CZ20003129A3 - Process for preparing fractionated pectin products - Google Patents

Abstract

A method for producing fractionated pectins from a starting point plant material that includes a two-step extraction plant material. This material is at first instance treated with a weakly acidic solution at a temperature and for a period of time sufficient to separate the non-sensitive pectin fraction calcium (NCSP). Next, the extracted juice is separated from of plant material and separated plant material treated with a solution of stronger acid at temperature and for a period of time sufficient to separate the calcium sensitive pectin fraction (CSP).

Description

Technical field

The present invention relates to a process for extracting fractionated pectin mixtures directly from the plant material in which the pectin is bound.

BACKGROUND OF THE INVENTION

There are many ways to extract pectin and there are many ways to use the products of these extractions. A typical extraction method comprises the following steps:

(1) extracting with water from the starting plant material, (2) purifying the liquid extract, and (3) separating the extracted pectin from the liquid.

In acid extraction processes, the plant material is typically treated with dilute acids such as nitric, sulfuric, hydrochloric, or other inorganic or organic acids at slightly elevated temperatures (70-90 ° C prescribed) to achieve separation of pectin from the cellulosic components of the plant starting material. raw materials. Commonly used starting vegetable raw materials are the citrus fruit peel left in the juice production and the apple residue in the juice and must production. The extraction conditions are selected such that the bulk of the pectin molecules contained in the starting plant material are transferred from the cell walls of the material to the extraction medium.

After the first step, ie acid extraction, the mixture of solid particles from the plant material and the pectin-containing liquid remain. This mixture is then separated by filtration, centrifugation, or other conventional separation techniques apparent to those skilled in the art. The wet cake of solid particles can be re-extracted or neutralized and sold as cattle feed. The reextraction can be carried out in single-stage, multi-stage or continuous countercurrent extractors customary for this process.

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• ·· ♦ · «· area. Pectin is precipitated from the extracted juice by addition of a suitable alcohol. Pectin is insoluble in the resulting alcohol / water mixture. The undissolved pectin is separated from this mixture by suitable means such as filtration, centrifugation and the like. The resulting pectin cake is dried and milled to the desired particle size.

The industrially produced pectins consist mainly of polygalacturonic acid chains in which rhamnose may be present. Neutral sugars may be attached to the rhamnose units. In order to qualify as pectins, anhydrous galacturonic acid must account for at least 65% of the ashless dry matter of their industrial species. The galacturonic acid units of vpectin are naturally partially esterified with methyl alcohol. By convention, pectins with more than 50% methyl esterified carboxyl groups are referred to as highly methoxylated pectins, whereas pectins with less than 50% methyl esterified carboxyl groups are referred to as low methoxylated pectins.

The industrially produced extract is composed of those molecules which are soluble under the conditions of pH, temperature and time used in the extraction. It consists of a mixture of molecules that differ in molecular weight, molecular weight distribution and degree of esterification. In most cases, the extract is composed of highly methoxylated pectins. The production of low methoxylated pectins requires additional processing of the extract to de-esterify the molecules.

The properties of highly methoxylated pectins are highly dependent on the specific molecular configuration of the isolated pectins. The resulting composition can only be controlled to a certain degree by the manufacturer by selecting the raw materials and extraction conditions. For these reasons, there are differences in pectin properties from extraction to extraction and from manufacturer to manufacturer, and normalization of properties is generally necessary. This can be achieved by mixing the various extracts and dissolving them in suitable solvents such as sugar, dextrose, fructose, etc., but the regulation of the specific properties of pectins is thereby limited.

For those skilled in the art, highly methoxylated pectin is not a well-defined molecule, but is in fact a complex mixture of different types of pectin molecules. Individual types of highly methoxylated pectins can have very useful properties. One of the major functional differences between highly methoxylated pectins is their sensitivity to the presence of varying concentrations of polyvalent cations such as calcium ions. Sensitivity to the presence of calcium ions is defined here as the sensitivity to ·· ··

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99 Calcium. It is known to those skilled in the art that calcium sensitivity is also a strong indication of sensitivity to other polyvalent cations. The industrially extracted highly methoxylated pectins contain a mixture of both calcium sensitive and non-calcium sensitive pectins.

U.S. Patent No. 5,567,462 discloses a process for preparing a pectocellulose mixture from a pectin-containing vegetable feedstock by treating the ground citrus peel in an acidified aqueous solution to dissolve the pectin. The pectin is then regenerated in the cellulose matrix of citrus peels by adjusting the pH of the solution and dried. The resulting pectocellulose product is added to foods and other products.

PCT International Application WO 97/03574 discloses a method wherein the highly esterified pectin starting material is treated in an acidic environment in the presence of at least one protein and a recombinant enzyme.

None of the foregoing techniques disclose the present invention. There is still a need for a simpler, more economical, safer and more efficient method of producing calcium-sensitive pectins (CSP) and calcium-insensitive pectins (NCSP).

SUMMARY OF THE INVENTION

The present invention relates to a two-step process for extracting different pectin fractions directly from the starting plant material, particularly citrus peels.

The extraction according to the invention is carried out in a sequential two-step process using different pH conditions in each of the extraction stages. In the first step, mild pH conditions are used to extract the pectin fraction with a low level of calcium sensitivity. This first fraction is known as calcium-insensitive pectin (NCSP). In the second extraction step, a more acidic medium is used to extract the pectin fraction with a higher degree of calcium sensitivity. This second fraction is known as calcium sensitive pectin or CSP.

More specifically, the present invention is directed to a treatment of the starting material that provides sufficient conditions to obtain an aqueous phase rich in NCSP. The invention also encompasses aqueous solutions containing calcium-insensitive pectins having a pH greater than 2.5 and containing less than 2% by weight of alcohol.

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Further, the present invention describes a process comprising (1) treating the starting material, wherein the conditions are set such that a modified pectin rich in CSP is formed, and (2) wherein the aqueous phase is rich in CSP. The aqueous phase also provides calcium sensitive pectin at a pH of less than 2.5, with an alcohol content of less than 2% by weight. The present invention also encompasses the composition of the starting material - including husks in which the ratio of CSP to CSP + NCSP is enriched.

The process of the present invention does not require the use of isopropyl alcohol (IPA) during the separation of the pectin fractions, and employs an apparatus commonly used in pectin extraction. It has further been found that the addition of a small amount of soluble calcium salt is advantageous in the extraction of NCSP, especially when the acidic conditions are more aggressive than normal. The present invention is simpler, relatively easy to apply, more efficient and cheaper than other methods used to separate CSP and NCSP pectin fractions.

Overview of the drawings

Giant. 1 shows a flow diagram of a method according to the invention.

Giant. 2 shows a diagram of an embodiment of the invention using a single extractor.

Giant. 3 shows a multi-stage, multi-chamber, countercurrent implementation of the present invention.

Surprisingly, it was found that CSP can be separated from NCSP from the same plant starting material using a simple method based only on a different pH. In other words, using different pH ranges, CSP and NCSP can be extracted directly from the plant starting material in situ, eliminating the need for the first co-separation of both fractions together and subsequent separation with isopropyl alcohol and filtering equipment. The fraction extraction process of the invention uses two solvents in sequence to extract the pectin fractions from the starting material. The first solvent contains a relatively weakly acidic solution, which may optionally contain small amounts of cationic salts for the extraction of NCSP, while keeping the CSP in solution. The second solvent is a relatively strongly acidic solution which subsequently extracts the remaining CSP. Once • 0 • 44 4444 •

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It has been found that weakly and strongly acidic solvents are in the pH range of greater than 2.5 for weak and less than 2.5 for strong.

The present invention describes a process for extracting two types of pectin differing in calcium sensitivity (calcium sensitivity) in solution from the same plant starting material. The invention described herein consists of a two-stage extraction process that uses a different pH in each of the steps. Pectins are usually extracted on an industrial scale only in a one-stage process. In the two-step process of the present invention, the first stage is carried out under mildly acidic conditions at pH greater than 2.5 and the second stage under strong acidic conditions at a pH lower than 2.5. Any inorganic acid may be used. Nitric acid is preferred. Organic acids can also be used as long as they are able to meet the requirements of the present invention. The low pH required in the second extraction step of the present invention disqualifies most organic acids for use in this step.

The first step extracts calcium-insensitive pectins (NCSP), which exhibit calcium sensitivity from 0 to 20 cps in a 0.5 weight percent solution at 25 ° C. More preferably, the NCSP has a calcium sensitivity of from 0 to 10 cps. The second stage extracts calcium-sensitive pectins or CSPs that exhibit calcium sensitivity greater than 20 cps in a 0.5 weight percent solution at 25 ° C. Particularly advantageous results were obtained in the "calcium sensitivity" tests measured between 100 and 1000 cps. . As used herein, the term " calcium sensitivity " is intended to mean that the properties of the pectin product are related to increasing the viscosity of the pectin product solution under the appropriate conditions, using the procedures described below as 'Analytical Procedures'. Since calcium sensitivity is a strong indicator of susceptibility to other polyvalent cations, this invention also includes susceptibility to these other cations, such as magnesium, copper, iron, zinc, aluminum, manganese, and barium.

Another important feature of CSP and NCSP is the degree of esterification. The term "degree of esterification" (DE) as used herein means the degree to which the carboxyl groups contained in the galacturonic acid chain are esterified (eg, by methylation) or otherwise rendered non-acidic (eg, by amidation). The degree of esterification of the pectin fractions produced by the process of the present invention varies from about 60 to about 60 to about ekt asi asi φφφφφφφektektekt.

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%. The NCSP fraction generally has a higher degree of esterification than CSP. For example, NCSP has an esterification degree of 70 to 80%, while CSP has an esterification degree of 60 to 70%.

According to the present invention, it has been found that the calcium content of the NCSP and CSP fractions is important for their use to stabilize milk acidity. The most preferred level of calcium in CSP pectins is less than 1500 ppm by weight. A calcium content of less than 750 ppm is preferred and less than 500 ppm is most preferred. This is achieved by means conventional in the art, for example by ion exchange. If conversion of NCSP to lower DE pectins is required, the calcium content is also less than 1500 ppm, more preferably less than 750 ppm, and most preferably less than 500 ppm.

As mentioned above, the methods of the invention include treating the plant starting material containing extractable pectin. These are typically citrus peels such as lemon, orange, grapefruit, lime, but may also be other fruits, such as apples or vegetables, such as sugar beet or sunflower seeds.

FIRST STAGE OF EXTRACTION

In the first stage, the husks, water and acid are weighed into the reactor. The acid in the first stage is fed to the reactor to adjust the pH to 2.5 to 4.0. The pH of the reaction medium affects both the ratio at which pectin can be extracted and the amount thereof. It is apparent from the present invention that pH also affects the type or fraction of the extracted pectin. Although pectin can be extracted from plant material under any pH condition of 0 to 7, NCSP can only be extracted in a pH range of 2.5 to 4.0 at temperatures of 70 to 90 ° C. Below pH 3.3, NCSP yields decrease, and at pH 2.7 or lower, it begins to extract in the first stage of CSP. Hence, it is preferable to select a lower pH limit of 2.7, and more preferably 2.8. The upper pH limit is 3.0 and preferably 3.3.

The lower limit of the extraction time in the first stage is at least 0.5 hours, more preferably 0.75 hours and most preferably 1.0 hour. The upper limit of the extraction time is 5.0 hours, preferably 4.0 hours, and more preferably 3.0 hours.

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If a less aggressive pH, for example 3.0 or higher, is used in the first step, it is not necessary to add calcium to prevent CSP extraction. However, the most preferred pH range without the addition of calcium ions is 3.0 to 3.3.

In cases where the first extraction step is carried out under more aggressive acidity conditions of pH 2.5 to 3.0 or at higher elevated temperatures than normal, for example at 75 to 90 ° C, it is preferable to add small amounts to the acid mixture used for extraction. the amount preferably calcium salt. Addition of calcium under these conditions was found to suppress the development of CSP at this stage. The concentration of divalent cations in the first extraction step can only vary within a relatively narrow range, e.g., from 1 to 50 mmol (mM) of the calcium ion concentration in the acid solution. A preferred lower limit of this range is 3 mmol and most preferably 5 mmol. The upper limit of this range is 33 mmol, more preferably 25 mmol, and most preferably 20 mmol. This added calcium is in addition to the calcium contained in the plant starting material, which content may typically be about 1% by weight of the dry starting material. The optimum amount of calcium or other divalent cations depends on pH and temperature and is a matter of simple optimization at defined parameters. For example, the pH of the first extraction step may be up to 2.5. In this case, it has been found that the concentration of calcium cations in the acid added to the plant material is about 20 mmol. When calcium ions are added, a pH range of 2.7 to 3.0 is most preferred.

The calcium salts that may be used in the first extraction step under aggressive acidity conditions may include hydroxide, chloride and calcium oxide. More preferred are calcium nitrate, acetate, propionate, gluconate and lactate. The most preferred calcium salt is calcium carbonate. Lime can be used as a source of calcium carbonate.

Examples of other calcium salts that may be used in the practice of the present invention are provided that they are reasonably soluble during extraction, calcium phosphate, calcium citrate, calcium oxalate, calcium dihydrogen phosphate, calcium formate, calcium glutamate, calcium glycerophosphate, calcium glycinate, hydrogen phosphate Calcium, calcium iodide, calcium lactophosphate, calcium-magnesium carbonate, calcium-magnesium inosithexaphosphate, trivalent calcium phosphate, ortho-calcium phosphate, calcium pyrophosphate, calcium succinate, calcium sucrose ions, calcium sulfite and calcium pyrophosphate.

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Salts of other polyvalent cations such as iron, barium, magnesium, copper and especially aluminum may also be used.

Temperature is also an important variable for the first extraction stage. The pectin must be extracted at temperatures between 70 and 90 ° C to be designated as pectin. Extractions can take place at lower temperatures, e.g. 50-70 ° C, but the products cannot be called pectins. It is most preferred and most economical to extract pectin at 70 ° C. Extraction at a higher temperature may accelerate the release of pectin from the plant material and thus shorten the process time. However, at elevated temperature, extraction may occur in the first stage of undesirable CSP and this must be avoided in this operation. Extraction at elevated temperatures also has a deleterious effect on the molecular weight of pectin. The most preferred temperature range for the first extraction step is 70-75 ° C.

Following the first extraction step, the juice containing NCSP is separated from the hulls which still contain CSP. This separation is accomplished by vacuum filtration or other means well known in the art. The separated liquid mixture is a pectin solution having a pH above 2.5 and containing less than 2% alcohol by weight. It is to be understood that although alcohol is not used directly in this process, minor amounts in the system may be, either as an impurity or formed during extraction; thus less than 2% by weight covers these minor minor amounts of alcohol. The juice from the first extraction stage containing NCSP is processed under conditions conventionally and conventionally used for pectin isolation.

The remaining skins are enriched with CSP and can be used where a fiber source and CSP are needed. However, these CSP hulls are usually transferred to second stage reaction vessels for further processing.

SECOND STAGE OF EXTRACTION

Following the first stage of extraction and separation, the husks are filled into the second stage reactor and additional water and acid are added for the second stage of extraction.

The second extraction stage takes place in a more acidic environment. The biggest difference is that the NCSP is already removed from the skins and the pectin extracted in the second stage is relatively pure CSP. Sufficient acid is added for the second extraction stage to adjust the acid to 9%. PH values between 1.5 and 2.2. The preferred lower pH limit is 1.6, and more preferably 1.7. The preferred upper pH limit is 2.1, most preferably 2.0.

Different temperatures in the range of 70-90 ° C can be used for the second extraction stage, but the preferred range for this second stage is 70-75 ° C without the addition of calcium. The addition of calcium at this stage to extract the CSP could be counterproductive because calcium can cause the CSP to gel or bind in the skins. Extractions could be carried out at lower temperatures, for example 50-70 ° C, but the products cannot be referred to as pectins. The duration of the extraction in the second stage is limited from below 0.5 hours, more preferably 0.75 hours, and most preferably 1.0 hours. The upper limit of the extraction time is 5.0 hours, more preferably 4.0 hours, most preferably 3.0 hours.

Upon completion of the second extraction step, the husks and the liquid are separated by filtration or other conventional methods. The CSP fraction is then precipitated from the aqueous solution by the addition of isopropyl alcohol (IPA). The CSP is then dried, milled and standardized for sale. The NCSP fraction can be processed in the same manner as is conventional in the art or can be used as an aqueous solution for other processes, for example, amidation or total de-esterification to produce low methoxylated pectins. Solid phase pectin fractions and preparation for sale are carried out by conventional techniques. Drying is accomplished by conventional techniques, for example by oven drying at atmospheric or reduced pressure to a moisture content of preferably less than 10%. The drying temperature should be kept below the temperature at which the pectin begins to lose its properties, such as color, molecular weight, etc. Grinding techniques are well known and any known technique can be used to grind pectins to the desired particle size. Most preferably, the end product is in a dry, powdered form with a moisture content of 10% or less. By dry, powdered form it is meant that the product will be free-flowing without substantial clumping. This is advantageous for ease of use.

Any conventional device may be used in accordance with the present invention. Although the process of the present invention is a two-step process, each of the steps may be multiple; that is, the two steps of the present invention relate only to two clearly different pH ranges required to extract different pectin fractions.

The device may be a fixed bed moving between the stages or a fixed reactor that is stirred to provide a tight internal contact or a fixed bed that is 4 4 4 4 · 4 · 4 4 4 leached with solvent. The only requirement is that the stages are designed so that the internal contact is formed for a time sufficient to effect separation. Therefore, a multiphase process can be used because the more phases, the better the contact and hence the separation. Processes in accordance with the invention may be either continuous or batch, with continuous being more preferred.

Figure 1 shows the most general block diagram of the invention to illustrate the simplicity of the invention. Figure 1 shows how water, acid and optionally calcium salt are added to vessel 1 in which they are reacted at 70 ° C for at least one hour to extract NCSP from citrus fruit peels that have been finely chopped for this process. During extraction, the NCSP solution, along with other products normally present in citrus peels, is removed and fed to ion exchanger 2, which reduces the cation concentration to below 1500 ppm. The NCSP solution is then fed to the evaporator 3 where the NCSP is free of excess water; in this evaporator, distillation can be carried out at normal temperature either under vacuum or at atmospheric pressure. The NCSP is then precipitated in the vessel 4 and the precipitate is sent to a dryer 5 and a crushing device 6 where the NCSP is dried and conditioned to the desired size and for commercial use.

After the NCSP is removed from the starting material (which can be ascertained by sampling), the CSP-enriched citrus skin is directed to step two 7 to extract the CSP. The extracted solution containing CSP is then fed to ion exchanger 8, which reduces the cation concentration to below 1500 ppm. The CSP solution is then fed to the evaporator 9 where the CSP is free of excess water; in this evaporator, distillation can be carried out at normal temperature either under vacuum or at atmospheric pressure. The CSP is then precipitated in the vessel 10 and the precipitate is sent to a dryer 11 and a crusher 12 where the CSP is dried and conditioned to the desired size and for commercial use.

The used citrus peels remaining after the second stage are removed and used in a conventional manner; they are usually sold to farmers as animal feed (cattle and pigs).

Figure 2 describes a more detailed representation of the present invention using a single sheathed 15 cylindrical container (extractor) 10 with a removable lid and a porous backing 11 which carries a layer of hulls 12 and a distributor 13 for distributing leaching extraction liquid; both extraction phases take place in the extractor 10. The extraction solvent is pumped through a pump 17 via line 14 from the first container 20 to the extractor 10

and back into the container for the time required to achieve the first extraction. The liquid flows through »50.

The recirculation cycle is carried out until it is indicated that the entire fraction has been extracted. Upon completion of the extraction, the layer may be drained through line 6. During the first extraction, valves V1 and V4 are opened and valves V2, V3, V5, V6 and V7 are closed; during the second extraction, valves V2 and V3 are opened and all others are closed. In this way, the plant material layer can be gradually extracted. During the second extraction, the second reservoir 30 collects the CSP fraction.

At the beginning of the process, the extraction solvent is fed into the system from the reservoir 20 or 30 depending on the cycle. This is done to ensure that the extraction liquid will be at the correct temperature before entering the extractor so that the system will function more efficiently.

The temperature of the extractor 10 is controlled during both extractions by circulating the ethylene glycol / water mixture through the jacket 15 via the heater and the jacket recirculator 16. The flow of heating fluid is controlled by the jacket valves J1, J2, J3 and J4. The flow is parallel to the reservoirs and serial to the extractor. The temperature can be carefully monitored by sensors (not shown) located in all containers 10, 20, and 30. The pressure drop across the layer of plant material can be controlled by the liquid level above that layer. All containers are vented to atmosphere. During the first NCSP extraction cycle, valves J2 and J3 are opened and the valves J1 and J4 closed to circulate and recirculate the heating fluid. During the second CSP extraction cycle, valves J1 and J4 are opened and valves J2 and J3 are closed. The container and extractor for each of the cycles are maintained at a constant temperature during that cycle.

Countercurrent extractors allowing the hydrolysis of more pectin from the plant material are preferred for industrial production. A preferred embodiment of the present invention is a continuous countercurrent process typical of the art. For example, a horizontal extractor can be used in which the solid particles move on a conveyor or a rotary countercurrent extractor Rotaček In any case, the extraction battery must be adapted so that two different solvents can subsequently enter and the respective product can be drained off. These adjustments can be made inside one device or by using a second unit for a second extraction.

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Figure 3 shows a countercurrent flow extractor having two stages, a first stage 101 for extracting NCSP and a second stage 102 for extracting CSP. As discussed previously in different stages, different extraction fluids are used. Each stage is divided into chambers a, b, c, d, e, f, g, h, i, j; the number of chambers will depend on the design of the device by a person skilled in the art and the desired effect. This design allows the complete removal of all NCSPs from the first stage 101 and the CSP from the second stage 102. In this fixed bed leaching process, a filler can be used which increases the flow rate of the extractant through the bed 105 or 106 as it moves on the conveyor 103 or 104 The filler is inert to the extraction solution, supports the bed and forms pores for liquid penetration. The fillers used are preferably natural materials such as peanut shells, sunflower husks, wood pulp or mixtures of the foregoing. Non-corrosive packaging materials such as Rashig rings, wire spools, etc. may also be used.

In both stages, the fixed bed moves on the perforated belt conveyor 103 or 104 while the extractant 111 or 112 moves through the bed in the opposite direction. As shown in the figure, the reagent is separated together with the extracted material and is used as the extracting agent in the permeable cells at both stages. The extracted material together with the extracting agent are separated at each stage at the bottom of the chambers via a line 107 or 108. The extracting agent and the extracted material are fed countercurrently into a bed 105 or 106 through pumps 109 or 110 and introduced into a downstream process via sprinklers 113 or 114.

Although the present device consists in a fixed bed moving on a linear belt conveyor, it may also be in the form of a rotary multistage device such as a Rotacel leaching extractor or other systems well known in the art. The main significance of this system is that the bed remains fixed during the process at a given stage so that the extraction agent is allowed to be in close contact with the plant material with minimal breakage of the bed so that no or insignificant amount of solid particles are present in the extract.

In accordance with the present invention, the compounds described herein provide unique performance characteristics not yet achieved. Highly methoxylated CSP has the ability to absorb more water than the corresponding material with a lower degree of esterification because it has a more open structure. The resulting gel is therefore softer, more deformable, which is important for many applications in the food, cosmetics, etc. The gel is easily adapted to particles of the desired size and its improved deformability leads to better edibility and softness. While the products of this invention can be used as fat substitutes due to their fat-like organoleptic properties, they can also be added to foods that normally do not contain fat to impart these properties to them.

Conventional low-methoxylated industrial pectins with a degree of esterification of less than about 50% have more space for calcium crosslinking and hence a denser structure with less water absorption capacity. Pectins with a lower degree of esterification than about 50% form stronger calcium gels, resulting in less digestible products.

The present invention has advantages over the prior art. For example, compared to unseparated pectin products, the CSP compositions of the invention are far more effective in many applications, for example, they are up to twice as effective as stabilizing agents in acidified protein systems such as acidophilic milk drinks and yoghurt products. As a measure of pectin stabilizing ability, a YOG assay (described in the analytical section below) is performed. Unfractionated pectins typically have YOG values of from about 100 to 140. According to the present invention, the CSP fraction of pectin has a YOG value of greater than 150, preferably greater than 160, more preferably greater than 180 and most preferably greater than 200. The higher the YOG value, the greater the stabilizing the ability of pectin in the final product.

Further, for example, the NCSP compositions of the present invention provide improved efficacy in applications requiring cation-unresponsive pectins. The NCSPs of the present invention have the advantage that they do not form gels in the presence of calcium, readily dissolve in solutions below 10 ° C, and can dissolve in solutions containing calcium ions. These features are beneficial for many applications.

The products made according to the invention are particularly useful in the meat and poultry industry, fish processing, dairy products such as milk, ice cream, yogurt, cheese, pudding, flavored dairy drinks, bakery products such as bread, cakes, crackers, biscuits, cakes , donuts, pretzels and crisps, mayonnaise, soups, sauces, dressings, frozen sweets, fruit preparations, jams, jellies, drinks, water gels, confectionery jellies and low fat spreads.

The invention also has use in the manufacture of disposable diapers, dressings, tampons and toilet paper. Further, pectins produced according to the methods of the invention are applicable to sun creams, sunshade compositions, creams containing emollients such as isopropyl myristate, silicone oils, mineral oils, vegetable oils that increase skin lubricity and skin cooling liquids such as menthol, menthyl lactate, menthyl pyrrolidine carboxylate N-ethyl-p-menthane-3-carboxyamide and other menthol derivatives, all of which enhance the feeling of cold skin, perfumes, deodorants whose function is to reduce or eliminate the micro flora on the surface of the skin, especially those that cause bodily odor, antiperspirants whose function is to reduce or eliminate sweating on the skin surface; and anticholinergic agents whose function is to prevent sweating before reaching the skin surface.

ANALYTICAL PROCEDURES

Determination of calcium sensitivity (CS) in pectin samples

A pectin solution of the desired concentration is prepared in distilled water and the pH is adjusted to 1.5 with 1M HCl. The sample of pectin must be in acid form or in the form of a monovalent salt. The initial concentration of pectin is 0.60% by weight.

Doses of 145 g of this pectin solution are added to the viscosity measuring vessels.

Five (5) ml of a solution containing 250 mmol of calcium chloride is added to 145 g of the pectin solution so that the final calcium concentration is 8.3 mmol.

25 ml of acetate buffer containing 1 M acetate ions, pH 4.75, are added with sufficient magnetic stirring, resulting in a pH of 4.2. The final concentration of pectin is about 0.5% by weight.

The magnet is removed and the vessel is left at room temperature (25 ° C) until the next day when the viscosity is measured at 25 ° C with a Brookfield viscometer.

While this method is most suitable for pectin samples with a viscosity of not more than

100, viscosity measurements up to 200 can provide good reproducibility

Brookfield units. High viscosity pectin samples tend to gel and result in less reproducible results. However, this method gives good indications of the relative sensitivity of the samples to calcium.

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If the viscosity of identical pectin samples to which calcium chloride has not been added is measured - instead diluted with distilled water, the contribution of calcium ions to total viscosity can be calculated by subtracting the value of the calcium-free solution - CS - from the value of the calcium-containing solution - CS +. This value is called the CS value (the delta CS is indicated in the table). For pectins with very low calcium sensitivity (CS), it is typically less than 20 eps.

The results reported in the examples are the difference between the viscosity measured in solutions with and without added calcium. If the viscosity difference is less than 20 eps, then the sample is classified as calcium-insensitive pectin or NCSP. If the viscosity difference is greater than 20 eps, then the sample is classified as calcium-sensitive pectin or CSP. CSP viscosities are typically greater than 100 eps.

Determination of Galacturonic Acid and Esterification Degree

Weigh 5 g of the sample to the nearest 0,1 mg and place in a suitable beaker. Stir 10 minutes with a mixture of 5 ml of hydrochloric acid TS (TS must be defined) and 100 ml of 60% ethanol. Place in a glass filter tube (30-60 mL capacity) and wash with six portions of 15 mL of HCl-60% ethanol followed by 60% ethanol until the filtrate is free of chloride. Finally, it is washed with 20 ml of ethanol, dried in an oven at 105 ° C for 2.5 hours, cooled and weighed. Transfer exactly one-tenth of the net weight of the dry sample (representing 0,5 g of the original unwashed sample) to a 250 ml conical flask and moisten with 2 ml of ethanol TS. Add 100 ml of freshly boiled and cooled distilled water, stopper and occasionally stir by swirling until everything is dissolved. Add 5 ml of phenolphthalein TS, titrate with 0.1 N sodium hydroxide and record the result as the initial titer (Vj).

Exactly 20 ml of 0.5 N sodium hydroxide are added, stoppered, shaken vigorously and allowed to stand for 15 minutes. Add exactly 20 ml of 0,5 N hydrochloric acid TS and shake until the pink color disappears. After adding three drops of phenolphthalein TS, titrate with 0.1 N sodium hydroxide TS until a slight pink color persists even after vigorous shaking; this value is recorded as the saponification titer V2.

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Transfer the contents of the conical flask quantitatively to a 500-ml Kjeldahl stoppered flask and a water-cooled condenser whose outlet tube reaches below the surface of a mixture of 150 ml carbon dioxide-free water and 20,0 ml 0,1 N hydrochloric acid TS in the outlet flask. Add 20 ml of 1v-10 sodium hydroxide solution to the distillation flask, seal the joints and heat gently to avoid excessive foaming. Continue heating until 80-120 ml of distillate. Add a few drops of methyl red to the outlet flask and titrate the excess acid with 0.1 N sodium hydroxide TS and record the necessary volume in ml as S. Carry out a blank test with 20 ml of 0,1 N hydrochloric acid TS and record the volume required. in ml as B. It is important to note the amide titer (BS) as (V ₃ ).

Calculate the degree of esterification (as% of total carboxyl groups) according to the formula:

V ₂

100 XVi + V ₂ + V ₃ and mg mg of galacturonic acid are calculated according to the formula:

19.41 x (Vi + V ₂ + V ₃ ) mg of galacturonic acid obtained in this way correspond to a content of one tenth of the weight of the washed and dried sample. The% free base-free galacturonic acid galacturonic acid is obtained by multiplying the obtained mg by 1000 / x, where x is the weight in mg of the washed and dried sample.

Determination of stabilization performance -8,5% Milk solids not fat MSNF -stage YOG analysis

Principle · i · · i _{β β β} * * * *

Pectin solutions ο of various concentrations are mixed with yoghurt, homogenized and heat-treated at 70 ° C for 10 minutes. After cooling to 5 ° C, the viscosity and the amount of sediment are measured.

The efficacy of the unknown dose is compared to the standard dose.

Instrumentation

1. Scales (to 2 decimal places)

2. Scales (to 3 decimal places)

3. Incubator, Hetotherm type 102 A 923 or similar

4. Water bath, thermostatically controlled at 5 ° C

5. Water bath, thermostatically controlled at 75 ° C

6. Mixer, Silverson or similar type

7. Homogenizer, APV Rannie Lab. Homogenizer, model MINI-LAB, type 8.30 H or similar

8. Magnetic stirrer JK Ika-Combimag Reo or similar type

9. 1500, 600 and 400 ml flasks

10. Test tubes, 15 ml

11. Centrifuge, Hereaus Christ, GL type or similar

12. Brookfield viscometer LVT

13. Viscosity measuring vessels (internal diameter: 50 mm, internal length: 110 mm)

14. pH meter

15. Automatic dispenser Fill-Master type 311

Way

Preparation of yogurt. 17% fat-free milk solids (MSNF)

Reference to Control Method 708, Yoghurt Product - 17% MSNF. Determination of stabilization factor

1. Prepare an X% solution of pectin in deionized water using a Silverson mixer. Stir for 5 minutes. Heat at 70 ° C for 10 min to dissolve the pectin, cool and replenish the evaporated water. Calculation X:

100 degrees YOG X = -% estimated YOG

Examples:

If 100 degrees YOG is assumed, a 1% solution is prepared.

If 200 degrees YOG is assumed, a 0.5% solution is prepared.

The YOG-8,5-STD2 standard, which by definition is 100 degrees YOG, is examined in parallel to a dose of unknown pectin.

2. Weigh the pectin solution and water into a set of 600 ml flasks and mix for 30 seconds according to the table below.

• 0 «0

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0 0 0 0 0 0

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0000004 00 3 *

Pectin concentration, final product,% X% pectin solution, g Deionized water, G 17% MSNF yoghurt, G 0,000 0 200 200 0,100 xX 40 160 200 0,125 xX 50 150 200 0,150xX 60 140 200 0.175 xX 70 130 200 0.200 x X 80 120 200 0.250 x X 100 ALIGN! 100 ALIGN! 200 0.300 x X 120 80 200 0,350 xX 140 60 200

3. While stirring with a magnetic stirrer, add 200 g of yoghurt (17%).

MSNF) to the pectin solution, using an automatic dispenser. Stirring is continued until the solution is homogeneous. The resulting product will be 8.5% MSNF yogurt. Final weight: 400 g.

4. Homogenize at 15-18 MPa (150-180 bar).

5. Heat to above 70 ° C in a 75 ° C water bath for 10 minutes.

6. Determine the amount of sediment as follows:

(a) Record the weight of the centrifuge tube (2 for each pectin concentration) to 3 decimal places.

(b) Fill centrifuge tubes (2 for each pectin concentration) about 1 cm to the overflow from the upper edge.

(c) Weigh all centrifuge tubes, including the sample. The weight shall be recorded to 3 decimal places.

d) Centrifuge the samples at 4500 rpm for about 20 minutes (about 3000 g).

• φ ♦ • ·

e) Decant the sludge and invert the tubes upside down for 30 minutes to drain the remaining liquid.

(f) Wipe the tube with a Kleenex tissue and weigh the tube. The weight shall be recorded to 3 decimal places.

(g) Calculate the weight of the sediment as a percentage of the weight of the centrifuged sample as follows:

test tube weight including sediment - empty test tube weight

-χ 100 =% sediment weight of test tube including sample - weight of empty tube

f) Preferably the scales can be connected to a computer with a calculation program.

7. The viscosity shall be determined as follows:

(a) Viscosity measuring vessels shall be filled with samples of varying concentrations and aged for 18 to 24 hours at 5 ° C.

(b) Viscosity is measured with a Brookfield LVT viscometer at 60 rpm. Viscosity is read after 1 minute rotation.

Calculation

1. Plot the results of the standard dose and the dose of the unknown sample into a diagram in which the x-axis is the pectin concentration and the y-axis is the percentage of sediment. Two curves are drawn, one for the standard and the other for the unknown sample, by connecting adjacent points with straight lines.

2. The pectin concentration interval shall be defined as follows:

Lower limit: The lowest concentration of Standard pectin that corresponds to half the highest sediment yield is recorded as the standard.

Upper limit: The lowest Standard pectin concentration corresponding to 1.25 times the lowest sediment yield is recorded as the standard.

• «

Φ · · · • φ φ φ • φ φ φ φ φ

3. The positions of all plots for the unknown sample are shifted by multiplying the distance from the y-axis by constant k. The constant k is determined by trial and error until the two curves overlap as much as possible within the interval defined above.

4. The YOG level of the unknown sample is now 100 x k.

5. Determine the result as YOG - 8,5 C.

Examples

The general experimental procedure used for the examples is described below. Each example differs only by experimental conditions or plant material. In Example 1, different experimental conditions were used with one plant material. In Example 2, the same experimental conditions were used for different plant materials. The results of both examples are shown in Table 1.

All experiments were carried out using 12 liter jacketed reaction vessels. Hot liquid was circulated to maintain the temperature at 70 ° C. The temperature was measured by a thermocouple. The reactor was equipped with a stirrer and the speed was moderate, sufficient only to lift the skins to the surface. An acid solution of the appropriate concentration was prepared in the reactor and warmed to the appropriate temperature. Nitric acid was used in these experiments. The plant material was grated and dried and contained about 12% moisture. The plant material was charged to the reactor and extraction was performed for a predetermined time. The weight of the plant material was 400 g. During this time, the pH was measured and adjusted because the plant material acts as a buffer. After completion of the reaction, the contents of the reactor were drained into a vessel and filtered in a large Buchner funnel or using a filter cloth and vacuum. The wet plant material was then either returned to the second stage extraction reactor at different pH conditions or re-extracted in a large beaker adapted to stir and control the temperature (hotplate) under the same pH conditions or water to increase the yield of the first fraction. The extract was subjected to ion exchange, evaporated to concentrate the solution and then precipitated with IPA. The precipitate was washed with IPA / water solution and dried in a vacuum oven with nitrogen sweeping. The resulting pectin material was passed through a 80 mesh sieve and sent for analysis and further testing.

4 44 4 4 4 4 9 9 9 9 9 9 9 9

9 9 9

9 9 9 4

Example 1

In this example, several extractions are described. All experiments in these examples used a single starting plant material designated A. In experiments 4A and 1 IA, no additional calcium was added to the reactor. In experiments 5A and 8A, an increased addition of calcium was added to increase the calcium level. Calcium was added as calcium nitrate. Experiments 4A and 5A show similar results, both having a high degree of calcium sensitivity, over 600 cps for the CSP fraction and a very low delta CS for the NCSP fraction. A low CS delta for the NCSP fraction indicates the absence of CSP in that fraction. The total yields and molecular weight of each fraction are similar, but the distribution is somewhat different. Experiment 8A was performed in a more aggressive acid environment, but increased calcium addition showed in many respects similar results to experiments 4A and 5A except that the calcium sensitivity of the CSP fraction was significantly lower, below 600 and the distribution was somewhat more uniform. The amount of NCSP in the extracted pectin varies inter alia according to the plant material used, but the expected maximum amount is about 45% of the total pectin. Experiment 11A was conducted under aggressively acidic conditions, but the absence of added calcium showed a distribution greater than 40% as well as a high CS delta for the NCSP fraction. This indicates CSP leakage into the NCSP fraction, indicating undesirable experiment conditions. Thus, experiments 8A and 11A did not run under preferred conditions, while experiments 4A and 5A did.

The galacturonic acid content is typically between 70 and 80% in all extracted pectin samples. The degree of esterification is higher for the NCSP fraction (74-77%) than for the CSP fraction (64-68%). Dilution ratios are derived from the weight of the plant material, for example 20 denotes 20 times more liquid than the plant material (by weight), so that 2 l of liquid would be used per 100 g of weighed dry material. An additional 10/1 acidic solution was used for reextraction.

Example 2

In this example, different plant materials are used to extract pectin under the same conditions. It can be seen from Table 1 that the results are similar, with the distribution being somewhat different as expected. All plant materials were from citrus fruits (dried lemon peels) from South America.

These examples show preferred conditions, especially pH. The preferred pH for the second extraction is between 1.7 and 2.0, which is also typical for normal pectin extractions. Advantageous · fr · «*« fr · fr * * * * * * * * * * * * fr fr fr fr The pH range for the first extraction is between 2.9 and 3.3, although it can be extended to 2.7 - 3.5 according to our discretion. A pH of 1.5 is too aggressive for the second stage and a pH of 2.5 is too aggressive for the first stage. Although these aggressive effects can be negated by the addition of additional calcium, it is not advantageous to do so.

This process uses a batch extraction device that is typically used in pectin processing rather than a complicated tiered extraction device and is therefore easier to implement. Because of its relative simplicity, this procedure should be more cost effective than the alternative methods used to extract calcium sensitive and calcium non-sensitive pectin fractions.

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00

Table 1. Fractionated extraction results. Experiments for Examples (4-11A) and 2 (4C and 4Y).

4A 5A 8A 11A 4C 4Y Step 1 Dilution (pH) time 20 / 3.3 / 3h 17 / 2.9 / 2h 20 / 2.5 / 3h 14 / 2.5 / lh 20 / 3.3 / 3h 20 / 3.3 / 3h Added 0 22.5 mmol 45 mmol 0 0 0 calcium Yield 23.18 16.31 30,00 32.58 21.92 36.28 NCSP, g Mol. 122,000 124,000 158,000 184,000 Weight CS-, cP 13.5 15 Dec 14.5 18 18 16 CS +, cP 16.5 20.5 17 218 24.5 16.5 Delta CS 3 5.5 2.5 200 6.5 0.5 GA 76.6 75.4 78.9 77.6 74.5 77.5 DE 74.6 76.9 76.2 74.7 77.9 78.5 Content calcium, 586 1500 4650 730 PPm Step 2 Dilution (pH) 17.5 / 2.0 / 17.5 / 1.75 / 17.5 / 1.5 / 17.5 / 1.5 / 17.5 / 2.0 / 17.5 / 2.0 / time 0.75 h 1.5 h 0.75 h 0.75 h 0.75 h 0.75 h Yield 47.85 56.93 49.68 43.44 56.07 56.63 NCSP, g Mol. 149,000 174,000 177,000 195,000 Weight CS-, cP 16.5 15.5 13.5 15.5 12 11 CS +, cP 888 650 556 472 568 366 Delta CS 871.5 634.5 542.5 456.5 556 355 GA 70.7 80.7 76.9 72.7 72.0 68.9 DE 64.8 67.4 66.3 65.9 69.7 68.1 Content calcium, PPm 195 229 401 222 YOG 215 202 172 169 NCSP / CSP 33/67 22/78 38/62 43/57 22/78 39/61

% share

Claims (58)

PATENT CLAIMS A method for producing pectin from a plant starting material, comprising: (a) contacting the starting plant material with a weakly acidic solution for a period and at a temperature sufficient to separate the calcium-insensitive pectin (NCSP) fraction in the first extraction step; and b) separating the extracted juice from the plant starting material. 2. A method for producing pectin from a plant starting material comprising: (a) treatment of the starting plant material with a strongly acidic solution at a temperature and for a time sufficient to form an aqueous phase rich in the calcium-sensitive pectin (CSP) fraction; and b) separating the extracted juice from the plant starting material. A method for producing pectin from a plant starting material, characterized in that:. includes: (a) contacting the starting plant material in the first extraction step with an aqueous weakly acidic solution for a time and at a temperature sufficient to separate the aqueous fraction of calcium-insensitive pectin (NCSP); and (b) separating the aqueous extract fraction from the plant starting material; and c) contacting the separated plant starting material with an aqueous acid solution stronger than in step (a) at a temperature and for a time sufficient to separate the calcium-sensitive pectin (CSP) fraction. The method of claim 3, wherein the CSP fraction is separated from the starting plant material. A method according to claims 3 and 4, characterized in that the sufficient time has an upper limit of 5 hours. • 99 99 ·· 99 9 · 9 9 9 9 9 • 9 9 9 9 9 9 9 9 9 9 9 9 9 999 99 99 The process according to claims 3 to 5, characterized in that the stronger acid solution in step c has a pH value for an upper limit of 2.2 and a lower limit of 1.5. Method according to claims 3 to 5, characterized in that the method is a countercurrent extraction process. The method of claim 7, wherein the method is a countercurrent extraction process with a moving fixed bed. The method of claim 8, wherein the method is a multi-stage countercurrent extraction process. The method of claim 9, wherein the method is a rotary multi-stage countercurrent extraction process. Process according to claims 1 and 3 to 10, characterized in that the weakly acidic solution has a pH value for the upper limit of 4.0 and for the lower limit of 2.5. 12. The method of claim 1, wherein the weakly acidic solution has a pH for the upper limit of 3.3. 13. The process of claim 12 wherein the weakly acidic solution has a pH for the lower limit of 2.7. Process according to claims 11 to 13, characterized in that the weakly acidic solution has a pH for the lower limit of 3.0. The method of claim 14, wherein the weakly acidic solution has a pH for the lower limit of 2.8. 16. The process according to claims 2 and 3 to 15, wherein the strong acidic solution has a pH for the upper limit of 2.2 and a lower limit of 1.5. 17. The method of claim 16, wherein the strong acid solution has a pH for the upper limit of 2.1. 18. The process of claim Y wherein the strong acid solution has a pH for the lower limit of 1.6. The method of claim 18, wherein the strong acidic solution has a pH for the upper limit of 2.0. · «* · 20. The method of claim 19, wherein the strong acid solution has a pH for the lower limit of 1.7. The method of any preceding claim, wherein the temperature has an upper limit of 90 ° C and a lower limit of 70 ° C. The method of claim 21, wherein the temperature has an upper limit of 80 ° C. A method according to claims 21 and 22, characterized in that the temperature has a lower limit of 71 ° C. The method of claim 23, wherein the temperature has an upper limit of 75 ° C. The method of claim 24, wherein the temperature has a lower limit of 72 ° C. A method according to any preceding claim, wherein the sufficient time has an upper limit of 5 hours. 27. The method of claim 26, wherein the sufficient time has an upper limit of 4 hours. The method of claims 2 and 16 to 20, wherein the sufficient time has an upper limit of 5 hours and a lower limit of 0.5 hours. The method of claim 27 wherein the sufficient time has an upper limit of 3 hours. 30. The method of claims 27 to 29, wherein the sufficient time has a lower limit of 0.75 hours. The method of claim 30, wherein the sufficient time has a lower limit of 1 hour. The method of any preceding claim, wherein the calcium content of the solution is less than 1500 ppm dry matter. 33. A method according to any preceding claim, wherein the upper limit of the degree of esterification of the NCSP fraction is 80% and the lower limit is 70%. 44 44 4 4 « 4 4 4 4 4 4 4 4 4 44 44 • 44 4 4 4 4 4 4 4 4 4 · 4 4 34. The method of claims 2 to 33, wherein the upper limit of the degree of esterification of the CSP fraction is 70% and the lower limit is 60%. The method of any preceding claim, wherein the starting plant material is selected from the group consisting of citrus fruit, apples, sunflowers and sugar beets. 36. The method of claim 35, wherein the starting plant material is citrus skin, which is a by-product of juice production. The method of any preceding claim, wherein the acid is an inorganic acid. 38. The process of claim 37, wherein the acid is nitric acid. A method according to any preceding claim, wherein the weakly acidic solution comprises an additional amount of a polyvalent cation from a salt of the same acid. 40. The process of claim 39 wherein the polyvalent cation is selected from the group consisting of calcium, magnesium, iron, copper, and aluminum. 41. The method of claim 40, wherein the polyvalent cation is a calcium ion. 42. The method of claim 41, wherein the calcium salt is selected from the group consisting of calcium nitrate, calcium hydroxide, calcium acetate, calcium propionate, calcium oxide, calcium carbonate, calcium gluconate, calcium lactate. 43. The method of claim 42, wherein the calcium salt is calcium carbonate. The process according to claims 39 to 43, wherein the concentration of the added polyvalent cation in the solution is 1 to 50 mmol. 45. The method of claim 44, wherein the concentration of the added polyvalent cation in the solution is 5 to 25 mmol. ΦΦ φ · · φ φ φ φ φ φ φ φ φ φ φ • • • · • · · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ The method of claims 1 and 3 to 45, wherein the NCSP has a calcium sensitivity (CS) value of less than 20 cps. 47. The method of claim 46, wherein the NCSP has a calcium sensitivity (CS) value of less than 10 cps. The method of claims 2 to 47, wherein the CSP has a YOG value greater than 150. 49. The method of claims 2 to 48, wherein the CSP has a calcium sensitivity (CS) value greater than 100 cps. 50. An aqueous composition comprising calcium-insensitive pectin (NCSP) having a pH greater than 2.5, containing less than 2% by weight of alcohol. 51. The aqueous composition of claim 50, wherein the upper pH is 4.0. 52. The aqueous composition of claims 50-51, wherein the NCSP has a degree of esterification DE for an upper limit of 80. 53. The aqueous composition of claims 50-52, wherein the NCSP has a degree of esterification DE for the lower limit of 70. 54. An aqueous composition comprising calcium sensitive pectin (CSP) having a pH of less than 2.2, containing less than 2% by weight of alcohol. 55. The aqueous composition of claim 54 wherein the lower pH is 1.5. 56. The aqueous composition of claims 54-55, wherein the CSP has a degree of esterification of DE for the upper limit of 70. 57. The aqueous composition of claims 54 to 56 wherein the CSP has a degree of esterification DE for the lower limit of 60. 58. A husk mixture comprising husks in which the proportion of CSP to the sum of CSP and NCSP is enriched.