Process for treatment of gases

This invention relates to a process for treatment of gases, which is useful for removal of hydrogen sulfide and carbonyl sulfide in from inert or reducing gases.
Sulfur comounds such as hydrogen sulfide and carbonyl sulfide are contained in carbon dioxide gas for beverages, coke furnace gas, blast furnace gas, converter gas, thermal cracking gas of petroleum fractions, natural gas, etc. Since these sulfur compounds, even in trace amounts, present characteristic bad smell andcan produce catalyst poisoning effect, they often give rise to various problems such as in carbonation of beverage mixtures and chemical reactions.
In order to remove these sulfur compounds, there have been proposed processes comprising washing with chemical solutions such as alkali solutions and alkanolamine solutions, removal processes by adsorption utilizing iron oxides, zinc oxide, activated carbon, etc. and the like. However, these processes exhibit inferior removal efficiency and encounter difficulties particularly in the removal of carbonyl sulfide.
The present inventors, in view of such circumstances, conducted extensive investigation, and as a result, found that incorporation into activated carbon of a copper compound, and an alkali metal compound and/or an alkaline earth metal compound led to highly efficient removal of hydrogen sulfide and carbonyl sulfide in gases. This finding has culminated in the completion of this invention.
Thus, this invention is concerned with a process for treatment of a gas containing hydrogen sulfide and/or carbonyl sulfide (hereinafter referred to as "sulfur compounds") but not substantially containing oxygen, which comprises contacting the gas with activated carbon (hereinafter referred to as "activated carbon containing metal compound") containing (1) a copper compound and (2) an alkali metal compound and/or an alkaline earth metal compound (alkali metal compound and/or alkaline earth metal compound are collectively or independently referred to hereinafter as "second metal compound") at a temperature of not higher than 150.degree. C., whereby sulfur compounds are removed from the gas.
The activated carbon, which is useful in this invention, may be any activated carbon which is manufactured by known processes utilizing coal, coke, charcoal, coconut shells, resins, etc. as raw material and shows a specific surface area of 200 to 2000 m.sup.2 /g. The activated carbon is used in a suitable shape, which varies with the intended process for treatment of gases, such as spherical beads, cylindrical pellets, crushed pieces, powder and treadlike pieces.
Examples of the copper compounds used in the present invention include oxides, hydroxides, and salts with inorganic acids (such as carbonates, basic carbonates, nitrates, sulfates, phosphates and halides) or with organic acids (e.g. carboxylates such as formates, acetates, oxalates, etc.).
Examples of the alkali metal compounds include compounds of Li, Na, K, Rb and Cs such as hydroxides, their inorganic salts exemplified by hydrogen carbonates, carbonates, nitrates, borates, silicates, sulfates, halides, etc., and their salts with organic acids, typified by formates, acetates, oxalates, citrates, tartrates, benzoates, phenolates, sulfonates, etc.
Examples of the alkaline earth metal compounds include compounds of Be, Mg, Ca, Sr and Ba, such as oxides and hydroxides, salts with inorganic acids, exemplified by carbonates, nitrates, sulfates, phosphates, halides, etc., and salts with organic acids, typified by formates, acetates, oxalates, etc.
The activated carbon containing metal compounds used in the present invention may contain both of the alkali metal compound and the alkaline earth metal compound.
The contents of the copper compound and the second metal compound in the activated carbon containing metal compounds are 0.1 mg atom to 3.0 mg atom as copper per g of activated carbon, preferably 0.2 mg atom to 2.0 mg atom, and 0.1 mg atom to 5.0 mg atom as alkali metal or as alkaline earth metal per g of activated carbon, preferably 0.2 mg atom to 4.0 mg atom, respectively. In case the activated carbon containing metal compound is one containing both of the alkali metal compound and the alkaline earth metal compound, the amount of one of the second metal compounds is 0.1 mg atom to 5.0 mg atom as metal per g of activated carbon, preferably 0.2 mg atom to 4.0 mg atom, and the amount of the other second metal compound is also 0.1 mg atom to 5.0 mg atom as metal per g of activated carbon, preferably 0.2 mg atom to 4.0 mg atom.
The activated carbon containing metal compounds may contain as a third component a compound of at least one kind of metal (hereinafter referred to as "third metal compound") selected from the group consisting of aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, cadmium and lead, and the presence of the third metal compound highly improves the removal efficiency for sulfur compounds.
Examples of the third metal compounds include oxides, hydroxides, salts with inorganic acids, exemplified by carbonates, hydrogencarbonates, nitrates, borates, silicates, sulfates, phosphates, halides, etc., ammonium salts and salts with organic acids typified by formates, acetates, oxalates, citrates, etc.
In case the third metal compound is further incorporated into the activated carbon containing metal compounds, the content of the third metal compound in the activated carbon is 0.1 to 5.0 mg atom as metal per g of activated carbon, preferably 0.2 to 4.0 mg atom.
The activated carbon containing metal compound according to this invention is prepared for example by the following processes:
A. In case of the preparation of the activated carbon containing a copper compound and a second metal compound;
(1) A process which comprises adding a copper compound and a second metal compound to a raw material for activated carbon and effecting carbonization and activation by a conventional method,
(2) A process which comprises adding a copper compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with a second metal compound, and drying or calcining the mixture, if necessary,
(3) A process which comprises adding a second metal compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with a copper compound, and drying or calcining the mixture, if necessary,
(4) A process which comprises admixing activated carbon simultaneously with a copper compound and a second metal compound, and drying or calcining the mixture, if necessary,
(5) A process which comprises admixing activated carbon with a copper compound, drying or calcining the mixture, and admixing with a second metal compound, followed by drying or calcining, if necessary, and
(6) A process which comprises admixing activated carbon with a second metal compound, drying or calcining the mixture, and further admixing with a copper compound, followed by drying or calcining, if necessary.
B. In case of the preparation of the activated carbon containing both an alkali metal compound and an alkaline earth metal compound as the second metal compound;
(1) A process which comprises adding a copper compound, an alkaline earth metal compound and an alkali metal compound to a raw material for activated carbon, and effecting carbonization/activation by a conventional method,
(2) A process which comprises adding a copper compound to raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with an alkaline earth metal compound and an alkali metal compound, separately, and drying or calcining the mixture, if necessary,
(3) A process which comprises adding an alkaline earth metal compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing to the resultant activated carbon with a copper compound and an alkali metal compound, either simultaneously or separately, and drying or calcining the mixture, if necessary,
(4) A process which comprises adding an alkali metal compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with a copper compound and an alkaline earth metal compound, either simultaneously or separately, and drying or calcining the mixture, if necessary,
(5) A process which comprises admixing activated carbon with a copper compound, an alkaline earth metal compound and an alkali metal compound simultaneously, and drying or calcining the mixture, if necessary,
(6) A process which comprises admixing activated carbon with a copper compound, drying or calcining the mixture, admixing it further with an alkaline earth metal compound and an alkali metal compound, either simultaneously or separately, and drying or calcining the mixture, if necessary,
(7) A process which comprises admixing activated carbon with an alkaline earth metal compound, drying or calcining the mixture, and admixing it further with a copper compound and an alkali metal compound, either simultaneously or separately, followed by drying or calcining, if necessary, and
(8) A process which comprises admixing activated carbon with an alkali metal compound, drying or calcining the mixture, and admixing it further with a copper compound and an alkaline earth metal compound, either simultaneously or separately, followed by drying or calcining, if necessary.
C. In case of the preparation of the activated carbon containing a copper compound, a second metal compound and a third metal compound;
(1) A process which comprises adding a copper compound, a second metal compound and a third metal compound to a raw material for activated carbon, and effecting carbonization/activation by a conventional method,
(2) A process which comprises adding a copper compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with a second metal compound and a third metal compound, separately, and drying or calcining the mixture, if necessary,
(3) A process which comprises adding a second metal compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with a copper compound and a third metal compound, either simultaneously or separately, and drying or calcining the mixture, if necessary,
(4) A process which comprises adding a third metal compound to a raw material for activated carbon, effecting carbonization/activation by a conventional method, admixing the resultant activated carbon with a copper compound and a second metal compound, either simultaneously or separately, and drying or calcining the mixture, if necessary,
(5) A process which comprises admixing activated carbon with a copper compound, a second metal compound and a third metal compound simultaneously, and drying or calcining the mixture, if necessary,
(6) A process which comprises admixing activated carbon with a copper compound, drying or calcining the mixture, admixing it further with a second metal compound and a third metal compound, either simultaneously or separately, and drying or calcining the mixture, if necessary,
(7) A process which comprises admixing activated carbon with a second metal compound, drying or calcining the mixture, and admixing it further with a copper compound and a third metal compound, either simultaneously or separately, followed by drying or calcining, if necessary, and
(8) A process which comprises admixing activated carbon with a third metal compound, drying or calcining the mixture, and admixing it further with a copper compound and a second metal compound, either simultaneously or separately, followed by drying or calcining, if necessary.
In these preparation processes, the procedure of admixing activated carbon with metal compounds is considered to involve impregnating or spraying activated carbon with a solution or suspension of metal compounds in water (inclusive of aqueous acid or alkali solution) or a variety of solvents.
In the above preparation processes, by "drying" is understood a step which comprises evaporating the water or solvent in the admixed activated carbon at a temperature of not higher than about 130.degree. C., and the term "calcining" denotes a step which comprises heating the admixed activated carbon thus dried under an atmosphere of a gas such as an inert gas, carbon dioxide gas, steam and waste combustion gas at a temperature of not lower than about 130.degree. C. to thermally decompose part or all of the metal compounds.
In the above processes, when activated carbon is admixed with compounds other than oxides of the copper, second metal compounds (except alkali metal compounds) and third metal compounds, it is favorable to effect heat treatment such as drying or calcining after the admixing; in cases in which activated carbon is admixed with a copper compound, a second metal compound (except alkali metal compound) and a third metal compound but is not subjected to heat treatment, it is preferred to use oxides of the copper, second metal (except alkali metal) and third metal compounds; when activated carbon is admixed with alkali metal compounds other than hydroxides, carbonates and hydrogen carbonates of alkali metal as the second metal compound, it is advantageous to effect heat treatment such as drying or calcining after the admixing; and in cases in which activated carbon is admixed with alkali metal compounds without subsequent heat treatment, it is favorable to use hydroxides, carbonates or hydrogencarbonates as the alkali metal compound.
The gas not substantially containing oxygen which is useful in this invention includes those having an oxygen concentration of not more than 2 vol.%. These gases may be exemplified by carbon dioxide gas, coke furnace gas, blast furnace gas, converter gas, thermal cracking gas of petroleum fractions, natural gas, etc.
The process of this invention is conducted by contacting the activated carbon containing metal compounds as obtained by the above procedure with a gas containing sulfur compounds. The solid-gas contacting method is by a known means such as the fixed bed, moving bed and fluidized bed, whereby the contacting temperature is not higher than 150.degree. C., preferably 0.degree. to 150.degree. C., and the gas pressure is not higher than 50 kg/cm.sup.2, preferably 0.1 to 40 kg/cm.sup.2, with the gas contacting time being 1/10 to 100 seconds as measured at 25.degree. C. and 1 kg/cm.sup.2, preferably 1/5 to 80 seconds.
The examples described below illustrate this invention more specifically.

EXAMPLE 1
An activated carbon A of 16 to 24 mesh having a B.E.T. specific surface area of 1040 m.sup.2 /g was sprayed uniformly with a solution of a certain amount each of copper nitrate and nitrate of an alkali metal. 50 ml of the admixed product thus obtained was packed into a 4-cm diameter column made of quartz glass. The column was heated at a heating rate of 2.degree. C./min. While allowing a nitrogen gas to flow therethrough at a linear flow rate of 10 cm/sec., the packed product was calcined at 350.degree. C. for 30 minutes.
The contents of the copper and alkali-metal compounds in the catalyst thus obtained were 0.2 to 2.0 mg atom as copper and 0.2 to 2.0 mg atom as alkali metal per g of activated carbon, respectively.
As a control for reference, the activated carbon was admixed with copper nitrate solely or with nitrate of an alkali metal solely by the same procedure as mentioned above, and was calcined in a nitrogen gas at 350.degree. C. for 30 minutes to prepare a catalyst.
15 ml each of the catalysts thus obtained was packed into a 1.6-cm diameter glass column. A gas of 40.degree. C. containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was allowed to pass through the column at a linear flow rate of 40 cm/sec. to conduct a break-through adsorption test on COS. The results are as shown in Table 1.
EXAMPLE 2
A 12 ml portion each of the catalysts A through M of Example 1 was packed into a 1.6 cm diameter glass column. A gas of 25.degree. C. containing 10.0 ppm of H.sub.2 S (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through the column at a linear flow rate of 40 cm/sec. to conduct a break-through adsorption test on H.sub.2 S. The results are as shown in Table 2.
EXAMPLE 3
A certain amount each of Li.sub.2 CO.sub.3, Na.sub.2 SO.sub.4, K.sub.2 SO.sub.4, Rb.sub.2 SO.sub.4, Cs.sub.2 SO.sub.4, HCOONa, CH.sub.3 COOK and (COONa) was incorporated into a coconut-shell raw material. After being mixed and crushed, the mixture was kneaded with various kinds of pitch, water, etc., and molded into cylindrical pellets of 4 mm diameter. The pellets were carbonized at 650.degree. C. and further steam-activated at 900.degree. C. The resultant activated carbon showed a B.E.T. specific surface area of 1000 to 1100 m.sup.2 /g and a content of the alkali metal compound of 0.8 to 1.1 mg atom as metal per g of activated carbon, as shown in Table 3.
Various kinds of the activated carbon were crushed and sieved to a uniform grain size of 16 to 24 mesh and each was sprayed with a solution of a certain amount of copper sulfate in water. 50 ml each of the admixed products thus obtained was packed into a 4 cm diameter column made of quartz glass. The column was heated at a heating rate of 2.degree. C./min., while a nitrogen gas was allowed to pass through it at a linear flow rate of 10 cm/sec., and the packed product was calcined at 350.degree. C. for 30 minutes. The contents of the copper compound in the resultant catalysts were 1.0 mg atom as metal per g of activated carbon.
15 ml each of the catalysts N through U thus obtained was packed into a 1.6-cm diameter glass column, and a gas of 40.degree. C. containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through the column at a linear flow rate of 40 cm/sec. to conduct a break-through adsorption test on COS. The results are as shown in Table 3.
EXAMPLE 4
A certain amount each of CuO, CuSO.sub.4, (CH.sub.3 COO).sub.2 Cu, (HCOO).sub.2 Cu and CuCl.sub.2 was incorporated into a coconut-shell raw material. After being mixed and crushed, the mixture was kneaded with various kinds of pitch, water, etc., and molded into cylindrical pellets of 4-mm diameter. The pellets were carbonized at 650.degree. C. and further steam-activated at 900.degree. C. The resultant activated carbon showed a B.E.T. specific surface area of 1000 to 1100 m.sup.2 /g and a content of the copper compound of 0.8 to 1.1 mg atom as metal per g of activated carbon.
Various kinds of the activated carbon were crushed and sieved to a uniform grain size of 16 to 24 mesh and each was sprayed with a solution of a certain of an alkali metal compound in water. 50 ml each of the admixed products thus obtained was packed into a 4-cm diameter column made of quartz glass. The column was heated at a heating rate of 2.degree. C./min., while a nitrogen gas was allowed to pass through it at a linear flow rate of 10 cm/sec, and the packed material was burnt at 300.degree. C. for 30 minutes. The contents of the alkali metal compounds in the resultant catalysts were 1.0 mg atom as metal per g of activated carbon.
15 ml each of the catalysts V through Z thus obtained was packed into a 1.6 cm diameter glass column, and a gas of 40.degree. C. containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through the column at a linear flow rate of 40 cm/sec. to conduct a break-through adsorption test on COS. The results are as shown in Table 4.
EXAMPLE 5
A 15 ml portion each of the catalysts F and I of Example 1 was packed into a 1.6 cm diameter glass column, and a gas containing 12.5 ppm of COS (CO-97.5 vol.% and H.sub.2 O-2.5 vol %) was passed through the column at temperatures of 25.degree., 60.degree., 80.degree. and 120.degree. C. (in all cases, the linear flow rate of the gas was maintained at 40 cm/sec. as converted to 25.degree. C.).
The COS concentrations in the gases withdrawn at the inlet and outlet of the column were measured by means of FPD gas chromatography, and the COS removal ratios were determined. The results are as shown in Table 5.
TABLE 1__________________________________________________________________________ Kind and Percent removal of COS at theAmount of amount of time points shown below (%) copper alkali metal 15 hrs. 25 hrs. 50 hrs. 75 hrs. 100 hrs.Catalyst (mg-atom/g) (mg-atom/g) later later later later later__________________________________________________________________________A (control) 0 0 0 0 0 0 0B (control) 2.00 0 98 68 8 0 0C (control) 0 K-2.0 100 50 0 0 0D (present 0.2 K-1.0 100 100 18 8 1invention)E (present 0.5 K-1.0 100 100 49 10 3invention)F (present 1.0 K-1.0 100 100 100 97 82invention)G (present 2.0 K-1.0 100 100 100 99 90invention)H (present 1.0 K-0.2 100 100 92 68 36invention)I (present 1.0 K-0.5 100 100 100 90 73invention)J (present 1.0 Li-0.5 100 100 85 63 54invention)K (present 1.0 Na-0.5 100 100 94 78 45invention)L (present 1.0 Rb-0.5 100 100 100 90 79invention)M (present 1.0 Cs-0.5 100 100 100 85 70invention)__________________________________________________________________________
TABLE 2__________________________________________________________________________ Kind and Percent removal of H.sub.2 S at theAmount of amount of time points shown below (%) copper alkali metal 50 hrs. 100 hrs. 150 hrs. 200 hrs. 250 hrs.Catalyst (mg-atom/g) (mg-atom/g) later later later later later__________________________________________________________________________A (control) 0 0 0 0 0 0 0B (control) 2.0 0 100 77 38 9 0C (control) 0 K-2.0 100 58 5 0 0D (present 0.2 K-1.0 100 100 83 64 42invention)E (present 0.5 K-1.0 100 100 100 93 81invention)F (present 1.0 K-1.0 100 100 100 97 92invention)G (present 2.0 K-1.0 100 100 100 98 95invention)H (present 1.0 K-0.2 100 100 99 92 79invention)I (present 1.0 K-0.5 100 100 100 95 90inventionJ (present 1.0 Li-0.5 100 100 90 83 69invention)K (present 1.0 Na-0.5 100 100 95 88 75invention)L (present 1.0 Rb-0.5 100 100 100 93 89invention)M (present 1.0 Cs-0.5 100 100 100 89 80invention)__________________________________________________________________________
TABLE 3__________________________________________________________________________ Kind of alkali Percent removal of COS metal salt and at the time points shownBET specific amount of alkali Amount of below (%) surface area metal copper 10 hrs. 25 hrs. 50 hrs. 100 hrs.Catalyst (m.sup.2 /g) (mg-atom/g) (mg-atom/g) later later later later__________________________________________________________________________N 1050 Li.sub.2 CO.sub.3 -0.85 1.0 100 100 78 65O 1100 Na.sub.2 CO.sub.3 -0.98 1.0 100 100 80 68P 1010 K.sub.2 SO.sub.4 -0.94 1.0 100 100 95 79Q 1090 Rb.sub.2 SO.sub.4 -1.05 1.0 100 100 93 84R 1050 Cs.sub.2 SO.sub.4 -1.00 1.0 100 100 89 70S 1100 HCOONa-0.93 1.0 100 100 78 63T 1080 CH.sub.3 COOK-0.89 1.0 100 100 93 84U 1020 (COONa).sub.2 -1.03 1.0 100 100 75 60__________________________________________________________________________
TABLE 4__________________________________________________________________________ Kind of copper Kind of alkali Percent removal of COS compound and metal salt and at a time point shownBET specific amount of amount of alkali below (%) surface area copper metal 10 hrs. 25 hrs. 50 hrs. 100 hrs.Catalyst (m.sup.2 /g) (mg-atom/g) (mg-atom/g) later later later later__________________________________________________________________________V 1050 CuO-0.95 LiNO.sub.3 -1.0 100 100 83 72W 1010 CuSO.sub.4 -1.10 NaNO.sub.3 -1.0 100 100 90 81X 1070 (CH.sub.3 COO).sub.2 Cu-0.91 KNO.sub.3 -1.0 100 100 98 83Y 1100 (HCOO).sub.2 Cu-1.00 RbNO.sub.3 -1.0 100 100 90 75Z 1050 CuCl.sub.2 -0.88 CsNO.sub.3 -1.0 100 100 85 71__________________________________________________________________________
TABLE 5______________________________________ Percent removal of COS at the time point shownContacting below (%)temperature 10 hrs. 25 hrs. 50 hrs. 100 hrs.(.degree.C.) Catalyst later later later later______________________________________25 F 100 100 95 88 I 100 100 84 8060 F 100 100 100 95 I 100 100 100 8980 F 100 100 100 98 I 100 100 100 88120 F 100 100 100 98 I 100 100 100 75______________________________________
EXAMPLE 6
The activated carbon A of 16 to 24 mesh having a B.E.T. surface area of 1040 m.sup.2 /g was sprayed uniformly with a solution in water of the two conponents (i.e. copper nitrate and nitrate of an alkaline earth metal), or the three components (i.e., copper nitrate, an alkaline earth metal compound and a third metal compound or alkali metal compound (nitrate)), 50 ml of the resultant admixed product was packed into a 4 cm diameter column made of quartz glass. The column was heated at a heating rate of 5.degree. C./min., while a nitrogen gas was allowed to pass through it at a linear flow rate of 10 cm/sec., and the packed product was calcined at 300.degree. C. for 30 minutes.
The contents of the copper compound, alkaline earth metal compound, alkali metal and third metal compound in the catalysts thus obtained were all 0.2 to 2.0 mg atom as metal per 1 g of activated carbon, as shown in Table 6.
As the control the activated carbon was admixed with copper nitrate, nitrate of an alkaline earth metal or a third metal compound alone, respectively, by the same procedure as mentioned above, and the admixed products were calcined in a nitrogen gas at 300.degree. C. for 30 minutes to prepare the catalysts.
15 ml each of the catalysts a through j (controls) and 1 to 47 thus obtained was packed into a 1.6 cm diameter glass column, and a gas of 50.degree. C. containing 12.5 ppm of COS (N.sub.2 -97.5 vol.%, H.sub.2 O-2.5 vol.%) was passed through it at a linear flow rate of 40 cm/sec to conduct a break-through adsorption test on COS. The results are as shown in Table 6.
EXAMPLE 7
A 12 ml portion each of the catalysts a through j (controls) and 1 through 47 of Example 6 was packed into a 1.6 cm diameter glass column, and a gas of 30.degree. C. containing 10.0 ppm of H.sub.2 S (N.sub.2 -97.5 vol.%, H.sub.2 O-2.5 vol.%) was passed through it at a linear flow rate of 40 cm/sec. to conduct a break-through adsorption test on H.sub.2 S. The results are as shown in Table 7.
EXAMPLE 8
A certain amount each of an alkaline earth metal compound and alkali metal compound or a third metal compound were added to a coconut-shell raw material. After being mixed and crushed, the mixture was kneaded with various kinds of pitch, water, etc., and molded into cylindrical pellets of 4 mm diameter. These pellets were carbonized at 650.degree. C. and further steam-activated at 900.degree. C. Various kinds of the resultant activated carbon showed a B.E.T. specific surface area of 950 to 1150 m.sup.2 /g, with their contents of the alkaline earth metal and third metal compounds being all within the range of 0.8 to 1.1 mg atom per g of activated carbon, as shown in Table 8.
Various kinds of such activated carbon were crushed and sieved to a uniform grain size of 16 to 24 mesh and sprayed with a solution of a certain amount of copper acetate in 2% aqueous acetic acid. 50 ml of each of the admixed products thus obtained was packed into a 4 cm diameter column made of quartz glass. The column was heated at a heating rate of 5.degree. C./min., while a nitrogen gas was allowed to pass through it at a linear flow rate of 10 cm/sec., and the packed product was calcined at 300.degree. C. for 30 minutes. The content of the copper compound in the catalyst was 1.0 mg atom per g of activated carbon.
15 ml each of the catalysts, 48 through 76 thus obtained was packed into a 1.6 cm diameter glass column, and a gas of 50.degree. C. containing 12.5 ppm of COS (CO-97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through it at a linear flow rate of 40 cm/sec. to conduct a break-through adsorption test on COS. The results are as shown in Table 8.
EXAMPLE 9
A 15 ml portion of each of the catalysts 3, 9, 13, 20, 30 and 37 of Example 6 was packed into a 1.6 cm diameter glass column, and a gas containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through it at 25.degree., 60.degree., 80.degree. and 120.degree. C., respectively (in every case, a gas linear flow rate was maintained at 40 cm/sec. as measured at 25.degree. C.).
The COS concentrations at the outlet and inlet of the column were measured by means of FPD gas chromatography to determine the COS removal rates at certain points of time. The results are as shown in Table 9.
TABLE 6__________________________________________________________________________ Kind and Kind and Percent removal of amount of amount of COS at the time pointAmount of alkaline alkali metal shown below (%) copper earth metal or third metal 25 hrs. 50 hrs. 75 hrs. 100 hrs.Catalyst (mg-atom/g) (mg-atom/g) (mg-atom/g) later later later later__________________________________________________________________________controla 0 0 0 0 0 0 0b 200 0 0 90 18 0 0c 0 Mg-2.0 0 35 0 0 0d 0 0 K-2.0 73 0 0 0e 0 Mg-1.0 K-2.0 78 0 0 0f 0 Mg-1.0 Al-1.0 40 3 0 0g 0 Mg-1.0 Cr-1.0 60 11 0 0h 0 Mg-1.0 Fe-1.0 48 15 0 0i 0 Mg-1.0 Zn-1.0 100 48 18 4j 0 Mg-1.0 Cd-1.0 100 40 10 0presentinvention 1 0.2 Mg-1.0 0 100 98 58 10 2 0.5 Mg-1.0 0 100 100 88 23 3 1.0 Mg-1.0 0 100 100 90 31 4 2.0 Mg-1.0 0 100 100 95 45 5 1.0 Mg-0.2 0 100 99 60 35 6 1.0 Mg-0.5 0 100 100 75 55 7 1.0 Be-1.0 0 100 100 70 30 8 1.0 Ca-1.0 0 100 100 68 25 9 1.0 Sr-1.0 0 100 100 88 3210 1.0 Ba-0.5 0 100 100 85 2411 0.2 Mg-0.5 K-1.0 100 100 100 8912 0.5 Mg-0.5 K-1.0 100 100 100 9513 1.0 Mg-0.5 K-1.0 100 100 100 9814 2.0 Mg-0.5 K-1.0 100 100 100 10015 1.0 Mg-0.5 Li-0.2 100 100 100 9916 1.0 Mg-0.5 Na-0.5 100 100 100 9817 1.0 Mg-0.5 Rb-1.0 100 100 100 9818 1.0 Mg-0.2 Cs-1.0 100 100 100 10019 1.0 Be-1.0 Na-1.0 100 100 100 9620 1.0 Sr-0.5 Na-1.0 100 100 100 9921 1.0 Ba-0.5 Na-1.0 100 100 100 9522 1.0 Mg-1.0 Pb-1.0 100 100 100 8523 1.0 Mg-1.0 Ti-1.0 100 100 100 5924 1.0 Mg-0.5 Al-0.5 100 100 99 6025 1.0 Mg-0.5 Cr-0.5 100 100 100 7526 1.0 Mg-0.5 Mn-0.5 100 100 94 7027 1.0 Mg-0.5 Fe-0.5 100 100 90 7528 1.0 Mg-0.5 Co-0.5 100 100 99 7029 1.0 Mg-0.5 Ni-0.5 100 100 98 5330 1.0 Mg-0.5 Zn-0.5 100 100 100 9831 1.0 Mg-0.5 Cd-0.5 100 100 90 6332 1.0 Mg-0.5 Pb-0.5 100 100 100 5333 1.0 Mg-0.5 Ti-0.5 100 100 91 4134 1.0 Mg-0.5 V-0.5 100 100 95 4835 1.0 Ca-0.5 Al-0.5 100 100 98 7036 1.0 Ca-0.5 Cr-0.5 100 100 100 6437 1.0 Ca-0.5 Zn-0.5 100 100 100 9238 1.0 Ca-0.5 Pb-0.5 100 100 100 7039 1.0 Ca-0.5 Cd-0.5 100 100 100 7540 1.0 Be-0.5 Al-0.5 100 100 81 3841 1.0 Be-0.5 Cr-0.5 100 100 94 5442 1.0 Sr-0.5 Zn-0.5 100 100 100 9043 1.0 Sr-0.5 Cd-0.5 100 100 92 5044 1.0 Ba-0.5 V-0.5 100 100 100 6945 1.0 Ba-0.5 Ti-0.5 100 100 85 4146 0.2 Ca-1.0 Al-0.5 100 100 88 4047 0.5 Ca-1.0 Al-0.5 100 100 85 71__________________________________________________________________________
TABLE 7______________________________________Percent removal of H.sub.2 S at thetime point shown below (%) 50 hrs. 100 hrs. 150 hrs. 200 hrs. 250 hrs.Catalyst later later later later later______________________________________controla 0 0 0 0 0b 100 79 39 13 0c 95 32 0 0 0d 100 58 5 0 0e 100 69 15 0 0f 100 30 0 0 0g 100 45 11 0 0h 100 25 0 0 0i 100 64 14 0 0j 100 48 6 0 0presentinvention 1 100 100 98 69 39 2 100 100 100 95 83 3 100 100 100 95 86 4 100 100 100 100 98 5 100 100 90 81 65 6 100 100 98 93 86 7 100 100 90 83 69 8 100 100 98 81 73 9 100 100 100 95 8910 100 100 99 98 8411 100 100 100 100 9812 100 100 100 100 9813 100 100 100 100 10014 100 100 100 100 10015 100 100 100 100 10016 100 100 100 100 10017 100 100 100 100 10018 100 100 100 100 9919 100 100 100 100 10020 100 100 100 100 10021 100 100 100 100 10022 100 100 100 95 8923 100 100 100 91 8524 100 100 100 100 9025 100 100 100 100 9826 100 100 100 100 9527 100 100 100 100 9828 100 100 100 95 8029 100 100 100 91 7830 100 100 100 100 10031 100 100 100 100 10032 100 100 100 100 10033 100 100 100 95 8134 100 100 100 100 10035 100 100 100 100 9836 100 100 100 100 10037 100 100 100 100 10038 100 100 100 100 8339 100 100 100 100 8640 100 100 100 98 9441 100 100 100 92 8842 100 100 100 100 10043 100 100 100 100 10044 100 100 100 100 10045 100 100 100 100 9846 100 100 100 86 7547 100 100 100 94 91______________________________________
TABLE 8__________________________________________________________________________ Kind of Kind of third alkaline earth metal compoundBET metal salt or alkali Amount of Percent removal of COSspecific and amount metal compound copper at the time point shownsurface alkaline earth and amount of compound below (%) area metal the metal (as metal) 25 hrs. 50 hrs. 75 hrs. 100 hrs.Catalyst (m.sup.2 /g) (mg-atom/g) (mg-atom/g) (mg-atom/g) later later later later__________________________________________________________________________48 1100 Be(NO.sub.3).sub.2 -1.0 -- CuO-0.89 100 95 76 4949 1060 Mg(NO.sub.3).sub.2 -1.0 -- CuSO.sub.4 -0.98 100 100 80 4550 980 Ca(NO.sub.3).sub.2 -1.0 -- (CH.sub.3 COO).sub.2 Cu-1.03 100 100 83 3551 1000 Sr(NO.sub.3).sub.2 -1.0 -- (HCOO).sub.2 Cu-0.94 100 100 86 5152 970 Ba(NO.sub.3).sub.2 -1.0 -- CuCl.sub.2 -1.07 100 93 61 2853 980 BeCO.sub.3 -0.95 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 93 58 2554 1110 MgO-0.83 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 100 75 3955 960 CaO-0.91 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 98 56 1656 1050 SrO-1.05 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 100 90 6357 1140 Ba(OH).sub.2 -0.98 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 90 64 4358 1000 MgCl.sub.2 -1.09 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 93 70 5159 1060 (CH.sub.3 COO).sub.2 Mg-0.94 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 99 85 6760 990 (HCOO).sub.2 Ca-0.87 -- (CH.sub.3 COO).sub.2 Cu-1.0 100 98 71 4361 1120 BaCO.sub.3 -0.95 Li.sub.2 CO.sub.3 -0.85 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 91 2562 1110 SrCO.sub.3 -0.82 Na.sub.2 SO.sub.4 -0.93 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 90 4263 980 BeCO.sub.3 -0.99 K.sub.2 SO.sub.4 -0.88 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 95 5364 980 MgCO.sub.3 -0.92 Rb.sub.2 SO.sub. 4 -1.01 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 100 6565 960 (CH.sub.3 COO).sub.2 Sr-0.83 Cs.sub.2 SO.sub.4 -1.00 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 89 3166 1100 MgCO.sub.3 -0.92 HCOONa-1.09 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 96 4567 1030 (HCOO).sub.2 Mg-1.04 CH.sub.3 COOK-1.10 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 100 7968 1010 CaCO.sub.3 -1.00 (COONa).sub.2 -0.90 (CH.sub.3 COO).sub.2 Cu-1.0 100 95 81 1369 980 BeCO.sub.3 -0.95 Al(NO.sub.3).sub.3 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 98 85 4970 1110 MgO-0.83 Cr(NO.sub.3).sub.3 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 87 5871 960 CaCO.sub.3 -0.91 Mn(NO.sub.3).sub.2 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 93 6072 1050 SrO-1.05 Fe(NO.sub.3).sub.3 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 91 7573 1140 Ba(OH).sub.2 -0.98 Co(NO.sub.3).sub.2 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 78 5374 1000 MgCl.sub.2 -1.09 Ni(NO.sub.3).sub.2 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 99 73 6175 1060 (CH.sub.3 COO).sub.2 Mg-0.94 Zn(NO.sub.3).sub.2 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 100 10076 990 (HCOO).sub.2 Ca-0.87 VOSO.sub.4 -0.5 (CH.sub.3 COO).sub.2 Cu-1.0 100 100 95 88__________________________________________________________________________
TABLE 9______________________________________ Percent removal of COS at theContacting time point shown below (%)Temperature 25 hrs. 50 hrs. 75 hrs. 100 hrs.(.degree.C.) Catalyst later later later later______________________________________25 3 100 97 83 69 9 100 94 80 6560 3 100 100 100 64 9 100 100 100 5180 3 100 100 100 86 9 100 100 100 73120 3 100 100 100 52 9 100 100 100 3525 13 100 100 98 95 20 100 100 97 9260 13 100 100 100 100 20 100 100 100 10080 13 100 100 100 100 20 100 100 100 100120 13 100 100 100 75 20 100 100 100 6125 30 100 100 95 88 37 100 100 100 9560 30 100 100 100 69 37 100 100 100 10080 30 100 100 100 78 37 100 100 100 100120 30 100 100 100 51 37 100 100 100 68______________________________________
EXAMPLE 10
The activated carbon A of 16 to 24 mesh having a B.E.T. specific surface area of 1065 m.sup.2 /g was sprayed evenly with a solution in water of a certain amount each of copper nitrate, nitrate of an alkali metal and nitrate of Al, Cr, Mn, Fe, Co, Ni, Zn, Cd or Pb, titanium sulfate or vanadium sulfate.
50 ml of the resultant admixed product was packed into a 4-cm diameter column made of quartz glass. The column was heated at a heating rate of 5.degree. C./min while a nitrogen gas was allowed to pass through it at a linear flow rate of 10 cm/sec., and the packed product was calcined at 300.degree. C. for 30 minutes.
The content each of the copper compound, alkali metal compound and the compounds of Al, Cr, Mn, Fe, Co, Ni, Zn, Cd, Pb, Ti and V in the catalysts thus obtained were 0.2 to 2.0 mg atom as metal per g of activated carbon, as shown in Table 10.
As the control the activated carbon was admixed by the same procedure as mentioned above with combinations of copper nitrate and nitrate of an alkali metal and a compound of Al, Cr, Mn, Fe, Co, Ni, Zn, Cd, Pb, Ti or V, and the admixed product was calcined in a nitrogen gas at 300.degree. C. for 30 minutes. By this procedure, catalysts were prepared.
15 ml each of the catalysts .circle.E through .circle.M thus obtained was packed into a 1.6 cm diameter glass column, and a gas of 50.degree. C. containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through it at a linear flow rate of 40 cm/sec to conduct a break-through adsorption test on COS. The results are as shown in Table 10.
EXAMPLE 11
A 12 ml portion each of the catalysts .circle.E through .circle.M of Example 10 was packed into a 1.6 cm diameter glass column, and a gas of 25.degree. C. containing 10 ppm of H.sub.2 S (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through it at a linear flow rate of 40 cm/sec to conduct a break-through adsorption test on H.sub.2 S. The results are as shown in Table 11.
EXAMPLE 12
A certain amount of each of Li.sub.2 CO.sub.3, Na.sub.2 SO.sub.4, K.sub.2 SO.sub.4, Rb.sub.2 SO.sub.4, Cs.sub.2 SO.sub.4, HCOONa, CH.sub.3 COOK and (COONa).sub.2 was added to a coconut-shell raw material. After being mixed and crushed, the mixture was kneaded with various kinds of pitch, water, etc., and molded into cylindrical pellets of 4 mm diameter. The pellets were carbonized at 650.degree. C. and steam-activated at 900.degree. C.
The activated carbon thus obtained all showed a B.E.T. specific surface area of 950 to 1150 m.sup.2 /g and a content of an alkali metal compound of 0.4 to 0.6 mg atom as metal per g of activated carbon, as shown in Table 12.
Various kinds of the activated carbon were crushed and sieved to a uniform grain size of 16 to 24 mesh and each was sprayed with a solution in a 2% aqueous nitric acid of the determined amount each of copper nitrate and nitrate of Al, Cr, Mn, Fe, Co., Ni, Zn, Cd or Pb, titanium sulfate or vanadyl sulfate.
50 ml each of the admixed products thus obtained was packed into a 4-cm diameter column made of quartz glass. The column was heated at a heating rate of 5.degree. C./min, while a nitrogen gas was allowed to pass through it at a linear flow rate of 10 cm/sec., and the packed product was calcined at 350.degree. C. for 30 minutes. The content of the copper compound in the resultant catalysts was 1.0 mg atom as metal per g of activated carbon, while the contents of the compounds of Al, Cr, Mn, Fe, Co, Ni, Zn, Cd, Pb, Ti and V were 0.5 mg atom as metal per g of activated carbon.
15 ml each of the catalysts .circle.N through .circle.U thus obtained was packed into a 1.6 cm diameter glass column, and a gas of 40.degree. C. containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through it to conduct a break-through adsorption test on COS. The results are as shown in Table 12.
EXAMPLE 13
A 15 ml portion each of the catalysts .circle.G.sub.7 and .circle.H.sub.3 of Example 10 was packed into a 1.6-cm diameter glass column, and a gas containing 12.5 ppm of COS (N.sub.2 -97.5 vol.% and H.sub.2 O-2.5 vol.%) was passed through the column at 25.degree., 60.degree., 80.degree. and 120.degree. C., respectively, to conduct break-through adsorption tests on COS, whereby the gas linear flow rate in every case was maintained at 40 cm/sec as measured at 25.degree. C. The test results are as shown in Table 13.
TABLE 10__________________________________________________________________________ Kind and Percent removal of COS at Kind and amount the time point shown below Amount of amount of of third (%) copper alkali metal metals 25 hrs. 50 hrs. 75 hrs. 100 hrs.Catalyst (mg-atom/g) (mg-atom/g) (mg-atom/g) later later later later__________________________________________________________________________ .circle.E.sub.1 (control) 0 Na-1.0 Al-1.0 49 4 0 0 .circle.E.sub.2 (control) 0 Na-1.0 Cr-1.0 68 15 0 0 .circle.E.sub.3 (control) 0 Na-1.0 Fe-1.0 51 18 3 0 .circle.E.sub.4 (control) 0 Na-1.0 Zn-1.0 100 60 26 11 .circle.E.sub.5 (control) 0 Na-1.0 Cd-1.0 100 55 13 0 .circle.F.sub.1 (present 1.0 Na-1.0 Pb-1.0 100 100 100 77invention) .circle.F.sub.2 (present 1.0 Na-1.0 Ti-1.0 100 100 100 69invention) .circle.G.sub.1 (present 1.0 Na-0.5 Al-0.5 100 100 98 68invention) .circle.G.sub.2 (present 1.0 Na-0.5 Cr-0.5 100 100 100 73invention) .circle.G.sub.3 (present 1.0 Na-0.5 Mn-0.5 100 100 95 63invention) .circle.G.sub.4 (present 1.0 Na-0.5 Fe-0.5 100 100 95 79invention) .circle.G.sub.5 (present 1.0 Na-0.5 Co-0.5 100 100 98 53invention) .circle.G.sub.6 (present 1.0 Na-0.5 Ni-0.5 100 100 96 49invention) .circle.G.sub.7 (present 1.0 Na-0.5 Zn-0.5 100 100 100 70invention) .circle.G.sub.8 (present 1.0 Na-0.5 Cd-0.5 100 100 96 56invention) .circle.G.sub.9 (present 1.0 Na-0.5 Pb-0.5 100 100 100 60invention) .circle.G.sub.10 (present 1.0 Na-0.5 Ti-0.5 100 100 93 48invention) .circle.G.sub.11 (present 1.0 Na-0.5 V-0.5 100 100 98 58invention) .circle.H.sub.1 (present 1.0 K-0.5 Al-0.5 100 100 100 73invention) .circle.H.sub.2 (present 1.0 K-0.5 Cr-0.5 100 100 100 61invention) .circle.H.sub.3 (present 1.0 K-0.5 Zn-0.5 100 100 100 88invention) .circle.H.sub.4 (present 1.0 K-0.5 Pb-0.5 100 100 100 69invention) .circle.H.sub.5 (present 1.0 K-0.5 Cd-0.5 100 100 100 78invention) .circle.I.sub.1 (present 1.0 Li-0.5 Al-0.5 100 100 95 59invention) .circle.I.sub.2 (present 1.0 Li-0.5 Cr-0.5 100 100 98 63invention) .circle.J.sub.1 (present 1.0 Rb-0.5 Zn-0.5 100 100 100 89invention) .circle.J.sub.2 (present 1.0 Rb-0.5 Cd-0.5 100 100 97 54invention) .circle.K.sub.1 (present 1.0 Cs-0.5 V-0.5 100 100 100 78invention) .circle.K.sub.2 (present 1.0 Cs-0.5 Ti-0.5 100 100 94 53invention) .circle.L (present 0.2 K-1.0 Al-0.5 100 100 90 40invention) .circle.M (present 0.5 K-1.0 Al-0.5 100 100 95 77invention)__________________________________________________________________________
TABLE 11______________________________________Percent removal of H.sub.2 S at thetime point shown below (%) 50 hrs. 100 hrs. 150 hrs. 200 hrs. 250 hrs.Catalyst later later later later later______________________________________ .circle.E.sub.1 (control) 100 48 12 0 0 .circle.E.sub.2 (control) 100 69 18 0 0 .circle.E.sub.3 (control) 100 54 4 0 0 .circle.E.sub.4 (control) 100 72 24 0 0 .circle.E.sub.5 (control) 100 60 13 0 0 .circle.F.sub.1 (present 100 100 100 98 90invention) .circle.F.sub.2 (present 100 100 100 95 90invention) .circle.G.sub.1 (present 100 100 100 99 94invention) .circle.G.sub.2 (present 100 100 100 100 92invention) .circle.G.sub.3 (present 100 100 100 100 90invention) .circle.G.sub. 4 (present 100 100 100 100 94invention) .circle.G.sub.5 (present 100 100 100 98 85invention) .circle.G.sub.6 (present 100 100 100 98 89invention) .circle.G.sub.7 (present 100 100 100 100 91invention) .circle.G.sub.8 (present 100 100 100 100 100invention) .circle.G.sub.9 (present 100 100 100 100 100invention) .circle.G.sub.10 (present 100 100 100 98 91invention) .circle.G.sub.11 (present 100 100 100 100 100invention) .circle.H.sub.1 (present 100 100 100 100 95invention) .circle.H.sub.2 (present 100 100 100 100 100invention) .circle.H.sub.3 (present 100 100 100 100 100invention) .circle.H.sub.4 (present 100 100 100 100 94invention) .circle.H.sub.5 (present 100 100 100 100 96invention) .circle.I.sub.1 (present 100 100 100 95 91invention) .circle.I.sub.2 (present 100 100 100 98 92invention) .circle.J.sub.1 (present 100 100 100 100 100invention) .circle.J.sub.2 (present 100 100 100 100 100invention) .circle.K.sub.1 (present 100 100 100 100 100invention) .circle.K.sub.2 (present 100 100 100 99 96invention) .circle.L (present 100 100 100 92 85invention) .circle.M (present 100 100 100 93 90invention)______________________________________
TABLE 12__________________________________________________________________________ Kind of alkaliB.E.T. metal salt Percent removal ofspecific incorporated Amount COS at the time pointsurface and amount of of Kind and shown below (%) area alkali metal copper amount of 25 hrs. 50 hrs. 75 hrs. 100 hrs.Catalyst (m.sup.2 /g) (mg-atom/g) (mg-atom/g) third metal later later later later__________________________________________________________________________ .circle.N 1100 Li.sub.2 CO.sub.3 -0.45 1.0 Al-0.5 100 100 93 48 .circle.O 1050 Na.sub.2 SO.sub.4 -0.49 1.0 Cr-0.5 100 100 98 65 .circle.P 980 K.sub.2 SO.sub.4 -0.48 1.0 Mn-0.5 100 100 95 60 .circle.Q 1000 Rb.sub.2 SO.sub.4 -0.51 1.0 Fe-0.5 100 100 93 63 .circle.R 1000 Cs.sub.2 SO.sub.4 -0.55 1.0 Co-0.5 100 100 100 68 .circle.S 960 HCOONa-0.46 1.0 Ni-0.5 100 100 96 55 .circle.T 1080 CH.sub.3 COOK-0.50 1.0 Zn-0.5 100 100 100 56 .circle.U 1100 (COONa).sub.2 -0.52 1.0 V-0.5 100 100 100 49__________________________________________________________________________
TABLE 13______________________________________ Percent removal of COS at theContacting time point shown below (%)temperature 25 hrs. 50 hrs. 75 hrs. 100 hrs.(.degree.C.) Catalyst later later later later______________________________________25 .circle.G.sub.7 100 100 90 85 .circle.H.sub.3 100 100 100 9260 .circle.G.sub.7 100 100 100 58 .circle.H.sub.3 100 100 100 10080 .circle.G.sub.7 100 100 100 59 .circle.H.sub.3 100 100 100 100120 .circle.G.sub.7 100 100 100 46 .circle.H.sub.3 100 100 100 65______________________________________

Number	Date	Country
57-15422	Feb 1982	JPX
57-37500	Mar 1982	JPX
57-37501	Mar 1982	JPX

Number	Name	Date
1812526	Gross et al.	Jun 1931
2513508	Morrell et al.	Jul 1950
2528517	Hormats	Nov 1950
3416293	Alexander	Dec 1968
3974256	Wheelock et al.	Mar 1976
4002720	Wheelock et al.	Jan 1977
4044114	Dezael et al.	Aug 1977
4088736	Courty et al.	May 1978
4233175	Delmon et al.	Mar 1980
4242226	Siren	Dec 1980
4310497	Deschamps et al.	Jan 1982
4358427	Urban	Nov 1982
4399112	Voirin	Aug 1983
4451442	Jeffrey et al.	May 1984

Number	Date	Country
362552	Dec 1931	GBX
370978	Apr 1932	GBX
1260030	Jan 1972	GBX

Process for treatment of gases

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