode that sulfur removal technology device and denitrating technique device realize; because process structure is complicated, consumed resource is large; have that reliability is low, Construction and operation high in cost of production problem, the traditional approach of desulphurization denitration reduces discharging and to pollute and the effect of protection of the environment is subject to serious restriction respectively.For available protecting atmospheric environment, the pollution that control sulphur and nitre cause, people need the emission-reduction technology of synthesization, greenization for a long time, expect the appearance having a kind of flue gas and desulfurizing and denitrifying process technology scheme of greenization.
The representative solution of flue gas and desulfurizing and denitrifying technical field mainly contains following several in the world:
DESONOX method, develops (Fig. 7) by companies such as German enlightening gazas (Degussa).First in flue gas, ammoniacal liquor (NH is sprayed into
3), then make flue gas enter the fixed bed reactors of double-layer catalyst, ground floor is denitrogenation reduction (SCR) catalyst that the noble metals such as vanadium are made, and NOx is by NH
3be reduced to N
2and H
2o, the second layer is noble metal desulfurization oxidation catalyst, SO
2be oxidized to SO
3, become sulfuric acid with after water absorption condensation.
PHOSNOX method, is developed by California, USA (California) university.O is produced with yellow phosphorus
3with O, NO is oxidized to NO
2, yellow phosphorus is oxidized to P simultaneously
2o
5become phosphoric acid.The NO generated
2in aqueous by SO
2be oxidized to SO
4 2-, self be reduced to azanol disulfonate, ammonium salt and other S-N compound.
PPCP method, by Japan Fukui, polytechnical university develops.Produce the gas molecule of high-power electron beam dissociation flue gas with accelerator, generate O, OH, HO
2isoreactivity radical oxidation SO
2and NOx, form sulphur ammonium and ammonium nitrate after ammonification.Etc..
The art solutions of domestic flue gas and desulfurizing and denitrifying technical field has: application number is 200610012525.2, name is called " a kind of liquid phase flue gas desulfurizing and denitrifying purification method and device ", North China Electric Power University develops, and it utilizes jet bubbling method and sodium chlorite absorption liquid to add the combined additive such as calcium hypochlorite, hydrogen peroxide, sodium hydrogen phosphate to absorb sulfur dioxide in flue gas and nitrogen oxide; The patent No. is 01105698.3, and name is called " a kind of method removing NOx in waste gas ", and namely second two ammonium closes cobalt (II) complex catalysis method, and East China University of Science develops, with Al
2o
3for carrier, load various metal oxide NiO, Co
3o
4catalyst, in alkaline solution, NO is oxidized to NO
2.Etc..
The common issue that existing simultaneous SO_2 and NO removal technical scheme exists is: in order to simultaneous SO_2 and NO removal, need to add valuable catalyst or/and absorbent in its processing procedure; Absorbent and catalyst particularly comprise the use of the industrial chemicals of valuable catalyst etc., cause resource and energy resource consumption too high, cause complex process, the reliability of process unit entirety be low, build and operating cost high, also there is secondary pollution problem in some, is thus difficult to apply.
Summary of the invention
The object of the invention is to, fundamentally overcome prior art shortcoming, there is provided a kind of do not need to add in addition valuable or that there is secondary pollution absorbent or/and catalyst, the energy that economizes on resources, technique simple and direct reliable, cost is low, the pollution emission reduction technical scheme of the synthesization greenization of non-secondary pollution, namely a kind of seawater that mainly utilizes is as the seawater method flue gas and desulfurizing and denitrifying method of absorbent and catalyst and device.
The technical scheme realizing the seawater method flue gas and desulfurizing and denitrifying method of the object of the invention is: a kind of flue gas-seawater method simultaneous SO_2 and NO removal method, and it comprises the steps: A) seawater catalytic laundry flue gas: with seawater to containing SO
2and the flue gas of NOx carries out catalytic laundry, to remove the SO in flue gas
2and NOx, then discharge the purifying smoke through desulphurization denitration and the acid seawater of discharging washing process formation; Described catalytic laundry is the iron catalytic laundry that carries out of the seawater or be added with a certain amount of iron ion or/and make seawater or/and flue gas is through the magnetic catalytic laundry of complementary field; B) acid seawater quality recovers: mix seawater to the acid seawater of discharging in described step A and carry out acid-base neutralization and blast air, the quality recovery of acid seawater is discharged after meeting environmental requirement.
Described simultaneous SO_2 and NO removal method, the iron catalytic laundry that the seawater of its a certain amount of iron ion carries out is the iron catalytic laundry that in washing step, iron concentration to be per kilogram Iron In Seawater ion be 3 micrograms are carried out to the seawater of 300 micrograms (3 ~ 300 μ g/kg).
Described simultaneous SO_2 and NO removal method, the iron catalytic laundry that the seawater of its a certain amount of iron ion carries out is the iron catalytic laundry that in washing step, iron concentration to be per kilogram Iron In Seawater ion be 10 micrograms are carried out to the seawater of 300 micrograms (10 ~ 300 μ g/kg).
Described simultaneous SO_2 and NO removal method, the seawater of its washing flue gas, its flow according to the acid of washing sea water flue gas alkali than choosing: the seawater alkali number value of washing flue gas/by the sour value that washs flue gas is 1 to 200; Wherein: the seawater alkali number value of washing flue gas is the product value of alkalinity of seawater value and seawater flow value, this alkalinity of seawater value equals value during total alkalinity (ALK) measuring this seawater with often liter mM (mmol/l), and seawater flow value equals the value that this seawater measures with milliliter per hour (ml/h); The described sour value by washing flue gas is the product value of flue gas sulfur-bearing concentration value and flue gas flow value, and this sulfur-bearing concentration value equals this flue gas with every standard cubic meter milligram (mg/Nm
3) measure its SO
2value during concentration, flue gas flow value equals flue gas with standard cubic meter (Nm per hour
3/ h) value of measuring.
Described simultaneous SO_2 and NO removal method, the iron catalytic laundry that its seawater being added with a certain amount of iron ion carries out, its adding method in acid seawater, arranges ferrite members or/and make the ferrous material of contact seawater become sacrificial anode or/and added the iron catalytic laundry of iron ion by a kind of device that can add iron-containing liquor.
Described simultaneous SO_2 and NO removal method, its magnetic catalytic laundry, be make seawater or/and flue gas through magnetic flux density be the magnetic catalytic laundry of 1 ~ 6000 gauss magnetic field.
A kind of technical scheme of the simultaneous SO_2 and NO removal device for flue gas-seawater method simultaneous SO_2 and NO removal method is: it comprises seawater catalytic laundry system and acid seawater quality recovery system; Described seawater catalytic laundry system comprises washer, washer smoke inlet, washer exhanst gas outlet, the seawater inlet of washing flue gas, the acid seawater outlet of washer, for increasing ferrite members or the iron ion adding set of seawater iron ion content, or/and make the seawater of washing flue gas or/and flue gas is in the magnetic devices of complementary field; Described acid seawater quality recovery system comprises quality recovery device, and what be connected with it has acid sea water passage, sea water passage, air blast, also has seawater outlet; Acid seawater inlet and seawater inlet adjoining in quality recovery device; Air blast is by blast channel and the aeration opening UNICOM be located in quality recovery device.
Described simultaneous SO_2 and NO removal device, its ferrite members arranges the iron filler that directly can contact with acid seawater in the washers or/and ferrous element that is fixing, that maybe can change.
Described simultaneous SO_2 and NO removal device, its iron ion adding set is the injector be connected with iron-containing liquor inlet that washer is arranged, or/and iron ion generating means.
Described simultaneous SO_2 and NO removal device, its magnetic devices be the magnetic fillers that arranges in washer or/and magnetic component, or/and washing seawater is or/and the magnetic component that arranges of exhaust gases passes.
The technological principle of the inventive method is:
Seawater catalytic laundry:
1, SO is dissolved with seawer washing flue gas
2form acid seawater, reaction equation is:
SO
2(g)+H
2O＝SO
2(l)+H
2O
SO
2(l)+H
2O＝SO
3 2-+2H
+
2, continue washing flue gas with acid seawater and dissolve NO.Not have a denitration function because NO is water insoluble different from general wet process, technical solution of the present invention has catalysis and impels NO to dissolve the physical and chemical condition of (hydrolysis): in the acid seawater that a) first step dissolved sulfur dioxide is formed, generate a large amount of SO
3 2-nO can be impelled to dissolve; B) first step dissolved sulfur dioxide formed acid condition under, in seawater and present invention process increase iron ion (Fe
2+, Fe
3+) there is catalytic action; C) under the acid condition of first step dissolved sulfur dioxide formation, iron ion (Fe
2+, Fe
3+) form complicated iron complex in the seawater, the SO of dissolving can be impelled
2with the O that flue gas is brought into
2reaction generates N
2, N
2o, dithionate, sulfate etc. compound, as following reaction equation 2 (NO)+SO
3 2-→ N
2o+SO
4 2-etc., the residue oxygen in flue gas in power station boiler is generally 5 ~ 8%; D) in the sour environment that first step dissolved sulfur dioxide is formed, the dissolving (hydrolysis) of the complementary field catalyzing N O of magnetic component.Nitrogen oxide reaction is in the seawater comparatively complicated, mainly collaborative autocatalyzed oxidation reduction reaction.Flue gas through simultaneous SO_2 and NO removal purification enters air.
Acid seawater quality recovers:
Seawater is acid because of washing flue gas, acid seawater quality must be returned to the degree compatible with ambient water quality, just can enter natural environment, as sea; Recovering the mode of water quality is add seawater and alkaline seawater to acid seawater and fully acid-base neutralization reaction is carried out in mixing, then blast air and carry out oxidation deacidification oxygenation, make the sulfurous acid in seawater be generated as sulphite and be reoxidised into the stable sulfate to marine environment close friend, drive the carbon dioxide that generates in seawater simultaneously out of and increase dissolved oxygen of seawater, as following chemical equilibrium reaction formula:
CO
3 2_+H
+＝HCO
3 _
HCO
3 _+H
+＝CO
2(g+l)+H
2O
SO
3 2_+1/2O
2＝SO
4 2_
The pH value of process drain, COD and dissolved oxygen are all returned to ambient water quality compatible, meet the quality of environmental requirement.The a small amount of soluble iron increased in process drain is environmentally friendly, not only because iron is not the element limited in Seawater environmental quality standard, and be the element that the increase of desertification phenomenon needs is improved in ocean.
Acid seawater quality recovery process, can in independent quality recovery device, or in the bottom of catalytic laundry device, or complete in the pipeline irrigation canals and ditches be associated.
The obvious technical effects of seawater method flue gas and desulfurizing and denitrifying method and apparatus of the present invention:
One, efficient emission-reducing, the polluter removal efficiency in flue gas reaches as high as SO
299%, NOx70%;
Two, resource and energy conservation, without the need to any industrial chemicals, especially when thermal power plant applies, because its cooling seawater energy consumption multiplexing is lower;
Three, environmental friendliness, a large amount of industrial chemicals need be consumed with other flue gas desulfurization and denitration technique and produce a large amount of waste residue unlike, present invention process does not have waste residue to produce, and its discharge seawater part relevant with present invention process all meets environmental requirement.
Accompanying drawing explanation
Fig. 1, be the step schematic diagram of flue gas-seawater method simultaneous SO_2 and NO removal method of the present invention.
Fig. 2, be the schematic diagram that apparatus of the present invention are applied in thermal power plant.
Fig. 3, be an embodiment schematic diagram of washer 1 structure in apparatus of the present invention, be wherein provided with flow regulator 1.7; Be provided with ferrite members 1.5 (magnetic component 1.5 ' can be replaced by when needing).
Fig. 4, be the another embodiment schematic diagram of washer 1 structure in apparatus of the present invention, wherein be provided with iron ion generating unit, be made up of the iron pipe of the seawater pond bottom the washer 1 immersing ferrite members 1.5 in acid seawater and the acid seawater of conveying, its ferrite members 1.5 immersed and iron pipe also can be changed or add.
Fig. 5, be the structural representation of quality recovery device 6 in apparatus of the present invention, have the pond body of mixed function and aeration performance.
Fig. 6, be the schematic diagram that the DESONOX method flue gas and desulfurizing and denitrifying method of one of existing flue gas and desulfurizing and denitrifying technical scheme is applied in thermal power plant, the method is developed by companies such as German enlightening gazas (Degussa).
The name of the associated components that the figure labelled notation shown in accompanying drawing is corresponding or structure is called:
In Fig. 1: A, seawater catalytic laundry flue gas; B, acid seawater quality recover; C, acid seawater are discharged after meeting environmental requirement; D, seawater; E, containing SO
2and the flue gas of NOx; The purifying smoke of F, desulphurization denitration; G, acid-base neutralization; H, blast air.
In Fig. 2-5: 1, washer; 1.1, filler; 1.2, support; 1.3, seawater distributor; 1.4, demister; 1.5, ferrite members; 1.5 ', magnetic component; 1.6, iron-containing liquor inlet; 1.7, flow regulator; 1.8, iron-containing liquor pump; 1.9, ferrite members changes aperture of door; 2, washer smoke inlet; 3, washer exhanst gas outlet; 4, washer seawater inlet; 5, the acid seawater outlet of washer; 6, quality recovery device; 7, acid seawater inlet; 8, seawater inlet; 8-1, first mix seawater inlet; 8-2, after mix seawater inlet; 9, acid sea water passage; 10, sea water passage; 11, air blast; 12, blast channel; 13, aeration opening in quality recovery device; 13x, aeration opening array; 14, seawater outlet; 15, boiler; 16, deduster; 17, induced-draught fan; 18, chimney; 19, sea water pump; 20, condenser of power plant; 21, flue gas reheater;
In Fig. 4: 22, flowmeter; 23, pH meter;
In Fig. 6: 24, ammoniacal liquor adds passage; 25, noble metal denitrogenation reducing catalyst; 26, noble metal desulfurization oxidation catalyst; 27, sulfuric acid absorption device.
Detailed description of the invention
A, further illustrate as follows to the detailed description of the invention of flue gas-seawater method simultaneous SO_2 and NO removal method of the present invention in conjunction with the accompanying drawings and embodiments.
Embodiment 1:
Be the step schematic diagram of flue gas-seawater method simultaneous SO_2 and NO removal method of the present invention as shown in Figure 1, Fig. 2 is the process that the present invention applies in thermal power plant; The present embodiment seawater method flue gas and desulfurizing and denitrifying method step is: A) seawater catalytic laundry flue gas: with seawater to containing SO
2and the flue gas of NOx carries out catalytic laundry, to remove the SO in flue gas
2and NOx, then discharge the purifying smoke through simultaneous SO_2 and NO removal and the acid seawater of discharging washing process formation; Catalytic laundry of the present invention, the iron catalytic laundry that carries out of the seawater or be added with a certain amount of iron ion or/and make seawater or/and flue gas is through the magnetic catalytic laundry of complementary field, with regard to the present embodiment, described catalytic laundry is the iron catalytic laundry that the seawater being added with a certain amount of iron ion carries out, specifically, be that ferrite members is set in acid seawater; B) acid seawater quality recovers: mix seawater to the acid seawater of discharging in described step A and carry out acid-base neutralization and blast air, the quality recovery of acid seawater is discharged after meeting environmental requirement;
Described iron catalytic laundry, be the iron catalytic laundry that in washing step, iron concentration to be per kilogram Iron In Seawater ion be 3 micrograms are carried out to the seawater of 300 micrograms (3 ~ 300 μ g/kg), the concrete iron concentration of the present embodiment elects 32 μ g/kg as; The seawater of described washing flue gas, its flow according to the acid of washing sea water flue gas alkali than choosing: the seawater alkali number value of washing flue gas/by the sour value that washs flue gas is 1 to 200; Wherein: the seawater alkali number value of washing flue gas is the product value of alkalinity of seawater value and seawater flow value, this alkalinity of seawater value equals value during total alkalinity (ALK) measuring this seawater with often liter mM (mmol/l), and seawater flow value equals the value that this seawater measures with milliliter per hour (ml/h); The described sour value by washing flue gas is the product value of flue gas sulfur-bearing concentration value and flue gas flow value, and this sulfur-bearing concentration value equals this flue gas with every standard cubic meter milligram (mg/Nm
3) measure its SO
2value during concentration, flue gas flow value equals flue gas with standard cubic meter (Nm per hour
3/ h) value of measuring; The acid of the present embodiment washing sea water flue gas alkali is than electing 6.5 as;
Further illustrate: the seawater of described washing flue gas adopts the seawater deriving from ocean, and namely used seawater is directly taken from ocean, or the multiplexing seawater deriving from ocean and discharge through industrial plants; Required seawater amount has two aspects: first seawater total flow, and needed for the alkalinity equivalent determination acid-base neutralization of the sour gas equivalent removed needed in flue gas and seawater, seawater amount is as the lower limit of seawater total flow; In most of Coastal Power Plant application scenario, seawater total flow needed for present invention process is less than or equal to power plant's refrigerated sea water flow, and can discharge or/and whole cooling seawater of cooling water pump output by direct multiplexing power plant condenser, its operation energy consumption will be saved especially; It two is seawater flows of catalytic laundry flue gas: a part for seawater total flow is used for the washing seawater of catalytic laundry flue gas step, and what the remainder of seawater total flow was used for quality recovery step mixes seawater;
The above-mentioned iron catalytic laundry carried out with seawater arranging ferrite members in acid seawater adopts to make to produce soluble iron in washing seawater or/and the method for redox reaction of molysite catalyst nox; Specifically, be strengthening removing NOx, adopt the method for placing iron filler in washing sour environment; Described seawater quality recovers, and is mix seawater to acid seawater and blast the step of air, and its mode blasting air adopts conventional aeration method, according to the design of chemical industry handbook, is aforesaid seawater total flow by the seawater flow blasting air; The seawater mixed is the seawater not maintaining basicity for washing absorption sour gas, is a part for seawater total flow; Seawater quality recovery process preferably completes in independent seawater quality recovery device, also in the bottom of catalytic laundry device, or can complete in the pipeline irrigation canals and ditches be associated; Described drain step be by blending, Air Exposure after seawater drain into marine site, when needs to draining do further comprehensive utilization such as extract sodium chloride, magnesium, also the seawater after can making blending, Air Exposure drains into rear operation, and this is also a kind of technical scheme; The seawater alkali number value of described washing flue gas is adjusted by changing the seawater flow washing flue gas with by the ratio washing the sour value of flue gas.
Be below the present embodiment major parameter:
Exhaust gas volumn 3,100,000Nm
3/ h (suitable 1000MW scale thermal power unit boiler exhaust gas volumn)
Former flue gas SO
21600mg/Nm
3, NOx 610mg/Nm
3
The acid of washing sea water flue gas alkali is than 6.5
Washing seawater iron concentration 32 μ g/kg
Purifying smoke SO
216mg/Nm
3, NOx 320mg/Nm
3
Seawater quality recovery device draining pH >6.8
Draining COD increment <1.5mg/l
Embodiment 2:
Be in the suds to add iron ion by a kind of device that can add iron-containing liquor with above-described embodiment 1 unlike: the iron catalytic laundry carried out with seawater; The present embodiment major parameter is:
Exhaust gas volumn 1,100,000Nm
3/ h
Former flue gas SO
2concentration 1900mg/Nm
3, NOx concentration 650mg/Nm
3
The acid of washing sea water flue gas alkali is than 1
Iron concentration 106 μ g/kg after washing seawater adds
Purifying smoke SO
276mg/Nm
3, NOx 380mg/Nm
3
Seawater quality recovery device draining pH >6.8
Draining COD increment <0.5mg/l
Embodiment 3:
With above-described embodiment unlike described iron catalytic laundry, be adopt the metal lower than the electro-chemical activity of iron make the part ferrous material in wash environment become sacrificial anode as negative electrode and disengage the method for iron ion; The present embodiment major parameter is: exhaust gas volumn 2,100,000Nm
3/ h
Former flue gas SO
21680mg/Nm
3, NOx 580mg/Nm
3
The acid of washing sea water flue gas alkali is than 200
Washing seawater iron concentration 300 μ g/kg
Purifying smoke SO
280mg/Nm
3, NOx 180mg/Nm
3
Seawater quality recovery device draining pH >6.8
Draining COD increment <4.3mg/l
Embodiment 4:
With above-described embodiment 1 unlike iron catalytic laundry that the seawater being added with a certain amount of iron ion carries out, adopt the method for placing ferrite members in washing sour environment to adopt the metal lower than the electro-chemical activity of iron make the part ferrous material in wash environment become sacrificial anode as negative electrode and disengage the method for iron ion simultaneously, in this example, in its washing step of iron catalytic laundry carried out with seawater iron concentration selection range for per kilogram Iron In Seawater ion be that 10 micrograms are to 300 micrograms (10 ~ 300 μ g/kg); The parameter different from embodiment 1 is: wash the acid of sea water flue gas alkali than being 15, washs seawater iron concentration 10 μ g/kg.
Embodiment 5
With above-described embodiment unlike: the present embodiment is taked to make flue gas in the complementary field provided by magnetic material, carry out the method for catalytic laundry, make seawater or/and flue gas through magnetic flux density be 1 ~ 6000 gauss magnetic field; Major parameter:
Exhaust gas volumn 2,900,000Nm
3/ h
Former flue gas SO
22100mg/Nm
3, NOx 670mg/Nm
3
The acid of washing sea water flue gas alkali is than 7.1
Complementary field magnetic flux density 6000 gauss magnetic field;
Purifying smoke SO
285mg/Nm
3, NOx 303mg/Nm
3
Seawater quality recovery device draining pH >6.8
Draining COD increment <1.6mg/l
Embodiment 6:
With above-described embodiment 5 unlike: the present embodiment is the iron catalytic laundry that the seawater being added with a certain amount of iron ion carries out, and takes to make flue gas in the complementary field provided by magnetic material, carry out the method for catalytic laundry, major parameter simultaneously:
Exhaust gas volumn 1,900,000Nm
3/ h
Former flue gas SO
21800mg/Nm
3, NOx 720mg/Nm
3
The acid of washing sea water flue gas alkali is than 16
Washing seawater iron concentration 3 μ g/kg
Complementary field magnetic flux density 3000 Gauss;
Purifying smoke SO
285mg/Nm
3, NOx 203mg/Nm
3
Seawater quality recovery device draining pH >6.8
Draining COD increment <2.8mg/l
Embodiment 7:
With above-described embodiment 6 unlike the present embodiment
The acid of washing sea water flue gas alkali is than 86
Washing seawater iron concentration 210 μ g/kg
Complementary field magnetic flux density 1 gauss magnetic field;
B: be described further as follows to the special purpose device of flue gas-seawater method simultaneous SO_2 and NO removal method of the present invention and the technical scheme of equipment in conjunction with the accompanying drawings and embodiments:
Embodiment 8:
As shown in Fig. 2-5, be: it has seawater catalytic laundry system and acid seawater quality recovery system also have control system for realizing the technical scheme of the flue gas and desulfurizing and denitrifying device of the inventive method; Seawater catalytic laundry system has washer 1, washer smoke inlet 2, washer exhanst gas outlet 3, the seawater inlet 4 of washing flue gas, the acid seawater outlet 5 of washer; Seawater catalytic laundry system of the present invention is in addition for increasing ferrite members or the iron ion adding set of seawater iron ion content, or/and make the seawater of washing flue gas or/and flue gas is in the magnetic devices of complementary field, the present embodiment selects the ferrite members scheme increasing seawater iron ion content, described acid seawater quality recovery system has quality recovery device 6, what be connected with it has acid sea water passage 9, sea water passage 10, air blast 11, also has seawater outlet 14; Acid seawater inlet 7 is adjoining in quality recovery device 6 with seawater inlet 8; Air blast 11 is by blast channel 12 and aeration opening 13 UNICOM be located in quality recovery device 6;
Further illustrate as follows.
As shown in Figure 4, ferrite members described in the present embodiment is in washer 1, arrange the iron filler that directly can contact with acid seawater, also can be ferrous element that is fixing, that maybe can change, can also arrange iron filler and ferrous element simultaneously; Described seawater catalytic laundry system washer 1 can manufacture and design by Chemical Engineering Design handbook or select; The washing seawater flow adjuster 1.7 that washer 1 is provided with adjustable gate, governor impeller is formed; Be provided with iron filler, its irony layer directly contacts with acid seawater, to increase the iron concentration in acid seawater; Iron filler can be changed aperture of door 1.9 by ferrite members and change;
As shown in Figure 5, acid seawater quality recovery system has quality recovery device 6, can realize the aeration time pond body of 1 minute to 25 minutes by volume, and the standard cubic meter flow blasting air with can be realized the air blast of 0.2:1 ~ 10:1, air duct and aeration opening by the ratio blasting the seawater flow of air and form; Described quality recovery device 6 is made up of the pond body with mixed function and aeration performance, its mixed function part is carry out acid seawater and seawater blending or/and hold the pond body of the seawater of blending, its mixed function part connects with the closed conduit of the acid seawater of conveying, make acid seawater with the condition of atmospheric isolation under import the Mixed Zone of the seawater quality recovery device that alkaline seawater floods, mix rapidly with alkaline seawater wherein, and in mixed process, do not make acid seawater current surface; A part for its mixed function can also be made up of the pipeline beyond quality recovery device, transports to the mixed function district of seawater quality recovery device after acid seawater is mixed in the duct with alkaline seawater again.Its aeration performance part can be that energy consumption is lower, the Inka aeration pond that carbon removal efficiency is higher, can be also middle level, deep shaft aeration tank, and its aeration opening or title aeration head can manufacture and design by Chemical Engineering Design handbook or select.Seawater quality recovery device is arranged separately, its seawater inlet 8 is made up of two inlet 8-1 and 8-2, one of them inlet is first mix seawater inlet 8-1 and be positioned near acid seawater inlet 7, and another seawater inlet mixes seawater inlet 8-2 at aeration opening and seawater outlet 14 along between flow path after being.Aeration opening 13 is connected with air blast by air duct, and the aeration opening array 13x that aeration opening 13 is made up of multiple aeration opening is formed.
Embodiment 9:
With above-described embodiment 8 unlike: as Fig. 4, washer 1 is provided with iron ion generating unit, it is made up of the iron pipe of acid seawater in the seawater pond bottom washer 1 and the ferrite members 1.5 wherein immersed and the acid seawater of conveying, the ferrite members 1.5 immersed and iron pipe can be changed or add, and also have iron-containing liquor pump 1.8 and iron-containing liquor inlet 1.6.
Embodiment 10:
With above-described embodiment 8 unlike: as shown in Figure 4, the present embodiment, for arrange iron ion adding set on washer 1, namely arranges the injector be connected with iron-containing liquor inlet 1.6, or/and iron ion generating means on washer 1.
Embodiment 11:
With above-described embodiment 8 unlike: as shown in Figure 3, described seawater catalytic laundry system has one to make the seawater of washing flue gas or/and flue gas is in the magnetic devices of complementary field, described magnetic devices is the magnetic fillers as magnetic component 1.5 ' arranged in washer 1, the material of its magnetic component is the ferrite with permanent magnetic property, also can be the rare-earth magnets such as steel alloy, or Nd-Fe-B powder powder metallurgy material;
Embodiment 12:
Unlike: the present embodiment seawater catalytic laundry system, there is the ferrite members that increases seawater iron ion content with above-described embodiment 11 and make washing be in the magnetic component of complementary field; Scheme is that seawater catalytic laundry device 1 bottom has as shown in Figure 4 for increasing a ferrite members for seawater iron ion content, its top have as shown in Figure 3 make the seawater of washing flue gas or/and flue gas is in the magnetic component of complementary field; Another program is the irony magnetic component that top has as shown in Figure 3, and its material selection has the ferrous material of permanent magnetic and makes it contact acid seawater.
Unit member in described washer and quality recovery device, all according to relevant Chemical Engineering Design handbook design or can select.Patent right protection domain of the present invention is not limited to above-described embodiment.
Flue gas and desulfurizing and denitrifying method of the present invention and device, without the need to industrial chemicals, emission reduction efficiency and reliability high, floor space is little, build and operating cost low, be specially adapted to the simultaneous SO_2 and NO removal of the boiler smokes such as large and medium-sized thermal power plant.
Claims (6)
1. a flue gas-seawater method simultaneous SO_2 and NO removal method, is characterized in that, it comprises the steps:
A), seawater catalytic laundry flue gas: with seawater to containing SO
2and the flue gas of NOx carries out catalytic laundry, to remove the SO in flue gas
2and NOx, then discharge the purifying smoke through desulphurization denitration and the acid seawater of discharging washing process formation; Described catalytic laundry, it is the iron catalytic laundry that the seawater that is added with a certain amount of iron ion carries out, adding method in acid seawater, arranges ferrite members or/and make the ferrous material of contact seawater become sacrificial anode to add iron ion, or/and make seawater or/and flue gas through magnetic flux density be the magnetic catalytic laundry of 1 ~ 6000 Gauss's complementary field;
B), acid seawater quality recovers: mix seawater to the acid seawater of discharging in described step A and carry out acid-base neutralization and blast air, the quality recovery of acid seawater is discharged after meeting environmental requirement.
2. simultaneous SO_2 and NO removal method according to claim 1, it is characterized in that, the described iron catalytic laundry having the seawater of a certain amount of iron ion to carry out is the iron catalytic laundry that in washing step, iron concentration to be per kilogram Iron In Seawater ion be 3 micrograms are carried out to the seawater of 300 micrograms (3 ~ 300 μ g/kg).
3. simultaneous SO_2 and NO removal method according to claim 1, it is characterized in that, the iron catalytic laundry that the seawater of described a certain amount of iron ion carries out is the iron catalytic laundry that in washing step, iron concentration to be per kilogram Iron In Seawater ion be 10 micrograms are carried out to the seawater of 300 micrograms (10 ~ 300 μ g/kg).
4. simultaneous SO_2 and NO removal method according to claim 1, is characterized in that, the seawater of described washing flue gas, and its flow is sour than choosing according to washing seawater, flue gas alkali: the seawater alkali number value of washing flue gas
/by sour value=1 ~ 200 of washing flue gas; Wherein: the seawater alkali number value of washing flue gas is the product value of alkalinity of seawater value and seawater flow value, this alkalinity of seawater value equals value during total alkalinity (ALK) measuring this seawater with often liter mole (mol/l), and seawater flow value equals the value that this seawater measures with liter per hour (l/h); The described sour value by washing flue gas is that flue gas contains SO
2the product value of concentration value and flue gas flow value, this SO
2concentration value equals this flue gas with every standard cubic meter milligram (mg/Nm
3) measure its SO
2value during concentration, flue gas flow value equals flue gas standard cubic meter (Nm per hour
3/ h) value of measuring.
5. for a simultaneous SO_2 and NO removal device for flue gas-seawater method simultaneous SO_2 and NO removal method, it is characterized in that, it comprises seawater catalytic laundry system and acid seawater quality recovery system; Described seawater catalytic laundry system comprises washer (1), washer smoke inlet (2), washer exhanst gas outlet (3), the seawater inlet (4) of washing flue gas, acid seawater outlet (5) of washer, for increasing the ferrite members of seawater iron ion content, or/and make the seawater of washing flue gas or/and flue gas is in the magnetic devices of complementary field; Described acid seawater quality recovery system comprises quality recovery device (6), and what be connected with it has acid sea water passage (9), sea water passage (10), air blast (11), also has seawater outlet (14); Acid seawater inlet (7) is adjoining in quality recovery device (6) with seawater inlet (8); Air blast (11) is by blast channel (12) and aeration opening (13) UNICOM be located in quality recovery device (6); Described seawater catalytic laundry Operation system setting has the seawater flow adjuster of washing flue gas; Described ferrite members in washer (1), arranges the iron filler that directly can contact with acid seawater or/and ferrous element that is fixing, that maybe can change.
6. simultaneous SO_2 and NO removal device according to claim 5, is characterized in that, described magnetic devices be the magnetic fillers that arranges in washer (1) or/and magnetic component, or/and washing seawater is or/and the magnetic component that arranges of exhaust gases passes.
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| CN103951025B (en) * | 2014-03-27 | 2015-10-14 | 北京龙源环保工程有限公司 | For the electrochemistry-chemically composited oxidation treatment method of sea water desulfuration recovery system |
| CN112237069A (en) * | 2020-10-26 | 2021-01-19 | 中国科学院东北地理与农业生态研究所 | Method for transforming soda saline-alkali land waste fishpond into cattail wetland |
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| CN1134852A (en) * | 1995-12-22 | 1996-11-06 | 彭斯干 | Aeration sea water type technology for removing sulphur from smoke and aeration device |
| CN1147415A (en) * | 1995-10-11 | 1997-04-16 | 彭斯干 | Seawater elution process and equipment for industrial fume |
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| CN1147415A (en) * | 1995-10-11 | 1997-04-16 | 彭斯干 | Seawater elution process and equipment for industrial fume |
| CN1134852A (en) * | 1995-12-22 | 1996-11-06 | 彭斯干 | Aeration sea water type technology for removing sulphur from smoke and aeration device |
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