MXPA02001853A - Improved liquid smoke coloring agent solution made from liquid smoke organic precipitate - Google Patents

Abstract

A liquid smoke coloring agent solution having total water miscibility, a low B(a)P under about 5 ppb, and a pH above about 11, and a related method for making same. The liquid smoke coloring agent solution may be made from commercially existing liquid smoke compositions.

Description

IMPROVED LIQUID SMOKE COLORING AGENT SOLUTION PREPARED FROM THE ORGANIC LIQUID SMOKE PRECIPITATE Technical Field The present invention concerns, in general, a liquid smoke composition. Said liquid smoke compositions are used to color and flavor edible foods. More particularly, the present invention concerns a precipitate from a liquid smoke composition, said precipitate provides an improved coloring agent solution. Table of Abbreviations HNjOH Ammonium Hydroxide B (a) P Benzo (a) Pyrene Ca (OH) 2 Calcium Hydroxide C Centigrade F Fahrenheit G Gram mg Milligram ml milliliter ppb parts per billion polynuclear aromatic hydrocarbons KOH potassium hydroxide? AOH hydroxide sodium REF. 135729 Background of the Invention Foods that have been smoked, since the first humans used the fire to prepare meals, to provide flavor, color and preservation. Initially, preservation was the last rrach to smoke food, but as advanced food preservation techniques, flavor and color become the main reasons for smoking food. When societies become more industrialized, the substitution of individual or home smoking to processes in specialized plants led to the need for improved control of smoking procedures, which include consistent smoking application techniques. Consequently, liquid smoke compositions (also known as liquid smoke solutions, and colloquially mentioned as liquid fumes), were developed as a replacement for the smoking of food by direct contact with smoke in a smoking chamber. Said compositions have become a standard industrial practice. When applied to the surface of meats and other proteinaceous foods, such as various types of sausages, frankizort sausages, mortadelas, beef rolls, hams, and the like, liquid smoke gives the product a characteristic smoky flavor and produces a dark smoky color. Achievement of the product as a smoking chamber by application of an aqueous smoke solution to a food liquid smoke compositions. Phenols and carbonyls can be measured as described in Nicholson Patent No. 4,431,032, mentioned above. The darkening potential of liquid smoke compositions can be measured by the Darkening procedure well known in the art, described in U.S. Pat. No. 4,994,297 of Underwood or by the procedure of the staining index well known in the art involving the reaction of liquid smoke with glycine. It was observed that acids and carbonyls are secondary in contributing to liquid smoke compositions. The color value can be measured as described in the aforementioned US Patent No. 5,681, 603 of Underwood. The patent ? 603 by Underwood also describes how to measure B (a) P, which is cecinnogenic and therefore should be below 10 ppb. As a general background, improved liquid smoke compositions and techniques for their manufacture are described in US Pat. No. ND. 4,154,866 by Dainus, Dane, and O'Hara (assigned to Stange Co.) And U.S. Pat. No. 4,994,297 from Undewood (assigned to Ensyn Engineering Associates, Inc.). As the arrival of the liquid smoke compositions has significantly improved the processing of the meats, attempts have been made during the past 20 years or by treat it like this, the problem of the precipitate of liquid smoke. In the storage of a liquid smoke product, the precipitate is separated by sedimentation forming a water-insoluble, adherer.te, viscous residue at the bottom of the container for liquid smoke. Furthermore, even though the liquid smoke is aqueous, the smoke is not completely soluble in water, which exacerbates the problem of the precipitate. More specifically, the precipitate can take place in the dilution of liquid smoke with water. However, the presipitate can be preserved in emulsion. For example, U.S. Pat. No. 4,442,868 by Smith and Kearby (assigned to Teepak), describes the treatment of liquid smoke with alkaline agents at a pH of 10 or higher to dissolve the precipitate so that they remain in solution and produce a flavoring / coloring agent for use in coatings. Furthermore, not only US Pat. No. 4,446,167 to Smith and Kea | rby (assigned to Teepak, Inc.) discloses the formation of a basic coloring / flavoring smoke from natural wood smoke, together with food coatings and food products using the colorant / sa Orizante, but also this US patent, is closely related to the description of? 868 by Smith and Kearby.Also, as described in US Patent No. 5,690,977 to Hammer, Mans, and Winter (assigned to Hoeschst AG), described is a modified liquid smoke solution containing an unmodified aqueous liquid smoke solution and an alkaline neutralizing agent. The composition may also include a natural or synthetic oil, a viscosity enhancing component and one or more emulsifiers. The liquid smoke mixture is described as containing the alkaline neutralizing agent in an amount such that the mixture has a pH of about 8 to about 14, and preferably about 8.5 to about 12. Alternatively, the precipitate may be removed, which can be achieved by a solvent extraction process used on the liquid juice to create a supernatant fraction of tar-depleted liquid smoke, followed by gravity separation of the two fractions, as described in US Pat. No. 4,431,032 of Nicholson (assigned to Union Carbide Corporation). Also, the Utente No. 4,604,309 and Goldberg (assigned to Teepak, Inc.) describes a method for producing a liquid smoke solution that includes the step of neutralizing liquid smoke with a base such as sodium hydroxide at a pH of 6 to 7 which causes tar precipitation. The precipitate is discarded.

The aqueous portion can be extracted with organic solvents before or after the treatment with the base. Besides, the U.S. Patent No. 4,834,993 of Chiu (assigned to Viskase Corporation), describes a liquid smoke pollution that is prepared by means of precipitated tars by neutralization of a liquid acid smoke compost, followed by subsequent discarding of the tars.

The neutralized liquid smoke composition preferably retains a pH of from 5 to 9. Additionally, U.S. Pat. No. 5,637,339 to Moeller (assigned to Hickory Specialties, Inc.), describes how to treat liquid smoke with activated carbon particles to remove tars and create a tar-depleted liquid smoke that is completely miscible with water. Of more particular interest in relation to the present invention is the process of U.S. Pat. No. 4,278,694 to Chiu (assigned to Union Carb) ide Corporation =, which describes methods for preparing aqueous compositions of liquid smoke, which include a concentrated aqueous composition of liquid smoke. The concentrated aqueous liquid smoke composition was prepared by substantial neutralization of a liquid smoke solution containing flavoring constituents and smoke dyes at a pH of more than 4 with an alkaline neutralizing agent to form a smoke tar precipitates. The precipitated smoke tar is then separated from the supernatant liquid and is then subsequently dissolved in a water soluble alcohol that solubilizes the agent to form a liquid smoke composition with smoke tar having more than about 15% by weight of dissolved smoke tar.

The pH range established for neutralized compositions is from about 4 to about 8. The precipitate is derived from a substantially unrefined liquid smoke source and thus includes a high concentration of tar, which includes high levels of undesirable tar components, which includes benzo (a) pyrene, currently known to be carcinogenic. An improvement is exposed in the most recent U.S. patent. Do not. ,681,603 from Underwood (assigned to Red Arrow Products). More specifically, Underwood describes how to make a flavoring / coloring composition by contacting sub-product of water-insoluble tar (of liquid smoke), with an alkaline solution at a pH higher than 10. The tar solution is then put in contact with certain resins based on non-ionic aromatic hydrocarbons to reduce the benzo (a) pyrene content to 10 ppb or less. The descriptions of all the aforementioned patents are incorporated herein by reference. In spite of the procedures discussed above for using the precipitated components removed from the liquid smoke (such as using tar as described in 694)from Chiu and x603 from Underwood), however, there are still problems with such procedures. For example, the Underwood 603 process has a flaw in that the process includes a time-consuming, time-consuming step of the resin to remove carcinogenic benzo (a) pyrene. Thus, it is desirable to find an improved liquid smoke composition that is manufactured from the precipitate and a method for manufacturing the same, the composition and method of which evidences the aforementioned problems. Summary and Objects of | Invention Accordingly, the present invention provides a method for manufacturing a liquid smoke coloring agent solution. The method comprises the step of contacting a liquid smoke composition as an initial material with water and an alkaline agent. The composition of liquid smoke as material i. The initial includes an organic component, which will fall as an organic precipitate when the liquid smoke composition as the initial material is brought into contact with water. The piesta in contact with water and an alkaline agent, produces a solution of liquid smoke coloring agent having an alkaline pH of approximately 11, which is completely miscible in water, and which has a benzo (a) pyrene content of less than 5. parts per trillion free of treatment, of the liquid smoke coloring agent solution for benzo (a) pyrene removal.

Additionally, the present invention provides a solution of liquid smoke coloring agent completely miscible in water, which (i) possesses a benzo (a) pyrene content of less than about 5 parts per billion absent from treatment for removal of benzo (a) pyrene, (ii) has a pH of about 11, and (iii) is derived from a liquid smoke composition as an initial material containing an organic component, wherein the organic component will separate as a precipitate from the contacting the composition of liquid smoke as starting material with water Preferably, the final liquid smoke coloring agent solution has a phenol content greater than about 35 mg / ml and / a color value greater than about 500. The present invention It also contemplates a food coating tr ate with the solution of liquid smoke coloring agent, The treatment can be by spraying the solution on a To the surface of the coating, or in the case where the coating is made of extruded polymeric plastic film, the solution can be sprayed onto a surface of the film or it can be incorporated into the extrusion with the polymer resin beads and thus mixed into the film. resulting plastic.

The present invention also contemplates a proteinaceous food, such as various types of sausages, frankfut sausages, mortadelas, meat rolls, hams, and the like, treated with the new solution of liquid smoke coloring agent. Therefore, e? It is an object of the present invention to provide a solution of liquid smoke coloring agent and related manufacturing methods, wherein the solution will not form a tar precipitate from dilution with water. Therefore, it is an advantage of the present invention that the coloring solution of liquid smoke coloring agent is completely miscible in water, since when applied to food or food re • coverings, it can be diluted with water pe: or not Will it form tar precipitates that stick to the? walls of the pipe system of the application apparatus. It is a further advantage that the liquid smoke coloring agent solution of the present invention is extremely low in B (a P and not otherwise carcinogenic, treatment for B (a) P removal, absent.) Some of the objects and advantages of the present invention have been previously established, other objects, as well as other advantages, will become apparent as the description proceeds, when relate to the Lab examples and detailed description that follows. Detailed Description of the Invention Traditionally, the water soluble precipitate, after isolation from the liquid smoke composition, is discarded. As will be demonstrated in the following, the present invention is directed to a method of preparing a flavor and smoke colorant from this water insoluble precipitate, to provide a commercially useful product and to: substantially reduce the volume of precipitate discarded. The present invention is directed to a solution of liquid smoke coloring agent manufactured by contacting a liquid smoke composition as an initial material with water to cause an organic component of the liquid smoke composition as the starting material to be separated by precipitation. Then, the pH of the organic precipitate is adjusted to about 11.0, more preferably about 11.4 or more, and equally more preferably about 11.8 or more, with an alkaline agent (such as NaOH, KOH, Ca (OH) 2, or NHQH), resulting in a solution of liquid smoke coloring agent. Optionally, a portion of the at-alkaline agent can be added to the liquid smoke composition before the addition of water, as further explained above. The solution of liquid smoke coloring agent resulting from the invention has a low content of B (a) P of less than about ppb, more preferably less than 3 ppb, and also more preferably less than about 1 ppb, free of any treatment of the resulting liquid smoke coloring agent solution, to remove B (a) P. In addition, the liquid smoke coloring agent solution resulting from the invention possesses excellent color capacity as well as flavoring ability. As is well known, water-insoluble precipitates of liquid smoke compositions typically contain in excess of 100 ppb of B (a) P. Many polynuclear aromatic hydrocarbon compounds, including B (a) P, are known carcinogens. Thus, until now, it was important to reduce the P.AH content of some compositions (made from the precipitate and used to be in contact with a food), as much as possible. Specifically, it was important to reduce the concentration of B (a) P, which is known as a potent carcinogen, up to about 10 ppb or radishes, and preferably up to about 1 ppb or less, but such treatment is unnecessary with the present invention. In the following Lab Examples, in order to produce a liquid smoke coloring agent solution, a liquid smoke composition (containing a component organic that is separated by precipitation from contact with water) treated by the method of the present invention was Code 10 as the starting material. Code 10 is commercially available from Hickory Specialties, Inc. of Brentwood, Tennessee. Additionally, the initial material of the liquid smoke composition employed may be SUPERSMOKE, also commercially available from Hickory Sspecialities, Inc., and manufactured by the well-known process of evaporation to the reservoir, which concentrates the Code 10 by removing some of the water from the reservoir. Code 10. As a result, SUPERSMOKE has a typical acidity of approximately 16 ° G f while Code 10 has a typical acidity of approximately 11%. Other commercially available liquid smoke compositions of the present invention for producing a liquid smoke coloring agent solution, while the liquid smoke composition as the initial material is not completely miscible with water (ie a precipitate is separated when water is added) , and has a low B (a) P of less than about 10, more preferably less than about 5, and more preferably less than about 1 ppb.

In addition, as can be seen from the following Lab Examples, the inventive method produced a solution of liquid smoke coloring agent as a result and when the result is then diluted with water, it does not precipitate tar, Thus, the result was completely miscible with water, With the present invention, the contact of the liquid smoke composition as the initial material, with water and the alkaline agent, in order to produce a solution of the liquid smoke coloring agent could be a conditions of temperature and pressure inferior to the environmental ones. Furthermore, the contact time is not particularly long, and depending on the particular type and amount of ingredients, the contact time only needs to be sufficient to cause the organic precipitate to separate and then internalize in the aqueous solution. discontinuous processes, wherein the liquid smoke composition is placed in a stirred container, followed by filtration to separate the organic precipitate from the liquid smoke composition, In addition, from the filtration, the method for separating the organic precipitate may include decanting by gravity, by means of cyclone for liquids and decantation by centrifugation. The resulting liquid smoke dye agent solution of the present invention typically has a phenol content (flavor indicator) of at least about 35, more preferably at least about 40, and likewise more preferably 45 or more mg / ml, and a color value of at least 500, more preferably at least about 600, and most preferably 650 or more. Additionally, the food coatings can be treated with the liquid smoke coloring agent solution. In the case where the coating is of the fibrous type, the treatment may be to spray the solution onto a surface of the coating. Typical fibrous coatings are cellulose in nature. In the case where the coating is made of extruded polymeric plastic film, the solution can be sprayed onto the surface of the film. Alternatively, the solution can be incorporated into the extruder with the polymer resin beads and thereby be mixed into the resulting plastic film. Typical polymeric plastic films include, but are not limited to, polymer films selected from the group consisting of ethylene vinyl acetate, ethylene acrylic acid, ethylene methacrylic acid, linear low density polyethylene, low density linear low density polyethylene. Sometimes referred to as ultra low density polyethylene), and combinations of polymers. Additionally, a proteinaceous food can be treated with the liquid solution of liquid smoke, such as by spraying on the surface of the proteinaceous food.

Examples of various types of proteinaceous foods include, but they are not limited to, sausages, frankfut sausages, mortadelas, meat rolls, hams, and combinations of proteinaceous foods. Laboratory Example B In the following Laboratory Examples, the methods used to determine phenols and carbonyls are well known to those skilled in the art and are published in columns 11 and 12 in U.S. Pat. No. 4,431,032 mentioned above from Nicholson. In addition, in the following Laboratory Examples, the methods used to determine the ppb of B (a) P and the color are well known to those skilled in the art and are published, respectively, in columns 7 and 8 and in the column 20, in the US Patent No. 5,681,603, previously mentioned by Underwood. Also in the following Laboratory Examples, the methods used to determine the dyeing index and the acid percent are well known to those skilled in the art, and are set forth as follows STAIN INDICATION 2.5% Glycine Reagent in Acetic Acid 95% Suspension of 2.50 grams of glycine (Eastman # 445) with 5.0 ml of distilled water in a? 150 ml precipitates. Addition of approximately 1 ml of glacial acetic acid and heating on a steam bath, stirring occasionally to dissolve the glycine. Transfer to a 100 metric volumetric flask, cooling to room temperature, and adjusting the volume with glacial acetic acid which is used to increase the volume to the original volume of the vessel. If some glycine is separated by crystallization, filter the solution before using it. This solution is stable for at least three weeks, and probably indefinitely: e. Liquid smoke solution at 5%. Dilute 2.5 ml of liquid smoke to 50 ml with glacial acetic acid. Reaction: 1. Use two 25 ml graduated test tubes, add 1.0 ml of the 5% liquid smoke solution to 10 ml of glycine reagent and add 1.0 ml of the 5% liquid smoke solution to 10 ml of glacial acetic acid (White) . 2. Cover each of the beakers tightly with a para-film square, and mix by turbulence and place in a water bath at 85 ° C for 30 minutes. 3. Transfer each of the beakers in a cold water bath and dilute them partially with distilled water for rapid cooling. When each one is at the terpinar ambient temperature, dilute them to the 25 ml mark and mix by inversion. 4. Set the spectrophotometer to zero using water distilled Read the absorbance of each solution in a 0.5-inch cell using a spectrophotometer at 440 millimicrons. 5. Calculate the net absorbance by subtraction the target reading (consisting of 1.0 ml of 5% liquid smoke solution, 10.0 ml of glacial acetic acid, and distilled water up to 25 ml) from the reading of the test sample. 6. Calculate the staining index (SI) SI = Net Absorbance X 100. Percentage of acetic acid: Pour 250 ml of. distilled water in a 400 ml beaker, li: t? pio. Introduce 6 ml of liquid smoke. Standardize the pH - meter with pH 7 buffer solution. The pH meter should be at 7.00. If not, use the control button and place it there (in pH-7). Rinse the glass electrodes with a?: Ua distilled from the spray bottle. Place the beaker of smoke-water mixture on the test platform, and lower the pH electrodes. Shake the mixture, add in normal sodium hydroxide solution of 1.0 of normality. Add the sodium hydroxide solution until the pH-meter reads 7.00. The amount of milliliters of sodium hydroxide placed in the smoke mixture is the percentage of acetic acid. For example, 1 ml of sodium hydroxide entering in the solution of liquid smoke - water will represent a point of acetic acid, until the pH-meter reaches a value of 7.00. in other words, if 9.4 ml of 1.0 N solution of sodium hydroxide D are introduced, the acetic acid reading will be 9.4% acetic acid by volume. The calculations are as follows:% acetic acid = [(ml of NaOH) X (Normal of NaOH) X 0.1 (correction to% X (equivalent weight of acetic acid)] divided by milliliters of liquid smoke of acetic acid [ (9.4 ml of NaOH) X (1.0 of Normality) X (approximately 60) divided by 6.0 ml of liquid smoke, and thus, 2 of acetic acid = 9.4 It was observed that some information was omitted in the previous tests, since it was not typical of the type of product involved. Acidity and carbonyls were not measured or they were not meant in an alkaline environment. The color test was not run on the low pH (acid) smoked products, since they were not examined by the staining index values. Example 1 A liquid smoke composition having a titratable acidity of 10.6% (Code 10 of Hickory Specialties, Inc. was placed in a container and mixed with water to a Jahla-l (%) Carbomlos Phenols (%) • B (a) P Sample Acidity Color (gflQQgj { Mg / ml) Dilution (ppb) of water Codß 10 10.8 2.1 ** 18 17. 0.5 (initial material) First 12 656 - 50 < 1 Second 12 650 50 Third 12 697 45 50 10 ** Instead of the color, it was determined that the staining index was 85 fifteen Example 2 A liquid smoke composition having a titratable acidity of 11.0% (Code 10 from Hickory specialties, Inc.) was placed in a container and treated with 50% NaOH until the pH was 6.0. The addition of NaOH caused an organic precipitate to form, which settled to the bottom of the container. One liter of the precipitate (38.8 g) was mixed with 17.5 ml of 25% NaOH sol. Then 17.5 ml of dilution water was added to adjust the viscosity. The final coloring agent solution had a pH of 12 and is indicated ep. Table 2 below as the first sample.

(%) Carbonyl Phenols (%) B (a) P Sample Acidity BU Ssler Wioog) (mq / l) Dilution íßfi) of water Codß 10 11.0 2.J 19 17.5 0.5 (initial material) First 11.8 673 49.8 0.8 - ** - Efi-ez-de-i-eo-Jr? -F- -se- det-rm-irn-ó- eXXpá ± cß- d -trtrc ± t5tr-crse-rj-é - d? - its T fifteen Table 3 (%) MüQStra (%) Carbonyl Phenols Dilution B (a) P Acidity gH Color .y / 100a "l (mo / mll gives water (ppb) SUPERSMOKE 16.0 2.0"37 38 - 0.8 (initial material) First - 12 690 - 50 < 1 fifteen Example 4 (Food processing) Various proteinaceous foods can be treated with the liquid smoke coloring solutions of Example 1 (samples 1 to 3) and Example 2 (sample 1). Foods can be treated by applying to each one, liquid smoke coloring agent solutions, to the surface of foods that are sausages, frankfurters, mortadella, meat rolls, and hams. Excellent cabbage and flavor is obtained, Example 5 (Treatment of food coatings! Food coatings can be treated with the liquid smoke coloring agent solutions of the Example 1 (samples 1 to 3) and Example 2 (sample 1). The selected coatings can be fibrous coatings and can be treated by individually spraying each with the solution of liquid smoke coloring agent on the surface of each of the respective coatings. The selected coatings can be polymeric plastic films ext. Noise and can be treated by spraying Individually cade, one with the solution of liquid smoke coloring agent softens the surface of each of the respective coatings The selected coatings can be films of extruded polymeric plastic and can be treated by individually incorporating each of the liquid smoke coloring agent solution with each of the respective classes of polymeric resin beads and thus mixing each of the solutions in each of the resulting films. The polymeric polymer films can be ethylene vinyl acetate, ethylene acrylic acid, ethylene methacrylic acid, linear low density polyethylene, linear low density polyethylene of very low density, and a combination thereof. The same foods (either treated or untreated) that are cited in Example 4 can be packaged with the various treated coatings, and the packaged food would have excellent color and flavor. It will be understood that various details of the invention can be changed without departing; = of the scope of the invention. In addition, the foregoing description is for the purpose of illustration only, and not for the purpose of limitation - the invention is defined by the claims. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is the invention for the manufacture of the objects or products to which it refers.

Claims (7)

1. RE VINDICATIONS Having described the invention as above, it is claimed as property 1 contained in the following claims: 1. A method for making a solution of liquid smoke coloring agent which is characterized in that it comprises the step of contacting with water and an agent alkaline, a liquid smoke composition as starting material, having a benzo (a) pyrene content of less than about 10 parts per billion and including an organic component, which is separated as an organic precipitate when the composition of liquid smoke as initial material is contacted with water, to produce, from the organic precipitate, a solution of liquid smoke coloring agent that (a) ternga an alkaline pH greater than about 11, (b) is completely miscible in water, and (c) possesses a benzo (a) pyrene content, less than about 5 parts per billion without treatment of the coloring agent solution of h umo liquid for benzo (a) pyrene removal.
2. 2. The method of claim 1, characterized in that the pH is greater than 1.4.
3. 3. The method of claim 2, characterized in that the liquid smoke composition as starting material has a lower benzo (a) pyrene content. approximately 5 parts per billion.
4. 4. The method of claim 1, characterized in that the solution of liquid smoke coloring agent has a color value greater than about 500.
5. 5. The method of claim 4, characterized in that the solution of liquid smoke coloring agent possesses a color value greater than about 600.
6. 6. The method of claim 5, characterized in that the liquid smoke coloring agent solution has a phenol content, taste indicator, greater than about 40 mg / ml,
7. 7. The method of claim 1, characterized in that the liquid smoke coloring agent solution has a content of phenols, taste indicator, greater than about 35 mg / ml. The method of claim 1, characterized in that the alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, and combinations thereof.