JPS60167205A - Electrically insulating oil - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrical insulating oil comprising a product obtained by processing a pyrolysis oil fraction from a pyrolysis process of petroleum heavy residual oil.

In recent years, due to the depletion of petroleum resources, heavier crude oil has been used, and as a result, the amount of by-product heavy residual oil such as distillation residue oil has also tended to increase. However, this heavy residual oil has low industrial utility value due to its high viscosity and high sulfur and metal content.

On the other hand, the only form of utilization of such heavy residual oil is as a raw material for thermal decomposition processes such as coking. From the coking process of this heavy residual oil, a liquid substance, that is, pyrolysis oil can be obtained along with coke, gas, etc. The yield of pyrolysis oil in normal coking is quite high, and a large amount of pyrolysis oil can be obtained. Become.

However, conventional methods for utilizing the pyrolysis oil produced in large quantities have been limited to the fact that this oil is relatively rich in aliphatic hydrocarbons,
Since it may not have a sufficient octane number, it cannot be used as gasoline for automobiles without further treatment such as fluidized catalytic cracking, and can only be used as a simple fuel for boilers. Therefore, the utilization of this large amount of by-product pyrolysis oil is becoming a major industrial problem.

By the way, petroleum-based light hydrocarbons such as naphtha are
The production of basic raw materials for the petrochemical industry, such as ethylene and propylene, by thermal decomposition at 850°C is widely practiced as so-called naphtha cracking.

At this time, it is difficult to generalize because it varies depending on the type of raw material oil supplied to the pyrolysis equipment, cracking conditions, etc.The pyrolysis by-product oil containing a large amount of aromatic hydrocarbons is α5 to 3.0 compared to the ethylene production amount. Weight% by-product.

In addition, in order to improve the octane number or increase the content of aromatic hydrocarbons such as benzene, toluene, and xylene to obtain aromatic hydrocarbons, naphtha or the like is converted into pt or Pt-Re/A1zO2 in the presence of hydrogen. The reformed oil obtained in large quantities from catalytic reforming in which it is brought into contact with a noble metal catalyst naturally also contains a large amount of aromatic hydrocarbons.

Furthermore, the residual oil that is separated and removed from benzene, toluene, and xylea-1ti from the above-mentioned pyrolysis byproduct oil and reformed oil by separation means such as solvent extraction mainly contains aromatic hydrocarbons such as C9 and C1o. Although there are fractions that can be used, they have not been fully utilized industrially because they are mixtures of many components and it is difficult to separate them into each component.

As a result of intensive research aimed at the effective use of fractions that are not sufficiently utilized industrially as described above, the present inventors have found that the thermal cracking oil fraction obtained from the thermal cracking of heavy residual oil has a thermal cracking byproduct. The raw oil fraction, reformed oil, pyrolysis by-product oil fraction, aromatic residual oil from the reformed oil, etc. are mixed together and treated with an acid catalyst to produce a material with excellent low-temperature properties suitable for electrical insulating oil. The present invention was completed by discovering that a high boiling point fraction can be obtained.

That is, the present invention provides (4) heating petroleum hydrocarbons to 400°C.
The above is a pyrolysis oil fraction obtained from a pyrolysis process in which pyrolysis is performed at a temperature not exceeding 700°C, with a boiling point of 120°C.
20 to 95% by weight of a pyrolysis oil fraction containing a hydrocarbon as a main component and an aliphatic olefin in the range of ~290°C;
(BXa) Pyrolysis by-product oil fraction obtained by thermally decomposing petroleum-based light oil at a temperature of 750 to 850°C and then performing treatment to reduce unsaturated content, (b) Petroleum-based light oil with a boiling point of 50 to 250°C A reformed oil fraction obtained by catalytically reforming oil, and then optionally subjected to treatment to reduce unsaturation, and (C
) The thermal decomposition by-product oil fraction of (a) above and/or (b)
One or more fractions with a boiling point of 150 to 250° C. 80 to 5 selected from the group consisting of aromatic fractions mainly containing aromatic hydrocarbons separated and obtained from the reformed oil fraction of
% by weight in the liquid phase in the presence of an acid catalyst at a reaction temperature of 30-3
The present invention relates to an electrical insulating oil characterized by being composed of a reaction product having a boiling point of 315°C or higher and having excellent low-temperature properties when treated at 30°C.

The petroleum-based heavy oil to be thermally cracked in the subject matter of the present invention refers to atmospheric distillation residue oil, vacuum distillation residue oil, thermal cracking or catalytic cracking residue oil, and various petroleum oils in the ordinary sense of the petroleum refining industry. Refers to refining residues, such as extraction residues with furfural, propane, pentane, etc., reformer residues, and mixtures thereof.

The decomposition temperature of the thermal decomposition process of the present invention is required to be 400°C or higher and not to exceed 700°C. 400℃
Thermal decomposition does not occur at lower decomposition temperatures;
In this case, regardless of the decomposition time, aromatic hydrocarbons, which are themselves highly reactive, will be excessive in the resulting pyrolysis oil, and acid catalyst treatment will easily form high polymers such as resin components. This is not preferable because the amount of aliphatic olefin having a boiling point in the range of 120 to 290°C is too small. The decomposition temperature is preferably 400-600°C, more preferably 400-550°C.

The decomposition time can be changed as appropriate depending on the main purpose of the thermal decomposition process, such as coke production, viscosity reduction of raw material heavy oil, etc., and can be adopted, for example, in the range of 10 sec to 50 hr. Water vapor or other non-reactive gaseous media can also be present during the decomposition. The decomposition pressure is usually relatively low, ranging from reduced pressure to about 50 KP/d.

A typical example of such a thermal decomposition process for heavy residual oil is Hydrocarbon Processin.
g, Vol, 6L A9 #5eptember 19
82. As described in I), 160-L65, there are visbreaking methods, coking methods, etc. In other words, visbreaking methods are relatively mild methods that suppress the generation of coke in the heating furnace tube. It is a process of thermal decomposition mainly for the purpose of reducing the viscosity of raw materials, and there are two types: coil type and soaker type. Normally, cracked oil leaving the cracking furnace is rapidly cooled to crack it and suppress coke. Examples of this include the 1, ummus method and the 5heH method.

In addition, the coking method is a process that co-produces coke. After the residual oil is heated in a heating furnace for a relatively short period of time, it is sent to a coke drum, where it is heated over a relatively long period of time to produce lump coke. Derate coking that generates (
UOP method, poster Wheeler method, M, W
, Kel Iogg method, Lummua method and C0N0
CO method, etc.), fluid coking method (Exxon method, etc.) in which residual oil is cracked on high-temperature fluidized coke, flexi coking method (Exxon method), which combines fluid coking method with gasification process of produced coke, and , which produces pitch by thermal decomposition and steam stripping at relatively low pressures such as normal pressure.
RBKA) process.

Among these thermal cracking processes, as a result of the sulfur content and metal content in the residual oil being concentrated in the produced coke, the cracked oil contains relatively few of these impurities, and therefore, even after acid catalyst treatment, refining is possible. The coking method is preferred because it is a comparison vessel and contains a relatively large amount of high-boiling point aliphatic olefin. Furthermore, among these, delByed coking is operated on a large scale because it produces lump coke that is useful as a carbon source for graphite for electrodes, and as a result, the cracked oil produced as a by-product is particularly large. Therefore, if it is effectively utilized according to the present invention, the benefits will be great, so it is an advantageous caulking method.

The composition of the pyrolysis oil obtained from the above pyrolysis process varies depending on the type of pyrolysis process, pyrolysis conditions, type of raw heavy oil, etc. Usually, it contains almost no aromatic olefins, Mainly contains paraffins such as normal paraffins and isoparaffins, as well as highly reactive aliphatic olefins such as normal olefins and isoolefins, and also includes alkyl-substituted monocyclic rings such as alkylbenzenes, alkylindanes, alkyl tetralins, etc. It includes aromatic hydrocarbons having alkyl-substituted complex rings such as alkyl-substituted complex rings, and alkyl-substituted condensed rings such as alkylnaphthalene.

Among the pyrolysis oils obtained from the above-mentioned various pyrolysis processes, in the present invention, pyrolysis oil distillates whose main component is hydrocarbons with a boiling point in the range of 120 to 290°C, more preferably 150 to 260°C are used. The amount is subject to processing. A fraction whose main component is a hydrocarbon having a boiling point outside the above range is not preferred because industrially useful reaction products cannot be obtained.

Furthermore, the pyrolysis oil fraction to be treated in the present invention needs to contain aliphatic olefins.

Typical compositions of pyrolysis oil fractions of interest are 30 to 70% by weight of hydroparaffins, 10 to 40% by weight of aliphatic olefins, and 5 to 20% by weight of aromatic hydrocarbons. However, as long as the above-mentioned conditions for the target fraction are satisfied, there is no problem in appropriately fractionating the pyrolysis oil or diluting it with unreacted oil or the like.

(a) Pyrolysis byproduct oil fraction, (b) reformed oil fraction, and (C) aromatic fraction as components in item is as follows.0 In other words, the thermal decomposition by-product oil fraction in (a) is obtained by converting light petroleum oil at a humidity of 7.
It is a thermal decomposition by-product oil fraction obtained during thermal decomposition at 50 to 850°C, and is a fraction that has been treated to reduce unsaturated content such as diolefins and monoolefins.

Aozode 3A 匪 しょう 葡 し L い H naphtha, kerosene, I, PG, 7
Examples include various petroleum-based light oils such as 'tan'. Considering the properties obtained before pyrolysis by-products, naphtha and kerosene are preferred as pyrolysis raw materials because they are more suitable for the purpose of the present invention.

The thermal decomposition method is not particularly limited, and various commonly used thermal decomposition methods at 750 to 850°C, such as a tubular decomposition furnace method using a tubular decomposition furnace, a thermal medium decomposition method using a heat medium, etc. can be used as appropriate.

The thermal decomposition by-product oil fraction, which is obtained by removing target products such as olefins and diolefins such as ethylene, propylene, and butadiene, from the products of this thermal decomposition is determined by the type of petroleum light oil that is the raw material, and the thermal cracking conditions. It contains a relatively large amount of aromatic hydrocarbons, including 2 to 10% by weight of paraffins, 3 to 10% by weight of naphthenes, 55 to 85% by weight of aromatic hydrocarbons, and 2 to 1% by weight of aliphatic olefins.
0% by weight, a fraction with 6 to 10 carbon atoms varying from 2 to 15% by weight of aromatic olefins.

Among these, in the present invention, a fraction having a boiling point of 150-280''C is used by mixing it with the above-mentioned thermally cracked oil fraction.

However, in the pre-distillation of thermal decomposition by-products of the present invention, the unsaturated content can be reduced to 0.
．． This is a fraction that has been treated to reduce it to 5% or less, preferably a1% or less. This treatment is achieved by a conventionally known catalytic hydrogenation treatment. For example, Pt, Pd, Ni
, Co., Mo., W.

Metal catalysts such as Co-Mo, Ni-W, or
A catalyst in which these are supported on a carrier such as alumina can be used.

The conditions for this treatment are usually a reaction temperature of 200 to 400℃.
'C1 hydrogen pressure 20-150? /d, hydrogen/oil% ratio 0.
5~20°LH8V0.1~10-t'.

The reformed oil fraction in (b) above has a boiling point of 50 to 250°C.
It is a reformed oil fraction obtained by catalytically reforming light petroleum oil, such as naphtha such as straight-run naphtha. Catalytic reforming is widely carried out in the fields of petroleum refining and petrochemistry to improve the octane number and to obtain t-benzene, toluene, xylene, etc. This catalytic reforming is carried out in the presence of hydrogen at a reaction temperature of 450 to 510°C, and the catalyst used is alumina or silica-alumina supported platinum, platinum-
Metal catalysts such as rhenium, molybdenum oxide, and chromium oxide. Industrial methods include fixed-bed UOP platforming and Standard Oil Company's ultra-homing, and there are also fluidized bed and moving bed methods. In catalytic reforming, dehydrogenation and cyclization reactions mainly occur, and the isomerization reaction also occurs, resulting in the production of BT such as benzene, toluene, and xylene.
The X content increases and the octane number improves. However, the obtained reformed oil is compared to the above-mentioned pyrolysis by-product oil.
It is characterized by a very low unsaturated content, with a bromine number of about 38 or less. A more preferred reformate has a bromine number of about 2 or less.

The typical composition of this catalytically modified oil is 30 to 35% paraffin.
% by weight, aromatic hydrocarbons from 65 to 70% by weight, and olefins from 0 to 2% by weight. In the present invention, a catalytic reforming oil fraction having a boiling point of 150 to 280°C is used.

As mentioned above, the fraction is generally low in unsaturation and can be treated, if necessary, to reduce unsaturation. This treatment can be carried out in the same manner as the treatment for reducing the unsaturated content of the thermal decomposition by-product oil described in (a) above.

Furthermore, using these catalytically reformed oils, the thermal decomposition by-product oils, or mixtures thereof as raw materials, an aromatic fraction mainly consisting of aromatic hydrocarbons obtained by an appropriate separation means is added to the above-mentioned (
It can be used as the aromatic fraction of C). This separation is used in the petrochemical field from catalytic reforming oil and pyrolysis byproduct oil.
It is carried out on a large scale to obtain TX, and usually,
It is carried out by solvent extraction or extractive distillation. Typical solvent extraction methods include the Udex method (DOW method) using diethylene glycol, triethylene glycol, etc. as an extraction solvent, and the sulfolane method (3-hell method) using sulfolane. In addition, in this extraction, in order to avoid clogging of the apparatus due to polymerization of unsaturated components, unsaturated components are usually removed by hydrogenation or the like as a pretreatment.

In this way, among the aromatic fractions mainly composed of aromatic hydrocarbons obtained by separation from catalytic reforming oil and pyrolysis byproduct oil, the fraction with a boiling point of 150 to 250°C ((C) of the present invention) The aromatic fraction (of the Although it is obtained in large quantities along with the BTX fraction, there has been no effective way to use it.

In the present invention, (6) (a) is added to the pyrolysis oil fraction of
) The pyrolysis sub-oil fraction, (b) the reformed oil fraction, and (C) the aromatic fraction are mixed and subjected to lA acid catalyst treatment. (a)-(c)
The fractions can be mixed as appropriate and used as the fraction (2). The mixing ratio of both is 20 to 95% by weight of the pyrolysis oil fraction (1) and 80 to 5% by weight of the fraction (6). When using the obtained reaction product as an electrical insulating oil, a more preferable mixing ratio is as follows:
The fraction (4) is 70 to 90% by weight, and the fraction B is 30 to 10% by weight.

Acid catalyst wires, solid acid catalysts, mineral acids, so-called 7-Riedel-Cla, fluorocatalysts, organic acids, etc. are preferably used. For example, specifically, acidic clay minerals such as acid clay and activated clay, amorphous or crystalline silica-alumina, solid acid catalysts such as AIF3 and Al2O3, strong acid type ion exchange resins, HF, AlC1m, BF3.8n
Friedel-Krauch catalysts such as 014, sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and other inorganic or organic compounds.

The reaction format for the treatment may be batch, semi-batch, or flow-through. When a solid acid is used, flow-through is preferably used.

The above-mentioned acid catalyst is applied to the fraction in a batchwise manner at a rate of 0.
2 to 20% by weight, preferably 1 to 10% by weight, and in the flow type, LH8ICL1 to 20, preferably (1,
Process under conditions 5-1(1). Reaction temperature is 30-300℃
℃, preferably 50 to 250℃. The treatment time varies depending on the reaction conditions, that is, the amount of catalyst, reaction temperature, raw material composition, etc. It is necessary to have enough time to complete the reaction.
Usually, the time can be selected within the range of 2 to 24 hours. The reaction pressure may be any pressure necessary to maintain the liquid phase.

In the present invention, the acid catalyst treatment is carried out in such a way that a reaction product having a boiling point of 315° C. or higher is obtained. The reaction product is mainly a reaction product of aliphatic olefins, and the main components are oligomers of aliphatic olefins and alkylates of aliphatic olefins and aromatic hydrocarbons. A reaction product with a boiling point lower than 315° C. has a low flash point and is therefore of no value as an insulating oil, and there is no point in acid catalyst treatment, so it is not preferred.

In the present invention, as mentioned above, a fraction with a specific composition from a specific source is subjected to a specific treatment with the raw material, so high molecular weight compounds that do not adversely affect various physical properties are not substantially generated, and the present invention The reaction product has a relatively low viscosity. Therefore, depending on the application, it is possible to use the oil as an insulating oil by simply separating the unreacted fraction (raw material fraction), for example, by distillation, without further separating the heavy fraction. Of course, the product can also be divided into suitable boiling range fractions if desired.

Due to the above treatment, the unsaturated content of the pyrolysis oil fraction is reduced, for example, the bromine number is reduced.
As mentioned above, unsaturation is reduced or eliminated by preferably performing a catalytic hydrogenation treatment (including the oligomerization process of aliphatic olefins).
The catalytic hydrogenation treatment can be performed on either the separated reaction product or a fraction containing a large amount of the reaction product, or the pyrolysis oil fraction itself subjected to the acid catalyst treatment.

Any conventionally known catalyst can be used for the catalytic hydrogenation treatment. Examples are PtXPd, Ni, CoXMo, W
,C.

Metal catalysts such as -Mo and N1-W can be used. The conditions for this treatment are usually a reaction temperature of 250 to 400°C, a hydrogen pressure of 20 to 100 KP/cI, and a hydrogen/oil molar ratio of 0.5.
-20, LH8V0.1-10. This hydrogenation treatment is carried out under conditions in which nuclear hydrogenation of the aromatic hydrocarbons does not substantially occur, and then the reaction products, if necessary, gas components, etc. are removed by an appropriate means such as distillation. To separate. Of course, the hydrogenation reaction product may be further separated into appropriate fractions.

The hydrogenation reaction product thus obtained has a boiling point of 6
The viscosity is 25 ca or less at 75°C, the pour point is -40°C or less, and the flash point is 140°C or more. In addition, its composition varies depending on the boiling point range of the raw materials, mixing ratio, etc. It contains almost no normal paraffins, and is composed of isoparaffins, aromatic hydrocarbons containing alkyl-substituted mono- or composite rings, etc. It is something.

The features of the present invention are summarized as follows.

(1) According to the present invention, cracked oil from the pyrolysis process of heavy residual oil and pyrolysis by-product oil of petroleum light oil, or high boiling point fraction (bp1so~250°C) in catalytically reformed gasoline
is highly available. That is, the industrial value is low, and the industrial value is high because it is possible to effectively utilize a large amount of surplus heavy residual oil. At the same time, high value-added benzene,
Products with high industrial value can be obtained by using high-boiling fractions with low industrial value, which are by-produced during the production of toluene, xylene, etc.

(2) Since the raw material is a fraction with a specific composition of a specific raw material and undergoes a specific treatment, virtually no high molecular weight substances that have a negative effect on physical properties are produced, and a relatively low viscosity product is produced. You can get something.

Therefore, if possible, it has the advantage that it can be used as an inexpensive electrical insulating oil by simply distilling off the unreacted oil fraction.

Furthermore, even though pyrolysis oil from heavy residual oil is used as a raw material, electrical insulating oil with low unsaturated content, metal content, and sulfur content can be obtained.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 A dilate coking device (decomposition temperature 4
(96°C, residence time 24 hours, cracking pressure 4KP/cIi) At the yield shown in Table 2, pyrolysis oil was obtained together with gas and coke.Of these, the fraction with a boiling point of 160 to 260°C was designated as fraction A, Its composition is shown in Table 3 O Specific gravity (015°C) API 20 Asphaltene wt% 2.6 Butane and light gas 8 30-160°C 13 160-260°C 22 260°C 40 Coke 17 Table 3 Pyrolysis oil fraction composition ( Fraction A) 160-260°C Type analysis (wt%) Paraffin content 68.6 Aliphatic olefin content 194 Aromatic content 12.6 In addition, naphtha is thermally decomposed at 780-810°C for the purpose of producing ethylene and propylene. This M
The raw oil extraction fraction acetylenes and diolefins contained a large amount of aromatic hydrocarbons such as mubenzene, toluene, xylene, and styrene.

Next, the fraction was subjected to hydrogenation treatment in a 1uni 7-I engineering Nguni stage hydrogenation equipment for the purpose of removing unsaturated components such as diolefins and desulfurization.The catalyst used was a cobalt-molybdenum catalyst supported on alumina. , the temperature of the first stage is 220℃
, the pressure is 5° KP/ad, and the temperature of the second stage is 330'C1.
The pressure was 5 o Kp/cd.
The fraction with an unsaturated content α of 01% or less is referred to as fraction a.

Next, naphtha with a boiling point of 50 to 250°C was heated in the presence of hydrogen at a reaction temperature of 470°C and a pressure of 50 KP/cII to produce gasoline, benzene, toluene, and haxylene.
The reformed oil obtained from the platform mink equipment, which undergoes catalytic reforming using a Shinkin catalyst, also has a low unsaturated content compared to the above-mentioned pyrolysis by-product oil fraction, which has a large aromatic content. Let's distill this. The bromine number of this fraction was about 10.

Subsequently, reformed oil fraction b 90vo with a boiling point of 60 to 250°C
1% and 1% of a fraction 1Qvo having the same boiling point range as the above-mentioned fraction a (thermal decomposition by-product oil fraction) were mixed, and the mixture was passed through a Udex extraction device to recover an aromatic fraction.

That is, supplying the mixture to the center of the aromatic extraction column,
On the other hand, ethylene glycol, which is an extraction solvent, is supplied from the upper part of the column to perform countercurrent catalytic extraction, and after purifying the extract, benzene, toluene, and xylene are fractionated and crushed. At this time, an aromatic fraction with a boiling point of 150 to 250° C. is produced as a by-product as a fraction of 0.09 or higher. It contains more than 99% aromatic content. This aromatic fraction is designated as fraction C. Among these, the properties of the fraction with a boiling point of 160 to 180°C (fraction cl) are shown in the table below (
Table 4) shows the results.

Table 4 Specific gravity Q60?150'F O,876 Hue Seybold +50 or higher Flash point (PMCC) 45 Mixed aniline point ``C,15 Aromatic (volume %) 995 Distillation properties (person 8TM) Initial distillation ℃ 160 Dry point ℃ 176 Above Fraction A (pyrolysis oil fraction) 450- and fraction c t
(Aromatic fraction) 5g of AlCl3 was added to a mixture (aliphatic olefin content 17.5%) consisting of 50-
℃ for 15 hours in a batchwise manner, the reaction mixture was treated with aqueous ammonia to neutralize and decompose AlCl5, and then dehydrated as a fraction at 315℃, yielding the reaction product 98.4&(
The bromine number of this product was S, 6.
cg/11, with an aromatic content of 80.2% and the remainder being mostly olefins, the product had a viscosity of 1a4c.
s t (Q75°C), pour point -47.5°C, and flash point 180°C.Next, this reaction product was heated using a CO-MO catalyst at a hydrogen pressure of 5oKp/crIs reaction humidity 260°C, and the reaction mixture 1
Hydrogenation treatment was performed under the following conditions: capacity/catalyst capacity/hr.

After hydrogenation, the light components produced by decomposition were distilled off, and the hydrogenated reaction product was recovered with a recovery rate of 811%.9 This hydrogenated reaction product had a bromine value of 0.3c.
g/#, the aromatic content was 7% and 5%, and nuclear hydrogenation of aromatic compounds was not substantially performed.

Physical properties of this hydrogenated reaction product and A8TM
-Electrical property test based on D-1934 and JI8-C
Table 5 summarizes the results of the oxidation stability test based on 2102. From the results in Table 5, which also shows the results for mineral oil for comparison, it is clear that the hydrogenation reaction product of the present invention has superior physical properties compared to mineral oil, so it is suitable for electrical insulation. Ideal for oil.

Table 5 Pour point ('C) -47,5-30 Dielectric breakdown voltage (KV / 2.5 m) 60 or more 60 or more Dielectric voltage junction (%, 080℃) C] "Before heat deterioration a, a, a 1o, o o 1 after deterioration (without catalyst) 0.017 0.194 after deterioration (with catalyst)
α066 2.323 Volume resistivity (Ω, 080℃) Before heat deterioration 7.0X10"6.3X10" After deterioration (
(No catalyst) 3.2xAO"2.5x10"Sludge after oxidation stabilization (%) o,os o,1゜Total oxidation (#KOH/#) 0.11 0.50Corrosive sulfur test 140℃X19hr No corrosion No corrosion Example 2 5 g of AlCl3 was added to a mixture (olefin content: 18.4%) consisting of 475 m of fraction A (pyrolysis oil fraction) of Example 1 and 25 fractions of fraction C' (aromatic fraction). , 185℃
After the treatment, the reaction mixture was treated with an ammonia aqueous solution.1 The catalyst was neutralized and washed with water. After sufficient dehydration, the reaction mixture was treated as a fraction at 515℃1.
This product has a viscosity of 1α6c
s t (075℃), pour point -415℃, flash point 18
Example 3 59 AI was added to a mixture (olefin content 97%) of fraction A, 250- of Example 1 and fraction c' 250-
After treatment, the reaction mixture was treated with an ammonia aqueous solution in a batchwise manner for 15 hours at 185°C.The catalyst 1 was neutralized, washed with water, and thoroughly dehydrated. 1α4%) was obtained. This product has a viscosity of 6.5 cSt (075°C) and a pour point of -50°C.
Example 4: Fraction A (pyrolysis oil fraction) 100- of Example 1 and fraction C
5 g of AlCl3 was added to a mixture (olefin content: 4.0%) consisting of 400 - (aromatic fraction) and treated in the same manner as in Example 1 to obtain reaction mixture 27 as a fraction at 315°C. The product obtained had a viscosity of 4.0 cSt (075°C), a pour point of -50°C,
The flash point was 180°C.

Example 5 51 of AlCl3 was added to a mixture (olefin content 17.5%) of fraction A, 450- and fraction C150- of Example 1.
The reaction mixture was treated in a batchwise manner at 185°C for 15 hours, and the reaction mixture was treated with an aqueous ammonia solution, and the catalyst was neutralized and removed by washing with water. After thorough dehydration, 97.2 g (yield 24.3%) of the reaction mixture was obtained as a fraction at 315°C. This product had a viscosity of f16c8t (Q75°C) and a pour point of -42.5
℃, flash point was 190℃ Example 6 A mixture consisting of fraction A of Example 1, 450- and 50tnt of fraction a (thermal decomposition by-product oil fraction) having a boiling point of 150 to 250℃ (olefin content 18.7%) with 51 AlCl3
After the treatment, the reaction mixture was treated with an aqueous ammonia solution and the catalyst was neutralized and removed by washing with water. After sufficient dehydration, a reaction mixture qz21c (yield 24.1%) was obtained as a fraction at 315°C. This product had a weight of 12.1 cSt, a pour point of -42.5°C, and a flash point of 186°C. .

Example 7 Fraction A450 of Example 1. p and fraction b (reformed oil fraction)
51 At(:]3 was added to a mixture (olefin content: 17.8%) consisting of 5o-, a fraction with a boiling point of 150 to 250°C, and the mixture was treated batchwise at 18.5°C for 15 hours. The mixture was treated with an aqueous ammonia solution, and the catalyst was neutralized and removed by washing with water. After thorough dehydration, a reaction mixture of 9s and 311 (yield 23.6%) was obtained as a fraction at 315°C. This product had a viscosity of 1t6cSt, Pour point -45℃, flash point 19
It was 0°C.

Example 8 A mixture of the fraction [1,450-] of Example 1 and the fraction C' 50- (olefin content 17.5%) was added with 5-B.
F, HgO was added and the reaction mixture was treated batchwise at 90°C for 5 hours. The reaction mixture was treated with an ammonia aqueous solution, and the catalyst was neutralized and washed with water. After thorough dehydration, the reaction product 729 (yield 17) was obtained as a fraction at 315°C. This product had a viscosity of 7.2 e8t (075°C), a pour point of -50°C, and a flash point of 180°C.

Example 9 The pyrolysis oil obtained by distilling the Minas vacuum residual oil of Example 1 under the conditions of a residence time of 15 hours, a temperature of 485°C, and a pressure of 15 to 9/cd was rectified. A pyrolysis oil fraction with a boiling point range of 120°C to 290°C (containing 85% of components in the range of 120 to 290°C) was obtained with a yield of 37%.

This pyrolysis oil fraction 450- and the fraction c' of Example 1, 50
m mixture (olefin content 18.0%) using silica/alumina as a catalyst, reaction temperature 200°C, 1 volume of mixed oil /
The treatment was carried out in a fixed bed flow system under the conditions of catalyst amount/Hr.

The reaction solution was directly heated to a hydrogen pressure of 50 using a CO-MO catalyst.
Kp/d1 reaction temperature 300°C, mixed oil 1 volume/catalyst volume/In.

After catalytic hydrogenation at a Ha/oil molar ratio of 10, a reaction product was obtained as a 615°C+ fraction.Subsequently, the hydrogenated reaction product was evaluated for its characteristics, The results of the test for oxidation stability are shown in Table 6.
The test results are also shown in Table 6.

Claims (1)

[Scope of Claims] 1 (4) A pyrolysis oil fraction obtained from a pyrolysis process in which petroleum-based heavy residual oil is pyrolyzed at a temperature of 400°C or higher but not exceeding 700°C, which has a boiling point of 120 to 290°C. Q3) (a) Petroleum light oil at a temperature of 750-850°C and 20-95% by weight of a pyrolysis oil fraction containing hydrocarbons in the range of ℃ and aliphatic olefins as a main component.
(b) Petroleum-based light oil with a boiling point of 50 to 250°C is catalytically reformed, and then treated as necessary to reduce the unsaturated content. and (C) the thermal decomposition byproduct oil of (a) above and/or (b).
1 selected from the group consisting of aromatic fractions mainly consisting of aromatic hydrocarbon water beds separated and obtained from the reformed oil fraction of )
Species or two or more fractions with a boiling point of 150 to 250°C 80~
5% by weight in the liquid phase in the presence of an acid catalyst at a reaction temperature of 30~
An electrical insulating oil comprising a reaction product having a boiling point of 615°C or higher and having excellent low-temperature properties obtained by processing at 330°C. 2. The electrical insulating oil according to claim 1, wherein the pyrolysis process is a Zuking process. 3 (4) A pyrolysis oil fraction obtained from a pyrolysis process in which heavy petroleum residual oil is pyrolyzed at a temperature of 400°C or higher but not exceeding 700°C, and has a boiling point in the range of 120 to 290°C. 20 to 95% by weight of a pyrolysis oil fraction containing hydrogen as a main component and aliphatic olefins and @(a) petroleum light oil are pyrolyzed at a temperature of 750 to 850°C, and then the unsaturated content is reduced. Thermal decomposition by-product oil fraction obtained by the treatment (b) obtained by catalytic reforming of petroleum light oil with a boiling point of 50 to 250°C, followed by treatment to reduce the unsaturated content as necessary Reformed oil fraction and (C) thermal decomposition byproduct oil of (a) above and/or (b)
1 selected from the group consisting of aromatic fractions containing mainly aromatic hydrocarbons that are separated and obtained from the reformed oil fraction of )
Species or two or more fractions with a boiling point of 150 to 250°C 80~
5% by weight in the liquid phase in the presence of an acid catalyst at a reaction temperature of 30~
By processing at 330°C, a reaction product with a boiling point of 315°C or higher with excellent low-temperature properties is produced, and then catalytic hydrogenation treatment is performed under conditions where nuclear hydrogenation of aromatic hydrocarbons does not substantially occur. An electrical insulating oil characterized in that it consists of the obtained product. 4. The electrical insulating oil according to claim 5, wherein the thermal decomposition process is a coking process.