CN107174931A - A kind of high effective flue gas processing unit using solar energy as power - Google Patents
A kind of high effective flue gas processing unit using solar energy as power Download PDFInfo
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- CN107174931A CN107174931A CN201710538949.0A CN201710538949A CN107174931A CN 107174931 A CN107174931 A CN 107174931A CN 201710538949 A CN201710538949 A CN 201710538949A CN 107174931 A CN107174931 A CN 107174931A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
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Abstract
The present invention relates to a kind of high effective flue gas processing unit using solar energy as power, including treating column, slurry tank and solar power generation unit.Treating column is divided into for the first processing section for removing SO 2 in waste gas, the second processing section for nitric oxide gas in oxidation gaseous effluent and the 3rd processing section for removing nitrogen oxides of exhaust gas from the bottom to top, first processing section and second processing be intersegmental to be provided with the first liquid collecting and rises device of air, and second processing Duan Yu tri-, which is handled, intersegmental to be provided with the second liquid collecting and rise device of air.Second processing section is connected by second circulation pump with oxidant storage tank, and the oxidant storage tank forms a closed cycle with second processing section, and second processing section adds catalyst.Inventive desulfurization denitration efficiency is high, operating cost is low, and oxidant usage amount greatly reduces, overall desulfurization efficiency 99.6%, and denitration efficiency is up to 98.5%.
Description
Technical field
The present invention relates to fume treatment technical field, more particularly to a kind of high effective flue gas processing dress using solar energy as power
Put.
Background technology
The waste gas pair containing sulfur and nitrogen oxides produced in the burning of fossil fuel and some Chemical Manufactures
Atmospheric environment causes serious harm, the desulfurization technology generally used to air contaminant treatment at present and dry method, semidry method and wet
Several classes such as method, but these technologies seem helpless in terms of denitration.
Wet Flue Gas Desulfurization Technology is the desulfurization technology being most widely used on our times, and its desulfuration efficiency is high and wet
The good vapour-liquid mass of formula scrubbing tower is a potential advantage for the absorption of nitrogen oxides, therefore, develops wet flue gas
Desulfurization and denitrification integral process has good development prospect.
In terms of wet denitration, oxidative absorption method denitration technology overcomes some shortcomings of SCR techniques, as research and development
Focus.But also there is the defect that cost is high, efficiency is low in existing wet desulphurization denitration.
The content of the invention
For the above mentioned problem of prior art, it is an object of the present invention to provide a kind of denitrification efficiency is high, run into
This low high effective flue gas processing unit using solar energy as power.
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of high effective flue gas using solar energy as power
Processing unit, including treating column and slurry tank, the slurry tank are arranged on the processing tower bottom, and connect with the treating column
Logical, the treating column is divided into the first processing section, second processing section and the 3rd processing section, first processing section from the bottom to top
With second processing is intersegmental is provided with the first liquid collecting and rises device of air, the second processing Duan Yu tri-, which is handled, intersegmental is provided with the second liquid collecting liter
Device of air, first processing section is provided with waste gas inlet port, and first processing section is used to remove the sulfur dioxide gas in waste gas
Body, the nitric oxide gas that the second processing section is used in oxidation gaseous effluent converts it into nitrogen dioxide, the 3rd processing
Section is used to remove the nitrogen oxides in waste gas, and the gas after processing is discharged into the treating column,
First processing section and the 3rd processing section are connected by first circulation pump with the slurry tank, the second processing
Section is connected by second circulation pump with an oxidant storage tank, and the oxidant storage tank forms an enclosed with second processing section
Circulation, the second processing section adds catalyst,
3rd processing section is also connected by first circulation pipeline with a circulating tank, and the circulating tank is used to collect described
Absorbing liquid in 3rd processing section, the circulating tank is provided with chemicals dosing plant, and the circulating tank passes through second circulation pipeline and institute
Slurry tank connection is stated,
Described device also includes solar power generation unit, the solar power generation unit and the first circulation pump and second
Circulating pump is electrically connected.
Further, it is provided with first processing section in the first spray-absorption device, the second processing section provided with the
The 3rd spray-absorption device is provided with two spray-absorption devices, the 3rd processing section, the 3rd spray-absorption device includes
The microchannel absorption plant that second liquid collecting rises device of air top is arranged on, the microchannel absorption plant is provided with hollow
Shower plate, the shower plate is connected with the outlet of the first circulation pump by the first spray pipeline, and the first circulation pump leads to
Cross the first spray pipeline and the slurries in the slurry tank are pumped to the shower plate, slurries are ejected into described micro- logical through shower plate
In road absorption plant.
Further, the catalyst is solid-loaded ionic-liquid low-temperature denitration catalyst, includes the work of 1-60% parts by weight
Property component and 40%-99% parts by weight carrier, described active component is the polyethers ionic liquid comprising Mg or Al ions.
Further, first spray-absorption device includes the first shower and packing layer, and first shower is set
Put on described filler layer top, first shower is connected with the outlet of the first circulation pump by the second spray pipeline,
Slurries in the slurry tank are pumped to first shower, slurries warp by the first circulation pump by the second spray pipeline
In first spray pipe inspection to first processing section.
Further, the waste gas inlet port is set to horizontal direction in 10~30 ° of angles.
Further, the treating column is being provided with demister at outlet port, and the demister is including removing
Day with fog body and self-stripping system, the self-stripping system include being arranged on the spray of the demister body upper part and bottom
Shower pipe and the industrial water tank connected with the shower.
Further, the slurry tank is connected with the entrance of the first circulation pump by the first suction line, and described
Tie point is separated on one suction line, one end of the tie point connects first suction line, its other end and institute
State and the second branch road is separated in circulating tank connection, the tie point, second branch road is used to connect fresh desulfurization slurry preparation
Tank.
The second aspect of the present invention also provides a kind of multisection type waste gas processing method, and the waste gas processing method utilizes above-mentioned the
On the one hand multisection type emission-control equipment of any one provided by power of solar energy, this method specifically includes following step
Suddenly：
1) pending waste gas enters the first processing section, pending waste gas and desulfurization agent, desulfurization in the first processing section
Agent absorbs the part sulfur dioxide in pending waste gas, obtains desulfurization slurry；
2) waste gas after the processing of the first processing section, which enters, carries out liquid phase oxidation and partially absorbs in second processing section, make
Oxidation of nitric oxide in waste gas into nitrogen dioxide；
3) waste gas after second processing section processing enters the 3rd processing section, in the 3rd processing section by after peroxidating
Waste gas and step 1) in desulfurization slurry contact, the desulfurization slurry absorbs nitrogen dioxide and remaining titanium dioxide in waste gas
Sulphur.
Contain substantial amounts of sulfur dioxide and nitrogen oxides in flue gas from boiler flue, nitrogen oxides is mainly with an oxidation
Based on nitrogen, nitric oxide is not easy to be absorbed, and is easier to be inhaled when it is oxidized to the nitrogen oxides such as nitrogen dioxide of high-valence state
Receive, first order absorption is carried out to flue gas by desulfurizing agent first, most sulfur dioxide in flue gas is removed, while desulfurizing agent absorbs
The desulfurization slurry rich in inferior sulfate radical is obtained after sulfur dioxide in flue gas, efficient liquid phase oxidation then is carried out to flue gas again, will
Oxidation of nitric oxide in flue gas is into nitrogen dioxide, and part is oxidized agent and absorbs to form nitrate slurries, and the nitrate passes through rear
Byproduct such as fertilizer etc., so that chlorite makees oxidant as an example, the reactional equation of specific oxidation reaction are can obtain after continuous processing
Formula is as follows：
2NO+ClO2 -→2NO2+Cl
4NO2+ClO2 -+4OH-→4NO3-+Cl-+2H2O
NO+ClO2 -→NO2+ClO
NO+ClO-→NO2+Cl
2NO2+ClO2 -+2OH-→2NO3 -+ClO-+2H2O
Finally using the desulfurization slurry after first grade desulfurizing to flue gas carry out two grades absorption, remove flue gas in nitrogen dioxide and
Remaining sulfur dioxide, forms sulfate slurries, and the sulfate slurries obtain accessory substance such as gypsum, two grades after subsequent treatment
The reaction equation that nitrogen dioxide is absorbed during absorption is as follows：
4SO3 2-+2NO2+→N2+4SO4 2-
Desulfurizing agent of the present invention is ammoniacal liquor, seawater, magnesium hydroxide or lime stone slurry, the pH value and liquid gas of desulfurizing agent
Set than the content according to sulfur dioxide in flue gas and selected desulfurizing agent species, it is as a kind of perferred technical scheme, described
Desulfurizing adsorbent calcium hydroxide or lime stone slurry.Oxidant used in the oxidant storage tank is hydrogen peroxide, chlorite
With the aqueous solution of at least one of hypochlorite；Described chlorite can select sodium chlorite, hypochlorite optional time
At least one of sodium chlorate, calcium hypochlorite.
But often there is NO in actual exhaust gas processing procedure and aoxidize insufficient, the excessive defect of oxidizer, for
Drawbacks described above, the present invention further, NO oxidation catalysts is loaded with the second processing section of the emission-control equipment, described to urge
Agent is solid-loaded ionic-liquid low-temperature denitration catalyst, includes the active component and 40%-99% parts by weight of 1-60% parts by weight
Carrier, described active component is the polyethers ionic liquid comprising Mg or Al ions.
The carrier is selected from MFI, ERI and MOR the type molecular sieve for having stronger absorption affinity to NO, particularly preferably 13X
With H beta-molecular sieves.
The polyethers ionic liquid has following structural formula：
[R1(OCH2CH2)mCH2CH2NR2 3]+·X-
R in formula1For C1-6 alkyl, R2For C2-6 hydroxy alkyl, the R2Each other can with it is identical can not also
Together.
The preparation method of the NO oxidation catalysts is：Active metal and ionic liquid are scattered in solvent and form molten
Liquid, retells carrier and immerses in the solution, at room temperature after agitating solution 18-24 hours, filters out the solution of dipping, finally, will soak
To obtain solid-loaded ionic-liquid with solvent of going out within 8-12 hours low as being dried in vacuo at 100 DEG C in positive empty drying box for carrier after stain
Warm denitrating catalyst.
Catalyst activity component is the microenvironment of the polyethers ionic liquid formation of active metal Mg and Al formation, can be effective
Ground prevents that active component is not easily runed off in contact of the active component with moisture content, course of reaction, so as to improve the use of catalyst
Life-span；Ionic liquid has the features such as not volatile, heat endurance is high, by ionic liquid with having stronger adsorption capacity to NO
Molecular screen material combines, and not only maintains ionic liquid high catalytic activity and also causes active component high degree of dispersion, activearm
The reunion of active component can effectively be prevented by point being evenly distributed in carrier surface, and the ratio surface of catalyst is big, and catalytic activity is high, instead
Should be selectively good.
A kind of high effective flue gas processing unit and multisection type waste gas processing method using solar energy as power of the present invention, has
Following beneficial effect：
By desulphurization denitration, it is integrated in a treating column present invention so that desulfurization workshop section is separate with denitration workshop section
It is again interrelated, technological process is greatly simplified, the floor space of equipment is reduced, reduces investment cost.
Sulfur dioxide in removing waste gas first before denitration oxidation, is taken off again after removing most sulfur dioxide
Nitre is aoxidized, and can reduce the side reaction of oxidant and sulfur dioxide, so as to reduce the consumption of oxidant, saves operating cost.
The shower plate used cooperatively in the 3rd processing stage using microchannel absorption plant and with the device, so that significantly
The contact area of waste gas and absorbing liquid is added, the time of contact of waste gas and absorbing liquid is extended, is conducive to fully removing dioxy
Change nitrogen, improve denitration rate.
By installing the solid-carrying type ionic liquid denitrating catalyst with high catalytic activity additional in the second processing stage, in reduction
Also significantly high denitration rate while oxidant usage amount.
Brief description of the drawings
, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical scheme
The accompanying drawing used is briefly described.It should be evident that drawings in the following description are only some embodiments of the present invention, it is right
For those of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings
Its accompanying drawing.
Fig. 1 is the structural representation for the high effective flue gas processing unit using solar energy as power that one embodiment of the invention is provided
Figure；
In figure：1- treating columns, 2- slurry tanks, 3- first circulation pumps, 4- second circulation pumps, 5- oxidant tanks, 6- circulating tanks,
The fresh desulfurization slurry preparation tanks of 7-, 8- solar power generation units, 9- chemicals dosing plants, 10- waste gas inlet ports, the processing sections of 11- first,
12- second processings section, the processing sections of 13- the 3rd, the liquid collectings of 14- first rise device of air, and the liquid collectings of 15- second rise device of air, 16- foam removals dress
Put, 17- outlet ports, 61- first circulation pipelines, 62- second circulation pipelines, the showers of 111- first, 112- packing layers,
131- microchannels absorption plant, 132- shower plates, 161- demister bodies, 162- self-stripping systems, 162a- showers,
163- industrial water tanks.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained on the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
It should be noted that term " first " in description and claims of this specification and above-mentioned accompanying drawing, "
Two " etc. be for distinguishing similar object, without for describing specific order or precedence.It should be appreciated that so using
Data can exchange in the appropriate case, so as to embodiments of the invention described herein can with except illustrating herein or
Order beyond those of description is implemented.In addition, term " comprising " and " having " and their any deformation, it is intended that cover
Lid is non-exclusive to be included, for example, the process, method, device, product or the equipment that contain series of steps or unit are not necessarily limited to
Those steps or unit clearly listed, but may include not list clearly or for these processes, method, product
Or the intrinsic other steps of equipment or unit.
Embodiment 1
The present embodiment provides a kind of denitrification efficiency height, the low multisection type waste gas using solar energy as power of operating cost
Processing unit, specifically, referring to Fig. 1.
As shown in figure 1, the multisection type emission-control equipment includes treating column 1 and slurry tank 2, the slurry tank 2 is arranged on
The processing tower bottom 1, and connected with the treating column 1.
The treating column 1 is divided into the first processing section 11, second processing section 12 and the 3rd processing section 13, institute from the bottom to top
State and the first liquid collecting liter device of air 14 is provided between the first processing section 11 and second processing section 12, at the second processing section 12 and the 3rd
Between reason section 13 device of air 15 is risen provided with the second liquid collecting.
First processing section 11 is provided with waste gas inlet port 10, and first processing section 11 is used to remove the dioxy in waste gas
Change sulphur gas.In one embodiment, waste gas inlet port 10 is set to horizontal direction in 10~30 ° of angles, is arranged such that
Being uniformly distributed for waste gas can be ensured, it is also ensured that spray liquid occurs without backflow phenomenon so that the waste gas in treating column 1 can
There are enough residence times.
The nitric oxide gas that the second processing section 12 is used in oxidation gaseous effluent, converts it into nitrogen dioxide, described
3rd processing section 13 is used to remove the nitrogen oxides in waste gas, and the gas after processing is discharged into the treating column.
The processing section 13 of first processing section 11 and the 3rd is connected by first circulation pump 3 with the slurry tank 2, and described
Two processing sections 12 are connected by second circulation pump 4 with an oxidant storage tank 5, the oxidant storage tank 5 and second processing section
12 form a closed cycle, and add catalyst in second processing section.Oxidant can be lifted using closed cycle
Utilization rate, reduces cost.
3rd processing section 13 is also connected by first circulation pipeline 61 with a circulating tank 6, and the circulating tank 6 is used to receive
Collect the absorbing liquid in the 3rd processing section 13, the circulating tank 6 is provided with chemicals dosing plant 9, and the circulating tank 6 is followed by second
Endless tube road 62 is connected with the slurry tank 2.
Described device also includes solar power generation unit 8, the solar power generation unit 8 and the first circulation pump 3 and
Second circulation pump 4 is electrically connected, for providing power electric to first circulation pump 3 and second circulation pump 4.It will of course be understood that, should
Solar power generation unit 8 can also need the equipment for consuming power electric to provide power electric to other.
In one embodiment, the first spray-absorption device, the second processing are provided with first processing section 11
It is provided with section 12 in the second spray-absorption device, the 3rd processing section 13 and is provided with the 3rd spray-absorption device.Pass through above-mentioned phase
The absorbing liquid of liquid phase is atomized by the spray-absorption device answered, and increases absorption efficiency.
3rd spray-absorption device includes being arranged on the microchannel absorption that second liquid collecting rises the top of device of air 15
Device 131, the microchannel absorption plant 131 is provided with hollow shower plate 132, and the shower plate 132 is followed with described first
The outlet of ring pump 3 is connected by the first spray pipeline 31, and the first circulation pump 3 is by the first spray pipeline 31 by the slurries
Slurries in groove 2 are pumped to the shower plate 132, and slurries are ejected into the microchannel absorption plant 131 through shower plate 132.
Contact area and the time of contact of absorbing liquid and waste gas are considerably increased by the setting of microchannel absorption plant 131, so as to
Mass transfer is enough effectively promoted, is conducive to improving the efficiency of desulphurization denitration.
First spray-absorption device includes the first shower 111 and packing layer 112, and first shower 111 is set
Put on the top of described filler layer 112, the outlet of first shower 111 and the first circulation pump 3 passes through the second shower
Road 32 is connected, and the slurries in the slurry tank 2 are pumped to described first by the first circulation pump 3 by the second spray pipeline 32
Shower 111, slurries are sprayed to first processing section 11 through the first shower 11.
In one embodiment, the treating column 1 is being provided with demister, the demisting at outlet port 17
Device includes demister body 161 and self-stripping system, and the self-stripping system includes being arranged on the demister body
The shower 162a of 161 upper and lower parts and the industrial water tank 163 connected with the shower 162a.The setting of Despumation device
The normal operation for the treatment of column 1 is ensure that, and be ensure that in the case where being in an emergency there is process water can use.
In one embodiment, the slurry tank 2 and the entrance of the first circulation pump 3 pass through the first suction line 33
Tie point 34, one end connection first suction of the tie point 34 are separated on connection, first suction line 33
Pipeline 33, its other end is connected with the circulating tank 6, and the second branch road 35, second branch road are separated in the tie point 34
35 are used to connect fresh desulfurization slurry preparation tank 7.
By desulphurization denitration, it is integrated in a treating column the present embodiment so that desulfurization workshop section is mutually solely with denitration workshop section
It is vertical and interrelated, technological process is greatly simplified, the floor space of equipment is reduced, reduces investment cost.
The shower plate used cooperatively in the 3rd processing stage using microchannel absorption plant and with the device, so that significantly
The contact area of waste gas and absorbing liquid is added, the time of contact of waste gas and absorbing liquid is extended, is conducive to fully removing dioxy
Change nitrogen, improve denitration rate.
Embodiment 2
The present embodiment provides a kind of multisection type waste gas processing method, the specially processing method of flue gas, and this method is using in fact
Multisection type emission-control equipment of any one in example by power of solar energy is applied, specifically, this method comprises the following steps：
1) pending waste gas enters the first processing section, pending waste gas and desulfurization agent, desulfurization in the first processing section
Agent absorbs the part sulfur dioxide in pending waste gas, obtains desulfurization slurry；
2) waste gas after the processing of the first processing section, which enters, carries out liquid phase oxidation and partially absorbs in second processing section, make
Oxidation of nitric oxide in waste gas into nitrogen dioxide；
3) waste gas after second processing section processing enters the 3rd processing section, in the 3rd processing section by after peroxidating
Waste gas and step 1) in desulfurization slurry contact, the desulfurization slurry absorbs nitrogen dioxide and remaining titanium dioxide in waste gas
Sulphur.
Specifically, the flue gas after dedusting is delivered to treating column 1 through air-introduced machine, enter in the first processing section 11 for the treatment of column 1
Row desulfurization link, desulfurization slurry meeting and SO2And sufficiently absorption and mass transfer are produced between thin dirt, and passing through second processing section
12 complete after oxidation link, and rise device of air using liquid collecting conveys to the denitration link of the 3rd processing section 13, is taken off with top-down
Nitre liquid produces reverse contact in the absorption plant of microchannel, and the nitrogen oxides in fully removing smoke finally recycles demisting dress
Put the removing for carrying out flue gas reclaimed water and mist and discharged by the outlet port 17 for the treatment of column 1.In second processing section, by oxidant
Oxidation of nitric oxide in flue gas is nitrogen dioxide by the oxidant that tank 5 is sprayed into.
Contain substantial amounts of sulfur dioxide and nitrogen oxides in flue gas from boiler flue, nitrogen oxides is mainly with an oxidation
Based on nitrogen, nitric oxide is not easy to be absorbed, and is easier to be inhaled when it is oxidized to the nitrogen oxides such as nitrogen dioxide of high-valence state
Receive, first order absorption is carried out to flue gas by desulfurizing agent first, most sulfur dioxide in flue gas is removed, while desulfurizing agent absorbs
The desulfurization slurry rich in inferior sulfate radical is obtained after sulfur dioxide in flue gas, efficient liquid phase oxidation then is carried out to flue gas again, will
Oxidation of nitric oxide in flue gas is into nitrogen dioxide, and part is oxidized agent and absorbs to form nitrate slurries, and the nitrate passes through rear
Byproduct such as fertilizer etc., so that chlorite makees oxidant as an example, the reactional equation of specific oxidation reaction are can obtain after continuous processing
Formula is as follows：
2NO+ClO2 -→2NO2+Cl
4NO2+ClO2 -+4OH-→4NO3-+Cl-+2H2O
NO+ClO2 -→NO2+ClO
NO+ClO-→NO2+Cl
2NO2+ClO2 -+2OH-→2NO3 -+ClO-+2H2O
Finally using the desulfurization slurry after first grade desulfurizing to flue gas carry out two grades absorption, remove flue gas in nitrogen dioxide and
Remaining sulfur dioxide, forms sulfate slurries, and the sulfate slurries obtain accessory substance such as gypsum, two grades after subsequent treatment
The reaction equation that nitrogen dioxide is absorbed during absorption is as follows：
4SO3 2-+2NO2+→N2+4SO4 2-
Desulfurizing agent described in the present embodiment is ammoniacal liquor, seawater, magnesium hydroxide or lime stone slurry, the pH value and liquid of desulfurizing agent
Gas is set than the content according to sulfur dioxide in flue gas and selected desulfurizing agent species, as a kind of perferred technical scheme, described
Desulfurizing adsorbent calcium hydroxide or lime stone slurry.Oxidant used in the oxidant storage tank is hydrogen peroxide, chlorous acid
The aqueous solution of at least one of salt and hypochlorite；Described chlorite can select sodium chlorite, hypochlorite and can select
At least one of sodium hypochlorite, calcium hypochlorite.
But often there is NO in actual exhaust gas processing procedure and aoxidize insufficient, the excessive defect of oxidizer, for
Drawbacks described above, the present invention further, NO oxidation catalysts is loaded with the second processing section of the emission-control equipment, described to urge
Agent is solid-loaded ionic-liquid low-temperature denitration catalyst, includes the active component and 40%-99% parts by weight of 1-60% parts by weight
Carrier, described active component is the polyethers ionic liquid comprising Mg or Al ions.
The carrier is selected from MFI, ERI and MOR the type molecular sieve for having stronger absorption affinity to NO, particularly preferably 13X
With H beta-molecular sieves.
The polyethers ionic liquid has following structural formula：
[R1(OCH2CH2)mCH2CH2NR2 3]+·X-
R in formula1For C1-6 alkyl, R2For C2-6 hydroxy alkyl, the R2Each other can with it is identical can not also
Together.
The preparation method of the NO oxidation catalysts is：Active metal and ionic liquid are scattered in solvent and form molten
Liquid, retells carrier and immerses in the solution, at room temperature after agitating solution 18-24 hours, filters out the solution of dipping, finally, will soak
To obtain solid-loaded ionic-liquid with solvent of going out within 8-12 hours low as being dried in vacuo at 100 DEG C in positive empty drying box for carrier after stain
Warm denitrating catalyst.
Catalyst activity component is the microenvironment of the polyethers ionic liquid formation of active metal Mg and Al formation, can be effective
Ground prevents that active component is not easily runed off in contact of the active component with moisture content, course of reaction, so as to improve the use of catalyst
Life-span；Ionic liquid has the features such as not volatile, heat endurance is high, by ionic liquid with having stronger adsorption capacity to NO
Molecular screen material combines, and not only maintains ionic liquid high catalytic activity and also causes active component high degree of dispersion, activearm
The reunion of active component can effectively be prevented by point being evenly distributed in carrier surface, and the ratio surface of catalyst is big, and catalytic activity is high, instead
Should be selectively good.
The present embodiment there is also sulphite in desulfurization link in slurries, this kind of product can return to place with slurries
In the slurry tank 2 for managing the bottom of tower 1, and desulfurization ring is recirculated to through the second spray pipeline 32 in the presence of first circulation pump 3
Section carries out desulfurization, and the remainder of slurry tank 2 can be then sent to through the first spray pipeline 31 in the presence of first circulation pump 3
Denitration link carries out denitration.The absorbing liquid that denitration link is produced then is entered in circulating tank 6 by first circulation pipeline 61, by adding
Medicine device 9 adds appropriate medicine into circulating tank 6 to promote the removing of nitrogen oxides.The bottom of circulating tank 6 is followed by second
Endless tube road 62 is connected with slurry tank 2, so as to which the slurries in circulating tank 6 are delivered in slurry tank 2, continues above-mentioned circulation.
Fresh desulfurization slurry, the fresh desulfurization can be supplemented into circulating tank 6 by the branch road 35 of tie point 34 and second in time
Slurries are entered in slurry tank 2 by second circulation pipeline 62.In circulating tank 6, slurries and medicine and the Novel slurry newly added
Can the fully individual mixing that you wait.
Embodiment 3
The preparation of polyethers ionic liquid：Monochloro is for polyethylene glycol (M=500) and triethanolamine in molar ratio 1:1.1 plus
Enter in reactor, using toluene as solvent, under nitrogen atmosphere, be stirred at reflux reaction 96 hours, stop reaction, respectively with third
Ketone, ethyl acetate and ether washing, vacuum drying obtains PEG-TEA ionic liquids afterwards several times for washing；
In the preparation of solid-carrying type ionic liquid low-temperature denitration catalyst：Under nitrogen protection, to appeal PEG-TEA ionic liquids
The AlCl of equimolar amounts is added in body3After stirring reaction 6h, a certain amount of ethanol is added, one is added after ionic liquid all dissolves
Quantitative 13X molecular sieves, are stirred overnight at room temperature, filtering, are placed under 150 degrees Celsius of vacuum drying chamber and are dried in vacuo 12h, gained is solid
Body is size-reduced, crosses 30-60 mesh sieves and obtains solid-carrying type ionic-liquid catalyst particle.
Embodiment 4
The preparation of polyethers ionic liquid：Monochloro is for polyethylene glycol (M=500) and triethanolamine in molar ratio 1:1.1 plus
Enter in reactor, using toluene as solvent, under nitrogen atmosphere, be stirred at reflux reaction 96 hours, stop reaction, respectively with third
Ketone, ethyl acetate and ether washing, vacuum drying obtains PEG-TEA ionic liquids afterwards several times for washing；
In the preparation of immobilized property ionic liquid low-temperature denitration catalyst：Under nitrogen protection, to appeal PEG-TEA ionic liquids
The MgCl of equimolar amounts is added in body2After stirring reaction 6h, add a certain amount of ethanol, after added after ionic liquid all dissolving by
Weight compares 1:2 H beta-molecular sieves, are stirred overnight at room temperature, filtering, are placed at 150 DEG C of vacuum drying chamber and are dried in vacuo 12h, cross 30-
60 mesh sieves obtain solid-carrying type ionic-liquid catalyst particle.
Embodiment 5
Device, the solid-loaded ionic-liquid catalyst prepared by 3kg embodiments 3 is loaded in the second processing stage as shown in Figure 1,
In 8m3Simulation of desulfurization flue gas denitrification process on the experimental simulation device of/h scales.Exhaust gas volumn 8m3/ h, flue gas composition is as follows：O2For
8%, SO2For 3000ppm, NO is 4 × 104Ppm, remaining is nitrogen, 100 DEG C of flue-gas temperature, 1 atmospheric pressure of pressure.Use quality
The sodium chlorite aqueous solution that fraction is 10% makes the ammoniacal liquor that mass concentration is 17% as desulfurizing agent, Oxygen in Liquid as oxidant
The liquid-gas ratio of change is 2L/m3, using the waste gas treatment process of the present invention, carry out desulphurization denitration.After testing, overall desulfurization efficiency
99.6%, denitration efficiency is up to 98.5%.
Embodiment 6
Device, the solid-loaded ionic-liquid catalyst prepared by 3kg embodiments 4 is loaded in the second processing stage as shown in Figure 1,
Remaining operation be the same as Example 5, using the waste gas treatment process of the present invention, carries out desulphurization denitration.After testing, overall desulfurization efficiency
99.3%, denitration efficiency is up to 98.0%.
Comparative example 1
Device, 3kg 13X molecular sieves are loaded in the second processing stage as shown in Figure 1, remaining operation be the same as Example 5, are utilized
The waste gas treatment process of the present invention, carries out desulphurization denitration.After testing, overall desulfurization efficiency 95%, denitration efficiency is up to 70%.
Comparative example 2
Device, 3kg H beta-molecular sieves are loaded in the second processing stage as shown in Figure 1, remaining operation be the same as Example 5, utilize this
The waste gas treatment process of invention, carries out desulphurization denitration.After testing, overall desulfurization efficiency 97%, denitration efficiency is up to 76%.
Comparative example 3
Device, any catalyst is not loaded in the second processing stage as shown in Figure 1, remaining operation be the same as Example 5, utilizes this
The waste gas treatment process of invention, carries out desulphurization denitration.After testing, overall desulfurization efficiency 94%, denitration efficiency is up to 76%.
By desulphurization denitration, it is integrated in a treating column present invention so that desulfurization workshop section is separate with denitration workshop section
It is again interrelated, technological process is greatly simplified, the floor space of equipment is reduced, reduces investment cost.
Sulfur dioxide in removing waste gas first before denitration oxidation, is taken off again after removing most sulfur dioxide
Nitre is aoxidized, and can reduce the side reaction of oxidant and sulfur dioxide, so as to reduce the consumption of oxidant, saves operating cost.
The shower plate used cooperatively in the 3rd processing stage using microchannel absorption plant and with the device, so that significantly
The contact area of waste gas and absorbing liquid is added, the time of contact of waste gas and absorbing liquid is extended, is conducive to fully removing dioxy
Change nitrogen, improve denitration rate.
By installing the solid-carrying type ionic liquid denitration provided by the present invention with high catalytic activity additional in second processing section
Catalyst is compared to only molecular sieve is loaded and is not loaded with the situation of any catalyst, under the same operating conditions, not only drops
Also significantly high denitration rate while low oxidant usage amount.
Described above has fully disclosed the embodiment of the present invention.It is pointed out that being familiar with the field
Scope of any change that technical staff is done to the embodiment of the present invention all without departing from claims of the present invention.
Correspondingly, the scope of claim of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of high effective flue gas processing unit using solar energy as power, including treating column and slurry tank, the slurry tank are set
Connected in the processing tower bottom, and with the treating column, it is characterised in that the treating column is divided into first from the bottom to top
Processing section, second processing section and the 3rd processing section, first processing section are filled with intersegmental the first liquid collecting liter gas that is provided with of second processing
Put, the second processing Duan Yu tri- handle it is intersegmental be provided with the second liquid collecting and rise device of air, first processing section enters provided with waste gas
Entrance, first processing section is used to remove the sulfur dioxide gas in waste gas, and the second processing section is used in oxidation gaseous effluent
Nitric oxide gas, convert it into nitrogen dioxide, the 3rd processing section is used to remove the nitrogen oxides in waste gas, and will
Gas after processing discharges the treating column,
First processing section and the 3rd processing section are connected by first circulation pump with the slurry tank, and the second processing section is logical
Cross second circulation pump to connect with an oxidant storage tank, the oxidant storage tank forms an enclosed with second processing section and followed
Ring, the second processing section adds catalyst,
Described device also includes solar power generation unit, the solar power generation unit and the first circulation pump and second circulation
Pump is electrically connected.
2. a kind of high effective flue gas processing unit using solar energy as power according to claim 1, it is characterised in that described
3rd processing section is also connected by first circulation pipeline with a circulating tank, and the circulating tank is used to collect in the 3rd processing section
Absorbing liquid, the circulating tank is provided with chemicals dosing plant, and the circulating tank connected by second circulation pipeline with the slurry tank.
3. a kind of high effective flue gas processing unit using solar energy as power according to claim 1, it is characterised in that described
Catalyst is solid-loaded ionic-liquid low-temperature denitration catalyst, includes the active component and 40%-99% weight of 1-60% parts by weight
The carrier of part, described active component is the polyethers ionic liquid comprising Mg or Al ions.
4. a kind of high effective flue gas processing unit using solar energy as power according to claim 1, it is characterised in that described
It is provided with first processing section in the first spray-absorption device, the second processing section and is provided with the second spray-absorption device, described the
The 3rd spray-absorption device is provided with three processing sections, the 3rd spray-absorption device includes being arranged on the second liquid collecting liter gas
The microchannel absorption plant on device top, the microchannel absorption plant is provided with hollow shower plate, the shower plate and institute
The outlet for stating first circulation pump is connected by the first spray pipeline, and the first circulation pump is by the first spray pipeline by the slurry
Slurries in liquid bath are pumped to the shower plate, and slurries are ejected into the microchannel absorption plant through shower plate.
5. a kind of high effective flue gas processing unit using solar energy as power according to claim 4, it is characterised in that described
First spray-absorption device includes the first shower and packing layer, and first shower is arranged on described filler layer top, institute
The outlet that the first shower is stated with the first circulation pump is connected by the second spray pipeline, and the first circulation pump passes through second
Slurries in the slurry tank are pumped to first shower by spray pipeline, and slurries are through the first spray pipe inspection to described the
In one processing section.
6. a kind of high effective flue gas processing unit using solar energy as power according to claim 1, it is characterised in that described
Treating column is provided with demister at close outlet port, and the demister includes demister body and auto-flushing system
System, the self-stripping system include the shower for being arranged on the demister body upper part and bottom and with the shower
The industrial water tank of connection.
7. a kind of high effective flue gas processing unit using solar energy as power according to claim 1, it is characterised in that described
Slurry tank is connected with the entrance of the first circulation pump by the first suction line, and first is separated on first suction line
Road, one end of the tie point connects first suction line, and its other end is connected with the circulating tank, described first
The second branch road is separated on road, second branch road is used to connect fresh desulfurization slurry preparation tank.
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| CN107638778A (en) * | 2017-09-28 | 2018-01-30 | 华夏碧水环保科技有限公司 | One kind spray odor removal |
| CN110585872A (en) * | 2019-10-11 | 2019-12-20 | 安徽天顺环保设备股份有限公司 | Dust removal SOx/NOx control integration tower |
| CN111495139A (en) * | 2020-04-27 | 2020-08-07 | 安徽顺达环保科技股份有限公司 | Wet-type desulfurization and denitrification device and process for high-sulfur-concentration flue gas |
| CN112439318A (en) * | 2019-09-05 | 2021-03-05 | 大连海事大学 | High-efficient SOx/NOx control integration system of low temperature tail gas |
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| CN110585872B (en) * | 2019-10-11 | 2021-08-10 | 安徽天顺环保设备股份有限公司 | Dust removal SOx/NOx control integration tower |
| CN111495139A (en) * | 2020-04-27 | 2020-08-07 | 安徽顺达环保科技股份有限公司 | Wet-type desulfurization and denitrification device and process for high-sulfur-concentration flue gas |
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