JPS58153519A - Treatment of gas - Google Patents

Abstract

PURPOSE:To remove efficiently H2S and COS contained in a gas, by bringing an inert gas or a reducing gas contg. no oxygen into contact with activated carbon contg. a specified metallic compd.. CONSTITUTION:An inert gas or a reducing gas contg. substantially no oxygen but contg. H2S or COS, such as beverage carbon dioxide, coke oven gas. blast furnace gas, converter gas, cracked petroleum gas, or natural gas, is brought into contact with activated carbon contg. a specified metallic compd. to remove H2S and COS by adsorption. As the specified metallic compd. in this case, sulfate, nitrate, or the like of copper; and carbonate, nitrate, borate, or the like of Li, Na, K, R6, Ca, or the like; and carbonate, sulfate, nitrate, halide, oxide, or the like of at least one of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cd, and Pb are used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides hydrogen sulfide in a reducing gas before an inert gas;
This article relates to a method for treating bushes to remove sulfidation power (boniμ).

Beverage carbon dioxide gas, coke oven I gas, blast furnace I gas, converter gas, petroleum fraction pyrolysis gas, natural gas, etc. contain metal sulfides such as hydrogen sulfide and IIl&/bonyl sulfide. These sulfur compounds exhibit a poisonous effect in their odor even in minute amounts, so they often pose a problem in processes such as beverage processing and chemical reactions.

To discuss these sulfur compounds, alkaline solution,
A chemical cleaning method using an amine solution or an adsorption method using iron oxide, T1m oxide, active #l2tk, etc., have been proposed, but the removal efficiency is poor, especially for sulfurized*e.
'Removal of Bonip is difficult.

In view of these circumstances, the inventors of the present invention have conducted intensive studies and found that activated carbon contains copperized metals, alkali metal compounds, aluminum, titanium, vanadium, talomnium, etc.
manrye iron s cobalt.

It was discovered that by containing a compound of nickel, zinc, iI domium, t, or lead, hydrogen sulfide and sulfuric acid μbony in the gas could be removed very efficiently, and the present invention was completed.

That is, in the present invention, when removing hydrogen sulfide and/or carbo sulfide (hereinafter referred to as sulfur compound) from an inert gas or reducing gas that does not substantially contain oxygen, the gas is converted into a copper compound. , ■ Alkali metalized metal objects and ■ Aluminum.

Chemicals of at least four selected metals (from the group consisting of titanium, panamium, diamium, manganese, iron, cobalt, nickel, zinc, idomium, and lead)
This is a method for treating a gas, which is characterized in that it is brought into contact with active* (hereinafter referred to as metallized metal-containing activated carbon) containing K (hereinafter referred to as the fifth metallized metal substance).

Activated carbon used in the present invention includes coal, coke, main carbon,
It is a round product manufactured by an omniscient method using wood, wood, etc. as raw materials, and its specific surface area is 200 to 2000 m
”/f, any item is fine, so long as it is 01
The # shape may be round, spherical, 9 cylindrical, crushed, powdered, fibrous, etc. depending on the gas processing method.

Examples of the copper compound used in the present invention include podate, m-based carbonate, nitrate, sulfate, s7e, 7, al
':y(5@, @, chi-1, i, □.

Examples of the inorganic acid salt include organic acid salts such as mineralized metals, formates, acetates, and V-oxalates.

Rb, Ca circles such as hydrogen carbonate, carbonate, nitrate salt,
Borates, silicates, sulfates, halides.

Inorganic acid salts such as hydroxides include inorganic compounds, organic acid salts such as formic acid salts, acetic acid salts, V oxalates, benzoates, pheno-μ salts, and sulfonic acid salts. .

The third metallized metals include Al, Ti, and V.

Or, Mn, Fe, Co, lli, Zn,
Inorganic compounds such as Cd, Pb, chloride, nitrate, sulfuric acid, phosphoric acid, halide, anhydride, oxide, hydroxide, etc. are inorganic compounds, formates.

Examples include organic acid salts such as acetate and V-oxalate.

The metal compound-containing activated carbon of the present invention is prepared by a method similar to Kutobagi O.

(1) Activated carbon raw materials include ■copper compound, ■alkali metal compound, ■mu1.〒1.Ma, Or, Mn, Fe, C
o, Ni, Kn, C(1,Pb()) are added and carbonized and activated using a conventional method.

(2) ■ Add a copper compound to the activated carbon raw material and carbonize and activate it using a normal method. 1. Add an alkali metal compound and 1. to the obtained nine activated carbon. 〒i, Y, Cr, Mn, Fe.

Co, Ni, Zn, Cd, Pb (2) compounds are simultaneously and separately applied, dried and fired as necessary.

(3) Active #! ■ Adding an alkali metal compound to the raw material,
Carbonize and activate using normal methods. The obtained active leg was treated with ■copper compound and ■mul, Ti, Y, Cr, Mn, re
, G.

.

(4) Activated carbon raw materials ■Al, Ti, V, Cr,
Mn, F'e, Go, Ni, Zn, Cd,
Pb C) compound is added and carbonized and activated in a conventional manner. 1) Copper compound and 2) alkali metal compound are impregnated simultaneously and separately on the obtained activated carbon, and if necessary, they are dried and fired.

(5) Activated carbon with ■copper metal compound, ■alkali metal compound, ■Al, Ti, V, Cr, Mn, T@, Go, lii
, Zn, Cd, and Pb are simultaneously attached,
Dry and bake if necessary.

(6) A copper compound is impregnated on activated carbon, dried or fired, and an alkali metal compound and Ti are added.

V, Cr, Mn, We, Go, Ml, Zn
, Cd, and Pb are applied simultaneously or separately, and if necessary, drying and baking are performed.

(7) A metal compound is impregnated on activated carbon, dried and calcined, and then a copper compound and Al and Ti are added.

V, Cr, Mn, Fe, Co, Ni, Zn,
Compounds of Cd and Pb are simultaneously attached to the substrate and dried or fired as required.

(8) Activated carbon with ■Mul, Ti, V, Cr, Mn
, 1'@.

Compounds of Co, Mi, Zn, Cd, and Pb are impregnated and dried or fired, and (1) a copper compound and (2) an alkali metal compound are applied simultaneously or separately, and if necessary, the first part is fired after drying.

In these preparations, the method for impregnating activated carbon with metallized metals is to dissolve the metal compound in water (including alkaline aqueous solutions), various types of solutions, etc., and then impregnate the activated carbon with the liquid. One possible method is to scatter the circles.

In addition, in the above preparation, drying means about 13-U-℃
The process of evaporating the water in the impregnated activated carbon at the following temperature is the process of evaporating the solvent, and firing is the process of evaporating the water in the impregnated activated carbon at a temperature of about 130°C or higher. S-Kan,
Some of the metal compounds are heated in an atmosphere such as combustion exhaust gas.
E refers to the process of thermally decomposing the entire material.

In the above method, if a copper compound or a third metal compound other than an oxide is impregnated onto activated carbon, heat treatment such as firing is preferably performed after impregnation and before drying. When impregnated with activated carbon and not subjected to heat treatment, it is preferable to use an oxide as the copper compound and third metal compound. Also, as alkali metal compounds, its hydroxides and hydrochlorides.

1 [When impregnating activated carbon with something other than podate, it is best to carry out heat treatment such as drying or calcination after impregnation, and when impregnating activated carbon with an alkali metal compound without prior heat treatment. It is best to use hydroxide for the acid, and bicarbonate for the *acid.

The content of the copper compound in the metal compound-containing activated carbon is as follows: activated carbon 1f@90. IIIg-atom ~3゜O~-
atoms, preferably from 0.2 to 1 to 2.0 cap-atoms,
The content of the alkali metal compound is 0.1 cap - 3 atoms per gram of activated carbon as metal. θ~1 atom, preferably 0.2
1L-atom ~2. O1F-atom, and the content of the third metal compound is J) 0.111 g-atom to 5.0 per gram of activated carbon.
"f-atom, preferably tie, 2q-atom~460■~
It is an atom.

The substantially oxygen-free inert gas or reducing gas used in the present invention has an oxygen concentration of 2% or less and a water vapor concentration of 7% or more, equivalent to that of a sulfur compound. Examples of these O gases include hydrogen gas, coke oven gas, blast furnace gas, converter gas, petroleum fraction pyrolysis gas, and natural gas.

The method of the present invention is carried out by bringing a gas containing a sulfur compound into contact with the active metal compound anastomosis 1 obtained in the above. As for the contact method, for example, fixed layer,
Known means such as a moving bed and a fluidized bed are used. The contact temperature in this case is 250°C or less, preferably 0 to 150°C.
℃, the pressure of the gas is 50 kg/(-1, preferably 0.1 to 40-40), and the contact time of the gas is 2
The heating time is 1/10 to 100 seconds, preferably 175 to 80 seconds at 5°C and 1 kgj layer count.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Implementation N/BLOT specific surface area 1065 27/7 16-24
sh (2) Predetermined amounts of nitric acid steel and alkali metal nitrate and mulch, Cr, Mn, Fe, Co,
lli, Zn.

Cd and Pb can be filled with nitric acid, titanium sulfate and vanadyl sulfate can be dissolved and an aqueous solution can be widely sprayed.

50 d of the obtained nine impregnated materials were filled into a quartz glass cuff of 4 csφ, heated at a temperature increase rate of 5 tl/win while flowing nitrogen gas at a linear flow rate of 10 cm/sea, and heated to 300°C.
Bake for 30 minutes.

Copper metals, alkali metal compounds, and Al, Cr, Mn, re, Go, Ni, and Z in the obtained round rope.
n, Cd.

As shown in Table 1, the content of Pb, Ti, and V compounds is 0.2 to 2 as metals per 1 g of activated carbon, and O
1l-atom and nine.

As a control, nitric acid steel was prepared in the same manner as above.

Alkali metal nitrates and mul, Cr, Mn,
F's.

Go, Ni, Zn, Cd, Pb, 〒1. A combination of two types of compounds of V (hereinafter referred to as the third metal in the table) was impregnated and fired at 300°C for 30 minutes in nitrogen gas to prepare a tip rope.

Each 16sZ of the precursors 11B-M obtained in this way was 1
．． Fill a 6CIlφ Kabu 5 made by Gaffs and add CO5-12
, 5ppm containing gas (N2-97.5v01
%, H2O-2,5 malo 1%) at a linear flow of 40 cm/ae
9, which circulates in c and performs breakthrough adsorption temate of COS. The results are shown in Table 1).

Example λ 12 mg each of Catalyst B-MO of Example 1 was packed into a 1.6 CIlφ glass cuff, and 25°C O: If) containing HH2S-10pp (N297.5VOIg6.N2
02.5 VOI, 1) was passed at a linear flow rate of 40 cm/sec, and a H, S breakthrough adsorption test was conducted. The results are shown in Table 2.

Example 3 Predetermined amount of Li2CO3,1Ia2804 in coconut guff raw material
゜ [2804, Rb2804. C82804, HCO
OIIa, CH3GOOK, (COOIIa)2
was added, mixed and pulverized, and then pitches, water, etc. were added and kneaded, and the mixture was molded into a cylindrical shape of 4 mwφ. This pellet was carbonized at 650°C [7] and then activated with steam at 900°C.

As shown in Table 3, the obtained nine activated carbon has a IIIT specific surface area of 950 to 1150-99, and the content of alkali metal compound is 0°4 to (16# one atom and .

These activated carbons are crushed and sized to 16-24 mash,
Predetermined amount of sulfuric acid steel and mulch, Cr, Mn, Fs, C
o.

Ni, Zn, Cd, PbO, titanium sulfate, and vanadium sulfate were dissolved and a 292% aqueous solution was sprayed.

50 m of the obtained impregnated material was packed into a 4 cvaφ quartz glass column, and nitrogen gas was passed through the column at a linear flow rate of 10 cm/sea (Table 1, Table 2). , heated at a temperature increase rate of 5°C/win, and heated at 350°C
A friend who baked for 0 minutes. The content of copper compounds in the catalyst is determined by the active leg i
f is 1.0111 one atom as a metal, ml, Or
, Mn, re, Co, Ml, Zn, Cd.

The content of Pb, Ti and V compounds is 0.5 to 1 atom per gram of activated carbon.

Each 15 sJ of the precursor KN-U thus obtained was 1.
Filled with 6CIlφ glass cuff, CO3-12,
Gas at 50℃ containing 5pp1m (t12-97.5vO
1%, H2O-2,5vol 1g) at a linear flow rate of 40cs
/aec, and a COS breakthrough adsorption test was conducted, and the results are shown in Table 3.

Example: 15 m each of catalysts G7 and H3 of Example 1 were packed into a 1°6C diameter kaom made of Gaffs, and 008-12.5 ppm.
Containing gas (Mg-97,5vO1 cap a2oz, 5
vo1g) wo25, 60', 80o! hill 20
℃1' distribution, COS breakthrough adsorption test was carried out. In both cases, the gas linear flow velocity is 40c at 25°C.
It was a/sea. The test results are shown in Table 4.

Claims (1)

[Claims] When examining hydrogen sulfide and/or carbonyl sulfide in a reducing gas, an inert gas that does not contain oxygen is ■A μ Ori pot belonging to the building and ■ Aminikufu, titanium, vanadium, termium, man I. IO, characterized in that it is brought into contact with activated carbon containing at least one metal O compound selected from the group consisting of iron, cobate, nickel*, li lead, cadmium and lead.
Shoruru method.