Patent Application
20140290129
1. Field of the Invention
This instant patent application relates to the field of bio-combustibles chemistry and provides a bio-combustible or an additive produced from any type of biological viscous and/or oil raw material including natural oil from marine seaweed that, in accordance with this instant process, may be incorporated into any other combustibles from a biological, fossil or mineral source both in the form of an additive or in the form of a pure bio-combustible.
One of the advantages provided by this invention hat the obtained product s waterfree, therefore it does not become degenerated when stored and does not attack any components in the motor besides being hydrofugant and having a high octane rating.
The product may be considered as a universal bio-combustible since it may be miscible with other combustibles as ethanol, gasoline, diesel oil or a mixture of all.
It is an object of this instant patent application to provide a process for obtaining a universal bio-combustible or additive having a low cost for industrial production together with features of low cost, reliability, practical and useful to over the chemical and similar economic segments an additional option in the market; further, unlike the conventional bio-combustible and additives, this instant object is provided with numerous possibilities and benefits which turn it into a product and process greatly expected and accepted in the related market.
2. Brief Description of the Related Art
Petroleum was discovered in the year 1859 at Pennsylvania, United States, and at that time it was mainly used for production of kerosene used for lightning; later on in the year 1895 Rudolf Diesel began a few searches in order to evaluate the use of petroleum by-products as a combustible for his new invention, that is, the compression diesel engine. However, in the year 1900 he used an oil made from peanut to demonstrate his new invention.
He used to say that the diesel engine could be run with vegetable oil and that such application would considerably contribute to develop agriculture in those countries employing vegetable oil in such application.
But the development in technology for obtaining petroleum derivatives as gasoline, diesel oil and others allowed costs of fossil combustibles to become much lower than costs of vegetable oils and thus allowed automotive industries to develop and to use those fossil combustibles.
The first petroleum crisis in the year 1973 was a mark to the end of an era of abundant and cheap combustible. Embargos placed by Arabian countries against the United States and reductions in the production and export of petroleum drove the prices of a single petroleum barrel to soar between October 1973 and December 1974 and with such scenario the petroleum exporting countries defined a new era for the rest of world: the era of scarce and costly petroleum.
Between the year 1981 and beginning of 1983 a new rise in the price of crude petroleum barrel took place and this was the second petroleum crisis; however, in the year 1986 the cost of petroleum dramatically fell down but the finite status of petroleum reserves and the menace of new rises in the costs required the development of more economic technologies.
Yet another factor to stimulate the search for new combustibles is the ever increasing level of pollution in urban areas caused by burning petroleum and its derivatives and further, recent campaign for environment preservation requires that less polluting options be employed and preferably renewable options as bio-combustibles.
Bio-combustible is a liquid or gaseous combustible produced either from vegetable and animal biomass or from forestry and related industries and from biodegradable fractions of industrial and urban residues.
In addition to others bio-combustibles bio-diesel, bio-gas and ethanol, an alcohol made from sugar-cane, are also classified as bio-combustibles
In such a context bio-combustible comes into scene as an alternative to diminish dependence on petroleum derivatives and as a new market for oleaginosae.
Bio-diesel refers to a diesel combustible made basically from vegetable oils or from animal fat and it is a bio-degradable combustible which may be used in all types of diesel engines either pure or combined with diesel oil.
Bio-diesel is manufactured from renewable sources like sunflower, soybean and others and it is distinguished from other combustibles for producing less amounts of carbon dioxide into the atmosphere and it is particularly one of the most environment friendly combustible. However, it is to emphasize that bio-diesel has specific solvent properties that may quickly accelerate wear condition of a few components in an automobile like gaskets, rubber tubes, filters, pumps and fuel lines amongst other components.
In order to decrease this harmful effect caused by biological combustibles a few solutions as additives were developed so as to ameliorate harmful effects or to solve said problems such as the solutions taught in the patents described next. Nevertheless, a definition for the word ester must me mentioned.
In biochemistry and organic chemistry ester is a product resulted from reaction of an organic or inorganic acid with a phenol hetero-arenol or enol alcohol due to formal loss of water which is formed by the acidic hydrogen of the phenol hetero-arenol with the hydroxyl group of the enol alcohol.
Brazilian patent application PI0803767-1 A2 filed on Jun. 30, 2008 taught a process for production of glycerin mono-ethers and its application as an additive for bio-diesel and such process is related to preparation of glycerin ethers from reaction of glycerin condensation under heterogeneous catalysis aiming at obtaining glycerol mono-ether with high selectivity. In a second aspect said patent application refers to an application of glycerol mono-ethers which result from reaction of glycerin condensation as an additive to bio-diesel in such a way to add value to bio-diesel and improve the diesel quality as a combustible. The glycerol employed in said process is a sub-product from said process for obtaining a bio-diesel.
Brazilian patent application PI0105888-6 A2 filed on Nov. 30, 2001 taught a process for production of bio-diesel and invention is related to an integrated process for production of bio-diesel from oleaginosae seeds, preferably castor plant, which consists of promoting a transesterification reaction whereof the seed per se react with anhydrous ethanol in the presence of an alkaline catalyst in order to generate ethyl esters that will later be separated by decantation and neutralized in order to be used as a combustible for diesel engines, also as co-solvents for mixing diesel and gasoline with anhydrous or hydrate ethanol and solid fractions that may be used either as fertilizers, as animal feed and as a raw-material for ethanol production.
Brazilian patent application PI0507963-2 A2 filed on Jan. 27, 2005 taught a process for manufacturing bio-combustibles, transformation of triglycerides into at least two families of bio-combustibles and fatty acid monoesters and ethers and/or glycerol soluble acetals and said invention refers to a process for manufacturing bio-combustibles by transformation of triglycerides into at least two families of fatty acid monoesters bio-combustibles and ethers and/or glycerol soluble acetals that comprises at least a transesterification step in which such triglyceride is reacted by heterogeneous catalysis with at least one primary mono-alcohol selected from methanol and ethanol to result, in one hand, at least one methyl ester and/or ethyl ester from the triglycerides fatty acids used at the beginning and, on the other hand a glycerol, such products free of sub-products. And a etherification step in which glycerol is reacted with at least one olefinic hydrocarbons with 4 and 12 carbon atoms and/or an acetalization step in which glycerol is reacted with at least one compound selected from aldehydes, ketones and acetals derived from aldehydes or from ketones,
Brazilian patent application PI0608734-5 A2 filed on Feb. 28, 2006 taught a process for preparation of a composition useful as a combustible oil and improvement in a process for preparation of a composition useful as a combustible and refers to said preparation process of a composition for combustible oil, that is, a diesel combustible or a heating oil, which consists of a mixture of transesterified fatty acid ester triglyceride with alcanol and a glycerol acetal. Preferably the process is provided with a previous step for formation of at least a part of transesterified triglyceride with alcanol containing glycerol to be used to form glycerol acetal. The composition may similarly be formed by a reaction of 1,1-dimethoxietane or 1,1-diethoxitane and glycerol to form acetal in transesterified triglyceride with alcanol.
Brazilian patent application PI0702373-1 A2 filed on May 30, 2007 taught a process for production of a bio-diesel from vegetable oils and fats using heterogeneous catalysts and refers to the field of fats and oils transesterification processes for production of diesel oil. The invention has provision of a new method for producing diesel oil through fatty acid esters transesterification found in vegetable oil and fats using a new compound catalyst from a group V metallic oxide with a formula X2O5 with Nb2O5 niobic pentoxide. Unlike processes traditionally found in the prior art conversion of oils into high purity products including glycerin reaches an output estimated in 100% by using an amount of catalyst significantly lower relative to the amount of processed oil when soybean oil, cotton oil, canola oil and others are processed through the method used in this invention.
Still considering improvements for obtaining bio-combustibles or additives and related reagents teachings of European patent EP1331260-A2 filed on Dec. 20, 2002 and U.S. Pat. No. 5,849,939 filed on Jul. 8, 1994 are included.
Even in those aforesaid patent applications the big trouble of degradation in the bio-combustibles is found in that they degrade rapidly both by their own causes and in relation to the parts of the engine. To mention a few troubles are microbiological contamination, oxidation, deterioration, impurities, low stability, higher grade in the solvent properties, higher grade of hygroscopicity and higher grade of degradability.
In view of the need to seek for a combustible in the form of a combustible or an additive that does not become degraded because of being water-free in its composition the well-skilled inventor in such area of chemistry was led to invent the object claimed in this instant patent application with a title as “process for obtaining a reagent combustible for mixing with other combustibles” which enables a combustible in the form of an additive or a combustible itself that does not absorb water and for not absorbing water it becomes stable itself and therefore allows no trouble to normally do with contaminations. Yet such combustible may be stored for a longer period of time and it is miscible with diesel oil in any proportion wanted without any danger of imparting deterioration to diesel oil.
Said invented bio-combustible may also be mixed with ethanol, may be added to gasoline as an additive in order to increase its octane rating and to decrease the existing amount of solvents.
Therefore, the invented combustible does not become oxidized with the passing time or for being exposed to light and may be mixed to any combustible without any danger of deterioration. Moreover, it directly may increase petroleum reserves, may be mixed with ethanol and diesel oil, may be mixed to a mixture of all types of combustibles and yet may be used to produce a new type of combustible.
These are a few uses and qualities of the claimed invention and additional uses and qualities may be further reported.
Thus the instant claimed invention was designed aimed at obtaining a bio-combustible or an additive miscible to any other combustible with less components as possible conveniently arranged to perform functions with unmatchable efficiency and versatility without the aforesaid inconvenient.
This instant claimed invention relates to a process for obtaining a combustible or an additive made from vegetable oils or from marine seaweeds (micro-seaweeds) used for explosion or combustion engines whose process is divided into two steps:
The first step relates to extraction of glycerin from a vegetable oil through a esterification, transesterification process or any other suitable means.
The second step is the phase in which the product obtained from the first step becomes to have a lower density and viscosity and even approaching close to or matching the same characteristics of mineral diesel. From such point on through a chemical process which is disclosed next the claimed product in this invention is obtained and may be used as a combustible or as an additive in any compounding proportion into any combustible. The resulted product is miscible to said any other combustibles as diesel oil, bi-diesel, ethanol, gasoline and kerosene and said resulted product may be used as an additive or may be used pure as a single combustible. However, this resulted product is not miscible with water since it is a bio-combustible and its main characteristics are that it does no absorb water and is totally stable.
Adding the product of this instant invention allows the mixture of ethanol with mineral diesel oil without the need of using sophisticated equipments and even with no need of emulsification or use of acids in the ethanol or diesel oil.
It is also possible to mix up all combustibles together in the proportion per combustible with the addition of the claimed product of this invention. Further, when the product resulted from this instant invention is used as an additive to gasoline it enables to increase the gasoline octane rating and to decrease the amount of solvents; the product resulted from this instant invention also can be used as an additive to ethanol and other combustibles.
The object of this instant patent application is found in the reaction used for obtaining the combustible and/or the additive and not in the equipment used to produce said combustible and/or additive. Neither is found the object of this instant patent application in the raw-material used to produce said combustible and/or additive since any vegetable oil may be used; therefore, it is basically a chemical reaction.
Transesterification, esterification or any other means to extract the glycerin are used just in the first step of the claimed process as aforesaid described and meant to be a cleaning action, reduction of density/viscosity of the vegetable oil and thereafter chemical reaction is used to change the substance resulted thereof into the combustible/additive of this instant claimed process.
At the first step of the instant claimed invention a type of selected oil is mixed to hydrated ethanol 93.8° INPM (96° GL) under ambient temperature in a proportion 2:1 p/p (two parts of oil with one part of ethanol) or 1:1 p/p (one part of oil with one part of ethanol) so as to decrease moisture and to provide a balance to oil pH. Otherwise, the oil may only be heated up for a few minutes under a temperature between 100 to 110 degrees Celsius (100° C./110° C.) without the need to use ethanol.
Ethanol was selected as a mixing ingredient; after mixing allow the mixture to rest until the phases become separated and as soon as separation occurs ethanol is taken apart and keep reserved away to re-use.
Now having the oil without ethanol available reagent R1 is mixed in with a mixing proportion from ten percent (10%) to fifty percent (50%) relative to weight of the oil under a constant temperature between forty and sixty-five degrees Celsius (40° C./65° C.) during a period of five minutes up to three hours under constant stirring and under a low speed between fifty to five hundred rotations per minute (50/500 ppm). Reagent generally referred to as R1 will be further explained in this patent specification.
It is to be noted that a variation exists relative to the amount of reagent used, temperature, period of time and stirring and this is because many types of oils may be used; therefore, a factor exists for every and all type of oil.
After the process is concluded the mixture should be allowed to rest until separation of phases occurs as well separation of glycerin and ethyl ester.
In a second step of the instant claimed invention neutralization, washing and drying of ester occurs. A solution of water with hydrochloric acid HCL between 0.5% to 01% acid p/p relative to the amount of ester is used for said neutralization process. For instance, for every kg of ester from 5 to 1.0 grams of HCL are mixed in one kg of water.
A new filtration is provided and the final product object of this patent application is ready,
Note: A H3BO3 solution with ethanol 93.8° INPM (96° GL) may also be used for the preparation of reagent generally referred to as R3 in order to save amounts of reagent to be used.
The process for obtaining a reagent combustible for mixing with other combustibles provides a combustible or an additive used in explosion motors which is produced from sunflower refined oil or any other type of vegetable oil or seaweed oil preferably without the use of conservatives which uses as reagent the following components:
Ethyl alcohol 96° GL (93.8° INPM) or 95.3 GL (92,8° INPM under 20° C.
Ethyl alcohol 77° GL (70° INPM) under 20° C.
Sodium hydroxide NaOH (97%).
Boric acid H3BO3 (99.7% min.)
Hydrochloric acid HCL
Purified or distilled water
The process for obtaining a reagent combustible for mixing with other combustibles uses the following reagents generally named:
Reagent generally referred to as R1: ethyl alcohol 70° INPM (77° GL) two hundred and eighty-six grams (286 g) with a higher or lower variation of thirty percent (30%) and NaOH fourteen dot eighty-five grams (14.85 g) with a higher or lower variation of thirty percent (30%).
Reagent generally referred to as R2: ethyl alcohol 93.8° INPM (96° GL) one thousand and two hundred grams (1200 g) with a higher or lower variation of fifty percent (50%) and NaOH twenty-two grams (22 g) with a higher or lower variation of twenty percent (20%).
Reagent generally referred to as R3: H3BO3 one hundred and ten grams (110 g) with a higher or lower variation of thirty percent (30%).
Reagent generally referred to as RN: HCL five grams (5 kg) with a higher variation of one hundred percent (100%) or with lower variation of just twenty percent (20%) and one thousand grams (1000 g) purified water with a higher variation of one hundred percent (100%) or with a lower variation of just twenty percent (20%).
Reagent generally referred to as R1 is prepared in the following way: 286 g ethyl alcohol 77° GL (70° INPM) (two hundred eighty-six grams) should be mixed with 14.85 g NaOH (fourteen dot eighty-five grams) for each 920 g (nine hundred twenty grams) oil or for a better understanding in percentage an amount of 31% (thirty-one percent parts by weight (p/w) ethyl alcohol relative to the amount of 5.1% NaOH relative to the amount of ethyl alcohol with a variation of 5% (five percent). After NaOH is fully dissolved the solution is filtered and kept apart for further use.
Reagent generally referred to as RN is prepared in the following way:
5 g HCL, or for a better understanding in percentage 0.5% (zero dot five percent) parts by weight (0.5% p/w) fur each ester kilogram is mixed with 1 kg purified water with a variation of 5% (five percent). The resulting solution is reserved apart. This solution refers to each ester kilogram (kg).
Starting with reagents generally referred to as R1 and RN the first proceeding is carried out as follows: 920 g (nine hundred and twenty) sunflower oil are placed in a container and heated under stirring and under a constant temperature of 50° C. (fifty degrees Celsius); following the whole content of reagent generally referred to as R1 is slowly mixed and maintained under stirring and constant temperature during 20 (twenty) minutes. After said period of time the mixture is removed from said container and put to rest into a separation funnel (it may be shaped as a pear) until the whole content of glycerin is laid down in the bottom of said funnel.
When the whole content of glycerin is laid down on said bottom of said funnel such content of glycerin is then removed from said bottom and the solution RN heated at 50° C. is then mixed with the ester. The new solution should now be fully stirred and put aside to rest until the solution becomes separated from ester. After separation is done the new solution is removed and 1 kg (one kilogram) purified water is added to the ester. The purified water is also preferably heated at 50° C. This new water-added solution should be fully stirred and put aside to rest so as to become separated from ester. After separation is provided said water is removed and measured for reading its pH. Water's pH should be set to 7. If said pH is not obtained the latest aforesaid proceeding should be repeated and one more 1 kg purified heated water is added in and mixed to said ester. Then a new separation proceeding should be provided and a new water's pH measuring is read. This operation should be repeated until pH reads 7 or a figure close to 7.
Mixing a solution containing in a proportion of 1:1 p/p for approximately five minutes under ambient temperature or in a range of 20° C. to 50° C. It then should be allowed to rest or put to centrifugation in order to obtain the phases separated. After having obtained separation solution should be removed from the container and again mix ester pure water preferably de-ionized until a neutral or close to neutral pH is achieved.
After neutralization ester should be dried.
Drying can be made by heating or by any other available process; after drying filtration of the contents is made and ester density is checked. Ester density weight must be at a maximum of 915 kg/m3 (20° C.) since the lowest the weight the best results will be.
Now the final phase of transformation follows.
This is the phase in which the ester viscosity and density becomes lower and come to the same level of mineral diesel or close to the same characteristics of said diesel.
Reagent generally referred to as R1 is obtained by mixing 1% to 5% sodium or potassium hydroxide with hydrated ethanol (70° INPM) containing a water weight of 5% to 50%.
Reagent generally referred to as R2 is obtained by mixing 20% (twenty per cent) to 200% (two hundred percent) p/p hydrated ethyl alcohol 93.8° INPM (96° GL) from ester with 2% (two percent) to 4% (four percent) sodium hydroxide p/p and for each ester kg an amount of two hundred fifty grams (250 g) to two thousand five hundred grams (2500 g) of hydrated ethyl alcohol is used together with 20 g to 40 g NaOH.
Reagent generally referred to as R3 is granular boric acid H3Bo3.
Reagent generally referred to as R2 Preparation:
Under ambient temperature reagent generally referred to as R2 is mixed under agitation with ester also in a proportion of twenty per cent (20%) to two hundred percent (200%) pp relative to the ester amount.
At the time reaction occurs by noting a change into a more homogeneous aspect with a darker color stirring of mixture should be interrupted.
After reaction R3 final reagent is added in a proportion of 7% (seven percent) to 20% (twenty percent) p/p relative to ester. Good results were obtained using a proportion of 10% (ten percent) p/p.
At the time of adding R3 reagent the mixture is stirred under ambient temperature until a new reaction is noted which at first has a more homogeneous aspect with darker and transparent color changing then into a lighter and transparent color.
When reaction is perceived stirring is interrupted and the mixture is allowed to rest for approximately thirty minutes (30 min) so that the solid reagent is laid down at the bottom of recipient.
Following liquid portion is separated from solid portion and filtration of liquid solution is carried out. Solid portion is then reserved apart for reuse to be added to new mixtures.
Now having the solution filtered solution should be washed with pure water preferably de-ionized in a proportion of 10% (ten percent) to one hundred percent (100%) p/p. Good results were obtained in a proportion of 50% (fifty percent) p/p relative to the amount of R2 reagent. Mixture is then allowed to rest until separation of phases is achieved whereof separation solution that remained in the bottom of recipient is removed and reserved to further purification and reuse of ethanol and water for the next reactions.
After solution is removed the ester will remain and said ester is mixed again under ambient temperature with content of 10% (ten percent) to 100% (one hundred percent) of pure water. The pH of the product is controlled in these two mixing phases with water by adding more or less water. Good results were obtained in a proportion of 50% (fifty percent) p/p relative to the ester amount.
The solution phases are again separated and the ester is dried by heating or any other available process until the whole water content becomes evaporated.
After neutralization said ester should be dried which is meant to say that all humidity should be eliminated. Such a process may be made with the use of centrifugation, heating or by mixing to said ester fifty percent (50%) parts by weight (p/w) of ethylic alcohol 96° GL (93.8° INPM) and afterwards allow it to rest until separation is obtained. After separation alcohol should be drawn from the mixture and said ester heated up to eighty degrees Celsius (80° C.) for a total evaporation of ethylic alcohol. When all said proceedings are done ester is now ready for the transformation phase.
For said transformation 890 g (eight hundred grams) ester are used and with the result of the first proceeding said 920 g (nine hundred twenty grams) ester are not obtained after glycerin is eliminated. This is owing to the fact that the oil density becomes decreased and so as a consequence the oil weight also becomes smaller.
Preparation of reagent generally referred to as R2 is the next step which is carried out as follows: 1200 g ethylic alcohol 96° GL (93.8° INPM) (one thousand two hundred grams) are mixed with 22 g (twenty-two) NaOH for each 890 g ester. Or for a better understanding in percentage amount a figure of 134.85% (one hundred thirty-four dot eighty-five) parts by weight (p/w) ethyl alcohol relative to the ester amount and 2.47% (two dot forty-seven) parts by weight NaOH also relative to the ester amount with a variation of 5% (five percent) and after mixing NaOH should be fully dissolved. Solution thereof should be then filtered and put apart to further use.
Reagent generally referred to as R3 is prepared as follows: 110 g H3BO3 (one hundred and ten grams) or in percentage amount 500% parts by weight (five hundred percent) relative to NaOH with a variation of 5% (five percent).
The whole content of said reagent R2 should be slowly mixed with 890 g ester (eight hundred ninety grams) under ambient temperature and constant stirring. The mixing proceeding should be interrupted when reaction occurs. Reaction is noted by a change into a very homogeneous aspect with a more transparent and darker color. Reaction takes place when pH in the mixture achieves a level close to 13.
After reaction said reagent R3 should be mixed with the resulting solution under ambient temperature and constant stirring. Stirring should be interrupted when a new reactions occurs in such a moment when the new solution shows a brighter color. Reaction takes place when pH in the mixture achieves a level close to 8.8. Following reaction should be allowed to rest so that the solid reagent R3 becomes totally laid down at the bottom portion of container,
Following the whole liquid content should be separated from the solid content and solution submitted to filtration. A 3 micra mash porosity filter or smaller should be used.
Now with the filtered solution 50% parts by weight relative to reagent R2 (p/w) (fifty percent) purified water should be mixed under ambient temperature. Such amount expressed in terms of weight refers to 611 g (six hundred eleven grams) purified water with a variation of 5% (five percent). It does not require too long for stirring; rather, just the necessary period of time to become thoroughly mixed. Following the solution should be allowed to rest until phases become separated. The solution that remained in the bottom of recipient should now be removed. The remaining ester in the upper portion of container should be now mixed under ambient temperature with more 50% (fifty percent) purified water parts by weight relative to the ester amount. In such case water amount corresponds to 445 g (four hundred forty-five grams) with a variation of 5% (five percent).
The resulting solution should be allowed to rest until phases separation occurs. After solution having become separate water should be removed and ester should be dried by centrifugation or heating. If heating method was selected heating under a constant temperature between 110° C. to 140° (one hundred ten to one hundred forty Celsius) should be carried out so that the whole content of water becomes evaporated. Now the solution should be allowed to cool and after cooled should be filtered with a 3 (three) micra mash or smaller filter. Ester pH should be now measured after ester becomes dry, cold and filtered. These are the two phases of being mixed with purified water that the claimed product's pH is controlled by adding more or less water. In case pH is noted not to have yet become alkaline the latest process step should be repeated but then with a lower amount of water which is around ten percent (10%) parts by weight relative to ester. A variation of five percent (5%) is allowed.
By the aforesaid processing step the product is now ready for use. If so wanted or commercially required a certain amount of ethyl anhydrous or hydrated alcohol may be added to the ready claimed product so that ready product is provided with the required density for its final use. Otherwise, the product may be simply used as a pure product.
All containers used in the processing steps should be made of a type of material that does not allow oxides to be aggregated to the ready product. Preferably, the container made material should be one of porcelain, stainless steel or vitreous type.
All ingredients used to produce said bio-combustible should be reused for new reactions after being properly treated so as to decrease the production final costs.
The instant descriptive patent application specification taught an innovative universal bio-combustible or additive that is provided with numerous differences over bio-combustibles or additives now available in the market as it may be evidenced through technical analysis carried out and illustrative figures. Further, said innovative universal bio-combustible or additive is provided with production technical features and functional features as well thoroughly distinctive from those now existing in the prior art.
Because of the advantages it offers and yet for being provided with truly innovative characteristics that meet every feature for novelty and originality in such field the instant invention “Process for obtaining a reagent combustible for mixing with other combustibles” brings to knowledge all required and sufficient conditions to be deserved an invention privilege.
| Number | Date | Country | Kind |
|---|---|---|---|
| 106059 | Dec 2011 | PT | national |
This application is a continuation of prior filed International Application No. PCT/IB2012/002605, as filed on Dec. 5, 2012, which claims priority to Portuguese Patent Application No. 106059, as filed on Dec. 15, 2011. The contents of which are herein incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/IB2012/002605 | Dec 2012 | US |
| Child | 14304584 | US |
