US2466632A - Carbon remover and metal surface cleaning composition - Google Patents

Description

Patented Apr. 5, 1949 orrlca CARBON REMOVER AND METAL SURFACE CLEANING COMPOSITION Ben Box-us, St. Louis, Mo., assignor to Shell Development Company, San Francisco, Call! a corporation of Delaware No Drawing. Application May 5, 1947, Serial No. 746,153

3 Claims. (CL 252-118) This invention relates to the removal of undesirable foreign deposits from metal surfaces. More particularly this invention pertains to the removal of hard carbonaceous materials, resins, varnish, lacquers, rust, abrasives, welded metal particles, and the like, from engines, turbines, industrial equipment and the like by applying thereto a novel chemical composition, each component thereof being within rather specific proportions, said composition having the ability of penetrating through the deposit, loosening it and facilitating in removing it from the metal surface, leaving the engine or other metal surfaces clean and undamaged.

The development of high power engines operating at relatively very high temperatures and heavy loads, such as internal combustion engines,

Diesel engines, gasoline aircraft engines, jet

engines, form, during their operation, carbon and sludge deposits which cause sticking, clogging, and wear of movable parts. This results in wear and corrosion of engine parts, and generally reduces the operating efliciency of the engine.

Present developments in gas turbine engines which operate at such elevated temperatures as from 1100 F. to 1800 F. greatly accentuate this problem. Thus, gas turbine engine parts such as the compressor blades and turbo-jet units such as turbo-super charged engines as well as other industrial units such as heat exchange elements, torque converter transmissions, air and gas compressor valves, etc., become coated within relatively short periods of time with thick layers of carbonaceous and other foreign deposits which must be removed. These deposits adhere so tenaciously to the surface that the only way to remove them at present is by hand scraping or by soaking in chemical solutions for long periods of time. Such drastic treatment usually results in damage caused by corrosion or pitting of the treated metal surface due to the chemical nature of the material used to remove the deposits, swelling or destruction of insulating and non-metallic parts, andchipping or cracking of metal surface due to hand scrubbing and cleaning. In addition present known deposit removers are highly toxic due to their high content of 2 phenolic and/or halogen-containing materials which are a hazard and are detrimental to the health of the user. Known deposit removers also introduce a fire hazard problem due to the fact that such materials have low flash points but are only effective at elevated temperatures.

It is an object of this invention to provide a cleaning and deposit-removing composition which can be easily and readily applied to heavily carbon-coated metal surfaces at room or at slightly elevated temperatures and leave the surface clean and rust proofed. It is another object of this invention to provide a cleaning composition which is non-corrosive to the metal being cleaned and which is non-reactive with nonmetallic parts with which it might come in contact. Still another object of this invention is to provide a cleaning composition which is safe to use within a relatively wide temperature range, and is non-toxic.

The above and other objects may be attained in accordance with the present invention by admixing, with a suitable hydrocarbon base, certain chemically active ingredients in rather specific proportions, each of which exerts a specific function and a co-ordinating one with the composition taken as a whole which results in a potent cleaning composition. The active ingredienm of this invention comprise a hydrocarbon base admixed with specific types of detergent, wetting and coupling agents, a penetrant and water, all of which are essential. A criteria of compositions of this invention is that all ingredients which comprise it must be present at all times and in relatively specific proportional relationship to each other.

The base comprises essentially a hydrocarbo having a boiling point above that of room temperature and up to boiling temperatures of mineral lubricating oil fractions. The selection of the type of hydrocarbon base to be used depends primarily upon the intended use of the composition. Thus, if the composition is to be used mainly as a carbon remover, a relatively light petroleum hydrocarbon fraction, such as kerosene, is preferred, although mineral seal oil, gas oil, various petroleum naphtha cuts, mineral 4 amounts varying from 2 to 15% and generally is kept between about 4 to 8% by weight.

The function of a good penetrant is to penetrate through interfering layers of deleterious materials and loosen them from the surface to which they adhere. To accomplish this a penetrant must possess low degree of volatility, low surface tension and high capillary or creeping properties so that once having penetrated as a mineral lubricating oil should be used. The

amount of base used can vary from between about 12% to about 50% by weight, and preferably between about 12% and 20% by weight of the composition.

Detergents of this invention function both in a chemical and physical manner. help to keep finely divided carbon and resinous particles formed during operation of internal combustion engines, turbines and the like or deposits already formed but loosened from a surface by suitable means, in a state of suspension thereby preventing their adherence to or buildup on a surface. This is due to the adsorptive action of the detergents, making the carbon particles and other deleterious matter with which they. come in contact large enough and light enough so that their settling rate is greatly retarded and therefore they tend to remain in suspension. with other constituent materials of this invention so as to aid in loosening and removing deposits from surfaces and at the same time not interfere with the activity of other additives present. They are also thermally stable, resist oxidation and attack by active corrosive materials.

It has been found that only a limited number of detergents have the above properties when employed in conjunction with other additives of this invention. Broadly they include the amine and ammonium salts of organic and inorganic acids, as well as the alkali metal salts thereof. They can best be formed by combining salts of primary, secondary and tertiary amines containing from about 8 to about 20 carbon atoms, e. g. octyl, nonyl, undecyl, stearyl, dibutyl, diamyl, dioctyl, didecyl, triethyl, tributyl amines; alkylolamines, e. g. mono-, diand triethanolamine, diethylethanolamine, dimethylethanolarnine, monoethylethanolamine, phenylethanolamine, phenyldiethanol amine, ethyl phenylethanolamine, mono-, diand-triisopropanolamine; heterocyclic amines, e. g. morpholine, methyl morpholine, ethyl morpholine, phenyl morpholine; cyclic amines, e. g. cyclohexylamine,dicyclohexylamine; and ammonium and alkali metals, e. g. sodium, potassium, lithium, with the following acidic materials: saturated and unsaturated fatty acids containing up to about 20 carbon atoms, terpene acid derivatives such as abietic and rosin acids, naphthenic and sulfonic acids as well as inorganic acids such as phosphoric acid and the like. The following detergents are particularly suitable for use in this invention: diethylethanolamine .oleate, diethylethanolamine stearate, laurylamine acetate,laurylamine stearate, laurylamine abietate, laurylamine naphthenate, laurylamine ricinoleate and laurylamine phosphate; morpholine oleate, ethyl morpholine oleate, morpholine stearate, morpholine naphthenate; cyclohexylamine ricinoleate, cyclohexylamine phosphate; ammonium ricinoleate; sodium petroleum sulfonate, etc. The detergent is used in Primarily they In addition the detergents co-act through the foul matter adhering to a surface it can displace it therefrom and leave on said surface a protective oiliness film which if desired can be easily removed by flushing, for example, with steam and the like. The protective film acts as a boundary separator between contacting surfaces thereby protecting them from wear and the like. Penetrants which are particularly suitable due to their co-ordinate action with other constituents of this invention so as to produce a product having maximum efiiciency in removing foul matter from surfaces are halogenated aliphatic and aromatic compounds, e.g. trichloroethylene, 2,2-dichloroethylether, O-dichlorobenzene, dichloroisopropylether, etc.; ketones, eIg. mesityl oxide, isophorone; and mixture of the above halogenated compounds and ketones. The penetrant generally comprises approximately 20% to 40% by weight of the composition.

To activate and improve the general properties of compositions under consideration a wetting agent is employed which co-acts with the above penetrants and wets the surface which has been rendered free of the deleterious materials by the active ingredients of this composition. The surface thus'wetted is protected and foul matter is prevented from re-adherlng to the cleaned surface. Wetting age ts which are suitable for this purpose are alkyl and alkyl substituted alkylol amines; cyclic amines; heterocyclic amines; alicyclic alcohols, etc. These types of compounds can best be illustrated by' such specific compounds as diethylethanolamine, laurylamine, morpholine, ethyl morpholine, cyclohexylamine, cyclohexanol, trimethylcyclohexanol and the like. The amines are particularly preferred, for in addition' to acting as wetting agents, they react with acidic materials thereby continuously replenishing the detergent agent. The amount of wetting agent used ranges between about 2% and about 25% and preferably is kept within 8% to 20% by weight of the total composition.

Water is an essential component of the present composition. The exact function or mechanism of it is not understood, but in cases where water was eliminated as a component of the present composition the efliciency of the latter as a deposit remover was reduced to such a degree as to render it almost useless. It is noted that the wetting power of the composition is increased and the foreign matter is kept in a more permanent dispersion due to the presence of water. It therefore appears that water exerts a synergistic effect and also acts as a carrier for foreign deposits loosened from. a surface. The amount of water used varies from between about 10% to about 20%, and preferably is kept between about 12% and 15 %by weight.

In order to stabilize compositions under consideration so as to prevent separation and break down, a coupling agent is added. The preferable coupling agents are polyhydric organic derivativessuch as alkylene glycols; dlglycols, e. g.

dipropylene glycol, dibutylene glycol,.diamylene glycol; triglycol, e. g. tripropyleneglycol; ether mimosa.

alcohols containing upto 20 carbon atoms jand more particularly glycol mono-alkyl ethers. e. g. the cellosolves,.e. g. ethylene glycol mono-ethyl ether, ethylene glycol mono-proply ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-tert.butyl ether, ethylene glycol mono-hexyiether, propylene glycol mono-ethyl ether, propylene glycol mono-isobutyl ether, etc.; diglycoi mono-alkyl ethers such as the carbitols', e. g. diethylene glycolmono-methyl ethyl, normal and isopropyl ethers,

To test the effectiveness of composition of this invention as removers or carbon and other "deleterious materials from various surfaces the following tests were performed and results come pared with the best known commercial materials.

used for the same purpose.

' I Example I Steel panels were sprayed with a solution of oil sludge in carbon tetrachlorideand baked at 220? C. in a forced draft oven. The steel panels werethen removed from the oven, cooled and some were immersed indeposit remover compositions of this invention while others were im-.

mersed in commercial deposit remover X reportedv to contain chlorinated aromatic, water, 'butyl cellosolve and ethanolamineoleate. The time of initial deposit removal as well as time of complete removal were noted at room temperatures and at approximately 185 F. In cases where complete removal of the deposit was not eflfected in minutes, the test was stopped and the percent of depositremoved was estimated aswell as the eflect of flushing the test piece with water noted.

' Temper- Time of Initial Time oi Complete Appearance after water Composmml ature Removal Removal flush F. 1 Commercial Productx.-. 185 None after 1l|r. No eflect, Panel still Composition of Ex. 1 Composition of Ex. 2 Composition oi Ex. 3 Composition of Ex. '4

None alter 2 hrs...

corroded with heavy deposit.

Panel absolutely clean.

Do. Do.

% and is preferably kept in the range of- 15 The above classes of additives which constitute the essential component parts of compositions of this invention have not been selected at random but have been selected after careful and painstaking research and because of their coordinating action in aiding to remove deleterious engine depositsas well as removal of undersirabie foreign deposits from various surfaces in general.

To more fully illustrate the present invention Example 11' The eifectiveness of the present deposit removers was tested on pancake valves from a 'cated in the table the temperature Wasmainthe following are a few compositions which have been compounded, tested and found extremely of the deposits was observed after the valvestained'at about 120 F. The time for removal were steam flushed.-

Com sition Tern r- Time of carbon removal Appearance of valves p0 sta r after flush treatment 1 comers Product ii in: .Yi'ftffi. Fiffi'iifiifilflffi'l.ff:::::13:33:: :3?"

Boom 2 hr. for substantial complete carbon removal... Valves were clean except 2 Product oiEx. 1.r. ioraiewspecks.

. 120 F. 14hr. for complete carbon removal Valves were perfectly clean. 3 Hand scraping 2 valves required 1 day ano naphthenic sulfonate eflicient for removing deposits from metal surfaces and the like.

. ages:

l trimethyl cyclohcxm amonium ricinoleate water 1 hiw'ih'iiiifa are parts by weight.

Example I" After a 500 hour test run of a GM-Vl single cylinder Diesel engine the piston rings were covered with heavy fouled deposits. The piston rings were immersed at room temperature in a composition of this invention and in a commercial product X and the time required for loosening and removing the fouled deposits noted.

minutes and valves and BMGQOSB E'zample IV The effectiveness of deposit removers of this invention was tested on hydrocarbon compressors,

equipment was by. sanding with fine emery cloth and required approximately 8 hours of sanding by one man to clean the cylinder walls alone and of an hour to scrape a valve clean. The time which vwas required to clean five cylinders with a composition of Example 1 was only 10 to 12 pistons were perfectly cleanafter a 10 minute soaking in a composition of Example 1 at room temperature and a one minute steam flush.

Example V i A, gas turbine eng e was run for a number of days until heavy fouling of the axial flow compressor was noted. The engine was cut down to about half speed and sprayed at room temperature into the air intake of the compressor during a 4 minute interval with 10 gallons of a composition of this invention referred to in the tabl as Example 1. This was followed by steam flushin the engine and it was observed that the compressor was absolutely clean. In addition the overall engine efiiciency of the clean engine increased by about 5.8% for a two hour performance test. Previous methods of cleanin such engines necessitated tearing it down which took about 24 to 32' hours and required approximately 32 hours to clean.

Example VI thereto or otherwise harmful effect-when in contact with the skin.

rubber, plastic surfaces and the like and can be applied by any known means such as spraying. immersing, di ping, swabbing, and the like.

It is to be understood that while the features of the invention have been described andillustrated in connection with certain specific examples, the invention, however. is not to be limited restricted, except by the prior art and the scope of the appended claims.

I claim as my invention:

1. A cleaning composition comprising a mix- "ture of R Per cent by weight Kerosene V 12 o-Dichlorobenzene' 40 'Dlethylethanolamine oleate 6 Diethylethanolamine 2 Ethylene glycol monobutyl ether 10 Water 12 2. A cleaning composition comprising a mixture of about 12% to about 50% of kerosene, about 2% to about 15% of diethylethanolamine oleate. about to about 40% oif o-dichlorobenzene, about 2% to about of diethylethanolamine, about 10% to about 20% of ethylene glycol monobutyl ether, and about 10% to about 20% of water.

3. A cleaning composition comprising a mixture of about 12 to 50% kerosene, about 2 to 15% of diethylethanolamine oleate, about 20 to of a chlorinated organic compound selected from the class consisting of o-dichlorobenzene, trichloroethylene, dichloroethyl ether and dichlorinvention at both room temperature and 185 F.

perfectly clean. The commercial product was still ineffective at the end of the test period.

Compositions of this invention are excellent for fective in removing dirt and grease from indus- .trlal equipment. They are non-corrosive, nonstripped the paint off the steel panel leaving it v isopropyl ether, about 2"to'25%of a diethylethanolamine, about 10 to 20% of ethylene glycol monobutyi ether-and about 10 to 20% water.

nan BQRUS.

REFERENCES CITED UNITE? s'ra'rns PATENTS Number Name Date 1,979,385 Harvey Nov. 6, 193

2,032,174 Johnson Feb. 25, 1936 2,244,721 Mitscherling June 10, 1941 2,303,551 Houghton Dec. 1, 1942 2,383,114 Villiers Aug. 21, 1945 2,398,242 Morgan Apr. 9, 1946 2,404,297 Kroll July 16, 1948 toxic and are not a fire hazard. They have no