DK163793B - FEED PRODUCT AND PROCEDURES FOR PRODUCING IT - Google Patents

Description

DK 163793 B

The present invention relates to a feed product containing the reaction product between a pectate and divalent or trivalent metal ions and having a pH within the range of from 5 to 8, S and a process for preparing the feed product. The feed product according to the invention is peculiar to the characterizing part of claim 1 and the method according to the invention is peculiar to the characteristic part of claim 6.

Many different gelling agents, binders and thickeners! detergents are used in the feed industry, including seaweed extracts, gelatine, modified starches, caseinates, egg albumin and galactomannan gums, for the manufacture of animal feed. However, these materials have the disadvantage of

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these are from raw materials that are not available in abundance, and in many cases the annual supply is exposed to the whims of the wind and tides. Furthermore, the materials are often costly, in part due to the complicated cleaning methods used in their manufacture.

In contrast, the sources of pectin raw materials are abundantly available as pectins are found in the tissues of all green land plants and are currently available from many different waste products, e.g. ei = trout pulp and shells and apple squash.

In particular, citrus shells and similar protopectin-containing sources are available in huge quantities. Eg. produced the state of Florida in the U.S.A. in 1972-73 alone, more than 600,000 tonnes of dried citrus waste product, most of which is used as animal feed. This citrus waste product is obtained by extracting fruit juices from oranges, lemons and other citrus fruits and consists of the peel and marrow of the fruit, which is in + 0-60 <fo of the whole fruit.

Although a smaller portion of the shell is dried and used for the production of high and pectins. low methoxyl, the majority is used as animal feed as no other uses for the material have been found. Orange peel in particular causes problems for the pectin manufacturer by being difficult to filter and by having a high concentration of enzymes which attack the pectin molecule.

About 30 years ago, U.S. Patent No. 2,132,065 disclosed a process for producing a crude, alkaline, deesterified pectate pulp, but this product does not appear to have found any major markets and is not currently being manufactured.

Pectins are complex, colloidal carbohydrate derivatives found in or made from plants. They consist predominantly of polymers of α-D-galacturonic acid, albeit small amounts of neutral sugars,. such as rhamnose, xylose and gulose, may occur in the rootstock of polygalacturonic acid or as side chains. The carboxyl groups in the polymers can be esterified with methyl groups to a greater or lesser extent, and unesterified groups can be completely or partially neutralized by one

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or more bases. The water-insoluble pectin found in plants is called protopectin and gives, by limited hydrolysis, pactic acids, which contain a considerable amount of methyl ester groups, and pectinins, which are the water-soluble pectic acids capable of forming gels with sugars and acid. "Pectin = acid" is the term used for colloidal polygalacturonic acids which are substantially free of methyl ester groups and formed by substantially complete hydrolysis of other pectins.

The behavior of pectic substances by gelling depends crucially on the part of the galacturonic acid residues which are methoxylated. In a completely esterified material esterified with methyl groups, i.e. with a lining degree (D.E.) of $ 100, the methoxyl content by weight is approx. $ 15. Industrial pectins currently available for gelling purposes can be divided into two classes: 1. High methoxyl pectins with a D.E. over $ 50, which forms gels of the traditional jam type. Pectins of this type only form gels at pH values below 3? 5 and in the presence of substances believed to cause dehydration of the pectin molecule. Sugar concentrations above $ 60 are generally used for this function, although materials such as alcohol or glycerine may be used. High methoxyl = pectins are primarily used as gelling agents in preservatives and confectionery products.

2. So-called low methoxylpectins, wherein usually between 20 and * + 0 $ of the galacturonic acid residues are esterified. Pectins of this type can form gels within a wider range of pHs in the absence of sugar, but require the presence of divalent soil alkali. They have the greatest stability in the pH range ^, 0 - ^, 5, especially when the pecting part is subjected to heat treatment (see British Patent No. 81 ^ +. 5 * + 9) · Low meth = oxylpectins have been used as gelling agents in foods such as dietetic jams and fruit milk desserts. Industrial low meth = oxyl pectins are generally produced from high methoxyl pectins, either by treatment with acids over a longer period or by the action of ammonia in alcoholic systems. In the latter case, the resulting pectin product will contain some galacturonic acid residues in which the carboxyl groups have been amidated.

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In some cases, it is desired to form gelled or thickened feed products with near neutral pH values and which have been subjected to heat treatment to achieve pasteurization or sterilization. The texture of the required gel can range from a solid, solid jelly to a viscous cloud. Such products generally consist primarily of meat or fish, but may also consist of vegetables or other foods. It has been found that it is not possible to form satisfactorily thickened or gelled can products under such conditions of heat treatment and pH using either high methoxyl peetins or pectins having methoxyl content in the range of 20 - + + 0 $. It is believed that one of the reasons for this is that pectins of these types depolymerize at high temperatures and neutral pH values, thereby losing their gelling properties.

It has now been found that if pectins which have less than $ 20 of the carboxyl groups are methylated and preferably less than $ 10, the molecule appears to have sufficient heat stability to maintain its gelling or thickening properties in products at neutral or near neutral pH values after heat treatment. These substances can therefore be used as gelling agents or thickeners or binders in pasteurized, sterilized, canned or otherwise heat-treated: feed products.

For convenience, pectic substances which have a D.E. below $ 20, hereinafter referred to as "pectates", this term not only including the ideal case in which substantially no methoxyl groups exist, but also pectinates with a D.E. up to $ 20. The preparation of pectates by cold alkaline hydrolysis of protopectin has been described in U.S. Patent No. 2,132,065.

The invention therefore discloses feed products comprising edible solid components contained in an aqueous phase thickened or gelled with a pectin having a D.E. less than $ 20 and preferably below $ 10. The invention is particularly valuable in providing thickening or gelling of nearly neutral meat-containing products, namely in the pH range 5-8.5 and especially 6.0-7.5. These products are generally heat pasteurized or sterilized and may be contained in 5

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canned packages such as cans. They may exhibit the stiffness characteristic of a gel, or the viscosity and irregularity also of the pseudoplastic or thixotropic properties required by thickened products as described below.

The pectic substances useful for the present invention include not only purified or isolated pectates, but also raw, natural pectin sources such as apple residues, citrus residues or sugar beet residues which have been subjected to deesterification, e.g. with alkali or enzymes, to decrease their D.E. for under $ 20. As a rule, natural pectins must be deesterified with intent, e.g. by alkaline hydrolysis or with an enzyme such as pectin = esterase. However, intentional deesterification may be unnecessary if a natural protopeetin source having a D.E. under $ 20, e.g. because the source contains pectin esterase. If the source contains such an enzyme, the mere soaking of the source material or its addition to a substantially neutral feed prior to pasteurization or sterilization may cause a reduction of D.E. sufficient for the purposes of the invention.

Thus, if orange peel is ground to a small particle size, preferably neutralized to pH 7-8 with an alkali such as sodium carbonate, e.g. for a period of 30 minutes, washed to remove sugars and harmful soluble compounds and dried, the milled product can be used as a thickener and gelling agent in canned goods. Since most of the orange aromatic constituents and color are in the surface layer of the shell (flavado) clay, it is advisable, when using the processed shell to thicken or gel products such as meat or fish, that this outer part of the shell is removed prior to processing, leaving a shell with a less distinctive aroma. Peel technique to remove the orange-colored outer part of the shell from crushed orange shells is described in the literature.

The reaction mechanisms by which the protopectin in the shell is converted to a gelling agent are not completely understood. Although the invention does not depend on any particular theory, it is possible that one explanation is that enzymes released during the grinding of the orange peel at least 6

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In part, the pectin molecule, which is believed to be bound to hemicelluloses or other materials in the protopectiricon configuration, partially demethoxylates and, upon subsequent heat treatment, in the substantially neutral feed product, further demethoxylation and solubilization of the pectin occurs. It is believed that the resulting pectate then reacts with soil alkali ions in the feed product to form a thickened or gelled system.

It will be appreciated that any hydrolysis or other treatment of the pecin substance should not cause too much reduction in molecular weight as this damages the gelling properties and the thickening properties.

It is believed that if the deesterification has been carried out with an enzyme, the characteristic features of the invention can be obtained with a higher DE than if deesterification is obtained by other means, presumably due to the continuous nature of this type of hydrolysis as opposed to the random removal of methoxyl groups along the chain when using acid or alkali hydrolysis. This is particularly evident with more severe heat treatments, such as in the retort treatment of canned products, and it can be assumed that the degree of depolymerization of the pectate under these conditions is less when it is material deesterified with enzyme.

Determination of the degree of esterification can be performed by measuring the methoxyl content of the material and measuring its galacturonic acid content. Although a modification of Hinton's saponification method is commonly used to measure the methoxyl content of high methoxylpectins, it has been found that this technique can give inaccurate results when the samples being tested are raw protopectin sources, presumably due to reaction with other components of the source material, such as protein.

According to the invention, both the modified saponification method and a more special method based on gas-solid chromatography, as proposed by Krop et al. (Foodstuff - Wiss.u.Technol., Vol. 7j 197 * +, no. 1). Both methods have yielded similar results for crude low-methoxyl protopectin sources, i.e. the preferred material of the invention.

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Modified saponification method

A sufficient sample of finely ground dry material, usually 2 g, to release a maximum of 0.02 g methanol, stirred with 250 ml of water and heated on a boiling water bath for 20 minutes with occasional stirring, after which the mixture is soaked with a rapid stirrer. The dispersion is cooled to 20 ° C and neutralized to pH 8, f using a pH electrode to track the end point and 0.1 - normal sodium hydroxide to effect the neutralization. Then 20.00 0.1-normal NaOH is added and after stirring is allowed to stand for 20 minutes. 20.00 0.1-normal HCl is added and excess HCl is determined by titration with 0.1-normal sodium hydroxide solution to a pH 8.4 end point, using a pH electrode to track this end point. Titer = B ml.

$ methoxyl = B

weight of sample GSC method 2 g of finely ground dry material is stirred with 100 ml of water and heated on a boiling water bath for 20 minutes with occasional stirring, after which the mixture is soaked with a fast stirrer. The dispersion is cooled to 20 ° C and 20 ml of 1N sodium hydroxide solution is added with stirring. After 20 minutes at 20 ° C, stir 5 ml of 50 $ concentrated hydrochloric acid and make up to 200 ml with distilled water. The dispersion is allowed to stand for 10 minutes so that the precipitate can settle.

The methanol content of the supernatant is then determined by gas chromatography using similar conditions as described by Krop et al. (Loc.cit.).

The galacturonic acid content of the sample is measured by repeating the procedure described above up to and including the standing for 20 minutes with 1 N sodium hydroxide, then adding 20 ml of concentrated hydrochloric acid with stirring. 800 ml of propan-2-ol is added and the dispersion is allowed to stand for 30 minutes.

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island

The precipitated solid is filtered off on a Buchner funnel and washed thoroughly with 60 volumes of propan-2-ol in water. The solid is then dispersed in water, 10 ml of 0.1N sodium hydroxide is added and the solid is dispersed using a fast-moving mixer. The dispersion is titrated to pH 8, ½ with 0.1N sodium hydroxide using a pH meter (titer = A ml).

f ° galacturonic acid = (A + 1 °) -%. Pi97Q-Z weight of sample # degree of esterification = - * nethoxyl content- x 625) 5 f> galacturonic acid content

Pectates are generally obtained as alkali metal salt, and it is usually necessary that a salt of a divalent or trivalent metal be present in the feed product together with the pectate if a satisfactory gel is to be obtained. Such metal ions may be unnecessary where only a thickening effect is required and the addition of such an ion can be avoided where a metal ion is naturally present in the feed product or in the peatine source or pectate itself. The preferred metal is ealcium, and suitable salts for addition to the product include di-calcium phosphate dihydrate, calcium sulfate dihydrate, calcium citrate, calcium lactate and calcium chloride.

It has been found desirable to include a complexing agent or a chelating agent in the product, especially when using a crude protopectin source where the pectate is in the form of a divalent or trivalent metal salt or where the product naturally contains high concentrations of divalent or trivalent metal ions. Suitable complexing agents include sodium tripolyphosphate, sodium hexa metaphosphate and trisodium citrate. Such a chelating agent serves to delay the formation of a gel and enables easier handling of the cold mixture and filling, e.g. in cans, and also faster heat penetration during pasteurization or sterilization. When meat is present, an alkaline chelating agent also contributes to counteracting the decrease in pH observed by the addition of divalent or trivalent salts to meat. This development of acidic conditions can also be counteracted by the addition of an alkali, 9

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such as sodium hydroxide, or an alkaline buffer.

The amount of pectate or crude deesterified pectin source required to form a thickened or gelled feed product; can vary widely. When a pure pectate is used, this may be present in an amount of from 0.1 to 10% by weight of the feed product, but preferably from 0.5 to 2.0 $. When a crude deesterified pectin source is used, the amount of this pectin source (on a dry basis) may range from 0.1 to 20% by weight of the product, but preferably from 0.5 to 3%. The crude deesterified pectin source must contain more than 5 $ pectin (and preferably more than 10 $ pectin) based on dry matter.

The crude deesterified pectin source can be used in the dried form or when the user e.g. located in the convenient vicinity of the processing site, it can be used without drying, in which case the required amounts depend on the solids content of the crude deesterified pectin source.

In a preferred embodiment of the invention, it has been found that deesterified citrus peel is surprisingly effective for gelling and thickening. Eg. For example, it has been found that a meat product gelled using $ 1.5 by weight orange peel was firmer than a similar product gelled with $ 1.0 pure pectate. This was surprising because analysis showed that the orange peel contained only $ 30 pectin (expressed as galac = turonic acid). The orange peel may be subjected to alkaline deesterification, but it has been found that this is not an essential step for the purposes of the invention.

The dried, processed shell contains approx. 20- ^ 5 $ pectin (expressed as galacturonic acid), depending on the fruit type, degree of maturity, variety and other factors, and the remaining dry solids include hemicelluloses, araban and other ballast substances. Newer nutritional ideas suggest that these cellulose materials, in the quantities they contain in the diet by such an addition, are certainly beneficial to health. A further advantage of using raw materials, such as processed shell, in accordance with the invention lies in the low calorific value of this material, which, together with its previously described properties, shows its useful use for dieting.

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diet and diabetic diet, where the processed must be used to obtain the necessary water-binding properties instead of caloric water-binding agents such as starch.

Many different feed materials, such as vegetables, fruits or sauces, can be thickened or gelled using pectate or processed protopectin materials, but it is particularly advantageous in canned meat products where the presence of insoluble, non-pectin-containing materials from the raw material, such as finely divided shell is masked by the finely divided meat resulting from heat coagulation of soluble meat proteins.

A very useful feature of certain gelling systems is the thermoreversibility. For the present purposes, a thermoreversible gel can be defined as a gel having a melting point and a solidification point within the temperatures encountered in the preparation and use of the gelled system.

It has been found that the melting point and solidification point in accordance with the invention of pectate gels can be adjusted by increasing or decreasing the available amount of calcium ion or other non-toxic di- or trivalent metal ion in the food product. The availability of the calcium or other metal for reaction with the pectane depends not only on the amount of calcium or other metal present, but also on the type of metal salt used and the type and amount of complexing agent present in the system.

Thus, with large amounts of available calcium, food structures that are stable in heat processing can be formed, while with lower amounts of available calcium, thermoreversible gelled or thickened systems can be obtained.

It has also been found that a thickened feed product, i.e. one in which the aqueous phase has an increased viscosity, either by direct use of a relatively high concentration of crude or pure pectate sources or advantageously by using much smaller amounts of the crude or pure pectate source in the presence of added calcium ions and complexing agent. . These lower amounts have such a concentration that a coherent gel structure cannot be formed, 11

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but viscose and pseudoplastic solutions are produced instead.

It has further been found that if psyllium seed peel or rubber is added to feed product mixtures containing processed orange peel, an unexpected synergistic effect occurs during the heat treatment step, which in the finished product produces a firmer, tougher, more elastic gel structure than is achieved with each of the systems. separately. Psyllium seed peel and rubber are obtained from a group of plants belonging to the genus Plantago and used for various pharmaceutical purposes.

Although it has been found that citrus peel is particularly useful for the described use, other sources of protopectin, e.g. apple squeeze or pear squeeze or sugar beet, also useful for the purposes of the invention.

The invention also discloses a process for the preparation of feed products wherein edible solid ingredients are mixed with an aqueous solution of pectate (as defined above) and preferably a source of alkaline earth metal ions and also a complexing agent, and the mixture is heat treated and then allowed to cool, whereupon the aqueous solution is thickened by gelation of the pectate.

This process can be performed with many different feed products in many different circumstances. Eg. For example, pectates can be used to produce feed products in sealed packages or containers, e.g. cans. Such products include ham, minced animal feed, especially for dogs and cats. Although the gel may melt below the temperature at which the cans are retorted, depending on the available calcium content, the pectate medium retains its gelling properties and solidifies again upon cooling.

Pectates can also be used as binders to provide a firm texture in the manufactured products, which do not reach as high a temperature as canned goods during processing, but are exposed to at least 12

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pasteurisation. Pasteurization can be defined as the use of sufficient heat, usually at temperatures below 100 ° C, to effectively eliminate vegetable bacteria, while sterilization is the use of heat at temperatures above 100 ° C to effectively eliminate both vegetable bacteria and spores.

Other examples of the use of peetates as binders include the preparation of imitated pieces of meat or shaped pieces of meat which are able to maintain their consistency, e.g. when in a canned product. Such products can be manufactured by molding, e.g. by extruding, a mixture of finely divided meat or meat by-products or vegetable protein together with the pectate material and suitably a complex binding agent. The product can be post-treated in a solution of soil alkali.

Pectates can also be used as binders in semi-moist food products, i.e. those which are stabilized by the addition of sufficient water-soluble substances to reduce the water activity to between 0.65 and 0.85, and containing an antimycotic substance.

The preferred compositions of products containing a peat gel or thickener according to the invention depend on the particular type of product concerned.

In the case of canned meat or meat by-products, the preferred compositions by weight include $ 20-95 $ meat or meat by-products, 0.1-5 $ pectate (or 0.1-10 $ finely divided citrus peel based on dry matter), 0-5 $ non-toxic alkaline earth metal compound, 0-5 $ complexing agent and 0-50 $ water (or 50-95 $ moisture content of the product).

In the case of molded meat products, including sausage, made by joining finely divided meat or meat by-products, the preferred compositions include * + 0-95 $ meat or meat by-products, 0.1-5 $ pectate (or 0.1-10 $ finely divided) citrus peel based on dry matter), 0-5 $ alkaline earth metal compound, 0-5 $ complex binder and 20-50 $ water (or 50-95 $ moisture content of the product).

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In the case of simulated meat cuts made from non-meat, e.g. vegetables, proteins, the preferred compositions include 5-50 $ vegetable protein, 0.1-5 $ pectate (or 0.1-10 $ finely divided citrus peel based on dry matter), 0-5 $ soil alkali metal compound, 0-5 $ complexing agent and $ 20-50 water (or $ 50-95 moisture in the finished piece).

The following are examples of the practice of the invention used for various, almost neutral products, showing the stability of the gelling agent or thickening agent in heat processing. All parts and percentages are by weight unless otherwise stated.

Example 1

Use of Isolated Pectate 5 g of industrially prepared sodium pectate (Sodium Polypacter, Sigma Chemical Company), which had approx. 1 $ residual methoxyl groups, dissolved in 200 ml of water and added to 250 g of chopped lung pieces. A slurry of 20 g of dicalcium phosphate dihydrate (CaHPO 3, 2 50) and 5 g of sodium tripolyphosphate (Na 2 P 3 ° 10) in 50 ml of water was added with stirring to the mixture of lung and polypectate, and the liquid mixture was filled. in 50 g * cans, sealed and sterilized for 1 hour at 1.36 ato. in a steam autoclave.

After being cooled, the cans were opened and the lung pieces were found to be embedded in a firm, clear, coherent jelly. The pH of the product was 6.2.

For comparison purposes, the effect of using higher methoxyl pectins was demonstrated by repeating this Example 1, except that the sodium pectate was replaced with a similar weight amount of pure low methoxyl pectin with a D.E. at $ 35 (H.P.Bulmer Ltd.). The sterilized product consisted of cooked lung pieces in a thin, aqueous liquid and had a pH of 6.1.

When this example was repeated again instead of sodium pectate of a similar amount by weight of an industrial composition of low methoxylpectinamide having an esterification rate of 20-33 $ and an amidation degree of 20-25 $ (manufactured by Cesalpinia), the sterilized product consisted of cooked lung pieces in a thin, aqueous liquid and had a nH-vfPT'di reach 6.1.

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Example 2 5 g of a sodium pectate industrial preparation (Sodium Polypectar, Sunkist Growers), containing essentially no methoxyl groups, was dissolved in 150 ml of water and added to 288 g of a mixture of waste meat pieces normally used for canned food for dogs. A slurry of 20 g of dicaleium phosphate and 5 g of sodium tripolyphosphate in 60 ml of water was added with stirring and the mixture was filled into cans and processed as described in Example 1.

After cooling, the cans were opened and the product turned out to be a coherent package of meat waste surrounded by a clear coherent jelly. The pH of the product was 6.2.

Example λ

Example 1 was repeated except that the 20 g of dicalcium = phosphate was replaced with 5 g of calcium sulfate dihydrate (CaSO 4

The sterilized product had a similar appearance as described in Example 1, although the jelly was marginally softer in texture. The pH of the product was 6.5.

Example h

Example 1 was repeated except that the amount of dicalcium = phosphate was reduced from 20 g to 5 g5 and the 5 g sodium tripolyphosphate was replaced by 0.25 g sodium hydroxide.

The sterilized product consisted of lung pieces embedded in a soft, cohesive jelly and had a pH of 6.1 *.

Example 5

Use of fresh, shredded orange peel

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(a) Treated orange peel was prepared as follows: 5.2 kg of South African umbilical veins were passed through a scraper to remove the outer yellow layer. They were then halved and pressed to remove the juice. The resulting shell (3, * + 5 kg) was passed through a chopper equipped with a * +, 5 mm plate. The ground shell was washed with 2 liters of tap water and pressed into a muslin bag. * +, 16 kg of washed orange peel appeared. The pH of the treated shell was 5.2.

(b) Preparation of a Selected Meat Product:

composition

Chopped lung 150.00 g

Trimmed meat 150.00 g

Water 37.50 g

Sodium tripolyphosphate 6.25 g

Finely ground calcium sulfate dihydrate 5.00 g

Treated should be 150.00 g

The ingredients were mixed in a bowl and enough sodium carbonate (about 0.4 g) was added to give the mixture a pH of 7.5, after which it was allowed to stand for 2 hours to reduce the pectin content of D.E. to less than 20%. The mixture was then filled into cans which were sealed and sterilized at 1.6 ato. for 50 minutes. After standing overnight, the cans were opened and found to contain a coherent meat package comprising pieces of meat suspended in a firm, brittle, clear jelly. The pH of the product was 6.0.

Example 6

Use of dried orange peel (a) The dried pulp was prepared as described in Example 5, except that after washing and pressing, the ground shell was dried in a fluid bed laboratory dryer at 60 ° C. Drying proved difficult due to the sticky nature of the ground shell and it took several hours to dry. THE. of the pectin content of the dried shell was less than 20%.

(b) Preparation of a gelled meat product 16

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Chopped lung $ 15.00

Mimicked meat $ 10.00 Meat trimming $ 22.50

Call $ 2.50

Ground leg $ 5.00

Sodium Tripolyphosphate $ 1.25

Calcium sulfate dihydrate $ 1.00

Treated must $ 3.00

Dye solution $ 0.30

Caramel $ 0.50

Water $ 33.95

The ingredients were mixed together, filled into cans that were sealed and sterilized in an autoclave at 1.6 oz. for 1 hour. After standing overnight, the product was found to consist of a solid meat pack containing pockets of a firm, brittle jelly. No or little orange flavor or flavor could be detected. The pH of the product was 5.85.

Example 7

Use of Alkali-treated Orange Peel · (a) 11.56 kg of whole California oranges were scraped to remove the outer yellow layer, halved and pressed to remove the fruit juice. The resulting 91 kg shell was passed through a chopper equipped with a U, 5 mm plate, washed with 3 kg of water and pressed.

2.5 kg of water was added to the pressed shell and the pH was adjusted to 8.5 by the addition of 55 g of sodium carbonate. The slurry was allowed to stand at room temperature for 18 hours and then pressed into a muslin bag. The dewatered shell was then dried at 60 ° C in a fluid bed dryer and coarsely ground. The pectin content of the treated shell was $ 10. The alkali treatment proved to support the dewatering of the shell.

(b) Preparation of a gelled meat product 17

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Chopped lung 1 * +, 1 $

Fibrous meat 7) $ 8

Mimicked meat 7) 0 $

Waste Meat $ 3.9

Ground leg $ 5.7 Meat trimming $ 12.0

Call $ 7.3

Water $ 9.9

Sodium Tripolyphosphate $ 1.1

Calcium sulfate dihydrate $ 0.9

Caramel 0, * + $

Dye solution 0.3 $ ^ Juice

Treated must $ 2.7

Water $ 25.7

The treated shell was thoroughly mixed with the caramel, dye and water and then added to a mixture of the other ingredients. After thorough mixing, the product was filled into cans which were sealed and sterilized at 1.6 ato. for 1 hour. After standing overnight, the product appeared to consist of a coherent, solid meat pack with pockets of clear,! firm, brittle jelly. The pH of the product was 6.6.

Example 8

Use of alkali-treated orange peel msd reduced amount of calcium and complexing agent

The orange peel of the dried alkali treated described in Example 7 was used in the following meat blend preparation:

Chopped lung $ 20.00

Imitated Meat $ 10.00

Cut meat $ 20.00

Call $ 5.00

Ground leg $ 5.00

Water $ 5.00

Calcium sulphate 2H20 $ 0.25

Treated must $ 2.00 $ 18

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juice:

Sodium Tripolyphosphate $ 0.50

Caramel $ 0.50

Dye solution $ 0.30

Treated must $ 1.00. Water 30, ^ 5 $

The juice was prepared by mixing the ingredients except the treated shell and heating to 90 ° C and then adding the treated shell with vigorous stirring. After 3 minutes, the viscous juice was added warm to the meat mixture and mixed thoroughly. The mixed product was filled into cans which were sealed and autoclaved at 1.6 ato. for 1 hour. After standing overnight, the appearance of the product turned out to be similar to that described in Example 7 ·

Example 9

Use of alkali-treated orange peel as a thickener without added calcium and without complexing agent

The dried, alkaline-treated orange peel described in Example 7 was used for the following meat blend preparation:

Chopped lung $ 30.0

Ground meat $ 30.0

Water $ 10.0

juice:

Treated should be 3? 0 $

Caramel 0.5 $

Dye solution $ 0.3

Water $ 26.2

The treated shell was added to the cold water containing caramel and dye solution, and after 3 minutes of mixing, the resulting slurry was mixed with the meat and the remaining water. The mixture was then filled into cans which were sealed and autoclaved at 1.6 ato. for 1 hour. After standing overnight, the product turned out to be 19

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be an incoherent package of swollen meat slices suspended in a viscous, thick, glistening juice. The pH of the product was 6.3.

Example 10

Use of dried, alkaline-treated orange peel with complexing agent, but no calcium ions added

The dried, alkaline orange peel described in Example 7 was used to prepare the following meat mixture:

Chopped lung $ 30.00

Ground meat $ 30.00

Water $ 20.00

Treated must $ 2.00

Juice Mix: Dried, ground orange peel $ 1.00

Sodium Tripolyphosphate $ 0.25

Caramel $ 0.50

Dye $ 0.30

Water $ 25.95

The juice mixture ingredients were mixed together and brought to a boil and then added to the meat mixture. After further mixing, the mixture was filled into cans which were sealed and autoclaved at 1.6 ato for 1 hour. After standing overnight, the product was found to consist of a firm, coherent meat package containing pockets of a clear, soft, brittle jelly, especially on the surface of the package. The pH of the product was 6.5.

Example 11

Use of dried, alkaline treated grapefruit peel

South African grapefruit was cut in half, masted to remove the juice and ground in a chopper equipped with a +, 5 mm plate. The 8lU g 20

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the resulting shell was washed with tap water and pressed to remove excess water. 500 ml of water was added to form a slurry and its pH was adjusted from * t, 6 to 8.5 by the addition of 11 g of sodium carbonate. The slurry was allowed to stand at room temperature for 18 hours and then pressed free of excess liquid, washed once with tap water, pressed again and then dried in a fluid bed dryer at 60 ° C. The treated shell with a pectin content with a D.E. less than $ 20 was ground into a fine powder and used in the following meat mixture:

Chopped lung $ 25.00

Ground meat $ 15.00

Fibrous Meat $ 10.00

Trimmed meat $ 10.00

Water $ 10.00

Sodium Tripolyphosphate $ 1.25

Calcium sulphate dihydrate | $ 1.00

juice:

Treated must $ 3.00

Caramel $ 0.50

Dye solution $ 0.30

Water $ 23.95

The treated shell was dispersed in the cold water containing the caramel and the dye solution, and this "juice" was then mixed with other meat ingredients under thorough mixing. After standing overnight, the product was found to consist of a firm, cohesive package with a soft, fragile jelly surface layer, the pH of the product was 6.2, and the product had a fleshy aroma with only slight overtones of grapefruit.

Example 12 Dried lemon peel was prepared from South African lemons in the same manner as described for the grapefruit in Example 11. A meat product was obtained.

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provided using dried lemon zest in the same manner as described in Example 11 was found to consist of a firm, coherent meat package with a soft layer of soft, brittle jelly. The pH of the product was 6.2 and it had a slight aroma of lemons.

Example 11

Use of orange peel with psvium seed peel Dried orange peel was prepared as described in Example 6, except that a drying temperature of 90 ° C was used. Powdered psyllium seed peel was purchased at the trade. These materials were used to prepare the following gelled meat product:

Shaped meat $ 3.7

Textured Vegetable Image Protein $ 26.3

Ground leg 9? 3 $

Cut meat $ 13.8

Call $ 9.3

Added water * +, $ 7

Calcium sulfate dihydrate $ 0.3

Psyllium Seed Shell $ 0.5

Juice Mixture:

Dye solution 0.5 $

Caramel 0.9 $

Sodium tripolyphosphate $ 0.5

Water $ 29.1

Treated must $ 1.0

The various components of the meat mixture were combined and, after heating to 95 ° C of the juice mixture, was added and mixed thoroughly. The mixture was filled into cans and sterilized at 1.6 ato. for 1 hour. After cooling and standing overnight, the product turned out to consist of a stiff meat package embedded in a firm, tough, elastic gel.

The product gel was firmer and tougher than those obtained using 22

DK 163793 B

either psyllium seed peel or processed orange peel separately.

Example 1H

(a) Preparation of processed orange peel 10 kg of South African umbilical oranges were cut in half, mast to remove the juice and then passed through a chopper equipped with a 5 mm plate. The ground shell was washed with tap water, pressed, slurried in water, and enough anhydrous sodium carbonate was added with mixing to raise the pH to 9µ. The slurry was allowed to stand for 18 hours and then pressed, washed, pressed and roller dried. The roll-dried flakes were ground to a fine powder. The yield was 520 g and D.E. of the pectin content was under $ 20.

(b) Use in molded pieces of meat Composition:

Treated to 1.6%

Water 31.7%

Sodium tripolyphosphate $ 0.2

Non-fibrous, trimmed meat $ 63.3

Dye solution 1.3 $

Caramel. 1.9 $

The sodium tripolyphosphate, dye and caramel were dissolved in the water which had been heated to the boiling point. The processed shell prepared as under (a) above was added with vigorous stirring and the solution was thoroughly mixed with non-fibrous meat. The mixture was squeezed into spherical pieces in a 10 $ calcium chloride solution and allowed to stand for k hours.

The solid pieces were then removed, washed in water and autoclaved in cans at 1.6 ato for 1 hour in the presence of minced meat.

After being cooled, the contents of the cans were examined and the shaped pieces of meat were found to have firmness and internal texture as a lung.

23

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Example 15

Use in imitated pieces of meat Composition:

Water $ 65.3

Caramel 2.2 $

Dye solution $ 1.5

Sodium tripolyphosphate $ 0.3

Wheat gluten $ 28.0

Treated must $ 2.6

The caramel, the dye solution, the sodium tripolyphosphate and the treated shell (prepared as described in Example 1U) were heated in the water to the boiling point and the wheat gluten was added with vigorous stirring.

The mixture was poured into a tray and allowed to cool. After standing for 1 hour, the solidified mass was cut into 2 cm pieces and processed with solution of gelling agent in cans at 1.6 ato. for 1 hour.

After cooling, the simulated pieces of meat were found to have retained their shape and to have a firm but rather brittle texture, similar to cooked kidney.

This example demonstrates the utility of treated shell for bonding denatured protein materials which have no aggregation properties to a coherent mass.

Example 16

Use in a fish / meat bread product.

(a) Whole Spanish Valencia oranges were scraped to remove the outermost layer, halved and pressed to remove the fruit juice. 1 kg of the resulting outer layer was passed through a chopper equipped with a U mm plate and mixed with 12 g of anhydrous sodium carbonate for 30 minutes.

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2k nuts. The outer layer was pressed into a muslin bag and then mixed for 5 minutes with an equal weight of water. This was then pressed again into a muslin bag, and after chopping through a 2 mm plate, the outer layer was dried on a roller dryer operating at 5 * + ato. It was observed that roll-dried material was much more mild in flavor and less yellow in color than air-dried material.

THE. of this material was 10 (b) The treated shell was then used as an alternative gelling agent for comparison with a binder of cereals in a fish / meat bread product.

Cereal composition: Meat by-products 92 parts

Totally 370 parts

Poultry products 186 parts

Cereals 375 parts

Saline 63 parts

Whole blood 322 parts

Water 770 parts

Cod liver oil 26 parts Milk protein source 65 parts

Dye solution 19 parts

Caramel 7 parts

Composition of processed shell: Meat by-products 92 parts

Totally 370 parts

Poultry products 186 parts

Treated should 9 ^ divide

Sodium tripolyphosphate 10 parts

Whole blood 322 parts

Water 1051 parts

Cod liver oil 26 parts Milk protein source 65 parts

Dye solution 19 parts

Caramel 7 parts 25

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In each case, the ingredients were mixed together, heated to boiling and kept at this temperature for 5 minutes. The mixture was filled into cans which were then sealed and sterilized in an autoclave.

After being cooled, the cans were opened and the products compared. The product containing the processed shell was found to be a package of coherent meat which was firmly similar to the cereal composition, but with an improved aroma and appearance.

Example 17

This example should demonstrate the relationship between the esterification rate of treated shell samples and their ability to produce thickened juices after heat sterilization. Three samples of treated orange peel were prepared as described in Example 16 except that in the first sample no sodium carbonate was added, in the second 10 g of sodium carbonate and in the third 15 g of sodium carbonate to the outer portion of the orange peel after chopping.

The degree of esterification of the three samples was determined as previously described and the following results were obtained:

Prove Forestrated 1 56 2 15 3 11

product Manufacturing

Oven baked pieces of meat were made from meat waste and binders in accordance with recipes and methods commonly used in the food industry. Three juices were prepared using three treated shell samples by heating to boil the ingredients of the following composition: 26

DK 163793 B

The treated must 0.7 parts

Caramel 1.6 parts

Dye solution 1.1 part

Sodium tripolyphosphate 0.5 parts

Water 96) 1 part * + 5 parts by weight of the shaped pieces of meat and 55 parts by weight of the juice in question were mixed together, filled in cans, sealed and sterilized in an autoclave. After cooling and opening, the products were subjectively examined and in addition objective viscosity measurements were made of the product juices.

Viscosity with Brookfield Viscometer LVT Model spindle 2,

Sample Appearance Speed 12 1 Shaped pieces of meat in a large volume of aqueous, brown liquid 100 cps 2 Shaped cuts of meat in a moderate volume of viscous, brown liquid 1225 cps 3 Shaped cuts of meat in a small volume very viscous, brown liquid 1750 cps

Example 18

Use in gelled meat products

The three samples of processed orange peel described in Example 17} were used to compare their ability to produce gelled meat products.

Product Composition:

Shaped pieces of meat 26.2 parts

Textured vegetable protein 2, ^ parts

Kallun 8.5 parts

Beef waste 19) 3 parts

Ground leg * +} 5 parts

Water 7) 1 part

Juice 31) 7 parts

27 DK 163793 B

Composition of juice:

Treated must * +, 7 parts

Sodium tripolyphosphate 1.6 parts

Dye solution 0.8 parts

Caramel 1.1 part

Water 90.6 parts

Calcium hydroxide 0.3 parts

Potassium chloride 1.0 part

The juice ingredients were mixed together and heated to a boil. The desired amount was then mixed with the other ingredients and the mixture was filled into cans which were sealed and sterilized in an autoclave. After being cooled, the cans were opened and the appearance noted:

Sample Product Issue 1 Very soft package that collapsed when removing the can, consisting of pieces of meat in a thin, aqueous juice.

2 Solid, cohesive package with a clear, glossy, firm gel.

3 As sample 2 except that the gel was slightly firmer.

Example 19

Use in semi-moist dog food preparations A: Trimmed meat $ 25.80

Sugar $ 31.00

Water $ 12.60

Glycerin monostearate 0, $ 0

Beef 6, * + 0 $

Citric Acid $ 0.20

Butylated hydroxyanisole 0.02 $

Propylene glycol $ 3.90

Dye solution 0.10 $ B: Treated shell as in Example 1 * + 12.90 $

Sodium Tripolyphosphate $ 1.30

Dicalcium Phosphate $ 3.60

Potassium sorbate 0, U0 $

Claims (16)

0Q DK 163793 B The ingredients of the Å mixture were mixed together and heated to the boiling point. After boiling for 10 minutes, the weight of the mixture was adjusted to the original weight by the addition of boiling water and the mixed ingredients of the B mixture were added with vigorous stirring. The whole mixture was then placed in a tray, allowed to cool and cut into pieces and sealed in plastic bags. The product had a pH of 6.5 and a firm, chewy texture and a pleasant meaty aroma, without the usual unpleasant soy flavor and flavor found when soybeans and flour in the usual products are used to achieve the binding effect. Claims. A feed product comprising the reaction product of a pectate and divalent or trivalent metal ion and having a pH within the range of 5-8.5, characterized in that it comprises 5-95% by weight of pieces or particles of a solid protein feed, preferably meat, meat by-products and meat substitutes which are bound together in a coherent gel composed of the reaction product between the metal ions and a pectate or natural pectin feedstock having a pectin content of at least 5% by weight based on the weight in dry state, the pectin's esterification degree being less than 20% and the pectin 0.1-20% by weight of the dry weight of the feed product. Feeding product according to claim 1, characterized in that the gel phase also contains psyllium seed peel or rubber. Feed product according to claim 1, characterized in that it is a preserved product comprising 20-95% by weight of meat or meat by-products, 0.1-5% by weight of pectate or 0.1% to 10% of finely divided citrus peel (based on dry wt), 0-5 wt% non-toxic alkaline earth metal compound, and 0-5 wt% complexing agent, and having a moisture content of 50-95 wt%. 29 DK 163793 B Feeding product according to claim 1, characterized in that it is a coherent shaped meat preparation comprising 40-95% by weight meat or meat by-products, 0.1-5% by weight pectate or 0, Ι-ΙΟ% by weight of finely divided citrus peel (calculated on dry wt), 0-5 wt% non-toxic alkaline earth metal compound and 0-5 wt% complexing agent, and having a moisture content of 50-95 wt%. Feeding product according to claim 1, characterized in that it is a mimicked meat composition comprising 5-50 wt.% Vegetable protein, 0.1-5 wt.% Pectate or 0.1-10 wt.% Finely divided citrus peel, 0-5 wt.% Non-toxic. alkaline earth metal compound and 0-5% by weight of complexing agent and having a moisture content of 50-95% by weight. Process for the preparation of a feed product according to claim 1 consisting of solids in a gelled aqueous phase having a pH in the range 5-8.5, characterized in that the aqueous phase is thickened or gelled by application of a pectate having a degree of esterification. of less than 20% and calcium ions to form a thermoreversible or heat stable gel reaction product. Process according to claim 6, characterized in that the pectate is introduced in the form of an isolated pectate with an esterification degree of less than 10%. Process according to claim 6, characterized in that the pectate is introduced in the form of a natural pecti citrus peel, with a pectin content of at least 5% on the dry weight, which pectin raw material is treated to lower the pectin esterification rate to below 20%. Process according to claim 8, characterized in that before being introduced the natural pectin raw material is pulverized and treated with alkali to reduce its degree of esterification to below 20%, preferably during removal of the colored outer layer (flavedo) if citrus peel is used. 30 DK 163793 B Process according to any one of claims 6-9, characterized in that psyllium seed peel or rubber is additionally added to the aqueous phase. Process according to claim 6, characterized in that a mixture containing 20-95 wt. * Meat or meat by-products, 0.1-5 wt. * Pectate or 0.1-10 wt. * Finely divided citrus peel (dry weight) is prepared. up to 5 weight * calcium compound and 0-5 weight * complexing agent and where the fungal content is adjusted to 50-95 weight *, after which the mixture is preserved in known manner. Process according to claim 6, characterized in that a mixture containing 40-95 wt. * Meat or meat by-products, 0.1-5 wt. * Pectate or 0.1-10 wt.% Finely divided citrus peel (dry weight) is prepared. up to 5 weight * calcium compound and 0-5 weight * complexing agent and adjust the moisture content of 50-95 weight *, forming the mixture into cohesively shaped pieces to form a heat stable gel. Process according to claim 6, characterized in that a mixture containing 5-50 wt * vegetable protein, 0.1-5 wt * pectate or 0.1-10 wt * finely divided citrus peel (dry weight) is prepared. to 5 wt * calcium compound and 0-5 wt * complexing agent and adjust the moisture to 50-95 wt *, forming the mixture into shaped pieces to form a heat stable gel. A process according to claim 1, characterized in that sufficient amount of water-soluble substances are added to the constituents contained in the product to reduce the water activity of the product to between 0.65 and 0.85, and in addition an antifungal agent.