CN103920384B - A kind of non-pressure process absorbs the equipment of high concentration nitrogen oxide - Google Patents
A kind of non-pressure process absorbs the equipment of high concentration nitrogen oxide Download PDFInfo
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Abstract
The present invention relates to the equipment that a kind of non-pressure process absorbs high concentration nitrogen oxide, it comprises first grade absorption tower, two-level absorption tower and three grades of absorption towers; Top, absorption tower at different levels is connected with air inlet pipeline and absorbing liquid feed tube, the air inlet pipeline of first grade absorption tower connects processed source of the gas, two-level absorption tower air inlet pipeline is connected with first grade absorption tower, three grades of absorption tower air inlet pipelines are connected with two-level absorption tower, the absorbing liquid feed tube of one-level, two-level absorption tower connects acid solution storage tank, the absorbing liquid feed tube on three grades of absorption towers connects alkali lye storage tank, each absorbing liquid feed tube is provided with liquid pump, be provided with the tower bottoms return duct be connected with corresponding storage tank bottom absorption tower at different levels, tower bottoms return duct is provided with water cooler.Utilize the present invention nitrogen oxide can be absorbed and one-level Alkali absorption through secondary acid, be converted into nitric acid and potassium nitrate, tail gas reaches discharging standards.Absorption tower adopts jet to absorb pattern, and gas, liquid all enter from top of tower, and structure is simple, and flow process is short, adapts to variable working condition requirement on a large scale.
Description
Technical field
The present invention relates to the equipment that a kind of non-pressure process absorbs high concentration nitrogen oxide, nitrogen oxide diluted acid is absorbed into nitric acid with hydrogen peroxide oxidation, and tail gas reaches discharging standards.
Background technology
Often high concentration nitrogen oxide (NO can be run in nitric acid industry
x) the process problem of tail gas, the discharge of nitrogen oxide, there is strict standard in country, and the process of high concentration nitrogen oxide, difficulty is very large, and cost is higher.The nitrogen oxide exhaust gas treating method used both at home and abroad is at present divided into dry method and the large class of wet method two.Dry method based on catalytic reduction, under high temperature, with reducing agent by NO
xcatalytic reduction is N
2deng gas, purely from environmental angle, handling object is low concentration of NO
x, for higher concentration NO
x, poor effect, and can not NO be recycled
x, and absorption can by NO
xbe converted into HNO
3, concerning nitric acid industry, economic implications is much larger than dry method.Absorption is the one of wet method, and absorption process uses water, acid or aqueous slkali absorbing NOx, is converted into nitric acid or nitrate.Be absorbed with non-pressure process, synthesis, middle-pressure process, high-pressure process and double pressurized method, mainly adopt double pressurized method at present, other method seldom adopts, because NO in the rear tail gas of process
xconcentration is higher.Be absorbed in countercurrent absorber and complete, industrial general employing multistage absorption.The net reaction of water absorbing NOx is:
3NO
2+H
2O=2HNO
3+NO+Q(1)
2NO+O
2=2NO
2+Q(2)
NO+NO
2+Na
2CO
3=2NaNO
2+CO
2(3)
NO
2+Na
2CO
3=NaNO
3+NaNO
2+CO
2(4)
Known by reaction equation (1), (2), 1molNO
2become the 1/3molNO not easily absorbed, NO be made to absorb, again must be oxidized to NO
2, again absorb, through oxidative absorption repeatedly, just can reach emission request, in the process, NO
2absorption reaction and NO oxidation reaction intersect carry out, process is very complicated.
The absorption process of nitrogen oxide, also has acid to absorb and Alkali absorption.There are some researches show, NO
2when absorbing in dust technology, the oxidation of NO is mainly carried out in gas liquid film and liquid phase, the oxidation of NO is a slow process, low temperature and pressurization are conducive to the carrying out of oxidation reaction, therefore adopt double pressurized method at present more, but the rising of pressure must make equipment cost and operating cost increase, and energy consumption increases; And current ordinary-pressure absorption process tail gas concentration is higher, seldom adopt.Reduce and absorb temperature, the oxidation rate of NO can be increased, improve oxidizability, be beneficial to absorption, but remove reaction heat and make device structure complicated.
Current absorption process all adopts the integrated processes of multistage acid absorption and multistage Alkali absorption, after acid absorbs, a large amount of NO is had to generate, after dry oxidation, the oxidizability of NO is increased to 40%, enter Alkali absorption level again, generate nitrite and nitrate, as reaction equation (3), (4), nitrite is strong carcinogen, discharge standard is 0.5ppm, and the content of nitrite generated in Alkali absorption is higher, the follow-up difficult problem that will run into process nitrite.
Summary of the invention
The technical problem to be solved in the present invention is the equipment that a kind of non-pressure process of exploitation absorbs high concentration nitrogen oxide; This equipment is atmospheric circulating absorption equipment, and at room temperature high concentration nitrogen oxide can be converted into nitric acid, tail gas reaches discharging standards, and nitric acid nitrite, lower than 0.5ppm, does not contain other secondary pollution.
Non-pressure process absorbs an equipment for high concentration nitrogen oxide, it is characterized in that: comprise first grade absorption tower, two-level absorption tower and three grades of absorption towers; Top, absorption tower at different levels is connected with air inlet pipeline and absorbing liquid feed tube, the air inlet pipeline of first grade absorption tower connects processed source of the gas, two-level absorption tower air inlet pipeline is connected with first grade absorption tower, three grades of absorption tower air inlet pipelines are connected with two-level absorption tower, the absorbing liquid feed tube of one-level, two-level absorption tower connects acid solution storage tank, the absorbing liquid feed tube on three grades of absorption towers connects alkali lye storage tank, each absorbing liquid feed tube is provided with liquid pump, be provided with the tower bottoms recovery tube be connected with corresponding storage tank bottom absorption tower at different levels, tower bottoms recovery tube is provided with water cooler.
The structure on three absorption towers is identical, it is a kind of jetting type ordinary-pressure absorption tower, comprise tower body, it is characterized in that: tower body top is installed into tracheae and feed tube, liquid distribution trough is installed on tower body top, feed tube outlet is connected with liquid distribution trough, admission space is provided with between tower body top and liquid distribution trough, below liquid distribution trough, packed tower is installed, space below packed tower is as gas-liquid separator, blast pipe is installed on gas-liquid separator top, is provided with liquid level gauge, installs back closed tube bottom gas-liquid separator outside gas-liquid separator.
Non-pressure process of the present invention absorbs the equipment of high concentration nitrogen oxide, and development process is mainly started with from the following technical issues that need to address:
One is the selection of absorbing medium, and can Quick Oxidation NO in the liquid phase, improves oxidizability as much as possible, makes it change NO into as soon as possible
2, make tail gas up to standard with the least possible absorption level;
Two is the structural designs on absorption tower, and make NO in absorption tower, have enough time of staying, complete oxidative absorption, Liquid Flow form is the key of dealing with problems.
Three is the methods removing heat, the absorption of high concentration nitrogen oxide, very large reaction heat is had to release, absorbing liquid temperature is more than more than 35 DEG C, assimilation effect is very poor, how removing reaction heat is in time the technical barrier absorbed, and namely will solve the problem of heat exchange mode, make absorption equipment structure simple as far as possible.The corresponding scheme solving above-mentioned three point problem is:
One, absorbing medium
With dust technology and hydrogen peroxide (H
2o
2) as absorbing medium, NO, under the co-oxidation of dust technology and hydrogen peroxide, is converted into NO in the liquid phase rapidly
2, as reaction equation (5), reaction speed is fast, and degree of oxidation is high, and in oxidative absorption repeatedly, the content decay of NO is very fast, just can reach very high degree of absorption with the less order of reaction, after the absorption of hydrogen peroxide acid solution, and NO in tail gas
xcontent very low, become KNO with KOH alkali liquor absorption
3with micro-KNO
2, as reaction equation (6), (7), KNO
2by H
2o
2be oxidized to KNO
3, as reaction equation (8).KNO in final absorbing liquid
2content is very low, can reach below 0.5ppm.
NO+H
2O
2=NO
2+H
2O(5)
2NO
2+2KOH=KNO
3+KNO
2+H
2O(6)
NO+NO
2+2KOH=2KNO
2+H
2O(7)
KNO
2+H
2O
2=KNO
3+H
2O(8)
Two, absorption tower structure
Absorption tower adopts jet to absorb pattern, and the gas not adopting prior art generally to adopt, liquid countercurrent enter tower.But gas, liquid all enter from top, absorption tower, admission space is provided with between tower body top and liquid distribution trough, tower top is equipped with liquid distribution trough, absorbing liquid from distributor spray and, formed jet, produce certain negative pressure, can gas be sucked in tower, even if air pressure is lower, also can overcomes packing layer resistance, pass through packing layer smoothly.After gas enters from tower top, impact liquid and make the liquid atomization, produce spray effect, can effectively promote gas-liquid contact degree, reach the object of abundant mass transfer.Adopt packed tower, filling ceramic ring filler in tower, to reduce resistance and liquid holdup.Jet and packing layer can make gas-liquid be uniformly distributed along tower section, and the possibility producing axial short circuit is little, and gas-liquid contact is abundant, and gas is from tower top to tower reactor, and gas circuit is long, long at dwell time in the tower, and NO has the sufficient time to be oxidized to NO
2, when gas-liquid is to tower reactor, in liquid, contained NO amount seldom, is easily overflowed, is realized gas-liquid separation in tower reactor from tower reactor liquid, even if containing NO in still liquid, and also can by H
2o
2continue oxidation; And during prior art counter-current absorption, first gas-liquid contacts in tower reactor, carry a large amount of NO in still liquid, when still liquid is discharged, NO can be expelled to absorbing liquid storage tank with still liquid, a large amount of acid mist of on-the-spot generation and tobacco.Absorption tower of the present invention adopts jet to absorb pattern, and jet absorbs the operating mode that can adapt to liquid-gas ratio, air pressure and flow and constantly change, energy interval and continued operation, and operating flexibility is more much bigger than adverse current, even if large liquid measure, also not easily occurs liquid flooding and leakage.Tower reactor is as gas-liquid separator, and tail gas is separated from tower reactor with absorbing liquid, and tail gas enters next stage absorption tower after entering the further precipitation of liquid droplets of cyclone hydraulic separators.Tower reactor controls certain liquid level, to realize fluid-tight.
Three, cooling method
Jet absorbs, the initial contact interface of gas-liquid is at tower top packing layer, tower top reaction is the most violent, and heat release is maximum, adopts large liquid spray flux, reaction heat can be taken away fast, effective reduction absorbing liquid temperature, do not need in tower to arrange cooling device, absorption tower structure is simple, the water cooler that tower reactor drain line is arranged cools absorbing liquid, circulates in order to absorbing liquid.
Absorption tower of the present invention have employed jet and absorbs pattern, and gas-liquid is uniformly distributed along tower section with the form of spraying, and mass transfer is abundant, and gas residence time is long, and NO has time enough oxidative absorption.Adopt the mode of large liquid spray flux and cooling reactor liquid to remove and absorb heat, make absorbing liquid temperature be down to less than 30 DEG C, absorption tower structure is simple, and flow process is short, and operating flexibility is large, adapts to variable working condition requirement on a large scale completely.High concentration nitrogen oxide can be converted into higher concentration nitric acid by the present invention, realizes waste reclamation, and tail gas and tail washings can reach discharging standards, environmental protection cost is low, and device structure is simple, and technological process is simple, operating cost is low, economic benefit and social benefit obvious.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention,
Fig. 2 is absorption tower structural representation.
In figure: in figure: 1-acid solution storage tank, 2-H
2o
2storage tank, 3-first order absorption liquid pump, 4-first order absorption liquid feed tube, be called for short feed tube, 5-first order absorption liquid electromagnetic flowmeter, 6-first order absorption liquid control valve, 7-first grade absorption tower, 701-air inlet pipe, 702-liquid distribution trough feed liquor is responsible for, 703-admission space, 704-pressure type liquid distribution trough, 705-tower body, 706-packing layer, 707-tower reactor, also gas-liquid separator is claimed, 708-cyclone hydraulic separators, 709-supporting leg, 710-packing support plate, 711-hold-down grid, 8-one-level liquid level gauge, 9-one-level still liquid switch valve, 10-one-level tower bottoms recovery tube, be called for short recovery tube, 11-N
2o
4waste gas source of the gas, 12-exhaust apertures flowmeter, 13-one-level air inlet adjustment valve, 14-two-level absorption tower air inlet pipeline, 15-two-level absorption tower, 16-secondary absorbs liquid pump, 17-secondary absorbing liquid feed tube, 18-secondary tower bottoms recovery tube, 19-three grades of absorption tower air inlet pipelines, 20-three grades of absorption towers, 21-alkali lye storage tank, 22-three grades of absorption liquid pumps, 23-three grades of absorbing liquid feed tubes, 24-three grades of tower bottoms recovery tubes, 25-join alkali case, 26-three grades of offgas duct, 27-acid solution discharge line, 28-alkali lye discharge line, 29-one-level water cooler, 30-two-stage water-cooling is device but, 31-tertiary effluent cooler.
Detailed description of the invention
Below in conjunction with accompanying drawing, device structure of the present invention is described in further detail.Non-pressure process absorbs an equipment for high concentration nitrogen oxide, comprises first grade absorption tower 7, two-level absorption tower 15 and three grades of absorption towers 20; Top, absorption tower at different levels is connected with air inlet pipeline and absorbing liquid feed tube; Namely first grade absorption tower 7 top is provided with one-level air inlet pipeline 701 and first order absorption liquid feed tube 4, two-level absorption tower 15 top is provided with two-level absorption tower air inlet pipeline 14 and top, secondary absorbing liquid feed tube 17, three grades of absorption towers 20 is provided with three grades of absorption tower air inlet pipelines 19 and three grades of absorbing liquid feed tubes 23; One-level air inlet pipeline 701 and processed N
2o
4waste gas source of the gas 11 connects, and is provided with offgas duct bottom absorption tower at different levels; Two-level absorption tower air inlet pipeline 14 is connected with first grade absorption tower offgas duct, and three grades of absorption tower air inlet pipelines 19 are connected with two-level absorption tower offgas duct; Three grades of offgas duct 26 outlets are directly communicated with air.
First order absorption liquid feed tube 4 is connected acid solution storage tank 1, three grades of absorbing liquid feed tubes 23 and connects alkali lye storage tank 21 with secondary absorbing liquid feed tube 17; Each absorbing liquid feed tube is provided with liquid pump, and namely first order absorption liquid feed tube 4 installs first order absorption liquid pump 3, and secondary absorbing liquid feed tube 17 is installed secondary absorption liquid pump 16, three grades of absorbing liquid feed tubes 23 and installed three grades of absorption liquid pumps 22; The tower bottoms recovery tube be connected with corresponding storage tank is provided with bottom absorption tower at different levels, tower bottoms recovery tube is provided with water cooler, namely the one-level tower bottoms return duct 10 be connected with acid solution storage tank 1 is provided with bottom first grade absorption tower 7, two-level absorption tower 15 is provided with secondary tower bottoms return duct 18, the three grades of absorption towers 20 be connected with acid solution storage tank 1 and is provided with the three grades of tower bottoms return ducts 24 be connected with alkali lye storage tank 21; One-level tower bottoms return duct 10 is provided with one-level water cooler 29, secondary tower bottoms return duct 18 is provided with two-stage water-cooling and but device 30, three grades of tower bottoms return ducts 24 is provided with tertiary effluent cooler 31.
One-level air inlet pipeline is provided with exhaust apertures flowmeter 12 and one-level air inlet adjustment valve 13, is respectively used to measure charge flow rate and regulate charge flow rate; The liquid outlet end of first order absorption liquid pump 3, first order absorption liquid feed tube 4 are installed successively first order absorption liquid electromagnetic flowmeter 5 and first order absorption liquid control valve 6, be respectively used to measure feed liquor flow and regulate feed liquor flow; One-level tower bottoms return duct 10 is installed one-level still liquid switch valve 9, one-level liquid level gauge 8 is electrically connected with one-level still liquid switch valve 9, and when liquid level reaches setting value, one-level still liquid switch valve 9 is opened automatically; Acid solution storage tank 1 is connected with H
2o
2storage tank 2, installs acid solution discharge line 27 bottom acid solution storage tank 1, alkali lye storage tank 21 is connected with joins alkali case 25, installs alkali lye discharge line 28 bottom alkali lye storage tank 21.
When non-pressure process absorbs the equipment of high concentration nitrogen oxide for absorbing high concentration nitrogen oxide, method roughly: with weight percent concentration be 3% ~ 5% dust technology and 0.1% ~ 2% hydrogen peroxide for main absorbing liquid, be placed in acid solution storage tank; With 16% potassium hydroxide assist absorption liquid, be placed in alkali lye storage tank; At ambient pressure, interval and continuous operation mode under, by concentration 40% ~ 60% (mol%), flow 100 ~ 400Nm
3the dinitrogen tetroxide of/h, pressure 0.01 ~ 0.2MPa is or/and nitrogen dioxide gas enters first grade absorption tower, and one-level tail gas enters two-level absorption tower, and secondary tail gas enters three grades of absorption towers again, and three grades of tail gas reach discharge standard and pass through high altitude discharge; Realize dinitrogen tetroxide or/and nitrogen dioxide gas absorbs and one-level Alkali absorption through secondary acid, be converted into potassium nitrate, tail gas concentration reaches 100mg/m
3discharging standards, absorbing liquid nitrite lower than the discharging standards of 0.5ppm, not containing other secondary pollution.
The structure on three absorption towers is identical, be jetting type ordinary-pressure absorption tower, this implementation method is described for the structure of first grade absorption tower to jetting type ordinary-pressure absorption tower: a kind of jetting type ordinary-pressure absorption tower, comprise tower body 705, liquid distribution trough feed liquor supervisor 702 is installed at tower body 705 top, liquid distribution trough 704 is installed on tower body 705 top, the outlet of first order absorption liquid feed tube 4 is responsible for 702 with liquid distribution trough feed liquor and is connected, liquid distribution trough feed liquor is responsible for 702 ports of export and is connected liquid distribution trough 704, admission space 703 is provided with between tower body 705 top and liquid distribution trough 704, packing layer 706 is installed below liquid distribution trough 704, space below packing layer 706 is as gas-liquid separator 707, first grade absorption tower offgas duct is installed on gas-liquid separator 707 top, first grade absorption tower offgas duct is connected with two-level absorption tower air inlet pipeline 14, liquid level gauge 8 is installed outside gas-liquid separator 707, one-level tower bottoms recovery tube 10 is installed bottom gas-liquid separator 707.Blast pipe 14 is connected to cyclone hydraulic separators 708.Be fixedly connected with supporting leg 709 bottom tower body 705.
Packing layer 706 comprises packing support plate 710 and hold-down grid 711, filler be arranged on packing support plate 710 and and hold-down grid 711 between, filler select Dg50 pottery Pall ring.
Oxides of nitrogen gas enters tower head from air inlet pipe, and absorbing liquid enters liquid distribution trough from tower head feed tube, and liquid distribution trough is a kind of pressure type comb, absorbing liquid can be uniformly distributed on tower body cross section.Tower head is the space of air inlet and feed liquor, and gas-liquid at tower head part contact, then enters packing layer at first, and gas-liquid completes oxidative absorption in packing layer.Tower reactor is the space of gas-liquid separation, and unabsorbed tail gas, after tower reactor is separated, is discharged from blast pipe, enter cyclone hydraulic separators, be separated the drop in tail gas further, absorbing liquid flows out from return duct, after water cooler cooling, flow into absorbing liquid storage tank, so that cyclic absorption.The liquid level gauge that tower reactor is installed, is convenient to Survey control liquid level.
Claims (5)
1. non-pressure process absorbs an equipment for high concentration nitrogen oxide, it is characterized in that: comprise first grade absorption tower (7), two-level absorption tower (15) and three grades of absorption towers (20), first grade absorption tower (7) top is provided with one-level air inlet pipeline (701) and first order absorption liquid feed tube (4), two-level absorption tower (15) top is provided with two-level absorption tower air inlet pipeline (14) and secondary absorbing liquid feed tube (17), and three grades of absorption tower (20) tops are provided with three grades of absorption tower air inlet pipelines (19) and three grades of absorbing liquid feed tubes (23), one-level air inlet pipeline (701) and processed N
2o
4waste gas source of the gas (11) connects, and is provided with offgas duct bottom absorption tower at different levels, two-level absorption tower air inlet pipeline (14) is connected with first grade absorption tower offgas duct, and three grades of absorption tower air inlet pipelines (19) are connected with two-level absorption tower offgas duct, three grades of offgas duct (26) outlets are directly communicated with air, liquid distribution trough feed liquor supervisor (702) is installed at tower body (705) top of first grade absorption tower (7), liquid distribution trough (704) is installed on tower body (705) top, first order absorption liquid feed tube (4) outlet is responsible for (702) with liquid distribution trough feed liquor and is connected, liquid distribution trough feed liquor supervisor (702) port of export connects liquid distribution trough (704), admission space (703) is provided with between tower body (705) top and liquid distribution trough (704), packing layer (706) is installed in liquid distribution trough (704) below, space below packing layer (706) is as gas-liquid separator (707), first grade absorption tower offgas duct is installed on gas-liquid separator (707) top, first grade absorption tower offgas duct is connected with two-level absorption tower air inlet pipeline (14), gas-liquid separator (707) outside is provided with liquid level gauge (8), one-level tower bottoms recovery tube (10) is installed in gas-liquid separator (707) bottom.
2. a kind of non-pressure process as claimed in claim 1 absorbs the equipment of high concentration nitrogen oxide, it is characterized in that: first order absorption liquid feed tube (4) is connected acid solution storage tank (1) with secondary absorbing liquid feed tube (17), three grades of absorbing liquid feed tubes (23) connect alkali lye storage tank (21); First order absorption liquid feed tube (4) installs first order absorption liquid pump (3), and secondary absorbing liquid feed tube (17) is installed secondary and absorbed liquid pump (16), and three grades of absorbing liquid feed tubes (23) install three grades of absorption liquid pumps (22); The one-level tower bottoms recovery tube (10) that first grade absorption tower (7) bottom is provided with is connected with acid solution storage tank (1), two-level absorption tower (15) is provided with the secondary tower bottoms recovery tube (18) be connected with acid solution storage tank (1), and three grades of absorption towers (20) are provided with the three grades of tower bottoms recovery tubes (24) be connected with alkali lye storage tank (21); One-level tower bottoms recovery tube (10) is provided with one-level water cooler (29), secondary tower bottoms recovery tube (18) is provided with two-stage water-cooling but device (30), three grades of tower bottoms recovery tubes (24) are provided with tertiary effluent cooler (31).
3. a kind of non-pressure process as claimed in claim 1 or 2 absorbs the equipment of high concentration nitrogen oxide, it is characterized in that: one-level air inlet pipeline is provided with exhaust apertures flowmeter (12) and one-level air inlet adjustment valve (13), the liquid outlet end of first order absorption liquid pump (3), first order absorption liquid feed tube (4) install first order absorption liquid electromagnetic flowmeter (5) and first order absorption liquid control valve (6) successively.
4. a kind of non-pressure process as claimed in claim 3 absorbs the equipment of high concentration nitrogen oxide, it is characterized in that: one-level tower bottoms return duct (10) is upper installs one-level still liquid switch valve (9), and one-level liquid level gauge (8) is connected with one-level still liquid switch valve (9); Acid solution storage tank (1) is connected with H
2o
2storage tank (2), acid solution discharge line (27) is installed in acid solution storage tank (1) bottom, and alkali lye storage tank (21) is connected with joins alkali case (25), and alkali lye discharge line (28) is installed in alkali lye storage tank (21) bottom.
5. a kind of non-pressure process as claimed in claim 4 absorbs the equipment of high concentration nitrogen oxide, it is characterized in that: two-level absorption tower (15) is same as first grade absorption tower (7) with the structure of three grades of absorption towers (20).
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