JPH0150394B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION Oranges, like most fruits and vegetables, have a specific growing season; oranges are subject to certain climatic conditions, such as Florida, Arizona, California, Texas, Brazil, Spain, Italy, Israel and Egypt. It grows only under climatic conditions such as those occurring in the region and is available only during a limited period of the year. That is, certain types of oranges are sometimes in short supply. For example, Florida balena, which is used in most commercially available orange youth products, is grown from April to August.
Available only in May. In order to make good quality orange juice available throughout the year, orange juice must be stored and processed for sale. In the following description, reference will be made to the aroma and flavor compounds present in orange juice and orange juice concentrate. It is well known that the organoleptic properties of any beverage product are important for gaining consumer approval. However, in the case of orange juice, such properties are unique. The term sensual is defined as "affecting or using one or more of the special sense organs," such as taste, smell, etc. In order to produce orange youth products that satisfy a wide range of consumers, it is necessary to have a flavor that is satisfactory,
That is, a superior product must be produced that has taste, aroma, odor, appearance, and feel. Aromatic and flavor components in oranges influence each of these organoleptic properties. This is surprising considering that although many components are present in orange juice, aroma and flavor components are only present in very small amounts. The difficulty of producing a unique orange juice concentrate of superior quality means that orange juice concentrate has been available for several decades and natural orange juice products are not enjoyed by a large portion of the general public. It makes sense when you think about it. That is, in order to gain widespread approval for new orange juice concentrates, the taste preferences already held by a large portion of the orange juice-consuming public must be overcome. However, one of the important objects achieved by the present invention is that a natural orange juice concentrate product is made and a process is provided which is quite different from previously known orange juice products and processes. It is. It is surprising that the orange juice of the invention, when diluted, is superior and distinguishable from freshly squeezed orange juice. This difference exists in both taste and product stability. These and other advantages are achieved because the products and processes described in this invention provide unexpected improvements in substantially all of the above sensory sensations. These unexpected improvements and advantages are discussed in detail below. Since orange juice contains about 80-90% water, the most economical way to store and distribute it is in concentrated form. The majority of industrially processed orange juice in the United States since 1950 has been frozen concentrated orange juice products. Most commercial concentration methods utilize evaporation techniques to remove most of the water from the youth. However, it is widely recognized that evaporation techniques result in the undesirable removal and loss of volatile aroma and flavor compounds along with water, thereby considerably degrading the quality, overall flavor and aroma of concentrated juices. . The evaporation method involves heating the youth under conditions that promote oxidation of the compounds in the youth. This may chemically alter the aroma and flavor compounds within the orange juice. For example, lipids can be oxidized and amino acids and sugars can undergo brown coloring reactions. Such degradation products can cause off-flavors in orange juice concentrates. Various methods have been devised to compensate for aroma and flavor loss during evaporative concentration methods. For example, US Pat. No. 3,140,187 discloses a method of minimizing the overall loss of aroma and flavor compounds by collecting the "essence" of the youth. "Essence" is a term applied to the first 15% to 20% of the water removed by evaporation, which contains significant amounts of volatile aroma and flavor compounds. The fugitive essence is concentrated, aroma and flavor compounds are recovered, and then returned to the concentrated juice. However, this method
It is not completely satisfactory since only a portion of the fugitive aroma and flavor volatile compounds are collected. That is, there is necessarily a net loss in the overall aroma and flavor of the final concentrated product. Others have attempted to add certain volatile compounds and essences back to concentrated orange juice in different ways to enhance the overall flavor and consumer satisfaction of the juice. Ahmed et al., J.Agri.Food Chemistry,
(1978, 386-372) describe a method in which certain volatile compounds and essences are added to the youth concentrate after it has been recovered from the evaporator. The aim was to match the aroma and flavor found in fresh orange juice. It is well recognized that although evaporative concentration methods are quite effective, significant losses of aromatic flavor compounds still occur. Freeze concentrators offer an alternative to the use of evaporators. In a freeze concentrator, the purpose is to remove water, in the form of ice crystals. US Patent No. 2187572
No. 1, by extracting the juice, centrifuging the juice, collecting the pulp part to give a liquid centrifuge, freeze-concentrating the centrifugate, and returning the pulp part to the concentrated juice. The concentrated juice produced is described. It is stated that the juice product obtained by this method can be diluted with water to obtain a taste similar to that of the original juice.
However, the specific concentrations of volatile aroma and flavor compounds and the identification of key compounds remaining in the product are not described. Schreier et al, Chem.
Microbiol.Technol.Lebensm., 6 , 78-83,
(1979) analyzed the behavior of volatile aroma compounds during freeze-concentration of orange juice. During the freeze-concentration process, aroma and flavor compounds are analyzed by gas chromatography and quantitatively determined in sequence in the youth concentrate and in sequence in the separated ice. It was found that a significant amount of aroma and flavor compounds were removed in the separated ice. The average loss of aroma and flavor compounds in ice at each concentration was estimated to be approximately 12%. It is clear that many oxidation products, such as nootkatone, carvone, geraniol and alpha terpineol, are formed in this freeze concentration process, resulting in an overall loss of quality. The formation of these oxidation products and similar compounds can result in youth products having significant off-flavors. Schreyer used a freeze-concentration method, but
His analytical data indicate that significant losses of volatile components have occurred. Additionally, oxidation products are formed due to the open process used in both the above-mentioned US Pat. No. 2,187,572 as well as the Schreyer et al. patent. Ideally, during freeze concentration only pure ice should be removed, without removing the aroma and flavor compounds originally present in the juice. If the recovered ice contains aroma and flavor components, an inferior quality juice concentrate is produced. As is clear from the above description, the common method for making orange juice concentrate is to first extract the juice from the orange and separate the juice from the core and seeds. Juice can be divided into pulp and juice. The pulp can be further processed to separate the useful pulp from any small seeds etc. and also to vary the amount and size of the pulp as desired. Finally, the pulp is recombined with the processed juice. The water is removed from the fruit juice to make it a concentrated fruit juice. Some methods of concentrating vegetables are carried out in the presence of fruit pulp. Typically, in the final step, the concentrate is blended with the desired amount of fruit pulp into a final concentrated product that can be packaged and shipped. It is known that the juice that remains behind the pulp, core, and seeds contains primarily water and compounds that give the distinct orange aroma and flavor. However, it is probably impossible to assign virtually any special function to a particular component. For example, chemicals that contribute to orange aroma likely also contribute to orange flavor. Can be a pasteurized product, containing virtually 100% of the non-volatile compounds originally present in the juice
and at least 65% of aroma and flavor volatile compounds
A method for producing an orange juice concentrate having a . Furthermore, if such a process does not result in oxidative degradation of the solids within the juice, the process should produce a concentrate that, when diluted, has a taste as good or better than the original juice. It will be. Another object of the invention is to produce a natural orange youth concentrate having a solids content of at least 35%. This solids content includes pulp, non-volatile compounds, and at least 65% of the aroma and flavor volatile compounds present in the orange juice. It is believed that such concentrated youth products have never been made before the present invention. These residual volatile and non-volatile compounds are the very compounds that contribute significantly to the pleasant flavor and aroma of the product. A useful contributing compound to the fruity character of orange juice aroma and flavor is ethyl butyrate. At least 0.1% of the aroma and flavor volatile compounds present in the orange youth concentrate of the present invention is ethyl butyrate. A second important volatile compound, limonene, also remains. Furthermore, it is an object of the present invention to produce an orange juice concentrate that tastes as good or better than the starting juice when diluted. It is also an object of the present invention to produce a fruit juice concentrate that tastes as good or better than the starting juice when diluted. Yet another object of the present invention is to provide beverages such as carbonated drinks, dry mixes and alcoholic drinks;
The purpose of the present invention is to produce a fruit juice concentrate that can be used as a flavoring agent in candy products, bakery products, cooking mixes, etc. A preferred object of the present invention is to produce a fruit juice concentrate that does not contain organoleptically detectable amounts of hydrogen sulfide and is substantially free of microbial enzyme activity and oxidative degradation products. These and other objects of the invention will become apparent from the following description of the invention. In this specification, all percentages are by weight unless otherwise defined. SUMMARY OF THE INVENTION A natural fruit juice concentrate made from fruit juice and comprising a granular solid portion and a fruit juice portion is disclosed. The juice portion consists of about 80% to 93% water and about 7% to 20% other compounds. These compounds include soluble and suspended solids, such as non-volatile and volatile aroma and flavor compounds. The volatile compounds include a low boiling component and a high boiling component, the low boiling component containing ethyl butyrate and the high boiling component containing limonene. The natural orange juice concentrate of the present invention contains the following ingredients. (1) A total solids content of at least 35% consisting of pulp, non-volatile and volatile flavor and aroma compounds, two of the volatile compounds being ethyl butyrate and limonene. (2) At least 0.1% of the volatile compound is ethyl butyrate. (3) The ratio of the ethyl butyrate to the limonene is approximately
in the range of 0.0015:1 to about 0.6:1 (the amounts and proportions of volatile compounds are based on gas chromatographic analysis of headspace volatile compounds emitted from a sample having a temperature of 40°C). The fruit juice concentrate of the present invention has at least 65% of the volatile flavor and aroma compounds originally present in the juice. Furthermore, a method for producing a fruit juice concentrate is disclosed, which includes the following steps (1) to (5). (1) Fruit juice is extracted from fruit, and the juice contains 7% to about 20% granular solids, about 7%
% to about 20% soluble and suspended solids, the balance being water; (2) separating the juice into a solids portion and a juice portion, the juice portion containing about 7% to about 20% (3) converting the juice portion to predominantly pure ice crystals without removing a substantial amount of attached solids; (4) conducting the separation step and the freeze concentration step under an inert atmosphere to substantially prevent oxidative deterioration of the solids; About 20 to about 52% solids content and about
recovering a frozen concentrate containing from 48% to about 80% water; and (5) blending the concentrate with the particulate solids separated in step (2). Also disclosed is a method for sterilizing juices, fruit juices, granular solids or concentrates in a closed system at 80-95°C for about 3-15 seconds. Yet another method for producing fruit juice concentrate includes the following steps (1) to (3). (1) About 7% to about 20% particulate solids, about 7% to about
(2) extracting fruit juice from the fruit with 20% soluble and suspended solids and the balance being water; (2) passing the juice together through a sublimation concentration zone where pure water vapor is removed; (3) Contains about 20% to about 87% solids and about 13% to about 80% water from the concentrated region. Collect the frozen concentrate. A combined method of freeze concentration and sublimation concentration can also be used. DEFINITIONS The natural fruit juice concentrate of the present invention is made from fruit juice. Juice contains a granular solid part and a fruit juice part. The juice may be freshly squeezed, sterilized or frozen. In the present invention, the granular solid portion mainly contains fruit pulp, and may also contain juice bags, juice lipids, cellulose, hemicellulose, pectin and protein. Some amount of fruit juice is always present along with a particulate solid fraction. Most of the chromatophore, ie, dyestuff, colored material is also present in the particulate solid fraction. The fruit juice part is about 80% to about 93% water and about 7% to about
Consists of 20% other or non-aqueous compounds. The non-aqueous compounds of fruit juice consist of both soluble and suspended solids and include non-volatile and volatile compounds. Non-volatile compounds include carbohydrates, carbohydrate derivatives, food acids, enzymes, lipids, minerals, flavonoids, carotenes, vitamins, etc. Carbohydrates are mainly sutucarose, fructose and glucose. Edible acids include citric acid, isocitric acid, ascorbic acid, malic acid, fumaric acid, oxalic acid and amino acids. Volatile compounds are compounds that are swept out of a fruit juice sample that is a concentrate diluted to a single strength juice (7% to 20% solids) such as: That is, volatile compounds are removed by passing 50 ml/min of nitrogen through the sample for 5 minutes. The temperature of the sample during this sweep operation is maintained at 40°C ± 0.5°C. The volatile components are then collected at liquid nitrogen temperature,
Measured by gas chromatography according to the method described herein. Volatile compounds include low boiling components, or highly volatile moieties, and high boiling components, or less volatile components. The low boiling point compounds are eluted first from the capillary gas chromatography column described in detail below. Those compounds are characterized by having a boiling point below 131°C. Specific examples of low-boiling compounds include, but are not limited to, acetaldehyde, methanol, ethanol, butanol, hexanal, and ethyl butyrate. High boiling components are compounds that elute later than low boiling components. These compounds have boiling points above 131°C. Specific examples of these less volatile compounds include, but are not limited to, telinalur, limonene, β-pinene, α-pinene, myrcene, geranial, octanal, and decanal. The ratio of low-boiling to high-boiling components is determined by dividing the total gas chromatographic counts of low-boiling compounds by the total gas chromatographic counts of high-boiling compounds excluding counts attributable to limonene. . The gas chromatograph count number is the automatically integrated peak area of the gas chromatograph recorder. They are directly related to the concentration of each compound present in the volatile mixture. The ratio of ethyl butyrate to limonene is determined by the following formula: Ethyl butyrate GC counts/Limonene GC counts "Substantially 100% non-volatile solids" means that at least 99% of these compounds are concentrated. It means to exist in a substance in a substantially unchanged form. Enzymes can be inactivated when sterilizing the product. "Substantially free" means less than 1% of the compound present in the concentrate. DETAILED DESCRIPTION OF THE INVENTION The natural fruit juice concentrate composition of the present invention is made from all natural products, ie, all fruit. In the following description of the method of the present invention, it is to be understood that although the method of making orange juice concentrate is specifically described, it is not limited thereto. The method of the invention is therefore equally applicable to other citrus fruits, such as grapefruit. Orange youth concentrate is primarily made from four types of oranges: pineapple, Hamlin, Parson Brown, and primarily Valencia oranges. Tangerines, mandarin orange, blood orange
orange) and naval orange
can also be used. The juices from these oranges can be used alone or in blends to obtain optimal flavor characteristics. One reason to mix oranges of different quality is
The trick is to adjust the sugar-to-acid ratio of the orange. Sugar to acid ratio is the ratio of total soluble solids to total acidity of orange juice. The sugar-to-acid ratio is closely related to the edible quality of oranges. Unripe oranges have a low sugar to acid ratio. As the orange ripens and approaches good edible quality, the sugar to acid ratio increases. 8:1～
A sugar to acid ratio of about 20:1 is considered satisfactory. The preferred sugar to acid ratio of the present invention is 12:1 to 16:1.
and the most preferable range is 14:1 to 16:1. In order to produce the superior natural orange juice concentrate of this invention, the orange juice must be processed with minimal exposure to oxygen and minimal exposure to temperatures above 0°C. The oranges are first cleaned with a disinfectant solution, preferably a hypochlorous acid solution. The oranges are then thoroughly rinsed with water before juice extraction. Diesel extraction can be performed using any automatic juice machine or by manually squeezing the oranges. The type of equipment used to extract the oil is not important. However, those that minimize the extraction of skin oils are preferred. The skin oil content of the youth should be less than 0.05%, preferably between 0.01% and 0.03%. Peel oil gives orange juice its bitter taste. Therefore, the concentration of the final product should not exceed 0.035%. Peel oil is present in both the fruit juice and the separated pulp. Since the pulp absorbs the skin oil, the concentration of skin oil in the pulp portion can often be greater than in the juice portion. When calculating the skin oil content of the final concentrate, the skin oil content of the pulp must be taken into account. The raw juice that comes out of the extractor or squeezer contains pulp, core, and seeds. The core and seeds are separated from the juice and pulp in a finisher. The size of the sieve in the finisher controls both the amount and size of pulp desired in the juice. The diameter of the sieve can vary from about 0.5 mm to 2.5 mm. Sieve is 2.5mm
If the amount exceeds 1,000,000, the small seeds will contaminate the youth. In order to maintain quality, freshness and retain aroma and flavor compounds, the orange juice should be immediately cooled to below about 30°C, preferably below 5°C, after being removed from the extractor and finisher. Juice is about 4% to about 25% pulp, about 7% to about
Contains 20% soluble solids, the remainder of the juice is water. The juice is then separated into a pulp (granular solid) portion and a juice portion. Separation takes place under an inert atmosphere. An inert atmosphere is achieved by using a nitrogen blanket or other non-reactive, non-oxidizing gas such as helium argon over the separation unit. It is important that this separation is achieved in the absence of oxygen. In this separation step, a separator that provides a cleanly separated pulp and juice portion is preferred.
The particle size of the suspended solids contained in the juice portion should be less than 80 microns. A high speed centrifuge is preferred for this separation. A preferred centrifuge is
It is a bowl-disk type Westfaria centrifuge operating at 8000-9500 rpm. The pulp portion is stored in a closed container away from light and at temperatures below about 0° C. for later addition to the concentrated fruit juice. The pulp portion includes the pulp, suspended solids, and adsorbed or associated solids soluble in the pulp. The fruit juice part is about 80% to 93% water and about 7% to
Soluble solids include both volatile and non-volatile compounds, including 20% soluble solids and non-aqueous solids that are suspended solids less than 80 microns in size. The juice portion is concentrated by freeze concentration or sublimation concentration. Freeze concentration is accomplished in such a way that water is removed substantially or primarily as pure ice crystals. Deposited solids or occluded solid compounds are not present in the ice and are therefore not removed with the ice. The system should be closed and under an inert atmosphere. The use of a closed system prevents loss of low boiling aroma and flavor compounds. The inert atmosphere prevents oxidation of volatile and non-volatile compounds. A highly preferred embodiment is one that includes a freeze concentrator with a scraped wall heat exchanger connected to an adiabatic recrystallization tank. This insulated tank allows crystal recrystallization and growth to occur under conditions such that substantially pure ice is formed. A filter at the outlet of the tank leaves all crystals larger than 100 microns in size within the tank. This leaves most of the ice nuclei for recrystallization. The recrystallized ice is separated from the concentrated juice using a washing column. The washing column rinses the concentrate adhering to the ice off the ice crystals. This speeds up the separation from the substantially pure cryoconcentrator. The preferred equipment used for freeze concentration is the Grenco freeze concentration unit. This unit is described in U.S. Pat. Nos. 3,777,892, 3,872,009 and 4,004,896. Sublimation concentration is an alternative concentration method. Sublimation concentration uses conventional freeze-drying equipment that removes water as pure vapor. Orange juice, with or without pulp, is frozen into a solid state. Preferably this is carried out in a closed system under an inert atmosphere and with stirring. Stirring causes large crystal growth. The frozen youth is then placed at a temperature below the eutectic temperature of the youth. Eutectic temperature refers to the melting/freezing point of a youth or fruit juice. For fresh youth at 12% solids, this is approximately -2.5°C at normal pressure. For youth at 35% solids concentration, this is approximately -25°C. As water is removed from the youth, the temperature must be carefully maintained to keep the frozen youth solid. This is important to ensure that the maximum amount of volatile compounds remains. Other methods for removing water from fruit juice as pure water include a freeze concentration step to a solids content of about 25% to 35%, followed by a sublimation concentration step to a solids content of about 40% to about 87%. . In this case, the sublimation process is 30
The surface temperature of the % solids solution must initially not exceed about -30°C to about -25°C. A vacuum of less than 100 microns is used. The water removal step, such as sublimation concentration or a combination of freeze concentration and sublimation concentration, must be carried out under conditions that avoid substantially any oxidative degradation of the solids present within the juice. That is, the freeze concentration system must remain closed and the juice entering the concentrator should preferably be placed under a blanket of inert gas such as nitrogen, argon, helium, etc. Concentrated fruit juices obtained from sublimation concentration or a combination of freeze concentration and sublimation concentration contain a solids content of at least 35% up to 87%. Substantially all of the non-volatile compounds originally present in the soluble solids portion of the fruit juice are present in the concentrated fruit juice. i.e. at least
99% of non-volatile compounds remain. Also, at least the volatile compounds originally present in the youth
65% remains in this concentrated fruit juice. Pulp content and pulp size vary depending on the method of pressing the juice and the method of separating the pulp from the juice before concentration. The size of the pulp affects the perceived amount of pulp in the juice. 0.50mm size pulp
It can be felt that the orange juice concentrate containing 10% pulp has a very small amount of pulp compared to the orange juice concentrate containing 10% pulp with a size of 10 mm. That is,
In producing a product that is satisfactory to the consumer, not only the amount of pulp present but also the size of the pulp is important. A pulp concentration in the range of 5% to 19% (volume/volume, hereinafter abbreviated as V/V) has been found to be a satisfactory concentration in orange juice concentrate. Percent pulp is determined by centrifugation. The size of the pulp should be between 0.1 mm and about 10 mm. Preferably, it should contain 6% to 12% (V/V) of pulp having a size of 0.50 mm to 5 mm. Concentrated fruit juice contains about 35% to about 87% solids. This concentrated fruit juice is blended with 30% to 100% pulp part to produce an orange juice concentrate having a pulp part of about 5% to about 15% (V/V) and a concentrated juice of about 85% to 95%. Ru. Preferably the blend should have 7% to 12% (V/V) pulp. The orange juice concentrate is then filled into cans, foil containers, bottles, etc. To ensure long-term oxidative stability, the packaging compound should be oxygen-impermeable. Also, packaging of the concentrate can optionally be carried out under a nitrogen atmosphere. Storage of the product is carried out at temperatures below 0° C. for long-term storage. Preferably it is stored at -20°C to -80°C. The natural orange juice concentrate produced by the method of the invention is characterized in that it retains at least 65% of the volatile compounds originally present in the orange juice. Gas chromatographic analysis of the volatile portion of fruit juice indicates that there are at least 250 compounds in the volatile portion of fruit juice, and probably significantly more. Complete identification of these volatile compounds has not yet been achieved. These volatile compounds are responsible for the aroma and flavor properties of the concentrate.
It is composed of alcohols, carbonyl compounds, acids, esters, pertenes, and other volatile hydrocarbons. As mentioned above, the low boiling point components include large amounts of ethanol and acetaldehyde. Other important low-boiling compounds include ethyl butyrate, methanol, butanol, and hexanal. Remaining ethyl butyrate at a concentration of 0.1% of the volatile compound, i.e. at least about the amount of ethyl butyrate originally present in the juice
A feature of the present invention is that 60% remains. Ethyl butyrate is only partially responsible for the fruity properties of orange juice.
Its presence alone, even when present along with ethanol, acetaldehyde and hexanal, cannot produce the overall orange aroma and flavor. The residue, together with the residue of at least 65% of the total volatile compounds, represents the residue of compounds present even in very small amounts. High boiling components, ie, compounds boiling above 131°C, include limonene, α-pinene, β-pinene, myrcene and geranial, and other less volatile compounds. Limonene is an important orange flavor and aroma component at low concentrations. The amount of limonene that should be present in an orange juice concentrate ranges from about 40% of the total volatile compounds in the concentrate to about
It is 98%. A more preferred composition is about 50% to about 80%
% limonene. The ratio of ethyl butyrate to limonene is approximately 0.0015:1 ~
It should be in the range of approximately 0.6:1. Preferably,
This range lies between 0.004:1 and 0.4:1. This ratio represents a preferred aroma and flavor composition. The ratio of low boiling point components to high boiling point components is at least 4:
Should be 1. This ratio may be as high as 17:1. Preferred compositions of the invention are those in which the ratio of low boiling components to high boiling components ranges from 6:1 to about 12:1. For purposes of determining this ratio, as discussed above, limonene concentration is not used in calculating gas chromatographic counts of high boiling components. Many fresh juices contain volatile sulfur compounds. One of these compounds is hydrogen sulfide. Hydrogen sulfide imparts a heavy tone to the aroma and flavor of orange juice or orange juice concentrate. 200ppb to 500ppb depending on the use
contains hydrogen sulfide. The juice must be allowed to stand for several hours in order for this hydrogen sulfide to evaporate. The orange juice concentrate of the invention contains only organoleptically undetectable amounts of hydrogen sulfide. That is, the hydrogen sulfide content is less than about 20 ppb. The optional sterilization step is important to maintain the storage stability of orange juice concentrate. Sterilization is the control of the concentration of bacteria and other microorganisms so that the product does not deteriorate during storage or when diluted after a significant period of time. Furthermore, pasteurization reduces the activity of pectin esterase enzymes. Pectin esterases are thought to be responsible for demethylating pectin and thus destroying the haze of orange juice. Pectin esterase has some activity even at 0°C. Accordingly, particularly preferred compositions of the invention are those containing minimal concentrations of pectin esterase enzyme. A pectin esterase activity of less than 1.5 (PE) _u x 10 ⁴ , preferably less than 0.5 (PE) _u x 10 ⁴ is achieved by pasteurization. Concentrated products are optionally sterilized by using high temperature, short residence time sterilization techniques. Heat the juice, pulp or concentrate to about 80°C to about 95°C for about 3 to 12 seconds. The juice or concentrate is then rapidly cooled to about -10°C to about 5°C. The system used to sterilize the young use must be closed and carried out in such a way that the young use is not exposed to an oxidizing atmosphere. The sterilization step can be performed at any stage of processing. The concentrate can be diluted with water to make an orange juice drink. The 41.8-44.8% solids concentrate is diluted with 1 part concentrate to 3 parts water. The 73.2% to 78.4% concentrate is diluted with 6 parts water for some concentrates. Also, carbonated water can be used to make a carbonated drink. Concentrated fruit juice is made with or without the addition of pulp.
It can also be used as a flavoring agent in drinking water, bakery products, cooking syrups, sugar coatings, salad dressings and other food products. Although the process of the present invention has been described with reference to oranges and orange juice concentrates, the invention is not limited thereto and can be equally applied to making juice concentrates from other citrus fruits. . Analytical Method Measuring Pulp Concentration Pulp concentration is determined according to Florida Citrus Code Part 16
(Florida Citrus Code, Part 16). It is measured by centrifuging the fruit pulp and juice at 367.3 g's for 10 minutes. The % pulp is then calculated on a volume-to-volume (V/V) basis. Gas Chromatographic Analysis - Method 1 Sampling System The sampling system consists of a cylindrical glass vessel with an opening connected to a three-way valve with a Teflon tube at each end. One valve (valve A)
is connected to a helium source, and a second valve (valve B) is fused to a collection coil submerged in liquid nitrogen. The collection coil is connected through a third valve to the inlet of a standard gas chromatograph equipped with a flame ionization detector. The cylindrical sweep container is placed horizontally in a constant temperature water bath. Method: Place 25 g of orange juice sample into a sweeping vessel. Samples can be fresh juice or concentrates diluted to 10% to 15% solids. The sweep container has a volume of 626 ml, an internal diameter of 5 cm and a length of 27.5 cm. Burrell set the vessel to the lowest vibration setting, i.e. 276 vibrations/min.
Suspend in a constant temperature bath at 40℃ using a Wrist-Action shaker. Place the container in the tank, and 15 minutes after starting the sheaker, a controlled flow of helium at 50 ml/min (measured with a Gilmont size “10” flowmeter) is passed through the container, made of stainless steel immersed in liquid nitrogen. into the collection coil. The outer diameter of the coil is 1/
8 inches (approximately 0.3 cm) and the length of the coil is 13.4
inch (approximately 34cm). This coil is vented to atmosphere. The passage of helium flow through the container is 5
Can last for minutes. After this 5 minute period, all valves are closed and the liquid nitrogen bath is removed from the collection coil. The collection coil was then heated to 200°C with a heat gun, and at the same time the adjacent tubes, namely the tube from the glass container to the collection coil and the tube from the collection tube to the gas chromatograph, were heated to approximately 105°C with a heat table. Heat. The coil
When the temperature reaches 200℃, start the gas chromatograph.
Valves A and B are opened to direct helium flow into the coil through tubing that bypasses the scavenge vessel. A valve on the coil is set to direct the helium flow to the gas chromatograph. Hewlett Packard
A Hewlett Packard 5880 gas chromatograph with a 5880A terminal is used. The detector is a flame ionization type. The glass capillary column is 150 m long and has an internal diameter of 0.5 mm. The capillary column is coated with SF-96 from Chromepack. SF-96 is a methyl silicone fluid. Gas chromatography is performed at a column flow rate of 2 1/2 ml/min. The initial oven temperature is 25°C and the initial oven time is 12 minutes. The chromatograph is programmed to automatically change the oven temperature at a rate of 3°C/min to a final oven temperature of 180°C and hold the final temperature for 16 minutes. The injector temperature is 250°C and the detector temperature is 300°C. The split port was set at 250 ml/min and the split ratio was 1:100. The auxiliary formulation flow is set at 40ml/min. After each run, the oven is kept at 180 °C for 10 minutes. The integrator has a threshold value of 1, a peak width of 0.02 seconds, and a damping constant of 2.
Set to ×2. A gas chromatograph diagram of a typical orange juice (pineapple variety) is shown in Figure 6. The recorder is a linear recorder whose attenuation constant does not change with peak height. Therefore, the maximum peak in the low boiling region (ethanol) and the maximum peak in the high boiling region (limonene) are flattened at the top. Representative integrals of the areas of some of these peaks are shown below.

[Table] Gas chromatographic analysis (method 2) A cylindrical glass container with a height of 15.2 cm, an inner diameter of 7.52 cm, and a total volume of 350 ml is used. The glass container is closed by a glass cap which is fitted onto the container by an O-ring. The container cap has one inlet pipe and one outlet pipe extending 15 cm into the glass container but not below the surface of the liquid. All of these pipes are made of 1/4 inch (approximately 0.6 cm) glass tubing. Place 10 ml of sample juice into a glass container. This sweep-out container is equipped with a Teflon-coated stirring rod (3 x 1 cm) to keep the sample thoroughly mixed during sweep. 50 ml nitrogen/min for 5 minutes is used for the sweep. During this time, the container is submerged in a constant temperature water bath at 40°C ± 0.5°C. The nitrogen swept out of the container is transferred to a glass-lined stainless steel condensing coil [3 inches (approx. 8 cm)].
long, 1/8 inch (approximately 0.3 cm outside diameter). This condensing coil is immersed in a liquid nitrogen bath. The condensing coil is a Perkin-Elmer
Elmer) model No. 99 gas chromatograph. The gas chromatograph is equipped with a sniff-port, a flame ionization detector, and a sulfur detector. The effluent is distributed between these ports in a ratio of 3:1:1. Manifold temperature is approximately 195°C. The flame ionization detector attenuation setting is "2" and the range is set to "1". The peaks obtained from the eluted compounds are
Measurements are made using an Autolab System 1 integrator from Physics. The recorder was a two-point Heuretsu Pats Card 3138-A recorder. The gas chromatograph temperature gradient was programmed as follows. 12 minutes at oven temperature 25°C, increasing by 3°C/min for 51 minutes, then further
Isothermal at 180°C for 16 minutes. Identification of compounds was performed by residence time of known standards, a combination of gas chromatography and mass spectrometry, and treatment with esterase. Typical orange juice using this method (Figure 2), concentrates made in the example (Figure 3), and concentrates made using ^the Contherm ^R freeze concentration method (Figure 4). ) and commercially available evaporated juice (Fig. 5), which seems to have added essence and fresh juice, etc., were obtained. The recorder used to create these chromatographs varied the attenuation constant depending on the peak height in order to maintain the peak area on the graph paper. The instrument automatically integrated peak areas. Some representative compounds have been identified for each spectrum.

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[Table] It is clear from these analyzes that natural orange juice contains different amounts of ethyl butyrate (0.79%).
and 3.59%) and limonene (76.4% and 45.18%)
has. However, only the orange juice concentrate made in the example has at least 0.1% ethyl butyrate, i.e. 0.34%, whereas the concentrates from the evaporation method and the open processing freeze concentration method each have
It is only 0.04%, a very small amount. The present invention (third
The ethyl butyrate to limonene ratio of the orange concentrate (Figure) is 0.005:1, whereas it is 0.0005:1 for the evaporative concentrate and approximately 0 for the open processed concentrate. Also, using the above method, the grapefruit concentrate obtained in the example by the method of the invention (Table 1),
Commercially available juices obtained according to conventional methods (Table 2)
and a gas chromatograph of freshly squeezed grapefruit juice (Table 3). Some representative compounds have been identified for each spectrum. As shown in these tables, 89% of the ethyl butyrate present in the freshly squeezed juice (Table 3) remains in the grapefruit juice concentrate made by the method of the invention (Table 1). Juice processed by conventional methods contains only trace amounts of ethyl butyrate. The method of the invention also allows for the retention of 88% of the total volatiles present in the fresh juice.

【table】

【table】

【table】

[Table] Hydrogen sulfide analysis A Perkin-Elmer Sigma 1 gas chromatograph with a flame photometer detector was used. An all-Teflon system was required because glass and metal columns tend to absorb hydrogen sulfide and other similar compounds. A Teflon column 24 feet (approximately 72 m) long and 1/8 inch (approximately 0.3 cm) in outer diameter was used. A 40/60 mesh Chromosorb support containing 12% polyphenyl ether phosphate was used. The carrier gas used in the analysis was air and the flow rate was 34 ml/min. A 10 ml sample was extracted from the 50 ml head space above the youth sample.
Calibration was performed using appropriate standards. Identification of ethyl butyrate Hexanal and ethyl butyrate have similar boiling points. Hexanal and ethyl butyrate are eluted from the column at approximately the same residence time. The presence of ethyl butyrate in the composition was therefore determined by the test method described below. Three parts of water were used per 10 ml of orange youth concentrate (44.8% solids diluted with water). The pH was adjusted to 8 using 1N sodium hydroxide. Three drops of esterase solution (Sigma E-3128 Lot 68C-8135, 8 mg protein/ml, 120 units/mg protein) were added to the alkaline orange juice. This solution was incubated in a sample container at 24°C for 30 minutes. Using gas chromatography analysis method 2 (FF-96-Perkin-
capillary column coated with Elmer GC),
The volatile compounds present were determined. After treatment with this esterase solution, the peak in the chromatogram that was experimentally identified as ethyl butyrate was absent. This peak had a residence time of approximately 30.5 minutes. The disappearance of ethyl butyrate after esterase treatment was also confirmed using a combination of gas chromatography and mass spectrometry. EXAMPLE Pineapple oranges with an average diameter of 3 inches (approximately 8 cm) were cleaned with a solution containing 100 ppm hypochlorous acid. The oranges were then rinsed with fresh tap water and placed in a juice extractor. An automatic mechanical extractor model No. 400 was used to cut the orange in half and then squeeze each half. The gap setting between the reamer and presser foot tip was 3/16 inch (approximately 0.5 cm). The core and seeds were separated from the youth using a finishing machine with a 0.238 cm screen. The youth contained 12.6% solids (non-aqueous compounds) and 0.031% skin oil. The Youth uses a bowl-shaped centrifuge (Westfalia model #SB-7-) operated at a speed of 900 rpm.
06-576). Nitrogen was passed through the bowl during the separation. The separated fruit juice was heated to 0°C.
and injected into a refrigerated feed tank with a 90 micron filter at the outlet. The tank was shielded from light. A continuous blanket of nitrogen gas was maintained within the supply tank. The size of the pulp ranged from 0.1 mm to 5 mm.
The pulp was stored at 0°C and protected from light. Grenco Freeze Concentration Unit Model
W8 was supplied with raw materials from the above refrigerated storage tank.
The Grenco system is a closed system. The recirculation pump, which circulates the refrigeration unit and the youth from the recrystallizer through the shaved wall heat exchanger, was started to cool the youth to -2°C. Cooling of youth to -2℃ and formation of recrystallized ice are
This was achieved after 2.5 hours, at which point ice removal via the wash column was started. After the ice was removed from the unit, the youth concentration began to increase steadily, reaching 50% concentration after 46 hours. An equal amount of fresh juice was pumped into the freeze concentrator with each ice removal step. After 50% concentration was achieved, the recrystallizer temperature was reduced to approximately -10.2°C. At this point, extraction of the concentrated orange juice was started. The concentrated orange juice was stored at −10°C until mixed with the pulp at the end of the experiment. The duration of this particular experiment was 201 hours. After reaching 50% concentration, approximately 6 ice cubes were removed every hour. Total amount
295.7 of 50% concentrated orange juice was produced. Approximately 1200 orange juice juice was required to produce this concentrate. The concentrated juice is then mixed with a 10% concentration of fruit pulp (V/
V) was blended. After blending the pulp with concentrated juice, the mixture was then filled into 6 ounce zippered cans and stored at -20°C until testing. The final product concentration was 46.8% solids. Gas chromatography showed a residual rate of volatile compounds of 93.0%. The residual rate of ethyl butyrate was 89.7% and was present at 0.34% of volatile compounds. Ethyl butyrate to limonene was 0.009:1. The ratio of low to high boiling compounds was 10:1. Hydrogen sulfide concentration in the concentrate was less than 20 ppb. A combination comparison test was conducted by a randomly selected panel of taste testers of orange juice concentrates prepared by the above method. Compared to the starting juice, orange juice concentrate was preferred by 62% of the panel testers. The example orange juice concentrate was preferred by 72% of the panelists when compared to an evaporative concentrate sample of the same starting juice. The evaporation sample contained primary condensate (essence) as well as 30% fresh juice (cut-back juice). The addition of these substances was made in an effort to develop the best evaporative concentration techniques. A Crepaco sterilizer was used to sterilize the concentrated fruit juice made in the example. The sterilizer is a closed string consisting of three swept surface heat exchangers. The first heat exchanger uses 30 psi steam at about 129°C to heat the juice to 88°C in 7 seconds while it is in ^the heat exchanger. The heated juice subsequently passes through a swept surface heat exchanger at approximately 4°C, rapidly cooling the concentrated juice. Bacterial analysis shows a bacterial plate count of less than 300 and a mold count of less than 100. Pectin esterase activity is
1.0(PE) _u ×10 has decreased to less than ⁴ . The skin oil content is approximately 0.025%. 90% of the volatile compounds that were present in the starting juice remain, including approximately 90% ethyl butyrate. Example Sublimation Concentration Contains approximately 10% pulp made in Example and approximately 35%
Solid concentration of orange juice concentrate 1.9 -7
Cooled to ℃. The juice was cooled in a sealed plastic bag placed in a dish measuring approximately 51 x 37 x 2 cm. The thickness of the youth layer was approximately 1 cm. The dish was attached to a vibrator. The dish was shaken for 2 hours at approximately -7°C to continuously mix the ice crystals to achieve recrystallization and growth of large ice crystals. After the shaking period, the temperature was increased to −60°C for approximately 2 hours.
It was lowered to ℃. During this cooling period, the mushy mixture of ice and concentrate solidified into a hard frozen mass. The frozen compound is then ^{vacuconductus®}
It was ground in a Buss-Condux ^R mill and separated using a Sweco continuous sieve unit. 800～
Particles in the 1500 micron range were selected. These particles were then concentrated by sublimation. The particles were placed in a standard freeze dryer with an ice condensation capacity of approximately 10. Rigid temperature and vacuum methods were used to prevent particle melting. For the first 30-45 minutes, the particles were kept at -30°C under a 20 micron vacuum. The temperature was then adjusted to -10°C and maintained at that temperature for 30 minutes under a 20 micron vacuum. The temperature was then adjusted to 10°C and then 30°C.
It was maintained for a minute. The third time the temperature increased to about 30°C. After a total sublimation time of 2.5 hours, the orange juice concentrate was removed from the dish while still frozen.
I put this in a jar and covered it with a cap. Gas chromatographic analysis of the sublimated concentrated sample after dilution to a 12.6% solids concentration showed 96.3% of the volatile compounds present in the original juice.
remained. The final solids concentration of orange juice was 60%. The volatile compound ethyl butyrate concentration was 0.37%. The ethyl butyrate to limonene ratio was 0.005:1. Example 35% containing approximately 10% pulp, made in Example
The orange juice concentrate is quickly frozen at -40°C. Approximately 500ml of concentrate in a 51 x 37 x 2 cm
frozen in a dish. Sublimation concentration was carried out using the same apparatus as in the example. The sublimation process was carried out under isothermal conditions at -30°C in a 20 micron vacuum for 16.5 hours. The plates of frozen orange youth concentrate did not melt during sublimation concentration. The final concentration was 67% solids content. The concentrated product was diluted in a ratio of 5 parts water to 1 part concentrate. A taste expert could not distinguish this from the starting concentrate. The residual rate of volatile compounds was 96%. EXAMPLE The concentration of the example was repeated using an isothermal drying temperature of -25°C for 17 hours to obtain a final concentrate with a solids concentration of 81%. The residual rate of volatile compounds, including ethyl butyrate, was 94% of those present in the starting orange juice. EXAMPLE Grapefruit with an average diameter of 4-1/2 inches (approximately 12 cm) were washed with a solution containing 100 ppm hypochlorous acid. The grapefruit was then rinsed with fresh tap water and placed in a juice extractor. An automatic mechanical extractor model No. 700 was used to cut the grapefruit in half and then squeeze each half.
The gap setting between the reamer and presser foot tip was 3/16 inch (approximately 0.5 cm). The core and seeds were separated from the youth using a finishing machine with a 0.05 cm screen. The youth contained 9.6% solids (non-aqueous compounds) and 0.003% skin oil. The juices were then placed in 5 gallon plastic buckets and frozen at 0°C for one week. The container is then transported to the processing area and the grapefruit juice temperature is reduced to 60〓 (approximately 16
Thaw carefully to keep it at a lower temperature (°C). At this point, the grapefruit juice contained 9.4% solids (non-aqueous compounds) and 0.003% peel oil. Juice was sterilized using a Crepaco sterilizer. The sterilizer is a closed system consisting of three swept surface heat exchangers. The first heat exchanger is 30 psi (approx.
2.1 Kg/cm ² ) of steam at about 120°C is used to heat the juice to about 88°C in 7 seconds. The heated juice then passes through a swept surface heat exchanger at approximately 4°C.
Cool the juice quickly. Bacterial analysis of the youth showed a total bacterial plate count of less than 250. The skin oil content was approximately 0.003%. The pulp was first separated from the juice by passing through a 30 mesh screen vibratory separator. Pulp removal and natural clarification is then carried out using a bowl-shaped centrifuge (Westfalia model) operated at a speed of 9500 rpm.
No. SB-7-06-576). During the separation, the centrifuge bowl was covered with a blanket of nitrogen. The separated juice was pumped to a refrigerated feed tank kept at 0°C and equipped with a 90 micron filter at the outlet. The tank was shielded from light. A continuous blanket of nitrogen gas was maintained within the supply tank. The tank was stirred periodically. The size of the pulp ranged from 0.1 mm to 5 mm.
The pulp was stored at -40°C and protected from light. Grenco Freeze Concentration Unit Model
W8 was supplied with raw materials from the above refrigerated storage tank.
The Grenco system is a closed system. The refrigeration unit and the recirculation pump, which circulates the juice from the recrystallizer through the shaved wall heat exchanger, were started to cool the juice to -2°C. Cooling of the juice to −2° C. and formation of recrystallized ice was achieved after 5.1 hours, at which point ice removal via the wash column was started. After removal of ice from the unit, the youth concentration begins to steadily increase;
After 31 hours, the concentration reached 49.5%. As ice was removed from the concentrator unit, an equal amount of fresh juice was pumped into the freeze concentrator. 49.5
After the % concentration was achieved, the temperature of the recrystallizer was lowered to approximately -9.5°C. At this point, the concentrated juice was removed. The concentrated fruit juice was stored at −40°C until mixed with the pulp at the end of the experiment. The duration of this particular experiment is 38
It was time. After reaching 49% concentration, approximately 12.0
Kg of ice was removed every hour. 48.7% of total amount 33.2
Concentrated grapefruit juice was produced. Approximately 800 g of grapefruit juice was required to produce this concentrate. The concentrated fruit juice is then pre-contained with approximately 10% concentrated fruit pulp (V/
V) was blended. After blending the pulp with concentrated juice, the mixture was then filled into 6 ounce zippered cans and stored at -20°C until testing. The final product concentration was 43.6% solids. A combination comparison test was conducted by a randomly selected panel of taste testers of the concentrates prepared by the above method. Re-diluted concentrates are better than commercially available juices processed by conventional methods.
Preferred by 59% to 90% of panel examiners. Others, tanjiyarin (ponkan), lemon,
Similar results were obtained when lime, kumquat and blends of these juices were concentrated by the example method.

[Brief explanation of drawings]

FIG. 1 is a flow diagram of the method used to produce orange juice concentrate. Here, the oranges are put into a juice extractor, the peel is removed, the oranges are passed through a finishing machine that removes the core and seeds, the oranges are separated into pulp and juice parts, and the juice is sent to a freeze concentrator or sublimation concentration. The water is separated from the fruit juice as pure ice in the freeze concentrator and as pure water vapor in sublimation concentration, and the concentrated fruit juice and pulp are then blended. Forms a natural orange juice concentrate. Figures 2-6 are comparative gas chromatograms of orange youth and orange youth concentrates.

[Claims]

1 Equipped with a magnetic field generator and a closed-type hollow magnetic body, a first communication port is located at the bottom of the hollow magnetic body, a second communication port is located above the first communication port, and a rod-shaped A magnetic body is inserted, a space is formed around the outer periphery of the rod-shaped magnetic body, and a hollow non-magnetic body that is porous is provided inside the hollow magnetic body, and one of the hollow non-magnetic bodies is inserted into the hollow magnetic body. The aquatic bacteria and the aquatic bacteria are connected to the magnetic field generating device so as to make the two magnetic bodies bipolar, and the aquatic bacteria have the function of traveling along the lines of magnetic force from the second circulation port. A solution containing a settleable solid substance other than bacteria is supplied to the hollow magnetic body, and the settleable solid substance that settles by gravity within the hollow magnetic body is collected from the first flow port, and the aquatic solid substance that gathers on the rod-shaped magnetic body side is collected. A method for separating and recovering aquatic bacteria, which comprises taking out the bacteria together with a solution through the third flow port. 2. Claim 1, characterized in that the rod-shaped magnetic body is located on the center of the hollow magnetic body.
Method for separating and recovering aquatic bacteria as described in Section 1. 3 Covering the rod-shaped magnetic material with a non-magnetic material

Claims (1)

2. The concentration zone is a freeze concentration zone, and the concentrated fruit juice in step (3) in the zone contains 20 to 52% by weight of non-aqueous compounds and 48 to 80% by weight of water, according to claim 1 the method of. 3. The method according to claim 1 or 2, wherein the concentrated fruit juice in step (3) and the granular solids separated in step (2) are remixed. 4 The fruit juice in step (1), the concentrated fruit juice in step (3), the granular solids separated in step (2), or the remixed concentrated fruit juice and granular solids in a closed thread. 4. The method of claim 3, wherein microorganisms and enzymes are substantially inactivated by sterilization by heating to a temperature of 80 DEG C. to 95 DEG C. for 3 to 15 seconds. 5. The method according to claims 1 to 4, wherein the separation step (2) is carried out by centrifugation using a high-speed centrifuge, and the youth introduced into the separation step (2) is preferably at a temperature of less than 30°C. The method described in any one of the above. 6. The method of claim 1, wherein the initial temperature of the sublimation concentration zone is lower than the eutectic temperature of the fruit juice, in which the concentrated fruit juice contains from 35 to 87% by weight of non-aqueous compounds. 7 Passing the fruit juice portion through a freeze concentration zone to form a concentrated fruit juice containing 25-35% by weight of non-aqueous compounds, and then passing the concentrated fruit juice through a sublimation concentration zone whose initial temperature is lower than the eutectic temperature of the concentrated fruit juice. 2. A method according to claim 1 for producing concentrated fruit juice containing 40 to 87% by weight of non-aqueous compounds. 8. The method according to claim 6 or 7, wherein the concentrated fruit juice in step (3) and the granular solids separated in step (2) are remixed. 9. Heat the fruit juice in step (1) or concentrated fruit juice in step (3) at 80℃ to 95℃ in a closed system.
9. A method according to any one of claims 6 to 8, characterized in that it is sterilized at a temperature of 3 to 15 seconds. 10 In a method for producing a natural citrus fruit juice concentrate other than an orange fruit juice concentrate, (1) fruit juice is extracted from a fruit (the juice contains 7 to 20% by weight of granular solids, 7 to 20% by weight);
% by weight of soluble suspended non-aqueous compounds and having a pericarp oil content of less than 0.05% by weight, the balance being water); (2) the juice is subjected to sublimation concentration in which substantially pure water vapor is recovered; (the sublimation concentration is carried out in a closed system under an inert atmosphere,
(3) removing from the concentration zone 20-87% by weight of total non-aqueous compounds and 13-80% by weight water; A method characterized in that: recovering a concentrated product containing: