JP2617214B2 - Production of high quality isoparaffin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD The present invention on the object industrial invention, particularly high-quality from the C ₄ fraction is an exploded product obtained by petroleum refining processes, relates to a method of obtaining odorless, and isoparaffin solvent and light lubricating oil of low ultraviolet absorption is there.

Prior art, the invention is Rafuneto extracted butadiene from C ₄ fraction from a decomposition reaction of challenges petroleum refining process to be solved and the spent BB fraction butene hydrocarbon - - butane contained in (butene butane fraction) Effective use is an important issue.

The present invention provides an IFP
Using the Porinafusa device, without undue polymerization as in the conventional method BB fraction in the fluid catalytic cracking process or pyrolysis process oil refining,該留instead fractions selectively C ₈ -C ₂₄ After the first hydrodesulfurization and then the adsorption desulfurization
The present invention relates to a method for producing high-quality isoparaffin by secondary hydrogenation.

A patent application was filed for a method of producing isoparaffin by subjecting the above BB fraction to oligomerization treatment and then subjecting it to a primary hydrogenation treatment (Japanese Patent Application No. 63-83120), but the present invention further improves the method for producing high quality isoparaffin. It is about.

B. Means for Solving the Problems The present invention relates to a fluid contact field process for petroleum refining and / or
Alternatively, a mixture of C ₂ -C ₅ saturated hydrocarbons and / or unsaturated hydrocarbons containing C ₄ hydrocarbons as a main component derived from the pyrolysis process product is subjected to a temperature of 15 to 200 ° C. in the presence of an oligomerization catalyst. After performing oligomerization at a liquid space velocity of 0.1 to 1.5, a pressure for maintaining the reaction system in a liquid phase, and a conversion of 25 to 98%, a polykerosene fraction having a distillation temperature of 130 ° C or higher is subjected to hydrogenation catalyst or hydrodesulfurization. Pressure 2 in the presence of catalyst
To 100 kg / cm ^2, the reaction temperature 80 to 400 ° C., a liquid hourly space velocity from 0.1 to 2.0
In, at least one stage treatment in a hydrogen atmosphere, and then subjected to adsorption desulfurization treatment, the distillation fraction of 320 ° C. or less under hydrogen flow in the presence of a nickel catalyst under a pressure of ^{2 to} 100 kg / cm ² ,
The present invention relates to a method for producing high quality isoparaffin, which is characterized by performing a hydrogenation treatment at a reaction temperature of 100 to 250 ° C. and a liquid space velocity of 0.1 to 3.0.

The raw material used in the method of the present invention is a mixture of C _{2 to} C ₅ saturated hydrocarbons and / or unsaturated hydrocarbons containing C ₄ hydrocarbons as a main component as described above. a C ₄ fraction of catalytic cracking or thermal cracking processes product.

(A) Oligomerization Step The oligomerization step is performed using a conventionally known IFP polynaphtha apparatus.

The catalyst used in the oligomerization step is a catalyst used in a usual oligomerization step, and is not particularly specified.

The oligomerization catalyst is, for example, an acid catalyst such as amorphous silica-alumina.

The reaction conditions for the oligomerization step are as follows.

Reaction temperature 15-200 ° C, preferably 50-160 ° C, liquid hourly space velocity (LHSV) 0.1-1.5, preferably 0.2-1.0, conversion 25
9898%, preferably 60-95%.

Conversion rate is The production ratio of the polynaphtha fraction (distillation temperature of 160 ° C. or lower) and the polykerosene fraction (distillation temperature of 130 ° C. or higher) obtained by the above-mentioned oligomerization step depends on the composition of the raw materials used, but the polykerosene fraction depends on the conditions. From 25%
It is possible to vary up to 100%.

The reason for selecting the oligomerization conditions as described above is to prevent excessive polymerization.

One example of the composition of the product (polynaphtha fraction, polykerosine fraction) obtained in the oligomerization step of the present invention is shown in Table 1.

(B) Hydrogenation reaction step and adsorption desulfurization step The catalyst used in the hydrogenation step is a catalyst usually used for hydrogenation or hydrodesulfurization, but is not particularly limited.

For example, the metal catalyst includes nickel (Raney nickel), cobalt, platinum, palladium and the like.

Examples of the metal oxide catalyst include oxides such as cobalt, nickel, chromium, and zinc, as well as V ₂ O ₅ and M ₀ O ₂ .

MoS ₂ , WS ₂ , Co ₉ S ₈ , Ni ₃ S ₂
and so on. As a composite metal catalyst, Co-Mo, Ni-Mo,
Ni-W or the like can be used. Particularly preferred is Ni-Mo.

Although the adsorption desulfurization catalyst is not particularly limited, zinc oxide (Zn
O), iron oxide (Fe ₂ O ₃ ) and the like can be used. Preferably it is zinc oxide.

The reaction conditions for the hydrodesulfurization step are a pressure of ^{2 to} 100 kg / cm ² , preferably 20 to 50 kg / cm ² , and a temperature of 80 to 400 ° C., preferably 150 to
380 ° C, liquid hourly space velocity (LHSV) 0.1-2.0, preferably 0.5-
1.5.

One example of the hydrogenated product of the polykerosene fraction obtained in the hydrodesulfurization step and the adsorption desulfurization step of the present invention is shown in Table 2.

(C) Secondary hydrogenation reaction step Of the fraction obtained in the step (B), hydrogenation was performed on a fraction at 320 ° C or lower using a nickel catalyst.

As a hydrogenation catalyst, 40-60% by weight of metallic nickel
A supported nickel supported catalyst (including Raney nickel) is preferred.

The catalyst carrier is preferably, but not limited to, silica, alumina, silica-alumina, diatomaceous earth and the like.

The reaction conditions are a pressure of ^{2 to} 100 kg / cm ² , preferably 20 to 60 k.
g / cm ^2, reaction temperature 100 to 250 ° C., preferably 150 to 200 ° C.,
The liquid space velocity is 0.1 to 1.0.

Hereinafter, the method of the present invention will be exemplified, but is not limited thereto.

Example (A) Oligomerization Step The raw material used in the method of the present invention is a butane-butene fraction having the composition shown in Table 3.

The above fraction was hydrogenated at a hydrogen pressure of 4 using an IFP polynaphtha unit.
The oligomerization was performed at 0 kg / cm ^{2 at} a reaction temperature of 90 to 120 ° C.

The olefin conversion is 60-74%. Table 4 shows typical examples of ASTM distillation properties and flash points of the obtained oligomerization product.

(B) Hydrodesulfurization reaction step and adsorption desulfurization step Using a product obtained from the oligomerization step as a catalyst, using Ni-Mo sulfide as a catalyst, a reaction temperature of 260 to 300 ° C, a pressure of 50 to 54 kg / cm ² , and a liquid space Hydrogenation was performed under conditions of a velocity (LHSV) of 0.4 to 0.5.

 Table 5 shows the composition of the obtained hydrogenated product.

(C) Second hydrogenation reaction step Among the products obtained from the step (B), a distillation temperature of 32
For fractions below 0 ° C, in the presence of Raney nickel catalyst (nickel content 50wt%), reaction temperature 150 ° C, liquid hourly space velocity 0.5,
The hydrogenation reaction was performed at a hydrogen pressure of 50 kg / cm ² and a hydrogen flow rate of 250 Nm ³ / kl / hr.

 The composition of the hydrogenated product is shown in Table 6.

Table 8 shows the properties of the isoparaffin obtained by the method of the present invention.

Table 7 shows that the isoparaffin obtained by the method of the present invention has a low bromine value, low ultraviolet absorption and low sulfur content.

Table 8 shows the relationship between the distillation temperature of the isoparaffin obtained by the method of the present invention and the fraction.

C. Effects of the Invention 1) Isoparaffin obtained by the method of the present invention has the following properties as a solvent.

i) Odorless, low UV absorption, low sulfur and low residue,
It is useful as a solvent for resin production and paint production.

ii) As a solvent for odorless paints, it is used in households, restaurants, hospitals, food factories, dryers, thinners, aerosol insecticides, etc.

iii) It is used as a polymerization solvent for polyolefins because of its high purity and high stability.

2) An excellent light lubricating base oil having a high viscosity index, good heat and oxidation stability, and a low pour point can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C07C 7/163 6958-4H C07C 7/163 9/22 6958-4H 9/22 C10G 50/00 C10G 50/00 // B01J 21/12 B01J 21/12 25/02 25/02 C07B 61/00 300 C07B 61/00 300 (72) Inventor Takehiko Kishibe 2-2-1 Otemachi, Chiyoda-ku, Tokyo Toa Oil (72) Inventor Hiroshi Musha 2-2-1 Otemachi, Chiyoda-ku, Tokyo Inside Toa Oil Co., Ltd.

Claims (1)

(57) [Claims] 1. A mixture of a C ₂ -C ₅ saturated hydrocarbon and / or an unsaturated hydrocarbon mainly composed of C ₄ hydrocarbons in the presence of an oligomerization catalyst at a temperature of 15 to 200 ° C. and a liquid hourly space velocity. 0.1-1.5, pressure to keep the reaction in the liquid phase, conversion rate 25-98%
After oligomerization at, distillation temperature 130
° C. or higher in the presence of a hydrogenation catalyst or a hydrodesulfurization catalyst, a pressure of ^{2 to} 100 kg / cm ² , a reaction temperature of 80 to 400
At least 1 ° C in a hydrogen atmosphere at a liquid space velocity of 0.1 to 2.0.
Step treatment, followed by adsorption desulfurization treatment, distillation temperature 32
The fraction at 0 ° C. or lower is subjected to a pressure of 2 to 100 in the presence of a nickel catalyst.
A method for producing high-quality isoparaffin, comprising subjecting to hydrogenation treatment at a kg / cm ² , a reaction temperature of 100 to 250 ° C, and a liquid hourly space velocity of 0.1 to 3.0.