TWI631989B - Device and process for multi-stage catalytic reaction occurring in at least two reaction modules including catalytic reactor and adsorption reactor - Google Patents

Abstract

The present invention relates to a device comprising at least two reaction modules connected in series, wherein each reaction module comprises a catalytic reactor in which a catalytic reaction takes place, and an adsorption reaction connected to the catalytic reactor without a separate cooling process The foregoing adsorption reactor uses a solid adsorbent to remove the catalytic reaction product; and a catalytic reaction process using the foregoing apparatus.

The efficiency of the catalytic reaction can be improved by balancing the breakthrough using the apparatus or process of the present invention.

Description

Apparatus and process for multi-stage catalytic reactions occurring in at least two reaction modules including a catalytic reactor and an adsorption reactor

The present invention relates to a device comprising at least two reaction modules connected in series, wherein each reaction module comprises a catalytic reactor in which a catalytic reaction takes place, and an adsorption reactor connected to the catalytic reactor without a separate cooling process The adsorption reactor is used to remove the catalytic reaction product using a solid adsorbent; and a catalytic reaction process using the apparatus.

A representative reaction in which the catalytic reaction (Formula 1) is combined with the exclusion reaction of the catalytic reaction product (Formula 2) is a perfluorochemical treatment process.

[Formula 1] CF ₄ + 2H ₂ O → CO ₂ + 4HF

[Formula 2] CaO+2HF→CaF ₂ +H ₂ O

Various hazardous exhaust gases are exhausted from each process in which the semiconductor is fabricated, and most of these gas systems are volatile and detrimental to human systems or consist of materials having a high global warming index and must therefore be removed. Among these gases, perfluorinated compounds (PFCs) which are mainly discharged in the process of manufacturing semiconductor etching and chemical vapor deposition (CVD) are very stable and are not easily excluded. PFC is more stable than chlorofluorocompound (CFC) used as cold coal, and has a problem of not only having a large global warming index but also a long decomposition time. Therefore, PFC accumulates in the atmosphere upon release. PFC emissions emitted from semiconductor manufacturing processes are increasing at high rates each year. Therefore, as the impact of PFC on global warming is increasing, countries are gradually strengthening their regulation of PFC.

Various technologies for removing PFCs, especially carbon-based PFCs, are being developed, which can be divided into PSA ( pressure swing adsorption ) and separation membrane separation and recovery fields. And the use of plasma, combustion or decomposition and elimination of catalysts.

In contrast to resource recovery, decomposition and exclusion techniques use various methods to decompose and remove PFC technology. The decomposition and elimination techniques can be basically classified into three types of direct/indirect thermal decomposition methods, plasma decomposition methods, and catalytic decomposition methods. The direct/indirect thermal decomposition method is a technique in which a combustion flame of a high temperature of 1,000 ° C or higher or a direct heating using an electric heating furnace is used to decompose a PFC by contact with oxygen, and the method has an advantage in that the system itself is convenient because it involves Simple heating. However, a disadvantage of this method is its low efficiency, and because it must operate at a high temperature of 1,000 deg.] C or higher, heat is generated NO _X. The plasma decomposition method is a decomposition technique in which a PFC-containing exhaust gas flows into the plasma after the use of microwave or high frequency waves or the like to generate a plasma of a high energy state, and is known to be very effective for a PFC decomposition system. However, when the gas is exposed to very high energy state of a plasma, not only the target PFC decomposition, and stable gas such as N ₂ reaction with oxygen to produce an excess of NO _X. Further, the problem is that although plasma can be favorably produced in a He or Ar atmosphere, it is disadvantageous in that it is difficult to generate plasma under N ₂ , especially in an O ₂ environment, and the decomposition efficiency is rapidly lowered.

The catalytic decomposition method is a technique in which a catalyst and water vapor are used to decompose a non-degradable PFC at a low temperature of 800 ° C or lower, and low temperature decomposition brings many advantages. By using a catalytic method, the decomposition temperature can be remarkably lowered, and since the reactivity is increased, the size of the scrubber can be greatly reduced, and there is an advantage that the overall size can be made smaller. Further, decomposition at temperatures less than 800 deg.] C of so may reduce the operating costs of a continuous operation, the easy to ensure persistence systems, and complete inhibition of the thermal NO _X of the present in exhaust gas of N caused by _2, and the corrosion of equipment Can be significantly reduced.

Meanwhile, in order to reduce PFC emissions, attempts have been made to develop new replacement gases, but so far no alternative gas which is more effective than CF ₄ and which is better in production performance can be used as a gas for etching the substrate during the semiconductor manufacturing process. Therefore, CF _{4 is} used in most semiconductor manufacturing processes.

The restrictions on the use of PFC are expected to damage the semiconductor industry. Therefore, the necessity to develop a technique for recovering or decomposing PFC gas generated in a semiconductor manufacturing process is urgent.

Therefore, there is a need to develop a PFC processing process that is applicable to the semiconductor manufacturing process.

Meanwhile, the PFC catalytic decomposition reaction (Formula 1) is an endothermic reaction, and a representative example of the exothermic reaction of forming a gas product from a gaseous reactant using a catalyst is a water gas shift reaction represented by the following Formula 3.

The fuel reacts with oxygen (or air) and water vapor in a gasifier to produce a synthesis gas (integrated gasification combined cycle, IGCC; integrated gasification combined cycle). The synthesis gas of IGCC has a high pressure. The fuel gas of CO to CO ₂ may be converted to increase the concentration of hydrogen gas and CO ₂ as needed. The CO _{2 is} then separated and only hydrogen is used in gas-fired power generation, fuel cells or chemical feedstock.

That is, H ₂ can be produced from the fuel recombination and/or water gas shift reaction. For example, the hydrocarbon fuel is partially oxidized to produce a synthesis gas comprising hydrogen and carbon monoxide. The synthesis gas is converted into carbon dioxide and hydrogen by reacting carbon monoxide with water vapor (the following formula 3) via a water gas shift reaction in a WGS (water-gas shift) reactor.

Specifically, CO ₂ may also be removed using a solid adsorbent and/or an absorbent such as an alkali metal, an alkaline earth metal, a dry amine, and a Li-based adsorbent such as Li ₄ SiO ₄ and Li ₂ ZrO ₃ .

The solid adsorbent reacts with CO ₂ to become a stable compound, and can release CO ₂ under other conditions and regenerate into the original compound.

It is an object of the present invention to provide a device comprising at least two reaction modules connected in series, wherein each reaction module comprises a catalytic reactor in which a catalytic reaction takes place, and adsorption to the catalytic reactor without a separate cooling process a reactor for removing a catalytic reaction product with a solid adsorbent; and a catalytic reaction process using the apparatus to lower the reaction temperature and increase catalytic efficiency during the endothermic reaction, or even to have a high reaction rate during the exothermic reaction Maintain high reactant conversion at elevated temperatures.

A first aspect of the invention provides at least two inverses comprising a series connection a modular apparatus, wherein each reaction module includes a catalytic reactor that uses a catalyst to produce a gaseous product from a gaseous reactant; and an adsorption reactor that is coupled to the catalytic reactor without a separate cooling process, the adsorption reactor The gas product is removed in whole or in part by a solid adsorbent; and the gas system discharged from the adsorption reactor of the upstream module is introduced into the catalytic reactor of the downstream module.

A second aspect of the invention provides a chemical process for forming a gaseous product from a gaseous reactant using a catalyst, wherein the chemical process is performed in a first aspect of the apparatus.

A third aspect of the present invention provides a method of treating a perfluorochemical (PFC) in a device of a first aspect, wherein a hydrolysis reaction of a gas containing a perfluoro compound is performed by a catalyst in a catalytic reactor, and is acidic The hydrolyzate gas of the perfluoro compound of the gas is treated with an adsorbent in the adsorption reactor to remove all or a portion of the acid gas from the hydrolyzate gas of the perfluoro compound.

A fourth aspect of the present invention provides a method for producing calcium fluoride (CaF ₂ ) from a perfluoro compound (PFC) in a device of the first aspect, wherein a hydrolysis reaction of a gas containing a perfluoro compound is borrowed in a catalytic reactor It is carried out by a catalyst, and a hydrolyzate gas of a perfluoro compound containing HF is chemically reacted with a solid adsorbent in an adsorption reactor to form calcium fluoride (CaF ₂ ).

The fifth aspect of the present invention provides an acid gas adsorption reactor in which a gas-solid contact reaction is carried out in a fluid containing a gas containing an acid gas to be treated and a solid adsorbent for an acid gas, and the acid gas is to be treated The solid adsorbent partially or completely removed in the gas and used for the acid gas is separated and discharged, the adsorption reactor comprising: a cyclone, wherein the acid gas-containing gas to be treated is supplied in the form of a vortex for the acid gas The solid adsorbent is supplied to the upper portion, mixed in the vortex flow, and is contacted with the acid gas-containing gas to be treated, thereby adsorbing all or a part of the acid gas in the gas to be treated, and from the gas stream by accelerating centrifugal force and gravity Separating, colliding with the inner wall, and separating from the gas partially or completely removed by the acid gas system vortexed from the center by the vortex effect, and discharged to the lower portion of the reactor; the inlet of the acid gas-containing gas to be treated The inlet is disposed above the cyclone; the inlet for the adsorbent of the acid gas, the inlet being disposed above the cyclone a gas discharge outlet extending from the center of the lower portion of the cyclone to the outside of the cyclone for discharging a gas swirling upward from the center by a vortex effect of the cyclone; and an adsorbent for acid gas adsorbing the acid gas The discharge outlet is disposed at a lower portion of the cyclone.

A sixth aspect of the present invention provides a method of producing calcium fluoride (CaF ₂ ), wherein a gas containing HF forms calcium fluoride (CaF ₂ ) by an HF adsorbent in a fifth-stage acid gas adsorption reactor.

A seventh aspect of the invention provides a method of treating an acid gas, wherein In the acid gas adsorption reactor of the fifth aspect, the acid gas is treated with an acid gas adsorbent to remove all or a part of the acid gas.

The invention is described in detail below.

The present invention relates to a catalytic reaction process involving gaseous reactants and gaseous products and a subsequent process of using a solid adsorbent to remove gaseous products without heating/cooling and increasing/decreasing pressure to accelerate by balancing breakthroughs. The positive reaction rate of the catalytic reaction, and the temperature of the catalytic reaction process is lowered during the endothermic reaction or the reactant conversion of the catalytic reaction is increased during the exothermic reaction. However, in a single reactor equipped with a catalyst and a solid adsorbent, when the lifespan of the catalyst and the solid adsorbent are different, there arises a problem that the operation must be stopped to replace the catalyst and/or the solid adsorbent. In addition, it is difficult to supply a uniform adsorbent powder (for example, CaO powder) to a plurality of conduits. Further, CaO is produced only in the form of a powder, but cannot be formed in the form of agglomerates. Therefore, in the reactor filled with CaO powder, there is a problem that a pressure drop occurs.

In view of such problems, the inventors of the present invention designed a single one by separating the catalytic reaction product exclusion reaction into the reactor for the catalytic reaction and the reactor for the product exclusion reaction, and the reaction modules are connected in series three ways. Reaction module. As a result of computer simulations, it was found that the effect of temperature reduction during the endothermic reaction is possible (Fig. 3). This effect is expected to occur in the integrated reactor in the form of shell and shell (Fig. 1), in which the catalytic reaction takes place in the shell. And the product exclusion reaction takes place in the tube.

Fig. 3 is a computer simulation result of the performance of a regenerative catalytic system (RCS) using a single reaction module for performing catalytic decomposition reaction and product exclusion reaction and three reaction modules. That is, it was found that when the catalytic decomposition reaction and the product exclusion reaction in the series connection shown in FIG. 4 are three separate reaction modules, the equilibrium breakthrough effect system is shown by simultaneously performing the catalytic reaction/product elimination reaction. It is possible. It has also been found that adding more reaction modules can more closely simulate what happens in a single reactor environment.

Accordingly, it has been found that although the catalytic reaction for forming a gaseous product from a gaseous reactant proceeds to a chemical equilibrium in the upstream catalytic module of the module, it is catalyzed by a module connected to the upstream without a separate cooling process. The reaction uses a solid adsorbent to remove all or a portion of the adsorption reaction of the gaseous product to break the aforementioned chemical equilibrium, while allowing the catalytic reaction to occur spontaneously in the catalytic module of the downstream module; and via at least two catalytic reactors / The reaction module of the adsorption reactor is operated to perform such a cycle at least once, and as the number of cycles increases, i.e., close to the effect of simultaneous reaction/product elimination (balance breakthrough) in a single reactor.

Further, the inventors of the present invention found that when at least two reaction modules connected in series, preferably at least three reaction modules, are used, the hydrolysis reaction of the perfluoro compound (g) and the hydrofluoric acid formed from the hydrolysis reaction (HF) (g) The reaction to form calcium fluoride (CaF ₂ )(s) is sequentially performed in each module, which exerts HF (g) by reacting calcium fluoride (CaF ₂ )(s). The effect is as usual in a single reactor, and the positive reaction of PFC hydrolysis becomes advantageous due to the equilibrium breakthrough, and therefore, the hydrolysis reaction efficiency of the perfluoro compound can be improved.

The present invention is based on this finding.

Accordingly, the apparatus of the present invention includes at least two reaction modules connected in series, wherein each reaction module includes a catalytic reactor that uses a catalyst to generate a gaseous product from a gaseous reactant; and in the absence of a separate cooling process therebetween An adsorption reactor coupled to the catalytic reactor for removing all or a portion of the gaseous product with a solid adsorbent and introducing a gas system discharged from the upstream of the module's adsorption reactor into a catalytic module of the downstream module.

As used herein, the term "adsorption" in this context encompasses not only adsorption in a narrower sense, but also the concept of both absorption and sorption, as long as it is capable of removing a portion of the gaseous product of the catalytic reaction. Thus, the adsorption reactor/adsorbent can be an absorption reactor/absorbent or a sorption reactor/sorbent.

In the present invention, the solid adsorbent may be in the form of a powder, a shaped body having a shape, or a separation membrane. In addition, the solid adsorbent can adsorb a portion of the gaseous product and convert it to another compound, either physically or chemically. The mode adsorbs a portion of the gas product, or selectively removes a portion of the gaseous product via a separation membrane.

The reaction module according to the present invention comprises a catalytic reactor and an adsorption reactor. As illustrated in Figure 2, the catalytic or adsorption reactors can each independently be a detachable cartridge, or each independently can take the form of a membrane. Further, the reaction module equipped with the catalytic reactor and the adsorption reactor may be in an integrated form, such as a shell and tube reactor.

According to the present invention, the apparatus in which at least two reaction modules are connected in series can be cycled at least twice by repeating the catalytic reaction and the product exclusion reaction to increase the efficiency of the catalytic reaction via the equilibrium breakthrough.

The apparatus according to the present invention can be used to perform a chemical process for forming a gaseous product from a gaseous reactant using a catalyst.

For example, the device according to the invention can be used to treat perfluorinated compounds (PFCs). Specifically, the hydrolysis reaction of the gas containing the perfluoro compound is performed by using a catalyst in a catalytic reactor and treating the hydrolyzate gas of the perfluoro compound containing the acid gas using an adsorbent, and all or a part of the acid gas may be The adsorption reactor is removed from the perfluorocarbon hydrolyzate gas.

Furthermore, the device according to the invention can be used to produce calcium fluoride from perfluorinated compounds (PFC). Specifically, the hydrolysis reaction of the gas containing the perfluoro compound is performed using a catalyst in the catalytic reactor, and the hydrolyzate gas of the perfluoro compound containing HF can form calcium fluoride by the solid adsorbent in the adsorption reactor ( CaF ₂ ).

Further, the apparatus according to the present invention can be used to perform a water gas shift reaction, and carbon dioxide as a product thereof is removed by a solid adsorbent.

In each of the reaction modules of the apparatus according to the present invention, the operating conditions of each of the catalytic reactors can be set to 50% to 99%, preferably 65% to 95% of the maximum catalyst throughput per catalytic reactor. %, and more preferably executed from 70% to 90%.

For example, when the device operates two reaction modules, and the catalyst treatment amount of each reaction module is 80% of the maximum value, the total catalyst treatment amount (%) = the processing amount of the first reaction module (%) + The processing amount (%) of the second reaction module = (100 × 0.8) + (20 × 0.8) = 80 + 16 = 96 (%).

For example, when the device operates three reaction modules, and the catalyst treatment amount of each reaction module is 70% of the maximum value, the total catalyst treatment amount (%) = the processing amount of the first reaction module (%) ) + treatment amount of the second reaction module (%) + processing amount of the third reaction module (%) = (100 × 0.7) + (30 × 0.7) + (9 × 0.7) = 70 + 21 + 6.3 = 97.3 (%).

The reactant conversion efficiency is a function of the reaction temperature, so the operating temperature of the catalyst bed is determined when the reactant conversion efficiency is determined.

Therefore, the reaction temperature (for example, 750 ° C) required to achieve the same catalyst treatment amount (for example, 97%) in the catalytic reactor using one reaction module can be compared to when the catalytic reactor using at least two reaction modules is used. Reduced because the catalyst throughput of each reaction module (70% in the case of three reaction modules) is reduced, whereby the reaction temperature required for the catalytic reactor during the exothermic reaction can be reduced (eg, 650 ° C) ). Further, the thermal stability of the catalyst is reduced in the catalytic reaction performed at a high temperature, however, the present invention can extend the life of the catalyst by reducing the reaction temperature during the exothermic reaction by using a catalytic reactor of at least two reaction modules.

In the case of an exothermic reaction, the problem of a decrease in the conversion rate of the reactant which occurs when the reaction temperature is raised in order to increase the reaction rate can be solved by using a catalytic reactor of at least two reaction modules. That is, in the exothermic reaction, the reaction temperature required for the catalytic reactor can be increased while maintaining a high reactant conversion rate.

Further, when the catalyst component reacts with HF to form a metal fluoride, the specific surface area of the catalyst decreases, and the decomposition activity also decreases. Thus, the present invention can alleviate the reaction product from the catalyst (e.g., HF) by reducing the amount of catalyst treatment (e.g., 70% of the maximum) in each catalytic reactor, i.e., reducing the amount of reaction product produced by the catalyst. Catalyst Poisoning problem.

In order to solve the problem that the operation must be stopped to replace the catalyst and/or the solid adsorbent, the apparatus according to the present invention may further comprise a standby reaction module, which may be operated in a cyclically alternate manner while being replaced in the reaction module in which the operation is stopped. Catalyst and / or solid adsorbent (Figure 8).

For example, the valve is mounted on a conduit connecting the two reaction modules, on a conduit connected between the catalytic reactor and the adsorption reactor, or both, to control the flow direction of the gas via opening/closing, And even when the operation of a portion of the catalytic reactor, the operation of a portion of the adsorption reactor, or the operation of a portion of the reaction module is stopped in order to replace the catalyst or solid adsorbent, the catalytic reaction and the adsorption reaction may be in the remaining reaction modes connected in series. The group continues (Figures 4 and 8).

The invention is characterized in that the reaction modules are connected in series in at least two, preferably seven or less, and more preferably three to five. Specifically, from an economic point of view, the reaction modules are preferably operated in three series connections (Figs. 4 and 7).

When a catalytic reactor is included and at least two reaction modules of the adsorption reactor connected thereto are connected in series without using a separate cooling process, or when a solid powder adsorbent is used, from a commercial point of view, The preferred adsorption reactor system includes a cyclone to be moved by a solid adsorbent Except gas products (Figures 5 and 7).

Meanwhile, in order to solve the problem that the life of the catalyst of the catalytic reactor is different from the life of the solid adsorbent of the adsorption reactor, the adsorption reactor for removing the gas product using the solid adsorbent can be designed in such a manner that the solid adsorbent is continuously supplied. The adsorption reactor is adsorbed and the gaseous product is adsorbed and/or reacted with the gaseous product to vent the solid adsorbent from the adsorption reactor (Fig. 7). The adsorption reactor can be designed as a cyclone (Figure 5).

The cyclone uses the principle of providing a vortex to a fluid floating on a particle to separate particles from the gas stream by accelerating centrifugal force and gravity, colliding with the inner wall of the body, and falling, and the fluid vortexes upward from the center due to the vortex effect. Emissions (Figure 5).

The cyclone only needs space that causes the fluid to vortex and is simple and does not require any operating components. High-temperature gas and high-concentration gas treatment systems are possible, and there are not many restrictions on the installation position, and the range of use can be expanded when connected in series or in parallel.

As the gas containing the product formed in the catalytic reactor is vortexed to the cyclone, when the solid adsorbent is supplied to the upper portion of the cyclone, the solid adsorbent is mixed in the vortex flow of the product-containing gas and adsorbed product. Then, the solid adsorbent is separated from the gas stream by accelerating centrifugal force and gravity, collides with the inner wall, and is discharged to the adsorption reactor. And the gas whose gas product is partially or completely removed vortexes upward from the center due to the vortex effect. Specifically, it is preferred that the solid adsorbent is sprinkled on the upper portion of the cyclone while rotating. A nebulizer can be used for this purpose.

An apparatus for treating a perfluoro compound according to an exemplary embodiment of the present invention includes three reaction modules connected in series, wherein each reaction module includes a hydrolysis catalytic reaction of a perfluoro compound filled with a catalyst and operated at 650 ° C And a cyclone incorporating the exhaust gas from the previous hydrolysis catalytic reactor and the HF adsorbent particles.

The optimal module design for the configuration of the three reaction modules can be a shell-and-tube type 3-bed switching reactor.

Each reaction module is a shell-and-tube reactor in which the adsorption reactor can be in the form of a tube and the catalytic reactor can be in the form of a shell. As illustrated in Fig. 6, the tubular cyclone adsorption reactor can be integrated in a shell-shaped catalytic reactor to miniaturize the reaction module.

Furthermore, by using the reaction module, as illustrated in FIG. 7, a device for connecting at least two shell-and-tube type reaction modules in series may be assembled, wherein each reaction module includes a cyclone adsorption reactor.

Further, the present invention provides an acid gas adsorption reactor in which a fluid containing a solid adsorbent of an acid gas-containing gas and an acid gas to be treated Performing a gas-solid contact reaction in which the acid gas is partially or completely removed in the gas to be treated and the solid adsorbent of the acid gas is separated and discharged, the adsorption reactor comprising: a cyclone, wherein the acid gas to be treated is to be treated The gas is supplied in the form of a vortex, and the solid adsorbent of the acid gas is supplied to the upper portion, mixed in the vortex flow, and contacted with the acid gas-containing gas to be treated, thereby adsorbing all or a part of the acid gas in the gas to be treated, Separated from the gas stream by accelerated centrifugal force and gravity, colliding with the inner wall, separated from the gas which has partially or completely removed the acid gas from the center by the vortex effect, and discharged to the lower portion of the reactor; The inlet of the acid gas-containing gas is placed on the upper part of the cyclone; the inlet of the acid gas adsorbent is placed on the upper part of the cyclone; the gas discharge outlet extending from the center of the lower part of the cyclone to the outside of the cyclone Is used to discharge a gas that vortexes upward from the center by the vortex effect of the cyclone; and absorbs the acidity of the acid gas. The discharge outlet of the adsorbent of the gas is placed under the cyclone.

Specifically, it is preferred to spray the solid adsorbent of the acid gas on the upper portion of the cyclone while rotating while using the atomizer.

An acid gas system becomes an acidic gas upon contact with water, and non-limiting examples of acid gases include halogen, hydrogen halide, nitrogen oxide (NO _x ), sulfur oxide (SO _X ), acetic acid, sublimed mercury, hydrogen sulfide, carbon dioxide. Wait. Since the acid gas causes corrosion, it is preferably removed with an adsorbent. The acid gas adsorbent may be a salt of an alkali metal or an alkaline earth metal, preferably a salt of a metal of the same group as Ca, or a salt of a metal of the same group as Mg.

When the acid gas adsorption reactor according to the present invention is connected in series after the perfluorochemical decomposition reactor, the exhaust gas contained in the perfluorochemical decomposition reactor as a reaction product produced by the reaction with the Ca salt or the Mg salt is removed. The acidic substance in the medium. Therefore, drainage does not occur from the perfluorochemical decomposition reactor.

Non-limiting examples of the adsorbent that adsorbs the acid gas may be a calcium salt such as calcium oxide (CaO), calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca(OH) ₂ ), or the like. If the acid gas system HF, it can form water or carbon dioxide from the reaction with the calcium salt.

Further, the present invention provides a method of generating calcium fluoride, characterized in that the adsorption reactor according to the present invention in an acid gas, the gas containing HF HF sorbent is formed by calcium fluoride (CaF _2). Further, the present invention provides a method of treating an acid gas, characterized in that in an acid gas adsorption reactor according to the present invention, an acid gas is treated with an acid gas adsorbent to remove all or a part of the acid gas.

According to the present invention, when a reaction module is designed to separate a catalytic reaction product exclusion reaction into a reactor for catalytic reaction and a product exclusion reaction, and at least two reaction modules are connected in series, the catalytic reaction is carried out. Efficiency can be increased by balancing breakthroughs.

For example, according to the present invention, when at least two reaction modules including a catalytic reactor for PFC hydrolysis and an adsorption reactor for treating a hydrolyzate gas from a catalytic reactor with a solid adsorbent are connected in series, the decomposition temperature may be significantly decreased to 650 ℃ or less, and is advantageous in that the cost can be easily reduced operation of continuous operation, to ensure persistence of the system, and a complete inhibition of the thermal NO _{X 2,} resulting from the presence in the exhaust gas of N. Further, when the hydrolyzate gas is consumed, the positive reaction of hydrolysis becomes advantageous due to the equilibrium breakthrough, so that the efficiency of the hydrolysis reaction of the perfluoro compound is improved, and it is advantageous that the reactor can be made smaller due to an increase in reactivity. And there is an advantage in the energy efficiency of the entire process.

200‧‧‧reactor

201‧‧‧HF adsorbent

202‧‧‧Second compartment

203‧‧‧ Catalyst

204‧‧‧First compartment

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a shell and tube reactor for treating a perfluoro compound exhibiting a balance breakthrough.

2 is a schematic diagram showing a reaction process when three reaction modules including a catalyst and an adsorbent are used, according to an exemplary embodiment of the present invention.

Figure 3 is a computer simulation of the RCS performance of a single CF ₄ catalytic decomposition reactor and three reaction module reaction separation configurations.

Figure 4 is a schematic diagram showing a high efficiency PFC exclusion process based on series.

Figure 5 is a schematic view of a general cyclone.

Figure 6 is a schematic illustration of an integrated apparatus for a PFC decomposition RCS reactor and a cyclone reduction reactor.

Figure 7 is a schematic illustration of a high efficiency PFC exclusion unit via catalytic decomposition/HF removal and its fluid paths connected in series.

Figure 8 shows a schematic diagram of three or four reaction modules including a catalyst and an adsorbent operating in a cyclically alternating manner in accordance with the present invention.

Hereinafter, the exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which can be easily accomplished in the technical field to which the present invention pertains.

As a representative reaction combining the catalytic reaction with the exclusion reaction of the catalytic reaction product, there is a perfluoro compound treatment process. Accordingly, the exemplary embodiments of the present invention will be described in detail based on the perfluoro compound treatment process, but the invention is not limited thereto.

The reaction module used in the PFC processing apparatus according to an exemplary embodiment of the present invention includes: a catalytic reactor that performs a hydrolysis reaction using a catalyst containing a perfluoro compound; and an adsorption reactor that is not cooled separately In the case of the process, all or a part of the hydrolyzate of the perfluoro compound is removed by treating the hydrolyzate gas of the perfluoro compound discharged from the catalytic reactor with a solid adsorbent.

Therefore, the PFC processing apparatus including at least two reaction modules according to the present invention is a dry type PFC decomposition apparatus which does not have a drain.

As an example of a gaseous reactant subjected to a catalytic reaction, a "perfluorochemical" (PFC) includes a carbon-containing perfluoro compound (PFC) containing at least two fluorine atoms (F), a nitrogen-containing perfluoro compound (PFC), and sulfur. Perfluorinated compounds (PFC). Carbon-containing PFCs contain not only saturated and unsaturated aliphatic components, such as CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₂ F ₄ , C ₂ F ₆ , C ₃ F ₆ , C ₃ F ₈ , C ₄ F ₈ , C ₄ F ₁₀ and the like, and contains cyclic aliphatic and aromatic perfluorinated carbons. The nitrogen-containing PFC typically comprises NF ₃ and the sulfur-containing PFC comprises SF ₄ , SF _{6 ,} and the like. However, in the present case, the perfluorochemical (PFC) can be extended to compounds which can be decomposed using a catalyst to form a gaseous product such as HF, and such compounds are also within the scope of the invention.

For example, a PFC treatment process by a catalytic decomposition method treats various gases discharged from a PFC collection tube via an alkali metal scrubber that processes an acid gas, and removes a regenerated catalytic system by a hydrolysis reaction represented by the following formula PFC in the system (RCS).

CF ₄ +2H ₂ O→CO ₂ +4HF CHF ₃ +(1/2)O ₂ +H ₂ O→CO ₂ +3HF C ₂ F ₆ +3H ₂ O+(1/2)O ₂ →2CO ₂ +6HF SF ₆ +3H ₂ O→SO ₃ +6HF

The acid gas containing hydrofluoric acid (HF) is removed via an acid gas scrubber and then discharged. However, hydrofluoric acid produced by hydrolysis causes severe corrosion problems in RCS and subsequent processes, and therefore, process design using expensive materials is often required.

The catalyst decomposing CF ₄ can decompose most of the PFC contained in the exhaust gas and can convert the carbon constituting the perfluoro compound to CO ₂ , and although the catalyst can be mainly used for treating exhaust gas generated in a semiconductor process, the catalyst is not only the catalyst It can be used in semiconductor processes, and can be used in processes or factories for manufacturing PFCs or PFCs as cleaning agents, etchants, solvents, reactive materials, and the like.

Most applicable decomposition catalyst based solid acid catalyst for catalyzing the reaction of perfluorinated compounds, the most widely user wherein Al ₂ O ₃ catalyst system. Further, as a catalyst for the hydrolysis reaction of the perfluoro compound, a catalyst having a spinel structure having an AB ₂ O ₄ composition and/or an aluminum phosphate catalyst can be used.

A catalyst having a spinel structure can be prepared by coprecipitation and an incipient wetness method.

Coprecipitation is a method in which two metal salts in the form of nitrate to be coprecipitated are dissolved in water, and then the pH is adjusted for coprecipitation, followed by a drying and calcination process to treat the substances. Conversion to a catalyst having a spinel structure. For coprecipitation, Ni, Zn or Ma can be used as the A metal, and Al or Cr can be used as the B metal.

When the B metal constituting the spinel is insoluble, and the required amount of the A metal precursor to be supported corresponding to the pore volume of the B metal oxide is dissolved in water, an incipient wetness method may be used, followed by drying and calcination. Specifically, drying can be performed at 120 ° C, and calcination can be performed at 700 ° C. For the A metal, Zn, Ni, Pd, Ti, Sn, Co, Zr, Ce, or the like can be used, and for the B metal, alumina can be used. For example, as the catalyst, a material composed of 80% by weight of alumina (Al ₂ O ₃ ) and 20% by weight of nickel oxide (NiO) can be used.

A phosphoric acid-based catalyst comprising aluminum uses evaporation by the metal salt Al(NO ₃ ) ₃ to be supported. 9H ₂ O, and NH ₄ H ₂ PO ₄ was prepared in the desired ratio are dissolved in water, and by the evaporation of water as a solvent. Further, the catalyst produced after the evaporation can be dried at 180 ° C and calcined at 800 ° C.

Meanwhile, a non-limiting example of a solid adsorbent capable of adsorbing HF may be calcium oxide (CaO), calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca(OH) ₂ ), or a combination thereof.

When the HF adsorbent is calcium oxide (CaO) and/or calcium carbonate (CaCO ₃ ), water or carbon dioxide can be formed together with calcium fluoride by the following reaction.

CaO+2HF→CaF ₂ +H ₂ O CaCO ₃ +2HF→CaF ₂ +H ₂ O+CO ₂

An apparatus for treating a perfluorochemical (PFC) according to an exemplary embodiment of the present invention includes at least two reaction modules connected in series, wherein each reaction module includes: a catalytic reactor for using a perfluoro compound The catalyst of the gas performs the hydrolysis reaction; and the adsorption reactor removes the hydrolyzate of the perfluoro compound by treating the hydrolyzate gas of the perfluoro compound discharged from the catalytic reactor by using a solid adsorbent without a separate cooling process All or part of it; and the gas system discharged from the adsorption reactor of the upstream module is introduced into the catalytic reactor of the downstream module.

The hydrolysis reaction between PFC and water is an endothermic reaction, and the higher the temperature, the faster the decomposition of PFC can be performed because a spontaneous reaction which is prone to decomposition can be induced. However, high temperatures reduce the thermal stability of the catalyst.

That is, the operating conditions of 500 ° C to 800 ° C are too high temperature conditions, so that the catalyst cannot be long without physical or chemical changes. Maintaining activity indirectly and ensuring the durability of the catalyst is the biggest obstacle to be solved. Specifically, the development of a catalyst having a durability in a reaction atmosphere of 500 ° C to 800 ° C in which HF and water vapor are produced as by-products has attracted commercial attention.

In the catalytic decomposition reaction of the PFC of the present invention, the internal temperature of the reactor may preferably be from 600 ° C to 750 ° C, more preferably from 600 ° C to 700 ° C, and most preferably from 650 ° C.

In a conventional reactor for treating a perfluoro compound, the reaction temperature during the hydrolysis reaction of the perfluoro compound is a temperature at which most perfluoro compounds can be hydrolyzed; that is, a temperature of about 750 ° C is required as exhibiting about 100%. The temperature of the decomposition rate. However, according to the present invention, when the hydrolysis reaction of the perfluoro compound and the reaction of hydrofluoric acid (HF) generated by the hydrolysis reaction to form calcium fluoride (CaF ₂ ) are continuously performed, if at least two reactions are used for the reactions The module, preferably performed using three reaction modules, will exert the effect of consuming HF via the reaction to form calcium fluoride (CaF ₂ ), as in a single reactor. Therefore, the efficiency of the hydrolysis reaction can be improved, and even at a temperature of about 600 ° C, the decomposition rate can be 85% or more, and at a temperature of about 650 ° C, the decomposition rate can be 95% or higher (Fig. 3). . Therefore, the present invention can reduce the internal reactor temperature and can achieve an energy saving effect by this heat reduction. Therefore, the hydrofluoric acid outflow can be prevented in the RCS, the RCS efficiency can be maximized, and the life of the catalyst can be prolonged.

Water can be introduced from the outside into the interior of the reactor to perform a hydrolysis reaction in the catalytic reactor. Water can be supplied via a separate configuration source external to the reactor, and prior to introduction into the reactor, water can be heated via a heat exchanger and supplied as water vapor. Preferably, pure water is used as the water supplied to the inside of the reactor, and the supply amount can be adjusted in view of the hydrolysis reaction formula.

Water vapor is included in the water vapor/PFC molar ratio in the range of 1 to 100, and the PFC can be decomposed using oxygen and water vapor in the range of 0% to 50% without the catalyst being passivated. If the content of water vapor exceeds the above range, the reactivity is lowered.

Meanwhile, since the PFC-containing exhaust gas discharged from the semiconductor manufacturing industry using PFC contains a processing gas other than oxygen, nitrogen, water vapor, or the like, the exhaust gas treatment process may include a plurality of steps. Therefore, before the decomposition and elimination of the PFC, the decane gas component which is a process gas which can be included in the exhaust gas, for example, SiH ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , SiF _{4 ,} etc., and a halogen gas component such as HCl, HF, HBr, F ₂ , Br _2, etc. may be separated or removed using water in advance. The off-gas containing the PFC that cannot be removed during the pretreatment process contains substantially oxygen and nitrogen, and in some cases may also include water vapor.

Therefore, according to the present invention, in order to decompose and remove the PFC using a catalyst in a temperature range of about 600 ° C to 750 ° C in a water vapor and an oxygen atmosphere, the pretreated exhaust gas must be preheated to the reaction temperature, and is prepared therein. In the process, water or steam may be added to the exhaust gas to control the amount of water vapor in the exhaust gas.

According to the present invention, the catalyst for performing the hydrolysis reaction in the catalytic reactor may itself be used in the form of particles which are prepared to decompose and remove the perfluoro compound in the exhaust gas or form in the form of spheres, agglomerates or rings. It is sized and then used to form a bed inside the catalytic reactor.

The catalytic bed formed inside the catalytic reactor can be operated in the form of a packed bed (or fixed bed) or a fluidized bed. When the PFC is decomposed and removed in the type of packed bed according to the present invention, the exhaust gas may flow from the upper portion to the lower portion of the catalytic bed, or conversely may flow from the lower portion to the upper portion. Meanwhile, in the case of a fluidized bed type catalytic bed, the exhaust gas flows from the lower portion of the catalytic bed to the upper portion, thereby fluidizing the catalyst particles, and decomposing and removing the PFC via contact with the catalyst particles in the flowing PFC component. And the remaining exhaust gas can be discharged through the upper portion.

When the exhaust gas flows through the catalytic reactor in the presence of water vapor, the PFC is hydrolyzed and removed by the catalyst, and the fluorine (F) component constituting the PFC is substantially converted into a fluoride such as HF, and depends on the type of the perfluoro compound. The carbon (C), nitrogen (N) or sulfur (S) components are converted into oxides such as CO ₂ , NO ₂ and SO ₃ , respectively.

In the HF adsorption reactor, HF can be removed by HF adsorbent, or HF can be fixed by forming calcium fluoride (CaF ₂ ) using an HF adsorbent. In the adsorption reactor, the HF adsorbent can produce water or carbon dioxide from the HF.

The HF adsorbent may contain a calcium salt capable of adsorbing HF to produce calcium fluoride, and non-limiting examples of calcium salts are calcium oxide (CaO), calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca(OH) ₂ ) or Its combination. The HF adsorbent can be a catalyst or reactant capable of producing water (H ₂ O) or carbon dioxide (CO ₂ ) from HF together with calcium fluoride (CaF ₂ ).

The HF adsorbent may be in the form of a powder or agglomerates, and in view of handling convenience, agglomerate forms are preferred. The agglomerates may form a cylindrical shape or a spherical shape, but are not limited thereto.

According to the present invention, in the apparatus in which at least two reaction modules are connected in series, the cycle of the catalytic hydrolysis reaction of the PFC and the HF adsorption reaction of removing the HF gas using the solid adsorbent can be repeated at least twice. Therefore, the efficiency of the catalytic reaction can be improved by balancing the breakthrough.

As shown in FIG. 4, a gas containing a perfluoro compound is introduced into the lower portion of the catalytic reactor, and is converted into a hydrolyzate gas of a perfluoro compound while being contacted with a catalyst in the reactor, and discharged to the upper portion of the catalytic reactor. The hydrolyzate gas of the perfluoro compound discharged from the catalytic reactor is introduced into the upper part of the HF adsorption reactor without a separate cooling process, and the hydrolyzate of the perfluoro compound is partially or completely removed by the adsorbent, and then can be sucked from A catalytic reactor with a reactor discharge and introduction into a downstream module.

Meanwhile, the cyclone principle can be applied to an adsorption reactor in which a hydrolyzate gas system of a perfluoro compound discharged from a catalytic reactor is treated with a solid adsorbent to remove all or a part of the hydrolyzate of the perfluoro compound. When a cyclone is used, a solid adsorbent in the form of a powder can be used.

For example, a cyclone principle for separating solid particles or droplets in a gas can be used to treat a gas containing HF using a solid HF adsorbent, wherein the HF is adsorbed and undergoes a chemical reaction with HF. Separated from the reacted and/or unreacted gases.

As the hydrolyzate gas of the perfluoro compound is vortexed to the cyclone, when the solid adsorbent is supplied to the upper portion of the cyclone, the solid adsorbent is mixed and adsorbed in the vortex flow of the perfluorocarbon hydrolyzate gas. A hydrolyzate of the compound (for example, an acid gas such as HF). Then, the solid adsorbent is separated from the gas stream by accelerating centrifugal force and gravity, collides with the inner wall, and partially or completely removes the residual gas of the hydrolyzate gas of the perfluoro compound from the center by the vortex effect. Separated, and the solid adsorbent can be discharged to the lower portion of the adsorption reactor.

For example, if the HF adsorption reactor is equipped with a cyclone, the solid HF adsorbent (solid reducing agent) can be continuously supplied, and CaF ₂ produced after the reaction can be continuously removed (Fig. 5 and Fig. 7).

Further, in the cyclone, separation can be performed by the difference in particle diameter or specific gravity of the solid particles in the gas, and by using this method, since the specific gravity of the solid adsorbent adsorbing HF becomes larger than that of the solid which does not adsorb HF The specific gravity of the HF adsorbent, so in the cyclone, due to the difference in specific gravity, the solid HF adsorbent adsorbing HF is separated from the solid HF adsorbent not adsorbing HF, whereby the solid HF adsorbent adsorbing HF is dropped to the cyclone. The lower, and non-adsorbed HF solid adsorbent can float in the cyclone together with the HF-containing gas to increase the reaction residence time. The classification cut point can be easily changed by controlling the centrifugal acceleration and dwell time of the cyclone.

In the present invention, in consideration of the high temperature of the PFC hydrolysis reaction and the HF adsorption reaction, the PFC decomposition catalytic reactor, the HF adsorption reactor, and the conduit therebetween may be made of stainless steel or inconel material. However, since the reaction temperature can be lowered as compared with the prior art, a material having lower heat resistance can be used.

Calcium fluoride (CaF ₂ ) is known as fluorite as a mineral. The pure calcium fluoride is white, and the calcium fluoride which fluorine escapes from the crystal lattice is purple due to the F center. This calcium fluoride has a good property of transmitting infrared rays or ultraviolet rays, and is widely used for the production of optical devices, and in addition to this use, calcium fluoride is also a useful source material as a raw material for solvents and fluorine compounds. Therefore, when the calcium fluoride producing method of the present invention is used, calcium fluoride, that is, fluorite, which is a useful source material from a perfluoro compound in an exhaust gas of a semiconductor process or the like, and which is effective in recycling resources, can be produced. There are advantages in terms.

Further, calcium fluoride can very easily treat calcium fluoride by using a mineral acid such as hydrochloric acid or sulfuric acid to produce a fluorine gas.

Referring to Figure 2, a reactor (200) for treating perfluorinated compounds according to an exemplary embodiment of the present invention includes a first compartment (204) containing a catalyst (203) for hydrolysis of a perfluorochemical (PFC); And a second compartment (202) comprising an HF adsorbent (201), wherein the reactor has a structure in which HF generated by hydrolysis of the perfluoro compound can be transferred from the first compartment (204) to the second compartment Between (202). Specifically, the first compartment (204) and the second compartment (202) are alternately stacked. The first compartment (204) and the second compartment (202) are installed in the form of a removable cartridge, and the catalyst for hydrolysis of the perfluoro compound can be separated from the reactor and then treated with a new catalyst. Instead, or regenerate the catalyst, it is then applied again to the reactor. Further, calcium fluoride as a final product can be easily separated and recovered from the reactor and used.

Hereinafter, the PFC processing process will be described using a PFC processing apparatus including three reaction modules as shown in FIG.

In the catalytic reactor of each reaction module, the operating conditions were adjusted to 70% of the maximum amount of catalyst treatment, and in the catalytic bed of each reaction module, the hydrolysis reaction of the perfluoro compound was at 650 ° C. Instead of at 750 ° C Execute. Further, in the shell-shaped catalytic reactor as a cyclone reactor, the adsorption reactor of each reaction module is installed in the form of a tube, and since there is no separate cooling process, it can be at the same temperature as the catalytic reactor. Intra-range operation.

In each reaction module, a gas containing PFC is introduced into the lower portion of the shell-shaped catalytic reactor and passed through the catalytic bed, and since 70% of the maximum amount of the catalyst treatment is after the 70% of the PFC is hydrolyzed, the untreated 30% of the PFC and the HF-containing hydrolyzate gas flow to the upper portion of the catalytic bed. The HF-containing hydrolyzate gas is vortexed into a tubular cyclone inside the casing of the catalytic reactor via a discharge unit for the HF-containing hydrolyzate gas installed in the upper portion of the catalytic reactor. Then, the CaO powder was sprinkled on the upper portion of the cyclone while rotating through an atomizer, and the CaO powder was mixed in a vortex flow to adsorb HF and generate CaF ₂ powder by a chemical reaction. CaF ₂ powder was separated by gravity and centrifugal acceleration in the vortex from the collision with the inner wall, and discharged to the adsorbing reactor section below. The PFC-containing untreated gas that has been vortexed from the center and has all or a portion of the HF gas removed by the vortex effect is separated from the CaF ₂ powder and then introduced into the catalytic module of the downstream module via a conduit. This chemical process cycle for each reaction module is performed in the first, second, and third reaction modules.

[Example] Example 1: Manufacturing three reaction modules for treating perfluorinated compounds

As shown in FIG. 4, three reaction modules are connected in series, wherein each reaction module includes a catalytic reactor for PFC decomposition and an adsorption reactor for HF. Specifically, a P/Al ₂ O ₃ commercial catalyst is packed in a catalytic reactor for PFC decomposition, and Si (40 wt.%)/CaO (60 wt%) as a reducing agent is filled in an adsorption reactor for HF. .%) beads.

Experimental Example 1: Investigation of the operational efficiency of three reaction module reactors for treating perfluorinated compounds

In order to evaluate the operational efficiencies of the three reaction module reactors for treating perfluorochemicals produced in Example 1, a hydrolysis reaction of a perfluoro compound and a fixed reaction of an HF solid reducing agent were carried out in each reactor, and The conversion of CF ₄ was examined at a reaction temperature of 700 °C. Specifically, as a condition for the hydrolysis reaction of the perfluoro compound, the CF ₄ injection concentration was set to 3,000 ppm, the water vapor injection concentration was set to 8%, and the remaining gas was nitrogen (N ₂ ). The space velocity is 2,000/h.

For comparison purposes and as a control, the conversion of CF _{4 was} examined using the same catalytic reactor and catalyst decomposed by PFC in the same reaction conditions as in Example 1 without the HF adsorption reactor.

₄ represents the conversion of CF CF CF ₄ ratio by hydrolysis of the initial conversion reaction of _4, and is calculated by the following equation.

Thus, when only the catalyst was used as a control, the CF ₄ conversion was 90%, and the CF ₄ conversion in Example 1 was 99%.

When performing the hydrolysis reaction of the perfluoro compound of Example 1 and three reactor modules generated when CaF ₂ HF adsorbed three cycles of chemical reactions, as reached by HF generated from the reaction of CaF ₂ of the HF is consumed in a single reactor The effect is, and the efficiency of the hydrolysis reaction can be improved to exhibit a decomposition rate of 99% at about 700 °C. Therefore, the internal temperature inside the reactor can be lowered, and since this heat is reduced, an energy saving effect can be achieved.

Claims (18)

A device comprising at least two reaction modules connected in series, each reaction module comprising: a catalytic reactor for producing a gaseous product from a gaseous reactant using a catalyst; and an adsorption reactor in the absence of a separate cooling process Connecting to the aforementioned catalytic reactor to remove all or a portion of the foregoing gaseous product using a solid adsorbent; and introducing a gas system discharged from the aforementioned adsorption reactor of the upstream module into the aforementioned catalytic reactor of the downstream module. The apparatus of claim 1, comprising at least two reaction modules connected in series, wherein the apparatus is for treating perfluorinated compounds (PFCs), comprising at least two reaction modules connected in series, each reaction module comprising a catalytic reactor for performing a hydrolysis reaction of a gas containing a perfluoro compound using a catalyst; and an adsorption reactor for treating the perfluorocarbon discharged from the catalytic reactor by a solid adsorbent without a separate cooling process The hydrolyzate gas of the compound removes all or a portion of the hydrolyzate of the foregoing perfluoro compound; and the gas system discharged from the aforementioned adsorption reactor of the upstream module is introduced into the aforementioned catalytic reactor of the downstream module. The device of claim 1, comprising at least two reaction modules connected in series, comprising at least two reaction modules connected in series The foregoing apparatus improves the efficiency of the catalytic reaction by chemically balanced conversion by repeating the catalytic reaction in the catalytic reactor and recycling the product at least twice in the adsorption reactor. The apparatus of claim 1, comprising at least two reaction modules connected in series, wherein when the catalytic reaction is an endothermic reaction, the temperature of the reaction is the same as when a reaction module having the same reactant conversion rate is used. The temperature comparison is reduced, and when the catalytic reaction is exothermic, the reactant conversion is increased compared to the reactant conversion when a reaction module is used at the same reaction temperature. The apparatus of claim 1, comprising at least two reaction modules connected in series, further comprising an additional reaction module for operating the reaction module in a cyclical alternate manner while stopping any of the reactions The aforementioned catalyst or solid adsorbent is replaced in the module. A device comprising at least two reaction modules connected in series as claimed in claim 1, wherein the valve is installed in a conduit connecting the two reaction modules, and a conduit connected between the catalytic reactor and the adsorption reactor Or both, to control the flow direction of the gas via the on/off switch; to stop the operation of a part of the aforementioned catalytic reactor, to replace the operation of a part of the aforementioned adsorption reactor or the aforementioned reaction, in order to replace the aforementioned catalyst or solid adsorbent When one part of the module is operated, the aforementioned catalytic reaction and the aforementioned adsorption reaction are connected in series to the remaining reaction modes. Continue in the group. The apparatus as claimed in claim 1 comprising at least two reaction modules connected in series, wherein the aforementioned reaction modules in operation are connected in three series. A device comprising at least two reaction modules connected in series as claimed in claim 2, wherein a gas system containing a perfluoro compound is introduced into the catalytic reactor, and is contacted with the catalyst in the reactor to be converted into a perfluoro compound. Hydrolyzing the gas and discharging; the foregoing hydrolyzate gas of the perfluoro compound discharged from the foregoing catalytic reactor is introduced into the adsorption reactor without a separate cooling process, and partially or completely removed by the aforementioned adsorbent The aforementioned hydrolyzate of the perfluoro compound, and the remaining hydrolyzate gas is discharged from the aforementioned adsorption reactor to introduce the aforementioned catalytic reactor of the aforementioned downstream module. The apparatus according to claim 1, comprising at least two reaction modules connected in series, wherein the solid adsorbent is continuously supplied to the adsorption reactor, and after the gas product is adsorbed, the solid adsorbent is from the foregoing Emission in the adsorption reactor. The apparatus according to claim 1, comprising at least two reaction modules connected in series, wherein the adsorbent is calcium oxide (CaO), calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca(OH) ₂ ) or combination. A device comprising at least two reaction modules connected in series as claimed in claim 1, wherein the adsorbent is capable of adsorbing HF and chemically reacting with HF to form calcium fluoride (CaF ₂ ). The apparatus according to claim 1, comprising at least two reaction modules connected in series, wherein the adsorption reactor is a cyclone. The apparatus of claim 12, comprising at least two reaction modules connected in series, wherein the gas containing the product formed in the catalytic reactor is supplied to the cyclone in a vortex form while the side is When the solid adsorbent is supplied to the upper portion of the cyclone, the solid adsorbent is mixed in the gas stream of the vortex containing the gas of the foregoing product to adsorb the product, and is separated from the gas stream by accelerating centrifugal force and gravity, and The wall collides and separates from the remaining gas vortexed upward from the center by the vortex effect, wherein the aforementioned product is partially or completely removed, thereby discharging the aforementioned solid adsorbent to the lower portion of the aforementioned adsorption reactor. The apparatus according to claim 12, comprising at least two reaction modules connected in series, wherein the solid adsorbent is supplied and sprinkled on the upper portion of the cyclone when rotated. A device comprising at least two reaction modules connected in series as claimed in claim 1, wherein the reaction module is a shell-and-tube reactor, the adsorption reactor is in the form of a tube and the catalytic reactor is in the form of a shell. A chemical process for forming a gaseous product from a gaseous reactant using a catalyst, wherein the foregoing chemical process is carried out in a device comprising at least two reaction modules connected in series as recited in any one of claims 1 to 15. One for inclusion as recited in any one of claims 1 to 15 A method of treating perfluorinated compounds (PFCs) in a device in which at least two reaction modules are connected in series, wherein a hydrolysis reaction of a gas containing a perfluoro compound is carried out by a catalyst in the aforementioned catalytic reactor, and the aforementioned all of the acid gas is contained The hydrolyzate gas of the fluorine compound is treated with an adsorbent in the aforementioned adsorption reactor to remove all or a part of the aforementioned acid gas from the aforementioned hydrolyzate gas of the perfluoro compound. A method for producing calcium fluoride (CaF ₂ ) from perfluorinated compounds (PFCs) in a device comprising at least two reaction modules connected in series as recited in any one of claims 1 to 15, which comprises The hydrolysis reaction of the gas of the perfluoro compound is carried out by the catalyst in the catalytic reactor, and the hydrolyzate gas of the perfluoro compound containing the HF described above is chemically reacted with the solid adsorbent in the adsorption reactor to form fluorine. Calcium (CaF ₂ ).