DE2549690A1 - Products from petroleum distillates and extracts - by air blowing followed by fractionation - Google Patents

Abstract

Prods. are obtd. from petroleum distillates and/or solvent extracts of petroleum distillates having a viscosity-gravity constant (VGC, ASTM D 2140) of >0.85 (pref. >0.90) by blowing with O2 (pref. as air) and fractionating to recover at least one fraction boiling in the 320-420 degrees C range at a pressure of 760 mm Hg. The process can be used to produce a light "treatment oil" with high oxidative stability (b.p. 320-375 degrees C), a mid-range "treatment oil" (b.p. 375-420 degrees C), and a heavy fraction with an initial b.p. of >=400 degrees C for use as an additive for gramophone disc moulding compsns., giving an increased rate of prodn. and better sound reproduction. The initial distillate or extract is suitably a lube oil distillate or extract with an av. mol. wt. of 150-600 (pref. 200-500). Air blowing is pref. effected in the presence of 0.01-2 wt% of Cr, Co, Ni, Fe, Cu, Mn or Zn in the form of an oxide or an org. salt (pref. a naphthenate, acetate, propionate or butyrate), pref. for >=7 hr. The org. matl. entrained in the off-gas is pref. condensed and recycled. The above three fractions can be recovered from the same fractionation column, but are pref. recovered from separate operations, each preceded by air blowing.

Description

Process for the production of new, technically valuable products

products made from mineral oil distillates or solvent extracts from such distillates Subject of the patent ... ,,. (Patent application P 25 19 038.9) is a process for the production of new, technically valuable products from mineral oil distillates or solvent extracts from such distillates, which is characterized in that one or more mineral oil distillates and / or solvent extracts from mineral oil distillates with a content of aromatically bound carbon , corresponding to a VGC value of at least 0.85, preferably at least 0.90, and with an average molecular weight of 150 to 600, preferably 200 to 500, are oxidized by blowing air in a known manner and that the oxidized distillate and / or the oxidized extract is distilled, with a product fraction in the temperature range from approx. 320 to approx. 375 ° C at 760 Hg being removed during the distillation and a second product fraction from the bottom fraction at temperatures above approx. 4000 C at 760 boiling mm Hg, is isolated.

The present invention represents a further development of the method according to patent ...... (patent application P 25 19 038.9) and is characterized by that one or more mineral oil distillates and / or solvent extracts of Mineral oil distillates with a content of aromatically bound carbon corresponding to a VGC value of at least 0.8, expediently at least 0.90, and an average molecular weight of 150 to 600, expediently 200 to 500, by blowing in of oxygen, expediently in the form of air, and the oxidized distillate and / or the extract fractionated, at least one product fraction with a Boiling interval in the temperature range from about 5200 C to about 4200 C at 760 mm Hg and another product fraction with a lowest cooking temperature of 400 ° C or above that at 760 mm Hg during fractionation.

It has now been found that, inter alia, a product fraction with a light oil that has extremely valuable properties in terms of stability against oxidation and which is used as a plasticizer, by oxidation of one or more Mineral oil distillates and / or solvent extracts from mineral oil distillates with a certain minimum content of aromatically bound carbon by blowing in of air and subsequent distillation of the oxidized distillate and / or extract and withdrawing certain product fractions at temperatures up to about 3750 ° C 760 mm Hg can be obtained. Another fraction of the product turned out to be valuable as an additive to molding compounds for records, thereby increasing production and an improved sound reproduction is enabled. A possible third faction that between these first two fractions can be used as a plasticizer. This third fraction has a boiling range of about 375 to 4200 C at 760 mm Hg.

The various product fractions obtained according to the procedure of Invention can be obtained over the entire temperature range of 320 to 4200 C or a smaller zone within this range.

If a lower flash point or a darker color the first Product fraction is regarded as tolerable, Is it possible, the cooking temperature of a minor part of the fraction is slightly below 320 ° C 760 mm Hg, for example down to about 3150 c and / or slightly above 420 ° C at 760 mm Hg. Similarly, lesser amounts of components are the Cook at temperatures a little below 4000 C at 760 mm Hg, permissible in the second Product fraction, if the stickiness of the product obtained is considered to be tolerable is seen.

According to an advantageous embodiment of the method of the invention the different product fractions are removed in separate stages, which each precedes an oxidation stage. The second product fraction can for example be obtained by the fact that the bottom fraction, which is obtained after the distillation of the the first product fraction remains, which is subject to oxidation by blowing in air, whereupon the components with a low boiling point below the boiling point range the desired fraction can be removed by distillation or stripping.

According to another preferred embodiment of the method of Invention can be a part of the substances that the distillate and / or the extract with leave the oxidizing gases in the oxidation stage, condensed and into the process to be led back.

According to a further advantageous embodiment of the method the invention, the oxidation is carried out in the presence of a catalyst which is soluble or converted to compounds in the oxidized distillate and / or extract is, which in the oxidized distillate and / or the extract by reaction with are soluble in the distillate and / or the extract. The product fraction with the lowest Cooking temperature of 4000 C or above will result in a higher depth of softening in this way given at the same softening point, which in practice is a reduction in the low Tear resistance of this product means.

According to the invention, the catalyst can, for example, be an organometallic Salt, a metal oxide or a mixture thereof, the catalyst being useful in amounts corresponding to 0.01 to 2% by weight of metal, calculated on the metal to be oxidized Distillate or extract.

The product fraction with the lowest cooking temperature of 4000 C or above it consequently contains from about 0.01 to about 3% by weight of metal, calculated on the weight the parliamentary group.

Any metal known to be used can be used as a catalyst by continuously varying its valence between two oxidation stages acts. Examples of such metals are chromium, cobalt, nickel, iron, copper and manganese. In addition, zinc has proven to be an excellent catalyst metal in the method of the present invention.

The organometallic salts are, for example, naphthenates or Salts of aliphatic carboxylic acids. The organic part of the salts should be appropriate be as small as possible.

Naphthenates, acetates, propionates and butyrates are particularly preferred Salts.

Regardless of whether the catalyst is in the form of an oxide or an organometallic compound is added, the metal is after the distillation contained in the residue in the same final form.

The oxidation is convenient both in the presence and in the absence a catalyst carried out over a period of at least 7 hours a softening point of the residue after distillation of at least 1000 C, expediently obtained in the range from 105 to 1400.degree.

Products with a softening point above 1400 C can be cooled by atomization not easily made into a particulate form, but are made by grinding brought into this form.

The product fraction, which boils at 375 to 4000 C, can be in a separate distillation stage can be taken, but it can also from the same Distillation column or taken from the other two fractions. in the In principle it is of course possible to use all three product groups from one and the same Column, but as mentioned above, the product fractions are appropriate taken in separate stages, each stage preceded by an oxidation stage.

Each oxidation stage can be divided into several sub-stages, if desired will. Such a division is especially considered for the strongest first stage of oxidation.

The oxidation is expedient at a temperature of 180 to 3000 C performed at 760 mm Hg.

The hot second product fraction from the process can be sprayed be cooled and leads to a preferred product form that is particularly light can be handled.

Any fraction obtained by distilling a mineral oil and has an aromatically bonded carbon content corresponding to one VGC value of at least 0.85, suitably at least 0.90, and an average Molecular weight from 150 to 600, expediently 200 to 500, can be used as the mineral oil distillate can be used to serve as starting material in the process according to the invention. Lubricating oil distilates with a boiling interval of 250 to 2950 C, 295 to 3400 C, 540 to 3850 C, 385 to 4400 C or 440 to 4900 C, according to an average Molecular weights of about 210, 250, 295, 350 and 425 are examples of such Factions.

The term "solvent extracts of mineral oil distillates" is used used here to designate products that are in any appropriate way by extraction of mineral oil distillates, for example with furfuraldehyde, cresol, Phenol or liquid sulfur dioxide can be obtained. To in the process according to According to the invention, the extracts should have an aromatic content Bound carbon and an average molecular weight, according to the information as mentioned above for mineral oil distillates.

The VGC value (VGC = Viscosity Gavity Constangl is a standard measure for the aromatic carbon content of mineral oil products and is determined according to ASTM D 2140. A VGC value of 0.85 generally corresponds to a content of aromatically bound carbon of about 10 to 30%, while a VGC value of 0.90 generally an aromatic carbon content of about 25 to 40% calculated on the total amount of carbon, that corresponds to that from the various fractions The proportions obtained can be determined by a precise choice of the oxidation time and the average Molecular weight of the starting material can be adjusted.

A longer oxidation time or a higher average molecular weight lead to higher yields of the second product fraction.

The invention is described using a few examples.

Examples 1.) 3.0 1 of an extract from a lubricating oil distillate with a boiling range from 295 to 3400 C and a VGC value of 0.958 were achieved by Injection of air (3 l / min) and heating under full reflux and separation of the water formed first 5 hours at 2400 C and then 4 hours oxidized at 5000 C. The viscosity at 98.90 C (2100 F) increased from 2 cSt to 80 cSt. This was followed by distillation under vacuum (approx. 0.3 mm Hg). Here was a peak fraction with a boiling point of up to 9250 C at 760 mm Hg was taken; yield 10%.

An intermediate fraction in the range from 325 to 3750 C was then obtained 760 mm Hg taken; Yield 30%. Another fraction was at 375-4000 C taken at 760 mm Hg; Yield 10%. A product was obtained as the residue that boiled over 4000 C at 760 mm Hg with a softening point (Ring and Kugei) of 1160 C; Yield 50% (all yields are based on the weighed amount related to distillation).

2.) Example 1 was repeated, using an extract from a Lubricating oil distillate with a boiling range of 440 to 4900 C was assumed. The VGC value of the extract was 0.961. The air was blown at 2400 for 3 hours C without condensate return and for 4 hours at 3000 C with condensate return. The yield of the top fraction was approx. 3%, of the product in the range from 325 to 5750 C about 8%, in the interval 375 to 4000 C about 5% and of the soil fraction 84%, all yields based on the weighed amount before distillation.

3.) 3.0 1 of an extract from a lubricating oil distillate with a boiling range from 340 to 3850 C and a VGC value of 0.960 were achieved by blowing air (3 1 / min) and heating under complete reflux and separation of the formed Water for 10 hours at 3000 C. The softening point of the material was at 880 C (ring and ball).

This was followed by distillation under vacuum (approx. 0.3 mm Hg).

Here, a top fraction with a boiling point of up to 5750 C taken at 760 mm Hg; the yield was 4% by weight. Thereupon became a parliamentary group taken in the range 375 to 4000 C at 760 mm Hg; the yield was 18% by weight. The residue was a product with a boiling point above 4000 C at 760 mm Hg and obtained a softening point (ring and ball) of 1240 C; Yield 71% based on on the amount weighed in before the oxidation.

4.) 3.0 1 of a lubricating oil extract with a boiling range from 540 to 3850 C and a VGC value of 0.960 were oxidized by blowing air into the extract (3 l / min) in the presence of 0.5 wt. 3 ZnO (0.44 wt. 5S Zn, based on the weight of the extract), under complete reflux and separation of the formed water, for 11 hours at 3000 C. The softening point of the material was then 830 C (ring and ball).

The distillation was then carried out under vacuum (about 0.15 mm Hg) carried out. It became a fraction with a boiling point at 760 mm Hg in the interval Taken from 320 to 5750 C; the yield was 4. Another faction was at Taken from 375 to 4000 C at 760 mm Hg; the yield was 16%. It became a homogeneous one Product boiling above 4000 C at 760 mm Hg and with a softening point (ring and Kugel) at 1230 C, obtained as a residue; the yield was 80 ffi based on the extract weight before oxidation. The depth of softening (according to IP 49) was measured and was 3 mm / 10 with a weight of 100 g in 5 seconds and in 500 Seconds. The depth of softening for a corresponding product fraction without use of a catalyst was 0 mm / 10 or 6 mm / 10 with a weight of 100 g - in 5 or 500 seconds.

5.) An extract according to Example 4 was made in the same way as there but the zinc oxide was replaced by 2% by weight cobalt naphthenate (0.25% by weight) Wt .-% Co, calculated on the weight of the extract) replaced as a catalyst and the Oxidation was carried out for 10 hours. The softening point of the material was then 850 C (ring and ball).

The distillation was then carried out under vacuum (about 0.3 mm Hg). It became a fraction with a boiling point at 760 mm Hg in the interval 320 to 4000 C taken; the yield was 19%. It became a homogeneous product, boiling over 4000 C at 760 mm Hg with a softening point (Ring and ball) obtained as residue from 1090 C; Yield 81% based on the weight of the extract before oxidation. The depth of softening (according to IP 49) was 2.5 and 5 mm / 10 in 5 and 500 seconds and with a weight of 100 g.

6.) There was an extract according to Example 4 in the same way as there described oxidized, but the zinc oxide was replaced by 1 wt .-% copper acetate (0.32% by weight Cu, based on the weight of the extract) as a catalyst and the oxidation was carried out for 12 hours.

The softening point of the material was then 800 C.

The distillation was then carried out under vacuum (about 0.1 mm Hg). It became a first fraction with a boiling point at 760 mm Hg in the 320 interval up to 3600 C and a second fraction with a boiling point at 760 mm Hg in the interval Taken from 560 to 4000 C, the yields being 2 and 18%. It became a homogeneous product, boiling above 400 ° C at 760 mm Hg with a softening point (Ring and ball) obtained from 1080 C as a residue; the yield was 80% based on on the weight of the extract before oxidation. The softening (according to IP 49) was 2 mm / 10 in 5 and also in 500 seconds with a weight of 100 g.

7.) There were 3.0 l of an extract from a lubricating oil distillate with a boiling range of 340 to 3850 C and a VGC value of 0.95 by blowing in of air into the extract (3 1 / min) in the presence of 0.5% by weight ZnO (0.44% by weight Zn, based on the weight of the extract) under complete reflux and separation of the water formed is oxidized at 2700 C for 12 SWen. The softening point of the The material was then 890 C (ring and ball).

The distillation was then carried out under vacuum (about 0.5 mm Hg). A fraction with a boiling point at 760 mm Hg in the range of 320 to 4000 C; -the Yield was 19.5%. One received a homogeneous product, boiling above 4000 C at 760 mm Hg with a softening point (Ring and ball) of 1250 C as residue; the yield was 80.5% based on the weight of the extract before oxidation.

8.) 3.0 1 of an extract from a lubricating oil distillate with a boiling interval from 295 to 3400 C and a VGC value of 0.958 were achieved by blowing air into the extract (3 1 / min) under complete reflux and separation of the formed Water is oxidized at 3000 C for 10 hours. The softening point of the material was then at 850 C (ring and ball).

One part by weight of the oxidized extract thus obtained was after Milled with 9 parts by weight of technical gasoline (boiling range 80 to 1200 C) in mixed in a vessel with stirring at room temperature for 50 minutes.

The topsheet was decanted and the residue was made up with gasoline washed, filtered and evaporated at 1300 C.

A homogeneous product with a softening point (ring and Sphere)> 1500 C and a lowest boiling point of 7 4200 C obtained as residue; the yield was about 50% based on the weight of the extract before oxidation.

The gasoline was stripped from the topsheet, followed by distillation was performed under vacuum (about 0.3 mm Hg). It became a faction with a Boiling point taken at 760 mm Hg in the range from 520 to 4200 C.

Claims (1)

Claims 2.) Process for the production of new, technically more valuable Products made from mineral oil distillates or solvent extracts from such distillates according to patent ...... (patent application P 25 19 058.9), characterized in that a mineral oil distillate and / or a solvent extract of a mineral oil distillate oxidized by introducing oxygen into the distillate or the extract, wherein the distillate or the extract contains aromatically bound carbon corresponding to a VGC value of at least 0.85, the oxidized distillate and / or the extract fractionated and at least one fraction with a boiling interval takes within the temperature range of about 520 to 4200 C at 760 mm Hg. 2.) The method according to claim 1, characterized in that one Fraction that boils at about 520 to about 3750 C at 760 mm Hg is withdrawn. 5.) Method according to claim 1 or 2, characterized in that a distillate or an extract with an average molecular weight used from 150 to 600. 4.) The method according to claim 3, characterized in that one is a Product with an average molecular weight between 200 and 500 is used. 5.) Method according to one of claims 1 to 4, characterized in that that one is a distillate or an extract with a content of aromatically bound Carbon with a VGC of at least 0.90 is used. 6.) Method according to one of claims 1 to 5, characterized in that that one uses oxygen in the form of air. 7.) Method according to one of claims 1 to 6, characterized in that that one another fraction with a lowest boiling point of 4000 C or above it separates at 760 mm Hg. 8.) Method according to one of claims 1 to 7, characterized in that that one oxidizes the distillate residue by passing in oxygen and one Fraction with a lowest boiling point of 4000 C or above by distillation or by stripping off the components with low boiling points. 9.) Method according to claim 7 or 8, characterized in that the hot fraction with the lowest boiling temperature of 4000 C or above cools by spraying. 10.) Method according to one of claims 1 to 9, characterized in that that one more fraction with a boiling point in the range between about 575 up to about 4000 C at 760 mm Hg. 11.) The method according to claim 10, characterized in that the another fraction is removed by distillation. 12.) Method according to one of claims 7 to 10, characterized in that that the various fractions are removed in separate distillation stages, each of these stages is preceded by an oxidation stage. 15.) Method according to one of claims 1 to 12, characterized in that that at least part of the substance that is associated with the oxidizing gases in the oxidation stage evaporate from the distillate or extract, condense and return to the process. 14.) Method according to one of claims 1 to 15, characterized in that that the oxidation is carried out in the presence of a catalyst which is oxidized in the The distillate and / or the extract is soluble or is converted into compounds, those in the oxidized distillate and / or the extract by reaction with the distillate and / or extract are soluble. 15.) The method according to claim 14, characterized in that as Catalyst an organometallic salt, a metal oxide or a mixture thereof used. 16.) The method according to claim 15, characterized in that as Metal used is chromium, cobalt, nickel, iron, copper, manganese or zinc. 17.) Method according to claim 15 or 16, characterized in that The organometallic salts are metal salts of naphthenic acid or aliphatic Used carboxylic acids. 18.) The method according to claim 17, characterized in that as Carboxylic acid acetic acid, propionic acid or butyric acid is used. 19.) The method according to any one of claims 14 to 18, characterized in, that an amount of catalyst is used which corresponds to 0.01 to 2% by weight of metal, based on the distillate to be oxidized or the extract. 20.) Method according to one of claims 1 to 19, characterized in that that the oxidation is carried out for at least 7 hours. 21.) Method according to one of claims 7 to 20, characterized in that that the oxidation up to a softening point according to ring and ball of at least 1000 C of the fraction with a lowest boiling point of 4000 C or above performs at 760 mm Hg. 22.) The method according to claim 21, characterized in that one is a Product with a softening point within the range of 105 to 1400 C was used. 25.) Product with a lowest boiling point of 4000 C or above at 760 mm Hg and a softening point of 1000 C or above, characterized in that that this product is made from mineral oil distillates and / or solvent extracts from Mineral oil distillates with a content of aromatically bound carbon accordingly a VGC of at least 0.85 and an average molecular weight from 150 to 600 by blowing oxygen and then fractionating the ingredients with a boiling point below the lowest boiling point of the product was won. 24.) Product according to claim 23, characterized in that it is 0.01 contains up to 3% by weight of a metal in bound form.