EP0000622A1

EP0000622A1 - Liquid dielectric composition

Info

Publication number: EP0000622A1
Application number: EP78300089A
Authority: EP
Inventors: Johann Gustav D. Schulz; Charles Myron Selwitz; Anatoli Onopchenko
Original assignee: Gulf Research and Development Co
Current assignee: Gulf Research and Development Co
Priority date: 1977-07-21
Filing date: 1978-06-27
Publication date: 1979-02-07
Also published as: CA1084693A; US4111824A; IT7825916A0; JPS5423086A; DE2860389D1; JPS6258083B2; IT1099582B; EP0000622B1

Abstract

A liquid dielectric composition obtained as a result of a process which comproses reacting benzene with ethylene in the presence of an alkylation catalyst to obtain an alkylation product containing largely unreacted benzene, ethylbenzene, polyethylbenezenes and heavier products, separating benzene, ethylbenezene and polyethylbenezenes from said alkylation product and thereafter recovering from said heavier products the entire fraction whose boiling point is in the temperature range of about 255° to about 420°C., preferably about 260° to about 400°C., most preferably about 268° to about 400°C., as said liquid dielectric composition.

Description

The invention defined herein relates to a liquid dielectric composition obtained as a result of a process which comprises reacting benzene with ethylene in the presence of an alkylation catalyst to obtain an alkylation product containing largely unreacted benzene, ethylbenzene, polyethylbenzenes and heavier products, separating benzene, ethylbenzene and polyethylbenzenes from said alkylation product and thereafter recovering from said heavier products the entire fraction whose boiling point is in the temperature range of about 255° to about 420°C., preferably about 260° to about 400°C., most preferably about 268° to about 400°C., as said liquid dielectric composition.
Polychlorinated biphenyls have been extensively employed commercially in the electrical industry over a long period of time as liquid insulating fluids, but because of environmental and toxicological problems associated therewith, substitutes therefore are required.
We have found that a liquid dielectric composition can be obtained from a process which comprises reacting benzene with ethylene in the presence of an alkylation catalyst to obtain an alkylation product containing largely unreacted benzene, ethylbenzene, polyethylbenzenes and heavier products, separating benzene, ethylbenzene and polyethylbenzenes from said alkylation product and thereafter recovering from said heavier products the entire fraction whose boiling point is in the temperature range of about 255° to about 420°C., preferably about 260° to about 400°C., most preferably about 268⁰ to about 400°C., as said liquid dielectric composition.
In the alkylation of benzene with ethylene an alkylation product is obtained containing largely unreacted benzene, ethylbenzene, polyethylbenzenes and a higher-boiling product. From said alkylation product the unreacted benzene, ethylbenzene and polyethylbenzenes are recovered and said higher-boiling product is said to have only fuel value. In U.S. Patent No. 4,011,274, dated March 8, 1977, Masaaki et al recover from said higher-boiling product 1,1-diphenylethane and state that the resulting residue is still available as fuels In the present application we have found, unexpectedly, that from said higher-boiling product we can obtain an entire fraction, defined below, useful as liquid dielectric compositions.
Briefly, the process employed in obtaining the new liquid dielectric compositions defined and claimed herein comprises reacting benzene with ethylene in the presence of an alkylation catalyst to obtain an alkylation product containing largely unreacted benzene, ethylbenzene, polyethylbenzenes and heavier, still higher-boiling, products, separating benzene, ethylbenzene and polyethylbenzenes from said alkylation product and thereafter recovering from said heavier products the entire fraction whose boiling point is in the temperature range of about 255° to about 420°C., preferably about 260° to about 400°C., most preferably about 268° to about 400°C., as said liquid dielectric composition.
The alkylation of benzene with ethylene that can he employed to obtain the new liquid dielectric compositions claimed herein can be any of the processes known in the for producing a product containing ethylbenzene, for example, either liquid phase alkylation or vancr phase alkylation. The molar ratios of benzene to ethylene empl can be, for example, in the range of about 25:1 to about 2 preferably about 10:1 to about 3:1. In the liquid phare reaction, for example, the benzene and ethylene, together with an alkylation catalyst, for example, a Friedel Crafts catalyse, such as aluminum chloride or aluminum bromide or some other organo-aluminum halide; Lewis acids, such as promoted ZnCl₂, FeCl₃ and BF₃; and Bronsted acids, inclnding sulfuric acid, sulfonic acid and p_-toluene sulfonic acid, hydrofluoric acid, etc., in an amount corresponding to about 0.002 to about 0.050 parts, preferably about 0.005 to about 0.030 parts, relative to ethylbenzene produced, are reacted in a temperature range of about 20° to about 175°C., preferably about 90° to about 150°C., and a pressure in the range of about atmospheric to about 250 pounds per square inch gauge (about atmospheric to about 17.6 kilograms per square centimeter), preferably about seven to about 200 pounds per square inch gauge (about 0.5 to about 14 kilograms per square centimeter), for about ten minutes to about 10 hours, preferably for about 20 minutes to about three hours. In the vapor phase, for example, the reactants can be passed over a suitable alkylation catalyst bed containing alkylation catalysts, such as phosphoric acid on kieselguhr, silica or alumina, aluminum silicates, etc. at a convenient hourly space velocity in a temperature range of about 250° to about 450°C., preferably about 300° to about 400°C., and a pressure of about 400 to about 1200 pound per square inch gauge (about 28 to about 85 kilograms per square centimeter), preferably about 600 to about 1000 per square inch gauge (about 42 to about 70 kilograms per square centimeter).
As a result of such reactions, an alkylation product is obtained containing unreacted benzene, the desired ethylbenzene, polyethylbenzenes, such as diethylbenzene and triethylbenzene, and higher-boiling products.
The alkylation product can be treated in any conventinal manner to remove any alkylation catalyst present therein.
For example, when aluminum chloride is used as catalyst, the alkylation product can be sent to a sett.ler wherein the aluminum chloride complex is removed and recycled to the reaction zone and the remaining product can then be water washed and neutralized.
The resulting alkylation product is then distilled at atmospheric pressure or under vacuum to resover unreacted benzene (B.P.80°C), ethylbenzene (B.P. 136°C.) and polyethylbenzenes (B.P. 176° - 250°C).
The heavier product remaining after removal of benzene, ethylbenzene and polyethylbenzenes, as described above, is a dark, viscous, high-boiling material from which the novel liquid dielectric compositions defined and claimed herein are obtained. To obtain the claimed novel liquid dielectric composition, the said heavier product is simply subjected to distillation and the entire fraction recovered whose boiling point at atmospheric pressure (14.7 pounds per square inch gauge or 760 millimeters of mercury) is in the temperature range of about 255° to about 420°C., preferably about 26₀° to about 400°C., most preferably about 268 to about 400°C., constitutes the desired and novel liquid dielectric composition. That portion whose boiling point is in the range of about 255⁰ to about 420°C. will contain a maximum of about 20 weight per cent 1,1-diphenylethane, that portion whose boiling point is in the range of about 260° to about 400°C. will contain a maximum of about 25 weight per cent 1,1-diphenylethane and that portion whose boiling point range is in the range of about 268⁰ to about 400°C. will contain a maximum of about 30 weight per cent, 1,1-diphenylethane. The remaining heavier material or residue is a black asphalt-like material solid at ambient temperature believed, in part, to be polynuclear structure having fuel value only.
A number of liquid dielectric compositions were prepared from the residue, or heavier products, obtained as a result of the production of ethylbenzene. This residue was obtained as follows. Benzene and ethylene in a molar ratio of 9:1 were contacted in the liquid phase, while stirring, in a reactor at a temperature of 130°C. and a pressure of 70 pounds per square inch gauge (4.9 kilograms per square centimeter) in the presence of AlCl₃ catalyst over a period of one hour, which was sufficient to convert all of the ethylene. The AlCl₃ complex catalyst was prepared by dissolving AlCl₃ in a polyethylbenzene cut from a previous run so that after the addition the composition of the catalyst complex was as follows: 31.5 weight per cent AlCl₃, 7.0 weight per cent benzene, 19.3 weight per cent ethylbenzene, 29.8 weight per cent polyalkylated benzenes, 3.4 weight per cent 1,1-diphenylethane and 9.0 weight per cent higher-boiling components. The amount of AlCl₃ present in the catalyst mixture amounted to 0.0034 parts by weight per one part by weight of ethylbenzene produced. Also present in the catalyst was ethyl chloride promoter in an amount corresponuing to 0.0034 parts by weight per one part by weight of ethylbenzene produced to maintain a high catalyst efficiency Analysis of the alkylation product showed the presence of 49.0 weight per cent benzene, 32.9 weight per cent ethylbenzene, 17.5 weight per cent of polyalkylated benzenes (6,0 weight per cent diethylbenzene, 2.7 weight per cent triethylbenzenes, 2.1 weight per cent tetraethylbenzenes ana 6.7 weight per cent other alkylbenzenes), 0.1 weight per cent 1,1-diphenylethane and 0.4 weight per cent residue. The alkylation product was subjected to distillation to recover unreacted benzene, ethylbenzene and polyalkylated benzenes, and the benzene and polyalkylated benzenes were recycled to the reaction zone. The residue remaining was a dark,viscous, high-boiling material, and was produced in an amount corresponding to 0.014 parts for each part of ethylbenzene produced. By using aged aluminum chloride complex, the amount of high-boiling residue formed can be increased substantially.
The residue obtained above was subjected to distillation at atmospheric pressure and a fraction was recovered having a boiling point at atmospheric pressure of 260° to 400°C. and subjected to tests (ASTM-D924) at 25°C. to determine its power factor and its dielectric strength. When this fraction was subjected to the above tests the following results were obtained: Dielectric Strength, kV: 50 and power Factor, Per Cent: 0.08.
It is understood that the present compositions can be further treated, if desired, for example, to further impro their properties for a particular purpose, for example, improve their flash point, interfacial tension, pour poir. viscosity, oxidation stability, corrosion resistance, etc For example, the power factor of the composition claimed h in can be further improved by recovering said composition from the heavier products defined herein by distillation in the presence of basic materials, such as Group I and Group II alkali metals and alkaline earth metals, their oxides and hydroxides, as defined in our copending U.S. Application Serial No. 817,694, entitled Liquid Dielectric Composition.
Obviously, many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

Claims

1. A liquid dielectric composition obtained as a result of a process which comprises reacting benzene with ethylene in the presence of an alkylation catalyst to obtain an alkylation product containing largely unreacted benzene, ethylbenzene, polyethylbenzenes, 1,1-diphenylethane and heavier products, separating benzene, ethylbenzene and polyethylbenzenes from said alkylation product and thereafter recovering from said heavier products the entire fraction whose boiling point is in the temperature range of about 255⁰ to about 420°C. as said liquid dielectric composition.

2. The composition of claim 1 wherein the boiling point of said fraction is in the range of about 260° to about 400°C.

3. The composition of claim 1 wherein the boiling point of said fraction is in the range of about 268° to about 400°C.

4. The composition of claim 1 wherein said catalyst is AlCl_3.

5. The composition of claim 1 wherein said benzene and said ethylene are reacted in the presence of AlCl₃ in a temperature range of about 20° to about 175°C.

6. The composition of claim 1 wherein said benzene and said ethylene are reacted in the presence of AlCl₃ in a temperature range of about 90° to about 150°C.