CA1232562A - Method of processing thermal-cracked oil distillates - Google Patents

Abstract

ABSTRACT

A hydrocarbon feed comprising a thermal-cracked oil distillate obtained from a process for thermal cracking of a petrolic heavy residual oil at a temperature not lower than 400°C and not exceeding 700°C, said distillate consisting mainly of hydrocarbons boiling in the range of 120° to 290°C and said distillate contain-ing aliphatic olefins, is treated at a reaction tempera-ture of 30° to 300°C in liquid phase in the presence of an acid catalyst, to obtain a reaction product having a boiling range which is higher than that of the hydro-carbons as the main component of the distillate and which is not lower than 260°C.

Description

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METilOD OF PROC~SSINC TII~RMAL-CR~CKED OIL DISTILL~T~S

BACKGROUND OF Tll~ INV~NTIO_ The present invention relates to a method of processing a distillate from a thermal-cracked oil obtained in a thermal cracking process using a petrolic heavy residual oil as a starting material.
Recently, because of the exhaustion of petroleum resorces, heavier crude oils have come to be used, thus giving rise to an inereasing tendeney of the amount of heavy oils by-produeed sueh as resid-ual oils in distillations. These heavy residual oils are of less industrial value by reason of their high viscosities or high sulfur and metal contents.
On the other hand, such heavy residual oils ean be utilized in thermal eraeking proeesses typified by eoking, whieh may be the only utilization mode of those oils. From the heavy residual oil eoking proeess is obtained a liquid substanee, i.e., thermal-cracked oil, as well as eoke and gas. Usually, the yield of 0 distillates from the eraeked oil is fairly high and the distillates are obtained in large amounts.
Since the e:cacked oil distillates thus obtained in large amounts eontain large amounts of unsaturated compounds and aliphatic hydroearbons and do not have a suffieiently high oetane number, they 1;~32S6~

have heretofore not been used directly as gasoline base stocks for automobiles, for which purpose they are required to be Eurther subjected to a reforming treatment such as a fluid catalytic cracking. At most, the distillates have been used as mere fuels for boil-ers, etc. Therefore, how to utilize such large amounts of thermal~cracked oil distillates is becoming a subject of discussion in the industrial world.

SUMMl~RY OF TEIE INVE:NTION
It is an object of toe present invention to effectively utilize a distillate from a crackc~
oil obtained in a large amount as a by-product, for example, in the coking process which distillate has been found useful merely as fuel for boilers or the like, and to enhance the utilization value of heavy residual oils by-produced in large amounts typical of which is petroleum asphalt, by processing those oils.
It is another object of the present invention to effec-tively utilize a high-boiling aromatic hydro-carbon distillate of little utilization value by-produced from a cracking apparatus for the production of ethylene.
According to the present invention, a hydro-carbon feed which comprise a distillate from a thermal-1~3ZS6;~

cracked oil obtained by thermally cracking a petrolicheavy residual oil at a temperature not lower than 400C and not exceeding 700C is -treated wi-th an acid catalyst, whereby there is obtained a liquid reaction product which is industrially useful, for example, as an insulating oil and the material for surfactant. Moreover, if this reaction product is separated from the said distillate by a physical separ-ation means such as distillation, the said distill.ate itself is reformed into a distillate which contain reduced amounts of unsa-turated compounds and which is useful as an industrial solvent, a starting material for the production of n-paraffin, etc.
. In U,S. Patent No.4,208,268 there is disclosed a process for treating a thermal-cracked by-pr~duct oil distillate with an acid catalyst. ~Iowever, this distillate is from a thermal cracking process for the preparation of lower olefins such as ethylene, and is rich in aromatics. Usually, heavy residual oils are not used as starting materials for such cracking.
Besides, the cracking temperature is as high as not lower than 700C because lower olefins are to be produc-ed.

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DESC~I~TION OF PREFERRED EMBODI ENTS
The petrolic heavy residual oils referred to herein indicate bottom residues in atmospheric distillation, vacuum distillation and thermal or catalytic cracking, and various residues in petroleum reEining, or example, residual oils in extraction with furfural, propane, pentane, etc., residual oils in reformers, as well as mixtures thereof, in the ordinary sense in the petroleum refining industry.
on the thermal cracking process of the present invention, the cracking temperature should be not lower than 400C and should not exceed 700C.
If the cracking temperature is lower than 400C, a thermal cracking will not occur, and if it exceeds 700C, regardless of the cracking time, the resultant thermal-cracked oil will contain excess aromatic hydro-carbons which per se are highly reactive, thus permit-ting an easy production of high polymers such as resins in the treatment with an acid catalyst, and the propor-tion of aliphatic olefins boiling in the range of 120 to 290C will become too small. Therefore, such temperatures outside the above-defined temperature range are not desirable. A preferable cracking tem-perature range is from 400 to 600C, more preferably from 400 to 550C. The cracking time may vary, depending on the main purpose of the thermal cracking ~23~2S6Z

process such as, for example, the production ox coke or the reduction in viscosity of the starting heavy oil. For example, the cracking time may be selected from the range ox 10 seconds to 50 hours. The cracking may be performed in the presence of steam or other non-reactive gaseous mediulll. The cracking pressure usually is relatively low, that is, ranging from vacuum to 50 kg/em or so.
As typieal examples of sueh thermal eracking proeess for heavy residual oils, mention may be made of the viseosity breaking process and the coking proeess, as deseribed in the "Elydrocarbon Processing,"
Vol.61, No.9 (September 198Z), pp.160-163.
The viscosity breaking process is a thermal cracking process mainly for lowering the viscosity of a feed material whieh is earried out under relative-ly mild eraeking conditions while suppressing the forma-tion of eoke in a tubular heating furnace. Usually, the eraeked oil leaving the eraeking furnace is quenehed or suppressing the formation of eoke. As eonerete proeesses are ineluded the Lummus proeess and Shell proeess.
In the coking proeess, whieh is a eoke produeing proeess, are included the delayed eoking process (e.g. UOP proeess, Foster Wheeler proeess, M.W. Kellogg proeess, Lummus proeess and CONOCO

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process) ln which the residual oil is once heated in a heating furnace for a relatively short time and then fed to a coke drum for forming an agglomerate coke over a relatively long period of time; the fluid coking process (e.g. Exxon process) in which the residual oil is thermally cracked over a high-temperature fluid coke; the Elexicoking process (Exxon process) which comprises the combination of the fluid coking process with the resultant coke gasifying process; and the EUREKA process which carries out not only a thermal cracking but also steam stripping at a relatively low pressure such as atmospheric pressure to prepare pitch.
of the thermal cracking processes referred to above, the coking process is preferred because the sulfur and metal components in -the residual oil are concentrated into the resultant coke so the content of these impurities in the cracked oil is relatively small and therefore the refining even after the acid catalyst treatment is relatively easy and also because the content of high-boiling aliphatic olefins is relatively large. Above all, the delayed coking process has been adopted on large scales because an agglomerate coke is obtained which is useful as a carbon source of graphite for electrode, etc. Since the delayed coking process affords a very large amount of cracked by-product oil, if it is utilized effectively by the present invention, it will bring about a great advantage.
The compositions of the thermal-cracked oils obtained by the above-described thermal cracking processes difEer according to types of the processes, thermal cracking conditions, kinds of the starting heavy oils, etc. Usually, however, those thermal-cracked oils, which scarcely contain aromatic olefins, mainly contain reactive aliphatic olefins such as n-olefins and iso-olefins in addition to n-paraffins and iso-paraffins, and further contain aromatic hydrocarbons having an alkyl-substituted single ring such as alkylbenzenes, having an alkyl-substituted composite ring such as alkylindanes and alkyltetralins and having an alkyl-substituted condensed ring such as alkylnaphthalenes.
Among the distillates from the thermal-cracked oils obtained in the above-described thermal cracking processes, the distillates to be processed in the present invention are those which consist mainly of hydrocarbons boiling in the range of 120 to 290C, preferably 150 to 260C and which contain aromatic hydrocarbons and at least 10 wt.~, preferably at least 15 wt.~, of aliphatic olefins. Distillates consisting mainly of hydrocarbons whose boiling range is outside the above-defined range cannot afford 256f;~

industriall.y useful liquid reaction products, and with distillates containing less than 10 wt.~ of aliphatic olefins, it is,impossible to recover reaction products in economical yields. ThereEore, both such distillates are not desirable.
typical composition of the distillates which may be used in -the i.nven-tion is 30-70 wt.
paraffins, 10-40 wt.% alipha-tic olefins and 5-20 wt.~
aromatie hydrocarbons. However, as long as the above-mentioned conditions required of the distillates aresatisfied, the thermal-cracked oils may be subjected to fractionation or diluted with unreacted oils recover-ed after acid.treatment.
according to the processing method of the present invention, in addition to the treatment of the thermal-cracked oil distillate itself with an aei.d catalyst, a hydrocarbon feed comprising a mixture of such thermal-cracked oil distillate and a dis-tillate or distillates containing various aromatic hydrocarbons may be treated in the same manner, whereby there is obtained a liquid reaction product having useful properties, for example, having a superior fluidity at low ternperatures.
More specifically, the thermal-cracked oil distillate may be mixed with one or more distillates boiling in the range of 150 to 280C, preferably 150 ~3Z5~Z

to 250C, selected from the group consisting of (a) a distillate from a thermal-cracked by-product oil obtained by thermally cracking a petrolic light oil at a temperature of 750 to 850C, (b) a reformate distillate obtained by a catalytic reforming of a petrolic light oil boiling in the range of 50 to 250C and (c) an aromatic distillate consisting mainly of aromatic hydrocarbons separated from the thermal-cracked by-product oil distillate of the above (a) and/or the reformate distillate of the above (b).
Further, if -the thermal-cracked oil distillate is mixed with aromatic hydrocarbons boiling below 150C
such as benzene, toluene, xylene and ethylbenzene, there will be obtained a useful liquid reaction product.
i5 The thermal-cracked by-product oil distillate of the above (a) is obtained when a petrolic light oil is thermally cracked at a temperature of 750 to 850C with a view to producing lower olefins such as ethylene and propylene.
As examples of the petrolic light oil there are mentioned naphtha, kerosene, light oil, LPG and butane. In consideration of properties of the result-ant thermal-cracked by-product oil, naphtha, kerosene and light oil are preferred as starting materials in the thermal cracking because those oils are more suit-able for the objects of the present invention.

~32562 The method of thermal cracking is not specifically limited. Various conventional thermal eracking methods earried out in the temperature range of 750 to 850C, for example, the method using a tubular eracking furnace and the method using a heat-transfer medium, can be adopted.
The thermal-cracked by-product oil distillate obtained from the thermal-cracked product after removal of the object products which are olefins, diolefins, ete. such as ethylene, propylene and butadiene, whieh distillate differs depending on the kind of the start-ing petrolic light oil and thermal cracking conditions, is a distillate having 6 to 10 carbon atoms, contain-ing relatively large amounts of aromatic hydrocarbons 15 and containing 2-10 wt.% paraffins, 3-10 wt.~
naphthenes, 55-85 wt.% aromatic hydrocarbons, 2-10 wt.% aliphatic olefins and 2-15 wt.~ aromatic olefins, of whieh the distillate boiling in the range of 150 to 280C may be mixed with the -thermal-cracked oil distillate in the present invention.
The reformate distillate of the above (b) is obtained by a catalytic reforming of a petrolic light oil boiling in the range of 50 to 280C, e.g.
a straight-run naphtha. Catalytic reforming has been widely conducted in the fields of petroleum refining and petrochemistry for improving the octane number ~'~32t~6Z

or for obtaining benzene, toluene, xylene, etc. It is carried out using an alumina or silica-alumina supported metal catalyst such as platinum, platinum-rhenium, molybdenum oxide or chromium oxide. As industrial methods, mention may be made of the Platforming oE UOP Co. which is a fixed bed type and the Ultraforming of Standard Oil Co. which is also a fixed bed type. In addi-tion fluidized bed type and moving bed type catalytic reforming methods are also employable. In the catalytic reforming, there mainly occur dehydrogenation and cyclization reaction, as well as isomerization reaction; as a result, the BTX
(benzene, toluene and xylene) content increases and the octane number is improved. However, the resultant reforma-te has a bromine number not more than about 3.8 and thus contain very small amounts of unsaturated components.
The catalytic reformate distillate typically has 6 to 10 carbon atoms and contain 30-35 wt.~
paraffins, 65-70 wt.~ aromatic hydrocarbons and 0-2 wt.~ olefins. The catalytic reformate distillate which may be used in the present invention has a boiling range of 150 to 280C.
Further, the aromatic distillate of the above (c), which consis-ts mainly of aromatic hydrocarbor.s, is obtained from the aforementioned catalytic reformate l~zls~

distillate, thermal-cracked by-product oil distillate and mixtures thereof by the use of a suitable physical separation. This separation has been performed on a larye scale in the petrochemical field for obtaining BT~ from catalytic reformate oils, thermal-cracked by-product olls and mixtures thereof usually according to the solvent extraction process or extractive distil-lation process. As typical examples of the solvent extraction process are mentioned Udex process (Dow process) which employs diethylene glycol or triethylene glycol as the extraction solvent and Sulfolane process (Shell process) which employs sulfolane as the extrac-tion solvent. Usually, this extraction is preceded by hydrogenation to remove unsaturated components for preventing the appara-tus from being blocked by polymer-ization of the unsaturated components.
The aromatic distillate (c) consisting mainly of aromatic hydrocarbons thus separated from the cata-lytic reformate distillate, the thermal-cracked by-product oil distillate and mixtures thereof consistsof Cg to C10 hydrocarbons and has a boiling range of 150 to 280C. It contains alkylbenzenes, polyalkyl-benzenes, naphthalene and many other aromatic hydro-carbons. Ilowever, the distillate of this boiliny ranye has heretofore no-t been utilized effectively although it is obtained in a large amount together 3~3ZSfi2 with the BTX distillate.
As to the mixing ratio, 20-95 wt.% of the thermal-cracked oil distillate from the residual oil may be mixed with 80-5 wt.~ of the distillate (a), S (b) and/or (c), or Wit]l 80-5 wt.% of aromatic hydro-carbons boiliny lower than 150C. A proportion of the thermal-cracked oil distillate smaller than 20 wt.% is not desirable because the yield of the reaction product would become lower. preferable mixing ratio is 70-90 wt.~ of the thermal-cracked oil distillate and 30-10 wt.% of the distillate (a), (b) and/or (c) or the lower aromatic hydrocarbons. If the alkyl-benzene content of the reaction product is to be increased, it is recommended to use the thermal-cracked oil distillate from the residual oil in arelatively small amount, e.g. 25-60 wt.%, and use 75-40 wt.% of the others.
In -the process of the present invention, a hydrocarbon feed comprising the thermal-cracked oil distillate from the residual oil is treated at a reaction temperature of 30 to 300~C in liquid phase in thy presence of an acid catalyst to obtain a reaction product having a boiling range which is higher than that of said -thermal-cracked oil distillate, and which is not lower than 260C.
Preferred examples of the acid catalyst are ~Z51~2 solid acid catalysts, mlneral acids, so-called Friedel-Crafts catalysts and organic acids. More concrete examples include solid acid catalysts such as acid clay minerals such as acid clay and activated clay, amorphous or crystalline silica-alumina, AlF3.~l2O3 and strong acid type ion-exchange resins;
Friedel-Crafts catalysts such as HF, AlCl3, sF3 and SnCl4; and inorganic and organic acids such as sulfuric acid, p-toluenesulfonic acid and trifluoromethane-sulfonic acid.
The reaction may be carried out accordingto any oE the batch process, semi-batch process and flow process. But, in the case of using a solid acid, the flow process is preferred.
The acid catalyst is used in an amount of 0.2 to 20 wt.%, preferably 1 to 10 wt.%, based on the weight of the hydrocarbon feed in the batch process.
In the flow process, it is treated at a liquid hourly space velocity (LIISV) of 0.1 to 20, preferably 0.5 to 10. The reaction temperature is in the range of 30 to 300C, preferably 50 to 250C. The treating time, which differs accordinq to reaction conditions such as the amount of catalyst, reaction temperature and the feed composition, should be long enough to complete the reaction, and usually it is selected from the range of 2 to 24 hours. The reaction pressure ~;~32'5~S2 is not specifically limited if only it can maintain the reaction system in liquid phase.
The acid catalyst treatment is performed so as to glve a reaction product having a boiling range not lower than 260C, and which is higher than the boiling range of the thermal-cracked oil distillate.
The reaction product consists mainly of oligomers of aliphatic olefins and alkylates of aliphatic olefins with aromatic hydrocarbons. In the case where the feed is mixture containing an excess distillate which contains aromatic hydrocarbons, the resultant reaction product consists mainly of alkylbenzene as alkylate.
If the boiling range of the reaction product is lower than 260C or lower than the boiling range of the thermal-cracked oil distillate, the reaction product will be of no industrial value, and the effect of the acid catalyst treatment cannot be expected.
In the present inven-tion, as described above, since the specific distillate from the specific source is used as a feed material and subjected to the specif-ic treatment, a high molecular weight compound which badly affects physical proper-ties is substantially not produced, and the reaction product obtained is a liquid product having a relatively low viscosity, 25 for example, in the range of 3 to 30 cSt at 75C.
Therefore, after the acid catalyst treatment, unreacted distillate (the starting thermal-cracked oil distillate), and unreacted o-ther distillate or lower aromatic hydrocarbons which are mixed to said thermal-cracked oil distillate, are separated by a physical separa-tion such as distillation, and then the reaction product can be put to practical use without the necessity of further separating heavier compounds. OE course, the reaction product may be divided in-to Eractions of suitable boiling ranges according to purposes of use, etc.
s a result of the above-mentioned treatment, the content of unsaturated componen-t of the thermal-cracked oil distillate is reduced, for example, the bromine number thereof is decreased, but the reaction product contains, particularly on its relatively high-boiling side, oligomers of aliphatic olefins as pre-viously no-ted, so it is preferable that the content of unsaturated components be decreased or made zero by a catalytic hydrogenation treatment. This catalytic hydrogenation treatment may be applied to any of the separated reac-tion product, distillate which contains a large amount of -the reaction product and the thermal-cracked oil distillate itself which has been subjected to the acid catalyst treatment.
In the catalytic hydrogenation treatment there may be used any conventional catalyst. For ~2~1~2 example, metallic catalysts such as Pt, Pd, Ni, Co, Mo, I, Co-Mo and Ni-W are employable. The catalytic hydrogenation treatment~is carried out usually under the conditions of a reaction temperature in the range of 250 to 400C, a hydrogen pressure in the range of 20 to 100 kg/cm2, a hydrogen/oil mole ratio in the range of 0~5 to 20 and an L~SV in the range of 0.1 to 10.
After the catalytic hydrogenation treatment, -the hydrogenated reaction product, and gases if requir-ed, are separated by any suitable means such as distillation. Of course, -the hydrogenated reaction product may be further separated into fractions accord-ing to purposes of use. The reaction product or the hydrogenated reaction product thus obtained has a boiling range not lower than 260C, a kinetic viscos-ity not higher than 30 cSt at 75C, a pour point not higher than -45C and a flash point not lower than 140C. As to its composition, although the quantita-tive relation varies, depending on the kind of thestarting petrolic heavy oil, thermal cracking condi-tions and the blending ratio of the aromatic distill-ate, the hydrogenated reaction product, which scarcely contains n-paraffins, contains iso-paraffins and aromatic hydrocarbons containing alkyl-substituted single or composite rings.

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The reaction product thus obtained has a good color and a reduced content of iMpurities such as sulfur and metal. It is sufficiently employable in almost all of the conventional uses of high-boiling hydrocarbon oils, for example, as a lubrica-t-ing oil, insulating oil, rubber processing oil, a special solvent for medicines, agricultural chemicals and dyes, a solvent for inks, paints and plastics, a plasticizer and a diluent. And, sulphonated reaction products by ordinary method are useful as surface active agents.
Moreover, after separation of the above reaction product from the processed thermal-cracked oil distillate, the remaining unreacted thermal-cracked oil distillate itself has a reduced contentof olefins and aromatic hydrocarbons and an increased content of n-paraffins. This indicates that the reforming of the thermal-cracked oil distillate is attained. Therefore, this unreacted thermal-cracked oil distillate itself is best suited as a n-paraffinic hydrocarbon solvent for paints, medicines, agricultural chemicals and dyes.
Further, since the distillate is rich in relatively high-boiling n-paraffins, it is suitable as a starting ma-terial for the production of n-paraffins using a physical separation means such as ~'~3'~56Z

a molecular sieve or a urea adduct process. The thus-separated n-paraffins are employable as starting materials for the preparation of chlorinated paraffins, soft type alkylbenzenes and higher alcohols.
The fol]owing examples are given to further illustrate the present invention.

Example 1 From a delayed coking apparatus (cracking conditions: temperature of 496C~ residence time of 24 hours, pressure of 4 kg/cm2) for coking a residual oil in vacuum distillation of such properties as shown in Table 1 obtained from Minas crude oil there was obtained a thermal-cracked oil in addition to gases and coke as shown in Table 2. The feed distillate used from this thermal-cracked oil was of such a composition as shown in Table 3~

Table 1 Properties of the heavy residual oil 7 _ Minas vacuum-distllled bottom residue 20 Specific gravity (@ 15C), PI 20 Asphaltene, wt.~ 2.6 Conradson residual carbon, wt.~ ___ ~3~56,Z

Table 2 Yield .
(wt.
Starting oil ' 100 Butane and light gas 8 . 30-160C (Distillate No.1) 13 . 160-260C (Dis-tillate No.2) 22 260C tDistillate No.3) 40 Coke 17 Table 3 Feed Composition (Distillate No.2) _ .
Bromine number, cg/~ 20.2 Type analysis (wt.~) <n-paraffins 31.7 Paraffins 68.3~
~iso-paraffins 36.6 Aliphatic olefins 19.4 Aromatics 12.3 Aromatic olefins _ _ Then, 40 g. of AlC13 was added to 4 of distillate No.2 followed by treatment at 50C for 20 hours according to the batch process. Thereafter, the reaction mixture was treated with aqueous ammonia _ 20 1~325~;2 for neutralization and decomposition of AlCl3, which WAS removed by washing with water. Subsequent dehydr-ation afforded a reaction product (870 g.~ 29~ yield) as a 340C distillate. This reaction product was found to have a bromine number of 6.4 cg/g and an aromatics content of 78.7~, most of the balance were olefins.
Unreacted distillate after removal of the reaction product from the processed distillate No.2 had a good color, a bromine number of 0.80 cg/g, an n-paraffins content of 44% and an aromatics content as small as 3.3%. In view of the reduced content of aromatics and olefins and increased content of n-paraffins, it is seen that reforming has been attained.
Therefore, the unreacted distillate is employable as a superior aliphatic hydrocarbon solvent or as a starting material for the production of n-paraffins, after a simple hydrogena-tion refining if required.
The reaction product was then subjected to a hydrogenation treatment using a Co-Mo catalyst under the condi-tions of a hydrogen pressure of 50 kg/cm2, a reaction temperature of 280C and one volume feed oil/catalyst volume/hr.
After the hydrogenation, the light fraction formed by decomposition was distilled off, and the hydrogenated reaction produc-ts was recovered. The _ 21 123ZS~i~

percent recovery was 92%. It proved to have a bromine number of 0.34 cg/g and an aromatics content of 76.6%.
Table 4 below shows physical proper-ties of the hydrogenated reaction product as well as results of electrical characteristic tests conducted in accordance with ~ST~ D- 1934 and oxidation stability tests conducted in accordance with JIS C2 101 .
Results obtaining using mineral oil are also set out in the same table for comparison. From the results shown in Table 4 it is apparent that the hydrogenated reaction product has superior physical properties even in comparison with the mineral oil and is there-fore very suitable as an insulating oil or a lubricating oil.

_ 22 ~232S62 Table 4 . . _.
Hydrogenated Reacticn Mineral _ ' Product oil _ Kinetic Viscosity (@ 75C,cStj 10.2 3.1 Pour Point (C) -47.5 -30 Flash Point (C) 202 132 ._ _ _ _ _ Electrical characteristics (heat deterioration) Dielectric loss tangent (%, @ 80C) Before deterioration 0.001 0.001 After deterioration 0.015 0.194 (without catalyst) After deterioration 0.066 2.323 (wi-th catalyst) Volume resistivity am @ 80C) Before deterioration 3.7x1016 6.3x1015 After deterioration 2.1x1014 2.5x1013 (without catalyst) After deterioration 9.6x1013 1.3x1012 (with catalyst) Oxidation Stability Sludge (%) 0.09 0.10 Total acid number 0.12 0.50 _ (mgKOI~/g) Example 2 40 ml. of BF3-H2O was added to 4 of distil-Nate No.2 in Table 2 obtained in Example 1 followed ~3'~5~2 by treatment at 50C for 2 hours according to the batch process. Then, the reaction mixture was -treated with an aqueous ammonia for neutralization of the catalyst, which was removed by washing with water. After a sufficient dehydration, 690 g. of reaction product was recovered as a 350C-~ distillate. The reaction product proved to have a kinetic viscosity of 10.2 cSt (@ 75C), a pour point of -47.5C and a flash point of 200C.

Example 3 The Minas vacuum-distilled bottom residue described in Example 1 was subjected to a thermal cracking under the conditions of a temperature of 485C, a pressure of 1.5 kg/cm2 and a residence time of 1.5 hours. The resultant thermal-cracked oil was rectified to obtain a thermal-cracked oil distillate having a boiling range of 100 to 300C (containing 85% components boiling in the range of 120 to 290C).
The yield was 37~.
The thermal-cracked oil distillate was treat-ed using a silica-alumina catalyst according to the fixed-bed flow process under the conditions of a reac-tion temperature of 200C and one volume feed oil/
catalyst volume/hr. The reaction solution was subject-ed to a catalytic hydrogenation treatment using a Co-Mo ~3~56Z

catalyst under the conditions of a hydrogen pressure of 50 kg/cm2, a reaction temperature of 300 DC one volume feed oil/catalyst volume/hr and an E~2/oil mole ratio of 10, to obtain a hydrogenated reaction product havlng a boiling range beyond 330C, a klnetic visco-sity of 5.4 cSt l@ 75C), a pour point of -52.5C
and a flash poin-t of 152C.
Unreacted thermal-cracked oil distillate after removal of the reaction product scarcely contain-ed aromatics, unsaturated components and sulfur, andit had good odor and color. Thus, it proved to be best suited for use as an aliphatic hydrocarbon solvent.
The catalytically hydrogenated reaction product was tested for electrical characteristics and oxidation stability in the same way as in Example 1. As a result, there were obtained about the same values as in Example 1.

Example 9 A by-product oil distillate having a boiling range of 61 to 250C was distilled out from a tubular thermal cracking furnace for thermal cracking of naphtha at 780 to 810C for the production of ethylene and propylene. The by-product oil distillate contained large amounts of aromatic hydrocarbons such as benzene, toluene, xylene and styrene in addition to acetylenes _ 25 ~L~32,5~

and diolefins.
Then, the distillate was subjected to a hydrogenation treatment using a ~nifining two-stage hydrogenation apparatus for the removal of unsaturated components such as diolefins and for desulfurization.
As a catalyst there was used a cobalt-molybdenum catalyst supported on alumina. The hydrogenation conditions were a temperature of 220C and a pressure of 50 kg/cm2 in the first stage and 330C and 50 kg/cm3 in the second stage.
The thermal-cracked by-product oil distillate thus hydrogenated proved to have a sulfur content - of 0.01% and an unsaturated components content not higher than 0.01~. This distillate will be hereinafter referred to as distillate (a).
In the next place, a reformate was obtained from a Platforming apparatus for a catalytic reform-ing of naphtha having a boiling range of 50 to 250C by the use of a platinum catalyst in the presence of hydrogen at a reaction temperature of 470C and pressure of 50 kg/cm for the production of gasoline and benzene, -toluene or xylene. This reformate also contained large amounts of aromatics, but had a less content of unsaturated components than that of the foregoing thermal-cracked by-product oil distillate. It will hereinafter be referred to as .:distillate I
Then, 90 vol.% of the reformate distillate (b) having a boiling ranye of 60~ to 250C was mixed with 10 vol.% of a fraction having the same boiling range from the distillate (a) (-thermal-cracked by-product oil distillate), and the mixture was fed to a Udex extractor to recover an aromatics distillate.
More specifically, the mixture was fed to the middle portion of an aromatics extraction column, while ethylene glycol as an extraction solvent was fed from the top of the column, and thus a countercurrent extraction was performed. After refining of the extract there were produced benzene, toluene, xylene and ethylbenzene by fractionation. At this time, an aromatic distillate having a boiling range of 150 to 250C was by-produced as a distillate of C9 or more. This aromatics distillate, containing 99% or more aromatics, will be hereinafter referred to as distillate a Table 5 below shows properties of a fraction (distillate (c')) having a boilil~g range of 160 to 180C from the distillate (c).

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Table 5 I Boiling Range - Properties , 160 - 180C
. (distillate (c')) Specific gravity @ 60F/60F 0.876 Saybolt color above +30 Flash point (PMCC) 45 Blended aniline poin-t, C 13 Aromatics (vol.~) 99.5 Distillation property (ASTM) Initial boiling point, C 160 Dry point, C 176 Table 6 helow shows the composition of the thus-extracted xylene distillate (c") having a boiling range of 135 to 145C.
Table 6 Composition of xylene distillate (c") Component Name Mixing Ratio Ethylbenzene 55.8 wt.%
p-Xylene 10.4 wt.%
m-Xylene 20.7 wt.%
o-Xylene 11.8 wt.%

Others ¦ 1.3 wt.%

~32562 5 g. of ~lC13 was added to a mixture (containing 17.5% aliphatic olefins) consisting of 450 ml. of the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 and 50 ml. of the distillate (c') (aromatics dis-tillate) followed by treatment at 185C for 1.5 hours accordiny to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization and decomposgtion of AlC13. Subsequent dehydration 10 afforded 98.4 g. ~24.4% yield) of reaction product as a 315C distilla-te. The reaction product proved to have a bromine number of 5.6 cg/g and an aromatics content of 80.2%. The balance were almost olefins.
Further, the reaction product was found to have a 15 kinetic viscosity of 10.4 cSt (@ 75C), a pour point of -47.5C and a flash point of 180C.
Then, the reaction product was subjected to a hydrogenation treatment using a Co-Mo ca-talyst under the conditions of a reaction temperature of 260C, a hydrogen pressure of 50 kg/cm2 and one volume reaction mixture/catalyst volume/hr. Thereafter, the light fraction formed by decomposition was dis-tilled off and the hydrogenated reaction product was recovered at a percent recovery of 81.1%. The reac-tion product thus hydrogenated had a bromine number of 0.3 cg/g and an aromatics content of 78.5%.

_ 29 2S~2 Table 7 shows physical properties of the hydrogenated reaction product as well as results of electrical characteristiç tests conduc-ted in accordance with ~STM D-1934 and oxidation stability tests conducted in accordance with JIS C2102. From the results shown in Table 7 it is apparent that the hydrogenated reac-tion product obtained according to the process of the present invention has superior physical properties as colllpared wi-th mineral oil and is therefore best suited for use as an insulating oil or a lubricating oil.

_ 30 ~251~;~

Table 7 , .. ..
Kinetic Viscosity (I 75C, cSt) 9~1 Pour point (C) -47.5 Flash point (C) 180 .
Electrical characteristics (heat deterioration) Dielectric loss tangent (I, @ 80C~
Before deterioration 0.001 After deterioration (without catalyst) 0.017 After deterioration with catalyst) 0.066 Volume resistivity am @ 80C) Before deterioration 7.0x10 After deterioration (without catalyst) 3.2x1014 Arter deterioration (with catalyst) 1.0x1014 Oxidation Stability Sludge to) 0.05 Total acid number (mgKOH/g) 0.11 Example 5 5 g. of AlC13 was added to a mixture (contain-ing 18.4% olefins) consisting of 475 ml. of the dis-tillate No.2 (thermal cracked oil dis-tillate) obtained in Example 1 and 25 ml. of the distillate (c') (aromat-ics distillate) followed by treatment at 185C for 1.5 hours according to the batch process. Thereafter, _ 31 ~Z325~6~
the reaction mixture was treated with an aqueous ammonia for neutralization of the catalyst, which catalyst was-removed by washing with water. After a sufficient dehydration there was obtained 96.4 g. (24.0~ yield) of reaction mixture as a 315C distillate. This product proved to have a kinetic viscosity of 10.6 cSt (@ 75C), a pour point of -47.5C and a flash point of 180C. Electrical characteristics and oxida-tion stability of the product after refining by hydrogenation were of about the same values as in Example 1.

Example 6 5 g. of AlC13 was added to a mixture (containing 9.7% olefins) consisting of 250 ml. of the distillate No.2 (thermal-cracked oil distillate obtained in example l and 250 ml. of the distillate (c') (aromatics distillate) followed by treatment at 185C for 1.5 hours according to the batch process.
Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization of the catalyst, which catalyst was removed by washing with water.
After a sufficient dehydration there was obtained 43.2 g. (10.4% yield) of reaction mixture as a 315C
distillate. This product proved to have a kinetic 25 viscosity of 6.5 cSt (@ 75C), a pour point of -50C

~'~32562 and a flash point of 180C.

Example 7 5 g. of AlC13 was added to a mixture (containincJ 4.0% olefins) conslsting of 100 ml. of the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 and 400 ml. of the distlllate (c') (aromatics distillate) obtained in Example 4 followed by treatment at 185~C for 1.5 hours according to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization of the catalyst, which catalyst was removed by washing with water. After a thorough dehydration there was obtained 97.2 g. (24.3% yield) of reaction mixture as a 315C distillate. This product proved to have 15 a kinetic viscosity of 11.6 cSt (@ 75C), a pour point of -42.5C and a flash point of 190C.

Example 9 5 g. of AlCl3 was added to a mixture (containing 18.7% olefins) consisting of 450 ml. of the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 and 50 ml. of a fraction having a boiling range of 150 to 250C from the distillate (a) (thermal-cracked by-product oil distillate) obtain-ed in Example 4 followed by treatment at 185C for ~3'~S~2 1.5 hours according to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization of the catalyst, which catalyst was removed by washing with water. after a thorough dehydration there was obtained 97.2 g. (24.1% yield) of reaction mixture as a 315C+ distillate. This product proved to have a kinetic viscosity of 12.1 cSt, a pour point of -42.5C and a flash point of 186C.

Example iO
5 g. of AlCl3 was added to a mixture (containing 17.8~ olefins) consisting of 450 ml. of the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 and 50 ml. of a fraction having 15 a boiling range of 150 D to 250C from the distillate (b) (reformate distillate) obtained in Example 4 followed by treatment at 185C for 1.5 hours according to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization of the catalyst, which catalyst was removed by washing with water. after a thorough dehydration there was obtained 95.3 g. (23.6~ yield) of reaction mixture as a 315C distillate. This product proved to have a kinetic viscosity of 11.6 cSt, a pour point of -45C
and a flash point of 190DC.

_ 34 ~23;Z~i2 Example 11 5 ml. of BF3.H2O was added to a mixture (containing 17.5~ olefins) consisting of 450 ml. of the distillate No.2 (-thermal-cracked oil dis-tillate) obtained in Example 1 and 50 ml. of the dis-tillate tc') (aromatic distillate) obtained in Example 4 followed by treatment at 90C for 5 hours according to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization of the catalyst, which catalyst was removed by washing with water. After a thorough dehydration there was obtained 72 g. (17.8% yield) of reae-tion product as a 315C distillate. This product proved to have a kinetic viscosity of 7.2 cSt (@ 75C), a pour point of -50C and a flash point of 180C.

Example 12 The Minas vaeuum-distilled bottom residue described in Example 1 was thermally cracked under the eonditions of a temperature of 485C, a pressure of 1.5 kg/cm2 and a residence time of 1.5 hours, and the resultant thermal-cracked oil was rectified to obtain a thermal-eraeked oil distillate having a boil-ing range of 100 to 300C (eontaining 85~ eomponents 25 boiling in the range of 120 to 290C). The yield _ 35 ~i~32562 was 37~.
A mixture (containing 1~.0% olefins) consist-ing-of 450 ml. of the thermal-cracked oil distillate just obtained above and 50 ml. of the distillate a (aromatics distillate) obtained in Example 4 was trea-t-ed using a silica-alumina catalyst according to the fixed-bed flow process under the conditions of a reac-tion temperature of 200C and one volume feed oil/
catalyst volume/hr.
The reaction solution was subjected directly to a catalytic hydrogenation treatment under the condi-tions of a reaction temperature of 300C, a hydrogen - pressure of 50 kg/cm2, one volume feed oil/catalyst volume/hr and an H2/oil mole ratio of 10, to obtain a reaction product as a 315C distillate having a kinetic viscosity of 5.2 cSt (@ 75C), a pour point of -52.5C and a flash point of 160~C.
Unreacted light distillate after removal of the reaction product scarcely contained unsaturated components and sulfur, and it had good odor and color.
Then, the hydrogenated reaction product was tested for electrical characteristics and oxidation stability. As a result, there were obtained about the same values as in Example 4.
The results obtained in Examples are tabulat-ed below as Table 8 with respect to viscosity, pour point, flash point, etc.
_ 36 ~;~3Z56Z

Table 8 _ _ _ . .... _ , _ Example No. 4 5 ¦ 6 _ _~
. Distillate of (A) thermal-cracked oil dis-tillate ldistillate No.2) . from thermal cracking of . vacuum-distilled bottom residue ... _ . I
Feed Distillate of (B) aromaties distillate Composi- (distillate (e')) having tion a boiling range of . 160-180C obtained by . solven-t extraetion Proportion of (B) 10 ¦ 5 Reaction Conditions AlC13 1.3 wt.% 185 hC x Yield (~) 24.4 24.0 10.4 _ Kinetie Viscosity 10.4 10.6 6.5 Reaction (cSt, @ 75C) _ _ Produet Pour point (C) ~47.5 -47.5 -50 Flash point (C) 180 180 180 Table 8 (continued) Example No. l _ -Distillate therma:L~cracked oil distillate of (A) distillate No.2) from thermal . cracking of vacuum-distilled . bottom residue , Feed Distillate aromatics aromatics thermal-Compo- of (B) distillate distillate cracked sition (distillate having a by-produc (c')) having boiling oil . a boiling range of distillate range of 150-250C (distillate . 160-180C (distillate (a)) obtained by (c)) solvent extraction Proportion of (B) (vol.%) 80 10 10 Reaction Conditions AlCl3 1.3 wt.% 185C x 1.5 hr Yield (~) 6.4 24.3 24.1 Kinetic Vis-cosity (cSt, 4.0 11.6 12.1 Reaction @ 75C) _ Product Pour point -50 4Z 5 Flash point 180 190 186 C) PMCC

_ 38 ~L~3Z56,'~

Table 8 (eontinued) . I _ .
Example No. 10 1 11 12 _ Distillate thermal-cracked oil thermal-of (A) distillate (distillate craeked . No.2) from thermal oil disti-eraeking of vacuum- llate at distilled bottom a short residue residence time Feed Distillate reformate same as same as Compo- of (B) distillate Example 4 Example 4 sition having a boiling range of (distillate (b)) _ Proportion o (B) (vol.~) 10 lO 10 Reaction Conditions ~lCl3 BF3 H2O fixed-bed 1.3 wt.~ proeess 185Cx1.5hr 1.0 vol.~ silica-. alumina _ _ Yield (%) 23.6 17.8 _ Kinetic vis-eosity (eSt, 11.6 7.2 5.2 Reaetion Q 75C) Produet Pout point -45 -50 -52.5 _ (C) PMCC 190 180 160 _ 39 ~32ci62 Example 13 8.4 g. of anhydrous aluminum chloride was added to a mixture (containing 7.4~ olefins) consisting of 400 ml. of the distillate No.2 ~thermal-cracked oil distillate) obtained in Example 1 and 600 ml. of the xylene distillate a obtained in Example 4 ollowed by -treatment at 130C for 1 hour according to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia for neutralization and decomposition of the catalyst. Subsequent dehydra-tion afforded 79.4 g. (9.5% yield) of reaction product as a 260C+ distillate. The reaction product proved - to have a bromine number of 1.0 cg/g and an aromatics content of 98%. Most of the balance were olefins.
Further, this product had a kinetic viscosity of 5.3 cSt (@ 75C), a pour point of -50C and a flash point of 172C.

Example 14 8.4 g. of anhydrous aluminum chloride was added to a mixture (containing 7.4% olefins) consisting of 400 ml. of the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 and 600 ml.
of benzene followed by treatment at 80C for 1 hour according to the batch process. Thereafter, the reaction mixture was treated with an aqueous ammonia _ 40 ~3Z'S~i2 for neutralization of the catalyst, which catalyst was removed by washing with water. After a thorough dehydration there was obtained 72.7 g. (~.7% yield) of reaction product as a 260C~ distillate having a kinetic viscosity of 5.7 cSt (@ 75C), a pour point of -50C and a flash point of 154C.

Example 15 8.4 g. of anhydrous aluminum chloride was added to a mixture containing 18.4% olefins) consist-ing of 950 ml. of the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 and 50 ml. of benzene followed by treatment at 100C for 1 hour according to the batch process. Thereafter, the reac-tion mixture was treated with an aqueous ammonla for neutralization of the catalyst, which catalyst was removed by washing with water. After a thorough dehydration there was obtained 192 g. (23.9% yield) of reaction product as a 260C distilla-te havlng a kinetic viscosity of 13.1 cSt (@ 75C), a pour point 20 of -42.5C and a flash point of 164C.

Example 16 300 ml. of benzene and 600 ml. of anhydrous hydrogen fluoride (purity: 99% or higher) were charged into a batch process reactor (content volume 5 ~L~3~ Z

cooled at 5C and allowed to cool sufficiently with stirring, then a mixture consisting of 300 ml. of benzene and 400 ml. of the fraction having a boiling range of 160-220C from the distillate No.2 (thermal-cracked oil distillate) obtained in Example 1 wasadded dropwise over a period of 10 minutes. The stir-ring was continued for another one hour. Thereafter, the reaction mixture was allowed to stand for separa-tion into oil layer and anhydrous hydrogen fluoride layer. Then, the oil layer was treated with a 10 wt.~ potassium hydroxide solution for neutralization and decomposition of the anhydrous hydrogen fluoride - incorporated therein, which hydrogen fluoride was removed by washing with water. After a thorough de-15 hydration there was obtained 85.3 g. (10.2~ yield) of reaction product having a boiling range beyond 260C, a kinetic viscosity of 3.5 cSt (@ 75C), a pour point of below -55C and a flash point of 144C.

(Surfactant Test) From the reaction product iunhydrogenated product) thus obtained, a distillate having a boiling range of 260 to 330C was recovered at a percent recovery of 88.1% and the distillate was subjected to a sulfonation reaction.
Surfactant tests were conducted on the _ 42 ~3256Z

sulfonate thus obtained.
That is, 95.1 g. of the above distillate of 260 to 330C was placed in a 500 ml. glass vessel and 19 ml. of anhydrous sulfuric acid was blown therein together with nitrogen gas for 1 hour while vigorously stirring at 50C to take place the sulfonation reaction.
After completion of the sulfonation, the reaction mixture was gradually added into 148.2 g. of a 6.7 sodium hydroxide solution to be neu-tralized to pH
7~0-7.5. The amount of the added reaction mixture was 81.1 g. The yield of the sulfonated product was 84.4~.
Then, the sodium sulfonate was tested for surfactant characteristics.
That is, under the conditions set forth in Table 9, 0.2 part of the sodium sulfonate obtained above was dissolved in 1.5 parts of water, 70 parts of heavy oil B was thoroughly mixed -therewith and 30 parts of fine carbon powder was thoroughly mixed therewith. Then, the mixture was allowed to stand and the sedlmentation velocity of fine carbon powder was determined. As a result, even after the lapse of 50 days, the sedimentation was not recognizable.
When the sodium sulfonate was not used, fine carbon powder was immediately settled.

_ 43 ~L~32S~2 Table 9 . I
Fine carbon powder used 85~ passed through 200 mesh _ Heavy Oil B 90 cp @ 28C, 17 cp @ 70C
Concentration of fine 30 wt.%
carbon powder Measuring temperature 30C
.

_ 44

Claims (7)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. Method of processing a hydrocarbon feed, characterized by treating said hydrocarbon feed at a reaction temperature in the range of 30° to 300°C in liquid phase in the presence of an acid catalyst, said hydrocarbon feed comprising a distillate from a thermal-cracked oil obtained in a thermal cracking process for thermally cracking a petrolic heavy residual oil at a temperature not lower than 400°C and not exceeding 700°C, said distillate consisting mainly of hydrocarbons boiling in the range of 120° to 290°C and said distillate con-taining aliphatic olefins, to produce a reaction product having a boiling range which is higher than that of said hydrocarbons as the main component of said distillate and which is not lower than 260°C.

2. A method according to claim 1 wherein said distillate from the thermal-cracked oil further contains aromatic hydrocarbons and at least 10 weight percent of aliphatic olefins.

3. A method according to claim 1 wherein said hydrocarbon feed is a distillate from a thermal-cracked oil obtained in a thermal cracking process for thermally cracking a petrolic heavy residual oil at a temperature not lower than 400°C and not exceeding 700°C, said dis-tillate consisting mainly of hydrocarbons boiling in the range of 120° to 290°C and said distillate containing aliphatic olefins.

4. A method according to claim 1 wherein said hydrocarbon feed is a mixture of:
(I) 20-95 weight percent of a thermal-cracked oil distillate obtained from a thermal cracking process for thermally cracking a petrolic heavy residual oil at a temperature not lower than 400°C and not exceeding 700°C, said distillate consisting mainly of hydrocarbons boiling in the range of 120° to 290°C and said distillate containing ali°jatoc olefins; and (II) (A) 80-5 weight percent of one or more distillate boiling in the range of 150° to 280°C and select-ed from the following (a) through (c):
(a) a thermal-cracked by-product oil distillate obtained by thermal cracking of a petrolic light oil at a cracking temperature in the range of 750° to 850°C;
(b) a reformate distillate obtaned by catalytic reforming of a petrolic light oil boiling in the range of 50° to 250°C; and (c) an aromatic hydrocarbon distillate consist-ing mainly of aromatic hydrocarbons and obtained by separation from said thermal-cracked by-product oil distillate (a) and/or said reformate distillate (b); or (B) 80-5 weight percent aromatic hydrocarbons having a boiling range lower than 150°C.

5. A method according to claim 1 wherein said thermal cracking process is a coking process.

6. A method according to claim 5 wherein said coking process is a delayed coking process.

7. A method according to claim 1 wherein said acid catalyst is aluminum chloride, boron fluoride, their complex, hydrogen fluoride or silica-alumina.