CN106621755A - Integral technology using liquid phase to jointly absorb glue gas for simultaneous desulfurizing and denitration - Google Patents
Integral technology using liquid phase to jointly absorb glue gas for simultaneous desulfurizing and denitration Download PDFInfo
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- CN106621755A CN106621755A CN201710017583.2A CN201710017583A CN106621755A CN 106621755 A CN106621755 A CN 106621755A CN 201710017583 A CN201710017583 A CN 201710017583A CN 106621755 A CN106621755 A CN 106621755A
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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
- B01D53/60—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
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
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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
- 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
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Abstract
The invention discloses an integral technology using strong alkaline liquid and strong oxidizing liquid to jointly absorb coal-fired flue gas for simultaneous desulfurizing and denitration, and belongs to the technical field of atmosphere control. The integral technology is characterized in that the integral technology adopting strong alkaline and strong oxidant serial combination can jointly absorb nitrogen oxide and sulfur oxide in the coal-fired flue gas. The integral technology has the advantages that the two types of pollutants can be simultaneously and efficiently removed in two absorbing reactors at normal pressure and normal/low temperature, the desulfurizing rate and denitration rate can respectively reach 99% and 85% or above, and the latest national standard of flue gas emission can be completely reached; the equipment is simple, the operation is convenient, the cost is low, and the land occupation area is small.
Description
Technical field
The present invention relates to technical field of air pollution control and desulphurization denitration technical field, and in particular to a kind of liquid phase highly basic
Combine chemical absorbing flue gas and desulfurizing and denitrifying integral process with strong oxidizer.
Background technology
At this stage China's atmosphere polluting problem is serious, particularly North China, and haze natural law increases.The newest flue gas row of country
The standard of putting is greatly improved.To protect health and ecological environment, strict desulfurization is carried out to the flue gas based on fire coal and has been taken off
Nitre specifies that limited production has been carried out to enterprise not up to standard with process of changing the line of production, and state treatment dynamics is unprecedentedly increased.
At present, flue gas desulfurization and denitrification technical elements industrially, the technology of domestic and international comparative maturity is still lime-gypsum
Ammonia reducing process under method desulfurization and high-temperature catalytic, it is lowly backward in technique that technical efficiency is taken off in this two-step method desulfurization, floor space
Greatly, operating cost is high.It is industrialized while the flue gas desulfurization and denitrification technology Galvanized pulse method and superhigh temperature that are mainly highly energy-consuming is non-
Selective reduction method, also without normal efficient cryogenic simultaneous SO_2 and NO removal integrated apparatus technology.
While under development in desulphurization denitration technology, the Chinese invention patent of Publication No. CN102698599A is to urinate
Element is absorbent with zeolite-loaded Ni-Ce as catalyst, forms slurry solidliquid mixture, solid matter Jing filter cloth mistakes after absorption
Filter Posterior circle is used, and technics comparing is complicated.
The Chinese invention patent of Publication No. CN105413399A is with the complex of two valency ferrum coordination as catalyst, one
Desulfurization and denitrification process are completed in individual complicated big tower, while being furnished with the regenerating unit of doctor solution and denitration absorbing liquor outside tower and changing
Thermal, whole absorption system disposal ability is limited, and removal efficiency is not high.
The Chinese invention patent of Publication No. CN105413399A is that ozone carries out oxidation denitration for gaseous oxidizing agent,
Desulphurization denitration is carried out with weak acid and weak base.And a kind of single column labyrinth simultaneous SO_2 and NO removal system has been invented, but be not given
Specific removal effect.
The Chinese invention patent of Publication No. CN1883768A is to utilize small-sized single column to be main body, is main using bleaching powder
Oxidant, gas crosses absorption liquid layer blistering reaction, and as the increase desulfurization degree and denitration rate of bleaching powder and auxiliary agent content increase,
Up to 95% and more than 85%.
The Chinese invention patent of Publication No. CN102580496A is the profit under 100-150 degree Celsius and an atmospheric pressure
Under independent role with calcium hydroxide or liquid phase strong oxidizer hydrogen peroxide, sodium hypochlorite and manganese chloride and iron chloride auxiliary agent,
The chemical absorbing structure twice of single column is devised, making the disposal ability of flue gas, to have reached 5m3/h even more big, takes off while preferable
Sulfur rate and denitration rate increase than above-mentioned.
The content of the invention
The present invention provides a kind of strong alkaline substance and strong oxidizer absorbs and the double tower joint flue gas simultaneous desulfurization of auxiliary agent takes off
Nitre integral process, solving existing flue gas desulfurization and denitrification needs using asking that two sets of single equipment are removed respectively
Topic, while improve removal efficiency and reducing removing cost.
The technical solution used in the present invention is：Aqueous solution joint by the use of highly basic and strong oxidizer and auxiliary agent is used as absorption
Agent, constitutes double tower process, and simultaneous SO_2 and NO removal is carried out to flue gas under normal pressure and normal low temperature.
Described double tower process refers to respectively the washing tower equipped with highly basic and the oxidizing tower equipped with oxidant, the arrangement of two towers
Order can be washing tower in front oxidizing tower rear, it is also possible to oxidizing tower rear, is used in series in front washing tower, or among these
A tower be used alone, two towers can be at same reaction condition or different condition.
Two kinds of described absorbing liquids are respectively the aqueous solution of strong alkali aqueous solution and strong oxidizer and auxiliary agent, and its concentration all exists
0.001-1.00mol/L scopes.
Described strong alkaline substance includes：The one kind therein such as potassium hydroxide, sodium hydroxide, calcium hydroxide.
Described oxidizing species include：Hydrogen peroxide, sodium hypochlorite, potassium permanganate, sodium chlorite, potassium dichromate etc.,
And its they are combined；Their auxiliary agent includes copper nitrate, ferric nitrate, magnesium nitrate, sodium carbonate etc., it is therein one or two.
The process conditions of the joint absorbing reaction are：The absorption temperature of two devices all can be in 0--70 degree Celsius and normal pressure
Under carry out, the pH of two absorbing liquids is controlled 4-14.
The Liquid Flow condition of the joint absorbing reaction device is：The gas of two devices is roused through the bottom-up liquid layer of crossing of liquid
Bubble absorbs, and absorbing liquid by the bottom-up circulation of pump circulation and can be sprayed, and tail gas is excluded from Hou Ta upper ends.
In the washing tower of the technique based on scrubbing CO_2, to remove supplemented by nitrogen oxides, there is oxidation with
And reaction；In oxidizing tower based on removing nitric oxide, supplemented by scrubbing CO_2, and while generation oxidoreduction is with
And reaction.Product in two towers based on sulfate, sulphite, nitrate, nitrite, recoverable.
The device fabrication of the wet method double tower joint simultaneous SO_2 and NO removal technique that the present invention is provided is simple, raw material is easy to get, and invests
Decline much with running cost compared traditional handicraft, floor space is little, efficiency is high, can reach the nitrogen oxides removal efficiency of 75-98%
With the desulfuration efficiency of more than 90-99%.
Description of the drawings
Accompanying drawing 1 is the structural representation of the invention simultaneous SO_2 and NO removal；
It is labeled as in accompanying drawing：1- alkali liquor absorption towers, 2- oxidants absorption tower, 3- alkali liquor storage tanks, 4- oxidants and auxiliary agent storage tank, 5-
NaOH solution circulating pump, 6- oxidation solution circulating pumps, 7- exhanst gas outlets, 8- exhanst gas outlets, 9, alkali liquor outlet, 10- oxidation solution outlets,
11st, 12- is respectively alkali liquor and oxidation solution and auxiliary agent plus entrance.
Specific embodiment
Wet method double tower joint simultaneous SO_2 and NO removal technique as shown in accompanying drawing 1, flue gas is entered from the bottom of alkali liquor absorption tower,
Oxidative absorption tower bottom is directly entered from the discharge of alkali liquor absorption top of tower, from oxidizing tower top discharge, the cigarette in two absorption towers
Gas is fully contacted with absorbing liquid, and the nitrogen oxides and sulfur dioxide in flue gas are discharged after absorption cleaning, alkali liquor and oxidative absorption
Liquid is stored in respectively in fresh alkali liquor and oxidative absorption liquid storage tank, is circulated with pump and is used, and to the absorption of part circulation
Liquid and the solid sediment periodic exhaustion for generating, are recycled into rear treating groove.As required periodically from fresh alkali
Liquid storage tank and oxidant storage tank are filled into from circulating storage groove top.
Embodiment 1
In 400ml aqueous solutions, compound concentration is the potassium permanganate solution of 0.04mol/L, and mixed flue gas flow is 600mL/
Min, oxygen content is 0.3-0.6%, carbon dioxide 18.1%, nitrogen dioxide 99.4ppm, and sulfur dioxide initial concentration is
1193ppm, nitric oxide initial concentration is 1968ppm, and under 15 degrees Celsius of room temperature and normal pressure, gas is from reactor bottom bubbling
By liquid layer, flow out from reactor head and discharge.The concentration for measuring exit sulfur dioxide with M9000 gas analysers is 0, one
The concentration of nitrogen oxide is 370ppm, and the concentration of nitrogen dioxide is distinguished for the conversion ratio of 18.5ppm, its sulfur dioxide and nitrogen oxides
For 100% and 80.3%.
Embodiment 2
In the experiment condition of embodiment 1, other conditions are basically unchanged, only in 0.04mol/L potassium permanganate potassium absorbing liquids again
The sodium hypochlorite of 20mL is added, sulfur dioxide in flue gas is measured and is respectively into the concentration of reactor and outflow reactor
1305ppm and 0ppm, nitric oxide and nitrogen dioxide flow in and out the concentration of reactor and are respectively 1964 ppm, 99.3ppm
With 141ppm, 7.6ppm, the conversion ratio of its sulfur dioxide and nitrogen oxides is respectively 100% and 88%.
Embodiment 3
In 400ml aqueous solutions, compound concentration is the sodium chlorite solution of 0.04mol/L, and mixed flue gas flow is 600mL/
Min, oxygen content is 0.3-1.0%, carbon dioxide 17.5-18.2%, nitrogen dioxide 97.3ppm, and sulfur dioxide initial concentration is
1351ppm, nitric oxide initial concentration is 1924ppm, and experimental period is 2 hours under 15 degrees Celsius of room temperature and normal pressure, gas
From reactor bottom bubbling by liquid layer, flow out from reactor head and discharge.The concentration for measuring exit sulfur dioxide is 0,
Nitric oxide production mean concentration is 9ppm, and the mean concentration of nitrogen dioxide is turning for 0.3ppm, its sulfur dioxide and nitrogen oxides
Rate is respectively 100% and 99.7%.
Embodiment 4
With the container of two 1L, tandem compound is carried out, be respectively charged into sodium hydroxide 2g and potassium permanganate 2.53g, mixed flue gas stream
Measure as 65L/h, oxygen content is 0.2-0.4%, under 25 degrees Celsius of normal pressure, carbon dioxide 17.8-18.3%, nitrogen dioxide
97.3ppm, sulfur dioxide initial concentration is 1351ppm, and nitric oxide initial concentration is 1924ppm, in 15 degrees Celsius of room temperature and
Experimental period is 2 hours under normal pressure, and gas, by liquid layer, flows out from reactor head and discharge from reactor bottom bubbling.Measure
The concentration of exit sulfur dioxide is 0, and nitric oxide production mean concentration is 9ppm, and the mean concentration of nitrogen dioxide is
The conversion ratio of 0.3ppm, its sulfur dioxide and nitrogen oxides is respectively 100% and 99.7%.
Embodiment 5
With the container tandem compound of two 1L, 400mL water is filled respectively, add sodium hydroxide 2g and sodium chlorite 0.9g, mix
Flue gas flow is 100L/h, and oxygen content is 0.4-1.2%, under 18 degrees Celsius of normal pressure, carbon dioxide 17.6-18.1%, and dioxy
Change nitrogen 210ppm, sulfur dioxide initial concentration is 3538ppm, and nitric oxide initial concentration is 4200ppm, in 15 degrees Celsius of room temperature
Under normal pressure, gas, by liquid layer, flows out from reactor head and discharges from reactor bottom bubbling.Measure exit sulfur dioxide
Concentration be 0, nitric oxide production mean concentration is 605ppm, and the mean concentration of nitrogen dioxide is 29.6ppm, its sulfur dioxide
100% and 84.5% are respectively with the conversion ratio of nitrogen oxides.
Embodiment 6
In diameter 0.12m, two identical cylinder towers of high 1m, tandem compound is carried out, first tower is followed equipped with tower reactor
Ring liquid bath, volume 19L adds 202g sodium hydroxide, the tower reactor in another oxidative absorption tower that oxidation solution circulating slot 89L is housed,
Potassium permanganate concentration is added to be 0.4mol/L, alkali liquor, by downward spray-absorption is carried out at the top of pump circulation to tower, is followed with oxidation solution
Circulation maintains 8-18L/min, and the flow of flue gas is sulfur dioxide and nitrogen oxides total concentration point that 1.0m3/h. works as entrance
Not Wei 1400ppm and 1064ppm when, measure sulfur dioxide average in the flue gas of exit and nitrogen oxides total concentration be respectively
The average removal rate of 0ppm and 140ppm, its sulfur dioxide and nitrogen oxides is respectively 100% and 86.8%.
Embodiment 7
In cylinder tower double-column in series group technology in embodiment 6, sodium chlorite and copper nitrate are separately added into, concentration is
0.01mol/L and 0.001mol/L, is equipped with potassium hydroxide 0.02mol/LpH=14 in second tower, and alkali liquor is with oxidation solution by pump
Circulate downward spray-absorption, the flow of flue gas is 1.8 m3/h. when the sulfur dioxide and nitrogen oxides total concentration of entrance are respectively
During 2643ppm and 1718ppm, measure sulfur dioxide average in the flue gas of exit and nitrogen oxides total concentration is respectively 120ppm
And the average removal rate of 210ppm, its sulfur dioxide and nitrogen oxides is respectively 95.5% and 87.7%.
Embodiment 8
In cylinder tower double-column in series group technology in same embodiment 6, potassium permanganate 590g, carbon are added in water respectively
Sour sodium auxiliary agent 20g and sodium hydroxide 650g, respectively 8.5 and pH=14.Flue gas first passes through liquid layer from two absorbing liquids of tower reactor
Upwards bubbling is entered in tower, then via the downward spray-absorption of circulating pump, the tail gas after absorption is excluded from top below.Flue gas
Flow is 3.0 m3/h, continuous operation 3 hours. when the sulfur dioxide and nitrogen oxides total concentration of entrance are respectively 1800-
During 2200ppm and 770-880ppm, measure sulfur dioxide average in the flue gas of exit and nitrogen oxides total concentration is respectively 60-
The average removal rate of 110ppm and 80-120ppm, its sulfur dioxide and nitrogen oxides is respectively 95-97% and 86-90%.
Claims (8)
1. a kind of liquid phase joint absorbs flue gas and desulfurizing and denitrifying integral process, it is characterised in that：Described absorbing liquid is two
Kind, one kind is highly basic, and another kind is strong oxidizer and the aqueous solution of auxiliary agent, and both are used in series.
2. require that described strong alkaline substance includes according to right 1：Potassium hydroxide, sodium hydroxide, calcium hydroxide etc. therein one
Kind.
3. require that described oxidizing species include according to right 1：Hydrogen peroxide, sodium hypochlorite, potassium permanganate, sodium chlorite,
And combinations thereof, its auxiliary agent include copper nitrate, ferric nitrate, magnesium nitrate, sodium carbonate, it is therein one or two.
4. the highly basic aqueous solutions of absorbent according to claim 1 and claim 2, it is characterised in that：Described absorbing liquid
The concentration of middle highly basic is 0.001-1.00mol/L.
5. the Strong oxdiative aqueous solutions of absorbent according to claim 1 and claim 3, it is characterised in that：Described absorption
The concentration of oxidizing species is 0.001-1.00mol/L in liquid.
6., according to claim 1, the tandem arrangement for absorbing is combined, it is characterised in that：Highly basic absorption plant absorbs with strong oxidizer
The ordering of device is, can with aqueous alkali in front strong oxidizer rear, it is also possible to strong oxidizer rear, also may be used in front aqueous alkali
With the exclusive use of one of both.
7. according to claim 1, the process conditions of the joint absorbing reaction, it is characterised in that：The absorption temperature of two devices is all
Can carry out under 0--70 degree Celsius of normal pressure, the pH of absorbing liquid is controlled 4-14.
8. according to claim 1, the Liquid Flow condition of the joint absorbing reaction device, it is characterised in that：The gas of two devices
Through the bottom-up liquid layer bubble absorption excessively of liquid, absorbing liquid is by the bottom-up circulation of pump circulation and sprays.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710017583.2A CN106621755A (en) | 2017-01-11 | 2017-01-11 | Integral technology using liquid phase to jointly absorb glue gas for simultaneous desulfurizing and denitration |
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| CN201710017583.2A CN106621755A (en) | 2017-01-11 | 2017-01-11 | Integral technology using liquid phase to jointly absorb glue gas for simultaneous desulfurizing and denitration |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364729A (en) * | 2018-12-14 | 2019-02-22 | 太和县大华能源科技有限公司 | The purification device for the sewage exhaust gas that reviver industry generates |
| CN109453631A (en) * | 2018-12-18 | 2019-03-12 | 姚传亮 | A kind of industrial production waste gas treatment process |
| CN109621670A (en) * | 2018-12-14 | 2019-04-16 | 四川龙蟒钛业股份有限公司 | A kind of method of promotor aid in treatment sulfuric acid titanium white calcining tail gas |
| CN113457421A (en) * | 2021-07-24 | 2021-10-01 | 德清绿能热电有限公司 | Oxidation absorption liquid for boiler flue gas treatment and boiler flue gas treatment system |
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| CN1883768A (en) * | 2006-05-29 | 2006-12-27 | 浙江大学 | Wet method combined process for desulfurization and denitration for chlorine-containing strong oxidizer absorption liquid |
| CN102580496A (en) * | 2012-03-14 | 2012-07-18 | 杭州天蓝环保设备有限公司 | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device |
| CN103157358A (en) * | 2013-04-15 | 2013-06-19 | 武汉大学 | Flue gas denitration method based on advanced oxidization technology |
| CN103272468A (en) * | 2013-06-13 | 2013-09-04 | 北京中环新锐环保技术有限公司 | Absorption tower for simultaneously removing sulfur dioxide and nitrogen oxide in smoke |
| CN104474857A (en) * | 2014-11-20 | 2015-04-01 | 浙江大学 | Method and device for pre-oxidizing and absorbing NOx and SO2 in coal-fired flue gas by active molecules |
| CN104971594A (en) * | 2014-04-08 | 2015-10-14 | 上海三卿环保科技有限公司 | Gas phase oxidization-liquid phase oxidization-absorption three-section type dry-wet-process flue gas denitration process |
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| CN1883768A (en) * | 2006-05-29 | 2006-12-27 | 浙江大学 | Wet method combined process for desulfurization and denitration for chlorine-containing strong oxidizer absorption liquid |
| CN102580496A (en) * | 2012-03-14 | 2012-07-18 | 杭州天蓝环保设备有限公司 | Liquid-phase oxidation multistage absorbed flue gas desulfurization and denitrification technology and device |
| CN103157358A (en) * | 2013-04-15 | 2013-06-19 | 武汉大学 | Flue gas denitration method based on advanced oxidization technology |
| CN103272468A (en) * | 2013-06-13 | 2013-09-04 | 北京中环新锐环保技术有限公司 | Absorption tower for simultaneously removing sulfur dioxide and nitrogen oxide in smoke |
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| CN104474857A (en) * | 2014-11-20 | 2015-04-01 | 浙江大学 | Method and device for pre-oxidizing and absorbing NOx and SO2 in coal-fired flue gas by active molecules |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364729A (en) * | 2018-12-14 | 2019-02-22 | 太和县大华能源科技有限公司 | The purification device for the sewage exhaust gas that reviver industry generates |
| CN109621670A (en) * | 2018-12-14 | 2019-04-16 | 四川龙蟒钛业股份有限公司 | A kind of method of promotor aid in treatment sulfuric acid titanium white calcining tail gas |
| CN109453631A (en) * | 2018-12-18 | 2019-03-12 | 姚传亮 | A kind of industrial production waste gas treatment process |
| CN113457421A (en) * | 2021-07-24 | 2021-10-01 | 德清绿能热电有限公司 | Oxidation absorption liquid for boiler flue gas treatment and boiler flue gas treatment system |
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Application publication date: 20170510 |