CN110887050B - Device for removing VOC (volatile organic compounds) and reducing odor from waste gas - Google Patents
Device for removing VOC (volatile organic compounds) and reducing odor from waste gas Download PDFInfo
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- CN110887050B CN110887050B CN201811051997.8A CN201811051997A CN110887050B CN 110887050 B CN110887050 B CN 110887050B CN 201811051997 A CN201811051997 A CN 201811051997A CN 110887050 B CN110887050 B CN 110887050B
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 87
- 239000002912 waste gas Substances 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 112
- 239000007800 oxidant agent Substances 0.000 claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 claims abstract description 45
- 238000002485 combustion reaction Methods 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 140
- 230000003647 oxidation Effects 0.000 claims description 102
- 235000019645 odor Nutrition 0.000 claims description 44
- 238000010926 purge Methods 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 48
- 239000011232 storage material Substances 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 230000001172 regenerating effect Effects 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 238000005338 heat storage Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000499 gel Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005200 wet scrubbing Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0216—Other waste gases from CVD treatment or semi-conductor manufacturing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Mechanical Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Incineration Of Waste (AREA)
Abstract
The invention discloses a device for removing VOC (volatile organic compound) from waste gas and reducing odor. The device for removing VOC and reducing odor from waste gas comprises: a thermal oxidizer configured to generate a combustion reaction of fuel and air and an oxidation reaction of the VOCs and a catalytic oxidizer configured to generate an oxidation reaction of the VOCs, which are connected in series with each other.
Description
Technical Field
The invention discloses a device for removing VOC and reducing odor from waste gas, in particular to a device for removing VOC and reducing odor from waste gas, which comprises a thermal oxidation chamber and a catalytic oxidation chamber which are connected in series.
Background
Exhaust gas discharged in a semiconductor process or the like is called waste gas (waste gas). Since such exhaust gas contains voc (volatile Organic compound) harmful to the human body, it should be properly treated before it is released into the atmosphere.
As the exhaust gas treatment technology thus including VOC, there are wet scrubbing (scrubbing), adsorption (adsorption), and combustion (oxidation) methods. However, in the case of wet scrubbing, the solubility of most VOCs in water is not high and high performance cannot be expected, and in addition, many adsorbents (adsorbents) are used for adsorption, so that the installation site is large, the replacement period is short, the operation cost such as waste disposal cost is high, and the manageability is also poor. In view of the heat contained by the VOC itself, the combustion method is most suitable in terms of efficiency and manageability.
The combustion processing method can be roughly classified into a direct Thermal Oxidation (TO), a Catalytic Thermal Oxidation (CTO), and a Regenerative Thermal Oxidation (RTO).
The direct Thermal Oxidation (TO) has the disadvantage of excessive fuel consumption, which results in the production of large amounts of thermal nitrogen oxides (thermal NO)x) Catalyst thermal oxidation mode(CTO) has a problem that the catalyst requires high investment cost in the early stage and needs to be replaced periodically.
Therefore, in recent years, a Regenerative Thermal Oxidation (RTO) method, which is relatively low in fuel consumption and investment cost at the early stage and does not incur catalyst replacement cost, is preferred in an actual industrial site. In particular, as a characteristic in a semiconductor process, an organic material containing a silicon (Si) element (for example, HMDSO (C)) is used2H18OSi2) When the catalyst is used in the exhaust gas, the exhaust gas is oxidized at a low temperature of 500 ℃ or lower using the catalyst, which causes incomplete decomposition and irreversible chemisorption on the surface of the catalyst, thereby causing a problem of a decrease in the activity of the catalyst. Therefore, a stage of direct thermal oxidation or regenerative thermal oxidation in which the combustion temperature is high should be performed.
Fig. 1 is a schematic view of a high temperature Regenerative Thermal Oxidizer (RTO) 10 for removing VOC from exhaust gas by high temperature incineration according to the prior art.
As shown in fig. 1, the regenerative thermal oxidizer 10 may include an intake port 11, flow path changing units 18-1 and 18-2, heat storage materials 14-1 and 14-2, a combustion zone 13, a burner unit 15, a combustion air supply fan 16, an exhaust fan 17, and an exhaust port 12.
The operation and effect of the regenerative thermal oxidizer 10 will be described in detail.
First, exhaust gas (not shown) flows in from the intake port 11 and then flows into the heat storage material 14-1 via the flow path changing unit 18-1. At this time, the heat of the heat storage material 14-1 is transferred to the exhaust gas, so that the temperature of the exhaust gas and the combustion zone 13 increases, and the temperature of the heat storage material 14-1 decreases. Therefore, the amount of heat supplied to the combustion zone 13 by the burner unit 15 is reduced, and the amount of FUEL (FUEL) used can be reduced.
Secondly, the VOC in the exhaust gas is oxidized in the combustion zone 13 and converted into carbon dioxide and water harmless to the human body. The combustion zone 13 is a position where a combustion reaction occurs between the fuel supplied from the burner unit 15 and the air supplied from the combustion air supply fan 16 by the action of the burner unit 15.
Then, the exhaust gas passing through the combustion zone 13 flows into the heat storage material 14-2. At this time, the heat of the exhaust gas is transferred to the heat storage material 14-2, so that the exhaust gas temperature decreases and the heat storage material 14-2 temperature increases.
Thereafter, the exhaust gas discharged from the heat storage material 14-2 is discharged to the outside through the exhaust port 12 via the flow path changing unit 18-2 and the exhaust fan 17.
When the regenerative thermal oxidizer 10 is operated for a long time in this manner, the heat of the heat storage material 14-1 is exhausted and the heat of the heat storage material 14-2 becomes saturated. At this time, the flow path of the exhaust gas is changed by the flow path changing units 18-1 and 18-2, and the exhaust gas flows in the direction in which the thermal storage material 14-1 flows via the thermal storage material 14-2. In this case, the heat of the thermal storage material 14-2 is transferred to the exhaust gas flowing into the thermal storage material 14-2 through the intake port 11, and the heat of the exhaust gas passing through the combustion zone 13 is transferred to the thermal storage material 14-1.
As described above, in the regenerative thermal oxidizer 10, the exhaust gas flow path is operated in an alternating manner by the action of the flow path changing units 18-1 and 18-2 along with the heat storage state of the heat storage materials 14-1 and 14-2. As these flow path changing units 18-1 and 18-2, dampers or rotary flow dividing valves may be used.
However, since the flow path changing units 18-1 and 18-2 frequently perform the flow path changing operation, there are problems that the durability thereof is deteriorated, the service life is shortened, or the exhaust gas leaks to generate odor, etc.
In addition, exhaust gas discharged during the treatment of silicon element such as semiconductor process includes various organosilicon components which are thermally oxidized to form silicon dioxide (SiO)2). The fine particle Silica (SiO) is used even if the thermal oxidation operation temperature for treating the organic exhaust gas is 850 ℃ or lower2) The efficiency and the life span of the heat accumulating materials 14-1 and 14-2 are remarkably reduced since the silica gel thus formed in the heat accumulating materials 14-1 and 14-2 cannot be removed by the maintenance work at the high temperature portion of the regenerative thermal oxidizer 10 where the flame portions of the burner unit 15 higher than 2000 c are melted and combined with each other to be accumulated in the form of silica gel on the upper end portions of the heat accumulating materials 14-1 and 14-2, in particular.
Operation for reducing heat accumulating type thermal oxidation device 10As a temperature, the silicon dioxide (SiO) can be reduced2) The oxidation of VOC is also reduced, and as a result, there is a problem that the VOC removal efficiency is lowered.
Fig. 2 is a schematic view of a high-temperature recovery thermal oxidizer (20) for discharging VOC in exhaust gas through a heat exchanger after high-temperature incineration according to the prior art.
In fig. 2, solid arrows indicate the flow path of VOC inflow exhaust gas (i.e., exhaust gas), and dotted arrows indicate the flow path of VOC treatment exhaust gas (i.e., purge gas).
As shown in fig. 2, the high temperature recovery type thermal oxidizer 20 may include a cylindrical shell 21, a tube bundle 22 composed of a plurality of tubes disposed in the shell 21, partition walls 23 disposed in the shell 21 in a zigzag manner, and burners 24.
VOC exhaust gas (i.e., exhaust gas) flowing into the intake Gi is supplied into the shell 21 by the exhaust fan F, and then flows toward the outside of the tube bundle 22 in a zigzag manner through the partition walls 23. Thereafter, the VOC exhaust gas is burned by the burner 24, then flows into the respective tubes constituting the tube bundle 22, and is then discharged to the outside of the housing 21, through another exhaust fan F, to the outside from an exhaust port Go formed on the stack.
The high-temperature recovery type thermal oxidizer 20 has a structure of even silicon dioxide (SiO)2) The gel and the silica gel are accumulated in the respective tubes, and the structure of the accumulated silica gel can also be removed by periodic maintenance.
However, the shell and tube heat exchanger (shell and tube heat exchanger) provided in the high temperature recovery thermal oxidizer 20 has a very low heat recovery rate of 40% to 70%, and discharges high temperature exhaust gas of about 350 ℃ even when the oxidation temperature is slightly lowered to 1400 ° f (760 ℃) and then the operation is performed. The problem of the heat exchanger volume is too big also exists in improving heat recovery efficiency.
Disclosure of Invention
The invention provides a device for removing VOC and reducing odor from exhaust gas, which comprises a thermal oxidation chamber and a catalytic oxidation chamber which are connected in series.
An apparatus for removing voc (volatile organic compound) and reducing odor from exhaust gas as an embodiment of the present invention comprises:
a thermal oxidation chamber and a catalytic oxidation chamber which are connected in series,
the thermal oxidizer is configured to generate a combustion reaction of fuel and air and an oxidation reaction of VOCs,
the catalytic oxidation chamber is configured to generate an oxidation reaction of the VOC.
The apparatus for removing VOCs and reducing odors from exhaust gases further comprises: at least one heat exchanger disposed between the thermal oxidation chamber and the catalytic oxidation chamber, the at least one heat exchanger being configured to cause heat exchange between the off-gas before being supplied to the thermal oxidation chamber and the purge gas discharged from the thermal oxidation chamber.
The at least one heat exchanger includes: a shell and tube heat exchanger (shell and tube heat exchanger) and a first plate heat exchanger connected in series with each other, a front end portion of the shell and tube heat exchanger being connected to a rear end portion of the thermal oxidation chamber, a rear end portion of the first plate heat exchanger being connected to a front end portion of the catalytic oxidation chamber, the shell and tube heat exchanger being configured to cause heat exchange between the off-gas before being supplied to the thermal oxidation chamber and the clean gas discharged from the thermal oxidation chamber after passing through the first plate heat exchanger, the first plate heat exchanger being configured to cause heat exchange between the off-gas before being supplied to the thermal oxidation chamber and the shell and tube heat exchanger and the clean gas after being discharged from the thermal oxidation chamber and passing through the shell and tube heat exchanger.
The shell-and-tube heat exchanger is a high-temperature heat exchanger higher than 550 ℃, and the first plate heat exchanger is a medium-temperature heat exchanger lower than 550 ℃.
The apparatus for removing VOCs and reducing odors from exhaust gases further comprises: a second plate heat exchanger connected to a rear end portion of the catalytic oxidation chamber, the second plate heat exchanger being configured to cause heat exchange between the exhaust gas before being supplied to the thermal oxidation chamber and the at least one heat exchanger and the purge gas discharged from the catalytic oxidation chamber.
The first plate heat exchanger is a medium temperature heat exchanger below 550 ℃.
The concentration of the exhaust gas is 500ppm to 3000 ppm.
The catalytic oxidation chamber comprises: at least one noble metal selected from platinum (Pt) and palladium (Pd); at least one transition metal selected from the group consisting of copper (Cu), cobalt (Co), chromium (Cr), manganese (Mn), iron (Fe), silver (Ag) and nickel (Ni); mixtures thereof; or an oxidation catalyst prepared from an alloy thereof.
The internal temperature of the thermal oxidation chamber is maintained at 750 ℃ to 850 ℃.
The internal temperature of the catalytic oxidation chamber is maintained at 350 to 450 ℃.
According to the embodiment, the VOC concentration of the organic exhaust gas discharged in the semiconductor process is 100ppm or less based on Total Hydrocarbons (THC), and the VOC concentration concentrated in high concentration by the adsorption and desorption process of the concentrator and flowed into the existing high temperature regenerative thermal oxidizer is about 1000ppm to 2000ppm (in THC standard), and at this time, the dilution factor of the odor is 3000 times or more. The existing high-temperature heat accumulating type thermal oxidation device generally has 90 to 98 percent of VOC removing efficiency (based on THC standard), and VOC is discharged at the exhaust port of the device at the concentration of more than 20ppm (based on THC standard). In particular, since the dilution ratio of the odor at this concentration is about 200 to 300 times, it is necessary to install an additional treatment device only for odor treatment in an odor-sensitive business.
According to the apparatus for removing VOC from exhaust gas and improving odor of the present invention, in the direct oxidation part, it is possible to achieve a VOC removal efficiency (in the THC standard) of 90% or more by compensating for a 2% to 5% reduction in efficiency due to leakage in the conventional high-temperature regenerative thermal oxidation apparatus, and it is possible to achieve a VOC removal efficiency (in the THC standard) of 99% or more by performing the secondary catalytic oxidation process on the residual VOC detected by odor, and it is possible to maintain an odor dilution factor of 50 times or less. In addition, even silicon dioxide (SiO) contained in the organic exhaust gas2) Silica gel is formed, but this silica gel is formed in the tubes of the thermal oxidizer and high temperature heat exchanger and can be removed by maintenance equipment.
Drawings
Fig. 1 is a schematic view of a high-temperature regenerative thermal oxidizer provided to remove VOC in exhaust gas by high-temperature incineration according to the prior art;
fig. 2 is a schematic view of a high-temperature recovery type thermal oxidizer for discharging VOC in exhaust gas through a heat exchanger after high-temperature incineration according to the prior art;
fig. 3 is a schematic view of an apparatus for removing VOC and reducing odor from exhaust gas according to an embodiment of the present invention.
Reference numbers in the figures:
10: a high-temperature heat accumulating type thermal oxidation device,
11: an air inlet is arranged at the bottom of the air inlet,
12: an air outlet is arranged on the air inlet,
13: the combustion zone is provided with a combustion chamber,
14-1, 14-2: a heat-storage material, a heat-absorbing material,
15: a burner unit for use in a gas turbine,
16: an air supply fan for combustion is provided,
17: an exhaust fan is arranged on the air inlet of the air conditioner,
18-1, 18-2: a flow path changing unit for changing a flow path of the liquid,
20: a high-temperature recovery type thermal oxidizer,
21: a cylindrical shell body, a plurality of cylindrical shell bodies,
22: a tube bundle of a plurality of tubes,
23: the partition wall is provided with a plurality of partition walls,
24: a burner, a gas-liquid separator and a gas-liquid separator,
30: a device for removing VOC and reducing odor,
31: a thermal oxidation chamber is arranged in the thermal oxidation chamber,
32: a shell-and-tube heat exchanger,
33. 35: a plate-type heat exchanger is provided with a heat exchanger,
34: a catalytic oxidation chamber.
Detailed Description
Hereinafter, an apparatus for removing voc (volatile organic compound) and reducing odor from exhaust gas according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
Herein, "VOC" means an organic chemical having a high vapor pressure at normal temperature (20 ℃ to 25 ℃).
Further, herein, "waste gas" (waste gas) means an exhaust gas discharged in a semiconductor process or the like.
In addition, herein, "purified gas" means a gas in which the exhaust gas is purified in the thermal oxidation process and/or the catalytic oxidation process.
Further, herein, "thermal oxidation" means a reaction of decomposing exhaust gas at a higher temperature than catalytic oxidation, and hydrocarbon pollutants (e.g., VOCs) in the exhaust gas are chemically oxidized into carbon dioxide and water by thermal combustion.
Further, herein, "catalytic oxidation" means a process of decomposing exhaust gas with a catalyst at a lower temperature relative to thermal oxidation, by which hydrocarbon pollutants (e.g., VOCs) in exhaust gas are chemically oxidized into carbon dioxide and water by catalytic action.
In addition, herein, "front end portion" means a portion located in the reverse direction based on the flow direction of the purge gas, and "rear end portion" means a portion located in the forward direction based on the flow direction of the purge gas.
Further, herein, "oxidizing" or "oxidation catalyst" means converting VOCs and/or carbon monoxide (CO) to carbon dioxide (CO), respectively2) And water and a catalyst.
Fig. 3 is a schematic view of an apparatus for removing VOC and reducing odor from exhaust gas according to an embodiment of the present invention.
As shown in fig. 3, the apparatus 30 for removing VOC from exhaust gas and reducing odor may include a thermal oxidation chamber 31 and a catalytic oxidation chamber 34.
The VOC concentration of the off-gas may be 500ppm to 3000ppm (on a total hydrocarbon volume basis).
The thermal oxidizer 31 may be configured to generate a combustion reaction of fuel and air and an oxidation reaction of VOC (i.e., a thermal oxidation reaction).
The thermal oxidation chamber 31 may have a gas burner (a portion indicated by a flame shape). The gas burners are supplied with fuel and air, respectively, to effect combustion reaction of the fuel and air in the thermal oxidizer 31. The fuel may be Liquefied Natural Gas (LNG). By the combustion reaction, the exhaust gas flowing into the thermal oxidation chamber 31 is heated, and in the process, at least a part of VOC contained in the exhaust gas is subjected to primary oxidation to be converted into carbon dioxide and water.
The internal temperature of the thermal oxidation chamber 31 may be maintained at 750 to 850 ℃. The exhaust gas before being supplied to the thermal oxidizer 31 is preheated to 210 to 610 c by at least one heat exchanger 32, 33, 35, which will be described later, so that it is possible to reduce the fuel consumption of the thermal oxidizer 31 and to reduce the fuel cost.
The VOC removal efficiency of the thermal oxidizer 31 may be 80% to 90%. The VOC removal efficiency can be calculated by the following equation 1.
[ equation 1]
VOC removal efficiency (%) (VOC intake air concentration-VOC outlet air concentration)/(VOC intake air concentration) × 100
In addition, the thermal oxidizer 31 may convert carbon monoxide (CO) contained in the incoming exhaust gas into carbon dioxide (CO)2)。
Further, since the thermal oxidation chamber 31 has a simple structure and does not include any kind of packing inside, even if silicon (Si) included in the exhaust gas flowing inside thereof is oxidized to form, for example, silicon dioxide (SiO)2) The amorphous substance of (2) is gelled (gelation) to form a silica gel, and a blocking phenomenon by the silica gel does not occur.
The catalytic oxidation chamber 34 may be configured to undergo an oxidation reaction (i.e., a catalytic oxidation reaction) of the VOC.
The catalytic oxidation chamber 34 includes at least one oxidation catalyst.
The oxidation catalyst is prepared from the following materials: at least one noble metal selected from platinum (Pt) and palladium (Pd); at least one transition metal selected from the group consisting of copper (Cu), cobalt (Co), chromium (Cr), manganese (Mn), iron (Fe), silver (Ag) and nickel (Ni); mixtures thereof; or an alloy thereof.
The internal temperature of the catalytic oxidation chamber 34 may be maintained at 350 to 450 ℃.
Even if the catalytic oxidation chamber 34 is operated at a lower temperature of 350 to 450 c due to its function including the oxidation catalyst, at least a part of VOC remaining in the exhaust purge gas of the thermal oxidation chamber 31 can be further oxidized. The internal temperature (350 ℃ C. to 450 ℃ C.) of the catalytic oxidation chamber 34 can be controlled by at least one heat exchanger 32, 33 described later to cool the high-temperature purge gas discharged from the thermal oxidation chamber 31.
In an environment (350 ℃ C. to 450 ℃ C.) where the internal temperature of the catalytic oxidation chamber 34 is low, NO is generatedxThe yield is not low, so NO is causedxThe amount of odor generated is reduced.
The apparatus 30 for removing VOC from exhaust gas and reducing odor can achieve a VOC removal efficiency of 99% or more and an odor dilution factor of 50 or less by the combination of the thermal oxidation chamber 31 and the catalytic oxidation chamber 34. The odor dilution factor can be calculated by the following equation 2.
[ equation 2]
Odor dilution factor (volume of exhaust gas + volume of dilution air)/(volume of exhaust gas)
In said equation 2, the "dilution air volume" is defined as the minimum dilution air volume required to prevent the generation of odor in the diluted exhaust gas when the exhaust gas is diluted with dilution air.
In addition, silicon (Si) and VOC substances contained in exhaust gas flowing in a semiconductor process are oxidized, such as carbon dioxide (SiO)2) Since the temperature at which the amorphous substance is gelated (gelation) is 800 ℃ or more, thereafter, the amorphous substance such as silicon dioxide (Si) is not gelated under the environment in which the internal temperature of the catalytic oxidation chamber 34 is 350 ℃ to 450 ℃, so that the phenomenon in which the oxidation catalyst layer is blocked by the gel of the amorphous substance (e.g., silica gel) does not occur.
In addition, the catalytic oxidation chamber 34 can convert carbon monoxide (CO) generated from incompletely combusted fuel in the thermal oxidation chamber 31 into carbon monoxide (CO)2)。
The apparatus for removing VOC from exhaust gas and reducing odor 30 may further comprise at least one heat exchanger 32, 33 disposed between the thermal oxidation chamber 31 and the catalytic oxidation chamber 34.
The at least one heat exchanger 32, 33 may be configured to cause heat exchange between the off-gas before being supplied to the thermal oxidizer 31 and the purge gas discharged from the thermal oxidizer 31.
Furthermore, at least one heat exchanger 32, 33 may have a structure and operating temperature that is not blocked by the gel of amorphous material (e.g., silica gel) formed by the thermal oxidizer 31.
To this end, at least one of the heat exchangers 32, 33 may comprise a shell and tube heat exchanger (shell and tube heat exchanger)32 and a first plate heat exchanger (plate heat exchanger)33 in series with each other.
The Shell-and-tube heat exchanger 32 may comprise a cylindrical Shell (not shown in the figure) and a tube bundle (not shown in the figure) disposed within the cylindrical Shell (https:// en. Therefore, even if the thermal oxidation chamber 31 or the like forms silicon oxide (SiO)2) But the gel can be easily removed by servicing the shell-and-tube heat exchanger 32 because it accumulates within the tubes included in the tube bundle.
The front end portion of the shell-and-tube heat exchanger 32 may be connected to the rear end portion of the thermal oxidizer 31, and the rear end portion of the shell-and-tube heat exchanger 32 may be connected to the first plate heat exchanger 33.
The shell-and-tube heat exchanger 32 may be configured to cause heat exchange between the off-gas before being supplied to the thermal oxidizer 31 after passing through the first plate heat exchanger 33 and the purge gas discharged from the thermal oxidizer 31.
The shell and tube heat exchanger 32 may be a high temperature heat exchanger above 550 ℃. That is, the shell-and-tube heat exchanger 32 may be a heat exchanger capable of withstanding high temperatures in excess of 550 ℃.
The first Plate heat exchanger 33 may be a heat exchanger (https:// en. wikipedia. org/wiki/Plate _ heat _ exchanger) that transfers heat between two fluids (i.e., exhaust gas and purge gas) using a plurality of metal plates.
The front end portion of the first plate heat exchanger 33 may be connected to the rear end portion of the shell-and-tube heat exchanger 32, and the rear end portion of the first plate heat exchanger 33 may be connected to the front end portion of the catalytic oxidation chamber 34.
The first plate heat exchanger 33 may be configured to cause heat exchange between the off-gas before being supplied to the thermal oxidizer 31 and the shell-and-tube heat exchanger 32 and the purge gas passing through the shell-and-tube heat exchanger 32 after being discharged from the thermal oxidizer 31.
The first plate heat exchanger 33 may be a medium temperature heat exchanger below 550 ℃. That is, the first plate heat exchanger 33 may be a heat exchanger that can withstand a low temperature of 550 ℃. For example, the first plate heat exchanger 33 may be a brazed plate heat exchanger (brazed plate heat exchanger). For example, brazed plate heat exchangers may be constructed from a plurality of stainless steel plates vacuum brazed (vacuum brazed) with copper or nickel.
The device for removing VOC and reducing odor from exhaust gas 30 may further comprise a second plate heat exchanger 35 connected to the rear end portion of the catalytic oxidation chamber 34.
The second plate heat exchanger 35 may be configured to cause heat exchange between the exhaust gas before being supplied to the thermal oxidizer 31 and the at least one heat exchanger 32, 33 and the purge gas discharged from the catalytic oxidizer 34.
The second plate heat exchanger 35 may have the same structure and performance as the first plate heat exchanger 33. Thus, the second plate heat exchanger 35 may be a medium temperature heat exchanger below 550 ℃, as in the first plate heat exchanger 33.
Since the first plate heat exchanger 33 and the second plate heat exchanger 35 are small in volume, the volume of the equipment, i.e., the device 30 for removing VOC from exhaust gas and reducing odor can be minimized.
Furthermore, the first plate heat exchanger 33 and the second plate heat exchanger 35 have a higher heat transfer efficiency than the shell-and-tube heat exchanger 32.
Further, plate heat exchangers can be divided into a shim plate heat exchanger, which is easy to maintain but can only be used below 200 ℃, and a brazed plate heat exchanger, which can be used at slightly higher temperatures but cannot be maintained cleanly, and the operating temperature of which is also limited to 580 ℃.
The apparatus for removing VOC and reducing odor from exhaust gas 30 may further include an exhaust fan F connected to the rear end portion of the second plate heat exchanger 35.
The exhaust fan F is used to compensate for the reduction of the flow of the purge gas due to the pressure loss generated between the devices 31, 32, 33, 34, 35 to achieve a smooth flow of the purge gas.
The above-structured apparatus 30 for removing VOC from exhaust gas and reducing odor has the following advantages: the thermal oxidizer 31 and the shell-and-tube heat exchanger 32 are used in a process such as carbon dioxide (SiO)2) The amorphous substance gel (e.g., silica gel) can be operated under high temperature conditions, is not easily blocked by the gel, and the gel is easily removed by maintenance, so that the problems of the conventional regenerative thermal oxidizer shown in fig. 1, i.e., the problems associated with poor exhaust due to increased pressure loss between devices, can be prevented, the device can be operated for a longer time, and at the same time, the high-cost heat storage material and the replacement cost thereof can be saved.
The operation of the device 30 for removing VOC from exhaust gas and reducing odor and the effect thereof will be described in detail with reference to fig. 3.
In fig. 3, solid arrows indicate the flow path of VOC inflow exhaust gas (i.e., exhaust gas), and dotted arrows indicate the flow path of VOC treatment exhaust gas (i.e., purge gas).
First, the exhaust gas having a temperature T1 (e.g., 70 ℃) passes through the intake Gi and the line L1 in order from the outside, thereafter flows into the second plate heat exchanger 35 and is heated to T2 (e.g., 210 ℃). The exhaust gases passing through the second plate heat exchanger 35 flow along line L2 into the first plate heat exchanger 33.
The exhaust gases flowing into the first plate heat exchanger 33 are then heated again in the first plate heat exchanger 33 to T3 (e.g. 410 c). The exhaust gas passing through the first plate heat exchanger 33 flows into the shell-and-tube heat exchanger 32 along line L3.
Thereafter, the exhaust gas flowing into shell-and-tube heat exchanger 32 is reheated to T4 (e.g., 610℃.) in shell-and-tube heat exchanger 32. The off-gas passing through the shell-and-tube heat exchanger 32 flows into the thermal oxidizer 31 along line L4.
Next, at least a part of VOC and carbon monoxide (CO) contained in the exhaust gas flowing into the thermal oxidizer 31 are subjected to primary oxidation in the thermal oxidizer 31. The purge gas discharged from the thermal oxidizer 31 has a temperature of T5 (e.g., 750 ℃) and flows into the shell-and-tube heat exchanger 32 through a line L5.
Thereafter, the purge gas flowing into the shell-and-tube heat exchanger 32 is cooled to T6 (e.g., 550 ℃) in the shell-and-tube heat exchanger 32. The purge gas discharged from the shell-and-tube heat exchanger 32 flows into the first plate heat exchanger 33 through line L6.
The purge gas flowing into the first plate heat exchanger 33 is then cooled again in the first plate heat exchanger 33 to T7 (e.g. 350 c). The purge gas discharged from the first plate heat exchanger 33 flows into the catalytic oxidation chamber 34 through a line L7.
Thereafter, at least a part of VOC and carbon monoxide (CO) contained in the purge gas flowing into the catalytic oxidation chamber 34 are secondarily oxidized in the catalytic oxidation chamber 34. The purge gas discharged from the catalytic oxidation chamber 34, which has a temperature T8 (e.g., 350 ℃), flows into the second plate heat exchanger 35 through a line L8.
Thereafter, the purge gas flowing into the second plate heat exchanger 35 is cooled again in the second plate heat exchanger 35 to T9 (e.g. 210 ℃). The purge gas discharged from the second plate heat exchanger 35 is sucked into the exhaust fan F through a line L9, flows into the stack through a line L10, and is discharged to the outside through an exhaust port Go formed in the stack.
In fig. 3, the relationship between the temperatures of the respective portions is as follows: t1< T2< T3< T4< T5, T9< T8(═ T7) < T6< T5, and T8(═ T7) < T3.
The apparatus 30 for removing VOC from exhaust gas and reducing odor having the above-described structure can be operated at a low temperature to reduce the amount of NOx generation of odor compared to the regenerative thermal oxidizer 10 of fig. 1, and since a single flow path manner in which exhaust gas and purge gas flow in one direction is adopted, i.e., flow path changing units 18-1 and 18-2 as in the regenerative thermal oxidizer 10 of fig. 1 are not required, leakage of exhaust gas does not occur, and as a result, odor can be reduced. Also, the device 30 for removing VOC from exhaust gas and reducing odor has a relatively low operating temperature compared to the regenerative thermal oxidizer 10 of fig. 1, but has a high VOC removal efficiency and can prevent Silica (SiO) from being generated2) Such that the solid substance is gelled (gelation) and blocks pores of the heat storage material or the catalyst, thereby causing a sudden increase in pressure loss.
Further, the apparatus 30 for removing VOC and reducing odor from exhaust gas having the above-described structure can generate final purified gas at a low temperature (e.g., 210 ℃) with a higher heat recovery rate than the high-temperature recovery type thermal oxidizer 20 of fig. 2 when the total volume of the apparatus is the same.
While the present invention has been described with reference to the embodiments shown in the drawings, these are by way of example only and it is to be understood that numerous changes may be made and equivalents may be resorted to by those skilled in the art. Therefore, the technical scope of the invention in essence should be defined according to the technical idea of the attached claims.
Claims (7)
1. An apparatus for removing VOCs and reducing odors from exhaust gases comprising:
a thermal oxidation chamber and a catalytic oxidation chamber which are connected in series,
at least one heat exchanger located between the thermal oxidation chamber and the catalytic oxidation chamber and configured to cause heat exchange between the off-gas before being supplied to the thermal oxidation chamber and the purge gas discharged from the thermal oxidation chamber,
wherein the thermal oxidizer is configured to generate an oxidation reaction of VOCs in a combustion reaction of fuel and air,
the catalytic oxidation chamber is configured to generate an oxidation reaction of the VOC,
wherein the internal temperature of the thermal oxidation chamber is maintained at 750 to 850 ℃,
wherein the internal temperature of the catalytic oxidation chamber is maintained at 350 ℃ to 450 ℃.
2. The apparatus for removing VOC and reducing odor from exhaust gas as claimed in claim 1, wherein,
the at least one heat exchanger comprises a shell-and-tube heat exchanger and a first plate heat exchanger in series with each other,
the front end part of the shell-and-tube heat exchanger is connected to the rear end part of the thermal oxidation chamber, the rear end part of the first plate heat exchanger is connected to the front end part of the catalytic oxidation chamber,
the shell-and-tube heat exchanger is configured to cause heat exchange between the off-gas before being supplied to the thermal oxidizer after passing through the first plate heat exchanger and the purge gas discharged from the thermal oxidizer,
the first plate heat exchanger is configured to cause heat exchange between the off-gas before being supplied to the thermal oxidizer and the shell-and-tube heat exchanger and the purge gas passing through the shell-and-tube heat exchanger after being discharged from the thermal oxidizer.
3. The apparatus for removing VOC and reducing odor from exhaust gas as claimed in claim 2, wherein,
the shell-and-tube heat exchanger is a high-temperature heat exchanger higher than 550 ℃, and the first plate heat exchanger is a medium-temperature heat exchanger lower than 550 ℃.
4. The apparatus for removing VOC and reducing odor from exhaust gas according to claim 2 or 3, further comprising:
a second plate heat exchanger connected to a rear end portion of the catalytic oxidation chamber and configured to cause heat exchange between the exhaust gas before being supplied to the thermal oxidation chamber and the at least one heat exchanger and the purge gas discharged from the catalytic oxidation chamber.
5. The apparatus for removing VOC and reducing odor from exhaust gas as claimed in claim 4, wherein,
the first plate heat exchanger is a medium temperature heat exchanger below 550 ℃.
6. The apparatus for removing VOC and reducing odor from exhaust gas as claimed in claim 1, wherein,
the waste gas has a VOC concentration of 500ppm to 3000ppm based on the volume of total hydrocarbons.
7. The apparatus for removing VOC and reducing odor from exhaust gas as claimed in claim 1, wherein,
the catalytic oxidation chamber comprises: at least one noble metal selected from platinum and palladium; at least one transition metal selected from the group consisting of copper, cobalt, chromium, manganese, iron, silver, and nickel; mixtures thereof; or an oxidation catalyst prepared from an alloy thereof.
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| DE4204603A1 (en) * | 1992-02-15 | 1993-08-19 | Kat Tec Ges Fuer Katalysatorte | Appts. for multistage catalytic combustion of nitrogen cpds. - in gas e.g. ammonia, stripped from water percolating from refuse tip, without emission of e.g. dioxin or excess nitrogen oxide |
| CN1546211A (en) * | 2003-12-05 | 2004-11-17 | 杭州天人环保设备有限公司 | Drying room exhaust gas purification and energy recovery system and apparatus |
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| CN105964141A (en) * | 2016-07-12 | 2016-09-28 | 重庆大学 | Treatment method and system for sprayed VOCs (Volatile Organic Chemicals) mixed gas |
| CN205867998U (en) * | 2016-06-23 | 2017-01-11 | 廊坊市隆进环保设备有限公司 | Catalyst burning formula exhaust gas purification system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4204603A1 (en) * | 1992-02-15 | 1993-08-19 | Kat Tec Ges Fuer Katalysatorte | Appts. for multistage catalytic combustion of nitrogen cpds. - in gas e.g. ammonia, stripped from water percolating from refuse tip, without emission of e.g. dioxin or excess nitrogen oxide |
| CN1546211A (en) * | 2003-12-05 | 2004-11-17 | 杭州天人环保设备有限公司 | Drying room exhaust gas purification and energy recovery system and apparatus |
| CN104258713A (en) * | 2014-10-08 | 2015-01-07 | 美景（北京）环保科技有限公司 | Acid gas treatment system and method based on ammonia-process desulfurization |
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