JPH04348188A - Removal of mercury and mercury compound from hydrocarbon oil - Google Patents

Abstract

PURPOSE:To remove mercury and mercury compound from a hydrocarbon oil with a simple method. CONSTITUTION:Mercury or mercury compound in a hydrocarbon oil can be removed by attaching sulfide ion to an anion exchange resin and contacting the anion exchange resin with a hydrocarbon oil. The process enables sufficient and easy removal of mercury and mercury compound in high efficiency.

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 mercury and mercury compounds from hydrocarbon oil.

0002

BACKGROUND OF THE INVENTION It is known that condensates contained in crude oil and natural gas contain mercury and mercury compounds on the order of tens of ppb from some sources. These mercury compounds easily form amalgams with metal materials such as copper, resulting in decreased activity of catalysts in catalytic reactions during petroleum refining processing and use as chemical raw materials, corrosion and strength of metal materials used in chemical equipment. This may cause deterioration, etc. As methods for removing mercury and mercury compounds, attempts have been made to remove them by adsorption using activated carbon, or by contacting them with copper, aluminum, and their compounds.

0003

[Problems to be Solved by the Invention] However, when the hydrocarbon oil is an aromatic hydrocarbon such as benzene or toluene, the adsorption removal method using activated carbon cannot sufficiently remove mercury and mercury compounds. Can not. Also, contact with copper, aluminum and their compounds can cause
Methods for removing mercury and mercury compounds require high temperatures for treatment, requiring complex equipment and causing problems in terms of cost. The present invention solves the conventional problems as described above,
The object of the present invention is to provide a method for efficiently removing mercury and mercury compounds from hydrocarbon oil using simple means.

0004

[Means for Solving the Problems] As a result of intensive studies, the present inventors were able to solve the above problems. That is, the present invention provides a method for removing mercury and mercury compounds from a hydrocarbon oil, which comprises attaching sulfur ions to an anion exchange resin and then contacting the anion exchange resin with a hydrocarbon oil. It provides:

[0005] The present invention will be explained in more detail below. The hydrocarbon oil from which mercury and mercury compounds can be removed by the present invention is any hydrocarbon oil, and is not particularly limited. Examples include hydrocarbon oils such as benzene and toluene, gasoline, light oil, and natural gas condensate. The type of anion exchange resin that can be used in the present invention is not particularly limited as long as it is a styrene-based strongly basic ion exchange resin, but examples include the Diaion SA series manufactured by Mitsubishi Kasei. can.

[0006] After the anion exchange resin as described above is washed by a conventional method, it is packed into a column and sulfur ions are further attached thereto. Any method may be used as long as the sulfur ions can be attached to the anion exchange resin.
Examples include a method in which S, (NH4)2S, etc. are dissolved in water and the solution is passed through a column. Anion exchange resin,
After attaching a sufficient amount of sulfur ions, it is preferable to wash the resin with ion-exchanged water until the ions no longer elute, and then wash the resin with a sufficient amount of 80% methanol by volume.

[0007] Furthermore, as for the column temperature, it is desirable to heat the column because the higher the temperature of the anion exchange resin, the higher the ability to retain sulfur ions. Generally, throughout the process of the present invention, the column temperature is usually between room temperature and 90°C.
, preferably 30 to 80°C. Mercury and mercury compounds can be removed by bringing hydrocarbon oil into contact with an anion exchange resin and a column prepared under the above conditions.

[0008]

[Examples] The present invention will be further explained below with reference to Examples. Example 1 (Preparation of hydrocarbon oil) As hydrocarbon oil, 40% by volume of n-heptane, 55% by volume of isooctane, and 5% by volume of toluene were used.
400w/v as mercury for a mixture consisting of volume%
Mercury (II) chloride was added in ppb. (Preparation of anion exchange resin column) Equipped with a Teflon cock at the bottom and a column constant temperature bath, inner diameter 20 mm.
A glass column was filled with an anion exchange resin (Diaion SA-10A manufactured by Mitsubishi Kasei) so that the height of the resin was 250 mm. 300 ml of a 5 w/w % Na2S aqueous solution was passed through the column at a column flow rate of 1 ml/min to cause sulfur ions to adhere thereto. After attachment is completed, 3-5m
Wash the resin by flowing ion-exchanged water at a column flow rate of l/min until the eluting water no longer turns the lead acetate test paper black;
Water-soluble sulfur ions were removed. Further washing was performed with 100 ml of 80% methanol to remove water remaining in the ion exchange resin, so that the hydrocarbon oil was sufficiently contacted with the anion exchange resin. The anion exchange resin column prepared as above with sulfur ions attached was kept at a column temperature of 20°C, 35°C, 50°C and 65°C in a column constant temperature bath, and the hydrocarbon oil prepared as above was heated. 200 ml was flowed from the top of the column at a column flow rate of 1 ml/min. The mercury content in the hydrocarbon oil collected at the bottom of the column was analyzed by atomic absorption spectrometry. The results are shown in Table 1.

[0009]

[Table 1] Table 1 ━━━━━━━━━━━━━━
━━━━━━━━━━━━━━━━ Column temperature (℃) Mercury content (w/vppb) ━━━━━━━━━━━━
━━━━━━━━━━━━━━━━━━
20
90 35
40
50
10 65
<10 ━━
━━━━━━━━━━━━━━━━━━━━━━━━━
━━━ Columnless processing
400

Example 2 (Preparation of hydrocarbon oil) As hydrocarbon oil, 40% by volume of n-heptane, 55% by volume of isooctane and 5% by volume of toluene were used.
400w/v as mercury for a mixture consisting of volume%
Mercury chloride was added in ppb. (Preparation of anion exchange resin column) Equipped with a Teflon cock at the bottom and a column constant temperature bath, inner diameter 20 mm.
A glass column was filled with an anion exchange resin (Diaion SA-10A manufactured by Mitsubishi Kasei) so that the height of the resin was 250 mm. Add to this separately 5 w/w% Na2
S, NaSH, (NH4)2S and K2S aqueous solutions were passed through the column at a flow rate of 300 ml and 1 ml/min, respectively, to attach sulfur ions. After attachment is completed, 3-5m
Wash the resin by flowing ion-exchanged water at a column flow rate of l/min until the eluting water no longer turns the lead acetate test paper black;
Water-soluble sulfur ions were removed. Further washing was performed with 100 ml of 80% methanol to remove water remaining in the ion exchange resin, so that the hydrocarbon oil would come into sufficient contact with the anion exchange resin. The anion exchange resin column with sulfur ions attached to it prepared as above was kept at a column temperature of 50°C in a column constant temperature bath, and the hydrocarbon oil prepared as above was added to the column head at a column flow rate of 1 ml/min. 200 ml was poured from the tube. The mercury content in the hydrocarbon oil collected at the bottom of the column was analyzed by atomic absorption spectrometry. The results are shown in Table 2.

[0011]

[Table 2] Table 2 ━━━━━━━━━━━━━━
━━━━━━━━━━━━━━━━ Sulfur compound used Mercury content (w/vp
pb) ━━━━━━━━━━━━━━━━━━
━━━━━━━━━━━━ Na2S

15 NaSH
10 (
NH4)2S
<10 K2S
15 ━━
━━━━━━━━━━━━━━━━━━━━━━━━━
━━━ Columnless processing
400

Example 3 Three anion exchange resin columns prepared in the same manner as in Example 1 were used.
1 ml of 200 ml of condensate is kept at 5°C and is entrained in natural gas containing 200 w/vppb of mercury.
The column was run at a flow rate of /ml. As a result of analyzing the mercury content in the eluted hydrocarbon oil by atomic absorption spectrometry, it was found to be 25w/vp.
It was pb.

Example 4 The condensate used in Example 3 contained low boiling point components, and when kept at 35°C, bubbles were generated in the ion exchange resin column, resulting in non-uniform flow. For this purpose, the condensate was distilled to remove low-boiling components by distillation, and the initial distillation point was set at 60°C. As a result, the mercury content in the condensate was 280 w/vppb. Except for changing the column temperature of this condensate from 35°C to 50°C.
As a result of treatment under the same conditions as in Example 3, the mercury content in the eluted hydrocarbon oil was 15 w/vppb.

[0014]

According to the present invention, mercury and mercury compounds can be efficiently removed from hydrocarbon oil by simple means.

Claims (1)

[Claims] 1. A method for removing mercury and mercury compounds from a hydrocarbon oil, which comprises adhering sulfur ions to an anion exchange resin and then contacting the anion exchange resin with a hydrocarbon oil.