JPH0823023B2 - Method for removing mercury in hydrocarbon oils - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for removing mercury mixed in a hydrocarbon-based oil, and particularly to a method for selectively removing mercury using a liquid-liquid contact mechanism of a tin compound, It relates to an efficient removal method.

<Prior Art> When reforming a hydrocarbon oil such as naphtha by hydrogenation or the like, a palladium-supported alumina catalyst or the like is used. However, when mercury is present as an impurity in the hydrocarbon oil, the catalyst is poisoned and the reaction is not sufficiently carried out.

Therefore, the following mercury removal methods have been conventionally performed.

a) Physical adsorption method using a porous adsorbent such as activated carbon, molecular sieve, silica gel, zeolite or alumina.

b) A method in which sulfur is added to a metal sulfide or a porous adsorbent and mercury is removed by a reaction / adsorption of mercury and sulfur.

However, in the physical adsorption method of a), although the heavy components and gums in the hydrocarbon-based oil are efficiently removed, the removal rate of mercury is as low as 30 to 70 wt%. Further, in the reaction / adsorption method (b), it is difficult to filter after the reaction / adsorption, and at the same time,
The mercury removal rate is low as in the physical adsorption method a).

Therefore, a method for selectively and efficiently removing mercury in hydrocarbon-based oil is desired.

<Problems to be Solved by the Invention> An object of the present invention is to provide a method for selectively and efficiently removing a trace amount of mercury in a hydrocarbon oil.

<Means for Solving the Problems> The present invention is a method for removing a trace amount of mercury contained in a hydrocarbon-based oil, wherein the hydrocarbon-based oil is a halide of tin and / or an oxide of tin. Provided is a method for removing mercury in a hydrocarbon-based oil, which is characterized by contacting it.

Here, the tin halide and / or the tin oxide is preferably an aqueous solution or powder.

The tin halide is preferably stannous halide and / or stannic halide.

<Structure of the Invention> The structure of the present invention will be described in detail below.

The hydrocarbon-based oil to which the method of the present invention is applied may be any hydrocarbon as long as it is a liquid hydrocarbon at room temperature.

Hydrocarbon oils include crude oil, straight-run naphtha, kerosene, light oil, distillate under reduced pressure, residual oil at atmospheric pressure, pyrolysis gasoline by-produced in a thermal cracker at an ethylene plant, heat-treated hydrocarbon oil, catalytic cracking. Examples include naphtha fraction and recycled oil produced by the device.

In particular, nat excluding liquefied petroleum gas (LPG) from natural gas
It is suitable for removing mercury in ural gas liquid (NGL), especially heavy natural gas liquid containing high boiling point components in NGL.

In the method of the present invention, the existing form of mercury in the hydrocarbon-based oil to be removed may be any form such as elemental mercury, inorganic mercury, and organic mercury, but in the hydrocarbon-based oil that is liquid at room temperature. It is particularly effective against the organic mercury present.

The concentration of mercury in the hydrocarbon oil is not particularly limited, but the reaction efficiency is good when it is 400 to 600 PPb or less, preferably 100 to 150 PPb or less.

If necessary, it is advisable to previously filter the sludge in the hydrocarbon-based oil with a filter membrane or a filter to remove the mercury that is filtered off together with the sludge.

The method of the present invention is a method for treating a hydrocarbon-based oil containing mercury by contacting it with a halide of tin and / or an oxide of tin. As the tin halide or tin oxide (hereinafter abbreviated as “tin compound”) used, the following compounds or a mixture thereof can be preferably used.

(1) 10 ppm or more, for example, 10 ppm to 40 wt%, preferably 0.5 to 10 wt% aqueous solution of stannous halide SnCl ₂ or the like. Alternatively, powders of SnCl ₂ , SnI _2, etc. may be added to the hydrocarbon oil.

(2) 10 ppm or more, for example, 10 ppm to 40 wt%, preferably 0.5 to 10 wt% aqueous solution of stannic halide SnCl _4, etc. Alternatively, powders of SnCl ₄ , SnI _4, etc. may be added to the hydrocarbon oil.

(3) Tin oxide SnO, SnO ₂ or the like is used by adding it to a hydrocarbon oil.

As a method for contacting the tin compound and the hydrocarbon oil, it is preferable to use the following reaction device and the like, but not limited to these.

FIG. 1 shows an apparatus having a reaction tank 3 equipped with a stirrer 11.

The reaction tank 3 is provided with a line for supplying the raw material 1 and a line for supplying the tin compound 2, and the reaction tank 3 is a stationary tank 4
Is in fluid communication with.

The stationary tank 4 has a purified product extraction line 9 and a mercury treatment line.
Ten respective outlets are provided.

The mercury treatment line 10 communicates with a mercury treatment device (not shown) via the valve 7 on the one hand, and communicates with the reaction tank 3 via the valve 8 and the pump 6 on the other hand.

A raw material 1 such as a hydrocarbon oil is supplied to the reaction tank 3, and the tin compound 2 is supplied to the reaction tank 3 in the form of an aqueous solution or powder from the other side.

In the reaction tank 3, the hydrocarbon oil and the tin compound are thoroughly mixed by the stirrer 11.

The mixed liquid is transferred to the stationary tank 4 and allowed to stand still to be separated into the purified liquid 13 and the mercury-containing phase 14, and the purified liquid 13 is taken out from the purified product take-out line 9. On the other hand, the mercury-containing phase 14 is transferred to the mercury treatment device (not shown) via the valve 7 and discharged.

The remaining liquid phase from which mercury has been removed is recovered in the reaction tank 3 by the pump 6 via the valve 8 if necessary.

FIG. 2 shows an apparatus in which the tin compound 2 is mixed with the raw material 1 and then transferred by the pump 7. Raw material 1 and tin compound 2
Since they are sufficiently mixed and come into contact with each other while being transferred by the pump 7, it is not necessary to provide a reaction vessel equipped with an agitator as shown in FIG. If necessary, the multistage stationary tanks 4 and 12 shown in FIG. 2 are provided, and the purified liquid 13 and the mercury-containing phase are provided as in FIG.
Separate from 14

<Examples> The present invention will be specifically described below with reference to Examples.

(Examples 1 and 2) heavy natural gas liquid (heavy natural gas liquid)
100 ml was filtered through a 0.2 μm Millipore filter. The sludge composition filtered out was as follows.

 Fe 10.0 wt% Si 18.3 wt% Hg 3.1 wt% S 2.3 wt% The mercury concentration in the filtrate was about 130 PPb.

The tin compound was added to the filtrate at the concentration shown in Table 1 and stirred well,
The mercury concentration in the purified liquid after 1 hour of standing was measured, and the results are shown in Table 1.

(Examples 3 and 4) In 100 ml of the same filtrate as that obtained in Examples 1 and ₂ , 1.0 g of each compound of SnI ₂ and SnO shown in Table 1 was added, sufficiently stirred and purified after standing for 1 hour. The mercury concentration in the liquid was measured, and the results are shown in Table 1.

(Comparative Examples 1 and 2) As a comparison, heavy natural ga
FeCl ₂ and FeCl ₃ shown in Table 1 were added to the filtrate obtained by removing sludge from s liquid (heavy natural gas liquid) in the same manner as in Example 1, and the mercury concentration in the purified liquid obtained in the same manner was measured,
The results are shown in Table 1.

<Effects of the Invention> In the method of the present invention, since the hydrocarbon-based oil and the tin compound are brought into contact with each other, mercury mixed in the hydrocarbon-based oil can be selectively and efficiently removed.

Since the hydrocarbon-based oil from which mercury has been removed does not contain a catalyst poisoning component, it can be widely used for a reaction using a catalyst such as a hydrogenation reaction.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of an apparatus for carrying out the method of the present invention. FIG. 2 is a diagram showing another example of an apparatus for carrying out the method of the present invention. Explanation of symbols 1 ... Raw material, 2 ... Tin compound, 3 ... Reaction tank, 4 ... Stationary tank, 5 ... Piping, 6 ... Pump, 7, 8 ... Valve, 9 ... Purified product removal Line, 10 …… Mercury processing line, 11 …… Stirrer, 13 …… Purified liquid, 14 …… Mercury-containing phase,

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Claims (3)

[Claims] 1. A method for removing a trace amount of mercury contained in a hydrocarbon-based oil, which comprises contacting the hydrocarbon-based oil with a tin halide and / or a tin oxide. Method for removing mercury in hydrogen oil. 2. The method according to claim 1, wherein the tin halide and / or tin oxide is an aqueous solution or powder.
The method for removing mercury in a hydrocarbon-based oil according to the item. 3. The tin halide is a halogenated first
The method for removing mercury in a hydrocarbon-based oil according to claim 1 or 2, wherein the method is tin and / or stannic halide.