JPH0322201B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for treating liquid hydrocarbons containing sulfur compounds and an adsorbent for sulfur compounds used in this method. Hydrocarbons such as petroleum distillate pyrolysis gas, LNG, and LPG contain sulfur compounds such as hydrogen sulfide, carbonyl sulfide, mercaptans, sulfides, and disulfides, and even in trace amounts, these sulfur compounds cause odor. It often causes problems in processes such as beverage processing and chemical reactions because it exhibits catalyst poisoning effects. In order to remove these sulfur compounds, chemical cleaning methods using alkaline solutions, alkanolamine solutions, etc. in the gas phase, or adsorption methods using iron oxide, zinc oxide, activated carbon, etc., have been proposed, but the removal effects are poor; This method has drawbacks such as the large size of the removal device, making it impractical. In view of these circumstances, the inventors of the present invention have made extensive studies and found that activated carbon contains copper compounds and alkali metals.
Alkaline earth metal compounds or Al, Ti, V, Cr,
By containing compounds of Mn, Fe, Co, Ni, Zn, Cd, and Pb, hydrogen sulfide, carbonyl sulfide, mercaptans, sulfides, and disulfides in liquid hydrocarbons can be removed very efficiently. The present invention has been completed. That is, the present invention provides: (1) activated carbon with a copper compound, (a) an alkali metal compound, (b) an alkaline earth metal compound, and (c) Al;
Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cd,
(2) An adsorbent for sulfur compounds in liquid hydrocarbons containing one or more Pb compounds;
(a) alkali metal compounds, (b) alkaline earth metal compounds and (c) Al, Ti, V, Cr, Mn, Fe,
A method for treating a liquid hydrocarbon containing a sulfur compound, the method comprising bringing it into contact with an adsorbent containing one or more of Co, Ni, Zn, Cd, and Pb compounds (sometimes referred to as the second component); It is. The adsorbent of the present invention can be manufactured by incorporating the first component and the second component into activated carbon. The activated carbon used in this case is manufactured by a known method using coal, coke, charcoal, coconut shell, resin, etc. as raw materials, and its specific surface area is
Any material may be used as long as it has a density of 200 to 2000 cm ² /g, and its shape may be spherical, cylindrical, crushed, powdered, fibrous, etc. depending on the gas processing method. Examples of the copper compound used in the present invention include inorganic acid salts or inorganic compounds such as carbonates, basic carbonates, nitrates, sulfates, phosphates, halides, oxides, and hydroxides, formates, and acetic acid. and organic acid salts such as oxalates. Alkali metal compounds include Li, Na, K,
Rb, Cs such as bicarbonate, carbonate, nitrate,
Inorganic acid salts or inorganic compounds such as borates, silicates, sulfates, halides, hydroxides, formates, acetates, oxalates, benzoates, salts of phenols, salts of sulfonic acids, etc. Examples include organic acid salts of In addition, examples of alkaline earth metal compounds include Be,
Mg, Ca, Sr and Ba such as carbonates, nitrates, sulfates, phosphates, halides, oxides,
Inorganic acid salts or inorganic compounds such as hydroxides, organic acid salts such as formates, acetates, oxalates, etc.
Al, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cd,
Pb compounds include inorganic acid salts of these metals such as carbonates, hydrogen carbonates, nitrates, borates, silicates, sulfates, phosphates, halides, hydroxides, ammonium salts, and oxides. or inorganic compounds, formates, acetates, oxalates, benzoates,
Examples include organic acid salts such as phenol salts and sulfonic acid salts. The adsorbent of the present invention is one in which activated carbon contains both a first component and a second component. In this case, the second component is an alkali metal compound (hereinafter also referred to as component (a)) alone, Alkaline earth metal compound [hereinafter sometimes referred to as component (b)] alone or Al, Cr, V, Mn, Fe, Co, Ni, Zn, Cd,
It may contain a single Pb compound [hereinafter also referred to as component (c)], but among these, component (a) and component (b), component (b) and component (c), Alternatively, it may contain two components, such as component (c) and component (a), or it may contain three components, component (a), component (b), and component (c), at the same time. Moreover, the first component may contain two or more kinds of compounds, and the second component may contain two or more kinds of compounds in the same kind of component, for example, two different kinds of components in component (a). It may also contain different components. The content of the first component in the activated carbon containing a metal compound is from 0.1 mg-atom to 3.0 mg-atom, preferably from 0.2 mg-atom to 2.0 mg-atom, as metal per gram of activated carbon, and the content of the second component is from 0.2 mg-atom to 2.0 mg-atom per gram of activated carbon. as metal
0.1 mg-atom to 5.0 mg-atom, preferably 0.2 mg-atom to 4.0 mg-atom. The adsorbent of the present invention may be one in which each component is supported or impregnated on activated carbon, or it may be obtained by adding each component to an activated carbon raw material and then activating this. Alternatively, a part of the first component and the second component may be added to the activated carbon raw material to activate it, and the remaining components may be impregnated with this. When each component is impregnated onto activated carbon, it is preferable to dry or bake it after impregnation. Possible methods for impregnating activated carbon with each component include impregnating or spraying activated carbon with a solution in which each component is dissolved or suspended in water (including acid or alkaline aqueous solutions), various solvents, or the like. In the above preparation method, drying refers to the step of evaporating the water or solvent in the impregnated activated carbon at a temperature of about 130°C or lower, and calcination refers to the step of evaporating the impregnated activated carbon that has been dried at a temperature of about 130°C or higher. A process in which part or all of a metal compound is thermally decomposed by heating in an atmosphere of active gas, carbon dioxide, steam, combustion exhaust gas, etc. In the above method, if a substance other than an oxide is impregnated onto activated carbon as the first component or second component (excluding alkali metal compounds), it is recommended to heat-treat the activated carbon by drying or firing after impregnation. , when a second component (excluding alkali metal compounds) is impregnated with activated carbon and no heat treatment is performed,
It is preferable to use oxides for the first component and the second component (excluding alkali metal compounds). When an alkali metal compound other than alkali metal hydroxide, carbonate, or bicarbonate is impregnated onto activated carbon as a second component, it is recommended to perform heat treatment such as drying or calcination after impregnation. If no heat treatment is to be carried out later, it is preferable to use hydroxide, carbonate, or bicarbonate as the alkali metal compound. Examples of the sulfur compounds to be removed in the present invention include hydrogen sulfide, carbonyl sulfide,
Mercaptans (e.g. methyl mercaptan,
ethyl mercaptan, etc.), sulfides (eg, methyl sulfide, ethyl sulfide, etc.), and disulfides (eg, methyl disulfide, ethyl disulfide, etc.). Any liquid containing a sulfur compound may be used, and examples of hydrocarbons include liquefied ethylene, liquefied propylene, liquefied natural gas, and liquefied petroleum gas. The method of the present invention is carried out by contacting the metal compound-containing activated carbon obtained above with a liquid hydrocarbon containing a sulfur compound. As the contacting method, known means such as a fixed bed, a moving bed, a fluidized bed, etc. can be used. The contact temperature in this case is
The temperature is 100℃ or less, preferably 0 to 100℃, and the gas pressure is 50Kg/ ^cm2 or less, preferably 0.1 to 40Kg/cm2 ^.
The space velocity of the liquid is 1/10 to 20 hr ^-1 , preferably 1/5 to 10 hr ^-1 at 25° C. in terms of 1 kg/cm ² . EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 A predetermined amount of ^the first component (copper nitrate) and second component (alkali metal nitrate, alkaline earth metal nitrate, and Al, Ti, and V , Cr, Mn, Fe, Co,
Nitrate of Ni, Zn, Cd, Pb (only V is sulfate)
An aqueous solution containing the above was evenly dispersed. 50ml of the obtained impregnated material was packed into a 4cmφ quartz glass column, heated at a temperature increase rate of 5°C/min while flowing nitrogen gas at a linear flow rate of 10cm/sec, and heated to 300°C.
Baked for 30 minutes. As shown in Table 1, the content of each metal compound in the obtained adsorbent was 0.2 to 2.0 mg atoms per gram of activated carbon. As a control, an adsorbent was prepared by impregnating activated carbon A with a nitrate of each metal alone and calcining it at 300° C. for 30 minutes in nitrogen gas in the same manner as described above. The adsorbents A to G and ~〓〓 obtained in this way are finely ground to 100 mesh or less and dried.
Put 1.0g into a 100ml stoppered flask and add H ₂ S to it.
-0.1mg/ml, cos-0.15mg/ml and _CH3SH-
10 ml of n-hexane at 25° C. containing 0.05 mg/ml was injected, the tube was tightly stoppered, and the mixture was shaken at 25° C. for 10 minutes. The concentration of these sulfur compounds in n-hexane was measured to determine the removal rate. The results are shown in Table 1.

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Claims (1)

[Claims] 1. Activated carbon containing a copper compound, (a) an alkali metal compound, (b) an alkaline earth metal compound, and (c) Al, Ti,
An adsorbent for sulfur compounds in liquid hydrocarbons containing one or more of the following compounds: V, Cr, Mn, Fe, Co, Ni, Zn, Cd, and Pb. 2 A liquid containing a sulfur compound is added to activated carbon with a copper compound, (a) an alkali metal compound, (b) an alkaline earth metal compound, and (c) Al, Ti, V, Cr, Mn,
A method for treating a liquid hydrocarbon containing a sulfur compound, which comprises bringing it into contact with an adsorbent containing one or more of Fe, Co, Ni, Zn, Cd, and Pb compounds.