KR20010093838A - Apparatus and method for point-of-use treatment of effluent gas streams - Google Patents

Abstract

The present invention relates to a system for reducing undesirable component (s) from undesirable component (s), such as halo compounds, acid gases, silanes, ammonia, and the like. Halo compounds such as fluorine, fluoride, perfluorocarbon, and chlorofluorocarbon may be purified in the presence of a reducing agent, such as sodium thiosulfate, ammonium hydroxide, or potassium iodide. In one embodiment, the purifying system includes a second " finishing " unit operated in a gas / liquid stream 120 flowing in a direction opposite to the first acid gas purifying unit operated in a gas / liquid flow 110 flowing in the same direction It achieves high removal efficiency while consuming a small amount of water. The purge system may utilize a removable insert bed made of a filled material in the porous diaphragm structure. The reduction system of the present invention is particularly useful for treating effluents of semiconductor manufacturing processes.

Description

[0001] APPARATUS AND METHOD FOR POINT-OF-USE TREATMENT OF EFFLUENT GAS STREAMS [0002]

In reducing semiconductor off-gases from in-point-of-use to wet cleaning methods, several methods require removal of hydride gases, acid gases, and entrained solids. This is a process that uses or produces SiH ₄ (silane), NH ₃ (ammonia), F ₂ (fluorine), HF (hydrogen fluoride), SiF ₄ (silicon tetrafluoride), or COF ₂ (carbonyl fluoride) , For example in certain CVD (chemical vapor deposition) processes.

In these effluent gas retention treatment processes, the related art generally uses a multi-component purification system. In such an apparatus, the silane and optional component ammonia are thermally oxidized through a one module reduction system and HF, F ₂ , SiF ₄ , COF ₂ and optional component NH ₃ are purified using water in another separate module. Disadvantages caused by thermal oxidation include (i) high energy consumption, and (ii) NOx production due to ammonia oxidation. Also, the module heated to a high temperature promotes the under-erosion of the thermal module because the acid gases (F ₂ and HF) are heated but not reduced in the thermal unit. Typically, the water purification module is located directly below the thermal module. Generally, where high temperature acid gas causes corrosion, it is the interfacial region containing high temperature moisture between the water purification unit and the thermal unit.

Therefore, a need has arisen for a simple and reliable reduction device capable of effectively treating effluent streams containing gaseous species of the type described above.

More particularly, among the fluoro compounds that are preferably reduced in effluent gas species during the treatment of effluent gas streams containing fluoro compounds, there is a need for a method of producing chips that produce F ₂ and fluorine radicals in situ using a plasma assisted reaction Perfluorinated gases are widely used. Once these highly reactive species are created, the silica is removed from the equipment chamber or materials such as nitrides, oxides or polysilicon are corroded from the wafer. The most widely used carbon-based perfluoro species are CF ₄ , C ₂ F ₆ , and C ₃ F ₈ . Nitrogen trifluoride (NF ₃₎ and sulfur hexafluoride (SF ₆₎ are also widely used.

Perfluorinated compounds (PFCs) are also higher than CO ₂ in the strongest greenhouse gases with global warming potential (GWP) by about 3 and 4. PFCs are also very stable molecules with atmospheric lifetimes for thousands of years to be. Although the semiconductor industry is not the main source of PFC emissions, the industry is actively pursuing a strategy to protect the environment by reducing PFC emissions.

Research is currently underway in four areas to reduce PFC emissions; Optimization, use of alternative chemicals, recovery / recycling technologies, and reduction processes.

The optimization process includes adjusting the process conditions in the reactor to achieve increased PFC conversion in the semiconductor manufacturing facility. Current non-optimized conditions in the semiconductor manufacturing process vary depending on the particular gas and process used. For example, oxide erosion using a combination of CF ₄ and CHF ₃ has the lowest process efficiency of 15%. The tungsten deposition process showed up to 68% utilization of NF ₃ . Recent developments in optimized plasma cleaning technologies have resulted in up to 99% utilization of NF ₃ in semiconductor manufacturing facilities.

High conversion rates of PFC inevitably form harmful air contaminants (HAP). The decomposition product contains a large amount of fluorine (F ₂ ) and silicon tetrafluoride (SiF ₄ ) gas and a smaller amount of HF and COF ₂ . If the fully fluorinated gas is destroyed, the amount of HAP is significantly increased compared to the initial PFC volume delivered to the semiconductor manufacturing facility. As an example, assuming that the PFC is stoichiometrically converted to F ₂ , the NF ₃ flow rate at 1 liter per minute (1 pm) will produce 1.5 liters per minute (Fpm) of F ₂ . In the case of the system, it is possible to produce up to 6 liters (slm) of fluorine gas per minute, possibly by mixing the exhaust streams of four chambers, so F ₂ is 3% (50 lpm ballast N ₂ ).

These estimates are double that of hexapulphurised PFC (compared to NF ₃ ), which is expected to rise further in future 300 mm wafer manufacturing processes. These estimates represent scenarios for poor cases, which include short term duration and periodic characteristics of the process due to the use of PCF, low F ₂ emission concentration at the initial clean stage, and at least two chambers simultaneously operating the PFC cycle Is not considered to be low. Nonetheless, such estimates represent severe and process deteriorating characteristics of PCF problems that arise in connection with semiconductor manufacturing processes.

The toxicity and corrosive properties of fluorinated HAPs poses a significant risk to health and the environment as well as to the reliability of the exhaust system. In particular, the oxidizing power of F ₂ is superior to other compounds produced or used in semiconductor manufacturing facilities and is much more reactive than other halogens. Large amounts of F ₂ and other harmful fluorinated inorganic gases released during optimization plasma processes require the use of point-of-use (POU) reduction techniques to reduce possible hazards and extend the operating life of the process plant.

There are several alternatives that can be presented in relation to the reduction of the use point F ₂ . At high concentrations, fluorine exothermically reacts with all elements except oxygen, nitrogen, and rare gases. As a result, a reasonable approach to F ₂ reduction is to use these naturally occurring reactions without adding energy to the system, . The main problem with this possible approach is to form heat dissipation and acceptable by-products.

Other methods of solving the problems associated with fluoride reduction include wet and dry reaction techniques and thermal reaction techniques.

In a dry process, the fluorine gas stream flows through a dry bed filled with a reactive material. Using a suitable dry chemistry, F ₂ can be converted to a nontoxic solid or mild gas without excessive heat dissipation. However, this last condition can be a limiting factor, especially if large amounts of F ₂ are involved.

In the case of a thermal reaction process, the heat reduction unit mixes F ₂ and the reactive material within the heated reactor using fuel or electrical energy. The by-products produced by the thermal reduction of F ₂ require the use of a water purifier after the reaction since it contains hot acid. The removal efficiency of such a post-reactor water purifier bed is often degraded often because the purge efficiency of most acid gases decreases as a function of temperature. In addition, containment of concentrated high temperature acid requires costly materials and structures that can prevent corrosion erosion due to temperature increase.

In wet process technology, fluorine gas has the advantage of reacting quickly and efficiently with H ₂ O. The main products from the reaction between water and F ₂ are HF, O ₂ and H ₂ O ₂ . The reason for opposing the use of water purifiers is the concern for undesired OF ₂ formation and the need for water consumption to achieve acceptable removal efficiencies at high concentrations of fluoride erosion.

Based on the assumption that OF ₂ byproduct formation and high concentration of water consumption can be solved, it can be seen that wet cleaning technology is the most attractive method in comparison with the above-mentioned treatment conditions.

Thus, the technique of point-of-use wet scrubbers requires a fluorine reduction system that inhibits the formation of unwanted OF ₂ , has acceptable fluorine removal efficiency under high fluorine concentrations, and at the same time minimizes water use.

Considering the silane as an undesirable component in the effluent gas stream which is preferably reduced through the present gas-phase treatment, this component is generally removed by thermal oxidation. Due to the very low solubility of the silane in water and the low reactivity with water, removal of the silane with a water clarifier has not been considered advantageous compared to thermal oxidation. In some cases, the prior art uses chemical agents such as KOH and NaOH to perform this purification, but purifying the silane using these hydrides results in significant process cost because it requires large amounts of chemical additives . Chemical purification is described, for example, in " Methods of Efficiently Handling Spillage Through Chemical Purification " in T. Herman and S. Soden, American Society of Physics Conference Proceedings, 166, Photovaltaic Safety, Denver, CO 1988 ≪ / RTI >

In addition to the above-described methods for achieving a reduction in silane, certain commercially available equipment for thermal oxidation of the silane prior to final purification of the effluent gas in the water purifier can be used. However, these devices have the problem of requiring an ignition source and fuel, or alternatively electricity, for heating. Related processes are also characterized by a high degree of exothermicity and thus tend to require excessive temperature and considerable exhaust gas immersion conditions.

Another problem encountered with the reduction of silane is that ammonia gas may be present in the effluent stream. It is particularly difficult to reduce these components to high levels when silane and ammonia are present at the same time.

Therefore, there is a need in the art for gas reduction systems that can effectively reduce these gases when silane and ammonia gases are present simultaneously in the effluent stagnation.

Methods and means for efficiently removing silane to avoid the disadvantages of thermal oxidation treatments are desired in the art.

It will also be appreciated by those skilled in the art that significant advances may be achieved by effectively removing silane at temperature or sub-ambient temperature levels, or otherwise substantially lower than those used for thermal oxidation treatment conditions. Therefore, there is a need for a " cooling burn " method and apparatus for effectively reducing the silane by low temperature oxidation of the silane.

The problem that arises when a water purifier is used in the treatment of the outflow stagnation is the blowing phenomenon. When applied to specific semiconductors, the effluent gas forms bubbles when entering the water purifier, which can cause detrimental effects inside the purifier. The most serious problem occurs when a large amount of foam accumulates to fill the internal volume of the purifier completely. When this happens, the foam can be entrained within the gas phase and be substantially discharged from the clarifier. Corrosion can occur if the extruded foam is agglomerated on the surface of the exhaust pipe. Also, cavitation phenomenon can occur when it is present in the purifier drainage. As a result, the bubbles can damage the pump recirculating the purge liquid. Finally, this foaming action significantly increases the pressure drop across the purifier, which has a detrimental effect on the process of the upper semiconductor production unit of pressure sensitive properties as well as the purifier and effluent treatment system.

In addition, another problem encountered during the operation of the water purifier for effluent gas treatment is the mineral component present in the water used in the purifier. In certain parts of the world and in the United States, make-up water supplied to the water purifier uses hard water with very high hardness, ie hard water containing high concentrations of calcium and magnesium and other ionic species. When the water purifier operates at a pH greater than about 8.5, the calcium present in the water tends to leach out as calcium carbonate (CaCO ₃ ). This tendency leads to many problems, one of which is that CaCO ₃ adheres to the sensitive surface in the recirculating pump that is in communication with the purifier. In this case, the pump becomes unusable. Another problem is that CaCO ₃ leaching water accumulated on the surface of the packed cleaners. This increases the pressure drop across the purifier and reduces the efficiency of the purifying process. Finally, CaCO ₃ leaching water is formed in the water supply line of the purifier increases the pressure drop may slow the water flow rate.

A more common problem with solids deposition is that the lines connected to the pressure sensing device in the reduction system are blocked by solids. The lines are used to measure the pressure at the inlet of the reduction unit, which allows facility engineers to know if any clogging is present in the reduction system. The line (pressure sensing port) is often clogged by particles or clogged by condensable gases in the effluent stream. When the solid matter accumulates in the sensing line, the reading of the pressure sensing device communicating therewith becomes inaccurate, thereby giving false alarm signals, thereby stopping the operation of the reduction system.

A problem that arises in this connection is the deposition of solids upon entry into the water clarifier, which may be due to the condensable gas present in the effluent stagnant being treated.

Therefore, there is a need for a reduction system that avoids or improves the solid deposition problem described above by minimizing or eliminating the extent of formation of solids.

In reducing the POU wet cleaning of semiconductor off-gases, acid gas removal and solids removal are performed in processes that produce Cl ₂ , F ₂ , HF, HCl, or NH ₃ , such as metal corrosion, LPCVD, EPI, and CVD processes If necessary, the purification system uses a single packed column in which the gas flows for processing. Above the filled column there is a spray device to wet the packing material with a cleaning liquid (usually water). The gas passes down the column in the same direction (in a side-by-side direction) as the falling water or upward in the column (in the opposite direction) to the falling water. It is advantageous to use an opposite design because the water at the gas outlet (top of the column) is clean and can perform the maximum purification process. On the other hand, water saturates to the acid gas given in the water at the gas outlet (column bottom) of the column operated in a side-by-side direction, thereby limiting the purification capacity.

Unfortunately, column size, packing wetting requirements, and efficient solids removal require that considerable water flow rates be considerably faster to exceed packaging in either a side-by-side or reverse process. In general, the flow rate of water through the packing is over 10 gallons per minute. Use of such a high flow rate of fresh water is undesirable from a cost point of view and is also undesirable especially in areas where water is scarce, because process equipment consumes a considerable amount of water. A common solution to this problem is to recycle the spent water using a recirculation pump back to the top of the packed column. The flow rate of fresh water (make-up water) can then be lowered. However, the recycling process reduces the purifying efficiency of the purifier of the above-mentioned gas species.

One way to reduce the flow rate of the freshwater makeup water while increasing the purification efficiency is to use a chemical filler. These formulations are activated by reaction with the dissolved gas, thus allowing additional gaseous molecules to enter the aqueous clarification liquid as a result of the maximum mass transfer gradient. However, the use of chemical agents in this way not only increases the cost, but also presents additional concerns about safety.

It is therefore desirable to provide a purification system that can efficiently remove solids and acid gases without requiring the use of additional chemical formulations. It is also desirable to provide a purification system for effluent gas treatment which significantly reduces the flow rate of the necessary freshwater makeup water as compared to a conventional water clarifier that does not use additional chemical formulations,

Therefore, a first object of the present invention is to solve the above-mentioned problems associated with prior art effluent gas treatment systems.

A second object of the present invention is to provide an effluent gas treatment system which overcomes these problems of the prior art.

A third object of the present invention is to provide an effluent gas treatment system using a water purifier in an efficient manner.

Other objects and advantages of the present invention will become more apparent from the following description and appended claims.

The present invention relates to reducing unwanted components such as gases from effluent streams containing fluorine, silanes, gaseous fluorides, hydride gases and halide gases, and more particularly, To a system using a wet scrubbing apparatus and method or the like to reduce unnecessary components of the apparatus.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a test instrument used to characterize effluent gas and temperature profiles during the reduction of F ₂ and SiF ₄ ;

2 is a cross-sectional perspective view of a water purification system according to an embodiment of the present invention;

3 is a graph showing the fluorine concentration (ppm) at the outlet as a function of the fluorine concentration at the inlet;

4 is a graph showing the concentration (ppm) of the selective compound measured at the outlet of the purifier unit operated in accordance with the present invention as a function of time;

5 is a schematic front view of an infusion structure (which is fluidly connected to a purifier unit) that can be used to remove the upstream of the silane of the purifier unit;

Figure 6 is a partial front view of another injection structure that can be used to remove silane from an effluent stagnant containing silane;

7 is a schematic front view of a water purifying apparatus according to another embodiment of the present invention;

8 is a graph showing the calcium carbonate precipitation rate (lbs / day) as a function of the pH of the water used for purification in the water purifier;

9 is a graph showing the total concentration of carbonic acid and its derivatives as a function of the pH of the purifying liquid of the water purifying apparatus;

10 is a graph showing the improvement factor (reduction in ammonia discharge concentration when a two-stage purifier is used compared to a conventional one-stage purifier) as a function of water flow rate and various ammonia flow rates;

11 is a partial enlarged sectional view of a mesh container of a purifying agent particle according to an embodiment of the present invention and an associated container casing of the purifier unit for receiving the mesh bag;

12 is a schematic explanatory view of a two-stage purification system according to an embodiment of the present invention;

13 is a front sectional view of an injection structure according to another embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

The following United States patent applications are incorporated by reference herein in their entirety:

US patent application Ser. No. 09 / 086,033 to Jose I. Arno, filed on May 28, 1998 ("Point-of-use Removal Apparatus and Methods for Fluoro Compounds"),

US Patent Application No. 08 / 857,448 to Joseph D.Sweeney et al., Filed May 16, 1997, entitled " Blocking Injection Structure for Entering Granular Solid Containing and / or Solid Forms into the Fluid Processing System " ),

Scott Lane, et al., U.S. Patent No. 08 / 778,386, filed December 31, 1996, entitled " Blocking Injection Structure for Introducing Granular Solid Containing and / or Solid Forms into a Fluid Processing System ".

The present invention proposes a effluent removal system comprising, for example, one or more compatible features selected from the following features (1) to (10):

(1) hydrolyzing the effluent gas in the presence or absence of a chemical additive (e.g., with the addition or injection of a chemical reducing agent such as KOH or NaOH);

(2) A process for purifying a silane-containing effluent gas, wherein the flow rate of the anhydrous air washed by the arrangement involved in the generation of the control signal from the material flow controller for flowing the silane- Double or triple injections of cleaned anhydrous air, for example, while heating the flow path through which the outflow gas or the outflow gas flows, for example, the injection port, in the case where ammonia coexists, Bubbling cleaned anhydrous air into the liquid in the structure, for example into the liquid in the flooding cup or the porous insert, or into the cleaning liquid, and introducing anhydrous air cleaned into the effluent gas or the purifying liquid);

(3) using a two-stage purification system comprising an equilibrium purification column and a " polishing " mass transfer column to reduce the make-up water required for the purification and maintain or increase the purification efficiency compared to the single stage purification unit;

(4) To the effluent gas discharged from the equilibrium purification column of (3), anhydrous air, which is washed before it is introduced into the polishing substance transferring purifying column, is added, together with ammonia in the effluent gas retention, Removing the silane (if present);

(5) using the liner-containing bed filler in the two-stage purification system of (3) as an insertion structure of the polishing material transfer column;

(6) contacting the effluent gas of the cleaning system with an OF ₂ reducing agent;

(7) controlling the foaming in the cleaning system by a chemical (antifoaming) and / or physical (orifice structure) approach;

(8) Preventing the production of CaCO ₃ in the purification system by one or more of the following (a) to (d):

(a) the magnetization of the makeup water used for the wash;

(b) pH adjustment of supplemental water;

(c) Soda lime softening of supplemental water; And

(d) sedimentation or flocculation of supplemental water;

(9) passing a cleaning stream of nitrogen or other cleaning gas through the spiral sensing line to prevent occlusion of the spiral outlet in the cleaning system, wherein the spiral sensing line may be heated; And

(10) heating the injection structure used in the purge system to inject the effluent gas into the purge zone.

The present invention is fully disclosed in the following description, which may be combined with other features of the present invention as well as having one feature in various embodiments of the present invention.

In one embodiment, the present invention utilizes a chemical treatment agent injection to enhance the rate of reduction of the fluorine compound during the hydrotreating treatment of the fluorocompound-containing effluent stagnation. The present invention is usefully employed in semiconductor fabrication operations that produce a fluorocompound containing effluent stagnant and require treatment for discharge in accordance with the applicable environmental effluent standard.

Whereas removal of high concentrations of fluorine and other fluoro compounds was not possible with standard water purification techniques, the present invention improves the performance of the water purification system and reduces the formation of undesirable by-products during operation of such systems, Realizing substantial improvements in the technical field.

Although the present invention has been illustrated and described herein as being applied to reducing fluorine gas in an effluent stream containing predominantly fluorine gas, the process and apparatus of the present invention may be applied to other fluorine compounds as well as other strong oxidizing gases (Such as ClF ₃ , Cl _2, etc.) and liquids.

Further, while the present invention is illustrated below as a unique purification unit, the purification apparatus and method of the present invention can be applied to a purification column and a post-thermal reduction column used in combination with, for example, May also be used in combination with other methods and apparatuses.

In the present invention, a reducing agent is used in order to increase the reduction efficiency of fluorine or other fluorine compounds and to prevent the formation of OF ₂ . These reducing agents may be put in solid form or as a solution phase using a reducing agent stable to oxidation in air. The reducing agent may include any suitable reducing agent effective in promoting the elimination of fluorine compounds in an aqueous purification environment have. Suitable examples of reducing agents include sodium thiosulfate, ammonium hydroxide, and potassium iodide. As the reducing agent, sodium thiosulfate, which is nontoxic, non-alkaline, easy to obtain and inexpensive, is most preferable.

The apparatus of the present invention is intended to reduce the fluoro compound in the effluent stream to be treated, which comprises means for monitoring the concentration or the presence of the fluoro compound in the fluoro compound-containing effluent stagnation, And means for adjusting the introduction of the reducing agent into the unit.

Examples of such means include a pH monitor device for monitoring the pH of the effluent to be treated and for introducing a reducing agent at a rate and content associated with the pH value sensed by the sensor in response thereto.

It is also possible to measure the content of the fluoro compound in the effluent stream and determine the concentration of the fluoro compound detected by the sensor in response to the concentration of the fluoro compound in the effluent stream, . ≪ / RTI >

The means for monitoring the concentration of the fluoro compound in the fluoro compound-containing effluent stagnant in general and for controlling the introduction of the reducing agent into the water purifier unit in response thereto may be broadly modified, May be used to minimize the amount of reducing agent added in the reduction of the compound.

The present invention effectively reduces fluoro compounds such as fluorine (as compared to those without such reducing agents by using a reducing agent) using a reducing agent that promotes fluorine reduction while maintaining the concentration of OF ₂ at an acceptable level.

Figure 1 shows an apparatus used to characterize the effluent gas and temperature profile in the reduction of F ₂ and SiF ₄ . An automated gas delivery manifold equipped with a mass flow controller is used to generate the nitrogen and F ₂ or SiF ₄ mixture entering the purifier. The water purifier unit 110 is provided for the effluent flow treatment. The exhaust of the water purifier unit (110) is provided with a filler bed countercurrent flow polishing unit (120).

To minimize corrosion at the inlet of the clarifier, the metal portion 130 of the inlet may be coated with nickel or other corrosion-resistant material. Alternatively, air or other oxygen-containing gas may be injected into the injection port to reduce unnecessary components in the gas stream. Thus, the addition of air or other gas at the injection port may be carried out in a bubbling or non-bubbling manner to the extent necessary or desirable to the application of the present invention.

The gas to be treated in the water purifier unit may be derived from any suitable upstream treatment such as plasma enhanced chemical vapor deposition (PECVD). In this way, ammonia (NH ₃ ) and silane (SiH ₄ ) are introduced into the reactor chamber during the deposition step to form a silicon nitride layer (typically Si ₃ N ₄ ) on the wafer surface.

In the cleaning step, nitrogen trifluoride (NF ₃ ) is introduced into the chamber to corrode the deposits from the walls of the chamber. NF ₃ may be decomposed into fluorine (F ₂ ) or nitrogen (N ₂ ) by the plasma in the reactor chamber or in the chamber immediately before the reactor chamber. F ₂ then " cleans " the chamber by corroding the deposit from the reactor chamber walls.

By-products of the cleaning process include other compounds such as F ₂ , silicon tetrafluoride (SiF ₄ ), hydrogen fluoride (HF), unreacted NF ₃ and potentially small amounts of carbonyl fluoride (COF ₂ ). Therefore, during the deposition step, the water purification system is exposed to SiH ₄ and NH ₃ , while the water purification system during the cleaning step is exposed to F ₂ , SiF ₄ , HF, NF ₃ , COF ₂ and other species.

Examples of other upstream treatments that produce gaseous effluents that are sensitive to treatment by the apparatus and methods of the present invention include metal corrosion, oxide corrosion, poly corrosion, nitride corrosion, low pressure chemical vapor deposition (LPCVD), laminated silicon But are not limited to, chemical vapor deposition (EPI), tungsten chemical vapor deposition (WCVD), tungsten etching, polysilicon, atmospheric pressure chemical vapor deposition (APCVD), and dielectric chemical vapor deposition (DCVD).

The temperature of the gas and water in the clarifier is measured at a point selected to monitor the process during the reduction process. The reduction system may be monitored by any suitable means, such as, for example, a process monitor including a computer and conditioning system 140.

The infrared active gas species present in the purge exhaust are detected with an FTIR spectrophotometer, for example the MIDAC I-2000 FTIR spectrophotometer commercially available from Mycd Company for quantitative analysis. This unit is equipped with a nickel coated gas cell 150 with a 10 m path length equipped with a ZnSe window and a liquid nitrogen cooled MCT detector. This spectrometer is set to an appropriate monitoring set point, for example, an average of 16 times over the spectral region of scanning 600~4,200 ㎝ ^-1 in the 0.5 ㎝ ^-1 resolution. The spectrum is collected periodically, for example every 30 seconds, to provide continuous real-time information on the nature and concentration of the species. Accurate quantitative analysis is appropriate when the analyzer is assayed in situ using known concentrations of SiF ₄ and HF. Concentration of absorbance of quartz oxygen (OF ₂ ) is converted into concentration using a quantitative spectrum library distributed by Mycdak Corporation.

The fluorine gas is continuously analyzed using a gas sensor cell 160, such as an F ₂ specific Pure Air gas sensor cell (Pure Air Monitoring Systems, Inc.). These electrochemical (pH) sensors use a gas membrane chemistry cell technique to monitor low concentrations of toxic gases. These sensors are specially designed to monitor F ₂ in situ under water vapor saturation. To provide continuous analysis within the detection limit of the monitoring device (3 ppm F ₂ ), dilute the purifier gas exhaust with known flow rate with a flow of metered nitrogen. In this way, the mixed stream is introduced into the mixing chamber 170 equipped with the F ₂ sensor. The monitor responds to changes in F ₂ concentration. The concentration data is input to the computer at intervals of 30 seconds. The sensor was tested for F ₂ whose concentration was known, and accurate quantification results were obtained.

Instead of using a pH meter to control the rate of compound injection, a reduction / oxidation (REDOX) potential electrode may be used for this purpose. Unlike a pH meter (suitably arranged to initiate the reductant addition based on the current acid concentration), the REDOX electrode can be arranged to initiate the reductant input when the ionic potential of the aqueous solution in the vessel reaches a predetermined value. The improvement achieved by the arrangement of the REDOX potential electrode as compared to the pH controller is that the introduction of the reducing agent based on the ion potential of the solution rather than the reduction of the reducing agent based on the pH makes it possible to equilibrate the chemical reaction in the solution more directly In the United States.

FIG. 2 shows a detail view of a water purifier 210 of a type similar to the water purifier unit 110 shown in the system of FIG. The water purifier is operated using vertical parallel flow of water and contaminated gas stream. The water active species hydrolyze upon reaction with water in the high surface area filled region 220. The generated liquid is dropped into the water reservoir or the vessel 230, and the generated purge gas stagnation is discharged from the purifier through the vertical pipe connected to the blower. The water mechanics of the water clarifier includes flowing fresh water or make-up water into the system, draining the water, and then continuously recirculating the water stored in the sump 230. The performance of the purifier is improved using a counter-flow charged polishing bed 240 installed at the gas outlet. The injection port 250 is nickel coated to minimize solid deposition and prevent corrosion erosion at the injection port. The temperature of the gas and water in the clarifier was measured at nine predetermined points as defined in FIG.

As another method of using a chemical feed to promote the reduction of fluorine gas and prevent OF _{2 from} being formed as a by-product,

F ₂ + e ^- = 2F ^- and

OF ₂ + 2H ⁺ + 4e ^- = 2F ^- + H ₂ O

May be provided to supply electrons to the aqueous solution so as to be completed.

Any suitable means for supplying electrons may be used, but it may be a preferred arrangement to use an electrode inserted into the purifier vessel and connected to an external direct current (DC) power source. In order to eliminate the need to add chemicals, generation of electrons is only required to use a small amount of DC power.

As another array of arrangements in which there is no need to inject a chemical that promotes the reduction of fluorine gas and prevents the formation of OF ₂ as a by-product, the electrons in the solution use a sacrificial anode consisting of a metal mesh or metal plate And can be immersed in the container of the purifier. The metal (M) is decomposed by the following reaction.

M = M ²⁺ + 2e ^-

In such an operation, the acidity of the aqueous solution of the purifier vessel prevents unnecessary formation of a passivation layer on the metal surface. Unlike the specific example of the electrolytic cell as described above, the use of a sacrificial anode eliminates the need to use an external power source. Instead, the operation using the arrangement of the sacrificial anode is by the principle of a voltaic cell or a chemical cell that generates electrons that require spontaneous oxidation of the sacrificial metal.

Other embodiments of the present invention are directed to the removal of bedobiotic oxygen within a water purifier without the addition of a chemical reducing agent. In one example, this can be accomplished by irradiating the effluent medium with appropriate radiation to effect photolysis of the quaternary oxygen, such as ultraviolet light, at a wavelength of 365 nm (gas phase photolysis of OF ₂ yields a quantum yield of 1 at room temperature Occurs at such wavelengths; see Gmelin Handbook, F. Suppl. Vol. 4, page 45). This radiation exposure may be performed at the gas outlet of the clarifier or may be performed in the main filling bed of the purifier unit.

As another method for removing the quaternary oxygen in the water purifier without adding a chemical reducing agent, the purge air exhaust stream can be heated to an appropriate temperature, for example, 250 ° C to 270 ° C. OF ₂ is degraded by a homogeneous mononuclear reaction at this temperature (Gmelin Handbook, F Suppl. Vol. 4, page 43].

As another method for removing the quaternized oxygen in the water purifier, the reactant species is introduced into the purifying liquid to reduce OF ₂ by reaction. Examples of chemically treating agents highly useful for this purpose include AlCl ₃ , NH ₃ , As ₂ O ₃ , Br ₂ , CO, Cl ₂ , (Cl ₂ + Cu), CrO ₃ , H ₂ , H ₂ S, But are not limited to, CH ₄ , O ₃ , (O ₂ + H ₂ O), Pd, P ₂ O ₅ , Pt, Rh, Ru and SiO ₂ .

In other embodiments, hydrogen bubbling may be used in the presence of hydrogen produced in situ by a silane decomposition reaction to produce hydrogen or hydrogen added from an external source, A platinum or palladium catalyst may be used downstream of the clarifier to provide a reactant hydrogen concentration.

The features and advantages of this embodiment will be apparent from the following examples.

Summary of the Invention

The present invention is directed to an apparatus and method for reducing these components from effluent streams containing undesirable components.

The foregoing undesirable components include fluorine, silane, gaseous fluorides, perfluorocarbons, acid gases, hydride gases, and halide gases. Specific examples of such gas components include SiH ₄ (silane), NH ₃ (ammonia), F ₂ (fluorine), HF (hydrogen fluoride), SiF ₄ (silicon tetrafluoride), or COF ₂ (carbonyl fluoride) But is not limited to.

Specifically, the present invention relates to an effluent gas treatment system using a wet scrubbing apparatus and method that reduces the undesirable components of the effluent gas retention resulting from the semiconductor manufacturing process.

In one aspect, the present invention relates to a method of reducing a gas component in a gaseous component-containing gas stream, comprising a gas / liquid contact chamber comprising a gas stream and means for introducing a purge liquid for contact with the gas / And has at least one of the following features.

(a) contacting a gaseous component with a chemical treating agent, optionally combined with a post-pressure triggering device arranged to at least partially reduce the bubbles in the purifying system upon injection of the chemical treating agent, to remove gaseous components from the gas stream / A chemical treating agent injector injecting a chemical treating agent to be removed;

(b) an injection port arranged to inject gas flowing through the gas stream to facilitate removal of the silane from the gas stream if silane is present in the gas stream;

(c) means for introducing a second purge liquid into the second gas / liquid contact chamber for gas / liquid contact in a second gas / liquid contact chamber, Wherein the first gas / liquid contact chamber is configured and arranged such that the gas stream and the purge liquid flow in the same direction, and the second gas / liquid contact chamber comprises a gas stay / The purge liquid is configured and arranged to flow in the opposite direction);

(d) optionally, in combination with a pre-pressurization device arranged to at least partially reduce the foam in the purge system as a result of defoamer injection, a bubble in the purge fluid in the gas / liquid contact to inhibit foaming in the purging chamber A defoaming agent injector for injecting a defoaming agent to suppress the defoaming agent;

(e) (1) a magnetizing zone for applying a magnetic field to the cleaning liquid before using the cleaning liquid in the contact chamber;

(2) means for adjusting the pH of the clarification liquid to maintain the pH of the purification liquid below 8.5;

(3) a soda lime bed arranged to flow a purge fluid prior to using the purge liquid in the contact chamber; And

(4) a precipitator for precipitating the calcium component of the cleaning liquid prior to using the cleaning liquid in the contact chamber

Means for inhibiting deposition of calcium carbonate from a cleaning liquid containing calcium, wherein the cleaning liquid is selected from the group consisting of: And

(f) means for flowing a cleaning gas through said passageway to inhibit solid formation in the passageway of the purification system, and means for heating said passageway to inhibit solid formation in said passageway Means for inhibiting solid formation within the passageway of the system; And

(g) (1) means for heating the gas stream before introducing the gas stream into the purification system; And

(2) the second gas / liquid contact chamber of (c), and the treated gas stream exiting the first gas / liquid contact chamber, is cleaned in the treated gas stream prior to introduction into the second gas / liquid contact chamber Means for introducing anhydrous air or other oxygen-containing gas

Means for reducing the silane from the gas stream with ammonia when the silane is present in the gas stream.

Another embodiment of the present invention relates to a purification system comprising an injection structure for introducing a gas stream containing a silane component into a purification apparatus. In this embodiment, the gas stream flows through the pouring structure, and the pouring structure includes means for introducing gas into the pore stream to facilitate removal of the silane component in the purging system. The gas may comprise cleaned dry air (or any other suitable oxygen-containing gas). The gas may be bubbled through the immersion tube, through the bore of the immersion tube, into the flowing water introduced through the porous immersion tube, in any suitable manner, for example by bubbling through the flooded water in the water floodation structure, Or through the top wall or side wall of the inlet, or through the side wall of the inlet tube.

One embodiment of the gas introducing means comprises, for example: (i) an upper injection section comprising a gas permeable wall adjacent to a gas flow passage of the upper injection section, the upper injection section including a ring-shaped gas input passage through which the silane removal promoting gas can flow; (ii) an annular flooded liquid reservoir having an inner wall having an inner wall surface defining a boundary with a gas flow passage through a lower inlet of the infiltration structure, wherein a falling film of liquid is formed on the inner wall surface during overflow, A lower injection section for cleaning the inner wall surface of solid and solid-forming components; And (iii) a gas injection tube extending into the gas flow passage and terminating at one lower end of the upper injection portion and the lower injection portion of the gas introduction means, the gas introduction means being adapted to purify And is configured and arranged to introduce silane-containing gas into the apparatus.

In another specific embodiment, a gas for promoting the removal of the silane component is introduced into the flow passage of the injection port containing the silane-containing gas stream, and the gas is introduced into the center portion of the silane- And the silane removal gas, for example, cleaned anhydrous air or other oxygen-containing gas, is completely mixed with the gas stream to allow cooling combustion removal of the silane component by oxidation.

The arrangement described above can be used in combination with a wet wall injection structure of the type described in more detail below.

Yet another embodiment of the present invention is directed to a purification system for treating an effluent gas comprising an acid gas component and a water-purifying component other than an acid gas component. The purifying system comprises a first purifier unit for purifying an outlet gas with an aqueous purge liquid to remove an acid gas component and a second purifier unit for purifying the outlet gas with a second aqueous purge liquid to remove residual acid gas components and water- A second purifier unit for removing water reactive gaseous components as well as a purifying component and means for flowing an outlet gas with reduced acid gas component from the first purifier unit to the second purifier unit, Is configured and arranged such that the aqueous purge liquid and the outlet gas contact each other while flowing in the same direction to produce a reduced effluent gas as well as an acid gas component and other water-purifying components other than the acid gas component, The second purifier unit is arranged so that the second aqueous purge liquid and the outflow gas are in contact with each other while flowing in opposite directions and the acid gas component and the acid gas component Different number of-life chemical conversion elements are configured and arranged so as to be generated as well as the reactive component decreases the output gas.

In the above-described purification system, the acid gas component and the water-soluble / water-reactive component will be reduced to a concentration corresponding to each equilibrium value of the acid gas component and the water-soluble / water-reactive component in the aqueous purge liquid in the first purifier unit.

Another embodiment of the present invention includes a gas / liquid contact product for detachably mounting in a purifier vessel having means for injecting gas and liquid by an internal volume of the purifier vessel for gas / liquid contact, The media assembly includes a fluid permeable diaphragm structure, such as a porous bag and a filler mass contained in such a fluid permeable diaphragm structure.

Herein, " foraminous " refers to openings, crevices, vias, or other openings or openings that provide the ability to flow fluid through the structure. The open space of the porous structure may vary depending on the size of the filling material to be contained in the structure.

Another embodiment of the present invention relates to a cleaning method for removing the gas component in a gas stream containing a gas component, the method comprising the steps of introducing a gas stream and a purge liquid into a gas / liquid contact chamber, / RTI > further comprising at least one of the following steps (a) to (f):

(a) introducing a chemical treating agent into contact with a gas component to remove a gas component from the gas stream upon contact with the gas / liquid;

(b) introducing a gas, which promotes the removal of silane from the gas stream, into the gas stream before introducing the gas stream into the contact chamber, if silane is present in the gas stream;

(c) flowing the effluent gas from the contact chamber to the second gas / liquid contact chamber and introducing a second purge liquid into the second contact chamber for gas / liquid contact in the second contact chamber, The first gas / liquid contact in the contact chamber comprises a flow in the same direction of the gas stream and the purge liquid, and the second gas / liquid contact in the second contact chamber includes a gas flow through the second contact chamber, Comprising the steps of:

(d) injecting a defoaming agent into the cleaning liquid during said gas / liquid contact to inhibit foaming in the contact chamber;

(e) (1) applying a magnetic field to the cleaning liquid before using the cleaning liquid in the contact chamber;

(2) adjusting the pH of the clarification liquid to maintain the pH of the purification liquid below 8.5;

(3) flowing a purge liquid through the soda lime bed prior to using the purge liquid in the contact chamber; And

(4) precipitating the calcium component of the purifying liquid prior to using the purifying liquid in the contacting chamber, wherein the step of inhibiting the deposition of calcium carbonate from the purifying liquid containing calcium ; And

(f) inhibiting solid formation in a passageway of a purging system including a conduit connected to a pressure sensing device, the method comprising the steps of: flowing a purge gas through the passageway to inhibit solid formation within the passageway; And heating the passageway to inhibit solid formation.

In another embodiment, the present invention provides a process for preparing a fluoro-containing compound, comprising contacting the gas stream with an aqueous medium in the presence of a reducing agent such as sodium thiosulfate, ammonium hydroxide, potassium iodide, or any other suitable reducing agent. And to a method for removing the fluoro compound from an effluent stream.

In another embodiment, the present invention comprises a water purifier unit arranged to discharge an effluent stream which is connected in flow relationship with a fluorocompound containing effluent stream and in which the fluoro compound has been removed, wherein the water purifier unit is equipped with a reducing agent, From an effluent stream containing a fluoro compound, which removes the fluoro compound contained therein by injecting sodium thiosulfate, ammonium hydroxide, potassium iodide, etc., and provides an improved fluorocompound removal effect compared to a corresponding system in which such reductant injection is eliminated And a device for removing the fluoro compound.

Yet another embodiment of the present invention relates to a semiconductor manufacturing facility comprising a semiconductor production processing unit for producing an effluent gas stream containing a fluoro compound and an apparatus for removing a fluoro compound in an effluent gas stream, The fluorine compound removing apparatus

A water purifier unit for gas / liquid contact;

Means for introducing the fluorocompound containing effluent stagnant into the scrubber unit;

Means for discharging the effluent gas stream from which the fluorocompounds are reduced from the water purifier unit;

And a reducing agent source operably associated with the water purifier unit and arranged to introduce a reducing agent into the water purifier unit during its operation.

The semiconductor manufacturing processing unit of the facility may be any kind of suitable, such as, for example, a plasma reaction chamber, a chemical vapor deposition chamber, an evaporator, a lamination growth chamber or a corrosion apparatus.

Yet another embodiment of the present invention is an effluent reduction purification system, comprising a water clarifier for purifying effluent gas and configured and arranged to perform one or more of the functions selected from the group consisting of the following (1) to (10) Lt; / RTI >

(1) a function of cleaning the outflow gas by addition or injection of a chemical reduction reagent;

(2) a function of purifying the outflow gas containing silane, in which the cleaned anhydrous air is introduced into the outflow gas or the purifying liquid;

(3) a function of using a two-stage purification system including a balancing purification column and a polishing material transfer column to reduce the number of replenishment required for purification while simultaneously maintaining or increasing the purification efficiency compared to the first stage purification unit;

(4) The cleaning material transferring purging column is charged with anhydrous air that has been cleaned in the effluent gas before the effluent gas discharged from the equilibrium purification column of (3) is introduced to reduce the silane present with the ammonia in the effluent stagnant function;

(5) a function of using a porous membrane structure containing a bed packing as an insert in a polishing material transfer column in the two-stage purification system of (3) above;

(6) contacting the effluent gas with the OF ₂ reducing agent in a purge system;

(7) the ability to regulate the bubble in the purifying system by limiting the orifice of the flow of the chemical defoamer and / or the purifying liquid;

(8) (a) the magnetization of the make-up water used for purification;

(b) pH adjustment of supplemental water;

(c) Soda lime softening of supplemental water; And

(d) a function of preventing CaCO ₃ accumulation in the softening system by at least one of precipitation of the make-up water or flocculation treatment;

(9) a function of suppressing clogging of a spiral port including a spiral sensing line in a cleaning system by passing a scrubber stagnant through a photohelic sensing line, which may be heated as needed; And

(10) The function of heating the injection structure used in the purification system and injecting the outflow gas into the purification zone.

Another embodiment of the present invention relates to an injection structure for a gas purification system, means and methods for removing that particular gas component from a gas stream containing a specific gas component, and a characteristic specific purification system, technique, subsystem and approach will be.

Accordingly, other embodiments, features and embodiments of the present invention will be more fully described below and will become more fully apparent from the following description and appended claims.

Example 1

In the general type of system shown in Figures 1 and 2, the reduction of SiF ₄ is performed using an effluent stream simulating the effluent produced in the semiconductor manufacturing facility by cleaning the plasma reaction chamber.

Table 1 summarizes the results of the reduction of SiF ₄ (decomposition and removal rate, DRE (%)) when corrosive agents are added and when they are not applied. The reduction in this case did not take into account the addition of reducing agent.

A fixed concentration (300 ppm) of silicon tetrafluoride balanced with 120 slpm of nitrogen was introduced into the water clarifier. The experimental conditions are chosen to represent or exceed the effluent gas concentration that is released during conventional plasma chamber cleaning. The reduction efficiencies were measured as a function of water flow rates (0.5 and 1 gpm) and clarifier pH (with or without caustic input). In all investigated cases, the measured HF and SiF ₄ purifier outlet concentrations were slightly higher than the detection limits of the spectrometer and significantly below the respective limits (TLV) (SiF ₄ TLV = 1 ppm, HF TLV = 3 ppm).

Summary of the reduction results at a fixed inlet concentration of 300 ppm SiF ₄ in 120 slpm N ₂ Water flow rate (gpm) Corrosive Injection (pH) HF concentration (ppm) SiF ₄ concentration (ppm) DRE (%) One No injection (3.85) 0.47 0.3 99.86 0.5 No injection (3.50) 0.46 0.3 99.86 One Injection box 10.5 0.15 0.1 99.95 0.5 Injection box (10.8) 0.13 0.075 99.96

Example 2

A fluorine gas with a flow rate of 0.5 to 5 slpm was delivered to a registered trademark Vector-100 water purifier equipped with a passivating manifold (ATMI EcoSys Corporation, San Jose, CA). These streams were diluted with the remaining nitrogen of 50 slpm to form an F ₂ concentration of 1 and 6%. Also, the effect of the residence time in the purifier was tested by increasing the nitrogen flow rate to 200 slpm. The performance of the purifier unit was tested using a standard flow rate of water (1.2 gpm) and a low flow rate (0.75 gpm). Sodium thiosulfate was used during the introduction of high concentration nitrogen gas to increase the removal of fluorine gas and to exclude the formation of OF ₂ as a byproduct.

Table 2 summarizes the experimental data and illustrates the improvement obtained by injecting sodium thiosulfate as a reducing agent.

Summary of fluoride reduction results Test number Water flow rate (gpm) N ₂ rest (slpm) F ₂ flow rate (slpm) Injection F ₂ (ppm) Chemical improvement Exhaust HF Concentration (ppm) Exhaust F ₂ Concentration (ppm) Emission OF ₂ Concentration (ppm) Exhaust F ₂ equivalent (ppm) DRE (%) One 1.2 50 One 20000 none 7.5 1.5 1.25 6.5 99.97 2 1.2 50 2 40000 none 12 2.5 3 11.5 99.97 3 1.2 50 3 60000 none 15 20 4 31.5 99.95 4 0.75 50 0.5 10000 none 4 0.5 <1 3.5 99.97 5 0.75 50 One 20000 none 6 One One 5 99.98 6 0.75 50 2.25 45000 none 20 5 5 20 99.96 7 0.75 50 3 60000 none 28 50 10 74 99.88 8 0.75 50 2.25 45000 has exist 2.25 0.5 <1 1.6 99.996 9 0.75 200 3 15000 has exist 25 38 <1 50.5 99.7 10 0.75 200 5 25000 has exist 42 120 <1 141 99.4

The decomposition and removal rate [DRE (%)] is determined using the following standard equation.

In the above equation, inlet F ₂ is the nitrogen inlet concentration in ppm, and the outlet F ₂ equivalent is defined as:

In the above equation, DRE (%) was measured using the adjusted inlet and outlet concentrations for the dilution effect, as the concentration was affected by dilution. These measurements provide a measure of the actual amount of fluorine from the purifier system versus the actual amount of fluorine to the purifier system.

Under all the conditions investigated, the water clarifier removes more than 99% of the transferred fluorine. The removal rates set forth in Table 2 are based on the worst case scenario for effluent gases released during conventional plasma chamber cleaning, Indicates the performance of the water purifier treatment.

The emission concentrations listed in the above table represent the equilibrium values reached after continuous delivery of the fluorine gas to the clarifier over a long period of time. This steady state typically occurs between 10 and 30 minutes after initiation of the test, depending on the initial F ₂ concentration. The chamber cleaning period is a fraction of the time required to reach this equilibrium.

Figure 3 illustrates the effect of water usage on fluorine reduction efficiency. As expected, the flow rate of the make-up water influences the purification efficiency, which is a limiting factor under a large amount of fluorine input. In the absence of chemical improvement, the OF ₂ concentration at the outlet of the clarifier would be greater than 3 ppm when delivering more than 3% and 6% F ₂ (50 slpm N ₂ ballast) using 0.75 and 1.2 gpm of water respectively do. Tests 8 to 10 (see Table 2) illustrate the prevention of OF ₂ formation besides increasing the purification efficiency by the introduction of chemicals. For example, the test conditions for Tests 6 and 8 are the same except for the delivery of chemical promoters. Injection of the chemical reduces the discharge concentration of HF and F ₂ to about 10 times, and OF ₂ is reduced below the detection limit.

Figure 4 shows the exhaust concentrations of HF and F ₂ and the pH in the purifier vessel over time. The graph shows that the breakthrough point of the gas is considerably retarded and is related to the pH of the water. Second, the concentration over time of F ₂ released during normal chamber cleaning is not constant. During the initial stage, most of the F ₂ produced in the chamber reacts with SiO ₂ and is used to release SiF ₄ gas. Excessive release of F ₂ by the apparatus is only after SiO ₂ is consumed.

As a result of analyzing the collected temperature data, it was found that the heat generated by the exothermic reaction was effectively released in the purifier. The only measurable temperature change was recorded at the first boundary between the inlet gas and water vapor inside the purifier inlet. The maximum temperature increase from 17 ° C to 26 ° C (ΔT = 9 ° C) was detected at the highest dose of fluoride. The heat capacity of the large amount of recirculating water that exchanges heat with the surroundings effectively cooled the heat generated by the hydrolysis reaction of F2. In addition, serious signs of corrosion or material aging were not found anywhere in the clarifier (including the inflow system) after the end of the test. Overall, the clarifier was exposed to effectively reduce fluorine gas of 3.2 lbs. (Or 855 L).

The foregoing data illustrate the advantages of the present invention in facilitating the removal of fluorine gas from a fluorine-containing effluent stream.

In yet another aspect, the present invention relates to an output gas treatment system for reducing the silane, SiR _4, R is for example hydrogen, halogen (F, Cl, Br, I) alkyl (e.g., C ₁ -C ₈₎ Alkyl, alkoxy, alkene, alkyne or other suitable substituent. It will be appreciated that the discussion that follows is directed to silane itself (SiH ₄ ), but other silane derivatives (eg, tetramethylvinylsilane (TMVS)) can be reduced as well.

Surprisingly, it has been found that when neutral water is used as the clarification liquid, the silane can be destroyed with an efficiency of less than about 50% in a highly efficient water cleaning unit. This is a very surprising result because the silane is extremely insoluble in water and is known to be non-reactive in non-basic aqueous solutions. This may be due to the catalytic action of a small amount of O ₂ that is naturally present in the water in order to remove the silane from the water.

In some cases, the silane removal efficiency obtained is less than 100%, but the fact that the silane can be reacted much more mildly in the water clarifier is a significant finding. As a practical matter, industrial facilities generating silane-containing effluents do not always require high destructive efficiency of the silane, but occasionally it is acceptable to simply reduce the silane concentration to below the LEL. Additional improved steps can be added to the water purifier, or simply by bubbling additional air into the make-up water.

A second way in which the silane can be reduced in the water clarifier is by using a pseudo-chemical injecting agent (e.g., KOH). The hydrator as previously described herein may have an integrated chemical injection system that meters the chemical injector into the water purifier at a rate determined by a set point of the purge liquid pH or at a predetermined rate.

An advantage of the above approaches is that thermal oxidation purifiers or thermal oxidation modules are not required for silane reduction, so that the cost of ownership of the emission treatment system is significantly reduced compared to systems using the thermal oxidizer treatment unit. Another advantage is that corrosion can be avoided because the acidic gas present is not heated. Another advantage is that the reaction by-product, silica, is formed in the clarifier and washed out with the wastewater. This is in contrast to clogging caused by silica or silica nitrogen, which often occurs in thermal oxidizer units.

In yet another embodiment, the silane can be reduced by the use of the injection module 300 shown in Figure 5, which is specially designed to reduce the flow of silane upstream of the purifier unit 314 in a reduction system comprising such purifier unit . The silane containing gas from the upstream flow processing unit (not shown) is introduced into the inlet port 304 of the inlet module 300 in the supply line 302 and then flows from the appropriate source of the same (not shown in Figure 5) To the inlet tube 306 where water in line 318 is supplied. In the inlet tube, the gas from line 302 is mixed with the water from line 318, and cleaned anhydrous air (CDA) is injected to help oxidize the silane component. The CDA can be continuously injected as shown in FIG. 5, and injection lines 308, 310 and 312, which occasionally emit CDA into the gas / water mixture along the inlet tube, are shown in FIG.

The gas / air / stream thus obtained enters the purifier unit 314 and purifies the gas stream with water to produce a silane reducer stagnant that is discharged from the purifier 314 to the discharge line 316.

The inflow module 300 may be formed of a suitable non-corrosive material, such as stainless steel, and acts as a non-thermal oxidizing device as the cleaned anhydrous air enters the inlet tube. Such a design is advantageous over conventional thermal oxidation apparatuses in that heat is required, NOx is not formed, and corrosion is avoided because of the low temperature (e.g., near ambient or room temperature).

In operation, the effluent passes into the stainless steel inlet tube 306 and the CDA is injected at a specific location. CDA reacts with silane to produce silica (SiO ₂ ), silicic acid (H ₂ SiO ₃ ) or slightly hydrated silicate (SiO ₂ · xH ₂ O). Although the influent concentration of the silane is below its LEL, no sparking or heat is required. A silane reduction efficiency as high as 95 +% can be achieved. The CDA flux required for silane destruction will vary depending on the characteristics of the incoming effluent gas (eg, silane concentration and N ₂ flow rate).

A CDA can be introduced at one or more points, or in successive stages, into the inlet. It can also be bubbled into the purifier liquid. In this way, the silane destruction efficiency can be selectively increased as required for a given treatment application. With multiple CDA steps, the distance between the CDA steps can be easily optimized experimentally without undue effort, which is a function of the total gas flow rate and the silane flow rate.

Another variation of this inflow structure may include connecting a silane-containing gas hold mass flow controller (MFC) having a valve to regulate the CDA to the inflow structure. Such a system may be arranged such that when the MFC fails, the CDA valve is opened such that the predetermined flow rate CDA enters the specific CDA stage. This extra CDA ensures that the additional silane flowing to the clarifier is reduced. The control system also may be performed by using N ₂ instead of CDA, N ₂ would simply be used as a diluent to ensure that the silane concentration is below the LEL concentration.

As a safety device, and a large amount of CDA is to light the silane to control ever be preferred, or it may be desirable to simplify the silane is diluted with an inert gas such as N _2. If the MFC is properly operated, it is undesirable to continue to run CDA or N ₂ intrinsically, because it is a waste of CDA or N ₂ .

In addition to CDA, water is also a necessary component for the manipulation of incoming structures. The water can be piped to the inlet structure to form a jacket chamber around the inlet tube through which the outlet gas passes. In an exemplary embodiment, water is pushed to the top of the inlet structure to flow over the weir to form a wet wall column over the tube through which the outlet gas passes. The wet wall column serves to keep the inlet structure cool and also to remove any solid by-products of the silane / O ₂ reaction. Such a structure is disclosed in U.S. Patent Application No. 08 / 857,448, filed May 16, 1997, entitled " Clog-Resistant Entry Structure for Introducing a Particulate Solids-Containing and / or Solids- Quot; Processing System &quot;; and U.S. Patent Application Serial No. 08 / 778,386, filed December 31, 1996 (Scott Lane et al., "Clog-Resistant Entry Structure for Introducing a Particulate Solids-Containing Stream to a Fluid Processing System"&Lt; / RTI &gt; wet-well column, which are hereby incorporated by reference in their entirety.

Another possible modification of the inlet structure involves bubbling CDA in the water forming a wetting wall column in the inlet tube passageway.

It will be appreciated that the optimal amount of CDA addition will depend upon the particular flow rate conditions of the SiH ₄ , N ₂ and other gases (eg, NH ₃ ) being processed in the installation. The optimal CDA flow rate can be, for example, within the range of about 0.1 standard cubic feet per hour (scfh) to about 100 scfh.

FIG. 6 is a schematic diagram of another type of implant structure 400 that may be used to reduce silane in an effluent stagnant containing the same.

The implant structure 400 receives a silane-containing effluent from an upstream source (not shown), such as a semiconductor manufacturing facility. The gas enters the line 402 and flows into the inflow tube 404 with the spiral port 406 mounted thereon. The spiral port can be heated at high temperature, or alternatively at ambient temperature, by a flow of nitrogen or other suitable gas, so that the port is not blocked through it (e.g., in the jacket surrounding the port or port of the port).

This arrangement overcomes the tendency of the optical spiral ports to clog whenever the effluent gas contains a condensable component.

The inflow tube 404 extends downwardly of the lower tubular passage portion 410, the cross section of which is larger than the inflow tube, to discharge the gas into the inner passage 460 of the lower tubular passage portion 410.

The lower tubular passage portion 410 includes a cylindrical outer wall having an upper compartment on which gas injection ports 414 and 416 are mounted. Nitrogen or other suitable gas pressurized to a suitable level flows in line 418 through the port to the inner circumscribed passage 412. The passageway 412 is constrained by the porous inner wall 420 in radially spaced relation to the outer wall. The porous inner wall may be formed of a sintered metal, a porous mesh, or other suitable gas permeable material that allows pressurized gas to flow through the permeable wall into the inner passageway 430 in communication with the inner passageway 460.

In this manner, the upper compartment is enclosed with a pressurized gas to protect its inner wall surface from contact with the gas, thereby minimizing the condensation and deposition of solids on the wall surface. The upper section of the tubular passage portion 410 is covered by an annular flange 452 that is sealed in place to the structure by O-rings 422 and 424. The annular flange 452 is held in place by a locking ring 450 that allows selective disconnection of the passive disconnection and access and disassembly of the interior of the structure.

The lower section of the tubular passage portion 410 is characterized in that the outer wall 440 in a radially spaced relation to the inner wall forms an annular volume therebetween. Communicating with this annular volume is the water inlet 448, which is connected to a suitable water source. The introduced water then enters the annular volume 444 and overflows from the upper end 446 of the inner wall 442 and flows down the inner surface of the wall 442 to protect the wall surface from contact with the gas stream to be treated, Pour off the wall and remove any particulate that can contact the water fall film thereon.

The lower section of the tubular passage portion 410 terminates in a radially extending flange 454 which is connected to a downstream unit (e.g., a water purifier unit, an oxidation reaction unit, a chemical dosing chamber, The gasket 456 is positioned on the lower surface to seal the injection structure in a leak-tight manner.

When injecting a silane containing gas stream into the purifier unit, the injection structure of FIG. 6 is effective to destroy the silane at a concentration below the lower explosive limit. When the cleaned anhydrous air is bubbled into the water at the inlet, 98% + of the silane removal efficiency can be achieved at an appropriate flow rate of the CDA (e.g., about 4-5 standard cubic feet per hour of flow). Alternatively, the CDA can flow through one or both of the nitrogen ports shown in FIG.

As a specific example of the silane removal efficiency of the injection structure of the type shown in FIG. 6 in the purification treatment of the gas stream containing the silane and introducing the untreated silane washed into the stagnation stream, Table A below shows the addition of NaOH As described elsewhere herein, this chemical addition is accomplished by a chemical inlet in a purifier unit) and the results of testing such a purge system with both of them not added.

The data in Table A shows the flow rates of clean dry seawater (standard cubic feet per hour, scfh) at a flow rate of one part per million (ppm) of silane, a silane flow rate of 480 standard cubic centimeters per minute (sccm) , An outlet concentration at a cleaning rate of 1 gpm (gpm) and a cleaning rate of 0.5 gpm (cleaning liquid flow rate), and% dry removal efficiency (dry time basis efficiency),% DRE of silane.

SiH4 breakdown at a silane flow rate of 480 sccm Caustic NaOH not added Exit SiH4 (ppm) CDA (scfh) Injection concentration 1 gpm 0.5 gpm % DRE (1 gpm) % DRE (0.5 gpm) 0 6920 3446.3 3578 50.2 48.3 2 6827 1571 1900 77.0 72.2 4 6737 130.4 290 98.1 95.7 6 6649 1663.8 1695 75.0 74.5

Caustic NaOH addition Exit SiH4 (ppm) CDA (scfh) Injection concentration 1 gpm 0.5 gpm % DRE (1 gpm) % DRE (0.5 gpm) 0 6920.4 762 1755 89.0 74.6 2 6827.5 1206 1616 81.3 76.3 4 6737.0 819 920 87.8 86.3 6 6648.9 765 930 88.5 86.0 6563.1 880 86.6

As can be seen from the above description, the introduction of CDA into the upstream stream of the purifier was very effective in reducing silane in the gas stream.

Other implant structures may be usefully employed in the broad practice of the present invention and are described in U.S. Patent Application Serial No. 08 / 857,448, filed May 16, 1997, entitled " Clog-Resistant Entry Structure for Introducing a Particulate Solids Resistant Entry Structure for Introducing a Particulate " filed on December 31, 1996, and U.S. Patent Application Serial No. 08 / 778,386, entitled "Quot; Solids-Containing Stream to Fluid Processing System ", all of which are incorporated herein by reference.

As another approach to removing the silane from the gas stream containing the same, potassium hydroxide or other suitable reagent may be contacted with the gas stream prior to or during the purge operation to achieve a substantial complete removal of the silane can do.

As regards the bubble behavior that can occur in the clarifier, the present invention can be achieved in another embodiment, for example, as a result of a material such as tetraethylorthosilicate (TEOS) or chlorinated silane, which may be present in the gas stream to be treated , Consider the use of means to inhibit foam formation which can cause significant foam formation in the cleaning liquid environment. In one embodiment of the present invention, a defoaming agent may be injected into the clarifier. In another embodiment, a physical deformation is made in the discharge line of the recirculation pump associated with the clarifier to reduce the flow rate and pressure at which the recirculated purge liquid is introduced onto the packing of the purge column. Optionally, an orifice plate may be provided in the recycle pump discharge line to reduce the flow rate and pressure of the recycle liquid. This orifice plate also creates a back pressure on the pump and reduces or eliminates the occurrence of initial bubbling or cavitation that can form bubbles in certain cases (especially when TEOS or chlorinated silanes are present).

More generally, the chemical vesicle additive may be added to the water purifier by the chemical injection unit of the type shown in FIG.

FIG. 7 shows a water purifier 500 in which the gas stream is introduced into an injection structure 504, shown schematically in the drawing at line 502. The gas stream is purified in the purifier chamber 506 with an aqueous purge medium to discharge the purge gas stream to the outlet conduit 508 and optionally pass through the rear purifier unit 510 and finally to the line 512 And is discharged from the purifier system discharge port 511. The purifier system includes a purge liquid recycle pump 514 that receives the purge liquid coming from line 505 and discharges the effluent and recycle purge medium to the discharge line 518. The chemical injector flows from the chemical injection tube 522 of the chemical injection unit 524 via line 520 to the recirculation pump 514. The preparation purge liquid flows to the rear purifier unit 510 via the supply line 516. A control module 526, including suitable monitoring means, sensing means, instrument means, computing means, conditioning means and actuating means, controls the purifier system and the chemical injection unit.

A chemical infusion system may be injected using a chemical infusion system 524. The antifoaming agent used is added in such a manner as to moderate the surface tension of the cleaning liquid so that foaming is suppressed. Examples of defoam materials that may be usefully employed in the practice of the present invention include Defoamers 1410 and 1430 (silicon based materials) purchased from Dow Corning Corporation. Such silicone fouling materials may be used in aqueous cleaning media at a concentration of between about 1 ppm and about 100 ppm by weight of active silicon. The defoamer concentration can be readily determined in certain applications by monitoring the foaming action in a clarifier by varying the defoamer dosage for the cleansing medium.

Another way to reduce bubbles is to deform the piping on the pump recirculation line. For example, a limited flow orifice can be mounted on the pump to reduce or eliminate foaming. This orifice reduces the recirculating liquid flow rate so that as time passes, fewer purge liquids enter the packing surface in the purifier chamber, which also acts as a pressure relief device. This effectively reduces the pressure at which the purge liquid exits the spray nozzle on the packed column.

In this approach, the limited flow orifice can be attributed to several possible system locations in the system (e.g., (i) a spray nozzle due to lowering the pressure drop across the nozzle, and (ii) (Iii) a pump inside the pump due to a lower liquid flow rate through the pump). It also creates a back pressure on the pump and reduces or eliminates the occurrence of initial bubbling or cavitation that can form bubbles in certain cases, particularly when TEOS or chlorinated silanes are present.

Various approaches can be used to alleviate the CaCO ₃ deposition problem in effluent treatment systems. One approach uses magnetization techniques in which the supplements are passed through a magnetic field. The second approach uses a pH control system. A third approach uses a soda-lime column to treat (supplement) the make-up water. The fourth approach is to sediment the solids upstream of the clarifier.

The use of soda ash for water training is described more fully in Pontius, FW, " Water Quality and Treatment &quot;, 4th Edition, McGraw Hill Publishing Co., 1990, p. 359, , Ca (HCO ₂ ) ₂ and Mg (HCO ₃ ) ₂ ], which are mainly caused by calcium ions or magnesium ions. By soda lime softening, these water soluble species are converted into insoluble precipitates of calcium carbonate [CaCO _{3 (S)} ] and magnesium hydroxide [Mg (OH) _{2 (S)} ].

The problem of calcium carbonate sedimentation is mainly seen when two factors are present at the same time. The first is that the national index contains a large amount of soluble calcium. Second, the gas phase to be treated contains ammonia, which increases the pH of the purifying liquid. This pH increase alternately causes the dissolved calcium to precipitate as calcium carbonate.

In one embodiment, the formation of calcium carbonate in the purification system is prevented by passing makeup water through the magnet. The magnet is used to align calcium carbonate ions and particles and then introduce them into the clarifier. Whereby the ions and particles are electrically aligned to be adhered to the surface of the purging chamber. The means of magnetization is well known in the art and is applied to an effluent gas purifying system according to the present invention in which a purifying liquid, for example calcium carbonate, through which water is passed through the magnetizing zone, It is possible to prevent deposition from occurring in the cleaning liquid of other deposition species.

In other embodiments, the pH of the clarification liquid solution can be controlled to prevent the formation of calcium carbonate in the purification system. 8, that is, the case of, as can be seen in sedimentation graph of CaCO ₃ function of the sump (pH of the purification unit of the sump tank purifying medium) pH, holding the purified liquid pH to about 8.5 CaCO ₃ is not precipitated will be.

9, which is a molar concentration graph of CO ₂ (aqueous), H ₂ CO ₃ (aqueous), HCO ₃ ^- (aqueous) and CO ₃ ^- (aqueous) which are pH functions of the sump liquid, Ca (HCO ₃ ) ₂ (calcium bicarbonate) is formed. The Ca (HCO ₃ ) ₂ is not precipitated because it is somewhat water-soluble. To adjust the pH, an integrated chemical injection system of the above purification system can be used (see FIG. 7). Any suitable chemical may be used to control the pH level, including, for example, sulfuric acid (H ₂ SO ₄ ) and acids such as hydrochloric acid (HCl).

In another embodiment, calcium may be removed from the cleaning medium upstream of the cleaning unit to prevent calcium carbonate deposition. For example, the makeup water for the cleaning unit may be passed through a column containing lime and soda fractions. When passing through the column, the calcium is precipitated with CaCO ₃ .

In other embodiments, the makeup water may be passed through an agglomeration chamber to precipitate or coagulate the calcium to prevent deposition of calcium carbonate. Within the chamber, a chemical additive such as sodium fluoride is used to precipitate calcium as insoluble CaF ₂ . Alternatively, agglomeration can be performed by passing the CO ₂ gas through the chamber while raising the pH using sodium hydride. In the basic solution, the CO ₂ gas is converted to a CO ₃ ^2- ion, which is then complexed with CO ₃ ^2- to form solid CaCO ₃ .

With regard to the aforementioned problems with solids formation and clogging at the pressure port of the purge system, it is necessary to communicate the inert gas with the pressure port at a suitable pressure and flow rate by means of a small scale purification process using an inert gas such as nitrogen So that the solid deposit of the pressure port can be removed. This purge process should be low enough that the back pressure is not loaded on the pressure sensing device, as it will make the pressure read incorrectly. However, the purge gas stream must be large enough to erode the diffusion of the existing condensable gas or to pass the particles through the pressure port. If a condensable gas is present, the inert purge gas may also be heated, thereby further suppressing the formation of solids in the port.

It is also desirable to minimize the generation of solids at the inlet of the purification system. In this regard, it is desirable to heat the inlet gas carrier tube, thereby assisting in maintaining all the condensable gases that are gaseous until the gas enters the purifier.

Another aspect of the present invention relates to a two-stage purification system that solves problems that may be encountered with a single stage purification unit, which is a prior art effluent treatment system. The two stage purification system of the present invention comprises an equilibrium column followed by a mass transfer column. The equilibrium column approaches equilibrium and very close to the ideal behavior of Henry's law, but the length of the column is very short. Subsequent mass transfer columns provide additional purge efficiency above the level that is limited by Henry's Law in the first column. By using a cocurrent equilibrium column, high efficiency can not be obtained at a low flow rate of water which can be obtained with a countercurrent flow column. Nonetheless, with the use of countercurrent flow columns, the length of the required column is longer than is acceptable for industrial installations, such as, for example, semiconductor equipment, and the column is longer than can be provided in such a facility.

By using an equilibrium column followed by a mass transfer column, the overall acceptable column length and excellent efficiency in reducing the effluent can be obtained by using a small amount of water. This is a significant advance in the art with respect to the two stage purification system of the present invention.

Moreover, the two-stage purification system of the present invention is highly advantageous in preventing particle formation and deposition during outflow retention processing. The equilibrium column takes the form of a " light opening " barrel with a slow water flow rate, which provides efficient purification performance during initial gas purge operations. The mass transfer column of the second purification unit is relatively small in diameter and the flow rate of water is substantially slower than that of the first purification unit. As such, the slow flow rate of the small diameter / water characterized by itself is very sensitive to flocculation during normal use, but since the mass transfer column is protected by the upstream equilibrium column, the two- It is possible.

Thus, the two-stage purification system of the present invention comprises a first rinsing step comprising a packed column through which the effluent gas is passed, for example, in a downstream direction through a column containing the purification medium. As mentioned briefly above, a means for recycling a packed column, such as a rotary atomizing hub, may be provided, thereby allowing very rapid recirculation of water from the sump at the bottom of the clarifier. The column is used to remove a large amount of acid gas and other hydrocarbons, and also removes a large amount of solids present in the incoming stream or formed by the reaction of water and feed gas in the scrubber.

The efficient removal of the first stage of the purifier to remove the supplied gaseous species depends on the flow rate and the makeup water flow rate which can be varied by varying the respective flow rates to determine the rate and extent of removal, By measuring the flow rate of the gas and purge liquid that will provide efficiency, it can be easily measured without being severely limited by experiment.

If the concentration of the undesirable components further decreases, the partially treated gas is communicated from the purifying unit of the first stage to the water purifier of the second stage. This so-called " polishing " column is a column through which the gas passes in a countercurrent manner as a vertical column. The column is typically much smaller than the first stage column. If the column size is small as described above, the packing material having a much lower water flow rate can be suitably wetted as compared with the case of the first-stage column. The required flow rate of water is low enough so that fresh make-up water can be used for the above purposes. Thus, the efficiency of the column is high, allowing the second stage purification system to operate without the use of chemical injection formulations or large amounts of fresh water.

There are a few ways to evaluate the benefits of using a two-stage water clarifier as compared to conventional one-stage water purifiers. With respect to the flow rate of the replenishing water supplied, the two-stage design may further enhance the cleaning efficiency. In other words, if a certain efficiency is required, the two-stage design can significantly reduce the flow rate of the make-up water. Finally, the two-step sorting scheme allows the purge system to accommodate the gas challenge while maintaining the efficiency and the flow rate of the make-up water the same as in a one-stage purge system.

In a two-stage purification system, if the flow rate of the make-up water is lower than that of the first stage cleaning design, the second stage can increase the purification efficiency. The use of a polishing clarifier eliminates the need to use a chemical injection formulation that is conventionally required to achieve an efficiency that is readily obtainable in a two-stage purification system.

Comparing the prior art single stage purification system and the two stage water purification system of the present invention to the cleaning of the fluorinated gas, respectively, the fluorine containing nitrogen stream is subjected to a water rinse treatment in each system. The obtained performance data is shown in Table B below.

Single-stage water purifier Supplemental Water (GPM) Total nitrogen (slpm) Chemical injection Fluorine injection amount (slpm) Equivalent emissions (HF) (ppm) 1.2 80 Never inject 0.5 10.5 1.2 80 Injection box 0.5 6.95 0.5 80 Injection box 3.0 745.5 Two-stage water purifier Supplemental Water (GPM) Total nitrogen (slpm) Chemical injection Fluorine injection amount (slpm) Equivalent emissions (HF) (ppm) 0.75 80 Never inject 0.5 4.2 0.75 80 Never inject 1.0 8.4 0.75 80 Injection box 2.25 2.5 0.75 230 Injection box 3.0 42.8 0.75 230 Injection box 5.0 98

As can be seen from the data, fluorine removal was improved and the consumption of water was reduced by the two-stage water purification system of the present invention.

In a particular embodiment, the first of the two-stage purification systems comprises a packed column having a diameter of 21 inches and a length of 18 inches through which the semiconductor processor effluent gas passes in a cocurrent manner. The second stage column may be 4 inches in diameter and 18 inches long, which allows water to be used for cleaning purposes at a much slower flow rate than in the case of the first stage column. Such a design would adequately wet the packing material at a flow rate of water ∠ 0.5 GPM; Fresh supplements may therefore be used for this purpose.

In certain embodiments, the novel column wall liners can be used in a (second) polishing purger, which aids in increasing the efficiency of the polishing purger. The liner also serves as a sock containing the packing material of the polishing purger. This design feature allows the cleaning purifier to be easily removed and replaced when a cleaning step is required. Moreover, the design can easily reverse-fix the polishing clarifier to a single purifier system present in the field.

10 is a graph of the improvement factor in which the ammonia exhaust concentration is reduced (as compared to a corresponding system in which the polishing purifier is not present), when a polishing purifier is used, as a function of the flow rate of water expressed in gallons per minute. The graph shows that the polishing clarifier reduces the NH ₃ outlet concentration (relative to the corresponding system where no polishing purifier is present) to less than 110 times the supplied make-up water flow rate. In addition, when only one-third of the first-stage purifying system make-up water is used, the polishing purifier can reduce the NH ₃ outlet concentration to less than 30 times.

The most favorable aspect of the optimal design of the polishing purger is in the wall liner. The polishing purger can be, for example, 4 inches in diameter when the packing material member used in such a polishing purger is 1 inch in diameter. The ratio of the column diameter to the packing diameter is 4. A commonly used design should, by experience, be a ratio of at least 8, preferably at least 10-15. This is because the void space present in the wall is excessively large compared to the void found in the interior of the column, and if the ratio is small, it hinders the channel formation of the purge liquid that goes down the column wall.

A wall liner can be used to hold the purging packing material in the polishing column while at the same time inhibiting channel formation of the wall and improving cleaning efficiency. In this respect, due to the pressure drop limits of the system, it is not possible to simply reduce the packing size simply to overcome the channel formation / passing phenomenon described above.

The wall liner used in the broad field of the present invention includes a bag, lid, basket, or other pourable container that can easily pass the treated gas and the purge liquid. In this way, the liner is gas permeable and liquid permeable, so that the gas / liquid can be contacted on the inner liner packing surface.

In one embodiment, the liner is structurally suitable to form an inert polymer such as, for example, polyethylene, polypropylene, polysulfone, polyvinyl chloride, polycarbonate, etc., glass fiber, or the liner, May be formed of an inert material, such as materials that can be used and any other material that is chemically inert.

Depending on the packing dimensions of the material used in the polishing clarifier to provide an expanded mass transfer area to the gas / liquid contact, the liner may be made of a plastic wire And may be formed of a plastic open mesh material having a mesh size of 1 cm x 1 cm. The thickness of the plastic wire is about 1/16 inch and the direction of the mesh can be the vertical or horizontal direction of the plastic wire. The mesh comprising a plastic wire having a smaller or larger space between the plastic wires; Thinner or thicker plastic wires; And / or a mesh in a diagonal (arbitrary angle) direction in which the wire is not in the vertical or horizontal direction. The material forming the mesh is preferably a hydrophobic, i.e., chemically inert material that is not well wetted.

The wall liner thus provides a detachable retention structure containing the packing material of the polishing clarifier. Such a plastic liner design is very advantageous since the packing liner can be easily separated when it is necessary to clean the packing material and / or the inner surface of the column. Field Inside Fixed Existing Water Purifier units are also promoted with liner design.

It will be appreciated that when specifically describing the liner with reference to a " polishing " or a second stage purifier of a two stage purifier unit, the liner structure may also be used in the first stage purifier unit. In the first stage unit, due to the size and dimensional characteristics of the container surrounding or holding the unit, there is no packing size mediated passage or channeling problem of the type seen in the polishing step, It is necessary to clean the inner surface of the substrate and the surface of the material packed therein.

Thus, the packing of the first stage unit of the two-stage purification system may also provide a liner of a type similar to that used in the second stage of the clarifier system.

Thus, the liner containing packing can be used as a " cassette " which can be removably mounted to a polishing purger, and optionally the first stage purger of the present invention provides a very effective action on the purger system, It prevents the wall effect that forms the channel while the gas passes through the use.

Figure 11 shows one embodiment of the present invention comprising a mesh bag 602 having an opening 604 defined by a crossed chain member 606 formed of a suitable polymeric material capable of preserving its structure even under clean conditions. Illustrate a wall liner and packing assembly 600 by way of example. The mesh bag 602 contains a large amount of the packing member 608. As shown, the mesh bag may be provided with an upper end sealing structure, such as a spring bias clip 612 and belt 614 structure, whereby the mesh bag can be snapped or loosened by the spring clip, Can be opened and closed.

The packing member 608 may be formed of any suitable shape, size, shape, and material that is useful or useful for the supplied gas cleaning application. For example, the packing member may be in the form of an annulus, a saddle, a spiral, a donut or other geometrically regular and / or irregular shape, such as a pawl ring, a lashing ring or other commercially available packing material Lt; / RTI &gt; The packing material is preferably characterized by a high ratio of surface to volume, so that the gas / liquid contact action during the purging operation is very effective.

A wall liner and packing assembly is shown in Fig. 11 that enlarges the connection with the top of the purge unit container 616, with the wall liner detachably mounted.

12 schematically illustrates a two-stage purifier system 700 according to one embodiment of the present invention.

The two-stage clarifier system includes a first purge vessel 702 that encloses an interior volume comprising a layer 704 of purge media. It is contemplated that the layer may be provided as a removable insert forming a gas / liquid contacting packing material layer, although it is shown in a preferred form such as a " loose " layer of packing material. The layer 704 is disposed on a support 706 that may include a structurally strong grid, mesh, screen, or other suitable porosity sufficient to protect the inner wall of the vessel 702 and support the packing material layer . Typically, the first clarification vessel will comprise a layer of packing material that does not include any liner or bag.

The layer of packing material 704 receives the processed gas from an upstream treatment facility 714 such as a semiconductor processing unit and communicates the effluent gas from line 716 to purge vessel 702, Into the inner space of the head space 706. The effluent gas may be in a flow through line 716 heated by heating member 720, for example, to more efficiently reduce the silane.

With this arrangement, the gas obtained from the upstream equipment is communicated downwardly through the packing material layer to the lower plenum space 708 and discharged from the cleaning vessel 702 to the line 760. The discharge line 760 is joined to the wall of the cleaning vessel 702 by a seam 742.

The plenum space 708 may also define a purge fluid medium 712, for example, a sump 710 for collecting an aqueous medium. The liquid is recycled from the sump 710 by the line 722 incorporated with the wall of the vessel 702 by the seam 724. The line 722 communicates the purge liquid to the pump 726 which discharges the liquid to the recycle line 728 and from which an atomisation nozzle 728 is mounted in protected form to an arm 734, To a drive module 730 that is operatively coupled to a hollow shaft 732, which in turn is connected to a hub 736 that holds the drive shaft 732. The drive module therefore communicates the purge liquid from line 728 and through the hollow shaft 732 to the nozzle 738 which atomically distributes this liquid to the packing material layer of the arm and bag 704, Is increased by the makeup water obtained from the line 770 connected to a suitable source (not shown). The drive module is rotated in the direction indicated by the arrow R in Fig. When polishing cleaning liquid is present, it is preferred that the make-up water is communicated in its entirety here because it provides the most optimal cleaning ability; This is because the line 770 contains liquid that is discharged from the polishing purifier 768.

The replenishing liquid in line 770 may optionally pass through magnetization region 796 to prevent deposition of calcium carbonate in the clarifier system. Alternatively, the region 796 may comprise a pH regulating region, a lime-soda ash column for treating (softening) the clarifying liquid, or a precipitation region in which calcium and magnesium precipitate from the clarifying liquid by suitable treatment , Wherein the cleaning liquid is consumed in the calcium and magnesium upstream of the cleaning chamber.

As a result, the liquid cleaning medium flows downwardly in the purge vessel 702 with the gas. In this way, a large amount of acid gas and a water-cleansable gas other than the acid gas are removed from the effluent gas to be treated, and a large amount of the solid in the gas is removed by the cleansing action.

The effluent gas, which has been treated by purifying in the first purifying vessel 702, then flows to the second purifying vessel 744 via line 760. The second purifying vessel has a bag 746 (described in connection with FIG. 11) containing a packaging material therein.

The second purifying vessel 744 may have certain size and certain dimensional characteristics that eliminate the need for a bag 746 of packaging material and that in this example the bed may be formed of a loose wrapping material. However, in the example where the bed diameter is small as described above, having the bag as shown prevents the anomalous detour and channel forming behavior that may result in improper gas purifying treatment and increases the efficiency in the polishing cleaning operation Thereby providing a wall-contacting structure that generates an appropriate hydrodynamic behavior to ensure that the wall-contacting structure is secure.

The bag 746 of filler in the second clarification vessel is relocated on the support structure 748, which may be of the same or similar type as used in the first clarification vessel. The new purge liquid is introduced via line 740 to the top of purge vessel 744, which can be combined with a suitable source of purge liquid (not shown). The cleaning liquid in line 740 optionally flows through the magnetization section 798 to inhibit or remove the precipitation of calcium carbonate in the purification system.

Alternatively, the section 798 may include a pH control section, a soda lime column for cleaning liquid treatment (softening), or a settling section where the calcium and magnesium precipitate from the cleaning liquid through suitable treatment to remove the cleaning liquid in the calcium and magnesium upstream of the purification chamber (I.e., a section where the exhaust gas is depleted).

The purifying liquid may be dispensed into the upper internal volume of the second purifying vessel by a dispensing means such as that shown coupled to the first vessel, but the diameter of the second purifying vessel is generally such that a single spray head, or nozzle, Is sufficiently small to be sufficient to introduce liquid across the cross-section.

The purge liquid then flows down through the fill of the bag 746 and contacts the gas introduced into the vessel 744 from line 760. Thus, gas exiting line 760 is introduced into the lower portion of the interior volume of the vessel and flows upwardly through the filler in bag 746 to perform close gas / liquid contact for gas purification.

Thus, the purified gas travels over the interior volume of vessel 744 and is released into line 764 with blower 766 to exhaust the treated gas from the system and overcome the upstream pressure drop associated with the gas treatment process do. Alternatively, a pump, compressor, turbine, fan, ejector, eductor, or other synchronous flow means may be used to discharge gas from the processing system.

After passing through the filler bed, the purge liquid is withdrawn from the bottom of vessel 744 via line 768 and may be further processed before final placement and / or recirculated (e.g., to be subsequently introduced into first purge vessel 702) Line 770).

Any magnetization sections 796 and 798 may be fabricated by any suitable magnetization device, such as a C-500 physical conditioner (Isaacson Enterprise product, Stockton, CA) and SoPhTec International (Costa Mesa, CA) A magnetization system commercially available under the trade name SoPhTec.

The two-stage cleaning system described above is very advantageous in that it minimizes the amount of purified water used in the purification treatment of the gas. In addition, the system involving multiple purification steps eliminates the need for chemical treatments, thereby achieving significant advances in the art, without using a significant amount of water, and without effecting high operating costs associated with the use of chemicals, Can be performed.

As another method that can be used in place of or in addition to the use of a bag containing a packaging material in a small diameter purifier to reduce the bypass or channeling behavior commonly present in wall effects, It may be desirable to provide a fluid flow breakdown structure (e.g., protrusion 790 shown in the inner wall of purifier vessel 744 in Figure 12) at least in part of the surface. The flow breakdown structure may be of any suitable shape, for example rod-shaped, bump-shaped, raised, hook-shaped, integrally formed wall protrusions (for example, , Gable of a wall, grit embedded in a wall, metal applica- tion soldered or welded to an internal structure, or fiber or rod-like attached to a wall surface. This destroying structure changes the fluid flow boundary layer of the purifier vessel wall and reorients the fluid flow stream direction of the wall into the bulk volume of the bed.

As an additional feature of the system of Fig. 12, the outflow stagnant flowing from the first clarifier 720 through line 760 to the second purifier unit 744 can be a cleaned anhydrous air or other suitable gas introduced from line 747 . Introducing the cleaned anhydrous air in this way may be advantageous for removal of unwanted components of the effluent stagnant, such as silane, especially when present together with ammonia in the gas stream. To this end, line 747 may be coupled to a source of cleaned anhydrous air (not shown) or other suitable gas used for this purpose.

Although a two-stage embodiment of a purge system has been shown and described, it will be appreciated that the present invention may employ other embodiments in which one or more purge vessels and associated purge steps are provided.

13 is a cross-sectional view of an injection structure 800 in accordance with another embodiment of the present invention.

As shown, the infusion structure 800 includes a housing 802 having a cylindrical outer wall 832, which has an annular volume 836 therebetween in a radially spaced relationship relative to the intermediate cylindrical wall 834, . The outer wall has an inlet port 860 through which cooling water is provided from a suitable source of the same (not shown) through line 862. The outer wall 832 also has an outer port 864 through which water circulating in the inner volume 836 can be discharged through the line 866. [

With this arrangement, the predetermined temperature in the inflow structure is maintained since the cooling water can be introduced and discharged into the annular internal volume for total circulation.

Although the cooling water has been described above, if heating of the inflow structure is required, the heating water may be similarly introduced, and liquid other than water may be used as the heat transfer medium in this manner.

The intermediate wall 834 may have a wall opening 815 through which cooling water may flow into the annular volume 842 between the intermediate wall 834 and the inner wall 838. As shown, The inner wall 838 extends upwardly and terminates below the top wall 854, which forms the boundary of the annular volumes 836 and 842. The liquid introduced into the annular volume 842 flows over the upper end of the wall 838 in the direction indicated by the arrow C and flows from the inner surface of the wall 838, which forms the boundary of the gas flow passage 840, . As an alternative to this wall opening 815, the intermediate wall 834 may be made of a porous material that allows liquid permeation. As another alternative, water or other liquid may be provided independently to the annular volume 842 by a separate liquid inlet or port (not shown).

A flanged wall 844 suspended downward is provided, which extends downwardly from the top wall 854, such that the flooding liquid is transmitted down along the inner surface of the wall 838.

The top wall 854 again supports a cylindrical wall 852 that extends upwardly by the top wall 850 with the top end closed thereby thereby forming an inner plenum space 870 in which air, Nitrogen or other gas may be introduced in the direction indicated by arrow A into the plenum space 870 and into the gas flow passage 840 in the direction indicated by arrow B. The gas thus introduced is preferably a cleaned anhydrous air.

The top wall 850 again defines a perimeter of the inlet conduit 814 and includes a side arm 812 that receives the process gas from the upstream source 808, such as a semiconductor manufacturing device, through line 810. The process gas containing the reduced component flows into the injection conduit 814 in the side arm 812 and flows from it to the main center section 816, which encompasses the interior volume 830. The vertically extending tube 818 extends through the inner volume 830 to the lower end 826 disposed within the gas flow passage 840. The tube 818 is defined by the wall surface 874 of the inlet conduit 814.

The upper end 824 of the tube 818 is coupled to a source of anhydrous air or other suitable gas 820 cleaned by line 822.

The outflow gas flowing into line 810 and flowing through the inlet conduit 814 passes through the inner volume 830 of the inner conduit and flows from its lower end to the bottom of the gas flow passage 840 . The gas flowing in line 810 can optionally be heated by a heating element 811 arranged to heat line 810 as needed.

At the same time, the liquid flows over the upper end of the inner wall 838 to form a liquid film flowing downward on the inner surface of the wall 838, which forms the boundary of the gas flow passage. At the same time, the cleaned anhydrous air or other gas is also introduced into the plenum space 870 as well as into the tube 818 to cover the wall surface of the inflow structure through contact with the outflow gas, May be mixed with anhydrous air or other gas, which may be useful to reduce certain unwanted components in the effluent stagnation. For example, the cleaned anhydrous air introduced into the plenum space 870 and the tube 818 may be introduced at a constant rate and at a constant rate, which acts to substantially reduce the silane content of the effluent gas. Another optional feature is that the injection conduit 814 can be heated by a suitable means (not shown).

Thus, the effluent gas flows downwardly in the gas flow passage 840 of the inlet, through the purifier 804, where gas / liquid contact may be performed to provide additional and concomitant reduction of the components in the effluent stagnation.

The infusion housing 802 may be secured to the clarifier 804 by welds 806 or other fixation or fixation means or methods (e.g., couplings, clamps, fixtures, etc.).

The present invention provides a purification system of various features. That is, using a reducing agent to enhance the cleaning efficiency of HF and F _{2 as} well as other halo compounds (e.g., fluoro compounds) and gases, and inhibiting the formation of harmful species such as OF ₂ ; Are readily arranged to destroy silane gas species; Minimize the frequency of foaming and the extent of foaming during the cleaning operation; Suitably arranged to prevent calcium carbonate precipitation and closure of the pressure sensing port, as well as formation of other solids in the cleaning system; To eliminate or at least substantially reduce the use of chemicals as well as to include multi-stage purification arrangements effective to significantly reduce the water requirements required for cleaning operations; The use of a packaging material in a containment structure useful for small diameter purging columns prevents bypassing and channeling behavior to achieve high gas / liquid contact efficiencies.

While the present invention has been described with reference to illustrative embodiments and features, it is not to be restricted by the scope of the present invention, but is understood to include other variations, modifications and alterations. Accordingly, the present invention should be broadly construed as encompassing all such variations, modifications and variations, and other embodiments within the spirit and scope of the invention consistent with the scope of the claims hereinafter set forth.

Claims (50)

A purifying system for reducing gas components in a gas stream containing a gaseous component, the purifying system comprising means for introducing a gas stream and a purge liquid into the contact chamber for gas / liquid contact inside the gas / liquid contact chamber (B) a purge system comprising a gas / liquid contact chamber comprising, additionally comprising one or more of the following: (a) (a) contacting a gaseous component with a chemical treating agent, optionally combined with a post-pressure triggering device arranged to at least partially reduce the bubbles in the purifying system upon injection of the chemical treating agent, to remove gaseous components from the gas stream / A chemical treating agent injector injecting a chemical treating agent to be removed; (b) an injection port arranged to inject gas flowing through the gas stream to facilitate removal of the silane from the gas stream if silane is present in the gas stream; (c) means for introducing a second purge liquid into the second gas / liquid contact chamber for gas / liquid contact in a second gas / liquid contact chamber, Wherein the first gas / liquid contact chamber is configured and arranged such that the gas stream and the purge liquid flow in the same direction, and the second gas / liquid contact chamber comprises a gas stay / The purge liquid is configured and arranged to flow in the opposite direction); (d) optionally, in combination with a pre-pressurization device arranged to at least partially reduce the foam in the purge system as a result of defoamer injection, a bubble in the purge fluid in the gas / liquid contact to inhibit foaming in the purging chamber A defoaming agent injector for injecting a defoaming agent to suppress the defoaming agent; (e) (1) a magnetizing zone for applying a magnetic field to the cleaning liquid before using the cleaning liquid in the contact chamber; (2) means for adjusting the pH of the clarification liquid to maintain the pH of the purification liquid below 8.5; (3) a soda lime bed arranged to flow a purge fluid prior to using the purge liquid in the contact chamber; And (4) a precipitator for precipitating the calcium component of the cleaning liquid prior to using the cleaning liquid in the contact chamber Means for inhibiting deposition of calcium carbonate from a cleaning liquid containing calcium, wherein the cleaning liquid is selected from the group consisting of: And (f) means for flowing a cleaning gas through said passageway to inhibit solid formation in the passageway of the purification system, and means for heating said passageway to inhibit solid formation in said passageway Means for inhibiting solid formation within the passageway of the system; And (g) (1) means for heating the gas stream before introducing the gas stream into the purification system; And (2) the second gas / liquid contact chamber of (c), and the treated gas stream exiting the first gas / liquid contact chamber, is cleaned in the treated gas stream prior to introduction into the second gas / liquid contact chamber Means for introducing anhydrous air or other oxygen-containing gas Means for reducing the silane from the gas stream when the silane is present together with ammonia in the gas stream. A purifying system comprising an inlet structure for introducing a gas stream containing a silane component into the purifier by flow of a gas stream through the inlet structure, the inlet structure being configured to inject gas into the gas stream flowing therethrough, And means for promoting removal of the silane component. 3. The system of claim 2, wherein the implant structure is connected to an oxygen-containing gas source. 3. The purifying system of claim 2, wherein the implant structure is connected to a nitrogen gas source. A purification system comprising an inlet structure for introducing a gas stream containing a silane component into a purifier by flow of a gas stream through the inlet structure, the purification system comprising a silane in the purification system at a flow rate through the inlet structure, Wherein the gas injecting means comprises (i) a gas permeable wall adjacent the gas flow passageway of the upper injection portion, the gas injecting means being capable of flowing the silane removal promoting gas An upper injection section including a ring-shaped gas introduction passage; (ii) an annular flooded liquid reservoir having an inner wall having an inner wall surface defining a boundary with a gas flow passage through a lower inlet of the infiltration structure, wherein a falling film of liquid is formed on the inner wall surface during overflow, A lower injection section for cleaning the inner wall surface of solid and solid-forming components; And (iii) a gas injection tube extending into the gas flow passage and terminating at one lower end of the upper injection portion and the lower injection portion of the gas introduction means, the gas introduction means being adapted to purify A purifying system configured and arranged to introduce a silane-containing gas into an apparatus. A purification system for treating an effluent gas comprising a water-purifying component other than an acid gas component and an acid gas component, An aqueous purge liquid is used which is constructed and arranged such that the aqueous purge liquid and the outflow gas flow in the same direction to each other to produce an acid gas component, a water-purifying component other than the acid gas component, and an effluent gas with reduced water- A first purifier unit for purifying the outflow gas to remove the acid gas component thereof; The second aqueous clarification liquid and the outflow gas being configured and arranged to flow in opposite directions to each other to produce an acid gas component, a water-purifying component other than the acid gas component, and a further reduced effluent gas of water- A second purifier unit for removing residual acid gas, remaining water-purifying component other than the acid gas component and residual water-reactive gas by purifying the outflow gas using the second aqueous purge liquid; And Means for flowing an acid gas component, a water-purifying component other than an acid gas component, and an effluent gas having a reduced water-reactive gas from the first purifier unit to the second purifier unit. 7. The purifying system of claim 6, wherein the volume of the second purifier unit is substantially less than the volume of the first purifier unit. CLAIMS What is claimed is: 1. A purification system for treating an effluent gas to remove the hydrolyzable components of the effluent gas by contacting the effluent gas with an aqueous purification medium in a gas / liquid contact chamber, the purification system comprising calcium carbonate Means for inhibiting the deposition of the second layer, (1) a magnetization zone for applying a magnetic field to the cleaning liquid before using the cleaning liquid in the contact chamber; (2) pH regulating means of the purifying liquid to maintain the pH of the purifying liquid below 8.5; And (3) a soda lime bed arranged to flow a purge liquid prior to using the purge liquid in the contact chamber. A purifying system for treating an effluent gas to remove the hydrolyzable components of the effluent gas by contacting the effluent gas with an aqueous purifying medium in a gas / liquid contact chamber, wherein the purifying system is adapted to use an aqueous purge medium in a contact chamber A precipitator for precipitating a calcium component of an aqueous purification medium, said precipitate comprising a chamber for contacting an aqueous purification medium, a chemical agent effective to precipitate the calcium component of the aqueous purification medium, and a chamber for contacting said chemical agent with said contact chamber And means for moving the cleaning system. A cleaning process for treating effluent gases to remove the hydrolyzable constituents of the effluent gases by contacting the effluent gases with an aqueous purge medium in a gas / liquid contact chamber comprising a chamber wall that encompasses the interior volume of the gas / liquid contact chamber The system comprising means for re-inducing fluid flow along the wall to an interior region of the interior volume of the chamber. A gas / liquid contact article for removably mounting in a purifier vessel having means for introducing gas and liquid into an interior volume of a purifier vessel for gas / liquid contact therein, the gas / liquid contact article comprising: Wherein the gas / liquid contact product comprises a filler mass contained within the filler mass. 12. The gas / liquid contact product of claim 11, wherein the bag is formed from a polymeric mesh. 12. The gas / liquid contact article of claim 11, further comprising a manually operable sealing member for the bag. An apparatus for reducing fluoro compounds in an effluent stagnant containing a fluoro compound, A water purifier unit for gas / liquid contact; Means for injecting a fluorocompound-containing effluent stagnant into the water purifier unit; Means for discharging a fluorocompound-reduced effluent gas stay from the water purifier unit; And And a reducing agent supply operatively connected to the water purifier unit for inputting a reducing agent to the water purifier unit during operation of the water purifier unit. 15. The apparatus of claim 14, wherein the reducing agent source comprises means for injecting a reducing agent into the water purifier unit. 15. The apparatus of claim 14, further comprising means for monitoring the fluorocompound concentration in the fluorocompound-containing effluent stagnant and in response thereto adjusting the introduction of the reducing agent into the scrubber unit. A semiconductor manufacturing processing unit for generating an outflow stagnant containing a fluoro compound; A semiconductor manufacturing facility comprising an apparatus for reducing fluoro compounds in the effluent stagnant, The device A water purifier unit for gas / liquid contact; Means for injecting a fluorocompound-containing effluent stagnant into the water purifier unit; Means for draining the fluorocompound-reduced effluent stagnant from the water purifier unit; And And a reducing agent supply operatively connected to the water purifier unit for inputting a reducing agent to the water purifier unit during operation of the water purifier unit. 18. The semiconductor manufacturing facility according to claim 17, wherein the semiconductor manufacturing processing unit comprises a processing unit selected from the group consisting of a plasma reaction chamber, a chemical vapor deposition chamber, an evaporator, a lamination growth chamber, and an etching tool. 18. The semiconductor manufacturing facility of claim 17, wherein the reducing agent source comprises means for injecting a reducing agent into the water purifier unit. 18. The semiconductor manufacturing facility of claim 17, further comprising means for monitoring the fluorocompound concentration in the fluorocompound-containing effluent stagnant and, in response thereto, adjusting the introduction of the reducing agent into the scrubber unit. A cleaning method for reducing gaseous components in a gas stream containing a gaseous component, the cleaning method comprising the steps of charging a gas / liquid contact chamber into a gas / liquid contact chamber and performing gas / liquid contact within the contact chamber And further comprising at least one of the following steps (a) to (f): (a) introducing a chemical treating agent into contact with a gas component to remove a gas component from the gas stream upon contact with the gas / liquid; (b) introducing a gas, which promotes the removal of silane from the gas stream, into the gas stream before introducing the gas stream into the contact chamber, if silane is present in the gas stream; (c) flowing the effluent gas from the contact chamber to the second gas / liquid contact chamber and introducing a second purge liquid into the second contact chamber for gas / liquid contact in the second contact chamber, Wherein the first gas / liquid contact in the contact chamber comprises a flow of gas in the same direction of the purge liquid and the second gas / liquid contact in the second contact chamber comprises a gas flow through the second contact chamber and a second purge liquid Comprising the steps of: (d) injecting a defoaming agent into the cleaning liquid during said gas / liquid contact to inhibit foaming in the contact chamber; (e) (1) applying a magnetic field to the cleaning liquid before using the cleaning liquid in the contact chamber; (2) adjusting the pH of the clarification liquid to maintain the pH of the purification liquid below 8.5; (3) flowing a purge liquid through the soda lime bed prior to using the purge liquid in the contact chamber; And (4) precipitating the calcium component of the clarifying liquid prior to using the purifying liquid in the contacting chamber; inhibiting deposition of calcium carbonate from the purifying liquid containing calcium; And (f) inhibiting solid formation in a passageway of a purging system including a conduit connected to a pressure sensing device, the method comprising the steps of: flowing a purge gas through the passageway to inhibit solid formation within the passageway; And heating the passageway to inhibit solid formation. A method for treating a gas stream containing a silane component to reduce the constituents of the gas stream, the method comprising: purifying the gas stream using an aqueous purification medium; And contacting the gas promoting removal of the silane component with the gas stream prior to purification in the purge step. 23. The method of claim 22, wherein the gas comprises an oxygen-containing gas. 23. The method of claim 22, wherein the gas comprises nitrogen gas. Flowing a gas containing a silane component to be purified through an inlet structure to a purifier, the method comprising the steps of injecting a gas flowing through the inlet structure into the purifier to promote removal of the silane component Wherein the gas injection structure comprises: (i) an upper injection portion including a gas permeable wall adjacent to a gas flow passage of the upper injection portion, the upper injection portion including a annular gas injection passage through which the silane removal promoting gas can flow; (ii) an annular flooded liquid reservoir having an inner wall having an inner wall surface defining a boundary with a gas flow passage through a lower inlet of the infiltration structure, wherein a falling film of liquid is formed on the inner wall surface during overflow, A lower injection section for cleaning the inner wall surface of solid and solid-forming components; And (iii) a gas injection tube extending into the gas flow passage and terminating at a lower end of one of the upper and lower injection portions of the gas injection structure, wherein the gas injection structure is purged from a source of silane containing gas Wherein the silane-containing gas is introduced into the apparatus. A purification method for treating an effluent gas comprising a water-purifying component other than an acid gas component and an acid gas component, An aqueous purge liquid is used in the first purge zone to remove the acid gas component of the effluent gas by creating an effluent gas in which the aqueous purge liquid and the effluent gas are flowing in the same direction to reduce the acid gas component, Purifying step; The second aqueous purge liquid and the outflow gas are in contact with each other while flowing in opposite directions to generate an outflow gas having reduced acid gas component and water-purifying component other than the acid gas component, whereby water- Purifying the effluent gas using a second aqueous purge liquid in a second purge zone to remove the components; And Flowing the reduced outflow gas from the first purifier unit to the second purifier unit, the inventor Joseweyn explains that both the acid gas component and the water-purifiable component other than the acid gas component flow in the same direction The concentration will decrease after passing the contact step. In addition, the water reactive gas will be reduced in the same direction of flow. The acid gas component and the water soluble component are reduced to a concentration approaching the concentration corresponding to the equilibrium value of each of the acid gas component and the water soluble component in the aqueous purge liquid in the same direction stage. &Lt; / RTI &gt; 27. The method of claim 26, wherein the volume of the second purge zone is substantially less than the volume of the first purge zone. A cleaning method for treating an effluent gas to remove the hydrolyzable component of the effluent gas by contacting the effluent gas with an aqueous purifying medium in a gas / liquid contact zone, the method comprising: removing calcium carbonate from an aqueous purification medium containing calcium , Wherein said inhibiting step comprises the steps &lt; RTI ID = 0.0 &gt; (1) applying a magnetic field to the cleaning liquid before using the cleaning liquid in the contact zone; (2) adjusting the pH of the cleaning liquid to maintain the pH of the cleaning liquid below 8.5; (3) flowing a purge liquid through the soda lime bed prior to using the purge liquid in the contact chamber. CLAIMS What is claimed is: 1. A purging method of treating an effluent gas to remove the hydrolyzable constituents of said effluent gas by contacting said purging medium with an aqueous purge medium in a gas / liquid contact chamber, said method comprising the steps of using an aqueous purge medium Wherein the precipitation step comprises contacting the aqueous purification medium with a chemical agent effective to precipitate the calcium component of the aqueous purification medium prior to the precipitation of the calcium component of the aqueous purification medium. A cleaning process for treating effluent gases to remove the hydrolyzable constituents of the effluent gases by contacting the effluent gases with an aqueous purge medium in a gas / liquid contact chamber comprising a chamber wall that encompasses the interior volume of the gas / liquid contact chamber The method comprising redirecting fluid flow along the wall to an interior region of the interior volume of the chamber. As a gas / liquid contacting method, The method comprising the steps of: detachably mounting a filler media assembly in a purifier vessel, the filler media assembly comprising a porosity membrane structure and a filler mass contained therein; and a purge fluid and purge liquid through the porous membrane structure for gas / And Inhibiting the wall effect in a purifier vessel containing the filling material by at least one step selected from the group consisting of blocking the flow from the inner wall surface of the purifier vessel by increasing the physical structure of the wall surface Gas / liquid contact method. 32. The method of claim 31, wherein the bag is formed of a polymeric mesh. 32. The method of claim 31, wherein the bag comprises a hand-operable sealing member. A method for reducing a fluoro compound in a gas phase containing a fluoro compound, comprising the step of purifying a gas stream containing a fluoro compound using an aqueous medium in the presence of a reducing agent. 35. The method of claim 34, wherein the reducing agent comprises at least one compound selected from the group consisting of sodium thiosulfate, ammonium hydroxide, and potassium iodide. 35. The method of claim 34, wherein the reducing agent comprises sodium thiosulfate. 35. The method of claim 34, wherein the reducing agent comprises ammonium hydroxide. 35. The method of claim 34, wherein the reducing agent comprises potassium iodide. 35. The method of claim 34, wherein the reducing agent is injected into the aqueous medium during purging. 35. The method of claim 34, wherein the fluorine compound comprises a fluorine gas. 35. The method of claim 34, wherein the fluoro compound comprises a gaseous fluoride compound. 35. The method of claim 34, wherein the fluoro compound-containing gas stream comprises an effluent derived from a semiconductor manufacturing process. 35. The method of claim 34, wherein the fluorocompound-containing gas stream comprises an effluent from a plasma reactor cleaning operation of a semiconductor manufacturing facility. 35. The method of claim 34, further comprising monitoring the treatment state of the gas stream and introducing a reducing agent in an amount according to the treatment conditions. 45. The method of claim 44, wherein the treatment conditions of the gas stream are pH. 35. The method of claim 34, wherein the process condition of the gas stream is a fluorocompound concentration in the gas stream. Contacting an aqueous medium with a gas stream in the presence of a reducing agent that reacts with a fluoro compound to form a fluoro compound in an effluent stream without forming OF ₂ to form a fluoro compound from an effluent stream containing the fluoro compound / RTI &gt; 48. The method of claim 47, wherein the reducing agent is selected from the group consisting of potassium hydroxide and sodium hydroxide. Purifying the effluent stream using an aqueous medium; And Introducing anhydrous air cleaned into at least one of the effluent stream and the aqueous medium in an amount and at a rate sufficient to reduce the silane concentration in the effluent stream &Lt; / RTI &gt; wherein the silane comprises a silane. An effluent reduction purification system comprising an effluent gas purification water purifier, (1) a function of cleaning the outflow gas by addition or injection of a chemical reduction reagent; (2) a function of purifying the outflow gas containing silane, in which the cleaned anhydrous air is introduced into the outflow gas or the purifying liquid; (3) a function of using a two-stage purification system including a balancing purification column and a polishing material transfer column to reduce the number of replenishment required for purification while simultaneously maintaining or increasing the purification efficiency compared to the first stage purification unit; (4) The cleaning material transferring purging column is charged with anhydrous air that has been cleaned in the effluent gas before the effluent gas discharged from the equilibrium purification column of (3) is introduced to reduce the silane present with the ammonia in the effluent stagnant function; (5) a function of using a porous membrane structure containing a bed packing as an insert in a polishing material transfer column in the two-stage purification system of (3) above; (6) contacting the effluent gas with the OF ₂ reducing agent in a purge system; (7) the ability to regulate the bubble in the purifying system by limiting the orifice of the flow of the chemical defoamer and / or the purifying liquid; (8) (a) the magnetization of the make-up water used for purification; (b) pH adjustment of supplemental water; (c) Soda lime softening of supplemental water; And (d) a function to prevent CaCO ₃ accumulation in the purification system by at least one of precipitation or flocculation of the make-up water; (9) a function of suppressing clogging of a spiral port including a spiral sensing line in a cleaning system by passing a scrubber stagnant through a photohelic sensing line, which may be heated as needed; And (10) The function of injecting the outflow gas into the purification zone by heating the injection structure used in the purification system Wherein the effluent reduction purge system is configured and arranged to perform at least one of the functions selected from the group consisting of: