DE3341736A1 - METHOD FOR PROCESSING THERMALLY CRACKED PETROLEUM DISTILLATES - Google Patents

Description

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description

The invention relates to a method for processing a distillate from a thermally cracked petroleum, which is at a thermal cracking process using a heavy residual oil as a starting material.

Recently, due to the shortage of available petroleum resources, heavier ones are becoming heavier Crude oils are used, which results in increasing amounts of by-produced heavy oils, such as distillation residue oils or residual oils. These heavy residue oils are because of their high viscosities and / or high sulfur and metal contents of lower industrial value.

On the other hand, such heavy residual oils can with thermal Cracking processes, e.g. used in coking processes will. This can be the sole purpose of using such oils. When coking heavy Residual oils are obtained as a liquid substance, i.e. the thermally cracked oil, as well as coke and gas. In general the yield of distillates from the cracked oil is quite high, so these distillates in large quantities attack.

Since the cracked petroleum distillates, which occur in large quantities, large quantities of unsaturated compounds and aliphatic Containing hydrocarbons is their octane number not high enough that they have not yet been used directly as a basis for motor vehicle gasoline.

For this purpose they have to undergo a further reform requirement.

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^ action, for example a catalytic liquid cracking process, be subjected. For the most part, these distillates are only used as heating oil for boilers and the like. There is therefore an increasing need for methods with which these thermally cracked petroleum distillates, which occur in large quantities, are used on a large scale can be.

The object of the invention is to provide a method for economical 2Q borrowed utilization of distillates from cracked petroleum, for example in large quantities in the coking process incurred as by-products and which have previously only been used as heating oil for boilers or the like, are available to deliver. The value of these in large quantities as ancillary, c The residual oils formed by products, e.g. petroleum asphalt, should be increased by processing these oils.

Object of the invention is also a possibility for low utilization, high boiling aromatic carbons 2Q hydrogen distillates that are incurred to provide at cracking process for the production of ethylene as byproducts.

Invention is a hydrocarbon supply (charge) , the. Distillate from a thermal-cracked oil obtained by _O thermal cracking c a heavy residual oil at a temperature not lower than 400 ⁰ C and has not been obtained over 700 ⁰ C, treated with an acid catalyst, thereby obtaining a reaction product liquid, which industrially exploitable is used, for example, as an insulating oil and as a raw material for surfactants. If this reaction product is separated from the distillate by a physical separation process, e.g. by distillation, the distillate itself is reformed into a distillate that contains reduced amounts of unsaturated compounds and is therefore used as a large-scale solvent, as a starting material for the production of η-paraffins and the like is valuable.

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In U.S. Patent No. 4,208,268 there is a method of treating a thermally cracked by-product petroleum distillate with an acidic catalyst. This distillate however, is from and has a thermal cracking process for the production of lower olefins such as ethylene high aromatic content. In general, heavy residual oils are not used as starting materials used for such cracking processes. Furthermore, high cracking temperatures are not used below 700 C, since lower olefins are to be formed.

Among the heavy residue oils are soil products of the atmospheric Distillation, reduced pressure distillation and thermal or catalytic cracking

as well as various residue products from petroleum refining-15

process, e.g. residual oils from extraction with furfural, propane, pentane and the like, residual oils from reforming, as well as mixtures thereof, to be understood as is common in the petroleum refining art.

In the thermal cracking process according to the invention, the cracking temperature should not be below 400.degree. C. and not above 700.degree. If the cracking temperature is below 400 ° C, there is no thermal cracking. At temperatures above 700 ⁰ C, the thermally cracked oil obtained contains regardless of the cracking

time an excessive amount of aromatic hydrocarbons, the are highly reactive and thus, when treated with an acidic catalyst, are easy to form highly polymerized Products such as resins. This will make the stake of aliphatic olefins with a boiling range of 120

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up to 290 C too low. Temperatures outside the temperature range defined above are therefore not desirable. The range is preferably the cracking temperature 400 to 600 ⁰ C and in particular 400 to 550 ⁰ C. The cracking may vary depending on the primary purpose of the thermal cracking process, for example,

Formation of coke or reduction in the viscosity of the as

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Heavy oil used as the starting material. For example Cracking times from 10 seconds to 50 hours can be selected. The cracking can take place in the presence of water vapor or other non-reactive gaseous media. The cracking pressure is generally relatively low, i.e. pressures from reduced pressure up to 50 bar or the like are possible.

As typical examples of processes for thermal cracking of heavy residual oils, reference is made to the process for viscosity reduction and the coking process according to "Hydrocarbon Processing", Vol. 61, No. 9 (September 1982), pp. 160-163.

! 5 The viscosity reduction procedure is describe a thermal cracking process for lowering the viscosity of a feed material which is produced under relatively mild cracking conditions in a tubular heating furnace under suppression the coke formation is carried out. Generally, the cracked oil exiting the cracking furnace is used for suppression quenched from coke formation. Examples of special procedures are the Lummus procedure and the Shell procedure,

The coking process includes the delayed coking process (e.g. the UOP method, Foster Wheeler method, M.W. Kellog method, Lummus method and CONOCO method), in which the residual oil is heated once for a relatively short time in a heating furnace and then in a coke drum is fed in, forming an agglomerated coke over a relatively long period of time will. Other coking processes are the liquid coking process (e.g. Exxon process), in which the residual oil is thermally cracked over a high temperature liquefied coke, the "Flexicocking" process (Exxon process), the one Combination of the liquid coking process with the gasification process of the coke obtained, and that

EUREKA process, in which not only thermal cracking but also steam stripping at relatively low pressure, e.g. at atmospheric pressure, for the production of pitch

be performed.
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The above-mentioned thermal cracking process becomes the coking process preferred because the sulfur and metal components in the residual oil accumulate in the coke formed so that the content of these impurities in the cracked oil is relatively low and hence the refining after treatment with the acidic catalyst is relatively easy and the content of high-boiling aliphatic olefins is relatively high. In particular, the delayed coking process carried out on an industrial scale, since agglomerated coke is obtained, which is a valuable one Represents carbon source for electrode graphite and the like. Because the delayed coking process is a very provides a large amount of cracked, by-product oils, brings its use in combination with the invention Process in which these oils are recycled, with great advantages.

The composition of the oils obtained by the thermal • cracking processes mentioned above varies depending on the type of process, the thermal cracking conditions, the types of heavy oils used as starting materials and the like. In general, however, thermally cracked oils which hardly contain aromatic olefins mainly contain reactive aliphatic olefins such as n-olefins and isoolefins, besides η-paraffins and isoparaffins. Also included they aromatic hydrocarbons with alkyl-substituted products with a single ring, such as alkylbenzenes, with alkyl-substituted multi-ring systems, such as alkylindanes and alkyltetralins, and with alkyl-substituted ones condensed Ring systems, such as alkylnaphthalenes.

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^ From the distillates from the thermally cracked oils that incurred in the aforementioned thermal cracking processes, it concerns with the process according to the invention Distillates around those consisting predominantly of hydrocarbons g with a boiling range from 120 to 290 C and in particular from 150 to 260 C and the aromatic hydrocarbons and contain at least 10 percent by weight and in particular at least 15 percent by weight aliphatic olefins. Distillates, which mainly consist of hydrocarbons,

■ j ^ Q whose boiling range is outside that defined above Range, do not lead to industrially valuable liquid reaction products. When using distillates with an aliphatic olefin content of less than 10 percent by weight, it is not possible to produce reaction products

to win c in economic yields. Hence the Both of the aforementioned types of distillate are undesirable.

The distillates used according to the invention typically contain 30 to 70 percent by weight paraffins, 10 to ¹ JO

«Ο weight percent aliphatic olefins and 5 to 20 weight percent aromatic hydrocarbons. As long as the aforementioned conditions for the distillates are met, you can the thermally cracked oils are fractionated or mixed with unreacted oils that occur after the acid treatment

“R- be thinned.

According to the inventive method, apart from treating the thermally cracked oil itself with an acidic catalyst also requires a hydrocarbon feed that

OQ a mixture of such a thermally cracked petroleum distillate and one or more distillates containing various aromatic hydrocarbons can be treated in the same way, producing a liquid reaction product with valuable properties, e.g. a superior flowability at low temperatures.

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In particular, the thermal cracked petroleum distillate may be mixed with a boiling range of 150 to 280 ° C and especially from 150 to 250 ⁰ C, which are selected from the following group of components with one or more distillates of: (a) a distillate from a thermal-cracked by-product oil which is obtained by thermal cracking of a light oil at temperatures of 750-850 ⁰ C, (b) a reformate, which has been obtained by the catalytic reforming of a light oil with a JO boiling range of 50 to 250 C, and (c) an aromatic distillate consisting predominantly of aromatic hydrocarbons separated from the thermally cracked by-product petroleum distillate according to (a) and / or from the reformate distillate according to (b).

Further, when the thermal cracked petroleum distillate, mixed with aromatic hydrocarbons having a boiling point below 15O ⁰ C, such as benzene, toluene, xylene and ethylbenzene, then one obtains a valuable liquid reaction product.

The thermally cracked by-product petroleum distillate according to

(a) is obtained by thermal cracking of a light oil at temperatures of 750 to 850 ⁰ C, whereby the formation of lower olefins, such as ethylene and propylene, ^{is based}

Examples of corresponding petroleum-based light oils are naphtha, kerosene, light oil, liquefied petroleum gases (LPG) and butane. With regard to the properties of the obtained thermal oQ cracked by-product oils are naphtha, kerosene and Light oil is preferred as the starting material in thermal cracking, as these oils are suitable for the purposes of the invention particularly suitable.

gg The thermal cracking process is not subject to any special ones

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Restrictions. Various conventional cracking processes carried out in the temperature range of 750 to 850 C. , for example, methods using tubular cracking furnaces and methods using a Heat transfer medium can be used.

In the case of the thermally cracked by-product petroleum distillate, which is obtained from the thermally cracked product after removal of the desired products, i.e. olefins, diolefins and the like such as ethylene, propylene and butadiene (The distillate depends on the type of light oil used as the starting product and on the thermal cracking conditions varies). If it is a distillate with 6 to 10 carbon atoms, the relatively large proportions of aromatic hydrocarbons and 2 to 10 percent by weight paraffins, 3 to 10 percent by weight naphthenes, 55 to 85 Weight percent aromatic hydrocarbons, 2 to 10 Contains weight percent aliphatic olefins and 2 to 15 weight percent aromatic olefins. Of these 'can according to the invention the distillate with a boiling range of 150 to 280 C can be mixed with the thermally cracked petroleum distillate.

The reformed distillate according to (b) is by catalytically reforming a light oil with a boiling range of up to 280 ° C, e.g. from straight-run naphtha.

Catalytic reforming is in the field of petroleum refining and petrochemicals are widely used to improve octane number and include benzene, toluene, xylene and the like to obtain. The reaction is carried out using one based on alumina or silica-alumina applied metal catalyst, e.g. platinum, platinum-rhenium, molybdenum oxide or chromium oxide. Examples for industrial processes are UOP Co.'s platforming process, which is a fixed bed process, and the Ultraforming process from Standard Oil Co., also a fixed bed process. Furthermore, cata-

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lytic reforming processes of the fluidized bed type and of Moving bed type are applied. In catalytic reforming, mainly dehydrogenation and cyclization reactions take place and isomerization reactions. The result is an increased BTX content (benzene, toluene . and xylene) and an improvement in octane number. However, the reformate formed has a bromine number of no more than about 3.8 and therefore contains very low levels of unsaturated components.

The reformate catalytic distillate typically contains 6 to 10 carbon atoms and 30 to 35 percent by weight paraffins, 65 to 70 percent by weight aromatic hydrocarbons and 0 to 2 weight percent olefins. The catalytic reformate distillate which can be used according to the invention has a boiling range of 150 to 280 C.

The aromatic distillate according to (c), which predominantly consists of aromatic hydrocarbons is made from the aforementioned catalytic reformate distillates, thermally cracked By-product petroleum distillates and mixtures thereof using appropriate physical separation processes obtain. This separation is carried out on a large scale in the field of petrochemicals in order to convert BTX from catalytic reformate oils, to obtain thermally cracked by-product oils and mixtures thereof. This is generally used a solvent extraction or an extractive distillation process. Specific examples of solvent extraction processes are the aforementioned Udex process (Dow process), in which diethylene glycol or triethylene glycol can be used as extraction solvent, and the sulfolane process (Shell process), in which suIfolane is used as an extraction solvent. In general, this extraction is preceded by a hydrogenation to remove unsaturated To remove constituents, thereby blocking the device through polymerization of the unsaturated constituents

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, parts is prevented.

The aromatic distillate (c) separated in this way from the catalytic reformate distillate, the thermally cracked by-product oil distillate and mixtures thereof, consisting predominantly of aromatic hydrocarbons, consists of Cq to CQ hydrocarbons and has a boiling range of 150 to 280 ° C . It contains alkylbenzenes, polyalkylbenzenes, naphthalene, and many other aromatic hydrocarbons, _n. So far, the distillate with this boiling range has not been used effectively, although it is obtained in large quantities together with the BTX distillate.

As for the mixing ratio, 20 to 95 percent by weight of the thermally cracked oil distillate of the residual oil with 80 to 5 percent by weight of the distillate (a), (b) and / or (c) or with 80 to 5 percent by weight of aromatic hydrocarbons with a boiling point below 150 ⁰ C. A proportion of the thermally cracked oil distillate below 20 percent by weight is not desirable, since this would result in a reduction in the yield of the reaction product. A preferred mixing ratio is 70 to 90 percent by weight of the thermally cracked oil distillate and 30 to 10 percent by weight of the distillate Ca), (b) and / or (c) or the lower aromatic hydrocarbons. If the alkylbenzene content of the reaction product is to be increased, it is advisable to use the thermally cracked oil distillate from the residual oil in a relatively small amount, for example 25 to 60 percent by weight and to use 75 to ² JO percent by weight of other ingredients.

In the process according to the invention, a hydrocarbon feed, containing a thermally cracked oil distillate from residual oil, at a reaction temperature of 30 to 300 C in the liquid phase in the presence of an acidic

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Treated catalyst, whereby a reaction product is obtained whose boiling range is higher than that of the thermal cracked oil distillate and not below 260 ° C.

Preferred examples of acidic catalysts are solid acidic catalysts, mineral acids, so-called Friedel-Crafts catalysts and organic acids. More specific examples of solid acid catalysts are acidic clay minerals, such as acid clay and activated clay, amorphous or crystalline silica-alumina, AlF-. AIpO., And strongly acidic ion exchange resins; Friedel-Crafts catalysts, such as HF, AlCl-, BF_ and SnCl ^; as well as inorganic and organic acids such as sulfuric acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.

The implementation can be carried out according to any batch-wise method, semi-continuous and continuous processes can be carried out. When using a solid acid is a continuous process (flow process) preferred.

In the batch process, the catalyst is used in an amount of from 0.2 to 20 weight percent, and preferably from 1 to 10 weight percent, based on the weight of the hydrocarbon feed. In the continuous process, the treatment is carried out at a liquid hourly space velocity (LHSV) of 0.1 to 20 and preferably 0.5 to 10. The reaction temperature is in the range from 30 to 300 ° C. and preferably from 50 to 250 ° C. Treatment time, which varies depending on the reaction conditions, such as the amount of catalyst, reaction temperature and composition of the feed, should be sufficiently long to ensure complete conversion. In general, it is selected in the range ¹ J hour 2-2 The reaction pressure is not particularly limited as long as it is sufficient to keep the reaction system in a liquid phase.

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The treatment with the acid catalyst is performed in such a manner that a reaction product is formed, whose boiling range is not less than 260 ⁰ C and is higher than the boiling range of the thermal cracked petroleum distillate. The reaction product consists predominantly of oligomers of aliphatic olefins and alkylates of aliphatic olefins with aromatic hydrocarbons. If the feed is a mixture with an excess of distillate with a content of aromatic hydrocarbons, the reaction mixture obtained consists predominantly of alkylbenzenes as alkylates. If the boiling range of the reaction product is below 260 ° C. or below the boiling range of the thermally cracked petroleum distillate, it is of no commercial value and the desired effect of the treatment by the acidic catalyst cannot be expected.

Since in the process according to the invention, as explained above, a special distillate from a special source is used as a starting material and is subjected to a special treatment, high molecular weight compounds, which adversely affect the physical properties are essentially not formed. Rather, acts the reaction product obtained is a liquid of relatively low viscosity, for example im Range from 3 to 30 cSt at 75 ° C. Therefore, after the Treatment with the acidic catalyst unreacted distillate (the one used as starting material thermally cracked petroleum distillate) and unreacted other distillates or lower aromatic hydrocarbons that contain are mixed with the thermally cracked petroleum distillate, by a physical separation process, for example by distillation, separated. The reaction product can then be put to practical use, without it being necessary to carry out a further separation of heavier compounds. Of course can be the reaction product depending on the intended

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Purpose divided into fractions of suitable boiling ranges will.

Due to the aforementioned treatment, the content of unsaturated Components of the thermally cracked petroleum distillate reduced, for example by a Shows decrease in bromine number. However, the reaction product contains - especially what the relatively high-boiling portion relates to oligomers of aliphatic olefins, as stated above. Thus is preferred the content of unsaturated constituents is reduced or brought to zero by catalytic hydrogenation. This catalytic Hydrogenation can be carried out on any of the separated reaction products, distillates, which make up a large proportion of the reaction product contain, and thermally cracked petroleum distillates themselves, which are treated with the acid catalyst have been subjected to.

In the catalytic hydrogenation, any conventional Catalysts are used. For example, metallic catalysts such as Pt, Pd, Ni, Co, Mo, W, Co-Mo and Ni-W can be used. The catalytic hydrogenation is generally at reaction temperatures of 250 to 400 C, a hydrogen pressure in the range from 20 to 100 bar, a hydrogen / oil molar ratio in the range from 0.5 to 20 and a space velocity (LHSV) in the range 0.1-10.

After the catalytic hydrogenation, if necessary the hydrogenated reaction product and gases are separated by suitable means such as distillation. Of course the hydrogenated reaction product can be further divided into fractions depending on the intended use. The reaction product or hydrogenated reaction product obtained in this way has a boiling range of not less than 260 C, a kinetic viscosity of not more than

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30 cSt at 75 ° C, a pour point of no more than -45 ° C and a flash point not below 140 ° C. The quantitative The composition of the reaction product varies depending on the type of heavy oil used as the starting product, the thermal cracking conditions and the mixing ratio of the aromatic distillate. Qualitatively, however, can found that the hydrogenated reaction product which hardly contains η-paraffins, isoparaffins and aromatic hydrocarbons with a content of alkyl-substituted one • j ^ q contains link or multi-link rings.

The reaction product obtained in this way has a favorable color and a reduced content of impurities, like sulfur and metals. It is in out-

^ g reaching mass in almost all conventional fields of application Can be used with high-boiling hydrocarbon oils, for example as lubricating oil, insulating oil, rubber processing oil, Special solvents for pharmaceuticals, agricultural chemicals and dyes, as solvents

2Q medium for printing inks, paints and plastics, Plasticizers and thinners. Sulfonated reaction products obtained by conventional methods are suitable as surfactants.

After the aforementioned reaction product has been separated from the processed, thermally cracked petroleum distillate the remaining unreacted, thermally cracked petroleum distillate even a decreased content of olefins and aromatic hydrocarbons and an increased one

₃ q content of η-paraffins. This shows that reforming of the thermally cracked petroleum distillate has been achieved. Therefore, this unreacted, thermally cracked petroleum distillate is itself very good as an n-paraffinic hydrocarbon solvent for paints, pharmaceuticals

Suitable for fabrics, agricultural chemicals and dyes .

Since the distillate contains a high proportion of relatively high-boiling η-paraffins, it is suitable when using physical Separation processes, e.g. using molecular sieves or urea adduct formation, for production of n-paraffins. The n-paraffins separated in this way are used as starting materials for the production of chlorinated paraffins, soft alkylbenzenes and higher alcohols usable.

The following examples illustrate the invention.

example 1

In a device for delayed coking (cracking conditions: temperature 496 ° C., residence time 24 hours, pressure ¹ J bar) for coking residual oil obtained in vacuum distillation and having the properties given in Table I (obtained from Minas crude oil), a thermally cracked oil is also obtained Gases and coke as given in Table II. The obtained from this thermally cracked oil, as a feed

The distillate used has the composition given in Table III.

Table I.

Properties of Heavy Residue Oil 25

Bottom product from the vacuum distillation of Minas crude oil

specific weight (15 ° C), API 20

Asphaltene, wt% 2.6

^ow Conradson residual carbon, weight percent 7.1

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Table II
yield

Wt%

Starting oil Table III 100 No. 2 Butane and light gas Composition of the feed 8th 3O-16O ° C (distillate no.1) 13th "n-paraffin
31.7
Isoparaffin
L 36.6 160-26O ⁰ C (distillate no.2) Bromine number, cg / g 22nd 260 ⁰ C ⁺ (distillate no.3) Paraffin analysis, wt .-% 40 coke aliphatic olefin 17th Aromatics aromatic olefins distillate
160-26O ⁰ C 20.2 68.3 ' 19.4 12.3 -

Subsequently, 40 g AlCl- to 4 liters of distillate no. 2 are added, followed by 20-hour treatment at 50 ⁰ C followed by a batch process. The reaction mixture is then treated with aqueous ammonia to neutralize and decompose AlCU, which is removed by washing with water.

After distillation, 870 g (yield 29 percent) of a reaction product are obtained in the form of a 340 ° C. ⁺ distillate. This reaction product has a bromine number of 6.4 cg / g and an aromatic content of 78.7 percent, the remainder being predominantly olefins. The unreacted distillate obtained after the removal of the reaction product from the processed distillate No. 2 has a favorable color, a bromine number of 0.80 cg / g, a content of η-paraffins of 44 percent

and an aromatic content of just 3.3 percent. From the The fact that the content of aromatics and olefins is increased and the content of η-paraffins is reduced can be seen that reform has been achieved. Therefore, the unreacted distillate is an aliphatic hydrocarbon solvent with favorable properties or as a starting material for the production of η-paraffins, where appropriate, a simple refining by hydrogenation is carried out beforehand.

The reaction product is then using a Co-Mo catalyst at a hydrogen pressure of Bar, a reaction temperature of 280 C and a ratio hydrogenated by 1 part by volume of feed oil per part by volume of catalyst per hour.

After the hydrogenation, the light fraction formed by decomposition is distilled off, and the hydrogenated reaction products are won. The yield is 92 percent. The product has a bromine number of 0.34 cg / g and an aromatic content of 76.6 percent. In Table IV are the physical properties of the hydrogenated reaction product as well as the results of according to ASTM D-193 ^ electrical tests carried out and tests carried out in accordance with JIS C2101 for oxidation stability. For comparison, the results obtained when using mineral oil are also given. From Table IV results found that the hydrogenated reaction product has superior physical properties compared to mineral oil and is therefore suitable as an insulating oil or lubricating oil.

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- 21 Table IV

hydrogenated

Reaction mineral

product oil

Kinetic viscosity (75 ° C, cSt) 10.2 3.1 pour point ( ⁰ C) -47.5 -30

Flash point ( ⁰ C) 202 132

Electrical Properties
(Impairment by heat)

dielectric loss angle, tangent (%, 80 ⁰ C)

before heat treatment 0.001 0.001

after heat treatment 0.015 0.19 * 1

(without catalyst)

after heat treatment 0.066 2.323

(with catalyst)

Volume resistance (Jl cm, 80 ⁰ C)

before heat treatment 3.7x10 6.3x10

1 JM 1-3

after the heat treatment 2.1x10 2.5x10

(without catalyst)

after heat treatment 9.6x1O ¹³ 1.3x10 ¹² (with catalyst)

Oxidation stability

Sludge (%) 0.04 0.10

Total acid number

(mgKOH / g) 0.12 0.50

Example 2

40 ml of BF - .. H ₂ O are added to 4 liters of distillate No. 2 according to Example 1, Table II. The treatment is then carried out at 50 ° C. in batches for 2 hours. The reaction mixture is then treated with aqueous ammonia to neutralize the catalyst. The catalyst is removed by washing with water. After sufficient dehydration, one obtains

690 g of reaction product in the form of a 350 ° C ⁺ distillate. The reaction product has a kinetic viscosity of 10.2 cSt (75 C), a pour point of -47.5 C and a flash point of 200 ⁰ C.

Example 3

The one obtained from the vacuum distillation of Minas crude oil
Bottom product according to Example 1 is at 485 ° C., a pressure of 1.5 bar and a residence time of 1.5 hours
subjected to thermal cracking. The thermally cracked oil obtained becomes a thermally cracked oil distillate
with a boiling range of 100 to 300 C (with a content of 85 percent components with a boiling range of 120

up to 290 ⁰ C) rectified. The yield is 37 percent.
15th

The thermally cracked oil distillate is using
a silicon dioxide-aluminum oxide catalyst treated according to the fixed bed flow process at a reaction ^{temperature of 200 °} C. and 1 part by volume of oil fed in per part by volume of catalyst per hour. The reaction solution becomes
a catalytic hydrogenation using a Co-Mo catalyst at a pressure of 50 bar, a reaction ^{temperature of 300 0} C, 1 part by volume of fed oil per part by volume of catalyst per hour and an H _? / Oil molar

Subject ratio of 10, whereby a hydrogenated reaction product with a boiling range below 330 ⁰ C ₁ a
kinetic viscosity of 5.4 cSt (75 ° C), a pour point of -52.5 ° C and a flash point of 152 ° C.

^ow The unreacted thermally cracked petroleum distillate remaining after the removal of the reaction product contains hardly any aromatic components, unsaturated components and sulfur and is favorable in terms of odor and color. It is therefore particularly suitable as an aliphatic hydrocarbon solvent.

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The catalytically hydrogenated reaction product is according to the example 1 with respect to its electrical properties and its oxidation stability. It will be about the . the same results as in Example 1 were obtained.

example H

A by-product oil distillate having a boiling range of 61 to 25O ⁰ C is distilled out from a tubular furnace for thermal cracking of naphtha at 780 to 81O ° C for the production ^of ethylene and propylene. The by-product oil distillate contains large amounts of aromatic hydrocarbons such as benzene, toluene, xylene and styrene in addition to acetylenes and diolefins.

The distillate is then subjected to hydrogenation using a unifining two-stage hydrogenation device to remove unsaturated constituents such as diolefins and for desulphurisation. A cobalt-molybdenum catalyst supported on aluminum oxide is used as the catalyst. The hydrogenation takes place at 220 ^° C. and a pressure of 50 bar in the first stage and at 330 ° C. and 50 bar in the second stage.

The thermally cracked nöbenproduct oil distillate obtained in this way has a sulfur content of 0.01 percent and a proportion of unsaturated components of not more than 0.01 percent. This distillate is hereinafter referred to as distillate (a).

Then a reformate from a platforming device for the catalytic reforming of naphtha with a boiling range from 50 to 250 ⁰ C using a platinum catalyst in the presence of hydrogen at a reaction temperature of 70 ° C and a pressure of 50 bar to form gasoline as well made from benzene, toluene or xylene. This reformate also contains high levels of aromatics, but lower levels of unsaturation than the above thermally cracked by-product oil distillate.

- 24 This product is hereinafter referred to as (b).

Then 90 percent by volume of the reformate

distillate (b) with a boiling range of 60 to 250 C with 10 percent by volume of a fraction with the same boiling range from distillate (a) (thermally cracked by-product oil distillate) mixed. The mixture is fed to a Udex extractor to add an aromatic distillate obtain. The mixture is fed into the middle area of an extraction column for aromatics while Ethylene glycol is applied as extraction solvent at the top of the column. This creates a countercurrent extraction carried out. After refining the extract, benzene, toluene, xylene and ethylbenzene are obtained by fractionation.

In this case, an aromatic distillate having a boiling range of 150 to 25O ⁰ C in the form is formed more of a distillate with C _g or as a byproduct. This aromatic distillate having an aromatic content of 99 percent or more is hereinafter referred to as distillate (c). Table V shows the properties of a fraction (distillate (c ¹ )) from the boiling range 160 to 180 ° C., which has been obtained from the distillate (c).

Table V

Properties boiling range

160 - 180 C (distillate (c ¹ ))

specific gravity 15.6 ° C / 15.6 ⁰ C 0.876

Coloring over +30

Flash Point (PMCC) 45

Aniline point, ⁰ C 13

Aromatic content, (vol .-%) 99.5

Distillation properties (ASTM)

initial boiling point, ⁰ C 160

_O

Dry point, C 176

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In Table VI is the composition of the thus extracted xylene distillate (c ") with a boiling range specified from 135 to 145 ° C.

Tabel VI Composition of Xylene distillate (c ") Components Proportion,% by weight Ethylene benzene 55.8 p-xylene 10.4 m-xylene 20.7 o-xylene 11.8 other 1.3

5 g of AlCl- become a mixture (with a content of 17.5 Percent aliphatic olefins) from 450 ml of distillate no. 2 (thermally cracked oil distillate) according to Example 1 and added 50 ml of the distillate (c ') (aromatic distillate).

The treatment is then carried out at 185 ° C. for 1 1/2 hours intermittently. The reaction mixture is then treated with aqueous ammonia to neutralize and decompose AlCl-. Subsequent dehydration gives 98.4 g (yield 24.4 percent) of reaction product in the form of a 315 C ⁺ distillate. The reaction product has a bromine number of 5.6 cg / g and an aromatic content of 80.2 percent. The rest consists almost exclusively of olefins. Further, the reaction product on a kinetic viscosity of 10.4 cSt (75 ⁰ C), a pour point of -47.5 ° C and a flash point of 18O ° C.

The reaction product is then subjected to a hydrogenation treatment using a Co-Mo catalyst at a reaction ^{temperature of 260 °} C., a hydrogen pressure of 50 bar and 1 part by volume of reaction mixture per part by volume of catalyst per hour. The light fraction formed by decomposition is then distilled off.

■ V V ~ 7- '-t-ν »V

The hydrogenated reaction product is recovered in a yield of 81.1 percent. The reaction product hydrogenated in this way has a bromine number of 0.3 cg / g and an aromatic content of 78.5 percent.
5

In Table VII the physical properties of the hydrogenated reaction product and the results of tests carried out in accordance with ASTM D-193 *) for electrical properties and compiled from tests for oxidation stability carried out in accordance with JIS C2102. From Table VII goes shows that the hydrogenated reaction product obtained by the process according to the invention in comparison to mineral oil Has superior physical properties making it particularly good as an insulating oil and lubricating oil suitable.

Table VII

Kinetic viscosity (75 ⁰ C, cSt) 9.1 pour point ( ⁰ C) -47.5

Flash point ( ⁰ C) 180

electrical properties (impairment by heat) dielectric loss angle, tangent (%, 80 ⁰ C) before the heat treatment 0.001

after heat treatment 0.017

(without catalyst)

after heat treatment 0.066

(with catalyst)

Volume resistance (ifl cm, 80 ⁰ C)

1 f \

before heat treatment 7.0x10

on 11i

° after heat treatment 3.2x10

(without catalyst)

TU after heat treatment 1.0x10

(with catalyst)

Oxidation stability

Sludge (%) 0.05

Total acid number (mgKOH / g) 0.11

- 27 Example 5

5 g of AlCl., Become a mixture (with a content of 18.4 Percent olefins) from 475 ml of distillate no.

cracked oil distillate) according to Example 1 and 25 ml of distillate 5

(c ') (aromatic distillate) given. This is followed by paragraphs Treated at 185 ° C for 1.5 hours. The reaction mixture is then to neutralize the catalyst with aqueous Treated ammonia and removed the catalyst by washing with water. After sufficient dehydration 96.4 g (yield 24.0 percent) of a reaction mixture are obtained in the form of a 315 C distillate. This product has a kinetic viscosity of 10.6 cSt (75 ° C), a pour point of -47.5 C and a flash point of 180 C. The electrical properties and the oxidation stability

tat of the product after refining by hydrogenation are in about the same as the product of Example 1.

Example 6

5g A1C1 _Q are added to a mixture (containing 9.7 percent olefins) of 250 ml of distillate no. 2 (thermally cracked oil distillate) according to Example 1 and 250 ml of distillate (c ^f ) (aromatic distillate). The treatment is then carried out at 185 ° C. in batches for 1.5 hours. Then the p. The reaction mixture is treated with aqueous ammonia to neutralize the catalyst and the catalyst is removed by washing with water. After sufficient dehydration, 43.2 g (yield 10.4 percent) of a reaction mixture are obtained in the form of a 315 ° C. ⁺ distillate. This _o _ product has a kinetic viscosity of 6.5 cSt (75 ° C),

ο η

a pour point of -50 C and a flash point of 180 C. on.

Example 8

5 g of Aid-, become a mixture (with a content of 4.0 Percent olefins) from 100 ml of distillate no. 2 (thermally cracked oil distillate) according to Example 1 and 400 ml of distillate

V * + I /

(c ¹ ) (aromatic distillate) according to Example 4 given. The treatment is then carried out at 185.degree. C. for 1 1/2 hours batchwise. The reaction mixture is then treated with aqueous ammonia to neutralize the catalyst and the catalyst is removed by washing with water. After thorough dehydration, 97.2 g (yield 24.3 percent) of a reaction mixture are obtained in the form of a 315 ° C. ⁺ distillate. This product has a kinetic viscosity of 11.6 cSt (75 ° C), a pour point of -42.5 ⁰ C and a flash point of 190 ⁰ C.

Example 9

5 g AlCl- to a mixture (with a content of 18.7 percent olefins) of 450 ml of distillate no. 2 (thermal-cracked oil distillate) of Example 1 and 50 ml of a fraction having a boiling range of 150 to 25O ⁰ C from the Distillate (a) (thermally cracked by-product oil distillate) according to Example 4 is added. Then 11.2 hours is intermittently treated at 185 ⁰ C. Then it will

The reaction mixture is treated with aqueous ammonia to neutralize the catalyst and the catalyst is removed by washing with water. After thorough dehydration, 97.2 g (yield 24.1 percent) of a reaction mixture are obtained in the form of a 315 C ⁺ distillate. This product has a kinetic viscosity of 12.1 cSt, a pour point of -42.5 ⁰ C and a flash point of 186 ° C.

Example 1 0

5 g of AlCl are to a mixture (with a content of 17.8 percent olefins) of 450 ml of distillate no. 2 (thermally cracked oil distillate) according to Example 1 and 50 ml of a fraction with a boiling range of 150 to 250 ⁰ C from the Distillate (b) (reformate distillate) according to Example 4 is given.

_o _ This is followed by 1.5 hours batchwise at 185 ° C

acts. The reaction mixture is then treated with aqueous ammonia to neutralize the catalyst and the

BATH ORIGINAL

Catalyst removed by washing with water. After thorough dehydration, 95.3 g (yield 23.6 percent) of a reaction mixture are obtained in the form of a 315 ° C. ⁺ distillate. This product has a kinetic viscosity of 11.6 cSt, a pour point of -45 ° C and a flash point of 19O ⁰ C.

Example 1 1

5 ml of BF-JH ₅ O become a mixture (with a content of

17.5 percent olefins) from 450 ml of distillate no. 2 (thermally cracked oil distillate) according to Example 1 and 50 ml of distillate (c ^f ) (aromatic distillate) according to Example 4 are added. Subsequently batch treated at 9O ⁰ C for 5 hours. The reaction mixture is then treated with aqueous ammonia to neutralize the catalyst and the catalyst is removed by washing with water. After thorough dehydration, 12 g (yield 17.8 percent) of a reaction product are obtained in the form of a 315 C ⁺ distillate. This product has a kinetic viscosity of 7.2 cSt (75 ⁰ C), a pour point of -50 ⁰ C and a flash point of 18O ° C.

Example 12

_oc . The bottom product obtained in the vacuum distillation of Minas crude oil according to Example 1 is thermally cracked at a temperature of 485 ° C., a pressure of 1.5 bar and a residence time of 1.5 hours. The thermally cracked oil obtained is formed with the formation of a thermally cracked oil distillate with a boiling range from 100 to 300 ⁰ C (with a content of 85 percent of constituents with a boiling range of 120 b;
is 37 percent.

range from 120 to 290 ° C) rectified. The yield

A mixture (containing 18.0 percent olefins) of 450 ml of the thermally cracked oil distillate obtained above and 50 ml of distillate (c ¹ ) (aromatic distillate)

^ t I 'ν / V

according to Example 4 is treated at a Rekationstemperatur of 200 ⁰ C and 1 part by volume of oil fed per volume of catalyst per hour in accordance with the fixed-bed flow method using a silica-alumina catalyst.

The reaction solution is subjected directly to a catalytic hydrogenation treatment at a reaction temperature of 300 ° C., a hydrogen pressure of 50 bar, 1 part by volume of oil fed in per part by volume of catalyst per hour and an H _? / Oil molar ratio of 10 treated. A reaction product is obtained in the form of a 315 C ⁺ distillate with. a kinetic viscosity of 5.2 cSt (75 ⁰ C), a pour point of -52.5 ° C and a flash point of 160 ° C.

The unreacted light distillate remaining after the removal of the reaction product contains hardly any unsaturated Constituents and sulfur and is found to be beneficial in terms of smell and color.

The hydrogenated reaction product is then tested for its electrical properties and oxidation stability. Approximately the same values as in Example H are obtained. Examples 4 to 12 are summarized in Table VIII, the values for viscosity, pour point, flash point and the like also being given.

ORfGINAL

- 31 Table VIII

example

• Distillate from (A)

Together- ; setting of the supply of thermally cracked oil distillate (distillate no. 2) from the
thermal cracking of the bottom product of Vakuumdestil] at i on

Distillate of (B) aromatic distillate
(Distillate (c ')) with a boiling range of 160-180C obtained by solvent extraction

Portion of (B)

185 ° C,

Reaction conditions kinetic
tat (cSt, Viscose
75 ⁰ C) AlCl- 1.3 Wt .-% 1.5 hours 10.4 20th yield Pour point ( ⁰ O 24.4 24, 0 6.5 React
functional Flash point
PMCC ( ⁰ C) 10.4 10, 6th -50 25th Per-
duct -47.5 -47, 5 180 180 180

BATH ORIGINAL

- 32 Table VIII (cont.)

example

Composition of the feed

Distillate from (A) thermally cracked oil distillate (Distillate No. 2) from the thermal cracking of bottoms vacuum distillation

Distillate of (B) aromatic distillate
lat (distillate
(c ^f )) with
a boiling range
from 160-18O ° C obtained by
Solvent extract
tion

Aromatic distillate with a
Boiling range
from 150-250 ⁰ C
(Distillate (c))

Proportion of (B) 80

thermally cracked by-product oil distillate (Distillate (a))

10

Reaction conditions 1.3% by weight 185 C, 1.5 hours.

Yield (%) 24.3

24.1

Reaction product

kinetic viscosity (cSt, 75 ^δ Ο 4.0

11.6

12.1

Pour point (C) -50

-42.5

-42.5

Flash point (C) PMCC 180

190

186

BATH ORIGINAL

- 33 - Table VIII (cont.)

example Distillate of
(A) kinetic
Viscosity,
(cSt, 75 C) 10 11th as in
at
game 4 12th Together
men
settlement
the
supply Distillate of
(B) Pour point ( ⁰ C) thermally cracked oil
distillate (distillate
No. 2) from the thermi
cracking of
Bottom product of the vacuum
distillation 10 thermal
cracked
Oil style
lat at
short
Stay
Time Proportion of (B) Flash point
( ⁰ C) PMCC Reformate
distillate
with a
Siedebe
rich of
150-250 ⁰ C.
(Distillate
(b)) BF _g .H ₂ O
1.0% by volume as in
At- ·
game 4 Reaction conditions 10 17.8 10 Yield (%) AlCl, 1.3
Weight 2%
185 ° C,
1.5 hours 7.2 Fixed bed
Flow
procedure,
Silicon
dioxide
Aluminum-
oxide React
functional
Per-
duct 23.6 -50 - 11.6 180 5.2 -45 -52.5 190 160

OO HJ / OU

"Ww" ^w · "**

_v * w>■> ■ · · »W ir * · ·· -φ ir

- 34 Example 13

8, ¹ I g of anhydrous aluminum chloride are added according to a mixture (with a content of 7.4 percent olefins) of 400 ml of distillate no. 2 (thermal-cracked oil distillate) Example 1 and 600 ml Xyloldestillat (c ") in accordance with Example 4. then batch for 1 hour at 130 ⁰ C is treated is then treating the reaction mixture for neutralization and decomposition of the catalyst with aqueous ammonia after dehydration to obtain 79.4 g (yield of 9.5 percent) reaction product in the form of a 260 ° C ^+.. - The reaction product has a bromine number of 1.0 cg / g and an aromatic content of 98 percent. The remainder consists largely of olefins. This product also has a kinetic viscosity of 5.3 cSt (75 C), a pour point of -50 C and a flash point of 172 C.

Example 1 4

8.4 g of anhydrous aluminum chloride are added to a mixture (containing 7.4 percent olefins) of 400 ml of distillate No. 2 (thermally cracked oil distillate) according to Example 1 and 600 ml of benzene. The treatment is then carried out at 80 ° C. in batches for 1 hour. Then the reaction. mixture treated with aqueous ammonia to neutralize the catalyst and the catalyst removed by washing with water. After thorough dehydration of 72.7 g (yield of 8.7 percent) are obtained of a reaction product in the form of a 260 ° C ⁺ -Destillats having a kinetic viscosity of 5.7 cSt (75 ° C), a pour point of -50 ⁰ C and

a flash point of 154 ° C.
30th

Example 15

8.4 g of anhydrous aluminum chloride become a mixture (containing 18.4 percent olefins) of 950 ml of distillate No. 2 (thermally cracked oil distillate) according to Example 1 and 50 ml of benzene were added. This is followed by paragraphs Treated at 100 ° C for 1 hour. Then it will

BAP ORfGINJAL

33A.1736

The reaction mixture is treated with aqueous ammonia to neutralize the catalyst and the catalyst is removed by washing with water. After thoroughly dehydrating 192 g (yield 23.9 percent) are obtained reaction product in the form of a 260 C ⁺ -Destillats having a kinetic viscosity of 13.1 cSt (75 ⁰ C), a pour point of -42.5 ° C and a flash point from 164 ⁰ C.

Example 16

300 ml of benzene and 600 ml of anhydrous hydrogen fluoride (purity 99 percent or above) are placed in a batch reactor (volume 5 liters) cooled to 5 C and thoroughly cooled with stirring. Subsequently, a mixture of 300 ml benzene and 400 ml of the fraction with a boiling range of 160 to 22O ⁰ C the distillate no. 2 (thermal-cracked oil distillate) of Example 1 within 10 minutes dropwise. The mixture is then stirred for a further hour. The reaction mixture is then left to stand for separation into an oil layer and a layer of anhydrous hydrogen fluoride. The oil layer is then treated with a 10 percent strength by weight potassium hydroxide solution to neutralize and decompose the anhydrous hydrogen fluoride it contains. The hydrogen fluoride is then removed by washing with water. After thorough dehydration, 85.3 g (yield 10.2 percent) of a reaction product with a boiling range above 260 ° C., a kinetic viscosity of 3.5 cSt (75 ° C.), a pour point below -55 ° C. are obtained

and a flash point of 144 ⁰ C.
30th

Surface active test

A distillate with a boiling point is made from the reaction product obtained in this way (non-hydrogenated product)

__ rich from 260 to 330 C in a yield of 88.1 percent 35

won. This distillate is subjected to a sulfonation reaction.

Tests for surface-active effect are carried out with the sulfonate obtained in this way.

95.1 g of the distillate from 260 to 330 ° C. are poured into a 500 ml given glass vessel. To carry out the sulfonation reaction 19 ml of anhydrous sulfuric acid are added together with nitrogen gas for 1 hour with vigorous stirring blown in at 50 C. When the sulfonation is complete, the reaction mixture gradually becomes 148.2 g of a 6.7 percent strength Added sodium hydroxide solution, which is neutralized to a pH of 7.0 to 7.5. The amount of added Reaction mixture is 81.1 g. The yield of sulfonated product is 84.1 percent.

Then the sodium sulfonate is on its surface-active Properties examined.

Under the conditions given in Table IX, 0.2 parts of the sodium sulfonate obtained above in 1.5 Part of dissolved water. The solution is made with 70 parts of heavy oil B thoroughly mixed. Then there are 30 parts fine coal powder mixed in thoroughly. The mixture is then left to stand and the sedimentation rate is determined of the fine coal powder. After 50 days no sedimentation can be seen. Without using the sodium sulfonate there is an immediate deposition of the carbon powder.

Table IX

fine coal powder 85% pass a sieve of the clear ones

Mesh size 0.074 mm (200 mesh)

Heavy oil B 90
17th ep,
ep, 28
70 ⁰ C Concentration of
fine coal powder 30th Weight -% Measuring temperature 30th ° C

ORSGfNAL

Claims (1)

Patent claims 15 Process for processing a hydrocarbon feed " characterized in that the hydrocarbon feed is added at a reaction temperature in the range of 30 up to 300 C in the liquid phase in the presence of an acidic Treated catalyst, wherein the hydrocarbon feed a liquid distillate from a thermally cracked oil, which has been obtained by thermal cracking of a heavy residual oil at a temperature not below 400 ⁰ C and'n not above 700 ⁰ C, which Distillate mainly of hydrocarbons having a boiling range of 120 to 29o ⁰ C and containing aliphatic olefins, thereby forming a reaction product having a boiling range which exceeds the boiling range of the hydrocarbons obtained as the main component of the distillate and not under 26O ⁰ C, was obtained. 2. The method according to claim 1, characterized in that the distillate from the thermally cracked oil further aromatic hydrocarbons and at least 10 percent by weight Contains aliphatic olefins. BATH ORIGINAL _ 2 - Been that it is in the Kohlenwasserstoffboschickung a distillate from a thermal-cracked oil that is not obtained 3- A method according to claim 1, characterized in that in a method for thermal cracking a heavy residual oil at a temperature below 400 ⁰ C and above C is, wherein the distillate consists predominantly of hydrocarbons with a boiling range from 120 to 29O ⁰ C and contains aliphatic olefins. H. The method according to claim 1, characterized in that the hydrocarbon feed is a mixture of the following components: (I) 20 to 95 weight percent of a thermal-cracked oil distillate of a heavy residual oil at a temperature has not been obtained at 400 ⁰ C and not more than 700 C by thermal cracking, the distillate mainly of hydrocarbons having a boiling range of 120 to 29o ⁰ C and contains aliphatic olefins, and (II) (A) 80 to 5 percent by weight of one or more distillates with a boiling range from 150 to 280 ⁰ C, selected from the following components (a) to (c): (a) A thermally cracked by-product petroleum distillate, that by thermal cracking a Light oil has been obtained at cracking temperatures in the range from 750 to 850 ⁰ C, (b) a reformate, which has been obtained by the catalytic reforming of a light oil having a boiling range of 50 to 25O ⁰ C, and (c) an aromatic hydrocarbon distillate composed predominantly of aromatic hydrocarbons and by separating the thermally cracked by-product petroleum distillate (a) and / or the reformate distillate (b) he has been held, odor BATH ORIGINAL 1 (B) 80 to 5 weight percent aromatic coals hydrogen with a boiling range below 150 C, 5. The method according to claim 1, characterized in that 5 the thermal cracking process is a coking process acts. 6. The method according to claim 5, characterized in that the coking process is a delayed 10 coking process. 7. The method according to claim 1, characterized in that the acidic catalyst is aluminum chloride, Boron fluoride, its complexes, hydrogen fluoride or silicon 15 is cium oxide-aluminum oxide. BATH ORIGINAL