US20010001652A1

US20010001652A1 - Process for treating flourine compound-containing gas

Info

Publication number: US20010001652A1
Application number: US09/005,006
Authority: US
Inventors: Shuichi Kanno; Toshiaki Arato; Shinzo Ikeda; Takeshi Yasuda; Hisao Yamashita; Shigeru Azuhata; Shin Tamata; Kazuyoshi Irie
Original assignee: Hitachi Ltd
Current assignee: Hitachi Ltd
Priority date: 1997-01-14
Filing date: 1998-01-09
Publication date: 2001-05-24
Also published as: US20060120938A1; US20040047784A1; US20040067186A1; US6855305B2; US6942841B2; US20060093547A1; US7347980B2; US20040047786A1; US20040067185A1

Abstract

A gas stream containing at least one fluorine compound selected from the group consisting of compounds of carbon and fluorine, compounds of carbon, hydrogen and fluorine, compounds of sulfur and fluorine, compounds of nitrogen and fluorine and compounds of carbon, hydrogen, oxygen and fluorine is contacted with a catalyst comprising at least one of alumina, titania, zirconia and silica, preferably a catalyst comprising alumina and at least one of nickel oxide, zinc oxide and titania in the presence of steam, thereby hydrolyzing the fluorine compound at a relatively low temperature, e.g. 200°-800° C., to convert the fluorine of the fluorine compound to hydrogen fluoride.

Description

BACKGROUND OF THE INVENTION

1) Field of the Invention

The present invention relates to a process for efficient decomposition treatment of a gas containing fluorine compounds such as C ₂F₆, CF₄, C₃F₈, C₄F₈, CHF₃, SF₆, NF₃, etc. at a low temperature.

2) Related Art

Fluorine compound gases such as CF ₄, C₂F₆, etc. are used in a large amount as a semiconductor etchant, a semiconductor cleaner, etc. However, it was found that these compounds, once discharged into the atmosphere, turn into warming substances causing global warming. Post-treatment of these compounds after their use would be subject to a strict control in the future.

Compounds having a high fluorine (F) content as a molecule constituent such as CF ₄, C₂F₆, etc. have a higher electronegativity of fluorine and thus are chemically very stable. From this nature it is very hard to decompose such fluorine compounds, and it is thus in the current situations that no appropriate processes for such decomposition treatment are not available yet.

JP-B-6-59388 (U.S. Pat. No. 5,176,897) discloses a TiO ₂—WO₃catalyst for hydrolysis of organic halogen compounds. The catalyst contains 0.1 to 20% by weight of W on the basis of TiO₂(i.e. 92% to 99.96% of Ti by atom and 8 to 0.04% by atom of W) and has a decomposition rate of 99% at 375° C. for a duration of 1,500 hours in treatment of CCl₄in ppm order. JP-B-6-59388 suggests that organic halogen compounds having a single carbon atom, such as CF₄, CCl₂F₂, etc. can be decomposed, but shows no examples of decomposition results of fluorine compounds.

JP-A-7-80303 discloses another Al ₂O₃—ZrO₂—WO₃catalyst for decomposition of fluorine compound gases. The catalyst is directed to combustion-decomposition of CFCs (chlorofluorocarbons) and has a decomposition rate of 98% for a duration of 10 hours in treatment of CFC-115 (C₂ClF₅) by combustion-decomposition reaction at 600° C. The disclosed process needs addition of hydrocarbons such as n-butane, etc. as a combustion aid, resulting in a higher treatment cost. Among organic halogen compounds to be treated, fluorine compounds are less decomposable than chlorine compounds. Furthermore, the more the carbon atoms of organic halogen compound, the less decomposable. Decomposition of compounds consisting only of carbon and fluorine such as C₂F₆, etc. are much less decomposable than CFC-115, but no examples of decomposition results of such compounds are shown therein.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a process for efficient decomposition treatment of compounds of carbon and fluorine, compounds of carbon, hydrogen and fluorine, compounds of sulfur and fluorine, compounds of nitrogen and fluorine and even compounds of carbon, hydrogen, fluorine and oxygen such as C ₂F₆, CF₄, C₃F₈, C₄F₈, CHF₃, SF₆and NF₃.

The present invention provides a process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing at least one fluorine compound selected from the group consisting of compounds of carbon and fluorine, compounds of carbon, hydrogen and fluorine, compounds of sulfur and fluorine, compounds of nitrogen and fluorine and compounds of carbon, hydrogen, oxygen and fluorine with a catalyst containing at least one of alumina, titania, zirconia and silica in the presence of steam, thereby hydrolyzing the fluorine compound to convent fluorine of the fluorine compound to hydrogen fluoride.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram showing a process for treating a fluorine compound-containing gas according to one embodiment of the present invention. [0010]
FIG. 2 is a graph showing performances of various catalysts for decomposing a fluorine compound. [0011]
FIG. 3 is a graph showing performances of various catalysts for decomposing a fluorine compound. [0012]
FIG. 4 is a graph showing performances of various catalysts for decomposing a fluorine compound. [0013]
FIG. 5 is a graph showing performances of various catalysts for decomposing a fluorine compound. [0014]
FIG. 6 is a graph showing performances of various catalysts for decomposing a fluorine gas. [0015]
FIG. 7 is a graph showing performance of catalysts with various composition ratios for decomposing a fluorine gas. [0016]
FIG. 8 is a graph showing performance of catalysts with various composition ratios for decomposing a fluorine gas. [0017]
FIG. 9 is a graph showing relations between reaction temperature and decomposition rate of various fluorine compounds. [0018]
FIG. 10 is a graph showing relations between reaction time and decomposition rate of a fluorine compound. [0019]
FIG. 11 is a graph showing relations between reaction temperature and decomposition rate of CHF[0020] ₃, CF₄and C₄H₈by an Al₂O₃—ZnO catalyst.
FIG. 12 is a graph showing relations between reaction temperature and decomposition rate of SF[0021] ₆and C₃F₈by an Al₂O₃—NiO catalyst.
FIG. 13 is a graph showing relations between reaction temperature and decomposition rate of C[0022] ₄F₈by an Al₂O₃—NiO—ZnO catalyst.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As a result of extensive studies on development of catalysts for decomposition of fluorine compound-containing gases, the present inventors have found that catalysts must contain a metallic component capable of forming an appropriately strong bond with fluorine as the nature of catalysts, and further have found that catalysts containing a metallic component having a higher fluoride formation enthalpy show a higher decomposition activity particularly in case of compounds consisting of carbon and fluorine, because molecules of such compounds are stable by themselves. Formation of too stable a bond will gradually lower the decomposition activity of catalysts, because fluorine compounds are less releasable from the catalyst surface, whereas too weak a bonding force will not attain a satisfactory decomposition rate. C[0023] ₂F₆, one of gases to be treated according to the present invention, is a compound of poor reactivity because of a higher intramolecular force, and it is said that a temperature of 1,500°to 2,000°C. is required for combustion of such a gas.
As a result of tests on various catalysts, the present inventors have found that catalysts of alumina (Al[0024] ₂O₃), titania (TiO₂), zirconia (ZrO₂), silica (SiO₂), a mixture of titania and zirconia, a mixture of alumina and magnesia (MgO), a mixture of alumina and titania, or a mixture of alumina and silica can hydrolyze fluorine compounds, and further have found that the fluorine compounds can be decomposed at a lower temperature than 800° C. thereby.
Among these catalysts, it has been found that a catalyst based on a mixture of alumina and titania has the highest activity and particularly a catalyst comprising 75 to 98% by weight of alumina and 25 to 2% by weight of titania has a particularly high activity. It can be presumed that the alumina of the catalyst based on a mixture of alumina and titania acts to attract fluorine compounds onto the catalyst, whereas the titania acts to depart the fluorine compounds from the catalyst surface. [0025]
The present inventors further have found that catalysts based on the mixture of alumina and titania further containing at least one member selected from the group consisting of zirconia, tungsten oxide, silica, tin oxide, ceria, bismuth oxide, nickel oxide and boron oxide can hydrolyze fluorine compounds. It has been found that above all the catalyst containing zirconia has a higher decomposition activity on fluorine compounds. It has been further found that the content of at least one member selected from the group consisting of zirconia, tungsten oxide, silica, tin oxide, ceria, bismuth oxide, nickel oxide and boron oxide is preferably 0.1 to 10% by weight on the basis of sum total of alumina and titania and particularly the content of zirconia is preferably 2 to 10% by weight on the basis of sum total of alumina and titania. It seems that these additive members exist in the form of single oxides or composite oxides and contribute to an improvement of decomposition activity on fluorine compounds. [0026]
In catalyst preparation, it has been found that it is preferable to use boehmite for alumina raw material and a titanium sulfate solution for a titania raw material. It has been confirmed that there are sulfate ions, SO[0027] ₄ ²⁻, in the catalysts prepared from the titanium sulfate solution and the decomposition activity on fluorine compounds can be improved by the presence of sulfate ions. It has been found that addition of sulfuric acid is preferable during the catalyst preparation.
The present inventors further tested catalysts containing other components besides alumina and titania, specifically catalysts containing alumina and one of zinc oxide (ZnO), nickel oxide (NiO), iron oxide, tin oxide (SnO[0028] ₂), platinum (Pt), cobalt oxide, zirconia (ZrO₂), ceria (CeO₂) and silica (SiO₂). As a result, it has been found that these catalysts can hydrolyze fluorine compounds and particularly catalysts containing zinc oxide or nickel oxide have a higher activity than catalysts based on the mixture of alumina and titania. It has been further found that catalysts comprising alumina and nickel oxide, admixed with sulfuric acid during the catalyst preparation have a higher activity than the catalyst without admixing with sulfuric acid. It has not been confirmed in which forms iron oxide or cobalt oxide of the catalysts containing the iron oxide or the cobalt oxide exists. Probably it seems to exist in the form of Fe₂O₃or Co₃O₄.
It has been found that the catalysts comprising alumina and one of Zinc oxide, nickel oxide, iron oxide, tin oxide, cobalt oxide, zirconia, ceria and silica as other components preferably contain 50 to 1% by atom of one metallic element of the other components, the balance being aluminum of the alumina, and the content of platinum is preferably 0.1 to 2% by weight on the basis (100% by weight) of alumina. It has been further found that these catalysts can further contain sulfur and the content of sulfur is preferably 0.1 to 20% by weight on the basis of the alumina catalyst. [0029]
Fluorine compounds to be treated according to the present invention include, for example, CF[0030] ₄, C₂F₆, C₃F₈, C₄F₈, C₅F₈, CHF₃, CH₂F₂, CH₃F, C₂HF₅, C₂H₂F₄, C₂H₃F₃, C₂H₄F₂, C₂H₅F, CH₂OCF₂, SF₆, NF₃, etc., among which CF₄, C₂F₆, C₃F₈, C₄F₈, CHF₃, SF₆and NF₃are used as etchants for semiconductors and CF₄, C₂F₆and NF₃are used as cleaners for semiconductors.
According to the present invention, all of these fluorine compounds can be hydrolyzed. Hydrolysis temperature depends upon kinds of fluorine compounds and catalyst components, and is usually 2000 to 800° C., preferably 400°to 800° C. According to the present process fluorine of fluorine compound gases can be converted to hydrogen fluoride. [0031]
Hydrolysis of fluorine compounds can proceed typically according to the following reaction equations: [0032]
CF₄+2H₂O→CO₂+4HF (1)
C₂F₆+3H₂O→CO+CO₂+6HF (2)
CHF₃+H₂O→CO+3HF (3)
SF₆+3H₂O→SO₃+6HF (4)
NF₃+3/2H₂O→NO+1/2O₂+3HF (5)
Hydrolysis according to reaction equations (2) and (3) can produce CO. The present catalysts also have an ability to oxidize CO, and thus CO can be further oxidized to CO[0033] ₂in the presence of oxygen.
The present invention provides a process for hydrolyzing a fluorine compound-containing gas by a catalyst comprising at least one member selected from the group consisting of alumina, titania, zirconia, silica, a mixture of titania and zirconia, a mixture of alumina and magnesia, a mixture of alumina and titania and a mixture of alumina and silica. [0034]
Furthermore, the present invention provides a process for treating a fluorine-containing gas by a catalyst comprising alumina and titania, further containing 0.1 to 10% by weight, on the basis of alumina and titania, of one of zirconia, tungsten oxide, silica, tin oxide, ceria, bismuth oxide, nickel oxide and boron oxide. [0035]
Still furthermore, the present invention provides a process for treating a fluorine compound-containing gas by a catalyst comprising alumina and at least one member selected from the group consisting of zinc oxide, nickel oxide, iron oxide, tin oxide, cobalt oxide, zirconia, ceria, silica and platinum as other components, a ratio of aluminum of alumina to the metallic element of at least one of other components by atom is 50 to 99:50-1, and further by the catalyst further containing 0.1 to 20% by weight of sulfur on the basis of the alumina. These additive components can contribute to improvement of decomposition activity of the catalysts on fluorine compounds in the form of single oxides or composite oxides with aluminum and/or other additive components. [0036]
Still furthermore, the present invention provides a process for converting fluorine in a gas to hydrogen fluoride, which comprises contacting a gas stream containing a fluorine compound comprising C[0037] ₂F₆with a catalyst comprising a mixture of alumina and titania and having a weight ratio of alumina to titania being 65 to 90:35 to 10, thereby hydrolyzing the fluorine compounds. Still furthermore, the present invention provides a process for converting fluorine in a gas stream to hydrogen fluoride, which comprises contacting a gas stream comprising a fluorine compound comprising C₂F₆with a catalyst comprising a mixture of alumina, titania and zirconia and having a weight ratio of alumina to titania being 65 to 90:35 to 10 and a weight ratio of zirconia to sum total of alumina and titania being 2 to 10:98 to 90, thereby hydrolyzing the fluorine compound.
Still furthermore, the present invention provides a process for converting fluorine in a gas stream to hydrogen fluoride, which comprises contacting a gas stream containing at least one fluorine compound selected from the group consisting of C[0038] ₂F₆, CF₄, C₄F₈and CHF₃with a catalyst comprising a mixture of alumina and zinc oxide and having an atomic ratio of aluminum to zinc being 90 to 70:10 to 30, thereby hydrolyzing the fluorine compound.
Still furthermore, the present invention provides a process for converting fluorine in a gas stream to hydrogen fluoride, which comprises contacting a gas stream containing at least one fluorine compound selected from the group consisting of C[0039] ₂F₆, CF₄, C₃F₈, CHF₃, NF₃and SF₆with a catalyst comprising a mixture of alumina and nickel oxide and having an atomic ratio of aluminum to nickel of 95 to 60:5 to 40, thereby hydrolyzing the fluorine compound.
Still furthermore, the present invention provides a process for converting fluorine in a gas stream to hydrogen fluoride, which comprises contacting a gas stream comprising a fluorine compound comprising C[0040] ₄F₈with a catalyst comprising a mixture of alumina, nickel oxide and zinc oxide, thereby hydrolyzing the fluorine compound.
Still furthermore, the present invention provides a process for converting fluorine in a gas stream to hydrogen fluoride, which comprises a hydrolysis step of contacting a gas discharged from a semiconductor-etching or cleaning step using a gas stream containing at least one fluorine compound selected from the group consisting of compounds of carbon and fluorine, compounds of carbon, hydrogen and fluorine, compounds of sulfur and fluorine, compounds of nitrogen and fluorine and compounds of carbon, hydrogen, oxygen and fluorine, after addition of air and steam to the gas, with a catalyst comprising at least one of alumina, titania, zirconia and silica, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas to hydrogen fluoride, as a poststep to the semiconductor-etching or cleaning step. [0041]
Still furthermore, the present invention provide a process for treating a fluorine compound-containing gas, which further comprises an alkaline washing step of contacting the gas from the hydrolysis step with an alkaline washing solution, thereby washing the gas as a poststep to the hydrolysis step. As the alkaline washing solution, there can be used conventional ones such as a solution of NaOH, Ca(OH)[0042] ₂, Mg(OH)₂, CaCO₃, etc., a slurry of Ca(OH)₂, etc.
In contacting of the gas stream containing a fluorine compound with the catalyst, the concentration of the fluorine compound in the gas stream is preferably 0.1 to 10% by volume, particularly preferably 0.1 to 3% by volume, and the space velocity is preferably 100 to 10,000 h[0043] ⁻¹, particularly preferably 100 to 3,000 h−¹. Space velocity (h⁻¹) is defined by reaction gas flow rate (ml/h)/catalyst volume (ml).
In the hydrolysis of the fluorine compound, it is desirable to add steam as a hydrogen source for hydrolysis to the gas stream so as to make the amount of hydrogen atoms (H) at least equal to the amount of fluorine atoms (F) contained in the fluorine compound, thereby making the fluorine atoms (F) of decomposition products into the hydrogen fluoride (HF) form that allows easy post-treatment. Hydrogen, hydrocarbons, etc. can be used as a hydrogen source besides the steam. In case of hydrocarbons as a hydrogen source, hydrocarbons can be combusted on the catalyst, thereby effectively reducing the heat energy to be supplied. [0044]
By adding an oxidizing gas such as oxygen, etc. to the reaction gas, oxidation reaction of CO can be carried out at the same time. When the oxidation reaction of CO is incomplete, the decomposition product gas is brought into contact with the CO oxidizing catalyst, after removal of HF from the decomposition product gas, to convert CO to CO[0045] ₂.
In the hydrolysis (decomposition) of fluorine compound, the reaction temperature is preferably about 200°to about 800° C. Above about 800° C., a higher decomposition rate can be obtained, but the catalyst will be rapidly deteriorated, and also the corrosion rate of apparatus structural materials will be abruptly increased, whereas below about 200° C. the decomposition rate will be lowered. [0046]
As the step of neutralizing and removing the formed HF, washing by spraying an alkaline solution is efficient and preferable because of less occurrence of clogging in pipings due to crystal deposition, etc. Bubbling of the decomposition product gas through the alkaline solution or washing with the alkaline solution through a packed column may be used for the neutralization and removal of the formed HF. Alternatively, HF can be absorbed in water, followed by treatment with an alkaline solution or slurry. [0047]
As the raw material for aluminum (Al) for preparing the present catalyst, γ-alumina and a mixture of γ-alumina and δ-alumina can be used besides boehmite. However, it is preferable to use boehmite as a raw material for Al to form an oxide through final firing. [0048]
As the raw material for titanium (Ti), titania sol, titanium slurry, etc. can be used besides titanium sulfate. [0049]
As the third metallic components for silica (Si), magnesium (Mg), zirconium (Zr), etc., their various nitrates, ammonium salts, chlorides, etc. can be used. [0050]
The present catalyst can be prepared by any of ordinary procedures for preparing catalysts, such as precipitation, impregnation, kneading, etc. [0051]
The present catalyst can be used as such or upon molding into a granular form, a honeycomb form, etc. by an desired molding procedure such as extrusion molding, tabletting, tumbling granulation, etc., or as a coating on ceramic or metallic honeycombs or plates. [0052]
Only a catalytic reactor for decomposing fluorine compounds and a facility for neutralizing and removing acid components in the decomposition product gas are required for an apparatus for carrying out the present process for treating fluorine compound-containing gas. [0053]
The present invention will be described in detail below, referring to Examples which are not limitative of the present invention. [0054]
FIG. 1 shows an example of using the present process for hydrolysis treatment of a fluorine gas in a cleaning step in a plasma CVD apparatus in the semi-conductor production process. [0055]
The plasma CVD apparatus is an apparatus for vapor depositing a SiO[0056] ₂film on a semiconductor wafer surface. Since the SiO₂film tends to deposit on the entire interior surfaces of the apparatus, and thus it is necessary to remove SiO₂depositions from unwanted surfaces. To clean the unwanted surface to remove SiO₂therefrom, gases containing fluorine compounds such as C₂F₆, CF₄, NF₃, etc. are used as a cleaning gas. Cleaning gas 1 containing these fluorine compounds is led to a CVD chamber to remove SiO₂under plasma excitation. Then, the chamber is flushed with a N₂gas 2, thereby diluting the cleaning gas to a desired lower fluorine compound concentration, and the diluted cleaning gas is discharged from the chamber. The discharged gas is admixed with air 3 to further lower the fluorine compound concentration by dilution with air 3 and the air-diluted discharged gas is further admixed with steam 4 and the resulting reaction gas 5 is led to a decomposition step, where the reaction gas is brought into contact with a catalyst at a desired space velocity (h⁻¹), which is defined by reaction gas flow rate (ml/h)/catalyst volume (ml) and at a desired temperature. In that case, the reaction gas may be heated or the catalyst may be heated by an electric oven, etc. The resulting decomposition gas 6 is led to an exhaust gas washing step, where the decomposition gas 6 is sprayed with an aqueous alkaline solution to remove acid components from the decomposition gas 6 and the resulting exhaust gas 7 freed from the acid components is discharged to the system outside.
CF[0057] ₄, C₂F₆and NF₃can be used as etchants for semiconductors, etc., and CHF₃, C₃F₆, SF₆and C₄F₈can be also used as etchants besides the above-mentioned fluorine compounds. These etchants can be treated and decomposed in the same manner as in FIG. 1 except that the cleaning step of FIG. 1 is only replaced with an etching step.
Activities or performances of various catalysts for composing fluorine compounds were investigated, and results thereof will be described below: [0058]

EXAMPLE 1

A C[0059] ₂F₆gas having a purity of 99% or more was diluted with air, and further admixed with steam to prepare a reaction gas. Steam for the admixture was prepared by feeding pure water into a reactor tube from the top at a flow rate of 0.11 ml/min. by a microtube pump and gasified. The reaction gas had a C₂F₆concentration of about 0.5%. Then, the reaction gas was brought into contact with various catalysts heated to 700° C. in a reactor tube at a space velocity of 3,000 h⁻¹. Heating of the catalyst was carried out by heating the reactor tube in an electric oven.
Reactor tube was an Inconel reactor tube having an inner diameter of 19 mm, where a catalyst bed was fixed at the center of the reactor tube and had an Inconel thermowell for a thermo couple, 3 mm in outer diameter, inside the catalyst bed. Decomposition product gas discharged from the catalyst bed was bubbled through an aqueous sodium chloride solution an then discharged as an exhaust gas. C[0060] ₂F₆decomposition rate was calculated by the following equation by determining concentration of C₂F₆in the reaction gas at the inlet to the reactor tube and concentration of C₂F₆in the decomposition gas at the outlet from the alkaline washing step by FID (flame ionization detector) gas chromatography and TCD (thermal conductivity detector) gas chromatography: $\begin{matrix} Decomposition \\ rate \end{matrix} = 1 - \frac{\begin{matrix} Concentration of discharged \\ fluorine compound \end{matrix}}{\begin{matrix} Concentration of fed \\ fluorine compound \end{matrix}} \times 100 (%)$
Catalyst 1:Al[0061] ₂O₃
Granular alumina (NKHD-24, trademark of a product commercially available from Sumitomo Chemical Co., Ltd., Japan) was pulverized, sieved to obtain a fraction of 0.5-1 mm grain sizes, followed by drying at 120° C. for 2 hours and firing (or calcining) at 700° C. for 2 hours. [0062]
Catalyst 2:TiO[0063] ₂
Granular titania (CS-200-24, trademark of a product commercially available from Sakai Chemical Industry Co., Ltd., Japan) was pulverized, sieved to obtain a fraction of 0.5-1 mm grain sizes, followed by drying at 120° C. for 2 hours and firing at 700° C. for 2 hours. [0064]
Catalyst 3:ZrO[0065] ₂
200 g of zirconyl nitrate was dried at 120° C. for 2 hours and fired at 700° C. for 2 hours. The resulting powders were placed in a mold and compression molded under a pressure of 500 kgf/cm[0066] ². The molded product was pulverized and sieved to obtain zirconia grains having grain sizes of 0.5-1 mm.
Catalyst 4:SiO[0067] ₂
Granular silica (CARIACT-10, trademark of a product commercially available from Fuji Silysia Co., Ltd., Japan) was pulverized and sieved to obtain a fraction of 0.5-1 mm grain sizes, followed by drying at 120° C. for 2 hours and firing at 700° C. for 2 hours. [0068]
Catalyst 5:TiO[0069] ₂—ZrO₂
Granular titania (CS-200-24) was pulverized to grain sizes of 0.5 mm and under. 100 g of the resulting powders was admixed with 78.3 g of zirconyl nitrate and kneaded while adding pure water thereto. After the kneading, the kneaded mixture was dried at 120° C. for 2 hours and fired at 700° C. for 2 hours. The resulting powders were placed in a mold and compression molded under a pressure of 500 kgf/cm[0070] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Ti:Zr=81:19 and in a weight ratio of TiO₂:ZrO₂=73.5 26.5.
Catalyst 6:Al[0071] ₂O₃—MgO
Granular alumina (NKHD-24) was pulverized to grain sizes of 0.5 mm and under. 100 g of the resulting powders were admixed with 56.4 g of magnesium nitrate and kneaded while adding pure water thereto. After the kneading, the kneaded mixture was dried at 120° C. for 2 hours and fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0072] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Mg=90:10 and in a weight ratio of Al₂O₃:MgO=91.9:8.1.
Catalyst 7:Al[0073] ₂O₃—TiO₂
Granular alumina (NKHD-24) was pulverized to grain sizes of 0.5 mm and under. 100 g of the resulting powders were admixed with 17.4 g of dried powders of a metatitanic acid slurry and kneaded while adding pure water thereto. After the kneading, the kneaded mixture was dried at 120° C. for 2 hours and fired at 700° C. for 2 hours. The resulting powders were placed in a mold and compression molded under a pressure of 500 kgf/cm[0074] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=90:10 and in a weight ratio of Al₂O₃:TiO₂=85.2:14.8.
Catalyst 8:Al[0075] ₂O₃—SiO₂
Granular alumina (NKHD-24) was pulverized to grain sizes of 0.5 mm and under. 100 g of the resulting powders were admixed with 13.2 g of dried powders of SiO[0076] ₂sol and kneaded while adding pure water thereto. After the kneading, the kneaded mixture was dried at 120° C. for 2 hours and fired at 700°C. for 2 hours. The resulting powders were placed in a mold and compression molded under a pressure of 500 mgf/cm². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Si=90:10 and in a weight ratio of Al₂O₃:SiO₂=88.3:11.7.
Test results of the above-mentioned [0077] catalysts 1 to 8 are shown in FIG. 2, from which it is evident that the Al₂O₃—TiO catalyst is preferable as a hydrolysis catalyst for a C₂F₆gas.

EXAMPLE 2

In this Example, influences of changes in composition ratios of alumina to titania in Al[0078] ₂O₃—TiO₂catalysts upon C₂F₆decomposition rate were investigated under the same test procedure and conditions as in Example 1. The results are shown in FIG. 4.
Catalyst 19:Al[0079] ₂O₃
Boehmite powders (PURAL SB, trademark of a product commercially available from Condea Co., Ltd.) were dried at 120° C. for 2 hours. 200 g of the resulting dried powders were fired at 300° C. for 0.5 hours and further fired at an elevated temperature of 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0080] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm, and tested. It was found that boehmite powders used as an alumina raw material had a higher catalytic activity than granular alumina.
Catalyst 20:Al[0081] ₂O₃—TiO₂
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were kneaded with 248.4 g of an aqueous 30% titanium sulfate solution, while adding about 200 g of pure water thereto. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0082] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=90:10 and in a weight ratio of Al₂O₃:TiO₂=85.65:14.35.
Catalyst 21:AlO[0083] ₃—TiO₂
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were kneaded with about 100 g of an aqueous solution containing 78.6 g of 30% titania sol in pure water. After the kneading, the kneaded mixture was dried at 120° C. for about 2 hours and then fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0084] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=91:9 and in a weight ratio of Al₂O₃:TiO₂=86.25:13.75.
It was found that the catalyst prepared from the titanium sulfate solution as a titanium raw material had the highest catalytic activity, probably because of the presence of sulfate ions SO[0085] ₄ ²⁻in the catalyst.

EXAMPLE 3

In this Example, influences of changes in composition ratios of Al[0086] ₂O₃to TiO₂in Al₂O₃—TiO₂catalysts upon C₂F₆decomposition rate were investigated under the same procedure and conditions as in Example 1.
Catalyst 22:Al[0087] ₂O₃—TiO₂
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 100 g of the resulting dried powders were kneaded with 82.4 g of an aqueous 30% titanium sulfate solution while adding about 120 g of pure water thereto. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0088] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=93:7 and in a weight ratio of Al₂O₃:TiO₂=90.0:10.0.
Catalyst 23:Al[0089] ₂O₃—TiO₂
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 100 g of the resulting dried powders were kneaded with 174.4 g of an aqueous 30% titanium sulfate solution while adding about 70 g of pure water thereto. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0090] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=87:13 and in a weight ratio of Al₂O₃:TiO₂=80.9:19.1.
Catalyst 24:Al[0091] ₂O₃—TiO₂
Boehmite powders (PURAL SB) were dried at 120°C. for one hour. 100 g of the resulting dried powders were kneaded with 392 g of an aqueous 30% titanium sulfate solution while adding the latter to the former. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0092] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=75:25 and in a weight ratio of Al₂O₃:TiO₂=65.4:34.6.
Activities of [0093] catalysts 19, 20 and 22-24 are shown in FIG. 5, from which is evident that the highest C₂F₆decomposition rate can be obtained at an alumina content of about 85% by weight.

EXAMPLE 4

In this Example, an influence of sulfuric acid during the preparation of the Al[0094] ₂O₃—TiO₂catalyst upon the C₂F₆decomposition rate was investigated. Catalyst 25:Al₂O₃—TiO₂
Boehmite powders (PURAL SB) was dried at 120° C. for one hour. 150 g of the resulting dried powders were kneaded with 58.5 g of 30% titania sol (CS-N, trademark of a product commercially available from Ishihara Sangyo Kaisha, Ltd., Japan) and an aqueous solution prepared by diluting 44.8 g of 97% sulfuric acid with 250 ml of pure water. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The resulting powders were placed into a mold and compression molded under a pressure of 500 kgf/cm[0095] ². The molded product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=91:9 and in a weight ratio of Al₂O₃:TiO₂=86.3:13.7.
Sulfate ions were present in the catalyst. Test conditions were the same as in Example 1, except that the space velocity was changed to 1,000 h[0096] ⁻¹. The test results revealed that a C₂F₆decomposition rate of 80% was obtained at a reaction temperature of 650° C.

EXAMPLE 5

In this Example, C[0097] ₂F₆decomposition rates were investigated by adding various components to the Al₂O₃—TiO₂catalysts. The catalysts were prepared as follows, but test procedure and conditions were the same as in Example 1.
Catalyst 9:Al[0098] ₂O₃—TiO₂
Granular alumina (NKHD-24) was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm, followed by drying at 120° C. for 2 hours. Then, the dried grains were impregnated with 176 g of an aqueous 30% titanium sulfate solution. After the impregnation, the grains were dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=90:10 and in a weight ratio of Al[0099] ₂O₃—TiO₂=85.1:14.9. The catalyst thus prepared was designated as catalyst A.
Catalyst 10:Al[0100] ₂O₃—TiO₂—ZrO₂
50 g of Catalyst A grains were impregnated with an aqueous solution of 6.7 g of zirconyl nitrate dihydrate in 38.4 g of H[0101] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:Zr=90:10:0.025 and in a weight ratio of Al₂O₃:TiO₂:ZrO₂=80.2:14.0:5.8.
Catalyst 11:Al[0102] ₂O₃—TiO₂—WO₃
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 6.5 g of ammonium paratungstate in H[0103] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:W=90:10: 0.025 and in a weight ratio of Al₂O₃:TiO₂:WO₃=76.6:13.4:10.0.
Catalyst 12:Al[0104] ₂O₃—TiO₂—SiO₂
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 7.5 g of 20 wt. % silica sol in H[0105] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of 90:10:0.025 and in a weight ratio of Al₂O₃:TiO₂:SiO₂=82.6:14.5:2.9.
Catalyst 13:Al[0106] ₂O₂—TiO₂—SnO₂
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 5.6 g of tin chloride dihydrate in H[0107] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:Sn=90 10:0.025 and in a weight ratio of Al₂O₃:TiO₂:SnO₂=79.1:13.9:7.0.
Catalyst 14:Al[0108] ₂O₃—TiO₂—CeO₂
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 10.9 g of cerium nitrate hexahydrate in H[0109] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:Ce=90:10:0.025 and in a weight ratio of Al₂O₃:TiO₂:CeO₂=78.4:13.7:7.9.
Catalyst 15:Al[0110] ₂O₃—TiO₂—MnO₂
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 7.2 g of manganese nitrate hexahydrate in H[0111] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:Mn=90:10:0.025 and in a weight ratio of Al₂O₃:TiO₂:MnO₂=81.6:14.3:4.1.
Catalyst 16:Al[0112] ₂O₃—TiO₂—Bi₂O₃
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 12.13 g of bithmus nitrate hexahydrate in H[0113] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:Bi=90:10:0.025 and in a weight ratio of Al₂O₃:TiO₂:Bi₂O₃=85.1:14.8 1.1.
[0114] Catalyst 17 Al₂O₃—TiO₂—NiO
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 7.3 g of nickel nitrate hexahydrate in H[0115] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:Ni=90:10:0.025 and in a weight ratio of Al₂O₃:TiO₂:NiO=82.0:14.4:3.6.
Catalyst 18:Al[0116] ₂O₃—TiO₂—BO₄
50 g of Catalyst A grains were impregnated with 38.4 g of an aqueous solution of 1.36 g of ammonium borate octahydrate in H[0117] ₂O. After the impregnation, the grains were dried at 120° C. for 2 hours and then fired at 700° C. for 2 hours. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti:B=90:10:0.005 and in a weight ratio of Al₂O₃:TiO₂:BO₄=85.65:14.827:0.008.
It was found from FIG. 3 that the Al[0118] ₂O₃—TiO₂—ZrO₂catalyst had the highest activity.

EXAMPLE 6

In this Example, various catalysts containing alumina as one member were investigated for C[0119] ₂F₆decomposition rates under the following conditions:
A C[0120] ₂F₆gas having a purity of 99% or more was diluted with air, and the diluted gas was further admixed with steam to prepare a reaction gas. Steam was prepared by feeding pure water to a reactor tube from the top at a flow rate of about 0.2 ml/min. by a microtube pump to gasify the pure water. The reaction gas had a C₂F₆concentration of about 0.5%, and was brought into contact with a catalyst heated to 700° C. by external heating of the reactor tube in an electric oven at a space velocity of 2,000 h⁻¹.
The reactor tube was an Inconel reactor tube having an inner diameter of 32 mm and had a catalyst bed fixed at the center of the reactor tube. An Inconel thermowell for a thermocouple, 3 mm in diameter, was inserted into the catalyst bed. Decomposition product gas from the catalyst bed was bubbled through an aqueous calcium fluoride solution and discharged to the system outside. [0121]
The following catalysts were prepared for the test under the foregoing conditions: [0122]
[0123] Catalyst 26
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders zinc nitrate hexahydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Zn=91:9 and in a weight ratio of Al[0124] ₂O₃:ZnO=86.4:13.6.
[0125] Catalyst 27
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 50.99 g of nickel sulfate hexahydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300°C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=91:9 and in a weight ratio of Al[0126] ₂O₃:NiO=87.3:12.7.
[0127] Catalyst 28
Boehmite powder (PURAL SB) were dried at 120° C. for one hour. 300 g of the resulting dried powders were admixed with an aqueous solution of 125.04 g of nickel nitrate hexahydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=91:9 and in a weight ratio of Al[0128] ₂O₃:NiO=87.3:12.7.
[0129] Catalyst 29
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 300 g of the resulting dried powders were kneaded with 354.4 g of an aqueous 30% titanium sulfate solution while adding about 300 g of pure water thereto. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 5 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ti=91:9 and in a weight ratio of Al[0130] ₂O₃:TiO₂=86.6:13.4.
[0131] Catalyst 30
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 115.95 g of iron nitrate nonahydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm, and tested. The resulting grain composition was in an atomic ratio of Al:Fe=91:9. [0132]
[0133] Catalyst 31
Boehmite powder (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 95.43 g of tin chloride hydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then dried at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Sn=91:9 and in a weight ratio of Al[0134] ₂O₃:SnO₂=77.4:22.6.
Catalyst 32 [0135]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution prepared by diluting 22.2 g of a dinitrodiamino Pt(II) nitric acid solution (Pt concentration: 4.5 wt. %) with 200 ml of pure water, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in a weight ratio of Al[0136] ₂O₃:Pt=100:0.68.
Catalyst 33 [0137]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 300 g of the resulting dried powders were admixed with an aqueous solution of 125.87 g of cobalt nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition was in an atomic ratio of Al:Co 91:9. [0138]
Catalyst 34 [0139]
Boehmite powder (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 76.70 g of zirconyl nitrate dihydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Zr=91:9 and in a weight ratio of Al[0140] ₂O₃:ZrO₂=80.7:19.3.
Catalyst 35 [0141]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 124.62 g of cerium nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Ce=91:9 and in a weight ratio of Al[0142] ₂O₃:CeO₂=75.0:25.0.
[0143] Catalyst 36
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 300 g of the resulting dried powders were admixed with an aqueous solution of 129.19 g of 20 wt. % silica sol, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm and tested. The resulting grain composition for catalyst was in an atomic ratio of Al:Si=91:9 and in a weight ratio of Al[0144] ₂O₃:SiO₂=89.6:10.4.
Test results of the foregoing [0145] catalysts 19 and 26-36 at a reaction temperature of 700° C. are shown in FIG. 6, C₂F₆decomposition activity is highest with the Al₂O₃—ZnO₂catalyst and is lowered in the order of the Al₂O₃—NiO catalyst, and the Al₂O₃—TiO₂catalyst. The highest activity of catalyst 26 seems to be due to the effect of S.

EXAMPLE 7

In this Example, changes in the activity of Al[0146] ₂O₃—NiO catalyst 28 were investigated by changing atomic ratios of Al:Ni. Test procedure and conditions were the same as in Example 6 except that the C₂F₆concentration was changed to 2% and the feed rate of pure water to 0.4 ml/min.
Catalyst 28-1 [0147]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powder were admixed with an aqueous solution of 8.52 g of nickel nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=99:1 and in a weight ratio of Al[0148] ₂O₃:NiO=98.5:1.5.
Catalyst 28-2 [0149]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 300 g of the resulting powders were admixed with an aqueous solution of 66.59 g of nickel nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=95:5 and in a weight ratio of Al[0150] ₂O₃:NiO=92.8:7.2.
Catalyst 28-3 [0151]
Boehmite powders (PURAL SB) were dried at 120°C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 210.82 g of nickel nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300°C. for about 2 hours and then fired at 700°C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni 80:20 and in a weight ratio of Al[0152] ₂O₃:NiO=73.2:26.8.
Catalyst 28-4 [0153]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 361.16 g of nickel nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300°C. for about 2 hours and then fired at 700°C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=70:30 and in a weight ratio of Al[0154] ₂O₃:NiO=61.4:38.6.
Catalyst 28-5 [0155]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with 562.1 g of nickel nitrate hexahydrate, and the mixture was kneaded while adding water thereto. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=60:40 and in a weight ratio of Al[0156] ₂O₃:NiO=50.6:49.4.
C[0157] ₂F₆decomposition rate 6 hours after the start of test is shown in FIG. 7. It was found that the Ni content of Al₂O₃—NiO catalysts is in a range of 5 to 40 atom %, preferably 20 to 30 atom %.

EXAMPLE 8

In this Example, changes in the activity of Al[0158] ₂O₃—ZnO catalyst 26 was investigated by changing atomic ratios of Al:Zn. Test procedure and conditions were the same as in Example 6 except that the C₂F₆concentration was changed to 2% and the feed rate of pure water to 0.4 ml/min.
Catalyst 26-1 [0159]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 215.68 g of zinc nitrate hexahydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Zn=80:20 and in a weight ratio of Al[0160] ₂O₃:ZnO=71.5:28.5.
Catalyst 26-2 [0161]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with 369.48 g of zinc nitrate hexahydrate and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Zn=70:30 and in a weight ratio of Al[0162] ₂O₃:ZnO=59.4:40.6.
Catalyst 26-3 [0163]
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 126.65 g of the resulting dried powders were admixed with an aqueous solution of 96.39 g of zinc nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Zn=85:15 and in a weight ratio of Al[0164] ₂O₃ZnO=78.0:22.0.
C[0165] ₂F₆decomposition rate 6 hours after the start of test is shown in FIG. 8. It was found that the Zn content of Al₂O₃-ZnO₂catalysts is in a range of 10 to 30 atom %, preferably 10 to 15 atom %.

EXAMPLE 9

In this Example, decomposition of CF[0166] ₄and CHF₃was carried out with a Al₂O₃—NiO catalyst 28-3 under the same test procedure and conditions as in Example 6, except that the space velocity was changed to 1,000 h⁻¹and the fluorine compound was diluted with nitrogen in place of air. Test results at various reaction temperatures are shown in FIG. 9. It was found that the decomposition activity of Al₂O₃—NiO catalyst upon CF₄gas and CHF₃gas is higher than upon C₂F₆gas and the Al₂O₃—NiO catalyst is a preferable hydrolysis catalyst for CF₄or CHF₃. Furthermore, it was found that a preferable reaction temperature is 600°-700° C. for the decomposition of CF₄and CHF₃, and 650°-700° C. for the decomposition of C₂F₆. The higher the reaction temperature, the higher the decomposition rate. However, substantially 100% decomposition rate can be obtained at 700° C., and thus a higher reaction temperature than 700° C. will be meaningless, and a reaction temperature must be as high as 800° C.

EXAMPLE 10

In this Example, influences of steam upon C[0167] ₂F₆decomposition were investigated under the same test conditions as in Example 6 except that the space velocity was changed 1,000 h⁻¹. Al₂O₃—NiO catalyst 28-3 was used at a reaction temperature of 700° C. while supplying steam for 2 hours from the start of test, then interrupting supply of steam for 3 hours, and then starting to supply steam again. Test results are shown in FIG. 10. It was found that during the supply of steam the C₂F₆reaction rate was elevated due to the occurrence of C₂F₆hydrolysis.

EXAMPLE 11

In this Example, decomposition of SF[0168] ₆was investigated with Al₂O₃—NiO catalyst 28-3 under the same test conditions as in Example 6 except that a SF₆gas having a purity of 99% or more was used, the space velocity was changed to 1,000 h⁻¹and the SF₆gas was diluted with nitrogen in of air. The reaction temperature was 700° C. Concentration of SF₆in the reaction gas at the inlet to the reactor tube and concentration of SF₆in the decomposition gas at the outlet from the alkaline washing step were determined by TCD gas chromatography and the decomposition rate was calculated by the following equation. It was found that the decomposition rate was 99% or more. $Decomposition rate = 1 - \frac{\begin{matrix} Concentration of \\ discharged {SF}_{6} \end{matrix}}{\begin{matrix} Concentration of \\ fed {SF}_{6} \end{matrix}} \times 100 (%)$

EXAMPLE 12

In this Example, decomposition of NF[0169] ₃was investigated with Al₂O—NiO catalyst 28-3 under the same test conditions as in Example 11 except that a NF₃gas having a purity of 99% or more was used. Reaction temperature was 700° C. Concentration of NF₃in the reaction gas at the inlet to the reactor tube and concentration of NF₃in the decomposition gas at the outlet from the alkaline washing step were determined by TCD gas chromatography and the decomposition rate was calculated according to the following equation. It was found that the decomposition rate was 99% or more. It was found preferable to carry out the decomposition of the NF₃gas with the Al₂O₃—NiO catalyst at a temperature of 600°-800° C. $Decomposition rate = \frac{\begin{matrix} Concentration of \\ discharged {NF}_{3} \end{matrix}}{\begin{matrix} Concentration of \\ fed {NF}_{3} \end{matrix}} \times 100 (%)$

EXAMPLE 13

In this Example, activity of Al[0170] ₂O₃—ZnO catalyst upon hydrolysis of a CF₄gas, a C₄F₈gas and a CHF₃gas was investigated. Decomposition of a CF₄gas was carried out in the following manner:
At first, a CF[0171] ₄gas having a purity of 99% or more was diluted with air, and the diluted CF₄gas was further admixed with steam. Concentration of CF₄in the reaction gas was about 0.5%, and steam flow rate was adjusted to about 50 times as high as that of the fluorine compound, i.e. CF₄. The reaction gas was brought into contact with the catalyst heated to a predetermined temperature in a reactor tube in an electric oven at a space velocity of 1,000 h⁻¹. Decomposition product gas from the catalyst bed was bubbled through an aqueous sodium hydroxide solution and then discharged to the system outside. Decomposition rate of CF₄was determined by TCD gas chromatography.
The Al[0172] ₂O₃—ZnO catalyst used for the test was prepared in the following manner:
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 126.65 g of the resulting dried powders were admixed with 96.39 g of zinc nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Zn=85:15 and in a weight ratio of Al[0173] ₂O₃ZnO=78:22.
FIG. 11 shows decomposition rates of CF[0174] ₄at various reaction temperatures and also those of CHF₃and C₄F₈as fed and decomposed in the same manner as above. Decomposition rates of CHF₃and C₄F₈were determined by FID gas chromatography, whereby it was found that the Al₂O₃—ZnO catalyst had a higher activity upon the CF₄gas, the C₄F₈gas and the CHF₃gas. It was also found that a higher decomposition rate can be obtained preferably at a reaction temperature of 650° C. or higher for the hydrolysis of the C₄F₈gas and even at a reactor temperature of 600° C. or lower for the hydrolysis of the CHF₃gas or the CF₄gas.

EXAMPLE 14

In this Example, the decomposition activity of as Al[0175] ₂O₃—NiO catalyst upon a C₃F₈gas, a C₄F₈gas and a SF₆gas was investigated in the same manner as in Example 13. The concentration of C₄F₈in the reaction gas after decomposition of C₄F₈was 0.1% by volume. The Al₂O₃—NiO catalyst used for the test was prepared in the following manner:
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with an aqueous solution of 210.82 g of nickel nitrate hexahydrate, and the mixture was kneaded. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours, and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in an atomic ratio of Al:Ni=80:20 and in a weight ratio of Al[0176] ₂O₃:NiO=73.2:26.8.
FIG. 12 shows decomposition rates at various reaction temperatures, where the decomposition rate of C[0177] ₃F₈and C₄F₈was determined by FID gas chromatography and that of SF₆by TCD gas chromatography. It was found from the test results that the Al₂O₃—NiO catalyst had a higher activity upon the hydrolysis of the SP₆gas, C₃F₈gas and the C₄F₈gas, and the reaction temperature was preferably 500° C. or higher for the hydrolysis of the SF₆gas and preferably 700° C. or higher for the hydrolysis of the C₃F₈gas. In the case of C₄F₈gas, the reaction temperature for the hydrolysis was preferably 650° C. or higher.

EXAMPLE 15

In this Example, decomposition activity of an Al[0178] ₂O₃—NiO—ZnO catalyst upon C₄F₈was investigated in the same manner as in Example 13. The Al₂O₃—NiO—ZnO catalyst used for the test was prepared in the following manner:
Boehmite powders (PURAL SB) were dried at 120° C. for one hour. 200 g of the resulting dried powders were admixed with 210.82 g of nickel nitrate hexahydrate and 152.31 g of zinc nitrate hexahydrate, and the mixture was kneaded while adding pure water thereto. After the kneading, the kneaded mixture was dried at 250°-300° C. for about 2 hours and then fired at 700° C. for 2 hours. The fired product was pulverized and sieved to obtain grains having grain sizes of 0.5-1 mm. The resulting grain composition for catalyst was in atomic ratios of Al:Ni=80:20 and Al:Zn=85:15 and in a weight ratio of Al[0179] ₂O₃:NiO:ZnO=60.7:22.2:17.1.
FIG. 13 shows decomposition rates at various reaction temperatures, where the decomposition rate of C[0180] ₄F₈was determined by FID gas chromatography.

Claims

What is claimed is:

1. A process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing at least one of compounds of carbon and fluorine, compounds of carbon, hydrogen and fluorine, compounds of sulfur and fluorine, compounds of nitrogen and fluorine and compounds of carbon, hydrogen, oxygen and fluorine with a catalyst containing at least one of alumina, titania, zirconia and silica in the presence of steam, thereby hydrolyzing the fluorine compound to convert the fluorine of the fluorine compound to hydrogen fluoride.

2. A process according to

claim 1

, wherein the catalyst is selected from the group consisting of alumina, titania, zirconia, silica, a mixture of titania and zirconia, a mixture of alumina and magnesia, a mixture of alumina and titania and a mixture of alumina and silica.

3. A process according to

claim 1

, wherein the catalyst comprising a mixture of alumina and titania is in a weight ratio of alumina to titania of 75-98:25-2.

4. A process according to

claim 3

, wherein the catalyst comprising a mixture of alumina and titania is a catalyst prepared from boehmite as an alumina raw material.

5. A process according to

claim 3

, wherein the catalyst comprising a mixture of alumina and titania is a catalyst prepared from titanium sulfate as a titania raw material.

6. A process according to

claim 3

, wherein the catalyst comprising a mixture of alumina and titania is a catalyst prepared by adding sulfuric acid thereto during the catalyst preparation.

7. A process according to

claim 3

, wherein the catalyst comprising a mixture of alumina and titania contains sulfate ions.

8. A process according to

claim 1

, wherein the catalyst comprises a mixture of alumina, titania and at least one member selected from the group consisting of zirconia, tungsten oxide, silica, tin oxide, ceria, bismuth oxide, nickel oxide and boron oxide and having a weight ratio of at least one member selected from the group consisting of zirconia, tungsten oxide, silica, tin oxide, ceria, bismuth oxide, nickel oxide and boron oxide to sum total of alumina and titania being 0.1-10:99.9-90.

9. A process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing a compound comprising carbon and fluorine with a catalyst comprising a mixture of alumina, titania and zirconia, and having a weight ratio of alumina to titania being 75-98:25-2 and a weight ratio of zirconia to sum total of alumina and titania being 2-10:98-90, thereby hydrolyzing the compound comprising carbon and fluorine.

10. A process according to

claim 1

, wherein the catalyst comprises a mixture of alumina and at least one member selected from the group consisting of zinc oxide, nickel oxide, iron oxide, tin oxide, cobalt oxide, zirconia, ceria, silica and platinum and has an atomic ratio of aluminum of the alumina to at least one element of at least one of the member except for platinum being 50-99:50-1, and the content of platinum being 0.1 to 2% by weight per 100% by weight of the alumina.

11. A process according to

claim 10

, wherein the catalyst further contains 0.1-20% by weight of sulfur on the basis of the catalyst.

12. A process according to

claim 12

, wherein the catalyst containing sulfur comprises a mixture of alumina and nickel oxide.

13. A process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing a fluorine compound comprising C₂F₆with a catalyst comprising alumina and titania having a weight ratio of alumina to titania being 65-90:35-10, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas stream to hydrogen fluoride.

14. A process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing a fluorine compound comprising C₂F₆with a catalyst comprising alumina, titania and zirconia and having a weight ratio of alumina to titania being 65-90:35-10 and a weight ratio of zirconia to sum total of alumina and titania being 2-10:98-90, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas stream to hydrogen fluoride.

15. A process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing a fluorine compound comprising at least one member selected from the group consisting of C₂F₆, CF₄, C₄F₈and CHF₃with a catalyst comprising a mixture of alumina and zinc oxide and having an atomic ratio of aluminum to zinc being 90-70:10-30, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas stream to hydrogen fluoride.

16. A process for treating a fluorine compound-containing gas, which comprises a gas stream containing a fluorine compound comprising at least one member selected from the group consisting of C₂F₆, CF₄, C₃F₈, C₄F₈, CHF₃, NF₃and SF₆with a catalyst comprising a mixture of alumina and nickel oxide and having an atomic ratio of aluminum to nickel being 95-60 5-40, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas stream to hydrogen fluoride.

17. A process for treating a fluorine compound-containing gas, which comprises contacting a gas stream containing a fluorine compound comprising C₄F₈with a catalyst comprising a mixture of alumina and nickel oxide, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas stream to hydrogen fluoride.

18. A process according to

claim 16

, wherein a reaction temperature is 650°-800°C. for the hydrolysis of C₂F₆, 600°-800° C. for the hydrolysis of CF₄and CHF₃, 700°-800° C. for the hydrolysis of C₃F₈, 650° C.-800° C. for the hydrolysis of C₄F₈, 600°-800° C. for the hydrolysis of NF₃and 500°-800° C. for the hydrolysis of SF₆.

19. A process according to

claim 15

, wherein a reaction temperature is 650°-800°C. for the hydrolysis of C₄F₈and 600°-800° C. for the hydrolysis of CF₄and CHF₃.

20. A process for treating a fluorine compound-containing gas, which comprises a hydrolysis step of contacting a gas discharged from a semiconductor-etching or cleaning step using a gas stream containing at least one fluorine compound selected from the group consisting of compounds of carbon and fluorine, compounds of carbon, hydrogen and fluorine, compounds of sulfur and fluorine, compounds of nitrogen and fluorine and compounds of carbon, hydrogen, oxygen and fluorine, after addition of air and steam to the gas, with a catalyst comprising at least one of alumina, titania, zirconia and silica, thereby hydrolyzing the fluorine compound to convert the fluorine in the gas to hydrogen fluoride, as a poststep to the semiconductor-etching or cleaning step.

21. A process according to

claim 20

, which further comprises an alkaline washing step of contacting the gas from the hydrolysis step with an alkaline washing solution, thereby washing the gas as a poststep to the hydrolysis step.