US2281648A - Process of producing a chlorinated mineral oil and the oil resulting therefrom - Google Patents
Process of producing a chlorinated mineral oil and the oil resulting therefrom Download PDFInfo
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- US2281648A US2281648A US57251A US5725136A US2281648A US 2281648 A US2281648 A US 2281648A US 57251 A US57251 A US 57251A US 5725136 A US5725136 A US 5725136A US 2281648 A US2281648 A US 2281648A
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- oil
- chlorine
- lubricating
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- chlorinated
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
Definitions
- Patented May 5, 1942 UNITED STATES PATENT OFFICE.
- My invention relates to lubricating oils and more particularly to a chlorinating process for producing an oil which is suitable particularly as an addition agent to an oil for lubricating machinery operating under conditions imposing ex-,
- Chlorine compounds are in some respects very desirable materials for incorporation in the mineral oils to improve their lubricating characteristics when the oils are used under extreme con- 40 ditions. While these chlorine compounds are of value in serving to protect the machinery by providing better lubrication, particularly under high pressure conditions, the use of such compounds isordinarily limited mainly by two factors. First, the chlorination compounds are al most invariably corrosive or become corrosive on standing, and in such condition their use is absolutely prohibited. Secondly, the chlorine compounds, particularly chlorine treated mineral oils are very apt to undergo a reaction in use with the formation of gums and resins.
- the chlorine compounds should become sufiiciently'active to provide the necessary lubrication not produced by the carrier oil.
- Another object is to provide an improved process for chlorinating a mineral oil such that the chlorinated oil wm be substantially free of corrosive and gum-forming characteristics.
- Still another object of theinvention is to provide an oil which when added to ordinary lubriqualities under ordinary operative conditions but when subjected to excessive high speed and pressure conditions, under which ordinary lubricatcating oil will possess only normal lubricating when chlorination is complete the cold chlorinated oil is mixed with alkali for example 30-35% by volume of a solution of 30-40 B.
- Corrosion-resisting materials are used while mixing and agitating the oil to prevent corrosive effacts which would otherwise be produced by the free chlorine and hydrochloric acid formed during chlorination.
- a small amount of air or other carrier gas is preferably blown throu h the oil during chlorination. This air serves the purpose of sweeping out free chlorine and gaseous hydrochloric acid generated during the chlorinating process, the oil having a tendency to foam when it approaches saturation with hydrochloric gas.
- a slight negative pressure instead of blowing with air might also be used to prevent foaming.
- Chloric acid gas carried away by the air is recovered by condensation or absorption methods to produce a high grade of technical hydrochloric acid of between 25 to concentration which constitutes a valuable and easily recovered by-product of this process.
- Chlorine used in the process may be recovered as 30% water solution of hydrochloric acid to the extent of 75% or more of such solution of hydrochloric acid on the basis of'the original chlorine used;
- This part of the process is known as the cooking ou of the oil, and has three main objectives.
- the combined chlorine may be rearranged and the molecule stabilized and the gumiorming compounds condensed and polymerized to form insoluble resins and gums which are then removed by suitable means, for example, centrifuging or filtering or simple decanting.
- the stabilizing of the oil is-apparently one of rearrangement rather than elimination of the chlorine for there is a loss of chlorine of usually only about rated into any desirablelubricating oil in the proper amounts .to give the pressure-carrying 5 properties desired. This may be determined by The chlorination of the oil is carried to the desired point, which may be determined by meas-- urement of the specific gravity of the oil at different times during the chlorination process.
- a specific gravity of 1.2 or greater results.
- the further chlorination proceeds the more efiective the final' material as a pressure carrying lubricant.
- m ate only to approximately 1.0 specific gravity or if other words, the chlorine appears to actmore efficiently.
- chlorination carried out below 50 R and preferably at about F., gives a more desirable product than one produced by chlorinating above 50 F.
- a lubri- 7o eating oil containing 5% of a base of 12% chlorine content, chlorinated below 50 R exhibited extreme Dressure'characterlstics far in excess or an oil containing an equivalent base chlorinated above 50 F.
- this base oil to be added to the ordinary lubricating oil may vary from of 1% 40' to 20%, although normally the amount is about 5% by volume of the ype of 1.00 sp. gr. chlorination.
- the mineral oil which I chlorinated was a light neutral oil having a Saybolt Universal viscosity of approximately 100 seconds at 100 F.
- oil may be made stable to temperature of about 350 F., although the break down point may be raised or lowered; for example to 400 E, or to 250 F., by the stabilizing treatment to produce one suitable for a specific use.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
Patented May 5, 1942 UNITED STATES PATENT OFFICE.
PROCESS OF PRODUCING A CHLORINATED THEBEFROM OIL AND THE OIL RESULTING Everett It. Wiles. Barnsdall. Okla, assignor to Bareco Oil Company, Tulsa, Okla., a corporation of Delaware No Drawing. Application January 2, 1936, Serial n 57,251
6 Claims. '(Cl. 260-654) My invention relates to lubricating oils and more particularly to a chlorinating process for producing an oil which is suitable particularly as an addition agent to an oil for lubricating machinery operating under conditions imposing ex-,
cessive lubricating requirements such as at unusually high speeds and high bearing pressures. Mineral oil lubricants have been developed to a high degree of efiiciency as lubricating agents but it is now apparent that certain types of ma-: m
chinery have come into use which are difficult to lubricate with any known refined mineral oil dinary oil film between the surfaces will brealn down or rupture allowing metal to metal'con-v tact. Various suggestions have been made for producing a lubricating oil having film characteristics suitable to meet these conditions usually present in machinery employing high speed and high bearing pressures. Such suggestions include the use of fatty oils and acids, the incorporation of elementary and combined sulphur, the use of various metallic soaps, either suspended or in solution in mineral oils, and the use of certain chlorine compounds added to the oil. Nearly all of these materials present some practical diflicult'y such as insolubility, abrasiveness and corrosiveness and furthermore their lubricative action under conditions of stress is not always satisfactory.
Chlorine compounds are in some respects very desirable materials for incorporation in the mineral oils to improve their lubricating characteristics when the oils are used under extreme con- 40 ditions. While these chlorine compounds are of value in serving to protect the machinery by providing better lubrication, particularly under high pressure conditions, the use of such compounds isordinarily limited mainly by two factors. First, the chlorination compounds are al most invariably corrosive or become corrosive on standing, and in such condition their use is absolutely prohibited. Secondly, the chlorine compounds, particularly chlorine treated mineral oils are very apt to undergo a reaction in use with the formation of gums and resins. This latter characteristic, unless controlled, is quite .detrimental from the lubrication standpoint because of the fact that the gums which settle out are' ditions of speed and load. Under extra/armdeposited in the gears and other movable parts of the machinery and interfere with its operation and cause these parts to-deteriorate because of lack of adequate lubrication. The chlorinating process of our invention is carried out in such a manner that these deleterious gums andresins are eliminated from the oil before it isused.
I have found that the undesirable corrosive characteristics of the chlorinated mineral oils result mainly from the instability of certain of the compounds formed during chlorination, and that certain other compounds are formed during this period with a stability making them desirable for use as base material for extra pressure lubricants.
It is very important that the stability or the chlorine compounds be exactly gauged, that is.,
they must be stable enough to stand storage without change and yet the stability must not be so great as to prohibit change under conditions which would give film rupture of the carrier oil. Under the latter conditions the chlorine compounds should become sufiiciently'active to provide the necessary lubrication not produced by the carrier oil. In other words, the material which is added to the ordinary lubricating oil to give it the necessary extra lubrica' quali= ties must of itself bea good lubricant, d must be stable. under certain conditions, non corrosive and non-gumming. It should be present pref erably in onLv small quantities and should even then not develop characteristics other than those of a normally good lubricant under ordinary con conditions, however, such as excve load and high temperature which cause the ordinary lub-' ricating oil to break down with-resultant film rupture and failure of the bearing, this added material should become operative and supply the additional necessary lubrication or other effect to protect the bearing. The chlorinated oils of our invention possess these desirable characteristics.
at extremely high speeds and pressures and un- W are at Present considered ext'remelubricating conditions.
Another object is to provide an improved process for chlorinating a mineral oil such that the chlorinated oil wm be substantially free of corrosive and gum-forming characteristics.
Still another object of theinvention is to provide an oil which when added to ordinary lubriqualities under ordinary operative conditions but when subjected to excessive high speed and pressure conditions, under which ordinary lubricatcating oil will possess only normal lubricating when chlorination is complete the cold chlorinated oil is mixed with alkali for example 30-35% by volume of a solution of 30-40 B.
. gravity caustic soda. This alkali causes a subing oil will fail and cause deterioration of the 5 machinery, will provide sufiici'ent extraordinary lubrication or other eflect to prevent such deterioration.
In accordance with my invention I have developed a process for treating mineral oil in such 1 a manner that it will possess all of the desired characteristics described above, so that when it is added in desired amounts to an ordinary lubricating oil the resulting mixture will fulfill stantial neutralization of the acids contained in he oil and also serves to remove the excess chlorine and HCl present. Next, the chlorinated oil and alkali is agitated and heated to approximately 200 R, which temperature is maintained for quite a number of hours, depending upon the type of oil being used, but usually sixty to seventy all of the requirements for lubrication of mal chinery operating under normal conditions and also under unusually high speed and high pressure conditions. In general my process comprises, as the first step, passing chlorine into a suitable neutral mineral 011 while the latter is constantly agitated and maintained at a relatively low temperature, preferably below-50 F.
Corrosion-resisting materials are used while mixing and agitating the oil to prevent corrosive effacts which would otherwise be produced by the free chlorine and hydrochloric acid formed during chlorination. A small amount of air or other carrier gas is preferably blown throu h the oil during chlorination. This air serves the purpose of sweeping out free chlorine and gaseous hydrochloric acid generated during the chlorinating process, the oil having a tendency to foam when it approaches saturation with hydrochloric gas. A slight negative pressure instead of blowing with air might also be used to prevent foaming.
Thehydrochloric acid gas carried away by the airis recovered by condensation or absorption methods to produce a high grade of technical hydrochloric acid of between 25 to concentration which constitutes a valuable and easily recovered by-product of this process. Chlorine used in the process may be recovered as 30% water solution of hydrochloric acid to the extent of 75% or more of such solution of hydrochloric acid on the basis of'the original chlorine used;
hours.
This part of the process is known as the cooking ou of the oil, and has three main objectives. First, the complete neutralization of the oil; second, production of exactly the proper stability of the oil, and third, removal of compounds that would form gums when the oil is used. By this operation the combined chlorine may be rearranged and the molecule stabilized and the gumiorming compounds condensed and polymerized to form insoluble resins and gums which are then removed by suitable means, for example, centrifuging or filtering or simple decanting. The stabilizing of the oil is-apparently one of rearrangement rather than elimination of the chlorine for there is a loss of chlorine of usually only about rated into any desirablelubricating oil in the proper amounts .to give the pressure-carrying 5 properties desired. This may be determined by The chlorination of the oil is carried to the desired point, which may be determined by meas-- urement of the specific gravity of the oil at different times during the chlorination process. The
specific gravity, of course, increases as the chlori-' '50 nation proceeds and the further the chlorination proceeds the more efi'ective is the final material as a pressure-carrying lubricant.
In certain cases it may be desirable to chlorin-.
desired chlorination may be carried out until a specific gravity of 1.2 or greater results. As a general rule the further chlorination proceeds the more efiective the final' material as a pressure carrying lubricant. By this is meant thatnot only less of the base ma erial is necessary to produce a certain result-but actually less total chlorine in the final blended material is needed. or m ate only to approximately 1.0 specific gravity or if other words, the chlorine appears to actmore efficiently.
l. have also round that chlorination carried out below 50 R, and preferably at about F., gives a more desirable product than one produced by chlorinating above 50 F. For example, a lubri- 7o eating oil containing 5% of a base of 12% chlorine content, chlorinated below 50 R, exhibited extreme Dressure'characterlstics far in excess or an oil containing an equivalent base chlorinated above 50 F.
the use-of any standard type testing apparatus, such as the Almen, Timken, or Floyd machines. The amounts of this base oil to be added to the ordinary lubricating oil may vary from of 1% 40' to 20%, although normally the amount is about 5% by volume of the ype of 1.00 sp. gr. chlorination. i
In one specific embodiment of the process of my invention, the mineral oil which I chlorinated was a light neutral oil having a Saybolt Universal viscosity of approximately 100 seconds at 100 F.
While any' other similar starting material would do as well from the standpoint of'extra pressure lubrication, I found that this oil is suitable from the standpoint of practical operation and manufacture. The oil, which had originally a specific gravity of .89 was run into a wooden tank and chlorine introduced into the oil at the bottom of the tank close to a mechanical agitator. The temperature of the oil was maintained by means of cooling coils between-30 F. and F. Chlorination was continued until the oil attained a specific gravity of 1.15. Such an oil has a chlorine content of approximately 25%. Approximately 1% of this product was found to be equivwas then heated to 200 F. and "cooked for apbricating oil and thus assist-in anemia ated indicating the upper stabilized limit. The
oil may be made stable to temperature of about 350 F., although the break down point may be raised or lowered; for example to 400 E, or to 250 F., by the stabilizing treatment to produce one suitable for a specific use.
I found that the resulting chlorinated oil from this illustrative treatment had been so modified or rearranged with particular regard to the chlorine compounds that they were in a stable form when subjected to ordinary conditions of lubrication but were sufllciently unstable at abnormal conditions of lubrication to become eflecprising chlorinating the oil at a temperature less than 50 F., neutralizing the acids inthe chrinated oil by mixing the'oil with an alkali solution, stabilizing the oil by heating it with alkali until practically all or the gums and resins settle out, and removing said gums and resins from the oil. p v
2. A process for chlorinating mineral oils to increase their lubricating efiiciency whicnconi0 sists in passing chlorine into a neutral mineral dro'chloric acid gas form 011 during constant agitation oi the oil, maintaining the oil at a temperature between F. and 50 F., blowing air throughthe oil during agitation to remove the excess chlorine and hyd during the chlorinating treatment 7 and treating the resulting chlorinated oil with an alkali by heating for a number of hours.
3. The process for producing an extra pressure lubricant consisting or chlorinating a min eral on, cooling the oil during chlorination to maintain the temperature below 50 F., neutralizing the oil with an alkaline substance, heating the oil and alkaline substance for severalhours at approximately 200 '1". to establish the desired tive in facilitating lubricationand preventingmetal to,metal contact.- Thus, they provide excellent lubrication under normal as well as high speed, high temperature, and high pressure conditions necessary for operation in many modern types oi machinery;
While I do not wish to limit myself to any theory, I believe that the unusually good lubricating qualities of the oil produced by my inventive process may result irom the fact that stability of the oil and to condense and polymerize the gums and resins filtering the stabilized oil, and adding the filtered oil to an .ordinary lubricating oil in such amounts that the filtered 30 oil constitutes from approximately V 0! 1% to 20% 01 the total weight oi "the oil. 4. A stabilized chlo ted neutral hydrocarbon lubricant suitable for use as a high pressure lubricating base andproduced by chlorin-.
3:5 ating a mineral oil while maintaining the temthe especially prepared. base oil which is .added to the ordinary lubricating oil remains practically inert under ordinary operating conditions but under extraordinary conditions, such as those 01' high temperature and high pressures, this base oil becomes operative and breaks down to some slight extent. locally and at pointsot high temperature, liberating chlorine which combines with the material 01' the bearing. This may 'form' a protective co'at which is highly retentive for lu-' preventing the perature oi the oil below 50 F., heating the oil for a prolonged period in the presence of an alkaline substance to a temperature approximately of 200 1 and removing polymerized gums and 40' resins.
5 of the oil below 1''.
failure or the bearings and associated parts.. As
soon as the extraordinary condition period has passed the base all again assumes its function or a normal lubricant without further liberation of chlorine.
It is to be understood that my invention is not limited to the specific processes described above by way 01 example, but is susceptible to various changes and modifications, the scope of which is limited only by the following claims.
What I claim is:
' 5. A stabilized chlorinated neutral hydrocar bon lubricant suitable for use as'a high pressure lubricating base and produced by chlorinating a mineral oil whilemaintaining the temperature heating the oil for a period oi about sixty to seventy hours in the presence oivan alkaline substance to a temperature 01' approximately 200 F. and removing polymerized gums and resins.
the oil during chlorination to maintain the temperature below 50 1 L, neutralizing the oil with an alkali, heating the oil and alkali iorja period of about sixty to seventy hours at approximately 1. The process of preparing a mineraloil suit- I able for lubricating machinery under normal operative conditions and also under conditions of extremely high temperature and pressure, "com- 200 1". to condense and polymerize the gums and resins in the oil. and to establish the desired stability of the oil, and filtering the stabilized oil.
EVERETT R. WILES.
s. a process for .producing a lubricating on consisting o! chlorinating a mineral oil, cooling
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US57251A US2281648A (en) | 1936-01-02 | 1936-01-02 | Process of producing a chlorinated mineral oil and the oil resulting therefrom |
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US57251A US2281648A (en) | 1936-01-02 | 1936-01-02 | Process of producing a chlorinated mineral oil and the oil resulting therefrom |
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US57251A Expired - Lifetime US2281648A (en) | 1936-01-02 | 1936-01-02 | Process of producing a chlorinated mineral oil and the oil resulting therefrom |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2664173A (en) * | 1949-08-05 | 1953-12-29 | Horace E Karig | Method of and apparatus for lubrication and cooling of surfaces |
-
1936
- 1936-01-02 US US57251A patent/US2281648A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2664173A (en) * | 1949-08-05 | 1953-12-29 | Horace E Karig | Method of and apparatus for lubrication and cooling of surfaces |
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