CN104150450B - A kind of nitric acid production plant and treatment process realizing the recycling of tail gas pressure energy - Google Patents
A kind of nitric acid production plant and treatment process realizing the recycling of tail gas pressure energy Download PDFInfo
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- CN104150450B CN104150450B CN201410415642.8A CN201410415642A CN104150450B CN 104150450 B CN104150450 B CN 104150450B CN 201410415642 A CN201410415642 A CN 201410415642A CN 104150450 B CN104150450 B CN 104150450B
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- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a kind of nitric acid production plant and the treatment process thereof that realize the recycling of tail gas pressure energy, the pressure energy in existing nitric acid absorption tower downstream is adopted to reclaim the pressure energy arranged again after compressor in the method recovery tail gas of pressure energy recycling tower, it is made to change refrigerant (water at low temperature) into by energy transformation, and the water at low temperature obtained is sent in the heat exchanger of nitric acid absorption tower as refrigerant, to remove nox adsorption reaction liberated heat in nitric acid absorption tower, and then reach the object controlling absorption liquid temperature.The cooling fluid that temperature rises after heat exchange sends pressure energy recovery tower back to, realizes circulation operate continuously.Nitric acid absorption tower, pressure energy are reclaimed compressor and pressure energy recovery tower three combination by the present invention, achieve the effective conversion between energy, and almost there is no mechanical friction loss, so effciency of energy transfer is high, utilize fully, energy consumption can be reduced directly to existing nitric acid production plant, improve assimilated efficiency and increase economic benefit.
Description
Technical field
The present invention relates to a kind of recoverying and utilizing method of pressure energy, particularly a kind of nitric acid production plant and treatment process realizing the recycling of tail gas pressure energy.
Background technology
China's nitric acid industry is fast-developing in recent years, and dilute nitric acid production ability rolls over 100% nitric acid from 4,300,000 t/a(of 2000, lower with) be increased to 9,330,000 t/a of 2010, production capacity adds 1.2 times, annual growth nearly 16%.Within 2010, China has become world's nitric acid production first big country.At present, the existing dilute nitric acid production method of China has 5 kinds, i.e. non-pressure process, middle-pressure process (0.25 ~ 0.50MPa), high-pressure process (0.7 ~ 1.2MPa), synthetic method (be oxidized to normal pressure, be absorbed as pressurization) and double pressurized method (oxidative pressure 0.45MPa, absorption pressure 1.1Mpa).Non-pressure process, middle-pressure process oxidation and to absorb required pressure not high, facility investment is low and power consumption is little, but obtained concentration of nitric acid is not high, be only 45% ~ 52%, in the tail gas that nitric acid absorption tower is discharged, nitrogen oxide NOx (general names of NO, NO2 and other nitride) content is high, seriously polluted, between 4 ~ 5 years, non-pressure process will be eliminated from now on.The oxidation of high-pressure process and double pressurized method and absorption process are carried out all under elevated pressure, facility investment and power consumption large, but obtained acid concentration is high, can 65 ~ 72% be reached, in tail gas, the comparision contents of NOx is low, easy process qualified discharge, so nitric acid industry mesohigh method and double pressurized method will become prevailing technology.Double pressurized method and high-pressure process are comparatively large due to tail gas pressure, therefore adopt tail gas turbine decompressor pressure recovery energy more.Due to the impact by the many factors such as turbine expansion engine efficiency and cost recovery, all pressure energies can not be reclaimed.The pressure energy of pressure lower than 2atm tail gas is not generally reclaimed, but due to exhaust flow very large, therefore the waste of this energy is very serious.
Summary of the invention
The object of the invention is to develop a kind of nitric acid production plant realizing tail gas pressure energy and recycle, and utilize described device can realize the recoverable method of tail gas pressure to reclaim nitric acid absorption tower comprehensively and discharge the pressure energy of tail gas, to promote the energy-saving and emission-reduction of nitric acid industry.
Specifically, the present invention is according to thermodynamic principles, tail gas expansion work with pressure is made directly to produce low-temperature receiver, realize energy transformation, and for the refrigerant cooled of absorption liquid in nitric acid absorption tower, improve absorption tower assimilated efficiency, reduce the residual of NOx in absorption tower outlet tail gas further, exhaust emissions noise can also be reduced simultaneously, kill two birds with one stone.
One aspect of the present invention provides a kind of nitric acid production plant realizing tail gas pressure energy and recycle, and described device comprises the nitric acid absorption tower, tail gas turbine device and the pressure energy recovery tower that connect successively;
Described nitric acid absorption tower top is provided with absorption liquid entrance and exhaust emission pipeline, and bottom is provided with oxides of nitrogen gas entrance and nitric acid discharge tube; Described exhaust emission pipeline is connected with tail gas turbine device, and described nitric acid absorption tower tower body is provided with at least one heat exchanger, and described heat exchanger comprises refrigerant inlet and refrigerant exit, and described refrigerant exit is connected to the top of pressure energy recovery tower via pipeline;
Described tail gas turbine device is connected to the bottom of pressure energy recovery tower via pipeline, the top of described pressure energy recovery tower is provided with exhaust emission pipeline, bottom is provided with heat transferring medium discharge tube, and described heat transferring medium discharge tube is connected to the refrigerant inlet of described heat exchanger via recycle pump.
Wherein, described pressure energy recovery tower is packing tower, is provided with the heat and mass inner member for gas-liquid direct contact heat transfer in tower, and preferred described filler is the plastic filler of height 1-20m, more preferably 5-10 rice.
Wherein, described pressure energy recovery tower upper lateral part is also provided with heat transferring medium supply pipeline, to adjust heat transferring medium balance in pressure energy recovery tower.
Also liquidometer is provided with, to monitor liquid level more easily bottom described pressure energy recovery tower.
In actual mechanical process, because the intensification of pressure energy recovery tower outlet tail gas can take away the part water yield, therefore the heat transferring medium balance in pressure energy recovery tower is supplemented by the heat transferring medium service of tower top, and magnitude of recruitment carries out regulation and control by the liquidometer at the bottom of pressure energy recovery tower tower.
Wherein, described heat exchanger is two of series connection mutually, to obtain heat exchange effect more fully.Further, described heat exchanger is also provided with the refrigerator of further coolant adding, when the heat transferring medium got rid of cannot meet heat exchange needs as the refrigerant of heat exchanger, the further coolant adding of refrigeration agent can be started bottom pressure energy recovery tower.
Another aspect of the present invention there are provided a kind of method utilizing said apparatus to carry out the recycling of tail gas pressure energy, comprises the following steps:
(1) from the oxides of nitrogen gas of ammonia oxidation unit bottom Cemented filling to nitric acid absorption tower, flow from bottom to top in nitric acid absorption tower, enter and top-down absorption liquid countercurrent flow with from apical sink liquid entrance, contact reacts generates nitric acid, release heat simultaneously and absorbed by heat exchanger, gained nitric acid is discharged from the nitric acid discharge tube of bottom, and high pressure exhaust gas drains into tail gas turbine device from exhaust emission pipeline;
(2) in described heat exchanger, refrigerant enters the heat transferring medium of pressure energy recovery tower as pressure energy recovery tower after heating up, high pressure exhaust gas drains into pressure energy recovery tower after tail gas turbine device recovery part energy, in pressure energy recovery tower, the low temperature exhaust gas risen sprays with tower top and lower heat transferring medium contacts and carries out direct heat exchange, and the exhaust emission pipeline from top after tail gas undergoes rapid expansion in pressure energy recovery tower absorbs heat is discharged;
(3) heat transferring medium in pressure energy recovery tower after cooling drops at the bottom of tower, by recycle pump by Cemented filling to absorption tower interchanger as refrigerant, to take away the reaction heat that reactive absorption in nitric acid absorption tower is released.
Wherein, the described method liquidometer also comprised bottom according to pressure energy recovery tower controls heat transferring medium supply pipeline to adjust the balance of heat transferring medium.
Wherein, the working pressure that pressure energy recycles tower is pressure-fired, is preferably 0.005-0.02MPa.
Wherein, the heat transferring medium in described pressure energy recovery tower and described refrigerant can adopt multiple usable medium, are preferably water.
Method of the present invention, wherein, the absorption pressure of nitric acid absorption tower high-pressure process is generally 0.7 ~ 0.8MPa, and two platen press is 1.1MPa.
The tail gas got rid of from nitric acid absorption tower contains nitrogen, oxygen and a small amount of oxynitride, and its pressure is close with nitric acid absorption tower, and it is conveyed to tail gas turbine device pressure recovery energy, and tail gas pressure will drop to 0.15 ~ 0.25MPa.Pass into pressure energy recovery tower through pipeline more afterwards, the working pressure of pressure energy recovery tower, a little more than normal pressure, is generally 0.005-0.02MPa.Pressure is the tail gas of 0.15 ~ 0.25MPa, and undergoes rapid expansion heat absorption in pressure energy recovery tower, in build-up of pressure energy recovery tower, temperature sharply declines.The low temperature exhaust gas risen sprays with tower top and lower heat transferring medium (water) contacts and carries out direct heat exchange.When the low temperature exhaust gas risen reaches tower top, the temperature of tail gas temperature that is basic and heat transferring medium (water) reaches balance, this is that required heat equals the heat that heat transferring medium (water) provides in theory because tail gas expands, therefore heat transferring medium (water) temperature will decline, be generally 5 ~ 15 DEG C, different according to the size of heat transferring medium (water) spray flux.After heat exchange, the temperature before being higher than heat exchange from the exhaust temperature of pressure energy recovery tower top discharge.
Heat transferring medium (water) in pressure energy recovery tower after cooling drops at the bottom of tower, in pressure energy recovery tower cooling after heat transferring medium (water) by recycle pump via heat exchanger on Cemented filling to nitric acid absorption tower as refrigerant, to take away the reaction heat that in nitric acid absorption tower, reactive absorption is released, to reduce heat exchanger refrigerant consumption, realize energy-conservation object.After the interchanger heat exchange of absorption tower, obtain the refrigerant of intensification again through being delivered to the top of pressure energy recovery tower by pipeline, enter in tower and carry out cycle heat exchange next time.
For realizing better control, the preferred described pressure energy recovery tower intake pressure of the present invention is greater than 0.15Mpa, and pressure energy recovery tower discharges refrigerant temperature lower than 10 DEG C, makes the method for the invention can pressure recovery energy more fully.
Nitric acid absorption tower, pressure energy are reclaimed compressor and pressure energy recovery tower three combination by the present invention, achieve the effective conversion between energy.Owing to being be directly heat energy by pressure energy, wherein almost thering is no mechanical friction loss, so effciency of energy transfer is high, and utilize fully, energy consumption can be reduced directly to existing nitric acid production plant, improve assimilated efficiency and increase economic benefit.
Accompanying drawing explanation
Fig. 1 is the structural representation of nitric acid production plant of the present invention, wherein: T1 nitric acid absorption tower; T2 is pressure energy recovery tower; 1 is oxides of nitrogen gas entrance; 2 is pipeline; 3 is nitric acid discharge tube; 4 is exhaust emission pipeline; 5 is gas pipeline; 6 is fluid pipeline; 7 is fluid pipeline; 8 is exhaust emission pipeline; 9 is absorption liquid entrance; 10 is heat transferring medium supply pipeline; F1 is tail gas turbine device; Q1, Q2 are heat exchanger; P1 is recycle pump.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The nitric acid production plant that realized tail gas pressure energy is as shown in Figure 1 recycled, comprises nitric acid absorption tower T1, the tail gas turbine device F1 and pressure energy recovery tower T2 that connect successively;
Wherein, nitric acid absorption tower T1 top is provided with absorption liquid entrance 9 and exhaust emission pipeline 4, and bottom is provided with oxides of nitrogen gas entrance 1 and nitric acid discharge tube 3; Exhaust emission pipeline 4 is connected with tail gas turbine device F1, nitric acid absorption tower T1 tower body is provided with two heat exchanger Q1 and Q2 mutually connected, heat exchanger Q1 is provided with refrigerant inlet and refrigerant exit (sign), and this refrigerant exit is connected to the top of pressure energy recovery tower T2 via pipeline 7;
Tail gas turbine device F1 is connected to the bottom of pressure energy recovery tower T2 via pipeline 5, the top of pressure energy recovery tower T2 is provided with exhaust emission pipeline 8, bottom is provided with heat transferring medium discharge tube, and this heat transferring medium discharge tube is connected to the refrigerant inlet of heat exchanger Q1 via recycle pump P1.
Embodiment 2
Compared with embodiment 1, distinctive points is only: in the present embodiment, and pressure energy recovery tower is packing tower, is provided with the heat and mass inner member for gas-liquid direct contact heat transfer in tower, and described filler is the plastic filler of height 1-20m, more preferably 5-10 rice.
Embodiment 3
Compared with embodiment 1 or 2, distinctive points is only, the present embodiment is also provided with heat transferring medium supply pipeline 10 at pressure energy recovery tower T2 top, and bottom is also provided with liquidometer.
Embodiment 4
Compared with any one of embodiment 1-3, distinctive points is only: the present embodiment is also provided with the refrigerator of further coolant adding on heat exchanger Q1 or Q2.
Embodiment 5
Certain factory 50,000 tons/year of high-pressure process nitric acid production plants (embodiment 1-4 arbitrary shown in), it is primarily of absorptive unit and pressure energy recovery unit composition, utilize this device to carry out the key step of tail gas pressure energy recycling and parameter as follows: about 22000Nm
3/ h oxides of nitrogen gas is delivered to bottom nitric acid absorption tower T1 by oxides of nitrogen gas entrance 1, and nitric acid absorption tower T1 is composed in series by two, front and back tower, and tower diameter is 2600.The absorption liquid of nitric acid absorption tower T1 is water, enter in tower by the absorption liquid entrance 9 at top, with rise oxides of nitrogen gas counter current contact reactive absorption and heat release, the pressure of nitric acid absorption tower T1 is 0.7MPa, after reactive absorption gained nitric acid by nitric acid discharge tube 3 export send to concentrated.Tail gas after absorption is then discharged by exhaust emission pipeline 4.The tail gas pressure of exhaust emission pipeline 4 is 0.61MPa, and after entering pressure energy recovery compressor F1 pressure recovery energy, tail gas pressure reduces to 0.186MPa, and tail gas directly sends into pressure energy recovery tower T2 by gas pipeline 5 again.After above-mentioned steps operation, the temperature of the heat transferring medium (water) obtained at the bottom of T2 tower is 4.2 DEG C, and the gas after energy recovery is discharged from exhaust emission pipeline 8.Reclaim and cycle heat exchange operation through above-mentioned pressure energy, in the constant situation of other operating parameters of nitric acid absorption tower T1, its service temperature on average drops to 5.3 DEG C.Due to the decline of absorption temperature, nitric acid absorption tower T1 is per hour can produce more 100% nitric acid 23kg, be equivalent to reduce discharging NOx to air in tail gas and be about 100t/a, can be enterprise increases direct economic benefit about 500,000 yuan simultaneously.
Embodiment 6
Certain factory 80,000 tons/year of high-pressure process nitric acid production plants (embodiment 1-4 arbitrary shown in), it is primarily of absorptive unit and pressure energy recovery unit composition, utilize this device to carry out the key step of tail gas pressure energy recycling and parameter as follows: about 33000Nm
3/ h oxides of nitrogen gas is delivered to bottom nitric acid absorption tower T1 by oxides of nitrogen gas entrance 1, and nitric acid absorption tower T1 is composed in series by two, front and back tower, and tower diameter is 3400.The absorption liquid of nitric acid absorption tower T1 is that water enters in tower by the absorption liquid entrance 9 at top, with rise oxides of nitrogen gas counter current contact reactive absorption and heat release, the pressure of nitric acid absorption tower T1 is 0.75MPa, and after reactive absorption, gained nitric acid is sent to concentrated by nitric acid discharge tube 3 output.Tail gas after absorption is then discharged by exhaust emission pipeline 4.The tail gas pressure of exhaust emission pipeline 4 is 0.69MPa, and after entering pressure energy recovery compressor F1 pressure recovery energy, tail gas pressure reduces to 0.17MPa, and tail gas directly sends into pressure energy recovery tower T2 by gas pipeline 5 again.After above-mentioned steps operation, the temperature of the heat transferring medium (water) obtained at the bottom of T2 tower is 4.4 DEG C, and the gas after energy recovery is discharged from exhaust emission pipeline 8.Reclaim and cycle heat exchange operation through above-mentioned pressure energy, in the constant situation of other operating parameters of nitric acid absorption tower T1, its service temperature on average drops to 5.1 DEG C.Due to the decline of absorption temperature, nitric acid absorption tower T1 is per hour can produce more 100% nitric acid 35kg, be equivalent to reduce discharging NOx to air in tail gas and be about 155t/a, can be enterprise increases direct economic benefit about 700,000 yuan simultaneously.
Embodiment 7
Certain factory 150,000 tons/year of double pressurized method nitric acid production plants (embodiment 1-4 arbitrary shown in), it is primarily of absorptive unit and pressure energy recovery unit composition, utilize this device to carry out the key step of tail gas pressure energy recycling and parameter as follows: about 62000Nm
3/ h oxides of nitrogen gas is delivered to bottom nitric acid absorption tower T1 by oxides of nitrogen gas entrance 1, and nitric acid absorption tower T1 is composed in series by two, front and back tower, and tower diameter is 4400.The absorption liquid of nitric acid absorption tower T1 is water, enter in tower by the absorption liquid entrance 9 at top, with rise oxides of nitrogen gas counter current contact reactive absorption and heat release, the pressure of nitric acid absorption tower T1 is 0.95MPa, after reactive absorption gained nitric acid by nitric acid discharge tube 3 export send to concentrated.Tail gas after absorption is then discharged by exhaust emission pipeline 4.The tail gas pressure of exhaust emission pipeline 4 is 0.84MPa, and after entering pressure energy recovery compressor F1 pressure recovery energy, tail gas pressure reduces to 0.22MPa, and tail gas directly sends into pressure energy recovery tower T2 by gas pipeline 5 again.After above-mentioned steps operation, the temperature of the heat transferring medium (water) obtained at the bottom of T2 tower is 4.4 DEG C, and the gas after energy recovery is discharged from exhaust emission pipeline 8.Reclaim and cycle heat exchange operation through above-mentioned pressure energy, in the constant situation of other operating parameters of nitric acid absorption tower T1, its service temperature on average drops to 6.4 DEG C.Due to the decline of absorption temperature, nitric acid absorption tower T1 is per hour can produce more 100% nitric acid 52kg, be equivalent to reduce discharging NOx to air in tail gas and be about 260t/a, can be enterprise increases direct economic benefit about 1,040,000 yuan simultaneously.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (11)
1. can realize the nitric acid production plant that tail gas pressure energy is recycled, it is characterized in that: comprise the nitric acid absorption tower, tail gas turbine device and the pressure energy recovery tower that connect successively;
Described nitric acid absorption tower top is provided with absorption liquid entrance and exhaust emission pipeline, and bottom is provided with oxides of nitrogen gas entrance and nitric acid discharge tube; Described exhaust emission pipeline is connected with tail gas turbine device, and described nitric acid absorption tower tower body is provided with at least one heat exchanger, and described heat exchanger comprises refrigerant inlet and refrigerant exit, and described refrigerant exit is connected to the top of pressure energy recovery tower via pipeline;
Described tail gas turbine device is connected to the bottom of pressure energy recovery tower via pipeline, the top of described pressure energy recovery tower is provided with exhaust emission pipeline, bottom is provided with heat transferring medium discharge tube, and described heat transferring medium discharge tube is connected to the refrigerant inlet of described heat exchanger via recycle pump.
2. nitric acid production plant according to claim 1, is characterized in that: described pressure energy recovery tower is packing tower, is provided with the heat and mass inner member for gas-liquid direct contact heat transfer in tower, and the filler in described packing tower is the plastic filler of height 1-20m.
3. nitric acid production plant according to claim 2, is characterized in that: the filler in described packing tower is the plastic filler of height 5-10 rice.
4. nitric acid production plant according to claim 1 and 2, is characterized in that: described pressure energy recovery tower upper lateral part is also provided with heat transferring medium supply pipeline.
5. nitric acid production plant according to claim 1 and 2, is characterized in that: be also provided with liquidometer bottom described pressure energy recovery tower.
6. nitric acid production plant according to claim 1, is characterized in that: described heat exchanger is two of series connection mutually.
7. the nitric acid production plant according to claim 1 or 6, is characterized in that: the refrigerator described heat exchanger being also provided with further coolant adding.
8. utilize nitric acid production plant described in claim 1 to carry out the method for tail gas pressure energy recycling, comprise the following steps:
(1) from the oxides of nitrogen gas of ammonia oxidation unit bottom Cemented filling to nitric acid absorption tower, flow from bottom to top in nitric acid absorption tower, enter and top-down absorption liquid countercurrent flow with from apical sink liquid entrance, contact reacts generates nitric acid, release heat simultaneously and absorbed by heat exchanger, gained nitric acid is discharged from the nitric acid discharge tube of bottom, and high pressure exhaust gas drains into tail gas turbine device from exhaust emission pipeline;
(2) in described heat exchanger, refrigerant enters the heat transferring medium of pressure energy recovery tower as pressure energy recovery tower after heating up, high pressure exhaust gas drains into pressure energy recovery tower after tail gas turbine device recovery part energy, in pressure energy recovery tower, the low temperature exhaust gas risen sprays with tower top and lower heat transferring medium contacts and carries out direct heat exchange, and the exhaust emission pipeline from top after tail gas undergoes rapid expansion in pressure energy recovery tower absorbs heat is discharged;
(3) heat transferring medium in pressure energy recovery tower after cooling drops at the bottom of tower, by recycle pump by Cemented filling to absorption tower interchanger as refrigerant, to take away the reaction heat that reactive absorption in nitric acid absorption tower is released.
9. method according to claim 8, is characterized in that, the described method liquidometer also comprised bottom according to pressure energy recovery tower controls heat transferring medium supply pipeline to adjust the balance of heat transferring medium.
10. method according to claim 8 or claim 9, is characterized in that: pressure energy recycles the working pressure of tower for being 0.005-0.02MPa.
11. methods according to claim 8 or claim 9, is characterized in that: described pressure energy recovery tower intake pressure is greater than 0.15Mpa, and pressure energy recovery tower discharges refrigerant temperature lower than 10 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395502A (en) * | 2000-01-14 | 2003-02-05 | 克鲁普犹德有限公司 | Method for removal of NOx and N2O from residual gas in nitric acid production |
| CN103566739A (en) * | 2013-10-24 | 2014-02-12 | 南京大学 | Method for resource recovery of nitrogen oxides (NOx) in nitric acid industrial waste gas |
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| JP2004263952A (en) * | 2003-03-03 | 2004-09-24 | Jfe Engineering Kk | Heat recovering method and device from exhaust gas |
| JP2010281525A (en) * | 2009-06-05 | 2010-12-16 | Mitsubishi Heavy Industries Mechatronics Systems Ltd | Exhaust gas heat recovery system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1395502A (en) * | 2000-01-14 | 2003-02-05 | 克鲁普犹德有限公司 | Method for removal of NOx and N2O from residual gas in nitric acid production |
| CN103566739A (en) * | 2013-10-24 | 2014-02-12 | 南京大学 | Method for resource recovery of nitrogen oxides (NOx) in nitric acid industrial waste gas |
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