CN102281939B - Reaction device and reaction method - Google Patents

Reaction device and reaction method Download PDF

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CN102281939B
CN102281939B CN201080004458.4A CN201080004458A CN102281939B CN 102281939 B CN102281939 B CN 102281939B CN 201080004458 A CN201080004458 A CN 201080004458A CN 102281939 B CN102281939 B CN 102281939B
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heat exchange
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reaction
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CN102281939A (en
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早坂裕二
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B01D53/70—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/406—Alkaline earth metal or magnesium compounds of strontium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/408—Alkaline earth metal or magnesium compounds of barium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2251/602—Oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/204—Alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20769—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2066—Fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0216—Other waste gases from CVD treatment or semi-conductor manufacturing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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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  • Engineering & Computer Science (AREA)
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  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
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Abstract

A reaction device (10) provided with: an outer tube (12) within which a reaction is performed; a heat exchanger (16) provided on one end side of the outer tube (12) and allowing exchange of heat between gas to be processed and a processed gas; the inner tube (14a) of a double-walled tube (14), the inner tube (14a) being adapted to supply to the heat exchanger (16) the gas to be processed; the outer tube (14b) of the double-walled tube (14), the outer tube (14b) being adapted to take the processed gas out of the heat exchanger (16); and an inner tube (18) connected to the heat exchanger (16), provided within the outer tube (12), and causing the gas to be processed to flow to the other end side of the outer tube (12), the other end side being the side spaced from said end side on which the heat exchanger (16) is provided. The reaction device is configured in such a manner that the device can be easily reduced in size and that the uniformity of the temperature distribution within the device is improved to make the device less likely to cause a variation in a reaction.

Description

Reaction unit and reaction method
Technical field
The present invention relates to such as for making reaction unit that fluorine compounds decompose etc.
Background technology
In the manufacturing process of present semiconductor devices, sometimes to carry out in order to form fine pattern etching, cleaning.Now a lot of situations will be used fluorine compounds.In addition, fluorine compounds are generally more stable, much harmless, therefore for example cooling medium use of air-conditioning of conduct in addition.
But these fluorine compounds, once be much to put in atmosphere to produce considerable influence to earth environment.That is, destroy atmospheric ozone layer, cause ozone cavity to produce.In addition, it is a reason that causes global warming as greenhouse oxidizing gases.And above-mentioned fluorine compounds are generally more stable, in a lot of situations, it affects long-term sustainable existence.
Therefore, in order earth environment not being exerted an influence, need to use fluorine compounds later to decompose, to become putting in atmosphere again after the harmless state of earth environment.
So, a kind of decomposing processor of the compound that contains fluorine is disclosed in patent documentation 1 for example, it comprises: be filled with the reactor containing Al catalysts, for to add the water adder of steam in the pending air-flow that contains fluorine and, carbon, sulphur or nitrogen compound of reactor, and, by being filled in catalyst in reactor and importing at least one in the air-flow that contains fluorine compounds in reactor, be heated to the heating arrangements of the temperature that can make fluorine compounds hydrolysis.
In addition, disclose a kind for the treatment of apparatus of the chemical compound gas that contains fluorine in patent documentation 2, it comprises: outer tube, inner tube, be arranged on the catalyst layer of inner tube inside and be arranged on the heater on outer tube.
Patent documentation 1: TOHKEMY 2001-224926 communique
Patent documentation 2: TOHKEMY 2008-126092 communique
Summary of the invention
The problem that invention will solve
But the preheater of the gas-heated that the decomposing processor that comprises the compound that contains fluorine of following part need to make to contain fluorine compounds, so energy efficiency is poor, device volume is large.Described part is: be filled with the reactor containing Al catalysts, for to add the water adder of steam in the pending air-flow that contains fluorine and, carbon, sulphur or nitrogen compound of reactor, and, by being filled in catalyst in reactor and importing at least one in the air-flow that contains fluorine compounds in reactor, be heated to the heating arrangements of the temperature that can make fluorine compounds hydrolysis.And near the temperature of the gas that contains fluorine compounds the outer wall of preheater is high, along with apart from outer wall is more and more far away, temperature reduces, so there is the inhomogeneous problem of reaction.
And then, the treating apparatus that comprises outer tube, inner tube, is arranged on the catalyst layer of inner tube inside and is arranged on the chemical compound gas that contains fluorine of the heater on outer tube can not carry out abundant preheating to the chemical compound gas that contains fluorine, so be difficult to equally make the Temperature Distribution for the treatment of apparatus inside identical, therefore also have the inhomogeneous problem of reaction.
In view of above-mentioned problem, the object of the invention is to, provide a kind of easy miniaturization, inner in addition Temperature Distribution more evenly, not to be prone to the uneven reaction unit of reaction.
In addition, another object is to provide the reaction method that can efficiently process processed gas.
The method of dealing with problems
Reaction unit of the present invention, it is characterized in that, comprise: the urceolus reacting in inside, be configured in an end side of above-mentioned urceolus, the main heat exchange department that carries out heat exchange between processed gas and the gas processed, to main heat exchange department, supply with the pipe of processed gas, from main heat exchange department, take out the pipe of the gas of processing, and, be connected with main heat exchange department, be configured in the inside of urceolus, make the logical inner core of the other end effluent of this urceolus that processed gas keeps away to the end side with disposing main heat exchange department.
Wherein, preferred processed gas contains fluorine compounds, and preferred reaction is that fluorine compounds are decomposed by least one and the reactant of aluminium oxide and alkaline earth metal compound containing in the compound that is selected from the metal in copper Cu, tin Sn, chromium Cr, molybdenum Mo, tungsten W, vanadium V.And then preferred reaction is carried out between above-mentioned urceolus and above-mentioned inner core.
And then, reaction unit of the present invention, it is characterized in that, comprise: the urceolus reacting at inner conversion zone, the gas communication that makes processed gas and processed, the dual pipe that carries out the 1st heat exchange between processed gas and the gas processed, be connected with dual pipe, the heat exchanger that carries out the 2nd heat exchange between processed gas and the gas processed, and, be connected with heat exchanger, be configured in the inside of urceolus, between processed gas and conversion zone, carry out the inner core of the 3rd heat exchange.
Wherein, preferably also comprise and be configured in the inside of inner core and the outside heater of above-mentioned urceolus, more preferably also comprise the fin in the outside that is arranged on above-mentioned inner core, and then preferred fin is arranged on the lower half side position of conversion zone.
In addition, reaction method of the present invention, it is characterized in that, the gas that makes processed gas and processed circulates in dual pipe, between processed gas and the gas processed, carry out the 1st heat exchange, processed gas is circulated in the heat exchanger being connected with above-mentioned dual pipe with the gas of processing, between processed gas and the gas processed, carry out the 2nd heat exchange, processed gas is circulated in the inner core being connected with heat exchanger, between processed gas and conversion zone, carry out the 3rd heat exchange, at conversion zone, make processed gas become the reaction of the gas of processing.
Wherein, preferred processed gas is the gas that contains fluorine compounds, and reaction is the reaction that these fluorine compounds are decomposed.
The effect of invention
The invention provides a kind of easy miniaturization, be not prone to the uneven reaction unit of reaction in addition.
The specific embodiment
Illustrate below with reference to accompanying drawings embodiments of the present invention.
Fig. 1 is for an illustration of the reaction unit that present embodiment is used is described.
Reaction unit 10 shown in Fig. 1, comprise: the urceolus 12 that portion reacts within it, the dual pipe 14 of the gas communication that makes processed gas and processed, be connected, be configured in urceolus 12 1 end side with dual pipe 14, between processed gas and the gas processed, carry out the heat exchanger 16 of the main heat exchange department of conduct of heat exchange, be connected, be configured in urceolus 12 inside with the heat exchanger 16 as main heat exchange department, make the logical inner core 18 of the other end effluent of the urceolus 12 that processed gas keeps away to the end side with disposing heat exchanger 16.
In addition, also comprise: the inside that is configured in inner core 18, processed gas is further heated, simultaneously for the required hot interior heater 20 as heater of the conversion zone supply response to urceolus inside, be configured in urceolus 12 outsides, for the required hot external heater 22 as heater of the conversion zone supply response to urceolus inside equally, be arranged on the outside of inner core 18, the fin 24 evenly conducting to conversion zone for the heat that interior heater 20 is produced, measure temperature, by not shown control device, control the temperature sensor 26a being formed by thermocouple etc. of the internal temperature of reaction unit 10, 26b, 26c, and, for filling the reactant input port 28 of reactant.
Urceolus 12 is reaction vessels, the reaction that can be scheduled in inside.In present embodiment, make as gas processed gas, that contain fluorine compounds at urceolus 12 internal circulations.And, between urceolus 12 and inner core 18, fill reactant, the reaction that these fluorine compounds is decomposed by this reactant.
As fluorine compounds, be equivalent to such as Chlorofluorocarbons class (hereafter is " CFC "), hydrochlorofluorocarazeotropic class (hereafter is " HCFC "), perfluorocarbon class (hereafter is " PFC "), HFC class (hereafter is " HFC "), perfluor ethers (hereafter is " PFE "), hydrogen fluorine ethers (hereafter is " HFE "), sulfur fluoride etc.
In more detail, as CFC, can list for example CClF 3, CCl 2f 2, CCl 3f, C 2cl 3f 3, C 2cl 2f 4, C 2clF 5deng compound, as HCFC, can list for example CHClF 2, C 2hCl 2f 3deng compound.In addition, as PFC, can list for example CF 4, C 2f 6, C 3f 8, C 4f 8compounds such as (octafluorocyclobutanes), can list for example CH as HFC 3f, CH 2f 2, CHF 3, C 2h 2f 4deng compound.In addition, as PFE, can list for example CF 3oCF 3, CF 3oCF 2cF 3deng compound, as HFE, can list for example CHF 2oCHF 2, CHF 2oCH 2cF 3, CH 3oCF 2cF 3deng compound.In addition, as sulfur fluoride, can list for example SF 6, S 2f 10deng compound.
These fluorine compounds can be independent or two or more mixtures.In addition, fluorine compounds are preferably usingd the inert gases such as helium, argon gas, nitrogen or air and are diluted as carrier gas.In the present embodiment, the concentration of the fluorine compounds in processed gas is preferably 0.01～10 volume %.
As reactant, can use at least one and the reactant of aluminium oxide and alkaline earth metal compound that contain in the compound that is selected from the metal in copper (Cu), tin (Sn), chromium (Cr), molybdenum (Mo), tungsten (W), vanadium (V).
Wherein, aluminium oxide is representational acidic materials (solid acids), uses separately it just can make fluorine compounds decompose.But decompose the fluorine generating, can make alumina surface fluoridize, with AlF 3form poisoning, make at short notice catalyst lose activity.
Here, in the present embodiment, contain alkaline earth metal compound.Can under the reaction temperature than in the past lower, make like this fluorine compounds decompose, the fluorine generating is fixed as alkali earth metal fluoride.To be described more specifically this below.
First, in present embodiment, the decomposition reaction of fluorine compounds for example represents with following formula.
CF 4+2CaCO 3/Al 2O 3→2CaF 2+3CO 2 …(1)
C 2F 6+3CaCO 3/Al 2O 3→3CaF 2+4CO 2+CO …(2)
The reaction temperature is here different and different according to the kind of the fluorine compounds that contain in processed gas.For example, PFC is classified into hard-decomposed compound, wherein CF in fluorine compounds 4, C 2f 6deng being the most hard-decomposed, only depend on thermal decomposition to decompose, need the high temperature of 1200 ℃～1400 ℃, but according to the method for present embodiment, so long as 550 ℃ just can be decomposed above.In addition, as the CHClF of HCFC 2, according to the method for present embodiment, so long as 200 ℃ of above temperature just can be decomposed.Different according to the kind of fluorine compounds like this, their decomposition temperature is also distributed in quite wide scope, thereby according to the kind of this compound, reactor to be set in to optimum temperature be important.
As alkaline earth metal compound, can use carbonate, hydroxide or the oxide of alkaline-earth metal.The more preferably carbonate of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) wherein, and then preferably as the calcium carbonate (CaCO of the carbonate of calcium 3).While using calcium carbonate in reactant, by coexisting with aluminium oxide, the fluorine that fluorine compounds can be decomposed to generation is with calcirm-fluoride (CaF 2) form fix.Performance prevents the effect that aluminium oxide is fluoridized thus, keeps the fluorine compounds decomposition function (activity) of aluminium oxide.
As to as compound one of reactant composition, that be selected from the metal in copper (Cu), tin (Sn), chromium (Cr), molybdenum (Mo), tungsten (W), vanadium (V), there is the co-catalyst effect that fluorine compounds are decomposed.In addition, different according to the kind of fluorine compounds, the carbon monoxide that can make the illustrated reaction decomposes going out of above-mentioned formula (2) generate divides to depress also in low oxygen and can be oxidized to carbon dioxide.
In above-claimed cpd, preferably use cupric oxide (CuO), tin oxide (SnO 2), vanadium oxide (V 2o 5) etc. oxide, more preferably use cupric oxide, tin oxide.
In present embodiment, the content of aluminium oxide and alkaline earth metal compound, preferred mass ratio is 1: 9～1: 1.In addition, the content of metallic compound, it is 1: 99～5: 95 that preferential oxidation aluminium and alkaline earth metal compound add up to the ratio of quality.
In present embodiment, this reactant is made to the shot-like particle of particle diameter 0.5mm～10mm, be filled in the space producing between urceolus 12 inner sides and the outside of inner core 18.As loading, with respect to this whole space, preferably reach 80%～90% height.So the part of having filled this reactant becomes the conversion zone reacting.
The material using as urceolus 12, reaction temperature, reaction product while needing only reaction have patience, are not particularly limited, preferably by making such as stainless steels.In addition, the shape as urceolus 12, is not particularly limited, from inner temperature homogeneity aspect and intensity aspect, the preferably cylindrical shape of internal diameter 100mm～2m.
Dual pipe 14 comprises as the inner tube 14a of inside tube with as the outer tube 14b of outboard tube.And processed gas is circulated in arbitrary pipe of inner tube 14a or outer tube 14b, the gas processed of circulation in another pipe, the while is carried out the 1st heat exchange by inside tube between processed gas and the gas processed.In this case, the dual pipe 14 that processed gas and the gas subtend of processing is circulated can be used as subtend streaming Double-wall-tube heat exchanger and understands.Processed gas can be in inner tube 14a and outer tube 14b any one in circulate, but from its heat exchanger effectiveness aspect, preferably in inner tube 14a, circulate.That is, if circulated in outer tube 14b, because outer tube 14b contacts with atmosphere, so can be to atmosphere heat release.Therefore, processed gas circulates and is advisable in the inner tube 14b that is difficult for generation heat release.In addition, the gas of processing, is preferably released to approach the temperature of room temperature as far as possible.From this viewpoint, also preferred processed gas circulates in inner tube 14a, and the gas of processing circulates in outer tube 14b.That is, because the heat of the gas of processing can discharge by outer tube 14b, so can reduce the temperature of the gas of processing.
As the heat exchanger 16 of main heat exchange department, be configured in urceolus 12 1 ends.And be connected with dual pipe 14, for example, by inner tube 14a heat exchanger 16, supply with processed gas, by outer tube 14b, from heat exchanger 16, take out the gas of processing.In addition, in heat exchanger 16, between processed gas and the gas processed, carry out the 2nd heat exchange.
In the present embodiment, when urceolus 12 and inner core 18 use cylindrical shape, heat exchanger 16 is by circular stainless steel making sheet is overlapped and is welded, and makes processed gas from different paths, pass through respectively with the gas of processing, circulate.And can make processed gas and the gas processed in the mode of tortuous subtend back and forth at heat exchanger 16 internal circulations, and carry out heat exchange by circular plate.Like this by making stream complications back and forth, heat that can be a large amount of with less volume exchange.In present embodiment, with processed gas and the gas processed respectively in the part of carrying out heat exchange this back and forth in the stream of complications back and forth the mode of 2.5 times form.Preferred this tortuous stream respectively back and forth more than 1.5 times back and forth.If also fewer than this, heat exchange is insufficient, the trend that the exhaust temperature that has this device to export uprises.
In addition the gas of processing, can enter heat exchanger 16 inside by the open a plurality of small-bore hole 30 of heat exchanger 16 sides at conversion zone.And the processed gas wearing out from heat exchanger 16 can be by entering in inner core 18 in open a plurality of holes 32, inner core 18 sides.
In addition, heat exchanger 16 is not limited to said structure.Can use the various heat exchangers such as votator, heat-exchangers of the plate type, multiple circular pipe type heat exchanger.
Inner core 18 is configured in urceolus 12 inside.And be connected with heat exchanger 16, urceolus 12 the other end effluents that processed gas is kept away to the end side with disposing heat exchanger 16 are logical.Processed gas, when by this inner core 18, carries out the 3rd heat exchange between conversion zone by inner core 18.Can further heat processed gas thus.Inner core 18 forms by 1 in the present embodiment, but can be also more than 2.In addition, the position of inner core 18, as the present embodiment in 1 situation about forming, is preferably arranged on urceolus 12 central parts.
In addition, in the present embodiment, inner core 18 has interior heater 20 in inside.This interior heater 20 can make processed gas further be heated, and the while is to the needed heat of conversion zone supply response of urceolus inside.In addition, in the outside of inner core 18, fin 24 has been installed.The heat that interior heater 20 produces is transmitted to conversion zone by inner core 18 and this fin 24.In addition,, by having this fin 24, the heat that can make interior heater 20 produce is conducted to conversion zone more equably.Here, when the reaction unit of present embodiment 10 being usingd to that side that heat exchanger 16 configured while using as downside, fin 24 is preferably mounted at second side position of conversion zone, is not arranged on first side part.That is, the top of conversion zone easily improves temperature by convection current, if fin 24 is installed in this part, easily makes the temperature of upside higher than downside.Therefore,, by being arranged on lower half side position, can make the Temperature Distribution of upper and lower of conversion zone more even.
In addition, fin 24 is preferably installed multi-disc.
Fig. 2 is the II-II profile of the reaction unit 10 shown in Fig. 1.
In the reaction unit 10 shown in Fig. 2,18 fin 24 have been installed in the outside of inner core 18.By such installation multi-disc, can make the Temperature Distribution of conversion zone more even.Here, the sheet number of fin 24 and length can suitably be selected according to the reaction condition in reaction unit 10.
The material using as inner core 18 and fin 24, as long as the reaction heat, the reaction product that produce during to reaction have patience, is not particularly limited.Preferably by making such as stainless steels.In addition, the shape as inner core 18, is not particularly limited, but from the viewpoint of the uniformity of internal temperature, pref. cylindrical.
In addition, interior heater 20 can be used for example because of Cornell (registration mark) heater.And for example can use 3 this because of Cornell (registration mark: inconel) heater, carry out triangle line, be accommodated in the inside of inner core 18.
In addition, in the present embodiment, in urceolus 12 outsides, there is external heater 22.By thering is this external heater, can be from the required heat of reaction in supply response region, outside.The heat that external heater 22 sends is transmitted to conversion zone by urceolus 12.And by have external heater 22 and interior heater 20 both, can heat from outside and inner side two sides of conversion zone.Therefore, can make the Temperature Distribution of conversion zone more even.
External heater 24 can be used for example INCOLOY (registration mark) heater.And from the viewpoint of heat supply equably, preferably this INCOLOY (registration mark) heater is arranged on around urceolus 12.
In addition, for the reaction unit of present embodiment when safeguard waiting easily with control device fractionation, preferably heater and/or temperature sensor are connected with for example metal connector with control device.
In addition,, in order further to prevent, to heat release in atmosphere, more effectively conversion zone being heated, preferably make urceolus 12 insulation material (not shown)s cover.As heat preserving agent, can use and to be formed by materials such as glass cloth, silica gel cloth.
In the reaction unit 10 of above-mentioned formation, as the gas that contains fluorine compounds of processed gas, first in the inner tube 14b of dual pipe 14, circulate.Now between processed gas and the gas processed, carry out the 1st heat exchange.Then, enter in the heat exchanger 16 being connected with dual pipe 14, flow to the inside of heat exchanger 16, again and between the gas of processing, carry out the 2nd heat exchange.Then enter in the inner core 18 being connected with heat exchanger 16.Processed gas, when in the interior circulation of inner core 18, and carries out the 3rd heat exchange between conversion zone, be heated by interior heater 20 simultaneously.From inner core 18 passes through, enter conversion zone, by inorganic agent, the fluorine compounds that comprise in processed gas are decomposed.By this reaction, processed gas becomes the gas of processing.The gas processed is current to circulate on one side in the outer tube 14b of heat exchanger 16, dual pipe 14, on one side and processed gas between carry out above-mentioned the 2nd heat exchange, the 1st heat exchange.And from dual pipe 14 by be placed in atmosphere.
Such reaction can be used as the reaction method with following characteristics and is understood: the gas communication that makes processed gas and processed in dual pipe 14, between processed gas and the gas processed, carry out the 1st heat exchange, the gas that circulates processed gas and processed in the heat exchanger 16 being connected with dual pipe 14, between the gas that makes processed gas and processed, carry out the 2nd heat exchange, processed gas circulates in the inner core 18 being connected with heat exchanger 16, between processed gas and conversion zone, carry out the 3rd heat exchange, at conversion zone, make processed gas become the reaction of the gas of processing.
The reaction unit 10 of present embodiment can make urceolus 12 and heat exchanger 16 integrated.In addition for processed gas and the gas processed being imported to the pipe arrangement of heat exchanger 16, are dual pipes 14.By thering is such structure, easily make reaction unit 10 miniaturizations.
And then, the 1st heat exchange of being undertaken by dual pipe 14 by the heat exchange in 3 stages, the 2nd heat exchange of being undertaken by heat exchanger 16, the 3rd heat exchange of being undertaken by inner core 18, can make processed gas by fully preheating, even in conversion zone, also become fully high temperature.Therefore, easily make conversion zone temperature distribution homogenization.Therefore, be not prone to reaction inequality.In addition,, when conversion zone temperature distributing disproportionation, the reactant consumption of the part that temperature is high is sometimes violent.Therefore, during the reactant end-of-life of this part, just need to change all reactants, uneconomical.The reaction unit 10 of present embodiment, easily makes conversion zone temperature distribution homogenization, so it is uneven not only to be prone to reaction, and easily makes the consumption of reactant identical, can extend the life-span of reactant.
And by so by inner core 18, carry out the 3rd heat exchange and heat by interior heater 20, can dwindle the volume of heat exchanger 16.Therefore can make the space between urceolus 12 and inner core 18 increase, can fill more reactant, therefore can react more efficiently, and can process more processed gas.
Spatial volume between urceolus 12 and inner core 18 is the conversion zone of urceolus inside, considers preferably 2 liters～3000 liters from uniformity aspect and the intensity aspect of inner temperature.Particularly preferably 2 liters～200 liters.The now installation of conticaster etc. is easy, is conducive to the exchanging operation of reaction unit 10.And from the viewpoint of uniformity and the reaction efficiency of inner temperature, and then preferably 40 liters～200 liters.
By having said structure, the reaction unit that can be used as reaction temperature and be 200 ℃～1000 ℃ is used, and can to make the gas temperature of reaction unit outlet be below 200 ℃.
In addition, in present embodiment, as processed gas, can list the gas that contains fluorine compounds, although the reaction that these fluorine compounds are decomposed is illustrated, be not limited to this.While using the gas beyond fluorine compounds as processed gas, as long as reactant is become to the reactant of the reaction that is applicable to this gas, just can use the reaction unit 10 of this enforcement.
For example for decompose the purge gas pipeline removed at semiconductor-fabricating device, from operating room, discharge contain superfluous anesthetic gases the nitrous oxide that contains, can be for using as reactant in the reaction etc. of solid catalyst.
Embodiment
As reaction unit, use the reaction unit 10 shown in Fig. 1 and Fig. 2.As reactant, using aluminium oxide and calcium carbonate mass ratio is 3: 7, and tin oxide is the reactant of 3 quality % with respect to the total weight of aluminium oxide and calcium carbonate.In addition,, as processed gas, make the CF as fluoride gas 4with the concentration of 6000volppm with the flow of 250L/min in the interior circulation of reaction unit 10.In addition, as carrier gas, use nitrogen.
The CF of the gas of processing as a result, 4concentration be 0ppm, confirmation can make CF 4decompose.In addition the now outside of assaying reaction device 10 and inner Temperature Distribution.
Fig. 3 is the figure of the Temperature Distribution of explanation reaction unit 10.
In Fig. 3, transverse axis represents temperature, and the longitudinal axis represents the short transverse position of conversion zone.And show external temperature and internal temperature in each position.The external temperature is here the temperature of measuring by changing successively the short transverse position of temperature sensor 26c (with reference to Fig. 1).In addition, internal temperature is the temperature of measuring by changing successively the short transverse position of temperature sensor 26b (with reference to Fig. 1).
As shown in Figure 3, internal temperature and external temperature are controlled at approximately 30 ℃ with interior temperature difference with respect to the short transverse position of conversion zone in the scope of 550 ℃～580 ℃, can know can realization response region in Temperature Distribution uniformly.
Accompanying drawing explanation
Fig. 1 is an illustration of the reaction unit that uses of explanation present embodiment.
Fig. 2 is the II-II profile of the reaction unit shown in Fig. 1.
Fig. 3 is for the figure of the Temperature Distribution of reaction unit is described.
Description of reference numerals
10... reaction unit, 12... urceolus, 14... dual pipe, 16... heat exchanger, 18... inner core, 20... interior heater, 22... external heater, 24... fin

Claims (8)

1. a reaction unit, is characterized in that, comprising:
At inner conversion zone, carry out the urceolus of the decomposition reaction of processed gas,
Be configured in an end side of above-mentioned urceolus, the main heat exchange department that carries out heat exchange between above-mentioned processed gas and the gas processed,
To above-mentioned main heat exchange department, supply with the 1st pipe of above-mentioned processed gas,
From above-mentioned main heat exchange department, take out the 2nd pipe of the gas of above-mentioned processing, and
Be connected with above-mentioned main heat exchange department, be configured in the inside of above-mentioned urceolus, make the logical inner core of the other end effluent of this urceolus that above-mentioned processed gas keeps away to the end side with disposing above-mentioned main heat exchange department,
The above-mentioned the 1st above-mentioned the 2nd pipe of managing and take out from above-mentioned main heat exchange department the gas of above-mentioned processing to the above-mentioned processed gas of above-mentioned main heat exchange department supply is formed on the dual pipe that carries out the 1st heat exchange between this processed gas and the gas of this processing,
Above-mentioned main heat exchange department, has with above-mentioned dual pipe and is connected, and the heat exchanger that carries out the 2nd heat exchange between above-mentioned processed gas and the gas of above-mentioned processing,
Above-mentioned inner core carries out the 3rd heat exchange between processed gas and above-mentioned conversion zone,
Described reaction unit also has and is arranged on the inside of above-mentioned inner core, the interior heater that above-mentioned processed gas is heated, and is arranged on the fin that the outside of above-mentioned inner core, heat that described interior heater is produced are transmitted to above-mentioned conversion zone equably.
2. reaction unit as claimed in claim 1, is characterized in that, above-mentioned processed gas contains fluorine compounds.
3. reaction unit as claimed in claim 2, it is characterized in that, above-mentioned reaction is that above-mentioned fluorine compounds are decomposed by least one and the reactant of aluminium oxide and alkaline earth metal compound containing in the compound that is selected from the metal in copper Cu, tin Sn, chromium Cr, molybdenum Mo, tungsten W, vanadium V.
4. the reaction unit as described in any one of claim 1～3, is characterized in that, above-mentioned reaction is carried out between above-mentioned urceolus and above-mentioned inner core.
5. reaction unit as claimed in claim 1, is characterized in that, also comprises the outside heater that is configured in above-mentioned urceolus.
6. reaction unit as claimed in claim 1, is characterized in that, above-mentioned fin is arranged on the lower half side position of above-mentioned conversion zone.
7. a reaction method, is characterized in that,
The gas that makes processed gas and processed circulates in dual pipe, carries out the 1st heat exchange between this processed gas and the gas of this processing,
Processed gas is circulated in the heat exchanger being connected with above-mentioned dual pipe with the gas of processing, between this processed gas and the gas of this processing, carries out the 2nd heat exchange,
Processed gas is circulated in the inner core being connected with above-mentioned heat exchanger, by the interior heater that is arranged on the inside of this inner core, above-mentioned processed gas is heated, the heat that described interior heater is produced by the fin that is arranged on the outside of this inner core is transmitted to conversion zone equably, between this processed gas and this conversion zone, carry out the 3rd heat exchange
At above-mentioned conversion zone, make described processed gas become the reaction of the gas of described processing.
8. reaction method as claimed in claim 7, is characterized in that, above-mentioned processed gas is the gas that contains fluorine compounds, and above-mentioned reaction is the reaction that these fluorine compounds are decomposed, and then above-mentioned fin is arranged on the lower half side position of above-mentioned conversion zone.
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