JPH0228122A - Production of light-colored heavy alkylate - Google Patents

Abstract

PURPOSE:To readily obtain a light-colored heavy alkylate useful as insulating oils, etc., by hydrogenating a heavy alkylate formed as a by-product in a process for producing alkylbenzenes by subjecting an olefin and benzene to alkylating reaction in the presence of hydrogen fluoride catalyst. CONSTITUTION:An olefin and benzene are subjected to alkylating reaction in the presence of hydrogen fluoride catalyst to produce alkylbenzenes. In the process, a heavy alkylate obtained as a distillation bottom residue is directly hydrogenated by a well-known method without removing high-boiling components to industrially and advantageously afford the objective heavy alkylate, useful as lubricating oils, vacuum pump oils, heating medium oils, rubber extender oils, high-boiling solvents and refrigerator oils in addition to the above-mentioned oils and improved in hue from yellowish brown to a light color.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to the production of heavy alkylates, particularly heavy alkylates that are lighter in color than the high-boiling fraction obtained by distillation and recovery of alkylbenzenes, which are used in the manufacturing process of alkylbenzenes as raw materials for detergents. Relating to a method of manufacturing.

(Prior art) Heavy alkylate is an aromatic compound whose main components are dialkylbenzenes and polyalkylbenzenes, and is generally used as a by-product with a score higher than alkylpenzene in the production of alkylbenzene, a raw material for cleaning agents. can get.

If the olefin used as a raw material for the alkylation reaction contains a diolefin, the heavy alkylate also contains diphenylalkane at.

It is known that such heavy alkylates are suitable for use as insulating oils, lubricating oils, vacuum pump oils, heat transfer oils, rubber extender oils, high boiling point solvents, and refrigeration oils. The residue obtained from the stilling of rubenzene is yellowish-brown in color and cannot be used as is for the above-mentioned purposes.

Methods for improving the hue of heavy alkylate include a method of treating it with sulfuric acid (Japanese Patent Publication No. 19084/1984), a method of treating it with sulfuric acid and clay (Japanese Patent Publication No. 17602/1984), and a method of treating heavy alkylate with A method of distilling to remove high-boiling components and then hydrogenating with a palladium or platinum catalyst (
Japanese Patent Publication No. 57-35809) and the like are known.

(Problem to be Solved by the Invention) However, the method using sulfuric acid (and white clay) as a processing agent has the problem that waste sulfuric acid is produced as a by-product, and its processing requires a great deal of effort and cost. . or,
The method of distilling heavy alkylate to remove high-boiling components and then hydrogenating it with a palladium or platinum catalyst has the problems of requiring a large number of steps, manual IHJ, and requiring an expensive palladium or platinum catalyst. have.

The present invention aims to provide a simple and industrially advantageous method for producing light-colored heavy alkylates that solves the above-mentioned problems.

(Means for Solving the Problem) As a result of intensive research into a method for producing heavy alkylate with improved hue, the present inventors found that heavy alkylate, a by-product of alkylbenzene production using hydrogen fluoride as a catalyst, was used as a raw material. In this case, the inventors have discovered that the hue of heavy alkylate can be improved by hydrogenation treatment without distilling off high-boiling components, and have arrived at the present invention.

That is, the present invention provides a method for producing a light-colored heavy alkylate, which is characterized by hydrogenating a heavy alkylate obtained in an alkylbenzene production process in which an olefin is alkylated with benzene in the presence of a hydrogen fluoride catalyst. This is what we provide.

The alkylbenzene consumed in Osname as a raw material for cleaning agents is lower olefin oligomers such as propylene n-
It is produced by dehydrogenating an olefin, chlorinating n-paraffin, dehydrochloridizing it, and reacting it with benzene using a catalyst.

The alkylation reaction is carried out in the presence of hydrogen fluoride at a molar ratio of benzene and olefin of 1 or more, preferably in the range of 3 to 10, and a volume ratio of hydrogen fluoride to hydrocarbon of 0.2 to 10, preferably 0.5 to 10. The reaction temperature is -20 to 95°C, preferably 15 to 70°C, and the reaction time is 5 to 60 minutes, preferably 10 to 30 minutes.

The reaction solution after the alkylation reaction is separated into an hydrocarbon phase and a hydrogen fluoride catalyst phase. Phase separation is carried out by passing the reaction liquid through the catalyst separation tank at a low gland velocity and a residence time of at least 90 seconds, preferably 15 minutes or more. In order to further improve the quality of the alkylbenzene raw material for cleaning agents, the hydrocarbon phase from which the catalyst phase has been separated may be contacted with fresh hydrogen fluoride.

The hydrocarbon phase from which the catalyst phase has been separated is subjected to distillation, and the slightly dissolved catalyst and excess benzene are recovered.

Thereafter, short-chain alkylbenzene and/or n-paraffin are separated from the middle distillate by distillation, and further distillation is performed to obtain a cleaning agent raw material alkylbenzene from the top of the column and a heavy alkylate from the bottom of the column.

Distillation of the middle distillate and the cleaning agent raw material alkylbenzene is usually carried out under reduced pressure.

In the present invention, if a hydrogen fluoride melting medium is used, 111
It may be a heavy alkylate produced with alkylbenzene using any of the raw materials mentioned above.

As a method for producing alkylbenzene using a catalyst other than hydrogen fluoride, it is often said that n-paraffin is chlorinated and chlorinated paraffin is reacted with benzene using aluminum chloride as a catalyst. When using the resulting heavy alkylate, it is necessary to remove high-boiling components as mentioned above, and expensive palladium or platinum catalysts must be used (Japanese Patent Publication No. 57-35).
(See Publication No. 809).

The hue of the heavily charged alkylate obtained using hydrogen fluoride as a catalyst varies depending on the raw material olefin used or the alkylation conditions, but is generally in the range of API (A) from 100 to 1000.

In the present invention, this heavy alkylate is hydrogenated without removing high-boiling components. The catalyst used may be any catalyst generally known as a hydrogen ratio catalyst, such as nickel, palladium, or platinum.

The catalyst is preferably supported on alumina, silica alumina, diatomaceous earth, carbon, or the like.

The supported metal content is 0.1 to 5% by weight when the catalyst is palladium or platinum, and 20 to 60% by weight when the catalyst is nickel.

Any type of hydrogenation reactor can be used as long as the heavy alkylate, catalyst, and hydrogen gas can come into contact with each other efficiently, but generally a batch type hydrogenation reactor is used in which the powdered catalyst and heavy alkylate are placed in an autoclave. A continuous reaction using a fixed bed packed column is adopted.

When carrying out a batch reaction, the catalyst supported on a carrier is used in an amount of 10 to 0.5% based on the heavy alkylate.

One reaction is carried out at a temperature of 100° C. or higher, preferably 15 (Ic or higher).

Hydrogen gas pressure is 5 to 100 A9/crA, even 20
The range of ~50A910wl is preferred.

The time required for hydrogenation depends on the color of the heavy alkylate before treatment, the type and amount of the catalyst, the reaction temperature, and the hydrogen pressure, but 1 to 5 hours is sufficient.

Once the hydrogenation reaction is complete, the catalyst is removed by standing and/or filtering.

(Example) The present invention will be explained in more detail with reference to Examples below.

Example 1 In an alkylbenzene production plant for cleaning agent raw materials, n-paraffins obtained by dehydrogenating n-paraffins having 10 to 12 carbon atoms are reacted with benzene through hydrogen fluoride contact and soot, and the catalytic phase was separated. After distilling the hydrocarbon phase to recover dissolved hydrogen fluoride and then excess benzene,
Furthermore, by distillation, a middle distillate mainly composed of n-paraffins,
Next, a heavy alkylate (hue A PH
Using nickel catalyst N-113 manufactured by Kuchiju Kagaku Co., Ltd. as a raw material, A4#tI##) was subjected to a hydrogenation treatment by depletion.

Heavy alkylate 25 in an autoclave with a volume of 500 d.
0 f and catalyst 7.52 were charged, and the system was sufficiently purged with nitrogen, and then further purged with hydrogen. After increasing the pressure to 54/cII with hydrogen, the temperature was raised to 150° C. and stirred for 3 hours.

After cooling to room temperature, the catalyst was removed by vacuum filtration. Table 1 shows the measurement results for the hue of the collected liquid.

Examples 2 to 5 The same procedure as in Example 1 was carried out except that the reaction temperature, hydrogen pressure, and reaction time were changed. Example 6 The results are shown in Example 1. Using the obtained heavy alkylate (APHA9oo), the reaction temperature was 200°C, and the hydrogen pressure was 20 Cape/cIiG for 4:10].
The hue of the heavy alkylate obtained was 10 or less.

Examples 7 to 12 Same as actual foaming example 1, using 2.57 g& of 1 wt 1% palladium supported on alumina for 250 y of heavy alkylate, and changing the reaction temperature, hydrogen pressure, and reaction time. The results obtained are shown in Figure 2.

Example 13. A small 1-page algylate (A
The pond using PH-containing 70) was prepared in the same manner as in Example 1. Hue of the resulting heavy alkylate /′
Rarely below 1APHA1o.

Table 1

Claims (1)

[Claims] 1. A method for producing a light-colored heavy alkylate, which comprises hydrogenating a heavy alkylate obtained in an alkylbenzene production process in which an olefin is alkylated with benzene in the presence of a hydrogen fluoride catalyst.