JPS60500990A - Tar reduction solution and method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Tar reduction liquid kun solution and method field of invention The present invention provides (a) tar reduction from smoke vapor; ) Manufacturing method for liquid-kun solution, (b) Tar-reducing liquid-kun composition, (C) Cool reduction Slightly, partially neutralized liquid composition, (colored with DL tar reduction liquid composition and a flavored food casing, (e) colored and flavored with a tar-reducing liquid-kun composition; (f) a method for producing a food casing with a casing; Concerning a method for producing smoke-flavored food.

Background of the invention Cellulose-based tubular food casings are widely used for meat products and other products. Widely used to process shaped foods.

Food casings are typically made from a variety of reconstituted materials, such as regenerated cellulose. It is a thin-walled tubing material with a diameter. Cellulosic food casing is also a fibrous web can also be made by embedding it within the walls of the casing; such casings are usually called ``fibrous food casing''.

Processed food industry to adapt to different tastes and even regional tastes The many different cooking methods and processing styles used in prize casings have a wide variety of characteristics. requires the use of For example, food casings should have multiple functions. There are some cases where this is required, in which case the food casing is It serves as a container during the processing of food products and as a protective packaging for finished products. It also plays a role. However, in the processed meat industry, many types of meat products, e.g. Various types of sausages such as na sausages and bologna sausages, beef rolls , slicing and/or final processing of food casings used to produce ham, etc. It is often removed from around processed meat products prior to packaging.

Appearance and flavor are important factors in the commercial and consumer acceptance of processed meat products. Yes, and the common feature of most types of such products is that the product has a characteristic flavor and color. This includes the use of ``1 smoke'' to impart. The “smoke” of food is one This is commonly done by food processors and involves the actual contact of food with gaseous or cloud-like smoke. It is something that can be done. However, such a “fumigation” process results in inefficiencies in the “fumigation” operation. This is not considered completely satisfactory for various reasons, including lack of uniformity and It wasn't. Due to the shortcomings experienced by many meat packers, they are often used in the food processing industry. It has been developed and used commercially to process many types of meat and other foods. Using various liquid bath solutions of water-induced smoke components, usually called "liquid solutions" There is. In this specification, for convenience, these commercially available "desired" The solution is prepared as is. It's called <.

An example of the method for producing liquid liquid as it is is given by Hollenpeck (October 8, 196'5). U.S. Patent Nos. 4106.475 and 1 issued to U.S. Patent No. issued to Melcer et al. on March 25, 1975 ! I, No. 873.741. The manufacturing method of liquid°kun is generally as follows. , (1) Heat the wood in an oxygen-controlled atmosphere to pyrolyze the wood and generate smoke, ( 2) From contacting the smoke with an aqueous solution to condense and recover the coloring and flavor components of the smoke. It can be explained that The condensed raw liquid solution is usually mixed with various It also contains tar-like substances and organic acids such as acetic acid.

The application of "liquid solution" to meat products is usually done by spraying the packaged food during processing. or by a variety of methods, including soaking, or by adding a "liquid solution" to the cooking method itself. This is done by adding it to the . Actual operation of "fumigation" by spraying or dipping should not be completely satisfied because it is not possible to uniformly process the packaged product. Adding a “liquid” to the meat cooking method will dilute smoke components. It does not necessarily give the desired appearance. Also, joining the cooking method is Decreases the stability of the emulsion and adversely affects taste when used at high concentrations. Ru. Food processors may apply liquid to packaged foods, such as by spraying or dipping. It also poses unwanted contamination and equipment corrosion problems for food processors. wake up In addition, packaged saws can be removed by applying liquid during commercial processing. If the sage is treated, after the casing is removed from the treated packaged food, the individual Sausages that lack uniformity of smoke coloring between individual sausages and batches of sausages It was found that this caused a large amount of damage. What is even more undesirable is the lack of uniformity in coloring. often appears on the surface of individual sausages, and such uniformity of coloration Lack of sex can be caused by dark and light streaks, dark and light spots, and even coloration that appears especially on the ends of the sausage. Includes spots that are not visible.

inside or outside the food casing, designed to meet specific processing requirements. Application of various liquid substances, e.g. substances that affect the adhesion of the casing. Some methods are known. Some of the coatings known in the art contains liquid as a component.

The known method of applying neat liquid solution to the inside of the casing is expensive. It has also been found to limit the speed of continuous high-speed production systems.

For casings, especially cellulose gel material (gel-stack) casings Known methods of applying neat fuming solutions are Problems arise due to the amount of oil contained. That is, during the application process, tar-like deposits are It deposits on the carrier roll and squeeze roll of the processing unit and ultimately destroys the processing system. forced to stop operating.

(For the above problem of imparting smoke color and flavor to food) One solution is to use a "tar-reduced" liquid bath to clean the inner surface of the casing. Alternatively, preferably the outer surface is coated. However, until recently, tar decreased Liquid liquid solution was not available and the method for making it was unknown. . As mentioned above, cellulosic foods made from fibrous or non-fibrous gel materials Treat the casing with a highly acidic (pH approximately 20-2.5) tar-containing aqueous liquid. If tar-like deposits are present on the carrier roll and squeezing roller of the fume treatment unit, deposits on the rolls, causing the casing to stick to the rolls and eventually shutting down the unit. I found that I was forced to. The acidity of the liquid also depends on the remover used, e.g. The peelability of the casing can be improved by blocking the action of carboxymethyl cellulose. It impairs peelability. Liquid aqueous solutions are usually extremely acidic. and has a pH of 2.5 or less and a titratable acidity of at least 3% by weight. have

By neutralizing the liquid as it is under constant temperature conditions and precipitating the tar. Tar can be removed from the liquid, and this neutralized tar-reducing liquid is used. Treating the gel material casing with I understand. This process was published by M.T. Nicolman on September 14, 1982. (M, l).

U.S. Patent Application No. 417,172 filed by N1cholson) K. as disclosed and claimed in .

Contrary to previous opinions in this field, Tar Reduction Liquid-kun 6 Machitosho GO-5009 90(4) It still has considerable smoke coloring ability. The tar in the liquid is mainly deposited on the liquid. It has been generally believed that it contributes to color ability. However, this is not true , other components of liquid, mainly carbonyl components, are responsible for the coloring ability of liquid It became clear to Ashichika that he had an even more important role to play.

Another method using a solvent extraction process can be used to produce tar reduction liquid. can. For example, such a process was introduced on September 14, 1982 by M.D. ・U.S. Patent Application No. 41 Zl 7 filed by Nicolman! Open to i issue As shown and claimed. This process consists of (a) a wavelength of approximately’s 40n A tar-containing water test solution having an absorption capacity of at least about 0.25 m A tar-rich solvent fraction with a hydrogen bond dissociation parameter of approximately 27 and tar reduction. A liquid that is immiscible and non-miscible in aqueous solutions under conditions sufficient to form a small liquid liquid fraction. Contact with a reactive or reactive-like liquid solvent and separate the BL liquid fraction to form a tar. It consists of forming a reduced fluid. If such a solvent extraction method is used, tar-containing High ability to impart smoke color, odor and flavor without the need for neutralization It is possible to produce a tar reduction liquid solution having the following properties.

Tar reduction liquids made from solvent extraction processes are usually highly concentrated if not neutralized. A certain divine 7i (vulgar) is a highly acidic substance that can also be used for casing. may interfere with the action of strippability aids such as cellulose ethers. To alleviate this problem, For this purpose, the tar reduction liquid can be partially neutralized. However, the coloring ability of liquid Since the force decreases as the pH increases, the tar reduction solution has a large strippability aid. It simply partially neutralizes the smoke to the extent that it retains its coloring ability without being seriously affected. Ru. As used herein, the term "partially neutralize" refers to pH, preferably within the range of about 3 to about 45, more preferably about We intend to refer to liquid compositions having a pH within the range of 6-5. solvent extraction pro By giving a partially neutralized tar reduction liquid made from tar Problems caused by acidity are largely eliminated while retaining a considerable degree of coloring ability in the original liquid. avoided.

The liquid compositions described above, whether intact or tar-reduced, are Found suitable for use with fibrous cellulosic food casings. Ta.

However, these liquid solutions are unrivaled when used on non-fibrous casings. Unconcentrated: Smoke color and odor in the as-manufactured state. flavor, which imparts flavor to food, but is sufficient to be acceptable for all commercial uses. It turned out that it was not a large amount. Non-fibrous casing is thinner than fibrous casing Therefore, liquid-kun always achieves the desired smoke color, odor and flavor in the actual process. The casing can be coated, applied or attached to the case sufficiently to be applied to the object. I can't. Therefore, the use of these compositions is primarily limited to fibrous casings. and cannot be used for general purposes.

Provides a liquid solution with sufficiently high coloring capacity to be used on non-fibrous casings. For example, on February 14, 1983, M.D. Nicolman and Jie - U.S. application filed by H. Beckman (J, H9 Beckman) As disclosed in National Patent Application No. 465.924, tar reduction solution has been concentrated to form a tar-reducing concentrate solution. Tar-reduced concentrate Kun solution has higher coloring capacity. Therefore, tar reduction and concentrate dissolution The liquid can be used to color light-colored foods even when using non-fibrous casings. It is possible to have sufficient coloring ability to

Tar Reduction Concentrate Kun solution is unneutralized tar reduction made from a solvent extraction process. A process consisting of semi-degrading the low liquid composition and concentrating the unneutralized tar reduction liquid. It can be manufactured by a process. Concentrated tar reduction liquid product is amazing Concentrates that have moderate and advantageous physical properties and are optionally neutralized and partially neutralized. It can be made into a tar-reducing liquid composition.

- The above-mentioned tar reduction concentrate solution is used to solidify when concentrating raw smoke. avoid the difficulties of existence. Such difficulties include undesirable chemical *e.g. It is desirable to contribute to increased concentration and flavor capacity, but at higher concentrations it becomes undesirable. 1. Increased residual dust of certain other ingredients that cause a "strong" or "creosote" flavor. There is a large one.

One of the problems when concentrating a liquid solution is to transfer the neutralized liquid to a non-fibrous casing. The viscosity is large and desirable when concentrated to a high degree suitable for application. The purpose is to make the concentrated liquid produced by increasing the concentration to such an extent that it becomes unsuitable for commercial use. . Neutralized intact and tar-reduced liquid solutions can be concentrated to increase viscosity. This is largely due to the presence of acids, mostly acetic acid, in the liquid. liquid-kun middle school When neutralizing acids, neutralized salts of these acids are formed and are the main cause of high concentrations. The substances used are these salts. In a non-concentrated fume solution that neutralizes, the concentration of these salts is usually not high enough to cause difficulties. However, there are places where neutralized smoke can be reduced. When the concentration of these salts increases linearly with enrichment, the normal This results in an undesirably high viscosity.

Youni-Nicholson and Beth, disclosed in U.S. Application No. 465.924, mentioned above. When concentrating unneutralized tar reduction liquid using It has now been found that the concentration of kun does not increase in proportion to its concentration. In other words, the unneutralized To a considerable extent, the acids that cause viscosity difficulties condense the smoke and reduce the It is clear that it evaporates. In this way, it concentrates while maintaining an appropriately low viscosity. It is possible to produce a liquid liquid solution.

The tar-reduced tar-reduced composition of No. 465.924 mentioned above has a total acid content of Due to its low content, it is neutralized and has a low viscosity. In addition, such compositions also contain The tar reduction solution is reduced, thereby reducing the Provides processing advantages previously found only in Such compositions may also be unconcentrated It also has significantly increased smoke coloring and flavor capacity than the tar reduction solution. Ru.

In addition, the increase in the viscosity of the concentrated raw fuming solution may be due to the liquid composition. This may be due to the presence of high molecular weight polymerized tar components in the product. tar The low amount of tar in the reduced concentrate composition also means that unneutralized and partially neutralized Both conditions contribute to the low viscosity.

Tar-reducing concentrated liquid-kun solution has many advantages, but in the past, it has been Further processing was required. The extra processing reduces the tar in the raw fumes. If a liquid is desired for processing and concentrating to reduce the amount of tar, the resulting tar reduction liquid is used. Includes processing to concentrate.

In this way, to produce concentrated and unconcentrated tar reduction liquid-kun solutions, Excessive processing of the liquid requires processing equipment and extra labor costs, which is costly. It takes. Therefore, tar reduction with the ability to color concentrated or unconcentrated liquid solutions Additional processing steps beyond forming a liquid solution by vertically combing the liquid liquid with smoke vapor It is advantageous to produce the product without further processing.

US Special Report No. 4 issued to Sm1ts et al. on November 6, 1982. ．． Subheading 359.481 describes fractional vertical assembly, i.e. cooling of fuming vapor in various stages. Discloses a method for producing liquid with reduced tar content by . Liquid products such as Sumitsu are manufactured for flavor binding and have high coloring ability. It has not been shown that it has.

Therefore, the purpose of the invention is to reduce tar without processing the liquid as it is. The purpose is to produce a small amount of liquid solution.

Another objective is to use fewer processing steps and less expensive equipment than previously possible. It is an object of the present invention to provide a method for producing a liquid solution characterized by reduced tar content.

Another object of the invention is to obtain from the condensation of fuming vapor the coloring ability equivalent to that of an uncondensed liquid solution. It is an object of the present invention to provide a method for producing a tar reduction liquid solution having high strength.

Another object of the invention is to produce a condensed liquid (with coloring ability equivalent to that of a liquid solution) from the condensation of smoke vapor. It is an object of the present invention to provide a method for producing a tar reduction liquid solution having high strength.

Another object of the invention is to produce a tar reduction solution having a high carbonyl content. be.

Another object of the invention is to produce a tar reduction solution having high coloring capacity. be.

Another object of the invention is to produce a concentrated tar reduction liquid having high coloring capacity and low viscosity. is to manufacture.

Other purposes will become apparent in the following description.

Summary of the invention 2 One aspect of the present invention is to (1) pyrolyze wood in an oxygen-controlled atmosphere to produce smoke vapor; (2) selectively extracting tar from the generated smoke vapor with a solvent; (3) ) <Absorbing smoke vapor into an aqueous medium to form a tar-reduced liquid solution. This is a method for producing a tar-reducing liquid-kun solution containing.

Another aspect of the present invention includes (1) pyrolyzing wood in an oxygen-controlled atmosphere to produce fumes; (2) <smoke vapor, water, and a solubility parameter greater than about 27; This is a method for producing a tar-reducing liquid solution using an organic solvent.

Another aspect of the invention provides a method for producing wood in an oxygen-controlled atmosphere, including: contacting the vapor with an organic solvent having a solubility parameter greater than about 2.7. The method is characterized in that tar is selectively removed from fuming vapor by a method. .

Another aspect of the invention is to contact the fuming vapor with water and solvent in a single contact zone. Any of the above methods.

Another aspect of the invention provides a method for contacting the fuming vapor with the solvent in the first contact zone. Any of the above methods of contacting water in two contact zones.

Another aspect of the invention is to prepare a tar-reduced liquid by any of the methods described above. After manufacturing, the tar reduction solution is partially neutralized to a pF+ of greater than about 3, preferably or between about 6 and about 65, most preferably between about 3 and about 5. and a method for producing a tar-reduced, partially neutralized liquid solution comprising:

Another aspect of the invention is the unneutralized or partially neutralized tag made from any of the above methods. This includes a liquid-reducing liquid composition.

Another aspect of the invention is to contact the tubular casing wall with any of the fluid solutions described above. Tar reduced smoke colored and smoke flavored tubular food casings includes.

Another aspect of the invention includes a method for producing any of the liquid solutions described above.

Another aspect of the invention is to fill the tubular casing as defined above with food and to produce a The packaged food is subjected to conditions sufficient to transfer smoke coloring and smoke flavor components to the packaged food. A method for producing smoke-colored and flavored food comprising processing it with includes.

Brief description of the drawing FIG. 1 shows a flow diagram of a continuous process for producing a tar-reduced liquid according to the invention. It is Yagram.

FIG. 2 is a schematic diagram of a laboratory apparatus for producing a tar-reduced liquid in accordance with the invention; Ru.

FIG. 3 shows a liquid composition prepared by the method of the present invention on the outer surface of a food casing. 1 is a schematic diagram of an apparatus suitable for processing in

FIG. 4 shows a device similar to the device shown in FIG. 6 and which performs the same function as the device shown in FIG. The casing treated with the liquid composition of the present invention is partially dried while in the expanded state. FIG.

Figure 5 shows a device that is similar to and performs the same function as the device shown in Figure 4; Flattening the casing treated with the liquid composition produced by the method of the invention 1 is a schematic representation of an apparatus with means for drying during a period of time;

Figure 6 is a schematic diagram of the apparatus for producing the tar-reduced liquid used in Example 5. be.

Description of the invention As used in this specification and the appended claims, the following terms are defined as follows: to justify

“Solution” includes homogeneous true solutions, emulsions, colloidal suspensions, etc. Ru.

“Fumigation, coloring, odor, and flavor components” refer to imperfections in hard-wood water. It exists in a natural liquid solution made by condensing the smoke vapor generated by combustion. (Refers to smoke coloring, odor and flavor components. Examples include smoke, as it is, or in commercially available form. Includes liquid solution in water.

"Absorption capacity" is a measure of the coloring ability of a liquid solution. The absorption capacity of the liquid to be tested Put 1t1m9 of Kun solution (tar-containing liquid or tar-reducing liquid) into a disposable bag. Place it in a vial, add 5 milliliters (Jl) of methanol to it, and measure. Ba Mix the two ingredients with the jar upside down, then measure the UV absorption value of the mixture to 34. Measure at a wavelength of 0 nm. Tar content significantly contributes to absorption capacity measurements However, tar alone contributes only a small amount, if any, to the coloring of foods. It should be noted that this is not the case. In this way, commercially available neat fuming solutions The absorption capacity depends on the tar content and coloring components such as carbonyls, phenols, and acids. Includes ++ constant. This applies to both the intact fume solution and the tar-reduced fume solution. We have shown that the absorption capacity of liquids can be used to grade them for their smoke coloring ability. means. However, due to the absorption effect of tar, the absorption ability of the liquid as it is is reduced. It is not possible to numerically compare the absorption capacity of the tar-reducing fume solutions used in the light. .

The "absorption index" is a measure of the coloring ability of casings treated with the inventive liquid solution.

The absorption index is determined by measuring 2 square inches (129 square centimeters) of the casing to be tested. Cut out the cut out part and place it in 10 ml of methanol. . After about an hour of soaking time, the methanol has extracted all of the smoke components from the casing. The ultraviolet absorption value of methanol containing smoke components produced was 540. measured at a wavelength of nm.

"Total acid content" refers to the acids present in the liquid, mainly acetic acid 6 The concentration of Total acid content is determined by the following procedure: 1 ml of liquid (filtered if necessary) in a 1250 ml beaker Accurately weigh and add the liquid.

2. Dilute with 100ml of distilled water and use standard 0, IN NaOH Titrate to pH 8.15 (measured with a pH meter).

5. Calculate the total acid content as weight percent of acetic acid (1-IAc) using the following conversion: .

1m1a, 1o　o　NNaOH=6.01119HAcThis method neutralizes Measure the total acid content of the tar-containing and tar-reducing bath solutions. It can be used for.

"Light transmittance" is measured on a mixture of liquid solution and water. This measured Light transmission (compared to pure water) is inversely related to the tar content of the liquid being tested. Ru. That is, a high tar content results in a cloudy liquid with low light transmission. light A means of measuring the transmittance of a liquid is to mix a 1 ml aliquot of the liquid with 10 ml of water. Thoroughly mix the water and measure the turbidity using a spectrometer with a light wavelength of 590 nm. It is to measure the transmittance. The higher the transmittance % reading, the more residual in the liquid composition. Tar concentration decreases.

"Fumigation vapor" refers to the primarily gaseous products of restricted combustion of wood. smoke steam has a complex mixture of wood combustion products and depends on the wood used and the combustion conditions. change. Fumigation vapors are primarily gaseous, but can also be a mixture of various liquids and solid substances. Also includes id suspensions.

The fuming vapor in the method of the invention limits or limits the amount of atmospheric oxygen available for combustion. is generated by the controlled incomplete combustion of wood. Fumigation steam is in our field. It can be manufactured by any suitable method known in the art. A suitable method is to air Openings for controlled introduction, backing house type smoke generators and indirect heating calciners are installed. externally heated retort, which is essentially a cylindrical retort that rotates within a cylindrical furnace. Including using tort. A suitable method for generating fuming steam is the above-mentioned method. National Patent Coffin No. 3,106,476 and 3. a Disclosed in No. 73.741 Ru.

By carrying out the invention, it is possible to use solvents that do not remove fume coloring and flavor components. The method of selectively removing tar from the steam mainly removes a large amount of tar from the generated smoke vapor. Selectively removes tar, which is a cyclic aromatic hydrocarbon. Extracting tar from fuming steam A suitable method for this includes contacting a gas and a liquid to absorb the tar into a gas-liquid and/or liquid. - Including methods of removal by liquid extraction.

(Solvent extraction of tar from fume vapor is the process of selectively removing tar from fume vapor and inhaling it. This is done by bringing fuming vapor into contact with an absorbing liquid under conditions that allow it to be absorbed into the absorbing liquid. I can do it. This is accomplished using known methods and apparatus for contacting liquids with gaseous phases. This can be done using A suitable device is a cross-flow plate, e.g. plates, pulp plates, and countercurrent plates, e.g. – Plate towers with flow plates, turbo grid trays and ripple trays includes. In addition, known fillers such as Laschichi rings, Lessing rings, Varsa rings, etc. dollar, interlock saddle, tel 1erette, ballli Packed columns with any of the following are also suitable. Liquid dispersion contact devices, e.g. spray towers, baffle plates or shower deck towers, gas-in-liquid dispersion contactors, e.g. bubblers -, spargers, high-speed stirring devices, rotating disk towers, ventilation devices, etc. are also suitable. Ru. General overview of various methods of contacting liquids with gases suitable for use in inventions A detailed explanation can be found in Berry and Chilton's Chemical Engineers Handbook, Volume 5. Edition, 18-3 to 1 B-, page 93.

The organic liquid solvent used in the invention is immiscible with water and has a ring in the liquid-gas contact area. It should have a hydrogen bond solubility parameter of at least about 27 at the boundary. organic liquid The body solvent is either non-reactive with the fume vapor or reactive with the fume vapor and is a derivative organic liquid. can form a body solvent. In the case of reactivity, derivative bath agents can also be used as above. should have the same solvent properties.

The hydrogen bond solubility parameters as used in this specification are based on known literature or at 25°C. It can be calculated from experimental vapor pressure data such as heat of vaporization. Total solubility parameters ( δT) can be determined using the relationship in equation (1).

Where: △H25 = heat of vaporization R at 25°C - gas constant T - absolute temperature d Density at -25℃ M = molecular weight.

Total solubility parameter values are determined by hydrogen bonding (δH) or polar (δP) and nonpolar (δHP) ) can be divided into components. The following relationship is the hydrogen bond parameter value (δH) It is useful for determining where: α = agglomeration number Tb = boiling point at absolute temperature T = critical temperature in absolute temperature.

The rationale for using solubility properties has been discussed in the literature. The tabulation of parameters is 1967, Copenno 1-Gen, Danitsche Technical Press, C.M.No. “Three-dimensional melting (rammeter and Published in ``Solvent Diffusion Coefficient''. The list of dissolution parameters is New Chassis 08 805. Bound Proof, River Road, available from Union Carbide Company 1975, Union Carbide Company, Gu. L, Hui (K, L.

Hoy), "Table of Solubility Parameters".

Suitable organic solvents include halogen di- or tri-substituted solvents, such as methylene dichloride, Bromochloromethane, etc.; Chloroform, bromoform, etc.; Acetophenone; Al Cole liquids such as 2-ethylhexanol, phenyl ether of ethylene glycol ether, monohexyl ether of ethylene glycol, n-octyl alcohol , n-hexyl alcohol, and n-butyl alcohol. The preferred solvent is Methylene dichloride (dichloromethane).

The resulting tar-reduced fume vapor, which contains smoke flavor, odor, and coloring components, is The method can be collected in an aqueous medium to produce a tar-reduced test solution. Wear.

These are described in U.S. Pat. Includes what is being done. Also included is the use of the gas-liquid contacting device described above.

In a preferred practice of the invention, the fuming vapor is added to the water and bath agent in a single contact means. Contacting, that is, bringing fuming vapor into contact with a solvent to extract tar components. Color, flavor and odor components are transferred into the aqueous medium using the same contact means used for collect. This is achieved by simultaneously introducing water and organic solvent into the gas-liquid absorption means. I will do it. The product of the process is the waste gas stream and the fumes and vapors generated. and some acetic acid that was in the two-phase liquid product. Two-phase liquid product odor The aqueous phase contains smoke flavor, color and odor components, and the tar reduction of the present invention It's liquid. The organic solvent phase contains the tar that was in the generated fumes. single Although contact means are preferred, separate vessels may be used to contact the solvent and water with the fuming vapors. It could also be done.

The gas-liquid contact conditions are such that color, flavor and odor components are transferred to the aqueous phase to ensure sufficient color and It is like forming a liquid solution with flavoring ability. A series like the one shown in Figure 1. In the subsequent process, the concentration of smoke coloring, odor and flavor components in the aqueous liquid phase is reduced. of smoke, water and solvents to give the desired color and flavor capacity high enough. Adjust the flow rate. In a batch process as shown in Figure 2 and Example 1, the coloring , the concentration of odor and flavor components is sufficiently high to provide the desired flavor and coloring capabilities. Continue the process until 1C. When calculating the amount of water to be introduced, the water It should be considered that it may also be introduced as a gas in smoke vapor. absorption process During this time, this water condenses. Although it is preferable to introduce additional water separately, ( This water in the fume vapor minimizes the addition of water to the condensate water from the fume vapor. Invented by forming a large amount of aqueous phase to absorb color, flavor and odor components It is possible to produce a tar reduction liquid.

By so adjusting the conditions as described above, color, flavor and odor compounds can be reduced. It is possible to make a tar reduction liquid with the desired concentration of minutes. Traditionally, tar Le Reduction Liquid Kun Solution is a commercially available Made from intact liquid liquid solution.

Among these commercially available as-is liquid solutions, one application (in C, the casing is casings to give sufficient color and flavor to certain types of foods, such as light-colored meats. None have a concentration high enough to coat the surface. Producing raw smoke into concentrated form Commercial liquefaction solutions contain undesirably high concentrations of tar and phenol. It has limited concentration due to problems involving. Tar reduction liquid Kun solution has low concentration Such solutions also have some uses. These tar-reducing solutions have flavor and coloring abilities unsuitable for the purpose of use. Further concentration processes are required to obtain the desired coloration and MQ4e capacity. It is essential. Concentrated or unprocessed without further processing by carrying out the invention. A tar with coloring and flavoring capabilities equivalent to a directly derived liquid solution in a concentrated form. It is possible to obtain a reduced liquid bath solution.

Separate the aqueous tar-reduced liquid phase and the tar-containing organic phase by a known method. do. These methods include gravity decanting, hydrocycloning and centrifugal decanting. ing, as well as the use of various types of separation systems used in solvent extraction methods.

A preferred method of the invention for making a tar-reducing liquid solution is illustrated by FIG.

In FIG. 1, fume vapor is generated by a suitable fume generator 51. In FIG. Occurred The fuming vapor is transferred from the pipe 52 to a countercurrent gas-liquid absorption tower 53, such as a packed tower, a plate tower, or transport to the spray tower. The organic solvent and water are passed through lines 54 and 55, respectively, to the tower. Introduce at the top. In the absorption tower 53, tar is absorbed into an organic solvent and attached. Color, flavor, and odor components are absorbed into water to form a two-phase liquid product, which is Exit the tower via line 56. The remaining unabsorbed gaseous components of the fume vapor are piped as a waste stream. Exit the tower from Route 57. The two-phase liquid product consists of an aqueous tar reduction liquid phase 58 and a tar reduction liquid phase 58. and a liquid solvent phase 59, these two phases can be separated using any known separation device, e.g. Separated into tar reduction liquid of the invention and tar-containing solvent in gravity settling tank 60 The former exits from conduit 62, and the latter exits from conduit 61.

The tar reduction liquid of the invention can be further concentrated.

In the tar reduction process of the invention, the liquid is preferably reduced to a temperature below about 70°C, preferably under reduced pressure. can be concentrated at temperatures below about 50°C. Other suitable concentration methods are As disclosed in U.S. Patent Application No. 465.924, cited above, freeze-drying, spray-drying or various other evaporation techniques, such as room temperature evaporation in a low humidity environment. This includes the use of forced circulation evaporators, long-tube vertical evaporators, and stirred film evaporators. Contains.

The tar-reduced smoke bath solution prepared by the method of the invention is optionally partially neutralized to a pH of about Thicker than 3, preferably between about 3 and about 65, more preferably between about 3 and about 5 to such an extent that During partial neutralization, the liquid should be pumped, preferably at controlled temperature. does not increase above about 40°C, more preferably above about 60°C. ・Do so.

Partial neutralization of the unneutralized tar reduction solution of the invention solids such as calcium carbonate, sodium bicarbonate, potassium bicarbonate, hydroxide Calcium chloride, sodium carbonate, soda lime, sodium hydroxide pellets or fluoride Either mix it with a liquid or mix it with a liquid with a high pH, such as sodium hydroxide. This can be done by mixing with an aqueous solution. Carbonates and bicarbonates are intense The acid and heavy carbon in the liquid may cause severe foaming and make driving difficult. The reaction with the acid salt is endothermic, eliminating the need for temperature control during neutralization.

The rate at which the neutralizing agent is added to the tar reduction solution is as understood by those skilled in the art. , depends on the cooling capacity of the mixing vessel as well as the efficiency of the mixing means. The temperature of a large amount of liquid Tar reduction as long as it is kept below about 40°C, preferably below about 60°C. The cooling capacity of the partially neutralized liquid is at least the temperature during the partially neutralizing process. It is not significantly affected by the difference.

The mixing vessel used for partial neutralization may be used by indirect means, e.g. Cooling should be provided by plines circulating through the dip coil. Refrigerant and tar reduction The reason for indirect rather than direct contact with Shozu-kun is to avoid contamination of the latter. It's a blessing.

Another possible way to at least partially neutralize tar reduction liquid is to use tar reduction liquid by contacting it with an ion exchange material.

The method of the invention for producing the tar reduction liquid solution is superior to the prior art in addition to being less expensive. It has many advantages over

As mentioned above, main + I! Due to A, the tar reduction solution has an undesirable concentration. free of tar and phenols and any desired concentration of flavor, color and odor components It can be made to have. Typically, the concentration of the coloring component is Chertzl (available from Consin, Manitobok, Red Arrow Products, Inc.) charsol, ) C-12, i.e. as is with an acid content of about 12X The coloring in the tar-reduced liquid made by the above-mentioned solvent extraction process from the liquid. This corresponds to about 1 to about 5 times the concentration of the component. The advantages of invention are made by the method of invention Tar reduction liquid kun solution has high coloring ability and high carbonyl content, correspondingly It does not have a high content of phenol.

Typically, the phenol content is about 10X higher than the carbonyl content. Less, preferably less than 2X, 15% is achievable. phenol is high concentration, which is the main cause of the strong or cresol flavor in some concentrate solutions. It is considered that By carrying out the invention, the concentration derived from the raw liquid can be reduced. It is possible to create a liquid solution with the same coloring ability as tar reduction liquid with a high degree of reduction. can. In this way, without a corresponding increase in undesirable phenol content. High coloring capacities are achievable.

Almost all of the tar was removed by the method of the invention, as shown by the light transmittance in the example below. The aqueous tar reduction liquid produced was gone from the product. By implementing the invention and the light transmittance is at least 50%, preferably at least 80%, more preferably It is expected that at least a 90% tar-reduced bath solution can be produced. In addition , part of the acid in the fume vapor, the main acid being acetic acid, is in the waste gas stream. τ remaining, thus reducing the concentration of undesirable organic acids in the tar reduction product can do.

The tar-reduced liquid composition of the present invention can then be used, either unneutralized or neutralized. Even applied to food casings. Foods suitable for use in inventions the casing is a tubular casing, preferably a tubular cellulosic casing; made by any one of the methods well known in the art. Such a casing is , usually soft, thin-walled, seamless tubing made of regenerated cellulose or cellulose ether For example, it can be made of hydroxyethyl cellulose in various diameters. Also, generally A tubular cell with a fiber-reinforced web embedded in the wall, called a “fiber food casing.” Lulose-based casing, as well as "non-fibrous" cellulose-based casing herein Cellulosic casings without fibrous reinforcement, called casings, are also suitable.

Casings conventionally known as "dry material casings" are used in the practice of the present invention. It can be used as Such casings typically contain water-containing casings. Based on the total weight, in the case of non-fibrous casings, 5 to about 14 weight percent, or In the case of a fibrous casing, the water content ranges from about 3% to about 8% by weight.

The casing, conventionally known as a "gel material casing," is dried beforehand. casings with a higher moisture content than the casings mentioned above. be.

Such casings may also be used in the practice of the present invention. gel base Material casings, whether fibrous or non-fibrous, contain intact tar. This type shows the problem of tar coating mentioned above when treated with liquid.

The tar reduction solution of the invention is applied by passing the casing through a bath of solution. It can be applied to the outer surface of the tubular casing. The casing emits the desired amount of smoke Penetrate the liquid into the casing for a sufficient time to incorporate the coloring and smoke flavor components. After drying, remove excess by passing the casing through a squeeze roll or wiper, etc. Scrape off all the liquid. A process also known in the art as a "skin bath" or "soak tank" The process of passing the casing through the bath can also be referred to in the art as a "soaking" process. . Alternatively, the liquid of the invention may be applied by methods other than dipping, such as spraying, brushing, or rolling. It can be applied to the outer surface of the casing by means of a cloth or the like.

Instead, some well-known procedures, such as Ch. U.S. Patent No. 4.171. ,! i Listed in Ej No. 1 The reduction of inventive tar on the inner surface of the casing by one of the following steps: A liquid composition can be applied. These are slugging ng) or coating with bubble coating, spraying, and shirring Includes

The slugging method, which coats the inside of the casing, coats a part of the casing. material, so that slapping of coating material is Usually the casing is draped over two parallel rollers. ) at the bottom of the U-shape formed by the casing thereby sealing the slug of coating material inside the casing. while the casing moves through the slap and the slap The inner walls are coated with a coating material contained within.

One method of treating casings with the fuming solution of the invention is shown in FIG. In Figure 3 The flattened tubular cellulosic sausage casing 10 is and an immersion tank 1 that passes over the upper guide roll 13 and accommodates the liquid solution of the invention. 1, it is externally treated with the inventive fuming composition. Keishin After leaving the dip tank, the rod passes over the lower and upper guide rolls 14 and then Minimize excess carryover of liquid composition through squeeze rolls 20 . The total contact time between the casing 10 and the liquid solution 12 is taken up by the casing. Determining the amount of smoke coloring and smoke flavor components of the tar-reduced concentrate composition Ru. The total contact time is measured from point A to point B in FIG. The casing is squeezed After passing through the roll 20, it passes over the guide roll 23 and is wound onto the roll 24. It will be done. The casing is then sent for further conventional processing, which processing is necessary. In such cases, conventional humidification and conventional shearing are included.

The embodiment shown in FIG. 4 is similar to that shown in FIG. The casing is then passed through a heating and drying chamber 21 where it is dried to an appropriate moisture content. The difference is that The air bubbles are squeezed by the sealing action of rolls 20 and 22. Inflate the casing by keeping it in a relatively fixed position between 20 and 22. Make it tense.

The heating chamber 21 can be used for any type of addition to dry the sausage casings to the appropriate moisture content. It can be a thermal device, for example a circulating heated air chamber. Is the casing in heating chamber 21? After passing through the squeezing roll 22, it passes over the guide roll 26 and is rolled. It is rolled up to 24. If necessary, dry the casing with conventional humidification and The material is then subjected to further conventional processing, including shirring.

The embodiment shown in FIG. 5 is different from that shown in FIG. The difference is that the drying process is performed in a flat state while passing over the pipe 25.

A preferred method of applying the tar reduction solution produced by the method of the invention is to A first flexible and elastic material that displaces the opening edge while applying the coating to the body through sliding contact. the outside of the casing by moving the casing through the inside opening of the This is due to the way the walls are coated.

The liquid coating then covers the inner opening of the rotating second flexible and elastic means. Leveled by moving through. This method and apparatus incorporating this method No. 4.35421 issued to Chu et al. on October 26, 1982. It is explained in No. 8.

In that patent, the device is (slightly smaller than the diameter of the outer wall of the expanded flexible tubing) a tenth flexible and resilient means having an inner circular opening having a small diameter; The expanded flexible tubing is positioned transversely to the tube axis and is moved longitudinally through the inner circular opening, thereby rubbing against the green of the inner circular opening. first means arranged to displace the opening edge while maintaining contact; (b) dispensing liquid by means of said first means (a), thereby preventing expansion during longitudinal movement; The first means (a ); (C) An inner circle with a diameter slightly smaller than the diameter of the expanded flexible tubing outer wall. a second flexible member having a shaped aperture and rotatable about the center of the aperture; It is an elastic means that is used to spread the coating liquid on the outer wall of the tubing material into a film of uniform thickness. tubing having a coating thereon rotates through the inner circular opening of the second means; The pipe material is moved so as to displace the opening edge while maintaining sliding contact with the opening edge. For tubing positioned transversely to the material axis and moving longitudinally. the first means (a) Vc, the second means adjacent to each other but spaced apart on the downstream side; d) during longitudinal movement of the tubing through said second means (c); is rotated around the axis of the tube material, thereby maintaining contact with the rubbing liquid and moving it forward. rotating means for leveling the liquid into a continuous coating of substantially uniform thickness on the outer wall of the tubing; A device for coating the outer wall of expanded flexible tubing with liquid while it is moving in the longitudinal direction. It is explained that there is.

The method consists of (a) continuously moving the expanded flexible tubing along a straight line in the longitudinal direction; a stage of moving; (b) with an inner circular opening of diameter slightly smaller than the diameter of the expanded tubing outer wall; providing a first flexible and elastic means for (C1 supplying liquid to the inner circular opening of the first means; (dl) Transfer the expanded tubing material to the inner circle 2 of the first means. moving through the aperture and maintaining sliding contact with the edge of the aperture, thereby changing the edge of the aperture. The liquid is applied to the outer wall of the expanded tube material at the same time as the expanded tube material is placed. distributing the application liquid around the exterior wall; (e) with an inner circular opening of slightly smaller diameter than the diameter of the expanded tubing outer wall; providing a 20th flexible resilient means; (f) rotating the second means about its central axis; (g) a second hand rotating the expanded tubing with the liquid applied to the outer wall; moving through the inner circular aperture and maintaining sliding contact with the aperture having an aperture edge; , thereby displacing the opening edge and simultaneously applying the liquid coating to the substance on the outer wall of the tubing material. a longitudinally moving expanding film comprising a leveling step as a continuous film of uniform thickness; This method is described as a method in which a liquid is applied to the outer wall of a soft tubing material.

Tar reduction applied or “coated” on the casing surface, whether external or internal. It should be noted that the Shozurikun composition does not flow off alone as a surface coating. be.

The smoke coloring, odor and flavor components applied to the surface are caused by cellulose absorbing the smoke solution. It absorbs into the cellulose structure of the casing. Cross section of casing wall When inspected, a color change appeared across the casing wall, indicating that it had been smoked. The face has a darker color than the color of the opposite face of the casing wall. Therefore, the present invention As used in the specification, the term ``applyed'' means ``applied'', which refers to the smoke component. It is meant to be applied not only to the coating but also to the casing wall impregnated with smoke components.

The coated casing is shirred or shirred by conventional methods. The coated casing is dried and/or humidified prior to shearing. The moisture content can be made suitable for processing into rings and/or more. liquid of the present invention The need for conventional drying and/or humidification after treatment with the Kun composition It depends on the moisture content of the casing after treatment and the casing manufacturer. Casing is non-textile If the casing is of high quality, it should be in the range of 11 to 13% by weight before shearing. After shearing, the moisture content within the range is typically between about 14 and 18% by weight. Ru. In the case of fibrous casings, the range of 5% to about 7% by weight before shearing After shearing, the moisture content is typically about 14 to 35%. % by weight, where % is based on the total weight of the casing, including water.

The fuming composition of the invention can also be used to treat tubular food casings applying fuming ingredients. Other ingredients, such as humectants or emollients, may be used as appropriate in the preparation of the Containing glycerin and/or propylene glycol, etc., which can be used as can be done.

If desired, in forming food casings or for further processing Other commonly used ingredients, such as cellulose ether and mineral oil, are present in the casing. may be present in the liquid compositions of the invention, and they may be present in It can be used in the same manner and in the same amounts as the

In particular, foods such as sausages, such as wiener sausages and bologna sausages. Optionally add an aid to improve the peelability of the casing from the tar-reduced concentrate. before or after external application of the composition to the casing, and before or during shirring. can be applied to the inner surface of the casing. Tar reduction liquid inside the casing When applying to a surface, it is preferred to apply a strippability agent first. This increased peelability Advancing agents include, but are not limited to: carboxymethyl cellulose, Chillcellulose and other water-soluble cellulose ethers, their uses 197 Disclosed in U.S. Patent No. 3H 898.348 issued to Chu et al. Alkyl ketene manufactured by Plowea, Wilmington, Vercules A trademarked product consisting of two pictures, [Aquapel J] Use is further disclosed in U.S. Patent No. 3.905. issued to Chu on September 16, 1975. No. 397; Praware, Wilmington, E.I. Dupot. “Kioy” is a trademarked product made of fatty acid chromyl chloride manufactured by Ndenemer. Quilon) J, its use was further published on August 25, 1959 by D'Aprue, F, Underwood (W.

U.S. Patent M 2.901.35 issued to F., Underwood, et al. It is disclosed in No. 8.

Adding the peelability enhancer to the tubular food casing using any one of a number of well-known methods can be applied to the inner surface of the ring. That is, for example, if the strippability enhancer is Published on April 16, 1968 by Shiner (5hiner), etc. Patent No. 1578. ? Liquid “splash” is prepared in a similar manner to that disclosed in No. i79. It can be introduced into the tubular casing in the form of a "lug". The case past the liquid slag. The inner surface of the casing is coated by advancing the coating.

Instead, on June 24, 1969, Bridgeford A method similar to that disclosed in U.S. Pat. No. 3,451,827 issued to In a method, the casing is sheared over it with a hollow mandrel, e.g. Apply the strippability enhancer to the inner surface of the casing through the pre-release layer. be able to.

The method of the present invention also provides printed packaging having smoke coloring and smoke flavor components incorporated therein. casing, such as a name plate, trademark, text, etc. printed on the casing It is also suitable for manufacturing products. An example of a printed casing was published on April 25, 1967. As disclosed in U.S. Patent No. 3.3'16,189 issued to Adams It is shown.

In addition, the casing made using the method of the present invention is conventionally known in the art as a dried sausage. It is also suitable for processing what is known as "di". before selling to customers Food processors or consumers preferably use other types of food that easily peel off from the food. Unlike non-fibrous and fibrous casings, "dry sausage" casings Preferably, it is bonded during and after processing into food. polyamide epichlorohydrin tree [Kymene] is a trademarked product manufactured by Bercules, which is a fat. J., whose use was further published in Shiner on April 16, 1968 in the United States Patent number? casing and casing disclosed in No. b578,379. optionally treated with an inventive smoke composition to improve adhesion with processed foods within It can be applied to the inner surface of the casing.

Next, the casing treated with the liquid composition of the present invention is processed into sausages, etc. Can be used in conventional processes to remove smoke flavor and color components from the casing. into the packaged food in the container.

Preparing grain products flavored with smoke using the aqueous tar-reducing solution of the present invention. However, the product can be used as a food additive. This reduces water-based tar This is done by mixing the liquor with grain, such as malt, and drying the mixture. suitable A suitable method is described in U.S. Pat. No. 77.077.

It is possible to make smoke-flavored tribute oil using the invented tar-reducing liquid-kun water bath liquid. can. This involves bringing the aqueous tar reduction liquid of the invention into contact with the actual oil, and converting the oil phase into an aqueous one. It is made by separating from the phases to form a smoke-flavored cooking oil. Appropriate The method is described in U.S. Pat. No. 3.4, issued to Hollenbeck on November 25, 1969 No. 80.446.

Now, I think the invention will be more clearly understood with the following example. Mentioned by way of example only and not intended to limit the invention in any way isn't it.

In the example below, the phenol and carbonyl content of the liquid can be determined by the following steps: Temeta. All samples to be evaluated must be filtered using Whatman No. 2 filter paper or equivalent. by filtering through water and cooling as soon as possible after preparation to avoid possible polymerization. It was prepared as follows. All samples were diluted with distilled water in two steps. In the first step, the sample Dilute 10ml to make a total volume of 200ml, and in the second step add the first Further dilute 10 ml of solution from the process to make a total volume of 100 ml. Ta. To quantify phenol, 5 milliliters of the solution from the second step was transferred to the third step. At this point, the mixture was diluted with distilled water to make a total volume of 10'0 mm IJ liter. Cal To quantify carbonyls, add 1 ml of the second solution to the The mixture was diluted with fresh methanol to a total volume of 10 milliliters.

The procedure for measuring the amount of phenol is I, W, Tuck. [Evaluation of phenols in internal and fat substances J, JACAC, XXV, 779 (1942). This was an improved method for detecting toxphenol.

The reactants used to quantify phenol were: 1. A solution with a pH of 8.3 made by diluting the following to 1 liter with distilled water. Boric acid-potassium chloride buffer 8.04 mol boric acid solution 125 ml b, 04 Molar potassium chloride solution 'I25 ml 0.04 molar sodium hydroxide solution 40ml, 2,06% by weight of hydroxide) IJium solution 3,N-2,6-)dichloro-ben Dissolve 0.25 g of zoquinone amine in 30 ml of methanol and use A coloring reagent made by storing it in a refrigerator until it is used. 4 Dissolve a known amount of DMP in a known amount of distilled water to give a concentration of 1 to 7 micrograms/milliliter. 2゜6-Simethoxyphenol (DMP) standard made by forming a solution between liquid.

Quantification of phenol was carried out according to the steps in the following order; 1. 5 milliliter of liquid sample 5ml of standard solution, or 5ml of distilled water (5ml of distilled water) (for use as a rank) was added to 5 milliliters of pH 8.3 buffer.

2. The pH was adjusted to 9.8 using 1 ml of sodium hydroxide solution.

6 Immediately before use, add 1 ml of coloring reagent to 15 ml of distilled water. One milliliter of diluted coloring reagent was added to the test sample.

4. Color was developed for 25 minutes at room temperature.

The absorbance was measured at a wavelength of 580 nm using a 5.1 cWL colorimeter tube. spectrophotometer is , Svectro, available from Bauche and Dromme, Lochinister, New York. 5 pectronic was 20.

6. From the data of the DMP standard solution, the absorbance was set as the abscissa and then interpolated.

The amount of 7 enols as DMP concentration in ~/ml in the Z liquid sample is as follows: Calculated using the formula.

[o,　o　o　i　J is a coefficient that changes microgsims to millitarams. Liquid To calculate the amount of phenol as DMP in 1 gram, use the above results. Divide by the weight of 1 milliliter of liquid.

The procedure for calculating carbonyl compounds is from Anal, Chem, 23,541' -542 (1959) Lappan, C1ark 1.2.4-dinitroph described in "Colorimetric determination method of trace amounts of carbonyl compounds" phenylhydrazine (DNP) sg in 500 ml of methanol and a few drops Carbonyl-free prepared by adding to HCI, refluxing for 3 hours, then distilling methanol.

DNP recrystallized 22 times was dissolved in carbonyl-free methanol and saturated. DNP melting strips made by forming a solution (storing the solution in a refrigerator) I made a new one every week. The solution was prewarmed before use to ensure saturation.

), ! Dissolve L KOHll in 20 ml of distilled water and remove the presence of carbonyl. KOH solution diluted to 100ml with methanol, 43.0~ A known amount of MEK between 10 μm and 100 ml of carbonyl-free methanol 2-Butanone (Methyl-Ethyl-Ketone) (MEK) standard made in addition to Tuttle solution (used to create a standard curve).

The procedure used to quantify the amount of carbonyl compounds was as follows: t DNP into a 25 ml volumetric flask containing 1 ml of reagent. 1 ml of diluted liquid liquid solution 41 1 ml of standard MEK solution, or 1 ml of methanol (sample) Add 2 concentrated HCl (105 milliliters) Add to all 25 liter flasks and mix the contents of each. Place in a 50°C water bath for 30 minutes. 5. Cool to room temperature and add 5 ml of KOH solution to each. 4 Dilute the contents of each flask with carbonyl-free methanol and Make it 5ml.

5. Spect that can be obtained from New York, Lochinister, Bauche and Drom Ronira 20 spectrophotometer and 05 x 4 inch (1.27 x 10.2 side) cuvette Using a methanol blank, read and absorb at a wavelength of 4130 Hni. Calibrate the spectrophotometer by setting the light intensity to 0, & MEK to program absorbance versus MEKy for the standard curve. to cut, 7. Interpolate the concentration of MEK equivalent in the diluted liquid solution from this curve. a. Calculate the carbonyl concentration using the following formula as ■MEK/liquid 100d. Ru; Here, "DF" is the sample dilution factor (200). Carbonyl @n1PVi In order to calculate E K/liquid g, upper 42 1 load 6O-50 (19 The result of Equation 90 (13) is obtained by placing 100 milliliters of the sample to be tested (Durham). divide.

The color browning index (Co1or Brovning Index) is as follows I created it as follows: (1) Q, 1M7 potassium hydrogen talate 500ml and 0.5M Na Dilute 76 ml of OH with distilled water to make 1000 ml and make 7 talets. Prepare a buffer solution (pH 5,5); (2) 2 grams of glycine in 100 milliliters of pH 5.5 7-talate buffer Prepare a 2% glycine buffer solution by dissolving it in (3) Add 10ml of 7-talate buffer solution to a 20X’150Hm test tube. Ru; (4) 10ml of glycine buffer solution in a 51" 20x150m turtle test tube add to; (6) Cover the tube with a marble lid and warm the tube with boiling water gauze for 5 minutes; (7) Mix the liquid solution to be tested with methanol to 1 part liquid to 5 parts methanol. Dilute to a ratio of 0 parts; (8) Glycine buffer (reaction sample) and phthalate buffer Add t0ml of diluted liquid to the tube containing liquid only (unreacted control). Ru; (9) After allowing the color reaction to proceed for exactly 20 minutes at 100°C 6 Then, remove the tube from the boiling water bath and set the cooling degree to 0 for 2 minutes in the water bath. of the reacted sample and unreacted control at a wavelength of 4 o o nm by reading Adjust the optical density.

I Optical density (ODR) of reacted sample and optical density (ODU) of reacted control Calculate the color browning index (CBI) using the following formula: CDI=((ODR-ODU)+a14)XDFXO65, where DF is the sample It is a dilution factor (50). Color browning index is the amount of color browning that exists per unit of liquid. is a measure of the amount of potential color-forming substance present in the colorant.

Gardner XL-23) Squirrel with 1 cm window standardized with white board Commonly used in industry to measure color using a stimulant colorimeter were used to obtain the colorimetric values "L" and "tL" for the sausage surface. Liquid-kun Five Viennese sausages from each treated sample were tested. Measurement is Winnaso This was done approximately 2.5 cs from each end of the sage and in the middle. “L” and “aj value The 15 values obtained were combined and averaged to arrive at the final number. “Lj value is brightness and darkness. The higher the "L" value, the brighter the color. "a" represents redness, " The higher the "a" value, the redder the color becomes.

Example 1 This example describes the inventive method using a batch process. equipment to use Shown in Figure 2. Rice Consin, Milwaukee, 7 Lantz Company Hardware Hard water sawdust, available from Tsudo Sawdust, can be sealed and heated. 775 grams of sawdust was placed in a smoke generator 71 consisting of a 6 liter metal container. Thermal decomposition produced fuming vapor. Heat the metal container on the Bunsen burner 72. The fume vapor generated by heating is passed from the generator through a stainless steel tube 73. The liquid was introduced into an absorption container 74. Absorption vessel 74 consisted of a 1 liter Erlenmeyer flask.

The fume vapor passes through a sintered glass sparger (gparger) 76 to an absorption vessel 7. I entered 4. 6 ood of methylene dichloride (dichloromethane) and water are placed in the absorption container 74. 100 WLl and stirred during absorption to increase gas-liquid contact.

While the smoke generator 71 can generate smoke (approximately 6 hours), it continues to generate smoke. Ta. The Xr# pressure forced the fumes into the absorption vessel 74. Absorption container 7 The organic solvent in 4, the methylene dichloride phase 77, absorbs the tar-like hydrocarbon component to form 1 The color became darker as the g&amp;p sevens progressed. The aqueous phase 78 is steam colored; Absorbed flavor and odor components. The absorption vessel is equipped with a glass water-cooled condenser (not shown). Attached and evaporated water and methylene dichloride 45 The steam was recondensed. During the absorption process, the temperature of the organic phase 77 is approximately 40°C; Waterproof phase 78 was also at about 40°C. The gas escaping from the absorption vessel should be odorless. It was clear and colorless. Add new sawdust every day and repeat this procedure twice in a row. Repeatedly for a total of 6 days, the charges under methylene dichloride and water were added. : I put it on hold in 775. The aqueous phase 78 is converted into methylene dichloride by decantation. A measured 200 milliliters of aqueous tar reduction liquid was obtained by separating it from the tar phase 77. .

A sample of tar reduction liquid was prepared and analyzed. Summarize the results of the analysis in person. Also , Table A shows typical values of the intact liquid (Chartzl C-12) for comparison. show.

C1r 1 to 10.5-12 Light transmittance (%) 1oo.

Phenol (Da/#) 1 13-2° Acid (%) 11. s　11s-1z5 shows a total reduction of the Le components. The coloring ability is intact as shown by CDI. It is comparable to Kun, and the phenol content is significantly lower.

This example shows that using the method of the present invention, the coloring ability is comparable to that of the commercially available neat liquid solution. Powerful tar reduction liquid-kun 467 bales Ha GO-50099 (1 (14) solution We show that it is possible to prepare This example also shows that its Phenol content and tar content of the liquid liquid solution of the invention compared to the liquid liquid liquid solution of the invention indicates that the value is low.

Example　■ Apply the tar reduction liquid from Example I to the casing and use the casing for cleaning. Made sage products. Partially neutralize the tar reduction liquid at a temperature of about 18℃ to a pH of about 5. and the method and apparatus described in U.S. Pat. No. 4,356,216, supra. It was enclosed in a non-fibrous gel material casing. Dry and shear the casing. Table B shows the formulation of the meat used.

Beef chuck 22.7 Regular balk trim 22.7 Water/Ice 91 Salt t1 Spices 05 Plague powder (sodium nitrite) 0.13 Processing conditions are smoke, odor and flavor This was sufficient to transfer the ingredients from the casing to the packaged sausage.

The sausages were exfoliated in a conventional manner and the colorimetric values were obtained.

7 These are summarized in Table C below. In addition, Table C shows liquid liquid as it is (Chartsl C -12), the solvents disclosed in U.S. Application No. 417173 (Solvent Extraction), supra. Showing the values obtained from the raw liquid (Chartzl C-12) using an extraction purcess. vinegar. The liquid solution made by the solvent extraction process is heated to a temperature lower than about 40°C. Partially neutralized and pH table C Invention 5α12 15.65 As is 49.46 14.89 Solvent extraction・5α09 15.24 Control 5α25 14.57 In this example, the tar reduction liquid of the present invention is added to food as it is and in a solvent extraction process. It is given by the tar reduction liquid-kun made from the original liquid by Wases. Indicates that a color that is substantially equal to that of

Example　■ The purpose of this example was to characterize the chemical properties of the tar reduction liquid produced in accordance with the present invention. The purpose of this study is to compare the chemical properties of the liquid produced by the above method.

Two trial runs were conducted using the apparatus and method described in Example 3. By invention In one operation, absorption vessel 74 absorbs 700 grams of methylene dichloride and 100 grams of water. Contained. In a comparative run, absorption vessel 74 contained 700 grams of water and methane dichloride. Didn't use Ren. In each test, fumigation was conducted for approximately 55 hours.

According to the invention (Inv@nt, ), when operating, the methylene dichloride layer is The water layer absorbed the color, flavor and odor components of the steam. Sucking The temperature of the two liquid layers in the container 74 was about 40°C. Decant the aqueous layer Therefore, the tar reduction liquid (220 grams) separated from the methylene dichloride layer and produced was Ram) was analyzed.

In the control operation, the fume vapor produced during the fume generation process was simply absorbed with water. and produce an aqueous mixture of tar-like hydrocarbon components and smoke-colored, flavor and odor components. accomplished. The temperature of the aqueous layer was approximately 100°C. Tar-like components settle and become liquid. The aqueous layer containing the components was separated by decantation and analyzed in a vacuum ( Comp, A).

This liquid is much more dilute than the tar reduction liquid produced in accordance with the invention. Therefore, the temperature was 50℃ and the pressure was 20tut! Concentrated by evaporation in L l (g It was concentrated to a weight ratio of 2.5:1. 220 grams of the produced concentrated liquid was analyzed (C amp, B). The results of the analysis are shown in the table. Also, on the surface, there is liquid as it is. The above values related to typical values for solutions and Sm1te et al. Values are shown for liquids as disclosed in the example of the US patent (Smits).

Table D Invent, 9.8 95.9 9 & 3 15 14.9 Comp, A 6 ．． 0 98.0 72.5 5.6 5.6 Comp, B 73 97.5 1 OA3 8.0 9.6 Sumitutsu - -25-8116-2,32-&4 As is 1115-12 0 70-100 13-20 115-12.5 iD's data compares the benefits of the inventive tar-reducing liquid solution with other liquid liquid solutions. A comparison is shown.

A liquid solution (C amp, A, Comp, B and as is) are all equivalent to the invention liquid shows a high content of 7 enols. This low content of 7-enol in the invention is Advantageously, this was achieved in addition to achieving a high content of carbonyls. Phenoh The high content of carbonyl relative to the content of Comparable to the liquid concentrate shown. % of the 7 enol in the composition of the invention is The content of carbonyl was only 16% (ts■/i-y enol/96.39/ g carbonyl). This is 6521 based on 2-butanone/DMP, and acetone/fluorescence. Equivalent to a carbonyl to phenol ratio of 84:1 on a phenol basis. This is aceto It has a carbonyl to phenol ratio of (17-47) + 1 on a carbonyl/phenol basis. This represents a significant improvement over the compositions disclosed in Sumitsu et al. This example is desirable A high content of carbonyl coloring components does not necessarily have a correspondingly high content of undesirable pigments. This can be achieved without resulting in phenolic flavor-imparting components.

Increased coloring capacity does not necessarily correspond to increased flavoring capacity. However, the invention The method produces a liquid solution that is highly effective in terms of coloring ability, and Although it has a low phenolic content, its flavoring ability is not sufficient for commercial use. be.

Typically, commercially and have a carbonyl content comparable to Comp, A and Camp, B. The liquid solution has extremely low light transmittance. This means that the light transmittance is 0%. Illustrated by a comparative commercial neat liquid solution. Sample Comp, A and Comp, B are also typically expected to have extremely low light transmission. be done.

However, due to the limited cooling capacity of the condenser, Comp, A and Cornp, B The conventional process was operated at a temperature of 100° C., which is higher than normal. In this extreme process An absorption temperature of between about 0°C and about 45°C is usually desirable. The higher temperature in this example is , Comp,A and Comp,B due to the lower acid content than expected. As shown, a higher percentage of the organic acid was lost by evaporation. acid in liquid solution dissolves the tar in the liquid solution. In Comp, A, the acid content dissolves the tar The tar was not sufficient for analysis and most of the tar fell out before Comp, A was analyzed. solid 50 grams of precipitated tar produced according to the invention as shown above The liquid is comparable to the commercially available neat liquid as shown by CBI. It had coloring ability.

Example　■ In this example, a non-fibrous material having a fold diameter of approximately 3 (L Omm to approximately 3 t 8 + am) is used. The quality casing was immersed in the liquid solution of Example ① for 60 seconds. 1 square meter of casing surface About 10 milligrams of liquid was absorbed per square centimeter (15 milligrams per square centimeter). 5 milligrams). The treated casings are dried and processed into egg albumens by conventional methods. The emulsion was packed and boiled for 2 hours at 100°C in a laboratory oven. egg albumin milk The cloudy liquid is powdered egg white albumin (Kra 7) (Kraft) Incobolete. Approximately 35% by weight of commercial powdered cellulose (Solfa floc) oek), Brown Company) approximately 12% by weight, water 53-'! %.

The consistency was thick and thick like a typical internal emulsion. egg al The color transferred to Bumin emulsion is a measure of the ability of the liquid solution to color proteins. be.

Visual inspection of the final product revealed that it had been treated with the liquid of the invention (Invent, ). Products processed in casings and products made by conventional processes (comp, A) Products processed in casings treated with concentrated liquid fume solution have very good fumigation properties. Showed color. The sample made by the conventional process (Camp, A) is white. It showed only a slight smoke color compared to the control material.

Example　■ This example describes an embodiment of the invention using a pilot-scale process. . The equipment used is shown in Figure 6. Sawdust is described in U.S. Patent 3.10A, No. 473. into a conventional smoke generator (not shown) essentially the same as that shown. Ta. The generated fumes are guided through the duct 101 to the bottom of the countercurrent absorption unit 102. The absorption unit is then sucked upward by a blower (not shown) through the duct 103. I took it out from Kit 102. The absorption unit 102 has a height of about 1 meter and a diameter of 15 centimeters. The Cimeter tower contained a bed 104 of packed bar saddles. methylene chloride is passed through conduit 105 and then through spray nozzle 106 to the top of absorption unit 102. After introducing the methylene chloride into the absorber unit 102, the methylene chloride passes downwardly and through the absorption unit 102. It flowed in a countercurrent to the upward flow of smoke. While the fuming vapor rises inside the absorption unit , the water in the fume vapor condenses from the fume vapor and flows downward through the absorption unit. Flows countercurrently with the fume vapor, thereby discoloring it from the fume vapor as it progresses. Absorbed , flavor and odor components. Also, methylene chloride flows countercurrently to the fuming vapor. Extracts tar from fume vapors and which may have been absorbed into condensate water. I put it out. The condensed water and liquid methylene chloride then pass through conduit 107 as separate phases. and got out of the tower. The two-phase liquid passes from conduit 107 to separator 10B where the liquid A liquid consisting of an aqueous liquid that is separated and contains mainly smoke coloring, flavor, and odor components. The lower phase of 109 and the higher density of methylene chloride containing mainly fuming tar. It became phase 110. Methylene chloride is sent from the separator 108 to the conduit 111 to the cooler. 112 and via conduit 113.105 and pump 114 to absorption unit 10 It was cycled to 2. Conduit 111.115.1 osG [? % stainless steel pie It was a tap. The aqueous liquid 109 is transferred to the separator 108 by the overflow 115. The tar reduction liquid of the invention was collected as a product.

24 pounds of maple sawdust ( 1α9 ky) was continuously supplied. into the absorption unit through duct 101. The temperature of the smoke vapor is approximately 250″F (120°C) at the beginning of the test and at the end of the test. The temperature rose to about 375 below (190°C). Approximately 65 pounds of dry ice (2q, methylene chloride is absorbed from line 105 using Keep the temperature entering the unit between approximately 30”F (-1℃) and approximately 44’F (7℃). It was. There were initially 16 liters of methylene chloride in the system. During operation, chloride Methylene chloride vapor is periodically added to ethylene and lost to the atmosphere through duct 103 was replenished. A total of 24 liters of methylene chloride was used, with 94 liters at the end of the run. )/l/ was collected. The remaining 14.6 liters is used as steam passing through duct 103. and lost. Aqueous tar reduction liquid condensate obtained through over 70-115 The total amount of material was 2850ml.

The test was conducted by first starting the pump 114 and equilibrating the temperature of the methylene chloride to approximately 3 It was started by lowering the temperature to below 3° C. (1° C.). Then, the smoke vapor is transferred to the duct 101. was introduced into the absorption unit 102. Add smoke steam for 45 minutes, 70 minutes After 100 minutes and 110 minutes, 2 liters of methylene chloride were added. smoke steam 45 minutes, 90 minutes and 125 minutes after adding - Flow samples of 400 m 1.900 g and 2 s o mt were collected respectively. . The samples were combined and analyzed as one sample (Inv, ). One of the combined samples evaporate at a temperature of 50°C and a pressure of 207 nm Hg to a weight ratio of 2:1. (:gnc, ), and then the concentrated product was analyzed.

The results of the analysis are shown in Table E. Do not measure values not shown for concentrated samples. Ta.

Table E Inv, Cone.

Light transmittance (%) ~60 Carbonyl (da/g) 152 180 Phenol (da/fl) 5 2t7 Acid (wt%) 9 - CBI 20 46.5 Apply the above tar reduction liquid product (Inv and Cone) to the casing Then, it was packed as in Example ■. "L" and "a" values for each casing. Measure the food packed in the container, and process the rLJ and r-J values by pumping the liquid. Measurements were made on food packed in control casings that were not tested. measurement results It is shown in Table F below.

Inv, 518 1&3 Cone, 4 & 6 1 B, 9 Control 55.5 17.0 This example shows how the tar reduction liquid of the invention with good coloring ability can be continuously processed. Shows how it can be manufactured in a process. Also, as shown by the value of light transmittance, It also shows that there is no tar in the tar reduction solution.

international search report

Claims (1)

[Claims] t(1) Pyrolyze wood in an oxygen-controlled atmosphere to generate smoke vapor,(2) Tar is selectively extracted from the generated fume vapor using a solvent, and (3) the fume vapor is aqueous. A tar reduction liquid comprising absorption into a medium to form a tar-reduced liquid solution. Method for producing Kun solution. , 2. (1) Pyrolyze wood in an oxygen-controlled atmosphere to generate fumes, (2) <Fume vapor, water, and an organic solvent with a solubility parameter greater than about 2.7. (3) to form a tar-containing liquid solvent phase and an aqueous liquid phase; The process involves separating the phase from the liquid solvent phase to form a tar-reduced liquid solution. A method for producing a liquid-reducing liquid-kun solution. Pyrolytic decomposition of five strands in a controlled atmosphere with oxygen generates smoke and vapor. In a method for producing a tar-reducing liquid solution comprising condensing air into an aqueous medium. , contacting the fuming vapor with an organic solvent having a solubility parameter greater than about 2.7. A tar reduction liquid characterized by selectively removing tar from fume vapor by Method for producing Kun solution. 4. Claim 2, in which fuming vapor is brought into contact with water and solvent in a single contact area. Method described. 5. Contacting the fuming vapor with the solvent in the first contact zone and in the second contact zone. The method according to claim 2, wherein the method is brought into contact with water. 4. Neutralize the tar reduction liquid to a pH greater than about 3. Claim 2 Method described. l　Tar reducing liquid is neutralized to give IIH between about 3 and 65.Claim No. 6 The method described in section. &　Claim 7: Neutralize the tar reducing liquid to a pH of about 3 to 5. Method described. 9. Claims in which the tar reduction solution has a light transmittance greater than about 50% The method described in box 2. 1α The tar reduction liquid-kun solution has a light transmittance greater than about 80%. The method described in Scope Item 9. 1t The tar reduction solution has a light transmittance of greater than about 90%. The method according to scope item 10. 12. The tar reduction solution has a phenol content of about 10% of the carbonyl content. 12. The method according to claim 11. 1 & tar reduction solution contains less than about 10% of the carbonyl content of phenol 3. The method according to claim 2, comprising: 14. The tar reduction liquid-kun solution has a phenol content of about 1.5% of the carbonyl content. 14. The method according to claim 13, comprising: Claim 2, wherein the temperature of the organic solvent phase in step 1 & step (2) is about 40°C. How to put it on. 1. A method according to claim 1, characterized in that the tar reduction solution is 1Z The method according to claim 2, characterized in that the tar-reducing liquid solution is used. 1a. The method according to claim 3, characterized by a tar-reducing solution. 19. Claim 1 in which the tar reduction liquid is neutralized to a pH greater than about 3. The method described in Section 6. 2α: Neutralize the tar reduction liquid to a pH greater than about 3. Claim 1 The method described in Section 7. 21. Claim 1 in which the tar reduction liquid is neutralized to a pH greater than about 3. The method described in Section 8. 22. (1) Pyrolyze wood in an oxygen-controlled atmosphere to generate fumes, (2) Selective solvent extraction of tar from the generated fume vapor, (3) in an aqueous medium to form a tar-reduced solution. A tar-reducing liquid composition prepared thereby. Claim 22: Contacting water and solvent in a single contact zone Compositions as described in Section. 24. Contacting the fuming vapor with the solvent in the first contact zone and in the second contact zone. 23. The composition of claim 22, wherein the composition is brought into contact with water. 2!5. Claim No. 3, wherein the tar reduction liquid is neutralized to a pH greater than about 3. Composition according to item 22. 2 & Tar reduction liquid is neutralized to a pH of between about 3 and about 65. Composition according to item 22. 2Z Neutralize the tar reduction liquid to a pH between about 3 and about 5 Claim 2 Composition according to item 6. 2. A range of islands where the tar reduction solution has a light transmittance greater than about 80%. The composition according to item 27. 29. The claimed tar reduction solution has a light transmittance of greater than about 90%. A composition according to Range 28. 6α　The tar reduction liquid-kun solution contains less than about 10% of the carbonyl content of phenol. 23. The composition of claim 22, comprising: 31 The tar reduction liquid-kun solution has a phenol content of about 2% or less of the carbonyl content. 31. The composition according to claim 30, comprising: 6'2. The tar reduction liquid-kun solution has a phenol content that is approximately 15% of the carbonyl content. 31. The composition according to claim 30, comprising: Claim 22, wherein the temperature of the organic solvent phase in step (2) is about 40"C. Compositions as described in Section. 64, with a light transmission greater than about 50% and a carboxylic acid greater than about 90tψ/9. and a phenol content of about 2% or less of the carbonyl content. Shozui-kun composition. 35. The composition of claim 34, having a pH greater than 35, about 3. 36. The composition of claim 35, having a pH between about 3 and about 45. 37. The composition of claim 36, having a pH of between about 3 and about 5. 35. The composition of claim 34, having a light transmittance greater than about 80 times 5a. . 39. The composition of claim 34 having a light transmittance greater than about 90%. thing. 4[l] Light transmittance of about 96%, carbonyl content m of about 961149/9, Approximately 16% phenol content of carbonyl gold wave 4t Tubular casing wall claimed Tar reduction produced by contacting with the tar reduction liquid described in Section 22 Tubular casing with a little smoke coloring and smoke flavor 0 4z Contact the tubular casing wall with the tar reduction liquid according to claim 34. The tar is reduced by making the smoke flavored pipes not only colored but smoked. casing 0 4) Bringing the tubular casing wall into contact with the tar reduction liquid recited in claim 22. of the smoke-flavored tubular casing, which includes tar reduction, smoke coloring, and smoke-flavoring. Production method. 4L Encapsulation produced by filling food into the tubular casing according to claim 41 The packaged food is packaged under conditions sufficient to transfer smoke coloring and smoke flavor components to the packaged food. A process for producing smoke-colored or smoke-flavored food, including processing it. 45. An encapsulation produced by filling the tubular casing according to claim 42 with food. The packaged food is packaged under conditions sufficient to transfer smoke color and smoke flavor components to the packaged food. A method of producing a fume-colored or smoke-flavored food comprising processing it.