JPH0586373A - Removal of heavy metal from hydrocarbon oil - Google Patents

Abstract

PURPOSE:To remove a heavy metal from a hydrocarbon oil at good efficiency by a simple means. CONSTITUTION:A hydrocarbon oil containing a heavy metal is mixed with 1-100mol, per mol of the heavy metal, of a chelating agent and the resulting mixture is brought into contact with active carbon to remove the heavy metal. As the chelating agent, dithizone, 8-quinolinol or the like is desirable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing heavy metals such as mercury and lead contained in hydrocarbon oil.

[0002]

2. Description of the Related Art In crude oil and petroleum products, the presence of lead compounds is known from some production areas. These lead compounds cause a decrease in the activity of the catalyst in the catalytic reaction when used as a petroleum refining process or as a chemical raw material.
As a method of removing a compound, a method of converting a lead compound into a sulfide to remove by precipitation is used.

Condensate contained in crude oil and natural gas has several tens of ppb from some production areas.
It is known that order-made mercury and mercury compounds exist, and these mercury compounds easily generate amalgam with metal materials such as copper, and are used for catalytic reaction when used as petroleum refining treatment or as a chemical raw material. It is a cause of deterioration of catalyst activity, corrosion of metal materials used in chemical industrial equipment, and deterioration of strength. As a method for removing the mercury and the mercury compound, a method for removing by adsorption using activated carbon,
Alternatively, a method of removing by contact with copper, aluminum and these compounds has been attempted.

[0004]

However, lead is
In the method of removing as a sulfur compound, sulfur and a sulfur compound remain in the hydrocarbon oil, which becomes an obstacle in utilizing the hydrocarbon oil. Further, in the method of adsorbing and removing mercury using activated carbon, when the hydrocarbon oil is an aromatic hydrocarbon such as benzene and toluene, there is a problem that mercury and a mercury compound cannot be sufficiently removed.

Further, in the method of removing mercury and mercury compounds by contact with copper, aluminum and their compounds, the apparatus requires a high temperature for the treatment, and the apparatus is complicated and there is a problem in terms of cost. An object of the present invention is to provide a method for solving the above-mentioned conventional problems and efficiently removing heavy metals and heavy metal compounds from hydrocarbon oils by a simple means.

An object of the present invention is to solve the above conventional problems and to provide a method for efficiently removing heavy metals from hydrocarbon oils by a simple means.

[0007]

As a result of earnest studies, the present inventor was able to solve the above problems. That is, according to the present invention, among the heavy metals or compounds thereof present in hydrocarbon oil, those present as salts are difficult to be adsorbed on activated carbon, so that they are changed to chelate compounds and compounds easily adsorbed on activated carbon. Then, it is brought into contact with activated carbon to be adsorbed together with the heavy metal and the organic compound of the heavy metal. This provides a method for removing heavy metals and heavy metal compounds from hydrocarbon oils.

The present invention will be described in more detail below.
In the present invention, the hydrocarbon oil is any hydrocarbon oil and is not particularly limited. For example, aromatic hydrocarbon oils such as benzene and toluene, gasoline, kerosene, light oil, natural gas condensate and the like can be used. The chelating agent that can be used in the present invention is not particularly limited, and examples thereof include dithizone, 8-quinolinol, acetylacetone, ethylenediaminetetraacetic acid and salts thereof, dithiocarbamic acid and salts thereof, and the like. Among them, dithizone, 8-
Quinolinol is preferred.

The amount of the chelating agent added to the hydrocarbon oil is 1 to 100 times, preferably 5 to 50 times, and particularly preferably 5 times the number of heavy metal atoms contained in the hydrocarbon oil.
~ 20 times the molar amount is used. If the amount of chelating agent is 3 times or less, the chelate formation with the heavy metal compound is insufficient, and even if it is added 50 times or more, the excess chelating agent is adsorbed by the activated carbon and the adsorption amount of the heavy metal and the heavy metal compound of the activated carbon Is decreased, which is not preferable.

After mixing the above chelating agent with the hydrocarbon oil, the mixture is contacted with activated carbon. The activated carbon that can be used in the present invention may be general one, and examples thereof include Diahope-008 (manufactured by Mitsubishi Kasei) and Diasorb-G (manufactured by Mitsubishi Kasei).
As a method of contacting the hydrocarbon oil mixed with the chelating agent and the activated carbon, either a batch type or a continuous type is possible, a method of filling the tubular body with the activated carbon and passing the hydrocarbon oil through it.
Examples include a method in which activated carbon and hydrocarbon oil are put in a container and mixed with stirring. Of these, a method of passing a hydrocarbon oil through a column packed with activated carbon is preferable. The contact with the activated carbon may be carried out by a generally used procedure in any method.

By this activated carbon treatment, the heavy metal and / or heavy metal compound and the heavy metal chelate contained in the hydrocarbon oil are adsorbed and removed from the hydrocarbon oil.
The present invention will be further described below with reference to examples.

[0012]

【Example】

Example 1 (Preparation of hydrocarbon oil) 100 wt% of mercury (II) chloride as mercury was added to a mixed hydrocarbon oil of N-heptane 40%, isooctane 50% and toluene 10% by volume.
/ Volppb, mercury (II) acetate 100w as mercury
t / volppb, added, dissolved and mixed.

(Confirmation of removal effect) Dithizone was dissolved in trichloromethane so as to have a concentration of 10 ^-4 Mol / liter, and 2 μl, 5 μl and 1 μl were added to 200 ml of the above hydrocarbon oil.
0 μl, 20 μl and 50 μl were added.

Internal diameter 1 with a Teflon cock at the bottom
Activated carbon (Diahope-008:
(Manufactured by Mitsubishi Kasei Co., Ltd.) was filled to a height of 100 mm. 200 ml of the hydrocarbon oil containing the mercury compound prepared by mixing in this column was flowed at a rate of 2 ml for 1 minute. The mercury content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 1.

[0015]

[Table 1]

Example 2 (Preparation of Hydrocarbon Oil) Mercury (II) chloride as mercury is 100 wt% with respect to a mixed hydrocarbon oil of 40% N-heptane, 50% isooctane, and 10% toluene.
/ Volppb and mercury (II) acetate as mercury 10
0 wt / volppb was dissolved.

(Confirmation of removal effect) A glass tube having an inner diameter of 10 mm equipped with a Teflon cock below was filled with activated carbon (Diahope-008: manufactured by Mitsubishi Kasei) so that the height was 100 mm. Hydrocarbon oil containing mercury compound mixed and prepared in this column was heated to 200 m at a speed of 2 ml for 1 minute.
l shed. The mercury content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 2.

[0018]

[Table 2]

Example 3 (Preparation of hydrocarbon oil) Mercury (II) chloride as mercury was 100 wt% with respect to a mixed hydrocarbon oil of N-heptane 40%, isooctane 50% and toluene 10% by volume.
/ Volppb and mercury (II) acetate as mercury 10
0 wt / volppb was dissolved.

(Confirmation of the removal effect) A solution of dithizone, 8-quinolinol, or acetylacetone dissolved in trichloromethane was added to 200 ml of the above hydrocarbon oil to give a concentration of 10 ^-4 Mol / liter. Inner diameter 10 mm with Tetoron cock on the bottom
The glass tube of was filled with activated carbon (Diahope-008: manufactured by Mitsubishi Kasei) so that the height was 100 mm. Hydrocarbon oil containing a mercury compound prepared by mixing in this column was
200 ml was run at a speed of 2 ml per minute. The mercury content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 3.

[0021]

[Table 3]

Example 4 (Preparation of hydrocarbon oil) Mercury (II) chloride as mercury was 100 wt% with respect to a mixed hydrocarbon oil of N-heptane 40%, isooctane 50% and toluene 10% by volume.
/ Volppb, mercury (II) acetate 100w as mercury
t / volppb, and ethyl mercury as mercury 10
0 wt / volppb was added, dissolved and mixed.

(Confirmation of Removal Effect) Dithizone was dissolved in trichloromethane so that the concentration was 10 ⁻⁴ Mol / liter, and 20 μl was added to 200 ml of the above hydrocarbon oil.
Activated carbon (Dia Hope-008: Mitsubishi Kasei) is placed in a glass tube with an inner diameter of 10 mm equipped with a Tetoron cock below.
Was filled to a height of 100 mm. Hydrocarbon oil containing mercury compound prepared by mixing in this column is 2 m for 1 minute.
200 ml was poured at a speed of l. The mercury content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 4.

[0024]

[Table 4]

Example 5 (Preparation of Hydrocarbon Oil) Lead (II) acetate as 100 wt / v as lead was added to a hydrocarbon oil mixed with 40% by volume of N-heptane, 50% of isooctane and 10% of toluene.
olppb, added, dissolved and mixed.

(Confirmation of removal effect) Dithizone was dissolved in trichloromethane to a concentration of 1 Mol / liter, and 20 μl and 50 μl were added to 200 ml of the above hydrocarbon oil.
1, 100 μl, 200 μl and 500 μl were added.
A glass tube having an inner diameter of 10 mm equipped with a Teflon cock below was filled with activated carbon (Dia Hope-008: manufactured by Mitsubishi Kasei) so that the height was 100 mm. 200 ml of a hydrocarbon oil containing a lead compound mixed and prepared in this column was flowed at a rate of 2 ml for 1 minute. The content of lead in the spilled hydrocarbon oil was analyzed by an atomic absorption method. The results are shown in Table 5.

[0027]

[Table 5]

Example 6 (Preparation of Hydrocarbon Oil) Lead (II) nitrate as lead was 100 wt / v with respect to a mixed hydrocarbon oil of 40% N-heptane, 50% isooctane and 10% toluene.
olppb and lead (II) acetate as lead at 100 wt /
It dissolved in volppb.

(Confirmation of Removal Effect) A glass tube having an inner diameter of 10 mm equipped with a Teflon cock below was filled with activated carbon (Diahope-008: manufactured by Mitsubishi Kasei) so that the height was 100 mm. 200 ml of a hydrocarbon oil containing a lead compound mixed and prepared in this column was flowed at a rate of 2 ml for 1 minute. The lead content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 6.

[0030]

[Table 6]

Example 7 (Preparation of Hydrocarbon Oil) Lead (II) nitrate as 100 wt / v as lead was added to a hydrocarbon oil mixed with N-heptane 40%, isooctane 50% and toluene 10% by volume.
olppb and lead (II) acetate as lead at 100 wt /
It dissolved in volppb.

(Confirmation of Removal Effect) 200 μl of dithizone, 8-quinolinol, or acetylacetone dissolved in trichloromethane was added to 200 ml of the above hydrocarbon oil to a concentration of 1 Mol / liter. Inner diameter 10 mm with a Teflon cock on the bottom
The glass tube of was filled with activated carbon (Diahope-008: manufactured by Mitsubishi Kasei) so that the height was 100 mm. 200 ml of a hydrocarbon oil containing a lead compound mixed and prepared in this column was flowed at a rate of 2 ml for 1 minute. The lead content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 7.

[0033]

[Table 7]

Example 8 (Preparation of hydrocarbon oil) Lead (II) nitrate as lead was 100 wt / v with respect to a mixed hydrocarbon oil of N-heptane 40%, isooctane 50% and toluene 10% by volume.
olppb, lead (II) acetate as lead 100wt / vo
lppb and tetraethyl lead as lead 100 wt / v
olppb was added, dissolved and mixed.

(Confirmation of Removal Effect) Dithizone was dissolved in trichloromethane so as to have a concentration of 1 mol / liter, and 200 μl was added to 200 ml of the above hydrocarbon oil. A glass tube having an inner diameter of 10 mm equipped with a Teflon cock below was filled with activated carbon (Dia Hope-008: manufactured by Mitsubishi Kasei) so that the height was 100 mm. 200 ml of a hydrocarbon oil containing a lead compound mixed and prepared in this column was flowed at a rate of 2 ml for 1 minute. The lead content in the spilled hydrocarbon oil was analyzed by the atomic absorption method. The results are shown in Table 8.

[0036]

[Table 8]

[0037]

According to the present invention, heavy metals can be efficiently removed from hydrocarbon oil by a simple means.

Claims (1)

[Claims] 1. A method of adsorbing and removing a heavy metal by adding a chelating agent in an amount of 1 to 100 moles to the heavy metal to a hydrocarbon oil containing the heavy metal, and then contacting with activated carbon.