US1999212A - Lubricating oil - Google Patents

Description

Patented Apr. 30, 1935 LUBRIOATIN G OIL John E. Schulze, Chicago, 111., assignor to Red River Refining Company, Inc., Chicago, 111., a

corporation of Louis iana No Drawing. Application August 24, 1931,

Serial No. 559,120

19 Claims. (01.196-151) This invention relates to lubricating oils; and

it relates more particularly to novel lubricating oils, especially those produced from paraflin base crudes, which are obtainable by the process disclosed and claimed in this applicant's prior application, Serial No. 544,931, filed March 18, 1922 (now Patent No. 1,448,709, March 13, 1923), and which are also disclosed in applicant's prior copending application Serial No. 624,826, filed March 13, 1923, of both of which prior applicationsthe present application is a continuation in part.

In, said prior Patent No. 1,448,709 there was disclosed a novel process of distilling petroleum, distillates and residua under very low absolute pressure and under non-oxidizing conditions, the distillation pressure most desirably being maintained as low as 2 to 4 millimeters mercury absolute and not exceeding 25 millimeters mercury absolute as a practical maximum. Said process enables the production of novel distillates, particularly lubricating oil distillates, that are characterized by narrow viscosity range and boiling point or distillation range, as well as by other desirable properties such as excellent color, and freedom from tarry and asphaltic constituents. The process by which these novel products can be obtained, as well as apparatus suitable for carrying out the process, were fully disclosed in said prior application. Said process and novel products were also claimed therein both broadly and specifically, the specific claims being, however, directed more especially to the novel products derived from naphthene base petroleum. Said prior application also disclosed novel products derived from paraflin base petroleum, but by 0111- cial requirement it was required that claims to the paraffin base products be divided out. Said application Serial No. 624,826 was therefore filed and directed more-particularly to such paramn base products; As stated in said prior application SerialNo. 544,931, the novel process described therein is also applicable to the treatment of topped or stripped crudes and still bottoms of paraflin base origin; but in order to treat such paraifin wax content which comes over during the entire distillation. One method of removing paramn from the distillates is by centrifuging, although it is to be understood that other methods f m duce commercial products commonlyknown to starting materials commercially it is necessary, to make spscial provision for the removal of the the trade as *100 Pennsylvania Neutral, 200 Pennsylvania Neutral, etc. according to the particular viscosity of the commercial grade in question; the highest viscosity known to the trade in this series being 220 seconds at100 F. The still 5 Saybolt Universal (at 100 F.), and even ashigh as 180 seconds Saybolt at 210 F. Moreover, the

color or these overheadzdistill'ates is far superior to prior commercial lubricating oils of comparable viscosity, the color of the new products of viscosity as-high as 1200 seconds (at 100 F.)

ranging from 2 to 5 N. P. A. just as the distillates come over and without any further refining treatment. These novel products are also of exceptionally high flash and fire test and are free of tarry matter, giving no precipitate with the standard precipitation test. This test, as is well known, consists in shaking -a measured quantity of the oil with a measured quantity of a known solvent such'as gasoline and allowing the mixture to stand for a definite length of time. Furthermore the novel products show an exceptionally low carbon residue by the Conradson carbon test.

The residuum or still bottoms remaining after distillation of the novel lubricating oils in accordance with the novel process is an extremely heavy cylinder stock of a viscosity that may be as high as 250 seconds Saybolt (at 210 F.) with a flash point of 630 F. and 700 F. fire test never having been obtained heretofore except by cracking and wasting lubricating fractions which are now obtainableby the process of said Patent 1,448,709 as finished overhead lubricating oil distillates.

For the sake of illustration examples of certain new paramn base lubricating oils that are typical of those comprised in the invention will now be given, but it is to be understood that the. inveni tion is; not limited to these specific oils. Data will be given first for two typical light motor oils corresponding to established commercial grades known as 150 viscosity and 200 viscosity, and comparative data will be given for the best obtainable corresponding oils of the prior art. It is to be understood that a variation of about 5 seconds plus or minus from a commercial viscosity grade is customarily permissible so that in referring to a 150 viscosity oil, for example, this is to be taken as approximate and as including a range of 145 to 155 viscosity in practice.

the novel lubricating oils having a viscosity of 150 seconds (at 100 F.) or less leave a Conradson carbon residue of from 0.005 to 0.015 per cent; while those whose viscosity approaches 200 sec- Parafiflnbase onds leave a carbon residue of from 0.01 to 0.03

per cent. New 0118 P5130113 It may be noted that the novel oils of the vis- (been cosities given in the above tables are ideal starting material for the manufacture of white 15%viscrgsit type a1 31 medicinal oils, and that the medicinal oils regg i i ig g' m 5, 540 SW sulting from the use of these starting materials 18 l B 1011 range A 2 to 5mm absolute) 50 F 0m R are in themselves novel and readily distinguish comm as. 0150: 10475. able by their physical constants from white me- Color (N. P. A. Flash point F W F, cncinal oils heretofore lrnown. Ihese new medici Fire point g9? g 5 m nal oils are not however specifically claimed in gg g ggg the present application.

Gravity As illustrating the character of typical novel Viscost an c at 100 F.) lmsec Over000sec. Di(stilliat i o n rings b 1 be) W F 0 140 F parafiin base 011s of higher viscosities (1. e. above At2to5mm.a S011 V81" oomdson who 033% 037% 0 e ond aybolt at 100 F.) that are also Color (was).-. i lg figcomprisedwithm the present invention, data of g fgg l if a series of such oils (medium, heavy and extra cold 25 heavy) of different typical viscosities is given below:

I Conradson Baum Viscoslty(at 3, i -fi a}? Color car 11 gravity F.) o F 0 F c F N. P. A residue P810915 30.0 250 450- 510 25 2.0 0.05 29.5 300 465 525 25 2.0 0.00 no 4a; 4a) sec 25 2.5 0.03 zas 000 500 500 25 2.5 010 2&0 800 510 s70 25 as 0.15 2&4 1000 520 580 2a 3.0 0.20 2s.0 m0 540 000 25 3.0 0.25

By theterm viscosityrange, as herein employed is to be understood the difierence in via-:

, cosity between the first 10% traction and the last 10% fraction obtained by distilling a sample of the oil at or below 5 (e. g. at from 2 to 5) millimeters mercury absolute pressure and under non-oxidizing conditions. While this viscosity range is always much narrower for the new oils than for the oils of the prior art, it is not to be inferred that it must necessarily be as narrow in all cases as in the specific examples given above. For example, in the case of a novel 150 viscosity oil, the viscosity range may even be as great as 420 seconds while still being sharply differentiated from the prior art oils of this commercial grade, while on the other hand a viscosity range as low as 65 seconds is obtainable. Similarly a viscosity range of as much as 500 seconds for a novel oil of the 200 viscosity type is still within the scope of the invention although ordinarily such oil is characterized by a much narrower viscosity range, say, 50 to 100 seconds. In the same way, the distillation ranges of 50 to 60 F. above specifled for the novel 150 and 200 viscosity oils are not to be understood as limiting, a range of from 15 to 75 F. in oils of these types being permissible within the scope of the invention; but ranges of from 25 to 75 R, and especially 0! from 25 to 60 F., are more particularly representative. Likewise the carbon residue by the Conradson test may in some cases be as much as 0.02% for the 150 viscosity oil and as high as 0.04% for the'200 The typical oils of which the physical constants are shown in this last table are strictly straight run overhead distillates, a fact that cannot be too strongly emphasized, since it radically and fundamentally distinguishes them from prior art oils of corresponding vlscosities, all of which have heretofore been manufactured by blending with a heavy cylinder stock or still bottoms enough of a lighter overhead lubricating distillate to obtain the viscosity called for by commercial specifications. Accordingly I such prior art commercial oils having viscoslties exceeding 220 seconds (at 100 F.) have in every instance been characterized by exceedingly wide viscosity and distillation ranges, which have been inherently essential characteristics of these oils. The color of these prior art oils has also been relatively poor because of the necessity for including the heavy cylinder stock in blending, this cylinder stock being usually of a very dark color. Furthermore the Conradson carbon test of these blended oils is always relatively high, the figure necessarily depending upon the percentage of the cylinder stock employed in the blend. In such blended oils the Conradson carbon customarily runs from a minimum of about 0.20% for a 250 viscosity oil to a maximum of well over 1% for heavier viscosities; In contrast to this, oils of the present invention whose viscosities are from 220 seconds up to 400 seconds, or even as high as 800 seconds (at 100 F.) leave a carbon residue by the Conradson carbon test usually not exceeding 0.15 per cent, and in some cases not exceeding 0.01 per cent. Those whose viscosities lie between 400 9.1111600 seconds commonly leave a Conradson carbon residue of from 0.015 to 0.15 per cent. For those having viscosities between 600 and 900 seconds the residue usually is from .from 0.5 to 0.9 per cent; and of viscosity between 130 and 180 seconds, a residue of from 0.8 to 1.2 per cent. In every case, these figures are far helowv those for previously known oils of corresponding viscosity. It may be noted here that a viscosity of 900 seconds Saybolt Universal at 100,

F. is equivalent to 75 seconds Saybolt Universal at 210 F.

The table above given shows that other physical constants of the aforesaid new oils of viscosities higher than 220 seconds (at 100 F.) also sharply distinguish them from the blended oils of the prior art. It is not-to be understood that the new oils are limited to the particular viscosity specified since these are only typical cuts obtainable by the newprocess. Taking the specific cuts given in the table, the viscosity range (1. e.

" the difference in viscosity between the first and last 10 per cent fractions obtained by distilling a sample) for any one of these oils does not ordinarily exceed 150'seconds Saybolt Universal of these types, and a viscosity range of between 50 and 250 seconds (at 100* F.) characterizes most of them. It is of course permissible within the invention tocombine a number of the above cuts given in the table into a single cut, or into two or more. Even if all the distillates given in the last table were to be combined into a single cut, the viscosity range of this cut would in practice be not more than about 1200 seconds which is very much less than the lowest viscosity range possible in the best oils of comparable viscosities heretofore known in the art.

It is to be. noted also that, like the lighter oils -given in the first table, all the new heavier hereinabove mentioned oils also distill over substantially completely (1. e. 98%) without substantial cracking at or below (e. g. 2 to 5) millimeters mercury absolute pressure and under nonoxidizing conditions, without exceeding about 650 F. as a maximum distilling temperature or end point, the minimum end point for novel oils of this type under such conditions being about 450 F. When the prior art blended oils are subjected to distillation under these'conditions,

on the other hand, they do not distil over sub-- stantially completely, but on the contrary a very substantial percentage remains as a residuum, the amountof this residuum depending upon the amount of heavy cylinder stock employed in the blend. Expressed generally, the amount 'of a prior art blended oil that will distil over under these conditions can beexpressed by the formula A+60% (approximately) of B, where A is the proportion of light overhead and B is the proportion of heavy cylinder stock used in the blend. This is evidently another convenient standard viscosimeter. This figure is in fact the mean or average viscosity of the oil in question. This should be distinguished from the viscosity range of the some oil which is hereinabove defined'and is used also in certain of the appended claims to aid in defining the novel oils of the invention.

What I claim is:

1. As a new article of manufacture, a straight overhead parafiln base lubricating oil distillate having a viscosity of not less than approximately 150 seconds Saybolt Universal (at 100 F.), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25 millimeters of mercury, without acid treatment or filtration, and being further characterized by the fact that a sample thereof distils substantially completely at from 2- to 5 millimeters mercury absolute pressure and under non-oxidizing conditions between temperatures difiering only by from about 25 to 75 F.

2. As a new article of manufacture, a straight overhead paraflin base lubricating oil distillate having a viscosity of not less than 150 seconds Saybolt Universal (at 100 F.) said distillate being a high-grade finished lubricating oil product bbtained directly by high vacuum distillation at absolute pressure not exceeding 25 millimeters of mercury, without acid treatment or filtration, and being further characterized by the fact that when a sample of said oil is substantially completely distilled under an absolute pressure of from 2 to 5 millimeters of mercury and under non-oxidizing conditions, the first ten per cent fraction and the last ten per cent fraction of the distillate differ in viscwity only by from about 50 to 250 seconds Saybolt Universal (at 100 F.)

3. As a new article of manufacture, a straight overhead parafiln base lubricating oil distillate having a viscosity of at least about 200v seconds Saybolt Universal (at 100. F.)', said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25 millimeters of mercury, Without acid treatment or filtration, and leaving a carbon residue by the Conradson carbon test of from 0.01 to about 0.04 per cent.

4. As a new article of manufacture, a straight overhead paraifin base lubricating oil distillate having a viscosity approximating 200 seconds Say bolt Universal (at 100 F.) said distillate leaving a carbon residue by the Conradson carbon test of from. 0.01 to 0.03 per cent, said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25 millimeters of mercury, without acid treatment or filtration, and being further characterized by the fact that a sample thereof distils substantially completely at from 2 to 5 millimeters mercury absolute pressure and under non-oxidizing conditions between temperatures diifering by from 25 to about F., the first ten per cent fraction and the last ten per cent fraction of the sample difiering in viscosity by from 50 to about seconds Saybolt Universal (at 100 F.).

5. As a new article of manufacture, a straight overhead parafiln base lubricating oil distillate having a viscosity higher than 220 seconds Savbolt Universal (at 100 F.) said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25- millimeters of mercury, without acid treatment or filtration, and

being further characterized by the fact that a sample thereof distils substantially completely at from 2 to 5 millimeters mercury absolute pressure under non-oxidizing conditions with a maximum distilling temperature or end point of from 450 to 650 F.

6. As a new article of manufacture, a straight overhead parafin base lubricating oil distillate having a viscosity lying between 220 and 400 seconds Saybolt Universal (at 100 F.) said dis-' tillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not substantially exceeding millimeters of mercury, without acid treatment or filtration, and leaving a carbon residue of from about 0.01 to 0.15 per centby the Conradson carbon test.

7. As a new article of manufacture, a straight overhead paraifin base lubricating oil distillate having a viscosity lying between 400 and 600 seconds Sayboit Universal (at 100 F.), said distillate being a high-grade finished lubricating oil product obtaineddirectly by high vacuum distillation at absolute pressure not substantially exceeding 25 millimeters of mercury, without acid treatment or filtration, and leaving a carbon residue of from about 0.015 to 0.15 per cent by the Conradson carbon test.

8. As a new article of manufacture, a straight overhead paraflin base lubricating oil distillate having a viscosity lying between 600 and 900 seconds Saybolt Universal (at 100 F), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not substantially exceeding 25 millimeters of mercury, without acid treatment or filtration, and leaving a carbon residue of from about 0.05 to 0.25 per cent by the Conradson carbon test.

9. As a new article of manufacture, a straight overhead parafin base lubricating oil distillate having a viscosity lying between and seconds Saybolt Universal (at 210 F), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not substantially exceeding 25 millimeters of mercury, without acid treatment or filtration, and leaving a carbon residue of from 0.2 to 0.6 per cent by the Conradson carbon test.

10. As a new article of manufacture, a straight overhead parafiin base lubricating oil distillate having a viscosity lying between 100 and seconds Saybolt Universal (at 210 F.), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum.

distillation at absolute pressure not substantially exceeding 25 millimeters of mercury, without acid treat-mentor filtration, and leaving a. carbon residue pf from 0.5 to 0.9 per cent by the Conradson carbon test. 7

11. As a new article of manufacture, astraight overhead paraflin base lubricating oil distillate having a viscosity lying between 130 and 180 seconds Saybolt Universal (at 210 F.) said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not substantially exceeding 25 millimeters of mercury, without acid treatment or filtration, and leaving a carbon residue of from 0.8 to 1.2 per cent by the Conradson carbon test.

12. As a new article of manufacture. a straight overhead parafiin base lubricating oil distillate having a. viscosity exceeding 220 seconds Sayaecaam bolt Universal (at 100 F), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation without acid treatment or flltration, and being further characterized by the fact that when a sample of said oil is distilled under an absolute pressure of from 2 to 5 millimeters of mercury and under non-oxidizing conditions, the first ten per cent fraction and the last ten per cent fraction differ in viscosity by from about 50 to 1200 seconds Saybolt Universal (at 100 F.).

13. As a new article of manufacture, a straight overhead parafiin base lubricating oil distillate having a viscosity of at least about 220 seconds Saybolt Universal (at 100 EU, said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation without acid treatment or filtration, and being further characterized by the fact that when a sample of said oil is distilled under'an absolute pressure of from 2 to 5 millimeters ofmercury and under non-oxidizing conditions, the first ten per cent fraction and the last ten per cent fraction differ in viscosity by from about 50 to v seconds Saybolt Universal (at 100 F.).

14. As a new article of manufacture, a straight overhead parafiin base lubricating oil distillate having a viscosity of not less than approximately 150 seconds Saybolt Universal (at 100 F.), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25 millimeters of mercury, without acid treatment or filtration, and being further characterized by the fact that a. sample thereof distils substantially completely at from 2 to 5 millimeters mercury absolute pressure and under non-oxidizing conditions between temperatures difl'ering only by from 50 to 75 F.

15. As a new article of manufacture, a straight overhead paraffin base lubricating oil distillate as defined in claim 2, the first and last ten per cent fractions of the distilled sample diii'ering in viscosity only by about 100 seconds Saybolt Universal (at 100 F.).

16. As a new article of manufacture, a straight overhead parafiin base lubricating oildistillate having a viscosity of at least about 150 seconds Saybolt Universal (at 100 F.), said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25 millimeters of mercury, without acid treatment or filtration, and leaving a carbon residue by the Conradson carbon test of from about 0.015 to 0.02

per cent.

1'7. As a new article of manufacture, a straight overhead paraflln base lubricating oil distillate as defined in claim 16, leaving a Conradson carbon residue of about 0.015 per cent.

18. As a new article of manufacture, a straight overhead parailin base lubricating oil distillate having a viscosity of at least about 200 seconds Saybolt Universal (at 100 1?), said distillate being a. high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressure not exceeding 25 milli- .meters of mercury, without acid treatment or filtration, and leaving a carbon residue by the Conradson carbon test of from about 0.03 to about 0.04 per cent. 1

19. As a new article of manufacture, a straight leaving a carbon residue by the Conradson carbon test of from about 0.03 to 0.04 per cent, said distillate being a high-grade finished lubricating oil product obtained directly by high vacuum distillation at absolute pressurev not exceeding 25 millimeters of mercury, without acid treatment or filtration, and being further characterized by the fact that a sample thereof distlls substantially completely at from 2 to 5 millimeters ab,-

solute pressure and under non-oxidizing conditions between temperatures differing by from about 60 to about 75 F., the first ten per cent fraction and the last ten per cent fraction of the sample differing in viscosity by from about 100 seconds to 500 seconds Saybolt Universal (at 100 F).

JOHN E. SCHULZE. I