JP3004761B2 - Non-carcinogenic light lubricant and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a useful light lubricating oil and
It concerns the manufacturing method. More specifically, the present invention relates to a non-carcinogenic light lubricating oil.

[0002]

BACKGROUND OF THE INVENTION In the refining of lubricating feedstocks, a series of color reduction techniques are used to remove undesirable components from the process feedstock. The most important treatments in this step include atmospheric distillation, vacuum distillation, deasphalting, solvent extraction, and dewaxing. These steps are essentially physical separation processes, since the recombining of the original crude oil when all the separated fractions are recombined.

Refineries do not produce a single feedstock,
Rather, it treats a plurality of distillation fractions and vacuum retentate fractions. Atmospheric distillation of crude yields several fractions depending on the type of crude used and the method of refining. The two fractions are generally considered middle distillates, which are straight kerosene with a boiling range of 174-266 ° C (345-510 ° F) and a boiling range of about 266-371 (5
10 to 700 ° F.). Products derived from these fractions include kerosene, jet fuel, diesel fuel, home heating oil and marine oil. Lighter middle distillates can also be used as special lubricants such as inorganic seal oils, spindle oils, honing oils and cold rolling oils such as aluminum, steel and copper.

In general, at least three vacuum distillation fractions differing in boiling range and residue may be purified. In the refining art, each of these four fractions is named, with the most volatile vacuum distillate fraction being called the "light neutral" fraction or oil and the other vacuum distillate being the "neutral neutral". It is known as oil and "heavy neutral" oil. Non-asphaltized,
The vacuum residue after solvent extraction and dewaxing is commonly referred to as "bright stock". Thus, the production of a lubricating base oil includes the step of making a slate of the base oil. In addition, each color reduction process yields by-products, which may be further processed or sold to industries utilizing them.

As noted above, conventional crude oil processing methods for recovering distillates suitable for improvement in various refining operations include multi-stage distillation. First, crude oil is distilled or rectified in an atmospheric distillation column, and the residue remaining at the bottom of the column is further separated in a vacuum distillation column. In this combined operation, gas and gasoline are recovered as overhead products of the atmospheric distillation column, heavy naphtha, kerosene, and gas oil are withdrawn as a distillation sidestream, and the remaining material is recovered as dilute crude from the bottom of the column. You. Vapors may be conducted to the bottom of the column and various side strippers are used to remove lighter substances from the heavier liquid product withdrawn. The remaining bottoms fraction or reduced crude oil is usually charged to a vacuum distillation column. The vacuum distillation process in lubricating refining yields one or more crude oils having boiling points in the range of about 288-566 ° C (550-1050 ° F), in addition to the vacuum residue by-products. The vacuum charge is often heated by a furnace to evaporate a portion of the charge. The preheated charge usually enters the lower part of the column, from which the vapors evolve up the column and are cooled at selected stages to produce a continuous light liquid. still,
This liquid is separately removed as a sidestream crude product.

[0006] Following vacuum distillation, each crude product is extracted with a solvent such as furfural, phenol or chlorex to remove unwanted components. Vacuum resids usually require one more step, typically propane deasphalting, to remove asphalt material prior to solvent extraction. The products made for further processing into feedstocks are known as raffinates. The raffinate obtained from the solvent purification is dewaxed by adding a solvent such as methyl ethyl ketone or toluene, processed, and processed into a final finished raw material oil.

[0007] The solvent extraction process separates the hydrocarbon mixture into two phases; one of which is the raffinate phase described above, which contains a material having a relatively high hydrogen to carbon ratio and is called a paraffin-type material. I have. The other contains substances with a relatively low hydrogen to carbon ratio in the extract phase and is called the aromatic hydrocarbon type phase. Solvent extraction is possible because different liquid compounds have different liquid affinities,
One combination is completely miscible, while another is almost immiscible. The ability to distinguish between a paraffinic type with a high proportion of hydrogen and carbon and an aromatic type with a low proportion is called "selectivity".
The finer the distinction, the higher the selectivity of the solvent. Furfural is a typical solvent extractant,
Due to its miscibility and physical properties, it is possible to use both high aromatic oils having a wide boiling point range and high paraffin oils. Diesel fuel and light and heavy lubricating stocks are often refined using furfural.

Some chemicals cause skin cancer in humans and laboratory animals by contact with the skin. In recent years, concerns have been raised regarding the relationship between the use of various lubricating oils, middle distillates and petroleum products and potential harm. Previous studies of high-boiling fractions recovered from vacuum distillation and processed into engine oils and other lubricating oils indicate that patterns of certain types of petroleum-producing substances cause tumors in laboratory animals. Deterministically established.

[0009] Oils that have been subjected to treatments such as solvent purification and intense hydroprocessing are polycyclic aromatic hydrocarbons (PA).
H) is known to contain only trace amounts. Therefore,
These oils are generally not tumorigenic;
Oils with high AH levels, especially compounds with four or more rings, are tumorigenic.

The middle distillate used as a special oil is
Because of its industrial use, it has many potentials for direct human exposure. Such a straight run middle distillate is 37
Boiling below 1 ° C. (700 ° F.), often containing only small amounts of PAH compounds, would not produce tumors in tests performed on animals in the laboratory. However, actual experiments using laboratory animals have yielded contradictory results.

The index of the degree of tumor occurrence is the time from the occurrence of a tumor to its observation. Substances that cause skin tumors in the majority of laboratory mice have relatively short latencies, whereas long latencies do not cause tumor development in many mice. However, it was found that this pattern was not followed when exposed to lubricants based on middle distillates. Some experiments do not use laboratory animals and do not perform long-term topical administration, so it is not always possible to identify the skin carcinogenicity of kerosene lubricants or middle distillate-based lubricants. According to one study, when exposed to such substances for some time, the average incubation period was 79 weeks,
Many mice had tumors. (GR Blackburn, RA Daich, CA Schleiner,
M. A. Mae Lam and C.I. R. Maccarla et al., "Predicting carcinogenicity of petroleum fractions using a modified Salmonella mutagenicity assay", Cell Biology and Toxicology, 2: 63-84, 1
986).

[0012] The industrial use of these substances is often exposed to these substances, ie, middle distillate-based lubricants, either continuously or for long periods of time, so that they cause tumors. Discovery has become a major concern.

Therefore, what is needed is a non-carcinogenic light industrial lubricant and the development of a process for its preparation.

[0014]

According to the present invention, there is provided an essentially non-carcinogenic light lubricant, and a method for producing the same. The process comprises an essentially non-tumorigenic effective amount of vacuum-distilled hydrocarbon of lubricating viscosity and an oncogenic atmospheric distillation having an initial boiling point of at least about 250 ° F (121 ° C). Consisting of a process of blending with a light hydrocarbon oil, the resulting blend is essentially non-carcinogenic and has an anti-friction viscosity.

It is therefore an object of the present invention to provide a light industrial lubricant which is essentially non-carcinogenic.
It is another object of the present invention to provide a method for producing a light industrial lubricant which is essentially non-carcinogenic.

[0016] Still another object of the present invention is to provide:
The purpose of the present invention is to provide a light industrial lubricant which does not cause skin irritation. It should be noted that other objects, viewpoints, and other advantages of the present invention can be easily understood by those skilled in the art by reading the following specification and claims.

[0017]

In order to obtain the non-carcinogenic light industrial lubricant of the present invention, it is possible to utilize a process stream from a conventional well-known purification process.
The light lubricant Putcess stream, which is most beneficial by the practice of the present invention, has an inherent tumorigenic level and has a boiling range of 121 ° C to 371 ° C (250 ° F to 700 ° F).
Is selected from the group consisting of: Such a hydrocarbon materials are known to have a hydrocarbon moiety of the essential C ₁₀ -C _20, are prepared only by atmospheric distillation,
Alternatively, it is produced by combining with other conventional processes, including gasoline-enhancing processes that produce middle distillate boiling range materials as by-products. Examples of such processes generally include heavy (non-gasoline) as a by-product.
Alkylation to produce alkylates. Other examples of useful hydrocarbon process streams include kerosene and light gas oil fractions used in specialty industrial lubricants. Streams produced by vacuum distillation following atmospheric distillation, either alone or in combination with other conventional lubricant purification steps, are also considered to belong to the category of materials that benefit from the process of the present invention. However, such hydrocarbon streams belong to the boiling point range of the having a hydrocarbon essential amounts of C ₁₀ -C _20, when the tests using experimental animals under standard evaluation process, essentially It has to be noted that it shows a typical level of tumor development. Such vacuum distillation materials include base stocks and spindle oils used as specialty oils and exhibit viscosities up to 40 SUS.

The present invention relates to a method of blending an effective amount of a heavier, higher boiling range hydrocarbon material with an oncogenic middle distillate, or reduced pressure distillation lubricant, resulting in a lightened oil. It is based on the discovery that it is possible to reduce the incidence of tumors to the extent that they are non-carcinogenic in nature. Such heavy, high-boiling hydrocarbon materials are produced by distillation of reduced-pressure crude oil under reduced pressure, and have a boiling point range of 316-5.
Includes materials that are at least 38 ° C (600-1000 ° F). Heavy hydrocarbon streams for which the practice of the present invention is beneficial are those that inherently contain hydrocarbon levels of C ₂₁ or higher,
Includes streams known as light neutral oil, intermediate neutral oil, heavy neutral oil and bright stock among those in the art. These streams that have been further processed by solvent treatment, hydroprocessing, etc., are considered process streams within the scope of the present invention. In the lubricating oil base stock containing C ₂₁ and higher hydrocarbons of 50% or more desirable in the practice of this invention, substantially consists of 100% of C ₂₁ and higher hydrocarbons, to reduce the level of aromatics It is even more desirable that the substrate is subjected to a solvent treatment or a vigorous hydroprocess treatment.

As noted above, the amount of heavy, high boiling range materials utilized in the light lubricant blends of the present invention is:
Refers to an amount in which the resulting blend with reduced tumorigenicity is essentially non-carcinogenic and effective enough to have an anti-friction viscosity.
The actual amount of material from which the resulting blend with reduced oncogenic properties is essentially non-carcinogenic and sufficiently effective to have an anti-friction viscosity will vary depending on the properties of the oncogenic light oil, but ultimately the amount when the lubricant resulting blend is comprised of at least about 20% of C ₂₁ and higher hydrocarbons have been found to be most desirable.

As will be appreciated by those skilled in the art, the upper limit for the above heavy materials will depend on the particular viscosity that is satisfied by the resulting blended product. Further, achieving the viscosity of a light lubricant may require starting with a somewhat lighter material and mixing the lighter lubricant with an effective amount of a heavy, higher boiling range material.

[0021]

The following examples illustrate the unexpected results obtained by the present invention. The invention will now be illustrated by the following non-limiting examples.

Example 1 The properties of the base component and light lubricant blend utilized in this example are as follows:

[0023]

[Table 1]

1. 1. Solvent treated base oil Not measured. The viscosity at 100 ° C (212 ° F) is 1
It turned out to be 30SUS. Not measured.

The test liquid A is a fine middle distillate light gas oil which has been hydrotreated and is used as a lubricant for cold rolling of aluminum. This boiling point range is 217-247 ° C (422-477 ° F) and consists of up to 10% aromatics having one or two rings. The balance of the hydrocarbon is straight chain, branched chain or cycloparaffin. Test fluid B is a furfural-treated bright stock base oil of the type used for blending engine oils used for automobiles and the like.

As is known to those skilled in the art, mice are the most desirable model for predicting the potential of a chemical compound to cause skin cancer in the human body.
To assess the carcinogenic and tumorigenic propensity of the above lubricating fluid, male C3H mice were obtained from the Bar Harbor Jackson Laboratory, Maine and were adapted to the test facility used in this experiment. Fifty healthy mice, approximately 8-9 weeks old, were assigned to each treatment group. One group of 50 animals was used as an untreated control group and another 50
A control group of animals was treated twice a week with 50 μl of 0.05% benzopyrene in toluene.

The mice were each placed in a stainless steel cage with a wire mesh at the front and bottom, each of 5 mice. The hair was cut from the back once every two weeks using an electric clipper. The test solution A was applied twice a week until the tumor appeared on the skin or for 80 weeks. At the time of application, 50 μl was applied to the back of the mouse at a time using a graduated pipette.

Test solution A and test solution B are 67% to 33%
The test solution C, blended in the ratio of 1, was applied 50 μl at a time, three times a week; thus, the same amount of test solution A was given to each mouse of the two test groups. Test liquid C was applied to the mice in that group as well.
The test was performed for 0 weeks or until a tumor was observed.
The mice were observed for 35 weeks after the application.

The state of the tumor in the application part was evaluated.
The evaluation tests included a biophase of the treated skin and weekly visual inspections performed during microscopic examination. If the tumor was large enough, or had become ulcerated and / or necrotic, the mice were killed prior to microscopic examination.

The results of the evaluation test are summarized in Table 2 for mice treated with test solution A, and in Table 3 for mice treated with test solution C. As can be seen by comparing the results in this table, mice treated with lubricant A developed much more tumors than mice treated with the blended liquid of A and B. It is not clear why this carcinogenic activity was reduced by Blend C solution, but given that all mice received the same amount of test solution A as described above, it is probably due to the interaction of competing biomolecules in the skin. And not just the result of dilution. The number of tumor-causing mice in the case of test solution A treatment was
There were 40 at week 04, of which 39 were found to be malignant. On the other hand, at the 104th week, four of the mice treated with test solution C developed skin tumors, three of which developed advanced tumors, and one of which remained benign. The average incubation period of test solution A is 76
The test solution C was 100 weeks.

In the mice treated with test solution A, skin irritation was always observed during the treatment. Intense skin effects, characterized by thickness and firmness with cracks and cracks, were found in almost all mice. In the case of the mice treated with the lubricant C, only slight peeling of the skin was observed. These results indicate that skin irritation and the incidence of tumors can be achieved by blending an effective amount of a non-tumorigenic, solvent-treated hydrocarbon oil of lubricating viscosity with a tumorigenic atmospheric distilled light hydrocarbon oil. The large decrease in the incidence strongly suggests that skin irritation is the primary cause of skin tumor development with the use of light industrial lubricants.

[0032]

[Table 2]

[0033]

[Table 3]

Example 2 The basic ingredients and blend properties used in the following examples are as follows:

[0035]

[Table 4]

1. 1. Solvent treated base oil Basic oil 3 consisting of C ₂₁ and higher hydrocarbons of about 50%. Not measured.

High Octane Blend The heavy alkylate material of Test Solution D, a by-product of stock alkylation, is commonly used in middle distillate diesel fuel / home heating oil refinery pools and is somewhat used in specialty oil blends. May be done. Heavy alkylates are usually 141-1
Boiling at 82 ° C. (285-360 ° F.), mainly C ₉
It is composed of hydrocarbon to C _12. On the other hand, the paraffinic light neutral oil of the test solution E is a 60 ¹¹ SUS furfural-treated inorganic oil (mineral oil) that boils in a boiling range of 327 to 391 ° C. (620 to 735 ° F.), and is mainly composed of C ₁₉ to C ₂₅ . It is composed of hydrocarbons. Test solution E was expected to contain about 50% C ₂₁ and higher hydrocarbons. When blended according to the test F ratio, the resulting liquid is available as a low water toxicity drilling mud oil that also functions as a fuel source on the drilling platform.

A test using a C3H laboratory mouse,
It was performed to determine the tumor incidence of sample F for the untreated group and the 0.05% benzapirene treated group. This was performed in essentially the same manner as in Example 1.

The results are shown in Table 5 below.

[0040]

[Table 5]

As described above, skin tumors were observed in the liquid application sites of the four mice. Three of these were benign (papilloma or keratoacansoma) and the other one was malignant. Of these, only one case could be observed without a microscope. Tumors occurred near the end of the mouse; the first tumors were observed
It was the 98th week of the test. The average incubation period was found to be 111 weeks. In contrast, in mice treated with 0.05 benzoapirene, about 80% or more of the mice developed skin tumors with an average incubation period of 43 weeks.

The heavy alkylate used to form the blend of Sample F is known to cause skin irritation, and it is expected that repeated exposure will cause skin tumors. By blending an effective amount of paraffinic light neutral oil with heavy alkylates, the resulting blend is less tumorigenic and essentially non-carcinogenic, reducing tumor incidence It turns out that it can.

Although the present invention has been described with reference to preferred embodiments, it will be readily apparent to one skilled in the art that modifications and variations can be made without departing from the spirit and scope of the invention. Will be understood. Such deformation
Changes are considered to be within the scope of the appended claims.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10N 30:00 30:02 70:00 (72) Inventor George Cruzan, New Jersey, USA 08551, Ringo's, Earl D. 3, Box 373 ( 72) Inventor Carl Robert McKeller, Blue Spruce Drive, Pennington, New Jersey, United States 08534, 5 (72) Inventor Joseph Jay Young, Warren, Stockade Load, 07060, New Jersey, United States 16 (58) Survey Field (Int.Cl. ⁷ , DB name) C10M 101/02

Claims (9)

(57) [Claims] 1. A a C ₂₁ or higher hydrocarbons at least 20%
An effective amount of a non-tumorigenic, vacuum-distilled hydrocarbon having a lubricating viscosity of from about 174 (345 ° F.) to about 371 ° C.
0 ° F) and a boiling point range of about 141 ° C (2 ° C).
85 ° F.) to about 182 ° C. (about 360 ° F.), wherein the non-tumorigenic vacuum distilled hydrocarbons are blended with an oncogenic, atmospheric pressure distilled light hydrocarbon oil selected from alkylates of about 360 ° F. Selected from neutral oil and bright stock; the resulting blend had anti-frictional viscosities; and long-term local administration experiments on a murine population showed that no more than 10% of the population had subcutaneous tumors A method for producing a non-carcinogenic light lubricant from a tumorigenic atmospheric distilled light hydrocarbon oil characterized by being non-carcinogenic, as can be seen from 2. The method of claim 1 wherein the vacuum distilled hydrocarbon is further processed to reduce aromatic hydrocarbon content. 3. The process according to claim 3, wherein the aromatic hydrocarbon content of the vacuum distilled hydrocarbon is reduced by a vigorous hydroprocess. 4. The method of claim 2, wherein the aromatic hydrocarbon content of the vacuum distilled hydrocarbon is reduced by solvent treatment. 5. The method according to claim 4, wherein the solvent used to treat the vacuum distilled hydrocarbon is furfural. 6. The vacuum-distilled hydrocarbon is at least about 50%
Including the C ₂₁ and higher hydrocarbons molecules The method of claim 2 wherein. 7. The vacuum-distilled hydrocarbon is at least about 75%
Including the C ₂₁ and higher hydrocarbons molecules The method of claim 2 wherein. 8. A non-carcinogenic light lubricant comprising at least about 2
Containing C ₂₁ and higher hydrocarbons molecules 0% The method of claim 1, wherein. 9. A non-carcinogenic light lubricant produced by the method of claim 1.