CN100540120C - The treatment of waste gas device and the processing method that produce in the semiconductor manufacturing process - Google Patents

The treatment of waste gas device and the processing method that produce in the semiconductor manufacturing process Download PDF

Info

Publication number
CN100540120C
CN100540120C CNB200610007988XA CN200610007988A CN100540120C CN 100540120 C CN100540120 C CN 100540120C CN B200610007988X A CNB200610007988X A CN B200610007988XA CN 200610007988 A CN200610007988 A CN 200610007988A CN 100540120 C CN100540120 C CN 100540120C
Authority
CN
China
Prior art keywords
waste gas
mentioned
reaction
catalyst
adsorption
Prior art date
Application number
CNB200610007988XA
Other languages
Chinese (zh)
Other versions
CN101007237A (en
Inventor
李到禧
洪雄基
李镇九
张源哲
金斗晟
Original Assignee
高化环保技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020060008037 priority Critical
Priority to KR1020060008037A priority patent/KR100654922B1/en
Application filed by 高化环保技术有限公司 filed Critical 高化环保技术有限公司
Publication of CN101007237A publication Critical patent/CN101007237A/en
Application granted granted Critical
Publication of CN100540120C publication Critical patent/CN100540120C/en

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67011Apparatus for manufacture or treatment
    • H01L21/67017Apparatus for fluid treatment
    • H01L21/67028Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H01L21/6704Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8659Removing halogens or halogen compounds
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67011Apparatus for manufacture or treatment
    • H01L21/67098Apparatus for thermal treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0216Other waste gases from CVD treatment or semi-conductor manufacturing
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/30Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Abstract

The invention provides the treatment of waste gas device that produces in a kind of semiconductor manufacturing process, this device comprises: the waste gas inflow entrance of inflow exhaust gas; Connect the air inlet that is arranged on above-mentioned waste gas inflow entrance and air is provided; Connect and be arranged on above-mentioned waste gas inflow entrance and have the adsorption reaction portion of adsorption treatment by the adsorption layer of the waste gas of inflow entrance inflow; Connect and be arranged on above-mentioned adsorption reaction portion and have the catalytic reaction portion that the waste gas of being discharged by adsorption reaction portion flowed into and this was carried out the catalyst layer of catalytic treatment; And connect in the flow path be arranged on the waste gas that flow into above-mentioned catalytic reaction portion and the water inlet of water is provided.According to the present invention, can remove the hard-decomposed perfluoro-compound that is comprised in the waste gas that from semiconductor manufacturing process or LCD manufacturing process, produces below 800 ℃, can handle the waste gas of the perfluoro-compound that contains a large amount of and/or high concentration according to the loading of catalyst.

Description

The treatment of waste gas device and the processing method that produce in the semiconductor manufacturing process
Technical field
The present invention relates to a kind of emission-control equipment and processing method thereof that is used for handling the waste gas that produces in semiconductor manufacturing process, particularly, relate to a kind of connect the catalytic reaction portion have the adsorption reaction portion of adsorption layer and to have a catalyst layer be set constitute emission-control equipment after, make the waste gas and the air that produce in the semiconductor manufacturing process pass through this emission-control equipment, thereby pack processing is contained in the emission-control equipment and the processing method thereof of the polluters such as perfluoro-compound in the waste gas.
Background technology
Though the discharge capacity of perfluoro-compound (PFCs) is thousands of/one of carbon dioxide only, but the global greenhouse effect index is higher than carbon dioxide, and can be in atmosphere in Undec state long-term existence, be considered to constitute the material of the main cause of global warmingization.Therefore, countries in the world have been signed the climate change pact in June, 1992 in Rio de Janeiro of Brazil, and perfluoro-compound is defined as the global warming oxidizing gases; Sign " Kyoto Protocol " November 10 calendar year 2001, takes this as a foundation, and determined the perfluoro-compound discharge standard and the planning time limit of various countries.Therefore, advanced countries such as the U.S., Japan, European Union cut down target with the discharging of perfluoro-compound and are defined as 2010 and cut down 10% than the nineteen ninety-five; Korea S is defined as 2010 and cut down 10% than 1997; Taiwan is defined as 2010 and cut down 10% than 1998.
On the other hand, cause in the perfluoro-compound of global warmingization, some material foul smellings etc., cause live in perfluoro-compound produce ground, as the resident's of semiconductor fabrication factory periphery resentment, therefore, need handle the perfluoro-compound of above-mentioned malodor source conscientiously.
Particularly, in the etching work procedure in semiconductor manufacturing process,, use BCl for the etched wafer surface 3, Cl 2, F 2, sour gas and CF such as HBr, HCl, HF 4, CHF 3, C 2F 6, C 3F 8, C 4F 6, C 4F 8, C 5F 8NF 3, SF 6Deng perfluoro-compound; In the deposition procedures in chemical vapour deposition (CVD) (CVD:ChemicalVapor Deposition) operation,, use as AsH for the surface deposition of wafer 3, NH 3, PH 3, SiH 4, Si 2H 2Cl 2Deng gas; In washing procedure, under the condition that plasma exists, use as NF 3, C 2F 6, C 3F 8Deng perfluoro-compound, therefore need to handle the operation of above-mentioned perfluoro-compound conscientiously.
As the method for removing above-mentioned perfluoro-compound, can enumerate direct firing method, indirect method, plasma method, catalyst method etc., above-mentioned direct firing method produce when utilizing liquefied natural gas (LNG) or combustion of hydrogen 1,400~1,600 ℃ spark makes the perfluoro-compound oxidation convert carbon dioxide, fluorine (F to 2) and/or HF remove.
But, because above-mentioned direct firing method is used liquefied natural gas or hydrogen etc. as raw material, therefore, existing manufactory (FAB) at the supply equipment that does not possess liquid natural gas or hydrogen can not use, and, the safety measure that needs problems such as corresponding fire and blast, the perfluoro-compound that needs to handle is 1, processed in 400~1,600 ℃ the high temperature, therefore there is problems such as increasing required running expense, in addition, owing in high temperature, burn, therefore produce the NOx that becomes reasons such as acid rain, photochemical smog, have the problem that causes the secondary atmosphere pollution.
Especially, above-mentioned direct firing method is used a large amount of fossil fuels for high-temp combustion, therefore, exist a large amount of dischargings to be considered to the problem of the carbon dioxide of global warming reason, and, in order to handle perfluoro-compound effectively, need to form the high temperature spark of wide scope, but this is difficult to reach, and therefore, the treatment of waste gas that contains a large amount of perfluoro-compounds is restricted.
On the one hand, the indirect method is to utilize heater, improves the temperature of reactor indirectly, thereby the method that makes the perfluoro-compound oxidation and remove as direct firing method generally 1,100~1, is moved in 200 ℃ the temperature range, so not only is difficult to remove as CF 4Etc. hard-decomposed perfluoro-compound, and, in the life-span owing to high temperature heating shortening heater, there is the problem that is difficult to work continuously.
Plasma method be utilize RF (Radio Frequency: radio frequency) or hot plasma decompose the method for removing perfluoro-compound, by plasma decomposes perfluoro-compound can be again in conjunction with and convert the perfluoro-compound of other kinds to, therefore the efficient of removing whole perfluoro-compounds is very low, and exists generation as COF 2Problem Deng noxious material, in addition, therefore the characteristics of plasma device are the vacuum height, are preferably disposed on the plasma device that turns round between high semiconductor-fabricating device of the activate of plasma and the pump, but have the etching problem of the pump that the fluorine that generated by reaction and HF cause.
In order to address the above problem, can use in the rear end of the low pump of vacuum, but this moment, the activate of plasma was a problem, can not obtain high removal efficient, and, because therefore the experimental data deficiency of the internal structure of article on plasma body device considers that from the semiconductor manufacturing process that needs are worked continuously its use is very restricted.
And in the above-mentioned plasma method, the complex structure of its plasma device is difficult to guarantee the security of plasma, therefore has the problem of the perfluoro-compound that can not remove high flow capacity/high concentration.
Therefore, in order to overcome the problem points of direct firing method, indirect method and plasma method, implement recently to utilize catalyst to remove the method for perfluoro-compound.
Utilize the removal method of the perfluoro-compound of catalyst, can reduce the decomposition activation energy of above-mentioned perfluoro-compound, thereby can in the low temperature below 800 ℃, remove CF 4Etc. hard-decomposed perfluoro-compound, loading according to catalyst, can handle the waste gas that comprises a large amount of and/or high concentration perfluoro-compound, even because of reasons such as earthquake and/or outage can not provide energy for the moment, but, can remove perfluoro-compound within a certain period of time according to the accumulation of heat effect of catalyst or heat-storage agent.
On the one hand, the processing method of the general perfluoro-compound that produces in the simple declaration semiconductor manufacturing process, the chemically stable perfluoro-compound that utilizes decomposition such as plasma in semiconductor manufacturing process, to produce, the fluorine that produces when utilizing above-mentioned decomposition, the solid metal (Si etc.) that will be present in etching work procedure or reactor and the pipe arrangement converts SiF to 4Form remove, and discharge unreacted fluorine and undecomposed perfluoro-compound.
In above-mentioned etching work procedure, except that being used for etched sour gas, the AlCl that etching produces 3, AlF 3, SiCl 4, SiF 4Be discharged from simultaneously Deng gas and unreacted perfluoro-compound.
And, be used for the AsH of the surface deposition process of wafer 3, PH 3, SiH 4, Si 2H 2Cl 2Deng gas at the oxidized As that converts to of catalyst layer xO y, P xO y, SiO 2Deng oxide, the AlCl that produces in etching or the washing procedure 3, SiCl 4, SiF 4Deng chlorination or fluorinated gas then at the oxidized Al that converts to of catalyst layer 2O 3, SiO 2Processed Deng soild oxide.
But the soild oxide that produces in the above-mentioned processing procedure etc. is stacked on catalyst layer, causes the phenomenon on blocking catalyst laminar flow road, therefore becomes the reason of the pressure loss that strengthens catalyst layer, particularly, and the AlCl that in the metal etch operation, produces 3Though under the temperature more than 120 ℃, exist with gas form, but in this temperature with the next particulate matter that converts solid forms to, therefore be inserted into when the catalyst layer of running below 120 ℃, become the reason of the pressure loss, and the sour gas in being included in waste gas is when flowing into catalyst layer with the state of not removing, because these acidic materials absorption and being reflected on the catalyst, exists the problem that becomes the reason that the non reversibility catalyst activity reduces.
Therefore, remove with catalyst under the situation of the waste gas comprise perfluoro-compound, must be before flowing into catalyst layer, remove sour gas, deposition gases, by chlorination and metal fluoride that etching and washing produced.
In order to overcome the problems referred to above, Korean Patent discloses 2003-0025777 number, the wet type gas cleaning unit that makes water or buck in the setting of catalyst layer front end is disclosed, thereby remove the method for water miscible sour gas and chlorination and metal fluoride, when utilizing above-mentioned water to carry out the wet type gas scrubbing, it is soluble in water and be removed that sour gas converts the form of HCl or HF to.
At this moment, because it is strong to contain the solution corrosion of above-mentioned HCl or HF, not only cause the corrosion of device, and in the time in above-mentioned wet type gas cleaning unit, can not removing above-mentioned HCl or HF fully, be deposited in and promote corrosion in the rearward end of wet type gas cleaning unit and the pipe arrangement pipeline between the catalytic reactor, in order to prevent the problems referred to above, utilize the expensive material constituent apparatus that sour gas is had patience, therefore there is problem that manufacturing cost uprises etc.But, up to the present,, also can take place owing to comprise the problem that the solution of above-mentioned sour gas causes corrosion of equipment even make wet cleaning equipment with above-mentioned expensive material.
In addition, in the metal etch operation of one of semiconductor manufacturing process, in order to prevent because of AlCl 3The clogging of the pipe arrangement pipeline that causes Deng material is heated to about 120 ℃ with the pipe arrangement pipeline, makes above-mentioned AlCl 3Can not exist with solid state, but heated waste gas and wet type gas scrubbing water reacted this moment, and existed the mist (mist) of the aerosol state that comprises sour gas to flow into the problem etc. of catalyst layer.
And, under the situation of the water when using buck to replace the wet type gas scrubbing, though acidic materials are washed with buck and can effectively remove acidic materials, but the buck as catalyst poison flow into catalyst layer, just become the reason that reduces catalyst activity, the alkaline matter that is neutralized by the reaction of sour gas and buck becomes acidity by acid, and reduced the removal efficient of acidic materials, therefore be necessary to continue to inject alkaline solution, cause accumulation at pipe arrangement and nozzle entrance, and bring out clogging.
In order to overcome the problems referred to above, Korean Patent discloses 2003-0025777 number, discloses in order to prevent SiF 4Decompose the SiO that is produced at catalyst layer 2Overlayed on catalyst layer and become the poisoning reason, at the catalyst layer front end wet scrubber is set, but can not removes SiF 4, the AsH low to the solubility of water 3, PH 3, SiH 4Deng material, the gas that therefore not only comprises these materials flow into catalyst layer and causes clogging, and exists and be contained in the waste water as the high heavy metal of harmfulnesses such as As, and causes secondary pollution problem.
Summary of the invention
In order to address the above problem, after problem of the present invention is that the adsorption reaction portion that provides a kind of front end connection setting in the catalytic reaction portion with catalyst layer to have adsorption layer constitutes emission-control equipment, the waste gas from semiconductor manufacturing process to this emission-control equipment and the air that produce in successively by, thus pack processing is contained in the devices and methods therefor of the polluter in the waste gas.
On the one hand, the invention provides the treatment of waste gas device that produces in a kind of semiconductor manufacturing process, this treating apparatus comprises: the waste gas inflow entrance of inflow exhaust gas; Connect the air inlet that is arranged on above-mentioned waste gas inflow entrance and air is provided; Connect and be arranged on above-mentioned waste gas inflow entrance and have the adsorption reaction portion of adsorption treatment by the adsorption layer of the waste gas of inflow entrance inflow; Connection is arranged on above-mentioned adsorption reaction portion and has by the waste gas inflow of adsorption reaction portion discharge and by the catalytic reaction portion of the catalyst layer of catalytic treatment; And connect in the flow path be arranged on the waste gas that flow into above-mentioned catalytic reaction portion and the water inlet of water is provided.
On the other hand, the invention provides the treatment of waste gas method that produces in a kind of semiconductor manufacturing process, this processing method comprises: make waste gas and air by having the adsorption reaction portion of adsorption layer, pack processing is contained in the adsorption treatment step of the perfluoro-compound in the waste gas; And after injecting water in the waste gas after above-mentioned adsorption treatment step finishes, make it pass through catalyst layer, thereby catalytic treatment is present in the catalytic treatment step of the perfluoro-compound that is untreated in the waste gas.
Waste gas of the present invention is meant and comprises BCl 3, Cl 2, F 2, sour gas or CF such as HBr, HCl, HF 4, CHF 3, C 2F 6, C 3F 8, C 4F 6, C 4F 8, C 5F 8NF 3, SF 6, NF 3Deng perfluoro-compound or AsH 3, NH 3, PH 3, SiH 4, Si 2H 2Cl 2Perhaps the waste gas of their mixture so long as comprise the gas of above-mentioned substance, all can be used as waste gas of the present invention, preferably means the waste gas of discharging in semiconductor manufacturing process or the LCD manufacturing process etc.
In addition, waste gas of the present invention is not processed separately in the emission-control equipment of handling this waste gas, but with oxygen, preferably in catalytic reaction portion with oxygen by reaction treatment, therefore, flow into the waste gas of above-mentioned emission-control equipment, particularly flow in the waste gas of catalytic reaction portion of above-mentioned emission-control equipment and must comprise oxygen, from considering economically, use oxygen separately with it, the preferred use is included in airborne oxygen, therefore, according to the gas that flow into emission-control equipment of the present invention, the waste gas that particularly flow into the catalytic reaction portion of catalysting processing waste gas is made up of waste gas and AIR MIXTURES.
Adsorption reaction of the present invention portion is used for adsorbing the perfluoro-compound that removal exists at the waste gas that flows into or waste gas and air, and NF is removed in preferred absorption 3, SF 6And BCl 3, BF 3, Br 2, CI 2, COF 2, F 2, HBr, HCl, HF, SiCl 4, SiF 4, WF 6Deng sour gas and AsH 3, NH 3, PH 3, SiH 4, Si 2H 2Cl 2Deng deposition gases etc., as long as can adsorb the removal above-mentioned substance, can use any adsorbent, but preferred the use filled by Ca (OH) 2, CaO, CuO, FeO (OH), Fe 2O 3, Fe 3O 4, MnO 2, Sr (OH) 2, Sr 2O 3Select the form of the adsorbent of at least a above material formation among the group who forms, more preferably use above-mentioned adsorbent is processed into spherical, graininess, sheet or cellular form of filling.
Adsorption reaction of the present invention portion, can move at normal temperatures, but also can in 250~500 ℃ temperature range, move as another kind of form, as its concrete form, can constitute in the following manner, promptly in order to remove the sour gas that exists in the waste gas and/or deposition gases etc., and be adjacent to be provided with heater with adsorption layer, with above-mentioned adsorption layer heating in 250~500 ℃ temperature range.
At this, operation at normal temperatures is meant, does not handle the NF that exists in above-mentioned waste gas or waste gas and the air in above-mentioned adsorption reaction portion 3, SF 6Deng, but after making them by bypass (by-pass), the catalyst layer that is arranged on the catalytic reaction portion of its rear end in connection is handled, if above-mentioned adsorption reaction portion maintains normal temperature, then can not remove a kind of NF as perfluoro-compound 3, SF 6, but in 250~500 ℃ temperature range, can handle NF 3, SF 6Deng.
Particularly, adsorption reaction of the present invention portion is maintained normal temperature and do not handle NF 3, SF 6Deng and when making it flow into the catalytic reaction portion that is arranged on the rear end, can handle NF according to the catalyst layer that is arranged on catalytic reaction portion 3, SF 6Deng, but in above-mentioned catalytic reaction portion, generate F this moment 2, HF, SO 2, SO 2F 2Deng accessory substance, also need later on to handle.
As required, adsorption reaction of the present invention portion can also be provided with and be used for removing the particulate matter that is included in waste gas, as metal and/or As such as As, B, Ga, Ge, Si xO y, B xO y, Ga 2O 3, Ge 2O 3, P xO y, SiO 2Deng the filter course of oxide, as the filter course that can use, can use as long as can remove the filter of above-mentioned particulate matter, but the normally used filter in preferred this area, preferred especially porous filter.
At this, be used to remove the porous filter of above-mentioned particulate matter, in order to prevent to produce clogging because of the accumulation of particulate matter, preferably adopt the higher filter of porosity, and,, preferably adopt the big filter of effective contact area with particulate matter in order to improve removal efficient, preferred ceramic honey comb (Ceramic Honeycomb), foamed ceramics (Ceramic Foam), foam metal (MetallicFoam), but be not limited to this.
The polluter that the waste gas that catalytic reaction of the present invention portion is used for handling through above-mentioned adsorption reaction portion exists, for example convert perfluoro-compound to carbon dioxide, HF and/or water etc. are handled, can use any catalyst that can achieve the above object, but the normally used catalyst that is used to remove perfluoro-compound in preferred this area, preferably be selected from gama-alumina, θ-aluminium oxide, the aluminium oxide of δ-aluminium oxide etc., on the carrier of at least more than one in boehmite or the boehmite, gallium and IA family metal have been flooded, sodium for example, lithium, the catalyst of potassium or their mixture.
At this moment, the gallium of preferred above-mentioned formation catalyst accounts for 1~50 weight % of total catalyst weight, preferably accounts for 0.1~5 weight % of total catalyst weight as sodium, lithium, potassium or their mixture of IA family metal.
As required, catalyst of the present invention can be by to being selected from aluminium oxide, boehmite or the boehmite of gama-alumina, θ-aluminium oxide, δ-aluminium oxide etc. In at least more than one carrier on, flooded gallium and IA family metal, for example sodium, lithium, potassium or their mixture and the catalyst that obtains, carry out vulcanizing treatment and make.As the above-mentioned method that catalyst is carried out vulcanizing treatment be, with the catalyst that has flooded gallium and sodium, lithium, potassium or their mixture in the above-mentioned carrier and obtained, be immersed in after the sulfuric acid solution of 0.01~1M, carry out drying and/or burn till, perhaps in above-mentioned catalyst, continue to provide sulfur dioxide.
Below, illustrate that the present invention is used for removing the example of manufacture method of the catalyst of perfluoro-compound.
At first, in breaking away from sub-exchanged water, add gallium nitrate solution, sodium nitrate solution, lithium nitrate solution, after potassium nitrate solution or their mixture are prepared dipping solution, impregnated carrier, make gallium account for 1~50 weight % of total catalyst weight, make sodium, lithium, potassium or their mixture account for after 0.1~5 weight % of total catalyst weight dry at normal temperatures about 24 hours as IA family metal.
Then, the above-mentioned catalyst that makes after under about 120 ℃ dry about 4 hours, is pressed the about 10 ℃ speed of per minute and heated up, under 700 ℃, burnt till approximately 2 hours.
Burn till the catalyst of end, add inorganic bond as required after, be processed into shapes such as spherical, graininess, sheet and use.At this moment, the material that can use as above-mentioned inorganic bond so long as inorganic bond usually used in this field can use, but preferably uses the oxidation aluminium glue, and its consumption is preferably 1~10 weight % of the vehicle weight of whole catalyst.
As required, when catalyst of the present invention is carried out vulcanizing treatment, burn till catalyst soakage after the end in the aqueous sulfuric acid of 0.01~0.1M with above-mentioned, dry at normal temperatures then about 24 hours, descend drying after about 4 hours at about 120 ℃ dried catalyst, press the about 10 ℃ speed of per minute and heat up, under 700 ℃, carry out about 2 hours burning till, make catalyst through vulcanizing treatment.At this moment, the catalyst that finally makes as mentioned above, is processed into the shape that needs by forming process and is used later on.
On the one hand, must comprise oxygen in the waste gas that flow into catalyst layer of the present invention, when using air as the supply source of above-mentioned oxygen, promptly air can be mixed the back with the waste gas that flow into the adsorption reaction portion with adsorption layer supplies with above-mentioned waste gas, also can be as required, do not mix with the waste gas that flow into above-mentioned adsorption reaction portion, but in the flow path of the waste gas that flow into catalytic reaction portion, the air inlet is set with catalyst layer, by this air inlet, in addition air is offered catalyst layer.
In addition, flow among the present invention catalyst layer waste gas need with flow into catalyst layer after water mixes, therefore, the flow path of waste gas that flow into catalyst layer from the discharge of adsorption reaction portion and air, the water inlet that water can be provided is set, the periphery adjacent with above-mentioned catalyst layer is provided with heater, above-mentioned catalyst layer is heated in 400~800 ℃ the temperature range.At this moment, the temperature of above-mentioned catalytic reaction portion is at least than above-mentioned adsorption reaction portion or can connect the temperature height of the decomposition reaction portion of the rear end that is arranged on above-mentioned adsorption reaction portion.
As required, emission-control equipment of the present invention can connect between adsorption reaction portion and catalytic reaction portion and the decomposition reaction portion with decomposition reaction layer is set uses.Above-mentioned decomposition reaction layer is to be used to prevent the material that is untreated that do not have enough time to handle in adsorption reaction portion, for example AsH 3, PH 3, SiCl 4, SiF 4, SiH 2Cl 2Deng converting to as As at catalyst layer xO y, P xO y, SiO 2On solid shape particle, and the phenomenon of the pore of physics blocking catalyst, and as long as can achieve the above object, decomposition reaction layer usually used in this field can use, and preferably will comprise AsH 3, PH 3, SiCl 4, SiF 4, SiH 2Cl 2Waste gas be heated in 300~550 ℃ the temperature range, be broken down into As, P, Si and be deposited in filter and handle, the preferred especially porous filter that in the filter course of adsorption reaction portion, uses that uses.
Here, the periphery of the decomposition reaction member of the above-mentioned decomposition reaction portion and the portion that sets within it is adjacent to be provided with heater, it can be heated to above-mentioned decomposition reaction layer in 300~550 ℃ the temperature range, and above-mentioned heater heating is at least than the high temperature range of temperature of above-mentioned adsorption reaction portion.
Emission-control equipment of the present invention, can washing portion further be set in the rear end of above-mentioned catalytic reaction portion, be used for washing fluorine and HF that the air handled by the catalyst layer of catalytic reaction portion exists, the device that can use as above-mentioned washing portion, so long as wash mill usually used in this field can use, but preferred wet scrubber.At this moment, above-mentioned wet scrubber can be by washing the fluorine that exists in the processed air and HF etc. to its inner supply water that continues, but as required, can utilize alkali compounds or water and Ca (OH) 2, mixture of alkaline compounds such as NaOH handles polluter.
, when using above-mentioned wet scrubber, can steam trap (trap) be set in further connection of the rear end of above-mentioned wet scrubber as required here, handle the HF and the employed water of trace not processed in wet scrubber.At this moment, above-mentioned steam trap inside be filled with molecular sieve, silica, aluminium oxide, zeolite, active carbon or the group that forms by them in the material selected.
On the one hand, emission-control equipment of the present invention, on the inlet air flow path of the rear end of the rear end of adsorption reaction portion and catalytic reaction portion, heat exchanger is set respectively, and be connected to each other setting heat exchanger separately, can from the gas that catalytic reaction portion discharges, reclaiming heat, this heat supplied with in the heat exchanger on the flow path that is arranged on waste gas, thus but the gas that preheating is discharged from adsorption reaction portion.
Have the waste gas processing method of the emission-control equipment of the present invention of said structure, comprising: make waste gas and air by having the adsorption reaction portion of adsorption layer, come pack processing to be contained in the adsorption treatment step of perfluoro-compound in the waste gas etc.; And after injecting water in waste gas after above-mentioned adsorption treatment step finishes and the air, make it pass through catalyst layer, thereby catalytic treatment is present in the catalytic treatment step of the untreated perfluoro-compound in the waste gas.
At this moment, above-mentioned air can not flow into the waste gas that flow into adsorption reaction portion yet, but be injected on the flow path of the waste gas that catalytic reaction portion flows, above-mentioned adsorption treatment step is preferred to be moved at normal temperatures or in 250~500 ℃ the temperature range, and above-mentioned catalytic treatment step is preferably moved in 400~800 ℃ temperature range.
Here, when above-mentioned adsorption treatment step is moved at normal temperatures, can be with the NH that is included in the above-mentioned waste gas 3And SF 6Deng not being adsorbed in the adsorbent, handle but flow into the catalyst layer that connects the catalytic reaction portion that is arranged on its rear end.But, handle NH with the catalyst layer that is arranged on above-mentioned catalytic reaction portion 3, SF 6Deng the time, in above-mentioned catalytic reaction portion, generate HF, H 2S, SO 2, SO 2F 2Deng accessory substance, need later on this is handled.
On the contrary, if above-mentioned adsorption treatment step maintains 250~500 ℃ temperature range, then be included in the NH in the above-mentioned waste gas 3, SF 6Deng, can be adsorbed on the adsorption layer of adsorption reaction portion and processed.
A kind of form as waste gas processing method of the present invention, can be between above-mentioned adsorption treatment step and catalytic treatment step, further comprise the material that can be converted to solid shape particle, preferably untreated material is converted to the granular resolution process step of handling at catalyst layer.
As the another kind of form of waste gas processing method of the present invention,, can further comprise the washing step that carbon dioxide, fluorine, HF or the water that exists in the processed air is washed as the back step of catalytic treatment step.
As another form of waste gas processing method of the present invention, adsorption reaction portion, decomposition reaction portion, catalytic reaction portion and washing portion are set constitute example by connecting successively with emission-control equipment of the present invention, this processing method comprises the steps:
I). waste gas and air be filter element and the adsorbent by maintaining 250~500 ℃ of temperature successively, removes the particulate matter, the NH that exist in the above-mentioned waste gas 3, SF 6, sour gas and/or deposition gases the adsorption treatment step;
Ii). make step I) in the waste gas handled and air by maintaining the decomposition reaction layer of 300~550 ℃ of temperature, convert the material that exists in the above-mentioned processed waste gas, can be exchanged into solid shape particle to the granular resolution process step of removing at catalyst layer;
Iii). to step I i) in the flow path of the waste gas the handled step that provides water to be mixed;
Iv). step I in ii) mixed water and waste gas and air will comprise the catalytic treatment step that the perfluoro-compound that exists in the exhaust-gas mixture of water converts carbon dioxide, fluorine, HF or water to above-mentioned by maintaining the catalyst layer of 400~800 ℃ of temperature;
V). the waste gas that step I is handled in v) is by washing portion, the washing step that carbon dioxide, fluorine, HF or the water that exists in the above-mentioned processed waste gas is washed; And
Vi). the gas after will washing is discharged into outside step.
Here, step washing step v) specifically can be undertaken by wet scrubbing, when utilizing above-mentioned wet scrubbing to carry out washing step, as required, as the back step of wet scrubbing, can further be provided with and remove the micro-HF that comprises in the processed air and the step of employed water.
In addition, can further comprise, at above-mentioned steps i) and step I i) between and step I v) and step heat exchanger is set between v) and reclaims heat, the heat that reclaims is supplied be arranged on by step I) in the heat exchanger on the flow path of the waste gas handled, thereby the step of preheating gas.
In addition, in waste gas processing method of the present invention, when in step I) waste gas in not during mixing air, front/rear in the above-mentioned steps step that water is provided iii), the step that air is provided can be set in addition.
According to the present invention, the hard-decomposed perfluoro-compound that can in the waste gas that removal below 800 ℃ produces from semiconductor manufacturing process or LCD manufacturing process, be comprised etc., according to the loading of catalyst, can handle the waste gas of the perfluoro-compound that comprises a large amount of and/or high concentration.
Description of drawings
Fig. 1 is the structure chart according to emission-control equipment of the present invention.
Fig. 2 is the structure chart of expression according to the another kind of form of emission-control equipment of the present invention.
Fig. 3 is the structure chart of expression according to another form of emission-control equipment of the present invention.
Fig. 4 is the figure of expression according to the conversion ratio of the embodiment of the invention.
Fig. 5 is the CF of expression according to embodiments of the invention and comparative example 4The figure of conversion ratio.
Wherein, description of reference numerals is as follows:
2: inflow entrance 4: adsorption reaction portion
6; Catalytic reaction portion 8: decomposition reaction portion
10: heater 12: filter course
14: adsorption layer 16: the decomposition reaction layer
18: catalyst layer 20: wet scrubber
22: steam trap 24: outlet
26: 28: the first heat exchangers of water inlet
28 ': second heat exchanger 30: washing portion
32: the air inlet
The specific embodiment
Below, the present invention is described in detail with reference to accompanying drawing, but following explanation not delimit the scope of the invention just in order to specify the present invention.
Fig. 1 is the structure chart according to emission-control equipment of the present invention, and Fig. 2 is the structure chart of expression according to the another kind of form of emission-control equipment of the present invention, and Fig. 3 is the structure chart of expression according to another form of emission-control equipment of the present invention.
As shown in Figure 1 to Figure 3, emission-control equipment of the present invention, say by the adsorption reaction portion 4 that handles the particulate matter that exists waste gas or waste gas and the air, sour gas, deposition gases etc. and catalytic reaction portion 6 with the catalyst layer 18 that is used for handling the perfluoro-compound that waste gas exists constitutes from macroscopic view, more particularly, by the waste gas inflow entrance 2 of inflow exhaust gas; Connect the air inlet 32 that is arranged on above-mentioned waste gas inflow entrance 2 and air is provided; Be filled with waste gas and flow into and be adsorbed the adsorption reaction portion 4 of the adsorption layer 14 of processing; Connect and to be arranged on above-mentioned adsorption reaction portion 4 and to have the waste gas of discharging from adsorption reaction portion 4 and air flows into and by the catalytic reaction portion 6 of the catalyst layer 18 of catalytic treatment; And connect on the flow path be arranged on the waste gas that flow into above-mentioned catalytic reaction portion 6 and air and and provide the water inlet 26 of water to constitute to waste gas and air.
As required, emission-control equipment of the present invention, between above-mentioned adsorption reaction portion 4 and catalytic reaction portion 6, can also be connected with decomposition reaction portion 8, the material that this decomposition reaction portion 8 will be in being filled in catalytic reaction portion can be exchanged into solid shape particle on 6 the catalyst layer 18 converts granular the processing to; The washing portion 30 that can also connect the waste gas that set handling discharged by above-mentioned catalytic reaction portion 6 in the rear end of above-mentioned catalytic reaction portion 6.
In the adsorption reaction of the present invention portion 4, flow direction along waste gas or waste gas and air is connected with filter course 12 and adsorption layer 14 successively, and filter course 12 is used for removing particulate matter that waste gas or waste gas and air exists, as metal and/or As such as As, B, Ga, Ge, Si xO y, B xO y, Ga 2O 3, Ge 2O 3, P xO y, SiO 2Deng oxide and/or as the AlCl that can become the material of solid under the room temperature 3Deng, its preferred porous filter 12, adsorption layer 14 are used for absorption and remove NF 3, SF 6And BCl 3, BF 3, Br 2, Cl 2, COF 2, F 2, HBr, HCl, HF, SiCl 4, SiF 4, WF 6Deng sour gas and AsH 3, NH 3, PH 3, SiH 4, Si 2H 2Cl 2Etc. deposition gases etc., and as required, adjacent above-mentioned filter course 12 and adsorption layer 14 ground are provided with heater 10, thereby the temperature of filter course 12 and adsorption layer 14 can be heated to 250~500 ℃.
At this moment, the place ahead that above-mentioned filter course 12 is arranged on adsorption layer 14 is because will remove SiF earlier 4, WF 6Deng, thereby prevent the above-mentioned SiF that exists in waste gas or waste gas and the air 4, WF 6Deng generating SiO with sorbent reactions 2Or WO 3The equigranular material.It is because the SF that will suppress to exist in the above-mentioned waste gas that air is offered adsorption reaction portion 2 with waste gas 6Be accumulated in pipeline (not shown) Deng material and the accessory substances such as sulphur that sorbent reactions generated that constitute adsorption layer 14, thereby suppress to cause the phenomenon of the pressure differential of emission-control equipment as the flow path of waste gas.
, as required, cyclone etc. is set here, so that remove particulate matter easily in the lower end of above-mentioned filter course 12.Remove NF as long as can adsorb 3, SF 6With the adsorbent of sour gas and/or deposition gases etc., above-mentioned adsorption layer 14 can use, but preferably will be by Ca (OH) 2, CaO, CuO, FeO (OH), Fe 2O 3, Fe 3O 4, MnO 2, Sr (OH) 2, Sr 2O 3At least a above material of selecting among the group who forms is processed into spherical, graininess, sheet or cellular the use.
Particularly, in the inflow entrance 2 of adsorption reaction of the present invention portion 4, as required, be provided with to the mobile air pump (not shown) that power is provided of air, the pressure differential that produces in the time of not only can offseting exhaust-gas treatment, and be provided for detecting the pressure gauge of the pressure amplification of emission-control equipment simultaneously in a side of inflow entrance 2.
Catalytic reaction of the present invention portion 6 connects the above-mentioned adsorption reaction portion 4 that is arranged on, more particularly, connection is arranged on from the flow path (not shown) of the waste gas of adsorption reaction portion 4 discharges, be used for handling perfluoro-compound that the waste gas of discharging from adsorption reaction portion 4 or waste gas and air exist etc., other is provided with the water inlet 26 that the flow path to the waste gas of being discharged by above-mentioned adsorption reaction portion 4 provides water, water and waste gas and air can be mixed; By the catalyst layer 18 that is used for removing the perfluoro-compound that above-mentioned water and waste gas and AIR MIXTURES exists and with above-mentioned catalyst layer 18 adjacent settings and be used for the temperature maintenance of catalyst layer 18 heater 10 at 400~800 ℃ is constituted.
Here, so long as can handle the catalyst of perfluoro-compound, above-mentioned catalyst layer 18 can use, but preferred catalyst usually used in this field, on at least more than one the carrier in the aluminium oxide, boehmite or the boehmite that are selected from gama-alumina, θ-aluminium oxide, δ-aluminium oxide etc., dipping with respect to whole catalyst weights be 1~50 weight % gallium and with respect to whole catalyst weights be the IA family metal of 0.1~5 weight %, the catalyst that obtains as sodium, lithium, potassium or their mixture.
The above-mentioned catalyst that is used to handle perfluoro-compound, as required, can use later on through vulcanizing treatment, as the method for above-mentioned catalyst being carried out vulcanizing treatment, can use so long as be used for the method for the vulcanizing treatment of catalyst, but preferred the use is being selected from above-mentioned gama-alumina, θ-aluminium oxide, the aluminium oxide of δ-aluminium oxide etc., on the carrier of at least more than one in boehmite or the boehmite, dipping is the gallium of 1~50 weight % with respect to whole catalyst weights and is the IA family metal of 0.1~5 weight % with respect to whole catalyst weights, as sodium, lithium, potassium or their mixture and obtain catalyst, with this catalyst soakage after the aqueous sulfuric acid of 0.01~1M, carry out the drying and/or the method for burning till, perhaps with the method for sulfur dioxide sustainable supply to above-mentioned catalyst.
As required, emission-control equipment of the present invention, can between adsorption reaction portion 4 and catalytic reaction portion 6, be connected with decomposition reaction portion 8, above-mentioned decomposition reaction portion 8 have can handle in above-mentioned adsorption reaction portion 4 not processed and discharge and can convert to as As at catalyst layer xO y, P xO y, SiO 2AsH on solid shape particle 3, PH 3, SiCl 4, SiF 4, SiH 2Cl 2On the decomposition reaction layer 16 of material, and above-mentioned decomposition reaction portion 8 is adjacent to be provided with heater 10 with above-mentioned decomposition reaction layer, so that decomposition reaction layer 16 maintained in 300~550 ℃ the temperature range.
In addition, emission-control equipment of the present invention, as required, be connected with washing portion 30 in the rear end of catalytic reaction portion 6, this washing portion 30 is used to wash the air of being discharged by above-mentioned catalytic reaction portion 6, so long as wash mill usually used in this field can use, but preferably use wet scrubber 20.
Here, the solution that is used for above-mentioned wet scrubber 20 preferably uses and can remove HF, the H that produces in the processing of catalytic reaction portion 6 2SO 4And SO xThe time, can in and the Ca (OH) of water 2Perhaps Na alkaline matters such as (OH), when using above-mentioned wet scrubber 20 to constitute washing portion 30, as required, in the rear end of above-mentioned wet scrubber 20, can further be provided for handling the HF of the trace that comprises in the air of discharging and the steam trap 22 of employed water by washing portion 30.
As required, emission-control equipment of the present invention, on the path of the processed gas flow of the rear end of above-mentioned adsorption reaction portion 4 and catalytic reaction portion 6 rear ends, connect respectively be provided with first heat exchanger 28 and second heat exchanger 28 ', and be connected to each other be provided with above-mentioned first heat exchanger 28 and second heat exchanger 28 ', after the heat of the gas of discharging by above-mentioned catalytic reaction portion 6 with second heat exchanger 28 ' recovery, offer connect be arranged on above-mentioned second heat exchanger 28 ' first heat exchanger 28 in, thereby but preheating discharge and gas by first heat exchanger 28 from adsorption reaction portion 4.
As a kind of form of the present invention, in the emission-control equipment of the present invention, the waste gas inflow entrance 2 of waste gas or waste gas and the air side by being arranged on above-mentioned adsorption reaction portion 4 be connected the air inlet 32 that is arranged on waste gas inflow entrance 2 and flow into, waste gas that flows into or waste gas and air are successively by decomposition reaction portion 8, after catalytic reaction portion 6 and the washing portion 30, the outlet 24 of the side of treated air by being arranged on above-mentioned washing portion 30 is discharged from, above-mentioned adsorption reaction portion 4, decomposition reaction portion 8 and catalytic reaction portion 6, adjust temperature according to the heater in the device that is arranged on separately 10, flow path along waste gas, be configured to adsorption reaction portion 4, the temperature of decomposition reaction portion 8 and catalytic reaction portion 6 increases successively.
Here, as required, above-mentioned air inlet 32 can be arranged in the flow path of the waste gas that flow into catalytic reaction portion 6, flow in the catalytic reaction portion 6 after making air and waste gas mixing, thereby can omit waste gas and the Air mixing that flow into adsorption reaction portion 4.
Action Specification to emission-control equipment of the present invention with aforesaid structure is as follows.
As a kind of form of the present invention, with the emission-control equipment of the present invention that is made of adsorption reaction portion 4 and catalytic reaction portion 6 is example, its effect is as follows: at first, with the waste gas that produces in semiconductor manufacturing process or the LCD manufacturing process with after the mixing ratio that after air mixes, for example is mixed into oxygen and is included in the perfluoro-compound in the waste gas reached 3: 1, the inflow entrance 2 of the side by being arranged on adsorption reaction portion 4 makes it flow into the inside of the adsorption reaction portion 4 that maintains normal temperature or 250~500 ℃ of temperature.
Secondly, flow into the waste gas and the air of above-mentioned adsorption reaction portion 4, by being arranged on the adsorption layer 14 of above-mentioned adsorption reaction portion 4, NF3, SF6 and sour gas and/or deposition gases etc. are attracted to above-mentioned adsorption layer 14 and are removed.
Here, front end at the adsorption layer 14 of above-mentioned adsorption reaction portion 4 is provided with under the situation of filter course 12, when flowing into the waste gas of above-mentioned adsorption reaction portion 4 and air by filter course 12, remove after the particulate matter that exists in the waste gas, flow into again in the adsorption layer 14 that is connected setting with above-mentioned filter course 12.
Secondly, in order to promote to add the water decomposition reaction, inject water in the flow path of waste gas that above-mentioned adsorption layer 14 is handled and air, the mol ratio that preferably makes water/perfluoro-compound is 1~100, more preferably 5~50.
Then, make above-mentioned waste gas that mixes with water and air, by maintaining the catalyst layer 18 of 400~800 ℃ catalytic reaction portion 6, the perfluoro-compound that will exist in above-mentioned waste gas and air is discharged to the outside after converting carbon dioxide, fluorine, HF and water and removal to.
At this, the air that mixes with above-mentioned waste gas can not mix with the waste gas that flow into adsorption reaction portion 4 yet, but mixes with the waste gas that flow into catalytic reaction portion 6.
In addition, on the gas flow paths of the rear end of above-mentioned adsorption reaction portion 4 and catalytic reaction portion 6 rear ends, be provided with respectively first heat exchanger 28 and second heat exchanger 28 ', and be connected to each other be provided with above-mentioned first heat exchanger 28 and second heat exchanger 28 ', after the heat of the gas of discharging by above-mentioned catalytic reaction portion 6 with second heat exchanger 28 ' recovery, offer in first heat exchanger 28 that is provided with above-mentioned second heat exchanger 28 ' be connected, thereby but preheating discharge and gas by first heat exchanger 28 from adsorption reaction portion 4.
As another kind of form of the present invention, be example with the emission-control equipment of the present invention that constitutes by adsorption reaction portion 4, decomposition reaction portion 8, catalytic reaction portion 6 and washing portion 30, its effect is as follows.With the waste gas that produces in semiconductor manufacturing process or the LCD manufacturing process etc. with after air mixes, the inflow entrance 2 of the side by being arranged on adsorption reaction portion 4 makes it flow into the inside of the adsorption reaction portion 4 that maintains normal temperature or 250~500 ℃ of temperature.
Secondly, flow into the waste gas of above-mentioned adsorption reaction portion 4 and air by being arranged on the filter course 12 of above-mentioned adsorption reaction portion 4, after removing the particulate matter that exists in waste gas or waste gas and the air, by being connected the adsorption layer 14 that is provided with above-mentioned filter course 12, NF3, SF6 and sour gas and/deposition gases etc. is attracted to above-mentioned adsorption layer 14 and is removed.
Then, processed waste gas and air in above-mentioned adsorption layer 14 flow into the decomposition reaction portion 8 that maintains 300~550 ℃, by being arranged on the decomposition reaction layer 16 in the above-mentioned decomposition reaction portion 8, and particulate matter, as converting As to xO y, P xO y, SiO 2Deng AsH 3, PH 3, SiCl 4, SiF 4, SiH 2Cl 2Be removed in catalyst layer 18 Deng material.
Afterwards, inject water in the flow path of processed waste gas and air in above-mentioned decomposition reaction portion 8, the mol ratio that preferably makes water/perfluoro-compound is 1~100, more preferably 5~50.
Secondly, make above-mentioned waste gas that mixes with water and air,, make the perfluoro-compound that exists in above-mentioned waste gas or waste gas and the air convert carbon dioxide, fluorine, HF and water and removal to by maintaining the catalyst layer 18 of 400~500 ℃ catalytic reaction portion 6.
Then, the waste gas of removing perfluoro-compound in above-mentioned catalytic reaction portion 6 flow into washing portion 30, through behind the wet scrubbing, is discharged into the outside.
At this moment, when adopting above-mentioned wet scrubbing, as required, steam trap 22 is set in its back-end, remove when wet scrubbing untreated micro-HF and employed water after, with treated toxic emission to outside.
At this, the air that mixes with above-mentioned waste gas can not mix with the waste gas that flow into adsorption reaction portion 4, but mixes with the waste gas that flow into catalytic reaction portion 6.
In addition, on the inlet air flow path of the rear end of above-mentioned adsorption reaction portion 4 and catalytic reaction portion 6 rear ends, be provided with respectively first heat exchanger 28 and second heat exchanger 28 ', and be connected to each other above-mentioned first heat exchanger 28 and second heat exchanger 28 ', behind the heat of the gas of discharging by above-mentioned catalytic reaction portion 6 with second heat exchanger 28 ' recovery, this heat is offered in first heat exchanger 28 that is provided with above-mentioned second heat exchanger 28 ' be connected, thereby but preheating is discharged by adsorption reaction portion 4 and the gas by first heat exchanger 28.
By the following examples the present invention is specifically described.But following examples are just in order to specify the present invention, and scope of the present invention is not limited on the following embodiment.
Embodiment 1
The manufacturing of catalyst
Break away from interpolation 22ml gallium nitrate solution (Ga (NO in the sub-exchanged water at 20ml 3) 3) [MCP, Britain] and 3.5g sodium nitrate (NaNO 3) [Sigma-Aldrich, the U.S.], behind the preparation dipping solution, impregnated alumina [Sasol, the U.S.], make gallium and sodium reach 40 weight % and 1 weight % respectively with respect to the weight of aluminium oxide after, dry 24 hours at normal temperatures, make catalyst.
Secondly, the above-mentioned catalyst that makes after under 120 ℃ dry 4 hours, with the speed intensification of 10 ℃ of per minute intensifications, was burnt till under 700 ℃ about 2 hours.
Afterwards, the catalyst soakage that burns till after the 0.2mol/l of 92ml sulfuric acid [industry of moral Chinese yam product, the Korea S] aqueous solution, is carried out 24 hours dryings at normal temperatures.
Afterwards, above-mentioned dry thing after under 120 ℃ dry 4 hours, with the speed intensification of 10 ℃ of per minutes, was burnt till under 700 ℃ 2 hours, make the catalyst through vulcanizing treatment of the present invention.
Secondly,, use oxidation aluminium glue [Alumina Sol 100, daily output chemistry (NissanChemical), Japan], make above-mentioned oxidation aluminium glue reach 5 weight %, mix stirring, make sheet catalyst with respect to the weight of whole aluminium oxide as inorganic bond.
Comparative example 1
Implement with the method identical, but omit the catalyst soakage that will burn till step, make the catalyst of handling without over cure at aqueous sulfuric acid with embodiment 1.
Comparative example 2
Implement with the method identical with embodiment 1, but with 65g nickel nitrate (Ni (NO 3) 26H 2O) [Sigma-Aldrich, the U.S.] replaces the 22ml gallium nitrate solution, makes catalyst.
Comparative example 3
Break away from dissolving 0.3g diammonium hydrogen phosphate ((NH in the sub-exchanged water at 15ml 4) 2HPO 4) after [Sigma-Aldrich, the U.S.], (Sasol, the U.S.) is impregnated in this solution with the 20g aluminium oxide, makes phosphorus reach 20 weight % with respect to the weight of whole aluminium oxide, afterwards, dry 24 hours at normal temperatures.
Then, with the above-mentioned catalyst that makes, after under 120 ℃ dry 4 hours,, under 700 ℃, burnt till 2 hours with the speed intensification of 10 ℃ of per minutes.
Embodiment 2
As shown in Figure 1, porous filter [Zebent Filter, KOCAT, Korea S] is set after, be filled with 8cm in the upper end of above-mentioned porous filter 3With Ca (OH) 2[vowing bridge マ イ Application パ Le Network, Japan] powder is processed into granular adsorbent, at the outer peripheral face of above-mentioned porous filter and adsorbent heater is set, and constitutes adsorption reaction portion.
Secondly, in reactor, fill 8cm 3The catalyst of making according to embodiment 1 of 10~14 orders (mesh) after, at the outer peripheral face of reactor heater is set, constitute catalytic reaction portion, above-mentioned adsorption reaction portion is connected with pipeline with catalytic reaction portion.
Then, be provided with on as the pipeline of the flow path of above-mentioned gas the water inlet of water can be provided after, be connected with this water inlet measuring pump [SP320D, English unicorn machine, Korea S] be set, quantitatively inject water to catalytic reaction portion.
Then, above-mentioned catalytic reaction portion connect wet scrubber is set after, above-mentioned wet scrubber the lower end connect steam trap be set.
Secondly, for emulation comprises the gas of waste gas, utilize mass flow controller [FC-260, Mykolis, the U.S.] with CF 4, NH 3, SF 6, N 2And O 2After mixing, offer in the porous filter of first handling part.Here, the proterties and the catalyst consumption that offer the emulation gas that comprises waste gas of above-mentioned porous filter are shown in Table 1, and with the temperature maintenance of adsorption reaction portion about 450 ℃, with the temperature maintenance of decomposition reaction portion at about 500 ℃, the temperature maintenance of catalytic reaction portion at about 700 ℃.
In addition, as all reaction conditions, with 4500h -1Space velocity experimentize.
In addition, adopt the IR[I4001 of the adjustable long optical path pipe (gas cell) that 10cm is installed, MIDAC, the U.S.] measure the air of discharging from washing portion, calculate perfluoro-compound (CF with following formula 1 4, NH 3, SF 6) removal efficient.
[formula 1]
Table 1
Reaction condition
The catalyst loading Gas flow Space velocity The water injection rate ??NF 3 ??SF 6 ??CF 4 ??O 2 ?N 2
??8cm 3 ??600SCC ??M ??4500h -1 ??0.36cm 3/min ??1V% ??1V% ??1V% ??10V% ?87V%
It is the results are shown in Fig. 4.
As shown in Figure 4, along with increase in temperature, NH 3Relatively be removed CF at low temperatures 4And SF 6Under 700 ℃, demonstrate the conversion ratio more than 97%.
Comparative example 4
Implement with the method identical, but replace catalyst among the embodiment 1, as waste gas, only with perfluoro-compound CF with the catalyst of manufacturing in the comparative example 1 with embodiment 2 4Mix with oxygen.
It is the results are shown in Fig. 5.
Comparative example 5
Implement with the method identical, but replace catalyst among the embodiment 1, as waste gas, only with perfluoro-compound CF with the catalyst of manufacturing in the comparative example 2 with embodiment 2 4Mix with oxygen.
It is the results are shown in Fig. 5.
Comparative example 6
Implement with the method identical, but replace catalyst among the embodiment 1, as waste gas, only with perfluoro-compound CF with the catalyst of manufacturing in the comparative example 3 with embodiment 2 4Mix with oxygen.
It is the results are shown in Fig. 5.
As shown in Figure 5, the CF of embodiment 2 4Conversion ratio demonstrates the CF than comparative example 4~comparative example 6 4Conversion ratio is good.
Comparative example 7
Implement with the method identical, but do not make waste gas or waste gas and air, handle but directly offer catalytic reaction portion by adsorption reaction portion and decomposition reaction portion with embodiment 2.
It is the results are shown in table 2
[table 2]
Conversion ratio and concentration
As shown in table 2, the CF of embodiment 2 and comparative example 7 4Conversion ratio is identical.But, the NF of embodiment 2 3, SF 6Conversion ratio demonstrate than comparative example 7 height, this is because in embodiment 2, is arranged in the adsorption reaction portion of catalyst layer front end and removes NF 3, SF 6, with the unreacted NF that does not remove 3And SF 6The cause of removing in catalytic reaction portion.
Therefore, the conversion ratio of embodiment 2 is than just removing NF at catalytic reactor 3, SF 6Comparative example 7 height.And, when using adsorbent as embodiment 2, NF 3, SF 6Before the inflow catalyst layer, be removed quite a few, can reduce NF 3, SF 6Decompose the HF amount that produces at catalyst layer, thereby improve the durability of catalyst.
On the one hand, as embodiment 2, do not produce NO, NO 2, N 2Accessory substances such as O, but in comparative example 7, produce NO, NO as can be known 2, N 2O.
As mentioned above, those skilled in the art in the invention as can be known, under the situation that does not change technological thought of the present invention or essential feature, available other concrete forms are implemented the present invention.Therefore, above-described embodiment nothing but example, can not limit the present invention in all respects.The detailed description done above-mentioned with it, scope of the present invention may be interpreted as the meaning that comprises the described scope of technical scheme described later and scope and all changes derived from its equivalent concepts or the form of variation.

Claims (27)

1. an emission-control equipment is used for handling the waste gas that semiconductor manufacturing process produces, and it is characterized in that described emission-control equipment comprises:
The waste gas inflow entrance, it is used for inflow exhaust gas;
Air inlet, its connection are arranged on above-mentioned waste gas inflow entrance and are used to provide air;
Adsorption reaction portion, its connection is arranged on above-mentioned waste gas inflow entrance and has the adsorption layer of adsorption treatment by the waste gas of waste gas inflow entrance inflow;
Catalytic reaction portion, its connection is arranged on above-mentioned adsorption reaction portion and has waste gas inflow of being discharged by adsorption reaction portion and the catalyst layer that this waste gas is carried out catalytic treatment; And
Water inlet, its connection are arranged in the flow path of the waste gas that flow into above-mentioned catalytic reaction portion and are used to provide water.
2. emission-control equipment as claimed in claim 1 is characterized in that, replaces above-mentioned air inlet to connect and is arranged on the waste gas inflow entrance, above-mentioned air inlet is connected be arranged in the flow path of the waste gas that flow into catalytic reaction portion, and air is provided.
3. emission-control equipment as claimed in claim 1, it is characterized in that, between above-mentioned adsorption reaction portion and catalytic reaction portion, further be provided with decomposition reaction portion, partly separate the material that is included in the waste gas of discharging and can be converted to solid shape particle in catalytic reaction portion by adsorption reaction portion in this decomposition reaction.
4. emission-control equipment as claimed in claim 1 is characterized in that, further comprises washing portion, and this washing portion connects and is arranged on above-mentioned catalytic reaction portion, is used to remove be included in the airborne untreated perfluoro-compound of being discharged by catalytic reaction portion.
5. as any described emission-control equipment in the claim 1~4, it is characterized in that above-mentioned waste gas is by the BCl as sour gas 3, Cl 2, F 2, HBr, HCl, HF or as the CF of perfluoro-compound 4, CHF 3, C 2F 6, C 3F 8, C 4F 6, C 4F 8, C 5F 8NF 3, SF 6, NF 3Perhaps AsH 3, NH 3, PH 3, SiH 4, Si 2H 2Cl 2Perhaps their mixture is formed.
6. as any described emission-control equipment in the claim 1~4, it is characterized in that be filled with adsorbent in the above-mentioned adsorption layer, described adsorbent is by Ca (OH) 2, CaO, CuO, FeO (OH), Fe 2O 3, Fe 3O 4, MnO 2, Sr (OH) 2, Sr 2O 3The material of more than one that select among the group who forms constitutes.
7. as any described emission-control equipment in the claim 1~4, it is characterized in that, be filled with catalyst in the above-mentioned catalyst layer, on the more than one carrier of described catalyst in being selected from gama-alumina, θ-aluminium oxide, δ-aluminium oxide, boehmite or boehmite, be impregnated with respect to total catalyst weight and be the gallium of 1~50 weight % and be sodium, lithium, potassium or their mixture of 0.1~5 weight % with respect to total catalyst weight.
8. as any described emission-control equipment in the claim 1~4, it is characterized in that, be filled with catalyst in the above-mentioned catalyst layer, described catalyst is to be selected from gama-alumina, θ-aluminium oxide, δ-aluminium oxide, on the more than one carrier in boehmite or the boehmite, be impregnated with respect to total catalyst weight and be the gallium of 1~50 weight % and be the sodium of 0.1~5 weight % with respect to total catalyst weight, lithium, the catalyst of potassium or their mixture, after being immersed in the aqueous sulfuric acid of 0.01~1mol/l, carry out drying or burn till, perhaps carry out drying and burn till made thus catalyst.
9. as any described emission-control equipment in the claim 1~4, it is characterized in that above-mentioned adsorption reaction portion comprises: the heater that the flow path that flows into along waste gas sets gradually and is used to handle the filter course of waste gas and adsorption layer and is adjacent to be provided with filter course and adsorption layer for the temperature that improves above-mentioned filter course and adsorption layer.
10. as any described emission-control equipment in the claim 1~4, it is characterized in that, above-mentioned catalytic reaction portion comprises: the catalyst layer that the air that contains waste gas flows into and this air is carried out catalytic treatment, and the heater that is adjacent to be provided with catalyst layer for the temperature that improves above-mentioned catalyst layer.
11. emission-control equipment as claimed in claim 3, it is characterized in that, above-mentioned decomposition reaction portion comprises: remove the decomposition reaction layer that is included in the waste gas of discharging and is converted into the material of solid shape particle in catalytic reaction portion by adsorption reaction portion, and and the heater that is adjacent to be provided with for the temperature that improves above-mentioned decomposition reaction layer and above-mentioned decomposition reaction layer.
12. emission-control equipment as claimed in claim 4 is characterized in that, above-mentioned washing portion is made of wet scrubber.
13. emission-control equipment as claimed in claim 12 is characterized in that, above-mentioned wet scrubber sustainable supply water, alkali compounds or their mixture.
14. emission-control equipment as claimed in claim 12, it is characterized in that, rear end at above-mentioned wet scrubber further is connected with steam trap, and this steam trap is used for handling the HF and the used water of the trace that the gas of being discharged by wet scrubber comprises.
15. emission-control equipment as claimed in claim 14 is characterized in that, is filled with molecular sieve, silica, aluminium oxide, zeolite, active carbon or their mixture in the above-mentioned steam trap.
16. as claim 3 or 4 described emission-control equipments, it is characterized in that, on the inlet air flow path of the rear end of above-mentioned adsorption reaction portion and catalytic reaction portion rear end, first heat exchanger and second heat exchanger are set respectively, and interconnect above-mentioned first heat exchanger and second heat exchanger are set, reclaim the heat of the air of discharging by above-mentioned catalytic reaction portion with second heat exchanger, and offer first heat exchanger that is connected setting with above-mentioned second heat exchanger, thereby the air of first heat exchanger is discharged and is passed through in preheating from adsorption reaction portion.
17. as any described emission-control equipment in the claim 1~4, it is characterized in that, be filled with catalyst in the above-mentioned catalyst layer, described catalyst is to be selected from gama-alumina, θ-aluminium oxide, δ-aluminium oxide, on the more than one carrier in boehmite or the boehmite, be impregnated with respect to total catalyst weight and be the gallium of 1~50 weight % and be the sodium of 0.1~5 weight % with respect to total catalyst weight, lithium, the catalyst of potassium or their mixture, after being immersed in the aqueous sulfuric acid of 0.01~1mol/l, sulfur dioxide is continued to offer the made catalyst of catalyst.
18. waste gas processing method, be used for handling the waste gas that semiconductor manufacturing process produces, it is characterized in that this waste gas processing method comprises: make waste gas and air by having the adsorption reaction portion of adsorption layer, come pack processing to be contained in the adsorption treatment step of the perfluoro-compound in the waste gas; And, in the waste gas that above-mentioned adsorption treatment step finishes, inject after the water, make it pass through catalyst layer, come the not processed perfluoro-compound that exists in the waste gas is carried out the catalytic treatment step of catalytic treatment.
19. waste gas processing method as claimed in claim 18 is characterized in that, injects air before the catalytic treatment step, replaces the mixing of waste gas of air and inflow by above-mentioned adsorption reaction portion thus.
20. waste gas processing method as claimed in claim 18 is characterized in that, above-mentioned waste gas is by the BCl as sour gas 3, Cl 2, F 2, HBr, HCl, HF or as the CF of perfluoro-compound 4, CHF 3, C 2F 6, C 3F 8, C 4F 6, C 4F 8, C 5F 8NF 3, SF 6, NF 3Perhaps AsH 3, NH 3, PH 3, SiH 4, Si 2H 2Cl 2Perhaps their mixture is formed.
21. waste gas processing method as claimed in claim 18, it is characterized in that, between above-mentioned adsorption treatment step and catalytic treatment step, further comprise the resolution process step, in this resolution process step, the material that will can convert solid shape particle in the catalytic treatment step to is converted to granular and removes.
22. waste gas processing method as claimed in claim 18 is characterized in that, the back operation as above-mentioned catalytic treatment step further comprises washing step, in this washing step, and carbon dioxide, fluorine, HF or water that washing exists in processed waste gas.
23. waste gas processing method as claimed in claim 18 is characterized in that, above-mentioned washing step is the wet scrubbing step.
24. waste gas processing method as claimed in claim 23 is characterized in that, as the back operation of above-mentioned wet scrubbing step, further comprise the trace that removal exists in the waste gas of above-mentioned wet scrubbing step process HF and the step of used water.
25. waste gas processing method as claimed in claim 18 is characterized in that, further is included in the gas of discharging from above-mentioned adsorption treatment step and from the gas flow path that the catalytic treatment step is discharged the step that heat exchanger reclaims heat is set.
26. waste gas processing method as claimed in claim 18 is characterized in that, above-mentioned adsorption treatment step is carried out under normal temperature or 250~500 ℃, and the catalytic treatment step is carried out under 400~800 ℃.
27. waste gas processing method as claimed in claim 21 is characterized in that, above-mentioned resolution process step is carried out under 300~550 ℃.
CNB200610007988XA 2006-01-26 2006-03-02 The treatment of waste gas device and the processing method that produce in the semiconductor manufacturing process CN100540120C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020060008037 2006-01-26
KR1020060008037A KR100654922B1 (en) 2006-01-26 2006-01-26 Cleaning apparatus of exhaust gas produced from semiconductor production process and method thereof

Publications (2)

Publication Number Publication Date
CN101007237A CN101007237A (en) 2007-08-01
CN100540120C true CN100540120C (en) 2009-09-16

Family

ID=37732414

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200610007988XA CN100540120C (en) 2006-01-26 2006-03-02 The treatment of waste gas device and the processing method that produce in the semiconductor manufacturing process

Country Status (5)

Country Link
JP (1) JP4768470B2 (en)
KR (1) KR100654922B1 (en)
CN (1) CN100540120C (en)
TW (1) TWI288655B (en)
WO (1) WO2007086624A1 (en)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100779363B1 (en) 2006-12-05 2007-11-28 동부일렉트로닉스 주식회사 Manufacturing method of porosity filter for hbr exclusion and cartridge with porosity filter for hbr exclusion is made by the same
KR101178918B1 (en) 2010-05-27 2012-09-03 주식회사 세미라인 An apparatus for treatment of Fluorine compound and method of treating for Fluorine compound gas
CN101898067A (en) * 2010-07-19 2010-12-01 北京雪迪龙科技股份有限公司 Gas purifier and regeneration method of molecular sieve thereof
CN102163643B (en) * 2010-10-09 2013-01-02 浙江哈氟龙新能源有限公司 Waste gas treatment thermal cycle drying system
KR101229946B1 (en) 2011-04-22 2013-02-05 주식회사 이엔 Fabrication method of catalyst based on the nano-silica to decompose PFC gaseous from semiconductor process, and Catalyst based on the nano-silicate to decompose the PFC manufactured by the same
KR101406198B1 (en) 2011-05-31 2014-06-12 주식회사 코캣 Catalyst for removing SF6 and preparatio method thereof
CN102294170B (en) * 2011-06-29 2013-04-17 宝纳资源控股(集团)有限公司 Titanium high temperature electrolytic furnace special-purpose tail gas processing system
KR101699217B1 (en) * 2011-10-19 2017-01-23 쇼와 덴코 가부시키가이샤 Perfluoride decomposition treatment method and treatment device
KR101407115B1 (en) * 2012-03-26 2014-06-13 (주) 세라컴 Method for treating hazardous gas generated in semiconductor manufacturing process
KR101387611B1 (en) 2012-04-23 2014-05-07 주식회사 글로벌스탠다드테크놀로지 Apparatus and method of treating perfluoro compounds
CN104548927B (en) * 2015-01-07 2017-01-25 黎明化工研究设计院有限责任公司 Process for removing trace nitrogen trifluoride in carbon tetrafluoride
KR101670461B1 (en) * 2015-06-11 2016-11-01 주식회사 테라세미콘 Apparatus for treating exhaust gas comprising hydrogen
KR101866994B1 (en) * 2015-10-30 2018-06-15 한국생산기술연구원 Method for Treating Perfluorinated compounds Using Liquid Metal
CN108290113A (en) * 2015-12-01 2018-07-17 昭和电工株式会社 The processing method of exhaust gas containing fluorine element
KR101802167B1 (en) * 2016-06-21 2017-12-04 선문대학교 산학협력단 Exhaust Line Structure in Apparatus for Semiconductor Processing
CN106179263A (en) * 2016-07-08 2016-12-07 常州天兴环保科技有限公司 A kind of TX GF JH 6 type boron chloride, lithium boron waste gas purification adsorbent
KR101825825B1 (en) * 2016-08-02 2018-02-06 주식회사 에코프로 INTEGRATED ABATEMENT SYSTEM FOR COMPLEX WASTE GAS INCLUDING NOx, NITROUS OXIDE, CHLOROFLUOROCARBONS, HYDROCHLOROFLUOROCARBONS, HYDROFLUOROCARBONS, AND PERFLUOROCOMPOUNDS
KR102041555B1 (en) * 2017-10-27 2019-11-06 (주)명성씨.엠.아이 Toxic gas treating system
KR20190053556A (en) 2017-11-10 2019-05-20 주식회사 에코프로 Method of removing nitrogen trifluoride(nf3) in waste gas-disposing apparatus
CN108525507A (en) * 2018-04-20 2018-09-14 苏州宏久航空防热材料科技有限公司 A kind of sulphur removal removes nitre integration filter pipe
KR102129988B1 (en) * 2020-03-06 2020-07-03 주식회사 퓨어스피어 Apparatus for treating waste gas in producing semiconductor and method for treating waste gas

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5248956B2 (en) * 1973-11-17 1977-12-13
JPH01139125A (en) * 1987-08-24 1989-05-31 Toshiba Corp Exhaust treatment equipment
GB8813270D0 (en) * 1988-06-04 1988-07-06 Plasma Products Ltd Dry exhaust gas conditioning
JPH03249920A (en) * 1990-02-27 1991-11-07 Mitsubishi Heavy Ind Ltd Method for decomposing gaseous fluorocarbon
JP2972975B2 (en) * 1993-12-22 1999-11-08 日本酸素株式会社 Hazardous exhaust gas abatement method and abatement agent
JPH09290128A (en) * 1996-04-25 1997-11-11 Babcock Hitachi Kk Exhaust gas processing apparatus and method for controlling its operation
JPH10216479A (en) * 1997-01-31 1998-08-18 Mitsui Chem Inc Detoxifying method of gaseous nitrogen trifluoride
JP3893023B2 (en) * 1997-10-17 2007-03-14 株式会社荏原製作所 Semiconductor manufacturing exhaust gas treatment method and apparatus
JP2001293335A (en) * 2000-04-12 2001-10-23 Ebara Corp Method for treating waste gas containing fluoride
JP3927359B2 (en) 2000-08-12 2007-06-06 高雄 福田 Exhaust gas treatment equipment
KR100444885B1 (en) * 2001-02-28 2004-08-18 주식회사 코캣 Cleaning method of particles and moisture contained in the exhaust gas
US20030072703A1 (en) * 2001-09-13 2003-04-17 Toshikazu Sugiura Method for removing the harmful effects of organic halogen compound gas, apparatus for removing the harmful effects of organic halogen compound gas, system for fabricating semiconductor devices, and method for fabricating semiconductor devices
JP3737082B2 (en) * 2001-12-04 2006-01-18 株式会社荏原製作所 Exhaust gas treatment method and apparatus

Also Published As

Publication number Publication date
WO2007086624A1 (en) 2007-08-02
JP4768470B2 (en) 2011-09-07
KR100654922B1 (en) 2006-12-06
TW200727971A (en) 2007-08-01
JP2007196204A (en) 2007-08-09
CN101007237A (en) 2007-08-01
TWI288655B (en) 2007-10-21

Similar Documents

Publication Publication Date Title
CN102658215B (en) SCR (selective catalytic reduction) flue gas denitration catalyst regeneration method
US10322403B2 (en) Coating for reducing nitrogen oxides
CN105233644B (en) Coal-fired flue gas dust-removing desulfurization and denitrification integrated compound technology system
CN100496676C (en) Wet ammonia flue gas cleaning technology simultaneously removing various pollutant and system thereof
CN103331142B (en) Magnetic adsorbent, preparation method and application of magnetic adsorbent in desulfurization of fuel oil
US8524186B2 (en) Carbon-based catalyst for flue gas desulfurization and method of producing the same and use thereof for removing mercury in flue gas
CN101422691B (en) Multi-pollutant removing technique and device of fuel coal smoke
CN103350004B (en) A kind of renovation process of SCR denitrating catalyst and for the mixture of SCR denitrating catalyst regenerated liquid
KR101298305B1 (en) Apparatus for removing of trace of toxic substance from exhaust gas and method of operating the same
CN102202767B (en) Method for removing mercury from combustion gas, and combustion gas cleaner
CN104492424A (en) Method for producing sulfuric acid by catalytic oxidation of sulfur dioxide in flue gas via ozone coupling with manganese dioxide/aluminum oxide
CN104289086B (en) A kind of method and device of the high concentrate dust removed in glass furnace fume
CN102974367B (en) Method for regenerating inactivation SCR denitration catalyst by using antitoxic renewable liquid
CN105056882A (en) Preparation method of modified charcoal-based adsorbent for removing hydrogen sulfide
WO2009049085A2 (en) Coal fired flue gas treatment and process
CN103480251B (en) System and method for performing desulfurization, denitration and demercuration to flue gas simultaneously
CN101274193B (en) System for purifying flue gas and recovering sulfur and technique
CN103007679B (en) Flue gas cleaning system capable of switching pollutant desorption technology and adsorbent regeneration technology and method thereof
CN101925394A (en) High temperature catalyst and process for selective catalytic reduction of NOx in exhaust gases of fossil fuel combustion
CN102515830A (en) Reproducible phosphorus-uptake ceramsite and preparation method thereof
CN103878035B (en) The regenerated liquid of a kind of vanadium, titanium based selective catalytic-reduction denitrified catalyst
CN203764106U (en) Flue gas denitrification device implemented by combining SNCR (selective non-catalytic reduction)-ozone oxidation with wet absorption
CN101856607B (en) Flue gas demercuration adsorbent
CN108176224A (en) A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device
CN101693162B (en) Method for desulfurizing and denitrating boiler gas simultaneously by using active carbon under microwave radiation

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090916

Termination date: 20170302

CF01 Termination of patent right due to non-payment of annual fee