CN100584435C - The devices and methods therefor of decompsing rhodanates - Google Patents
The devices and methods therefor of decompsing rhodanates Download PDFInfo
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- CN100584435C CN100584435C CN200610080310A CN200610080310A CN100584435C CN 100584435 C CN100584435 C CN 100584435C CN 200610080310 A CN200610080310 A CN 200610080310A CN 200610080310 A CN200610080310 A CN 200610080310A CN 100584435 C CN100584435 C CN 100584435C
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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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Abstract
The invention provides a kind of method and device of decompsing rhodanates, under lower reaction temperature,,, then remove sulphur fluorine compounds in the waste gas in the mode of washing again to form the compound of highly-water-soluble by two step decompsing rhodanates.
Description
Technical field
The present invention relates to a kind of method and device of waste gas decomposition, particularly relate to the method and the device that decompose the sulfur-bearing fluorine compounds.
Background technology
Photoelectricity, semiconductor industry all are to use the gas (Perfluorochemicals that comprises perfluorochemical in thin film manufacture process, etch process and ion implantation etc. at present; PFCs), for example, CF
4, C
2F
6, C
3F
8, c-C
4F
8, CHF
3, NF
3And SF
6Deng.SF wherein
6The cleaning surfaces that generally is used for dry ecthing procedure and chemical vapor deposition process board inside especially.
The treatment technology that the tool of the IPCC of the United Nations approval at present 90% is removed efficient (DRE) only has: combustion-type (fueled combustion), plasma (Plasma) and high temperature catalyst three kinds of modes such as (catalytic).
At first, the combustion-type waste gas treatment equipment need add fuel C H
4, the combustion adjuvant air, the energy that utilizes burning to produce decomposes the S-F key, produces SO
2F
2, SO
2, SO
3With CO, CO
2, HF.In general, the rear end of the combustion-type waste gas treatment equipment wet scrubbing tower of all connecting is in order to remove corrosive gas and particulate.The shortcoming of this technology is to add CH
4As fuel, produce CO, C simultaneously
2H
4Deng accessory substance.
The equipment of plasma treatment PFCs generally installs between turbine pump (turbo pump) and dried pump (drypump).PFCs is behind plasma free electron bump, and the bond fission of C-F key is again by importing steam (H
2O) after, PFCs is converted into HF and CO/CO
2Plasma technique only is used in etch process at present, and occupation rate of market is relatively low.Possible reason be waste gas behind plasma bombardment, produce the numerous and diverse high harmful gases of kind (as HCN, COF
2), even installing the wet scrubbing tower additional, the rear end still may not effectively remove all derivatives.In addition, be installed in the vacuum end position and may reclaim the doubt of polluting by the initiation reaction groove.
At the etch process of photoelectricity, semiconductor industry, the mode of the exhaust-gas treatment general choice high temperature catalyst of its etch process.The waste gas treatment equipment of selling the high temperature catalyst formula on the market installs the wet scrubbing tower additional at the catalyst bed front end mostly, in order to remove particulate and the corrosive gas that produces in the processing procedure, make simultaneously to wash waste gas with water, participate in the PFCs cracking reaction so that enough hydrogen atoms to be provided.In the catalyst bed rear end, can install the wet scrubbing tower again additional, purpose is to catch PFCs and decomposes the HF that the back produces.
As described in HITACHI European patent (EP 1205234), a kind of method of decomposing fluorine compounds and device thereof at first import the gas C for example contain fluorine compounds
2F
6, CF
4, CHF
3, SF
6And NF
3To reactor, then aerating oxygen and water contact with fluorine compounds to above-mentioned reactor, and fluorine compounds are decomposed.But its reactor control temperature needs more than 650 ℃.
Along with the expansion of relevant photoelectricity, semiconductor industry processing procedure, with the pressure of PFCs decrement, thereby to the rush of demand of the waste gas treatment equipment of high temperature catalyst.Therefore, develop effective resolution process PFCs, and to have the emission-control equipment that reduces the harmful side product conversion ratio be a kind of imperative trend.
Summary of the invention
In view of this, the present invention's first purpose is effectively to decompose the gas of sulfur-bearing fluorine compounds, provides a kind of in not providing under oxygen, the cryogenic conditions with the method for two-period form catalyst decomposes sulphur fluorine compounds (PFCs), comprises the following steps:
At first, provide the sulphur fluorine compounds to contact, form first analyte to decompose these sulphur fluorine compounds with first catalyst; Then, provide second catalyst to contact, form second analyte to decompose this first analyte, wherein this second analyte water soluble with this first analyte.The method of two-period form decompsing rhodanates of the present invention can be carried out in lower reaction temperature, and can not need aerating oxygen, and wherein range of reaction temperature can be controlled between 500～800 ℃, and for example reaction temperature can be 580 ℃.And the sulphur fluorine compounds can be decomposed to form the material of highly-water-soluble, for example HF and SO
3, afterwards can be directly remove sulphur fluorine compounds in the gas with water-washing method.The method of two-period form decompsing rhodanates wherein of the present invention finally converts water-fast material to less than 0.1mol%, and removes efficient (DRE) up to 99.9%.
The present invention's second purpose provides a kind of device of decompsing rhodanates, comprising:
First reactor has first inlet and first outlet, and this first inlet provides the sulphur fluorine compounds to contact with first catalyst, forms first analyte to decompose these sulphur fluorine compounds; Second reactor has second inlet and second outlet, and this second inlet provides this first analyte to contact with second catalyst, forms second analyte to decompose this first analyte; Wherein this first outlet is connected with this second inlet, to import this first analyte to this second reactor.
The device of two-period form decompsing rhodanates of the present invention can carry out in lower reaction temperature, and can not need aerating oxygen, and wherein range of reaction temperature can be controlled between 500～800 ℃, and for example reaction temperature can be 580 ℃.And the sulphur fluorine compounds can be decomposed to form the material of highly-water-soluble, for example HF and SO
3, afterwards can be directly remove sulphur fluorine compounds in the gas with water-washing method.The device of two-period form decompsing rhodanates wherein of the present invention finally converts water-fast material to less than 0.1mol%, and removes efficient up to 99.9%.
The present invention includes:
1. the method for a decompsing rhodanates comprises the following steps:
Provide the sulphur fluorine compounds to contact, form first analyte to decompose these sulphur fluorine compounds with first catalyst; And
Provide second catalyst to contact, form second analyte to decompose this first analyte, wherein this second analyte water soluble with this first analyte;
Wherein this second catalyst is prepared by the following step, and described step comprises:
Second carrier is dipped in the second metallic salt aqueous solution;
Carry out drying steps, to remove moisture content;
Carry out calcination step, to form this second catalyst;
Wherein this second carrier comprises aluminium oxide, and this second metallic salt aqueous solution is the copper nitrate and the cerous nitrate aqueous solution.
2. as the method for 1 a described decompsing rhodanates, wherein the sulphur fluorine compounds comprise: SF
6, SO
2F
2Or SOF
2
3. as the method for 1 described decompsing rhodanates, wherein before these sulphur fluorine compounds and step that this first catalyst contacts, also comprise and carry out the humidification step.
4. as the method for 3 a described decompsing rhodanates, wherein this humidification step comprises with the injection system importing aqueous solution, behind this aqueous solution of vaporizing, mixes in these sulphur fluorine compounds with the water vapour state again.
5. as the method for 4 a described decompsing rhodanates, wherein the volume ratio of water vapour gas and these sulphur fluorine compounds is 30～120.
6. as the method for 1 a described decompsing rhodanates, wherein this first catalyst is prepared by the following step, and described step comprises:
First carrier is dipped in the first metallic salt aqueous solution;
Carry out drying steps, to remove moisture content;
Carry out calcination step, to form this first catalyst.
7. as the method for 6 a described decompsing rhodanates, wherein this first carrier comprises aluminium oxide.
8. as the method for 6 a described decompsing rhodanates, wherein the metal of this first metallic salt aqueous solution comprises tungsten, nickel, zinc or cerium.
9. as the method for 6 a described decompsing rhodanates, wherein this first metallic salt aqueous solution is zinc nitrate aqueous solution.
10. as the method for 8 or 9 described decompsing rhodanates, this first metallic salt aqueous solution wherein, it is 5～20mol% that zinc ion accounts for whole solution proportion scope.
11. as the method for 6 described decompsing rhodanates, wherein to be dipped in the time range of this first metallic salt aqueous solution be 3～12 hours to this first carrier.
12. as the method for 6 described decompsing rhodanates, wherein this first carrier step of being dipped in this first metallic salt aqueous solution is lower than an atmospheric pressure.
13. as the method for 6 a described decompsing rhodanates, wherein this drying steps temperature range is between 100～150 ℃.
14. as the method for 13 a described decompsing rhodanates, wherein this drying steps time range is between 8-12 hour.
15. as the method for 6 a described decompsing rhodanates, wherein this calcination step temperature range is between 650～800 ℃.
16. as the method for 15 a described decompsing rhodanates, wherein this calcination step time range is between 4.5～5.5 hours.
17. as the method for 1 a described decompsing rhodanates, wherein this first analyte comprises SO
2F
2, HF and SO
3
18. as the method for 1 a described decompsing rhodanates, wherein this second catalyst is prepared by the following step, described step comprises:
Second carrier is dipped in the second metallic salt aqueous solution;
Carry out drying steps, to remove moisture content;
Carry out calcination step, to form this second catalyst.
19. as the method for 18 a described decompsing rhodanates, wherein this second carrier comprises aluminium oxide.
20. as the method for 18 a described decompsing rhodanates, wherein the metal of this second metallic salt aqueous solution comprises manganese, copper, zinc or cerium.
21. as the method for 18 a described decompsing rhodanates, wherein this second metallic salt aqueous solution is the copper nitrate and the cerous nitrate aqueous solution.
22. as the method for 20 or 21 described decompsing rhodanates, this second metallic salt aqueous solution wherein, the proportion that copper ion and cerium ion account for whole solution is 3-20mol%.
23. as the method for 18 described decompsing rhodanates, wherein to be dipped in the time range of this second metallic salt aqueous solution be 3～12 hours to this second carrier.
24. as the method for 18 described decompsing rhodanates, wherein this second carrier step of being dipped in this second metallic salt aqueous solution is lower than an atmospheric pressure.
25. as the method for 18 a described decompsing rhodanates, wherein this drying steps temperature range is between 100～150 ℃.
26. as the method for 25 a described decompsing rhodanates, wherein this drying steps time range is between 8-12 hour.
27. as the method for 18 a described decompsing rhodanates, wherein this calcination step temperature range is between 650～800 ℃.
28. as the method for 18 a described decompsing rhodanates, wherein this calcination step time range is between 4.5～5.5 hours.
29. as the method for 1 a described decompsing rhodanates, wherein this second analyte comprises SO
3And HF.
30. as the method for 1 a described decompsing rhodanates, the temperature range of wherein decomposing these sulphur fluorine compounds is 500～800 ℃.
31. as the method for 1 a described decompsing rhodanates, wherein this sulphur fluorine compounds flow and this first catalyst volume are than between 100～2200.
32. as the method for 1 described decompsing rhodanates, wherein this sulphur fluorine compounds flow and this second catalyst volume are than between 100～2200.
33. the device of a decompsing rhodanates comprises:
First reactor has first inlet and first outlet, and this first inlet provides the sulphur fluorine compounds to contact with first catalyst, forms first analyte to decompose these sulphur fluorine compounds;
Second reactor has second inlet and second outlet, and this second inlet provides this first analyte to contact with second catalyst, forms second analyte to decompose this first analyte; And
Wherein this first outlet is connected with this second inlet, to import this first analyte to this second reactor;
Wherein this second catalyst is prepared by the following step, and described step comprises:
Second carrier is dipped in the second metallic salt aqueous solution;
Carry out drying steps, to remove moisture content;
Carry out calcination step, to form this second catalyst;
Wherein this second carrier comprises aluminium oxide, and this second metallic salt aqueous solution is the copper nitrate and the cerous nitrate aqueous solution.
34. as the device of 33 a described decompsing rhodanates, wherein this first inlet is connected with sulphur fluorine compounds supply, so that this first reactor sulphur fluorine compounds to be provided.
35. as the device of 34 described decompsing rhodanates, wherein between this first inlet and this sulphur fluorine compounds supply, humidifier is set also, to add aqueous vapor to these sulphur fluorine compounds that enter this first reactor.
36. as the device of 35 a described decompsing rhodanates, wherein this humidifier comprises:
Syringe is in order to import water to this decomposer;
Vaporizer, have the 3rd inlet, the 3rd outlet and injection port, this injection port is connected with this syringe to import water to this vaporizer, use water vapor, the 3rd inlet is connected with this sulphur fluorine compounds supply, water vapour is added in these sulphur fluorine compounds, the 3rd outlet and this first inlet connect, and these sulphur fluorine compounds that add aqueous vapor are imported in this first reactor.
37. the device as 33 a described decompsing rhodanates also comprises the inert gas supply, to provide inert gas in order to detect gas leakage or to dilute this sulphur fluorine compounds.
38. as the device of 37 a described decompsing rhodanates, wherein this inert gas comprises nitrogen.
39. as the device of 33 a described decompsing rhodanates, wherein this first catalyst comprises that the mode to pile up is arranged in this first reactor.
40. as the device of 33 described decompsing rhodanates, wherein this first reactor also comprises outward heater is set, to heat this first reactor.
41. as the device of 33 a described decompsing rhodanates, wherein this first reactor also comprises thermocouple, to control this first reactor temperature.
42. as the device of 33 described decompsing rhodanates, wherein this second catalyst comprises with accumulation mode and being arranged in this second reactor.
43. as the device of 33 described decompsing rhodanates, wherein this second reactor also comprises outward heater is set, to heat this second reactor.
44. as the device of 33 a described decompsing rhodanates, wherein this second reactor also comprises thermocouple, to control the temperature in this second reactor.
45. as the device of 33 a described decompsing rhodanates, this second outlet is connected with container, uses wet scrubbing and removes this second analyte.
46. as the device of 45 a described decompsing rhodanates, wherein this container comprises bubble bottle or tank.
47. as the device of 33 a described decompsing rhodanates, wherein this first analyte comprises SO
2F
2, HF and SO
3
48. as the device of 33 a described decompsing rhodanates, wherein this second analyte comprises SO
3And HF.
Description of drawings
The 1st figure is the first catalyst preparation step flow chart;
The 2nd figure is the second catalyst preparation step flow chart;
The 3rd figure is the installation drawing of decompsing rhodanates of the present invention;
4a-4c figure is after detecting decomposition with IR, the analysis chart of sulphur fluorine compounds residual quantity.
The primary clustering symbol description
The device of 1～decompsing rhodanates;
2～sulphur fluorine compounds supply;
4～inert gas supply;
5～valve;
6～flow controller;
8～humidifier;
9～thermocouple;
10～the first reactors;
11～heater;
12～the first catalyst;
13～the first inlets;
14～the first outlets;
20～the second reactors;
21 heaters;
22～the second catalyst;
23～the second inlets;
24～the second outlets;
30～container;
81～syringe;
82～vaporizer;
83～injection port;
84～the 3rd inlets;
85～the 3rd outlets.
The specific embodiment
Next with embodiment and cooperate graphicly describing the present invention in detail, graphic or describe, similar or identical part is used same-sign.In graphic, the shape of embodiment or size can enlarge, to simplify or convenient the sign.The part of assembly will be to describe explanation in graphic.Apprehensiblely be that the assembly that does not illustrate or describe can be to have the various forms of haveing the knack of known to this skill person.
The making of first catalyst
The 1st figure is shown to be the first Preparation of catalysts flow process, at first gets the aluminium oxide (Al of 15g
2O
3) as the carrier of first catalyst, certain carrier of the present invention does not exceed with aluminium oxide, has the preferable carrier of high surface area and absorption affinity all applicable to the present invention, for example silica gel, magnesia or sieve and silica-sesquioxide etc.
Then, above-mentioned aluminium oxide is dipped in contains in the immersion liquid again, this contains immersion liquid is by metallic salt aqueous solution made, and this salt that contains in the immersion liquid can be oxalates, nitrate or sulfate etc., contains in this enforcement that preferable salt is a nitrate in the immersion liquid.The above-mentioned metal that contains in the immersion liquid can be tungsten, nickel, zinc or cerium, and the immersion liquid preferred metal that contains of first catalyst is a zinc in the present embodiment.The amount of wherein choosing this aluminium oxide is relevant with the metal that contains immersion liquid, for example uses zinc nitrate (Zn (NO in this example
3)
2) aqueous solution is as containing immersion liquid, wherein to account for the ratio of whole solution (zinc and aluminium) be between 5～20mol% to zinc ion, for example impregnation ratio can be 10mol%.
In specific words, the aluminium oxide of above-mentioned 15g is dipped in the zinc nitrate solution of 0.1 liter of 10mol%, and at room temperature (25 ℃), reach pressure and be lower than operation under 1 atmospheric pressure, impregnation 3～12 hours uses that active ingredient is adsorbed on the carrier, for example zinc is adsorbed on the aluminium oxide, to prepare first catalyst.
After finishing the impregnation step, then above-mentioned first catalyst is carried out drying, shown in the 1st figure.When this drying steps, preferable baking temperature scope is between 100～150 ℃, and preferable drying time, scope was between 8～12 hours.In a preferred embodiment, this first catalyst is with 120 ℃ of dryings of temperature 10 hours, with the structural strength that obtains first catalyst and zinc is uniformly distributed on the aluminium oxide.
Through behind the drying steps, again first catalyst to be handled with calcination step, wherein preferable calcination temperature scope is between 650 ℃～800 ℃, preferable calcination time range is between 4.5～5.5 hours.In the present embodiment, this first catalyst, reaches and obtains suitable catalyst activity to increase the hardness of first catalyst with 800 ℃ of calcination of temperature 5 hours.
The making of second catalyst
The 2nd figure is shown to be the second Preparation of catalysts flow process, at first get the carrier of the aluminium oxide of 15g as second catalyst, certain carrier of the present invention does not exceed with aluminium oxide, have the preferable carrier of high surface area and absorption affinity and all belong to the scope of the invention, for example silica gel oxide, magnesia or sieve and silica-sesquioxide etc.
Then, above-mentioned aluminium oxide is dipped in contains in the immersion liquid again, this contains immersion liquid is by metallic salt aqueous solution made, and this salt that contains in the immersion liquid can be oxalates, nitrate or sulfate etc., contains in this enforcement that preferable salt is a nitrate in the immersion liquid.The above-mentioned metal that contains in the immersion liquid can be manganese, copper, zinc or cerium, and in the present embodiment, the immersion liquid preferred metal that contains of second catalyst is copper and cerium.The amount of wherein choosing this aluminium oxide is relevant with the metal that contains immersion liquid, for example contain immersion liquid in this example and be respectively the zinc nitrate aqueous solution and the cerous nitrate aqueous solution, the metal that contains immersion liquid is copper and cerium, and the ratio that copper ion and cerium ion account for total solution (copper, cerium and aluminium) is all between 3～20mol%, and wherein for example impregnation ratio is 3mol% all.
The aluminium oxide of above-mentioned 15g is dipped in the mixed solution of 0.1 liter 5mol% copper nitrate and 5mol% cerous nitrate, and at room temperature (25 ℃), and pressure is lower than operation under 1 atmospheric pressure, impregnation 3～12 hours, use active ingredient is attached on the carrier, for example copper, cerium are invested on the aluminium oxide, to prepare second catalyst.
After finishing the impregnation step, then the second above-mentioned catalyst is carried out drying, shown in the 2nd figure.When this drying steps, preferable baking temperature scope is between 100～150 ℃, and preferable drying time, scope was between 8～12 hours.In a preferred embodiment, this second catalyst is with 120 ℃ of dryings of temperature 10 hours, with the structural strength that obtains catalyst and copper, cerium are uniformly distributed on the aluminium oxide.
Through behind the drying steps, again second catalyst to be handled with calcination step, wherein preferable calcination temperature scope is between 650 ℃～800 ℃, preferable calcination time range is between 4.5～5.5 hours.In the present embodiment, this second catalyst is with 800 ℃ of calcination of temperature 5 hours, increasing the hardness of second catalyst, and obtains suitable catalyst activity.
What deserves to be mentioned is that above-mentioned aluminium oxide not only can be used as outside the carrier of first and second catalyst, aluminium oxide itself also can be used as a catalyst, to increase the efficient of decomposing the sulphur fluoride.
The method of decompsing rhodanates
See also device 1 figure of the shown decompsing rhodanates of the 3rd figure, use sulphur fluorine compounds supply 2, so that the gas that contains the sulphur fluorine compounds, for example SF to be provided
6, SO
2F
2Or SHOF
2Provide the SF that contains concentration range 200～12000ppm in this example
6Gas, SF wherein is provided
6Gas flow relevant with the amount of first and second catalyst of setting.SF for example
6Gas flow is 100～2200h with first and second catalyst volume than scope
-1Between (gas hour space velocity; GHSV), wherein the volume of first, second catalyst is identical in this example, and the volume of first, second catalyst also can be inequality certainly, and this mode only is for convenience of description, but does not limit the present invention.Before feeding the sulfur-bearing fluorine compounds, use inert gas supply 4, provide inert gas for example nitrogen, helium etc., with the step of leaking hunting of the pipeline to this decomposer 1.In addition, this inert gas also can be used to dilution, balance sulphur fluorine compounds.
After leaking hunting with inert gas, close inert gas supply 4, and open sulphur fluorine compounds supply 2, to feed SF
6Gas to decomposer, SF wherein
6Concentration for example is 10000ppm.This SF
6Gas through valve 5, this valve 5 connects above-mentioned inert gas supply 4 and sulphur fluorine compounds supplies, the gas that feeds with control.
Next, above-mentioned SF
6Gas through behind the valve 5, enter damping device 8 via the 3rd inlet 84 again, use and add aqueous vapor SF so far
6Gas in.This SF
6Gas before entering damping device 8, can feed the flow of gas with control earlier through flow controller 6.
Above-mentioned damping device 8 has syringe 81, vaporizer 82, and this syringe 81 is connected with external water source, behind the importing water, enters vaporizer 82 through injection port 83 again, and these vaporizer 82 temperature are 150 ℃, can make water vapor.Form with vaporization is added and is added water to SF
6In the gas, because water is mode and SF with gaseous state
6Gas mixes, and makes SF
6Gas can obtain relatively large aqueous vapor.Wherein this syringe 81 imports the flow and feeding SF of water
6The concentration of gas is relevant, and wherein the water addition also can be converted into water vapour gas and SF
6The volume ratio of gas is between 30～120.
SF
6Gas is via the 3rd inlet 84 when entering damping device 8, can derive this via the 3rd outlet 85 again and be mixed with the SF of aqueous vapor with after the aqueous vapor that vaporizer 82 provides is mixed
6Gas.
Then, the above-mentioned SF that is mixed with aqueous vapor
6Gas imports in first reactor 10 via first inlet 13, is provided with first catalyst 12 in this first reactor 10, this first catalyst 12 and the SF that is mixed with aqueous vapor
6Gas contacts, with reaction decomposes SF
6Gas produces first analyte, and this first analyte contains SO
2F
2, HF and SO
3Gas.Above-mentioned first reactor 10 is provided with heater 11 and thermocouple 9 in addition, and this heater 11 can be a heater coil, and is looped around around first reactor 10, to heat this first reactor 10 to reaction temperature.Use the reaction temperature in above-mentioned thermocouple 9 detectings first reactor 10, maintain certain temperature to control first reactor 10.
Derive first analyte via first outlet 14, import in second reactor 20 via second inlet 23 again, be provided with second catalyst 22 in this second reactor 20, in order to contact with first analyte, reaction decomposes first analyte is to produce second analyte, and this second analyte contains SO
3And the gas of HF.Above-mentioned second reactor 20 is provided with heater 21 and thermocouple 9 in addition, and this heater 21 can be a heater coil, and is looped around around second reactor 20, to heat this second reactor to reaction temperature.Use the reaction temperature in above-mentioned thermocouple 9 detectings second reactor 20, maintain certain temperature to control second reactor 20.
What deserves to be mentioned is, above-mentioned first analyte of handling through first reactor 10, can not derive first reactor 10 earlier yet, and directly contact with second catalyst 22 at first reactor 10, decompose first analyte, producing second analyte, then derive these second analytes to container 30 through first outlet 14 again, remove sulphur fluorine compounds in the gas with water-washing method.That is to say, the present invention does not limit and uses two reactor decompsing rhodanates, can directly first catalyst 12, second catalyst 22 be placed in first reactor 10, contacts with the sulphur fluorine compounds, after being decomposed to form second analyte, remove the sulphur fluorine compounds with water-washing method again.
Then, before second inlet 23 imports second reactor 20 with first analyte, optionally pass through the damping device (not shown) again, to add aqueous vapor so far in first analyte.The aqueous vapor that the humidification step of this moment not only can be supplied first analyte also can utilize water to remove water-soluble composition in first analyte, for example HF and SO
3, can increase the content of water-fast composition in first analyte by this, for example SO
2F
2To improve decomposition efficiency.
Then, derive second analyte through second outlet 24, feed in the container 30 again and handle, wherein this container for example is tank, bubble groove and washing chamber.Second analyte is all water miscible compound, for example HF and SO
3, therefore, can utilize this second analyte of mode place of washing.
4a figure and 4b figure detect SF after decomposer of the present invention is handled with infrared spectrum (IR)
6, SO
2F
2The analysis chart of residual quantity, transverse axis are the time, and the longitudinal axis is SF
6, SO
2F
2Residual concentration.A point in 4a figure is SF
6Import the time point of decomposer at the beginning, the SF of this moment
6Concentration can be learnt by Y-axis, wherein SF
6Concentration is about 11719ppm.Cooperate 4a figure and 4b figure to learn, begin to import SF
6Behind decomposer of the present invention, this SF
6Can be broken down at once and contain SO
2F
2Analyte (this checkout gear only detects at the compound that contains the sulphur fluorine, so all the other analytes do not show), continue to observe after 50 hours, the B point in 4b figure is almost detected less than SO in the exit as can be seen
2F
2, wherein Detecting device minimum detected concentration (low detection limitation LDL) is 16.9ppm, that is to say that the sulphur fluorine compounds almost have been broken down into water-soluble compound.Next, it is shown to see also 4c figure, and this is the schematic diagram of the removal efficient (DRE) of decomposer of the present invention, wherein can learn from importing SF
6The removal efficient that begins its sulphur fluoride to apparatus of the present invention is several greater than 99.9%.
Embodiment one
At first providing concentration by sulphur fluorine compounds supply 2 is the SF of 12161ppm
6Gas, wherein sulphur fluorine compound gas flow is all 100h with the ratio of first catalyst 12 and second catalyst, 22 volumes
-1(gas hour space velocity; GHSV).Above-mentioned damping device 8 adds and adds water in the sulphur fluorine compounds, and the form that above-mentioned water adds is that the mode with water vapour is added in the sulphur fluorine compounds, and the ratio of adding water vapour amount and sulphur fluorine compound gas flow is 30.Then, import in gas to the first reactor 10 of the sulphur fluorine compounds that have aqueous vapor through first inlet 13, afterwards, after the sulphur fluorine compound gas after this interpolation aqueous vapor decomposes by first catalyst 12, to become first analyte.Then, import first analyte to the second reactor 20 via second inlet 23, and contact, form second analyte to decompose first analyte with second catalyst.Wherein first and second temperature of reactor is 680 ℃.Second analyte comprises SO
3, HF and SO
2F
2, wherein the clearance of sulphur fluorine compounds is 99.9%, and remaining SO
2F
2Be scaled conversion ratio and be lower than 0.1mol%, that is to say that the sulphur fluorine compounds that decompose through this device almost are broken down into water-soluble compound, so can remove the sulphur fluorine compounds for water.
Embodiment two
At first, providing concentration by sulphur fluorine compounds supply 2 is the SF of 11719ppm
6Gas, wherein sulphur fluorine compound gas flow is all 100hW (gas hour space velocity with the ratio of first catalyst 12 and second catalyst, 22 volumes; GHSV).Above-mentioned damping device 8 can add and adds water in the sulphur fluorine compounds, and the form that above-mentioned water adds is that the mode with water vapour is added in the sulphur fluorine compounds, and the ratio of adding water vapour amount and sulphur fluorine compound gas flow is 50.Then, import in gas to the first reactor 10 of the sulphur fluorine compounds that have aqueous vapor, after the sulphur fluorine compound gas after this interpolation aqueous vapor decomposes by first catalyst 12, to become first analyte through first inlet 13.Then, import in first analyte to the second reactor 20 through second inlet 23, and contact, form second analyte to decompose first analyte with second catalyst.Wherein first and second temperature of reactor is 580 ℃.Second analyte comprises SO
3, HF and SO
2F
2, wherein the clearance of sulphur fluorine compounds is 99.9%, and remaining SO
2F
2Be scaled conversion ratio and be lower than 0.1mol%, that is to say that the sulphur fluorine compounds that decompose through this device almost are broken down into water-soluble compound, so can remove the sulphur fluorine compounds for water.
Embodiment three
At first, providing concentration by sulphur fluorine compounds supply 2 is the SF of 1073ppm
6Gas, wherein sulphur fluorine compound gas flow is all 1216h with the ratio of first catalyst 12 and second catalyst, 22 volumes
-1(gas hour space velocity; GHSV).Above-mentioned damping device 8 can add and adds water in the sulphur fluorine compounds, and the form that above-mentioned water adds is that the mode with water vapour is added in the sulphur fluorine compounds, and the ratio of adding water vapour amount and sulphur fluorine compound gas flow is 120.Then, import in gas to the first reactor 10 of the sulphur fluorine compounds that have aqueous vapor, after the sulphur fluorine compound gas after this interpolation aqueous vapor decomposes by first catalyst 12, to become first analyte through first inlet 13.Then, import in first analyte to the second reactor 20 through second inlet 23, and contact, form second analyte to decompose first analyte with second catalyst.Wherein first and second temperature of reactor is 780 ℃.Second analyte comprises SO
3, HF and SO
2F
2, wherein the clearance of sulphur fluorine compounds is 99.9%, and remaining SO
2F
2Be scaled conversion ratio and be lower than 1.6mol%, that is to say that the sulphur fluorine compounds that decompose through this device almost are broken down into water-soluble compound, so can remove the sulphur fluorine compounds for water.
Embodiment four
At first, providing concentration by sulphur fluorine compounds supply 2 is the SF of 1007ppm
6Gas, wherein sulphur fluorine compound gas flow is all 2160h with the ratio of first catalyst 12 and second catalyst, 22 volumes
-1(gas hour space velocity; GHSV).Above-mentioned damping device 8 can add and adds water in the sulphur fluorine compounds, and the form that above-mentioned water adds is that the mode with water vapour is added in the sulphur fluorine compounds, and the ratio of adding water vapour amount and sulphur fluorine compound gas flow is 75.Then, import in gas to the first reactor 10 of the sulphur fluorine compounds that have aqueous vapor, after the sulphur fluorine compound gas after this interpolation aqueous vapor decomposes by first catalyst 12, to become first analyte through first inlet 13.Then, import in first analyte to the second reactor 20 through second inlet 23, and contact, form second analyte to decompose first analyte with second catalyst.Wherein first and second temperature of reactor is 780 ℃.Second analyte comprises SO
3, HF and SO
2F
2, wherein the clearance of sulphur fluorine compounds is 97.6%, and remaining SO
2F
2Be scaled conversion ratio and be lower than 3.5mol%, that is to say that the sulphur fluorine compounds that decompose through this device almost are broken down into water-soluble compound, so can remove the sulphur fluorine compounds for water.
Embodiment five
At first, providing concentration by sulphur fluorine compounds supply 2 is the SF of 237ppm
6Gas, wherein sulphur fluorine compound gas flow is all 916h with the ratio of first catalyst 12 and second catalyst, 22 volumes
-1(gas hour space velocity; GHSV).Above-mentioned damping device 8 can add and adds water in the sulphur fluorine compounds, and the form that above-mentioned water adds is that the mode with water vapour is added in the sulphur fluorine compounds, and the ratio of adding water vapour amount and sulphur fluorine compound gas flow is 75.Then, import in gas to the first reactor 10 of the sulphur fluorine compounds that have aqueous vapor, after the sulphur fluorine compound gas after this interpolation aqueous vapor decomposes by first catalyst 12, to become first analyte through first inlet 13.Then, import in first analyte to the second reactor 20 through second inlet 23, and contact, form second analyte to decompose first analyte with second catalyst.Wherein first and second temperature of reactor is 680 ℃.Second analyte comprises SO
3, HF and SO
2F
2, wherein the clearance of sulphur fluorine compounds is 99.9%, and remaining SO
2F
2Be scaled conversion ratio and be lower than 7.1mol%, that is to say that the sulphur fluorine compounds that decompose through this device almost are broken down into water-soluble compound, so can remove the sulphur fluorine compounds for water.
Therefore, decomposer treatment S F of the present invention
6Though still have SO
2F
2Residual, but SO wherein
2F
2Exit concentration be concentration less than LDL, represent the SF that then handles if be scaled conversion ratio through apparatus of the present invention
6Be converted to SO
2F
2Almost be less than 0.1mol%, so the SF that imports
6Almost all be converted to water-soluble HF and SO
3, therefore, sulphur fluorine compounds decomposer of the present invention has the decomposition efficiency of height, and the analyte after handling nearly all is water-soluble compound, so the mode of tank or washing that can directly feed is removed.Though the present invention discloses as above with preferred embodiment; right its is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; permitted to change and retouching when doing this, so protection scope of the present invention attached claim after looking defines and is as the criterion.
Claims (19)
1. the method for a decompsing rhodanates comprises the following steps:
Provide the sulphur fluorine compounds to contact, form first analyte to decompose these sulphur fluorine compounds with first catalyst; And
Provide second catalyst to contact, form second analyte to decompose this first analyte, wherein this second analyte water soluble with this first analyte;
Wherein this second catalyst is prepared by the following step, and described step comprises:
Second carrier is dipped in the second metallic salt aqueous solution;
Carry out drying steps, to remove moisture content;
Carry out calcination step, to form this second catalyst;
Wherein this second carrier comprises aluminium oxide, and this second metallic salt aqueous solution is the copper nitrate and the cerous nitrate aqueous solution.
2. the method for decompsing rhodanates as claimed in claim 1, wherein said sulphur fluorine compounds comprise: SF
6, SO
2F
2Or SOF
2
3. the method for decompsing rhodanates as claimed in claim 1 wherein before these sulphur fluorine compounds and step that this first catalyst contacts, also comprises and carries out the humidification step.
4. the method for decompsing rhodanates as claimed in claim 3, wherein this humidification step comprises with injection system and imports the aqueous solution, behind this aqueous solution of vaporizing, mixes in these sulphur fluorine compounds with the water vapour state again.
5. the method for decompsing rhodanates as claimed in claim 4, wherein the volume ratio of water vapour gas and these sulphur fluorine compounds is 30～120.
6. the method for decompsing rhodanates as claimed in claim 1, wherein this first catalyst is prepared by the following step, and described step comprises:
First carrier is dipped in the first metallic salt aqueous solution;
Carry out drying steps, to remove moisture content;
Carry out calcination step, to form this first catalyst.
7. the method for decompsing rhodanates as claimed in claim 1, wherein this first carrier comprises aluminium oxide.
8. the method for decompsing rhodanates as claimed in claim 6, wherein the metal of this first metallic salt aqueous solution comprises tungsten, nickel, zinc or cerium.
9. the method for decompsing rhodanates as claimed in claim 6, wherein this first metallic salt aqueous solution is zinc nitrate aqueous solution.
10. the method for decompsing rhodanates as claimed in claim 8 or 9, wherein in this first metallic salt aqueous solution, it is 5～20mol% that zinc ion accounts for whole solution proportion scope.
11. the method for decompsing rhodanates as claimed in claim 6, wherein in the step of preparation first catalyst, the time range that this first carrier is dipped in this first metallic salt aqueous solution is 3～12 hours, the pressure that this first carrier is dipped in the step of this first metallic salt aqueous solution is lower than an atmospheric pressure, this drying steps temperature range is between 100～150 ℃, and this drying steps time range is between 8-12 hour.
12. the method for decompsing rhodanates as claimed in claim 6, wherein, in the step of preparation first catalyst, the calcination step temperature range is between 650～800 ℃, and the calcination step time range is between 4.5～5.5 hours.
13. the method for decompsing rhodanates as claimed in claim 1, wherein this first analyte comprises SO
2F
2, HF and SO
3
14. the method for decompsing rhodanates as claimed in claim 1, wherein in this second metallic salt aqueous solution, the proportion that copper ion and cerium ion account for whole solution is 3-20mol%.
15. the method for decompsing rhodanates as claimed in claim 1, wherein, the time range that this second carrier is dipped in this second metallic salt aqueous solution in the step of preparation second catalyst is 3～12 hours, and wherein this second carrier step of being dipped in this second metallic salt aqueous solution is lower than an atmospheric pressure.
16. the method for decompsing rhodanates as claimed in claim 1, wherein, in the step of preparation second catalyst, this drying steps temperature range is between 100～150 ℃, this drying steps time range is between 8-12 hour, this calcination step temperature range is between 650～800 ℃, and this calcination step time range is between 4.5～5.5 hours.
17. the method for decompsing rhodanates as claimed in claim 1, wherein this second analyte comprises SO
3And HF.
18. the method for decompsing rhodanates as claimed in claim 1, the temperature range of wherein decomposing these sulphur fluorine compounds is 500～800 ℃.
19. the method for decompsing rhodanates as claimed in claim 1, wherein this sulphur fluorine compounds flow and this first catalyst volume are than between 100～2200, and this sulphur fluorine compounds flow and this second catalyst volume are than between 100～2200.
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