JPS5951593B2 - Heavy oil composition with good storage stability - Google Patents

Description

[Detailed description of the invention] The present invention relates to heavy oil with good storage stability.

More specifically, the present invention relates to heavy oil obtained by adding heavy oil produced as a by-product during the decomposition of petroleum to heavy oil.

Traditionally, due to the poor storage stability of heavy oil, deposits are formed in the heavy oil while it is stored in tanks, etc., and as a result, when put into practical use, filters are clogged, nozzles are blocked, etc., resulting in combustion problems and poor fluidity. This causes many problems such as the formation of tank bottom deposits.

There are two types of deposits: rust, wood chips, cotton shavings, and other substances other than oil, and those derived from the oil itself.The latter, in particular, is caused by asphaltenes, which are colloidally dispersed in the residual oil. It is thought that it is formed by

On the other hand, there has been a growing demand for low-sulfur heavy oil from the perspective of pollution prevention, and recently, hydrogenation treatment has become popular in many cases to remove sulfur from heavy oil.

However, when carrying out this hydrotreatment, especially hydrodesulfurization, a deasphaltene reaction is also progressing at the same time, and even though the asphaltene content is reduced, the storage stability of the desulfurized heavy oil obtained in this way is extremely low. The bad things are also true.

Taking these circumstances into consideration, the present inventors investigated various compounding materials and found that the storage stability of heavy oil could be improved by adding a limited amount of a specific compounding material to the base heavy oil. It was discovered that this could be greatly improved and led to the completion of the present invention.

The present invention uses heavy oil that has gone through various processes as a base material, and has a boiling point (converted to normal pressure) of 250 to 400, which occurs when petroleum is decomposed.
It is a heavy oil composition to which a fraction of ℃ is added.

The second component (B) used in the present invention can be obtained as follows.

Petroleum is subjected to steam cracking, thermal cracking, and catalytic cracking (herein, for simplicity, the above three types of cracking will be simply referred to as thermal cracking) at a temperature of 600°C to 900°C to produce ethylene and propylene. A relatively heavy fraction with a boiling point of 250 to 400°C, which is obtained as a by-product when producing lower olefins such as olefins, is used.

In order to actually obtain this fraction, it is necessary to separate all the residual oil (cracked oil) containing carbon atoms of 09 or more from the liquid obtained during the above thermal decomposition and separating the 08 or less used for the production of benzene, toluene, and xylene. ) is distilled under reduced pressure to obtain a boiling point of 250-400℃ (
By separating the fraction contained in the water (converted to normal pressure) by distillation.

In addition, the cracked oil is first distilled under reduced pressure to separate it into a liquid with a boiling point of 400°C or less and a heavier substance with a boiling point higher than that (usually called pitch), and then this liquid (which usually has a bromine number of 10 to 80) It contains saturated substances and is brown in color.

) at a temperature of about 200°C or less under normal pressure or increased pressure.
A polymer product with a boiling point higher than 400°C that is produced by heat treatment for a period of time or catalytic heat treatment using a free craft catalyst to polymerize and condense alkylindenes and other unsaturated compounds to make them heavy. can be removed by distillation to obtain a fraction with a boiling point of 250 to 400°C as distillate oil.

In the present invention, it is better to use the fraction obtained by such thermal or catalytic treatment in terms of affinity when mixed with mineral oil.

However, if the fraction can be further hydrorefined as required, even better results can be obtained.

In this case, various conventional catalysts can be used as the hydrorefining catalyst, but preferably one in which an oxide or sulfide selected from nickel, molybdenum, and cobalt is supported on an aluminum oxide-containing carrier is used.

Most preferably, it is a pre-sulfurized nickel oxide-molybdenum oxide supported on an alumina antibody.

The reaction pressure is also usually 20 to 100 kg/crr12G, preferably 25 to 60 kg/cm2G, and the reaction temperature is 230 to 40
The temperature is 0°C, preferably 260-340°C, and the hydrogen used is 100 to 10.00 ONm", preferably 200 to 1,00 ONm3 per 1 kl of supplied oil.

Hydrogenation is carried out under conditions that prevent nuclear hydrogenation of aromatics in the supplied oil as much as possible.

Therefore, it is preferable to select the catalyst and reaction temperature.

As the heavy oil serving as the base material of the composition of the present invention, heavy oil that has undergone various steps of petroleum refining can be used.

Specifically, it can be widely applied to bottom oil from an atmospheric distillation column, heavy oil obtained from a vacuum distillation apparatus, or desulfurized heavy oil obtained by hydrogenating such heavy oil.

This effect is particularly noticeable in desulfurized heavy oils that have undergone hydrogenation treatment.

Here, the hydrogenation treatment of heavy oil can be carried out by various reaction formats such as fixed bed type and fluidized bed type, and the reaction conditions are also as follows:
50~450℃, hydrogen pressure 100~200kg/cm2G
, LH8VO11-1.0, and the catalyst is carried out by selecting appropriate conditions from those made by supporting a group VI metal or a group VI metal on a carrier such as aluminum, sulphur, silica-alumina, or the like.

Furthermore, in the composition of the present invention, the amount of the second component (B) depends on the base heavy oil, but is preferably added at least 10 parts by weight, preferably 20 to 3 parts by weight, per 100 parts by weight of the heavy oil.
00 parts by weight is appropriate.

Examples of the present invention are listed below.

Example Production of desulfurized heavy oil (A) Using atmospheric residual oil of Middle Eastern crude oil (Arabian Light) as a raw material, using a cobalt-molybdenum-alumina catalyst, reaction temperature 400°C, hydrogen pressure 150 kg/cm2G, LH8V
Hydrodesulfurization was carried out using a fluidized bed reaction tower under reaction conditions of =0.5.

Production of desulfurized heavy oils (B) and (C) The vacuum residues of two Middle Eastern crude oils (Arabian Light and Arabian Medium) were used as raw materials, and a nickel-cobalt-molybdenum-alumina catalyst was used at a reaction temperature of 42.
0℃, hydrogen pressure 150kg/cm2G, LH3V-0,2
Hydrodesulfurization was carried out using a fixed bed method under the following reaction conditions.

Preparation of heavy oil Using heavy oil (A) and (B) as base materials, JIS standard (JIS
B heavy oil formulations and C heavy oil formulations were prepared using an appropriate diluent (cutter material) so as to comply with K2205-1960).

A storage stability test was conducted on the thus obtained formulation.

Diluent (D) Vacuum gas oil (VGO) of Middle Eastern crude oil was hydrodesulfurized according to a conventional method.

Hydrodesulfurization conditions fixed bed type Co-Mo-alumina catalyst temperature 360℃, hydrogen pressure 95kg/cm'GLH5
V = 2.0 Diluent (E), (F) Naphtha was pyrolyzed at 850°C and the remaining pyrolyzed heavy oil, excluding up to the C9 fraction, was placed in an iron container and heated to 1Q at 300°C under normal pressure.
Heat treated for hr.

This heat treatment reduced the bromine number of the pyrolyzed heavy oil from 82 to 57.

This heat-treated oil is distilled under reduced pressure to a temperature of 280 to 400℃ converted to normal pressure.
A fraction was collected.

Its properties are specific gravity d 01.032, refractive index 11201
, 6076, viscosity (100°F) 5,31 cSt,
H/C mo/L, ratio 0.95, fractional distillation properties are 5% distillation temperature 2
The temperature was 79.5°C, the 50% distillation temperature was 289°C, and the 95% distillation temperature was 380°C.

(E) This fraction was then treated with nickel (Nio3.owt
%) and molybdenum (MOO314wt%) supported on alumina were introduced into a flow-through reaction tube filled with a reaction pressure of 3.
5 kg/cm"G, reaction temperature 330℃, liquid hourly space velocity (LH5V) 3, hydrogen 50ONm per 1kl of feedstock oil"
It was hydrorefined under the following conditions.

The obtained refined oil was distilled under reduced pressure to remove light components, and a fraction with a normal pressure equivalent boiling point of 270 to 370°C was collected, and treated with active 1 soil at 23 kg/kl at 60° C. for 3Qmin to remove impurities.

The properties of this oil are specific gravity dA51.020, refractive index n20
1,594, viscosity (100'F) 6,74, (21
0 below) 1,76, pour point -50℃ or less, flash point 146℃
, CA61.3%CN30.3 by nd-M ring analysis method
%, CP8.4%, and the fractional distillation properties are 5% distillation temperature 2
80℃, 50% 0% distillation temperature 306℃ 95% distillation temperature 3
The temperature was 70°C.

(F) Heavy oil storage stability test 12 ml of sample oil was poured into a glass wide-mouth reagent bottle (capacity 250 m).
1) and stored in a hot air dryer maintained at 100°C with a loose stopper, and a spot test was performed every 2 to 3 days.

Sample oils of heavy oil C and heavy oil B were stored indoors in a dark place, and spot tests were conducted monthly.

The spot test is a method in which a drop of a sample is placed on a filter paper (A30 manufactured by Toyo P Paper Company) under certain conditions, and the state of spotting is determined after drying at 100° C. for 2 hours.

As a measure of the number of days until a ring appears on a spot (deposit occurrence days; hereinafter abbreviated as Ti) and the tendency of increase in deposits, the number of days when the spot ring becomes clear (equivalent to 0.4 wt% in terms of deposit amount; The stability was evaluated using Ts (hereinafter abbreviated as Ts).

The results are shown in the table. As is clear from the results in the table, it can be seen that the heavy oil composition of the present invention exhibits extremely high storage stability.

Claims (1)

[Claims] 1 (A) 100 parts by weight of heavy oil, (B) 6 parts of petroleum
Good storage stability obtained by adding 10 parts by weight or more of a fraction with a boiling point (normal pressure equivalent) of 250 to 400°C, which is produced as a by-product when decomposing at 00°C to 900°C to produce ethylene, propylene, etc. heavy oil composition.