CN104190235A - Regenerable oily denitration absorption liquid used for absorbing nitric oxides in smoke as well as preparation method and application of absorption liquid - Google Patents
Regenerable oily denitration absorption liquid used for absorbing nitric oxides in smoke as well as preparation method and application of absorption liquid Download PDFInfo
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- CN104190235A CN104190235A CN201410359107.5A CN201410359107A CN104190235A CN 104190235 A CN104190235 A CN 104190235A CN 201410359107 A CN201410359107 A CN 201410359107A CN 104190235 A CN104190235 A CN 104190235A
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- oiliness
- flue gas
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses regenerable oily denitration absorption liquid used for absorbing nitric oxides in smoke as well as a preparation method and application of the absorption liquid. The regenerable oily denitration absorption liquid is prepared from the following components in percentage by volume: 5%-30% of an oil phase, 25%-40% of a water phase and 30%-60% of an emulsifier. The preparation method of the regenerable oily denitration absorption liquid comprises the following steps: taking a surfactant and a co-surfactant according to a ratio at the temperature of 15 DEG C-50 DEG C, uniformly mixing, sequentially adding the oil phase and the water phase according to the ratio, and stirring a solution until the solution is clear. The absorption liquid has a good effect of removing pollutants; the removal rate of nitric oxides can reach over 60%; the absorption liquid can be regenerated and recycled, so that the catalyst can be cyclically used; meanwhile, the absorption liquid is stable in property, simple in process and low in investment and operation costs, and can be implemented on existing wet desulphurization equipment.
Description
Technical field
The invention belongs to air pollution control technique field, be specifically related to a kind of renewable oiliness denitration absorbing liquor for the nitrogen oxide in flue gas with removal effect and its preparation method and application.
Background technology
Containing SO
2and NO
xa large amount of discharges of waste gas caused serious problem of environmental pollution, as broken ring of acid rain, ozone layer etc.In the research of flue-gas denitrification technology, SCR (SCR) and non-selective catalytic reduction technology (SNCR) have obtained the industrial applications of certain scale.But these two kinds of technology exist, investment is high with operating cost, catalyst easily lost efficacy, operating temperature range is narrow, easily cause the shortcomings such as secondary pollution.
Flue gas and desulfurizing and denitrifying technology is the hot spot technology that begins one's study nearly ten years and develop.China's boiler smoke has been built desulfurization facility substantially at present, and 90% above employing wet desulphurization, particularly medium and small Industrial Boiler, is the simple and easy wet processing that adopts ammonia process, calcium method, magnesium method etc. to be desulfurizing agent substantially.That wherein ammonia process of desulfurization high efficiency, low power consuming, abundant raw material, accessory substance are worth is high, can realize complete resource, non-secondary pollution.As a Wet Flue Gas Desulfurization Technique that has an independent intellectual property right, there is vast potential for future development.
Consider from the various aspects such as economy, technology factor, on existing ammonia desulfurizing process, introduce the NO that a kind of recovery capable of circulation is used
xthe oxidant of absorbent and promotion NO oxidation, make original wet method fume desulfurizing system there is high efficiency denitration function simultaneously, and realize complete resource, thereby form the desulfurization and denitrification integral technology that the small investment, the operating cost that adapt with China's national situation are low, meet China's discharge standard.
For example, the Chinese invention patent application document that publication number is CN102553416A discloses a kind of method of power-plant flue gas denitration and absorption liquid used thereof.The method of described denitration utilizes absorption tower, adopts by H
2o
2, control temperature and be under the condition of 30-80 DEG C as absorption liquid with the Fenton-like reagent of ferric sulfate composition and the aqueous solution using EDTA as additive, thereby NO is oxidized in absorption tower and then is absorbed by liquid absorption to complete denitration power-plant flue gas is carried out to denitration; H in described absorption liquid
2o
2concentration is 0.5-1mol/L, Fe
2(SO
4)
3concentration is 0.01-0.025mol/L, and additive EDTA concentration is 0.02-0.05mol/L, and the pH of absorption liquid is 5-6.
Publication number is the absorbent that the Chinese invention patent application document of CN 102228779A discloses a kind of liquid phase flue gas and desulfurizing and denitrifying, calculate according to the amount of making 1L absorbent, its oxidant by 60-300ml, the additive of 0.5-80g and the water of 633.33-939.58ml form; Described oxidant is at least one in the peroxide acetate aqueous solution that concentration is 30% aqueous hydrogen peroxide solution, concentration is 15%; Additive is at least one in sodium carbonate, sodium acetate and calcium carbonate; The oxidant of described amount, additive are added in container, add the water of described amount, and mix.But these absorption liquids all cannot cycling and reutilization.
Summary of the invention
The invention provides a kind of regeneration oiliness denitration absorbing liquor absorbing for nitrogen oxides in effluent and its preparation method and application, this absorption liquid is good for the removal effect of pollutant, can reach more than 60% the removal efficiency of nitrogen oxide, renewable recovery realizes and recycling, and stable in properties, technique are simple, investment and operating cost cheap, on existing wet desulphurization equipment, can implement.
The renewable oiliness denitration absorbing liquor absorbing for nitrogen oxides in effluent, by volume percentage meter, made by following component:
Oil phase 5%-30%
Water 25%-40%
Emulsifying agent 30%～60%.
Preferably, by volume percentage meter, made by following component:
As preferably, described oil phase is at least one in benzinum, silicone oil, diesel oil, kerosene, gasoline and paraffin oil.Further preferably, described oil phase is silicone oil, diesel oil or paraffin oil.
As preferably, described water is at least one in dimethyl sulfoxide (DMSO), diethyl sulfoxide, thionyl chloride, diphenyl sulfoxide and sulfolane.Further preferably, described water is dimethyl sulfoxide (DMSO).
As preferably, described emulsifying agent is the mixture of surfactant and cosurfactant.
As preferably, described surfactant is at least one in class of department, Qu Latong, tween, OP-10 (OPEO) and TX-10 (NPE).
As preferably, described cosurfactant is at least one in normal propyl alcohol, n-butanol, isobutanol, isoamyl alcohol and n-octyl alcohol.
As preferably, described surfactant accounts for 15%～30% of raw material composition; Cosurfactant accounts for 15%～30% of raw material composition.This percentage refers to percentage by volume.
Further preferably, described surfactant and cosurfactant be combined as any one in following combination: class 60 of department and n-butanol; Tween and isoamyl alcohol; Class 80 of department and isoamyl alcohol; OP-10 and normal propyl alcohol; Qu Latong and n-octyl alcohol; TX-10 and isobutanol.
Most preferably, described surfactant and cosurfactant be combined as department class 80 and isoamyl alcohol.
The present invention also provide a kind of as described in the preparation method of renewable oiliness denitration absorbing liquor, comprise the steps:
Under 15 DEG C of-50 DEG C of temperature conditions, get surfactant and cosurfactant by proportioning, mix, add successively in proportion oil phase and water, be stirred to solution and become clarification.
Most preferably, comprise the steps:
Under 15 DEG C of-50 DEG C of temperature conditions, get in proportion class 80 of surfactant department and cosurfactant isoamyl alcohol, mix, add in proportion diesel oil, mix, finally add in proportion dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.
Along with the rising of temperature, the forming process of microemulsion is faster, and the assimilation effect of microemulsion is also better, but in Practical Project, considers the energy consumption of intensification, generally select to carry out under normal temperature, and 25～35 DEG C, carry out at normal temperatures, can greatly reduce production costs.
Principle of the present invention:
NO is insoluble in water, needs first oxidized dose of oxidation, could in the aqueous solution, be absorbed.
NO+H
2o
2=NO
2+ H
2o or 2NO+H
2o
2=N
2o
3+ H
2o
NO
2for polar gas molecule, molecular structure is V-type, and soughing in dimethyl Asia is polar non-proton organic solvent, has larger dipole moment (4.03D), and molecular formula is (CH
3)
2sO.Be easy to dissolve the principle of polar solute according to polar solvent, dimethyl sulfoxide (DMSO) has good absorbability to the nitrogen oxide of polarity.Sulfoxide group (S=O) in dimethyl sulfoxide (DMSO), can be by NO
2micel is altogether coalescent, absorbs thereby realize.
NO
2+(CH
3)
2SO＝(CH
3)
2SO·NO
2
Although dimethyl sulfoxide (DMSO) is to NO
2there is good assimilation effect.But in traditional handicraft, use dimethyl sulfoxide (DMSO) denitration a bit deficient in aspect recycling.In the application, use dimethyl sulfoxide (DMSO) microemulsion can make up this point not enough, the microemulsion adopting is water-in-oil type, oil continuous phase surrounds water core, and main component in water core is dimethyl sulfoxide (DMSO), and the composition that plays denitration in this microemulsion remains dimethyl sulfoxide (DMSO).When adding appropriate deionized water, ammoniacal liquor and passing into air, absorption liquid absorbs NO
2after can generate denitration product ammonium nitrate, ammonium nitrate has water-soluble.
4(CH
3)
2SO·NO
2+O
2+2H
2O＝4(CH
3)
2SO+4HNO
3
HNO
3+NH
4OH＝NH
4NO
3+H
2O
When ammonium nitrate molecule is during due to dimethyl sulfoxide (DMSO) molecular separation in space steric effect and water-in-oil microemulsion water core, the architectural feature of absorption liquid of the present invention will impel oil phase again to surround water core, thereby make absorption liquid return to the state before absorption.If also have nitrogen dioxide molecules to exist, methyl-sulfoxide can continue to absorb nitrogen dioxide, in the situation that condition is suitable, can continue to generate ammonium nitrate.So repeatedly carry out until nitrogen dioxide is all removed.After dimethyl sulfoxide (DMSO) molecular separation in ammonium nitrate molecule and water core, leave standstill after a period of time, due to proportion difference, oily absorption liquid can with aqueous solution layering, upper strata is oily absorption liquid, can recycle; Lower floor is the aqueous solution that contains ammonium nitrate, after concentrated purification, can obtain highly purified ammonium nitrate.
The content proportioning of every kind of component produces certain impact to the assimilation effect of absorption liquid, a kind of preferred technical scheme, and described renewable oiliness denitration absorbing liquor by mass percentage, is made up of following component:
Described oil phase is silicone oil, diesel oil or paraffin oil, and water is dimethyl sulfoxide (DMSO); Surfactant and cosurfactant be combined as any one in following combination: class 60 of department and n-butanol; Tween and isoamyl alcohol; Class 80 of department and isoamyl alcohol; OP-10 and normal propyl alcohol; Qu Latong and n-octyl alcohol; TX-10 and isobutanol;
And preparation by the following method: under 15 DEG C of-50 DEG C of temperature conditions, get surfactant and cosurfactant by proportioning, mix, add successively in proportion oil phase and water, be stirred to solution and become clarification.
After the renewable oil phase denitration absorbing liquor being obtained by above-mentioned optimal technical scheme mixes with desulfurization absorption liquid, for flue gas desulfurization and denitrification, ensureing that smoke desulfurization efficiency is greater than under 99% prerequisite, denitration efficiency is more than 70%.
After desulphurization denitration finishes, reclaim oil phase denitration absorbing liquor, the denitration absorbing liquor reclaiming again mixes and carries out flue gas desulfurization and denitrification with desulfurization absorption liquid, desulfuration efficiency and denitration efficiency all remain on 99% and 70% left and right, recycle after a period of time, absorb composition and have certain loss, affect absorption efficiency, should suitably be supplemented.
A kind of most preferred technical scheme, described renewable oiliness denitration absorbing liquor by mass percentage, is made up of following component:
Described oil phase is diesel oil, and water is dimethyl sulfoxide (DMSO); The combination of surfactant and cosurfactant: class 80 of department and isoamyl alcohol.
And preparation by the following method: under 25 DEG C of temperature conditions, get surfactant and cosurfactant by proportioning, mix, add successively in proportion oil phase and water, be stirred to solution and become clarification.
After the renewable oil phase denitration absorbing liquor being obtained by above-mentioned optimal technical scheme mixes with desulfurization absorption liquid, for flue gas desulfurization and denitrification, ensureing that smoke desulfurization efficiency is greater than under 99% prerequisite, denitration efficiency is more than 70%.
After desulphurization denitration finishes, reclaim oil phase denitration absorbing liquor, the denitration absorbing liquor of recovery again mixes and carries out flue gas desulfurization and denitrification with desulfurization absorption liquid, and desulfuration efficiency and denitration efficiency all remain on 99% and 70% left and right.Recycle after a period of time, absorb composition and have certain loss, the proportion of goods damageds of one day (24 hours) absorption liquid of average operation continuously, in 5%-15% left and right, affect absorption efficiency, should suitably be supplemented.
The present invention also provide a kind of as described in the application of renewable oiliness denitration absorbing liquor, comprise the steps:
Described renewable oiliness denitration absorbing liquor and desulfurization absorption liquid are configured to blend absorbent, blend absorbent is pumped to top, absorption tower by water circulating pump, atomizing spray and under, in flue gas, spray into oxidant simultaneously, flue gas after oxidation is entered by bottom, absorption tower high-speed rotational, operation from bottom to top, flue gas and absorption liquor counter current contacting in absorption tower, remove the NO in flue gas
x, the flue gas after purification after demister demist by chimney qualified discharge.
Desulfurization absorption liquid is preferably ammoniacal liquor, the volume ratio of renewable oiliness denitration absorbing liquor in blend absorbent is 15～40%, along with the increase of renewable oiliness denitration absorbing liquor volume ratio, blend absorbent increases the clearance of nitrogen oxides in effluent, in the time that the volume ratio of renewable denitration absorbing liquor in blend absorbent reaches 40%, ensureing that desulfuration efficiency is greater than under more than 99% prerequisite, denitration efficiency is up to more than 70%.
Described oxidant is at least one in hydrogen peroxide, potassium permanganate and clorox.
In process in above-mentioned purifying smoke pollutant, absorbent can be recycled, and denitration product can separate with oiliness absorption liquid, enters in the aqueous solution, thereby absorption liquid is regenerated, and continue to absorb the nitrogen oxide in flue gas.Reacted solution left standstill can layering, and lower floor's drying separates can obtain byproduct ammonium nitrate, and upper strata oiliness absorption liquid returns to denitrating system and recycles after separating.
The present invention compared with prior art tool has the following advantages and beneficial effect:
1) absorption liquid raw material sources are convenient, and storage and use are simple, and production and application is with low cost;
2) process choice is flexible, and integrated artistic is simple, and easily, contaminant removal efficiency is high in operation operation.The present invention is to SO
2clearance more than 95%, to NO
xclearance more than 70%, and can reclaim nitrogenous byproduct as composite fertilizer material.
3) existing coal-burning boiler is only needed to carry out appropriate reconstruction and can move enforcement, floor space is little, strong adaptability, and overall operation is with low cost, no matter is that large-scale coal-burning power plant or small-sized coal-burning boiler can be applied.
Detailed description of the invention
Oiliness absorption liquid of the present invention for the technological process of purifying smoke pollutant is: the flue gas after oxidation enters absorption tower by bottom, absorption tower high-speed rotational; The oiliness absorbent preparing and ammoniacal liquor composition composite absorbent liquid, adds circulating sedimentation tank by dosing pump, is delivered to efficient absorption tower top subsequently by circulating pump, from upper spray and under; Composite absorbent liquid and flue gas be counter current contacting reaction in absorption tower, the NO in flue gas
xabsorb the final removals such as nitrate that generate Deng being absorbed agent, the flue gas after purifying after demister demist by chimney qualified discharge.Composite absorbent liquid is exported by absorption tower after absorption reaction, enters circulating sedimentation tank, leave standstill after a period of time, due to proportion difference, oily absorbent can with aqueous solution layering, upper strata is oily absorbent, can recycle; Lower floor is the aqueous solution that contains ammonium nitrate, after concentrated purification, can obtain highly purified ammonium nitrate.
Percentage described in following examples is percentage by volume, and raw material is commercial goods.
Embodiment 1
Certain 35t/h biomass boiler amount of flue gas emission is 5.0～6.0 ten thousand m
3/ h, records and purifies front flue gas SO
2concentration is 600～750mg/m
3; NO
xconcentration is 350～550mg/m
3.Absorption tower adopts spray column, tower height 15m, and tower diameter is 3m, gas residence time > 4s.In absorption process, controlling absorption liquid reaction temperature is 50 DEG C of left and right, and pH is 6-7.
Under 25 DEG C of temperature conditions, get 25.7% class of surfactant department 60 and 25.7% cosurfactant n-butanol, mix, add in proportion 15.6% diesel oil, mix, finally add in proportion 33% dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.Get 15% oiliness absorption liquid, remain as ammoniacal liquor, be mixed with absorption liquid.
In production process, the absorption liquid configuring is delivered to efficient absorption tower top by circulating pump, sprays into oxidants hydrogen peroxide in flue gas, the flue gas after oxidation is imported by bottom, absorption tower simultaneously, and both are counter current contacting reaction in absorption tower, the SO in flue gas
2, NO
xbe absorbed by liquid absorption final generation (NH
4)
2sO
4, NH
4nO
3, purify after flue gas after demister demist by chimney qualified discharge.After absorption liquid absorption is saturated, is derived and entered nitrogenous byproduct recovery system recovery byproduct by pump, the waste water of generation enters Waste Water Treatment and processes qualified discharge.Described in employing the present embodiment, after technical scheme, record SO in absorption tower outlet flue gas
2average removal rate >95%, NO
xaverage removal rate > 60%.
Embodiment 2
Certain 35t/h biomass boiler amount of flue gas emission is 5.0～6.0 ten thousand m
3/ h, records and purifies front flue gas SO
2concentration is 600～750mg/m
3; NO
xconcentration is 350～550mg/m
3.Absorption tower adopts spray column, tower height 15m, and tower diameter is 3m, gas residence time > 4s.In absorption process, controlling absorption liquid reaction temperature is 50 DEG C of left and right, and pH is 6-7.
Under 25 DEG C of temperature conditions, get 28% surfactant tween and 29% cosurfactant isoamyl alcohol, mix, add in proportion 10% silicone oil, mix, finally add in proportion 33% dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.Get 20% oiliness absorption liquid, remain as ammoniacal liquor, be mixed with absorption liquid.
In production process, the absorption liquid configuring is delivered to efficient absorption tower top by circulating pump, sprays into oxidants hydrogen peroxide in flue gas, the flue gas after oxidation is imported by bottom, absorption tower simultaneously, and both are counter current contacting reaction in absorption tower, the SO in flue gas
2, NO
xbe absorbed by liquid absorption final generation (NH
4)
2sO
4, NH
4nO
3, purify after flue gas after demister demist by chimney qualified discharge.After absorption liquid absorption is saturated, is derived and entered nitrogenous byproduct recovery system recovery byproduct by pump, the waste water of generation enters Waste Water Treatment and processes qualified discharge.Described in employing the present embodiment, after technical scheme, record SO in absorption tower outlet flue gas
2average removal rate >97%, NO
xaverage removal rate > 65%.
Embodiment 3
Certain 35t/h biomass boiler amount of flue gas emission is 5.0～6.0 ten thousand m
3/ h, records and purifies front flue gas SO
2concentration is 600～750mg/m
3; NO
xconcentration is 350～550mg/m
3.Absorption tower adopts spray column, tower height 15m, and tower diameter is 3m, gas residence time > 4s.In absorption process, controlling absorption liquid reaction temperature is 50 DEG C of left and right, and pH is 6-7.
Under 25 DEG C of temperature conditions, get 23.4% surfactant TX-10 and 12.5% cosurfactant isobutanol, mix, add in proportion 26.8% diesel oil, mix, finally add in proportion 37.3% dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.Get 40% oiliness absorption liquid, remain as ammoniacal liquor, be mixed with absorption liquid.
In production process, the absorption liquid configuring is delivered to efficient absorption tower top by circulating pump, sprays into oxidants hydrogen peroxide in flue gas, the flue gas after oxidation is imported by bottom, absorption tower simultaneously, and both are counter current contacting reaction in absorption tower, the SO in flue gas
2, NO
xbe absorbed by liquid absorption final generation (NH
4)
2sO
4, NH
4nO
3, purify after flue gas after demister demist by chimney qualified discharge.After absorption liquid absorption is saturated, is derived and entered nitrogenous byproduct recovery system recovery byproduct by pump, the waste water of generation enters Waste Water Treatment and processes qualified discharge.Described in employing the present embodiment, after technical scheme, record SO in absorption tower outlet flue gas
2average removal rate >99%, NO
xaverage removal rate > 67%.
Embodiment 4
Certain 35t/h biomass boiler amount of flue gas emission is 5.0～6.0 ten thousand m
3/ h, records and purifies front flue gas SO
2concentration is 600～750mg/m
3; NO
xconcentration is 350～550mg/m
3.Absorption tower adopts spray column, tower height 15m, and tower diameter is 3m, gas residence time > 4s.In absorption process, controlling absorption liquid reaction temperature is 50 DEG C of left and right, and pH is 6-7.
Under 35 DEG C of temperature conditions, get 29.6% Surfactant OP-10 and 23.8% cosurfactant normal propyl alcohol, mix, add in proportion 14.6% paraffin oil, mix, finally add in proportion 32% dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.Get 30% oiliness absorption liquid, remain as ammoniacal liquor, be mixed with absorption liquid.
In production process, the absorption liquid configuring is delivered to efficient absorption tower top by circulating pump, sprays into oxidants hydrogen peroxide in flue gas, the flue gas after oxidation is imported by bottom, absorption tower simultaneously, and both are counter current contacting reaction in absorption tower, the SO in flue gas
2, NO
xbe absorbed by liquid absorption final generation (NH
4)
2sO
4, NH
4nO
3, purify after flue gas after demister demist by chimney qualified discharge.After absorption liquid absorption is saturated, is derived and entered nitrogenous byproduct recovery system recovery byproduct by pump, the waste water of generation enters Waste Water Treatment and processes qualified discharge.Described in employing the present embodiment, after technical scheme, record SO in absorption tower outlet flue gas
2average removal rate >99%, NO
xaverage removal rate > 70%.
Embodiment 5
Certain 35t/h biomass boiler amount of flue gas emission is 5.0～6.0 ten thousand m
3/ h, records and purifies front flue gas SO
2concentration is 600～750mg/m
3; NO
xconcentration is 350～550mg/m
3.Absorption tower adopts spray column, tower height 15m, and tower diameter is 3m, gas residence time > 4s.In absorption process, controlling absorption liquid reaction temperature is 50 DEG C of left and right, and pH is 6-7.
Under 25 DEG C of temperature conditions, get 19.3% surfactant Qu Latong and 16.7% cosurfactant n-octyl alcohol, mix, add in proportion 25.3% diesel oil, mix, finally add in proportion 38.7% dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.Get 35% oiliness absorption liquid, remain as ammoniacal liquor, be mixed with composite absorbent liquid.
In production process, the absorption liquid configuring is delivered to efficient absorption tower top by circulating pump, sprays into oxidants hydrogen peroxide in flue gas, the flue gas after oxidation is imported by bottom, absorption tower simultaneously, and both are counter current contacting reaction in absorption tower, the SO in flue gas
2, NO
xbe absorbed by liquid absorption final generation (NH
4)
2sO
4, NH
4nO
3, purify after flue gas after demister demist by chimney qualified discharge.After absorption liquid absorption is saturated, is derived and entered nitrogenous byproduct recovery system recovery byproduct by pump, the waste water of generation enters Waste Water Treatment and processes qualified discharge.Described in employing the present embodiment, after technical scheme, record SO in absorption tower outlet flue gas
2average removal rate >99%, NO
xaverage removal rate > 65%.
Embodiment 6
Certain 35t/h biomass boiler amount of flue gas emission is 5.0～6.0 ten thousand m
3/ h, records and purifies front flue gas SO
2concentration is 600～750mg/m
3; NO
xconcentration is 350～550mg/m
3.Absorption tower adopts spray column, tower height 15m, and tower diameter is 3m, gas residence time > 4s.In absorption process, controlling absorption liquid reaction temperature is 50 DEG C of left and right, and pH is 6-7.
Under 25 DEG C of temperature conditions, get 25.2% class of surfactant department 80 and 28% cosurfactant isoamyl alcohol, mix, add in proportion 14.6% diesel oil, mix, finally add in proportion 32.2% dimethyl sulfoxide (DMSO), stir while adding until solution becomes clarification homogeneous liquid, form stable oiliness denitration absorbing liquor, can leave standstill for a long time not stratified.Get 25% oiliness absorption liquid, remain as ammoniacal liquor, be mixed with absorption liquid.
In production process, the absorption liquid configuring is delivered to efficient absorption tower top by circulating pump, sprays into oxidants hydrogen peroxide in flue gas, the flue gas after oxidation is imported by bottom, absorption tower simultaneously, and both are counter current contacting reaction in absorption tower, the SO in flue gas
2, NO
xbe absorbed by liquid absorption final generation (NH
4)
2sO
4, NH
4nO
3, purify after flue gas after demister demist by chimney qualified discharge.After absorption liquid absorption is saturated, is derived and entered nitrogenous byproduct recovery system recovery byproduct by pump, the waste water of generation enters Waste Water Treatment and processes qualified discharge.Described in employing the present embodiment, after technical scheme, record SO in absorption tower outlet flue gas
2average removal rate >99%, NO
xaverage removal rate > 71%.
In this absorption liquid use procedure, have certain loss, the proportion of goods damageds of average a day (24 hours), at 5%-15%, recycle after a period of time, absorb composition and have certain loss, affect absorption efficiency, should suitably be supplemented.
Claims (10)
1. the renewable oiliness denitration absorbing liquor absorbing for nitrogen oxides in effluent, is characterized in that by volume percentage meter is made up of following component:
Oil phase 5%-30%
Water 25%-40%
Emulsifying agent 30%～60%.
2. renewable oiliness denitration absorbing liquor according to claim 1, is characterized in that, described oil phase is at least one in benzinum, silicone oil, diesel oil, kerosene, gasoline and paraffin oil.
3. renewable oiliness denitration absorbing liquor according to claim 1, is characterized in that, described water is at least one in dimethyl sulfoxide (DMSO), diethyl sulfoxide, thionyl chloride, diphenyl sulfoxide and sulfolane.
4. renewable oiliness denitration absorbing liquor according to claim 1, is characterized in that, described emulsifying agent is the mixture of surfactant and cosurfactant.
5. renewable oiliness denitration absorbing liquor according to claim 4, is characterized in that, described surfactant is at least one in class of department, Qu Latong, tween, OP-10 and TX-10.
6. renewable oiliness denitration absorbing liquor according to claim 4, is characterized in that, described cosurfactant is at least one in normal propyl alcohol, n-butanol, isobutanol, isoamyl alcohol and n-octyl alcohol.
7. renewable oiliness denitration absorbing liquor according to claim 4, is characterized in that, described surfactant accounts for 15%～30% of raw material composition; Cosurfactant accounts for 15%～30% of raw material composition.
8. a preparation method for renewable oiliness denitration absorbing liquor as claimed in claim 1, is characterized in that, comprises the steps:
Under 15 DEG C of-50 DEG C of temperature conditions, get surfactant and cosurfactant by proportioning, mix, add successively in proportion oil phase and water, be stirred to solution and become clarification.
9. an application for renewable oiliness denitration absorbing liquor as claimed in claim 1, is characterized in that, comprises the steps:
Absorption liquid is pumped to top, absorption tower by water circulating pump, atomizing spray and under, simultaneously in flue gas, spray into oxidant, flue gas after oxidation is entered by bottom, absorption tower high-speed rotational, operation from bottom to top, flue gas and absorption liquor counter current contacting in absorption tower, remove the NO in flue gas
x, the flue gas after purification after demister demist by chimney qualified discharge.
10. application according to claim 9, is characterized in that, described oxidant is at least one in hydrogen peroxide, potassium permanganate and clorox.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410359107.5A CN104190235A (en) | 2014-07-25 | 2014-07-25 | Regenerable oily denitration absorption liquid used for absorbing nitric oxides in smoke as well as preparation method and application of absorption liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410359107.5A CN104190235A (en) | 2014-07-25 | 2014-07-25 | Regenerable oily denitration absorption liquid used for absorbing nitric oxides in smoke as well as preparation method and application of absorption liquid |
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| Publication Number | Publication Date |
|---|---|
| CN104190235A true CN104190235A (en) | 2014-12-10 |
Family
ID=52075687
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|---|---|---|---|
| CN201410359107.5A Pending CN104190235A (en) | 2014-07-25 | 2014-07-25 | Regenerable oily denitration absorption liquid used for absorbing nitric oxides in smoke as well as preparation method and application of absorption liquid |
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| CN104946296A (en) * | 2015-05-18 | 2015-09-30 | 江苏新世纪江南环保股份有限公司 | Gasoline-oxidation ammonia-process desulfurization method |
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| CN108479383A (en) * | 2018-04-16 | 2018-09-04 | 昆明理工大学 | SO in a kind of flue gas2, NOx and heavy metal removing method |
| CN109200807A (en) * | 2018-09-14 | 2019-01-15 | 潍坊职业学院 | A kind of method of denitration of desulfurization fume |
| CN110813030A (en) * | 2019-11-11 | 2020-02-21 | 苏州仕净环保科技股份有限公司 | Desulfurization and denitrification process for oily auxiliary agent |
| CN111097257A (en) * | 2019-11-11 | 2020-05-05 | 苏州仕净环保科技股份有限公司 | Preparation method of desulfurization and denitrification auxiliary agent and product thereof |
| CN111097258A (en) * | 2019-11-11 | 2020-05-05 | 苏州仕净环保科技股份有限公司 | Denitration process of oily auxiliary agent |
| CN111389208A (en) * | 2020-03-25 | 2020-07-10 | 山东骏逸环境科技有限公司 | Amino denitration agent and preparation method thereof |
| CN112791569A (en) * | 2021-03-09 | 2021-05-14 | 昆明理工大学 | Method for purifying acid gas by electrochemical synergistic microemulsion |
| CN113663450A (en) * | 2021-09-08 | 2021-11-19 | 昆明理工大学 | Deep purification process for industrial silicon smelting flue gas |
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| CN104946296A (en) * | 2015-05-18 | 2015-09-30 | 江苏新世纪江南环保股份有限公司 | Gasoline-oxidation ammonia-process desulfurization method |
| CN105944505A (en) * | 2016-06-08 | 2016-09-21 | 廖张洁 | Composition for absorbing residual harmful substances in decorative materials |
| CN108479383A (en) * | 2018-04-16 | 2018-09-04 | 昆明理工大学 | SO in a kind of flue gas2, NOx and heavy metal removing method |
| CN108479383B (en) * | 2018-04-16 | 2020-12-15 | 昆明理工大学 | SO in flue gas2NOx and heavy metal removal method |
| CN109200807A (en) * | 2018-09-14 | 2019-01-15 | 潍坊职业学院 | A kind of method of denitration of desulfurization fume |
| CN110813030A (en) * | 2019-11-11 | 2020-02-21 | 苏州仕净环保科技股份有限公司 | Desulfurization and denitrification process for oily auxiliary agent |
| CN111097257A (en) * | 2019-11-11 | 2020-05-05 | 苏州仕净环保科技股份有限公司 | Preparation method of desulfurization and denitrification auxiliary agent and product thereof |
| CN111097258A (en) * | 2019-11-11 | 2020-05-05 | 苏州仕净环保科技股份有限公司 | Denitration process of oily auxiliary agent |
| CN111389208A (en) * | 2020-03-25 | 2020-07-10 | 山东骏逸环境科技有限公司 | Amino denitration agent and preparation method thereof |
| CN112791569A (en) * | 2021-03-09 | 2021-05-14 | 昆明理工大学 | Method for purifying acid gas by electrochemical synergistic microemulsion |
| CN113663450A (en) * | 2021-09-08 | 2021-11-19 | 昆明理工大学 | Deep purification process for industrial silicon smelting flue gas |
| CN115582136A (en) * | 2022-10-14 | 2023-01-10 | 国能龙源环保有限公司 | Sulfoxide catalyst for desulfurization and denitrification and preparation method thereof |
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