CN109012085A - Method and device that is a kind of while removing sulfur dioxide in flue gas and nitrogen oxides - Google Patents
Method and device that is a kind of while removing sulfur dioxide in flue gas and nitrogen oxides Download PDFInfo
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- CN109012085A CN109012085A CN201810702959.8A CN201810702959A CN109012085A CN 109012085 A CN109012085 A CN 109012085A CN 201810702959 A CN201810702959 A CN 201810702959A CN 109012085 A CN109012085 A CN 109012085A
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- flue gas
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 107
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003546 flue gas Substances 0.000 title claims abstract description 74
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 90
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 42
- -1 persulfuric acid salt Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 19
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 52
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 16
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 239000007792 gaseous phase Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 235000019504 cigarettes Nutrition 0.000 claims 2
- 238000000746 purification Methods 0.000 abstract description 14
- 239000002918 waste heat Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010014561 Emphysema Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention discloses method and device that is a kind of while removing sulfur dioxide in flue gas and nitrogen oxides, the permonosulphuric acid saline solution of pH2~4 is added in persulfuric acid salt cellar, reaction generates persulfate gas under the conditions of air capacity 1-10mL/min, 90-100 DEG C of temperature, enter oxidation reaction tank by pipeline, while by the 100-250 DEG C of (SO containing sulfur dioxide2) and nitrogen oxides (NOx) flue gas be passed through oxidation reaction tank, react 10-60s, realize the removal of sulfur dioxide in flue gas and nitrogen oxides.The method of the present invention can remove the SO in flue gas simultaneously2And NOx, the reaction time is short, good purification, and the waste heat for flue gas being utilized itself and having, and does not need heat needed for being additionally provided reaction, is the flue gases purification of a low-consumption high-efficiency.For the SO of concentration 50-500ppm2And 100-1000ppmNOxExhaust gas, as residence time 10-60s, the removal efficiency of the two can respectively reach 90% and 80% or more.
Description
Technical field
It is the present invention relates to the purification of industrial smoke, in particular to a kind of using in hot activation gas phase persulfate removal flue gas
It is living to generate a large amount of strong oxidizing properties by the activated at persulfate that flue gas itself has for the method for nitrogen oxides, dioxide
Property particle participate in the oxidation reaction of nitrogen oxides, sulfur dioxide, to obtain preferably removal effect.
Background technique
Nitrogen oxides (NOx) and sulfur dioxide (SO in flue gas2) it is the gaseous state for polluting atmospheric environment, being detrimental to health
Pollutant is the predecessor to form the pollutions such as acid rain, photochemical fog, depletion of the ozone layer, gray haze.NOx and SO2It is discharged into big
After gas, under the action of oxidant and catalyst, complicated chemical reaction can be participated in, generates the substances such as ozone, nitric acid or sulfuric acid,
Cause acid rain, photochemical fog etc..On the other hand these pollutants also have a great impact to human body, plant, animal health, right
The irritating effect of respiratory apparatus may cause the diseases such as bronchitis, asthma and pulmonary emphysema under long-term exposure.Therefore, NOx
And SO2Contamination control become research hotspot.
Currently, for NOx in flue gas and SO2Contamination control be broadly divided into burning before (in) control and burning after control two
Major class.The former includes fuels cleaning, selection clean fuel, optimization combustion process etc., and the latter then includes absorption process, catalysis reduction
Method, absorption method, microbial degradation method etc..In these burning post-control technologies, all there are respective advantage and disadvantage in every kind of technology, especially
It is absorption process and absorption method, its essence is the covert transfer of pollutant, NOx and SO2It is not removed, the absorbing liquid of generation
Secondary treatment is also needed with adsorbent, investment and processing cost are higher.Although microbial degradation method can thoroughly purify these dirts
Object is contaminated, but for high-temperature flue gas, before carrying out biological cleaning, it is necessary to cooling system be set, temperature is reduced to suitable micro-organisms
The condition of growth, and the loss of this partial heat is extremely uneconomic.Therefore, the new skill of research and development energy simultaneous SO_2 and NO removal
Art becomes research hotspot.
Advanced oxidation is a kind of pollutant control technology risen recently, has that reaction rate is fast, reaction condition is mild, net
Change the features such as high-efficient, is concerned.High-level oxidation technology passes through the input such as some luminous energy, electric energy, chemical energy, and empty gas and water
Equal media react, and generate some substances with strong oxidizing property, improve the oxidation effectiveness to pollutant.
It is used as with the persulfate that peroxy-monosulfate (peroxymonosulfate, PMS) is representative a kind of novel oxidized
Agent is received and is widely paid close attention in drinking water advanced treatment and organic wastewater with difficult degradation thereby process field, studies and application is very living
Jump.Peroxy-monosulfate can be by many kinds of substance or energy activated (such as ultraviolet, hot, metal oxide oxidation catalyst in normal temperature and pressure system
Agent etc.), OH can not only be generated, moreover it is possible to generate the higher SO of oxidation-reduction potential4(3.1ev), the oxidability having are past
Toward higher than ozone, hydrogen peroxide system.
For peroxy-monosulfate as a kind of new oxidants, the research and application in smoke gas treatment are relatively fewer.It is existing
Report is to absorb the solution of flue gas peroxy-monosulfate, then ultraviolet irradiation or metal oxide is recycled to be activated
Some strong oxidizing property active particles are generated, to aoxidize absorbed NOx and SO2。
Compared with liquid phase oxidation reaction, gas phase oxidation is fast with reaction speed, reaction is not influenced by solvent molecule
Feature.Further, since the hot properties that flue gas itself has, can use the mistake one in the energy hot activation gas phase that high temperature has
This portion of energy, while NOx and SO is not only utilized in sulfate2Liquid phase scrubbing is needed not move through by direct oxidation, gas is not present
Influence of the phase pollutant solubility to oxidation effectiveness, therefore the efficiency that pollutant is removed will greatly promote.
Based on this, sulfur dioxide in flue gas is removed using hot activation gas phase peroxy-monosulfate the invention proposes a kind of
(SO2) and nitrogen oxides (NOx) method, it includes gas phase persulfate generating unit and oxidation reaction unit, utilizes flue gas
Itself have the characteristics that temperature is higher, activates the peroxy-monosulfate in gas phase to generate the active group of strong oxidizing property, aoxidize SO2、
NOx is SO3、NO2, then recycle water absorption that mixed acid is made, not only thoroughly purified gaseous pollutant, also achieved SO2、
The recycling of NOx.
The patent No. 201510140971.0 disclose it is a kind of using persulfate production waste water to flue gas carry out denitration process
Method, its essence is utilize the NO in liquid phase scrubbing flue gasxAfter carry out liquid phase oxidation reaction, realize NO in flue gasxRemoval.
After liquid phase scrubbing, the temperature of flue gas reduces the hot activation degree that much will affect persulfate in liquid phase, and then can shadow
Ring NOxDegree of oxidation.The patent also discloses the removal efficiency 87.4% of NOx simultaneously, but NOx is gone due to absorbing actually
That removes is still oxidized and removes, unknown.The technical characterstic of published method of the present invention is obviously different from above-mentioned patent, directly
It connects the characteristic using gas phase reaction and fume high-temperature while realizing SO2、NOxWhile remove, and those skilled in the art without
Method associates technology disclosed by the invention by above-mentioned patent, if studying without gas phase, does not grasp gas phase persulfuric acid
The generation rule of salinity, is that can not associate technology disclosed by the invention；Meanwhile whether this method is to SO2Also removal imitates
Fruit, and whether reaction condition is similar to NOx, if without research, those skilled in the art can not be joined by above-mentioned patent
Expect technology disclosed by the invention.Therefore, technology disclosed by the invention has novelty.
Summary of the invention
The present invention provides method that is a kind of while removing sulfur dioxide in flue gas and nitrogen oxides, directly utilizes gas phase reaction
SO is realized simultaneously with the characteristic of fume high-temperature2、NOxWhile remove.
The technical solution adopted by the present invention:
The present invention provides a kind of while removing sulfur dioxide in flue gas (SO2) and nitrogen oxides (NOx) method, the side
Method is carried out using hot activation permonosulphuric acid salt treatment flue gas device, and the hot activation permonosulphuric acid salt treatment flue gas device included
Sulfate generating unit and oxidation reaction unit, the persulfate generating unit is by persulfuric acid salt cellar, water-bath tank, air tank group
At the oxidation reaction unit is made of oxidation reaction tank, flue gas tank and tail gas absorption tank, and the oxidation reaction tank is equipped with flue gas
Air inlet, gas phase air inlet and exhaust outlet；The persulfuric acid salt cellar is placed in the water-bath tank equipped with temperature control device；The persulfuric acid
Salt cellar is equipped with thermometer, air intlet and gaseous phase outlet, and the air intlet is connected by the pipeline and air tank for being equipped with flowmeter
It is logical, it is used for the air-blowing into persulfuric acid salt cellar, the gaseous phase outlet to be connected by the gas phase air inlet of pipeline and oxidation reaction tank；Institute
It states oxidation reaction tank gas inlet to connect by the pipeline and flue gas tank for being equipped with flowmeter and hygrometer, the oxidation reaction tank row
Port is connected to by pipeline with exhaust collection tank；
The permonosulphuric acid saline solution of pH2~4 is added in persulfuric acid salt cellar, in air capacity 1-10mL/min, temperature 90-
Reaction generates persulfate gas under the conditions of 100 DEG C, enters oxidation reaction tank by pipeline, while containing dioxy for 100-250 DEG C
Change sulphur (SO2) and nitrogen oxides (NOx) flue gas be passed through oxidation reaction tank, react 10-60s, realize sulfur dioxide in flue gas and nitrogen
The removal of oxide.
Further, the peroxy-monosulfate is permonosulphuric acid sylvite or permonosulphuric acid sodium salt.
Further, the peroxy-monosulfate concentration of aqueous solution is 0.5-10g/L, pH 2-4, more preferable permonosulphuric acid salt water
Solution concentration is 1g/L, pH 3.0.
Further, the air capacity is preferably 10mL/min, and bath temperature is preferably 90 DEG C.
Further, SO in the flue gas2Concentration 50-500ppm, NOxConcentration 100-1000ppm, the NOxFor NO2And NO
Mixture, content are respectively 5% and 95%.
Further, reaction time 60s in oxidation reaction tank.
The present invention removes sulfur dioxide in flue gas (SO using hot activation gas phase peroxy-monosulfate2) and nitrogen oxides (NOx),
Including gas phase persulfate generating unit and oxidation reaction unit, there is temperature higher (100-250 DEG C) using flue gas itself
Feature activates the persulfate in gas phase to generate the active group (SO of strong oxidizing property4, OH isoreactivity particle), oxidation
SO2、NOxFor SO3、NO2, then recycle water absorption that mixed acid is made, thoroughly purify gaseous pollutant.It is simultaneously maintenance oxidation
The high efficiency of reaction, gas phase peroxy-monosulfate generating unit must be placed in high temperature bath device.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: what the present invention had using high-temperature flue gas itself
Heat activates the peroxy-monosulfate in gas phase, generates the active particle with Strong oxdiative, aoxidizes the SO in flue gas2And NOxFor
SO3、NO2, and using the gas after water absorbing reaction, mixed acid is made, realizes the purification and recycling of exhaust gas.The method of the present invention
The SO in flue gas can be removed simultaneously2And NOx, the reaction time is short, good purification, and the waste heat for flue gas being utilized itself and having, no
Heat needed for needing to be additionally provided reaction, is the flue gases purification of a low-consumption high-efficiency.For concentration 50-500ppm's
SO2And 100-1000ppmNOxExhaust gas, as residence time 10-60s, the removal efficiency of the two can respectively reach 90% and 80%
More than.
Detailed description of the invention
Peroxy-monosulfate concentration measurement apparatus schematic diagram in Fig. 1 gas phase, 1- persulfuric acid salt cellar, 2- water-bath tank, 3- water absorb
Tank, 4- temperature control.
Fig. 2 hot activation permonosulphuric acid salt treatment flue gas device schematic diagram, 1- persulfuric acid salt cellar, 2- water-bath tank, 3- temperature control dress
It sets, 4- air tank, 5- flowmeter, 6- flue gas tank, 7- oxidation reaction tank, 8- thermometer, 9- hygrometer, 10- exhaust collection tank.
Permonosulphuric acid potassium content figure in gas phase under Fig. 3 difference permonosulphuric acid concentration of salt solution and pH.
Permonosulphuric acid sodium content figure in gas phase under Fig. 4 difference bath temperature.
The NO of Fig. 5 permonosulphuric acid potassium purification different temperaturesxExhaust gas effect picture.
The NO of Fig. 6 permonosulphuric acid potassium purification various inlet concentrationxExhaust gas effect picture.
The SO of Fig. 7 permonosulphuric acid sodium purification various inlet concentration2Exhaust gas effect picture.
The purification of Fig. 8 permonosulphuric acid potassium contains NOxAnd SO2Mixed flue gas effect picture.
Specific embodiment
It elaborates with reference to the accompanying drawings and examples to the present invention, but the contents of the present invention are not limited only to this.
Embodiment 1: permonosulphuric acid potassium content variation in gas phase under various concentration solution and pH
Referring to Fig. 1, the device for measuring gas phase permonosulphuric acid salinity includes persulfuric acid salt cellar 1, water-bath tank 2 and water tourie
3；Air is passed through sulfuric acid salt cellar by being equipped with the pipeline of flowmeter, and the sulfuric acid salt cellar is placed in the water-bath tank equipped with temperature control device
Interior, the sulfuric acid salt cellar is connected to by pipeline with water tourie.
Selection permonosulphuric acid potassium (potassium peroxymonosulfate, hereinafter referred to as KPMS) was used as a sulphur
Hydrochlorate represents, and studies its gas phase occurrence characteristic.The KPMS aqueous solution of 0.5,1,2.5,5 and 10g/L of concentration is respectively configured, pH is all provided with
3 are set to, is placed in gas phase generating bottle, setting air capacity is 5mL/min, and bath temperature setting is at 90 DEG C, outlet deionized water
It is absorbed, soak time is set as 1h.
The KPMS aqueous solution of configuration concentration 1g/L, pH are respectively set to 2,3 and 4, are placed in gas phase generating bottle, and air is arranged
Amount is 10mL/min, and bath temperature is arranged at 90 DEG C, and outlet is absorbed with deionized water, and soak time is set as 0.5h.
After absorption, KPMS concentration is measured with KI+ spectrophotometry in absorbing liquid, according to KPMS standard curve, is obtained
KPMS liquid concentration converts its gas phase concentration for liquid concentration according to formula (1).
KPMS standard curve: NaHCO3(about 0.2g) and 4g KI are added in 40mL distilled water, and manual agitation of solutions 15 is divided
Clock is uniformly mixed it.Configuration KPMS concentration is respectively the aqueous solution of 2,4,8,16,32mg/L, and 100 μ L of taking-up, which are added to, have been mixed
It closes in uniform above-mentioned solution, absorbance value is measured in wavelength 464nm after shaking up, using KPMS concentration as abscissa, with light absorption value
KPMS standard curve is made for ordinate, curvilinear equation y=0.008x+0.021 obtains the same terms according to standard curve and inhales
KPMS concentration in liquid is received, obtains corresponding gas phase concentration further according to formula 1.
Gas phase concentration=KPMS liquid concentration (mg/L) * absorbs aqueous solution volume (L)/[meter readings (mL/min) * suction
(min)/1000 (mL/L) between time receiving] formula (1)
The concentration that Fig. 3 is KPMS in outlet after converting.As can be seen that increasing of the KPMS gas phase concentration with initial concentration solution
Add and increase, but increased amplitude gradually becomes smaller；It is reduced with the raising of pH.By comparing under different initial concentrations and different pH
The gas phase content that lower per unit concentration generates, the preferably initial concentration of KPMS aqueous solution are 1g/L, pH value of solution 3.0.
Embodiment 2: permonosulphuric acid sodium content changes in gas phase under different bath temperatures
The device of gas phase permonosulphuric acid salinity is measured with embodiment 1.Select permonosulphuric acid sodium
(sodiumperoxymonosulfate, hereinafter referred to as NaPMS) is represented as peroxy-monosulfate, studies bath temperature to it
The influence of gas phase occurrence characteristic.The NaPMS aqueous solution that initial concentration is 1g/L is configured, pH is set as 3, is placed in persulfuric acid salt cellar
In, setting air capacity is 5mL/min, and bath temperature is separately positioned on 80,90 and 100 DEG C, and outlet is absorbed with deionized water,
Soak time is set as 1h.After absorption, NaPMS concentration is measured with KI+ spectrophotometry in absorbing liquid.Thus it measures
NaPMS liquid concentration can be converted into its gas phase concentration, and the production of NaPMS standard curve is the same as KPMS in embodiment 1, curvilinear equation
For y=0.0048x+0.056, as a result as shown in Figure 4.
Fig. 4 is the NaPMS concentration that gas phase occurs under different bath temperatures.As can be seen that temperature is higher, NaPMS in outlet
Concentration is higher.Preferably, bath temperature is arranged at 90 DEG C.
Embodiment 3: the NO of permonosulphuric acid potassium purification different temperaturesxExhaust gas
Referring to Fig. 2, the hot activation permonosulphuric acid salt treatment flue gas device is as shown in Fig. 2, include that list occurs for persulfate
Member and oxidation reaction unit, the persulfate generating unit are made of persulfuric acid salt cellar 1, water-bath tank 2, air tank 4, the oxygen
Change reaction member to be made of oxidation reaction tank 7, flue gas tank 6 and tail gas absorption tank 10, the oxidation reaction tank is equipped with flue gas air inlet
Mouth, gas phase air inlet, exhaust outlet and thermometer 8；The persulfuric acid salt cellar 1 is placed in water-bath tank 2, and the water-bath tank 2 is equipped with temperature
Control device 3；The persulfuric acid salt cellar 1 is equipped with air intlet and gaseous phase outlet, and the air intlet passes through the pipe equipped with flowmeter 5
Road is connected to air tank 4, is used for the air-blowing into persulfuric acid salt cellar, and the gaseous phase outlet passes through pipeline and 7 gas phase of oxidation reaction tank
Import is connected；The oxidation reaction tank gas inlet is connected by the pipeline and flue gas tank 6 for being equipped with flowmeter 5 and hygrometer 9, institute
Oxidation reaction tank exhaust outlet is stated to be connected to by pipeline with exhaust collection tank 10.
Select permonosulphuric acid potassium (KPMS) as gas phase persulfate occurring source, configuring pH3.0 initial concentration is 1g/L's
KPMS aqueous solution is added in persulfuric acid salt cellar, and air capacity 5mL/min, bath temperature maintains 90 DEG C, in persulfuric acid salt cellar
Reaction generates gas phase KPMS.By the NO of different temperatures (150,175,200,225 and 250 DEG C)xExhaust gas (contains NO and NO2, unified to roll over
Calculate is NO, initial concentration 150ppm) it is passed through in oxidation reaction tank, while the air-flow with the gas phase KPMS of persulfuric acid salt cellar generation
The residence time is 10,15,20,25,30s in oxidation reaction tank after mixing, using in flue gas analyzer detection tail gas absorption tank
NO concentration, as a result as shown in Figure 5.
Fig. 5 is NO concentration in tail gas absorption tank with reaction time change curve.It can be seen from the figure that reaction temperature is to going
Except rate has a certain impact, and with the raising of reaction temperature, removal effect also has to be promoted to a certain extent.It is between when reacted
When 30s, under tested reaction temperature, the removal rate of NO has all reached 85% or more.It determines simultaneously in no gas phase
The removal effect of NO under the reaction condition of KPMS participation (replacing KPMS aqueous solution to be placed in gas phase generating bottle with distilled water).Knot
Fruit discovery, no matter how high flue-gas temperature is, and it is almost the same that NO imports and exports concentration, if illustrating, there is no KPMS in gas phase, and NO is almost
It cannot be removed.
Embodiment 4: the NO of permonosulphuric acid potassium purification various inlet concentrationxExhaust gas
With 3 hot activation permonosulphuric acid salt treatment flue gas device of embodiment.Select permonosulphuric acid potassium (KPMS) as gas phase mistake
Persulfuric acid salt cellar is added in sulfate occurring source, the KPMS aqueous solution that configuration pH2.0 initial concentration is 5g/L, and air capacity is set as
10mL/min, bath temperature maintain 80 DEG C.The various concentration NO for being 200 DEG C by temperaturexExhaust gas (contains NO and NO2, unified to convert
For NO, initial concentration is separately positioned on 100,250,500,800 and 1000ppm) it is passed through in oxidation reaction tank, while and persulfuric acid
The residence time is 10,20,30,60s in oxidation reactor after the gas phase KPMS air-flow mixing generated in salt cellar, using flue gas point
Analyzer detects NO concentration in tail gas absorption tank, as a result as shown in Figure 6.
Fig. 6 is NO in outlet under various inlet concentration with reaction time change curve.It can be seen from the figure that inlet gas concentration
Lower, it is shorter to completely remove the required time, and such as NO inlet gas concentration 100ppm, removal rate just reaches when reaction time 30s
100%.Between when reacted when 60s, the removal rate of 500,800 and 1000ppm has reached 80% or more.
Embodiment 5: the SO of permonosulphuric acid sodium purification various inlet concentration2Exhaust gas
With 3 hot activation permonosulphuric acid salt treatment flue gas device of embodiment.Select permonosulphuric acid sodium (NaPMS) as gas phase mistake
Sulfate occurring source, the NaPMS aqueous solution that configuration pH4.0 initial concentration is 5g/L are added in persulfuric acid salt cellar, air capacity setting
For 8mL/min, bath temperature maintains 100 DEG C.(the SO containing various concentration for being 150 DEG C by temperature2Exhaust gas initial concentration is set respectively
Set in 50,100,150,250 and 500ppm) SO2Exhaust gas is passed through in oxidation reaction tank, at the same with the gas that is generated in persulfuric acid salt cellar
The residence time is 10,20,30,45,60s in oxidation reaction tank after the mixing of phase NaPMS air-flow, measures tail using flue gas analyzer
SO in aspiration closed cans2Concentration, as a result as shown in Figure 7.
Fig. 7 is SO in outlet under various inlet concentration2With reaction time change curve.It can be seen from the figure that working as SO2Into
When gas concentration is lower (< 150ppm), removal rate reaches 100% in 60s；Work as SO2(250 Hes when inlet gas concentration is higher
1000ppm), in 60s removal rate also 90% or more.
Embodiment 6: the purification of permonosulphuric acid potassium contains NOxAnd SO2Mixed flue gas effect
With 3 hot activation permonosulphuric acid salt treatment flue gas device of embodiment.Select permonosulphuric acid potassium (KPMS) as gas phase mistake
Sulfate occurring source, the KPMS aqueous solution that configuration pH3.0 initial concentration is 1g/L are added in persulfuric acid salt cellar, and air capacity is set as
10mL/min, bath temperature maintain 90 DEG C.The flue gas of different temperatures (100,150,200 and 250 DEG C) (is mainly contained into NOxWith
SO2, NOxUnified conversion is NO, and NO initial concentration is 250ppm, SO2Initial concentration is 150ppm) exhaust gas is passed through oxidation reaction tank
In, while the residence time is 60s in oxidation reaction tank after mixing with the gas phase KPMS air-flow generated in persulfuric acid salt cellar, is used
Flue gas analyzer measures SO in tail gas absorption tank2With NO concentration, Fig. 8 is as a result seen.
Fig. 8 is treatment effect figure under the experimental condition.It can be seen from the figure that when being 60s between when reacted, the technique pair
The SO contained in flue gas2And NOxThere is preferable treatment effect, removal rate respectively reaches 90% and 80% or more.
Claims (8)
1. a kind of method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously, it is characterised in that the method utilizes hot activation
Permonosulphuric acid salt treatment flue gas device carries out, and the hot activation permonosulphuric acid salt treatment flue gas device includes that list occurs for persulfate
Member and oxidation reaction unit, the persulfate generating unit are made of persulfuric acid salt cellar, water-bath tank, air tank, the oxidation
Reaction member is made of oxidation reaction tank, flue gas tank and tail gas absorption tank, and the oxidation reaction tank is equipped with smoke air inlet, gas phase
Air inlet and exhaust outlet；The persulfuric acid salt cellar is placed in the water-bath tank equipped with temperature control device；The persulfuric acid salt cellar is equipped with temperature
Degree meter, air intlet and gaseous phase outlet, the air intlet are connected to by being equipped with the pipeline of flowmeter with air tank, are used for mistake
Air-blowing in sulfuric acid salt cellar, the gaseous phase outlet are connected by the gas phase air inlet of pipeline and oxidation reaction tank；The oxidation reaction
Tank gas inlet is connected by the pipeline and flue gas tank for being equipped with flowmeter and hygrometer, and the oxidation reaction tank exhaust outlet passes through pipe
Road is connected to exhaust collection tank；
The permonosulphuric acid saline solution of pH2~4 is added in persulfuric acid salt cellar, in air capacity 1-10mL/min, temperature 90-100
Reaction generates persulfate gas under the conditions of DEG C, enters oxidation reaction tank by pipeline, while containing sulfur dioxide for 100-250 DEG C
It is passed through oxidation reaction tank with the flue gas of nitrogen oxides, reacts 10-60s, realizes the removal of sulfur dioxide in flue gas and nitrogen oxides.
2. the method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously as described in claim 1, it is characterised in that the mistake
One sulfate is permonosulphuric acid sylvite or permonosulphuric acid sodium salt.
3. the method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously as described in claim 1, it is characterised in that the mistake
One sulfate solution concentration is 0.5-10g/L.
4. the method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously as described in claim 1, it is characterised in that the mistake
One sulfate solution pH is 3.0.
5. the method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously as described in claim 1, it is characterised in that the sky
Tolerance is 10mL/min, and bath temperature is 90 DEG C.
6. the method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously as described in claim 1, it is characterised in that the cigarette
SO in gas2Concentration 50-500ppm, NOxConcentration 100-1000ppm, the NOxFor NO2With NO mixture, content is respectively 5% He
95%.
7. the method for removing sulfur dioxide in flue gas and nitrogen oxides simultaneously as described in claim 1, it is characterised in that oxidation is anti-
Answer reaction time 60s in tank.
8. a kind of for removing the hot activation peroxy-monosulfate of sulfur dioxide in flue gas and nitrogen oxides described in claim 1 simultaneously
Handle flue gas device, it is characterised in that the hot activation permonosulphuric acid salt treatment flue gas device include persulfate generating unit and
Oxidation reaction unit, the persulfate generating unit are made of persulfuric acid salt cellar, water-bath tank, air tank, the oxidation reaction
Unit is made of oxidation reaction tank, flue gas tank and tail gas absorption tank, and the oxidation reaction tank is equipped with smoke air inlet, gas phase air inlet
Mouth and exhaust outlet；The persulfuric acid salt cellar is placed in the water-bath tank equipped with temperature control device；The persulfuric acid salt cellar be equipped with thermometer,
Air intlet and gaseous phase outlet, the air intlet are connected to by being equipped with the pipeline of flowmeter with air tank, are used for persulfuric acid
Air-blowing in salt cellar, the gaseous phase outlet are connected by the gas phase air inlet of pipeline and oxidation reaction tank；The oxidation reaction tank cigarette
Gas import is connected by the pipeline and flue gas tank for being equipped with flowmeter and hygrometer, the oxidation reaction tank exhaust outlet by pipeline with
The connection of exhaust collection tank.
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| CN201810702959.8A CN109012085A (en) | 2018-06-30 | 2018-06-30 | Method and device that is a kind of while removing sulfur dioxide in flue gas and nitrogen oxides |
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| US20140050643A1 (en) * | 2010-06-23 | 2014-02-20 | Baoquan Zhang | Flur-Gas purification and reclamation system and method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140050643A1 (en) * | 2010-06-23 | 2014-02-20 | Baoquan Zhang | Flur-Gas purification and reclamation system and method thereof |
| CN103691279A (en) * | 2013-12-13 | 2014-04-02 | 江苏大学 | System and method for desulfurization and denitrification by high temperature activating of sodium persulfate through flue gas afterheat |
| CN203899431U (en) * | 2013-12-13 | 2014-10-29 | 江苏大学 | Desulfurization, denitrification and demercuration system based on photoactivated ammonium persulfate |
| CN205886562U (en) * | 2016-07-28 | 2017-01-18 | 杭州中兵环保股份有限公司 | Jointly atomize waste gas pollution control and treatment device of oxidant of photodestruciton |
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Application publication date: 20181218 |