CN100490943C - Apparatus for processing waste air including oxynitride - Google Patents

Apparatus for processing waste air including oxynitride Download PDF

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Publication number
CN100490943C
CN100490943C CNB2007100615152A CN200710061515A CN100490943C CN 100490943 C CN100490943 C CN 100490943C CN B2007100615152 A CNB2007100615152 A CN B2007100615152A CN 200710061515 A CN200710061515 A CN 200710061515A CN 100490943 C CN100490943 C CN 100490943C
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packed absorber
absorption
gas
absorption liquid
liquid
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CNB2007100615152A
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Chinese (zh)
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CN101036851A (en
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胡双启
晋日亚
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中北大学
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Abstract

The invention relates to a processing method and a processing device for nitric oxides-containing exhaust gas. The processing method comprises the steps of collecting the nitric oxides-containing exhaust gas into a nitric oxide oxidator to have an oxidation react with ozone from ozone generator to convert the whole nitric oxides into CO2; introducing the CO2-containing exhaust gas and polyethylene glycol absorption liquid into a first filling absorption tower via an gas inlet and a liquid inlet respectively to have a counter current contact in the filling layer, after the first-stage absorption, introducing said gas obtained by first-stage absorption into a second filling absorption tower to have a second stage absorption, and exhausting the absorbed exhaust gas via an exhaust port. Polyethylene glycol is used as absorbent in the invention with stable absorption capability and high absorption saturation, thereby improving removing rate of nitric oxides and reducing processing cost of nitric oxides-containing exhaust gas.

Description

The treating apparatus of nox contained waste gas

Technical field

The present invention relates to a kind of processing method of nox contained waste gas, specifically relate to a kind of method of utilizing polyethylene glycol to handle nox contained waste gas as absorption liquid.The invention still further relates to a kind for the treatment of apparatus that is used to realize this method.

Background technology

Nitrogen oxide (NOx) is one of atmosphere pollution that has a large capacity and a wide range.Its main harm is: 1. shining upon down, can a series of photochemical reactions take place with hydrocarbon, generate photochemical fog; 2. generation acid rain; 3. the nitrogen oxide that is present in the stratosphere has destruction to ozone layer; 4. human respiratory is produced spread effect, even bronchitis takes place; 5. crop production reduction, trees withered or died, metal are damaged or the like.In recent years, by SO 2, the atmosphere pollution that causes of CO and flue dust decreases, but along with the fast development of petrochemical industry, the scope of application of nitric acid and consumption phenomenal growth produce that increase in the source contain NOx waste gas, scale strengthens, the concentration of nitrogen oxide in atmosphere is on the rise, and environmental issue is very urgent.

The treatment technology of nitrogen oxide mainly contains dry method and wet method two big classes in the flue gas at present.Dry method treatment technology comprises catalytic reduction method, absorption method and electron beam irradiation method etc.Catalytic reduction method is under catalyst action, utilizes reducing agent that nitrogen oxide is reduced to harmless nitrogen.This method is used in the improvement of boiler smoke more, and its catalytic temperature generally needs more than 300 ℃, can also recovery section heat energy in governance process, but investment and operating cost are higher, are difficult in medium-sized and small enterprises universal.As patent 99126262 disclosed a kind of method and apparatus of handling high concentration nitrogen dioxide waste gas promptly be adopt with liquefied gas with contain the method that nitrogen dioxide gas burns in special-purpose incinerator, its ignition temperature reaches 800～1400 ℃.Absorption method is with adsorbents such as silica gel, molecular sieve, active carbons nitrogen oxides from exhaust gas to be adsorbed, and desorb and water or alkali lye absorb to remove nitrogen oxide then.Reasons such as this method is many owing to the adsorbent consumption, equipment is huge, regeneration frequency height cause that investment is big, operating cost is high, regulation effect is unstable, therefore use not extensive.Electron beam irradiation method then is to adopt electron beam irradiation combustion tail gas, make the nitrogen oxide and the solia particle that contain in the tail gas form the acid mist mixture, with electric vacuum cleaner it is separated, this method still is in the operation of bench-scale testing stage at present, does not reach the industrially scalable degree as yet again.The major defect of dry method treatment technology is to reclaim the nitrogen oxide resource effectively.

The method of wet-treating nitrogen oxide is many, mainly adopts single-stage or two-stage absorption process such as packed tower, bubble column, sieve-plate tower.Aspect the absorbent selection, enterprise is according to production characteristics separately, and some utilizes clear water as absorbent, or adopts rare nitric acid to carry out Physical Absorption as absorbent; Some adopts akaline liquids such as sodium carbonate, NaOH to carry out chemical absorbing as absorbent and handles.Wet-treating has advantages such as technology and equipment are simple, small investment, and some can also reclaim NOx, has certain economic benefits, but that shortcoming is a purification efficiency is low.

The main method of above-mentioned several improvement nitrogen oxide is carried out the Technological Economy estimation, and the result shows that except that alkali absorb method still has certain profit economically, other method all causes loss economically to a certain extent.Though alkali absorption method can carry out under normal pressure, absorption rate is fast, and exhaust emissions is up to standard easily, have reduced investment, advantage that operating cost is lower, but the salt value of the product that generates is low, and the alkali lye system has corrosivity usually simultaneously, and careless manipulation causes secondary pollution easily.

For many years, the researcher is being devoted to the process modification research of nitrogen oxide wet-treating always, comprise attempting absorbing, using active filler etc. with a plurality of tower series multistages, but effect is very limited, is difficult to reach processing requirements.

Summary of the invention

The purpose of this invention is to provide a kind of processing method of new nox contained waste gas, this processing method as absorbent, can improve removal efficiency of nitrogen oxides with polyethylene glycol, reduces the processing cost of nitrous oxides exhaust gas.

A kind for the treatment of apparatus that is used to realize nox contained waste gas processing method of the present invention is provided, and is another goal of the invention of the present invention.

Polyglycol solution has good assimilation effect to nitrogen dioxide, and absorbent properties are stable.According to polyethylene glycol at absorption of N O 2The infrared spectrum of front and back changes, and thinks that polyethylene glycol is at absorption of N O 2After, with NO 2In conjunction with the new construction that has formed a kind of similar nitrate:

This combination makes the ether-oxygen bond of original polyethylene glycol weaken to some extent, causes the characteristic absorption peak skew of ether-oxygen bond.In the new construction, NO 2N and the adhesion between the O of polyethylene glycol much more weak than the N in the typical nitrate structure-O key.

Principle thus, the present invention is earlier with the process of the nitrogen oxide in nox contained waste gas ozone oxidation, all change nitrogen dioxide gas into, adopt the organic compound polyethylene glycol again, utilize the two-stage tandem packed absorber that nitrogen dioxide is absorbed processing as absorption liquid.

The processing method of nox contained waste gas of the present invention specifically may further comprise the steps:

A, nox contained waste gas is fed in the nitrogen oxide oxidator, give birth to oxidation reaction, nitrogen oxides from exhaust gas all is converted into nitrogen dioxide with ozone hybrid concurrency from ozone generator;

B, the waste gas that contains nitrogen dioxide and absorption liquid are introduced in first packed absorber by air inlet and inlet respectively, counter current contacting in the packing layer of first packed absorber, after carrying out first order absorption, waste gas after the absorption and absorption liquid are discharged by exhaust outlet and leakage fluid dram respectively;

Waste gas after c, the absorption is introduced in second packed absorber by air inlet, carries out second level absorption at packing layer and absorption liquid counter current contacting, after the tail gas after the absorption is discharged by exhaust outlet, through blast pipe emptying.

The present invention adopts the absorption liquid of polyethylene glycol as nitrogen dioxide, particularly, is to adopt a kind of in polyethylene glycol 100, Macrogol 200, Liquid Macrogol or the PEG400 as absorption liquid.

Contain waste gas and polyethylene glycol absorption liquid counter current contacting in the packing layer of packed absorber of nitrogen dioxide, carry out NO 2Absorption and improvement, the gas-liquid mass ratio that suits that feeds absorption liquid and waste gas in the packed absorber is 2～5: 1.

Be used to realize that a kind of nox contained waste gas treating apparatus of the above-mentioned processing method of the present invention includes ozone generator, the nitrogen oxide oxidator, first packed absorber and second packed absorber, ozone generator is connected with the nitrogen oxide oxidator respectively with the nitrous oxides exhaust gas air inlet pipe, nitrous oxides exhaust gas and ozone feed in the nitrogen oxide oxidator and carry out oxidation reaction, nitrogen oxides from exhaust gas all is converted into nitrogen dioxide, the outlet of nitrogen oxide oxidator connects the air inlet of first packed absorber, the exhaust outlet of first packed absorber is connected with the air inlet of second packed absorber, the exhaust outlet of second packed absorber connects blow-down pipe, polyethylene glycol absorption liquid basin connects the inlet at first packed absorber and the second packed absorber top respectively, the liquid outlet that is positioned at first packed absorber and second packed absorber bottom then is connected with the absorption liquid sump pit, the waste gas that enters by tower bottom with from the cat head spray and under absorption liquid in the packing layer counter current contacting, the absorption liquid that has absorbed nitrogen dioxide enters in the absorption liquid sump pit, and the gas after nitrogen dioxide is removed in the secondary absorption is from blow-down pipe emptying.

Nox contained waste gas treating apparatus of the present invention is respectively on the connecting pipeline between the air inlet of the exhaust outlet of first packed absorber and second packed absorber, and on the exhaust outlet of second packed absorber and the connecting pipeline between the blow-down pipe, respectively be connected with an air-spray device, form negative pressure by the air-spray device in the absorption tower exhaust ports, for gas provides a part mobile power.

Nox contained waste gas treating apparatus of the present invention also is provided with the absorption liquid liquid distributor that is connected with the cat head inlet at first packed absorber with the top of second packed absorber respectively, the bottom is provided with the nitrogen dioxide gas pipe that connects air inlet at the bottom of the tower, with evenly gas distribution and cloth liquid in tower.

Absorption liquid sump pit of the present invention is communicated with the absorption liquid basin, and the polyethylene glycol absorption liquid can recycle.When having absorbed NO 2When the absorption liquid of gas does not reach capacity, send into the absorption liquid basin and recycle, absorption liquid reaches and absorbs when saturated, is then discharged by tapping valve, reuses after the regeneration.Experimental result shows that polyethylene glycol is to NO 2The saturated absorption degree be polyethylene glycol: NO 2=1: 4.5, saturated absorption liquid is bottle green.

In the nox contained waste gas treating apparatus of the present invention, all equipment that relate to, pipeline, filler, pipe fitting etc. all adopt resistant material CPVC to make.

The present invention earlier through ozone oxidation, makes NO with industrial nitrogen oxide tail gas xAll change NO into 2, adopt the organic compound polyethylene glycol as absorption liquid again, adopt two-stage tandem absorption tower absorption pattern that NOx is absorbed improvement.Filler is set to increase gas-liquid contact area, NO in the absorption tower 2Gas is risen in tower and is flowed by the even gas distribution in tower of gas pipe, and evenly to Ta Neibu liquid, spray and descending is with rising NO by liquid distributor for the polyethylene glycol absorption liquid 2Gas absorbs in the packing layer counter current contacting, has constituted the two-stage absorption tower of the gas, liquid circulatory system.Tail gas after being absorbed is discharged in the atmosphere through blow-down pipe.

The present invention is provided with the air-spray device in the back on every grade of absorption tower, and the air-spray device has diluted the NO that is discharged by the absorption tower on the one hand 2Gas, the exhaust ports on the absorption tower forms negative pressure on the other hand, with the NO before the absorption tower 2Measuring pump provides the power of gas flow together.Through overtesting, above-mentioned structure of the present invention obtains satisfied result.

The present invention adopts polyethylene glycol as NO 2The absorbent of gas, absorbent properties are stable, absorb the saturation degree height, polyethylene glycol: NO 2Mass ratio the highlyest can reach 1: 4.5, and the polyethylene glycol absorption liquid can recycle, the absorption liquid after reaching capacity both can be used as liquid fuel, the recycling of also can regenerating.Therefore, absorbent amount ratio of the present invention is wanted much less with rare nitric acid, and does not have the problem of by-product NO.

Description of drawings

Fig. 1 is the structural representation of nox contained waste gas treating apparatus of the present invention.

The specific embodiment

Embodiment 1

The structure of nox contained waste gas treating apparatus of the present invention mainly is made up of ozone generator 1, nitrogen oxide oxidator 3, first packed absorber 6, second packed absorber 15, polyethylene glycol absorption liquid storage tank 26 and absorption liquid sump pit 24 as shown in Figure 1.The industry nitrous oxides exhaust gas enters in the nitrogen oxide oxidator 3 through nitrogen oxide flow measurement pump and nitrous oxides exhaust gas air inlet pipe 2, the ozone that ozone generator 1 produces also enters in the nitrogen oxide oxidator 3 through ozone flow measuring pump, nitrogen oxide is carried out oxidation, make NO xAll be converted into NO 2Gas.

Absorption liquid in the polyethylene glycol absorption liquid basin 26 under the dynamic action of feed pump through valve regulated, control by the absorption liquid flow controller, enter in the tower through the inlet 9 at first packed absorber, 6 tops and the inlet 17 at second packed absorber, 15 tops respectively, under the effect of absorption liquid liquid distributor 8,16, descend along the absorption tower spray.

NO 2Gas enters first packed absorber 6 by after the measuring pump metering by air inlet 4, by the even gas distribution in tower of gas pipe 5, and flows along rising on the absorption tower, enters packing layer 7, and following absorption liquid counter current contacting absorbs remaining NO after absorbing with spray at this 2Gas is discharged the back by exhaust outlet 10 and enter second packed absorber 15 through air inlet 13 under the effect of air-spray device 11.The main effect of second packed absorber 15 is that the NO2 gas that first packed absorber 6 does not absorb is fully further absorbed, absorption pattern is identical with first packed absorber 6, by the even gas distribution in tower of gas pipe 14, and it is mobile along rising on the absorption tower, enter packing layer 7, absorption liquid counter current contacting under with spray absorbs, and the tail gas after the absorption is discharged the back by exhaust outlet 18 and taken out of by air-spray device 19 and discharged by blow-down pipe 21.Air-spray device 11 and 19 provides air by air pump 12 and 20 respectively.

The liquid outlet 22 that is positioned at first packed absorber 6 and second packed absorber, 15 bottoms is connected with absorption liquid sump pit 24 by tapping valve with 23, has absorbed NO 2The absorption liquid of gas enters in the absorption liquid sump pit 24.Absorption liquid sump pit 24 is communicated with absorption liquid basin 26, when having absorbed NO 2When the absorption liquid of gas does not reach capacity, send into absorption liquid basin 26 by the absorption liquid circulating pump and recycle, when absorption liquid become bottle green reach absorb saturated after, discharge through tapping valve 25, carry out the regeneration of absorption liquid and use.

Also be provided with sampling at blow-down pipe 21 places and detect NO in the tail gas 2The sample cock 27 of gas content.

At beginning absorption of N O 2Before the gas, after elder generation uses the polyethylene glycol absorption liquid that the fillers in first packed absorber 6 and second packed absorber 15 are all soaked,, and then begin the polyglycol solution absorption processing operation of nox contained waste gas according to above-mentioned steps with the absorption liquid emptying.

Embodiment 2

Adopt the nox contained waste gas treating apparatus and the processing method of the embodiment of the invention 1 that certain enterprise's nox contained waste gas is carried out integrated treatment.The Raw exhaust amount 694m of this enterprise's nox contained waste gas 3/ h, original discharge concentration 18000mg/m 3

Treating apparatus is according to embodiment 1 design, and some specific design parameters are as follows:

1. packed absorber adopts Φ 159cm * 10mCPVC to manage making, the two-stage absorption tower is set;

Every grade of absorption tower be divided into two-layer, bed stuffing height 2.1m in the absorption tower;

3. adopt Liquid Macrogol as absorption liquid, absorption liquid recycles by circulating pump;

4. first order packed absorber gas-liquid mass ratio is 2: 1, and second level packed absorber gas-liquid mass ratio is 5: 1;

5. the ozone addition in the nitrogen oxide oxidator is 5m 3/ h;

6. fall 3 * 10 according to the filler theoretical pressure -4MPa/m and calculating fallen in loine pressure, air-spray device pressure is 0.2MPa behind the design absorption tower.

By measuring the NO in the discharging tail gas 2Content is estimated the effect for the treatment of apparatus.

Measure scene temperature: 16.1 ℃;

On-the-spot atmospheric pressure: 92.03Kpa;

Sampling position: near point: apart from exhaust port 10cm; Far point: apart from exhaust port 3m;

Sampling time: 20min;

Sampling flow: 0.5L/min;

Sampling volume 10L.

The result that collected specimens is measured shows: handle NO in the tail gas of back 2Content near point (thief hatch is apart from exhaust port 10cm) is 1.78mg/m 3, far point (thief hatch is apart from exhaust port 3m) is 0.0975mg/m 3, the nox contained waste gas obvious processing effect.

Claims (3)

1, a kind for the treatment of apparatus of nox contained waste gas, include ozone generator (1), nitrogen oxide oxidator (3), first packed absorber (6) and second packed absorber (15), ozone generator (1) is connected with nitrogen oxide oxidator (3) respectively with nitrous oxides exhaust gas air inlet pipe (2), nitrous oxides exhaust gas and ozone feed in the nitrogen oxide oxidator (3) and carry out oxidation reaction, nitrogen oxides from exhaust gas all is converted into nitrogen dioxide, the outlet of nitrogen oxide oxidator (3) connects the air inlet (4) of first packed absorber (6), the exhaust outlet (10) of first packed absorber (6) is connected with the air inlet (13) of second packed absorber (15), the exhaust outlet (18) of second packed absorber (15) connects blow-down pipe (21), polyethylene glycol absorption liquid basin (26) connects the inlet (9 at first packed absorber (6) and second packed absorber (15) top respectively, 17), be positioned at the liquid outlet (22 of first packed absorber (6) and second packed absorber (15) bottom, 23) then be connected with absorption liquid sump pit (24), the waste gas that enters by tower bottom with from the cat head spray and under absorption liquid in packing layer (7) counter current contacting, the absorption liquid that has absorbed nitrogen dioxide enters in the absorption liquid sump pit (24), gas after nitrogen dioxide is removed in the secondary absorption is from blow-down pipe (21) emptying
Wherein, respectively be connected with an air-spray device (11,19) on the connecting pipeline between the air inlet (13) of the exhaust outlet (10) of first packed absorber (6) and second packed absorber (15) and on the exhaust outlet (18) of second packed absorber (15) and the connecting pipeline between the blow-down pipe (21).
2, the treating apparatus of nox contained waste gas according to claim 1, it is characterized in that being provided with absorption liquid liquid distributor (8 at the top of first packed absorber (6) and second packed absorber (15) respectively, 16), connect with the inlet (9,17) of cat head respectively.
3, the treating apparatus of nox contained waste gas according to claim 1, it is characterized in that first packed absorber (6) and the bottom of second packed absorber (15) respectively be provided with one be connected tower at the bottom of air inlet (4,13) nitrogen dioxide gas pipe (5,14).
CNB2007100615152A 2007-02-09 2007-02-09 Apparatus for processing waste air including oxynitride CN100490943C (en)

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CN102772987A (en) * 2012-07-24 2012-11-14 徐州市龙泰臭氧设备制造有限公司 Waste gas oxidation treatment system
CN103394279A (en) * 2013-08-15 2013-11-20 北京化工大学 System device and method for deeply removing nitric oxide in industrial tail gas

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CN105214457B (en) * 2014-06-05 2018-04-17 魏雄辉 A kind of fume desulfuring and denitrifying Processes and apparatus
CN103977681A (en) * 2014-06-06 2014-08-13 长沙奥邦环保实业有限公司 Denitration method for high-concentration nitric oxide flue gas
CN106031841B (en) * 2015-03-20 2020-01-07 北京博源恒升高科技有限公司 Gas denitration process and equipment
CN106031844B (en) * 2015-03-20 2020-01-07 江西永丰博源实业有限公司 Desulfurization and denitrification agent
CN106145071A (en) * 2015-04-03 2016-11-23 北京航天试验技术研究所 A kind of dinitrogen tetroxide spent liquor processing means and method for treating waste liquid thereof
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CN102772987A (en) * 2012-07-24 2012-11-14 徐州市龙泰臭氧设备制造有限公司 Waste gas oxidation treatment system
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