CN102836614A - System and method for adsorbing nitrogen oxides by use of mordenite - Google Patents
System and method for adsorbing nitrogen oxides by use of mordenite Download PDFInfo
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- CN102836614A CN102836614A CN2012103385492A CN201210338549A CN102836614A CN 102836614 A CN102836614 A CN 102836614A CN 2012103385492 A CN2012103385492 A CN 2012103385492A CN 201210338549 A CN201210338549 A CN 201210338549A CN 102836614 A CN102836614 A CN 102836614A
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Abstract
The invention discloses a system for adsorbing nitrogen oxides by use of mordenite. The system comprises a pretreatment system, an adsorption-desorption system and a cooling collection system in sequential connection. The method comprises the steps of using a blower to convey waste gas to a cooling tower, and cooling to (-5) to 5 DEG C; uniformly distributing gas and intercepting particulates through a screen filter; introducing into a first, a second, a third and a fourth adsorber, all of which are filled with mordenite, wherein at this moment, a valve between the first adsorber and a heater is in closed state; introducing the liquid after adsorption by the first adsorber into a cooler, and cooling to 15-25 DEG C; counting acid generation amount through an acid metering tank and regulating flow through a rotor flow meter; and finally collecting. The system and method have the advantages of continuous operation, repeated regeneration and utilization of adsorbent, little adsorbent consumption, high adsorption efficiency, and high recycled utilization benefits.
Description
Technical field
The present invention relates to the nitrogen oxide process field, relate in particular to the system and the method thereof that adopt the modenite nitric oxide adsorption.
Background technology
Nitrogen oxide comprises multiple compound, like nitrous oxide, nitric oxide, nitrogen dioxide, nitrogen trioxide, dinitrogen tetroxide and dinitrogen pentoxide etc.Except that nitrogen dioxide, other nitrogen oxide are all extremely unstable, meet light, wet or thermal change becomes nitrogen dioxide and nitric oxide, and nitric oxide becomes nitrogen dioxide again.Therefore, what contact in the occupational environment is that several kinds of admixture of gas often are called the smoke of gunpowder (gas), is mainly nitric oxide and nitrogen dioxide, and is main with nitrogen dioxide.Nitrogen oxide all has toxicity in various degree, under the high-temp combustion condition, and NO
XMainly the form with NO exists, the NO of initial discharging
XMiddle NO accounts for 95%.But NO very easily reacts with airborne oxygen in atmosphere, generates NO
2So, NO in the atmosphere
XGenerally with NO
2Form exist.Airborne NO and NO
2Through photochemical reaction, transform each other and reach balance.Big or when having cloud and mist to exist in temperature, NO
2Further form second important acid branch---the nitric acid (HNO in the acid rain with the hydrone effect
3).When having catalyst to exist, as add suitable meteorological condition, N0
2Be transformed into speeding up of nitric acid.Particularly work as NO
2With SO
2When existing simultaneously, catalysis each other, the speed that forms nitric acid is faster; Main suitable ammonia and nitrogen oxide generation chemical reaction neutralize nitrogen oxide in the industry, and ammonia and decompose nitrogen oxides reaction back produce nitrogen and water, but ammoniacal liquor volatilizees easily; Cause secondary pollution, the adsorbent that the adsorption method for purifying nitrogen oxide is commonly used at present has molecular sieve, activated carbon, silica gel, mud coal etc., and absorption method is because the adsorbents adsorb capacity is little; The adsorbent use amount is big, and equipment is huge, and the regeneration period is long; Technological deficiencies such as intermitten service fail to use on a large scale always, and poor to the adsorption effect of nitrogen oxide, are unfavorable for the development of enterprise.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of system and method thereof that adopts the modenite nitric oxide adsorption is provided, this system and method thereof can be moved continuously, and the regeneration period is short, and adsorbent is reused, good absorbing effect.
The absorption principle of native system is: the molecular sieve of use is a modenite natural or through processing; Be a kind of silica alumina ratio very high (greater than 10-13), heat endurance and the very high alumino-silicate of acid resistance; Commonly used have a h-mordenite, and specific area can reach 500-1000m
2/ g, polarity is very strong.
When the waste gas of nitrogen oxide passes through modenite, the NO in the waste gas
2And H
2The O molecule is optionally adsorbed from the teeth outwards, and reacts:
NO
2→NO
2 ＊
?H
2O
→H
2O
＊
NO
2 ＊+H
2O
＊ →2HNO3 ＊ +NO
The NO that emits just face on is catalyzed into NO with oxygen at zeolite together with the NO in the waste gas
2, generate HNO with the water reaction
3
NO
→NO
＊
O
2→O
2 ＊
2NO
＊+O
2 ＊ →NO
2 ＊
Adsorb saturated after, heat up (like steam) with the HNO that generates with heater
3Desorption comes out, and the modenite behind the desorption is regenerated through drying, gets into adsorbed state again.
The object of the invention is realized through following technical proposals: adopt the system of modenite nitric oxide adsorption, comprise the preprocessing system, adsorption-desorption system and the cooling gathering system that connect successively.
Further, said preprocessing system comprises blower fan, sour pump, cooling tower and wire gauzee filter; Wherein blower fan, cooling tower and wire gauzee filter link to each other successively, and sour pump links to each other with the bottom of cooling tower, and connect blower fan simultaneously on the pipe network of cooling tower, wire gauzee filter and adsorption-desorption system connectivity.
Because molecular sieve adsorption steam can be emitted a large amount of heat, and the adsorption operations temperature requirement is lower than 25 ℃, so before the waste gas entering absorber of blower fan conveying, earlier waste gas is delivered to cooling tower and is cooled to 0 ℃, to offset the intensification of adsorption process.The main effect of wire gauzee filter is air-flow to be arranged evenly and with particle hold back.
Further, said adsorption-desorption system comprises absorber and the heater that is communicated with absorber, and absorber is communicated with wire gauzee filter and cooling gathering system simultaneously.
Further; Said absorber comprises absorber one, absorber two, absorber three and absorber four; Absorber one, absorber two, absorber three and absorber four all are communicated with heater, wire gauzee filter and cooling gathering system, and absorber one, absorber two, absorber three and absorber four to lay respectively at the heater be that foursquare four angles at center are located.
The quantity of absorber is according to the needs of production setting; But will be set to four at least, system's main processing has absorption, desorb, drying, four operation stage states of cooling, guarantees that the continuation of technological operation is carried out; Adopt the absorber more than four, can increase the disposal ability of system.
Further, said cooling gathering system comprises cooler, sour measuring tank and spinner flowmeter, and the three links to each other successively, and cooler is communicated with absorber one, absorber two, absorber three and absorber four simultaneously.
The acid measuring tank is used to measure the quantity that absorber produces nitric acid; Output for the accurate Calculation system is helpful; And spinner flowmeter is claimed spinner flowmeter; The device of flow is calculated in (position) that is located at the rotatable parts in the direct current pipeline through measurement, and the handled easily personnel are to the control of flow, in the collection of subsequent operation to acid.
Nitric acid temperature through the adsorption-desorption system desorbs is higher, must be cooled to 20 ℃ through cooling tower, behind sour measuring tank and spinner flowmeter, collects.
Adopt the method for modenite nitric oxide adsorption, may further comprise the steps:
(a) waste gas is under the conveying of blower fan; Be delivered to cooling tower, be cooled in-5 ℃ to 5 ℃ after, behind even gas distribution of wire gauzee filter and trapped particles thing; Get into absorber one; In absorber one, absorber two, absorber three and the absorber four modenite is installed all, the valve between absorber one and the heater is in closed condition at this moment, gets into cooler at liquid after absorber one absorption and is cooled in 15 ℃ to 25 ℃; Add up the amount and spinner flowmeter adjustment flow of the acid that produces through sour measuring tank after, collect at last;
When (b) valve between absorber one and heater is in closed condition, valve opening between absorber two and the heater, absorber two is in parse state;
(c) when carrying out step (b), valve opening between absorber three and the heater, absorber three is in drying regime;
(d) when carrying out step (b) and step (c), valve closing between absorber four and the heater, absorber are everywhere in the state of cooling.
Said absorber one, absorber two, absorber three and absorber four are in absorption-desorption-drying-cooling one of four states respectively and move in circles.
The chilling temperature of said cooling tower is 0 ℃, 20 ℃ of the chilling temperatures of said cooler.
Because temperature will rise to 120 ℃ earlier during desorption, continues to rise to 150-190 ℃, just can carry out desorb, the final drying temperature will arrive 175-250 ℃, 2-4 hour drying time, and then bed is cooled to below 30 ℃, could adsorb again.Therefore the present invention is provided with four absorbers, and to guarantee the continuous service of technological operation, four absorbers that are in operation are in absorption, desorb, drying, four operation stage states of cooling respectively; Each absorber independent operating, independent four operation stages of absorption, desorb, drying, cooling of accomplishing technology, so just can guarantee system continue run without interruption, and unaffected mutually.This technology nitrogen oxide eliminating efficiency can reach 98%.
In sum, the invention has the beneficial effects as follows: this system and method thereof can be moved continuously, and adsorbent is the repetition regeneration, and the adsorbent use amount is little, and adsorption efficiency is high, recycles profitable.
Description of drawings
Fig. 1 is a system schematic of the present invention.
Mark and corresponding parts title in the accompanying drawing: 1-blower fan; 2-sour pump; 3-cooling tower; 4-wire gauzee filter; 5-absorber one; 6-absorber two; 7-absorber three; 8-absorber four; 9-heater; 10-cooler; 11-sour measuring tank; 12-spinner flowmeter.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done further detailed description, but embodiment of the present invention is not limited only to this.
Embodiment 1:
As shown in Figure 1, the system of employing modenite nitric oxide adsorption comprises the preprocessing system, adsorption-desorption system and the cooling gathering system that connect successively.
Said preprocessing system comprises blower fan 1, sour pump 2, cooling tower 3 and wire gauzee filter 4; Wherein blower fan 1, cooling tower 3 and wire gauzee filter 4 link to each other successively, and sour pump 2 links to each other with the bottom of cooling tower 3, and connect blower fan 1 simultaneously and lead on the pipe network of cooling tower 3 wire gauzee filter 4 and adsorption-desorption system connectivity.Acid pump 2 extracts the cooling towers 3 inner acid that generate, and the waste gas that blower fan 1 is carried cleans, and goes out impurity such as dust in the waste gas; Acid in the cooling tower 3 is the formation soluble in water of part waste gas, collects in the bottom of cooling tower 3, adopts sour pump 2 to extract; Can either prevent that the acidity in the cooling tower 3 is easy to generate deposition, cause the reduction of cooling tower 3 efficient, can avoid occurring corrosion phenomenon again; Prolonged service life, wire gauzee filter 4 even gas distribution and trapped particles things.
The heater 9 that said adsorption-desorption system comprises absorber and is communicated with absorber, and absorber is communicated with wire gauzee filter 4 and cooling gathering system simultaneously.Feed thermals source such as hot-air in the heater 9, with being communicated with between the absorber through the open and close valve gate control.
Said absorber comprises absorber 1, absorber 26, absorber 37 and absorber 48; Absorber 1, absorber 26, absorber 37 and absorber 48 all are communicated with heater 9, wire gauzee filter 4 and cooling gathering system, and absorber 1, absorber 26, absorber 37 and absorber 48 to lay respectively at heater 9 be that foursquare four angles at center are located.Absorber 1, absorber 26, absorber 37 and absorber 48 are identical with distance between the heater 9; When carrying out the operation of each link; The identical intermittent duty time can be arranged, make the operation of system realize continuously, the part can not occur and walk empty phenomenon generation.
Said cooling gathering system comprises cooler 10, sour measuring tank 11 and spinner flowmeter 12, and the three links to each other successively, and cooler 10 is communicated with absorber 1, absorber 26, absorber 37 and absorber 48 simultaneously.Salpeter solution in the absorber is passed into sour measuring tank 11 after being cooled to 20 ℃ through cooler 10, and the volume of the nitric acid that sour measuring tank 11 flows through mensuration enters into the speed that spinner flowmeter 12 control nitric acid flow again, and the handled easily personnel are to the collection of nitric acid.
Adopt the method for modenite nitric oxide adsorption, may further comprise the steps:
(a) waste gas is under the conveying of blower fan 1; Be delivered to cooling tower 3, be cooled in-5 ℃ to 5 ℃ after, behind wire gauzee filter 4 even gas distributions and trapped particles thing; Get into absorber 1; In absorber 1, absorber 26, absorber 37 and the absorber 48 modenite is installed all, the valve between absorber 1 and the heater 9 is in closed condition at this moment, gets into cooler 10 at liquid after absorber one 5 absorption and is cooled in 15 ℃ to 25 ℃; Add up the amount and spinner flowmeter 12 adjustment flows of the acid that produces through sour measuring tank 11 after, collect at last;
When (b) valve between absorber 1 and heater 9 is in closed condition, valve opening between absorber 26 and the heater 9, absorber 26 is in parse state;
(c) when carrying out step (b), valve opening between absorber 37 and the heater 9, absorber 37 is in drying regime;
(d) when carrying out step (b) and step (c), valve closing between absorber 48 and the heater 9, absorber 48 is in the state of cooling.
Four working stages of absorber:
Phase I, the absorber temperature is controlled at the 25-35 degree during absorption; Second stage during regeneration, is warming up to the 120-125 degree, kept 10 minutes, after rise to the 150-190 degree, kept 25 minutes; Phase III, the regeneration baking temperature is the 175-250 degree, keeps 2-4 hour; Stage, dry back bed is cooled to less than 30 degree.This system can be with nitrous oxides concentration by 1800-3600mg/m
3Reduce to 60 mg/m
3, the nitric acid output that from tail gas, reclaims can reach 2.5% of plant output.Reduced the demand of factory, reduced production cost, realized the utilization once more of resource nitric acid material.
Said absorber 1, absorber 26, absorber 37 and absorber 48 are in absorption-desorption-drying-cooling one of four states respectively and move in circles.The chilling temperature of said cooling tower 3 is 0 ℃, 20 ℃ of the chilling temperatures of said cooler 10.When absorber 1 carries out desorption state; Absorber 26 is in drying regime, and absorber 37 is in the state of cooling, and absorber 48 is in adsorbent equipment; So circulation; Make to constitute a complete absorption-desorption-drying-cooling all the time in four absorbers that the work of treatment of nitrogen oxide is being carried out always, and the efficient of processing is high.
The molecular sieve of the use of this test is a modenite natural or through processing; Be a kind of silica alumina ratio very high (greater than 10-13), heat endurance at 500 ° of C ~ 1000 ° C, specific heat is about 0.2 cal/g ° * C, and the bug hole volume accounts for 45% of cumulative volume; About 0.2 cc/g of pore volume; The alumino-silicate that acid resistance is very high, commonly used have a h-mordenite, and specific area reaches 8000m
2/ g, polarity is very strong.
Adopt quality to be modenite and the activated carbon of 100g, in the absorber among modenite placement and the present invention, active carbon adopts the tank body splendid attire of an end opening, feeds concentration respectively and is 2000mg/m
3Nitrogen oxide 5m
3, the modenite absorber is through above-mentioned four working stages, when this system moves; Waste gas is under the conveying of blower fan 1; Be delivered to cooling tower 3, after being cooled to 0 ℃, behind wire gauzee filter 4 even gas distributions and trapped particles thing; Get into absorber 1, (valve between absorber 1 and the heater 9 is in closed condition at this moment; Valve is all opened between absorber 26 and absorber 37 and the heater 9, is in parse state and drying regime respectively; Valve closing between absorber 48 and the heater 9 is in the state of cooling.) be cooled to 20 ℃ at liquid entering cooling tower 10 after absorber one 5 absorption, get into sour measuring tank and spinner flowmeter, collect at last.The active carbon adsorption device takes existing conventional to adsorb to deviate from mode, after 5 hours, measures, and obtains the data like following table:
| The material title | Concentration (the mg/m of residual nitrogen oxide in the air 3） | The quality (mg) of adsorbent weightening finish | Absorption eliminating efficiency value (%) |
| The modenite absorber | 38 | 2 | 98.0 |
| The active carbon adsorption device | 100 | 50 | 94.5 |
Draw modenite absorption eliminating efficiency 98% through last table numerical value, the active carbon adsorption eliminating efficiency is less than 95%, so the absorption eliminating efficiency of modenite is high, can effectively nitrogen oxides from exhaust gas be absorbed, and has realized the purpose of environmental protection.
In last contrast test, owing to adopt absorption-desorption-drying-cooling one of four states to move in circles, the quality of adsorbent weightening finish is very low simultaneously, and modenite can circulate and use chronically, only need control temperature during regeneration and get final product.And the quality of activated carbon weightening finish is big, and desorb during regeneration, activation need use the NaOH of 10%-20% to soak respectively 22 hours, realize second use in 1 hour ability of logical steam, and every use once, and efficient just reduces once.Active carbon adsorption length consuming time, and big to the consumption of adsorbent, be unfavorable for the long-run development of enterprise.And modenite can move continuously, and adsorbent is the repetition regeneration, and the adsorbent use amount is little, and adsorption efficiency is high, recycles profitable.
Embodiment 2:
Adopt now the catalytic reduction method treatment of nitric acid tail gas more thorough on the market, but the metal platinum of wanting consume expensive with produce a large amount of ammonia, and the nitrogen oxide in the tail gas do not obtain recycling, wherein the price of metal platinum is for above 550/ yuan of every gram; Adopt metal platinum as the catalyst treatment nitric acid tail gas, because the amount of tail gas is very big and be long-term process, the use amount of metal platinum is big, and the cost of processing is high; And cause pollution of waterhead easily, the water-soluble ammoniacal liquor that obtains of the ammonia of generation, ammoniacal liquor is because its volatility has the danger of blast; Can't effectively handle, occur air pollution easily, nitrogen oxide does not but reclaim; All the time be present in the tail gas, do not reach the basic goal of processing, be unfavorable for the development of enterprise; And utilize the present invention, and can sponge the nitrogen oxide in the tail gas, finally be converted into salpeter solution; Conveniently it is handled, reduced the amount of nitrogen oxides in the tail gas simultaneously, increased the raw material of chemical enterprise.
Embodiment 3:
Adopt liquid absorption method simpler; But absorption efficiency is merely 60 ~ 70%; The most of the nitrogen oxide is water insoluble or other liquid, has no idea to absorb processing, and adopts modenite to absorb; Efficient reaches 98%, and the content of nitrogen oxide satisfies country to the air emission standards in the tail gas after the absorption.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction, every foundation technology of the present invention, method to any simple modification, equivalent variations that above embodiment did, all fall within protection scope of the present invention in fact.
Claims (8)
1. adopt the system of modenite nitric oxide adsorption, it is characterized in that: comprise the preprocessing system, adsorption-desorption system and the cooling gathering system that connect successively.
2. the system of employing modenite nitric oxide adsorption according to claim 1 is characterized in that: said preprocessing system comprises blower fan (1), sour pump (2), cooling tower (3) and wire gauzee filter (4); Wherein blower fan (1), cooling tower (3) and wire gauzee filter (4) link to each other successively; And sour pump (2) links to each other with the bottom of cooling tower (3); And connect blower fan (1) simultaneously on the pipe network of cooling tower (3), wire gauzee filter (4) and adsorption-desorption system connectivity.
3. the system of employing modenite nitric oxide adsorption according to claim 2; It is characterized in that: the heater (9) that said adsorption-desorption system comprises absorber and is communicated with absorber, and absorber simultaneously with wire gauzee filter (4) with cool off gathering system and be communicated with.
4. the system of employing modenite nitric oxide adsorption according to claim 3; It is characterized in that: said absorber comprises absorber one (5), absorber two (6), absorber three (7) and absorber four (8); Absorber one (5), absorber two (6), absorber three (7) and absorber four (8) all are communicated with heater (9), wire gauzee filter (4) and cooling gathering system, and absorber one (5), absorber two (6), absorber three (7) and absorber four (8) to lay respectively at heater (9) be that foursquare four angles at center are located.
5. the system of employing modenite nitric oxide adsorption according to claim 4; It is characterized in that: said cooling gathering system comprises cooler (10), sour measuring tank (11) and spinner flowmeter (12); The three links to each other successively, and cooler (10) is communicated with absorber one (5), absorber two (6), absorber three (7) and absorber four (8) simultaneously.
6. adopt the method for modenite nitric oxide adsorption, may further comprise the steps:
(a) waste gas is under the conveying of blower fan (1); Be delivered to cooling tower (3), be cooled in-5 ℃ to 5 ℃ after, through wire gauzee filter (4) evenly behind gas distribution and the trapped particles thing; Get into absorber one (5); In absorber one (5), absorber two (6), absorber three (7) and the absorber four (8) modenite is installed all, the valve between absorber one (5) and the heater (9) is in closed condition at this moment, gets into cooler (10) at liquid after absorber one (5) absorption and is cooled in 15 ℃ to 25 ℃; Add up the amount and spinner flowmeter (12) adjustment flow of the acid that produces through sour measuring tank (11) after, collect at last;
When (b) valve between absorber one (5) and heater (9) is in closed condition, valve opening between absorber two (6) and the heater (9), absorber two (6) is in parse state;
(c) when carrying out step (b), valve opening between absorber three (7) and the heater (9), absorber three (7) drying regimes;
(d) when carrying out step (b) and step (c), valve closing between absorber four (8) and the heater (9), absorber four (8) is in the state of cooling.
7. the method for employing modenite nitric oxide adsorption according to claim 6 is characterized in that:
Said absorber one (5), absorber two (6), absorber three (7) and absorber four (8) are in absorption-desorption-drying-cooling one of four states respectively and move in circles.
8. the method for employing modenite nitric oxide adsorption according to claim 6 is characterized in that: the chilling temperature of said cooling tower (3) is 0 ℃, 20 ℃ of the chilling temperatures of said cooler (10).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104677770A (en) * | 2015-02-07 | 2015-06-03 | 同济大学 | Adsorbing material performance testing device and using method thereof |
| CN106482355A (en) * | 2016-10-10 | 2017-03-08 | 郑州大学 | A kind of Coupling Adsorption thermal converter preparation and the method that superheated steam is dried |
| CN112423861A (en) * | 2018-07-17 | 2021-02-26 | 奥迪股份公司 | Utilization of nitrogen oxides from ambient air |
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| JPH0576753A (en) * | 1991-09-24 | 1993-03-30 | Kobe Steel Ltd | Adsorbent for nitrogen monoxide, its production and method for adsorbing and removing nitrogen monoxide |
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| CN202751930U (en) * | 2012-09-14 | 2013-02-27 | 四川四通欧美环境工程有限公司 | System adopting mordenite to absorb nitric oxides |
Family Cites Families (1)
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|---|---|---|---|---|
| JP5076753B2 (en) * | 2007-09-05 | 2012-11-21 | 三菱マテリアル株式会社 | Method for producing high-concentration metal nanoparticle dispersion |
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| JPH0576753A (en) * | 1991-09-24 | 1993-03-30 | Kobe Steel Ltd | Adsorbent for nitrogen monoxide, its production and method for adsorbing and removing nitrogen monoxide |
| CN1803253A (en) * | 2005-12-07 | 2006-07-19 | 成都华西化工研究所 | Process for removing SO2 and NOX from flume gas adopting circulated moving bed |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104677770A (en) * | 2015-02-07 | 2015-06-03 | 同济大学 | Adsorbing material performance testing device and using method thereof |
| CN106482355A (en) * | 2016-10-10 | 2017-03-08 | 郑州大学 | A kind of Coupling Adsorption thermal converter preparation and the method that superheated steam is dried |
| CN112423861A (en) * | 2018-07-17 | 2021-02-26 | 奥迪股份公司 | Utilization of nitrogen oxides from ambient air |
| US11826693B2 (en) | 2018-07-17 | 2023-11-28 | Audi Ag | Utilization of nitrogen oxides from ambient air |
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| CN102836614B (en) | 2014-07-23 |
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