CN100537001C - Method for processing waste gas containing perfluorochemical or hydrofluorocarbon - Google Patents
Method for processing waste gas containing perfluorochemical or hydrofluorocarbon Download PDFInfo
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- CN100537001C CN100537001C CNB2004100584856A CN200410058485A CN100537001C CN 100537001 C CN100537001 C CN 100537001C CN B2004100584856 A CNB2004100584856 A CN B2004100584856A CN 200410058485 A CN200410058485 A CN 200410058485A CN 100537001 C CN100537001 C CN 100537001C
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- hydrofluorocarbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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Abstract
The invention discloses a method for treatment of waste gas containing total fluorine compounds and/ or hydrogen fluorine hydrocarbon, which contains that: the waste gas containing total fluorine compounds and/ or hydrogen fluorine hydrocarbon contacts with ferrum oxide catalyst and generates a electric grout oxidation reaction, and then the gas acts as a catalyst gas and generates a gas- solid contact oxidation reaction to decomposes the fluorine compounds and/ or hydrogen fluorine hydrocarbon contained gas. Invented operates at a much lower temperature and it is very suit for treatment of the waste gas containing total fluorine compounds in semi-conductor plant and photo-fabrication factory.
Description
Technical field
The present invention relates to a kind of method of handling waste gas containing fluoride, particularly relate to the method that a kind of processing contains perfluorochemical and/or hydrofluorocarbon waste gas.
Background technology
From the United Nations in 1992 by " climate change outline pact " afterwards, reducing the discharge capacity of greenhouse gases builds consensus internationally.According to the protocol that the capital of a country meeting is passed through, various countries should be with CO during 2008 to 2012 according to the difference of industrialization degree
2, CH
4, N
2O, hydrofluorocarbon (HFC), perfluorochemical (PFC) and SF
6The total release mean value of six kinds of greenhouse gases is reduced to the percentage that various countries promise to undertake.Therefore, all use the industry of perfluorochemical and hydrofluorocarbon all need carry out decrement at perfluorochemical and hydrofluorocarbon gas at present, to meet international convention, avoid suffering economic sanctions.
Nearly three kinds of the existing Decrement Technique of perfluorochemical: processing procedure improves, and for example promotes perfluorochemical utilization rate and employing instead of chemical product in the processing procedure; Recycling; With pipe end reason.Though pipe end reason is not best selection, be to handle to contain perfluorochemical and/or the most ripe and most economical effective method of hydrofluorocarbon toxic emission at present.In the reason of pipe end, the burning destroy method is to develop most complete processing perfluorochemical technology at present, and the temperature of its destruction needs approximately more than 1200 ℃.It is to handle perfluorochemical with lower temperature (500 ℃～750 ℃) and catalyst that catalyst combustion destroys.Plasma method is to utilize high pressure plasma localized hyperthermia (central temperature can reach more than 3000 ℃) to handle perfluorochemical.These processing methods all are that energy resource consumption reaches the fire hazard height greatly.
Disclose for No. the 20020150527th, U.S. patent application case and WO the 01/21304th A1 number and a kind ofly destroy the processing method that contains perfluorochemical and/or hydrofluorocarbon with catalyst composition, this catalyst composition comprise aluminium oxide and preferable through for example adding stabilization agent such as titanium, zirconium, cobalt or its mixture stabilization.But its operating temperature is about about 500 ℃ to 800 ℃.
This shows that above-mentioned existing processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas in method and use, obviously still has inconvenience and defective, and demands urgently further being improved.In order to solve the problem of handling the method existence that contains perfluorochemical and/or hydrofluorocarbon waste gas, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and general processing method does not have appropriate method to address the above problem, and this obviously is the problem that the anxious desire of relevant dealer solves.
Because above-mentioned existing processing contains the defective that the method for perfluorochemical and/or hydrofluorocarbon waste gas exists, the inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and professional knowledge, and the utilization of cooperation scientific principle, actively studied innovation, contain the method for perfluorochemical and/or hydrofluorocarbon waste gas in the hope of founding a kind of new processing, can improve the method that general existing processing contains perfluorochemical and/or hydrofluorocarbon waste gas, make it have more practicality.Through constantly research, design, and after studying repeatedly and improving, create the present invention who has practical value finally.
Summary of the invention
The objective of the invention is to, overcome the defective that existing processing contains the method existence of perfluorochemical and/or hydrofluorocarbon waste gas, and provide a kind of new processing to contain the method for perfluorochemical and/or hydrofluorocarbon waste gas, technical problem to be solved be make it can solve above-mentioned known techniques energy resource consumption reaches the high problem of fire hazard greatly about the perfluorochemical processing method, thereby be suitable for practicality more.
Another object of the present invention is to, the method that provides a kind of processing to contain perfluorochemical and/or hydrofluorocarbon waste gas, technical problem to be solved are to make it can effectively decompose perfluorochemical and/or hydrofluorocarbon, thereby are suitable for practicality more.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of processing that proposes according to the present invention contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and it may further comprise the steps: this contains the waste gas of perfluorochemical and/or hydrofluorocarbon with a plasma treatment; And handle the waste gas that this contains perfluorochemical and/or hydrofluorocarbon with a catalyst, and described catalyst is the chosen from Fe oxide, it is to carry out below 300 degree Celsius that wherein said plasma treatment and catalyst are handled.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and wherein said catalyst is to be selected from the group that di-iron trioxide, hydrated ferric oxide, tri-iron tetroxide, hydration tri-iron tetroxide are formed.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and it is that this carries out after containing the step of waste gas of perfluorochemical and/or hydrofluorocarbon with plasma treatment at this that wherein said catalyst is handled this step that contains the waste gas of perfluorochemical and/or hydrofluorocarbon.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein after with plasma treatment, before handling with catalyst, also comprises the step that this waste gas that contains perfluorochemical and/or hydrofluorocarbon is mixed with an oxide additive matter.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and wherein said oxide additive matter is to be selected from the group that hydrogen, oxygen and water are formed.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and the oxide additive matter concentration of wherein said influent stream is perfluorochemical and/or hydrofluorocarbon exhaust gas concentration ratio 0.001～10 times.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein before carrying out this plasma treatment step, also comprises this waste gas that contains perfluorochemical and/or hydrofluorocarbon being heated to room temperature or more than the room temperature.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein after carrying out this catalyst treatment step, also comprises with the inorganic acids in saturated this formed gas in catalyst processing back of a cleaning solution.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and wherein said perfluorochemical comprises CF
4, C
2F
6, C
3F
8, NF
3, SF
6Or its combination, this hydrofluorocarbon is CHF
3
The object of the invention to solve the technical problems also adopts following technical scheme to realize.A kind of processing that proposes according to the present invention contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and it may further comprise the steps: carry out one first catalyst treatment step, the employed catalyst chosen from Fe of described first catalyst treatment step oxide; Carry out a plasma treatment step; And carrying out one second catalyst treatment step, the employed catalyst chosen from Fe of described second catalyst treatment step oxide, the wherein said first catalyst treatment step, plasma treatment step and the second catalyst treatment step are to carry out below 300 degree Celsius.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and wherein said first, the employed catalyst of this second catalyst treatment step is to be selected from the group that di-iron trioxide, hydrated ferric oxide, tri-iron tetroxide, hydration tri-iron tetroxide are formed.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein said plasma treatment step be this first and this second catalyst treatment step between carry out, and this first catalyst treatment step is to carry out before this plasma treatment step.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein after with this plasma treatment, before carrying out this second catalyst treatment step, also comprise this waste gas that contains perfluorochemical and/or hydrofluorocarbon after the plasma treatment is mixed with oxide additive matter.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and wherein said oxide additive matter is to be selected from the group that hydrogen, oxygen and water are formed.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and the oxide additive matter concentration of wherein said influent stream is perfluorochemical and/or hydrofluorocarbon exhaust gas concentration ratio 0.001～10 times.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein before carrying out this first catalyst treatment step, also comprises this waste gas that contains perfluorochemical and/or hydrofluorocarbon being heated to room temperature or more than the room temperature.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, wherein after carrying out this second catalyst treatment step, also comprises with the inorganic acids in saturated this formed gas in second catalyst processing back of a cleaning solution.
Aforesaid processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and wherein said perfluorochemical comprises CF
4, C
2F
6, C
3F
8, NF
3, SF
6Or its combination, this hydrofluorocarbon is CHF
3
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, in order to reach aforementioned goal of the invention, major technique of the present invention thes contents are as follows: the invention provides the method that a kind of processing contains perfluorochemical and/or hydrofluorocarbon waste gas, be to handle the waste gas that contains perfluorochemical and/or hydrofluorocarbon with catalyst earlier, to remove acid gas or impurity.Then,, carry out gas-solid contact and oxidation reaction with catalyst more afterwards, with the content of perfluorochemical and/or hydrofluorocarbon in the reduction waste gas again with plasma treatment.
Described according to the embodiment of the invention, above-mentioned processing contains in the method for perfluorochemical and/or hydrofluorocarbon waste gas, before containing the waste gas of perfluorochemical and/or hydrofluorocarbon, can earlier waste gas be mixed with oxide additive matter, to promote its treatment effeciency with the catalyst processing.
In addition, described according to the embodiment of the invention, if it is low excessively to contain perfluorochemical and/or the hydrofluorocarbon waste gas temperature before preceding catalyst is handled, for example be to take out and temperature only has Celsius-10 to spend even-20 when spending, can be heated earlier by steel cylinder.
Described according to the embodiment of the invention, employed catalyst comprises ferriferous oxide in the said method, and this ferriferous oxide is to be selected from the group that di-iron trioxide, hydrated ferric oxide, tri-iron tetroxide, hydration tri-iron tetroxide are formed.
Described according to the embodiment of the invention, above-mentioned waste gas also comprises with the inorganic acids in the formed gas after the saturated catalyst reaction treatment of a cleaning solution after carrying out the catalyst reaction treatment.
Described according to the embodiment of the invention, the manageable perfluorochemical of method of the present invention comprises CF
4, C
2F
6, C
3F
8, NF
3, SF
6, or its combination; And this hydrofluorocarbon is CHF
3
Via as can be known above-mentioned, a kind of processing of the present invention contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, the method is to carry out gas-solid with the ferriferous oxide catalyst and contact containing perfluorochemical and/or hydrofluorocarbon waste gas, and carry out plasma oxidation and react, carry out gas-solid contact and oxidation reaction with catalyst more afterwards, to reach the purpose of decomposing perfluorochemical and/or hydrofluorocarbon.Because the present invention can operate under the temperature much lower than prior art, its energy resource consumption is little and do not have a fire hazard, therefore, is fit to very much with removing the waste gas that contains perfluorochemical that semiconductor and photoelectricity manufacturing works are produced.
By technique scheme, the present invention handles the method that contains perfluorochemical and/or hydrofluorocarbon waste gas and has following advantage at least:
1, because the present invention can operate under the temperature much lower than prior art, and its energy resource consumption is little and do not have a fire hazard, therefore, is fit to very much with removing the waste gas that contains perfluorochemical that semiconductor and photoelectricity manufacturing works are produced.
2, the present invention handles the method that contains perfluorochemical and/or hydrofluorocarbon waste gas, can effectively handle to contain perfluorochemical and/or hydrofluorocarbon waste gas, and especially perfluorochemical is the processing procedure raw material of semiconductor and opto-electronics.
3, in addition, the present invention makes perfluorochemical and/or hydrofluorocarbon and plasma and catalyst reaction, and it is decomposed in the process of reaction, does not therefore have problems such as the big and fire hazard height of secondary public hazards, energy resource consumption that discharging waste gas contains other pollutants.
In sum, particular processing of the present invention contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and energy resource consumption reaches the high problem of fire hazard greatly about the perfluorochemical processing method can to solve above-mentioned known techniques.The present invention simultaneously can also effectively decompose perfluorochemical and/or hydrofluorocarbon.It has above-mentioned many advantages and practical value, and in class methods, do not see have similar design to publish or use and really genus innovation, no matter it is all having bigger improvement on method or on the function, have large improvement technically, and produced handy and practical effect, and the method that more existing processing contains perfluorochemical and/or hydrofluorocarbon waste gas has the multinomial effect of enhancement, thereby is suitable for practicality more, is a new and innovative, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is the schematic diagram of the waste gas treatment equipment that illustrates according to embodiment of the present invention.
Fig. 2 is the flow chart of the waste gas processing method that illustrates according to embodiment of the present invention.
Fig. 3 is that pro-oxidant of the present invention is respectively H
2And O
2, when different input power, its H
2/ SF
6And O
2/ SF
6Influent stream is than increasing to 5 SF by 0
6Resolution ratio.
100: waste gas treatment equipment 102: heater
110: preceding catalyst treating apparatus 112: mixing arrangement
120: plasma treatment appts 130: the catalyst treating apparatus
140: scrubbing tower 150: detecting and automaton
The specific embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, the processing that foundation the present invention is proposed contains its specific embodiment of method, method, step, feature and the effect thereof of perfluorochemical and/or hydrofluorocarbon waste gas, describe in detail as after.
The present invention be with ferriferous oxide as catalyst, and cooperate isoionic use, contain perfluorochemical and/or hydrofluorocarbon waste gas to handle efficiently.
The transition metal oxide catalyst can be applicable to purposes such as oxidation reaction and hydrogenation, dehydrogenation reaction.In transition metal oxide, the oxide of iron has H
2, CO, CH
4, and the activity of paraffin oxidation reaction intermediate degree, it can be as the chemical catalyst of high temperature reacting condition, styrene list based polyalcohol synthetic reaction, ammonia synthesis reaction and hydrogen sulfide removal reaction.The present invention utilizes the oxide of iron and cooperates plasma to handle to contain perfluorochemical and/or hydrofluorocarbon waste gas.
Isoionic oxidizing force is extremely strong, is widely used in semiconductor and the photoelectric process.But, when handling polluter,,, also have the polluter of part can't decompose or produce residue, and cause secondary pollution though specific polluter can be decomposed if only handle with plasma.Therefore, need high-energy, reaction for a long time when list is with plasma treatment perfluorochemical and/or hydrofluorocarbon waste gas usually, maybe necessary installing subsequent processing device as scrubbing tower, can be destroyed perfluorochemical and/or hydrofluorocarbon waste gas fully.The present invention as catalyst, and cooperates isoionic use with ferriferous oxide, is a kind of method that can efficient processing contains perfluorochemical and/or hydrofluorocarbon waste gas.
Seeing also shown in Figure 1ly, is the schematic diagram of the waste gas treatment equipment that illustrates according to embodiment of the present invention.The present invention handles the waste gas that contains perfluorochemical and/or hydrofluorocarbon via the equipment 100 with plasma treatment appts and catalyst reactor.In waste gas treatment equipment 100 of the present invention, each device unit and pipeline are preferably corrosion-resistant and high temperature resistant, but because of operating temperature of the present invention below 300 ℃, so harsh unlike prior art to the requirement of heatproof.In the waste gas treatment equipment of the present invention, and contain the optional usefulness of material that perfluorochemical and/or gases such as hydrofluorocarbon waste gas or plasma contact for example SS316 stainless steel, pottery, quartz or fe fluon etc.
The manageable waste gas of the present invention comprises perfluorochemical and/or hydrofluorocarbon, and wherein perfluorochemical comprises CF
4, C
2F
6, C
3F
8, NF
3, SF
6, or its combination; And hydrofluorocarbon is CHF
3Accessible waste gas load capacity can be 100～50000ppm, preferable 1000～10000ppm.Usually, handled waste gas also can comprise the material that is produced in many processing procedures except perfluorochemical and/or hydrofluorocarbon, for example is chlorine, hydrofluoric acid or other acid gas or impurity.In order to increase the usefulness of processing, catalyst treating apparatus 110 before emission-control equipment 100 of the present invention can also comprise is to enter the acid gas of removing earlier before the plasma treatment appts 120 in the waste gas at waste gas.
In addition, before containing the waste gas of perfluorochemical and/or hydrofluorocarbon, earlier waste gas is mixed with oxide additive matter, will help the usefulness of plasma treatment waste gas with plasma treatment.Therefore, emission-control equipment 100 of the present invention can also comprise a mixing arrangement 112, mixes in order to the waste gas and the oxide additive matter that will contain perfluorochemical and/or hydrofluorocarbon, again with plasma treatment.Wherein, oxide additive matter for example is hydrogen, oxygen, water etc.The hydrogen of influent stream, oxygen or water concentration can be perfluorochemical and/or hydrofluorocarbon exhaust gas concentration ratio 0.001～10 times, preferable 1～3 times.Because handled waste gas may contain corrosive substance, therefore, the material of mixing arrangement with corrosion-resistant, heatproof person is preferable.
The plasma generator of plasma treatment appts 120 can be generally can produce plasma with electric energy.In the plasma treatment appts 120, the plasma concentration of influent stream can be 0～50000MHz, preferable 1～100MHZ.
Preceding catalyst treating apparatus 110 and plasma catalyst reaction unit 130 can use vertical or horizontal catalyst bed, and comprise ferriferous oxide (iron oxides) or copper Zinc catalysts in its reactor, or other activated aluminum absorbents, wherein ferriferous oxide for example is di-iron trioxide, hydrated ferric oxide, tri-iron tetroxide, hydration tri-iron tetroxide (Fe
2OOH) or its mixture, be preferably hydrated ferric oxide, particularly the hydrated ferric oxide of needle-like shape (claims goethite (goethite) again, FeOOH).
Consider with economy, waste exhaust gases can be 0.1～10 second in the time of staying of catalyst bed, also can surpass 10 seconds, but is not inconsistent benefit.
Above-mentioned desire is handled contains perfluorochemical and/or hydrofluorocarbon waste gas, in through the catalyst reactor, contact with catalyst carry out oxidation after, perfluorochemical and/or hydrofluorocarbon can be broken down into CO
2, H
2O, and inorganic acids.Preferably at discharging CO
2, H
2O, and inorganic acids before install a scrubbing tower 140 additional, remove the inorganic acids that is produced after the exhaust-gas treatment with cleaning solution.Cleaning solution can be the liquid that contains liquid caustic soda.By liquid flow controller control flow, use to be disposed to the waste water treatment plant after saturated.In addition, inlet front end before exhaust-gas treatment or the outlet rear end after the exhaust-gas treatment can be installed according to circumstances and be collected the windmill that waste gas is used.
The present invention contains perfluorochemical and/or hydrofluorocarbon treatment of waste gas under normal temperature, rather than therefore general perfluorochemical treatment technology serviceability temperature, can reduce a large amount of energy resource consumptions more than 500 ℃.It should be noted that, if waste gas is to be stored among the gas bomb, waste gas is before handling, temperature when steel cylinder is discharged is about-10 ℃, even reach-20 ℃, waste gas treatment equipment 100 of the present invention can also comprise a heater 102, to heat before waste gas is handled, avoids waste gas sedimentation when handling.
On the other hand, the present invention can be according to circumstances before waste gas and heating such as oxide additive matter such as oxygen, hydrogen or water or carry out gas-solid contact before after by oxygen, hydrogen or water concentration, temperature and the plasma frequency of temperature, humidity and plasma frequency detecting and control device 150 detecting gas streams, relatively its variation, as temperature, humidity, plasma influent stream concentration, and the control of wash liquid flow, in order to do adjusting controlling elements to keep the stable high treatment efficiency of integration equipment; Particularly can be applied to the perfluorochemical and/or the hydrofluorocarbon gas treatment of high concentration and load unusual fluctuation fierceness.
Seeing also shown in Figure 2ly, is the flow chart of the waste gas processing method that illustrates according to embodiment of the present invention.The present invention handles the method for the waste gas that contains perfluorochemical and/or hydrofluorocarbon, is to carry out plasma treatment step 206 earlier, makes the waste gas that contains perfluorochemical and/or hydrofluorocarbon excite oxidation.Then, carry out catalyst treatment step 208 again, carry out with catalyst that gas-solid contacts and oxidation reaction so that contain the waste gas of perfluorochemical and/or hydrofluorocarbon, so that it is decomposed into CO
2, H
2O and inorganic acid etc.
If also comprised the material that is produced in many processing procedures in the waste gas, for example be chlorine, hydrofluoric acid or other acid gas or impurity, catalyst treatment step 202 before then can be earlier via one before carrying out plasma treatment step 206 is to remove the acid gas in the waste gas earlier before waste gas carries out plasma treatment.
Consider with economy, waste exhaust gases can be 0.1～10 second in the time of staying of catalyst bed, also can surpass 10 seconds, but is not inconsistent benefit.
In addition, before carrying out, after the catalyst treatment step 202, carry out before the plasma treatment step 206, can carry out the step 204 that waste gas mixes with oxide additive matter earlier, to promote the usefulness of plasma treatment waste gas.Oxide additive matter for example is hydrogen, oxygen, water etc.The hydrogen of influent stream, oxygen or water concentration can be perfluorochemical and/or hydrofluorocarbon exhaust gas concentration ratio 0.001～10 times, preferable 1～3 times.
In addition, if waste gas is to be stored among the gas bomb, waste gas is before handling, temperature when steel cylinder is discharged is about-10 ℃, even reaches-20 ℃, can heat 201 before waste gas is handled, for example be to be heated to room temperature or more than the room temperature, to avoid waste gas sedimentation when handling.
When waste gas carries out catalyst treatment step 208 and after being decomposed into carbon dioxide, water and inorganic acid, can carry out washing step 210 earlier before discharging, to remove formed inorganic acid.Removing the method for inorganic acid and can utilize a cleaning solution, for example is one to contain the liquid of liquid caustic soda, to neutralize it, treats that it is disposed to the waste water treatment plant after saturated again.
See also shown in Figure 3ly, what it illustrated is that pro-oxidant is respectively H
2And O
2, input power is respectively 5,20 and during 40W, its H
2/ SF
6And O
2/ SF
6Influent stream is than increasing to 5 SF by 0
6Resolution ratio.No matter the result by Fig. 3 shows that pro-oxidant is H
2Or O
2, SF
6The F-that is decomposed all improves and increases along with power.What is particularly worth mentioning is that pro-oxidant is H
2The time, fluoro free radical easily and hydrogen form thermodynamically stable HF product.In addition, under the high power (40W), owing to form the fluoro free radical of more tool etch capabilities, and therefore, even SF
6Do not adding hydrogen (R=0) or low hydrogenation than under the situation, all because of forming SiF
4Reach products such as fluorine oxysulfide, and can reach the resolution ratio more than 99%.
Comprehensive the above, the present invention can directly be applied in the incineration technology of perfluoro-compounds waste-gas and accessible perfluorocompound gases, and concentration range.In addition, operating temperature of the present invention is lower than 300 ℃, can avoid a large amount of energy resource consumptions of incineration technology of prior art and the danger that may catch fire.Moreover the present invention also can stablize the situation of handling the perfluorocompound gases that high concentration and load unusual fluctuation fierceness are arranged, and suitable perfluorocompound gases concentration and kind scope are wider.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (18)
1, a kind of processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that it may further comprise the steps:
This contains the waste gas of perfluorochemical and/or hydrofluorocarbon with a plasma treatment; And
Handle the waste gas that this contains perfluorochemical and/or hydrofluorocarbon with a catalyst, described catalyst is the chosen from Fe oxide,
It is to carry out below 300 degree Celsius that wherein said plasma treatment and catalyst are handled.
2, processing according to claim 1 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said catalyst is to be selected from the group that di-iron trioxide, hydrated ferric oxide, tri-iron tetroxide, hydration tri-iron tetroxide are formed.
3, processing according to claim 1 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that it is that this carries out after containing the step of waste gas of perfluorochemical and/or hydrofluorocarbon with plasma treatment at this that wherein said catalyst is handled this step that contains the waste gas of perfluorochemical and/or hydrofluorocarbon.
4, processing according to claim 3 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that after with plasma treatment, before handling, also comprise the step that this waste gas that contains perfluorochemical and/or hydrofluorocarbon is mixed with an oxide additive matter with catalyst.
5, processing according to claim 4 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said oxide additive matter is to be selected from the group that hydrogen, oxygen and water are formed.
6, processing according to claim 5 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and the concentration that it is characterized in that the oxide additive matter of wherein said influent stream is perfluorochemical and/or hydrofluorocarbon exhaust gas concentration ratio 0.001～10 times.
7, processing according to claim 3 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that, before carrying out this plasma treatment step, it also comprises and this waste gas that contains perfluorochemical and/or hydrofluorocarbon is heated to room temperature or more than the room temperature.
8, processing according to claim 3 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that after carrying out this catalyst treatment step, also comprises with the inorganic acids in saturated this formed gas in catalyst processing back of a cleaning solution.
9, processing according to claim 1 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said perfluorochemical comprises CF
4, C
2F
6, C
3F
8, NF
3, SF
6Or its combination, this hydrofluorocarbon is CHF
3
10, a kind of processing contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that it may further comprise the steps:
Carry out one first catalyst treatment step, the employed catalyst chosen from Fe of described first catalyst treatment step oxide;
Carry out a plasma treatment step; And
Carry out one second catalyst treatment step, the employed catalyst chosen from Fe of described second catalyst treatment step oxide,
The wherein said first catalyst treatment step, plasma treatment step and the second catalyst treatment step are to carry out below 300 degree Celsius.
11, processing according to claim 10 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said first, the employed catalyst of this second catalyst treatment step is to be selected from the group that di-iron trioxide, hydrated ferric oxide, tri-iron tetroxide, hydration tri-iron tetroxide are formed.
12, processing according to claim 10 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said plasma treatment step be this first and this second catalyst treatment step between carry out, and this first catalyst treatment step is to carry out before this plasma treatment step.
13, processing according to claim 12 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that after this plasma treatment, before carrying out this second catalyst treatment step, also comprise this waste gas that contains perfluorochemical and/or hydrofluorocarbon after the plasma treatment is mixed with oxide additive matter.
14, processing according to claim 13 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said oxide additive matter is to be selected from the group that hydrogen, oxygen and water are formed.
15, processing according to claim 14 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, and the concentration that it is characterized in that the oxide additive matter of wherein said influent stream is perfluorochemical and/or hydrofluorocarbon exhaust gas concentration ratio 0.001～10 times.
16, processing according to claim 12 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that before carrying out this first catalyst treatment step, also comprise this waste gas that contains perfluorochemical and/or hydrofluorocarbon being heated to room temperature or more than the room temperature.
17, processing according to claim 12 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that after carrying out this second catalyst treatment step, also comprise with the inorganic acids in saturated this formed gas in second catalyst processing back of a cleaning solution.
18, processing according to claim 10 contains the method for perfluorochemical and/or hydrofluorocarbon waste gas, it is characterized in that wherein said perfluorochemical comprises CF
4, C
2F
6, C
3F
8, NF
3, SF
6Or its combination, this hydrofluorocarbon is CHF
3
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100584856A CN100537001C (en) | 2004-08-19 | 2004-08-19 | Method for processing waste gas containing perfluorochemical or hydrofluorocarbon |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100584856A CN100537001C (en) | 2004-08-19 | 2004-08-19 | Method for processing waste gas containing perfluorochemical or hydrofluorocarbon |
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| 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 |
| 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 |
| CN108815996A (en) * | 2018-07-02 | 2018-11-16 | 江苏三美化工有限公司 | A kind of hydrofluorocarbon exhaust treatment system and its application method |
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