Hydrocarbon fume suppression by higher vapor pressure temperature oils
Methods and compositions for suppression hydrocarbon fumes, and cooking oil fumes, by applying a non-volatile organic compounds having a vapor pressure temperature greater than the vapor pressure temperature of the hydrocarbon fume constituents, or cooking oil fume constituents; said compositions may include delivery vehicles such as 70% ethanol, or thixotropic lotions, to produce remediation formulations that may be sprayed or spread onto the surfaces from which the fumes are emanating; also included is an insect repellant, comprising non-volatile organic compounds having a vapor pressure temperature greater than the vapor pressure temperature of the human pheromones and body odors with attract biting insects.
This application claims priority from Provisional Application U.S. 60/647/953 file Jan. 28, 2005, entitled “Suppression of Petroleum Hydrocarbon Fumes by Higher Boiling Point Oils”
FIELD OF THE INVENTIONThe field of the invention is in environmental biotechnology, health care, and more specifically in consumer household products that are marketed for elimination of noxious fumes from minor petroleum hydrocarbon spills
BACKGROUND OF THE INVENTIONPetroleum hydrocarbons such as home heating oil, diesel fuels and gasoline pose a serious challenge as environmental pollutants when they enter the environment. Oil spills that occur in the open waters are primarily dealt with by immediate and proper notification of agencies that require the responsible parties to take action as required by statutes at the local and state levels. For major oil spills the oil polluted areas must be cleaned up within 48 hours by government approved immediate response teams. These clean up efforts are monitored by the Environmental Pollution Agency (EPA) and must meet standard guidelines for attaining minimal residual oil levels.
Oil spills in open waters from tanker operations are regulated by international convention whether they occur as a accidental spill or by oil discharge from engine maintenance and machinery used in ordinary ship operations. The oil spill standard is set at less than 10 ppm seen in open waters as a slight oil sheen. All of these sources of oil spills can indirectly result in minor petrolatum hydrocarbon oil contamination of work clothes and skin by ship personnel. It is this latter source of fumes that the present invention is directed.
Ganti, S in U.S. Pat. No. 6,267,888 discloses a method for removal of free-floating oil from water by biodispersion and bioutilization. The method employs a living mixture of bacterial species that have the ability to utilize hydrocarbons as the only source of carbon in an oleophilic liquid vehicle that provides oil soluble source of nitrogen and phosphorus for the bacteria. In principle, petroleum hydrocarbon fumes are remediated by the bacteria consuming any residual oil.
U.S. Pat. No. 4,237,780 describes a method for disposal of hydrocarbon fumes through the use of a prefilter and filter made from wood chips and carbonized wood chips, respectively. The primary or intended application of this invention is for use in paint spray booths to dispose of noxious organic solvents that contribute to air pollution. The use of fans to vent the fumes to the outside air is a common practice for hydrocarbon oil fumes in oil-polluted basements. Unfortunately, this practice rarely is completely effective as oil residues can persist in porous concrete and wood that slowly r3eleases the fumes over long period of time.
Borden R C and Lee M D disclose in U.S. Pat. No. 6,398,960 a method for remediating aquifers and groundwater contaminated by toxic halogenated organic compounds, certain inorganic compounds, and oxidized heavy metals and radionuclides. They teach the use of innocuous oil preferably edible food grade oil such as soybean oil, formulated in a microemulsion. We include their literature reference list here by way of its teaching that the use of vegetable oil is based on its supposed acceleration of reductive dehalogenation via a chemical reaction mechanism.
The aforementioned methods for treating hydrocarbon fumes are designed primarily for remediation of either free-floating oil in water or hydrocarbon residues that have entered into aquifers and ground water. They do not address oil contamination of human body skin. In particular, the patent art does not pertain to methods for decontamination of oil and gasoline contamination of personal effects such as clothes, household or office furniture and carpeting. There also remains one of the problem of concern that is the focus in the present invention, i.e., hydrocarbon fumes associated with minor home heating oil spills in home basements, and commercial or private machine shops. Still another source of harmful petroleum fumes occurs during routine filling of auto gasoline tanks and diesel oil spilled on hands and clothing during the filling and maintenance of autos, road vehicle, recreational off-road vehicles, pleasure boats, and ordinary household equipment such as lawn tractors and other garden equipment.
In the case of gasoline spills on hands or clothing the gasoline fumes persist even after meticulous cleansing of the affected areas with ordinary soap and water. This situation is all too frequent and unfortunately there is no available product on the market to meet this unmet consumer need. Likewise in the case where homeowners are confronted with noxious heating oil fumes due to oil furnace maintenance work, repairs or accidental spills, the fumes can permeate the entire house posing a serious health problem for the inhabitants. Typically, heating oil spills have been cleaned up with old rags, absorbent pads and wipes that may clean up the overt spilled oil but fail to eliminate oil fumes that remain in the concrete or sand surface. These unseen oil spills still emit noxious fumes and often require vacating the domicile until more extensive excavations and removal of contaminated materials. This can be costly and time-consuming form the homeowner and may pose future problems to the homeowner in meeting petroleum oil spill standards preparatory to resale of the property. Still another problem is the inadvertent contamination of furniture and household carpeting by petroleum hydrocarbon oils. Ordinary detergent-based cleansers fail to completely eliminate fumes from these hydrocarbon oil spills as long as they remain embedded in the soiled material.
Many household products are available to rid malodors arising from microbial action on organic wastes associated with bathrooms and kitchens. They generally provide a temporary solution by masking malodors through devices that release of a pleasing scent or fragrance. The most common method listed by a recent survey in Happi (Household and Personal Products Industry Magazine, September, 2004) is the burning of scented candles, followed closely by scented air fresheners. Again, these methods do not suppress malodors or prevent their escape into the air.
The present invention discloses a novel and unobvious solution to minor petroleum hydrocarbon fumes that not merely masks or perfumes the fumes but permanently suppresses their vaporization from the oil-affected sites.
SUMMARY OF THE INVENTIONThe present invention provides methods and formulations that effectively suppress petroleum hydrocarbon fumes. Various formulations of high vapor pressure temperature non-volatile organic compounds, such as fatty acid oils (certain alcohols and mineral oils, as described below), suppress the fumes of lower vapor pressure temperature fume producing hydrocarbons. The non-volatile organic compounds may be applied “neat” (undiluted), or may be formulated into a spray, when mixed with appropriate vehicles, such as ethanol, acetone or methanol. The non-volatile organic compounds may also be formulated into “thixogel” lotion formulations. When applied to the source of the fume producing hydrocarbons, the non-volatile organic compounds suppress the fumes.
The fume suppression teaching of the present invention has applications beyond the suppression of petroleum hydrocarbon fumes. The formulations of the present invention may also be used to contain the odors of rancid or decarboxylated and esterified cooking oils and fats, such as butylated stearic acid fats, on household, restaurant, or industrial kitchen surfaces. In particular, 12% oleic acid in 70% alcohol, is effective when applied to cold cooking surfaces.
Another application of the present invention concerns an improvement in insect repellents. While it is know that vegetable oils such as soybean oil, can be as effective as DEET in some experimental studies (Fradin M S and Day J F, “Comparative efficacy of insect repellents against mosquito bites, New Engl. J. Medicine 347:13-18, 2002), other volatile botanicals were reported to be ineffective. The present application provides an explanation for these results and suggests that use of fatty acid and vegetable oils with vapor pressure temperatures above 150 degrees will be effective mosquito repellents. In particular, 12% oleic acid in 70% alcohol, is effective when applied to the exposed skin of several human subjects.
For a full understanding of the present invention, reference should now be made to the following detailed description of the preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention concerns methods and formulations that effectively suppress petroleum hydrocarbon fumes. The concept arose from observations made by the inventor that the application of a complex mixtures of bacteria in an oleophilic liquid vehicle to a plot of oil polluted clay-rich earth quickly damped the fumes and replaced it with a vegetable-like odor. These observations were repeated a number of time and led to a quest to determine if a simpler system of vegetable oils had the property of suppressing petroleum hydrocarbon fumes. This search revealed that fatty acid vegetable oils such as oleic acid were very effective in eliminating diesel oil fumes applied to various substrates. The scientific, technical and rational basis for this property was further explored and a general principle emerged from these studies. We formed the hypothesis that fume suppression occurred when oil with a relatively higher vapor pressure temperature (vpt, non-fume producer) is applied to the surface of a lower vpt oil (volatile fume producer). The Chemical Rubber Publishing Company's Handbook of Physics and Chemistry, 35th Edition, 1953, defines vapor pressure temperature as the degree centigrade at which the vapor of a compound (at one atmosphere, or 760 mm of Mercury); and has the pressure indicated in a table of vapor pressure temperatures at pp. 2177-2225, for organic compounds with vapor pressures less than one atmosphere and carbon-atom chain length below C29.
In the instance of diesel oil, the two major low vapor pressure compounds responsible for the petroleum hydrocarbon fumes are naphthalene (vpt=218 degrees C.) and dodecene (vpt=208 degrees C.). The inventor discovered that immediate fume suppression occurred when a 12% emulsion of oleic acid in 70% ethanol was sprayed on sand saturated with diesel oil. The vapor pressure temperature of oleic acid is 350 degrees C. The finding was generalized by graphically plotting on XY plane the vapor pressure temperature of saturated and unsaturated petroleum (fume producing) hydrocarbons against their carbon atom chain length (see
A rule of prediction was developed. In order to find a given fatty acid oil that will predictably-suppress the fumes of a particular petroleum hydrocarbon, reference is made to the vapor pressure temperature of their primary constituents. These values are founds in CRC Handbook of Chemistry and Physics, 35th Edition, pp 2177-2225). Once the primary constituent(s) is identified, and its vpt determined by reference to the chart, one may select a fatty acid, alcohol or mineral oil with a notably higher vapor pressure temperature. This is done by choosing a higher vpt on in
A simple test system was devised to screen various fatty acid oils, vegetable oils, and Silicon oils. For this purpose, 35 grams of dry fine sand was placed in a clean 150 mL plastic sample container with a screw-capped lid. Pure diesel oil (2.0 mL) was carefully layered on to the surface of the sand and the container capped to prevent further fume loss. For the test control, 1.5 mL of water is was added to the diesel oil contaminated sand. For the experimental test, 1.5 mL of the chosen fatty acid or vegetable oil was carefully layered on to the diesel oil soaked sand so as to cover the entire exposed surface area. The sample container is capped to prevent further loss of fumes. The following fatty acid and vegetable oils were tested for their fume suppressing properties: oleic acid, linoleic acid, soy bean oil, corn oil, olive oil, meadowfoam oil and Triacetin® (Eastman, Bristol, Tenn.). The different vegetable oils are comprised of different types and amounts of fatty acids as shown in The table in
The experimental test results for pure fatty acids and test vegetable oils are given in the table in
The purpose of the proof of principle experiment was to test the concept presented above. According to this concept, suppression of hydrocarbon fumes can be achieved by choosing an oil that has a higher vapor pressure temperature than the vapor pressure temperatures of the component compounds present in the petroleum hydrocarbon fumes. For diesel oil these were the vapor pressures of naphthylene and dodecene. As in Example 1, 35 grams of clean dry fine sand was placed in the 150 mL plastic containers and 2.0 mL of diesel oil layered on the sand and the containers sealed with a screw-capped lid. According to the data shown in
An oil that has a vapor pressure temperature lower, equal to or not significantly higher than diesel is predicted to fail to suppress diesel oil; fumes. This prediction was confirmed in a trial using the silicone oil, dimethicone (Fluid 245, Dow Corning, Midland, Mich.); with a vapor pressure temperature below 210 degree centigrade, which, as predicted, failed to suppress diesel oil fumes in the dry sand experimental test. By contrast, the more viscous silicone oil, decamethylcyclopentasiloxane (Fluid 200-350CST, Dow Corning Midlands, Mich.) with an estimated vapor pressure temperature above 300 degrees centigrade readily suppressed diesel oil fumes. In all case where suppression of diesel oil fumes was immediately observed, suppression lasted for greater than 24 hours.
EXAMPLE 3 Suppression of Volatile Fumes from Commercial SourcesThere are many commercial products beside gasoline and diesel oils that have a disagreeable hydrocarbon smell associated with their use. One of these is lubricating oils found in such products as “WD-40.” Consumers using such products often end up with lubricating oils on their hands or clothes that literally many take days to wear off. Therefore, we examined the fume suppressive effect of one aerosol spray formulation that has successfully suppressed diesel oil fumes: Formulation A (12% Oleic acid in 70% ethanol) in a pump spray bottle.
For this purpose a “No-Mess Pen” WD-40 pen applicator with a depressible tip was employed to apply the WD-40. Within seconds after application of the WD-40 lubricating oil to different surfaces a strong and distinctive WD-40 odor was detected. Formulation A was immediately applied to the affected areas, including one test wherein the WD-40 lubricating oil was applied to the dorsal surface of a subject's hand. In all cases the distinctive WD-40 hydrocarbon odor was immediately eliminated. Suppression was complete and long lasting. Simple washing of the hands with warm soapy water left the hands free of any odors. This test has been repeated many times with identical results.
EXAMPLE 4 Fume Suppression of Fumes from Diesel Oil Soiled CarpetsClean carpet samples measuring (2′×3′) with a polyester synthetic fiber pile was chosen as the test material. Spray formulations Formulation A, containing 12% oleic acid in 70% ethanol, and Formulation B, and a spray formulation containing 10% soybean oil in 70% ethanol, were tested to see if they completely suppress diesel oil fumes from a small known amount diesel oil is applied to a measured circular carpet area.
Experiment 1: One (1.0) mL of diesel oil was applied to two separate circular areas of 19.65 square inches each, of a carpet sample. The oil was rubbed into the nap of the carpet with a glass rod and allowed to air dry of 30 minutes. Fumes were still overwhelmingly detectable at 30 minutes and remain so for many weeks. One diesel oil soiled areas was left untreated; it served as a positive control. The second diesel oil soiled carpet area was sprayed twice with 5 mL of Formulation A. This treatment regime was sufficient to cover the entire diesel oil soiled area, and more importantly completely suppressed any fumes from the diesel oil soiled area. The suppression lasted several days. Several repetition of this experimental design gave similar results. It was sometimes necessary to have an additional spray treatment due to breakthrough of diesel oil fumes from fibers that had not been completely exposed to the suppressive formulation.
Experiment 2: In this experiment the amount of diesel oil used to soil the carpet was reduced to 0.2 ml, and Formulation B (10% soybean oil emulsion in 70% ethanol) replaced oleic acid as the spray formulation. Again, diesel oil was applied to two separate carpet areas measuring approximately 19 square inches each. An aerosol spray of formulation B was applied to one of the diesel oil soiled areas, rubbed in with a glass rod. And air-dried for 30 minutes. It completely suppressed the diesel oil fumes relative to the untreated positive control carpet area.
Together, the results of experiments 1 and 2 confirm the prediction that a fatty acid (oleic acid), and a vegetable oil (soybean oil), both with vapor pressure temperatures well above diesel oil, suppress diesel oil fumes from diesel oil soiled carpets.
EXAMPLE 5 Test of Fume Suppressive Vegetable Oil Formulations on Diesel Oil Contaminated Human SkinA fume suppressant hand lotion (Formulation C) was made according to the methods and compositions previously described (Wille, J J. “Thixogel, a novel topical delivery system for hydrophobic plant actives,” in Delivery System Handbook for Personal care and Cosmetic Products, Meyer R. Rosen (ed.), pp. 761-794, William Andrews, Inc; and U.S. patent application Ser. No. 10/873,590, filed Jun. 22, 2004, entitled “Novel Topical Delivery System for Plant Derived Anti-irritants”, and incorporated herein by reference). The oil phase of the thixotropic emulsion of Formulation C was composed entirely of soybean oil. The resulting starch gel emulsion of the lotion of Formulation C encapsulates the soybean bean oil phase.
In order to determine the efficacy of both the aerosol spray formulation (formulation B) and the newly formulated hand lotion (Formulation C), 10 microliters of diesel oil was applied to the both the dorsal hand skin and the volar arm skin of several human subjects. The fumes arising from both skin sites was easily detectable in each subject. The diesel oil contaminated hand skin was treated with the aerosol spray formulation and the volar arm skin was treated with the hand lotion. In all cases there was an immediate and lasting suppression of fumes issuing from the diesel oil contaminated skin sites. This experimental design was repeated several times with identical results, indicating that petroleum hydrocarbon fumes due to contact of diesel oil with human skin can be eliminated by either an aerosol formulation containing a suppressive vegetable oil or a lotion containing a suppressive vegetable oil.
Other vegetable oils such as olive oil, meadowfoam oil and corn oil were formulated as described above, substituted for the soybean oil phase of the hand lotion, and they performed equally well in suppressing diesel oil fumes on human skin.
EXAMPLE 6 Suppression of Volatile Oleophilic Vapors by Oleic Acid-Containing FormulationsGasoline is a volatile mixture of petroleum hydrocarbons, such as octane, the major fuel component. Octane has a high flash point and a vapor pressure temperature at 760 mm of (100-120 degrees Centigrade). Incidental contact with gasoline during routine auto gas fill-ups can cause breathing difficulties especially in a confined space such as the interior of an auto. Removal of gasoline from hand skin is difficult even with thorough washing with soap and water. In this example, 1.0 ml of gasoline was added a clean white cotton cloth and allowed to air dry in open air for one hour. The fumes from the gas-soaked cloth were apparent even after 1 hour of air-drying. Formulation A containing 12% oleic acid in 70% ethanol was sprayed from a pump spray bottle on those portions of the gas-soaked cloth so as to cover entirely cover the affected gas soiled cloth. Within minutes no more gas fumes could be detected. This suppression lasted for up to 6 hours, when an additional aerosol treatment immediately suppressed any further fumes for another 24 hours.
EXAMPLE 7 Other Applications of the Fume Suppression TechnologyThe fume suppression technology of the present invention has applications beyond the suppression of petroleum hydrocarbon fumes. These include household, restaurant, or industrial kitchen surfaces contaminated with rancid or decarboxylated and esterified cooking oils and fats. Many of these smells are unpleasant such as butylated stearic acid fats. Breakdown products of animal fats or oils from high temperature cooking also produce unpleasant odors. Cooking surfaces contaminated with these breakdown products of animal fats can be suppressed by application of a fine aerosol spray of Formulation A (12% oleic acid in 70% alcohol) on to cold cooking surfaces.
Another application of the present invention concerns improvement in insect repellent technology. Almost all present effective insect repellents have DEET (N,N-diethyl-m-toluamide) as their active ingredient. It is know that vegetable oils such as soybean oil, can be as effective as DEET in some experimental studies (Fradin M S and Day J F, “Comparative efficacy of insect repellents against mosquito bites, New Engl. J. Medicine 347:13-18, 2002). Other volatile botanicals were reported to be ineffective. The present application provides an explanation for these results and suggests that underlying reason for the suppression of mosquito bites by soybean oil is accounted for by its ability to suppress a skin-derived fatty acid product that is attractive to mosquitos and possibly other biting insects. The existence of human pheromones is well established and their chemical identity is in fat-soluble compounds with vapor pressure temperatures less than 150 degrees centigrade. Therefore, the use of fatty acid and vegetable oils with vapor pressure temperatures above 150 degrees are predicted to be effective mosquito repellents. For this purpose, an aerosol spray having the composition of Formulation A was applied to the exposed skin of several human subjects just prior to dusk and the subjects allowed to sit for 1 hour outside in an mosquito inhabited area. Several other subjects without protection afforded by application of exposed skin to Formulation A were also grouped together with the Formulation A treated subjects. None of the Formulation A treated subjects received a single mosquito bite during the trial period. By contrast two out of three of unprotected subjects recorded one or more bites. These preliminary results support the proposal that fatty acids with a relatively high vapor pressure temperature are effective in suppressing skin-generated volatile “attractant
There has thus been shown and described a novel hydrocarbon fume suppressant which fulfills all the objects and advantages sought therefore. Many changes, modifications, variations and other uses and applications of the subject invention will, however, become apparent to those skilled in the art after considering this specification and the accompanying drawings which disclose the preferred embodiments thereof. All such changes, modifications, variations and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention, which is to be limited only by the claims which follow.
Claims
1. A method for suppressing petroleum hydrocarbon fumes comprising:
- a) identification of the primary volatiles responsible for the petroleum hydrocarbon fumes
- b) determination of the vapor pressure temperature for each of the suspected primary volatiles with vapor pressures less than one atmosphere,
- c) selection of a nonvolatile organic compound with vapor pressure temperatures that are at least 30 degrees centigrade higher than the highest vapor pressure temperature of the volatile components of the petroleum hydrocarbon fumes, said nonvolatile organic compound selected from the group consisting of fatty acids, alcohols, fats, mineral and vegetable oils, waxes, silicon oils.
- d) applying the remediation formulation to the petroleum hydrocarbon.
2. The method of claim 1, further comprising the step of:
- combining a sufficient amount of the nonvolatile organic compound with a delivery vehicle therefore, selected from the group consisting of acetone, methanol, ethanol, fatty acid esters and alcohols of carbon chain length greater that 18; to form the a remediation formulation; before applying to the petroleum hydrocarbon.
3. A remediation formulation for suppressing the fumes of a petroleum hydrocarbon containing various fume producing constituents, said formulation comprising one or more fume suppressors selected from the group consisting of nonvolatile fatty acids, alcohols, mineral and vegetable oils, silicon oils with a vpt at least 30 degrees C. higher that the highest vpt of the fume producing constituents.
4. The remediation formulation of claim 3, wherein more than % by volume of the selected fume suppressors have carbon atom chain lengths equal to or greater than C18.
5. The remediation formulation of claim 3, further comprising a delivery vehicle selected from the group consisting of acetone, methanol, ethanol, fatty acid esters and alcohols of carbon chain length greater that 18, said delivery vehicle comprising between 0.5 and 100% by volume? of the formulation.
6. The remediation formulation of claim 3, wherein the selected fume suppressor is oleic acid.
7. The remediation formulation of claim 5, wherein the selected fume suppressor is oleic acid.
8. The remediation formulation of claim 6, wherein the oleic acid, present at between 5-15% (v/v) of the remediation formulation.
9. The remediation formulation of claim 7, wherein the oleic acid, present at between 5-15% (v/v) of the remediation formulation.
10. The remediation formulation of claim 7, wherein the delivery vehicle for the oleic acid is ethanol at concentration greater than 50% (v/v) in aqueous solution.
11. The remediation formulation of claim 3, wherein the fume suppressor is selected from the group consisting of: soybean oil, olive oil, corn oil, and meadowfoam oil, nonvolatile, biodegradable oils and edible oils.
12. The remediation formulation of claim 3 formulated as topical sprays, lotions, creams and gels for application to the human skin to suppress volatile hydrocarbon fumes, said formulation comprising a delivery vehicle comprising ethanol, stearate and palmitate esters, and alcohols.
13. A method for suppressing fumes from rancid fats comprising:
- a) identification of the primary volatiles responsible for the rancid fat fumes
- b) determination of the vapor pressure temperature for each of the suspected primary volatiles with vapor pressures less than one atmosphere,
- c) selection of a nonvolatile organic compound with vapor pressure temperatures that are at least 30 degrees centigrade higher than the highest vapor pressure temperature of the volatile components of the rancid fat fumes, said nonvolatile organic compound selected from the group consisting of fatty acids, alcohols, fats, mineral and vegetable oils, waxes, silicon oils.
- d) combining a sufficient amount of the nonvolatile organic compound with a delivery vehicle therefore, selected from the group consisting of acetone, methanol, ethanol, fatty acid esters and alcohols of carbon chain length greater that 18; to form the a remediation formulation; before applying to the petroleum hydrocarbon, and
- e) applying the remediation formulation to the rancid fat.
14. A composition for suppressing fumes due to rancid fats such as butylated fats and fatty acids, and partially decarboxylated breakdown products of edible fats and cooking oils, for the decontamination of cooking surfaces, kitchen appliances, and other surfaces soiled with decomposed cooking fats and oils, said composition comprising the remediation formulation of claim 3.
15. An insect repellant comprising the remediation formulation of claim 3, applied topically to the skin, to prevent volatilization of skin-generated pheromones attractive to mosquitoes and other biting insects.
Type: Application
Filed: Jan 30, 2006
Publication Date: Sep 28, 2006
Inventor: John Wille (Trenton, NJ)
Application Number: 11/342,469
International Classification: C10G 21/02 (20060101);